United States
             Environmental Protection
             Agency
              Office of Solid Waste
              and Emergency Response
              Washington, DC 20460
EPA/530-SW-86-042
October 1986
             Solid Waste
r/EPA
Waste  Minimization
             Issues and Options
             Volume  II

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Waste Minimization Issues and Options
    Volume 2:  Appendices A and B
           Submitted by:

            Versar, Inc.
         6850 Versar Center
           P.  0. Box 1549
     Springfield, Virginia  22151

                and

      Jacobs Engineering Group
         25 1 S. Lake Avenue
     Pasadena, California 91101
           Submitted to:

             Elaine Eby
        Office of Solid Waste
      Waste Treatment  Branch
U.S. Environmental Protection Agency
         401 M Street, S.W.
      Washington, D.C.  20460
           In Response to:

    EPA Contract No. 68-01-7053
      Work Assignment No. 17
          October 1, 1986

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                  LIST OF APPENDICES

A.  DATA BASES USED IN THIS STUDY

    A.I    Description of  Data Bases
    A.2    Questionnaire for RIA Generator Mail Survey
    A.3    Questionnaire for RIA TSD General Mail Survey
    A.A    Questionnaire for Industrial Studies Data Base Survey

B.  PROCESS STUDIES

    B.I    Acrylonitrile Manufacture
    B.2    Agricultural Chemicals Formulation
    B.3    Electroplating
    B.4    Epichlorohydrin Manufacture
    B.5    Inorganic Pigments Manufacture
    B.6    Metal Surface Treatment
    B.7    Organic Dyes and Pigments Manufacture
    B.8    Paint Manufacturing
    B.9    Petroleum Refining
    B.10   Phenolic Resins Manufacture
    B.I 1   Printed Circuit  Boards Manufacture
    B.I 2   Printing Operations
    B.13   Synthetic Fibers Manufacture
    B.14   Synthetic Rubber Manufacture
    B.15   1,1,1-Trichloroethane Manufacture
    B.16   Trichloroethylene/Perchloroethylene  Manufacture
    B.17   Vinyl Chloride Monomer Manufacture
    B.18   Wood Preserving
    B.19   Good Operating Practices
    B.20   Metal Parts Cleaning
    B.21   Paint Application
    B.22   Process Equipment Cleaning

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         APPENDIX A
DATA BASES USED IN THIS STUDY
             A-l

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A. 1        Description of Data Bases

    This  study  was based  on information  compiled from  a  variety  of  sources,
including  the  Regulatory Impact Analysis (RIA) Mail Survey, Biennial Report  Data
Base, Industrial  Studies  Data Base, National Small  Quantity  Generator  Hazardous
Waste  Survey, State information, industrial  information, and other literature.  This
appendix  contains descriptions  of  the computer data  bases,  how  they  are  used,
deficiencies or  data  gaps  associated with  them, and  the extent  to  which  these
deficiencies can  be rectified.  We have also included copies of the survey forms used
to collect data for the  RIA Mail Survey and the Industrial Studies Data Base.

    I.      Regulatory Impact Analysis (RIA) Mail Survey

    The RIA Mail Survey is a computerized data base that  contains the results of a
1982 national  survey of hazardous waste generators and  treatment, storage, and
disposal  facilities (TSDFs).   The  survey, sponsored  by  the Office of Solid Waste,
produced  a  statistically weighted data base containing more  than 6,000 elements
describing hazardous waste generation and  management activities in  1981, including
data on the  volumes of waste  that were generated, recycled, reused, and  reclaimed.
The  survey  identifies  specific facilities and Standard Industrial Classification  (SIC)
codes that generate and recycle hazardous waste, and distinguishes  between onsite
and offsite treatment of recycled wastes.

    In  this study, the RIA Mail  Survey  is  the  basis for identifying trends in the
generation and recycling of hazardous  waste.  The survey is  the most  comprehensive
source  of information  on  volumes of wastes  being  handled and recycled.  Sample
data have been  extrapolated to the  entire nation.   All  quantities  were  given  in
gallons per  year and were sorted by the five waste categories (halogenated organics,
solvents,  metals, corrosives, and cyanides and other  reactives); the  SIC categories;
and  EPA's  RCRA Codes (e.g., K011,  D001).  Because of the magnitude of  the data
base, the listing of industrial categories was screened to  eliminate those source
categories  that  generate  or  recycle  relatively  small quantities of  waste  material
                                      A-2

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(i.e.,  less than  50,000 gal/yr).  For  this  study,  we used  data obtained from two

sample  populations  surveyed  by  the   RIA  Mail  Survey:   (1) Generators  and

(2) Treatment,  Storage,  and Disposal  (TSD) facilities.  Both  the generator and TSD

survey forms are included in Appendices A-2 and A-3.


    During our review of the data base, we identified certain ambiguities, gaps, and

inconsistencies.   Such  limitations   must  be  considered  when   these data are

interpreted.  Specifically, the  restrictions include:
    •   Statistical Reliability of the  Data Base.  The statistical limitations of the
        data  base  have been well documented in the "National Survey of Hazardous
        Waste Generators and Treatment, Storage, and Disposal Facilities Regulated
        Under RCRA in 1981,"  which was prepared for  EPA  by Westat, Inc. in April
        1984. This report  states that "	quantity estimates (or ratios  of  quantity
        estimates)  are subject  to  considerably  more   estimation  error than are
        estimates   about   the  number  or  percentage  of  sites  with   certain
        characteristics."   Skewed  distributions  of  volumes  of  wastes  handled by
        TSDFs and generators were,  in  fact, quite  common.  Also, because of the
        numbers of facilities  surveyed, comparisons of the numbers of facilities that
        conduct  certain practices, e.g.,  onsite vs. offsite recycling, may  be  limited
        to  one or  two  data points. This can result in an inaccurate projection of the
        frequency  of occurrence of a  practice nationally.

    •   Age of the Data.  The RIA Mail Survey, containing 1981 information,  may be
        somewhat  dated.   Quantities  of  waste  generated and treated may have,  in
        certain  instances,   changed   markedly   over  the   past  four   years.
        Implementation  of  RCRA  requirements  and   public  concern  about the
        impacts  from  land disposal have  encouraged new technology and  increased
        materials-handling capacity.

    •   Generation Rates.  The generation survey  requested  respondents to  provide
        a breakdown by percent of total  waste  that comprises "F"  or "K," "P," "U,"
        ignitable,  corrosive,  reactive,   and  EP-toxic   wastes.  Translating  these
        divisions  into  the five  waste streams of  this  waste  minimization  study
        (halogenated   organics,   solvents,  metals,  corrosives,  and cyanides and
        reactives)  presented difficulties  in obtaining  generation  volumes  for  other
        than  the  characteristic wastes.  The "F" or "K," "P," and "U" wastes  could
        very  easily fit  into any or a few of the five waste categories. In addition  to
        lack  of   generation   volumes   of   solvents   and  halogenated  organics,
        participants may  have  occasionally  responded  incorrectly;  for example,  in
        one particular instance  for a specific SIC category, a total was given for the
                                      A-3

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   volume  of F  or K waste generated. The  same total was given for ignitable,
   and the  same for corrosive.  The  respondent may  have reasoned  that his
   waste  fit all three categories and  entered the same percentage  in  each
   category. The result is that the value in  the total waste column is the sum
   of all  categories,  thus  misrepresenting  the amount of waste the  facility
   generated by three  times.  For those SIC  categories  in which only a few
   companies  were  surveyed (usually  one  or  two), such responses can  cause
   gross  misinterpretations of volumes of waste generated  for  that particular
   industrial subcategory.  In categories  in which there are many respondents,
   such discrepancies are not  as evident and  are  essentially  "hidden  in  the
   noise."

•  Regional Extrapolations.  This study provides regional breakdowns of  waste
   generation   as  well   as  national  breakdowns.   Unfortunately,  regional
   breakdowns  are not accurate  because  of  the lack of data in  some instances
   upon which  to statistically base  projections. For  example, in Region  II,
   three  of the major  TSD facilities  in  the  State of  New York  were  not
   surveyed. Reasonable  extrapolations could be made on a  nationwide  basis,
   however. This deficiency may be rectified by relying on  information  from
   individual States as reported in the Biennial Report  Data Base  described
   below.

•  Discrepancies  in  Recycled  Proportions.   Westat  (1984)  indicates  that
   estimates of the  proportion of generated wastes that  are  recycled  may  be
   inaccurate.   "The  proportion  estimate  is  based  upon  the  Generator
   Questionnaire,  which   understates  the   quantities  of   hazardous   waste
   generated with onsite TSD facilities.  To the extent that these generators
   recycle  greater  proportions  of  their  hazardous  wastes  than  does  the
   generator population  as  a  whole, the proportion  is  understated.  To  the
   extent that  these generators  recycle smaller proportions of their hazardous
   waste, the proportion is overstated."

•  Inability to  Determine  True  Waste  Volumes.  It  is  apparent that,  on
   occasion, the reported volume generated and handled by a facility  may  be
   exaggerated.  This sometimes occurred  when the waste  stream was diluted
   with water (this  also contributed to the  previously  noted  skewed data).   A
   significant  portion of  the waste stream  may not be recyclable because the
   stream   is  too dilute   (with  water).  In  order  to  properly  evaluate  the
   recyclability of a stream, additional information is needed  on the makeup of
   the waste.   Unfortunately, it is not possible to compare  the  quantities of
   wastes  that  are  technically  and practically  recyclable,  and those volumes
   that actually were recycled.

•  Total Amount of Waste  Landfilled, Treated, or Otherwise  Handled Was Not
   Reported.  The RIA General and TSD  Mail Surveys present the total amount
   of waste (by SIC code) generated, shipped  offsite,  and recycled onsite  or
   offsite.  These surveys did not ask for  the  total amount  of waste that  is
   landfilled (onsite or offsite),  treated,  or  otherwise handled.  Examining the
                                  A-4

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       other RIA Mail Surveys (e.g., Land Disposal, Treatment, and Incineration)
       will provide volumes  of  wastes handled in  these ways, but such surveys do
       not provide information on a SIC level.  Thus, the Land Disposal Survey can
       provide information on the amount of waste landfilled, but not the portions
       that  came  from  SIC 28, 26,  35,  etc.  Total  wastes and their  handling
       methods and volumes can  be  obtained in this manner, but the Land Disposal
       Survey  and other  management  practice-specific  surveys  do not survey the
       same population  as  the  Generator Survey, so the results are  not directly
       comparable.

    •  Inconsistencies in  the Data Base.  On  rare occasions,  data  did not correlate.
       For example, in isolated instances, the sum  of  the  wastes recycled onsite
       and offsite for an  industrial category did not match  the total waste recycled
       within that SIC. The problem is likely  to be  inherent in  the data base.  For
       example, a facility may have  responded  to the  questionnaire  by  listing  a
       quantity of waste that  was recycled, but did not  enter an estimate of the
       volume(s) recycled onsite or offsite.

    •  Facility Size  Correlation.  Information  on  size  did  not  show   a  good
       correlation  with   the  amount  of  waste  generated.   For  each   facility
       identified in the RIA  Mail Survey, the number of  employees at each  facility
       was  obtained  from  data compiled  by Dun  &  Bradstreet.  The  resulting
       correlation between  waste generated and  number of  employees per  facility
       was  0.19,  which   is   low.  This has  been  partially  rectified  by  providing
       information on the number of facilities nationwide within  each SIC category
       for which waste generation volumes are presented.
    II.     Industrial Studies Data Base (ISDB)


    The  information contained in this data base was retrieved from  questionnaires

sent to  industries  under Section 3007  of  RCRA.  The  ISDB contains data for 12

major  industries within  the Chemicals and  Allied  Products  (SIC   28)  industry,

comprising approximately 300 facilities, 4,000  waste  streams, 500  processes, and
1,000 products.  It differs from the RIA Mail Survey in that it is structured  to obtain
information  on  the various  processes  within  each  of  the industrial categories

surveyed.  (A survey  form  for the rubber  and plastics industry  is included  as an
example  of the  questions used to structure the data base. It is provided in  Appendix
A-4.)  In addition, the  waste stream data are  more  comprehensive,  since  they

provide the  constituent  components  of the waste  streams  and  the  percentage of

each component to the  total waste stream volume.  More  detailed  information  is
                                      A-5

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available in this data base on the  type of recycling technologies used for the various
waste streams and the final disposition of and uses for the recovered materials.


    This data base also has its limitations, however, which include:
    •   Data Base Limited to Chemical and Allied Products (SIC 28) Industry.  Only
        information  from the chemical  and  allied products industry  is included in
        this data base. Therefore, it is not representative of all industries.

    •   Lack of  Information  and Limited  Access  to Two  Industrial  Categories.
        Because of lack  of information within 1  of  the 12 industrial categories and
        limited access to another, we  have determined that 10 of  the  12  surveyed
        have data of potential use for this study.

    •   Limited Information on Metal and Cyanide/Reactive Wastes. Since the  ISDB
        only  contains information for  the  chemicals and allied products  industries
        (SIC  2800s),  information on  the recycling  of  metals and cyanide/reactive
        wastes  is limited, because these industries do not generate those  wastes to
        any great extent.
    Though metal  and cyanide  wastes  may  be  underrepresented,  the  chemical

manufacturing industries generate the largest fraction of hazardous waste according

to other data sources.


    III.    National Small Quantity Hazardous Waste Generator Survey


    This source  contains the results of a national survey,  sponsored by EPA's Office
of Solid Waste,  of small quantity generators (SQGs)  undertaken by ABT  Associates,
Inc. between January  1983 and October 1984.   The survey,  distributed to nearly

50,000 selected  generators, resulted in a data base comprising approximately 19,000
responses.   The  survey  was  designed  to  obtain  a  profile of  generators  and
information  regarding  their   hazardous waste  streams  and waste management

practices.  One  hundred twenty-five standard industrial classification  codes  were

selected  and combined into 22 groups  as industries of  primary  concern; data for

these groups were  statistically weighted in order to generalize from   the  sample

population.  For each industry  group, the survey presents a breakdown of quantity of
                                      A-6

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waste generated  by  waste stream.  It  profiles the onsite  and offsite management
practices,  including   various  recycling  methods, according  to  the  number  of
establishments and quantity of waste.  In  addition,  three  sizes  of  generators are
distinguished:  those  producing less than 25 kilograms per  month, those producing
from  25  to  100  kilograms  per  month, and   those  producing   from  100  to
1,000 kilograms  per  month.  Waste stream-specific information  on management
methods,  however, is  only  available for the six  largest 5QG waste  streams.  For
these waste streams, the 22 industry groups are no longer  distinct.  Aside from the
inherent discrepancies taken into  account by its  investigators, the survey  has two
apparent disadvantages for  the purposes of this report,  which is based on five major
waste streams:  lack of the waste  stream-specific information  and  the fact that
RCRA waste codes are not given.

    IV.     Biennial Report Data Base

    The Biennial  Data  Base is  an electronic data base containing   1983  Biennial
Report Data Summaries from 45 States  for hazardous waste  treatment, storage, and
disposal facilities. This  electronic data base is managed by DPRA using the Office
of Solid Waste Prime 2250 computer system.

    The Biennial  Report is designed  to  collect  information  on hazardous  waste
activities for  generators and TSDFs.  Individual generators  and TSDFs are required
to complete the appropriate  form(s) providing  general facility information,  detailed
information on quantities  generated and handled  by  specific waste  code,  and the
final disposition of the waste. The individual Biennial Report forms are collected by
the State  or  Region  every  even  numbered  year and include information for the
previous odd  numbered year.  A summary of the data is  prepared and the  Biennial
Report Summary is submitted to EPA.

    The types of data contained in the Biennial Report Summaries and input to this
data base include: lists  of hazardous waste generators and  treatment, storage, and
                                      A-7

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disposal facilities onsite, offsite, and both onsite and  offsite (with "offsite" defined

as a TSDF where no waste was generated at  the facility itself); quantities of waste

generated by EPA waste code; quantities of waste shipped out-of-State and brought

into the  State; quantities  of  waste (identified by RCRA waste codes) managed by

specific methods (e.g., treatment, landfill, incineration).


    The  main deficiencies  in  the  Biennial  Data  Base  involve the  design  of the

Biennial  Report  forms used to collect the raw data and the manner in  which data are

submitted by States to EPA. These  limitations include:
        Limited Information on Recycling.  The EPA Biennial  Report forms for 1983
        did not differentiate between  recycling and other forms of treatment.  Only
        six States requested a breakdown between  recycling and treatment  on  their
        forms.  The  remainder lump recycling  into one  of at  least four treatment
        codes:  tank, surface impoundment, incinerator, or "other."

        Generation  Quantities.  The generation values in this  data base may  have
        been  overreported.  The  smallest  reporting  unit is  one  ton  unless the
        generation rate is indeed zero; thus, 100 pounds is reported as one ton.

        Handled Quantities Are Based on  Final  Disposition.  The  reported waste
        handling method for a particular waste represented the final disposition for
        that waste during  1983, If a waste was treated prior to  disposal (i.e., final
        disposition),  this  information  would not have  been reported.  As a result,
        treatment values may  be underreported.

        Waste Volumes Generated on a State Level.  Waste volumes generated are
        presented in  this data base  on the  State level, not on  a facility level.  The
        numbers presented are for the  waste types or total wastes  generated within
        that State,  but the numbers cannot be matched to a facility ID. Information
        at the facility ID level is limited to questions that can be answered yes  or no
        (e.g., Did you  ship wastes offsite?  Did you land  dispose waste?)  Thus, it is
        not possible  to match waste generation volumes  with  facility IDs and then
        subsequently match these IDs with SIC codes in the RIA Mail Survey.

        Double-Counting  When  Waste Volumes Are Broken  Down by Management
        Practice. Waste volumes  handled by various waste  management practices
        are not broken down as to the portion that is kept in-State, and the  amount
        shipped out of State.  Thus, for a given State, a  quantity  of  waste  that  is
        reported to be landfilled offsite may contain portions that have been  shipped
        from other States,  and which have been reported in that State as also having
        been  shipped  offsite.   As  a   result,  there  is a  built-in  mechanism for
        double-counting.
                                      A-8

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       California's  Different  Treatment  Codes.  The  California  Department  of
       Health Services has  established  its own biennial  report  with  more detailed
       waste  treatment codes and information on recycling.  However, California
       waste  codes, which  focus  on  constituents rather than waste  streams,  are
       independent of EPA codes, and there is  no  simple translation between  the
       two.  Both California's and the States' data  bases  fail to break down  the
       hazardous waste facilities into SIC codes.
    States have  been contacted  and  several  have provided  status  reports  with

information  on  their hazardous  waste  management  and  alternative treatment

methods.  Overall,  the  Biennial  Report  Data  Base is  a  thorough  inventory  of

EPA-coded wastes generated and handled by hazardous waste facilities.
                                      A-9

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                                                   >e t
    U.S.  ENVIRONMENTAL PROTECTION  AGENCY
HAZARDOUS WASTE GENERATOR QUESTIONNAIRE
       PLEASE: RECORD THE FOLLOWING INFORMATION ONLY IF DIFFERENT FROM LABEL ABOVE.
 Name of Installation:

 Installation's EPA
 loentification Numoer:
I   I
 Mailing Address:
                                STREIT OR P.O. SOX
            CITY
               STATE
                                                         *YQ
                                                         I.J.P
1.   Please record the location of this installation.*
      •°L£ASc GIVE THE ACTUAL PHYSICAL LOCATION, RATHER THAN THE MAILING AC-CRESS, OF THE
       INSTALLATION CORRESPOND ING TO THE EP4 IDENTIFICATION MJ^ES ABOVE.
   ACDRESS:

   CI7Y: 	

   STATE:
                    COUNTY:
                                        :i? CCCE:

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      >*Tom  should we contact for follow-uo at this installation?
      NAME:
      TITLE:
PHONE NUMBER:  I   I _ I _ I  - I _ I    |    |  . |    |
                AREA CODE
                                                                                 (J
                    _ I _ I _ I  - I _ I _ | _ |  . | _ | _ | _ } _ ]    EXTENSION:  I_I_I_1_J
 3.   In the table below, please list the primary SIC (Standard
                                                          Industrial Classification)  code
     of this installation, and up to three secondary SIC codes,' if more than one code is
     required to describe this installation.   [IF YOU DO NOT  KNOW THE SIC  CCOE  TOR  THIS INSTAL-
     LATION, PLEASE SELECT THE MOST APPROPRIATE CCDE(S)  TRpM_THE SIC  CODE  LIST  INCLUDED IN
     APPENDIX C OF THE GENERAL INSTRUCTIONS]             :  ' "r
             a.  Primary SIC code
                                                                   i	i Q_ i 31n \
                 Secondary  SIC. codes [PLEASE  LIST  IN
                 DESCENDING ORDER OF IMPORTANCE]:
                                                                        i_ii_i3jij
                                                                        r    i 6^  i -2 i O i
u.
Please indicate  the  typ«(s)  of  hazardous waste  activity(ies)  in which this
installation  was engaged  during  the  1981 calendar year.  [CIRCLE ALL CCCES  THAT  APPLY]
                                         ». Hazardous waste generation
                                         b. Hazardous waste treatment
                                         e. Hazardous waste storage
                                         d. Hazardous waste- disposal
                                         e. Hazardous waste- transportation-.
                                         f. Recycling of hazardous waste
                                         g. None of the above
                                                                                    u fL

01
02
G6
37
                     IF C3DE "01- IS CIRCLED, PLEASE SKIP TO QUESTION 7.
                                                                                               . 90-91
                                                                                               792-93
                                                                                               •9a_95
                                                                                               796-97
                                                                                               '96-?9
                                                                                               ••CC-1Q1
                                                                                               /•::-•; 03
                                            -2

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 5.   'wnicn of the following statements 3es:  essences  the  hazardous waste veneration           ^
      activities at cms installation?  ^ClSC.i  ONLY  :N£  CCCE ]                               G2_ ^

           a.  No hazardous wast* «as gereratso  curing  1981, none  «as generated during
               the five years prior to 1?91,  and Hazardous  waste  is  lot  expected to be
               generated in any quantities during  tne  'ive  years  following 1981 .......  01

           b.  No nazardoua waste was generated  during  1931, none  «as generated during
               the five years prior ta 1931,  out hazardous  waste  is  expected  to be
               generated at some point during tne  five  years following 1981 .........  02

           c.  No hazardous waste was generated during  1981, but hazardous waste was
               generated at some point during the  five  years prior to 1981, and
               hazardous waste ia expected to be generated  af same point  during the
               five years following 1981  ................  .' .  ........  03

           d.   No hazardous waste was generated during  1981, but hazardous waste was
               generated at some point during the  five  years prior to  1981.   Hazardous
               waste  is not, however,  expected to be generated again  at  this  instal-
               lation  during the five years following 1981  .....  . ...........  C-
           e.   Hazardous waste was generated in 1981, but no ,nore than  1000 leg, of
               Hazardous waste (and no more than 1 kg. of acutely hazardous waste/
               was  generated during any single month (small quantity generator).  .
           f.  Hazardous  waste was  generated in 1981, but all quantities df the
              hazardous  waste generated were or will be used beneficially, reused,
              recycled,  or  reclaimed within one year of generation	06

           g.  Hazardous  waste was  generated in 1981, but all quantities were
              generated  in  farming ooeratlons ana disposed of in accordance with
              aoplicaole RCHA regulations	07
          h.  Hazardous waste was  generated  in  1981,  but the waste has since been
              exempted from regulation  or  de-Listed  as a hazardous waste under RCHA ....  08

          1.  Hazardous waste was  generated  in  1981,  and at  least 10CO kg. of
              hazardous waste (or  1 kg-, of acutely hazardous waste)  was generated
              during a single month [SKIP  TO QUESTION 7].\	09
6.   Why was a Notification Torn suboi-tted to EPA indicating  that  hazardous waste
     would be generated at this inatallation?
                      PLEASE SIGN THE CERTIFICATION STATEMENT ON PACE 22
                      CT THIS QUESTIONNAIRE AND RETURN THIS "ORM TO £?A.

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7.   What was the total Quantity of hazardous wests generated at this installation during
     the 1981 calendar year?  [ENTIS QUANTITY AND CIRCLE UNIT CCCE]
       NOTE:  STATE THE QUANTITY OF WASTE GENERATED IN PRODUCTION OR OTHER PROCESSES PRIOR  TO
              THE ALTERATION OF SUCH WASTES THROUGH TREATMENT (SUCH AS OEWATERING) OR OTHER
              WASTE MANAGEMENT PROCESSES.  INCLUDE WASTES 'HAT WERE OR HILL SE USED, RECYCLED,
              OR RECLAIMED, OR SUBSEQUENTLY RENDERED NONHAZAROOUS.
                                         TOTAL QUANTITY OF -HAZARDOUS
                                           WASTE GENERATED IN 1981:
                                                                          tit  7-
                                                                                                     '110-118
3.
                                    [CIRCLE ONE]:
                                                                                / •  7-u *~
                                         Metric tonnes	Cf . I.  .•<• ."*•".   31
                                         English (or short) tons	02
                                         Gallons	03
                                         Other [SPECIFY]: 	       '	              C-
What quantity of the hazardous waste that «a» generated at this, installation during  1981  (as
specifies: in Question 7) waa or will be used, reused, recycled, or reclaimed (either on  sit;
or off site)?  (ENTES QUANTITY AND CIRCLE UNIT CODE.].

                                    QUANTITY GENERATED IN 1981
                                      THAT WAS/*ILL BE USED,
                                      REUSED, RECYCLED, OR                     , •; ^
                                     .RECLAIMED:                               ^  -
                                    [CIRCLE ONE]:
                                         Wet metric tonnes. . . .
                                         English (or short) tons.
                                         Gallons.  .	
                                   	- Other-[SPECIFY]: 	
                                                                                                     /I 5-24
                                                                                         01

                                                                                         02

                                                                                         03

                                                                                         CA

-------
9.   Of the total quantity of hazardous waste generated at  this  installation  (ap  soecifiee
     in Question 7), please indicate the percentage handled as hazardous  for  the  following
     reasons:
      NOTE:   TOTAL MAY EXCEED IOCS BECAUSE SOME WASTE MAY BE CLASSIFIED AS HAZARDOUS  FOR  MORE
             THAN ONE REASON.  HOWEVER, THE TOTAL SHOULD NOT BE LESS  THAN 1005 OF  THE QUANTITY
             OF HAZARDOUS WASTE GENERATED THAT IS SPECIFIED IN QUESTION 7.




a.

b.
c.
d.
e.
f.
9-

h.




i.


-


REASON FOR HANDLING AS HAZARDOUS
Because it was listed with an EPA Waste

Because it was listed with an EPA Waste
Number beginning with P 	
Because it was listed with an EPA Waste
Numoer beginning with U 	
Because it exhibited the characteristic of
Icnitabilitv (EPA Waste Numoer 0001) 	
Because it exhibited the characteristic of
Corrosivitv (EPA Waste Number 0002} 	
Because it exhibited the characteristic of
Reactivitv (EPA Waste Sunder 0003) 	 	
Because it exhibited the characteristic of
EP Toxicity (EPA Waste Numbers D004-0017). . . .
Because it was identified or listed as a
hazardous waste by a state 	
[DESCRIBE WASTES INCLUDED IN THIS CATEGORY]:


Even though it was not identified or listed
as a hazardous waste by EPA or by a state. . . .

PERCENT OF
HAZARDOUS
WASTE
GENERATED

(jf'^fl- ',

k *\C, 5
0.10 * '
£16 S
* °\ F s :
t
cu. i G~ *
"
L, q h t *

/••». _ _
i ;~ Ci LJ / '
VL^ ) Ti O^_ i


C^ ^ L. 5

                                                                                                     /TO-3:
                                                                                                     739-41
                                                                                                      'iS-50
                                                                                                     /53-55
                                                            c"J  Reu-rci  U

-------
.n ;ne soaces orovvaea oe.:«,  .ist  t.-'s  Lri -azar-xus -«aste Nuooers  :"ur  all
-astea sctuaiU aeferscae  st  tnia  :nstaiii::2n iuring t.ie '981 caxenaar  year,   if *asies
•ers generated in  iiixsa  -'sen,  list  :>e  £3- '»aste 'iumoer for- *acn of  .ne  eomoonent -astss
in :ne mixture separate!/.  '.lr-  •-;".  CZCES ARE '.13TED IN APPENDIX  A Or  THE GENERAL
INSTRUCTIONS;
NOTE: IF NO EPA WASTE NU'-^ER AP6'.
IES :: A 'ARTICULAR WASTE THAT IS HANDLED AS HAL
OUS, PLEASE USE TI-£ SPACE 3ROVICE; TO DESCRIBE "HE UNNUMBERED WASTE, INCLUO
ITS CHEMICAL AND PHYSICAL COMPOSITION AND THE PRUCESS • THROUGH WHICH IT WAS C
ERATED (e.g., SPENT MINERAL SPIRITS IN CONCENTRATED SLUDGE, CADMIUM LADEN
SLUDGE FROM WASTE WATER TREATMENT PROCESS, ETC.)

EPA WASTE COOES BEGINNING WITH THE
a. 1 	 I 	 1 	 1 	 I d. 1 	 I 	 !_
b. 1 	 I 	 1 	 1 	 i e. 1 	 1 	 l_
c. I 	 1 	 1 	 I 	 I f. | 	 1 	 |_
LETTERS "K", "IT AND "P": [LIST WASTE CODES ONI
J 	 1 g. 1 	 1 	 I 	 1 	 I j. I 	 1 	 l_
_l 	 1 h. 1 	 1 	 1 	 ! 	 I k. 1 	 1 	 I 	
_l 	 1 i. 1 	 1 	 1 	 1 	 1 1. l_ 	 1 	 i 	
EPA WASTE COOES BEGINNING WITH THE LETTERS '-'D" AND "F": [LIST WASTE CODES, AND "A
DESCRIPTION OF EACH WASTE, INCLUDING ITS CHEMICAL A.NO PHYSICAL COMPOSITION, AND THE
PROCESS THROUGH WHICH IT WAS GENERATED]
si. I ! I I ! Description:
•
VRC-
INC

-t]
J 	 ! 756-71
J 	 772-37
J 	 ,'88-103
,cl;
"6-19
n. 1 1 1 1 1 Description: '20-2.3
c. i 1 1 ! ! Description:
s. 1 1 1 1 1 Description:
q. 'i 1 1 1 1 Description:
r. I 1 I ! ! Description:
s. I 1 1 1 I Description:
t. I 1 ! I I Description:.
u. 1 1 I 1 ! Description:
v. T '! 1 | | Description:
<». 1 1 1 ! 1 Description:
x. I 1 1 ! I Description:
-


^




_


DESCRIPTIONS
OF UNNU^ERED WASTES:

/:t-2T
'28-31
'32-35
736-39
/iC-43
/4A-47
748-51
752-55
756-59
76C— s3


'6—65
-



IF ADDITIONAL SPACE IS REQUIRED, PL
PROVIDED FOR THIS QUESTION ON PAGE

EASE CHECK HERE AND USE THE ADDITIONAL SPACE
zj. ^^ . {,} H c y
VJ<^ L^ /A i

766
0

-------
 TT.    Did  this  installation  snip  hazardous waste off site for treatment,  storage1, anc,'or  •
       disposal  during  1981?   [CIRCLE  ONLY  ONE CODE]

                                           Yes [GO ON TO QUESTION 12]	>X  j I  .  .  '

                                           •No   [SKIP TO QUESTION 19]	I


 T2.    '"hat was  the total quantity of  hazardous waste that was shipped off site for treatment,
       storage,  and/or disposal during the  1981 calendar year?

                                           QUANTITY SHIPPED            -  •         ,^
                                            OFT SITE:  	U^ \ ,A.
                                                                          ;                 "            .Sd-7
                                      [CIRCLE  ONE]:
                                                                                  /'"  i •}  | , f
                                           Metric tonnes	V^  Y^ .  .  0'

                                           English (or  short)  tons	C2
                                           Gallons	'	CJ
                                           Other [SPECIFY]: 	  -±
TJ.   Of the total quantity of hazardous waste-shipped  off  site  for. treatment,  stsrac-.
      and/or disposal in 1981 (as specified in Question TZ),  wnat  percentage was snisoes
      to facilities owned bv other fims?
            IF MO HAZARDOUS 'HASTE WAS SHIPPED TO FACILITIES  OWNED  3Y  OTHER  FIRMS
            CURING 1981, PLEASE CHECK HERE
AND SKIP TO QUESTION 16.
                                          PERCENTAGE  SHIPPED  TO FACIL-            .^
                                            IT1ES OWNED BY OTHER FIRMS:   	Cl  \  ~^	5
                                                                                                       '80-52

14.    During 1981, what *«s the coat incurred by this installation  for transporting these
      hazardous wastes to facilities owned by other firms?  [PLEASE  INCLUDE  THE  COST OF
      LA8QR AND MATERIALS FOR 1981, IF THIS INSTALLATION PROVIDED ITS OWN TRANSPORTATION
      SERVICES.  IF TRANSPORTATION SERVICES WERE PROVIDED TO  THIS INSTALLATION FOR  A FEI,
      INCLUDE THE FEES PAID FOR SERVICES USED IN 1981.]

                                          COST OF HASTE TRANSPORTATION
                                            SERVICES IN 1981:	S

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15.    During 1981,  what was this installation's total cost,  inelugir; traraoortatign rsats
      reported in Question 14,  Tor tne treat.iient,  storage, and/or iisoosal of these •nazacscus
      wastes at facilities owned by other firms''  [PLEASE INCLUDE THE AMOUNT PAID TO FACIL-
      ITIES FOR TREATMENT, STORAGE, AND/OR OR DISPOSAL SERVICES,  AS *ELL AS AMOUNTS "AID CR  CCS73
      INCURRED FOR  TRANSPORTATION]

                                          TOTAL COST OF TREATMENT,
                                            STORAGE, AND/OR  DISPOSAL
                                            BY FACILITIES OWNED BY
                                            OTHER  FIRMS FOR  1981:  . .  S	
                                      ".                                               '                 /92-100

16.    Of  the total  quantity  of  hazardous  waste shipped off site for treatment, storage,
      and/or disposal  in 1981 (a3 specified in Question 12),  "hat percentage was snipoed
      out  of state?

                                          PERCENTAGE SHIPPED  OUT  OF STArr:       C^  \ (c       '-.

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'lease ;rcvis» the C?» Identification Sunoer for each off-sits  facility  to  «nicP.  this
installation snisces "aiarsoua waste far treatment, storage, and/or  Jisoosji  luring  tne
1981  caiencar year, and indicate tne total quantity of hazardous -asts sniooetf  and tne
total nunoer of -senifested shipments sent to eacn  facility during the 1981  calendar  year.
[PLEASE USE THE SAME UNIT OF >€ASURE THROUGHOUT THE TABLE.  REHEMSE3  TO  CIRCLE  UNIT  C3CE
AT THE acne* OF THE PACE]
                                                                  1341
    IF  AOOITIONAL  SPACE  IS REQUIRED TO ANSWER THIS QUESTION, PLEASE CHECK HERE I[
    ANO USE  THE AOOITIONAL SPACE PROVIDED FOR THIS QUESTION ON PAGE 26.  ,,,     '	'
                                                                  /16





r'ACILITY EPA IDENTIFICATION NUMBER
a. 1 1 1 1 1 1 1 1 Q\ 1 iT" 1 $1 \ 1
a. 1 ! ! I 1 1 1 1 Q\ 1 ! 7 1 S 1 1 1
c. 1 1 1 1 1 1 ! 1 0 1 1 !~?"l £•! | 1
d. ! 1 1 1 1 1 1 \ U\l \7-'\ D\ '} \
e. 1 1 1 i I 1 1 " ! Q. \ ) \~h \£ \ -1 |
'. I 1 I 1 1 1 I l ^T/ I ri F i 1 i



Total quantity of
hazardous waste
snipped to facil-
ity during 1981*
fil?/9i
G I r/^^
^ / ? C 2." "
ti/?OZ.
C,f?El
Oi7 Fl
*"
Total numoer
of manifests^
shipments
sent to
facility
during 13S1
$1703

C 1 r C J
GIZ&J
Oi7£3
GT/ 7F9 i

•[CIRCLE ONE]:

     Metric tonnes ............ .
     English (or snort) tons

     Gallons
     Other  [SPECIFY]:

                                                                                        01
                                                                                        Q2
                                                                                        33
                                                                                                ''65-38

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 18.   Please orovide the EPA  Lflentification Numeer  for  eacn  transoortsr  -nose  services ««:
      used oy this  installation  for the  Cransoortation  of  nazarcous  wasts  off  sue aurir^g
      1.981.  [IF THIS  INSTALLATION"PROVIDED SOME OR ALL  OF  ITS OWN  TRANSPORTATION SE3VICI;
      PLEASE INCLUDE THIS INSTALLATION'S EPA  lOENnriCAriON  NUMBER SELCV
          IT ADDITIONAL SPACE  IS REQUIRED  TO ANSWER  THIS QUESTION,  PLEASE  CHECK  HERE I    [
          AND USE THE ADDITIONAL SPACE PROVIDED FOR  THIS QUESTION ON  PAGE  24.  ,.. ^  '	'
Hazardous waste transporter identification numoers:

a. I	I	I	I	I	I	I	_!	1^1  '  I"  I ft  I

b. I	I	I	I	!	I	I	I	I  Q I i  I 2  I 6 '

c. I	i	I	I	!	I	I	i	I  U. I  \  I?  ! C '

d. I    !    I    !    I    I    I    I   I  ^ !  I  ' "I  I 0 !
                                                                                                      /57-7
The following Questions relate to the quantity of waste »«nich  is  recycled  beneficially  ratr-.er
tnan treated or disposed.  This would include wastes wrricn  are used or  reused,  sucfl  as  for raw
materials in production processes; or reclaimed, sucn as  solvent  redistillation,  scrao  -netai
reclaimed by secondary smelter, or wastes wnich are slenaed to nake fuels.   Beneficial  use also
includes "wastes used in a manner constituting disposal"  sucn  as  waste  aooliea  directly ta *.r\e
land as dust suppressants or as fertilizers.
19.  ' Oid this installation generate any hazardous waste that was used,  reused,  recycled,
      or reclaimed (either on site or off site) before  1981?  [CIRCLE  ONLY  ONE  CXE]
                                          .Yes.  .  .  .

                                          NO  .  -._...
ZQ.   Will any hazardous waste generated at this installation be used,  reused,  recycled,  or
      reclaimed (either on site or off site) after 1981?   [CIRCLE ONLY  ONE CODE]
                                                                                    ~  3.0
                                          Yes.
Z1.   Old this installation generate any hazardous waste that was used, reused,  recycled,  ar
      reclaimed (either on site or off site) curing 1981?  [CIRCLE ONLY ONE CCDE]

                                          Yes [GO ON TO QUESTION 22]	C*. -C- .' .  .  1

                                          So [SKIP TO QUESTION 26]	2
                                                10

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  •22.   In the taole below, please  specify  the  total  quantity of hazardous -as;; generated at this
        installation that -as used,  reused,  recycled  or  reclaimed (either on site or off sits)
        Airing 1961.  Of this total,  indicate the  quantity  that was recycled on sile at this  instal-
        lation during 1981; the quantity that was  sfuooed off site during 1991  for recycling  at a
        facility owned by this firtn;  and the quantity  that  was snipped off site during 1981 for
        recycling at a facility owned bv another firm.   [ENTER QUANTITIES AND CIRCLE UNIT CODE;.
        PLEASE USE THE SAME UNIT OF  MEASURE  THROUGHOUT  THE  TABLE]
                                                                                   QUANTITY
a. Total quantity  generated  that  was used,
   reused,  recycled,  or  reclaimed during 1981                          j
   [THE TOTAL QUANTITY REPORTED  ON THIS LINE                           j
   SHOULD EQUAL  THE SUM  OF  THE QUANTITIES ON             ^             j
   LINES b, c, AND" d  9ELOW]	    	(^ £ £  f\    i
                                                    i  _^____^^^^_
                                                    i

D. Quantity recycled  on  site during  1981	j    (j.- -•*->-. O

c. Quantity shipped off  site auring  1991            j
   for recycling at a facility owned  by            '•-,_,
   this firm	!    (j•>  ^     '.

a. Quantity snipped off  site during  1981
   for recycling at a facility owned  by
   another firm.	      (j*j


            '[CIRCLE ONE]:

                 Metric tonnes	rC.-^a--, ^ 5~".   01

                 English  (or short) tons	32
                 Gallons	03

                 Other [SPECIFY]:  	-	   o&
                                                                                                          -2-
•Please note that this question, and Questions 23 through 25,  refer  to  waste that was reevelee.
 or snieoed off site for recycling, during 1991. regardless of  the year in -nich it was generated.
 The total in Line A of Question 22 -ill not necessarily equal  the quantity reported in Question 3,
 Since Question 3 refers to the waste generated in 1981 that was/is  destined for recycling (either
 on site or off site), regardless of the year in -nich it was  recycled.
                                               11

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23.   Please comolete the following taole far tns '..s -.uarrn.s
      lation -nich -ere sniooed off site in greatest volume  'ar
      tion curing the- 1931 calenear rear.  [R£"IS '3 •';c:viC s-iGi
      EACH COLUMN OF THE TABLE]
                                                                ••ate*  jene rated it this instal-
                                                               .SB,  reuse,  recycling,  or reclama-
                                                                .'33  INSTRUCTIONS FOR COMPLETING
               IF THIS INSTALLATION DID NOT SHIP ANY HAZARDOUS rfASTES OFF SITE  TO
               3E USED, REUSED, RECYCLED, OR RECLAIMED DURING 1981, CHECX HERE FH
               ANO SKI? TO QUESTION 24.     '                 f~>, ,5.-  ,   •">  i  '	'
                                                              (j^O-*
                                                                              f 01  Krl.
                                                                                                    755
         COLUMN A
E?* number and oescnotion
of -astes snipped off-site
for use, reuse, recycling,
or reclamation
                                                   COLUMN 8
                                EPA Identification Numbers of three facilities
                                to which «aste was sent in greatest volume  for
                                use-, reuse-,  recycling, or reclamation-.
                                                                                      COLUMN C
  Quantity jf
  waste shisped
i  to each facil-
  ity during
  1981*
  a.
        Description:
         C£ Ai A- '
                                                                                   M.-11C
                  <-'
                                                                                        31^, C 03
  b.
                               1*443
      Description:  -.-
       iJ >• i  -%  c J
       U) 5- 3s A  0 6
    C  >3 Cr.-,
      Description:
       £ 3L2>  ^'
       C,.^J
  d.  i Q i *5 * 1  1 ° i
        Description:
         / \  -^ •n  /^v_ \ v
         1 /  r>^ ^  r^ ' «

         I 1  '"N 1.  &.  I ^
         v<  > ^2>  "  I -J

                                                                                          C I  \   !
                                                                                      ^ C >
       ^
                                                                                   c  ^ b  e
                                   •[CIRCLE ONE]:
                                        Metric tonnes	01

                                        English  (or short)  tons	C2
                                        Gallons	03
                                        Other [SPECIFv]: G^CkC t' j ^%U3C UC /S  C4

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C2LUM* A;  E.NIC3 £?* »AS7c: suf-SERS AND ShGPT DESCRIPTIONS  OF  THE  FIVE BASICS INCLUDING DESCRIP-
COLUMN Bs
COLUMN C:
COLUMN D:
COLUMN E:

TIONS OF THE 'RCCISSES THROUGH «HICH EACH WASTE *AS GENERATES. [EPA WASTE C3CES *3£
LISTED- IN APPENDIX A CF IHE GENERAL INSTRUCTIONS] t
ENTER THE EPA IDENTIFICATION SUM8ERS OF THE THREE FACILITIES TO WHICH EACH WASTE WAS
SHIPPED IN GREATEST VOLUME.
INDICATE THE QUANTITY OF WASTE SHIPPPED TO EACH FACILITY AND CIRCLE THE UNIT CXE AT
THE BOTTCM OF THE COLUMN. PLEASE USE THE SAME UNIT OF MEASURE FOR ALL WASTES IN THE
TABLE.
CIRCLE THE CODE OR CODES THAT INDICATE HOW EACH WASTE WAS STORED PRIOR TO SHIPMENT 3F^ ;
SITE FOR USE, REUSE, RECYCLING, OR RECLAMATION.
FOR EACH FACILITY, INDICATE THE AVERAGE NUMBER OF DAYS EACH WASTE WAS STORED PRIOR TO |
SHIPMENT OFF SITE FOR USE, REUSE, RECYCLING, OR RECLAMATION.
COLUMN D
How was waste stored prior to shipment off site for use, reuse,
recycling, or reclamation? [CIRCLE ALL THAT APPLY FOR EACH FACILITY]
In con-
tainers
Ci_JSP\CI
(i. jLi'ju-V
01
U_ -i V 0 1 o<
01
01 ""
<- J-iOtcij
01
15
J 1
^Vi""^
U. £J- V
01
In above
ground
tanks-
a, jiioic,^
' "|tf
(trll'-ijlC/
<-c J-jOji'-l
W XJOoL'i'T
02
Ly -i\ 01 1 1
02
IS
In belov
ground
tanks
03
v^j 3*1 Q^ C ~ j
o3
Q% ji*iC 3^3
w-^C,
-^Ji 3 Ojt~7
Ci.J.J/J^c']
Q,-ii4?3j»a
S 3.5J34 /-A.
03
V> jj^J LT
03
In
piles
04 ^
QA *7
DA
ww "^tf Yt y"
Lj'jywi/
04
04 J
^J
In
surface
impound-
ments
^Jft 05^- /.
,"". ;J ^ ^A""* • ^
05
05 -*
^Cci
^05
05 ^
Other [SPECIFY]:
06- C3-104 0\
06 G ^ 3 0 (. C ju_
06 6c>3D6C^
COLUMN E
Average numoer
of days -asts
-as starec prior
to sn lament aff
Site for use,
reuse, recy-
cling, or
reclamation.
UVj^tv. i Oays
G^2^cwU. Days
1-MC<-_i 3avs

06 Cv ^5 0£ ^ V
06 C- -3 5 Ii ^- C_i
VJ. -i £ <-' *? Days
^^t^' Davs
06 C 3. i J6 C6 G- ^ ; r> C- Davs

06 (~- "5- ^>-D^O f.
06 C£ 9^ 3 Q 4- c_v
C-J \&J-r Cays
* "^
06 CJc^"b06>C) iCt-^3 £ *• / Oavs

06 «*•' J-J> D ^ -1 O '•£$*:& 1- 3av*
06 C_2VE>(-, il -5.2^}{ -ays
06 C;^.J:nG/3^ Ci-6,'^.3avs

06 Q.^-2 D(~ /-i ' ^'^"-^ "- -avs
06 u ^ t, o(, i y
^-^i-/1- Oavs
06 C^Jii^^/r" C'-^'^Oars
1
1 '^j '" ^Vrxo^,-
                                                                                                       10731
                                               13

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                                                                                                      /be

24.    Pleaae comoiete t.-.e .'silo-inq taole for the five hazarcoua ««st.c3 genern'.yo  at  :nis  instillation

      «nicn were used, reused, recycled, or reclaimed an site in greatest voi«.-vs sunnq  tne  "?31  caltn-

      oar year.   [REfES TO TACl.sC '4GE FOR INSTRUCTIONS TOR COMPLETING £ACH CCL.MN OF  :-i£  liSLl]
              IT THIS INSTALLATION DID NOT USE, REUSE, RECYCLE, OR RED-AIM ANY lAZARCCUS
              WASTES ON'SITE IN 19S1, CHECK HERE!   I AND GO TO QUESTION :s.
                                                 I—I                     u' >j~x qy
COLUMN A
EPA Number and
description of
-as tea used, re-
used, recycled
or reclaimed on
site :
a. 1 1 1 1 1
Description:
<£ -21 /PftC 1
b. ! ! 1 1 1
Description:
(^ 9.M A0p J-
c. 1 I 1 1 1
Description:
d. 1 1 1 1 1
Description:
L^o^fn'^ (-' '
e. ! 1 1 1 !
Descriotion:
COLUMN B
How was this waste used, reused, recycled, or reclaimed
on site? [CIRCLE ALL THAT APPLY]
As feed-
stock in
manufac-
turing
process
01
01
Q$Htyc±.
01
01
01
As fuel
or fuel
supple-
ment
02
02
^JWgxfCj;
02
02
02
In manner
consti-
tuting
disposal
' 03
03
03
$iV£3«-'3
03
03
V
Reclaimed
04
04
04
34
04
y»*^
Other
[SPECIFY]:
05
SjlfSSw,

05
nin4ic>.

05
CtWlit. ]

05
kAVdj-c*,

COLUMN C
Quantity' of
»aste usec,
reused, re-
cycled or
reclaimed
during 1981*

C; 2-'~'C c '

^

Ct if CCS

u ->«'c -Ji
05 ;
' ^1'^CS

'~ iwcc ••"

                                                14
•[CIRCLE ONE]:


      Metric tonnes	01


      English (or short) tans	02


      Gallons	G3

      *•>»•.... rcscpTrvi..
                                                                                                    T C U

-------
CCL'JMN A;  ENTER EPA WASTE NUMBERS AND SHORT DESCRIPTIONS  Or  THE  FIVE WASTES, INCLUDING DESCRIP-
           TIONS OF THE PROCESSES  THROUGH nHICH EACH WASTE WAS  GENERATED.   [EPA WASTE CODES ARE
           LISTED IN APPENDIX A OF t*E GENERAL  INSTRUCTIONS]
COLUMN 3;  CIRCLE THE CODE OR CODES  THAT INDICATE HOW  THE  WASTE WAS  USED,  REUS5D, RECYCLED OR
           TCLAIMS.C ON SITE.
COLUMN C;  INDICATE THE QUANTITY OF  WASTE USED, REUSED, RECYCLED  OR  RECLAIMED DURING 1981 AND
           CIRCLE THE UNIT CODE AT THE BOTTOM Of THE TABLE.   PLEASE  USE THE SAHE UNIT OF MEASURE
           FOR ALL WASTES IN THE TABLE.
COLUMN D;  CIRCLE THE CODE OR CODES  THAT INDICATE tiOW  EACH WASTE  WAS STORED AT THIS FACILITY
           PRIOR TO USE, REUSE, RECYCLING, OR RECLAMATION.
COLUMN E;  INDICATE THE AVERAGE NUMBER OF DAYS EACH WASTE  WAS STORED PRIOR TO USE, REUSE,        	
           RECYCLING, OR RECLAMATION.                                                            ICSRi
COLUMN D
How was waste stored' prior to use, reuse, recycling, or reclamation?
[CIRCLE ALL THAT APPLY]



In con-
tainers
Lu.i'itf/el
^ 01
-r°*
01
$ jHOlc y
01
01


In above
ground
tanks
Q.jm^d
02
(^JllQji^s-
"02
02
02
02


In below
ground
tanks
5vo)c-,
0-
03
««*•«
03
^03^'



In
piles
,Jtow

04 =^
Viva,
04^
i^y0fc
04 *}*
C4'C.r

In
surface
unpound-
ments
V^-'c,
05
05
Q_jV^"Cj
05
Q i'r^S'Ci.-
(^^ Cj




Other [SPECIFY]:

COLUMN E

Average num-
ber of days
waste «as
stores prior
to use, reuse.
recycling, or
reclamation

06 0 yL^, 0^ C i ^jiTc:'. 1 Days

^

06 (7. A.V 0£ O"^>

06 \^^ '-^ ( O^* c /

' ^^
06 , 71 J~ *i 0 (: C '-»


Ct'X'.'w'->-Oays

CVvE-j Oays

C. >vc -^ Oavs

V-'^C v-> Oays

                                                                        c i
                                               15

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 25.    For  eacn  waste  indicates in Question 24 as being used in a manner constituting disposal
       ("03"  circled  in  Column  3), please describe the specific manner in wnicft the ^aste »as used:
2&.   The RCSA regulations allow installations with  tanks wnich  are  a  part  of a wastewater treat-
      ment system tnat is suoject to regulation under  the Clean  Water  Act,  and -nicn receive anc
      treat or store wastewatsr wnich is hazardous,  to operate these tanks  without  ootainir.g a
      permit or interim status.  This exemption,, which was  issued  on Novenoer 17,  1980,  is called
      the wastewater treatment exemption.  During  1981, were  there any  tanks  at this installation
      which were aeing operated under the wastewater treatment exemption?   [CIRCLE  CNLY  ONE CEDE;
                                          Yes [CO. ON  TO QUESTION 27]

                                          No  [SKIP TO QUESTION 29]
27.   Curing 1981, how many tanks at this installation were used  for wastewater  treatment uneer
      the wastewater treat-TMsnt exemption?

                                           NUffiES OF TANKS USED UNDER               n  - _
                                             WASTEWAfER TREATMENT EXEMPTION:       U. yi  ~
23.   '*iat is the averace design caoacity of a tank used for wastewatsr treatment during 1?81?
      (That is, how inucn wastewater could the average wastewater treatatent tank hold?)   CENTER
      QUANTITY AND CIRO.E UNIT C20E]

                                           AVERAGE CAPACITY CF WASTEWATER
                                             TREATHENT TANK:
                                       CCIRO.E ONE]:

                                           Metric tonnes

                                           English (or short) tons .............    32

                                           Gallons .....................    C3
                                           Other [SPECIFY]: .................    QA
                                               16
                                                                                                      731-::

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 29.   The 8CHA regulations allow waste generators to accumulate -azarcoua  waate  ar\ site 'or up to
       90 days without obtaining a remit or interim status, sraviced  these generators accumulate
      'waste in accordance with certain standards.  This is called the  90-day  rule.   During 1981,
       •ere wastes accumulated at this installation uncer the 90-day rule?   [CIRCLE  ONLY ONE CODE]

                                          Yea [CO CN TO QUESTION 30]	£, Q Cj .  .  1

                                          Vo  [SKIP TO QUESTION 45]	2

                                          don't know [SKIP TO QUESTION  45)	3
 JC.  'On  an average  day  curing 1981,  how much accumulated (90-day rule) hazardous waste  waa  being
       iteot  at  this  installation?  [ENTER QUANTITY AND CIRCLE UNIT CODE"]

                                          QUANTITY Or ACDJMULATED WASTE              -
                                          "^
                                      [CIRCLE  ONE]:

                                          Metric tonnes	H. .-^ ......  01

                                          English (or short)  tons	02

                                          Gailona	23

                                          Other  [SPECIFY]:	3i
      During *?8"!, how many on-aite  areas did  this  installation have in «hicn hazardoua waste
      was accumulated unaer the 90-day rule?

                                         NUMBER Of  ON-SITE
                                         ACCUMULATION AREAS: 	f-< 3 1	
32.   Please -specify how many of tie on-site hazardoua -aate  accumulation areaa «ere located:

                                                                              Mumtaer- of- Areas

           a.  Within the manufacturing or industrial area  (i.e.,  at  or
               near locations wner« hazardoua wastes are generated ) .  .  .
           b.   Adjacent to.  er separate fron, the manufacturing or
             • industrial area (1.0., a loading deck, staging area, or
           •    other location outside of the generating area) ...... _ (-2  3 -^ ^3
                                               17

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 J3.    Please  scecify  how  many  of  the  on-site  hazardous waste accumulation areas were supervised by
       personnel:
            a.   With  thorough knowledge  of  plant  operations,  including
                the process  that produced the hazardous  wastes,  and
                knowledge of other hazardous materials,  if  present: .  .
            b,   With  knowledge of plant  operations  limited  to  the
                operation of the accumulation area  (i.e., when andr
                how to load  and unload containers or  transfer
                wastes into  and out of the  area):  	
                                                                              Numoer of Areas
u
                      754-56
                         757-5?
      Of the hazardous waste accumulated under the  90-day  rule  in  1961,  wnat
      percentage was accumulated in:
           a.  f-anks	

           b.  55 gallon containers	

           c.  Other containers [SPECIFY TYPE AND CAPACITY): 	*
               TOTAL SHOULD EQUAL.
                                                                                Pereentaae
Q
 C?
      C  \
     w C
                                                                                            100 5
                       SU-Oi

                      .'53-65
55. .  During 1961, how many tanks at this installation were used  for  hazardous  waste accumulation
      under the 90-day rule?
             IF TANKS WES£ NOT USED 8Y THIS INSTALLATION FDR HAZARDOUS WASTE  ACCUMULATION
             UNDER THE 90-OAY RULE DURING 1981, CHECK HERE I   I AND SKIP  TO QUESTION  37.
                                                           1	'             ^ 8-* 2 \-
                                         NU«ER OF TANKS USED
                                         FOR ACCUMULATION
                                         UNOER 90-OAY RULE:
                      771
                                               18

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            w«s the average  design caoacity of a tank used for hazardous waste accumulation  uncer
       the 90-oay  rule  during  1981?  (That is, how much waste could the average accumulation :anx
       hold?)   [ENTER QUANTITY  AND CIRCLE UNIT COCE]                              '

                                          AVERAGE CAPACITY OF WASTE             ,
                                          ACCUMULATION TANK:                    ^  3 v»	
                                      [CIRCLE ONE]

                                          Metric tonnes 	
                                          English (or snort) tons

                                          Gallons	• •  •
                                          Other [SPECIE]: '	
            C.
                  01

                  02
                  03

                  04
37.   During  1981, how many  areas  were used for hazardous waste accumulation in containers
      under the 90-day rule?
         IF CONTAINER ACCUMULATION  AREAS  WERE  NOT USED 3Y THIS INSTALLATION FOR HAZARDOUS
              ACCUMULATION UNDER  THE  90-OAY  RULE  DURING 1981,  CHECK HtRE
        CUEST10N 39
AND SKIP
                                                                                      2 r '
                                          NUMBER OF  CONTAINER
                                          ACCUMULATION AREAS:

38.   '*ial was the average Quantity  of  hazardous  waste held in container accumulation area(s)
      under tne 90-day rule during  1981?   [ENTER  2UANTITY AND CIRCLE UNIT CCCEJ
                                          AVEflACE  QUANTITY BEING HEJ.D IN
                                          CONTAINCR  ACCUMULATION AREAS:  _

                                      [CIRCLE  ONE]:

                                          Metric tonnes 	

                                          Englisn  (or short)  tons .  . .  .

                                          Gallons	

                                          Other
         O <
                  02

                  03
                         , en..;;;
                         'OO,- ')
39.   During 1981, wa« any of the accumulated  {90-day  rule),  hazardous  waste processed en site
      in any of the following ways?   [CIRCLE ONE  C20E  fOR  EACH  PROCESS]
                                                                                               NO
                                          a. On-site  treatment
                                          b. On-site  disposal
                                                                          '1  a 
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 4C.    during  '991,  was  any  of  the  accumulated  (50-aav  ru.«)  nazarccus naste shipped to any off-site
       treatment,  disposal or recycling  facility?   [CISC.!  ONLY  ONE CCCE]

                                          •'es [CO  ON  TO IL'ESTICN -i<: ........ *. 6^X.L(^ .   r

                                          NO  [SKIP  TO  C-LESTICN  45] ..............   2     /iQ7

                                          Don't  know  [SKI?  TO QUESTION 45] ...........   3


 41.    During  1981, how • much waste  constituted a normal load  for snipping off site to a treatment,
     -disposal or recycling facility? " [ENTER QUANTITY AND CIRCLE UNIT CODE]

 --.-..       '              '            SIZE Or  NORMAL LOAD: _ (-£4 ! _     /1C8-

                                     [CIRCLE ONE]:

                                          Metric tonnes ............ r<  ..'...    01

                                          Engiisn  (or snort)  tons ..............    02
                                          Gallons  ............ • ..........    03

                                          Other  [SPECIFY]:                                        34
      '<*iat size *aste shipment da you consider  to- be- the opti/num size for this installation''
      [ENTER QUANTITY AND CIRCLE UNIT CODE]
4A.   During 1981, now often was it necessary to make  an off-aite  shipment that «as smaller than
      optimum (as specified in Question 42) in order to meet  the  special arovisions of the 90-say
      rule?  [ANSWER AS PERCENTAGE OF THE NU^ER CF 1981 WASTE  SHIP^NTS]
                                         PERCENTAGE  OF WASTE  S
                                         SMALLER THAN OPTIMUM IN  1981:            d-
                                                20
                                         SIZE  OF OPTIMUM LOAD: _ i ,1  M  ^L

                                    [CIRCLE ONE]:

                                         Metric tonnes  ............ Qt .^.^ .  .S   01
                                         English (or  short)  tens  ..............   02
                                         Gallons ...... ' ................   03
                                         Other [SPECIFY]: _ '                             CA
43.   During '931, at your normal operating rate,  approximately  ho» many days dad it take to
      generate a »«ste shipment of the oot i=iusi-aiitr-(as specified in Question 42)7

                                             £H  CF JAYS TO  OLNEHATE: 	       C t-' 3             /27-:5

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45.    Waste excnarvge is the process -rir»2-<
      to treat waste) in another insuEtry .
                                         -as:-? from an  incustry  is  usel  as  raw  iiat-.-iai • -r
                                         Is ir-is fins interested  :n pa.rticio*ti.~g  .n s^'crt;
  by  EPA  or  other  organizations to facilitate the oevelooment of  waste  exchanges'5  (C!RCL
  CNLY ONE CODE]
                                         "es [OS ON  TO QUEST :CN  46]
                                         No
                                          [PHASE SIGN THE CERTIFICAIION STATEMENT
                                          CN PACI 22 OT THIS QUESTIONNAIRE  AND  RETURN
                                          THIS TORM TO EPA] ...  1
  OPTIONALi  Please  list  the  Chemical  Abstract Service Registry Noncer or Nunbers  for each
  waste generated at this-installation during the 1931 calendar year.
NOTE:  ALTHOUGH THIS QUESTION  IS OPTIONAL,  TME DATA OBTAINED f?0v 'ESPONSES TIN =E  '.iSr?  ='
INTERESTED PARTIES TO FACILITATE THE USE, REUSE,  RECYCLING, CR "ECLAMiTICN CF rtAZAHCCUS
WASTES AND PERHAPS DIMINISH  THE COMPLIANCE  3UROE.N IMPOSED 3Y RC2A.  THIS ^'- -I-.t  3E  JStD
3Y EP4, STATES, PRIVATE ENTERPRISES, AND  OTHERS WHO MAY HAVE AN INTEREST .N >E £CL'SCI3  :'
INDUSTRIAL WASTE THAT HAY BE RECYCLABLE.
  Chemical Abstract Service Registry Nunoers:
                                                                                         c
                                                                                         'c
                       PLEASE  SIGN  THE  CERTIFICATION STATEMENT ON
                       NEXT  PAGE  AND" RETURN THIS QUESTIONNAIRE TO
                                          21

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                                  CERTIFICATION STATEMENT
      THE GENERATOR OR HIS AUTHORIZED REPRESENTATIVE MUST SIGN AND DATE  THE  CERTIFICATION
      WHERE INDICATED.  THE PRINTED OR TYPED NAME OF.THE PERSON SIGNING  THE  CERTIFICATION '
      HUST ALSO BE INCLUDED WHERE INDICATED.
CERTIFICATION!

I certify under penalty of law that I nave personally examinee and  am  familiar  witn tfe inf"or-
raation submitted in this and all attached documents, and that Dased on my  inquiry  of tnose
individuals immediately responsible for obtaining the information,  I oelieve  tnat  the suonuttsc
information is true, accurate, and complete.  I am aware that there are significant penalties
for suomitting, false information, including the possibility of fine and imorisonmenr..
          PRINT OR TYPE NAME
SIGNATURE
DATE SIGNED
            AFTER COMPLETING THIS QUESTIONNAIRE, RETURN IT TO EPA IN THE ENVELOPE
            ENCLOSED IN THE QUESTIONNAIRE PACKAGE.

            IF THIS FACILITY HAS RECEIVED MORE THAN ONE QUESTIONNAIRE, PLEASE  RETURN  .j
            ALL COMPLETED QUESTIONNAIRES IN THE SAME ENVELOPE.
                                             22

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                                           TABLE A

                              CONTINUATION SHEET TOR QUESTION 10
EPA WASTE CODES BEGINNING WITH THE LETTERS "X," "U," AND "P":   [LIST WASTE
COOES ONLY]
                                                                                                    ,nR|
                                                                                                    ,,,-31
b.
c.
». !
n. I
a. 1
P. 1
JJ. 1
r. 1
s. I
t. 1
u. 1
y. 1
-. 1
x. !
EPA WASTE COTES BEGINNING WITH
AND A DESCRIPTION OF EACH WASTE
SIT ION, AND THE PROCESS THROUGH
1 I.I 1 Description:
1 1 1 1 Descriptions
! 1 1 1 Description:
1 1 1 1 Description:
1 1 1 1 Description:
1 1 I 1 Description:
111! Description:
1 1 1 1 Description:
1 1 1 1 Description:
1 1 ! 1 Description:
1 1 1 1 Description:
1 1 1 1 Description:
ISCRIPTIONS OF UNNUI-BERED WASTES:
THE LETTERS "0" AND T": (LIST WASTE CODES
, INCLUDING ITS CHEMICAL AND PHYSICAL C3MPO-
WH1CH IT WAS GENERATED]
& 1 <~>A& O/ 7"y C. | o <* A \ •}-
CjlO/JAOi fC C] |0 ,i fj i o c A i ^.
fi \toQAcL +?, C It PA 1.3.
r.>icjv,:^o. -1-5, C^^Gl^/-5~
/-, -prr'Aci -n: Ci:. /cK^'-^
' Q ( CT/a c, -7^ C i c T/? / -4L
(^ /c r&Ci —^ C /L Tfii 3-
C !O UA cv -fSi G? I C. u ft j±
& [ G V ft C- f -fo (2 1 o ^ ^ / jL
(£ 1 Q LJ fit—C / ~f*r, C? IO LJ/4
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                                         TABLE 3

                                         SHEET FOR  QUESTION 17
                ^;.,,t_  -ij
          FACILITY EPA IDENTIFICATION NUhSER
                                                            Total quantity of
                                                            hazardous waste
                                                            shipped to facil-
                                                            ity during 1981»
                 Total numoer
                 of raanifesteo
                 shipments
                 sent ta
                 facility
                 during 1981
 1.

 2.

 3.
 4.

 5.

 6.
 7.

 a.

 9.

10.

11.

12.
                                                                        \
                                          "?-V*icl

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                                               one »:   2000-0^:
                                              Spires: Decemcer
        U.S. ENVIRONMENTAL PROTECTION AGENCY
HAZARDOUS WASTE TREATMENT, STORAGE AND  DISPOSAL
                  GENERAL QUESTIONNAIRE
          PLEASE RECORD THE rou.owi.vc INFORMATION, ONLY cr DIFFERENT mw USE;. AEOVE.
     Name of Facility: _____^______^—__

     Facility EPA
     Identification Numer: I	I	I	I	I	I	I	!	!	I	I	I	I

     Hailing Address: .^__.___.^_^_«—_^_^—
                                STREET OR P.O. SOX
               CITY
                                  STATE
                                                      CCDE
     1.  Please record tfw location of tnis facility.'
•«L£ASE GIVE THE ACTUAL PHYSICAL LOCATION CF
THE EPA IDENTIFICATION WJ«E3 ABOVE, RATHES
ACCRESS:
CITY:
STATE:
THE FACILITY CORRESPONDING '3
THAN ITS HAILING AOCR£55.

COUNTY: ^J/ / P~
ZIP CXE: (^} 1 B

/S3-70
771-72

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     «hom *nould «e contact  for  fsllo—uo  at  -.113 'ac-lity
     TITLE: 	

     PHONE NUP8ER:  I	I	I	I  -  I	I	!	!  - I	I	I	!	I  EXTENSION:
                     AREA CODE
J.    Please indicate the  type^s) of  hazardous waste. activity( IM)  in wnich- this
     installation was engaged  during the  1981 calendar year.  [CIRCUS  ALL  CODES  THAT AP°\.f]

                               a. Hazardous waste generation. .  :-r. *P .'T  .   0'
                               S. Hazardous waste treatment . . Cr. V .O.  .   C2 —    ,	
                               d.  Hazardous  waste discosal. .  . <-»<•-? •i*'.  .   JA  —
                                                                   /-^ a  ~
                               e.  Hazardous  waste transportation.  wK w  — .   05

                               f.  Recycling  or  nazaraous «aste.  .  &.—. T  .   Co
                               g.  None  of the aoov'e
        IF CODES "02", "03" ANO/CR  "04"  ARE  CIHC'-iD, ?LEASt GO  TO QUESTION  .1.

        IF YOU HAVE NOT CIRCLED  CODES  "21,"  "OJ" OR "04," ."-E.4SE SI07)  'v-t ~"T'.-
        rICATION STATEMENT ON PACE  J7  AND  RETURN THIS 3UE5T:C.V«1IRE  TO  £?;.
     **hat -as the year in *oich *»ste  management operations first Seqan  at  this  '"
     (That is, in «nat year «as the  original constructlon/aeveiooment  of :.-ie  -asts
     •nanagement operations completed?)

                                              YEAR <*ASTE MANAG£"£Nr 3EGAN:
                               e.  Hazardous *aste storage .  . .  ^.OS—.  .   ^5       •                  "-"3

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5.    please give tne sizes of sacn of tne following waste .•naoagefen;  treas  3C  '."it facility.

     CENTER SIZES AND CIRCLE UNIT CODE BELOW.  PLEASE USE  THE  SAK  UNIT  CF  -CASURE FOR THE           _

    'ENTIRE TABLE]                                                     '                              I02J



                                                                                Size of aria



                    a.  Landfill	          Q .<* A	     716-23


                    a.  Surface impoundments	          O ^  5            72^-31
                                                                                  /

                    c.  Wasta piles	• . ".	          rt £" C	     732-39


                    d.  Incinerators.	          /) ^" C)
                                               [CIRCLE ONE]:
                                                     Scuare feet	


                                                     Souare 
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(jF   ivifcr*^-**. >ot av.tu\a.bU  JC^fa^ fr-rC^^Y e «• -j   g/v*.  •'*(••:.
                                                                 'tfefCnh-4.  fW '-
 3.   'lease -complete cne following taole  for the employees  -093060  in  the  -*st» narfa
      operations at this facility.
                                                                               ace-n-nt
              aa:
         . INC so:
CN LINES 6e
  THROUGH an:
               Inter tne usual numeer of employees from eacn of  tne -occupation  categories
               •no are engaged in cne waste .-nanagrmeot ooe rations.

               inter tne average nouriv «aoe of tne emolavesa «itnin eacn occucational
               category »no are engages in waste nanagement ooerations.   (If  THIS 1NF3RMA-
               riON IS NOT AVAILA19LE SEPARATELY TOR WASTE HA.NACE.HCNr CMPLOVEES.  °'-Cv4SE
               CHECX HERE _ AND GIVE rHE INFORMATION, 9Y OCCUPAUONAL CATEGORY, "OR
               THE ENTIRE fAClLlTY]  .
                     Indicate the total number of oeraon-noura per  xeek  aevotefl to eacn of the
                     listed ooerations by the »«ste management employees  in  eacn of the occuoa-
                     tiontl categories.  CfOR EXAMPUE,  IP  THREE LABORATORY 'nQRKERS USUALLY SPEND
                     TEN HOURS PER WEEK EACH ENGAGED  IN ACTIVITIES  RELATED TO THE LANDFILL
                     OPERATION AT THIS FACILITY, ENTER  "30" ON LINE oc UNDER THE :3LU.HN LABELED
                     "LABORATORY AND PROFESSIONALS"']
•
6a. Numeer of emoloveea engaged
:n waste management opera-
tions at this facility
60. iverace hourlv «aae for
waste -nanaqeflerLt emcioyeea
in each occupational
cacegorv
ic. Total person-nours per
weeie in landfill ooerations
•Laooratory &
professionals
— . JL 1
Q(.Al

Q(.B /'
c>6C 1
Drivers 4
equipment
operators

££/R

Qi&z.
Q(.C2-
All other
skilled
employees

QfeA^

9^33
cp4C3
Non-skillea i !
employees | TjTiL ;

$*>*"- ;C^~

^ f rs. v -"• ' 5 ^"
Ly1 (, ^ > L-/1 b J-— '
c94C V !04CT
ad. 'seal ;erson-oours per
•e«K in surface imoouna-
•nent ooerations
ae. Total serson-noura per w«ek
in -taste piles ooerations

if. Total person-ooura per «*ek
in incinerator operations

eg. Total serson-noura per week
in iana treatment (including
land aooiication, land
fanning; operations

QtoD'
a*'

QLFl



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Sn. Total person-noura per
week in trsstswit tank
operations
61. Total person-oours oer week
in csntainer storaoe
operations
6j. Total person-hours per week
in star ace tank operations

6k. Total person-flours per
•eek in underground
in lection well operations

61. Total person-noun per week
in recycling operations
6m. Total person-flours per week
in at-ier »aste iwnacetnent
operations
6n. Total person-floura per week
in ALL waste tianaceinent
operations it tnis facility
[TOTAL ON LINE sn SHOULD
tOUAL THE SUM OF LINES
6c THROUGH 6ffl]:
Laooratary i
professionals
O4 ///

 ^

-6/^u ^r:
v

/^» / / A/ C^Y ' <""
O t ^- < ^/ta««— .
^ 
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In :-• :«ie :si'j«, slssse  I'.v.  f-  iri.rsr, Sit  I'.ar^a
;r :r is 'sc.li:.. 3nc  *c  :;  •<•:.-•*  secancar-. i'.~ -.-—s.
xtc.-ise :ILS 'acii.'.'.   liF  fCO DO  NO'  -viC» '••£ KZ  M
                                                         :  l-;_sir:al Class: f .cat ;:i .  coo-
                                                         '  -;..-;  "ar  jre :t,-is :s  -'cmr-f  '.
        a.  "rimarv SIC  coee
                                                                      Q  7/r
            Seconoary  SIC  coces C"-£AS£ LIST
                 NOING  ORDER  OF IMPORTANCE):
                                                                                                   66-o5
s'.jsse soecifv tne  iw
                              itatus of tf
                                                              i3.  is  :n
-v t^e 'sanral government,  3  state government, a ioeai covernment  (sucn ss 5 rn*.
•.c-r, councv 3r sansn),  ar -.a. it  privacelv owoes"7   CCC3Ci£  CMUf  C.v:£ CC2£.]
                                     Solely awned 2y  ,'»ieral  ^ov

                                     So lei v awiec Sy  stats  sovernmeit
                                     Soielv awnsc- 3-'  .scsi  ^vf-m-n
                                     Qtner r.S?SCIF'v]:
'lease soecify tne status  of  cne  eoerator of tnis 'acility.   fnat  is,  ;s :~e
'aciiity operatea ay tne  feaeral  5overnment, a state ;overrment,  a  iocai government
'.sucn as 3 city, town,  county,  or oansn),  or is it srivateiv  aoeratss''  [CIPC-E
                                 Solely scerates 3y  Iscai  ;=v-r~ment	C'
                                 ^Tivateiv cceratea  	
                                                          x^~  O                         15
                                 3tr.er [SFt:"" ;:         ^   	_	—	

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1Q.   v*iat «as trie total quantity  of  -asie  (both  hazardous ana tonhazarsous)  chat  this
      facility treated, stared  ar  iiipssaa  on  thi3 3ite during '93i?  [ENTIS  CUtf-TITY ->.\0
      CI3C-E UNIT CCCE]
        NOTE:  WHAT IS DESIRED HERE  IS  THE  QUANTITY OF WASTE THAT "CA»€ THROUGH  THE PWNT
               COCR," OR ENTERED  THE  PACILITY'S  TREATKNT,  STORAGE, OR DISPOSAL  CPE3ATICNS,
               IN 1981, COUNTING  ONLY ONCE  ANY QUANTITIES OF WASTES OR WASTE MIXTURES  THAT
               WERE REPROCESSED THROUGH  MULTIPLE TECHNOLOGIES,  OR TREAT^NT, STORAGE,  CR.
               DISPOSAL CHAINS.
                                           QUANTITY OF
                                             VttSTE  HANDLED:
                                      [CIRCLE  ONE]:
                                           ^"etric  tsrnes	
                                           English (or anort) tons.
                                           Callcns	
                                           Otrter  [SPECIFY]:  	
11.    What..waa tne total quantity of waats  (Sotn  dazardaua and nonnazarcoua) that tnis  'acil^Cr
      could have- treated, stared or disposed  on sits during ^81,  if tne facility f.ad Seen  sea ratine
      at full capacity the -rfiole year?   [SEE  .NOTE TO CUESTICN 10.   LN 
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12.
      *hat was the total quantity of hazardous  waste  that  this facility treated, stored
      tt disposed on site during  i98f   [SEE  NOTE  TO  QUESTION !0.  ENTER QUANTITY AND
      CIRCLE UNIT CODE]

                                           QUANTITY  OF HAZARDOUS      ^_-
                                            WASTE HANDLED:
                                      [CIRCLE  ONE]:

                                          Metric  tonnes	01

                                          English (or  short)  tow-.	   02-

                                          Gallons	G3

                                          Other  [SPECIFY]:     (*?, I x  U (L-	  C-


I3.    'What was the total quantity of  nazarsous waste that  this facility could    e
      treated, stored or disposed on  site during  198T,  if  the facility  had oeei
      operating at full capacity the  whole  year'   [SEE  NOTE  TO QUESTION 10.  Dl    :u.5NTITv
      AND CIRCLE UNIT CCDE]

                                          QUANTITY  OF  HAZARDOUS *ASTE THAT 7SLO

                                            HAVE  SEEN  HANDLED:    -^~     / 3	

                                      [CIRCLE  ONE]:

                                          Metric  tonnes	~'
                                          English (or  snort)  tons	"

                                          uallora	3?

                                          Other  [SPECIFY]:     Q  / 3 LL C	  '*


14.    During 1981, wnat percentage of the hazaraous »aatg  (soeeifiea  in Question '2)
      entered into the treatment, storage and/or  disposal  operation  by:

                                                                                       Percent

                                          a.  Containers	   ^ / <-'/3

                                          D.  Tank trucks	/^ / V -^f

                                          c.  Dump trucxs	£ i 
-------
 15.   Plaaae provice the following information  in  the  taole  oeiow.

       LINE A;  Enter the quantities of wastes (both  hazardous  and lomazarooua/  that war?
                disoosed of, treated, and/or stored,  at  the facility  during 1981:  [SEE NOTE 3EL3>]
       IINE 3:  Enter the quantities of wastes (both  hazardous  and nonhazardous)  that could nave
                been disposed of, treated, and/or stored,  at  the  facility  during  '931,  ±£ the
                facility had been operating at full capacity  the  wnole  year;  [SEE  NOTE SELCw]

       LINE C;  Enter the quantities of hazardous wastes that were disposed of, trestes),  and/or
                stored,  at the facility during 1981;  [SEE  NOTE  sELOW]

            £:  Enter the quantities of hazardous wastes that could have been disposer  cf,
treated, and/or stored, at the facility during 1981, i£ the facility had been
ooerstinq at full csoacitv the whole year. [SEE NOTE BELOW]


ENTER QUANTITIES ON THE TABLE SELOW AND CIRCLE THE UNIT CODE BELOW THE TABLE
THE SA*€ UNIT OF MEASURE FOR ALL ANSWERS ON THE TABLE.
NOTE: TOTALS IN LINES A THROUGH D MAY EQUAL OR EXCEED ASSOCIATED TOTAL QUAN
IN QUESTIONS 10, 11, 12 AND 13, DUE TO MULTIPLE PROCESSING OF INDIVID
WASTE MIXTURES. *1AT IS DESIRED HERE IS TIC TOTAL QUANTITY CF WASTE
OS COULD SE INPUT, TO EACH PROCESS DURING 1981, REGARDLESS CF WHATEYE
MAY HAVE BEEN APPLIED PREVIOUSLY OR SUBSEQUENTLY- TO THE SAME WASTE, 01
'
a. Quantities of wastes that, were:
b. Quantities of wastes that could
have Been:
c. Quantities of hazardous wastes
that were:
d. Quantities of hazardous wastes
that could have been:

.' PLEASE USE
TITIES PROVIDED
UAL WASTES OR
THAT WAS INPUT,
R OTHER PROCESSES
R PORTIONS THEREOF.

Finally Q&fJSf
disposed
of at facility
	 Did not dispose
in 1981
C) '5~ A /
£ic-* | •

o,^,
Treated
at facility"
__ Did not treat
in 1981
O.^aa
&^A
Gl^J ~
»,.^.P
'"*• ^ x / ^~"
••^ ^ A '-^ *•—
•
Stored
at facility
__ Old not store |
u\ 1981
0>s-P ^
0«r-^
i
O /
                                     [CIRCLE ONE]:

                                          Metric tonnes	01

                                          English (or snort) tans	02
                                          Gallons	QJ

                                          Other [SPECIFY]:  ^' / S" 
-------
li.    In the taole selow, please indicate wnich waste  arocessing technologies »ere operating at
      this facility during- 1981.  [CIRCLE ONE CODE  'Cfi  LACH  TECHNOLOGY]

      Circle ;oee 1 if tne technology *as in existence  at  tne  facility during 1991, was opera-
tional during 1981 ,
and processed hazardous waste during 1981 ;
Circle code 2 if the technology was in existence at :~e 'aciiitv during 1981, "as spera-
tional
during 1981,
but did not srocess hazardous waste during 1981;
Circle cade 3 if the technology w«a in existence at the facility during 1981, but was
not operational during 1981;
Circle code 4 if the
Circle code 5 if the
technology ««s under construction at the facility during 1981.
technology wi
is not in existence and not under construction at the
facility during 1981.
Waste processing
technology
£j I (& /-f-
a. Underground
injection well '
b. Landfill Cs / (a 3
c. Land application
area £ / k 0
e. Disposal surface
impoundment ^/(^ £
In existence,
operational,
processed
hazardous
waste
in 1981
1
1
1
1
1
s it ***
f. Treatment lames '
O > (a Cr
d. Treatment surraee
impoundment
/-N / / It
h. incinerator— f ' <* ~
i. Storage containers
j. Stsrace tanvs
k. -rasta ailei— Y I ^ ' \
C> 1 ' L.
1. storage surface G
m. Other [ SPECIF Y]:^1^1

1
1
1
1
1
!
1
In existence,
operational,
did not
process In existence,
hazardous \ not
waste operational
in 1981 in 1981
2 3
Under Not in
construction existence
in 1981 in 1981
4 5
2 345
i
2 3
2 3
2 3
1
•i 5
5 .
4 5
2 3 i ' 5
I
2 3 . _
2 j 3
2 3
4 5
4 5
4 5 i
2 f 3 i 4 ! 5 j
2 345
\ i
2 345
2 3
4 5
I
                                                                                                         50
                                                                                                        .'51
                                                                                                        '56
                                                10

-------
17.    Please esmolete the following taole  'or  Che  tin  hazardous wastes handiid in largest volume
      3y  this facility in 1981.  [PLEASE RECORD  TH£  E?A  rfASTE  .NUMBERS Of PASTES HANDLED, SE-INMsG
      WITH THE L.ARCEST '/CLUH WASTE,  IN THE COLUMNS  ACROSS  THE TOP OF THE TABLE.* A iIS: OF C = a
            COOES IS INCLUDED  IN IHE GENERAL  INSTRUCTIONS AS  AP<>£NOU A.]
                              EPA WASTE NUMSE3:

                      AND DESCRIPTION OT WASTE:
17a.   Wiat was the total quantity of  this waste
      that was handled Dy this facility during
      1981?  [ENTEK QUANTITY AND CIRCLE UNIT
      CODE FOR EACH WASTE]

                     QUANTITY HANDLED  IN 1981:

                [CIRCLE ONE]:

                     Metric tonnes 	

                     English (or short) tons.  .
                     Gallons	

                     Other [SPECIFY]:	
                                                        01
                                                        02-
                                                        03
                                                        04

                                                       ,/7A/
                                                                                   C)iri -a
 01
 32
 03
 04
 03
I7b.  was this  «aste  stared  at  this facility'
      [CIRCLE ONLY ONE CODE]

                 Yes [GO  TO QUESTION 17c]  .  .  .
                 No  [SKIP  TO  5UESTION 17e
                    FOR  THIS  WASTE]	
17c.  what was the total quantity  that
      entered storage  in 1981'   [ENTER
      QUANTITY AND CIRCLE UNIT CODE]

       __    _    	TOTAL QUANTITY STORED  .

                [CIRCLE ONE]:

                     Metric tonnes  	
                     E.-igiisn  (or snort)  tons
                     Gallons	
                     Other [SPECIFY]:.  .  .  .
                                                       01
                                                       02
                                                       03
                                                       04
                                                           //
01

02

03

04
                01
:3

-------
                                                        ei
                                            1X3N 34.  NO
                             r:
                             22
                             1C
?G
CC
                                          to
             cc
             ZD
             1.0
        J
70


ZG
10
c:
zc
LC
                     =576/0

                                                       co
                                                       10
                                                                     vt
                           ZO
                           ID
                                                                •7 #6/ r;
                                                                                  LO
                    !  nlTJ LI :
                    \
                    \       «
                    I
                    i       re
                    !       :c
                    I
                    !       i r,
st-0=

-------
EPA' WASTE DUMBER:


;?j, «HV 
-------
n
A;
•) ^, 0 Jj 0
M
"•>
CJ u fl 0

,
/,
>)
1 J CJ O O

M
t
P
U U CJ O
II

~" -v
A
- W LI S ?.
i\
•<'\
i J 11 1_> 1 J
J • V. M
-h
\
t 1 « i i ) « 1

^
c'
r>
^
n
^
-^

^
/i
^

^
t«
^
cr
0
n
ki
(^
h
^
'.\
>
I) '
(Y~

1
M
o
?\>
"~
fh
•O
^~
rj — j
"i
(xj
o
— *—
- o
0|

>o
M " 0
n»
o
0
HI
*.y\
c^
* * j *
.'r
c>"

-J
ill
c»



^
























?}
~- o <_> o a o
>:
;^
-^ o o a o o
^ w» c- v^ f3 -•
O
h
?1
•^ i-J O O O O

^
^
^,
\ tJ CJ 0 O O
-'
^
^ CJ CJ tl O O
^
''
j t > iij wl iJ CJ


^

J - '- - M -

\ .'

-------
EPA WAS IE NU^ER:

!7g. what treatment process -as used for this
-aste? [CIRCLE ONLY ONE CODE. IF MORE
THAN ONE METHOD WAS USED FOR A SINGLE
WASTE TYPE, CIRCLE CODE "Oft" AND SPECIFY
CODES "01" THROUGH "03," CORRESPONDING TO
THE METHODS USED, IN ORDER FROM THE MOST
PREVALENTLY USED METHOD TO THE LEAST]
Treatment in tank(s) . . .
Treatment in surface

Treatment Dy


Other [SPECIFY]: 	
"


17h. Was this. -aste disoosed aC this facility7
[CIRCLE ONLY ONE CODE]

Yes [GO TO QUESTION 17i]. . . .
No- [SKIP- QUESTIONS T7i Afffl
17j FOR THIS WASTE] ....
I7i. what «as the total Quantity disposed in
1981' [EN TES QUANTITY AND CIRCLE UNIT
CODE]
TOTAL QUANTITY DISPOSED:
I
[CIRCLE ONE]:

English (or snort)


Other [SPECIFY]: 	


, , , , ;








01

02

03

04
/ ' '





'

z



fi/7 T ,
i

01

02
03
04
/*  T^ Q.


01

C2
03
04


I ! i ' •
1

1




•
•01

02

03
I
3—
/' / ^ ("^ *^


(~ ,7-5


1

2



X*""N ^ """ ^


01

32

04


16

-------
"l i 1 1 ! 1 1 1 1

i



01
02
!
j 03

04
j
1 .' "^

1
1

1
1
1
1




01
02

03

i I I I I I i I : i I I ! I i i i I I i i , , , .





01
02

03

04 . - 04
^^
/O !^f~,^~ i :)7f-~ £.





Qnx?- (2/7^(0
1



2 2


r\



01
02
03

04
^ k
r ,~ • 'U


^\
^ ^ i T.S
i

01
02
03

1



2




i

01
02
03

04 04
_ i~ \




01




01
02 02
!



01
02

03 03 03
i
i
! iTTi
[
:•
02 :
i
03
>
04 04
i
- 34 34

o ''?''«- ~ .^TX/*?^^- s~.i~7~—c< *~ , ,--- - -i_-«,



<£/7-V7
,



2
.

^^^^
C'/'7"'>"/7


01
02
03



cnr?
1





^ ' f — C C •' ~ ~" -
1-


— i
2 2 ! : 36~'


	
"~--~\
•**• 	 ^" — x" i /:6-'05

01 .01 01 ;
"02" | 02" | ::
03
03 23

04 :a 04 ^i
-V _ ** — ^tf*1 	
r _, t — 7~/£\ / . *7 ' /£, ^ ' > r> ' y4 '•"•'• v" I/ '/ ^ /O
^^
' ^" r " 'Ci-'::
I - , . . ,_»


CUESTICN 17 IS CCNTI.NUED ON THE NEXT PACE.

17

-------
EPA *AST£ NUMBER:

V7j. '«hac disposal process *«s used Tor tfus
-•ate? [CIRCLE ONLY ONE CODE. IF M3RE
THAN ONE METHOD WAS USED TOR A SINGLE
WASTE TYPE, CIRCLE CODE "05" AND SPECIFY
COOES "01" THROUGH "04," CORRESPONDING TO
THE METHODS USED, IN ORDER FROM THE MOST
PREVALENTLY USED METHOD TO THE LEAST]
Diapoa*! in injection
•ails 	
Disposal in landfill . . .
-Oisocsal in surface

Qispoaal by land

Other [SPECIFY] 	


I ! I I I









01
02

03

OA
05
rtll J /

1 i 1 1 1









01
02

03

04
05
/*} n T o
x
1 I ! 1 1









01
02

C3

04
35
(^ '^~3-

18

-------
                             o   o
                             M   -»
            o       o
            t>       V
      p   t>       p       p    p
      O   0
      ui   V
  >
                             a
                             M
 O   »   £
   t
                    o       a    o
o
 il

-------
 18.     During  1981,  did tfus facility receive any hazardous waste  for  treatment,  storage or dis-
        posal thac  M*S  generated off aite?  [CIRCLE ONLY ONE CGOE]
                                          Yea [GO TO QUESTION 19]

                                          No  [SKIP TO QUESTION 25]
19.    )*iat was  the  total  Quantity of hazardous waste received for treatment,  storage or disposal
       by this  facility  from off-site sources during 1981?  [ENTER QUANTITY AND  CIRCLE UNIT CCCE]

                                          dUANTITY ROM                             „    Q
                                          CFT-STTE SOURCES:                        UJ  I  I
CCIRCLI ONE]:

     Metric tonnes

     English (or snort) tons.

     Gallons

     Other [SPECIFY]:
                                                                                                 01

                                                                                                 02
                                                                                Cj_ \ ^  "^\ C
20.    nhat percentage of  this  quantity  of hazarsous waste (as specified  in_Question  19)  was
       received -int
     a.  Containers-

     b.  Tank tnjda

     c.  Ovono trucks
     e.

     f.  Other [

                                                                                     /**  ^ » c_
                                                                                     S£  ^ —
                                          d.  Railroad csrs ............. G «3O  Q
                                                                                   Oy £.0  i~ J.
                             TOTAL SHOULD ESUAL
                                                                                             :00  5
21.    '*i«t percentage of thia quantity  of  hazardous  waste (as specified in Question  19) came
       from sources owned bv other  firw?
                                                  rsoM s
                                          OWNED  3V OTHEH TIRMS:
                                                                  ,'63-7;
                                                 20

-------
 22.     *>at percentage af this quantity of hazardous  ««ts  'as  sseci'iso in "i.est
        from smaii generators • «no sre suoject  Co  tne  soe;:a.  ;:r'j» <.s ;ans jr..:er ^C1
                                          PERCE.NT FROM  SMALL
                                                ' GENERATORS:
                                                            n -
        In  Column A of tne tatale below, list the SIC codes  of  the  five  industries from -nicr.  -.-,
        facility  received the greatest quantity of hazardous »aste  rcr  treatment, storacs ir
        disoosai  in 1981.  [IF YOU 00 NOT KNOW THE SIC CEDES CF  THESE  INDUSTRIES, °LEASE SC;.::'
        THE APPRCPSIATE CCDES FROM AP=£NDU C IN THE GENERAL  INSTRUCTIONS. ]

        In  Colunn 3,  inoicate the percent of the total amount  of hazardous  -aste r-csives rrcm
        off-Site  sources (soecified in Question 19) that was received  from  each of tn» f:ve
        industries.
i
C3LUMN A
| alC csces of"
five largest
Tsneritars
a. 1 •- I0*0! '~ ! I
b. Iw l<23l£ : ! .
c. 1^ !cl31 C | \ i
d. ;G i^3i D i N •
e. i d I 2-?| E; 1 |

"CL :•". -
=.._,„.. ,.•
tatd. -azarso'.j
^^^ ^^^^ "*' **
'^•ff r^ ^ ,"*' -»-— "*,
L. ^ 5 C ^ 5
—
^ ?!. 5 ^ ~ i

24.     How was the hazardous waste  content  of  waste shipments receives 3y this  'acilit,  :ur:-q
       1981 determined?  Please specify  the percentage  of snisments ^ar -mch:

                      a. Laooratory analyses were  performed 3y                vp 0 H f\
                         this  facility	             >
a. Documentation- of waste characteristics  -as
   provided by the off-site source
                                                                                V.*-" U
                      c. Documentation of waste  characteristics was
                         taxen from data on similar  wutea	
                      d. Other [S?ECIFV]:
                                                 21

-------
                                          II.  GROL'NOWATER MONITORING
25.     ?lsase  indicate *nethsr this facility has ever used or currently  uaea  any  of the following
        methods  to  prevent contamination of trie aquifers or groundwatsr.   for  each method used,
        indicate the  year anc cast of installation.  (CIHCL£ ONE CODE  FOR  iACH METHOD,  AND ENTER
        YEAR  AND COST .WHERE APPLICABLE]
•
a. Slurry wall 	

e. Other [SPECIFY]:
,Vu T*PJ c 4 eft* r mt £«Ar J^cJ.'f.

Y*.
GJ3S
1^
lQ.ol
^ Q^S

NO-
Al
2
sa<2
jcl,
•C4

Year, started'.
<&>S/9J
tf^5 A?3L
cp^rc^


Cc3t
$ ^^5/93
s £ ^r s 3



                                                                                                       /16-29

                                                                                                       /30-A3
26.   Does this  facility have  groundwater  monitoring -ells'  [CIRCLE ONLY ONE CCCE]
                                          Yes  [GO ON TO GUESTION 27]

                                          No   [SKI?* '0 CISSTION. 29J.
,'60
27.    How Bany nycTiulically upgradient,  and  how uany  rwdraulically downgracient  «eiis  rsr
      groundwater monitoring ooes  this  facility  have?
                                          a.  .SU«ER  OF

                                          b.  NUI-SEH  OF
                                                22

-------
IS.     Please oeacnbe uo "a six of this facility's groundwater swnitcnnq -«lls, giving
       specifications for at least one ^ydraulical-y- uogradient -ell, anc a: least :nree
       nydraulically oownqraaient »ells wnicn ars used to romply »ith the groundwatsr
       standards.

a. Is this an uprjradient or
oawngradlent well?
[CIRCLE ONLY ONE coos]
Uogradient 	
Cowngradient ....
B. What is the dep,
Cy<^ g & i

01
02
03
C*^e/u




G2m
(YEAR)








<" i
L*^ -x t- 'Z. A

01
02
03
c>«Y£JM




p?D3
(YEAR)









^ >» > — "^

01
02
03
?«r=^




MCH
("EAR)









(~ jt ' ^ '

01
02
03
GilfUJ.




GMte
CYEAR;









> aT ?C" \

01

03
'>V?£5-



1
I
( ''EAR )
•







"1 £/"
^ •* « *^ ^

01
02
03
us? 2- --K

                                                                                                      '65-TO
                                                23

-------
29.    Are  there any geologic/hydrogeolojic studies  of  this  facility'  [CIRCLE  ONLY Qr£ CCC£]


                                       	£*?...,
                                                                                                ,  124
                                       No	2
                                    III.   SITE  GEDCaAPHY



30.     la thoa facility located within one  mile of  a  fault that has  had displacement within  the

       past 10,000 years (Holoewe time)?  [CIflO£  ONLY ONE COOS]

                                                                             ( ^  *"' —

                                       Ye« [GO  ON TO QUESTION 31]	7^	1        •


                                       No  [SKIP  TO QUESTION 37]	2


                                       Don't know [SKIP TO QUESTION  77]	3





31.     How close is this facility to the fault?   I


                                                                           f^  "5k \
                                       DISTANCE FROM FAULT:  	L^  O \     feet     /1;5-'2S
                                            24

-------
 iZ.     rtas this facillty  experienced any seismic grauno motion activity  (e.g.,  suosicencs,             1131
        snaking, disolacsment !  since its construct ion '  [CIRCLE ONLY ONE  CODE]
                                                                                d} 53."
                                          Yes [CO ON TO QUESTION. 33] ......  ...  ..... 1
                                          No-  [SKIP TO QUESTION 37]  .............. 2      /16
                                          Don't know [SKIP TO QUESTION 37] ........... 3
 33.     *iat  type  of  seismic  ground motion has this facility experienced?   [CIRCLE  ONE  CCOE rOR
      '  CACH  ITEM]

                                                                                          Yes   NO
                                          a.  Ground failure (liouifaction      n  _     .
                                             or slope staflility) ....... ^  .~. ~.  .  .   l      2    ,'1 7
                                          b.  Cartlvjuakes (snaking) ...... Qt  . .-^. — .         :    ,  '5

                                          C.  fault displacement ..... .•  .^  .- .~. S  .   :      2    ,M9
                                          d.  urouna subsidence	"i

                                          e.  Other [SPECIFY]:  	lg_33 ~  ^      •      2     '2'

                                             	;__.	^ 13 ^ -X               /2:-2;i


34.    **iat was the intensity of  the most  severe  seismic  event  experienced by this  'aciiity  =a
       measure* by the ftichter M«qm.tuae« Scale?   [CIRCLE  ONLY ONE CCCC]

                                          Less  than 2  on  the  Ricnter  scale. . . . V". ~T  /  ...  01
                                          Trom  2 up to 4  on  the  ^icnter scale	32
                                          'rom  i up to 6 on  the  Sic.nter scale	03
                                          From  6 up to 3 on  the  Richter scale	OA
                                           or  greater on  the  Richter scale	05
                                         Con't know	98     /2S-Z5


35.    Old any seismic around motion event ever camsge- any portion af this facility''  [CIRCLE
       ONLY ONE CCDE]

                                          Yes	   1

                                         So	
                                               25	-

-------
 36.    Has this facility incorporated  any  of  trie  following design or locational criteria to
        mitigate the seventy of ground motion  inaucea  damages?  [CIRCLE ONE CODE "OR EACH i'EH]

                                                                                           III   US.
                                                                             u/3£ >r
                                          a. Structural  reinforcement .  .  .  ~ ."V". '. . .  1      2     727
                                          b. Site  analysis  (geologic) .  .  .  .<*•. 3. ». <3» . .  1      2     /2S
                                          c. Construction materials ..... ^ 3 6. ^- . .  1      2     ,'29
                                          0. Structural  design  magnitude.  .  . Q.-?6 P. .  1      2     /JO
                                          • . Otner  [SPECIFY]: _ C?3> 6 ' _  1      2     /31
                                                                          tt^^E ^                    /32-33
 37.     la this facility,  or a portion of this  facility,  located  in a flocdplain?  [CIRCLE ONLY
        CN£ CODE]
                                                                                   C2 3?
                                          Yea [GO O.N  70 QUEST I av  J3J ....... .  ......
                                          .No  [SKIP  TO GUEST ICN 40]	2    ,34

                                          Oon't know [SKIP  TO QUESTION  uO]	3


 32.     Wiicn  of the following beat describes the floodplain on .wiicn thi.s  facility  is locates""
                ONLY ONE" CSCE]

                                          River ire	01

                                          Csastai	02

                                          Other [SPECl/'Y]: _____	 33
J9.    «*ucft of  the  following  Beat  describes the frecuencv of flooding of  the  floodolain  ~r.
       this  facility  13  located?   [CIRCLE ONLY ONE CCOE]
                                                                                  <__/  29
                                          Floods annually 	  01
                                          Ten year floodolain	02
                                          Fifty year floodplain	03

                                          On« hundred year floddplain	04

                                          Five hundred year floodolain	35
                                          Other [SPECIFY]: 	  06

                                          	         "-33


40.   Has this facility ever be~i flooded"7   [CISC.! CM.Y ONE CCCEj

                                                                                   uZ H a
                                          Yea  CSC  ON TO  CUES TIEN  41]	-i
                                                                                                       '39
                                          .So   [SKIP  TO OLtSTION 43]	2
                                               26

-------
                                                                                    t


41.   *iit »as the magnitude  of  the  most  severe flood experiences 3y  this  facility''  [CIRCLE CMV
                                          A 50 year flood	   01



                                          A 100 year flood	-	   02


                                          A 500 year flood	   03


                                          Otner [SPECIFY]: 	 04
                                          Don't knowr	   98     /40-
42.   Has hazardous waste  ever  been released from this facility as  a  result  of a flood?  [CIRCL£

      ONLY ONE CODE]
                                          Yes
                     ,                     Don't know	3
                     i         :





i3.   fchat. typeS'Of  flood protection  do»s-t.lis~ facility-currently nave  in  place?  [CI3C.I C.NE

      CCDt FOR EACH  TYPE" OF  PROTECTION]
                           IT  THIS  FACILITY DOES NOT CURRENTLY HAVtT FLCCD  ."OTECTIOV,


                           CHECK  HEXE r~| AND SKIP TO OUESTICN 45.     ^ o ,> y

                                     LJ  .
                                                                                            'S3   '10


                                          ».  Levee	M;l "1 % .  .  .  1      2      -a



                                          D.  Elevation	H ^. ->. .  .  .  '.      2     '45



                                          e.  Structural reinforcement  .... T^- .'.'-'...  1      ;      ^6



                                          d.  Warning system (waste  removal     «

                                             prior ta flood)	V . •.-:  9 .  :      2     XT



                                          e.  Other [SPECIFY]: 	£ U 3 £ i       1      ?      -5
                                                27

-------
 44.    why wma the flood protection instituted  at  this installation?  [CIRCLE ON£ CCDE 'OP £ACH
       REASON]
                                                                                                  So
h
r*
d
ft ;
r.




Other [SPECIFY]:
 1-i
. .UL
CP ^
c;^
^
M
^H
1
t f
6. . . i
c . . 1
fP. . 1
iz
~i i
2
?
2
^
•j
/52
/SI-
x'S*
/55
/So
The  following  questions relate to the quantity of waste  which  is  recycled rather than liscarsec.
This *ould  incluoe  wastes xnich are used or reused, as  for  raw materials in production processes;
or t-eeveled or reclamed, such as solvent reaistillation, scrap raetal  reclaimed Py tecondary
sneltsr, or xaates  which are blended to make fuels.  Beneficial use  also includes "wastes jaea
in » ncrner constituting disposal" such ss waste* applied  directly. Co the land sa cuaf auoorsa-
sants or as fertilizers..
       Old this  facility  generate or receive any haiBrfloua waste  that  was  useo,  reused, rs
       or reelaiwe«l (either-on site or or'f aits) safore  19617   [CIi?CL£ CNLT  OfC  CCCS]
                                          Yes	T< .  r. .     1
                                          No	     2
46.    Will any hazardous  waste generated or received ay this  facility  te  used,  reused, rscyciea.
       or reciai.ned  (either  on  site or off site) after 1981?   [CIRCLI CNUY ONE  CSOE]

                                          Yes	CS.V. fc .     i
                                                                                                       /60
                                          No
47.    Old this  facility generate  or  receive hazardous wastes that were used,  reused,  recycles,
       or reclaimed (either on  site or  off site) during 1981?  [CISCLI ONLY  ONE  CCCE]
                                                                                         a^t ™i
                                          .=» ,.«. -, ,u ««.-.*«.-. -»j	: :  .  . i
                                                                                                       ,61
                                          No   [SKIP TO QUESTION 52]
                                                23

-------
ifl.    In ".he table SeLo«, olease soectf* tin total suant ;tv  of  lazaroous «aste sen^rstss ~r
      received at this facility tnat »as usea, reused,  reeycieo or  reclaimed (sitner on site or
      aff site) during 1931.  Qf tnis total, indicate the quantitv  tnat *as recycled on site at
      this facility during 1981; the quantity that was  sniooee  off  site during 1981 for recycling
      at a facility ownea Bv this fira; and the quantity that was snipped off sits during '931
      for recycling at a facility owned bv another fim.  [ENTER QUANTITIES AND CIRCLE UNIT CCCE.
             USE THE SAME UNIT CF MEASURE THROUGHOUT THE TABLE]
                                                                                  CUANT tT
                         a. Total quantity generated or  received  that  was
                            used, reused, recycled, or reclaimed  during
                            1981 [THE TOTAL QUANTITY REPORTED C.N  THIS  LINE
                            SHOULD E2UAL THE SUM QF THE  QUANTITIES  CN
                            LINES b, c,  AND d 3ELOW]	
                         b. Quantity-recycled on site-during 1931

                         c.. Quantity snipped off site during '981
                            for recycling at a facility owned oy
                            this firm	
                         d.  Quantity snipped off site during 1981  '
                            for recycling at- a facility owned by
                            anotner firm	
C
          n
                                                                                                       35-:
                                              [CIRCLE CNE]:
                                                Metric tonnes.

                                                English (or short) tons
                                                Gallons
                                                Other [SPECIFv]:
                                                29

-------
49.     Please complete the following  ;.aole  for  the  five principal  Hazardous wastes senerated or
       received by- this facility •nicn  *ere snipped  off site  in. greatest volume for use, reuse,
       recycling or reclamation during  the  1981 calenoar  year.   [REFER TO FACING PAGE FOR
       INSTRUCTIONS "OR COMPUTING  WO COLUMN  OF  THE  fA8L£]
              IF  THIS FACILITY  010  NOT  SHIP ANY HAZARDOUS WASTES CF"  SITE  TO S£  USED,  REUSED,
              RECYCLED OR  RECLAIMED DURING 1981, CHECX HERE iI AND  SKIP  TO QUESTION 30.
             	LJ	Q & X  ^^
                                                                                         ci  rc
                                                                                                    /100
                                                                                                     rioi
               COLUMN A
    E?4  Number  A\Q  description  of
    waste  snipped off  site  for  use,
    r-use,  recycling,  sr
    reclamation
                                                    C3LUMN  9
                                        EPA  IdentificaCion  Nwnoers  of three
                                        facilities  to  -nicn oasts «as sent
                                        in greatest volii-ne  for  use,  reuse
                                        reeyciine,  er  reclamation-
                                       COLUMN C
                                   Quantity of  -
-------
-COLUMN  A;   ENTER  1HE  EPA WASTE SUPERS AND SHORT  DESCRIPTIONS OP THE TIVE WASTES,  INCLUDING
            DESCRIPTIONS 'OF THE "ROCESSES THROUGH  WHICH EACH WASTE HAS GENERATED.   U?=>
            CODES  ARE  LISTED IN APPENDIX A OF  THE  GENERAL INSTRUCTIONS]
COLUMN 3;   ENTER  THE  EPA IDENTIFICATION NUMBERS OF THE THREE FACILITIES  TO WHICH  EACH  WASTE WAS
            SHIPPED  IN GREATEST V
COLUMN C:   INDICATE  THE  QUANTITY OF WASTE SHIPPED TO EACH FACILITY AND CIRCLE  THE  UNIT  CODE  AT
            THE BOTTOM  OF THE COLUMN.  PLEASE  USE THE SAME UNIT OF MEASURE FOR  ALL  WASTES  IN  THE-
            TABLE.

COLUMN D;   CIRCLE  THE  CODE OR CODES THAT  INDICATE HOW EACH WASTE WAS STORED PRIOR  TO  SHIPMENT  OFF
            SITE FOR  USE,  REUSE,  RECYCLING^  OR RECLAMATION.
COLUMN E';  FOR EACH FACILITY,  INDICATE THE AVERAGE NUMBER OF DAYS -EACH WASTE WAS  STORED  PRIOR  TO
           SHIPMENT CTF  SITE FOR USE,  REUSE,  RECYCLING,  OR RECLAMATION.
                                                                                 119RI
                                           COLUMN 0
  "to* was waste stdred  prior to shipment  off site far use,  rsuse, recycling, or
  reclamation?  [CIRCLE ALL THAT APPLY  FOR  EACH  FACILITY]
> In con-
' tamers
            In above
            ground
            tanks
In aeloo
 ground
 tanks
  In
 plies
  In
surface
impound-
 ments
                                                   I
 Other [SPECIFY]:
      COLUMN- E
   Average  numoer
 i                  ]
 i  «as  stored priori
~|  to  shipment     ;
   off  sice  '-:
   use,  reuse,
 i
 !  recycling,  or
 i  reclamacicn.
   01-
             02
                     05
                     /aj
                     05
                   06

                   06-

                   06 '
                                                                                    10 -'fr--;
                                                     -sys

                                                    . Cavs
                         03
                         r?
                         CD
                             06

                             06
                             06
                                                          C H 9 060 >*
            frj
             02
                                            05
                             06
                             06

                             06
                                                           G V 9 D<2 0 *?
                                                                                              Oava
    iD
   07
    iC
   01
  03
   JC
'  03
 C4
 f^
          '05
06

06

06
                                                                 (. / C
                                                                     ' J Oavs
                                                     Cav3
           ^ 02    S
             ^
             02
             ^
             02
                                                0
  03
  o^
  03

i** ^ 'T/T
 C4
          06

          06

          06
                                           IV- 1:3
                            u °s o 6  i <-i
                                          
-------
50.   Pleaae comolete the following table for the five principal hazardous waatss wnicn  triia
      facility used, reused, recycled, or reclaimed, on aite in greatest volume during the  1981
      calendar year.  [REFE3 TO FACING PAGE FOR INSTRUCTIONS FOR COMPLETING EACH CCLUHN  Cf  THE
      TABLE]                                                                 '
                    IF THIS FACILITY DID NOT USE, REUSE, RECYCLE, OR RECLAIM ANY HAZARDOUS
                    WASTES ON SITE IN 1981, CHECX' HERE F"! AN0 3KIP TD 2UESTION 52.
                           	                     I—I                  O &*x
                                                                                                      /1G3
COLUMN A
EPA Nureer AND
description of
waste used, re-
used, recycled
or reclaimed on
sita
a. 1 1 I I 1
Descnotion:
3.TO /9-Ci

o. 1 1 1 1 1
Description:
GToPr*3-

c. 1 ! ! 1 1
Description:
Q5"^fro3

d. I 1 ! 1 1
Description:
6> JT3 1^ 0 M,

e. ! 1 ! ! 1
Description:
G^^cr
i
COLUMN 3
How was this waste used, reused, recycled or reclamed?
[CIRCLE ALL THAT APPLY]
As feed-
stack in
manufac-
turing
pracssa
OT
QSooio)
01
QfcS'0,1
01
Ci-T^jo^
01
Q S*j iOi
01
QroGi'i'
Aa fuel
or fuel
suople-
ment
02
GuTx^C)
02-
cist^iP^
02
QS**53§s
02
Q-Ti32?r
02
as=^3?r
In manner
consti-
tuting
disposal
03
GriO3te4
03
<JC^
03
^^33^,
03
35-330 ^
03
Q.szisj'f
Reclaimed
04
Qi^lSvOl
ca
Q5^6V0i
cw.
Q^fiVo2>
oa
c^rcsvoV
M
£i**$tef
Other [S?EC:.rv]:
GLUMN C
Quantity or"
.taste jsei,
reused, rs-
cyciad or
rsclaimed
=unng "981*
05

Q^i-ii"o ,

CtS* C-C^
35

C 5~C >'~iS C • 3»

05

C^GS^rs

05

^5^eo~CM

05

^^Tdr^r

CS-c-?-

Q r: c ^=

ui5-cc-^

^^c.r
•CCIRCJ: ONE]:

        Metric tonnes
        English (or snort) tons
        Gallons
        Other [SPECIFY]:
                                                                                               31

                                                                                               02

                                                                                               03
                                              32

-------
CC'.'JPN A:  ENTER THE EPA WASTE  NUMBERS  W£ SHORT DESCRIPTIONS  OF  T^  FIVE WASTES, INCLUDING   7-t
           NAMES OF T'-E WASTES  AND  CCSCS1PTIONS CF THE PROCESSES  THROUGH WHICH EACH WASTE  *A3
           T^ERATED".  [£": v,iST£ CCCES ME LISTED IN APPENDIX  A  OP  THE 0£*£RAL INSTRUCTIONS]
                                                                                t
nu,"N 9:  CIRCLE  *h£ .CODE OR COOES THAT DESCRIBE rOW THIS -ASTE  -AS  USES,  REUSES, RECYCLED  OR
           "ECLAIJ-CD DURING :981.

CC'.'JVN C:  INDICATE THE AVERAGE QUANTITY OF WASTE USED.  REUSED, RECYCLED OR RECLAIMED DuflING 1981
           AND. CIRCLE THE UNIT  CODE AT  Tr£ BOTTOM OF THE TABLE.   PLEASE USE THE ;AME UNIT  OF
           '•CASURE FOR AIL WASTES IN THE TA3LE.

COLUMN 0:  CIRCLE  THE CODE OR CODES THAT INDICATE HOW EACH n'ASTE  'WAS  STORED PRIOR TO USE,  REUSE,
           RECYCLING, OR RECLAMATION.

CSLL'HN E1:  FOR EACH FACILITY, INDICATE  THE AVERAGE"NUMBER- OT DAYS- EWH  WASTE WAS" S7CRS5 .3
-------
 51.   For eacfl waste  indicated  :n  Question 50 as Ssing jsed ;n 3 -nanner  cartst lining iiscosai ['"33"
       circled in Coluon 3), Biease  oescriae  tne scecir'i; nanner in «nicn  cne  -asce  -as uded.
                                         X.  FINANCIAL  ASSURANCE
 52.    How will closure and/or post closure casts be  cov-rra far tnis facility?  [CI
       'Ca EACH COVESACE METKCO]
1
| " COVERAGE 3Y:
d c 2 /T.
*. Trust fund 	 Sr( P.*: V ...
'" ?~0 ^

c. Letter of credit. . . . . > v •** ^"" .

i. Insurance solicy. . . '. X ^ "*""
f. Corporate guarantee . . . ^-,^.3^".
g. State guarantee 	 .'-S^T . . . .
n. federal or state exemotion. '5?*' ? . .
i. Otner [SPSCirY]: (£ 5 A fl
^5<^ ra.

i
Closure
t
| costs
I only

1

1
1


1
1
1


Post -closure
coats only
I

*
,
2


2
2
2


2=tn
ciusurs and
| cost-closure
i

j

3
3
t
•t

3
3


closure r*or
pbst-cicaure




,


4

4

•
                                                                                                       ,'25
53.
           are tfte annual aoninistratave  charges  for maintaining t.^e financial  assurance necnaniama
      Listed in Sueation 52?
                                                                                   Collars  ;er »»ar
a. Closure	$   C 5 "3

b. Post-closure	$   £ -S"i
                                                                                                        :?- —
c. TOTAL ADMINISTRATIVE  CSSTS.  .  .    $  C_ £ 2

       34
                                                                                                       'iT-55

-------
54.   Old this  'acility  or  the company that owns this 'acility put uo collateral *for '-.nancial
      assurance  coverage''   [CIHCLi  C.NLT  3.NE ZCDE ]
                                          .  .
[SKIP TO QUESTION 56] ............... 2
                                          Yes [co ON ro QUESTION  55;  .....  C-^'.  ^ .  .  .  .  .   •
                                                                                                       ,'5e
55.   *hat  is the  value  of  the  collateral?  •

                                          VALUE. OF- COLLATERAL:  S-
56.   Does this  facili'ty have  liaoility  insurance for tnirc1 party aamages  'i.e.,  Bodily injurv
      and property damage-)  resulting  from sudden or nonsudden releases af  lazarcous  waste7
      [CIRCLE CNLY ONE CODE]

                                          Yes [CO CN TO QUESTION 57j  ........  ^ ST '& .

                                          NO  CREASE SIGN THE crsT:r:cATio.N STATEMENT
                                              CN PAGE 37 AND RETURN 'H13 "ORM  T3  E?A] ......
57.   In wnat year did this  facility  ootain  liability insurance far third part-,  sanages"1   ['.'
      MORE THAN ONE POLICY HAS 3EIN WRITTEN  TCH  THIS" TACXiTV, 3tEASc GIVE.  rKE"^AR  THE. MOST
      •RECENT POLICY *AS OBTAINED]

                                          YEAR  LIABILITY INSURANCE OBTAINED:          ^C.  <~^7

58.   In order to ootain  liaoility  insurance,  »>s  it  necessary to ucgraoe tnis  'aciiity,  ncoif
      current practices at  this  facility,  or  have- a risk assessment of this facility  serfomeo
      [CIRCLE ONE CSCE TOR  EACH  ITEM]

                                                                                          res
                                          a. Uograae facility .......... ^r.-^^^i

                                          b. Modify  current  practices ...... y-.'O-.  L> 1
                                                                               ^^  ^^^ .•(
                                          -. Obtain  risk  assessment ...... s<.*J. -i  W :
59.    How -nany facilities, INC. 'JC INC this  facility,  coes  the  liaoilitv insurance caver"1

                                         WM8ER Or FACILITIES CCVESED: _   L^^
                                                 35

-------
 SO.    In the tattle below, please indicate the ncmoer  of  policies  held,  the amount of coverage,
       the annual coat of the policy, and the amount of the  deductible  for  the liaoiiity insurancs
       [IF *3RE THAN ONE POLICY IS HELD, INDICATE  THE  TOTAL  COVERAGE,  THE  TO^AL COST, AND 'HE
       AVERAGE DEDUCTIBLE FOR ALL POLICIES IN EACH CATEGORY  CF  THE  TABLE BELOW]
           IT  MORE THAN ONE FACILITY IS COVERED BY THE POLICY, CHECX HERE!   |ANO ENTER THE
           AMOUNT  OT  OVERAGE,  CCST AND DEDUCTIBLE FOR ALL FACILITIES COVERED.
 /82
                                                                                                       122!
Type of
Policy
a. Sudden
a. Norsudden
c. Combined policy
Numoer of
Policies

 le
S^tr.A^
C-)/^ ^ /^V
&/LOP ^

a!.   Coes the policy  cover  accidents  resulting from sudoen or nonsudden releases or" na;arcoua
      «aste wnicn .nay  have occurred  pridr  to  the year in «nicn the policy »«3 detained"*
      [CIRCLE ONLY ONE  CSC£]

                                          Yes  [CO CN TO QUESTION 62]	G/. Vc ./ .  .   '

                                         ,-ta   [SKIP TO QUESTION 63]	2


62.   For how iiany ye«« prior to  the  year the  soliev waa ootained ia accident liaoility  insurance
      providea?
                                          NUMBER  OF  YEARS PRIOR COVERAGE:
63.   Does tne policy caver legal aefera*  costs?   CCIRCLI  CM.Y  ONE C3DE]
                                        YM
                                        MO
/"C6
                            PLEASE SIGN THE CERTIFICATION  STATEXNT  ON  ?ACE 37
                            RETURN THIS FORM TO EPA IN  THE  ENVELOPE  °SOVID£D.
                                                 36

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                                  CERTIFICATION  STATEMENT
        THE OWNER OR  THE OPERATOR OF  THE FACILITY,  OR  HIS  AUTHORIZED REPRESENTATIVE,
        SIGN AND DATE  THE CERTIFICATION WERE  INDICATED.   THE  PRINTED OR TYPED NAME OF  THE
        PERSON SIGNING THE CERTIFICATION MUST  ALSO  3£  INCLUDED *HE-RE INDICATED.
CERTIFICATION;

I certify under penalty of la* that I nave personally  examined  ana  am familiar «ith the infor-
mation suomitted in this and all attached documents, and  that baaed on my inouiry of those
individuals immediately reaponsiole for obtaining  :he  information.  I oelieve that the suomittsd
information is true, accurate, and complete.   I am aware  that there are significant oenalties
'or susmitting false in format ion, including the possibility of  fine and imorisonment.
         3RINT.OR TYPE
                                                       SIGNAruRE.
                                                                                      DATE
          j  AFTER COMPLETING THIS QUESTIONNAIRE, RETURN  IT  TO EPA  IN  THE  ENVELOPE     '
          i  ENCLOSED IN THE QUESTIONNAIRE PACXAGE.                                     i
          \

            IF THIS FACILITY HAS RECEIVED MORE THAN CNE QUESTIONNAIRE,  PLEASE  RETURN   J
            ALL COMPLETED QUESTIONNAIRES IN THE SAME"ENVELOPE.                         ;
                                              37

-------
                                                                        OMB No: 2000-0396
                                                                    Expiration Date:  6/30/84
RCRA Section 3007 Questionnaire
Organic Rubber Processing Chemicals Manufacturing Industry
Return within 45 days from date of receipt to:

Ms. Dina Villari (WH 562)
Characterization and Assessment Division
Office of Solid Waste
U.S. Environmental Protection Agency
401 M St., S.W.
Washington D.C. 20460
1.  Corporate/Plant Data
A. Name of Corporation _
B. Address of Corporation Headquarters

   Street	
   City  	    State  	   Zip.
C. Name of Plant
D. Address of Plant

   Street	
   City  	    State  	   Zip.

   Hazardous waste generator ID number: 	
E.  Mailing Address of Plant (if different from above)
F.  Namels) of personnel to be contacted for additional information pertaining to this questionnaire

   Name                                  Title                          Telephone

-------
2. Type of Plant Operation
A. Indicate whether the following organic rubber processing chemicals1 were manufactured at this facility in  1983:2

     1. CAS No.:                                                            Manufactured:    D  Yes    G No
       Chemical Name:
     2. CAS No.:                                                            Manufactured:    C  Yes    G No
       Chemical Name:
     3. CAS No.:                                                            Manufactured:    u  Yes    G No
       Chemical Name:
     4. CAS No.:                                                            Manufactured:    G  Yes    D No
       Chemical Name:
     5. CAS No.:                                                            Manufactured:    G  Yes    D No
       Chemical Name:
     6. CAS No.:                                                            Manufactured:    D  Yes    D No
       Chemical Name:
     7. CAS No.:                                                            Manufactured:    D  Yes    G No
       Chemical Name:
     8. CAS No.:                                                            Manufactured:    D  Yes    G No
       Chemical Name:
     9. CAS No.:                                                            Manufactured:    u  Yes    G No
       Chemical Name:
   10. CAS No.:                                                            Manufactured:    D  Yes    G No
       Chemical Name:
   Complete this questionnaire for each chemical listed above which you manufactured. If none of these chemicals
   were  manufactured, return pages 1 and 2 of this questionnaire.


B. Identify as follows the chemical intermediate(s) produced at this facility in the production of the chemicals
   identified above:
             CAS Number                    Chemical  Name                     Common Name
    'Rubber processing chemicals are defined as the synthetic organic compounds that are added to natural or synthetic rubber to produce or
    enhance specific properties in the final product.

    2lf additional space is needed for listing products or intermediates, attach an additional sheet.

    Intermediate means any chemical substance (1) which is intentionally manufactured and removed from the equipment in which it is
    manufactured, and (2) which either is consumed in whole or in part in chemical reactions(s) used for the intentional manufacture of other
    chemical substance(s) or mixture(s).
2

-------
C.  Indicate those classes of chemical products or intermediates which were produced at this facility in  1983. Circle
    appropriate code number(s).
    Cod*
    Number
Classes of Products
and Intermediatea
    ORGANIC DYES & PIGMENTS

    286 52   Organic Dyes

    286 53   Organic Pigments

    CYCLIC INTERMEDIATES

    286 61   Aromatic Acids & Derivatives

    286 62   Aromatic Acids, Anhydrides & Esters

    286 63   Aromatic Ketones & Aldehydes

    286 64   Aromatic Alcohols

    286 65   Aromatic Hydrocarbons

    286 66   Cyclic Amines
Coda     Classes of Products
Number   and Intermediates

286 67   Halogenated Aromatics NEC

286 68   Alicyclic Chemicals

286 69  Cyclic Intermediates NEC

CYCLIC CHEMICALS NEC

286 71  Salts of Aromatic  Acids

286 72   Other Cyclic Chemicals

ACYCLIC CHEMICALS

286 81  Halogenated Hydrocarbons

286 82   Monohydric Acyclic Alcohols

286 83   Polyhydric Alcohols &  Ethers
Coda     Classes of Products
Number   and Intermediates

286 84   Acyclic Acids, Anhydrides & Esters

286 85   Acyclic Aldehydes

286 86   Acyclic Ketones

286 87   Acyclic Nitrogens

286 88   Acyclic Compounds NEC

286 89   Acychcs NEC

ORGANIC CHEMICALS NEC

286 91   Flavor & Perfume Materials

286 93   Plasticizers

NEC  —  Not elsewhere classified
3.  Process and Treatment Residual Information

    This information will  be used to address industry wide variation  in type and quantity of residuals generated.
    Residuals include any process stream generated during the manufacture of a product which is not used as a
    raw material or principally sold as a commercial product. Treatment residuals include wastes from the treatment
    of process residuals.  Residuals may be solids (e.g., still bottoms), liquids (e.g., wastewater), confined gases
    (e.g.,  gases that are containerized to facilitate disposal), and unconfined gases generated by the  management
    of solid or liquid residuals (e.g.,  incinerator stack emissions) or unconfined gases containing condensable
    gases (e.g., vented light ends).

    For each unit process provide a  general process block flow diagram that identifies major unit operations and
    treatment processes and indicates the types and points of introduction/generation of feedstocks,  products,
    co-products/by-products, and residuals  (See  Examples I and II.)  Include the information requested in Questions
    3-A through  3-D in the flow diagram. Provide the information  requested in Questions 3-E and 3-F in an
    attachment.

A.  Identify the product process, intermediates, co-products and by-products produced by  the process.

B.  Provide a block for each major unit operation (e.g.,  reactor, washer, filtration, air emission control, aeration
    lagoon, etc.) in the production process  and in each  residuals management process.

C.  Identify process input such as raw materials, reagents and solvents by chemical or common name or chemical
    formula, and indicate the point of introduction with  arrows.

D.  Assign a Residual  Identification Number to each of the following types of residuals and indicate its point of
    generation with an arrow:
    1.  Residuals generated by unit operations in the product  process, including  unit operations that produce/
       recover co-products, by-products and solvents; and
    2.  Final treatment residuals (i.e., residuals generated by physical, chemical (including incineration and other
       thermal treatment)  or biological treatment and that are not  intermediate treatment residuals generated within
       a treatment train).
   When more than one process block flow diagram is provided (i.e., for multiple product processes), assign
   unique, sequential Residual  Identification Numbers to the residuals for each flow diagram.

-------
                                                         Example  I —  Process Block Flow Diagram
Production
OH sue
Landlill
Treatment
                                                              VdLuum Jet Condense
                                                              to Treatment
                         NaOH
                                                Spent
                                                                     Dryer
Na2S Byproduct (sold off site)



                Xylene Recyt la
      Product: 2 Mercaptobenzothiazole and its Zinc  Salt

      Intermediates: None
                                                                                                                                    10% Sludge lo
                                                                                                                                                        •^•Treated Effluent 10
                                                                                                                                                          NPDES Discharge

-------
E.  If residuals from this product process are combined with the residuals from other product processes at this
    facility prior to treatment, identify the product process residual by Residual Identification Number and specify
    the source of the other residuals  using the codes provided in Question 2-C.

F.  Indicate the typical annual production, the 1983 production,  and system capacity (specify), for each: product,
    co-product and by-product.
                              Example II — Response to Questions 3-E and 3-F
 Product Process: 2-Mercaptobenzothiazole, Zinc salt (MBT) Production

 A. Mixing of MBT Production Residuals with Other Residuals
                   MBT Residual
               Identification  Number
               (from Flow Diagram)

                        2,5
               Source of Other Residuals
       (Manufacturing Code from Question 2-B)

                     286 66, 286 65
B. Annual Production (1983)

      Product   .

        Technical MBT
        MBT, Zinc Salt
1,000,000 Ibs (1983)
1,500,000 Ibs (typical)

2,000,000 Ibs (capacity)

12,500,000 Ibs (1983, typical)

15,000,000 Ibs (capacity)
     Co-product/ By-product

        Sodium Sulfide
250,000 Ibs (1983)

300,000 Ibs (typical)

400,000 Ibs (capacity)

-------
4.  Residuals Characterization Information

For each process used to manufacture the chemicals listed in Question 2, complete Table 1 by providing the
following information for each identified residual. An example is provided below (Example III).

A.  Identify the product process.

B.  List each residual by Residual Identification  Number (include by-products and residuals generated from the trea
    ment of process residuals.)

C.  If the residual has been identified in  the facility RCRA notification, indicate whether it was identified as
    ignitable (I), corrosive (C), reactive (R), EP toxic (E), listed by EPA or reported by the facility as toxic (T), or
    acutely hazardous (H).

0.  For each residual, describe the following properties where appropnate: physical state [e.g., liquid (specify
    whether aqueous or organic),  solid, slurry (indicate solids content), gas]; pH; flash point; Btu content;
    viscosity; toxicity.

E.  List the compounds which are known by analysis to be present in the residual and specify, as known, the
    concentration ranges as follows:

                           Code                               Range

                             A                              > 50%

                             B                              > 10% to 50%

                             C                              >1% to  10%

                             D                              >0.1%to1%

                             E                              > 0.01%  to  0.1%
                   [Actual concentration]*                     <0.01%

F.   If residual analyses are not available,  list the compounds which are expected to  be present in the residual anc
    expected concentrations based on chemical engineering principles.

                                   Example III — Response to Question 4

A.  Product Process: MBT Production

         B.               C.                    D.                      E.                       F.
      Residual           RCRA               Properties            Known Compounds,         Other Expected
     Identification      Identification           of Residual              Concentrations.             Compounds
       Number       (I,C,R,E,T, or H)                                     Ranges

    	3	     Not identified     	Solid	    	Sulfur- C	
                                                                     Aniline: C	        Carbon Disulfide
                                                                      MBT: C           	
                                                                 Sodium Sulfide: C
                      Not identified          Aqueous Liquid        	Water: A
                     	   	pH=7.8	       MBT:   200 pern

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                                        Table I — Response to Question 4
A.  Product  Process:

          B.
       Residual
     Identification
       Number
      C.
    RCRA
 Identification
(I.C.R.E.T, or HI
    D.
 Properties
of Residual
        E.
Known Compounds,
  Concentrations,
      Ranges
      F.
Other Expected
 Compounds
•RESIDUAL CONSTITUENT CONCENTRATION CODE
           Code

             A

             B

             C

             D

             E

    [Actual concentration It
     Range

      >50%

      >10% to 50%

      >1% to 10%

      >0.1% to 1%

      >0.01% to 0.1%
                           t If concentration is less than 0 01%. specify, as known, the
                             typical concentration in ppm

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5.   Residuals Management Information  — General

For each process used to manufacture the chemicals listed in Question 2, complete Table II by providing the
following information for each identified residual. An example is provided below. (Example IV).

A.  Identify the product  process.

B.  Specify the Residual Identification Number.

C.  Specify residual category in accordance with codes provided.
    Code  Categories of Residuals
     C1.    Process precipitates or filtration residues
           and process sludges
     C2.    Process decantates or filtrates
     C3.    Treatment sludges: (specify)
           a.  biological  b. other
     C4.    Spent activated carbon or other adsorbent
           (specify)
     C5.    Spent catalyst
     C6.    Heavy ends:
           a.  distillation  residues  b. misc. heavy ends
    '"Acidic: pH < 2.0,  Neutral 2.0 < pH < 12.0,  Caustic, pH > 12.0
    2lLight ends are condensable if primarily composed of gases which are
 Code  Categories of  Residuals (continued)
  C7.   Spent solvents
  C8.   Untreated process wastewater:
        a.  acid   b.  caustic   c.  neutral"1
  C9.   Treated wastewater  discharge
  C10.   Containers, liners, cleaning rags, gloves, etc.
  C11.   Off specification products and feedstock
  C12.   Other (specify)
  C13.   By-product
  C14.   Light ends:
        a.  condensable'2'  b.  noncondensable

liquid at ambient temperature  and pressure.
D.  Specify management methods in accordance with codes provided. If a residual is subject to a sequence of
    methods (e.g., storage in a tank, incineration), list the methods in sequence. If a residual is handled alterna-
    tively by more than one method (e.g., either incinerated or burned in a boiler),  identify the alternate methods.
    Code  Management Methods
     M1.   Storage in:
           a.  tank  b.  container  c.  pile
           d.  surface impoundment
     M2.   Treatment in:
           a.  tank  b.  container  c.  surface
           impoundment
     M3.   Burning in boiler
     M4.   Recovery/reclamation:
           a.  recovery  b. reused same process
           c.  reused different process  d.  sales
     M5.   Incineration
     M6.   Landfill
 Code   Management Methods (continued)
  M7.   Underground injection
  M8.   On-site wastewater treatment in:
        a. tank  b.  surface impoundment  c. container
  M9.   Discharge to publicly owned wastewater
        treatment works
 M10.   Discharge to surface water under NPDES
 M11.   Discharge to off-site privately owned
        wastewater  treatment works
 M12.   Other  (specify)
 M13.   Scrubber:
        a. caustic   b. water   c. other (specify)
 M14.   Flare
E.  Indicate the amount of each residual managed by each method in 1983 (specify units). Include any clarification
    needed to describe the waste stream.

F.  Indicate whether the residual is managed on-site or off-site. If managed off-site, identify the site in the space
    provided in Table III.

G.  For residuals managed off-site, except for discharges to a POTW or surface water under a NPDES permit,
    indicate the average management cost per unit quantity of residual in 1983.

H.  Indicate planned changes in residual management methods by specifying the codes for the new management
    methods, and indicate the anticipated date of change.
8

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                                     Example IV — Responses to Question 5




A.  Product  Process:  MBT Production
B.
Residual
Identification
Number
1


3

c.
Residual
Code
C8


C1

D.
Management
Code
M4-a
(Sodium sulfide
recovery)
M1-c
M-6
E.
1983 Residual
Quantities
25.000.000 oal*


400 tons

F.
On-site or
Off-site
Management
On-site
recovery

On-site storaqe
Off-site disposal
G.
Costs
for Off-site
Management
N.A.


NA
$15/wet ton
H.
Changes in
Management
Methods
None
None

None
M4 11984)
                           C9
                                          M-IO
                                                      50 million gal.
                                                                         Off-site
                                                                                          N.A.
                                                                                                           None
•Prior to drying stage, NazS content is approximately 5% by weight of Residual /1.
                                       Table II — Response to  Question 5
A.  Product Process:
B.
Residual
Identification
Number

C. D.
Residual Management
Code Code


E.
1983 Residual
Quantities
(specify units)

F.
On-site or
Off -site
Management*

G.
1983 Costs
for Off -site
Management
(cost/ton)
H.
Changes in
Management
Methods


'Identify off-site waste management or recycling /reuse facility as indicated in the following Table (Table III).

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                                   Table III — Response to Question 5-F
Name of Facility:  	      Name of Facility: 	
Residual Identification Numbers: 	      Residual Identification Numbers:
Facility Mailing Address:                                  Facility Mailing Address:
  Street or P.O. Box:  	        Street or P.O. Box:  	
  City or Town:   	        City or Town:  	
  State:	 Zip:	        State:	Zip:.
Facility Location (if different from above):                  Facility Location (if different from above):
  Street, Route Number or Other Specific Identifier:         Street,  Route Number or Other Specific Identifier:
  City or Town:   	        City or Town:	
  State:	 Zip:__	        State:	 Zip:	
Hazardous Waste Facility I.D. Number (if any):             Hazardous waste Facility I.D. Number (if any):
10

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6.  Specific On-site Residuals Management Information

Provide specific information for residuals managed on-site using available information to complete the following sec-
tions which pertain to your residuals management operations.
 A.  Storage or Treatment in Tanks*

 B.  Storage or Treatment in Containers*

 C.  Storage or Treatment in Piles*

 D.  Burning in a Boiler
E. incineration

F.  Land Treatment*

G. Surface Impoundments*

H. Landfills*
 "If residuals are managed by these methods, provide the following information:

        (1) Are groundwater monitoring data available?

        (2) Are geologic or hydrogeologic  data available?

 A.  Storage or Treatment in Tanks

    Have identified residuals been stored or treated in on-site tanks at
    any time since January 1, 1983?

    If yes, provide the following information for the 10 largest tanks:
                                  D Yes

                                  n Yes
D No
n NO
                                  D Yes    D No
                                       Type of
        Residuals   Design   Storage or  Treatment  Avg. Length
  Tank  Managed1  Capacity^ Treatment    Used3    of Storage
    1

    2

    3

    4

    5

    6

    7

    8

    9

   10
            Part of Wastewater
             Treatment Train
             (Circle Yes or No)

                 Yes   No

                 Yes   No

                 Yes   No

                 Yes   No

                 Yes   No

                 Yes   No

                 Yes   No

                 Yes   No

                 Yes   No

                 Yes   No
Covered
(Circle Yes or No)
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
No
No
No
No
No
No
No
No
No
No
Secondary
Containment
Provided5
(Circle Yes or No)
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
No
No
No
No
No
No
No
No
No
No
1Use Residual Identification Numbers to identify residuals.
2Use the following codes to designate the tank capacity:
       A    <10,000 gallons
       B    >10,000 gallons to 100,000 gallons
       C    >100,000 gallons to 1,000,000 gallons
       D    >1,000,000 gallons
4Treatment train from which wastewater is discharged under a NPDES permit or through a sewer system to a
 publicly-owned treatment works.
Secondary containment is provided when the tank is located inside a dike area where the volume of liquid
 that the diked area  can contain is at least equivalent to the capacity of the  largest tank.
                                                                                                             11

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B.  Storage or Treatment in Containers*
    Have identified  residuals been stored or treated on-site in containers
    at any time since January 1,  1983?                                              D  Yes  LJ  No

    If yes, provide the following information  (if the facility has several container storage areas, provide information
    only on the primary container storage area):

    1. Check typical and maximum quantity stored on any day in  1983  for each residual:

                                                                                                 Average
                                       Average                    Maximum                   Length of
       Residual No.1              Daily Quantity2            Daily Quantity2                 Storage
    1Use Residual Identification Number to identify residuals
    2Use the following code to designate the quantity of residual(s) in storage on any day in 1983:
          A   ^550 gallons
          B   > 550 to 5500 gallons
          C   >5500 to 55,000 gallons
          D   > 55,000 gallons

    2.  Identify the storage area base material:

    D  Concrete     D  Asphalt     D  Soil     D  Other (specify) 	
    3.  If liquid residuals or residuals containing free liquids* are stored, is the storage area designed and operated
       to collect and contain surface runoff?

    G  Yes     C  No     D  Liquids are not stored

    "Container means any portable device in which residuals were stored, treated or otherwise handled.
    TA  residual contains free liquids if liquids readily separate from the solid portion of the residual under ambient temperature
     and pressure.
 12

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C. Storage or Treatment in Piles

   Have identified residuals been stored or treated in on-site piles
   at any time since January 1,  1983?

   If yes, provide the following information for the 10 largest piles:
   Pile


     1

     2

     3

     4

     5

     6
     7

     8

     9

    10
Residuals
Managed1
 Typical
Quantity2
Managed
  Under Roofed
    Structure
(Circle Yes or No)
             El  Yes


  Containment3
     Provided
(Circle Yes or No)
C No


    Synthetic4
    Liner Base
(Circle Yes or No)
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
No
No
No
No
No
No
No
No
No
No
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
No
No
No
No
No
No
No
No
No
No
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
No
No
No
No
No
No
No
No
No
No
   1Use Residual Identification Numbers to identify residuals.
   2Use the following code to designate the typical quantity of residual(s) contained in the pile on any day in 1983:
         A   <20 cubic yards
         B   >20 to 200 cubic yards
         C   > 200 to 2,000 cubic yards
         D   > 2,000 to 20,000 cubic yards
         E   > 20,000 cubic yards
   3Containment is provided when the pile base is designed, operated, and maintained to contain leachate
    and run-off.
   4ls a synthetic liner installed in the pile base? Waste may lie directly on synthetic liner or the liner may  be
    covered with clay layer.
                                                                                                         13

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D.  Burning in a Boiler
    Have identified residuals been burned in an on-site boiler
    at any  time since January 1  1983?
    If yes,  provide the following information for each boiler:
    1.  Boiler and fuel type:
                                                                    D Yes     LJ No
    Type

   Fire tube
   Water tube
 Boiler Capacity
 (Heat Input in
 Million Btu/hr)

I]  <10 million
I!  >10 million to
     100 million
H  >100 million
  Primary
Boiler Fuel

Oil
Gas
Coal
Wood or other
  Percentage of Fuel
Replaced by Residuals
  (Heat Input Basis)
                                                         > 5-10%
                                                         > 10-25%
                                                         > 25-50%
                                                         >50%
 Typical Boiler Load
When Firing Residual
  (% of Capacity)

Z  £50%
~  > 50-75%
C  >75%
    2.  Provide the following information for each  of the residuals burned:
 Use Residual Identification Numbers to identify residuals.

    3.  Provide the following information on the total feed mixture when residual is burned:

          Feed Rate (Pounds per hour)                 	

          Typical BTU Content (BTU/lb)               	

          Typical Total Ash Content (% by wt.)         	
          Typical Total Halogen Content (% by wt.)    	

          Typical Total Water Content (% by wt.)      	
     Boiler
Temperature (°C)
Inlet     Outlet
Typical BTU
Residual Feed Rate Content
No.1 (Ibs. per hour) (BTU/lb)
Typical Total
Ash Content
{% by wt.)
Typical Total
Halogen
Content
(% by wt.)
Total Water
Content
(% by wt.)



    4.  If the boiler is equipped with an air pollution control device, specify the type of device:
    D  Scrubber    G  Electrostatic precipitator    C Other (specify)	
    5.  Are residual-burning stack emissions data available?
                                                                       Yes
                                                         G  No
14

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E,  Incineration
   Have identified residuals been incinerated on-site at any time since
   January 1, 1983?

   If yes, provide the following information for each incinerator:

   1. Incinerator type:
                                                         : Yes
       Type
D Liquid injection
D Rotary kiln
D Hearth
D Other	
          (specify)
    Incinerator Capacity
 (Heat input in MMBtu/hr.)
U  <10 million
D  > 10 million to
      100 million
Ll  >100 million
   2. Combustion Chamber Design Parameters:


          Combustion Chamber Temp.

          Location of Temp. Monitor

          Residence Time
        Feed Type

C Liquid — nozzle type
     	(specify)
— Atomizing pressure
     	(specify)
D Solid
   D Batch charge
   C Continuous charge
                            Primary Chamber
                                      No
     Percentage of
Auxiliary Fuel  Required
   (Heat Input Basis)
                            Secondary Chamber
                                               (sec)
                                               .(sec)
   3. If the incinerator is equipped with an air pollution control device, specify the type(s) of device(s):

   C Scrubber    ~L Electrostatic precipitator    G Other (specify)	
   4. Are incinerator stack emissions data available?

   5. Provide the following information for each of the residuals burned:
                                                           Yes
                                     No

Typical BTU
Residual Feed Rate Content
No.1 (Ibs. per hour) (BTU/lb)

Typical Total
Ash Content
(% by wt.)
Typical Total
Halogen
Content
(% by wt.)

Total Water
Content
(% by wt.)



Use Residual Identification Numbers to identify residuals.
                                                                                                         15

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F.   Land Treatment
    Have identified residuals been  managed in an on-site land treatment
    operation at any time since January  1, 1983?                                    D  Yes    G No

    If yes, provide the following information:

    1. Year land treatment initiated at site:  	
    2. Year land treatment of identified residuals initiated:.
    3.  Have residuals other than identified residuals been land treated
       at any time since January 1, 1983?                                           D  Yes    G No

    4.  What was the total area actively used for land treatment in 1983?  	acres

    5.  What is the average slope of the land treatment site?	 percent

    6.  Is surface water  run-off from the site collected for treatment,
       re-application to  the site,  or analyzed prior to discharge?                       Q  Yes    D No

    7.  Check method(s) used to apply residuals to the land treatment site.

       a.  G Surface spreading or spray irrigation without plow or disc incorporation. Indicate residuals applied in
            this manner  using Residual Identification  Numbers:	
       b.  D  Surface spreading or spray irrigation with  plow or disc incorporation to a depth of 	 (specify).
             Indicate residuals applied in this manner using Residual Identification Numbers:	

       c.  D  Subsurface injection to a depth of  	 (specify).  Indicate residuals applied in this manner
             using Residual Identification Numbers:	
       d.  G  Other methods (specify methods and residuals):	
    8.  Is soil core monitoring performed?                                           G  Yes    G No

    9.  Is soil pore water monitoring performed?                                     G  Yes    G No
16

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G.  Surface Impoundments*
    Have identified residuals been stored, treated, or disposed of in an  on-site
    surface impoundment at any time since January 1, 1983?                         [H  Yes     [H  No

    If yes, complete Table IV.

*A surface impoundent is defined as holding, storage, settling, and aeration pits, ponds,  or lagoons formed primarily of earthen materials.


                                    Table IV — Response to Question 6-G

If more than 5 surface impoundments  have been used since January 1, 1983 to manage  identified residuals, provide
information only on the 5 impoundments with the largest capacities.  Use Residual Identification Numbers to identify
residuals. If you do not know whether a liner has been installed, circle  both "Yes" and "No." If you do not know
the thickness of a  liner, indicate "UNK" for unknown.

                                                                                                     Leachate Collection
                                                            Synthetic Liner             Clay Liner             System
                                              Specify
               Residuals    Total    Storage or  Treatment
               Disposed   Capacity  Treatment   Type if           Thickness  No. of         Thickness No. of           Leachate
 Impoundment     (HINI    (Gallons)1   (specify)  Applicable2  Installed   (mils)   Liners Installed    (in)    Liners  Installed  Generated
1 Y«s
2 " YBS
3 VPS
4 Yes
5 Yes
No
No
Nn
No
No
Yes
Yes
Yes
Yes
Yes
No
No
No
No
No
Yes
Yes
Yes
Yes
Yes
No
No
No
No
No
Yes
Yes
Yes
Yes
Yes
No
No
No
No
No
1Use the following code to designate the quantity of residual(s) in storage on any day in 1983:
       A    < 550 gallons
       B    > 550 to 5,500 gallons
       C    > 5,500 to 55,000 gallons
       D    > 55,000 gallons
 Use the following codes to specify treatment type:
       A   Neutralization
       B   Settling/Clarification
       C   Aeration
       D   Equalization
       E  Mixing
       F  Evaporation
       G   Other (specify)
                                                                                                               17

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H.  Landfills
    1.  Have identified residuals been landfilled on-site at any time that
       you owned or operated this facility?
       If yes, answer questions 2 and 3.

    2.  Has any on-site landfill (or landfill cell) that was used to dispose of
       identified residuals been closed (i.e, no longer used to dispose of wastes)?
       If yes, complete Table V.

    3.  Have any identified residuals been landfilled on-site at any time since
       January 1, 1983 in a cell that  has not been  closed?
       If yes, complete Table VI.

                                   Table V — Response to Question 6-H-2
 D  Yes    D No
 D  Yes    C No
D Yes     D No
Closed Landfill Cells

If more than 5 cells containing identified residuals have been closed, provide information only on the 5 cells that
were most recently closed. Use Residual Identification Numbers to identify residuals. If you do not know whether a
layer or liner was installed, circle both "Yes" and "No."  If you do not know the thickness of a layer or liner,
indicate "UNK"  for unknown.

                                        A. Cap/Cover Design
Call
1
2
3
4
5

Drainage Layer
Residuals
Disposed Thickness
(RIN) Installed Material (in)
Yes
Yes
Yes
Yes
Yes
No
No
No
No
No
Cap Design
Clay Layer
Installed
Yes
Yes
Yes
Yes
Yes
No
No
No
No
No
Thickness
(in)





Synthetic Liner
Installed Material
Yes
Yes
Yes
Yes
Yes
No
No
No
No
No
Thickness
(Mils)





                            B. Bottom Liner Design/Leachate Collection


                        Synthetic Liner                     Clay Liner
Leachate Collection
     System
Cell Number
(As Assigned Thickness
Above) Installed (mils)
1
2
3
4
5
Yes
Yes
Yes
Yes
Yes
No
No
No
No
No
No. of Thickness
Liners Installed (in)
Yes
Yes
Yes
Yes
Yes
No
No
No
No
Nn
No. of
Liners Installed
Yes
YBS
Yes
Yes
Yes
No
No
No
No
No
Laachate
Generated
Yes
Yes
Yes
Yes
Yes
No
No
No
No
No
18

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                                Table VI — Response to Question 6-H-3

Landfill Cells Used to Dispose of Identified Residuals at any Time Since January 1, 1983

If more than 5 cells have been used since January 1,  1983 to dispose of identified residuals, provide information
only on the 5 containing the greatest quantities of identified residuals. Use Residual Identification Numbers to
identify residuals.  If you do not know whether a liner has been installed, circle both "Yes" and "No."  If you do
not know the thickness of a liner, indicate "UNK" for unknown.
                              Bottom Liner Design/Leachate Collection


                             Synthetic Liner                       Clay Liner
Leachate Collection
     System
Residuals
Disposed Thickness No. of Thickness No. of
Cell (RIN) Installed Material (mils) Liners Installed (in) Liners Installed
1
2
3
4
5
Yes
Yes
Yes
Yes
Yes
No
Mo
No
No
No
Yes
Yes
Yes
Yes
Yes
No
Nn
No
No
No
Yes
Yes
Yes
Yes
Yes
No
No
No
No
No
Leachate
Genrated
Yes
Yes
Yes
Yes
Yes
No
No
No
No
No
                                                                                                         19

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  APPENDIX B
PROCESS STUDIES

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1.0  INTRODUCTION
                                                                    t
This appendix contains 22 exploratory studies of various industrial processes and
practices known to generate (or influence the generation of) hazardous wastes.
The list of  the analyzed processes and practices is given below:

     Study No.        Description
         1            Acrylonitnle Manufacture
         2            Agricultural Chemicals Formulation
         3            Electroplating
         4            Epichlorohydrin Manufacture
         5            Inorganic Pigments Manufacture
         6            Metal Surface Treatment
         7            Organic Dyes 4 Pigments Manufacture
         3            Paint Manufacturing
         9            Petroleum Refining
         10           Phenolic Resins Manufacture
         11           Printed Circuit Boards Manufacture
         12           Printing Operations
         13           Synthetic Fiber  Manufacture
         14           Synthetic Rubber Manufacture
         15           1,1,1-Trichloroethane Manufacture
         16           Tnchloroethylene/Perchloroethylene Manufacture
         17           Vinyl Chloride Monomer Manufacture
         18           Wood Preserving
         19           Good Operating Practices
         20           Metal Parts Cleaning
         21           Paint Application
         22           Process Equipment Cleaning

The  studies  were  performed  in  order to  accomplish  the  following set   of
objectives:

     o     Identify and  characterize  source  reduction technologies  currently
           being used.

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     o     Identify and characterize new  technological approaches which may
           reduce waste generation.
     o     Provide an  assessment of the  current  extent  of waste  reduction
           achieved due to implementation of the considered methodology.
     o     Provide an assessment of the future  extent of waste reduction due
           to further implementation of  both current and new technologies.

Accomplishing these objectives was approached in the manner outlined below.

2.0  APPROACH AND METHODOLOGY

It  is important to  note that source control measures are highly process- or site-
specific. The preparation of a truly accurate assessment of the extent  to  which
wastes have been  and can be minimized by industry nationwide would require an
extensive  site-by-site  inspection,  coupled with  engineering   and  economic
analyses of many processes and  large  numbers  of facilities.   The simplified
approach  used  here  relies on  the  concept  of  an "average"  process.   The
"average" process is  one which represents a synthetic approximation  of  major
variations  encountered  from facility to  facility.  Process configurations were
evolved mainly from descriptions available in  the  public domain and general
literature. In most cases, the appropriate degree of  resolution was judged to be
at the level of a generic block flow diagram.

The approach used to accomplish the objectives listed in  Section 1 consisted  of
the following steps:

     (a)   Definition of  a manageable  set of  waste-producing processes and
           practices to be analyzed.
     (b)   Data   collection  and  engineering  analysis   of  each  process and
           practice  to  produce  a  comprehensive  list  of  source  reduction
           techniques,  including those that are currently practiced and those
           that may be practiced  in  the  future.
     (c)   Review of the compiled source reduction techniques by industry and
           consultants.  In this review  process,  each  technique would  ideally
           receive  an   independent   rating   as  to   its   waste   reduction
           effectiveness,  extent  of  current   use  and  future  application

-------
           potential.    Additional   objectives  of  such  review   consist  of
           broadening the  compilation  to include techniques  not  considered
           originally and to limit  the necessarily conjectural nature of some
           results obtained  from part (b) above.
     (d)   Derivation of estimates  for  current  and future extents of waste
           reduction for each process, based on ratings obtained from (c), and
     (e)   Derivation of  nationwide estimates  for the  current  and  future
           extents of waste reduction, based on the composite profiles for each
           industry  category.   The industry  composites are obtained, in turn,
           from the averaged extent of waste reduction achieved and potential
           future reduction for  the individual representative processes.

The  sample set of  22 processes and  practices  was  selected  based on  EPA
guidance, production volumes, the RIA Mail Survey database and on  the "F" and
"K" waste stream RCRA listings.

Data collection  involved  inspection of  the  pre-compiled source reduction
bibliographies,  automated  bibliographic  searches,  consultation with  standard
references  (e.g.  Kirk-Othmer's  Encyclopedia   of   Chemical  Technology),
government studies (e.g. U.S. EPA Effluent Guidelines development documents),
and  consultations  with experts  and industry  contacts.  After the  data were
compiled, a standardized format for data  categorization was developed for each
process and practice. Section 9 of  each  individual process study was prepared
following  identification  of  source  control  methods  through   preliminary
engineering analysis  of the process and review of the compiled information.

Following their description, all of the identified source  control techniques were
assembled  in  a summary  table and preliminary ratings were generated  by
project staff for  each source reduction technique in  the  following  categories:
waste  reduction  effectiveness,  extent of current use, and  future  application
potential.  Additionally, ratings were  given to the quantity and quality  of  the
available data.  All  ratings were based on the integer scale of zero  (none),  one
(low), two (medium), three (high), four (all).   Product substitution  options were
identified  mainly  through  database review  and  are described in  a  separate
section (Section 10) of each process study.

-------
Following the  preparation  of a  preliminary  draft,  each process  study  was
submitted for an independent review by interested industrial firms involved  in
that particular  process.    In  other cases, the  reviewers were  independent
consultants or resident technical staff with experience in a particular process.

The reviewers were asked to comment on the technical substance of the  report
with special  emphasis  on the integer  ratings given to  each source control
technique.  Additionally,  the reviewers were asked to provide information on
the actual source reduction applications known to them  and to augment the
compiled list with any techniques that they felt were worth considering.

After  the individual  process study  review  comments  were  received  and
evaluated, drafts were revised and the  extent of waste reduction due to  source
control was  computed  for  each study  from the ratings  developed  using the
computational methodology described below.  Waste reduction estimates were
calculated for each wastestream and for each process overall.

For each process, two sets of numbers were generated:

      1)    Qualitative estimates  of waste reductions which firms  as a group
           are currently achieving, and

      2)    Qualitative estimates of waste reductions   achievable in the  future
           using techniques suggested and identified in the study.

The intent in furnishing  these qualitative  estimates  is to provide  a basis for
crude  projections of the overall  extent of waste  reduction  possible for the
entire industry.  Under  no circumstances should these estimates be construed as
definitive thresholds or limits on  reductions achievable by the individual firms
employing the analyzed process.

It must be noted that, in  many cases, both RCRA and non-RCRA wastestreams
were  analyzed  for  their  minimization potential.   This  was done primarily
because  of concern that control  of non-RCRA  waste  streams  can  be indirectly
responsible  for  RCRA  waste generation.   For  example, control  of  solvent

-------
emissions into the air has,  in  the  past,  been frequently accomplished  using
adsorption on  activated  carbon.   The regeneration  of  carbon  usingt steam
produced  in certain cases  a  non-recyclable mixture of solvent and water that
had to be  disposed of.

The interactions between hazardous and non-hazardous wastes are complex and
not readily visible. Therefore, it was deemed prudent to  apply the analysis to
all  principal  wastestreams  or  residuals  and not  just  to  those which are
considered RCRA streams under  current regulations.  However, each  process
study clearly  differentiates between the listed RCRA "F" and "K" wastes  and
other streams, and this distinction is utilized in the final analysis (see  Section 3
of the main report).

3.0   COMPUTATIONAL PROCEDURES

The text below explains how  qualitative ratings based on engineering judgement
were  given to effectiveness,  extent of current  use,  and  future application
potential  for each source control method and how  they were  combined to yield
qualitative estimates  of  the waste  that  has  been reduced  based on  current
practice  and  the  degree  of  reduction  achievable based on potential  future
practices. These estimates, or indices, were  determined for each  individual
method, each  individual  wastestream,  and  each  individual  process  or  study.
Following the discussion of methodology development, sample calculations are
provided.

Current Waste Reduction Index

The  current  waste reduction index  (C)  is  a  qualitative measure  of past waste
reduction from the employment of current waste reduction measures.  In  other
words, it  represents the  reduction in waste that occurred because of  measures
already implemented.  The derivation of equations  allowing for computation of
C from the ratings given to each waste reduction method is presented  below.

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Consider a process which, in the past, generated  waste at a specific rate Wp.
Assume that due to implementation of certain source control  techniques, the
same process now generates  waste at a  specific rate W0.  Hence, the current
overall reduction index of waste generated is:

      (1)   C = S (Wp-W0)/Wp

      where:      C =     current  reduction  index of  waste  produced  by the
                        process. Index  is  based on  a range of  0 to  S  (for this
                        study, a range of 0 to 4 was employed).
                 S =     the upper bound of the integer range selected (4).
                 Wp =   past specific waste  generation  rate  (Ibs  waste/lbs
                        product).
                 V/0 =   current specific waste generation  rate (Ibs waste/lbs
                        product).

Now  consider that the process has N different wastestreams and that  for each
wastestream (j, where j=l,2,..N) there are  M different source control  methods
(i, where i=l, 2,..Mj) available.  Each individual method can be characterized by
its  effectiveness (ejp, its extent  of  current use (ujj),  and  its extent  of further
application  or application potential (pu).  The first  parameter, effectiveness
(ejj), is defined as the measure of volume  or toxicity  reduction for  a specific
wastestream  (j) due  to  full implementation of  an identified  source  control
method (i).  The second parameter, the extent of current use (ujj), is  defined  as
the  measure of the current level  of  use of the particular method to control  a
specific wastestream.   Finally,  the future application  potential  (pjj),  is  a
measure of probability that a given source  control method will  be implemented
to  control a  specific  wastestream.   Such a  variable  depends on capital and
operating cost, level  of  difficulty in implementation, implementation period,
technological risk, and the risk of detrimental effects on product quality.

In mathematical terms, the current reduction index  of the  specific wastestream
(j) by the implementation of the  identified source control method (i) is given by:
      (2)

-------
Now that the  current reduction index for each source control method has been
calculated, the current reduction index for the wastestream (j) is given by:
(3)
                     c2j  l-cijS  + c3j
The above equation shows that the current reduction index for a wastestream is
equal  to  the  reduction due  to implementation of  the  first source  control
measure plus the reduction of the remaining waste  due to  implementation  of
the second source control measure and so on.

However, use of equation (3) can be unwieldly when  a large number of  control
methods must be analyzed.  In  addition, estimates of C;  equal to 100 percent
reduction will occur many  times after accounting for the  GJJ'S of  only three  or
four methods.   The problem  is not with  the equation however,  but with the
relative coarseness  of the rating scale  used (more accurate or quantitative data
on percent effectiveness and extent of current use ratings would be required  to
use this equation).  Therefore, using the single  most  effective applied  control
method  (GJ;  maximum) to represent  the overall reduction achieved for  a
wastestream  greatly simplifies the estimate while  keeping it conservative (the
actual reduction index should account for the most effective  measure plus all  of
the other source control measures).  Limiting  C; to  a single  most effective
control method is given by  the equation:

      (3a)  C, =  maximum (cji, i=l,2,...M;)

Now that C; is determined  for the  wastestream,  the current reduction index (C)
for the process (all  wastestreams) can be determined.  Recalling that:

      (1)   C = 5 (Wp -  W0)/Wp

the equation  may be rewritten in terms  of a single wastestream and rearranged
so that:

      (4)   Wpj = Woj
                   N
     (5)   Wp   =  Z  Wpj

-------
                    N                                               *
 .   (5a)    Wp  =   S     W0j/(S-Cj)
                   j=l

To obtain the  current reduction index C for the whole process (all waste streams),
equations (5) and (1) are combined to yield:


                      N
      (6)   CrS-W0/E   S (Woj/(S -Cj) )
                      j=l

Since it  is usually  easier to estimate the  fraction of waste (Zp that  a  wastestream

represents as  part  of the total waste  generated  (as opposed to  estimating  the  actual

waste generation rate), the following equations are used to calculate C:

      (7)   Zj = W0j/W0

      (7a)  Woj  =   W0Zj

                    N
      (8)   C = S- 1/Z     (Zj/(S -Cj))
                    j=l

The  above equation relates the estimated  current extent of waste reduction for the
entire process to  the  current  fraction  Zj  of  each  process  wastestream  and to the
current extent of waste reduction C; for each wastestream.


Future Waste Reduction Index


In  addition to the  current  reduction  index C, an estimation of the potential  future
reduction index (F) is required.  Individual future  reduction  indices  (fjj) for each
control method can be calculated by using the equation:
     (10)  fjj = e-,j (S-Ujj) Pij/s2
Now  that  individual  future  reduction  indices  for  each source control measure are

known, future reduction indices for each wastestream (F;) can be determined.  As was

the  case  for the  current  reduction  index,  a conservative  approach was used for

-------
estimating the future reduction index  of  each wastestream.   This approach assumed

that  industry  would  implement  only  a  single  source  control  method  for  each

wastestream and not multiple methods.



The problem faced in this calculation is that  it is even more difficult to predict which

source control methods will be implemented in the future by individual facilities than

to estimate the current levels of reduction. The variable F; is subject to a high degree

of uncertainty and is dependent  on  a  number of factors including capital and operating

costs, level of difficulty in implementation, implementation period, technological risk,

and the risk of detrimental effects on product quality.  Therefore, in estimating Fj,

two  different  scenarios were assumed based  on  implementation  of  a single source

control  measure by industry.



The  first scenario (F probable) assumes  that  industry  as a whole will  implement  a

range of methods. This implies  that averaging of fjj's will yield a probable value of FJ:



                                    Mj
         (11)   FJ (probable) = (1/Mj)   I f^
                                    j=l

This estimation of future reduction can be viewed as being a lower bound. The second

scenario (F  maximum)  assumes  that  only  the  single,  most  effective method  per

wastestream will be implemented by industry.  This  implies that  a conservative upper

bound for F; can be taken as:



         (12)   F; (maximum) = maximum (fjj, i = l,2,...Mj)

-------
Finally, for the entire process, the future probable and maximum waste reduction
indices were taken as weight-fraction averages:                        *
                              N
         (13)  Fpj-Qbabie  =    E    Fj (probable) ZQJ
                              N
         (14)  Fmaximum =    £     Fj (maximum)
Future  reduction  indices  F,  expressed  by  equations (13) and  (14)  are  qualitative
measures of expected waste reduction from the process due to implementation of a
range of methods for a given wastestream (F probable) or implementation of the single
most effective control option for each wastestream (F maximum). Due to the need for
two  differing scenarios, the estimate of future waste reduction  is presented as a range
rather than a single value as shown for the current reduction index.

In summary, the method described above is based on an  approach where the estimates
of waste reduction  were derived from  the  qualitative  ratings  based on engineering
judgement given to the variables e-,;, u,;, and p;;.  In actual applications however, it is
usually not possible to obtain  precise fractional values of e, u, and p.  Instead, the
variables were rated using an  integer scale of zero to  four.   If this  scale had to be
converted into  an  equivalent  range  of   percentages,   then  this range   would
approximately  be:

                 Integer
                    0
                    1
                    2
                    3
                    4
Rating
None
Low
Medium
High
All
Ranqe, %
0-5
5-35
35-65
65-95
95-100
                                        10

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Sample Calculation
                                                                    <
The following steps  are  provided to guide the reader through the various calculations
required  in determining C  and F.  The first step required is to list all control methods
by wastestream. Next, ratings  are assigned to each method's effectiveness, extent of
current use, and future application potential using the scale previously discussed (zero
to four).   In  addition, fractional  waste  generation rates  were  assigned  to each
wastestream.  As an example, see Table  3-1.

Now  that  the ratings and  fractional  waste  generation  rates  have been assigned,
calculations can begin. Using method #1, wastestream //I  as an example,  the  current
reduction index for method //I is computed using equation (2):

      (2)    c-.j   = ejjUjj/S
           cn  = 2 x 4/4  = 2.0

This calculation is repeated for  all the methods.  As a side note, the above calculation
must  be  slightly modified whenever a  current reduction index of 4 occurs (method  #2,
wastestream #2).  The modification consists of restricting the maximum c value to 3.9
and not 4.  This modification is required  so that division by zero in equation (8)  will  not
occur.

Now that the  individual  c  values have been  determined, the current reduction indices
for the wastestreams are calculated using equation (3a):

(3a)   C;  = maximum (cji, i=l, 2,..M.)

      Ci  =  maximum (C;Q,  021, 03^) =  2.0

      G£  =  maximum (cj2,  C22> C32^ =  '.9

      Cj  -  maximum (0^3,  023, 033) =  1.5
                                        11

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TABLE 3-1 EXAMPLE SOURCE CONTROL METHODOLOGY TABLE
1
Haste Source |
1
Hastestream II |l.
12.
13.
1
Hastestream 1? |1.
12.
13.
1
Hastestream 13 |1.
12.
13.
1
| All Sources |
L 	 4__
Control Methodology

Control Mthod
Control iiethod
Control «ethod
Overall
Control Mthod
Control method
Control method
Overa 1 1
Control *ethod
Control method
Control nethod
Overall

number
number
number

number
nu*ber
number

number
nurcbtr
number


1.
2.
3.

1.
2.
3.

1.
2
3.

All Methods
| Hast* | Extent of | further | Traction of | Current
| Reduction | Current Use | Application | Total Haste | Reduction
| Effectiveness j
1 2 1
1 « I
1 3 |
1 3.00 |
1 1 1
1 < 1
1 2 1
1 2.33 I
1 2 |
1 3 1
1 3 |
1 2.67 |

| Potential | |
< I
0 1
1 1
1.67 |
2 1
< 1
1 1
2.33 |
1 1
2 1
1 1
1.33 |

0 1 1
1 1 1
1 1 1
0.67 | 0.35 |
2 1 1
0 1 1
3 1 1
1.67 | 0.20 |
1 I 1
2 1 1
2 1 1
1.67 | 0.45 |
1 LOO |
ndex
2
0
0
2
0
3
0
3
0
1
0
| Future Reduction
i. 	 . 	 	 	 	 	
1

| Probable
0 1
0 1
8 1
0 1
5 1
s I
5 1
9 1
5 I
5 1
8 1
1.5 |
3
» 1
0
1
0
0
0
0
1
0
0
0
1
0
0

Index |
	 .. i
1
| Maximum |
0 1
0 1
6 1
5 1
3 1
0 1
1 1
5 1
< 1
8 1
1 1
8 1
6 1
1
1.0 |
1
1.0 |
1
1
1.1 |
1.1 |
1
1
1.1 |
1.1 |
1.1 |

-------
and the current reduction index for the process is calculated using equation (8):
               N
(8)    C =S-l/Z(Zj/(S-Cp)


      C  =4-                1
                 0.35    +  0.20     +   0.45
                 4-2.0      4-3.9      4-1.5
         ~   "
                 0.175    *   2.0     +   0.18
To calculate the future reduction index for each method, equation (10) is used:


(10)   f,j = ejj(S-u,p Pij/s2


      fll = 2 x (4-4) x 0/16 = 0.0


and so on.  Then, the  probable and future reduction indices  are  calculated  for  each
wastestream using equations (11) and (12):


                          N
(11)   Fj(Probable) =  (1/Mj) z f,j
                         i = l

      F1(probable) = (1/3) x (0.0 + 1.0 + 0.6)     = 0.5


(12)   Fj(rnaximum) = maximum (f j, i = l,2,...Mp

      Fj_(maximum) = maximum (0.0, 1.0, 0.6)   = 1.0
                                        13

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Finally, equations  (13) and  (14)  are  used to compute  the  overall  future  reduction
indices for the process:
                    M
(13)  F(probable) =   £   Fj (probable) Z0j
                   j=l
     F(probable) =  0.5 x 0.35 + 0.5 x 0.20 + 0.8 x 0.45  = 0.6

                    M
(14)  F(maximum) = £ Fj (maximum) Z0j
                   j=l
     F(maximum) = 1.0 x 0.35 + 1.1 x 0.20 +  1.1 x 0.45 = 1.1
                                        14

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1.    PROCESS: ACRYLONITRILE (VINYL CYANIDE) MANUFACTURE

2.    SIC CODE:  2869

3.    INDUSTRY DESCRIPTION

The acrylonitrile  manufacturing industry comprises facilities which tend to be part of
large multiproduct corporations.  In the  U.S., the  acrylonitrile industry is controlled
by four large producers.

3.1  Company Size Distribution

Nearly all of the world's supply of  acrylonitrile is manufactured by the ammoxidation
of propylene using  the Sohio Process.   Plant  capacities are large  in  order  to take
advantage  of  economics  of  scale.  The  total  U.S.  production  capacity  of  the
acrylonitrile  industry in 1983 was 1,112,500  short tons.  Plant capacity at the  six U.S.
acrylonitrile   production  facilities  ranges  from  132,500  to  230,000  short  tons.
Competition  has reduced the number of acrylonitrile producers to the four companies
listed in Table 3-1.

3.2  Principal Producers

There are four major producers of acrylonitrile:

     American Cyanamid Company               Monsanto Co.
     E.I. du Pont de Nemours & Co. Inc.           Standard Oil Company of Ohio

3.3  Geographical Distribution

Of the six plant locations listed in Table 3-1,  four are located in Texas.  Five  of the
establishments are located in EPA Region VI and one in Region V.

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                   Table 3-1 Acrylonitrile Producers in the United States
Company
American Cyanamid Co.
Avondale, LA
E.I. du Pont de Nemours &. Co.
Beaumont, TX
Monsanto Co.
Chocolate Bayou, TX
Texas City, TX
The Standard Oil Co.
Lima, OH
Green Lake, TX
TOTAL
Capacity
(short tons/yr.)
132,500

175,000

230,000
225,000

150,000
200,000
1,112,500
% of Total
11.9

15.7

20.7
20.2

13.5
18.0
100.0
Source:  Chemical Economics Handbook (SRI 1982) and industry comments.
                                     B.l-2

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4.    PRODUCTS AND THEIR USE

The  production  of acrylonitrile increased rapidly  during  World  War  II due  to  the
demand  for  its use  in  oil  and  solvent  resistant  rubber  used  for  tires.   Later,
acrylonitrile  became  an integral  raw  material  for fibers,  synthetic  resins,  block
copolymers, elastomers, and intermediates in organic synthesis (Groet 1979).   Table
4-1 contains a breakdown of the uses of acrylonitrile.

             Table 4-1 1984 Acrylonitrile Products and Use Distribution

     Product                                                       Percentage

     Acrylic Fibers                                                    44%
     Acrylonitrile-Butadiene-Styrene (ABS)                             26%
       and Styrene-Acrylonitrile (SAN) resins
     Adiponitrile                                                       14%
     Acrylamide                                                        7%
     Nitrile Elastomers                                                3.5%
     Others (including materials unaccounted for)                        5.5%

Source:    Project staff estimates

5.   RAW MATERIALS

The  principal raw  materials used to produce acrylonitrile are propylene, ammonia, and
air.

6.   PROCESS DESCRIPTION

The  Sohio  ammoxidation process (see  Figure 6-1)  is the  most significant process route
responsible for nearly 90 percent of the world's acrylonitrile production.  In the Sohio
ammoxidation process, propylene,  ammonia,  and  air are exothermically reacted in a
fluidized bed catalytic  reactor at about 750-950°F and 5-30 psig.  The reaction may
be represented as follows:
                                    Bl-3

-------
PROPYLENE'
AMMONIA
[ NOTE A }
VENT 6AS
A
~ 	 1 ' CD
H2S04 | W
~T
r-
FLUID 1
BED |
REACTOR '
**-S j

QUENCH /
ABSORPTION
SECTION

T

AIR


*


STEAM


©@




'

VASTENATER
STRIPPIN8

( NOTE A {
CRUDE HCN
A
@


1 	 A
f








RECOVERY
SECTION



k
j

( NOTE A )
'
tJ tr-
ACRYLONITRILE ACRYLO -
PURIFICATION NITRILE
	 j. PRODUCT
T


k
}


'
1

") ,.7
^ ©
(NOTE A )


,j J



ACETONITRILE
PURIFICATION


^ ircTnuTTnn p
COPROOUCT

                                                                                                -».  AQUEOUS
                                                                                                    MASTE  TD
                                                                                                    UNDER8ROUND
                                                                                                    INJECTION
         NOTE A . THESE STREAMS CAN BE INCINERATED
           PROCESS HASTE CATESORIESI
           (T)   VENT 6AS                    j
           ©   AN PRODUCT COLUMN BOTTOMS

           ©   CRUDE HCN
           ©   SPENT CATALYST

           ©   ABSORBER EFFLUENT

           ©   ACE COLUMN BOTTONS

           (7)   MASTEVATER STRIPPER BOTTOMS
                      Figure 6-1  The Sohio Aaaoxidation Recess for Acrylonitrile Manufacture
                                                   Bl-4

-------
                                 catalyst
     2CH2 = CHCH3 + 2NH3 + 302	-> 2CH2 = CHCN + 6H2O + by-products

The catalyst  has been undergoing continuous  improvement to produce higher yields of
acrylonitrile.  The early  process  version used a bismuth-phosphomolybdate catalyst,
followed by introduction of  antimony-uranium (catalyst 21)  in  1967.  A ferrobismuth-
phosphomolybdate (catalyst 41) was  introduced in 1972  boosting the capacity up to
35 percent.   Currently,  two  catalysts  are  used:   "Catalyst 49" with  undisclosed
composition and antimony-tellurium catalyst  manufactured by Nitto Corporation.

A once  through (non-recycle)  reactor operation mode with  a residence time of a few
seconds is employed. Commercially  recoverable quantities of acetonitrile (0.02 Ib/lb
propylene feed) and hydrocyanic acid (0.1-0.2 Ib/lb propylene feed)  are  produced as
by-products*.  The reactor  effluent is quenched and countercurrently scrubbed with a
dilute sulfuric  acid solution.   The  vent gas,  primarily  consisting of nitrogen  with
acrylonitrile, carbon oxides, propane, propylene, and trace amounts of acetonitrile and
ammonia, is incinerated.

The  organic-rich stream  from the quench/absorption section  is  sent to the recovery
section  where crude  acrylonitrile (AN) is separated  and  sent  to  the AN  purification
section  to  yield AN product,  crude  HCN stream and  heavy-ends  (AN product column
bottoms).

Crude hydrocyanic acid (HCN) can be purified and sold or incinerated  The AN product
column  bottoms are typically  combined with the aqueous effluent from the  quench-
absorption section upstream of the wastewater stripping section (wastewater column).
In some facilities, the AN product column bottoms are incinerated**.

The  crude acetonitrile from the recovery section can be further purified or incinerated
directly, depending on whether or not there is a commercial demand for it.
 * E.I. du Pont de Nemours & Co. 1985:  Personal communication.
 **Monsanto Co. 1985: personal communication.
                                      Rl-5

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The aqueous  effluent from the quench-absorption section is typically comingled with
the AN product column bottoms, steam stripped in the wastewater column, sent to the
settling pond fronn  which it  is  routed  to underground injection.   The wastewater
stripper overhead  is  recycled  back to the quench-absorption sections for organics
recovery.

7.    WASTE DESCRIPTION

The primary  wastes  evolved in the Sohio process are listed in Table 7-1.  Generally,
the undesirable heavy  compounds formed as the  result  of  side  reactions  during
ammoxidation are separated as distillation column bottoms, combined with process
water used to quench the reactor off-gas and absorb ammonia, and  disposed of via
underground injection.

Based  on  the information obtained,  all  operational facilities  in  the United States
dispose  of streams #2, 6 and  7 via  underground  injection.   As mentioned before,
stream #6 (ACE Column Bottoms) may not be produced by  some facilities because of
incineration  of  the  crude acetonitrile.    The constituents of  these  streams  were
reported as being not amenable  to biological or chemical treatment (PRI 1977).

The disposal  methods for minor wastes,  such as spent catalyst,  spills cleanup and
equipment cleanup  wastes  could  not be totally ascertained,  although  landfilling
appears likely.

8.    WASTE GENERATION RATES

The specific  waste generation rates for selected waste streams from the Sohio process
were given  in  terms of Ib  of  waste/lb  of product (PRI 1977)  and are reported in
Table 7-1. Overall waste generation  rates for the  manufacturing of acrylonitrile in
the United States were unavailable. Fractional waste generation  (percentage of waste
each wastestream represents as compared to all  waste generated)  was estimated by
the project staff based on available information and industry comments. These values
are shown in  Table 9-1.
                                   Bl-6

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                          Table 7-1 Wastes from Sohio Acrylonitrile Manufacture Process
No.    Description
                     Process Origin
                         Composition (Ib/lb AN)
                                RCRA Codes
1.
Vent Gas
8.

9.
Quench-Absorption
Section
       AN product column    AN purification
       Bottoms              (AN Product Column)
       Crude HCN
       Spent Catalyst
       Wastewater
                     Lights column
                     Reactor
                     Absorber
       Acetonitrile Column   ACE Purification
       Bottoms              Section
Wastewater          Wastewater stripper
Stripper Bottoms

Spills & Leaks        Process Eqpt. &. Piping

Equipment Cleaning  Process Eqpt. Cleaning
Carbon Monoxide - .20
Propane - .05
Propylene - .02
Trace Organics & NH}

High rnol. wt. nitriles-
and polymers-0.002
Acrylonitrile

HCN  0.1
Light Impurities

Catalyst 49 or
Nitto

Water-1.02
Ammonium Sulfate
Acetonitrile- 0.02
Acrylomitrile
HCN, solids
Water
Acetonitrile 0.02
Heavy ends 0.003

See //2,  5 above
                                                                                   K012
                                                                                   (delisted)
                                                                                    K013
                                                                                    K014
                                                                                          K011

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9.   WASTE REDUCTION THROUGH SOURCE CONTROL

This section deals with the problem of how to reduce the volumes and/or toxicities of
the  Sohio  acrylonitrile  process  waste  streams.   The  off-gas,  HCN,  and  crude
acetonitrile will not be considered in this report.  Both HCN and crude acetonitrile are
often incinerated.  The  off-gases, containing substances such as acetonitrile,  HCN,
propane,  propylene,   carbon  monoxide,   and   acrylonitrile,   are  incinerated   or
catalytically abated.

9.1  Description of Techniques

The  summary of source  control methodologies  is given in Table 9-1.  Sections  below
deal with the description of the listed methods.  In addition to  the  waste reduction
measures classified as  being process  changes or  material/product  substitutions,  a
variety  of waste reducing measures labeled as "good  operating practices" has also been
included.   Good  operating practices  are defined  as being procedural or institutional
policies which result in a reduction of waste. The following  items highlight the  scope
of good  operating practice:

     o     Waste stream segregation
     o     Personnel practices
                management initiatives
                employee  training
     o     Procedural measures
                documentation
                material handling and storage
                material tracking and inventory control
                scheduling
     o     Loss prevention practices
                spill prevention
                preventive maintenance
                emergency preparedness
                                   Bl-8

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For each  waste stream, good  operating practice applies  whether it  is listed or not.
Separate listings have been provided whenever case studies were identified.

9.1.1       Aqueous Waste to Underground Injection

This principal process waste stream is mostly water which  contains low concentrations
of ammonium sulfate, acrylonitrile, acetonitrile and  heavier organic impurities which
are formed as a  result of side reactions.   Generally,  waste  minimization can  be
addressed using four different approaches:

     o     Avoiding formation  of undesirable byproducts in the reactor.

     o     Decrease of concentration of acrylonitrile (and acetonitrile) in the bottoms
           of their respective purification columns.

     o     Segregation and destruction of  concentrated  wastes (AN  column bottoms
           and ACE column bottoms)  instead  of  mixing  them with  the agueous
           absorber effluent.

     o     Detoxification of aqueous waste.

The above measures would reduce the toxicity of the  waste stream, but will not have a
large impact on its volume.  The volume reductions equate to reductions in  water use
and these can be addressed using the following approaches:

     o     Increasing  concentration of sulfuric  acid with the  attendant decrease in
           water use.

     o     Use of a  reboiler instead of steam in the wastewater stripper.

     o     Evaporation of water.

While these measures may  reduce the  volume of the ultimate waste, their effect on
toxicity  will  be  negative, i.e.,   the  hazardous  organics  will  tend  to   be  more
concentrated thus making the entire stream more toxic.  For this reason, the principal
                                    BJ-9

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thrust  of  waste minimization should be toward toxicity  reduction and  the  first  four
approaches indicated.   The discussion  of  the  specific measures identified for each
approach is provided below.

9.1.1.1     Avoidance of Heavy Impurities Formation

This can be accomplished through the following measures:

     o     Increase in catalyst selectivity toward AN formation.
           In the past,  catalyst  improvements have  contributed  significantly  to the
           increase  of  AN yield with attendant decrease in the yields of  ACE and
           heavier  impurities.  The  research  should  be  continued to  develop  more
           selective and stable catalysts.

     o     Reduction of ammonia concentration along the reaction path.
           Literature indicates that some of the impurities are formed because of the
           excess  ammonia present  during the primary  reaction (Jones 1971, Lurgi
           1975).  Conceptually  a decrease in ammonia concentration in the reaction
           zone can lower  the  formation rate of the undesirable byproducts.  The
           following avenues were identified.

                staged  NH3 addition e.g.  using multiple  ring distributors or multiple
                beds.

                direct  quench  of  hot reactor  offgas  without  heat  recovery  to
                minimize byproduct formation in the absence of catalyst contact.

     o     Improved  contacting  between gas and  catalyst in  the  ammoxidation
           reactor.
           According to present  knowledge, the interchange  rate of gas between the
           bubble  and emulsion  phase is diminished,  as bubble size increases  due to
           coalescence  (Kunii & Levenspiel  1977).    As  a result,  gas-to-catalyst
           contact is decreased, along with an attendant drop in  product yield and an
           increase  in  by-product formation.  It would  follow  that  by keeping the
           effective bubble size  small, the ammonia residence time  in the emulsion
           phase  (where most of the catalytic reaction  takes place),  will  increase,
                                    Bl-10

-------
           thus  reducing  ammonia bypassing along with by-product  formation.  The
           disadvantage is present in the decrease of the solid flux in  the reactor with
           attendant drop of heat transfer rate. This can be overcome by  using more
           heat  transfer area or a cooler heat transfer medium.  The bubble size can
           be controlled  by  cooling coil  pitch, bed aspect (length-to-diameter  ratio)
           and distributor design.  It is suggested that consideration be given  to  all
           means of increasing the gas-to-catalyst contact.

           Rapid quench of the reactor off-gas.
           The  rationale  behind  proposing  this   method  is  that  the  by-product
           formation rate may be curtailed by limiting the time elapsed between the
           moment the reactor off-gas leaves the catalytic zone and  the moment it is
           cooled  down  sufficiently  to  arrest the  undesirable  reactions.   These
           reactions  would occur in the interim when the gas is hot and not in  the
           intimate  contact with selective catalyst.  The following specific measures
           are noted:
                installation of cooling coil in the freeboard space of the reactor.
                moving the cooler or venturi  as close as possible to the reactor.
                elimination  of cyclone  in  favor  of  an  integral  high temperature
                ceramic  fiber filter to reduce freeboard space requirement.
                use of cooling jacket or radiator fins on the reactor exit piping.
                elimination of indirect cooling in favor of direct quench.
                use of cooler with low residence time (higher heat transfer rate).

           Raw  material purification.
           Most facilities that purchase their raw materials  (as opposed to producing
           them),  utilize  standard (99.8% purity) grade  ammonia and  chemical  grade
           propylene in the production of acrylonitrile.  In principle, the generation of
           certain by-products, such  as tars might be reduced by using a higher  grade
           of feed-stock.  Results from a test reactor study performed by DuPont,
           however, indicated that there  was no difference in tars formation between
           a polymer grade  and a chemical  grade propylene feed*.   The effect  of
           ammonia  purity was  not established, although  it is doubtful  that it is
           significant.
* E.I. du Pont de Nemours & Co. 1985: Personal communication.

                                    Bl-11

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Some of  the above measures are purely suggestions which  ultimately may or may not
deserve an in-depth  consideration, however, it  is felt that  a further  assessment is
warranted.

9.1.1.2     Decrease of AN and ACE concentrations in the purification column
           bottoms.

This  approach  will  reduce  the  amounts of both  compounds discharged  with  the
principal waste stream.   The decrease of AN or ACE  concentration  in the bottom
stream means an increase of concentration of heavier impurities.  In principle, this can
be  accomplished  through additional distillation, e.g.  an increase  in the number of
stages in the stripping section of both AN and ACE columns or secondary recovery.

9.1.1.3     Segregation and destruction of AN and ACE column bottoms.

Presently,  these  streams are  mixed together with the aqueous effluent  from  the
quench-absorption section (AN product bottoms  upstream and  ACE bottoms down-
stream of the wastewater column).  By segregating these streams and their subsequent
incineration  at  high  temperature,  the  content  of  hazardous  compounds  in  the
discharged  wastewater  will  be  lessened.    There  are   industrial   precedents  to
incineration of both streams.

9.1.1.4     Detoxification of the aqueous waste.

Various  approaches  to  the  detoxification  problem have  been  reported.   Alkaline
hydrolysis  was in operation at Du Pont's now  defunct Memphis  facility, where a
biodegradable effluent was produced and routed to a municipal sewer (Lowenbach and
Schlesinger  1978).    Inorganic   compounds  recovery  from the  wastewater   was
considered.   The  process  developed  by  Erdolchemie  recovers  fertilizer  grade
ammonium  sulfate (Groet  1979).   Difficulties  with  metallic compound  impurities
(present because  of catalyst metals carryover) and with control  of crystal  size make
this process questionable; no one in the United States uses it.
                                     Bl-12

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9.1.2 Spent and Lost Catalyst

There are two causes of catalyst loss:  attrition and deactivation.  Attrition involves
breakup of catalyst particles into fines  which are elutriated out of the reactor ending
up as solids leaving the process via wastewater column.  Deactivation appears  to be
caused by loss of active metal from the catalytic  sites due to volatilization (e.g. of
molybdenum).

In comparison to the wastewater,  these  wastestreams  are minor, yet  they could be
minimized by:

     o     Development of tougher, more attrition-resistant catalyst support.

     o     Lowering the frequency  of high  temperature upsets in the fluid bed.

9.1.3       Equipment Cleanup Wastes

Usually, the wasteloads associated  with equipment cleaning are small and periodic in
nature (once every 1 or  2 years). Further reductions may be obtained through:

     o     Provision of  more drainage time before cleanup or steamout.

     o     Use  of  non-stick  (electropolished  or  Teflon*) heat  exchanger tubes to
           reduce deposit clingage  (Anonymous 1985b).

     o     Use of in-process heat exchanger tube cleaning devices (Anonymous 1985a).

     o     Lower  process  film  temperatures  and  increased  turbulence at the heat
           exchange surfaces  to reduce fouling rates.
•^Registered trademark of E.I. du Pont de Nemours &. Co.
                                    Bl-15

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9.1.4       Spills and Leaks

As mentioned before, spills and leaks constitute a very minor waste stream owing to
extensive implementation of preventative  maintenance  measures in facilities dealing
with hazardous  materials.   Further source reduction is possible, in principle, through
better operating practices (see practice study entitled "Good Operating Practices").
Additionally, some consideration should be  given to:

      o     Use of bellows-sealed valves.

      o     Replacing single mechanical seals with double mechanical  seals on pumps
           or use of canned seal-less pumps,

      o     Use of leak detection systems and portable monitors.

      o     Enclosed sampling and analytical systems.

      o     Use  of   vapor-recovery systems  for loading,  unloading  and  equipment
           cleaning.

9.2   Implementation Profile

Some of the identified source  control options may require extensive engineering and
economic analysis before implementation.  The  four  U.S.  producers  of acrylonitrile
are large organizations with excellent technical  capabilities. Therefore, analyses of
technical and economic feasibility are best performed by  their  resident  technical
staff.  No process-specific source control implementation avenues have been identified
here.

9.3   Summary

Table  9-1 presents a  summary of proposed source  control  methodologies.   Each
technique described in the text was rated  using the input from industrial reviewers in
three  categories:   effectiveness, extent  of  current  use  and   future  application
potential.  The  ratings were combined into current and future  reduction  indices for
each  technique, waste stream and the  entire process.
                                     Bl-14

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                    TABLE 9-1 SUMMARY OF SOURCE CONTROL METHODOLOGY TOR THE ACRYLONITRILE  MANUFACTURING  INDUSTRY
1
| Waste Stream
1
| Aqueous Waste to
| Underground
| Injection (*)
1
1
!
1
1
1
1
| Spent and Lost
| Catalyst
1
1
I Equipment Cleanup
rjrj 1 Wastes
ij
| Spills and Leaks
1
1
1
1
1
| All Sources
1
1
1
12.
13.
l».
15.
16
IT.
18
1
It
12.
1
|2.
(3.
l<
1
1'
I?
|3
1*.
1
1
Control Methodology
Develop more selective catalyst
Reduce ammonia concentration
Improve gas/catalyst contact
Quench reactor offgas rapidly
Purify raw material feed
Decrease AN/ACE cone in col botto»s
Segregate/destroy AN/ACE col bottoms
Detoxification of aqueous waste
Overall
Develop tougher catalyst support
Minimize reactor hot zone
Overall
Increase equipment drainage time
Lower heat exchanger film temperature
Electropolish heat exchanger tubes
Use in-process H.X cleaning devices
Found Documentation ! Waste i Extent of 1 Future Fraction of | Current | Future Reduction Index
Quantity | Quality | Effectiveness 1 Potential | | Index I Probable | Maximum
21 1 | 31 2| 4 | | 1.5 | 1 5 | 15
t | 1 i t | 01 1 | I 0 0 | 03
01 0 ! 2 ! 21 3 | | 1.0 | 0 8 | |
01 0 | 2 ! 1 | 2 0.5 | 0.8 |
1 I 2 | 11 M 1 I 1 0 3 | 02 |
1 1 1 | 2 | 1 | 2 | 0.5 | 0.3 |
'I 1 | 2 | 11 3 i 051 1.1 | !
1 I 1 | 1 | 0 2| | 0.0 | 0 5 | |
0 38 | 0 83 | 1 75 1 1 00 i 2 25 | 0 90 | 1 5 | 0 7 | 1.5 I
1 | 1 | 2 | 1 1 | i 0.5 | 0.4 | 0.4 i
1 1 1 I 11 0 1 | | 00| 0.3 | |
1 00 | 1.00 | 1 50 I 0 50 | 1.00 | 0 01 | 0 5 | 0.3 | 0.4 |
'I '1 3 | 3| 2 | 1 2 3 | 0.4 | |
1 I 1 I 2 | 1 | 1 | | 0.5 | 0 4 |
21 1 | 3 | 0| 2| | 001 1 5 | 1.5 |
21 1 | 21 1 2 | 0 5 | 0.8 |
Overall I 1 50 ! t DO | 2.50 | 1 25 1 ! 75 ( 0 02 1 2 3 I 08 1.5 I
Use double mechanical seals on pumps | 1 | Ij 3 | 4 2 | 30) 00| j
Use leaK detectors | 3 | 3 I 2 | 3 | 1 | | 1.5 | 0.1 j 0 1 |
Enclosed sampling and analy systems 3 | 2| 21 3 1 | | 1 5 | 0.1 0 1 |
Use of vapor recovery systems | 2 | 2 | 4 | t | 1 | | 3.9 | 0.0 | |
Overall | 2 25 | 2 00 | 2 75 | 3.50 | 1.25 | 0 01 | 3 9 | 0 1 | 0.1 |
All Methods | 1 00 | 2 0 | 0.7 | 1.5 j
(*)  These waste streams include listed T' and/or "K"  RCRA wastes

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It  appears  that the currently  achieved reduction of waste  due to  the present level of
implementation of all methods listed  is characterized by the  current reduction index
(CRI) of 2.0 (50 percent) on a scale of zero to four.  This is  a measure of how much
waste was  reduced with respect to the quantity that would have been produced if none
of the methods listed were employed at their current level. High  CRI value indicates
that acrylonitrile producers have  reduced their waste considerably.

It  also appears that  the  future reductions are  characterized by future reduction index
of 0.7 to 1.5 on a scale of zero to four (18 and 38 percent respectively).  This means
that by implementing all  listed  techniques  to their full rated potential,  the current
waste can be further reduced only to a moderate extent.

Many of the  noted techniques were arrived  at through engineering  analysis of rather
limited  available process information and do  require  further evaluation.  Among  the
techniques that appear especially worthy of further investigation (as evidenced by high
individual  future  reduction index)  are the improvement of catalyst selectivity  and
segregation and destruction of AN and ACE column bottoms.

10.  PRODUCT SUBSTITUTION  ALTERNATIVES

Today's major use of acrylonitrile is  in  the making of acrylic and modacrylic fibers.
Acrylic fibers  contain about  90% acrylonitrile.   These fibers are essential in  the
production of various knit fabrics, carpets,  blankets, draperies,  upholsteries,  felts
fiberfils, hairpieces, industrial filtration  systems, and paint roller covers.  Due to  the
many uses  of acrylic fiber, it's demand  has been sharply increasing, thus, so has  the
demand for acrylonitrile.

In  1973,  limitations on  propylene  supplies  (the  raw  material  used  for producing
acrylonitrile) began  to occur.  This,  coupled with an increase in  demand for acrylic
fibers, led to an  acrylonitrile shortage.  The raw material  shortage  affected  fiber
producers in several ways.  Textile mills  began to place emphasis on increasing fabric
yardage by producing lighter weight fabrics  and on increasing production of the more
profitable better  quality fabrics (as opposed to more abundant low and medium priced
ready-to-wear garments).  This precedent indicates the possibility that  fabric yardage
can be extended.
                                   Bl-16

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11.  CONCLUSIONS


The  acrylonitrile  industry  appears  to  have  reduced  its  waste  generation  rates
considerably, in the  range of  50 percent.  The  extent  of  future  reductions of toxic
components in  all  wastestreams appears  moderate, in the estimated range of 18 to 38
percent.


Most of the identified techniques need further evaluation.  Catalyst improvement  and
bottoms stream segregation and destruction appear to be most promising  routes to
minimize  waste.  The only  product  substitution alternative identified was fabric
yardage extension.
12.  REFERENCES


Anonymous.  1983.  Hydrocarbon Processing.  62(11): 74.

	.  1984.  Production by the U.S. chemical industry.  Chem.
Enq. News.  62(24):37.

	• 1985a Chemical Engineering Progress, 81(7):  7.

	. 1985b Chemical Engineering Progress 81(7): 104-5

Crumpler, G.  1980. Treatment alternatives for hazardous waste management  in nine
industry groups.  Washington, D.C.:  U.S. Environmental Protection Agency.

Groet, L.T.    1979.    Acrylonitrile.   In  Kirk-Othmer  Encyclopedia  of  Chemical
Technology.  3rd ed. Vol. 1, pp. 414-426. New York, N.Y.:  Wiley.

Jones,  H.R.   1971.  Environmental control in the organic and petrochemical industries.
Park Ridge,  N.J.: Noyes Data Corp.

Kunii D., Levenspicl O. 1977. Fluidization Engineering, J. Wiley and Sons Publ.  Co.

Lowenbach W., Schlesinger J. 1978.  Acrylonitrile manufacture:   Pollutant prediction
and abatement, Mitre Technical Report MTR-7752.

Lurgi Corp.  1975. Hydrocarbon Processing.  54(11): 158-9.

MCA.  1974. Manufacturing Chemists Association. Chemical safety data sheet 50-31:
acrylonitrile. Washington, D.C.:  Manufacturing Chemists Assoc.

PRI.  1977.   Process Research, Inc.  Alternatives for hazardous waste  management in
the  organic  chemicals,  pesticides,  and explosives  industries.    EPA-530-SW-151C.
Cincinnati, Ohio: U.S. Environmental Protection Agency.
                                   B1-J7

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Stiles, A.B.  1983.  Catalyst manufacture. Vol. 14. Marcel Dekkel, Inc.

UCBSA.  1975.  Maleic anhydride.  Hydrocarbon Processing.  54(11):  160.


13.   INDUSTRY CONTACTS

J.R. Cooper, Manager, Environmental Affairs and Occupational Health, E.I. du Pont de
Nemours & Co., Wilmington, DE.

J.M. Schroy, Fellow, Monsanto Co., St. Louis, MO.

K.R. McClain, Manager, Acrylonitrile  & Field Sales, Sohio  Chemical Co., Cleveland,
OH.
                                   Bl-18

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1.   PROCESS: AGRICULTURAL CHEMICAL FORMULATION AND APPLICATION
2.   SIC CODE: 2879
3.   INDUSTRY DESCRIPTION

The industry includes companies which formulate and prepare agricultural pest control
chemicals or pesticides. This  includes insecticides, herbicides, and fungicides.  These
products are formulated from pesticide concentrates manufactured elsewhere and are
distributed to farmers in ready-to-use form.

3.1  Company Size Distribution

The industry is comprised of roughly 330 establishments nationwide.  More than 64% of
the establishments employ less than 20 people, although this group comprises only 7%
of the  total work force.  A  small number of large companies employ the majority of
workers. Table 3-1 summarizes company size distribution.

                      Table 3-1 Company Size Distribution
No. of employees per facility

No.
No.

of establishments
of employees
Total
330
16,500
1-9
166
800
10-49
113
2600
50-99
23
1700
100-249
15
2200
250+
13
9400
Source:    1982 Census of Manufacturers (USDC 1985).

3.2  Principal Producers

There are clearly no major producers which dominate the industry. Some formulation
plants  are owned by large  pesticide  manufacturers,  while  others  are owned by
independent formulators.

3.3  Geographical Distribution

The  geographical  distribution  of  establishments  in  the  agricultural chemicals
formulation industry is shown in  Table  3-2  and  Figure  3-1.  Approximately  59% of
                                     B2-1

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the establishrnents are located in 10 states, although no one state accounts for a major
share of the industry.  Most  of the establishments are located near the agricultural
areas which make use of the products.

                  Table 3-2  Location of Facilities by EPA Region
EPA Region
I
II
III
IV
V
VI
VII
VIII
IX
X
Number of
Establishments'3)
-
33
-
52
32
37
13
25
43
5
                         National
Source:    1982 Census of Manufacturers (USDC 1985)
(a) Includes only those establishments in states with 150 or more employees.
v^) The discrepancy between  Table 3-1 and  Table 3-2 is caused by  the  exclusion of
   establishments in states with less than 150 employees.

4.   PRODUCTS

The  agricultural  chemicals  industry (SIC   2879)  produces  pesticides and  other
agricultural chemicals not elsewhere classified, such as soil conditioners.  This study is
mainly  concerned  with  pesticides.  In the  U.S., over  600 different  pesticides are
                                       B2-2

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                           VIII
CO
1X3
I
to
              o-i
2-5
6-10
11-20
21-50
                    Roman numerals show EPA regions

  Figure   3-1  Pesticide Formulating Plants in the U.S

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produced  (Kryeger 1983).   Most  pesticides can be  classified as either insecticides,
herbicides, or fungicides, although many other minor classifications  exist.   Table 4-1

below  lists the  production  of the  major classes of pesticides.   Each  division is
subdivided according to chemical type.


Roughly 75% of all insecticides and herbicides, and 66% of all pesticides, are used on

agricultural cropland.  The  remainder are used in  private homes and gardens and on

commercial and industrial property (Dillon 1981).   The majority of pesticides are used

on only a few  major crops.  Currently, cotton, corn, and apples receive 67% of  all

insecticides used in agriculture.  Corn and soybeans receive 60% of the herbicides
used, and  84%  of the fungicides are applied to fruits and vegetables (Dahlston 1983).

Only 48%  of the total U.S. cropland is treated with  pesticides (Dahlston 1983).


                  Table 4-1  1982 Pesticide Production in the U.S.


Product                                                        Quantity Produced
                                                                (tons per year)

Insecticidal formulations
   Inorganic compounds                                              54,300
   Organic compounds                                              206,750
       Chlorinated hydrocarbons                                      18,900
       Carbamates                                                   78,400
       Organophosphates                                             73,150
       Biological (botanical, bacterial)                                11,250
       Other organics                                                25,050
Herbicide  formulations
   Inorganic compounds'3'                                            N/A
   Organic compounds                                              541,750
       Phenoxy                                                     101,400
       Metal organic                                                 9,450
       Triazine                                                      97,250
       Urea, Amide, Benzoic, other organics                          333,150
Fungicide  formulations
   Inorganic compounds^3'                                            N/A
   Organic compounds                                               56,250
Other pesticidal formulations
   Fumigants                                                        17,450
   Defoliants and dessicants                                         3,500
   All others^3'                                                     N/A


Source:    1982 Census of Manufacturers (USDC 1985).
(a)Data not available.
                                      B2-4

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5.   RAW MATERIALS

As listed below, input raw materials include the pesticide concentrates from pesticide
manufacturing  plants as  well  as  diluents and  other  chemical additives used in the
formulating process (Metcalf 1981):

Pesticide Concentrates

           Organic/Inorganic      Insecticides, herbicides, fungicides, others

Formulation and Preparation Materials

           Dust Carriers          Organic flours, sulfur, silicon oxide, lime,  gypsum,
                                 talc, pyrophyllite , bentonites, kaolins, attapulgite,
                                 volcanic ash

           Solvents               Kerosenes,  xylenes,  methyl isobutyl  ketone,  amyl
                                 acetate

           Others                Wetting and dispersing agents, masking agents,
                                 deodorants, emulsifiers

6.   PROCESS DESCRIPTION

There are  two  major steps in  the production  of  pesticides for agricultural use.  The
first step  is the manufacturing of the  pesticide concentrate  from  basic  chemical
feedstocks including petrochemicals, inorganic acids, gases such as chlorine, and other
chemicals. This produces the pesticide, but not in a form which is ready for use.  The
second major step, which is the focus of this report, is the formulation and preparation
of the pesticide for final use.

The  formulation  process depends on  the  desired form of the pesticide.   Common
pesticide  formulations  include dusts,   wettable  powders,  emulsions,  granules,  and
aerosols (USEPA 1979).  Wettable powders are the most  widely used formulation in
agriculture.  While each of  these formulations is  produced differently, the major  unit
                                      B2-5

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operations common to them all include the dry mixing and grinding of solids, dissolving
or melting of solids into solution, and blending.  A typical liquid pesticide formulation
process is shown in Figure 6-1.

The  application of pesticides to agricultural crops is  an entirely separate operation,
but is  included here since  it also results in  the  generation  of pesticide  wastes.  The
three  major methods of pesticide  application  in agriculture  are  spraying (of  liquid
pesticides), dusting (of powders),  and fumigation (of aerosols) (Metcalf 1981).  Aerial
spraying accounts for roughly two-thirds of all applications of pesticide in agriculture.
Wastes are generated during the cleaning of the application equipment.

7.   WASTE DESCRIPTION

The  primary wastes from the formulation and application of pesticides along with their
process origin  and composition are  given in Table  7-1.  Pesticide  formulations  are
generally produced in a batch  mode.  As a result, the same  formulating  equipment is
often used  to produce  a variety  of products.  This  results in the  need  to clean  the
process  equipment   prior  to   every  product   switch-over  in   order   to  prevent
contamination  between batches.   The  resulting  cleaning  wastes  account for  a
substantial  amount of the  waste produced during pesticide formulation.  The cleaning
wastes may be either aqueous or organic liquids, or solid materials  such as powders or
granules, depending on the type of pesticide being formulated.

Used drums, bags, and  other packaging  material may contain up to several ounces of
pesticides  or other raw materials, thus becoming an additional waste source. Other
wastes produced  during the  formulation  process  include  spills,  off-specification
batches  of pesticides, and air pollution  scrubber wastewater (Gruber  1975).  Poor
process control often results  in the production of off-specification  material.  This is
either  disposed of as  a waste,  or recycled within the  process and upgraded  to  an
acceptable quality.

The  application  of pesticides to crops also results in waste  generation.   As in  the
formulation process,  sprayers and other application equipment are often  used to apply
more than  one product.  The equipment  is  usually cleaned  between applications of
                                       B2-6

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                           PESTICIDE
                          CONCENTRATE
SPECIAL
PURPOSE
ADDITIVES


MIXER
CD©©

J FILTER
1 CD

|

PACKAGING
AND
STORAGE
FINAL
PRODUCT
GO
K3
                             SOLVENT
                             STORAGE
PROCESS NASTE CATEGORIES
(T)   NASTE RINSE MATER
~    HASTE CLEANING SOLVENTS
      DISCARDED RAM MATERIAL CONTAINERS
      PESTICIDE DUSTS
      OFF- SPECIFICATION  PRODUCTS
                                                      Figure 6- 1   Liquid Pesticide Formulation Process

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                                    Table 7-1 Pesticide Formulating Process Wastes
       No.
    Waste Description
    Process Origin
     Composition
RCRA
Codes
03
         5.

         6.
                 Waste rinse water
                 Waste solvents
                 Leftover raw materials
Pesticide dust



Off-specification products

Scrubber water
                              Equipment cleaning,
                              spills, area washdown
                              Equipment cleaning,
                              spills

                              Raw material containers
Air pollution equipment



Formulating

Air pollution equipment
                           Dissolved organics,
                           suspended and dis-
                           solved solids.

                           See Section 5.
Bags, fiber drums,
steel drums with
small amounts of
residual raw material.

Pesticide dust,
inert carrier dust.
See Section 5.

See Section 5.

Dissolved organics,
suspended and dis-
solved solids.
                              F002
                              F003

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different chemicals to prevent cross contamination.  The cleaning wastes produced are
similar to those produced in the formulation process.

Evaporation is the most popular method of wastewater disposal at formulation plants
(USEPA 1976).  An evaporation system consists of  a pit  lined with concrete  or  an
impervious plastic liner, and it may be heated or have a transparent cover to keep out
rainfall. Spray irrigation has also been used to dispose  of wastewater at some plants
(USEPA 1976).   Spray  irrigation  is  sometimes  limited  by climatic conditions,
necessitating disposal of the  wastewater to a sewer during certain periods of the year.
Rinse water from  the cleaning of application equipment can be applied to land.  This is
a permissible practice under  FIFRA and many individual farmers do it routinely.

8.   WASTE GENERATION  RATES

Very little data was  available  on  specific waste  generation rates from agricultural
chemical formulation  and application operations.   In  1975,  it was  estimated  that
0.0033 pounds of waste  per pound of pesticide formulated was produced (Gruber 1975).
This rate did not include waste from application  of the pesticide.  More  recently, the
nationwide waste generation rate (which includes waste produced during the cleaning
of pesticide application equipment)  was estimated to be over 100  million gallons per
year (Dillon 1981).  These wastes were mostly very dilute (less than 500 ppm) pesticide
solutions, the large majority of which originated  from the cleaning  and washing  of
equipment  and containers.  Fractional rates have been estimated by the project staff
based  on best available  information  and  engineering  judgment  and are  shown  in
Table 9-1.

9.   WASTE REDUCTION THROUGH SOURCE CONTROL

9.1  Description of Techniques

The various wastes produced during the formulation  and application of pesticides are
shown  in Table  7-1.  The available  methods of  reducing  waste production through
source  control can generally be grouped as either process modification methods or as
those belonging to  the group known as good operating  practices.
                                      B2-9

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Good  operating practices  are defined as  being  procedural  or institutional  policies
which result in a reduction of waste.  The following items highlight the  scope  of good
operating practice:
     o     Waste stream segregation
     o     Personnel practices
                management initiatives
                employee  training
     o     Procedural  measures
                documentation
                material handling and storage
                material tracking and inventory control
                scheduling
     o     Loss prevention practices
                spill prevention
                preventive maintenance
                emergency preparedness

For each waste stream, good operating practice applies  whether it  is listed or not.
Separate listings have been provided whenever case studies were identified.

9.1.1   Equipment Cleaning Wastes

Most  of the  wastewater produced at  pesticide formulation plants results from  the
cleaning of process equipment. As noted earlier, a typical formulation plant produces
a variety of different  pesticides, all on a batch basis.  Between batches,  the mixing
tanks and all  other equipment exposed to  the  pesticide must be cleaned  to  avoid
contamination between different  products.

If  powders or  other "dry" pesticides are formulated,  then  cleaning  is accomplished
using a  dry, inert material, such  as clay.  If liquid pesticides are formulated, cleaning
is  normally performed by rinsing with water.  More than  one rinse is usually required
to adequately clean a tank.  The following waste reduction methods are noted:

     o     Storage and reuse of rinse water and other cleaning wastes.
           Many plants  collect and store  rinse  water from  equipment  cleaning  and
           reuse it as  make-up water during the  next formulation of the same product
                                      B2-10

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           (USEPA 1976).  This greatly reduces wastewater generation, in addition to
           allowing  for  product recovery.   This idea has  also  been used  in  the
           formulation  of solvent-based  products.   One  plant  cleaned all of their
           equipment with solvent, which  was then collected and  reused in the next
           compatible batch formulation (USEPA 1976).

           If it is not practical to use the  waste rinse water as make-up during a later
           formulation, it can be  reused  as  rinse water.  In those instances  where
           more than one rinse is needed to clean the equipment,  the first rinse can be
           performed using old rinse water from a previous  formulation.  This rinse
           will remove  the bulk of the pesticide residue from the  equipment, then a
           second rinse with fresh water can be used to complete the cleaning.

     o     Use of high pressure spray nozzles.
           High pressure  spray nozzles can be used in place of the standard rinsing
           hoses.  According  to a  study of equipment cleaning  in the paint industry
           (USEPA  1979), water   consumption can  be cut  by  80-90%  when high
           pressure rinsing systems are used.

For  additional information  and examples of low-waste approaches to equipment
cleaning, the reader is  referred to the study  of  process  equipment cleaning  in  this
appendix.

9.1.2   Spills and Area Washdowns

The cleanup of spills and area washdowns often contributes significantly to  the total
waste volume produced at formulation plants.  Spills are caused by  the accidental
discharge of pesticides during transfer operations or from equipment failures such as
leaks.  Area washdowns with water  hoses are performed routinely at some formulation
plants, and are necessary in the event of contamination of the working area (USEPA
1976).   Waste reduction methods  available for these wastes include the use of  dry
cleanup methods for spills. Rather than cleaning spills with water and discharging the
water to the sewer, many formulating plants use dry absorbents for spill  cleanups
                                     B2-11

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(USEPA 1976).  This greatly decreases the waste  volume associated with the cleanup.
In addition, floor  sweeping can be  used  to  collect spills for product reformulation.
Such  practice  was reportedly  performed by Chevron  Chemical  Co.  to  reduce their
waste generation volume (LWVM 1985).

9.1.3   Off-Specification Products

Off-specification batches of pesticide  formulations are produced as  a result of poor
process control  and operation.  Ideally, this  waste source could be eliminated  totally
by making use of the following source control techniques:

      o     Strict quality control and process  automation
           The formulation of pesticides is a relatively simple process.  Nevertheless,
           process automation  and control during formulation ensures repeatable high
           quality products and avoids generation of off-spec batches due to operator
           error.

      o     Reformulation of off-specification batches
           If  a batch  of  off-specification  pesticide  is  produced,  it  should   be
           reformulated to an acceptable quality rather than discarded as a waste.

9.1.4   Packages and Drums

Drums or other  packaging materials contribute to  the waste output from a formulating
plant.  After the drums, which are  used to store or transport pesticides, are emptied, a
small amount of pesticide residue remains. To clean the drums, it is necessary to rinse
them  with water or use an inert solid, such as clay.  Thus, additional cleaning waste is
generated.   If the drums and packaging material  are not cleaned or  decontaminated,
then they must  be treated and disposed of as a waste.  Some formulation plants  sell
used drums to a drum  reconditioner, while others reuse them internally.   There is thus
a tradeoff  between disposing uncleaned drums as a waste, and producing a waste by
cleaning them.  From a waste  reduction standpoint, both of  these methods should be
considered, and  the most efficient  method should be chosen on a plant  by plant basis.
                                      B2-12

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As  an example, Chevron Chemical  Co.  combined the  use of water conservation
techniques in triple-rinsing pesticide containers to be returned to the  manufacturers.
This practice  reduced approximately  50% of  the  containers discarded.  In  addition,
non-returnable  pesticide-containing  drums were replaced by returnable bulk  tote bins
to reduce the overall waste generation amount (LWVM 1985).

9.1.5   Dust From Air Pollution Equipment

Dusts  generated during  handling, grinding,  and other formulation  operations are  a
potential  waste source.  It  is common practice  to install dust collection equipment,
such as hoods  served  by  a  baghouse  filter,  on all dust-generating  operations.   This
allows for the recycling of the dust,  thereby reducing waste production and decreasing
worker exposure to hazardous  substances (USEPA  1976).  For example, Daly-Herring
Co. reportedly  altered their dust collection equipment operation so that waste streams
containing organic chemicals from various production areas were collected separately
rather than mixed in  a single baghouse. The uncontaminated streams  collected were
recycled to the processes where they were generated (Huisingh et. al. 1985).

9.2  Implementation  Profile

The  major thrust  of  source control in the  pesticide  formulation  process should be
towards reduction  of the principal waste stream, i.e. equipment cleaning wastes.  The
two  methods identified are the storage and reuse of rinse water and other  cleaning
wastes, and the use of  high pressure  spray systems.   Storing cleaning  wastes for future
reuse would require the establishment of a storage area with  tanks, pumps, piping and
instrumentation.   The installation of  a high  pressure  spray  system would require  a
spraying  unit,   pump,  and piping at  each cleaning  area.  The space  requirements for
such a system  would  not  be large.  Both of these source  reduction measures would
require a  capital  expenditure.   This expense  would be  offset by  the  savings  in
wastewater treatment due to the smaller volumes of waste produced.

9.3  Summary

The  waste sources and the associated source control  techniques are  summarized in
Table 9-1.  The ratings listed in this table are based on a  scale of 0 to  4 and  are used
                                     B2-13

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                    TABLE 9-1  SUMMARY OF SOURCE CONTROL METHODOLOGY FOR THE AGRICULTURAL CHEMICALS  FORMULATION  INDUSTRY
!
1
1
t
1
1
1
1
4
1
1
1
1
i
1
1
1
1
+
1
1
g!
si
1
+•
1
Haste Stream
Equipment Cleaning
Wastes (')
Spills and Area
Washdowis
Off-Gpec Products
Packages and Drums
Dust /Air Pollutlo
Equipment
All Sources
1
1
1
|1
12.
1
It-
12
1
I'-
|2
1
|t
1
i|t
1
1
Control Methodology
Reuse waste rlnseuater/solvent
Use high pressure sprays
Found Documentation i
Quantity I Quality |
3 I 3|
1 1 3 I
Overall i 2 00 | 3 00 I
Setter operating practices
Use of dry clean up methods
Overall
Quality control/automation
Reformulation of off-spec batches
Overall
Clean and re-use
Overall
Collect dust and reuse
Overall
All Methods
1 1 1 i
2 1 21
1.50 i 1.50 i
1 1 1 i
2 i 2 |
1 50 I 1.50 |
11 2 |
1 00 | 2 00 |
1 1 2 !
1 00 | 2 00 I

Waste 1 Extent of i Future Fra
Reduction i Current Use | Application i Tot
Effectiveness | 1 Potential
3 | 3 | 3
31 2| 3 |
3 00 | 2.50 | 3 00 I
3 | 3 i 2|
2| 21 2
2.50 | 2 50 | 2 00 |
3 | 2 i 2
31 3 i 2 |
3 00 j 2 50 | 2 00 |
3 | 1 | 3
3.00 | 1 GO | 3 00
3 | 3 | 1
3 00 | 3 00 | 1 00 |

:tion of Current future Reduction Index I
| Index Probable | Maximum 1
| 2.3 0 6 | |
1 1.5 1.1 111
0 60 1 2.3 | 08 111
i 23 0 4 | i
1 0 | 05| 051
0 05 | 2 3 | 0 4 | 051
| 1 5 | 0.8 | 03|
2 3 i 04| I
0.05 | 23| 061 001
| 08| 171 17',
0 25 | 0 8 I 1 7 | 1 7 I
| 2.3 | 0.2 | 0 2 |
0.05 2.3 | 0.2 | 021
1 00 2 0 | 1 0 | 1.2 !
(') These streams include listed "F" and/or "IT RCRA wastes

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to evaluate each  technique for its waste  reduction effectiveness,  extent of  current
use, and future application  potential.  The ratings were derived by project staff based
on a review of the available information.

It appears that  the current level of waste  minimization in the pesticide  formulation
industry is relatively high, as evidenced by the current reduction index (CRI) of 2.0 (50
percent).   CRI is  the  measure of waste reduction  achieved due  to  the  current
application level of all the techniques listed.

Any future reductions of waste generation  appear to be moderate as characterized by
the future reduction index (FRI) of 1.0 to 1.2 (25 to 30 percent).  FRI is the measure of
waste  reduction achievable through implementation of the listed techniques to their
full rated potential. The most effective measures for achieving this reduction  involve
reusing  waste rinse water,  using  high  pressure spray  systems,  using dry  cleanup
methods for spills, increasing  the use of automation, and reusing empty drums.

10.  PRODUCT SUBSTITUTION ALTERNATIVES

The  discussion has, so far,  been concerned with  reducing the  wastes  associated with
the formulation of pesticides.  While this  is a valid concern,  this approach does not
consider the hazards associated with the pesticides themselves.  The wastes produced
during   the formulation  process are  basically  dilute  pesticide solutions  and  off-
specification  pesticide  formulations.  These are often no more hazardous than the
pesticide formulations  being produced.   Therefore,  since pesticides are hazardous
substances  themselves,  it  is of  major importance  to evaluate  safer,  substitute
products.

Pesticides represent only one  means  by  which to protect agricultural  crops  from
insects and other pests.  Many  other  methods  of crop  protection exist which do not
rely  solely on the  use of man-made chemicals.  Integrated Pest Management (IPM) is
an ecologically-based pest  control strategy involving  a variety of  control methods.
Pests are defined here as organisms which interfere with the production of agricultural
crops.  Pests include insects, diseases, parasites, and weeds.
                                      82-15

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The main underlying principle of IPM is that no single control method can be effective
over the long term because  of  the adaptive powers of insects and  other  pests.  The
goal of IPM  is not to eradicate pest populations, but rather to keep them just below
the level at  which the  loss is  deemed economically  acceptable.   The pest  control
methods used in an IPM program include (Bottrell 1979):

     o     Biological control
           Natural enemies such as parasites,  predators,  and diseases  are used to
           regulate and  balance pest populations.  For example, if no natural enemies
           of a pest  exist on a farm,  farmers can purchase insects from insectaries
           and introduce them onto the farm (Smith 1985).  This form of control is of
           major importance in  IPM.

     o     Genetic control
           The breeding  of  plant species which are  resistant  to certain  diseases or
           insects is highly effective and is used widely today.  The  large  majority of
           U.S. cropland is  currently planted  with crop varieties which are resistant
           to, at least, one disease.

     o     "Cultural" control
           Cultural control of pests include farming practices such as land cultivating
           crop rotations, and strategic timing of  planting, irrigation, and harvesting
           of crops.  These practices can be used to prevent the proliferation of many
           pests.

     o     Chemical control
           Chemical  control using pesticides is   also  an  important  part  of IPM.
           Pesticides are applied only when absolutely necessary and in small amounts
           in order  to keep pest populations from rising above  the threshold level
           where  they  cause economic loss.   The selective use of pesticides also
           avoids  the  needless  destruction of parasites, predators,  and diseases that
           can aid in the control of a pest population.

IPM  has been  used  successfully on many  farms to date, reducing pesticide use  by
50-90% while maintaining crop  yields (Metcalf 1981,  Bottrell 1979).  Since IPM is an
                                     82-16

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ecologically-based control strategy, each  farm requires the development  of its own
program.  While IPM has been used for  the past two decades with much success, it is
not being  used  extensively  today.   Several  barriers exist which have  hindered its
widespread use.  These include:

     o     Lack of knowledge
           Implementing  an  IPM program requires extensive scientific knowledge of
           the crop and its surrounding  ecosystem.  Growth  characteristics of both the
           crop and  its pests, as well as their interrelationships, must be understood.
           Such knowledge is often lacking and is difficult to establish.

     o     Lack of trained IPM personnel
           Before a farmer can begin an  IPM program, an IPM  specialist must be
           contacted.    Since  IPM requires   extensive  scientific  information, the
           average farmer is dependent upon  the help of an expert.  Such experts are
           in short supply and are often unavailable. In contrast, there

     o     Farmers'  attitudes
           Farmers  are  often  skeptical  of   incorporating IPM  into their farming
           practices. Those  who have had much success with using pesticides as their
           primary means of pest control see no reason to change over to  IPM.

     o     Lack of incentives
           IPM  has been used  successfully  on  many  farms, drastically reducing
           pesticide consumption (Metcalf 1981, Bottrell 1979). Nevertheless, it has
           not yet gained widespread popularity; pesticides continue to be the primary
           means of protecting many crop from pests.  The major advantages of IPM
           over current  pesticide  use are mainly  environmental.   There does not
           appear to be  a general consensus concerning  the economic benefits of IPM
           compared to  traditional chemical  methods of pest control.  It is not clear
           whether or not IPM is economically advantageous.

           One  method which has been proposed to decrease pesticide use is to  lower
           the appearance standards  set  on food  (Dahlston  1983).    The  current
           demands  on  such appearance qualities as color  of fruits and vegetables in
                                    B2-17

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           the U.S.  prohibits many farmers from adopting IPM, which often results in
           food of lower cosmetic quality compared to food produced using pesticides.

11.  CONCLUSIONS

Several methods of reducing the waste generated during the formulation of pesticides
are available,  it is estimated that the total waste output could be moderately  reduced
by implementing the source reduction methods discussed.  The most effective methods
available for waste reduction are reusing waste rinse  water and other cleaning media,
using  high pressure spray  systems for equipment cleaning,  and  incorporating  dry
cleanup methods for spills.

The  greatest  environmental concern  stemming from the use of pesticides is  the
toxicity  of  the  pesticides  themselves.   Concern  over the  wastes  associated  with
pesticide production is of secondary importance.  This is evident from  incidents in the
past concerning  the  contamination  of water supplies  with pesticides,  the  build up of
pesticides in the food chain, and farm workers' exposure to pesticides.

The use of pesticides on some farms has been greatly  reduced by the use of Integrated
Pest Management (IPM).  IPM  does not eliminate  the  use of pesticides, but  reduces
their consumption rate by placing more emphasis on natural and biological pest control
methods.

12.  REFERENCES
Atkins, P.R., 1972.  The pesticide  manufacturing industry - current waste treatment
and disposal practices.  Texas University, EPA-12020-FYE-01/72.  Washington, D.C.:
U.S. Environmental Protection Agency.
Bottrell, D.R.,  1979.  Integrated pest  management.  Washington, D.C.:  Council on
Environmental Quality.
Dahlston, D.L., 1983. Pesticides in an era of IPM.  Environment.  25(10):45-54.
Dillon, A.P., ed., 1981. Pesticide disposal and detoxification processes  and techniques.
New Jersey:  Noyes Data Corp.
                                     82-18

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Gruber,  G.I.,  1975.   Assessment of  industrial hazardous  waste practices,  organic
chemicals, pesticides and explosives industries.  TRW Systems Group. EPA-530-SW-
118c. Washington, D.C.: U.S. Environmental Protection Agency.

Huisingh, D.,  Martin,  L.,  Hilge, H.,  et  al.  1985.   Proven  profit  from pollution
prevention.  Washington, D.C.:  The Institute for Local Self-reliance.

Johnson, H., 1973.   A study of hazardous waste  materials, hazardous effects and
disposal  methods.   Vol.  2.   Booz-Allen Applied  Research, Inc.  EPA-670-2-73-15.
Washington, D.C.: U.S. Environmental Protection Agency.

Kryeger,  R.,  ed.,  1983.   Treatment  and  disposal of  pesticide wastes.   In ACS
Symposium Series 259.

LWVM,  1985.   League of Women Voters of Massachusetts.  "Waste  reduction, The
untold story".  Conference at the  National Academy of Sciences, Conference Center
on June 19-21.  Woods Hole, Mass.: Conference materials.

Metcalf, R.L.,  1981.  Insect control  technology.   In Kirk-Othmer Encyclopedia of
Chemical Technology. 3rd ed., Vo. 13.  New  York, N.Y.: Wiley.

Miller, G.T., 1985.  Living in the environment.  Belmont, Calif.:  Watsworth Pub. Co.

Parsons, T.B., 1977.   Industrial process profiles for environmental  use.  Chapter 8;
pesticide industry.  Radian Corp. EPA-600-2-77-0234.  Research Triangle Park,  N.C.:
U.S. Environmental Protection Agency.

Pimental, D., 1981. Handbook of pest management in agriculture.  CRC Press.

Plummer, J.R.,   1981.    Herbicides.   In  Kirk-Othmer  Encyclopedia  of   Chemical
Technology. 3rd ed., vol 12.  New York, N.Y.:  Wiley.

Smith, G., 1985.  Insects help farmers to spray  less, grow  more.  L.A. Times.  August
23 issue, p.l, view section.

TRW, 1983.  TRW Systems Group. Recommended methods  of reduction, neutralization,
recovery, or disposal  of hazardous waste. Vol. 5.   EPA-670-2-73-053e.  Washington,
DC: U.S. Environmental Protection Agency.

USC, 1985.   U.S.  Congress,  Office of  Technology Assessment.  Pest  management
strategies in crop protection. Washington, D.C.: U.S. Government Printing Office.

USDC, 1985.  U.S. Department of Commerce, Bureau of the Census.  Agricultural
Chemicals.  In 1982 Census of Manufacturers.  MC82-I-2886.  Washington, D.C.:  U.S.
Government Printing Office.

USEPA,  1976.   U.S.  Environmental  Protection Agency, Office of  Water and  Waste
Management.  Development document for final  effluent limitation quidle lines for the
pesticide chemical  manufacturing  industry.   EPA-440-l-73-060d.  Washington,  D.C.:
U.S. Environmental  Protection Agency.
                                    R2-19

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	,  1979.  U.S. Environmental Protection Agency, Office of Water and Waste
Management.  Development document for proposed  effluent guide  lines,  new source
performance  standards,  and pretreatment standard  for the paint  formulation point
source category.   EPA-440-l-79-049b.   Washington,  D.C.:   U.S.  Environmental
Protection Agency.
13.  INDUSTRY CONTACTS

Confidential source.
                                     B2-20

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1.    PROCESS: ELECTROPLATING

2.    SIC CODES:  3471

3.    INDUSTRY DESCRIPTION

Electroplating is a process by which a metal  object is coated with one or more thin
layers of another metal by means of an electrical current, in order to alter  the surface
characteristics  of the object.  The electroplating industry is generally divided into two
major segments: job shops which process materials owned by others on a contract basis
and captive shops owned by larger manufacturing facilities.

3.1  Company  Size Distribution

There were  an  estimated 13,000 job and captive  electroplating  shops in  the  United
States (USEPA 1979).  Roughly 69% of these are small captive shops which employ less
than 20 people.  Table  3-1 summarizes  the  industry size distribution for job  shops;
specific size distribution for captive shops is unknown.

   Table 3-1 Company Size Distribution for U.S. Electroplating Job Shops in 1982
No. of employees per facility
Total
1-19 20-49 50-99 100+
No. of establishments        3,450       2,394          725        230       101
No. of employees^         61,900      13,080       21,750     14,950    12,120

Source:   Dunn's Marketing Services (1983), 1982 Census of Manufactures (USDC 1985)

(a)   Breakdown  of  total  was  approximated  from  number  of  establishments  and
     corresponding company size.
                                   R3-1

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3.2  Principal Producers

The  industry is dominated by small captive shops  with  less than 20 employees each.
Thus, there are no major producers with a very large share of the entire market.

3.3  Geographical Distribution

The  geographical distribution of electroplating shops is shown in Figure 3-1.  As seen,
the highest concentration  of shops are in California, the Midwest, and the East Coast.
The EPA regional breakdown is given below in Table 3-2.

  Table 3-2 Geographical Distribution of U.S. Electroplating Industry by EPA Region
EPA Region
I
II
III
IV
V
VI
VII
VIII
IX
X
Total
Number of Establishments
343
415
137
208
1088
190
69
negligible
615
32
3103^)
Source:    1982 Census of Manufacturers ( USDC 1985).
(a'   The discrepancy between Table 3-2 and Table 3-1 is caused by exclusion of states
     with less than 150 employees.

4.   PRODUCTS

Principal product areas in which electroplating processes are involved include:
           automotive exterior/interior parts     hydraulic cylinders
           boat hardware                        shafts
           plumbing fixtures                     bearings
           cabinet hardware                     seals
                                    R3-2

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                             VIII
(CO
oo
0-30
131-200
                                   31-60
                                   201-300
61-130
over 300
                      Roman numerals show EPA regions
       Figure    3-1  Electroplating Plants in the U.S.

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Products (Continued)
           kitchen appliances                    solar heated panels
           utensils                               defense hardware
           tools                                 computer chassis
           valve trim                            printed circuit boards
5.   RAW MATERIALS

Raw materials used in the  electroplating  industry  include cleaning agents, plating
solutions and metal anodes.  Nationwide plating metal consumption rates are shown in
Table 5-1 for selected metals.

        Table 5-1 1982 Consumption of Metals by U.S. Electroplating Industry
Metal
tin
nickel
silver
gold
cadmium
zinc
copper
Consumption
(metric tons/yr)
11,434
20,889
123
14.5
971 •
342,044^)
no data
Source:    1982 Minerals Yearbook (USDC 1982).
'a^ Includes hot dip galvanizing.

6.   PROCESS DESCRIPTION

Electroplating is a process in which metal is coated with one or more other  metals by
electrodeposition.   Electroplating  is  used to increase  the corrosion  resistance of  a
metal, to improve  or alter the appearance of a metal, or to otherwise create a product
which serves some useful end.

Electrodeposition  is  achieved by  passing an  electric  current  through  a solution
containing dissolved metal ions as  well as the metal object  to be plated.  The metal
object becomes a cathode in an electrochemical cell, resulting in the deposition of the
                                     P3-4

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dissolved  metal ions onto the  surface  of  the metal object.  Ferrous or nonferrous
objects  are  commonly  electroplated  with  aluminum,  brass,  bronze,  cadmium,
chromium, copper, iron,  lead,  nickel, tin,  and zinc.   Precious metals such  as  gold,
platinum,  and silver are also used widely.

The  following  processes  are specifically excluded  from  this study  since  they are
covered in other studies of this report:

     o     Electronic Circuit Board Manufacturing
     o     Anodic Oxidation
     o     Electroless Plating

An  electroplating  process  generally  calls  for  moving  the  object  to  be  coated
(workpiece) through a series  of  baths arranged in a sequence designed to produce the
desired  end  product.   Typically,  the sequence consists of cleaning,  rinsing, and a
number  of alternating electroplating and rinsing steps.  The workpiece  can be carried
on racks or in barrels.  Large parts to be plated are mounted on  racks which transfer
the workpiece from  bath  to  bath.  If many small parts  are to be plated,  they can be
contained in  barrels  which rotate in the  plating bath.  As an example, a flow chart of a
chromium plating  operation  is shown  in Figure 6-1 (Tavlarides 1982).  A number of
excellent  detailed  process descriptions are available (ASM 1964, Lowenheim 1979).

Electroplating produces a large  variety  of wastes, as  discussed in Section 7.  Most of
the wastes produced contain metals and other compounds used in the various plating
baths.  Table 6-1 lists the  constituents of the most commonly used plating baths.

7.   WASTE DESCRIPTION

The ten primary electroplating process wastes and their respective points of origin and
composition are listed in Table 7-1. The wastes produced at a particular plant will be
similar  to those listed, but  their  precise composition  will depend upon  the specific
process  employed. Some  or all  of the ten waste types may be  combined into a single
stream  before  treatment  and  disposal.    It is  common  to  combine  the  highly-
concentrated  cyanide  wastes from the plating  and  cleaning  solutions  with  filter
sludges.  These are kept separate from  the acidic wastes and from the dilute cyanide
solutions.

                                     B3-5

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CLEAN
WTER
                  FINISHED PRODUCT
i  PROCESS IASTE  CATESORIES:

  0   SPENT  ALKALINE CLEANIN* SOLUTIONS

  0   SPENT  ACID CLEANINS SOLUTIONS

  0   SPENT  CYANIDE CLEANINI SOLUTIONS

  0   SPENT  PLATINS SOLUTIONS

  0   FILTER SLUDSES

  0   HASTE  RINSE HATER

  (?)   KASTENATER TREATNENT SLUOSE
            Figure 6-1   Blocic  Flo* Diagra for Chroiiui Plating Operation
                                                   R3-6

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               Table 6-1 Common Electroplating Bath Compositions
Electroplating Bath
Composition
Brass & Bronze
Cadmium  Cyanide
Cadmium  Fluoroborate
Copper Cyanide
Copper Fluoroborate
Acid Copper Sulfate
Copper  Pyrophosphate
Fluoride  Modified
 Copper  Cyanide


Chromium
Chromium with
 Fluoride  Catalyst
Copper cyanide
Zinc cyanide
Sodium cyanide
Sodium carbonate
Ammonia
Rochelle salt

Cadmium cyanide
Cadmium oxide
Sodium cyanide
Sodium hydroxide

Cadmium fluoroborate
Fluoroboric acid
Boric acid
Ammonium fluoroborate
Licorice

Copper cyanide
Sodium cyanide
Sodium carbonate
Sodium hydroxide
Rochelle salt

Copper fluoroborate
Fluoroboric acid

Copper sulfate
Sulfuric acid

Copper pyrophosphate
Potassium hydroxide
Ammonia

Copper cyanide
Potassium cyanide
Potassium fluoride

Chromic acid
Sulfuric acid

Chromic acid
Sulfate
Fluoride
                                   83-7

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                              Table 6-1 (continued)
Electroplating  Bath
Composition
Gold  Cyanide
Iron
Lead  Fluoroborate
Lead-Tin
Nickel (Watts)
Nickel-Acid Fluoride
Black Nickel
Metallic gold
Potassium cyanide
Sodium phosphate

Ferrous sulfate
Ferrous chloride
Ferrous fluoroborate
Calcium chloride
Ammonium chloride
Sodium chloride
Boric acid

Lead fluoroborate
Fluoroboric acid
Boric acid
Gelatin or glue
Hydroquinone

Lead fluoroborate
Tin fluoroborate
Boric acid
Fluoroboric acid
Glue
Hydroquinone

Nickel sulfate
Nickel chloride
Nickel fluoroborate
Boric acid
Nickel sulfate
Nickel chloride
Nickel sulf amate
Boric acid
Phosphoric acid
Phosphorous acid
"Stress-reducing agents"

Hydrofluoric acid
Nickel carbonate
Citric  acid
Sodium lauryl sulfate
 (wetting agent)

Nickel ammonium sulfate
Nickel sulfate
Zinc sulfate
Ammonium sulfate
Sodium thiocyanate

-------
                              Table 6-1 (continued)
Electroplating Bath
Composition
Silver
Acid Tin
Stannate Tin
Tin-Copper Alloy
Tin-Nickel Alloy
Tin-Zinc Alloy
Acid Zinc
Zinc Cyanide
Silver cyanide
Potassium cyanide or Sodium cyanide
Potassium carbonate or Sodium carbonate
Potassium hydroxide
Potassium nitrate
Carbon disulfide

Tin fluoroborate
Fluoroboric acid
Boric acid
Stannous sulfate
Sulfuric acid
Cresol sulfonic acid
Beta naphthol
Gelatin

Sodium stannate
Sodium hydroxide
Sodium acetate
Hydrogen peroxide

Copper cyanide
Potassium stannate
Potassium cyanide
Potassium hydroxide
Rochelle salt

Stannous chloride
Nickel chloride
Ammonium bifluoride
Sodium fluoride
Hydrochloric  acid

Potassium stannate
Zinc cyanide
Potassium cyanide
Potassium hydroxide

Zinc sulfate
Ammonium chloride
Aluminum sulfate or Sodium acetate
Glucose or  Licorice

Zinc oxide
Sodium cyanide
Sodium hydroxide
Zinc cyanide
                                    R3-9

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                                                 Table 7-1 Electroplating Process Wastes
      No.

      17"
  Waste Description
      Process Origin
                                                                             Composition
                         RCRA
                         Codes
00
      2.
      3.
4.



5.

6.



7.
Spent alkaline cleaning
solution
Spent acid cleaning
solutions
Degreaser sludges
                  Solvent recycle
                  still bottoms
                  Spent plating solutions

                  Filter sludges



                  Waste rinse water
Aqueous cleaning
Acid pickling
Solvent cleaning
                             Solvent recycling



                             Electroplating

                             Electroplating
                             Drag-out, equipment
                             cleaning, spills
                                                                         NAOH,Na2CO3,Na2SiO3,   E009
                                                                         (NaPO3)4, cyanide,
                                                                         soils, EDTA+ Mg/Ca,
                                                                         saponified and/or
                                                                         emulsified grease

                                                                         HC1,H2SO4,HNO3,
HBE4,Me+, oils,
soils

kerosene, naphtha,
toluene, ketones,
alcohols,ethers,
halogenated
hydrocarbons, oils,
soils, water

same as above solvents.
May contain HC1 from
solvent decomposition

see Table 6-1

Silica,  silicides,
carbides, ash, plating
bath constituents

same as No. 1 and 2, but
in lower concentrations
                                                                                                   E001, F002
                                                                                                   F003, F005
                                                          F001, F002
                                                          F003, F005
                                                           F007

                                                           F008
      8.


      9.

      10.
Wastewater treatment
sludge

Vent scrubber wastes

Ion exchange resin
reagents
Wastewater treatment
Vent scrubbing

Demineralization of
process water
                                                                         Metal hydroxides,
                                                                         sulfides, carbonates

                                                                         similar to No. 7

                                                                         brine, HC1, NaOH
                          F006

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Contaminated rinse water  accounts for the large majority of waste produced on a
volume basis.  Rinse water is used to remove the drag-out from a workpiece after it is
removed from a bath.  Drag-out refers to the excess cleaning  or plating solution that
adheres to the  workpiece  surface, and  gets  carried  out of the solution  bath upon
withdrawal of the workpiece from the bath.  In general, the use of small part barrels in
the plating process (barrel plating)  produces more drag-out than rack plating.  This is
because a barrel carries with it  more plating solution upon withdrawal from the bath
than a rack does, and because drainage of  the  drag-out back into  the  bath  is  more
difficult with barrels.  If the drag-out from one bath  is  carried into the next  bath in
sequence due to incomplete rinsing, it  is referred  to as "drag-in", and is considered a
contaminant  in the  later  bath.    Large amounts of rinse water  are used  on  the
workpiece at several points in a typical process, as shown in Figure 6-1.

Spent cleaning  and plating solutions  are  another waste source.   Several types  of
cleaning solutions are used to prepare a metal  surface  for electroplating.  Stripping
wastes are a special type of cleaning waste.  They result from the stripping off of the
old plated deposit prior to the deposition of a new metal plate.  As shown in Table 7-1,
cleaning solutions may be acidic  or basic, and may contain organics.  Heavy metals are
usually  not present, although some cleaning solutions contain cyanide.   Spent plating
solutions contain  high  concentrations of metals.  These solutions  are  not regularly
discarded like cleaning solutions, but may require purging if impurities build up.

Wastes  produced  from  spills  and  leaks are  usually  present  to some  extent  in  an
electroplating process.  Water is  used to  wash  away floor spills,  and  the resulting
wastewater  contains  all   of  the  contaminants  present in  the  original solutions.
Wastewater is also produced from the wet scrubbing of ventilation exhaust air.

The wastewater produced in the electroplating process may contain  a variety of  heavy
metals  and  cyanide. The metals  are  removed by adding lime or other precipitating
agents,  and precipitating under alkaline pH. The resulting metal hydroxide  precipitate
forms a dilute sludge, which is thickened and then disposed of by landfilling.   Figure
7-1 shows a typical electroplating wastewater treatment system.
                                     B3-11

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ca
OJ
 i
HEXAVALENT
CHROMIUM
I _
ACID 	 >

S02 OH _^
NAHS04
CAUSTIC 	 	 ->
CL2 OH 	 f,
NAOCL

CHROMIUM
REDUCTION
	
r
CYANIDE
OXIDATION




	
I _J
1 ACID 	 >
CN-
CAUSTIC 	 >
ACID /ALKALI
WASTES


£^


"1
I I





FLOCCULANTS SOLID NASTE
DISPOSAL
n
f V

NEUTRALIZA
i ti IIRRF
"ON 	 MIXER " ^UDGE
* blUHAbt UH
SYSTEM CLARIFIEH 1 	 J THICKENING
                                                                                             EFFLUENT

                                                                                             DISCHARGE
                                           Figure  7-1   Mastenater Treatment System for Electroplating Hastes

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8.    WASTE GENERATION RATES

Very little data were  available on overall  waste generation rates from  the  electro-
plating industry.  In 1976, Battelle Columbus Laboratories reported waste generation
rates of metal  hydroxides and degreaser sludges  from the industry.  Since these rates
are 10 years old  and  narrow  in  scope (they  do  not account for current  industry
practices, nor do they cover all wastes generated), no annual volumetric rates  could be
obtained.  Fractional waste generation rates (the  percentage  each waste represents of
the total  waste generated ) were estimated by project staff,  based on the available
information and on industry comments.  These values are shown in Table 9-1.

9.    WASTE REDUCTION THROUGH SOURCE CONTROL

9.1  Description of Techniques

The  ten primary waste streams are  presented in Table 7-1  along with their process
origin.  From a source reduction standpoint, these waste streams can be grouped as
follows to reflect their common process origin:

           Work cleaning wastes
           Spent plating solutions and sludges
           Waste rinsewater
           Treatment wastes

In  addition  to  the  waste reduction measures  classified as being process changes or
material/product substitutions, a variety of waste reducing measures labeled  as "good
operating  practices" have also been included.  Good operating practices are defined as
being procedural or institutional policies which  result in a reduction of waste.   The
following  items highlight the scope of good operating practices:

     o    Waste stream segregation
     o    Personnel practices
                Management initiatives
                Employee training
     o    Procedural  measures
                Documentation
                Material handling and storage
                                    R3-33

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                Material tracking and inventory control
                Scheduling
      o     Loss prevention practices
                Spill prevention
                Preventive maintenance
                Emergency preparedness

For each waste stream, good operating practice applies whether  it is  listed  or  not.
Separate listings have been provided whenever case studies were identified.

9.1.1   Work Cleaning Wastes (Nos. 1-4, Table 7-1)

Work  cleaning wastes from electroplating processes are similar to the cleaning wastes
produced  in  many  other  manufacturing processes.  A detailed  discussion of source
reduction methods for cleaning wastes is provided in a separate practice study entitled
"Metal Parts Cleaning", Section 820.

9.1.2   Spent Plating Solutions and Sludges (Nos. 5 and 6, Table 7-1)

Plating solutions such as those listed in Table  6-1 contain high concentrations of heavy
metals, cyanides, and other toxic constituents.  They are not discarded frequently, but
rather are used for long periods of time.   Nevertheless,  they  do require periodic
replacement  due to impurity  build-up or the  loss of solution contituents by  drag-out.
When a plating solution is contaminated or exhausted,  the resulting waste solution  is
highly concentrated with toxic compounds  and requires extensive treatment.   The
source control methods available for reduction of spent  plating waste include:

      o     Increasing the longevity of the plating solution.
           The  lifetime of  a  plating   solution is  limited  by the accumulation of
           impurities  and/or by  depletion  of constituents  due  to drag-out.   The
           impurities come from five sources: racks, anodes,  drag-in, water  make-up,
           and air. The impurities buildup can be limited by the following techniques:

                Purer anodes.
                During the plating  process, metal from  the anode  is dissolved in the
                plating solution and deposited  on the  cathode (workpiece).  Some of
                the impurities contained in the original anode matrix will stay behind
                                    B3-14

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in the plating solution, eventually accumulating to prohibitive levels.
Thus, the use of purer metal for the anode  will extend  the  plating
solution life.

Drag-in reduction by better rinsing.
Efficient  rinsing of the  workpiece between different  plating baths
reduces the drag-in of plating solution into the next bath.

Use of deionized or distilled make-up water.
To  compensate  for evaporation, water  is  required  for  makeup of
plating solutions.  Using deionized or distilled water is preferred over
tap water, since tap water may have a high mineral or solids content,
which can lead to impurity buildup.

Plating solution  regeneration through impurity removal.
There are  methods that have been successfully used  to increase the
longevity  of  plating  solutions  through  impurity removal.   More
efficient filtering of a plating solution kept  levels of impurities low
and extended  solution life (McRae 1985).  In cyanide baths, carbonate
tends to build up in solution over time  due to CC>2 absorption from
the air.  This  leads to solution deterioration. Reducing the carbonate
concentration has been accomplished using a technique developed by
the  U.S.  Army  (U.S.  Pat.,  4,365,481),  which  involves freezing the
carbonates out  of solution.   A metal  box  containing dry ice  and
acetone is immersed in the plating bath.  Carbonates  are precipitated
directly  onto the outside metal surface  of  the box, which  is then
removed from the  solution.  The carbonates are scraped  off the box
and discarded as solid  waste, with a volume considerably smaller than
that of the sludge associated with the spent plating solution.

Proper rack design and maintenance.
Corrosion  and  salt  buildup deposits  on  the rack  elements  will
contaminate  plating  solutions upon  chipping  and  falling into the
solution.  Proper design and maintenance (cleaning) will  minimize this
form of contamination.
                     B3-15

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          Replacement of cyanide plating solutions with cyanide-free solutions
          A cyanide-zinc solution  was replaced  with  a non-cyanide, non-chelated
          alkaline zinc solution (Olsen  1973, Lowenheim 1979).  This eliminated the
          problem of handling cyanide-containing wastes.  Other cyanide-free zinc
          solutions*, along with cyanide-free pyrophosphate copper plating solutions,
          have been  used  as replacements  (Lowenheim 1979).   Replacing cyanide
          solutions with non-cyanide solutions, however,  often requires upgrading of
          the  degreasing/cleaning techniques used.  This is because the non-cyanide
          replacements  may  require a much more  thoroughly  cleaned  surface to
          ensure  high quality plating (USEPA 1981).   The primary  barrier to non-
          cyanide bath use is that military contracts often specify the use of cyanide
          solutions,   thereby  preventing  electroplaters  from   using  non-cyanide
          replacements**.

          Replacement of cadmium-based plating solutions with zinc solutions.
          The use of cadmium has been replaced  with  zinc  in many applications*.
          See  Section  10.1.1   for  a detailed   discussion  of  cadmium  plating
          alternatives.

          Replacement of hexavalent chromium with trivalent chromium.
          Trivalent chromium, which can easily be precipitated from wastewater, has
          been used  in place  of toxic  hexavalent  chromium  (Lowenheim  1979).
          However, trivalent chromium produces a lower quality surface, and has not
          seen widespread use.

          Return of spent plating solution to manufacturer.
          This option requires on-site segregation  of solutions according to the metal
          in  the  solution.   Only a few suppliers  (Harshaw,  CP Chemical) reprocess
          some spent bath solutions from their customers.
*    Alexandria Metal Finishers 1985: Personal communication.
**   National Association of Metal Finishers 1985: Personal communication.
                                    B3-16

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9.1.3  Waste Rinse Water (No. 7, Table 7-1)

Waste  rinse  waters account for the  largest fraction  of  waste volume produced  in
electroplating processes.  Any method of reducing the amount of rinse water used will
significantly  reduce the total waste volume from a process.  Large amounts of rinse
water are used to rinse off drag-out  on  a metal surface after  the metal is removed
from a  plating or  cleaning bath.  Rinse  waters usually  contain  dilute solutions  of
several  toxic  materials,  such  as cyanides  and heavy  metals.  There are  several
methods available  to reduce the amount of toxicity of waste  rinse  water produced.
They can all  be grouped into two major  techniques:  drag-out minimization and rinse
water minimization.  It must be pointed out that reducing drag-out  will result in a
decrease of the heavy metal content of the ultimate waste (treatment  sludge),  but the
decrease in water  consumption will affect only the volume of the  co-precipitated
calcium  and  magnesium  hardness.   Decreasing the amount  of rinsewater without
reduction in drag-out may thus result in the smaller, but more highly toxic, volume  of
treatment sludge.

9.1.3.1    Drag-out Minimization

By  minimizing the amount  of drag-out carried from a plating  or  cleaning bath  to a
rinsing bath, a smaller  amount of water is  needed to rinse off  the workpiece.  Also,
less of the plating  solution  constituents  leave  the process, which ultimately produces
savings in  raw  materials and  treatment/disposal costs.   The amount of drag-out
depends on the following factors:

                Surface tension of the plating solution.
                A  plating solution  with a high surface tension tends to be retained  in
                the crevices and surface imperfections of the workpiece  when  it  is
                removed from the  plating bath, thus increasing  drag-out.

                Viscosity of the plating solution.
                Highly viscous solutions result in larger amounts of drag-out.

                Physical shape and surface area of the  workpiece.
                The  shape  of the  workpiece affects the  amount  of  plating solution
                that gets  dragged  out  of the  bath.   With  all other  parameters
                                      B3-17

-------
                remaining the same, a larger workpiece surface area results in  more
                drag-out.   It must  be noted that barrel plating operations produce
                more drag-out than  rack plating.

                Speed of workpiece  withdrawal and drainage time.
                The rate at which the workpiece is withdrawn, the time allowed for
                drainage over the mother tank, as well as the orientation with which
                the work is withdrawn from the  bath, affect the  amount of drag-out
                produced.

Generally, drag-out minimization techniques include:

     o    Increasing plating solution temperature.
          The increased temperature lowers both the viscosity and surface tension of
          the solution, thus reducing drag-out.  The resulting higher evaporation rate
          may  also inhibit  the carbon dioxide   absorption rate,  slowing  down the
          carbonate formation in cyanide solutions.  Unfortunately, this benefit may
          be lost due  to the formation of carbonate by the breakdown  of cyanide at
          elevated  temperatures*.   Additional  disadvantages of this  option  would
          include  higher  energy  costs,  higher   chance for  contamination due  to
          increased  make-up  requirement,  and increased  need  for  air  pollution
          control due to the higher evaporation rate.

     o    Lowering the concentration of plating bath constituents.
          A decrease  in the concentration of metal salts and other components of the
          plating solution  leads  to lower solution  viscosity.   This results  in less
          dragout volume and lower metal losses. Additionally, lower concentration
          will also  reduce  the rinsing requirement.  For example, it has been found
          that acceptable chromium plate can be obtained from baths containing only
          25-50 g/1 CrC>3 compared  to  traditional concentration  of   250 g/1  003
          (USEPA 1981).  The  lower chromium concentration also  results  in a lower
          solution viscosity, which reduces drag-out.
* National Association of Metal Finishers 1985: Personal communication
                                    B3-J8

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           Reducing the speed of withdrawal of workpiece from solution and allowing
           ample drainage time.
           The faster the workpiece is removed from the bath, the higher the drag-out
           will be.  The workpiece should  be removed  as  slowly and as smoothly  as
           possible.  Ample time should  be allowed for draining  the solution back  to
           the tank,  especially for higher viscosity solutions.   Usually, 30  seconds
           allows  most  of the  dragout  to  drain back to the  tank.   However,  in
           applications where  quick  drying is a problem,  a  10 second draining still
           permits good drag-out recovery*.

           Use of  surfactants.
           Wetting agents  have  been used to lower  the  surface tension of plating
           solutions.  A solution with a high surface tension is retained  in the crevices
           and surface imperfections of the workpiece upon removal from the plating
           bath.   By  reducing the  surface  tension,  drag-out  is greatly  reduced.
           Applied in only small amounts, wetting  agents can lower a solution surface
           tension enough  to reduce drag-out by up to 50% (USEPA 1981).  Only non-
           ionic wetting  agents,  which will not  be degraded  by electrolysis in the
           plating bath, should be used.   The use  of surfactants is sometimes limited
           due to their adverse effect on the quality of the  plate produced**.

           Proper positioning of the workpiece on the plating rack.
           When a workpiece is lifted out of a plating solution on a rack, some of the
           excess  solution  on  its  surface  (drag-out) will drop  back  into  the  bath.
           Proper positioning of the workpiece on a rack will facilitate  the dripping  of
           the drag-out  back into the  bath.  The position of  any object which will
           minimize the carry-over of drag-out  is best determined  experimentally,
           although the following guidelines were found to be effective  (USEPA 1981):

                Orient the surface as close to vertical as possible.
                Rack with  the longer dimension of the workpiece  horizontal.
                Rack with the  lower  edge  tilted from the  horizontal so  that the
                runoff is from a corner rather than an entire edge.
* Westinghouse Electric Corporation 1985: Personal communication.
**National Association of Metal Finishers.
                                    83-19

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          By redesigning racks for better drainage and reducing the metal concentra-
          tion in the plating bath, drag-out was reduced at one plant by 55%.  This, in
          turn, greatly decreased rinse water requirements (Anonymous 1985a).

     o    Improved drag-out recovery.
          A drain board positioned between a plating bath and rinse bath can capture
          the dripping solution off of a workpiece and  route it back to  the plating
          bath.  This is a simple operation  which has been  incorporated into  many
          electroplating processes.  The drain board can be made of either plastic or
          metal.  For acidic solutions, it has been suggested that drain boards  be
          made of vinyl chloride, polypropylene, polyethylene, or Teflon*-lined steel
          (USEPA 1981).  Another commonly practiced option is to incorporate a drip
          tank between the plating  bath and the rinsing bath.  The drip tank is  an
          empty tank for collecting the  dripping solution, which can be  returned to
          the plating bath.

9.1.3.2    Rinse Water Minimization

Another  method of waste  rinse water  reduction  is to  rinse off the workpiece in the
most  efficient manner,  using the smallest volume of  rinse  water.  Traditionally, a
workpiece would be  immersed  into a single rinsing bath following a plating bath, and
then moved  on to the next step in the process.  Several methods exist which use less
rinse  water  than  the traditional  rinsing  method, while still  adequately  rinsing the
workpiece.  These include:

      o     Multiple rinsing tanks.
           The use of multiple rinsing tanks is one of the most commonly  used source
           reduction techniques.  Virtually all new electroplating plants are designed
           with multiple rinsing tanks, which can reduce rinse water requirements by
           66%**' with  possible theoretical reductions of over 90% reported (USEPA
           1983, USEPA 1981, Olsen 1973).  Multiple rinsing  tanks are aligned either
           in series or in parallel.   In a three-tank  rinsing  system, a  workpiece  is
           moved  from a plating solution  to the first rinse tank, then onto the second
           rinse tank, then to the  third, and finally onto the next step in the process.
* National Association of Metal Finishers 1985: Personal communication.
**  Registered trademark of E. I. Du Pont.
                                     B3-20

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           In the parallel arrangement, each  rinsing tank is individually fed with fresh
           rinsing water. The more common  series arrangement  differs in that it is a
           counterflow  system.    In  a  three  tank  counter-current  system, the
           workpiece enters  the  first  rinse  tank, which has the most contaminated
           rinse  water.   It is then moved to the second tank, and then to the last,
           where it contacts  fresh rinse water.  Fresh rinsewater enters only the last
           (third) rinsing tank.  The  water  from the third  tank then flows  into the
           second  tank, then  into the first  tank from which it can  be routed into
           treatment and/or to the plating tank as a make-up.

           Fog nozzles and sprays.
           Spraying water droplets directly onto a workpiece is  much more efficient
           than immersing a workpiece into a liquid water bath.  The only limitation is
           that spraying is  not effective  on oddly-shaped  objects, since the  spray
           cannot  make direct contact with the entire surface of the object.  For
           simple workpieces, such as sheets, it is highly effective.

           A variation on the spray nozzle is  the fog nozzle.  A fog nozzle uses water
           and air  pressure to produce a fine mist. Much less water is used than with
           a conventional spray nozzle.  It is  possible to use a fog nozzle directly over
           a heated plating bath to rinse the  workpiece. This allows for simultaneous
           rinsing and replenishment of the evaporated losses from the tank.  Spray or
           fog rinsing is used on  rack plating, which  represents  a third  of  all plating
           operations.  Nozzles are not applicable for barrel plating (two thirds  of all
           plating operations) because of the  odd shape of the parts *.

           Rinse water reuse.
           By using the  same rinse water stream at more than one step in the process,
           the total amount  of  waste rinse  water  produced is  drastically reduced.
           After a rinse  water  is  used  once,   it picks  up  contaminants from the
           workpiece that was rinsed. If these contaminants do not interfere  with the
           quality  of a  subsequent plating step, the same water can be used again.
           ^or example, in  a  nickel plating process,  the same rinse  water stream
* Baxter and Wardman Eng. 1985: Personal communication.
                                      33-2.1

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           was used for the rinses following the alkaline cleaning, acid dip, and nickel
           plating tanks.  Instead of  having three different rinse streams, only one
           stream was  used, greatly  reducing the overall rinse  water requirements
           (USEPA 1983).

      o     Still rinsing.
           Installing  a still (or dead) rinsing  tank immediately  after  a plating bath
           allows for metal recovery and lowered rinse water requirements.  In such a
           system, the  workpiece  is  immersed  in  a still rinse  tank  following the
           plating bath.  Since  the still rinse  has  no  inflow or outflow  of water, the
           concentrations of  the plating bath constituents build  up  in  it.  When the
           concentration becomes sufficiently high,  the contents  of the still bath are
           used to replenish the upstream plating bath.

      o     Automatic flow controls.
           The lowest possible rinse  water flow  rate  which can efficiently  rinse a
           workpiece  can be determined for all  systems.  This flow then  can 'be
           automatically controlled to avoid variations associated  with water line
           pressure changes and manual control by operator.
                                                                   i
      o     Rinse  bath agitation.
           Agitating  a  rinsing  bath mechanically or with air  increases  the  rinsing
           efficiency and cuts down on water demand.

9.1.4   Treatment Wastes (Nos. 8-10, Table 7-1)

In  electroplating,  toxic metal  sludges  result  from   the  conventional  treatment
processes used to remove metals from aqueous wastes. Metals are usually precipitated
as hydroxides or carbonates, resulting in a sludge which requires further treatment and
disposal.  Lime is commonly used  as the precipitating agent.  The  volume and toxicity
of the sludge produced can be  lowered  by reducing the metal content in the plating and
rinse  waste waters, or by using different precipitating agents.   Methods available to
accomplish this include:

      o     Use of different precipitating agents.
           Normally, hexavalent chromium in  waste rinse water or plating solutions is
           treated  by being  reduced  to trivalent chromium with a reducing agent,
                                     B3-22

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followed by precipitation with lime.  In one instance, sodium hydroxide was
used in place of lime (Chacey  1983). Lime precipitation produced 2.24 dry
solids/lb  Cr (VI), while sodium  hydroxide precipitation produced only 1.98 Ib
dry solids/lb Cr (VI).

Use of trivalent chromium instead of hexavalent chromium for plating.
One operation  reported  a 70%  reduction  in  sludge  production  when
trivalent chromium was used  for plating  instead of hexavalent chromium
because  of avoided necessity  to precipitate gypsum associated with the
excess sulfate ions that would have been introduced during reduction step.
(Anonymous 1985a).

More efficient sludge  dewatering.
The volume  of sludge produced can be greatly  reduced through  the  use of
new dewatering technologies which remove a greater percentage of water
than traditional dewatering techniques  (Anonymous 1985b).

Better operating practices (stream segregation).
The type of waste requiring treatment can be  controlled  to  some  extent
through  waste  stream segregation.  By isolating cyanide-containing waste
streams  from waste  streams  containing  iron  or  complexing agents, the
formation of  cyanide-complexes  is avoided,  and  treatment made much
easier  (Dowd  1985).   Segregation  of   wastewater  streams  containing
different metals also  allows for metals recovery or reuse. For example, by
treating  nickel-plating wastewater separately from other waste  streams, a
nickel  hydroxide sludge is  produced which can be reused to produce fresh
nickel  plating  solutions.   In  one  instance,  the scrubber  waste from  a
chromium plating bath was segregated and could then be returned  to the
bath.  This resulted in less discarded waste  and increased the longevity of
the plating solution.

Metal recovery techniques.
Decreasing the  heavy metal  content  of wastewater can be accomplished
through  drag-out minimization and also through recovery of  these  metals
prior to  treatment.   By recovering the metals  from the rinse waters, the
toxicity  and  volume   of the  treatment  sludge will  be reduced,  if not
                          B3-23

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eliminated.  In addition, better  raw material utilization will help to offset
higher operating costs.  The metal recovery techniques examined include:

      Evaporation
      Reverse osmosis
      Ion exchange
      Electrolytic metal recovery
      Electrodialysis
      Use of separate treatments for individual solutions

Evaporation - Waste rinse water is evaporated  by heating, leaving behind a
concentrated  solution.   The  equipment  used  includes  single or multiple
effect evaporators.  Also, vapor recompression applications were reported
(Seaburg and Bacchetti 1982).  The solution is  concentrated until its metal
concentration is equal  to  that  of the  plating bath, then  this solution  is
reused.   Using  this  method, 90-99%  efficient metal  recoveries  can be
achieved  (Clark 1984).   Depending on the design, the evaporated water
vapor  can either be  condensed and re-used as rinse water, or it  can be
vented off into  the atmosphere (Campbell and Glenn 1982).  Evaporation
has been  used frequently for chromium recovery.   One plant was  able to
recover  8,000 Ibs  of  chromium  per  month,  resulting  in  savings  of
$100,000/yr,  with  a one-year return on  investment (Campbell  and Glenn
1982). It has also been proven  effective for the recovery  of gold,  nickel,
copper,  and  cadmium  (Kohl and Triplett 1984).   Evaporation  is best
established of all  the  metal  recovery techniques  used in electroplating.
Although  it is the most energy intensive  recovery  technique, its simplicity
and reliability make it  an attractive option for metal recovery. In order
for evaporation  to  be economical, multiple counter-current rinse tanks or
spray/fog rinsing should be used  to minimize  the  amount of rinse water
being processed (MDEM 1984).

Apart from  the   energy  cost,   a  distinct  disadvantage  is  that  the
concentrates may also contain the calcium and magnesium salts originally
present in the rinsewater.   Adding them  to the plating solution  may result
in more rapid deterioration.  This problem is alleviated in situations where
rinsewater is de-ionized or softened prior to use.
                          B3-24

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Reverse Osmosis - In reverse osmosis, a semi-permeable membrane is used
to concentrate a dilute  waste rinse water stream.  The  dilute waste  is
applied with  high pressure to  a membrane which allows the water  to pass
through, but  retains the  metals and other solutes present.  Thus,  on one
side of the membrane,  a  concentrated metal solution is produced which can
be returned to  the plating bath; on the  other side of the membrane, pure
water is obtained which can be reused as rinse water.

Reverse osmosis  has been used  most  successfully for nickel recovery,
although  it is also used  to recover copper, zinc, and cadmium (Campbell
and Glenn 1982, Kohl and Triplett 1984).  It has not been extensively used
for chromium recovery (Campbell and Glenn 1982).  Reverse osmosis is less
energy  intensive  than   evaporation,  but the  characteristics  of  the
membranes available limits the type of waste streams that can be treated.
For example, only very  dilute streams can be  treated, and  the  solution
must be pre-filtered to extend membrane life (MDEM 1984).

Ion Exchange - Ion exchange involves exchanging one  ion  from a solution
with another ion in order to recover certain ions (such as metal ions) or to
purify the solution.  This occurs by passing a solution over  an ion exchange
resin which has the capacity of exchanging one of its own ions for an ion  in
solution.  Once a resin has reached its capacity in terms of  ions exchanged,
it must be regenerated.  Regeneration is usually accomplished using an acid
or a base, depending on  the type of resin.  The acid or base  removes the
accumulated  metal from the resin.  Another step may be necessary to
remove the metal  from the acid  or base before the metal can  be  reused.
Ion exchange  is often used for  purification of rinse  water, rather than
simple metal recovery.  Ion exchange  has been effective  for recovery of
nickel, chromium, cyanide, gold, silver, and other metals (Kohl and Triplett
1984).

Ion exchange  is  a  relatively complicated  and delicate process  which
demands a high level of process control  and maintenance.  For this  reason,
as well as  for  other technical reasons such as regeneration problems, ion
exchange is not currently a popular method for metal recovery.
                         B3-25

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           Electrolytic Metal Recovery - In electrolytic metal recovery, metal ions in
           solution are reduced electrochemically onto a cathode  surface  within the
           solution.   When the cathode becomes fully  coated with the metal, it  is
           removed  from the solution  and  placed into  a  plating  bath  as  an anode,
           replenishing the bath with the metal.  Up to 99% of the metal in waste
           rinse water can be recovered using this method (Campbell and Glenn 1982).
           One great advantage of the electrolytic method  over other metal recovery
           techniques is  that it recovers only the plating metal, not the  impurities,
           from the waste rinse water.  Electrolytic metal recovery is most efficient
           on  concentrated solutions.   For  solutions with  less than 100 mg/1 of the
           metal  ion, low  current  efficiencies  limit  the  process  effectiveness.
           Electrolytic recovery systems have been  used to recover copper, tin, gold,
           silver,  cadmium,  and  other  metals  (Campbell  and Glenn 1982, Kohl and
           Triplett 1984).  In one application, the metal was recovered directly from a
           cyanide - destruct tank*.

           Electrodialysis  -  In  electrodialysis,  an electric  current  and selective
           membranes are employed to  separate the positive and negative ions from a
           solution into  two streams.   This is accomplished by  feeding  a solution
           through a series of alternating  cation  and anion selective membranes,
           through which  a  current is passed.   Electrodialysis  is used  mainly  to
           concentrate dilute solutions of salts or  metal ions.  Electrodialysis has been
           used to remove  nickel,  copper,  cyanide, chromium, iron and  zinc  from
           waste rinse water (MDEM 1984, Kohl and Triplett 1984). This  technology
           has not been  used as widely in  the electroplating industry as  have  other
           metal recovery techniques (Campbell  and Glenn  1982,  Kohl and Triplett
           1984).

           Use of Separate  Treatments - Use  of separate treatments  for individual
           solutions results in a sludge  that bears a single  metal.   The  sludge (metal
           hydroxide) can then be sold, e.g., to a chemical producer.
* National Association of Metal Finishers 1985:  Personal communication.
                                    B3-26

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9.2  Implementation Profile

The use of multiple rinse tanks, often with counterflow arrangements, is currently one
of the most  effective and  widely  used methods  of  waste reduction available.  Most
large  plating operations, in fact, are built with  multiple rinse tanks.  Smaller shops,
however,  often  use  only a single  rinse following immersion in cleaning  and plating
solutions.

The installation of a second and/or third rinse tank following a plating bath drastically
reduces rinse water consumption,  as discussed earlier.  It  also  involves  substantial
process modifications.    Since  all of  the  baths  and  mechanical equipment in most
electroplating  shops  are built  in  a  series  type of  arrangement,  the  inclusion  of
additional  tanks  may require some changes  in the  shop lay-out.   Besides the  tanks
themselves, piping, pumps,  flow controllers, and racks for transporting the  workpieces
will  need  to  be  added.   In  some instances,  the availability  of  space may be  the
determining factor in the use of multiple rinse tanks.

In smaller electroplating shops, rinsewater tanks may be over-sized for their specific
applications. Instead of installing  a second tank, it is often possible  to simply divide
the existing tank in half by constructing a wall (Dowd 1985).  This effectively converts
the single large tank into two smaller tanks. The  additional piping needed is minimal.

A second  waste reduction method with a high implementation potential is the reuse of
rinse water.  Electroplating operations  use rinse water at several stages in the process,
and it is often possible to use the same  stream at  more than one step.

Adding rinsing steps to  an existing operation  would necessitate  modification  of the
piping system.   The  main technical problem  with this technique is that the quality of
the product must be monitored carefully.  A rinse stream can  be used a second  time
only if the contaminants from the first rinse do  not interfere with the quality of the
second rinse.  Monitoring the rinse  water composition and the quality of the  workpiece
after each rinse might be required.
                                    B3-27

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As  hazardous waste  treatment  and disposal  costs rise,  there  is  an  incentive  to
implement waste  reduction  methods for the purpose  of achieving  cost reductions.
Some  of  the waste  reduction techniques  discussed  here  involve  minimal  capital
outlays.  Examples of these would be good operating practices and rinse  water reuse,
which  often  entail minor equipment changes and/or  simple changes in procedure.
Smaller shops (roughly two-thirds of the industry) may find these methods practicable,
but  may  be   capital-constrained  in   the  implementation   of   more   extensive
modifications.  It has been shown that the use of multiple rinse tanks and other rinse
water  conservation  methods,  which  vary  considerably  from  one  to  the other  in
expense, can  reduce waste treatment costs by $10,000 -$99,000 per year (David 1985).

9.3  Summary

The waste sources and their respective source control technologies are summarized in
Table 9-1. The ratings listed in this table  are based on a scale of 0-4.0 and are  used to
evaluate each technique for  its waste reduction effectiveness,  extent of current use,
and further application potential.  The ratings shown  are based  on  a review of  the
available literature, as well as the opinions of industry personnel.

The most effective waste reduction methods include the use of multiple rinse tanks,
the installation  of drain boards  and drip tanks,  the reuse of rinse water, and  the
installation of  metal recovery systems.  Since waste  rinse  water accounts  for  the
majority of the volume  of waste  produced,  the methods which decrease rinse water
consumption  offer the greatest potential for waste reduction.

Based  on the measures currently  undertaken  to  reduce waste,  a current  reduction
index of 1.8 (45 percent) has  already been achieved by the electroplating  industry.  By
implementing additional  waste reduction methods  or  increasing the use of existing
measures, the  current  quantity  of waste produced could  be  reduced  to  the  level
corresponding to  a future reduction index of 0.8 to  1.9 (20 to 48 percent).  The above
values mean  that  currently employed measures have reduced waste generation by  45
percent from the levels  that otherwise would exist, and that  future measures  could
reduce wastes by 20 to 48 percent from the current waste generation levels.
                                    B3-28

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                           TABLE 9-1  SUMMARY OF  SOURCE CONTROL  METHODOLOGY FOR  THE ELECTROPLATING  INDUSTRY
m   1
OL>
10
Naste Stream

Cleaning
r ] j. lnnc * 4 \

Spent Plating
Solutions and
Sludges (•)


Waste Rinse Hater












Treatment
Hastes («)




All Sources
i
I
i


1
II-
12
13.
I*
i
n.
12
13.
|4
|5
16
IT
|8
1'
|10
111
|12
1
|1.
!2
13.
!'•
15.
1
1
| Found Documentation i

I Quantity |
See study on Metal Parts Cleaning | — '

Overall ! — |
Increase plating solution life | 1 \
Use non-cyanioe olat'ng solutions | 1 |
Replace cadmium plating with zinc | 1 I
Replace hexavalent chromium with tri | 1 |
Overall j 1 00 I
Increase solution temperature | 1 |
Use less concentrated plating soln | 1 1
Withdraw workpiece slowly from soln. | 2 1
Add wetting agents to plating soln. | 2 '
Position workpiece properly on rack | 3 |
Recover drag-out of plating solutions] 2 |
Install multiple rnse tanks | 3 |
Install fog nozzles and sprays ) 2 |
Reuse rinse water elsewhere in plant | t |
.Install still rinsing tanks | 1 |
.Install automatic flow controls | 2 |
.Use mechanical/ai" agitation of bath | 1 |
Overall | 1 75 |
Use efficient precipitating agents | 1 |
Use trivalent instead of hex chromium) 1 I
Install sludge dewatering systems | 1 |
Implement better operating practices | 1 |
Install metal recovery systems | 3 |
Overall | 1.10 |
All Methods
i
Quality |
—

— 1
1 1
2 1
2 1
2 1
t 75 |
2 1
2 i
2 1
1 1
3 1
1 1
3 |
2 1
2 1
1 I
1 1
1 i
1.75 |
2 1
2 1
2 1
2 1
3 1
2 20 |

haste | Extent of | Future | Fraction o' | Current
Reduction | Current Use | Application 1 Total Waste | Reduction
Effectiveness |
— 1

— 1
' 1
2 1
2 1
3 1
2.00 |
1 1
3 1
2 1
1 1
2 1
2 1
« 1
3 i
< 1
2 1
3 1
1 1
2.33 |
2 1
3 1
• 1
3 1
3 1
3 00 |

| Potential |
— ! — I

— 1 — 1
1 | 2 |
1 1 2|
1 ! 2|
' 1 1 1
1.00 | 1.75 |
2 | 1 |
1 | 2 |
'I 3 1
1 | 2 |
3 I 2|
2 | 3 |
2 1 2 |
21 31
1 1 3 |
2 ! 3|
2 1 2 |
2 | 1 !
1.75 | 2 25 |
1 2 |
1 ' 1
1 ' 1
1 2 |
1 3 |
1 00 | 1 80 |

| Index
I 2

0 10 I 2
! o
i °
1 o
1 o
0 IS | 0
1 0
0
0
1 o
1 1
1 1
1 2
1 1
1 '
1 1
| 1
I 0
0 65 i 2
0
1 O
1 .1
0
0
0 10 1
1 00 | 1
1
1-
1
0 1

o !
1 !
1 !
1 1
2 I
2 I
5 1
8 i
5 1
3 1
5 1
0 1
0 1
5 1
0 1
0 1
5 1
5 1
0 1
5 I
8 1
0 1
8 1
8 '
0 1
8 !
Future Reduction Index '

Probable
1

1
0
0
0
0
0
0
t
1
0
0
0
1
t
2
0
0
0
0
0
0
0
1
1
1
0

1
2 1

2 1
4 I
8 1
8 1
6 1
6 1
1 1
1 1
1 1
» 1
3 I
8 1
0 1
1 !
3 I
8 1
8 1
i i
8 1
* I
6 1
8 i
1 1
7 I
o !
8 1
	 1
Maximum |
1 9 '

1.9 !
,
0.8 |
0 8 1
1
0 8 |
1
I
1

1
1
1
1
2 3 |
1
1
1
2 3 !
i
1
1
i
1 7 1
1 1 '
1 9 1
       (*)  These  waste  streams  include listed  "F"  and/or  "K"  RCRA wastes

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10.  WASTE REDUCTION THROUGH PRODUCT SUBSTITUTION

This study has so far examined methods of reducing the  amount of waste produced in
electroplating operations through  process modifications or other  changes.   It is also
possible  to  reduce  or eliminate  the generation of certain wastes  through product
substitution.   A  complete   investigation  of  product  substitutions  has  not  been
attempted; rather, two possible product substitutions are  briefly discussed below.

10.1       Cadmium Plating Alternatives

Cadmium is used in a wide variety of products for  its excellent protective properties.
Cadmium-plated  products are highly  resistant to  corrosion  in land  and  marine
environments. For this reason, the U.S. military specifies cadmium plating for a large
variety of naval and aerospace equipment*.  Roughly  35-40% of  the total amount of
cadmium  consumed  in  the country  is used by  the U.S. military**.   Unfortunately,
cadmium  is extremely  toxic  and  there  is concern over the introduction of  soluble
cadmium salts into the environment.

It  may be possible in some instances to replace cadmium plating with other  materials
such as:

     o     Zinc  using  plating (zinc  graphite  has  been  considered an  alternative to
           cadmium).
     o     Titanium dioxide using vapor deposition.
     o     Aluminum using ion vapor deposition (Ivodizing).

None of the above-mentioned  coatings have exactly the  same properties as cadmium,
but  nonetheless  may  prove   to be  satisfactory substitutes.   Aluminum  ion vapor
deposition  is a  very attractive  process, but  is  considerably more  expensive  than
electroplating*.
* Cadmium Council 1985: Personal communication.
**  National Association of Metal Finishers 1985:  Personal communication.
                                    B3-30

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The elimination of cadmium from industrial use has already been attempted.  In 1979,
Sweden began the first stage of a ban on the use  of cadmium in electroplating  and in
various pigments.  It was hoped that this would lower the concentration of cadmium
found in the environment over time.  The ban has not achieved this end, and Sweden is
considering removing the current regulations on the use of cadmium*.

The elimination  of the use of  cadmium is not being endorsed by the electroplating
industry.  The implementation  of such a change would require major modifications to
many   electroplating  shops,  and  could  result  in  the closing  down  of  some   shops
altogether.

10.1.2      Chromium Plating Alternatives

Chromium  is used to  plate a multitude  of products ranging from automobile parts to
paper clips.  In some instances, the chromium plate  is required for its hardness and
durability.  In other cases, it is used purely for decorative reasons.

Because there is a substantial  amount of waste produced during a chromium plating
operation,'the elimination of any  unnecessary use of chromium would be beneficial
from  the  environmental  standpoint.   For  example,  chromium-plated  automobile
bumpers could be replaced with nickel-plated bumpers, although customer preference
for a shinier finish may play a major role. Of course, the substitute product must have
less  waste  associated with  its production  than  does the  original product.   Many
automobile bumpers  are  currently being painted rather than plated  during  finishing
operations*.

As with cadmium,  industry does not seem to be promoting the  elimination of chromium
use on certain products.  The economic  reasons that could justify such a change today
are not present.  Since the majority of electroplating  operations are small and employ
less than 20 people, (Dun's 1982, USDC 1985) the capital needed to implement major
process changes is  often not available.
  General Motors Corp., 1985: Personal communication.
                                    33-31

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11.   CONCLUSIONS

To reduce the problems of waste treatment and disposal in the electroplating industry,
many methods of waste reduction through source control have been identified.   It is
estimated that the  total waste output from electroplating can be further reduced by
20 to 48% by  implementing or expanding the use  of  the  source reduction methods
discussed.   The  most  efficient  methods available for  waste  reduction  are  using
multiple  rinse tanks,  installing drain boards and drip tanks,  and  reusing rinse water.
The  electroplating  industry  already  appears  to  have implemented waste  reduction
measures to a fairly high degree, as evidenced by the  current waste reduction  index
value of 1.8 (45 percent).

The  technology  associated  with  the waste  reduction  methods  discussed  is readily
available and  well understood.  Economic constraints have been the major  barrier  to
implementation.

12.  REFERENCES
Anonymous,  1985a.  Finishers face  increasing environmental pressure.  Plat.  Met.
Finish. 72 (4): 36-9.
              1985b. Plat. Surf. Finish. 72 (4): 20-4.
ASM, 1964.  American Society for Metals. Metals Handbook.  Metals  Park,  Ohio:
American Society for Metals.
BCL, 1976.   Battele  Columbus  Lab.  Assessment  of  industrial  hazardous  waste
practices;  Electroplating and metal finishing industries job shops.  EPA - 530  -SW -
136C.  Washington, D.C.:  U.S. Environmental Protection Agency.
Campbell,  M.E, and Glenn,  W.M., 1982.   Proven profit  from pollution prevention.
Toronto, Canada: The Pollution Probe Foundation.
CDHS,  1984. State of California, Department of Health  Services.   Second  Biennial
Report.  Alternative technologies for recycling and treatment of hazardous wastes.
Chacey, K., et. al. 1983.  Chrome electroplating waste BAT. Poll. Enq.  15 (4): 20-3.
Clark, R.,  ed. 1984.  Massachusetts hazardous waste  source  reduction.  Conference
proceedings, October  17, 1984.   Boston,  Mass.:    Massachusetts Department  of
Environmental Management.
Dowd, P. 1985.  Conserving water and segregating waste streams. Plat. Surf. Finish.
72 (5):  104-8.
Dunn's Marketing Services, 1983.

                                     B3-32

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Hsu,G.F.  1984.  Zinc-nickel  alloy plating: an  alternative to cadmium.   Plat. Surf.
Finish.  71 (4):  52-5.

Kohl, J.,  and  Triplett,  B.  1984. Managing  and minimizing  hazardous waste metal
sludges.  North Carolina State University.

Lowenheim,  F.A.   1979.  Electroplating in Kirk-Othmer Encyclopedia of Chemical
Technology.  3rd ed. Vol. 8, pp. 826-69.  New York, N.Y.: Wiley.

McRae, G.F. 1985.  In-process waste reduction:  part 1. Plat. Surf. Finish.  72 (6):  14.

MDEM 1984, Massachusetts Department of Environmental  Management, Massachusetts
hazardous  waste source  reduction:  metallic waste session.  Conference proceedings
May  23,   1984.    Boston,  Mass.:   Massachusetts  Department   of  Environmental
Management.

Miller, G.T. 1985.  Living in the environment; Wadsworth Publ.  Co.

Olsen, A.E. 1973. Upgrading metal finishing facilities to reduce  pollution.  Oxy Metal
Finishing  Corp.,    EPA-625-3-73-002,   Washington,  D.C.  :   U.S.   Environmental
Protection Agency.

Radimsky, J.,  Piacentini,  R., and  Deibler, P. 1983.  Recycling and/or  treatment
capacity for hazardous waste containing cyanides.  Staff report  of the Department of
Health Services, State of California March, 1983.

Seaburg, J.L., and Bacchetti,  J.A, 1982, Chemical Processing  45  (12):  30-31.

Tavlarides,  L.L. 1982, Process  modifications toward minimization of environmental
pollutants  in the chemical processing  industry.   Chicago,  111.:    Illinois  Institute of
Technology.

USDC. 1982, U.S.  Department of Commerce,  1982 Mineral Yearbook.   Washington,
D.C.: U.S. Government Printing Office.

	.   1985.   U.S.  Department  of Commerce,  Bureau  of  the  Census
Electroplating.   1982 Census of manufactures.   Washington, D.C.:  U.S.   Government
Printing Office.

USEPA. 1979.  U.S. Environmental  Protection  Agency.  Development document  for
existing sound pretreatment  standards  for the electroplating point source category.
EPA-440-1-79-003.  Washington, D.C.:  U.S. Environmental Protection Agency.

	 . 1981.  U.S. Environmental Protection Agency,  Industrial Environmental
Research  Lab.   Inplant changes for  metal  finishers.    Cincinnati,  Ohio:   U.S.
Environmental Protection Agency.

	. 1983.  U.S. Environmental Protection Agency, Office  of Water Regulations
and Standards.  Development document for effluent limitation guidelines and standards
for the metal finishing point source category.  EPA-440-1-83-091.  Washington, D.C.  :
U.S. Environmental  Protection Agency.

VERSAR,  Inc.  1984. Technical  assessment of treatment  alternatives  for  wastes
containing  metals and/or cyanides.  Versar, Inc. Contract no. 68-03-3149, final draft
report for U.S. Environmental Protection Agency. Springfield, Va. : Versar,  Inc.
                                     83-33

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WSDE. 1985.  Washington State,  Department of Ecology.  Progress report, priority
waste management study for Washington State  hazardous waste.  Washington  State:
Department of Ecology.

U.S. Pat 4,365,481. To the U.S. Army.

13.   INDUSTRY CONTACTS

Art Pierdon, Past president of the American Electroplater Society, Alexandria Metal
Finishers, Fairfax, VA.

Patrick Dowd, Baxter  and Woodman Engineers, Crystal Lake, IL.

Technical Representative, Cadmium Council, New York, NY.

Jeff Jolicoeur, Chemical Consultants, City of Industry, CA.

Joseph P.  Chu,  Environmental  Activities Staff, General Motors Technical Center,
Warren, MI.

David Anzures, National Association of Metal Finishers,  San Fernando, CA.

Walter G. Vaux,  Principal Engineer, Chemical and Process Engineering, Westinghouse
Electric Corp, Pittsburgh, PA.
                                     B3-34

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1.    PROCESS: EPICHLOROHYDRIN MANUFACTURE

2.    SIC CODE:  2869

3.    INDUSTRY DESCRIPTION

The  epichlorohydrin manufacturing  industry  comprises  firms engaged in both the
production and  use of  epichlorohydrin.   The  establishments  are  part of  large
multiproduct corporations.

3.1  Company Size Distribution

In  the U.S., crude and refined epichlorohydrin  is currently produced at three locations
by only two  companies.   The total  U.S.  production capacity of the epichlorohydrin
industry  in  1982  was  290,000  short  tons.   An  epichlorohydrin  facility  employs
approximately 50-60 persons; the work force includes production  workers (operators),
supervisory personnel, and maintenance personnel (Bales 1978).

3.2  Principal Producers

There are two major producers of epichlorohydrin in the United States:

           Dow Chemical Company
           Shell Chemical Company

3.3  Geographical Distribution

Of the three epichlorohydrin manufacturing facilities in the United States, two are  in
Texas, and one is in Louisiana.  All are located in EPA region VI.  See Table 3-1 for a
listing of company locations.
                                    B4-1

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             Table 3-1 Epichlorohydrin Producers in the United States
       Company
Production
 tons/year
Capacity
tons/year
Percent
of Total
Dow Chemical USA
 Freeport, Texas

Shell Chemical Co.
 Deerpark, Texas
 Norco, LA
123,000
 33,500
 33,500
210,000
 80,000
 incl.
     72
     28
   incl.
Total
190,000
290,000
  100.0
Source:  Chemical Economics Handbook (SRI 1982) and industry comments.


4.    PRODUCTS AND THEIR USE


Based on 1982 statistics, approximately 19% of the crude epichlorohydrin produced in

the U.S. was used to  make synthetic glycerin.  Glycerin is used  in the  making of alkyd

resins, explosives,  polyether polyois,  cosmetics  and  drugs,  cellophane,  food  and

beverages,  and  in other  miscellaneous applications.    Approximately  62%  of  the

epichlorohydrin (after further refining) was used in  the  making of unmodified epoxy

resins. These resins  are used for  making protective coatings, reinforced plastics, and

adhesives.    About   2.3%  of  the  refined  epichlorohydrin   was  used  to  make
epichlorohydrin elastomers.  The remaining 14% was  used for making  a variety  of

other miscellaneous products including glycidyl ethers, some types  of modified epoxy
resins, wet strength resins for the paper industry, water treatment resins, surfactants,

and ion exchange resins. Table 4-1 presents a breakdown of epichlorohydrin uses.
           Table 4-1 1982 Epichlorohydrin Products and Use Distribution
                 Epichlorohydrin Use
                         Breakdown
                          Percent
           Glycerin
           Unmodified epoxy resins
           Epichlorohydrin elastomers
           Miscellaneous
                            18.6
                            62.0
                             2.3
                            14.1
             Total
                            97.0(a)
Source: Chemical Economics Handbook (SRI 1982).
a) Some epichlorohydrin is lost during the refining process.
                                    B4-2

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5.    RAW MATERIALS

The raw materials used to produce epichiorohydrin are shown in Table 5-1. Both Dow
and  Shell  Chemical  make  epichiorohydrin  from  an  allyl chloride  intermediate
synthesized from propylene and chlorine.

    Table 5-1 Raw Materials Used by the Epichiorohydrin Manufacturing Industry
               Raw Materials                      _ Usage _
                                                    Ib/lb product
              Propylene                              Not Found
              Chlorine                               Not Found
              Allyl Chloride                           .997
              Chlorine                               .9025
              Slaked Lime                            1.009

Source: Assessment of Hazardous Waste Practices (Gruber 1975).

6.   PROCESS DESCRIPTION

Currently,  both  producers of epichiorohydrin use a process  involving the  use of allyl
chloride as an intermediate  reactant.  Simplified process  flow diagrams are depicted
in Figures  6-1 and  6-2.   The first  step  is the  production of  allyl chloride from
propylene and chlorine:
     H2C = CHCH3 + Cl2 - — H2C = CHCH2C1 + HC1
The byproducts include 1,2-dichloropropane and isomers of 1,3-dichloropropene.
The second step is chlorohydroxylation of allyl chloride to dichlorohydrin (C3H60C1):
     C1CH2 - CH = CH2 + HOC1 --
                                   C1CH2 - CHC1 - CH2OH  1,2 - dichlorohydrin

The byproduct formed in this reaction is 1,2,3  - trichloropropane.
The third reaction step is the conversion of dichlorohydrin to epichiorohydrin:

     2 C3 H6 O CL2 + Ca(OH)2 --72C1CH2 - CH - CH2 + CaCl2 + 2H2O
                   or                      \  /        or
                2NaOH                     O        2NaCl
                                   B4-3

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CHLORINE
     o
               VAPORIZER
PROPYLENE
fi
           DRYERS
                                PROPYLENE
                   PROPYLENE      PREHEATER
                    RECYCLE
               PROPYLENE
                 HCL
               SEPARATOR
          PHE-
       FRACTIONATOR
                V
                    LI6HT
                     ENDS
                    COLUNN
                                   Y
                                                   X!
                                                      REACTOR
                                                                        COOLER
                                                   X!
                                            REACTOR
                                                              COOLER
                                                          ALLYL CHLORIDE
                                                        PURIFICATION
                                                         COLUNN
       r
       j  PROCESS HASTE CATEGORIES!

         (?)   HCL BY-PRODUCT

         (?)   LIBHT ENDS

         (T)   HEAVY ENDS
                   Figure 6-1   Allyl Chloride Synthesis froi Propylene and Chlorine
                                       B4-4

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 CL
ALLYL CHLORIDE
PROCESS NASTE CATEGORIES!
©
©
®
OFF 6AS
SALT BRINE BOTTOMS
HEAVY ENDS
                                                                STEAM
                                                                                   STRIPPER
                                                                                                        HATER AND
                                                                                                      DICHLOROHYORIN
                                                                                                        TO RECYCLE
                                                                                                         EPICHLORO-
                                                                                                           HYORIN
                                                                                                         TRICHLORO-
                                                                                                    1      PROPANE
                                                                                                          SOLVENT
                                                                                                         TO  RECYCLE
                                                                                                    FRACTIONATOR
                             Figure 6-2   Epichlopohydrin Production fro« Allyl  Chloride
                                                   84-5

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In the first  step,  excess  propylene and  chlorine  gas  are continuously fed into an
adiabatic non-catalytic reactor at 930-950°F and 30 psia to produce allyl chloride and
HC1.  The reactor effluent is cooled to about 120°F and sent to a pre-fractionator to
separate HC1 and propylene. The overhead stream gas stream is subsequently split at
cryogenic conditions;  propylene  is  recycled to the propylene preheater and HC1  is
taken off for other  uses in  the integrated halogenated hydrocarbon facility.

After initial removal of HC1 and propylene,  the organic chloride fraction is separated
in a two-step distillation.   Low  boiling constituents are taken overhead in the first
column.  These include various  saturated chlorides such  as 2-dichloropropane.  The
heavy-boiling fraction which is taken off as a bottom product in the second column, is
made  up  largely  of  unsaturated dichlorides  and  other  allyl chloride degradation
products such as benzene,  tars, and  carbon (DeBenedictis 1979). This fraction, rich in
1,3 - dichloropropene,   is  used   as  a  feedstock to  the  process  of  manufacturing
fumigants or nematicide formulations,  such  as D-D (Shell  Chemical Co.) or Telone II
(Dow Chemical)

The allyl chloride overhead stream from the second column is fed continuously to a
stirred tank where it reacts in the liquid phase (at atmospheric pressure and 85-105°F)
with a solution of hypochlorous  acid.  The hypochlorous acid  is produced in a packed
tower by dissolving  chlorine in water.  The  reaction tank effluent  is fed to a gravity
separator:  the upper layer (aqueous phase) is recycled to the hypochlorous acid  tower.
The underflow, chiefly dichlorohydrins,  is fed to the second reactor, where virtually
complete conversion to epichlorohydrin by reaction  with aqueous NaOH or lime takes
place. Trichloropropane, one of  the  reaction co-products is used as a solvent for the
epichlorohydrin.  The effluent  from the second reactor is steam  stripped, removing
epichlorohydrin as  the water azeotrope.  The undercut (calcium chloride or sodium
chloride solution and  excess lime in suspension) is sent to by-product recovery.  The
distillates, water,  and organic  phases  are  separated, with  the  undercut  fed to a
fractionating tower for recovery of epichlorohydrin and solvent.  The epichlorohydrin
is purified and sent  to storage.  The recovered trichloropropane solvent  is recycled to
the product reactor.  Some process configurations, however, do not incorporate this
recycle stream.
                                     B4-6

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The  small  amount of dichlorohydrins carried over  from the steam stripper  in  the
epichlorohydrin-water azeotrope is  mostly discharged in  the water  phase  from  the
second separator.  This aqueous dichlorohydrin is recycled. The heavy  ends, discharged
as still  bottoms  from  the  fractionator,  contain  some  epichlorohydrin,  5 percent
dichlorohydrin, 7 percent chloroethers, 35 percent  trichloropropane, and 50 percent
heavies or tars (Gruber 1975).

7.   WASTE DESCRIPTION

The wastes evolved in the epichlorohydrin manufacturing process come primarily from
the off-streams  or bottom streams of the various  recovery steps.  The specific  RCRA
codes and waste stream compositions are given in Table 7-1. Most of the by-products
from  the process have  found application as feedstocks to  other   processes.   For
example, light ends from the allyl chloride synthesis step  are oxidized to recover HC1
and heat of combustion.  Therefore, the label "waste stream" would not apply to those
facilities which reprocess the light ends  in the  above  fashion.   Sections below give
descriptions of  treatment and disposal practices found in the literature or through
contacts with  the  industry*.

     o    HC1 Byproduct from Allyl Chloride Synthesis.
           In  an  integrated  chlorohydrocarbon facility,  HC1 is  recovered, e.g.,  by
           routing it  to  the oxychlorination unit associated with the vinyl chloride
           monomer production.

     o    Light Ends
           The light ends from the allyl chloride synthesis step are oxidized to recover
           HC1 and heat.

     o    Heavy Ends
           The  heavy ends from the allyl chloride purification column contain 1,3 -
           dichloropropylene,  an  active  ingredient  of  fumigant  or  nematicide
           formulations.  Hence, this stream is often used as a feedstock  to a process
           to manufacture such formulations.  The remainder is either  landfilled or
           oxidized   for   HC1  or  heat  recovery.    The  heavy   ends   from  the
 * Dow Chemical Co. 1985:  Personal communication
                                     B4-7

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                                         Table 7-1 Epichlorohydrin Process Effluent Streams
CO

I
oo
No.
1.
2.
3.



4.
5.



6.
7.
8.
Waste/Residual Process Origin
HC1 By-Product HC1 Separator
Light Ends Light Ends Column
Heavy Ends Allyl Chloride
Purification
Column
Epichlorohydrin
Fractionator

AC Reactor Tars Allyl Chloride Reactor
Off Gas Tail Gas Absorber
•
Epoxidation Reactor

Salt Brine Bottoms Salt Stripper
Equipment Cleaning Sludge Cleaning of Columns, Tanks
and Heat Exchangers
Spills and Leaks
Composition^3) RCRA
(Ib/lb epichlorohydrin) Codes
HC1 (1 Ib/lb allyl
chloride)
N/A
N/A

Heavy Ends
Chloroethers
Epichlorohydrin
Dichlorohydrin
Trichloropropane
N/A
Allyl Chloride
Chlorine
HC1
Allyl Chloride
Epichlorohydrin
Trichloropropane
Chlorine
HC1
CaCl2 or NaCl
N/A
N/A
—
—
—

.053 K017
.0074
.001
.0057
.037
F024
.002
Trace
Trace
.002
.0015
.0005
Trace
Trace
.600
F024
—
      (a) Source:  Assessment of Industrial Hazardous Waste Practices (Gruber 1975) for composition data.

-------
           epichlorohydrin fractionator are either landfilled, burned to recover HC1 or
           energy  or used  as feedstock  to other  processes.   They  contain  high
           concentrations of 1,2,3-trichloropropane,  a  byproduct of chlorohydroxyla-
           tion reaction.

     o     Salt Brines
           Salt brines from the epichlorohydrin stripper leave the process via  bio-
           oxidation treatment units to remove organics.  The water solution of salts
           (CaCl2 or NaCl)  is not considered hazardous.

     o     Miscellaneous Process Equipment Cleaning Wastes
           The cleanup  sludges from heat exchanger tube cleaning  and  steamout oils
           from  columns  or tanks  are  generated  infrequently,  (at  1  to  2 year
           intervals).   The  main  waste  stream  in  this category  is  generated by
           cleaning  of  the allyl  chloride  reactor,  which  occurs presently  every
           2 months*.  The  current  disposal  practice  at  all  sites is  not  known,
           although  one  facility  reported  that these  wastes  are  recycled  to  the
           process.

     o     Spills and leaks
           Because of the  toxicity of epichlorohydrin  and its process intermediates,
           the potential leak sources,  such as valve packings, pump seals, and  flange
           gaskets are  routinely inspected and  maintained.  Consequently, leakage is
           minimal (Bales 1978).

Epichlorohydrin is shipped  in drums,  tank cars, or via pipeline.   Epichlorohydrin is
pumped  directly   from  storage  tanks  and  introduced  into  the  drums  through a
retractable pipe with a cut off valve immediately above the drum.  During the filling
operation,  the  drum opening is  surrounded by a hinged ventilation  hood.  Exhaust is
discharged to the atmosphere following scrubbing (Bales 1978).

8.   WASTE GENERATION RATES

The  composition  of selected waste streams from the production of epichlorohydrin
were  given in terms of Ib. of waste/lb. of product (Gruber  1975), and are reported in
  Dow Chemical Co. 1985:  Personal communication.

                                      B4-9

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Table 7-1.  Overall waste generation rates for the whole industry, however, could not
be determined due to the  lack  of sufficient  data.  Fractional waste generation (the
percentage  each waste represents of the total waste generated) was estimated based
on available information and industry comments.  These values are shown in Table 9-1.

9.   WASTE REDUCTION THROUGH SOURCE CONTROL

This section deals with the problem of how to reduce the volume and/or toxicity of the
epichlorohydrin production  process  waste streams.  Off-gas  and  HC1 generation will
not be considered  in this report.  HC1 has various industrial uses and is a  salable by-
product; the off-gases,  containing relatively minute  amounts of  substances  such  as
allyl chloride, chlorine, and epichlorohydrin are flared.

9.1  Description of Techniques

In addition  to the waste reduction  measures classified as being  process  changes  or
material/product substitutions, a variety of waste reducing measures labeled as "good
operating practices" has also been included.  Good operating practices are defined as
procedural or institutional changes which result in a reduction of waste.  The following
items highlight the scope of good operating practices:

     o    Waste stream segregation
     o    Personnel practices
                Management  initiatives
                Employee  training
     o    Procedural measures
                Documentation
                Material handling and storage
                Material tracking and inventory control
                Scheduling
     o    Loss prevention practices
                Spill prevention
                Preventive maintenance
                Emergency preparedness
                                     B4-10

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For each  waste stream,  good operating practice  applies whether it is listed or not.
Separate  listings  have been provided  whenever  case studies  were  identified.   A
summary  of  the  source control  methodology  is given in Table  9-1.   Sections below
describe the listed methods.

9.1.1   Heavy and Light Ends from Allyl Chloride Synthesis Step

The reduction of the volumes of these  effluent streams will be considered as waste
minimization only  to  the extent that these streams are still land disposed.  In the
facilities  which  currently process these streams, e.g., recover HC1  following thermal
oxidation,  source  reduction  methods may be viewed as either  not applicable  or  as
means to increase the allyl chloride yield.

Formation of heavy and  light ends  is governed by side reactions.  In principle, the
desired substitution reaction to  form allyl chloride (~ 570° F) is accompanied by:  a
low   temperature   (<400°F)   addition   chlorination   reaction,   an   unsaturated
monochloride isomer  formation, an unsaturated  dichloride  formation  by  further
chlorination of allyl chloride, and by thermal  degradation (>1100° F) to tars, carbon,
and benzene. The following source reduction methods were considered:

      o    Alternate reactor design.
           Present reactor design encompasses the features of  a strongly backmixed
           plug  flow reactor. A thorough review of the kinetic data for the reactions
           may  reveal that the current degree of mixing  can  be  improved with  an
           attendant yield increase for  allyl chloride.  At one facility, reactor design
           modifications to  provide better mixing resulted in a drastic  decrease in the
           tars  formation  rate*.   In  evaluating  different  modification schemes,
           consideration  should  be  given  to  staged  addition of chlorine.  Also, the
           concept  of  a  fluidized bed  reactor with  inert solids (e.g.,  sand)  appears
           worthy  of consideration because of excellent mixing  and thermal stability
           characteristics.
* Dow Chemical Co. 1985:  Personal communication
                                    B4-1]

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      o    Preheat of chlorine feed.
           It is postulated that curtailment of the low  temperature addition reaction
           can be achieved  through  preheating of  the chlorine feed (e.g., utilizing
           reactor effluent  waste heat)  prior to mixing with hot propylene.   The
           preheat temperature of the propylene can  be  consequently decreased.

      o    Thermal oxidation with HC1 and heat recovery.
           This  efficient   technique   is  extensively   used  in   the   integrated
           chlorohydrocarbon facilities.   Energy recovery  results in a lowered steam
           requirement,  leading  to  lower  boiler  blowdown  rates  and  associated
           wasteloads. Recovered HC1 can be routed to oxychlorination units serving
           other processes (such as VCM  or PCE/TCE). This technique may be viewed
           both as recycling  or as source control, depending on the process boundary.

      o    Purified feed stock.
           In  allyl chloride  manufacturing,  the propylene  feed impurities usually
           encountered are water and propane (De Benedictis 1979).  Water may react
           with chlorinated  hydrocarbons to form undesirable  by-products  and  may
           also provide a corrosive environment.  Propane and other  hydrocarbons are
           chlorinated  to undesirable saturated  chlorides.   The  level of  feedstock
           purification required  to offset the  undesired  byproduct  formation can  be
           worth re-assessing in light of increasing waste generation costs.

9.1.2   Heavy Ends from Epichlorohydrin Production

Heavy  ends  come  from the  epichlorohydrin  fractionator  and  originate  in   the
chlorohydroxylation reactor.  A decrease  in the volume of heavies production could be
achieved through implementation of the following:

      o    Thermal oxidation with HC1 and heat recovery.
           Currently  this technique  is   extensively  used  in the highly  integrated
           chlorinated hydrocarbon facilities.
                                     B4-12

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      o     Alternate process routes.
           The  alternate  method  for  producing  epichlorohydrin  starts  with the
           chlorination  of  acrolein to  give  2,3-dichloroproprionaldehyde  (Furman,
           Fiach,  and Hearn 1958).  Reduction of the aldehyde with sec-butyl alcohol
           (using   aluminum  sec-butoxide   as  a  catalyst)  yields  glycerol  and
           dichlorohydrin.  Dehydrochlorination with lime then forms epichlorohydrin
           as is  currently  done.    Epichlorohydrin  can  also  be prepared  by the
           epoxidation of  allyl  chloride  with peracids (Phillips  and Starchier  1957,
           Kellaetal  1974,  Kleemann et al.  1971),  perborates (Bruenie and Crenne
           1965),   or by  epoxidation  with tert-butyl  hydroperoxide over  vanadium
           (Sakan, Sano, and Hattori 1970),  tungsten (Sakan, Sano, and Hattori 1970),
           or  molybdenum compounds  (Sakan,  Sano,  and  Hattori  1970,  Oshin,
           Shakhovtseva, and Krasotkina 1975) or by oxidation with air  over a cobalt
           catalyst (Mokrousia,  Oshin,  and  Tregar 1976).   One  route relying on
           chlorination of allyl alcohol to dichlorohydrin followed by epoxidation was
           patented in Japan.  These alternate process routes may have  proven to be
           economically unfavorable in the past.  However, advancing technology and
           recent   increases in  disposal costs could warrant new  investigations of
           economic  feasibility for some of these alternate routes for new grass roots
           plants.

      o     Reevaluation of chlorohydroxylation reaction kinetics and reactor designs.
           Clear understanding of how byproducts (such as 1,2,3 -trichloropropane) are
           formed in the  chlorohydroxylation  reactor is necessary to examine low-
           waste alternative designs of the  reactor (i.e., the  designs which  minimize
           byproduct formation). Such  study  may be warranted in light of increasing
           disposal costs.

9.1.3   Allyl Chloride  Reactor Tars

The formation of  these  tars can be reduced  by  alteration of the reactor design, as
discussed in Section 9.1.1.  Provision for more mixing  to eliminate stagnant areas in
                                     84-13

-------
the reactor resulted in the decrease of tar cleanup frequency from 10 days to 2 months
at one facility*.   The tars  can be combusted  for heat  and HC1  recovery  in  certain
incinerator designs.

9.1.4   Miscellaneous Equipment Cleanup Wastes

Usually, the wasteloads associated with  equipment cleaning are small and periodic  in
nature (once every 1 or 2 years). Further reductions may be obtained through:

     o     Complete drainage of process piping or equipment prior to cleaning.

     o     Use of non-stick (electropolished  or Teflon**)  heat  exchanger tubes  to
           reduce deposit clingage.

     o     Use of in-process heat exchanger tube cleaning devices (Anonymous 1985a).

     o     Lower  process  film temperatures  and  increased turbulence  at the heat
           exchanger surfaces to reduce fouling rates.

All the suggestions  listed  above  will  have only a  minor  impact on overall waste
generation, since  equipment cleaning  wastes  are but a  small  fraction  of  the  total
waste.  The  reader  is further referred  to  the separate  study  of process  equipment
cleaning in this appendix.

9.1.5  Spills and Leaks

As  mentioned before, spills  and leaks constitute a rather minor waste stream because
of the  extensive level of preventive maintenance practiced.  Further source  reduction
is possible, in principle, through better operating practices (see separate process study
entitled "Good Operating Practices").   Additionally, some consideration  should be
given to:

     o     Replacing single mechanical  seals with double mechanical seals on pumps
           or using canned seal-less pumps.
*     Dow Chemical Co. 1985:  Personal communication
**    Registered trademark of E.I. Du Pont.
                                   B4-14

-------
     o     Using leak detection systems and portable monitors.

     o     Enclosed sampling and analytical systems.

9.2  Implementation Profile

The  identified  source  control options require  considerable engineering and economic
analyses before implementation. The two U.S. producers of epichlorohydrin are both
large organizations with  excellent  technical  capabilities.   Therefore,  analyses of
technical and economic feasibility are best performed by  their  resident technical
staff.    No  process-specific  source  control  implementation  avenues have  been
identified.

9.3  Summary

Table 9-1  represents  a  summary  of proposed source control methodologies for the
epichlorohydrin manufacturing industry. Each  method was rated for its effectiveness,
extent of  current  use  and future application  potential.  Based on  these  ratings, a
current reduction index  of 3.1  on  a  scale  of 0-4 (78 percent) was derived, which  is
indicative  of  the  high   level  of  waste  reductions  already  achieved  by  the
epichlorohydrin industry. (The current reduction index represents  the amount of waste
that was reduced compared to the waste  volume that  would currently be  generated
without all the measures listed and their current level of application.)  It appears that
by implementing additional waste reduction measures, the  amount  of waste currently
being generated  can  be  further  reduced  to  the  level characterized  by  a future
reduction  index  of 0.7 to 0.9 (18  to  22 percent reduction  from current  waste
generation levels).  Potentially, the most effective  measures for  achieving reductions
in waste are  those  that are characterized by high value of the future reduction index.
As shown in Table 9-1, these include: use of an alternate allyl chloride reactor design,
further   application  of burning  the  chlorinated  waste  for HC1  and  heat  recovery,
additional  purification  of  propylene feedstock, reevaluation of chlorohydroxylation
reactor design and use of non-stick heat exchanger tubes.
                                    B4-15

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                    TABLE 1-1 SINURY OF SOURCE CONTROL NETHOOOL06Y FOR THE EPICHLOROHYORIN MNUFACTURIN6 INDUSTRY
03
f
I—"
ON
Hast* Stream
Heavy/Light Ends
Ally! Chloride
Production (')
Htavy Ends
Eplchlorohydrln
Production (')
Tirs
Ally! Chloride
Reactor (')
Equ1p«mt Cleaning
Hastes (»)
Spllli and Leaks
All Sources
( 	
1
1
1
I'-
|2-
|3-
!<•
1
|1.
12-
13.
1
1'.
12.
1
I'-
ll-
|3.
l«-
1
!'•
|2.
13.
l<.
1
1
• + --
1
«**«_*.__! M.*-k.J« 1 «_,, 1
Found Documentation j
| Quantity | Quality | Effe
Alternate reactor design |
Preheat the chlorine feed |
Recover the HCl/heatlng value |
Purify feedstock |
Overall |
Recover the HCl/heatlng value |
Use alternate process route |
Re-evaluate chlorohydroxylatlon |
Overall |
Alternate reactor design |
Recover the HCI/heattng value |
Overall |
Increase equipment drainage tlie |
Lower heat exchanger file twperature|
Non-stick heat exchanger tubes |
Use In-process H.X. cleaning devices |
Overall |
Use double Mchanlcal seals on puips |
Use leak detectors |
Enclosed saipllng and analy. systees |
Use vapor recovery systeis |
Overall |
All Methods
	 * 	
2 1
0 1
2 1
1 1
1.25 |
2 I
3 I
0 I
1.67 |
2 I
2 I
2.00 |
1 1
1 1
2 1
2 1
1.SO |
1 I
3 I
3 I
2 I
2.25 |
	 A 	
2 I
0 I
2 I
1 1
1.25 |
2 I
2 I
0 I
1.33 |
2 1
2 1
2.00 |
1 1
1 1
1 1
1 1
1.00 |
1 1
3 1
2 1
2 1
2.00 |
	 1 	
Waste | Extent of | Future | Fraction of | C
duct Ion | Current Use | Application | Total Haste | Re
ictlveness | | Potential | |
3 1
1 1
4 1
2 1
2.50 |
4 1
1 1
2 1
2.33 |
3 1
< 1
3.50 |
3 1
2 1
3 1
2 1
2.50 |
3 1
2 1
2 1
4 1
2.75 |

2 1
0 1
3 1
1 I
I 50 |
3 I
0 I
0 I
1.00 |
2 1
3 1
2.50 |
3 1
1 1
0 1
1 I
1.25 |
4 1
3 1
3 1
< 1
3.50 |

2 1 1
1 1 1
3 1 1
2 1 1
2.00 | 0.35 |
3 1 1
' 1 1
2 1 1
2.00 | 0.35 |
2 1 1
3 1 1
2.50 | 0.24 |
2 1 1
1 1 1
2 1 1
2 1 1
1.75 | 0.05 |
2 I I
1 1 1
' 1 1
1 1 1
1.25 | 0.01 |
1 LOO |
	 A 	 A 	
jrrent | Future Reduction
Index |
Index | Probable | Maxlftue |
1.5 |
0.0 |
3.0 |
0.5 |
3.0 |
3.0 |
0.0 |
0.0 |
3.0 |
1.5 |
3.0 |
3.0 |
2.3 |
0.5 |
0.0 |
0.5 |
2.3 |
3.0 |
1.5 |
1.5 |
3.9 |
3.9 |
3.1 |
	 A 	
0.8 |
0.3 |
0.8 |
0.8 |
0.6 |
0.8 |
0.3 |
1.0 |
0.7 |
0.6 |
0.8 |
0.8 |
0.4 |
0.4 |
1.5 |
o.e |
0.8 |
0.0 |
0.1 |
0.1 |
0.0 |
0.1 |
0.7 i
0.8 |
1
0.8 |
0.8 |
0.8 |
1
1
1.0 |
1.0 |
0.8 |
0.8 |
0.8 |
1
1
1.5 |
1
1.5 |
1
0.1 |
0.1 |
1
0.1 |
O.S |
(*) These waste streais Include listed  T  and/or  'K1 RCRA wastes.

-------
10.  PRODUCT SUBSTITUTION ALTERNATIVES

There  does not appear  to  be any  viable  alternative for epoxy resins, a  principal
consumer of epichlorohydrin.  Epoxies have uniquely desirable physical properties, such
adhesiveness combined with toughness and resistance to chemical attack.  It  would be
difficult to find an epoxy substitute of comparable quality.

Approximately 19%  of the crude epichlorohydrin produced is used to make synthetic
glycerol.  Glycerol has wide  applications, as listed in Section  4.  The  alternative to
synthetic glycerol is the  glycerol obtained as a by-product during the  production of
soaps from animal and vegetable fats and oils (a principal source of glycerol prior to
1948).  Alternatively, sorbitol offers a viable substitute for glycerol in pharmaceutical
and cosmetic applications.

11.  CONCLUSIONS

As  is the case with other  organic  chemical processes, -the  epichlorohydrin  industry
appears to have reduced  their wastes considerably by implementing the source control
techniques noted.  However, it is also apparent that moderate  further reductions are
possible.  Based on the available informatipn, it appears  that  the following methods
deserve further consideration:

     o     Alternate allyl chloride reactor design to provide more mixing.
     o     Combustion of waste with attendant HC1 and heat recovery.
     o     Use of purer feedstock.
     o     Reevaluation of kinetics and design for chlorohydroxylation reactor.
     o     Use of non-stick heat exchanger tubes.

The identified product substitution alternatives were natural glycerol from  vegetable
fats and oils instead  of from epichlorohydrin, and use of sorbitol  in place  of glycerol.
                                    B4-17

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12.   REFERENCES

Anonymous. 1985a  Chemical Engineering Progress, 81(7):7.

	. 1985b  Chemical Engineering Progress, 81(7):104-5.

Bates,  R.E. 1978.  Epichlorohydrin  manufacture and use.  Industrial Hygiene Survey.
NIOSH.

Buienie,  J.C.,  and Crenne, N.   1965.   Fr. Pat. 1,447,267 (June 1, 1965)  to Societe
Chimique des Usines Rone-Poulenc.

Brzezicki,  A.,  et  al.  1984.   A mathematical model  of epichlorohydrin  synthesis.
Inzynieria Chemiczna Procesowa. 5(2):  201-14.

DeBenedictis,  A.  1979.  Allyl  chloride.  In Kirk-Othmer Encyclopedia of Chemical
Technology. 3rd ed. vol. 5, pp. 763-769. New York, N.Y.:  Wiley.

Faith,  W.L., Keyes, D.B.,  and Clark, R.L.  1975.  Industrial Chemistry, 4th ed.   New
York, N.Y.: Wiley.

Furman,  K.E., Fiach, H., and  Hearne, G.W. 1958.  U.S. Pat. 2,860,140 (Nov. 11, 1958).
to Shell Development Co.

Gruber,  G.I.  1975.   Assessment  of  industrial hazardous  waste  practices, organic
chemicals, pesticides and  explosives industries.  TRW Systems Group.  EPA-530-SW-
118C.  Washington, D.C.:  U.S. Environmental Protection Agency.

Henderson, J.B., and McKay,  N.H.  1952.  Paper presented at an annual meeting of the
American Chemical Society, Southwest Region, Little Rock, Ark.

Keller, R., et al. 1974.  U.S. Pat. 3,799,949 (March 26, 1974) to Degussa.

Kleemann, A., et al.  1971.  OLS (Ger. Pat. Disci.) 1,942,557 (March 18,  1971).  To
Degussa.

Mokrousua, I.Y., Oshin, L.A., and Tregard, Y.A. 1976. Kinet. Katal.  17(2):515.

Oshin, L.A., Shakhovtseva, G.A., and Krasotkina, B.E.  1975.  Neftekhimija.  15:281.

Phillips,  B., and Starchier, P.S.  1957.   Brit. Pat.  784,620.  (Oct. 9, 1957).   To Union
Carbide Corp.

Sakan, S.,  Sano, M., and  Hattori, K.   1970.  Jpn. Pat.  7,017,645 (June 18,1970). To
Japanese Chemical Industries.

SRI.  1982. Stanford Research Institute. Chemical Economics Handbook, 1982. Menlo
Park, Calif.: Stanford Research  Institute.

Steen, D.E. 1960.  U.S. Pat.  2,966,525 (Dec. 27 1960).  To Monsanto Chemical Co.
                                    B4-18

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USDC.  1985.  U.S. Department of Commerce, Bureau  of  the  Census.   Industrial
organic chemicals. In 1982 Census of manufacturers.  MC82-I-28F.  Washington D.C.:
U.S. Government Printing Office.

13.   INDUSTRY CONTACTS

S.L. Arnold, Manager, Environmental Information Clearinghouse, Dow Chemical Co.
Midland, MI.
                                   B4-19

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-------
1.    PROCESS: INORGANIC PIGMENTS MANUFACTURE
2.    SIC CODE: 2816
3.    INDUSTRY DESCRIPTION

As defined by Standard Industrial Classification  (SIC) 2816, the inorganic pigment
industry  includes  establishments  engaged  in  the manufacture  of  inorganic  black
pigments (except furnace and  channel carbon black), white pigments,  and colored
pigments.

3.1   Company Size Distribution

In  1982,  the  industry  included  106  establishments nationwide, and employed  11,200
people.  Roughly 63% of the total work force was employed at 13 large establishments.
Table 3-1 summarizes company size distribution.

                   Table 3-1  1982 Company Size Distribution
No. of employees per facility


No.
No.


of establishments
of employees
Total
t
106
11,200
1-19

43
400
20-99

39
1,800
100-499

17
4,100
500+

7
4,900
Source:    1982 Census of Manufacturers (USDC 1985).

3.2  Principal Producers

The principal producers of inorganic pigments in the U.S. include the companies listed
below (Versar 1980, Williams et al. 1976):

         American Cyanamid Co.                    Kerr-McGee Corp.
         CIBA-GEIGY Corp.                        NL Industries, Inc.
         E.I. du Pont de Nemours & Co., Inc.          SCM Corp.
         Hercules
                                   B5-1

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3.3  Geographical Distribution


The geographical distribution of  inorganic pigment  plants is shown in Figure 3-1 and
Table 3-2 below.  Half of the total number of plants are located in just five states, and
the majority are clustered  in the  industrialized regions stretching between Illinois and
New Jersey.
   Table 3-2  Geographical Distribution of Inorganic Pigment Plants by EPA Region
                EPA Region               Number of Establishments
                I
                II                                     24
                III                                    16
                IV                                    11
                V                                     22
                VI
                VII                                    3
                VIII
                IX              "                      10
                X
                National                             106 ({
Source:    1982 Census of Manufacturers (USDC 1985).

(a'    The discrepancy between the national total  and the sum of the ten EPA regions
      listed above is due to the exclusion of establishments in states with less than 150
      employees.


4.    PRODUCTS AND THEIR USES
Inorganic pigments include black, white, colored, colorless, and metallic pigments and
are used for a variety  of decorative, protective, and functional  purposes.  They are
used for automotive finishes, industrial coatings, oil and latex paints, and many paper,
plastic, rubber, glass, cement,  and porcelain  products  (Scheik 1982).   A  list  of the
various inorganic pigments produced in the U.S. is given in Table 4-1.
                                     B5-2

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                           VIII
CO
tn
i
             CHJ 0-2
/tt 6-10
JZtA over 10
                    Roman numerals show EPA regions

    Figure   3-1  Inorganic Pigment Plants in the U.S.

-------
                Table 4-1 Inorganic Pigments Produced in the U.S.
                                                           Quantity Produced
Product                                                    (thousands of tons)
Titanium pigments                                                 886.0

Other white opaque pigments, including basic                           6.6
   carbonate and sulfate pigments, white lead, excluding
   white lead in oil
   Zinc oxide pigments                                             128.6

Chrome colors
   Chrome oxide green                                               4.0
   Chrome yellow and orange                                        21.0
   Molybdate chrome orange                                          6.2
   Zinc chromate
   other chrome colors

White extender pigments, including barytes, blanc                      51.1
     fixe, whiting colors and lakes and toners
Color pigment other than chrome colors, lakes, and toners
   Iron oxide pigments
   Colored lead pigments
   Carbon black (excluding furnace and channel carbon                  5.0
     black and charcoal)
   Cadmium sulfide pigments                                         2.9

Ceramic colors and all others
Source:    1982 Census of Manufacturers (USDC 1985) and industry comments.


5.   RAW MATERIALS


The  raw materials used  in the production of inorganic pigments consist of  a broad

range of chemicals including basic organic and inorganic chemicals as well as a variety

of ores and minerals. These  materials,  along wih their respective consumption rates,

are listed  in Table 5-1.
                                    B5-4

-------
   Table 5-1  Raw Materials Used in the Production of Inorganic Pigments for 1982
                                                             Consumption Rate
Raw Material                                                 (thousands of tons)


Organic chemicals
   Alcohol, ethyl                                                       *
   Other alcohols                                                      *
   Plastic  resins                                                      8-3
   Other organic chemicals                                             *

Inorganic chemicals
   Acids, except spent acids
     Hydrochloric acid                                               13.6
     Hydrofluoric acid                                                 *
     Nitric acid                                                      5.7
     Phosphoric acid                                                  1.0
     Sulfuric acid                                                   254.8
   Ammonia                                                          5.1
   Chlorine                                                         304.1
   Phosphorus                                                          *
   Sodium carbonate                                                   *
   Sodium hydroxide                                                 62.1
   Salt in brine                                                        *
   Acetylene and other industrial gases compressed and                   *
     liquified,  including argon, carbon dioxide, nitrogen,
     nitrous oxide, etc.

Crude  materials
   Bauxite                                                            *
   Phosphate rock                                                      *
   Sulfur                                                              *
   Sulfuric acid sludge                                                 *
   Zinc and zinc based alloy refinery shapes                             *
   Iron and ferrous alloy ores                                           *
   Nonferrous  metal ores                                               *
   Crude non-metallic minerals                                         *

*    No data
Source:    1982 Census of Manufacturers (USDC 1985).
6.    PROCESS DESCRIPTION

There are a variety  of processes  used  to  produce the pigments listed in Table 4-1.
Since  titanium dioxide (TiO2)  is  the   most  widely  used  inorganic  pigment,  the
                                    B5-5

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remainder  of  this study will  focus  on the  production  of  TiO2 and associated 'Source
reduction practices.

Titanium dioxide is  produced by  two major processes -  the sulfate  process and the
chloride process. While both processes are widely used at present, the  chloride process
is  likely  to displace the sulfate process in  the future.  The sulfate process has been
hurt by a combination of economic,  environmental  and  market forces. Environmental
problems and waste disposal costs associated with the large amounts of spent acid and
iron salt wastes which are produced during the sulfate process have  resulted in the
closure of  certain U.S.-based plants  (Ryser  1985).   In addition, TiO£ pigment from the
chloride process is preferred for use  in paint products, which accounts for roughly half
of TiO2 use. For these reasons, further discussion  will be limited to the  production of
TiO2 by the chloride process.

In the  chloride process, two types of raw materials may be used.  Ilmenite ore, which
contains  40-70% TiO2, is one raw  material.   The other  is either rutile ore or upgraded
ilmenite  ore, both of which contain  more than 90% TiO2 (Versar 1980, USEPA 1980a,
Ryser 1985). The ore is mixed with coke and reacted with chlorine at 800 to 1000°C in
a fluidized bed reactor.  The reaction produces titanium tetrachloride, carbon dioxide,
carbon monoxide, iron chlorides,  and small amounts  of  other  metal  chlorides.   The
gases are  cooled stepwise to remove impurities.   The first cooling  step lowers the
temperature to 250°C to remove iron and other  heavy metal  chloride.   These are
removed as solids by  filtration.   Further cooling  of the remaining gases to ambient
temperatures  condenses the titanium tetrachloride  and some dissolved chlorine.   The
uncondensed gases remaining include carbon  monoxide, carbon dioxide,  unreacted
chlorine, hydrochloric acid, some  titanium  tetrachloride, and other trace gases.   The
uncondensed gas stream  is scrubbed before being discharged to the atmosphere or
incinerated for its CO (heating) content. The condensed titanium tetrachloride stream
contains  impurities  such as aluminum chloride and silicon  tetrachloride  which are
removed through distillation.   Copper  and/or  proprietory organic complexing agents
are added  during the  distillation  step to aid in the decomposition of trace phosgene
(present  as an  impurity) and to help separate  titanium tetrachloride from other
chlorides.

The purified  titanuim  tetrachloride product is then  oxidized  with air  or  oxygen at
150QOC  to  produce  titanium  dioxide and  chlorine gas.   The  chlorine  gas  is often
                                    B5-6

-------

CHLORINE







COPPER —














UPSRADED ILNCNITE
OR RUTILE 0«C
REACTION
1
COOLINI
V
1
FILTRATION
1
COOLINI AND
CONDENSATION
-» 4 rl
PURIFICATION
AND
DISTILLATION
©
1 r-
OXIDATION

TIOj SOLIDS
SEPARATION
1
^ f~
•ASHIM AND
FILTRATION
©
1



•1 	 COKE




LituiD n

©©
IIUIO
TICL.


	 AIR/ OXYOEN

LINE OR CAUSTIC -i
CHLORINE
j 	 J ABSORPTION ' 	 ^ tgmm
i LIRUIFICATIO* 0
1
t 1
' HTPOCHLORITC
DECONPOIITION

^ '
!
|     HILLINI
    no, PIIHCNT
                                                    PROCESS «ASTE CATEOORIEi:
                                                   I 0   IASTENATER
                                                   I 0   FILTER ILUDKI
                                                   I 0   DIITILULTION IOTTONI
                                                   | 0   VENT IAIEI
             Figure 6- 1   Titaniui Dioxide Prediction by the Chloride Process
                              B5-7

-------
recycled to the chlorination reactor.  The solid titanium dioxide is separated from the
gas phase using  filters, cyclones,  or  other proprietary methods.  The gases from  the
oxidation reaction are scrubbed with lime or caustic soda before being discharged to
the atmosphere.   The solid  titanium dioxide  is then  washed  with  alkali  to  remove
hydrochloric acid and  residual chlorine.  It  is  then dried,  milled,  coated  with  an
inorganic oxide such  as  alumina to increase its weathering resistance, and packaged
(Versar 1980, USEPA  1980a).

7.    WASTE DESCRIPTION

The major waste streams along with their process origins and  compositions are listed
in  Table 7-1.  Air pollutants are  generated  during oxidation,  distillation, and drying.
The major air pollutants produced include titanium  tetrachloride,  hydrogen chloride,
and carbon monoxide  from the chlorination and oxidation reactions,  as well as chlorine
and particulates from drying  and  milling.   The  gases from the  chlorination  and
oxidation reactions are  normally  treated in wet  scrubbers producing a  wastewater
stream which must undergo further treatment.

Wastewater is also generated from washing, filtering, drying,  milling,  and equipment
cleaning, and from processing of distillation bottoms.  Wastewater is typically  treated
by in-plant systems  using such conventional treatment  processes as pH  adjustment,
precipitation, and clarification. At plants where ilmenite ore  with a high iron content
is used as a raw material, large amounts of acidic iron chloride wastes are produced.
This waste stream  has been disposed of by deep-well injection or ocean dumping at
some  locations.   Solid  wastes produced  during  the  chlorination   reaction  include
unreacted  ore, coke, and  metal salts.   These  are  either recycled  or disposed  of in
landfills.   For  those  plants using ilmenite with a high  iron content,  ferric  chloride
waste poses a major  disposal problem.  However,  markets exist  for  the use of ferric
chloride as a flocculant or a wastewater treatment chemical. In these  application,
ferric chloride  can be used to  clarify drinking water,  to treat sewage, and to  remove
phosphorus  from  wastewater (Du  Pont 1985a).  Du Pont presently  recovers and sells
roughly 100,000  tons per year of ferric chloride from one  of  its  titanium  dioxide
plants.  While the supply of ferric chloride appears to be greater  than its demand as a
wastewater treatment chemical, this market does absorb large quantities of the waste.
Ferric  chloride produced by titanium dioxide plants competes  with the ferric chloride
                                    B5-8

-------
                          Table 7-1 Manufacturing Wastes From TiO2 Production (Chloride Process)
    No.    Waste Description
                       Process Origin
     Composition
Concentration (lb/1000 Ib product) RCRA
 95% TiO2 ore   65% TiO2 ore     Codes
i
\O
Chlorinator wastes   Chlorination reactor
           Chlormator scrubber  Chlorination gas
           wastes               scrubber
           Distillation
           Oxidation scrubber
           wastes

           Finishing
           operations
           wastes
                     Distillation
                     Oxidation tail gas
                     scrubber

                     Washing,  filtering,
                     drying, milling
unreacted ore                  16
coke                           37
iron chlorides                   2
other metal chlorides
titanium tetrachloride          25
HC1                         130

titanium tetrachloride          25
HC1                           50
chlorine
phosgene

metal oxides and chlorides
organic complexing agents

hypochlorite
titanium dioxide                10
NaCl + NaoSO^                16
                                                                                                    25
                                                                                                    68
                                                                                                   380

-------
produced  by the steel industry during steel pickling operations for the wastewater
treatment market.

8.    WASTE GENERATION

The  1980 waste generation rates from  the production of titanium dioxide by  the
chloride process are given in Table 7-1.   The exact  types  and quantities of wastes
produced  are  dependent  upon the raw ore  used  in  the process.   Waste  rates  for
processes  using high quality ore (95% TiC^) and lower  quality ore (65% TiC^) are both
given.  The  major difference in waste output between the two is the amount  of ferric
chloride produced.   Plants using  lower grade ilmenite  ores  produce much  greater
amounts of iron chloride waste  than do plants using high grade ore.

9.    WASTE REDUCTION THROUGH SOURCE CONTROL

9.1   Description of Techniques

The  wastes  which are  produced during the manufacturing of titanium dioxide by  the
chloride process are listed in Table 7-1.  Various source  reduction methods available
for reducing these waste streams are discussed below.

In addition to the  waste  reduction measures classified as being process changes or
material/product substitutions, a  variety of waste reducing measures labeled  as "good
operating  practices" have  also been included.  Good operating practices are defined as
being procedural or institutional  policies  which result in a reduction of waste.   The
following  items highlight the scope of good operating practice:

      o    Waste stream segregation
      o    Personnel Practices
                Management initiatives
                Employee training
      o    Procedural  measures
                Documentation
                Material  handling and storage
                Material  tracking and inventory control
                Scheduling
                                    B5-10

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     o     Loss prevention practices
                Spill prevention
                Preventive maintenance
                Emergency preparedness

For each  waste stream, good operating practice  applies whether  it is  listed  or not.
Separate listings have been provided whenever case studies were identified.

9.1.1 Ferric Chloride Waste

As  mentioned  previously,  for plants using  ores  with  high  iron  content,  the ferric
chloride produced  during the chlorination reaction  poses a major disposal problem.  In
addition, chlorination of the unwanted iron represents an economic disadvantage since
the chlorine must  then be disposed of as waste.  Source reduction  measures to reduce
the amount of ferric chloride produced include:

     o     Use of  high-purity ores.
           The  use of a  high purity  ore will minimize  the  amount  of  impurities
           entering the  process,  greatly reducing  waste  generation  rates.    As
           discussed earlier,  two types  of ore, ilmenite and  rutile, have traditionally
           been used to produce titanium dioxide by the chloride process.

           Plants   utilizing ilmenite  ore  generate  large  amounts of  iron  chloride
           wastes. Ilmenite ore contains  40-70%  titanium dioxide and large amounts
           of iron.  During  the chlorination reaction this  iron is  converted  to iron
           chlorides which are either sold  as a by-product (see below) or disposed of as
           a waste, often by deep well injection.

           Rutile  ore, containing  greater than 90%  titanium  dioxide and  only  small
           amounts of iron, results in substantially less waste generation.  Rutile  ore
           however, is  much  less abundant than ilmenite ore,  and  is more  expensive.
           To achieve the benefits of a higher purity ore, ilmenite can be  blended with
           ferro-titanium  slag  to  produce a raw material of  roughly 75% titanium
           dioxide (McNaulty 1986).
                                    B5-11

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           A third  type  of  ore  called anatase (25%  titanium-dioxide) is being tested
           for  use  at a  few titanium  dioxide  facilities (Ryser  1985).    The main
           advantage of  using anatase is economic since it may only cost 10% as much
           as rutile ore.  The process, designed by Du Pont, is a modification of an old
           chloride  route  developed  several  decades  ago.   No  other  technical
           information is available and the comparative  waste generation character-
           istics are unknown.

           Recovery of valuable products.
           Chlorine  can  be  recovered from  ferric chloride by  oxidizing the material
           with oxygen or air in a fluidized  bed reactor.  Based on pilot plant tests,
           99% recovery of chlorine was achieved (Ogawa 1980).  An important part
           of  the process was that the ferrous chloride was mixed  with iron oxide
           particles (also produced  in the reaction)  before being introduced into the
           reactor.  The oxide  acted as a catalyst and increased the  reaction rate.
           The major disadvantage  of  the process,  however, was low conversion of
           oxygen (only  75  percent). Oxygen, if present with  the recycled chlorine,
           would  increase the amount of coke required in the chlorination reactor and
           the  amount of off-gas generated.  Going to a  larger oxidation  reactor  was
           expected to  increase  the  conversion of  oxygen  to 85 percent.   It  was
           reported  that a Canadian firm attempted  to recover chlorine from ferric
           chloride in the early 1970's but that no current work is being performed*.
           Currently, Du Pont continues to  investigate this  option but their efforts
           have not yet overcome the difficulties encountered in previous attempts.

           Another process  for converting ferric  chloride  waste into valuable products
           is to first slurry the waste with water and then spray the slurry into  a
           roasting  furnace operating  at  1000°C (Setoguchi  1980).   The reaction
           produces iron oxide  and HC1 containing  gases  which  are scrubbed  to
           produce  18 weight percent hydrochloric  acid.   This  acid can be  used
           elsewhere in  the  facility or  further processed  to produce chlorine  and
           hydrogen (for example, using the  Kel-Chlor or electrolysis process).  Fuel
           for  operating the  roasting  furnace  can  be taken  from  the  chlorination
           reactor off-gas which contains a high level of CO.
Confidential source 1985: Personal communication.
                                   85-12

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     o     Ore pretreatment.
           Ilmenite  is the major type of titanium ore available  domestically.   As
           noted above,  ilmenite often has a high iron  content which  leads  to  the
           generation of iron salts as a waste. One possible way to reduce this waste
           stream is to pretreat the  ore prior to  digestion  to  remove  the iron.
           Ilmenite  can  be  converted  to  an  alkaline earth titanite, such as sodium
           titanate.  When sodium titanate is used in the chloride process, the waste
           produced  is sodium  chloride or sodium sulfate, which leaves the process as
           inert  dissolved  solids (Versar 1980).  While this  process  is attractive
           environmentally, it may not be practical from  an economic standpoint*.

           Other methods of  upgrading ilmenite ore for TiO2 production are  the
           Benilite  process  (which  has  been commercialized  in  India, Japan,  and
           Taiwan) and the Murso process. In both processes,  iron is leached  out of
           the ore  using  hydrochloric  acid  thereby producing a feed  material of
           greater than 90%  titanium dioxide.  After the iron is leached out as ferrous
           chloride,  it  is  converted  to  iron  oxides and  hydrochloric  acid.    The
           hydrochloric  acid  can  be   reused   within  the  process  (Versar  1980).
           Pretreatment of  the  ore (oxidation and reduction)  and addition of ferrous
           chloride  to the hydrochloric  acid  leach  solution have been  reported to
           increase  or improve the teachability of the ore and reduce fines generation
           (Sinha 1980).

9.1.2 Scrubber Wastes

Air emissions are commonly  treated in a wet scrubber, producing substantial amounts
of wastewater. In the production of  titanium dioxide  by the chloride process, scrubber
water accounts  for  as much as  20  percent of the total  wastewater stream (USEPA
1980a).  Unreacted chlorine gas from the chlorination reactor is removed  from the  tail
gas by scrubbing with either water  or  caustic.  Reduction of chlorine content in  the
tail gas  will result also in reduction of scrubber wastewater, treatment chemical usage
and chlorine loss.  The discharge of unreacted chlorine in the tail gas can be reduced
or eliminated by  chlorine liquefaction  achieved by pressurization  and subsequent
refrigeration to condense chlorine from the tail gas (USEPA 1980a).
*E.I. du Pont de Nemours & Co. 1986: Personal communication.
                                   B5-13

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9.1.3 Filtering and Washing Wastes

The ore impurities will at some point have to be separated from the desired product,
resulting  in  a  waste  stream  which  must  be  treated.   A  substantial  portion  of
wastewater generated in  TiO2 plant is from the rinsing and washing of the pigment.
Rinsing  and  washing  serves  the  purpose  of  removing   residual  chlorine   and
hydrogen  chloride,  soluble salts, and other  impurities  from the final  product.   The
amount of impurities is largely controlled by  ore composition and the efficiency of the
upstream  distillation  process to purify titanium tetrachloride.  However, the use of
water can be reduced  using countercurrent rinsing and the amount of pigment carry-
over can be reduced by using  more efficient filtration.

9.2  Implementation Profile

The major source of waste from titanium dioxide pigment manufacturing is simply the
impurities separated  out  from  the ore.   Thus, the most important source control
methods are concerned  with the quality of ore used.   The  use  of  high-purity ores
reduces the amount of impurities  introduced into  the  process.   However, a manu-
facturer may have little control over  the  quality of  the  ore  which  is used if the
availability  of  high-puriy ore is limited.  In this  case,  ore  pre-treatment  and the
recovery of chlorine and iron oxide gain significance.  The use of efficient rinsing and
washing  techniques  for  product purification  along  with the reduction  of scrubber
wastes through chlorine recovery from the tail gas are, in essence, water conservation
measures  and,  as such,  may  not  be prime  waste minimization  issues  of current
environmental concern.

9.3  Summary

The  waste sources  and their respective source control  techniques are summarized in
Table 9-1. The ratings listed in this table are based on a scale of zero to four and are
used to  evaluate each technique  for its  waste reduction effectiveness, extent of
current use, and future application potential. The ratings were derived by the project
staff based on the available information.

It appears that the current level  of waste minimization  in  titanium  dioxide manu-
facturing  based on the chloride process is significant. This is evidenced by  the current
                                    B5-14

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                    TABLE 9-1 SUMMARY OF SOURCE CONTROL METHODOLOGY FOR THE TITANIUM DIOXIDE MANUFACTURING INDUSTRY
1

1
| Ferric Chloride
Haste


Scrubber Wastes

Filtration and
Washing Wastes


All Sources

Control Methodology
J
1. Use high-purity ore
2. Recover products from «aste
3. Pretreat ore to remove iron
Overall
t Chlorine Hquifaction for reuse
Overall
|1. Use more efficient filters
2 Use efficient washing/rinsing methods
3. Process control/automation
Overall
All Methods
round Documentation |
	 	 - — i
Quantity | Quality f
31 3|
21 2|
3 1 3 |
2.67 | 2.67 |
1 1 2 |
1 00 | 2.00 !
1 | 2 I
2| 2 |
1 1 11
1.33 I 1.67 |

Haste 1 Extent of I Future | Fraction of

Effectiveness | | Potential |
« 1 2 1 1 1
31 0| 1 |
2 I 2| 21
3.00 | 1.33 | 1.33 | 0.05
2 1 2 | 1 |
2.00 I 2.00 | 1.00 | 0.20
1 1 2 1 2 1
3| 3| 1 |
21 2 ! 2 |
2.00 | 2.33 I 1.67 | 0.75
| 1.00
Current | future Reduction Index |

Index j Probable | Maximum |
2.0 | 0.5 | I
0 0 | 0.8 | 0.8 |
1.0 | 0.5 | |
2.0 I 0.6 | 0.8 I
1.0 | 0.3 | 0.3 |
1.0 I 0.3 | 0.3 I
0.5 | 0.3 | |
2 3 | 0.2 | 1
1.0 | 0.5 | 0.5 I
2.3 | 0.3 | 051
2.1 | 0.3 | 0.5 |
(*)  These streams include listed "F1 and/or "K" RCRA wastes.

-------
reduction index  (CRI) of 2.1 (53 percent), which is a measure  of reduction of waste
that would have been generated if none of the listed methods  were applied at their
current level of use.

Future  reductions appear to be rather modest  as  evidenced  by the  future  reduction
index (FRI) of 0.3 and 0.5 (8 to 12 percent).  FRI is  the  measure of waste  reduction
achievable through the implementation of the listed techniques to their full rated
potential.  From  the standpoint  of  future  application,  the  most  promising source
control techniques found were product recovery from  waste  (Cl2  and  Fe2O3), ore
pretreatment to remove iron, and use  of high purity  ore.

10.  PRODUCT SUBSTITUTION ALTERNATIVES

10.1 Paint Usage

Paint and paint-related  products, such  as automotive finishes, account  for a large
portion of total titanium dioxide pigment  usage.  No substitute for  titanium dioxide
was identified  in  paint pigment application.  However,  any reductions in the use of
paint will have a direct  impact on the demand for titanium  dioxide.  For additional
discussion of this issue  the  reader is referred to  the study  of paint  manufacturing
included in this appendix.

10.2 Paper Products

Paper products account for roughly 18% of the  total  use of titanium  dioxide, which is
the  most widely used inorganic pigment  (USEPA  1980a).   In  paper manufacturing,
titanium dioxide (TiO2) is  used as an opacifier. In  place of TiO2, alumina or silica
clays have been tried, however the main advantage of TiC>2 over the  other substances
is that it has a superior reflectance.

11.  CONCLUSIONS

The facilities using the chloride process for production of titanium dioxide  appear to
have minimized their waste significantly  by using high-purity  ore.   Water use  was
reduced by  the application of efficient washing and rinsing  techniques.  Any  future
reductions appear to be modest, in the range of 8 to 12 percent,  primarily  resulting
                                    B5-16

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 from wider adoption of ore pretreatment, use of high purity ore and, possibly, recovery

 of  C\2  and Fe£O3  from  FeCl3  waste  stream  (potentially,  the  most  effective
 technology which has not yet been commercialized).


 12.REFERENCES

 Campbell,  M.E., and  Glenn,  W.M.,  1982.  Profit from pollution prevention.  Toronto,
 Canada: The Pollution Probe Foundation.

 E.I.  Du  Pont  de Nemours and  Co.  1985a.  Statement  to  Tennessee water quality
 control board  concerning  consideration of adoption of  rules of the  water guality
 control board.  Chapter 1200-4-6. Underground Injection Control.  Feb. 7, 1985.

 	 1965b Ocean dumping permit.  Certified report on implementation
 plan (special condition  - 7(a)(2)).  Submitted to the Marine and  Wetlands Protection
 Program.  U.S. Environmental Protection  Agency, Region II, New York, NY.  June 13,
 1985.

 FTA, 1983. Frontier Technical Associates, Inc.  Development document for effluent
 limitations guidelines and standards for the inorganic chemicals point source category.
 Contract no.  68-01-6701,  revised  working draft  for  Office  of Water and  Waste
 Management.  Washington, D.C.:  U.S. Environmental Protection Agency.

 Ogawa, Minour et. al. 1980.   A study  of titanium resources  and  its  chlorination
 process.   In Titanium' 80.   Science  and Technology.   Proceedings  of the Fourth
 International Conference on Titanium.  3rd vol.  Kyoto, Japan.  May 19-22, 1980.

 Ryser, J. 1985.  New feed,  new technique enliven the TiO9 scenario.   Chem. Enqr.
 Nov. 25, 1985:  18-20.

 Scheik, R.C.,  1982.  Inorganic pigments.   In Kirk-Othmer Encyclopedia of  Chemical
 Technology. 3rd ed., vol. 17, pp. 788-838.  New York, N.Y.: Wiley.

 Sinka,  H.N. 1980.  Effects  of oxidation and reduction temperatures, and the addition
 of ferrous  chloride  to hydrochloric  acid, on the  leading  of Ilmenite.  In Titanium' 80.
 Science  and technology.   Proceedings of  the  Fourth  International Conference on
 Titanium.  3rd vol.  Kyoto, Japan May 19-22, 1980.

 Setoguichi, Masahiko  1980.  Pollution  prevention for titanium tetrachloride plant. In
 Titanium' 80.   Science and  technology.   Proceedings  of the  Fourth  International
 Conference on Titanium. 3rd vol. Kyoto, Japan  May 19-22, 1980.

 UNESC,  1979.  Urated Nations Economic  and Social Council.  Production of titanium
 white from ilmenite by the  sulfate method with reprocessing of the quantitatively
 most import waste products.  ENV/WP.2/5/Add. 21.

 USDC,  1985.   U.S.  Department of Commerce, Bureau  of  the  Census.  Industrial
 inorganic chemicals.  In 1982  Census of manufacturers.  Washington, D.C.:   Govern-
 ment Printing Office.

USEPA,  1979.  U.S. Environmental Protection  Agency, Office of Water and Waste
Management.  Development documents for proposed effluent guidelines, new source

                                   B5-17

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performance  standards,  and pretreatment standards  for the paint formulating  point
source category.   EPA-440-1-790-0406.   Washington,  D.C.:    U.S.  Environmental
Protection Agency.

	, 1980a.  U.S. Environmental Protection Agency, Office of Water and Waste
Management. Development documents for effluent limitation guidelines and standards
for the inorganic chemicals point source category.   EPA-440-1-79-007. Washington,
D.C.: U.S. Environmental Protection Agency.

	, 1980b.  U.S. Environmental Protection Agency, Office of Research and
Development. Treatability Manual;  Vol. 2.  Industrial descriptions.   EPA-600-8-80-
042b. Washington, D.C.: U.S. Environmental Protection Agency.

Versar, 1980. Versar, Inc.  Multimedia assessment of the inorganic chemicals industry.
Cincinnati, Ohio: U.S. Environmental Protection Agency.

Williams, R., et  ah, 1976.  Economic assessment of potential hazardous waste control
guidelines for the inorganic chemical  industry.  Arthur D. Little, Inc.  EPA-530-SW-
134C. Washington, D.C.:  U.S. Environmental Protection Agency.


13.  INDUSTRY CONTACTS

Confidential Source

C.R. Steward, E.I. Du Pont de Nemours & Co. Wilmington, DE..
                                   B5-18

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 1.    PROCESS: METAL SURFACE FINISHING
 2.    SIC CODE: 3471
 3.    INDUSTRY DESCRIPTION

 Metal finishing is  a part of the  plating and polishing industry classified under Standard
 Industrial Classification (SIC) 3471.   This  industry  is comprised  of establishments
 primarily engaged in all  types of electroplating, plating,  anodizing, coloring,  and
 finishing of metal and formed products for the trade.  Most of the work performed by
 this industry is done  on materials owned by  others. Though metal surface finishing is
 classified under SIC  3471, metal finishing operations are performed by  many other
 industries included in SIC groups 34 through 39 (USEPA  1980).  The metal finishing
 process  includes  some  44  unit  operations  and  only  the  metal  surface  finishing
 operations that use chemical means are discussed in this report.

 3.1   Company Size Distribution

 Since metal surface finishing operations are  performed by various industries classified
 under many SIC codes, company size distribution data for metal surface finishing as an
 industry was  not  separately  available.   In  1980,  there  were approximately  160,000
 manufacturing facilities  in  the U.S.  which were covered by the  metal  finishing
 category (USEPA  1980).  These facilities varied greatly in size, age, and number of
 employees.  They  ranged from  very small independent job shops  with less than  ten
 employees, to small shops  within large corporations, to large facilities employing large
 work forces.

 3.2   Principal Producers

 The metal surface finishing  industry is  dominated by small job  shops employing less
 than 20 employees each.  There are no  major producers who control  a large share of
 the market.

 3.3  Geographical Distribution

The geographical distribution of the metal surface  finishing industry was not available
due to the reasons  stated above.
                                    B6-1

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4.
PRODUCTS AND THEIR USE
The  metal surface  finishing  industry deals mostly with the treatment of metallic or
non-metallic products manufactured by  others.   Each  product requires  a specific
process sequence  to  obtain  the  desired  physical, chemical, or aesthetic properties
desired by the  user.  The  principal products  of  the  metal surface finishing industry
include:
      Printed circuit boards
      Coil coating
      Automotive parts
                                      Kitchen utensils
                                      Jewelry
                                      Mechanical (non-automotive) parts
5.   RAW MATERIALS

Reagents       phosphoric  acid,  secondary or  tertiary metal  phosphates, sodium
                dichromate, sodium nitrate, sodium cyanide, barium chloride, sodium
                chloride, sodium carbonate, sodium cyanate, ammonia, silicon tetra-
                chloride, zinc oxide, chromic acid

Accelerators    quinoline,  toluidine,  nitrophenols,  various  oxidizing agents such  as
                peroxides,  and sulfites

Metals          zinc, aluminum,  chromium,  cadmium, magnesium,  iron, nickel,
                copper, silver, molybdenum, vanadium, tungsten

Alloys          tin, lead-tin alloys, bronze, brass

6.   PROCESS DESCRIPTION

Metal  surface  treatment  consists  of  various  processes   such  as  electroplating,
electroless  plating,  anodizing, chemical conversion  coating,  cleaning, etc. (USEPA
1980, BCL  1976,  Schneberger 1981,  Durney 1984).   Since  electroplating and metal
surface  cleaning  are discussed   in  separate  studies  in this  appendix,  this  study
considers only chemical surface  treatments such as  electroless plating,  chemical
                                     B6-2

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conversion  coating,  etching,  chemical milling,  and some  forms of  case hardening
treatment.  Metal surface treatment is performed mainly to modify the metal surface
to  be  less  reactive  and more corrosion-resistant and  is dependant on  the  type of
required surface modification.  All  the metal surface treatment processes have three
basic steps:  surface cleaning or preparation, surface treatment, and rinsing or post-
finishing operations.   The cleaning and post-finishing operations are  specific  to the
surface  treatment method  used.   The  following sections  describe various  surface
treatment methods with the exception  of coil coating. All chemical surface treatment
operations are  essentially batch operations, where the metal object is dipped in a bath
containing various reagents to achieve  the required surface modification.

6.1  Electroless Plating

Electroless  plating allows for the deposition  of  metal  on an object's surface  without
the use of external electrical energy.  This  is achieved by a chemical reduction process
which  depends upon  the catalytic reduction of a metallic ion in an aqueous solution.
This process has found widespread  use due to several  advantages  over conventional
electroplating which  include ability to  produce a  uniform coat on all areas of the part
regardless  of its geometry  without the need to supply external  electrical  energy.
Copper and  nickel electroless plating are the most common.

The basic  ingredients  of  electroless  plating  solutions  are  a  source of  metal ions
(generally copper or nickel), a complexing agent to maintain ions in  solution  at the
operating pH value, a compatible reducing agent, a material to adjust the  pH  of the
bath,  and   stabilizers,  wetters,  stress  relievers,  etc.   Table 6-1  lists the  bath
constituents for copper and nickel electroless plating operations.

The electroless plating operation consists of cleaning the object surface, immersing it
in a bath containing the previously described constituents for a specific period of time,
and then  rinsing the  object  (after removal from  the bath) to  remove process solutions
adhering to  the surface.

Plating bath solutions last only a few  hours because  catalytic particles precipitate in
the bath.  The bath life is usually increased by periodic filtration, and by the addition
                                     R6-3

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                              Table 6-1 Bath Constituents for Copper and Nickel Eiectroless Plating
      Function
          Copper Plating Operation
        Nickel Plating Operation
 Metal ion source
 Complexinq agent
oReducing agent
ON
i
 pH adjuster

 Stabilizers


 Other additives
Cupric sulfate (3-15 g/1)


Rochelle salt (sodium potassium tartarate,
ethylenediaminetetracetic acid (EDTA), sodium
salts of EDTA, nitrilotriacetic acid, gluconic
acid, gluconates, triethanol amine,  n-hydroxy
ethylene diamine tetracetate (20-50 g/1).

Formaldehyde, paraformaldehyde, trioxane,
dimethylhydantoin, sodium and potassium
borohydride.

Sodium or potassium hydroxide

2-mercaptobenzothiazole, thiourea, methanol
Water soluble metal cyanides, polysiloxanes,
methyl dichloro si lane
Nickel chloride, nickel sulfate, nickel
sulfamate, nickel hydrophosphite

Lactic acid, dicarboxylates
Sodium hyposphosphite
Sodium or potassium hydroxide

Molybdic acid anhydride, arsenious acid,
hydroxyl amino sulfate, hydrazine.

Thiourea, soluble fluorides, alcohol
sulfonates, ethylene oxide  derivatives,
sodium sulfate.
 Source:    Development Document for Effluent Limitation Guidelines (USEPA 1980).

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of stabilizers.   The bath  is eventually dumped thereby generating  a  waste stream.
Other waste streams are generated by  rinsing operations and periodic cleaning  of the
process equipment.  Other electroless plating operations, such as vapor deposition, are
purely physical operations and are not considered in this report.

6.2   Chemical Conversion Coating

This operation includes phosphating, chromating, metal coloring,  and  passivating.  The
coating deposited on metal objects is for decorative or corrosion protection purposes,
and in some instances  to prepare the surface for painting.  The mode of operation and
waste generation are similar to the electroless plating operation described in Section
6.1.   The following sections  discuss the  four different chemical  conversion coating
methods listed above.

6.2.1  Phosphating

Phosphate coatings are  formed  on  the  surfaces of  iron, steel, galvanized  steel,
aluminum, and  electrodeposited zinc and  cadmium to promote adhesion  of organic
coatings, to  retard interfacial corrosion, to retain and enhance the performance  of
corrosion resistant oils, and to assist in cold deformation processes.  Small parts are
coated  in barrels  immersed  in the phosphating  solution  and large parts  are spray
coated  or continuously passed  through the phosphating solution.   The object to  be
coated  may be dipped  successively in a series of processing  tanks.

The phosphating solution consists of a phosphoric  acid solution of metal  dihydrogen
phosphate.  The coating time  and  temperature  depends on the type  of metal to  be
coated  and  whether  a spray  or  immersion coating  scheme  is  used.    Sometimes
accelerators (to  improve  quality), stabilizers (to prolong bath life) and oxidizing  agents
(to control the coating rate) are added  to the phosphating solution.

There are certain parameters,  such 'as the ratio of free to combined phosphoric acid,
total  acid,  metal-ion concentration, accelerator concentration,  and  the process
temperature that must be controlled to achieve a suitable coating  and maintain the
                                     R6-5

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integrity  of  the  bath.   The  coated  object,  after  phosphating,  may be  given a
conditioning rinse  with dilute chromic and/or chromic-phosphoric acid for surfaces to
be protected against corrosion, or an alkaline rust-inhibiting treatment  for objects to
be cold-deformed.  Concerns about the environmental effects  of chrome have  led to
the development of chrome-free rinses.  Though these are less effective  than their
chrome-containing counterparts, they are suitable for applications where corrosion is
not a major concern.

6.2.2   Chromating

Chromate  coatings  are  most  frequently  applied  on  zinc,  cadmium,  aluminum,
magnesium, copper, brass,  bronze,  and silver  to  minimize  rust  formation  and to
guarantee paint adhesion.  Chromate-type conversion coatings are  produced primarily
by a simple immersion process although  a spray or brush treatment can be used.

The chromating solution consists of chromic  acid, one or  two mineral  acids such as
sulfuric  or nitric, and  often  some  activating  compounds.    Chromate  conversion
                                                                      •
coatings are formed because the metal surface  dissolves to a  small extent, causing a
pH rise at the surface-liquid interface.  This results  in the  precipitation of  a thin
complex chromium metal gel on the surface, composed of hexavalent and trivalent
chromium and the  coated metal itself.  This gel is normally so'ft when formed and must
be handled carefully.  After drying, the coating  becomes hard and relatively abrasion-
resistant.

The thickness and color  of the chromate coating depends on the solution composition,
temperature, pH,  and  the length of treatment.  The coated  object  is  usually  rinsed
with cold water containing  sodium hydroxide or sodium carbonate to provide a clear
noniridescent coating.  This is followed by a warm water rinse  to prevent the removal
of the  coating.

6.2.3   Metal Coloring

While  coloring  of steel, copper,  aluminum,  and their alloys is  done  primarily  for
aesthetic purposes, this  surface treatment often imparts  other favorable properties
such as  improved corrosion resistance  and better abrasion and wear characteristics.
The coating operation is  primarily of the immersion type.
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Many formulations are  available for the  coloring of metals  and most  of  them  are
proprietary.  The major coloring process for steel uses a treatment solution of sodium
hydroxide and sodium nitrate in water.  The  processing temperature may vary from
275-320°F, and the immersion time may vary from 5 to 30 minutes.  The coating color
and  characteristics  are largely a  function  of  the  alloy  being  treated,  surface
characteristics, concentration of the bath, temperature, and immersion time.

6.2.4  Passivation

Passivation  refers to forming a protective film on metal, particularly stainless steel
and copper, by immersion in an  acid solution.  Stainless steel is passivated to dissolve
embedded  iron particles and to  form a  thin  oxide  film  on its  surface.   A typical
treatment  solution  for  stainless steel is  nitric  acid  or  nitric  acid  with  sodium
dichromate.  Copper is  passivated using a solution of ammonium  sulfate and copper
sulfate.

6.3   Chemical Etching

Chemical etching is used to produce specific  design  configurations and tolerances on
metallic or metal-clad plastic (printed  circuit boards) by controlled dissolution of  the
metal with  chemical etchants.  Typical etching solutions  are ferric chloride,  nitric
acid, ammonium persulfate, chromic  acid, cupric chloride, hydrochloric  acid, etc.
"Bright dipping"  is a special form of  chemical etching used to remove oxide layers
from ferrous and non-ferrous materials.

6.4   Cyanidinq

Cyaniding is a type  of case hardening  that produces  a hard surface on a metal whose
core remains relatively soft.  The product is a hard, wear-resistant surface backed by
a strong, ductile, and tough core. Carbon and alloy steels are usually immersed  in  the
cyaniding bath for a specific period of  time to achieve the required degree of surface
hardening.

The  most common cyaniding solution consists of 30 percent sodium cyanide, 40 percent
sodium  carbonate, and  30 percent sodium  chloride.   Baths containing  97, 75, and 45
percent  sodium cyanide  are also used.   Oxygen from  the air oxidizes the sodium

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cyanide to sodium cyanate which, at high temperatures, decomposes to form nascent
carbon  and nitrogen.   The carbon  and  nitrogen are  absorbed by  the  steel, which
increases  surface hardness.  The processing temperatures may vary from 1200-1350°F
for low penetration  to  1650-1725°F  for  high penetration.  A combination treatment
using high temperature immersion followed by low temperature immersion is also used.

The depth of surface that is hardened is controlled by the temperature and the cyanide
content.  As drag-out and carbon depletion occur, special salt compositions are added
to replenish and regenerate the bath.  At the end of the treatment, the objects are
immersed  in  a water  or  oil bath, where  quenching and  rinsing   is accomplished
simultaneously.  The quench water is potentially hazardous  and is treated for cyanide
destruction followed by  clarification  prior  to discharge.   The  quench  oil is also
potentially hazardous and is disposed of by incineration.

7.   WASTE DESCRIPTION

The  primary wastes associated with  metal surface finishing,  along with their process
sources, are listed in Table 7-1.   The  wastes produced in  metal  surface  finishing
operations come mainly from  two sources:  dumping of process tanks, and rinse waters
used to wash off process solutions adhering to the product surface or entrapped in the
crevices due to the shape  of the product piece (Durney 1984, AESI 1981,  CP Staff
1984).   Additional waste is generated as a result of process solution filtering.  The
process solutions  are  periodically  filtered  to remove precipitated metals  and  are
reused. These filtered solids are mixed with solids removed from the rinse  waters and
are either landfilled or sold  for metal reclamation.

Other wastestreams include spills and leaks plus stripping wastes.

Spent Bath Solution

The  activity of the plating solution  decreases with  time due to the precipitation of
salts and   depletion of constituents.    After 3-6 regeneration cycles,  the bath  is
eventually  discharged*.   This  waste stream usually  contains  cyanides or  metallic
*National Association of Metal Finishers 1985: Personal communication.

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03
ON
                                        Table 7-1  Metal Surface Finishing Wastes
No.
Waste
Description
Process Origin
Composition
RCRA
Code
     1.     Spent bath solution
Dumping of the process
solutions after depletion
OT loss of activity.
cyanides, cyanide com-
plexes, hexavalent
chrome, copper, nickel,
zinc, cadmium, and other
metals and their salts
in water
                   F011
            Waste rinse water
Rinsing treated objects,
equipment cleaning,
quenching of case
hardened steel.
same as spent bath
solution
            Filter waste
Filtration of process
solution, spent baths,
and treated waste rinse
water.
Complexes of various       F010
metals, cyanides, etc.       F012
            Spills and leaks
Overflows and leaks
from various process
equipment
same as
(1)
            Stripping waste
Removal of coatings
from improperly treated
objects.
not available

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complexes.  In the recent past, this stream was treated together with the rinse water
stream. However, the need for obtaining the necessary permits and also the perceived
regulatory compliance difficulties have discouraged treatment of spent baths*.  This
stream is often sent off-site for disposal.

Waste Rinse Water

Rinse water is used to  wash  off process solutions adhering to the product surface or
entrapped in its crevices due to its geometrical shape.  The rinse water  stream is
usually discharged to municipal  treatment facilities  with or without any  treatment,
depending on its composition.  The treatment procedure includes oxidative destruction
of cyanides reduction of chromates, neutralization, and solids removal.

Filter Waste.

The  filtration step in the  regeneration  of  plating solution and the solids removal in
rinse water treatment each generate a  solid waste.   These  solids  contain oxides or
complexes of metals and are either  landfilled or sent off-site for metal reclamation.

Spills and Leaks

The  overflow and leaks from various process equipment  are usually mixed with the
rinse water stream and disposed of as explained above.

Stripping Waste

Before coating   an  object, the  previous  coatings on it  are removed by  a  striping
operation.  This is also done to remove coatings from  an improperly coated object. In
small job shops, the same stripping solution could be used for removing different types
of coating.  The disposal of the spent bath from such operation is similar to that of the
spent baths discussed earlier. The rinse waters are  usually discharged to municipal
treatment facilities with or without  treatment.  The  untreated streams may  contain
various cyanides and cyanide complexes,  hexavalent chrome,  copper,  nickel,  zinc,
*Westinghouse Electric Corporation, 1985: Personal communication
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cadmium and other metals.  The treatment includes oxidative destruction of cyanides,
reduction  of chromates, neutralization, and solids removal.  The  treatment sludge  is
expected  to be landfilled.   Spills and overflows that occur can be mixed and treated
with other liquid wastes and treated as discussed.

8.   WASTE GENERATION RATES

Since metal finishing operations are often performed  along with electroplating and
other operations,  the  waste  generation  rates specifically  attributable   to  metal
finishing are difficult to determine.  No waste generation data were in evidence at the
time of the final document preparation. While no specific waste generation rates were
reported,  fractional rates  were estimated by  project  staff based on  the  available
information and engineering judgements.  These values are shown in Table 9-1.

9.   WASTE REDUCTION THROUGH SOURCE CONTROL

9.1  Description of Techniques

The  list  of  individual  waste  streams and  sources and their corresponding source
reduction  methods is presented  in  Table 9-1.  The following sections discuss the
various  waste reduction methods based on a literature survey and industry contacts.

In addition to  the  waste  reduction  measures  classified as being process  changes  or
material/product substitutions, a variety  of waste reducing measures labeled as "good
operating  practices" has also been included.  Good operating practices are  defined  as
being procedural or institutional policies which  result  in a  reduction of waste.  The
following  items highlight the scope of good operating practice:
     o     Waste stream segregation
     o     Personnel practices
                management initiatives
                employee training
     o     Procedural measures
                documentation
                material handling and storage
                material tracking and inventory control
                scheduling

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      o     Loss prevention practices
                spill prevention
                preventive maintenance
                emergency preparedness

For each  waste stream, good operating practice applies whether  it is  listed  or not.
Separate listings have been provided whenever case studies were identified.

9.1.1   Spent Bath  Solutions

Most  of the metal surface finishing operations  are performed by immersing an object
into tanks containing specific  reagents. Due to the precipitation of  salts  and depletion
of constituents, the bath becomes ineffective and must be regenerated or discarded
when  necessary.  This  waste, containing  cyanide, cyanide  complexes of metal, and
other  metallic  complexes,  is often sent to a  treater  for disposal.   The following
methods could reduce this waste stream:

      o     Extending bath life.
           During the  surface treatment operation,  many insoluble salts (such as
           ferric phosphate in the case of ferrous metal phosphating) precipitate out
           of solution  and  thereby  decrease  its  effectiveness.   In  addition, the
           depletion  of metal in  the solution  causes the activity of  the bath to
           decrease.    The bath  life,  if  prolonged,  can  contribute  toward  waste
           reduction since the frequency of process solution dumping decreases.  The
           bath life can be increased by periodic or continuous filtering of the  bath,
           regeneration of  the spent  bath solution, and preventive measures  against
           bath contamination.  As the insoluble metallic  salts  precipitate onto the
           cooling/heating coils and the object,  the  effectiveness of the  bath goes
           down.  By  periodically filtering the process solution, its activity  can be
           maintained (Durney 1984,  Saubestre 1957).   This  is already  practiced at
           many metal finishing operations, especially those with chemical  conversion
           coatings.

           Removal of the soluble salts formed during the treatment process can also
           extend bath life. The soluble metallic salts that form during the treatment
           process accumulate in the bath and reduce  its effectiveness.  These salts

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can sometimes be removed by temporarily lowering the bath temperature
so as  to form solid crystals.  In the case of electroless nickel plating, the
sodium  sulfate  that  forms  can  be  crystallized  by  lowering  the  bath
temperature to 41-50°F (Durney 1984).  The crystals can then be removed
by filtration.

Another  process,  patented by the  U.S. Army, involves  the removal  of
sodium carbonate from sodium cyanide-based plating baths by cooling. Dry
ice is used to cool the plating  bath, thereby causing the precipitation of the
carbonates.  The plating solution, free of carbonates, can then be reused.
So  far,  this method  has  not  found widespread use (Arienti 1985, Versar
1985).

Use of an electrolytic diaphragm  cell for regenerating spent chromic acid
used in etching operations has been reported (AESI 1981).  The process uses
electrolytic  diaphragm cell to oxidize  trivalent  chromium  to  hexavalent
chromium  and remove contaminants.    The quality of  the regenerated
etchant was reported to  be equal to or better than fresh  etchant.  This
process, which was still in the developmental  stage, would have a  great
potential for reducing spent chromic acid waste.  In one  such application,
extensively  tested  at the  U.S. Bureau  of  Mines  in Rolla, Mo., copper
etching  solution  was  regenerated  and metallic copper recovered  at the
same  time.  Recovery was accomplished by depositing the copper onto the
cathode of the electrolytic diaphragm cell (Basta 1983).

Other measures that can  extend  bath life are to  use automatic control
systems,  maintain all rack and barrel systems, and practice good house-
keeping at all times.   Automatic control devices  can be  used to  maintain
the concentration by conductivity  measurement.  A significant change in
conductivity would initiate pumping of fresh  concentrate into the  tank.
This type of automatic control is used  by  large facilities  especially for
chromate  conversion  coating (Durney 1984). If the  racks  or barrels (used
for transferring  objects  to be  coated) do not  have proper  protective
coatings, the bath could become  contaminated.  The process solution can
attack the weak spots in  the racks  or barrels, causing  the formation  of
metallic salts in the bath and thereby lower  its activity.  Fluorocarbon
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          coatings applied to the racks or barrels have been found  to be effective in
          minimizing  such contamination (Lane 1985).  Such a coating  will also be
          helpful in  lowering  dragout since less bath solution that remains in the
          corroded crevices on the racks or barrels. Special measures that constitute
          good operating practices are discussed at the end of this section.

          Metal/acid recovery from spent bath solutions.
          By  using electrolysis  on  the spent bath solutions,  useful metals can be
          recovered and at the same time the hazardous nature of the spent bath can
          be  reduced (Lewis 1980, Campbell and  Glenn 1982).   This  method  was
          implemented  in one facility by insertion of electrodes  directly into the
          cyanide destruction tank*.  However, electrolysis is used only  to a limited
          extent by the industry  (USEPA 1982).

          In addition to recovering metals from the spent bath, spent acid can also be
          recovered and  recycled by means of ion-exchange (Basta 1983).  Eco-Tec
          Ltd.,  in Ontario, Canada, markets an acid purification system that uses a
          propcietary resin that recovers mineral acids. The metals are  recovered in
          a concentrated (but still dissolved) form.   The concentrated  metals can
          than be recovered by  electrolytic means.  This process is used  by Modine
          Manufacturing,  in  Trenton, Mo.,  to  treat  copper-contaminated  sulfuric
          acid/hydrogen peroxide solution  which was used  to brighten  brass (Basta
          1983). Sodium phosphate salts, formed in nickel/copper electroless plating,
          can be converted into useful  hypophosphite salts by  using ion exchange
          resins activated with hypophosphorous acid.  The use of ion exchange resins
          for regeneration,  however,  suffers from  the  disadvantage of generating
          additional wastes such  as spent resins and resin regeneration solutions.

          Another noneiectrolytic means of metal reclamation, still in developmental
          stages, is  the use of bacteria  (Basta  1983).  Here,  the microbes  form
          complexes  with the metals  in solution,  creating a biomass.   The  biomass
          can then be burned to  recover elemental metal.  Laboratory studies in this
          area  are in progress  at  Polbac Corp. (Allentown,  Pa.)  and  the O'Kelly
          Companies (Tulsa, Ok.).
* National Association of Metal Finishers 1985:  Personal communication
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Another  new  trend is the  use  of so-called  liquid  membranes.   These
membranes  are composed  of  polymeric  materials  loaded  with  an  ion-
carrying  solution  (Basta  1983).   Liquid membranes were  used at Bend
Research Inc.,  in Bend, Ore., to remove chromium from rinse waters and
spent baths.  Here,  chromium  in the form of  dichromate is drawn across
the membrane, forming a tertiary amine metal complex.  This complex is
then broken down on the other side of the membrane with sodium  hydroxide
solution.    Similar  experiments are  in  progress  at  the  Warren  Springs
Laboratory in Stevenage, England, for treating wastes from printed circuit
board manufacturing.

Spray/brush methods instead of immersion methods.
The  use of spray/brush methods, which  use reagents in  a  more efficient
manner, will reduce the total amount of spent reagents generated. How-
ever, spray methods are useful only  in continuous applications and when the
objects are  flat or geometrically simple.  Brush  application methods are
also  useful  only where  the geometry of the object and/or the nature of the
operation permits it.

Use of thinner foils in printed circuit boards manufacture.
Printed circuit  boards  are made by  the controlled dissolution of  the metal
foil present on  a plastic substrate in an etching solution.  By using a thinner
metal  foil  on   the plastic  board, lower  amounts  of etching solution are
needed and more dilute solutions can  be  used.  This will result in  less spent
bath wastes. Other techniques allowing  for reduction in etching solution
use are described in the study of printed circuit boards manufacture (Bll).

Alternatives to conventional metal surface treatment techniques.
In cyaniding, liquid cyanide salts are  used to generate nascent carbon and
nitrogen  that diffuse  into  the  metal surface,  causing it to harden.  The
same result can be achieved when carbon and steel are exposed to ammonia
gas.  Ammonia decomposes at about 1550°F to produce  nascent nitrogen.
Combined with  carbon, the gas will diffuse into the metal surface.  The use
of gas  phase carbonitriding  alleviates the need for a cyanide solution bath.
In addition, the quench-rinsing  sequence present  in  the liquid phase
carbonitriding  (cyaniding) process would  also be avoided. Thus,  the waste
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generated by spent bath  solutions  can be eliminated totally.  Cyaniding,
however,   does  have   several   advantages   over   gas   carbonitriding
(Schneberger 1981).  These  include more  flexible operation  illustrated by
the ability  to  simultaneously treat   many  small  batches  which  require
different cycle  times, and  a  higher heating rate.   This is  important for
cases where the time needed for  the object  to  reach the conditioning
temperature may be a large  fraction of the total cycle time.

Vacuum  evaporation  methods for  coating  nickel, aluminum,  and  other
metals have been developed.  Here, metals are evaporated at low pressure
using an electron beam and the  vapor condenses,  as a coating, onto the
substrate.  This method could be a viable alternative to electroless nickel
plating,  which  generates  spent bath wastes.    However,  the  vacuum
evaporation method has  several disadvantages,  e.g.,  it  requires relatively
expensive equipment which becomes effective only  when a large number of
substrates  are  to be coated, and  the uniformity  of coating thickness is
generally very difficult to control.

Chromium  and  cadmium can be  deposited on  steel  using ion  plating
methods instead  of electrodeposition.  Ion plating uses high-energy ions
that bombard the depositing metal  which  evaporates and then condenses on
the substrate.  In the  U.S., this method is used only when other techniques
are found inadequate. However, ion plating is in wide use in Japan where it
successfully competes with electrodeposition  (Durney  1984).

Chemical vapor  deposition  (where a  chemical  reaction  decomposes the
reactant  gases to produce  the   desired coating  material which  then
condenses on the substrate) can  be used  for almost any coating operation
(Durney 1984).  However, its use has been  limited  to  the  semiconductor
industry, and commercial systems  for other  applications are not available
at the present time.

Ion beam processing techniques, still in the development stage, will be an
excellent alternative  to  case-hardening treatments (Anon 1984).   Here,  a
high energy ion beam is  used  to harden the surface by implanting  the ions
in the material.
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           Use of less toxic solutions.
           Whenever possible, the use of less toxic solutions for metal finishing will
           lower the hazard  of  spent solutions.  In the case  of  electroless copper
           plating, water  soluble  cyanide compounds of many  metals are added  to
           eliminate or minimize the  internal stress of the deposit.  It  was found that
           polysiloxanes,  such   as  General  Electric  silicon  fluid  SF-96, are  also
           effective  stress relievers  (Durney 1984).  By  substituting  cyanides  with
           polysiloxanes,  the  hazardous  nature  of the spent  bath  solution  can be
           reduced.   Use  of trivalent  chrome  instead  of hexavalent  chrome  in
           chromate conversion  coating can  eliminate the  toxicity  of the  spent
           electroplating baths.   Though some  manufacturers use trivalent chrome*,
           its use  is not growing rapidly because  the quality of trivalent chromium
           coatings  is  not  as   good  as  that  of  hexavalent  coatings  in   many
           applications.*  Currently, there were at least five companies that  offer
           trivalent systems (Chementator 1982).  Trivalent  chromium  baths can also
           use  lower  metal  concentrations.    One such  solution,  developed by
           W. Canning Materials Ltd.  in Birmingham, England, uses only 3.5 gms/liter
           of total chromium  compared to  the level  of  130 gms/  liters used  in
           traditional hexavalent baths.

           More dilute process solutions.
           The use of dilute bath solutions, whenever possible,  would also reduce the
           hazardous nature of the dumped bath.  In the case  of cyaniding, a typical
           bath solution composition is  30 percent  sodium  cyanide, though  some
           facilities  use 45,  75, and  92  percent  solutions.   By using  a  30 percent
           solution instead of a solution of higher concentration, substantial reduction
           in the  cyanide  content of the spent  bath solution  can be achieved.   In
           electroless copper  plating for printed circuit  board manufacture,  dilute
           solutions  have  been  tried successfully by many manufacturers (USEPA
           1981).   The use of dilute  bath solution could also lower  subsequent  rinse
           water requirements and metal dragout into rinsewater.
* National Association of Metal Finishers 1985:  Personal communication.
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     o    Better operating practices.
          By frequent monitoring of the  bath  activity and regular replenishment of
          reagents or stabilizers, bath  life can be prolonged (Durney  1984).  These
          reagents or stabilizers differ from process to process.  Stabilizers such as
          2-mercaptobenzothiozole and methanol are found effective  in electroless
          copper plating used for manufacturing  printed circuit boards. The addition
          of stabilizers can sometimes decrease the deposition  rate, but can still be
          economical in the long run.

          Good control of the bath  temperature is important from the viewpoint of
          performance predictability and is another method of prolonging  bath  life.
          Many  of  the surface  treatment operations  use tanks  with  immersed
          cooling/heating coils.  As the  salts precipitate and form scales on the coils,
          the heat transfer is impeded and temperature control becomes increasingly
          difficult.  The heat  transfer efficiency  can be maintained by periodic
          cleaning of the coils or by using jacketed tanks instead of coils.

          Proper storage of the process solutions can also  reduce waste generation.
          Usually, the process solutions  are stored  as a  two-part solution and  are
          mixed when a batch is needed.  Prolonged storage of these  solutions  may
          allow some chemical reactions to occur that could generate contaminants
          that reduce bath life.   In electroless  copper plating, if formaldehyde (using
          as a reducing agent) is stored with a hydroxide, the hydroxide can cause the
          formaldehyde to breakdown into formic acid and methyl alcohol. Thus, it
          is better to  only store non-reactive mixtures of materials or to store each
          item separately.

9.1.2   Waste Rinse Water

At  the end  of surface treatment, objects are  rinsed  with  water, alkali,  or acid to
remove reagents adhering to the surface  or trapped in the crevices of the object.  This
rinsing may  be repeated several times, and the rinse water represents about 90 percent
                                    B6-18

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of the total waste volume gererated (AESI 1981). This stream, containing cyanides and
cyanide  complexes  along  with  other  metal  complexes,   is  treated  for  cyanide
destruction  and discharged  to  the sewer.  The  following source control methods are
suggested:

      o     Reduction of drag-out.
           In  an immersion-type  treatment  process,  small  objects are placed inside
           barrels and bigger objects  are  supported on  racks for immersion into the
           bath.   When the object is removed from the bath, the rack or barrel (and
           object) carry some  reagents with it, called "drag-out".   Methods that can
           be  used  to  reduce   drag-out  and   subsequently  lower   rinse  water
           requirements are: proper racking of the parts; keeping  the  racks free of
           metal buildup  and corrosion; increasing drainage time above the process
           tank; using stationary recovery rinses by installing save rinse  or  drip rinse
           tanks; using air blowoff or  tumbling to ensure drainage; and using drainage
           agents (Cheremisinoff, Peina,  and Ciancia  1976,  AESI 1981, and  Cook et.
           al.  1984).

      o     Effective rinsing methods.
           By using  an efficent rinsing sequence, the quantity of rinse water required
           can be reduced substantially. Rinsing efficiency  can be improved by using
           properly designed rinse tanks, using  air agitation in the rinse tanks, using
           fog sprays, using automatic valves that control flow rates  based on  the
           movement  of  parts  through the processing line,  and  by using  counter-
           current rinsing (Cheremisinoff, Peina, and Ciancia 1976,  AESI 1981, and
           USC 1983).

           An estimated 90 percent reduction in rinse water can be achieved by using
           a  countercurrent rinse  instead of  a  single  running rinse  (AESI  1981).
           Converting to  a  countercurrent rinse requires only the addition  of one or
           more tanks, appropriate plumbing, and an air agitation system.  Because of
          space  limitations or  the use of preprogrammed  hoist lines, installation of
          an  additional rinse tank may not be possible at many  job shops.   However,
           many  facilities  have   reported  substantial  savings by  converting  to
          countercurrent rinsing.
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     The use of flow control  valves can  reduce rinse  water use by 50 percent
     with minimal capital costs (AESI 1981).  In many instances, excess water is
     used  indiscriminately  to  ensure  total  rinse  to  protect  product  quality.
     Though many facilities have installed flow control valves, concerns about
     reduced product quality  have contributed to  opposition to such measures
     (AESI 1981).

     Fog sprays, though  efficient,  are  not suitable  for all  applications.   In
     instances where the coating has little strength initially (as in the case of
     chromate coatings), fog sprays are generally not used.  Use of air agitation
     in the  rinse tanks promotes  turbulence  in the tank which increases the
     rinsing  efficiency.  The use of air  agitation in tanks is fairly  widespread
     (AESI 1981).

o    Use of immiscible rinses.
     The use  of non-aqueous  immiscible solvent  for  rinsing  would allow the
     rinsed solution to either  sink or rise during decantation,  and the solution
     could then be returned to the surface treatment bath for reuse without any
     pretreatment.  The rinsing solvent could also be recycled.  This process,  if
     feasible,  could  reduce or eliminate  rinse  water  wastes.   Tests with five
     solvents for use in the chromating process were conducted at  the  United
     Technologies Research Center (AESI 1981).  A major disadvantage  of this
     method would be the potential for increased air emissions  and the need to
     dispose of spent solvent.

o    The use of no-rinse coating processes.
     As the name suggests, no-rinse  coatings do not require  rinsing  after  a
     coating is formed  and dried, as there are no residuals left to interfere with
     the subsequent  treatment.  Recent  developments in chromate conversion
     coating for the coil coating industry have resulted  in a solution that can be
     applied to steel, galvanized steel, or aluminum, without  the need for any
     subsequent  rinsing (USEPA 1982).  After the  coating is formed, it is dried
     in air at about 150°F.  This no-rinse process, though  used by only a few coil
     coating facilities, can be used for other coating applications (USEPA 1982).
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The no-rinse process does  have some disadvantages.   These  are:   the
inherent high speed of operation requires very efficient control;  existing
facilities  are  difficult  and  expensive  to  adapt  to  no-rinse  coating
operations; and the no-rinse conversion coatings are not FDA approved for
food grade coatings.

Reuse/recycle of rinse water.
A literature  review on the reuse and recycle of process water in the metal
finishing industry was conducted (Mathews 1980). The following paragraphs
deal with some of the reuse/recycle options that are already in use or were
suggested for use.

In the chromate process, the first rinse (high in chromic acid), can  be
recycled to  the chromating  tank (UNECE 1982).  The  last  rinse can  be
regenerated  using ion-exchange  resins and can then be recycled  to  the
rinsing process.  Or,  by  sending the  rinse water to an evaporator,  the
concentrate  from the  evaporator can be recycled to the coating bath, and
the overhead from  the evaporator can be condensed and used  for rinsing
(AESI 1981, Basta 1984).  This scheme (illustrated in Figure 9-1) can reduce '
rinse water requirements drastically. The method requires sufficient water
to  be  evaporated  and recycled to satisfy  rinsing requirements.   The
economics of such  systems has been discussed in  detail elsewhere (AESI
1981).  Case  studies of facilities  using evaporators have also been reported
(Lewis 1980). The use  of atmospheric evaporators, while decreasing energy
requirements, requires significantly more floor space than conventional
evaporators.   Such systems  are  in  use at some facilities  (Campbell and
Glenn 1982).

Concentration of rinse water for recycle to plating baths or for reuse can
be achieved using ion  exchange resins.   A reciprocating  flow ion exchanger
for drag-out recovery from chromium, copper, and mixed coating processes
is in current usage.  The use of similar  ion  exchange columns for rinse
water  treatment and  reuse  is  expected  to have  great  potential in the
future.  The  use of ion exchange columns does have some  disadvantages.
These  are: ion exchange  is  more  expensive  than conventional chemical
                         B6-21

-------
CD
ho
N3
              HAKE UP _
              SOLUTIONS
                                       PRODUCT  AND DRAG-OUT
                                                     . -
                                SURFACE
                               TREATMENT
                                  BATH
CONCENTRATED
  TREATING
  SOLUTION
                              RINSE
                              TANK
                                                                         r
RINSE
 TANK
                                                               DISTILLATE
                                                         EVAPORATOR
                                                                                             FINISHED
                                                                                              PRODUCT
                                                                                                                         HAKE UP
                                                                                                                       RINSE HATER
                             Figure 9-1   Closed Loop Evaporation System for Metal Surface Treatment Haste Reduction

-------
treatment; regeneration steps generate their own  wastes; and the process
is only favorable for streams with a low concentration of contaminants (up
to approximately 250 ppm).

Reverse  osmosis for concentrating  rinse waters  has found limited use.
Here, water is preferentially forced through the pores of a semi-permeable
membrane and two  streams are generated:  a concentrated salt solution
that can  be sent to the bath, and a pure water stream that can be used for
rinsing.   Some  of the limitations confronting  the  process  are that the
membranes operate in the high pH  range only (pretreatment to assure high
pH  is  necessary); the  reliability  or durability  of the membranes  under
variable  conditions characteristic  of mixed  wastewater  is  questionable;
supplemental evaporation (to boost concentration) may be necessary before
the salt solution can be recycled to the coating process; and the  process is
economical only for processes with high drag-out rates (something that can
be controlled by  good operating practices).  Cellulose acetate membranes
are  used  by  some nickel coating  facilities.   Other potential  membrane
applications include copper, zinc coating, and chromating operations.

The  electrodialysis process  uses   alternately  placed  anion and  cation
permeable membranes and separates the rinse waters into a dilute stream
that can be used for rinsing and into a concentrated stream that can be
recycled  to the coating operation.  The process is continuous and  the  major
operating cost  is  for  electricity.  Currently,  some  nickel,  zinc,  and
chromating facilities use this process.

Replacing hexavalent chromium with trivalent chromium.
In chromate conversion coatings,  hexavalent chromium can be  replaced by
trivalent chromium, which  reduces the  hazardous  nature of  rinse waters.
This method is discussed in more detail in Section 9.1.1.

Replace cyaniding by gas carbonitriding.
As explained in  Section 9.1.1, cyaniding requires a quench-rinse  operation
to wash  cyanides present on the objects.  The  use  of gas  carbonitriding
eliminates the need  for this rinsing operation that generates a  hazardous
waste stream.
                          B6-23

-------
Use of still rinsing.
The work piece can be immersed in a  still rinse  tank  following the metal
finishing bath.  The still rinse  tank has no inflow or outflow of rinse water,
and the finishing bath constituents build up in it.  When the rinse  water in
the still  rinse  tank  becomes concentrated  enough,  it  can  be  used  to
replenish  the finishing bath solution. The use of still rinsing can cut  down
the quantity  of  rinse water required.  This process, when used for initial
rinsing, can facilitate metal recovery from the rinse water. Still rinsing is
usually followed by a spray or countercurrent rinse to ensure the complete
removal of contaminants.

Metal reclamation from rinse water  wastes.
By using electrolytic or  non-electrolytic methods, as explained in Section
9.1.1, metals present in the rinse waters  can be  recovered.  This reduces
the hazardous nature of this stream.

Changing rinse composition.
                                                         i
Changing the rinse  composition  to  reduce its hazardous  nature should be
attempted whenever possible.  In a  zinc-based phosphating bath,  the final
rinsing of the  object is usually  done with dilute chromic acid.   Environ-
mental concerns about chrome caused several facilities to develop and  use
chrome-free  rinses,  even though  these  rinses were not as effective as  the
chrome-containing rinses (Schneberger 1981).

Minimizing process water use.
By  reusing  rinse  water  effluents  from  certain  operations   in   other
operations with lower rinse water  quality requirements, overall aqueous
wastes can be minimized.  The use of water from fume scrubbers  has been
shown to be  practical for rinsing in certain  cases  (Cheremisinoff, Peina,
and Ciancia 1976).  Used cooling water or steam  condensate might also be
used for rinsing if technically  permissible and  economically justified.

Better operating practices.
A typical metal  finishing  facility  has various coating  operations  being
performed at the same  time, and  mixing  of various rinse streams  is  not
                          B6-24

-------
           uncommon.   By segregating various  rinses,  their reuse or recycle can be
           promoted.  Metal reclamation by electrolysis from these various streams is
           easier if they are not mixed together. In the recent past, rinse waters and
           spent baths  were  mixed  and treated together.  Segregating  spent bath
           wastes from rinse water wastes is quite common at present.

9.1.3   Solid Wastes

Solid  wastes are generated during the filtration of the bath to remove precipitated
metallic salts, and by the clarification, dewatering,  and  filtering operations performed
during waste treatment.  These  solid wastes are usually disposed of by landfilling or
are sent to an  outside  reclaimer.   The following  source  reduction  techniques are
considered:

      o     Metal reclamation from the solid waste.
           It was reported by Lisanti and Helwick (AESI 1981) that a  certain facility
           hauled  solids  to another plant within its  corporation for metal reclamation.
           Depending  on  waste  volume,  such  recovery  can  be   an uneconomical
           proposition in terms of capital costs.  Individually, the quantities generated
           might not be large enough  to justify  a  dedicated recovery system.   The
           alternative to individual  treatment systems for metal recovery  would be a
           centralized   waste  treatment  facility,  where  the   wastes   could  be
           collectively treated.  In such a facility, the recovery options would be  more
           economically  attractive.    Such centralized treatment  facilities  are in
           operation in West Germany.

      o     Effective dewatering of the solids.
           Solids are dewatered by some  facilities using a filter press.  By  effectively
           dewatering the solids, the quantity of waste sent  for  landfilling can  be
           decreased by  about 50 percent (AESI 1981).  More effective dewatering can
           be achieved using disc, scroll, or basket type  centrifuges, vacuum drums or
           belt filters.
                                    B6-25

-------
9.1.4   Spills and Leaks

Spills are  the  result  of overflow  from various process tanks and  other inadvertent
discharges,  such  as  valve  closure  failure, leaky gaskets, and drips.  The following
source reduction method is postulated:

      o     Better operating practices.
           By using  splash guards and drip boards,  spilled  liquids can be  recycled and
           spilled cleaning wastes  can  be avoided.   Use  of  float  valves or alarm
           systems are inexpensive options to prevent overflows. Other possibilities
           include liquid level  controllers.   Good housekeeping measures such as
           periodic  inspection of process equipment and  piping, periodic relining of
           the tanks,  and  training  and  educating  personnel to  be  cognizant  of the
           importance of controlling waste generation can reduce the number and size
           of spills and leaks occuring in a facility.

9.1.5   Stripping Wastes

Stripping  wastes,  which are  generated most commonly  in  small job shops, are the
result of removing old or bad coatings on objects prior to the required surface finishing
operation.  The  operation  is essentially  an  etching  type  treatment,  whereby the
coating is dissolved in  an acid. Since the same bath  may be used to strip various metal
objects,  this  waste  is difficult  to  deal with  since recycling  or regeneration is not
generally  possible. The following source reduction techniques are  suggested:

      o     Use of non-chrome etchants.
           Whenever  possible, ferric   chloride,  or ammonium   persulfate solutions
           should be  used  instead  of chromic-sulfuric  acid  etchants.   However,
           compatibility  with  the  planned   surface  treatment must  be carefully
           examined.   The  use  of  such  etchants  will reduce  the  toxicity  of the
           stripping solution that ends up as a waste.

      o     Decrease the generation of off-spec coatings that require stripping.
                                     B6-26

-------
                          TABLE 9-1  SUMMARY OF  SOURCE  CONTROL METHODOLOGY FOR THE METAL SURFACE TREATMENT  INDUSTRY
1
Haste Stream |
1
Spent Bath |l
Solutions («) |2
|5
IS
8
1
Waste Rinse Hater |t.
12
|3
IS
is.
li-
lt-
|10
1
Filter Wastes (*} |1.
i
Spills and Leaks |1.
1
Stripping Haste |1.
|2.
I
| All Sources |
I
Control Methodology |~
I
Extend bath life I
Metal/acid recovery from spent baths |
Spray/brush Heirs instead of immerse )
Use thinner foil for P.C.B.'s |
Alternative treatment techniques I
Use of less toxic solutions |
More dilute process solutions |
Better operating practices |
Overall 1
Reduce dragout of solution from tank |
Employ effective rinsing methods |
Use of immiscible rinses |
Use of no-rinse coatings |
Reuse and recycle spent rinse water |
Replace hex chrome with trlvalent j
Replace cyanidlng with gas carbon. |
Use still rinsing technique |
Reclaim metal from rinse water wastes |
Change rinse composition |
Minimize process water use i
Better operating practices i
Overall |
Metal reclamation from solid waste |
Effective dewatering of the solids |
Overall |
Better operating practices |
Overall |
Use of non-chrome etchants |
Reduce generation of off-spec coat ing |
Overall |
All Methods
Found Documentation |
Quantity |
2 !
1
1
1
1
1
1
1.25 |
2 1
2 !
1 1
1 1
1 1
1
1 i
1 1
3 1
1 1
i !
' i
1.33 |
1 1
' 1
1.00 |
2 1
2 00 |
1 1
1 1
t 00 |

Quality 1
2 1
2 1
1 1
1 1
2 :
2 !
2 i
2 1
1.75 |
2 1
2 1
2 !
2 !
2 !
2 I
1 1
1 |
3 1
2 I
2 1
2 1
1 92 |
1 1
2 !
1.50 |
t !
1 00 1
1 I
1 1
i oo !

Haste | Extent of |
Reduction | Current Use |
Effectiveness | 1
t 1
2 1
1 1
2 1
2 I
2 i
2 1
2 1
K75|
2 1
3 I
3 1
2 1
2 1
3 1
2 1
2 I
2 1
2 1
2 i
2 17 !
2 1
2 |
2.00 |
2 1
2 00 |
2 1
2 1
2001

1 1
t 1
2 1
3 !
1 1
2 1
1 1
2 1
1.63 |
1 1
1 1
0 1
1 1
J 1
1 1
1 1
1 1
2 1
1 I
1 1
1 1
1 08 |
1 1
t 1
1.00 |
2 1
2.00 |
1 I
1 1
1 00 !

Future | Fraction of | Current
Application | Total Haste | Reduction
Potential | | Index
2 1
2 !
l 1
' 1
' 1
2 1
2 !
3 I
1.75 |
3 I
3 1
1 1
2 1
3 1
' 1
1 1
2 1
2 1
1 1
2 1
2 1
1.92 |
1 1
2 1
1.50 |
2 1
2.00 |
2 1
2 1
2.00 i
1
1 0
1 0
1 '
1 1
! 0
1 1
0.15 | 1
1 o
t o
1 o
1 '
1 ®
1 o
1 1
1 0
1 o
1 o
0.65 | 1
1 o
1 o
0.05 ! 0
1 1
0 OS | 1
1 o
i o
0 10 0
i oo i i
| Future Reduction Index |
i 	 	 1
1
1
3 1
5 1
5 1
5 1
5 I
0 1
5 1
0 1
5 1
5 1
• 1
0 1
> 1
o 1
1
1
1
1
1
1
5 1
0 1
5 I
5 1
5 1
0 1
0 1
5 1
5 I
5 !
0 1
Probable
0
0
0
0
0
0
0
0
0
1
1
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
| Maximum |
— * 	 4
4
8
1
1
4
5
8
8
5
t
7
3
1
8
4
6
8
5
4
8
8
8
4
8
1
0.8 |
1
1
1
1
O.I |
08 |
	 4
0.8 |
1
1.7 |
1
1
1
1
1
1
1
1
i
1
1.7 |
1
08 |
6 I 0 8 I
5| 0 5 |
5 I 05|
8| 0 8 |
8 | 08!
8 0 8 |
T I 1 3 !
CD
cr>
 i
ro
      (') Ihese streams Included listed 'F' and/or 'K' RCRA wastes

-------
9.2  Implementation Profile

The source control methods discussed for use by the  metal surface finishing industry
have different potentials for application depending on whether the facility is  a captive
shop or a job shop.  Job shops are usually required by their clientele to follow certain
operating  procedures,   and  most  job   shops  buy  their   process  solutions   from
manufacturers.  Thus,  modifications in  certain  operating  procedures and changes  in
process solutions are not feasible in many job shops  without the guidance and approval
of the  customer.   Also, because smaller operations usually have  space limitations,
installation of additional tanks for countercurrent rinsing may not  be practical.  For
facilities  which  have preprogrammed hoist  lines in operation, changes in operations
such as rinsing may be  difficult.  However,  measures such as the installation of flow
control valves, splash guards, etc., which do not require much capital or space can be
used by all facilities.   Efficient use  of  water can  be  made  by reusing spent process
water  at places  that require low quality water.  Improvements in operating practices,
such as spill and leak prevention, are additional  measures which require little capital
to implement.

Reclamation  of  metals  from wastes is  an effective  way to reduce or eliminate the
hazardous constituents  of these  wastes.  In many  job shops, the volume  of wastes may
be too  low for economical  recovery of metals.  In  such cases, the  use  of centralized
waste  treatment facilities to collect  and treat wastes from various plants has proven
in some to be a long-term economical solution.

9.3  Summary

The  summary of  all noted  source control  techniques is given in Table  9-1.   Each
technique was rated for its  effectiveness, extent of current use and future application
potential on scale  of 0  to 4. The ratings were derived by project staff based on review
of the  available  data and in consultation with the industry.   The estimates of current
level  of  waste  reduction  achieved  (current reduction  index)  and possible  future
reduction (future reduction index) were obtained  from the  ratings in  accordance with
the methodology presented in the introduction to this appendix.
                                    B6-28

-------
The current reduction index (CRI) is a measure of reduction of waste that would be
generated if none of the methods  listed  were implemented to their current level of
application.  For the entire metal surface finishing industry, CRI is 1.0 (25 percent)
which is indicative of the low  to moderate level of waste minimization that  already
has taken place.  Current measures that  have proven effective as a whole have been
the use  of less toxic bath solutions, the reuse  and  recycling of spent rinse water,  the
reclaiming of metal from waste, and the implementation of better operating practices.

The future reduction index  (FRI) is an indication of the level to  which the currently
generated  waste  can be reduced  if all  of  the  techniques  noted were  implemented
according to  their rated potential.  The FRI value of 0.7  to  1.3 (18 to 33 percent) is
indicative of the  moderate  extent  of future waste reductions.  Among the techniques
that were  found  most  effective  and applicable  (as  evidenced by high  FRI  value),
employment of effective rinsing methods, metal/acid recovery from spent baths,  use
of more dilute process solutions,  and  further  implementation of better  operating
practices appear to promise the greatest level of reduction for the industry as a whole.

10.  PRODUCT SUBSTITUTION ALTERNATIVES

Since many metal objects can be coated with several alternative metals to achieve  the
same  quality   of  treated  surface, certain substitutions  could  contribute towards
hazardous waste  reduction.  The  replacement of  nickel by  zinc is possible in some
instances.   In other applications, zinc  can  be  substituted  by  manganese or iron.
Electroless nickel plating, used by  some printed circuit boards manufacturers,  can be
substituted with  electroless copper plating.   Cadmium and  silver can generally  be
substituted with other metals.

11.  CONCLUSIONS

The  estimates indicate  that moderate reductions  of waste  generated by the metal
surface  finishing industry are possible, probably in the 18 to 33 percent  range.  Several
effective source  control  measures  include  use  of  efficient  rinsing  techniques,
recovering metal/acid  from spent  baths, use of  more dilute process solutions  and
further  implementation  of better operating practices.
                                   B6-29

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12.   REFERENCES

AESI. 1981.  American Electroplater's Society, Inc. Conference on advanced pollution
control  for the metal finishing industry. EPA-6QO-2-81-028.  Cincinnati, Ohio:  U.S.
Environmental Protection Agency.

Alban, L.E.   1981.   Metal  surface  treatments:   case hardening.   In  Kirk-Qthmer
Encyclopedia of Chemical Technology.  3rd ed. Vol. 15, pp. 313-24.  New York, N.Y.:
Wiley.

Arienti, M.  1985.  GCA  Corporation.  Waste category assessment  report, Solvent
waste;  draft final report.  EPA Contract No. 68-03-3243.   Cincinnati, Ohio:  U.S.
Environmental Protection Agency.

Basta, N.   1983.  Total  metal recycle is metal finishers' goal.  Chemical Engineering.
90(10)816-19.

Basta, N.   1984.   Ion-beam processing:  new surface  treatment  method.   Chem.
Process. 91(16): 18-21.

BCL.   1976.   Batelle  Columbus Lab.   Assessment  of industrial  hazardous  waste
practices: electroplating and  metal finishing  industrial job shops.  EPA-530-SW-136C.
Washington, D.C.:  U.S. Environmental Protection Agency.

Campbell,  M.E., and Glenn,  W.M.  1982. Profit from pollution prevention.  Ontario,
Canada:  Pollution Probe Foundation.

Chementator. 1982. Chemical Engineering. 89(14):9-10.

Cheremisinoff, P.N., Peina, A.J., and Ciancia, J. 1976.  Ind. Wastes.  22(6):31-4.

Cook, T.M., Cubbage, M.L.,  and Fister, L.J., 1984.  Draining  process solutions from
sheets, baskets, pipes, threads and fins, Metal Finishing, (7):33.

C.P. Staff.  1984. Hexavalent chromium waste detoxified by chemical system, dewater
through filter press.  Chem. Process.  47(10):38.

Durney, L.J., ed.  1984.  Electroplating engineering handbook.  4th ed.  New York,
N.Y.: Van  Nostraud Reichold Co.

Lane, C., 1985. Fluorocarbon coating eliminates corrosion of acid bath racks.  Chem.
Process. 48(10): 72.

Lewis, T.A. 1980. Ind. Finish.  April 1980.

Mathews, J.E.  1980. Industrial reuse and recycle  of wastewater;  literature review.
Robert  S.  Kerr Environmental Research Lab.  EPA-600-2-80-183.   Ada, Okla:  U.S.
Environmental Protection Agency.

Olsen, A.E.  1973. Upgrading metal finishing facilities to reduce pollution. Oxy Metal
Finishing Operation.  EPA-625-3-73-002 (USEPA Technology Transfer).   Washington,
D.C.: U.S. Environmental Protection  Agency.
                                   B6-30

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Saubestre, E.B.,  1957. Proc. Am. Electroplating Soc.  46:264.

Schneberger, G.L.  1981.   Metal  surface  treatments:   chemical and electroplating
conversion  treatment. In Kirk-Othmer encyclopedia of chemical technology.  3rd ed.
Vol. 15, pp. 304-12. New York, N.Y.:  Wiley.

UNECE. 1982.  United Nations Economic Commision for Europe.  Compendium on low
and non-waste technology.  Vol. 4.  Monograph 73.  Geneva:  United Nations Economic
Commission for Europe.

USC.  1983. U.S.  Congress,  Office  of  Technology  Assessment.   Technologies  and
management strategies  for hazardous  waste  control.    Washington,  D.C.:   U.S.
Government Printing Office.

USEPA.  1980.  U.S.  Environmental  Protection  Agency,  Office of Water Regulations
and Standards.   Development document  for  effluent  limitation;   guidelines  and
standards for  the  metal  finishing  industry.   EPA-440-1-80-091A.  Washington, D.C.:
U.S. Environmental Protection Agency.

	.  1981.  U.S. Environmental Protection Agency, Industrial
Environmental Research  Lab.  Implement  changes for  metal finishers.   Cincinnati,
Ohio:  U.S.  Environmental Protection Agency.

	:  1982.   U.S.  Environmental Protection Agency, Effluent
Guidelines  Division.   Development document for effluent limitations;  guidelines and
standards for the coil coating industry.  EPA-440-1-82-071.  Washington, D.C.:  U.S.
Environmental Protection Agency.

Versar,  Inc.  1985. Versar.   National Profiles  Report for Recycling/a preliminary
assessment, Draft  report  for waste treatment branch.  EPA Contract No. 68-01-7053.
U.S. Environmental Protection Agency.

13.   INDUSTRY CONTACTS

Dr.  J. Chu, Environmental Activities Staff, General Motors Corp., Warren, MI.

D. Anzures, National Association of Metal Finishers, San Fernando, CA.

W.G.  Vaux, P.E.,  Chemical  and Process Engineering, Westinghouse  Electric Corp.,
Pittsburgh, PA.
                                  B6-31

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-------
1.    PROCESS: ORGANIC DYES AND PIGMENTS MANUFACTURE

2.    SIC CODE:  28652, 28653

3.    INDUSTRY DESCRIPTION

Manufacturers of  organic dyes and pigments are included as part of the cyclic crudes
and  intermediates manufacturing  industry.   The companies  are  engaged  in  the
conversion of cyclic organic chemicals into more complex intermediates, and/or in the
subsequent formulations of these products into dyes and pigments,

3.1  Company Size Distribution

The  1982 Census  of  Manufacturers (USDC  1985) reported a total of 143 companies
involved  in   the  manufacturing  of cyclic  crudes  and  intermediates,  with   189
manufacturing plants located  throughout the U.S.  As  of 1983, 22 companies produced
only  dyes, 21 produced  only pigments, and 12 produced both dyes and  pigments.  Since
no specific size data were found for the organic dyes and pigments sector, Table 3-1
gives the company size  distribution  in terms of the number of employees for the entire
cyclic crudes and  intermediates manufacturing industry.

                      Table  3-1  Company  Size Distribution

No. of
establish-
ments

Total
189
No. of Employees Per Facility
1-49 50-99 100-249 250-499 500-999
93 25 41 18 8

1000-250C
4
No.  of
employees  27,075    2,325    1,875     7,175      2,700      6,000      7,000
Source:    1982 Census of Manufacturers (USDC 1985).
                                   B7-1

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3.2   Principal Producers
The principal producers of organic dyes and pigments are listed below:
      Mobay Chemical Corporation
      Sandoz Chemicals Corporation
      Toms River Chemical Corporation
      ICI United States, Inc.
      Crompton & Knowles Corporation
      Atlantic Industries, Inc.

3.3   Geographical Distribution
     BASF Wyandotte Pigments
     Sun Chemical Corporation
     American Hoechst Corporation
     Harshaw-Filtrol Partnership
     Galaxie Chemical Corporation
     Ciba-Geigy Corporation
According to data from 1977,  there  were 55 companies producing organic dyes and

pigments at 87  manufacturing  sites.   Among these,  89  percent of the plants  were

located in  11 eastern  states.  The remaining sites  were distributed throughout the

country as shown in Figure 3-1 and Table 3-2 below:
                Table 3-2 Location of Organic Dyes and Pigments
                        Manufacturing Facilities in th U.S.
                    EPA Region
No. of Establishments
                     I
                     II
                     III
                     IV
                     V
                     VI
                     VII
                     VIII
                     IX
                     X
         8
        38
        11
        13
        12
         0
         1
         0
         3
         0
                     National
        86
Source:  Industrial Process Profiles (Radian Corp., 1977).

(a) The location of one plant was not reported.
                                    B7-2

-------
                           VIII
CD
I
OJ
           0
                           2-5
r^d 6-10
^;^j over 10
                    Roman numerals show EPA regions

  Figure   3-1  Organic Dj^/Pigment Plants in the U.S.

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4.   PRODUCTS AND THEIR USE

There  are  over 1000 different  dyes  and pigments being produced in  the  U.S., with
pigments being fewer in number (approximately 10 percent).  These products are sold
as  pastes,  powders,  lumps, dispersions  in  organics,  or  aqueous  solutions  with
concentrations between 6% and 100%.  Of the total  quantity of dyes produced, two-
thirds  is used  as colorants in the textile industry, one-sixth is used in  coloring paper,
and the rest is used in producing organic pigments and in the dyeing of leathers and
plastics. For pigments, one-half of the quantity produced is used in printing, while the
rest is used as colorant for paints, plastics, textiles, and paper.

According to  their applications, dye  products are classified into 10 principal  classes.
These  are:  (1) acid dyes,  (2) basic dyes, (3) direct dyes, (4)  disperse dyes, (5) reactive
dyes,  (6) fluorescent brightening  agents,  (7) food, drug and cosmetic colorants, (8)
mordant dyes, (9)  solvent dyes,  and (10) vat  dyes.  U.S. annual production  of dyes  in
1983 was 122 thousand short tons per year  (TPY) (US1TC  1983).  The production  of
direct  and solvent dyes  decreased as  compared  to the previous years,  while the
production  of  the remaining 8 classes increased.  Fluorescent  brightening agents
accounted for the  largest portion of dyes produced in 1983  (25%).  For the remaining
classes, vat dyes,  disperse dyes, direct dyes, and acid dyes accounted for  21%, 15%,
12%, and 11% of the annual total production,  respectively.

Pigments are  classified either as toners or lakes.  Toners are full-strength organic  or
metallo-organic colorants that  do not  contain  any  inorganic  pigments or  carriers.
Lakes, on the other hand, are combinations of  a  dye  with an inorganic  carrier, usually
alumina hydrate.  The production  rate  of pigments in 1983 was 39 thousand tons per
year, with 99% of  the amount produced as toners (USITC 1983).

5.    RAW MATERIALS

A wide variety of  organic and inorganic materials are used in the production of organic
dyes and pigments.  Large manufacturing plants produce their  own dye intermediates
from  basic units such as benzene or naphthalene.  Small manufacturers, however, will
bring  in intermediates  from  other  sources,  often  foreign.   Most of the  organic
intermediates  are  hazardous in nature, with  some being identified as carcinogenic.
                                     B7-4

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The common types of raw materials used in this industry are listed below (Catino and
Farris 1979, Bannister, Olin, and Stingle 1979, Fytelson 1982, Radian 1977, SRI 1984):
Organics:
Inorganics:
Acids:
derivatives  of benzene,  toluene,  naphthalene, anthraquinone, and
other aryl systems including heterocyclics, which contain functional
groups  such   as   sulfonic   acid   substituents,   hydroxyl,   amino,
alkylamino,  chloro, nitro, carboxyl, alkoxyl and others; reagents such
as   lower    alcohols   and   amines,    formaldehyde,    phosgene,
dimethylsulfate, acetic acid, and glycerine.

alumina hydrate, aluminum salts, ammonium  salts, calcium chloride,
sulfur, chlorine, bromine,  chromium salts, copper and copper salts,
iron  and iron salts, iodine, nickel salts, sodium salts,  potassium salts,
lead  peroxide, phosphorous chlorides.

sulfuric acid, oleum,  nitric acid,  hydrochloric acid,  chlorosulfonic
acid, acetic  acid, chloroacetic acid.
Bases:
ammonia, calcium carbonate, sodium hydroxide, calcium oxide.
Catalysts:       zinc chloride, aluminum chloride, ferric chloride,  iron,  Raney nickel
                catalyst,  stannous  chloride, magnesium  oxide,  manganese  dioxide,
                lead peroxide.

6.   PROCESS DESCRIPTION

Organic dyes and pigments are produced from a great variety of cyclic intermediates
using many processes.  Manufacturers often purchase organic chemicals, usually in the
form of cyclic benzenoids, and convert these into  more complex intermediates,  and
ultimately   into  dyes  and  pigments.    The  distinction   between  dyes  and   dye
intermediates is somewhat arbitrary, since some dye intermediates may  be  used as
dyes, or they can  be further processed  to form other dyes or  pigments.   Similarly,
pigments  are differentiated  from  dyes based  on  application  methods rather  than
chemical constitution.  Pigments are much less soluble and  they  retain their granular
form throughout the application process.
                                    B7-5

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Although  the  number  of  different types of organic dyes and  pigments produced  is
large, the majority of  these products can be classified  into eight basic classes  which
are based on the chemical structure of the common color-bearing units (chromophores)
in the molecules.  These include:

     o     azo dyes and pigments,
     o     anthraquinone dyes and pigments,
     o     stilbene dyes and fluorescent brightening agents,
     o     diphenyl methane and triarylmethane dyes and pigments,
     o     methine and polymethine dyes and pigments,
     o     xanthene dyes and pigments,
     o     phthalocyanine dyes and pigments,
     o     sulfur dyes.

Of  the  eight  classes,  azo dyes and  pigments represent the most  important  class
commercially  produced in the  U.S., accounting for 35 percent of all U.S. dye and
pigment production in 1978. Since data on U.S. production by structural class have not
been reported  since 1978, the information on present relative and total production of
these dyes and  pigments, by  class,  remains uncertain.  Nevertheless, based  on the
information provided in a recent EPA report on the waste generation from the organic
dyes and pigment industry (SRI 1984), it is believed that azo dyes and pigments still
represent the  largest  volume of dyes and pigments produced.  Therefore,  this report
will  focus on  the production of azo dyes  and pigments.  Their manufacturing process
will  be  examined in  detail to exemplify the  degree  of complexity  which can  be
encountered in the production of organic dyes or pigments.

Figure 6-1 presents the flow chart for the manufacturing  of azo dyes and pigments.
There are basically three general stages in the  production of  any  dye  or pigment.
These are:

                Synthesis stage.
                Operations performed in this  stage vary widely  among the dyes and
                pigments due to the differences in the sequence of reactions required
                to obtain the desired structure of a specific dye or dye intermediate.
                                    B7-6

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                         87-7

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                Precipitation stage.
                Dyes which  are  still soluble  after the last  of the reaction sequence
                are often precipitated out  by the  addition  of salts.   Similarly,
                pigments can  be obtained  directly  or from the precipitation of dye
                intermediates on resin, or by the addition of metal salts.

                Finishing stage.
                This stage is common to the production  of all dyes and pigments.  It
                usually involves  the processing of dyes and  pigments into  their final
                forms through operations such as drying, grinding and standardizing
                as required by the dye users.

The following sections describe in detail the steps involved in each of the stages for
the production of azo dyes and pigments.

6.1  Synthesis of Azo Dyes and Pigments

Azo  dyes  are compounds  containing  one  or more  azo  groups (-N=N-)  in  their
molecules.  Azo  dye products consist of direct dyes, acid  dyes, pigments, and a small
amount of azoic compounds which are incomplete dyes that require coupling during the
application process.  Azo dyes  and pigments are  produced  via  a  two-step process
consisting of  the diazotization and coupling of aromatic amines.

The manufacturing process begins with a diazotization reaction.  In this  first  stage,
arylamines such as anilene are reacted with nitrous  acid to form diazonium chloride
salt according to the reaction:

                ArNH2 + NaNO2 + 2HC1   - -  , ArN = N+C1" + NaCl + 2H2O

where  Ar is an aromatic  group.   Since nitrous acid  is very unstable, it is produced  as
needed from  the reaction of an  aqueous solution of sodium  nitrite and hydrochloric
acid.  The batch reaction is carried out at 32°F - 40°F in a period of  1-3  hours using
arylamine,  NaNO2, and HC1 in a molar ratio of 1:2:3.

The product is an aqueous solution containing 15% diazonium chloride and 7% NaCl.  In
the production of azo dyes, as well as of any other dyes  and pigments, the reactions

                                    B7-8

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are almost always carried out in batch reactors because the small total demand does
not justify the use of a continuous process.  The reactions are carried out batchwise in
one or several reactor trains.  Each train includes at least one diazotizing reactor, one
coupling reactor, and  one filter press.  The kettles are made from cast iron, stainless
steel, glass-lined steel, wood, or brick, and have a capacity of 500 to 10,000 gallons.
The reactors are equipped with mechanical agitators, temperature recorders,  and pH-
probes. Jackets or coils are  used for heating and cooling.  Unjacketed reactors are
also used,  and the temperature is controlled by direct introduction of steam or ice.

The yield  from a diazotization reaction is  fairly high. The use of HC1, however, may
result  in  the  formation  of  byproducts.   For  example,  the  diazonium  salt  may
decompose  into  compounds  which  may be further chlorinated  into  polychlorinated
organic byproducts.   Furthermore,  the decomposition products  may  react  with the
original arylamine to form  secondary amine compounds.  These  secondary amine
compounds can then react with nitric acid and  form insoluble compounds.

A  clarification operation is often performed to remove these solid by-products before
the intermediate is transferred  to the coupling  reactor.  The  resulting solid waste is
often sent to land disposal.  In addition to these byproducts, other major contaminants
include undecomposed diazotic  acids.  Once clarified,  the intermediates from the
diazotization reactor are then transferred to the coupling reactor.

In  the  second stage where coupling occurs, the diazonium salt is reacted with another
aromatic  compound,  called  a "coupling component," which  has a strong electron-
donating substituent such as a phenolic, amino, or  substituted  amino functional group.
The reaction forms azo compounds in the following manner:
                Ar-N=N+Cl-+ Ar'-H —. Ar-N=N-Ar' + HC1.
Coupling is generally conducted  in a mildly alkaline condition by the addition of NaOH.
The reactor is operated at 32°F-40°F  for 4-24 hours.   The  ratio  of  diazo  salt to the
coupling component varies  depending  on the degree of coupling  required.  High pH is
often avoided so as to minimize non-coupling reactions leading to the formation of
undesirable byproducts, e.g. triazene compounds:
                                      NaOH       H
                ArN2 + Cl- + Ar'NH2	v Ar-N=N-N-Ar' + H2O +  NaCl
                                    B7-9

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Furthermore,  coupling  reactions  must  compete  with  the  decomposition  of  the
diazonium salts to form phenols as byproducts from the reaction:

                                           x   NaOH
                ArN=N+Cl---   N2 + (Ar+Cl-)  	  - ArOH+NaCl

In addition,  undecomposed diazotic acids carried  over  from the diazotization  reactor
may react in the basic medium to form diazotate salts.  These salts are insoluble and
often require  filtration of the  coupling reactor effluent  to  remove  them   from  the
soluble dye solution.  The resulting filter press cake is sent to land disposal.

6.2   Soluble Dye Precipitation  and/or Pigment Production from Selected Dyes

Dyes formed  from  the coupling reaction,  or  formed at the  end of  the  synthesis
sequence in general, can be either soluble or insoluble.  Insoluble dyes (or pigments)
are often filtered, and the products  are collected in the form of filter press cakes.
These are  then sent  to  dye/pigment finishing  operations before being sold as final
products.  Soluble  dyes are precipitated by the addition  of salts.  The resulting slurry is
filtered, and the press cake is  air blown to remove  the mother liquor.  The dyes  are
then transferred to finishing steps.  The mother liquor which contains byproducts and
residual dyes and  pigments is  treated  on-site with other  process wastewaters before
being discharged.  Similarly, dyes that are too  easily soluble in water and/or  organic
solvents  can  be  converted   into  pigments   with  the  requisite  low   solubility
characteristics.  These pigments (lakes)  can be  formed  by precipitation  of water
soluble  dyes on an adsorptive  surface  such  as  resin or alumina hydrate, or from  the
precipitation of an acid or basic dye using inorganic salts.  Lakes formed from acid
dyes  are precipitated by the addition  of soluble  salts  of  alkaline-earth  metals, while
lakes formed from basic  dyes  are made from precipitation with regular metal salts.
The precipitation process is carried out by stirring dyes and dye precipitants in a steel
vat.  The reacting solutions are heated  to 120°F-170°F, and  fed  in at  a prescribed
rate. The product slurry is  then cooled to obtain the  desired crystalline form of  the
pigment products.  The product slurry  is filtered, and  the resulting filter press cakes
are sent to  finishing operations. The mother liquor containing residual dyes, pigments
and metal salts is  not recovered and is sent to wastewater  treatment.
                                    B7-10

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6.3   Finishing Operations

After the  dyes or pigments are collected  in cake  form or as slurries,  they are sent
through a series of finishing steps before being sold as  final products.   The physical
form  of the  product plays  an important part in the marketing of  the  material.
Pigment attributes such  as crystal size,  specific,  surface,  and particle shape have
enormous influence on the quality and performance of a pigment.

One important finishing operation is called flushing. This is used to transfer pigments
from  a water-borne phase to an organic or oil-borne phase  (67 percent of pigments are
sold in  this organic  form).  The flushing  operation  is usually done in more than  one
charge in steel tanks equipped with high speed stirrers or blade agitators. The residual
water from these charges is then removed by vacuum stripping.  The finished products
are pigment dispersions or dye solutions.  Resins and surfactants are usually added to
stabilize the dispersion.  Wastewaters from the flushing operations  containing  organic
chemicals are sent to treatment before being discharged.

Conventional final finishing is  accomplished through dry grinding of the  product.  The
crude product  press  cakes or  slurries are dried and then  ground.   Typically, ball or
hammer mills  are used. Drying is done in hot air or  vacuum using ovens,  rotary dryers,
drum  dryers, or most frequently, spray dryers.  The dry grinding process is losing its
popularity, however, due to dusting which causes air pollution problem.  This operation
can be  replaced by wet grinding which is done in ball or sand mills.  Surfactants  are
often added to facilitate the  grinding process.   The resulting product is  a ground
aqueous paste  which can be subsequently dried by spray drying.

The last important finishing step is  a  standardization step in which inert salts  are
often added to meet  product specifications, which  can vary  widely.  For example, of
the total amount of organic pigments sold, 45  percent is sold  as dry  powder without
dilution, 40 percent is sold as colorants in oil with up to  65 percent dilution  by inerts,
and the  remaining 15  percent is sold  as wet filter cake without further processing.
                                   B7-11

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7.    WASTE DESCRIPTION

The  primary   specific  wastes  associated  with  the  organic   dyes  and  pigments
manufacturing industry are listed in Table  7-1.  Wastes or process residuals from  this
industry were  classified as follows:

Discarded  Shipping  Containers:   Empty  containers, paper  bags,  or fiber drum liners
that contain residual amounts of organic intermediates or other raw materials.

Synthesis Wastes;   Generally,  these  include  the  byproducts of the various reaction
steps prior to  finishing.  The byproducts are  formed  as a  result of  undesirable side
reactions that  occur in series or in parallel to the main reaction leading to the desired
product.  Synthesis  wastes also contain unconverted  reactants  and coproducts (e.g.
salts), all dissolved in the reaction medium such as water or solvent.

As  to the form, composition, and the point of  exit from the process, synthesis  wastes
vary. In the case of soluble azo dyes, these wastes exit as a solid cake from filtration
following coupling and in liquor following filtration of the precipitated dye. In case of
anthraquinone  dyes, the synthesis wastes would be present  in the distillation column
bottoms, which also  contain organic solvent.

Considerable variability in  the treatment and  ultimate disposal of synthesis wastes is
expected given the  large number of manufacturing facilities.  Some plants treat the
filter cakes with hypochlorite solution to reduce the amount of organic  material prior
to land disposal of the left-over solids. The aqueous waste containing  residual organic
and  inorganic  compounds can be also treated  by oxidation  to reduce  oxygen demand,
color and  turbidity  to acceptable levels prior  to discharge.  The alternatives  for
solvent  waste  include solvent recovery  and/or disposal of residuals via  landfilling or
incineration.

Product Finishing Wastes;  Since equipment cleaning and spill/off-spec product  wastes
are considered separately, the wastes  from the finishing steps include  dusts generated
during drying  and grinding  which are  collected  in the  baghouse.  Additionally, these
wastes would include residual water or organics from the flushing step.  Usually, these
wastes are minor in  comparison to other waste categories noted.
                                   B7-12

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                                 Table 7-1  Organic Dye/Pigment Manufacturing Process Wastes
         No.
         Waste
      Description
     Process Origin
     Composition
RCRA
 Code
                    Used containers
                              Unloading of raw materials
                                paper bags and fiber drums
                                containing residual amounts
                                intermediates
03
^l
i
                    Synthesis wastes
Product finishing
wastes
                    Equipment cleaning wastes
                    Spills and off-spec
                    products
                              Reaction steps
Product drying, flushing,
grinding, standardizing,
packaging

Cleaning of equipment
between batches
                              Cleaning of spills, off-
                              spec product generation
water, organic solvents,
metal salts, inter-
mediates, side reaction
byproducts

dyes, pigments, inter-
mediates, inert salts,
auxiliary oils

dilute alkaline or acidic
aqueous solutions or sol-
vents with small amounts
of residual organics

dyes, pigments, organic
intermediates.
                                                               F002
                                                               F003
                                                               F004
                                                               F005

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Equipment Cleaning Wastes;  These include  aqueous and solvent streams associated
with the cleaning of reactors, transfer lines and equipment.  Cleaning is done between
consecutive dissimilar batches in order to prevent contamination. It is expected that
in an  average facility employing  a number  of  reactors,  tanks  and filter presses,
cleaning  is  performed  using  a  clean-in-place system  employing either  flow-over or
fill-and-empty techniques. The  ball mills and other mechanical equipment used in the
finishing operations is expected to be cleaned using fill-and-empty approach.

The  cleaning  medium can be alkaline aqueous solution  or solvent.   At  times,  an
oxidizing agent, such  as hydrogen peroxide, may be added.  The sludge separated  from
the cleaning solution can  be co-mingled with  other solid process residuals prior to
possible  treatment  and  disposal.   The  aqueous  effluent  is  neutralized  prior  to
discharge, but can also be  mixed with liquid streams from the synthesis step prior to
neutralization, treatment and discharge.

Spills and Off-Spec Products:  These wastes  are generated  as a result of inadvertent
operation,  usually attributable to human error. Again, diversity  of chemical species,
availability of  treatment, and plant operating procedures  prevent one from  compiling
precise information on handling  and disposal of  these wastes. However, it is expected
that a high degree of  effort is expended in  attempts to  recover valuable  chemicals
from spills or spoiled batches before spill  wastes are  disposed of  as residuals, probably
through landfilling.

8.   WASTE GENERATION RATES

Recent effort  has been made to characterize the waste streams generated from the
manufacturing of organic dyes  and pigments (SRI 1984).   Information  about the
quantity of these  wastes,  however, was not  in  evidence  at the time of the  final
document preparation.  The relative proportions of each waste stream were  estimated
by project staff based on the available information and  are given in Table 9-1.
                                     87-14

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9.   WASTE REDUCTION THROUGH SOURCE CONTROL

9.1   Description of Techniques

A summary of the waste sources and the corresponding source reduction methods  is
given in Table 9-1.  This section  deals  with  the  description of the listed  methods,
including known application cases.

In addition  to the waste reduction measures  classified  as  being  process  changes or
material/product substitutions, a variety  of waste reducing measures  labeled as "good
operating practices" has also been included.  Good  operating practices  are defined as
being procedural or institutional policies which  result in a  reduction of waste.   The
following items highlight the scope of good operating practice:

     o     Waste  stream segregation
     o     Personnel practices
                management initiatives
                employee training
     o     Procedural measures
                documentation
                material handling and storage
                material tracking and inventory control
                scheduling
     o     Loss prevention practices
                spill prevention
                preventive maintenance
                emergency preparedness

For  each waste stream,  good operating  practice  applies whether  it is listed  or  not.
Separate listings have been provided whenever  case studies were identified.

9.1.1  Containers

Raw materials used in the production of  organic dyes and pigments are  usually shipped
in paper bags or fiber drums.  Since some of these materials are toxic in  nature, the
discarded  containers containing  residual  amounts  of these substances  can  be
considered as hazardous.  The following source  reduction techniques were noted:
                                    yB7-15

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      o     Use rinsable/recycleable drums and plastic liners.
           The use of polyethylene bags to line steel drums is already well established
           in the industry along with the use of reusable tote bins. The residual use of
           paper bags or liners should be eliminated.

      o     Maximize size of container.
           Here, the underlying principle  is that the same  volume of material has a
           smaller external surface if supplied in a  single container  as  opposed to a
           number of smaller containers.  As the residual amount depends on the size
           of  the "wetted" surface, less waste  residue  will result  from  the  use  of
           larger containers.  Switching from drums  or bags to  mega-drums, tote bins
           and,  where possible, to bulk  handling has already been accomplished to a
           significant degree, but  a  moderate improvement margin probably exists.

      o     Container segregation.
           Since only  the  organic  intermediates   and  a  few  other  reagents  are
           hazardous while  a large amount of other  raw materials, such as inert salts
           used  for dye and pigment standardization  operations, are not, separation of
           the different types of  empty disposable containers can greatly reduce the
           amount of potentially hazardous waste generated from  this source.

9.1.2  Synthesis Wastes

In the azo dyes example, synthesis steps include diazotization, coupling and precipita-
tion.  In a more general context, the  synthesis of all dyes and pigments from raw
materials can result in  the  generation of hazardous waste due to (1) the  formation of
by-products, (2)  the use of toxic  catalysts,  or  (3)  the use of toxic raw materials.
Modification  of  the synthesis process can lead  to substantial  waste  reduction.  The
following source reduction techniques were noted:

      o     Eliminate the use of toxic catalysts.
           Catalysts containing toxic metals  are often used to manufacture dyes and
           pigments. Mercury catalyst used  to  produce anthraquinone  dyes  for  the
           coloring of cottons was replaced with a less toxic substance (NJDEP 1985).
                                    B7-16

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Reduce the use of toxic raw materials.
Reduction of the toxicity of hazardous waste can be achieved through the
elimination  or  reduction   of  the  use  of  highly  toxic  reactants  and
intermediates.    For  example,  since  benzidine  has  been  identified  as
carcinogenic, its use has been eliminated by most of the  U.S. dye  and
pigment  manufacturers (Radian  1977).   In addition,  some manufacturers
who used to make intermediates for the  production of anthraquinone dyes
(which requires the use of toxic  mercury catalysts)  have  stopped their
production and  import these intermediates instead (Catino and Ferris 1979,
Bannister, Olin, and Stingle 1979, Fytelson 1982).  While this measure  will
reduce the overall amount of hazardous waste generated in the U.S., it only
shifts the problem to the foreign suppliers. In general, the use of less toxic
substitutes should be explored most intensively in the area of auxiliary  raw
materials, i.e.  those that  do not undergo conversion  to the  final product.
For example, the use of xylene as a solvent can be re-examined from the
standpoint of substitution with less toxic  solvent, e.g. acetone.  Also, use
of non-chromate treatment for cooling  water will lower the toxicity  of the
blowdown sludge (which is not a part of  "synthesis  waste"—its inclusion is
intended to illustrate the approach).

Minimize byproduct formation.
Modifications of the synthesis process to increase yields and reduce by-
product  formation  are extremely  specific to  the manufacturing  of each
different dye or pigment.   Each process  should be  investigated separately
to  identify  potential  waste  reduction  techniques.    To exemplify  the
approach, the following process  modifications applicable to  azo dyes were
identified as candidates for future evaluation:

      Use an  optimum pH range  for  a   particular  combination of diazo
      salt/coupling components.  Since higher pH increases both the rate of
      the coupling  reaction  and  the  rate of  formation of  undesirable
      byproducts, it is likely  that  there  is an optimum  pH range  which
      maximizes the yield of the desired product.

      Shorten  the  residence  time  before   coupling to   minimize   the
      decomposition of diazonium salts.  Since diazonium salts can readily
                         B7-17

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                decompose in the coupling medium to produce phenolic compounds as
                byproducts, the time it takes to transfer these salts to the  coupling
                reactor should be minimized. This can be accomplished by combining
                clarification operation  with a fast transfer to the coupling  reactor,
                e.g. by using a pump  with the associated filter.  The piping and filter
                casing can be emptied  using pressurized  nitrogen  following  the
                transfer.   Pre-cooling  of the coupling  reactor would help  to limit
                detrimental temperature rise.

In  general,  the  avenues which may,  upon  exploration,  lead to further increases in
reaction yields and thusly to the decrease of  byproduct waste generation include:

                search for more selective catalysts.
                modification of reaction temperature trajectory.
                modification of reaction addition strategy (rate of sequence).
                modifications to provide higher degree of mixing.

      o     Modification of filtration process.
           By eliminating  the need for filter aids, the amount of solid waste generated
           can be reduced. For cases in which a precoat-type pressure filter is being
           used for clarification, switching to  a bag-  or a leaf-type filter (LWVM
           1985) would  eliminate the need  for filter aids,  which does  result in  a
           reduction of the volume of discarded cake.

           Generally,  improvement  in   filtration  efficiency  will  result in  better
           product recovery and, subsequently, in less waste.  Such improvement  can
           be obtained through the use of multistage versus single stage filtration,  the
           recycle of  mother liquor during the initial cake-building period, the use of
           a  cake-gasketed recessed plate  instead  of  the  conventional  plate-and-
           frame  (or the use of recessed plate filters to  reduce leaking and wearing of
           the filter medium), or the use of low-temperature air to blow dry the filter
           cake to prevent the filter cloth's deterioration, which can result in leaking,
           and other techniques.
                                    B7-18

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9.1.3   Product Finishing Wastes

Drying of dyes and pigments is done with rotary dryers, spray dryers, or drum dryers in
hot air or in vacuum ovens.  The following source control technique is proposed:

     o     Replace steam jets with vacuum pumps.
           In cases where steam jets are used to generate a  vacuum, wastewater can
           be generated  through contamination  by process vapors  or  dusts  of the
           cooling  water used in the barometric condenser.   This  may  represent  a
           significant source of  waste from the production of dyes which require
           extensive use of  organic  solvents (e.g. anthraquinone dyes).   The  waste-
           water generated  can be avoided  through the use of  vacuum  pumps  with
           surface  condensers.   The  use  of a surface condenser  will  increase  the
           potential recyclability of condensate.

Solid waste is  generated from  the  collection of dust in baghouses  during  material
handling,  grinding,  blending, and  standardizing  operations.   The  following  source
control techniques are noted:

     o     Use wet instead of dry grinding.
           Dye and  pigment products can be ground wet using ball or sand mills and
           subsequently spray-dried.   This  operation will reduce the amount of  dust
           emitted in comparison to  the  use of  the  conventional  dry grinding step.
           This method is used only for water-insoluble dyes and pigments.

     o     Increase the use of dust suppression techniques.
           Dust emission can be suppressed through the use of atomized water sprays,
           enclosed   weigh-transfer  hoppers, or  better  care  in  manual  material
           handling.

     o     Recycle baghouse fines.
           Baghouse hopper emptying  should be scheduled for possible recycling of the
           dye or pigment fines.  Baghouse hoppers should be  cleaned before and after
           the  manufacturing of a large quantity of  a particular dye or pigment to
           recover these products.  This practice is feasible  only  for plants producing
           a very limited number of dyes or pigments.

                                   B7-19

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9.1.4   Equipment Cleaning Wastes

These constitute a significant fraction of the total waste generated during organic dye
and pigment manufacture, which is typical for any batch process.  The subject of  how
to minimize equipment cleaning waste is discussed in a separate study (#322) found in
this appendix, and is of universal importance to the entire chemical process industry.
The reader is referred to that study for a general characterization of source  control
approaches.

Based on the information available, it appears that a two-step rinse with a maximum
utilization  of cleaning solution  as  a make-up in the  next  compatible batch is an
approach utilized to a  significant degree by the organic dye and pigment industry.

9.1.5   Spills and Off-Specification Product Waste

As previously mentioned, spills and off-specification products result from inadvertent
operations  usually attributable to human error.  At times, such losses can also result
from inadequate provisions  for contingencies.  For example,  a diazotization reaction
requires that solution  is maintained at 32-40°F, which necessitates the use of coolant
maintained by  a  refrigeration system.  If  a  refrigeration system  malfunctions  and
coolant flow is stopped, the  batch can be spoiled.  Provision for  an  adequate surge
capacity of chilled coolant  may extend  the  time  in which  the refrigeration plant can
be brought back on stream  without spoiling  the batch.  In general,  avoidance of spills
and generation  of off-spec products could be promoted by the following source  control
techniques:

     o     Increased use of  automation.
           This includes automated batching systems,  monitoring of the  adequate
           number of  process function, and  automatic control of fail-safe  and "fail-
           clean"  shutdown  features.   Use  of supervisory  computer  control is
           recommended for exploration.

     o     More intensive in-process quality  control.
                                    B7-20

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     o     More thorough cleaning of process equipment and piping.
           This  measure  would  reduce contamination  that may cause  an off-spec
           batch.

     o     Better operating practice.
           This  includes  personnel  training,  better  supervision,  spill  prevention
           programs,  and   other  measures  that   fall   under  the  category   of
           procedural/institutional  modifications.   For  a detailed discussion,  the
           reader is referred to the separate study in this appendix.

9.2  Implementation Profile

Reduction  of wastes  from  the  manufacture  of organic  dyes and  pigments can  be
achieved either  through process modifications in the synthesis of  the dye, or through
improvements in operating  practices  in  the area  of  product  finishing, equipment
cleaning and  materials  handling.   A  detailed  characterization  of optimal waste-
reducing process modifications  which  lower  the generation of synthesis  waste is
difficult to accomplish due to the large number of processes used to produce the wide
variety  of  dyes  and pigments  currently on  the  market.  Process modifications may
require  significant research and development expenditures and lengthy periods of time
to become established.  Given the shift from domestic production  to imports, some
companies  may lack sufficient incentives to pursue additional development work.

Improvements  in  operating practices, on  the  other  hand, are applicable  to  all
processes.  These are easily implemented as they typically require only minor changes
in operational procedure  or  the  addition of simple  equipment or controls.  However,
they are not as effective  as  process modifications in reducing  the generation  of
hazardous waste.

9.3  Summary

The  sources  of  waste from the manufacture of organic  dye and  pigment and their
respective  source control techniques are summarized in Table  9-1.  The ratings listed
in the table are  based on  a scale of 0 to 4 and are used  to evaluate each technique for
                                    B7-21

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                          TABLE 9-1 SUMURY OF SOURCE CONTROL METHODOLOGY FOR THE ORGANIC DYE / PIGMENT MANUFACTURING  INDUSTRY
4 	

Haste Source

Used Containers



Synthesis Haste (*




Product Finishing
Hastes



Equipment Cleanlni
Hastes
Spills and Off-
Specification
Product Hastes


| All Sources
1

1
1
li-

is.
1
)M

|3.
!«•
1
M-
12.
|3.
l«.
1
|1-
1
I'-
|2.
13
I'-
1
1
1

Control Methodology |-
1
Use liners and recyclable drums |
Max1n1ze container size |
Container segregation |
Overall |
Eliminate use of toxic catalyst |
Eliminate use of toxic raw materials |
Minimize byproduct formation !
Modify filtration process I
Overall |
Replace steam Jets with vacuum pumps |
Use wet grinding |
Dust suppression |
Recycle baghouse fines |
Overall 1
See study on equipment cleaning (B22)|
Overall |
Increased automation |
Intensify quality control |
Thorough equipment cleaning |
Better operating practices |
Overall 1
All Methods
Found Documentation | Waste | Cxtent of | Future | Fraction of | Current | Future Reduction index I


Quantity | Quality I Effectiveness | | Potential | | Index | Probable | Maximum |
1 | 1 | 3 | 3 | 2 | 2 3 | 0.4 | 04)
t | 1 I 2 | 3 | 1 | | 1.5 | 0.1 | |
1 | 1 1 3 | 3 | 1 | 2.3 | 02| i
1.00 | 1.00 | 2.67 | 3.00 | 1 33 | 0.02 | 2.3 | 0 2 | 0 4 |
t 1 1 I 3 | 1 | t I | 0 8 | 0 6 | |
1 | 1 | 3 | 1 | 2 | | 0 8 | 11| 1.1 |
t | t | 3 | 3| 3 | | 2.3 | 0.6 | |
0 | 0 | 1 | 3 | 2 | I 0 8 | 0 1 |
0.75 | 0.75 | 2.50 | 2.00 | 2 00 | 0.60 | 2.3 | 0.6 | 1.1
1 | 1 | 2 | 2 | 3 | | 1.0 | 0.8 | 08
0 | 0| 3 | 3 | 1 | I 23| 0.2 |
0 | 0 | 1 | 1 | 1 | | 0 3 | 02|
0 | 0 | 2 | 0 | 1 | | 0 0 | 0.5 | |
0.25 | 0.25 | 2 00 | 1.50 | 1.50 | 0 05 | 2.3 | 0.4 | 03
— | — | — | — | — | | 2 6 | 0 7 | 1.4
— | — | — | — | — | 0.32 | 2.6 | 0.7 | 1.4
1 | 1 | 3 | 2 | 3 | | 1 5 | 1 1 | 11
l| 1 | 2 | 3 | 2 | | 1.5 | 0.3 |
1 | 1 | 2 | 3 | 2 | | 1.5 | 0.3 | |
1 | 1 | 3 | 3 | 3 | 2.3 | 0.6 |
1.00 | 1 00 | 2.50 | 2.75 | 2 50 | 0.01 | 2.3 | 0.5 | It
| 1.00 | 2.4 | 0.6 | 1.2
00
       (•)  These waste streams contain listed "F" and/or 'K' RCRA wastes.

-------
its  waste  reduction  effectiveness,  extent  of  current  use  and future application
potential.  The ratings were derived by project  staff from  the available information
and from industry comments.

It appears that the current level of waste minimization in the manufacture of organic
dyes and pigments is high.  This is evidenced by the current reduction index (CRI) of
2.4  (60  percent) which measures the extent  of reduction in the waste that  otherwise
would be generated if none of the listed methods  were applied as they are currently.

The  potential  for  future reductions appears  modest,  as  evidenced by the  future
reduction index (FRI) of 0.6 to  1.2 (15 to 30 percent).   The future reduction index is
the  measure  of waste  reduction  achievable  through  implementation of the  listed
techniques to their rated extents.  The greatest potential for future reductions appears
to reside  in eliminating  the use of toxic raw  materials and increasing the  degree of
automation within the production process.

10.   PRODUCT SUBSTITUTION ALTERNATIVES

The  production of  organic  dyes and pigments is inherently  dynamic in nature since
changes in the demands for these products are easily induced by several factors. Such
factors include the possibility of creating new dyes with  better qualities, the invention
of new  products that require completely different types of dyes for coloring purposes,
or the  improvement of existing  dye technology which will  affect the selection as well
as the  quantity of the dyes  being used. For  example, disperse dyes have attained wide
usage due to the growth  of synthetic fabrics.   Furthermore, improvements in dyeing
operations,  such as increased use of automation, or the introduction  of new dyeing
techniques,  such as low-liquor jet dyeing, will enhance the  performance of one  dye
over another,  and thus will  make its selection  more favorable.  The growth of inactive
dyes serves as a good  example  for  this  effect.   Reactive dyes are  used to color
cellulose-based materials, and are preferred  over other dyes due to their wide range of
shades, excellent wet fastness, and simple application method. However, problems are
encountered in the use of these dyes due to  the  low degree  of exhaustion and fixation
observed.  This defect creates problems in the form of  difficult pollution control  and
excessive energy  usage  which  tend  to discourage  the use  of these dyes.  Research,
however,  is being  done   to counteract  these  problems through  the use of  fixation
                                    B7-23

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accelerators  or  the  development of short-liquor dyeing and low  temperature dyeing
techniques (Abeta, Yoshida, and Imada 1984).  Once these  barriers are overcome, the
production of reactive dyes is expected to increase significantly.

In summary, changes  in  the  dyeing industry,  as  well as increasing focus  on  the
selection and manufacture of less toxic dyes and pigments,  will significantly affect the
future production of  organic dyes and pigments.

11.    CONCLUSIONS

Although significant  waste reduction efforts have been made by the manufacturers of
organic  dyes  and pigments,  opportunities for  potential  future reduction  remain
numerous.  Based on  available information, an  additional 15 to 30 percent of waste can
probably be reduced if the proposed source  reduction techniques are implemented.
While source reduction measures associated with the dye synthesis stage of production
are individually  quite effective, implementation of these  techniques can  be difficult
due to the diversity  of the processes used  to produce dyes and pigments in a single
plant. Furthermore, the  extent of waste reduction in one plant  may differ  greatly
from  another one.   The  most  promising universal approach  to waste reduction for
synthesis stage,  however,  would be to eliminate the use of toxic raw materials, or to
modify the existing process to achieve better product yield.

In addition  to source  reduction methods, changes in  dyeing technology  and/or  the
development of  new  materials by the textile industry can also significantly affect the
production demand for organic dyes  and pigments.   This  in turn can alter the waste
load generated from  the manufacturing process.

12.    REFERENCES
Abeta, S.,  Yoshida,  T.,  and Imada, K. 1984.   Problems and progress in reactive dyes.
American Dyestuff Reporter.  73(7): 26-31.
Anonymous, 1984. New products review.  American Dyestuff Reporter.  73(12).
Bannister, D. W., Olin, A.  D., and Stingle,  H. A. 1979.   Dyes and  dye intermediates. In
Kirk-Othmer Encyclopedia of Chemical  Technology.  3rd ed. Vol. 8, pp. 159-212.  New
York, N.Y.: Wiley.
                                   B7-24

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Catino,  5.  C., and Farris,  R.  E.  1979.   Azo dyes.   In Kirk-Othmer Encyclopedia of
Chemical Technology. 3rd ed.  Vol. 3, pp. 387-432. New York, N.Y.: Wiley.

Fytelson, M. 1982.  Pigments: organic.   In Kirk-Othmer Encyclopedia of Chemical
Technology. 3rd ed. Vol. 17, pp 838-71. New York, N.Y.: Wiley.

Griffiths,  J.  1984. Developments  in the chemistry  and  technology of organic dyes.
Oxford: Blackwell Scientific Publications.

LWVM,  1985.  The League of  Women Voters in Massachusetts.  Waste reduction; the
untold  story.  Seminar Proceeding at the National  Academy of Science, Conference
Center,  June  18-21.    Woods  Hole,  Mass.:   The  League  of  Women   Voters  in
Massachusetts.

MRI 1981.  Midwest Research  Institute.  Material balance for dyes and pigments from
benzidine and the benzidine derivatives.  EPA-560-2-81-001.  Washington, D.C.:  U.S.
Environmental Protection Agency.

NJDEP, 1985.   New Jersey  Department of Environmental Protection, Division of
Waste  Management.   Source  reduction of hazardous  waste.  Seminar Proceeding at
Douglas College, Rutgers University, August 22,  1985. New Jersey:  N.J.  Department
of Environmental Protection.

Radian  Corp.  1977.   Industrial process profiles for environmental use:   Chapter 7;
organic dyes and pigments industry.   EPA-600-2-77-023g.   Cincinnati,  Ohio: U. S.
Environmental Protection Agency.

SRI  1984.   Stanford Research  Institute.   Wastes from manufacture of dyes  and
pigments;  Vols 1-9.   PB   84  -  200 864.   Washington,  D.C.:  U.  S.  Environmental
Protection  Agency.

USDC 1985.  U.S. Department of Commerce, Bureau of the Census.  Industrial organic
chemicals in 1982  Census  of Manufacturers.  MC82-1-28F.   Washington, D.C.:  U.S.
Government Printing Office.

USITC 1983.  U. S. International Trade Commission.  Synthetic organic chemicals, U.S.
production  and sales.  USITC Publication  No. 1588.  pp. 57-89.Washington,  D.C.: U. S.
Government Printing Office.

13.  INDUSTRY CONTACTS

Newby, W.E., E. I. duPont de Nemours & Co., Inc. (retired), Wilmington, DE.

Bowers, D.P.,  Senior, Director of  Environmental  Control,   Merck  Chemical Manu-
facturing Division, Merck &. Co., Inc., Rahway, N.J.
                                   B7-25

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1.    PROCESS: PAINT MANUFACTURE
2.    SIC CODE:  2851
3.    INDUSTRY DESCRIPTION

As  defined  by Standard Industrial Classification (SIC)  2851,  the paints and allied
products industry "comprises establishments primarily engaged  in the manufacture of
paints  (in paste and ready  mixed form), varnishes, lacquers,  enamels and shellacs,
putties, wood fillers and sealers, paint and varnish removers, paint brush cleaners, and
allied  paint products".   Establishments  engaged in the  manufacture  of pigments
(organic or inorganic), resins, printing inks, adhesives and sealants, or artist materials
are not included.

3.1  Company Size Distribution

Of the 1,441 paint manufacturing facilities located in the U.S. in 1982, more than 55
percent employed less  than  twenty people each.   Overall, the  Bureau of the  Census
(USDC 1985) estimated  that 54,100 people were employed by the paint manufacturing
industry.  Table 3-1 lists company size  distribution as  a function  of total number of
employees at a given site.

                       Table 3-1 Company Size Distribution


No.
No.


of establishments
of employees

Total
1,441
54,100
No. of Employees per Facility
1-19 20-49 50-99
819 331 171
6,400 10,500 11,800

100+
120
25,400
Source:     1982 Census of Manufacturers (USDC 1985).

3.2   Principal Producers

The  paint  manufacturing  industry  is  composed  of  a small number of multi-plant,
multi-product companies and a large number of single-plant companies.  The  eight
major paint producing companies in the U.S. are listed below:
                                   B8-1

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           Sherwin-Williams                           Clorox
           PPG Industries                             Valspar
           SCM Corp (Glidden)                        De Soto Paints
           Inmont                                    Insilco Corp.

3.3   Geographical Distribution

     Due to the  expense of transporting products over long  distances, paint plants
     tend to be clustered around population centers.  Approximately 44 percent of all
     paint sites are  located in five states (California, New Jersey, New York, Illinois,
     and  Ohio),  with 67  percent being located in ten states.  Distribution by  EPA
     regions are shown in Figure 3-1 and Table 3-2 below.

                 Table 3-2 Location of Facilities by EPA Region
EPA Region
I
II
III
IV
V
VI
VII
VIII
IX
X
No.
1-19
55
133
54
110
191
58
46
12
134
26
of Employees
20+
31
87
51
99
168
50
31
5
81
19
per Facility
Total
86
220
105
209
359
108
77
17
215
45
                National             819         622            1441
Source:    Assessment of Industrial Hazardous Waste Practices (WAPORA 1975)
           adjusted to reflect number of establishments listed in the 1982
           Census of Manufacturers (USDC 1985).
                                   B8-2

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00
03

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4.   PRODUCTS AND THEIR USE

Most small plants produce paint in 10 to 500 gallon batches.  Plants with more than 20
employees tend to produce paint in 1,000 to 3,000 gallon batches*.  Overall, the paint
industry sold 8.6 billion dollars worth of product in 1983 ($3.9 billion for architectural
coatings,  $3.0  billion  for product  coatings,  and $1.7 billion  for  special  purpose
coatings) (Webber  1984).  The  amounts and distribution of products manufactured by
the paint industry in 1983 are shown below.
                Table 4-1 1983 Paint Products and Use Distribution

     Architectural Coatings                              463  million gallons
     Product Coatings                                    331  million gallons
          Metal containers                                     19%
          Automotive                                          16%
          Machinery                                            6%
          Sheet, strip and coil                                   6%
          Metal furniture                                       5%
          Other                                               48%
     Special Purpose Coatings                             130  million gallons
          High performance maintenance                        31%
          Automotive and machinery refinishing                 29%
          Traffic paint                                         14%
          Other                                               26%

     Source: Chemical and Engineering News (Webber 1984).

For an average paint  plant  located  in  the  U.S., 60  percent of its total  annual
production would be solvent-based  paint, 35 percent would be  water-based paint, and 5
percent would  be  allied products.   While  a  large  percentage of  paint used  for
architectural coating  is  water-based (more than  70 percent), solvent-based paint is
still predominately used for product and special purpose coatings.

5.   RAW MATERIALS

Annual consumption rates of raw  materials used by the paint manufacturing industry
are shown in Table 5-1.
•"•Confidential source 1985: Personal communication.

                                  B8-4

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     Table 5-1 Raw Materials Used by the Paint Manufacturing Industry in 1982
       Materials
       Usage
Resins
Solvents
Pigments
Extenders
             Alkyd
             Acrylic
             Vinyl
             Other
             Aromatic
             Aliphatic
             Ketones
             Alcohols
             Other
             Titanium dioxide
             Inorganic^3'
             Organic
             Calcium carbonate
             Talc
             Clay
             Other
Miscellaneous
             Drying Oils
             Plasticizers
             Other
1844 million  Ibs/yr.
   33%
   19%
   19%
   29%

3774 million  Ibs/yr.
   30%
   27%
   17%
   12%
   14%

1062 million  Ibs/yr.
   65%
   33%
    2%

1162 million  Ibs/yr.
   31%
   25%
   23%
   21%

  220  million Ibs/yr.
   41%
   18%
   41%
Source:    Chemical Economics Handbook (SRI 1981) data for 1977 adjusted for 1982
           production rates.

(a)         Approximately 60 percent of the inorganic pigments used consisted of iron
           oxide, zinc  oxide, zinc  dust, and aluminum paste; 27 percent consisted of
           lead and chrome compounds; and 13 percent consisted of other.
                                   58-5

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The  major raw materials used to manufacture paint  are  resins, solvents, drying oils,
pigments, and extenders.  Based on the wide variety of paints produced, no one type of
material dominates the market.

6.   PROCESS DESCRIPTION

Detailed process flow diagrams  of  paint  manufacturing  have  been presented in the
open literature (Haines 1954, Payne 1961).  The following description briefly highlights
the production of the industry's  two main products:  solvent-based paint and  water-
based paint.   At a typical plant, both  types  of  paint  are  produced.  A block flow
diagram of the steps involved in manufacturing paint is presented in Figure 6-1.

The  production of solvent-based paint begins  by  mixing resins, ground pigment,  and
pigment extenders together in  a high speed mixer. During this  operation,  solvents and
plasticizers are  also added.  Following  the mixing operation, the batch is transferred
to a  mill for additional grinding and mixing. The type of mill is  dependent  on the types
of pigments  being  handled,  so that no one  style is universal.   Next,  the paint  is
transferred to an agitated tank where tints and thinner (usually a volatile naphtha or
blend of solvents)  are added.   Upon reaching the proper  consistency,  the paint  is
filtered to remove any  non-dispersed pigment and transferred to a  loading hopper.
From the hopper, the  paint is poured into cans, labeled, packed, and moved to storage.
The  typical batch size for a small plant will  range from 10 to 500 gallons while the
average batch size for a large plant will be 1,000 to 3,000 gallons.

The  typical paint plant produces about 60 percent solvent-based paint, 35  percent
water-based paint, and 5 percent allied product. The water-based paint process is very
similar to the solvent-based process.  The major difference is the substitution of water
for solvent and the sequencing of material  additions.  Preparation of water-based paint
begins by  mixing together water, ammonia,  and a  dispersant in a  mixer.  To  this
mixture, ground  pigment and pigment extenders are added. After mixing,  the material
is ground in a mill and then transferred to an agitated mix tank.  Four additions of
materials occur  in this tank.  First, resin  and plasticizers are  added  to  the mixture;
second, a preservative and an  antifoaming agent  are added; third, a polyvinyl acetate
emulsion is added; and fourth, water is added as a  thinner.  Following  this  mixing
operation,  the handling  of  the paint is  similar to that for  solvent-based paints.   At
                                    B8-6

-------
RESINS ,_
PIGMENTS <
EXTENDERS
SOLVENTS
PLASTICIZERS
I
GRINDING AND 1
NIXING-..- _|
©0©|
(
MATER
"a AMMONIA
DISPERSANT
PI6NENT
EXTENDERS
TINTS
THINNER


V
1
1
GRINDING |
\
NIX

I
r«e L 5
r^

RESIN
PRESERVATIVE
ANTIFOAM
PVA EMULSION
MATER
                               FILTERING
                              PACKAGING
                            FINAL PRODUCT
 PROCESS  NASTE  CATEGORIES:

 (7)    DISCARDED  RAM  MATERIAL CONTAINERS

 (?)    BA6HOUSE PISMENT DUSTS

 (D    OFF-SPECIFICATION PAINT

 (7)    FILTER CARTHIDBES

 (?)    EQUIPMENT  CLEANING HASTES
         Figure  6- 1   Block Flow Diagram for Paint Manufacture
                                    B8-7

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many facilities the grinding  and  the  mixing and grinding operation may be bypassed
with all the dispersion operations occurring in a single high-speed mixer.

7.    WASTE DESCRIPTION

Typically, paint facilities segregate and store waste only to the degree required by the
waste disposal contractor.  Since  the  degree of segregation can affect the amount of
material having  to be classified as hazardous, and the  cost of disposing of hazardous
material is  increasing,  paint  facilities  are  taking a  more  active  role  in  waste
management.  The major wastes  that the paint industry must manage are empty raw
material packages, dust from air  pollution control equipment, off-specification paint,
spills,  and  equipment cleaning wastes.   Equipment cleaning wastes  are  a dominant
waste stream.

The  primary  specific wastes associated  with  paint manufacturing  are listed in Table
7-1. Waste generated by the industry is  usually managed in one of  four ways:  on-site
reuse,  on-site  recycling, off-site  recycling, and  off-site  treatment/disposal (Ryan
1984).  On-site reuse involves the  reuse of waste (without treatment) as a feed or wash
material for producing other  batches of paint. Also included is the sale or in-house use
of off-specification paint as utility paint.  On-site  recycling involves the reclaiming of
solvent by distillation or recovery of heating  values by incineration.  Usually, on-site
recycling is  performed by large companies (those that produce  more  than 35,000
gallons of solvent waste each year) while small companies (those that produce 20,000
gallons or less per year) send  the waste to an off-site recycler.  The fourth  option, off-
site  treatment/disposal involves  incineration or land  disposal.  The extent of waste
currently being land disposed is unknown.

8.    WASTE GENERATION RATES

The  most recent published estimates of the  nationwide waste generation rates by paint
industry date back to 1974 and are presented in  Table 8-1 below.   While the  total
amount of waste  due to bags and  packages was reported to be 302,000 metric tons per
year  (WAPORA  1975),  the  actual  amount  of  hazardous waste (bags  containing
hazardous pigments) was only 2000 TRY. Since the estimate of 302,000 TRY included
recycled drums and pallets,  and because  the current industry practice is to segregate
hazardous from non-hazardous waste, only the hazardous amount is  presented so as not
                                    B8-8

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                                    Table 7-1 Paint Manufacturing Process Wastes
         No. Waste Description
                                         Process Origin
                         Composition
RCRA Codes
         1.   Leftover raw materials in original
             containers
         2.   Pigment dusts from air pollution
             equipment

         3.   Off-specification paint
                                         Unloading of materials
                                         into mixing tanks
                                         Unloading of pigment
                                         into mixing tanks

                                         Color matching (small
                                         scale) production
                         Paper bags with a
                         few ounces of left-
                         over pigments

                         Pigments
                         Paint
CD
co
i
\o
4.  Spills
Accidental discharge      Paint
         5.   Waste rinsewater
         6.   Waste solvent
         7.   Paint sludge
                                         Equipment cleaning
                                         using water and/or
                                         caustic solutior\s

                                         Equipment cleaning
                                         using solvent
                                         Equipment cleaning
                                         sludges removed from
                                         cleaning solution
                         Paint, water, caustic
                         Paint, solvent
  E002
  FOD3
  F005
                         Paint, water, caustic,
                         solvent
         8.   Filter cartridges
                                         Undispersed pigment      Paint

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to distort the hazardous waste generation picture.  In addition, the amount of solvent
discarded only represents the amount of solvent considered by WAPORA to be toxic.

Current  waste generation rates were not in evidence  at the  time of final document
preparation.  According to one source,  these rates have changed  dramatically in the
last six years due to RCRA*.

      Table 8-1 1974 Nationwide Generation Rates of Specific  Wastes from the
               Paint Manufacturing Industry in metric tons per year
Wastestream
Empty bags and packages
Dust from air pollution equipment
Off-specification product
Spills
Cleaning of Equipment
Total
Total
TPY
2,000
1,600
4,900
5,400
82,000
95,900
Toxic
Solvents
TPY
--
--
580
85
13,600
14,265
Toxic
Metals
TPY
128
80
41
5
590
844
Source:  Assessment of Industrial Hazardous Waste Practices (WAPORA 1975).

9.   WASTE REDUCTION THROUGH SOURCE CONTROL

9.1  Description of Techniques

The  list  of  individual  primary waste streams and their sources along with a list of
source reduction methods  is presented  in Table 9-1.  The following sections  discuss
recommended waste  reduction  methods  and identified procedures.   The basis for
identification came  from published  accounts in the  open  literature  and  through
industry  contacts. It should be noted  that not many published accounts were available.
The reason for the lack of published data is probably that many of the methods used by
the paint industry are common sense measures (i.e. good housekeeping) and are not
viewed as being special  waste reduction  techniques  worth  extensive documentation,
analysis, or presentation.
  National Paints and Coatings Association 1986:  Personal Communication.

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In addition to the  waste reduction measures  classified as being process changes  or
material/product substitutions, a variety of waste reducing measures labeled as "good
operating practices" has also been  included.  Good operating practices are defined  as
being procedural or institutional policies which result in  a reduction of waste.  The
following items highlight the scope  of good operating practice:

     o     Waste stream segregation
     o     Personnel practices
                Management initiatives
                Employee training
     o     Procedural measures
                Documentation
                Material handling  and storage
                Material tracking  and inventory control
                Scheduling
     o     Loss prevention practices
                Spill prevention
                Preventive maintenance
                Emergency preparedness

For  each waste stream, good  operating practice applies  whether it is listed or not.
Separate listings have been provided whenever case studies were identified.

9.1.1      Bags and Packages

Inorganic pigments, which contain heavy metals and  may therefore  be classified  as
hazardous are usually shipped in 50 pound bags.  After emptying the bag, an ounce  or
two  of pigment  usually remains inside.  Empty containers  of liquid raw materials that
constitute hazardous waste (e.g.  solvents and resins) are typically cleaned or recycled
to the original raw material manufacturer  or to a local drum recycler.  Empty liquid
containers are excluded from the following  discussion.  The following waste reduction
techniques for bags and packages were noted:

     o     Use of water soluble bags for toxic pigments and compounds used in water-
           based paints.
           When empty, the bags could be dissolved or mixed in with the paint. Such a
           method  is commonly used for handling mercury compounds and other paint
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           fungicides*. This method could not be used, however, when producing high
           quality, smooth finish paint since the presence of this material could affect
           the paint's film forming property**.

     o     Use of rinseable/recyclable drums with plastic liners instead of paper bags.

     o     Better operating practices (Identified).
           Through industry contacts, it was established that the most effective way
           of reducing  hazardous  waste associated with  bags and  packages (or  any
           other waste stream) was to  segregate the hazardous materials from the
           non-hazardous  materials  As an example,  empty  packages  that contained
           hazardous materials should be placed into plastic bags (so as to reduce or
           eliminate  dusting  which  can lead  to contamination  of  non-hazardous
           material and should be stored in a special container to await collection.

9.1.2       Pigment Dust from Air Pollution Equipment

Some of the dusts generated during the handling, grinding, and mixing of pigments can
be  hazardous.   Therefore,  dust collection equipment- (hoods, exhaust  fans,  and
baghouses) are  provided to minimize a worker's exposure to localized  dusting and to
filter ventilation air exhaust.  As of  1974, 15 percent of the  pigment dust collected in
baghouses was reused to make low-grade paint with the remaining 85 percent drummed
for disposal (WAPORA 1975). The waste reduction methods considered consist of:

     o     Dedicated baghouse system for pigment loading area (Suggested).
           At Daly-Herring Co.,  in  Kinston, N.C., (while Daly-Herring is engaged in
           formulation  of pesticides and not paints, there are many material handling
           problems common to both  industries) dust streams from several different
           production areas were handled  by  a  single  baghouse.   Since  all of the
           streams were mixed, none  of the waste could be recycled  to the process
           that generated  them.  By installing separate dedicated baghouses for each
           production line, all of the collected pesticide dust recycled (Huisigh et al.
* Confidental source 1985:  Personal communication.
**  E.I. Du Pont de Nemours & Co.  1985: Personal communication.

                                    B8-12

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           1985).  While this example is not intended to  imply  that most of the dust
           generated by the paint industry could be recycled, it does show the  overall
           importance of keeping waste streams segregated.

     o     Use of pigments in paste form instead of dry powders.
           Pigments in paste form are  dry pigments  that have  been  wetted or mixed
           with resins.  Since  these  pigments are wet, less or no  dust  is generated
           when the package is opened.  In addition, most pigments in paste form are
           supplied in drums (which  can be  recycled) and therefore would eliminate
           the  waste   due  to empty  bags.   While this method  would increase the
           amount of  pigment  handling occurring at  the  supplier's facility, it can be
           argued  that the overall number of handling/transfer  points for dry  powder
           would be  greatly reduced along with the  probability of spills and dust
           generation.

     o     Better operating practices.
           Scheduled  baghouse hopper emptying  could  be done  to reduce  the  amount
           of hazardous waste generated.  The major portion of solid waste collected
           by   the  air  pollution  equipment  is  titanium  dioxide and  extenders.
           Hazardous  pigments make up only a small fraction of the waste and would
           only be present during colored  paint  production.   Since many facilities
           produce colored paints on  a non-continuous basis (i.e., once a week  or once
           a month),  scheduled cleaning  of  the  equipment  to  coincide with  colored
           paint production  would allow for segregating the  waste that contained
           hazardous pigments  from that which did not.

9.1.3       Off-Specification Paint

Most off-specification paint is produced by small shops that deal in specialty paints.
Since these paints  cost more to produce, and therefore sell at a premium price, most
off-spec  paint  is reworked into a salable product. Since elimination of off-spec paint
production has built-in economic incentives, the following  techniques are widely used:

     o     Increased automation.
                                    B8-13

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     o     Better operating practices.
           Industry contacts indicated that better operating practices (better operator
           training,   closer  supervision,   and   tighter  equipment  inspection   and
           maintenance), and increased use of  automation  were extremely effective
           at reducing the amount of  waste generated.   Overall, better operating
           practices are widely used by the paint industry while increased  automation
           is just starting  to  be implemented.   As the  cost of digital electronic
           controls further declines, more of the paint  industry is expected to take
           advantage of automation.

9.1.4       Spills

Spills are due to accidental or inadvertent discharges usually occuring during  transfer
operations or equipment failures (leaks).   Spilled  paint and the  resulting  clean up
wastes  are  usually   discharged  to  the  wastewater treatment system   or  directly
drummed for disposal. If the plant has  floor drains, large quantities of water are used
to clean  up water-based  paint spills.   Dry  cleaning  methods (using sawdust) are
employed for cleaning of solvent-containing spills or for water-based spills  where  floor
drains  are not  available.   The average amount  of paint  spilled at each facility  is
approximately  5 gallons per year, however,  a  few  large spills can  move it  to 100
gallons  per year (WAPORA 1975).     Similar to the case  of off-spec paint,  waste
reduction methods include:

     o     Increased automation.

     o     Better operating practices.
           The  use of dry cleanup  methods (sawdust, mopping) should be maximized
           wherever possible.  By closing floor drains, employees are discouraged from
           grabbing  a hose and washing down the area (WAPORA 1975, USEPA 1979).
           In addition, a large decrease  in wastewater  is  achieved  since the floors
           cannot be routinely washed.
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9.1.5       Equipment Cleaning Wastes

For a general discussion of equipment cleaning in the process industries, the reader is
referred to a separate study (#B22) included in this appendix. The text below discusses
issues specific to the  paint manufacturing  process.  Equipment cleaning is responsible
for most of the waste generated  during the  paint manufacturing process.  Following
the  production of  either solvent  or  water-based paints,  considerable waste  or
"clingage" remains affixed to the sides of  the preparation tanks.  The three specific
methods of  tank cleaning used in the paint industry are  solvent washing for solvent-
based paint,  caustic  washing for either   solvent or  water-based  paint, and  water
washing for  water-based paint.

Equipment used for preparation of solvent-based paint is  rinsed with solvent, which is
then generally reused in  the following ways:

           Collected  and  used in the next compatible batch of paint as  part  of the
           formulation.
           Collected and re-distilled either on or off-site.
           Collected  and  used with or  without settling for equipment cleaning  until
           spent.  When the solvent is finally  spent, it is  then drummed for disposal.

As of 1974,  thirty-five  percent of the solvent  waste  produced was recycled off-site
and eight percent was recycled on-site (WAPORA 1975).  Recycling  of spent solvent is
usually  not  practical  whenever the  solids  concentration  exceeds ten  percent  or the
level of inhibitors and stabilizers in the recycled solvent is low. Of all the solvent that
is recycled, seventy-five percent  is  recovered with  the remaining portion disposed of
as sludge.

Caustic rinse is used for equipment cleaning of both  solvent and water-based paints. It
is used  more often with  water-based paints, since water rinsing is usually insufficient
in removing  paint that has dried  in the mix tanks.  Solvent  rinsing can usually remove
solvent-based paint that has dried and therefore  the need for caustic is reduced.

There are two major types of caustic systems commonly used by  the paint  industry. In
one  type of  system, caustic  is maintained in a holding  tank (usually heated)  and is
                                    B8-15

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pumped into the tank to be cleaned.  The caustic drains to a floor drain or sump from
where  it is returned  to  the  holding  tank.  In the second type  of  system, a caustic
solution is prepared in the tank to be cleaned, and the tank is soaked until clean. Most
plants  reuse the caustic solution until it loses most of its cleaning ability.  At  that
time, the caustic is disposed of either as a solid  waste or wastewater with or without
neutralization.

Water  wash of equipment used in the production  of water-based paint is the source of
considerable wastewater volume. Wastewater resulting from rinsing is usually handled
as follows:

           Collected  and used in the next compatible batch of paint as part  of  the
           formulation.
           Collected  and used with or without treatment for cleaning until spent.
           Disposed  with or  without treatment as wastewater  or  as a solid waste in
           drums.

Sludges from settling tanks are drummed and disposed of as solid waste.  Spent recycle
rinsewater  is  drummed  and  disposed of as solid  waste after  the solubles content
prohibits further use.

The  percentage of solvent-base and water-base paints produced is the most important
factor that affects  the volume of  process wastewater generated  and  discharged at
paint plants.  Due to their greater use of water-wash, plants producing 90 percent or
more water-base paint discharge more wastewater than plants producing 90 percent or
more solvent-base paint.  Additional factors  influencing  the  amount of wastewater
produced include  the  pressure of the rinse water, spray head design, and the existence
or absence of floor drains.  Where  no troughs or  floor drains exist, equipment is often
cleaned externally by hand with rags; when wastewater drains are present, there  is a
greater tendency to  use hoses.  Several plants  have  closed floor drains to  force use of
dry clean-up methods and discourage excessive water use.

Waste associated with equipment  cleaning represents the largest source of waste  in a
paint facility.  Methods that reduce  the need  or frequency of tank cleaning or allow
                                   B8-16

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for reuse of the cleaning solutions are  the most effective.  Waste reduction methods
considered  include:

     o     Use of mechanical devices such as  rubber wipers.
           In order to reduce the amount of paint left clinging to the walls of a mix
           tank, rubber wipers are used to scrape the sides of the tank. This operation
           requires manual labor and hence the percentage  of waste reduction is a
           function of the operator*.  Since  the benefits will be offset  by increased
           labor, mechanization/automation should be considered.  Many new mixers
           are  available that are designed  with automatic wall scrapers (Weismantel
           and Guggilam 1985).   These  mixers can be used with any cylindrical mix
           tank (flat or conical bottom).

     o     Use of high pressure spray heads and limiting wash/rinse time.
           After scraping the tank walls, high pressure spray hoses can  be  used  in
           place  of regular hoses to clean water-based paint tanks.  Based on studies
           (USEPA 1979),  high pressure wash systems can reduce water  use by  80  to
           90 percent.  In addition, high pressure  sprays can remove partially dried-on
           paint  so  that the need for  caustic is reduced.  Tanks  used for  making
           solvent-based paints  normally employ a  built-in  high  pressure  cleaning
           system. At Lilly, in High Point, N.C., a high pressure  cleaning system was
           installed  in several mix tanks.  By continuously pumping a fixed amount  of
           solvent into  a tank  until  it was  clean, the  overall volume  of  solvent
           required for cleaning was reduced (Kohl, Moses, and Triplett 1984).

     o     Use Teflon** lined tanks to  reduce  adhesion and improve drainage.
           The reduced  amount of "clingage" will make dry cleaning more attractive.
           This method  is probably applicable only to small batch tanks amenable  to
           manual cleaning.
*   Confidential source 1985:  Personal communication.
** Registered trademark of E.I. Du Pont de Nemours & Co.
                                    B8-17

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           Use a plastic or foam "pig" to clean pipes.
           It was reported that much of the industry is currently using plastic or foam
           "pigs" (slugs)  to clean paint from pipes*.  The "pig" is forced through the
           pipe from the mixing tank to the filling machine hopper.  The "pig" pushes
           ahead paint left clinging to  the walls of the pipe.  This, in turn, increases
           yield and reduces the subsequent degree of pipe cleaning  required.  Inert
           gas  is used  to propel the "pig"  so as to minimize drying of paint inside the
           pipe.  Piping runs   and the equipment (launcher and  catcher)  must  be
           carefully designed so as to  prevent plugging, spills, sprays, and potential
           injuries.

           Better operating practices.
           At Desoto, in Greensboro,  N.C.,  wash  solvent  from each solvent-based
           paint batch is separately collected  and  stored.   When  the same  type of
           paint is going to be produced, waste solvent from the previous batch is used
           in place of virgin solvent.   In  1981, Desoto produced  25,000 gallons of
           waste mineral spirits.  In 1982, when the system  was implemented, waste
           solvent  production  amounted  to  400 gallons.    This same  technique is
           currently being applied  to  their latex  paint production operation (Kohl,
           Moses and Triplett 1984).

           At Thiele-Engdahl, in Winston-Salem, N.C., a similar procedure of solvent
           segregation and reuse was attempted. However, due to the large variety of
           products made, segregation proved to be too complicated.  In addition, the
           high  cost of  raw  materials  (Thiele-Engdahl  produces specialty  inks for
           rotogravure printing)  and the risk  of contaminating the entire batch far
           outweighed the savings in virgin solvent cost (Kohl, Moses and Triplett
           1984).
*  E.I. Du Pont de Nemours & Co. 1986: Personal communication.
   National Paint and Coating Association 1986:  Personal communication.
                                    B8-18

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           Other waste reduction measures based on good operating practices would
           be to schedule paint production for long runs or to cycle from light to dark
           colors so  that the need for equipment cleaning  would be  reduced.  For
           facilities using small portable mix tanks for water-based paints, immediate
           cleaning after use would reduce the  amount of paint drying in the tank and
           hence reduce the need for caustic. Many times, dirty  equipment is sent to
           a central  cleaning operation  where  it waits until a given shift (usually
           night) to be cleaned*.  While  tanks  wait  to be cleaned, the residual paint
           dries  up often  necessitating   the use of caustic solution for  cleaning.
           Avoidance of accumulation of  dirty tanks can be achieved by designing and
           performing the  cleaning operation to handle any  peak load continuously.
           This  would  reduce  the  need  for caustic cleaning   and  promote  water
           cleaning instead.

For plants employing CIP (clean-in-place) recycle systems for wash/rinse  operations,
the inventory replacement  frequency (and therefore waste volume) can be minimized
by using these waste reduction methods:

     o     Use of a countercurrent rinsing sequence.
           For facilities  that have additional storage space available, countercurrent
           rinsing can be employed. This technique uses recycled "dirty" solution to
           initially clean the tank.   Following  this step, recycled  "clean" solution  is
           used to  rinse  the "dirty"  solution from the tank.    Since the level of
           contamination builds  up  more slowly in the recycled  "clean" solution than
           with  a   simple  reuse   system,  solution   life   is   greatly   increased.
           Countercurrent rinsing is more common with CIP systems, but can be used
           with all systems.
•"•Confidential source 1985:  Personal communication.
                                     B8-19

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     o     Sludge dewatering by filtration or centrifugation.
           Sludge removed from spent rinse water can be dewatered so as to minimize
           total waste volume.  Several paint plants have installed belt filters and are
           assessing their effectiveness*.  At some facilities, dewatered sludge (which
           still contains solvents  and resins)  is mixed  with paint  sludge from solvent
           recovery and incinerated. For  facilities  not producing  solvent-based paint,
           incineration would not be an attractive option since  the  heating value of
           the sludge would be  low.   In addition,  the  capital  cost and  regulatory
           requirements for  building an incinerator could be prohibitive to  all but the
           largest producers.

     o     Provision for adequate  solid  settling time in spent rinse solution.

     o     Use de-emulsifiers  in  rinse water  to  promote emulsion  breakdown and
           organic phase separation.

Another  item  included  under  the  heading of cleaning  wastes   are  the  used  filter
cartridges produced  during the  paint loading operation.  These cartridges are designed
to remove undispersed pigment from the paint during loading and  will be saturated
with paint  when removed. Hence, waste  minimization and economy both call  for as
small a cartridge as possible so as to reduce  the amount of paint lost and the capital
spent for the  filters.  If frequent  filter plugging is  a problem, then  it should be first
addressed  from the standpoint of improving  pigment dispersion, and not  from the
standpoint  of increasing  filter area.
^Confidential source 1985:  Personal communication.
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9.2  Implementation Profile

The  main source reduction methods discussed for use by the  paint industry include
segregation of solid  waste by prior content, reduction or elimination of hazardous
pigments  (hazardous  pigments that could not be  eliminated  should  be used in  paste
form),  use of wipers on mix tanks, high pressure spray systems, use of  countercurrent
rinse sequence on tanks, and  sludge dewatering before  sending it to a landfill.  Reuse
of cleaning solutions  as  part of paint  formulation  is promoted  by good  operating
practices  which include segregation.  Incineration of  sludges (especially from solvent-
based operations) destroys the organics present, but still may produce  toxic inorganic
residuals  requiring dispoal.   Since incinerators are  difficult and expensive units  to
build, operate, and maintain, their use is only practical at large paint facilities.

While  segregating solid  waste  by prior  content  and reducing  the use of hazardous
pigments  would  not be difficult to implement, fitting all tanks with  wipers would  be
difficult.  Square tanks would require custom modification and installation, since the
wiper  could  not- be  installed  on the mixer (the normal  method  of installation).
Retrofitting existing  mixers with  wipers is  impossible since most mixers  used by the
paint industry are single-shaft and a mixer/wiper  unit  requires a dual  shaft.  There-
fore,,  mixer/wiper units  would  only be   considered  for new  installations  or  as
replacements.  Since  much of the hardware  in the  paint industry is over 20 years old,
detailed  return  on investment analysis could be  performed  to determine if a unit
should  be repaired or  replaced.  Because the cost of  repairing a unit can  range  from
2,500 to  10,000 dollars, replacement could  be an attractive  alternative (Weismantel
and Guggilam  1985).

Installation of a high  pressure spray system would require the installation of a  pump
and some piping at each cleaning station.  While the space requirements  for a  pump
are small, the layout of the additional piping would have to be given  special attention
so as not  to impede operations in  the area.   The economics of a high  pressure  spray
system has been worked  out in detail (USEPA 1979), with the  average cost running
about  20,000  dollars per system.   Using  a  countercurrent  rinse  sequence  and
dewatering sludges would require  installation of at least two cleaning solution storage
tanks and a belt filter or similar unit.  Besides the  added space requirements for  these
units and  the  significant  capital cost, operators would  need to be fully versed  in the
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theory and method of their operation.  The economics of installing a  filter unit and/or
sludge incinerator has been  addressed in  detail elsewhere  (WAPORA  1975,  USEPA
1979).  For all  but  the largest  of  producers, the cost of installing, operating, and
maintaining the units was prohibitive.

When viewed in  light  of  increasing hazardous waste disposal costs, many of the waste
reduction measures  identified  appear economically  practicable.   By segregating
wastes, savings  in disposal costs could be  achieved at little cost to  the facility.  No
special equipment would be required and the  additional labor would be  minor.  While
reducing  or eliminating  the  use  of hazardous  pigments  would  also  be  easily
irnplernentable,  the economic costs  would  be much greater:  either  higher  costs  for
using less hazardous pigments would  have to be incurred or the company  would  have to
forego competing in a given market,  e.g. red lead primer.

9.3   Summary

Table 9-1 presents summary data on paint industry waste sources and  control methods.
The ratings shown in the table for each of the noted methods  were based on review of
the  available  literature and consultations with industry personnel.   Based  on  the
measures already undertaken by the paint  manufacturing industry, the  waste  appears
to have been minimized significantly to a  level characterized by a current reduction
index of 2.2 (55 percent).  The index is a measure  of  reduction relative to the waste
that would have been produced if none of the  measures listed were applied at their
current level.  By implementing additional  waste reduction-measures  or  increasing  the
use  of  existing  measures, the  amount of waste  currently being generated  can be
reduced to a level characterized by  a future reduction index of 0.7  to  1.7 (18 to 43
percent) which is indicative of a moderate to  significant potential for  reduction.

Based on  the extent of  waste  generated due to equipment cleaning, it appears that
installation  of  a high pressure wash  system and  further  implementation of better
operating practices are the two most  effective  measures that can be taken.  Of  the
remaining control methodologies, use of "pigs" to clean lines, dewatering of spent rinse
sludge, and  increased use of automation also  show high promise, as evidenced by their
high individual future reduction indexes.
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                    TABLE 9-1 SUWARY OF SOURCE CONTROL  METHODOLOGY FOR THE PAIKT NANUFACTURING INDUSTRY


1
Haste Stream |
1 1




Leftover Inorganic |1.
Pigments in Sags |2
and Packages |3.
i._
1



Pigment Dust from |1.
Baghouses |3.
(3-
1 1


Off -Specification |1.
Paint |2.
1
I Spills |1.
03
-n
.
N3
12.
|3.

r
Equipment Cleaning |1








Wastes (*) |2.
13.
|4.
|5-
16
|7
18.
|9
1
All Sources 1
1
Control Methodology |-
1
Use water soluble bags and liners |
Use recyclable/lined containers |
Implement better operating practices |

Overall |
Install dedicated baghouse systems |
Use pigments in paste form |
Implement better operating practices |
Overall |
Increased use of automation I
Implement better operating practices |
Overall |
Increased use of automation J
Maximize use of dry clean-up methods |
Implement better operating practices |

Overall |
Use mechanical wipers on mix tanks I
Install high pressure wash system |
Install Teflon liners on mix tanks |
Use foam/plastic "pig" to clean lines|
Implement better operating practices |
Use a countercurrent rinse sequence |
Oewater spent rinse sludge |
Increase spent rinse settling time |
Use de-emulsifiers on spent rinse |
Overall |
All Methods
Found Documentation

Quantity | Quality
1 1
1 1
1 1

1.00 | 0
1 I
t 1
1 1
1.00 | 1
3 1
3 1
3.00 | 1
3 1
3 1
3 1

3 00 | 1
3 I
3 1
0 1
1 1
3 I
' I
3 1
0 I
0 1
1.56 { 1

1
... |
1
0 1
o 1
o 1

00 |
1 1
1 1
1 1
00 |
1 1
2 1
50 |
1 |
' 1
2 1

33 |
1 I
2 1
0 1
1 1
2 !
1 !
2 1
0 1
0 1
00 |

Waste I
Reduction |
Effectiveness I
3 1
2 1
3 1

2 67 I
2 1
3 1
2 1
2.33 i
4 I
4 1
4.00 !
4 1
3 1
4 1

3 67 |
2 1
3 i
1 1
3 1
4 1
3 1
3 1
1 1
1 1
2 33 1

Extent of |
Current Use |
1
1 1
1 1
2 1

t 33 |
1 1
1 1
1 1
1 00 i
1 !
3 1
2.00 |
1 |
1 1
3 1

1.67 |
1 1
i !
0 1
2 1
2 I
1 1
2 1
c I
0 1
1 00 [

Future | Fraction of |
Application | Total Haste |
Potential | |
0 1 1
' 1 1
2 1 1

t 00 1 0.02 |
1 1
3 1 1
t 1 1
1.67 | 0.02 |
2 1 1
2 1 1
2 00 | 0.05 |
2 1 1
3 1 I
2 1 1

2.33 | 0.06 |
< 1 1
3 1 1
' I I
2 I 1
2 1 1
' 1 1
2 1 1
1 I I
0 I I
1 44 | 0 85 j
i 1 00 |
Current |
Reduction |-
Index |
0.8 I
0.5 |
1.5 |

1.5 I
0.5 |
0.8 |
0.5 |
0.8 |
1.0 |
3.0 |
3.0 |
1 0 |
0.8 |
3 0 I

3.0 |
0.5 |
0 8 |
0.0 |
1.5 1
2.0 |
0.8 |
1.5 |
0.0 |
0.0 |
20 |
2.2 |
Future


Probable
0
0
0

0
0
t
0
0
1
0
1
)
I
0

1
0
1
0
0
1
0
0
0
0
0
0
Reduction Index


| Maximum
•0 1
•4 1
.8 | 0

.4 | 0
•4 1
.7 | 1
•4 I
8 I 1
.5 | 1
•5 1
.0 | 1
•5 I
.7 | 1
•5 1

.2 | 1
•4 I
.7 | 1
•3 I
.3 I
.0 I
•6 I
8 I
•3 I
•0 I
.6 | 1
.7 | 1
1


1
1
1
8 1

8 1
1
^ \
1
7 1
5 !
1
5 1
|
7 1
1

7 I
1
7 I
1
1
1
1
|
1
1
^ \
^ 1
(*)  These waste streams include listed "F"  and/or  "1C RCRA wastes

-------
10.  PRODUCT SUBSTITUTION ALTERNATIVES

3y altering the composition of paint,  the amount and toxicity of hazardous materials
(and  the  overall toxicity of the paint itself) required  to be landfilled can be reduced.
Another  way of reducing waste associated  with paint production would be  to reduce
the demand  and therefore the production of paint. By producing a paint with a longer
life span  or by utilizing building materials that do not require painting (e.g., precolored
concrete, stucco,  vinyl  coated  siding,  brick), a  reduction  in  the  amount  of
architectural coatings produced could be achieved.   Reductions  in the  demand for
product coatings could  occur by increasing  the  use of powder or plastic coatings.  A
complete environmental assessment of each alternative is required before its overall
benefits  and disadvantages can be determined. Such an assessment was not performed;
therefore, no specific product substitutions can be recommended.

10.1       Pigment Substitution

Two  cases of pigment substitution were identified. The first case concerned the use of
     •
lead  pigment.  While the paint industry has  eliminated the use  of lead  to  a  large
extent, a market still exists for red  lead primers (red lead makes an excellent primer
and few substitutes exist).  Most plants produce a wide variety of paints, and typically,
red  lead primers represent  a small  percentage of  a  plants'  total  output.   A
commitment by management not to produce red lead primer would eliminate the  need
to manage lead pigments (the loss of this  market would have to  be weighed against
handling  and disposal costs for each facility). Because of the increasing regulations on
the use of all lead pigments, some plants have ceased production of lead primer*.

The  second  case involves chrome  yellow.   Chrome yellow  is used mainly  in traffic
paint and provides a very bright color.  In  order to avoid the use of chrome yellow in
other products, some companies have switched to organic pigments (expensive)  or to
yellow iron  oxide (dirty color).  One such company is Environmental Inks and Coatings
Corporation  in  Morganton, N.C.  (Kohl,   Moses,  and  Triplett  1984).     Again  a
commitment by management is required in  light of the added expense versus disposal
cost  savings.   Customer's specifications  stand in the way  of total  elimination  of
chrome yellow use, since it is required to be used in yellow traffic paint*.
      Confidental source 1985:  Personal communication.
                                    B8-24

-------
In weighing the environmental pros and cons of toxic pigment substitution with less
toxic alternatives, it must be noted that the use of heavy metal pigments in  product
coatings extends the durability of the product*.  It is  also  important  to  note that
substitution  of pigments  in  existing  formulations  will alter  both  the color and
performance of the  coating; hence, it must be done with the approval of changed
specifications by a customer.

10.2       Increased Quality of Home Market Paints

While  most paint  sold  is  of  very high quality (commercial  architectural coatings,
product coatings, and special purpose coatings have very long  lifetimes), paint sold to
the home market  can vary widely.  This  is due, in part, to  market conditions that
demand  that  a paint  producer  supply  a low  cost  paint if he  wishes to  remain
competitive. If the home consumer showed preference for a higher quality paint, then
the production of lower quality paints would decrease. In addition, less paint would be
produced overall each year since  the need for repainting  would be lessened.  Related
to this issue is the  level of consumers' awareness as to  the proper ways of selecting
and  applying paint.   If  the level of awareness is  found to  be  low,  then  consumer
education   efforts  could  be  conducted  through  various   approaches,   such  as
dissemination  of  information  about paint  application  economics.    Additionally,
durability of coatings can be promoted by improvement of the  general  knowledge of
proper  application techniques, specifically, surface preparation.   Even the  highest
quality paints will perform poorly  if misapplied or if they  are inappropriate for the job.

10.3       Architectural Coating  Substitutes

Many  substitutes  exist for architectural coatings.   For building  exteriors,  anodized
metal, brick, marble, glass, colored concrete, and vinyl coated sidings have been used.
For interiors, wood paneling, fabric coverings, and wallpaper are very popular.  Since
the use of these materials is mostly for aesthetic rather than functional purposes, each
one's position in the  market place  will fluctuate based on demand.
*   National  Paint and Coatings Association 1986:  Personal communication.
                                     88-25

-------
10.4       Product Coating Substitutes

Unlike  some  architectural  coatings,  product  coatings  must  provide  functional
protection  as well as an aesthetic function.  Recent substitutions that  are  finding a
market  place are powder and plastic coatings.  Because powder  coatings contain no
solvent  and most of the waste generated can be recycled, equipment manufacturers
view powder coatings as a way  of meeting EPA standards.  Coupled with  the savings in
energy and labor, there is increased productivity.  It is expected that the  current share
of the powder coating market (5 to 6 percent in 1983)  will increase to  15 percent by
1993. While numbers were not reported for the U.S., some European finishers report
that over 70 percent of all new production lines being  installed  are powder (Church
1984).

11.   CONCLUSIONS

While the paint  industry has  done much to reduce the amount of waste  it produces, it
appears that further reductions are possible. Our estimates indicate that future waste
reduction potential can be characterized as  significant  with reductions ranging  from
18 to 43 percent.  Several methods that appear to be quite effective and feasible  for
future implementation  were identified and include high pressure spray systems  for
cleaning of water-based paint  manufacturing equipment,  further  implementation of
better operating practices, use of "pigs" for cleaning lines, dewatering  of wastewater
sludge,  and increased use of automation.  Reductions  will occur  as more and  more
facilities initiate and continue waste reduction programs and as older equipment wears
out and is replaced.

12.   REFERENCES
Church,  F. L., ed. 1984.  Powder coating sales reach near-boom levels.  Reprint from
Modern Metals.  January 1984.
Haines, H.  W.,  ed. 1954.  Resin  and paint production-1954 style.  Ind. Enq. Chem.
46(10):  2010-22.
Huisingh, D., Martin,  L., et  al. 1985.   Proven  profit  from pollution  prevention.
Conference draft. Washington, D.C.; The Institute for Local Self-Reliance.
Kohl, J., Moses, P., and Triplett, B.  1984.  Managing and recycling solvents.  North
Carolina practices, facilities, and regulations.   Raleigh, N.C.; North Carolina  State
University.
                                   B8-26

-------
Payne, H. F. 1961.  Organic coating technology. 2 vols.  New York, N.Y.; John Wiley &
Sons.

Ryan, William C. 1984.  MASSPIRG,  Massachusetts Public Interest Research  Group.
Hazardous waste reduction potential in the paint manufacturing industry.   Sponsored
by the Massachusetts Department of Environmental Management. Boston, MA.

Shreve,  R. N., and Brink, J. A. 1977. Chemical process industries. 4th ed.  New York,
N.Y.;  McGraw Hill Book Co.

SRI 1981. Stanford Research Institute.  Chemical  economics handbook, 1982.  Menlo
Park,  Calif.: Stanford Research Institute.

USDC 1985.  U.S. Department of Commerce, Bureau of the Census.  Paint and applied
products.  In 1982 Census of  manufacturers.  MC82-I-28E.  Washington, D.C.:  U. S.
Government Printing Office.

USEPA  1979.  U. S. Environmental Protection  Agency,  Office of  Water and Waste
Mangaement.  Development document for proposed effluent limitation guidelines, new
source performance standards, and pretreatment standards for the  paint formulating
point  source category.   EPA-440-l-79-049b.   Washington, D.C.:  U.S.  Environmental
Protection Agency.

	,  1980, U.S.  Environmental Protection  Agency,  Office  of  Research  and
Development.  Treatability  Manual Vol.  2; industrial  descriptions.  EPA-600-8-80-
042b.  Washington, D.C.: U. S. Environmental Protection Agency.

WAPORA 1975.   Wapora, Inc.  Assessment of industrial hazardous waste  practices,
paint  and applied product industry, contract solvent reclaiming operations, and factory
application of coatings.   EPA-530-SW-119c.  Washington, D.C.: U. S.  Environmental
Protection Agency.

Webber, D.  1984.  Coating  industry heading for record year.  Chem. Eng. News.
62(40): 51.

Weismantel,  G., and Guggilam,  S. 1984.   Mixing  and  size  reduction.    Chem. Eng.
92(13): 71-109.

13.   INDUSTRY CONTACTS

Confidential sources

Dr. G.J. Hollod, Senior  Environmental Engineer, Petrochemical Dept., E.I. du Pont de
Nemours & Co. Wilmington, DE.

R.J. Nelson, Associate  Director, Environmental Affairs  Technical Division, National
Paint and Coatings Association, Washington, D.C.

W.G.  Vaux,  Principal   Engineer,  Chemical and Process Engineering,  Westinghouse
Electric Corp., Pittsburgh, PA.
                                    B8-27

-------

-------
 1.    PROCESS:  PETROLEUM REFINING
 2.    SIC CODE:  2911
 3.    INDUSTRY DESCRIPTION
                                                                   •

 The petroleum refining industry  is comprised of establishments primarily engaged in
 the manufacture  of gasoline, kerosene,  distillate and residual fuel oils, lubricants and
 other products from  crude  petroleum and its fractionation products.  Excluded  from
 this industry are establishments  engaged in producing  natural  gasoline  from natural
 gas, the manufacture of lubricating oils and greases by blending purchased materials,
 and those re-refining  used lubricating oils.

 3.1   Company Size Distribution

 Table 3-1 presents the number of establishments  and  number of employees for the
 petroleum industry  in 1982.  Output and employment in the  industry is dominated by
 the larger establishments.  The largest 65 of the  434 petroleum refining establishments
 accounted for more than 65 percent of the  total industry employment and more  than
 63 percent of the total industry output in terms of value  added by manufacture.

                     Table 3-1 1982 Company Size Distribution

                         	No. of  employees per facility	
                           1-99     100-499     500-999         1000+    Total

No. of establishments        241        128          41          24           434
No. of employees          6,600     31,300      27,700     43,200^)   108,800

Source:     1982 Census of Manufacturers (USDC 1985).
(a)    Excludes totals for two establishments with  more than 2500 employees to avoid
      disclosure of individual company data.
3.2    Principal Producers

In 1982,  the following  companies maintained  the largest refining capacities  in  the
United States:
                                   R9-1

-------
     Exxon
     Standard Oil of California
     Standard Oil of Indiana
     Shell (Royal Dutch) Oil
     Texaco

3.3   Geographical Distribution
                                           Gulf Oil
                                           Atlantic Richfield
                                           Mobil
                                           Phillips Petroleum
                                           Marathon Oil
Table 3-2 and Figure 3-1 shows the number of petroleum refining establishments by
EPA  region.   EPA  Region  VI  contained  171 petroleum  refineries  in 1982,  or
approximately 40 percent of  all  establishments.  Region  IX, containing 54 refinery
establishments, and Region  V, containing  52  establishments,  also  contained large
numbers of refineries.  The four leading states in employment were Texas, California,
Louisiana, and Pennsylvania, accounting for 64 percent of the industry's employment.
                  Table 3-2 Location of Facilities by EPA Region
EPA Region
I
II
III
IV
V
VI
VII
VIII
IX
X
Number of Establishments
. _
14
34
21
52
171
13
30
54
11
              National
                                                  400(a)
     Source:  1982 Census of Manufacturers (USDC 1985).
(a)   Establishments in  states with less than 150 employees in the petroleum refining
     industry are not included.
                                   P9-2

-------
                             VIII
OP
•ID
I
CO
                         11-20
                                    2-5
                                    21-50
                          6-10
                          51-100
        Figure   3
 Roman numerals show EPA regions
1  Petroleum Refineries in the U.S.

-------
4.    PRODUCTS AND THEIR USE

The  types of products shipped and the dollar value of these shipments in 1982 are
presented in Table 4-1. Gasoline, light fuel oils, jet fuel, and heavy  fuel oil shipments
accounted for over  80 percent of the total value of product shipments  from the
petroleum refining industry.

       Table 4-1 1982 Product Shipments by the Petroleum Refining Industry

                                     Shipment Value               Percentage of
          Product                     (millions) $Total Shipment
                                                                     Value
Gasoline
Jet fuel
Kerosene
Light fuel oils
Heavy fuel oils
Lubricating oils and greases
made in refineries
Unfinished oil and lubricating
oil base stock
Asphalt
Liquified refinery gases
Aromatics
Other
Total
95,115
14,862
1,887
37,298
11,391
2,891
8,066
2,980
8,396
1,354
7,130
191,370
49.7
7.8
1.0
19.4
6.0
1.5
4.2
1.6
4.4
0.7
3.7
100.0
Source: 1982 Census of Manufacturers (USDC 1985).

5.   RAW MATERIALS

The  types of materials consumed as  feedstock by the petroleum refining industry  in
1982 are presented in  Table  5-1.  The  delivered cost of each material type is  also
shown.   Crude petroleum is  the  major raw  material consumed by  the  petroleum
                                   B9-4

-------
 refining industry,  representing  over 80 percent  of the total delivered  cost  of  all
 materials consumed by the industry in 1982.
                                                                    t
    Table 5-1 Raw Materials Consumed by the Petroleum Refining Industry in 1982

                                     Delivered Cost              Percentage of
Material
Crude petroleum
Unfinished oils
Natural gas liquids
Benzol
Toluene and xylene
Additives
Chemical catalytic preparations
Caustic soda
Sulphuric acid
Containers
Other
Total
(millions) $
137,870
558
7,901
74
459
1,199
679
80
120
156
17,742
166,838
Total Delivered Cost
82.7
0.3
4.7
--
0.3
0.7
0.4
0.1
0.1
0.1
10.6
100.0
 Source:  1982 Census of Manufacturers (USDC 1985).

 6.    PROCESS DESCRIPTION

 Crude oil  contains a wide  variety of hydrocarbon compounds which  range  from light
 gases to residual fractions that cannot be separated by distillation. Crude oil is made
 up primarily  of paraffin compounds,  olefins,  naphthenes,  and  aromatics  in varying
 proportions.  Apart from carbon and hydrogen, the elemental analysis  shows sulfur,
.oxygen, nitrogen and heavy  metals present in small quantities.

 Most refinery processes fall into one of three classifications: separation, conversion,
 or upgrading. Detailed descriptions are available in the literature (Jahnig 1982, Shreve
 1967).   The following  discussion  highlights   the  main  process  activities.    For
 convenience, an overall block flow diagram is presented in Figure 6-1.
                                    B9-5

-------
                                                                                         SULFUB
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            MOCEIS  litre cmtomi

            0    SEH04TIOM MOCCSS MSTIS  (riLTEH CLiTS)


            0    CONVCRSIOH MOCESS H5TES  (ciTiLTST FINES/ SPENT  CiTilTSTJ


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                  UTILJTT PRODUCTION liSTES »«E NOT SHOIN
         Figure 6-1  Process  Block Flo* Oiagrai for a Typical Refinery
                                   B9-6

-------
6.1   Separation Processes
                                                                     i
Separation processes are  used  to provide feedstocks of specified physical and chemical
properties to other refining unit processes.  Typical separation processes are desalting,
primary  distillation, deasphalting, solvent refining,  and lube oil finishing.    These
operations are discussed individually below.

The  first step in crude  oil refining is the desalting  operation.   Crude oil typically
contains salts, water,  and suspended  matter  in  the  form of droplets  or  as  a fine
emulsion. These materials are present naturally in the oil and also may be introduced
during shipping or storage.  It  is particularly important to remove  these  contaminants
so as to avoid corrosion  or plugging and buildup problems in the refinery equipment.
The crude oil is pumped from storage into the heated desalter unit.  Some of  the larger
droplets settle out during storage.  The remaining  droplets and emulsified materials
are removed by  the addition  of  water and  flocculants.  The  oil/water emulsion is
separated by electrostatic precipitation with 95 percent removal efficiency.

Distillation  follows the desalting process. Typically, the crude oil is separated or "cut"
into  three categories of products, each cut differentiated by  boiling range.   These
products are:  naphtha, middle  distillate, and a heavy bottoms residual.  Also from this
process, light fractions (Cj  to C^ hydrocarbon) are recovered  for  further purification
in the gas treating operation.

The  naphtha  cut  is  the primary  precursor  to motor gasolines.  It is upgraded  by
hydrotreating (primarily  to remove sulfur,  oxygen,  and metals) and  then  further
improved by the process of reforming.  The middle  distillate cut includes jet fuel,
diesel, and home heating oil. The end point of the  middle distillate cut is about 300°C
(Jahnig 1982).  Fractions boiling above this temperature come out  in the bottoms cut.
The bottoms fraction provides feed-stock  for  the vacuum distillation  process.  The
vacuum stills  remove the remaining  heavy  gas oil not recoverable in  the atmospheric
stills, and provide asphalt and lube oil  stocks  and coker  feed.  The residue from  the
vacuum stills  goes  to the coker where  the  volatiles are removed,  leaving coke as the
final product.

Deasphalting removes asphalt  or resins from the bottoms fractions, to produce stocks
suitable  for subsequent  lube  oil  or catalytic cracking  processes.   The  asphaltic

-------
materials are  extracted  through the use of a solvent, such as propane.  The process is
carried out in  an extraction tower, where  pipe still bottoms or other heavy stock are
mixed with propane. After the asphalt has been removed the propane is recovered.

Solvent refining includes a large number of alternative subprocesses designed to obtain
high-grade lubricating  oil stocks or aromatics  from feedstocks containing naphthenic,
acidic, organornetallic,  or  other  undesirable  materials.   Basically, it is  a solvent
extraction process dependent on the  differential solubilities of  the  desirable  and
undesirable  components  of  the feedstock.  The  principal  steps  are  countercurrent
solvent  extraction, separation of solvent and product by  heating  and  fractionation,
removal  of trace solvent from the product, and solvent recovery.  Recent advances  in
solvent   refining include a Residuum  Oil Supercritical Extraction  (ROSE)  method
developed by Kerr-McGee Refining Corporation (Anon. 1981).

Lube oil  finishing is used to further  refine solvent-refined or dewaxed lube  oil stocks,
and involves clay or acid treatment to remove  color-forming and other undesirable
materials.  The  two methods most  widely used  by industry  are continuous contact
filtration in which  the  oil-clay  slurry is heated  and the oil removed by  vacuum
filtration; and percolation filtration,  in which the oil is filtered by percolation through
clay beds.  Percolation also  involves naphtha washing and kiln burning of spent clay  to
remove carbon deposits  and other impurities from the clay so it can subsequently be
reused.

6.2  Conversion Processes

Many primary  distillation  products undergo  some  form  of conversion  operation.
Conversion  processes  are used to  purify  or  change  the   chemical  and/or  physical
properties of  the distillates,   usually by breaking large  molecules into  smaller ones.
Typical  conversion  processes are  hydrotreating,  catalytic  and  thermal cracking,
hydrocracking, and coking.

In most  refineries, usually  only the  naphtha and  middle distillate cuts or low metals
content  residuum are  hydrotreated.  The hydrotreating process converts the heavier
components of  these cuts  to  lower  boiling products  by  mild cracking  and by adding
hydrogen to the  molecules  using a fixed  bed catalytic reactor.  The  reactor products
are cooled, and  the hydrogen with  impurities and high grade product  are  separated.
                                    B9-8

-------
Among  the  catalysts most  commonly used in hydrotreating is cobalt molybdate  with
various  promoters on silica-alumina supports.
                                                                      i
Hydrotreating was first  used primarily on the relatively clean lighter feedstocks, but
with  more  operating experience  and  improved  catalysts, hydrotreating  has  been
applied  to increasingly heavier fractions.  The process improves the quality of the  feed
to subsequent operations by  removing sulfur compounds, nitrogen, oxygen, and  metals
carried  over from primary distillation. Hydrotreating of kerosene, jet, and diesel fuel
components  stabilizes and  saturates  the  diolefins  and  other compounds which  form
gums and deposits.   Fixed  catalyst bed hydrotreating of atmospheric or vacuum still
heavy oils has been limited to those feedstocks where the metals content is  low.  The
metals  quickly  degrade  the  catalysts by buildup  and  subsequent pore blocking.  In
recent years, progress in applied catalysis has resulted in the development of longer-
life  hydrotreating catalysts. Along  with hydrocracking, hydrotreating is one  of the
most rapidly growing refinery processes.

Cracking  includes fluid catalytic  cracking,  thermal  cracking,  hydrocracking,  vis-
breaking,  and coking. The  old  process of thermal cracking, or now more  generally
applied, fluidized-bed catalytic cracking, are processes used on the heavy distillates
from the  vacuum still.  In each of these operations, heavy oil  fractions are  broken
down into lighter fractions such as gasoline,  domestic heating oil, etc.  At this time,
about half of the gasoline  sold in the United  States is obtained from petroleum  by
fluidized bed cat cracking of heavy oils.  The reactors are so designed as to allow for
continuous catalyst regeneration. Thermal cracking, which  was an  important  process
before  the development of fluid catalytic cracking, is being phased  out.  Visbreaking
and  coking  units  are   installed  in  a  significant  number  of  refineries,  and their
application is expected to increase.

Catalytic cracking, like  thermal cracking, breaks heavy fractions (principally gas  oils)
into lighter fractions, and  is the key process in the production of  large  volumes  of
high-octane  gasoline stocks, furnace oils, and other useful middle distillates. The use
of a catalyst permits operation at lower  temperatures and pressures  than  those  of
thermal cracking and also  inhibits the formation  of undesirable by-products.  Fluid
catalytic  cracking  processes have,  in  most  cases,  replaced  the  fixed-bed  and
moving-bed  processes   which used  a beaded  or  pelleted  catalyst.   The  catalyst
presently used in the  process is primarily zeolite.
                                    B9-9

-------
Hydrocracking is a catalytic method of converting refractory middle-boiling or heavy
sour feedstocks into high-octane gasoline, reformer charge stock, jet fuel, and/or high
grade fuel oil.  This process has a high degree of flexibility  in adjusting production to
meet changing product  demands.   It is  one  of  the  most  rapidly  growing refinery
processes.  The  types of catalysts commonly used are tungsten sulfide-silica alumina,
iron-HP clay, nickel-silica alumina, and molecular sieves.

Coking is used to process the heavy asphaltic vacuum  still residuals which do not pass
into the  cat cracking  or lube oil  operation  after  vacuum  distillation.   The  coking
operation  involves destructive  distillation of  the  very heavy low  value  residuum.
Coking this material produces lighter materials by  means of  thermal cracking.   The
products  of this operation  include gas,  naphtha, gas  oils, and coke.  Coke is  the
carbonaceous material remaining after the volatiles are removed.

The coking process occurs either in a semibatch operation called delayed coking or is
performed continuously in a  fluidized bed process.  In the delayed coking, the feed is
heated and pumped into large drums.  The material is then cooled to  remove the heat
of  reaction and  is maintained  at  a  fixed pressure  which  vaporizes the  remaining
volatile materials in the  feed.  When  the drum is full, the process is stopped and the,
drum is opened.  The coke is removed using hydraulic cutters.

In  the fluidized bed process, the  residum feed is  heated and  sprayed  into  a  hot
fluidized bed of  coke.  The coke particles grow and are removed from  the system when
their size exceeds the  maximum  size required  for  fluidization.  Seed  particles of
smaller size are added  continuously to the process  to maintain the bed particle  size
distribution in the required operating range.

6.3   Upgrading Processes

Many products and by-products obtained from conversion steps undergo upgrading  to
generate  a salable product which meets  certain defined characteristics and increase
the yield.  Typical upgrading  processes  are  alkylation, polymerization,  reforming,
isomerization,  and drying/sweetening.  The upgrading  process used  is dependent on
feedstock  and desired end product.
                                    B9-10

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Alkylation is the addition of an isoparaffin (usually isobutane) to  an olefin (propylene,
butylene,  etc.) in the presence of a catalyst to produce a high-octane alkylate,  which
is  one of the most  important components of  automotive fuels.  Sulfuric acid  is the
most  widely used catalyst, although hydrofluoric acid and aluminum chloride are also
used.  Alkylation process capacity is expected to continue to increase with the demand
for high-octane gasoline.

Polymerization  converts  olefin  feedstocks  (primarily  propylene)  into  a  higher
molecular  weight polymer gasoline.  While  polymerization  yields, per  unit of  olefin
feed,  are  less than alkylation yields, newer  promoted cat cracker catalysts  produce a
feed that favors polymerization.  Because of the higher ratio of  olefins to  isobutane
produced,  alkylation  cannot  convert  all of the  olefins  to high-octane   alkylate.
Therefore, while only  a  few  refineries  currently  use  polymerization, its  use may
increase depending on the use of newer catalysts for cracking.

An example of a polymerization process is Dimersol, a process used  to  dimerize light
olefins  such  as ethylene,  propylene,  and  butylene  (Anonymous 1984).   The  main
applications of this process include dimerization of propylene to produce a high-octane
low-boiling gasoline called Dimate,  and the dimerization of n-butylene  to produce CB
olefins for plasticizer synthesis. Dimerization is  achieved in a liquid phase at ambient
temperature by means of a soluble  catalytic complex.  The catalyst is removed by a
caustic  wash process which  generates an aqueous waste stream.  After the catalyst  is
removed  from  the  reaction  mixture, the products are  separated  by  means  of
distillation.

Reforming is  a process of molecular rearrangement to convert low-octane feedstocks
to high-octane gasoline blending  stock, or  to produce aromatics for  petrochemical
uses.  The principal  reactions are dehydrogenation, dehydrocyclization and isomeriz-
ation.  The undesired hydrocracking also occurs to a small  degree.   Multi-reactor,
fixed-bed  catalytic  processes  have  completely replaced  the older thermal  processes.
There are many  variations, but the essential difference  is  the composition  of the
catalyst involved.  The types of catalyst commonly used in this process  are  bimetallic
platinum-rhenium and various combinations of group VIII elements.
                                   B9-11

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Isomerization  is  another  molecular rearrangement process which  is very  similar to
reforming. The charge stocks generally  are lighter and more specific (normal butane,
pentane, and  hexane).   The  catalysts  used  are  platinum supported om  alumina, or
platinum supported  on molecular  sieves.  The desired products  are  isobutane for
aikylation feedstocks and  high-octane  isomers of the original feed materials for motor
fuel.

Drying  and sweetening are processes  concerned  primarily with  removal of sulfur
compounds, water, and other  impurities, from gasoline, kerosene,  jet fuels, domestic
heating oils, and other middle distillate products.  "Sweetening" is the removal  from
these products of hydrogen sulfide, mercaptans,  and other sulfur  compounds, which
impart  a  foul  odor  and/or decrease  the tetra-ethyl lead susceptibility  of gasoline.
Drying  is  accomplished by salt filters  or adsorptive clay  beds.  Electric  fields are
sometimes used to facilitate separation of product from treating  solution.

6.4   Offsites  and Auxiliary Processes

In addition to  the  main  process  unitsj the  refinery will have other  processes or
operations  which support  the overall  primary process.   These processes include gas
recovery and  treatment, sulfur recovery, hydrogen manufacturing,  wastewater treat-
ment, steam and cooling water utilities,  and blending/packaging.

Gas  recovery  and treatment  facilities are provided  to sweeten  and recover the  light
ends produced by  the refining process.   Typically, the light ends  from  the  primary
distillation operation and  tail  gas from hydrotreating and cat cracking will contain Cj_
thru Cg hydrocarbons, hydrogen sulfide,  and water.  This material can be upgraded to
fuel gas and liquefied petroleum gas (LPG) in  the. gas plant.  Typical operations include
recovery of hydrocarbons via  compression or lean-oil absorption, removal of hydrogen
sulfide  by amine  scrubbing   and  then separation  of  the C^ + hydrocarbons by
distillation.   The 04  +  hydrocarbons  can  also  be  converted  to  gasoline  or  used
elsewhere in the refinery.

Hydrogen sulfide  from amine units and from  the sour water stripper (which treats
nearly all aqueous process streams in the refinery),  is then converted  to elemental
sulfur in a Claus plant. Conversion to elemental sulfur is obtained by  burning part of
the hydrogen  sulfide to form  sulfur dioxide.  The sulfur dioxide is then reacted with
hydrogen sulfide to  form  elemental sulfur and water  vapor in a series of vapor phase
                                   B9-12

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catalytic  reactors.  Tail  gas  containing sulfur  and  sulfur compounds from  the  Claus
plant  is further treated by Beavon or other processes before being released  to  the
atmosphere.  The ammonia present in the  feed gas to  the Claus plant is oxidized to
nitrogen and water.

Hydrogen  manufacturing is another auxiliary process.  Some  of the refinery hydrogen
demand is satisfied by catalytic  reforming, but not all.  It is therefore necessary to
manufacture hydrogen to  meet the full process  demand.  The  most common  method of
manufacture  is by reacting methane (natural gas) with  steam over a nickel catalyst.
The products are  hydrogen and carbon dioxide.  Carbon dioxide is removed by amine
scrubbing  and a hydrogen product of about 95 to 98 percent purity is obtained.

The  required utilities,  which  include electric  power, steam, and cooling  water  are
produced  on site.  Steam flows of up to 1000 tons per hour, at several pressure levels,
are generated  to provide process power  and  heat.  The  fuel source  is gas,  oil, or
refinery byproducts.  Electric power is purchased from utilities and  supplemented by
cogeneration or generation onsite where feasible (e.g. through FCC power recovery
train).  Cooling water is supplied as either once-through water or recirculated cooling
tower water.

Blending is the final step in the production of finished petroleum products.  Blending is
required to meet quality  specifications  and market demands.   The  largest  volume
operation  is  the blending of  various gasoline  stocks,  including  alkylates  and  other
high-octane components, with anti-knock (such as  tetra-ethyl lead), anti-rust, anti-
icing,  and other  additives.   Diesel fuels, lube oils, waxes,  and  asphalts  are  other
refinery products which  normally  require  blending  of various components  and/or
additives.  Packaging at refineries is generally highly automated and  restricted to high
volume, consumer-oriented products such as motor oils.

7.    WASTE DESCRIPTION

The  primary specific wastes associated  with  petroleum  refining,  along  with their
process sources, are listed in  Table  7-1.  While  these wastes have been classified  into
seven distinct groups (separation process wastes, conversion process  wastes, upgrading
process wastes, wastes from  auxiliary processes, equipment  cleaning  wastes,  waste-
water   treatment  wastes, and waste  from  utilities production), many other more

                                   R9-13

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                                         Table 7-1 PetroSeurn Refining Process Wastes
         No.
    Waste
Classification
Process
 Origin
Description
RCRA
 Code
on
i
i—*
c-
          1.   Separation process wastes

          2.   Conversion process wastes


          3.   Upgrading process wastes
            .   Auxiliary process
               wastes
           5.   Equipment cleaning wastes
          6.   Wastewater treatment wastes
          7.   Utility production
               wastes
                             Kerosene or lube oil refining

                             Fluid catalytic cracker
                             Hydrotreating, hydrocracking

                             Alkylation, reforming,
                             isomerization
                             Alkylation
                             Dimersol

                             Amine scrubbing
                             Stretford process
                             Claus process, steam
                             reforming, sulfuric acid plant

                             Heat exchangers
                             Crude storage tank bottoms
                             Leaded gasoline tank bottoms

                             API separator
                             Dissolved air  flotation
                             Slop oil tank
                             Vacuum filter
                             Biological treatment
                             Storm water settling basins
                         Filter clays

                         Spent catalysts


                         Spent catalysts

                         Acid sludge and lime
                         Spent caustic

                         Spent amine
                         Spent Stretford
                         solution

                         Spent catalysts
                         Sludge
                         Sludge
                         Leaded sludge

                         Sludge
                         Oil, water
                         Sludge
                         Sludge
                         Sludge
                         Sludge
                             Raw water treatment               Sludge
                             Once-through cooling water         Sludge
                             Cooling tower blowdown treatment  Sludge
                             Boiler feedwater treatment         Sludge
                      K050

                      K052

                      K051
                      K048
                      K049

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detailed  classifications are  possible due  to  the diverse and complex nature  of  the
industry.  Additionally, the exclusion of RCRA codes from many of the waste streams
only means that no specific "F" or "K" RCRA code exists.

7.1   Separation Process Wastes

Principal  wastes associated  with  separation processes are spent filter clays used  for
lube oil  and  kerosene refining.   Spent  clay   is produced  in  significantly  greater
quantities from the clay contacting process than  from the fixed bed process.  In a
contacting process,  the clay  is mixed  with the  oil and subsequently removed  with a
rotary  vacuum filter.   Treatment with fixed bed clay is presently more  predominant
and is used to remove color, chemical treatment  residues, and traces of moisture from
product streams such  as gasoline, kerosene, jet  fuel, light fuel oil, and BTX  (benzene-
toluene-xylene) fraction from catalytic reformate.  The spent clay  from either of  the
above processes is usually disposed of in a landfill.

7.2   Conversion Process Wastes

Conversion  process  wastes originate  from operation  of  the fluid catalytic cracker,
hydrotreating  operations,  hydrocracking  operations,  and  coking operations.   Fluid
catalytic  cracker (FCC) catalyst is continously  regenerated by burning off the coke
formed on the catalyst during the  cracking process.  The flue  gas from the  regenerator
passes  through a series of cyclones that recover most of the catalyst. This recovered
catalyst  is then returned  to  the reactor vessel.   Because of  air pollution  regulations,
refineries have installed electrostatic  precipitators or equivalent tertiary separation
devices to significantly limit catalyst fines in the regenerator flue gas.  These catalyst
fines are  either landfilled, or in some cases sold. They are generated on  a continuous
basis, but are generally disposed of on an intermittent basis.

A  number of  refinery processes require  the   use of  a fixed-bed catalyst.   These
processes include catalytic   reforming, hydrodesulfurization, hydrotreating,  hydro-
cracking,  and others.  These catalysts become inactive (viz six months to three years)
and are eventually replaced in the reactors with  fresh catalyst during a unit shutdown.
Many of  these  catalysts contain valuable metals which can be recovered economically.
Some of  these  metals, such as platinum and palladium, represent the active catalytic
component;  other metals are contaminants in  the feed  which  are deposited  on  the

                                   B9-15

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catalyst during use (e.g.  nickel and vanadium).  After valuable metals are recovered (a
service usually performed by the outside companies), the residuals are expected to be
disposed of as solid waste.

The  major contaminating metals found on catalytic  cracking  catalysts are vanadium,
nickel, copper, chromium, and iron.  Small amounts of these metals are present in the
crude petroleum and, except for some of the  iron, all are in the form of metal-organic
compounds. Some of these  compounds are volatile and when the vacuum gas oil feed
to the catalytic cracking units is  prepared, they  appear in the gas oil.  A  fraction  of
the iron,  and  probably chromium, found  on  the catalyst is the  result of erosion and
corrosion  either in the lines or equipment.

Coke which is produced in the  course of fluid coking and delayed coking, is sold  as
solid industrial fuel or for use in electrode manufacturing.  Coke fines are generated
intermittently  and their quantity  is  a  function  of  handling  techniques.   A  certain
amount of spillage, and consequent contamination with dirt, results during  the course
of loading operations  onto trucks and railroad cars.

7.3   Upgrading Process  Wastes

Process wastes from upgrading operation  include  primarily sludges resulting  from
neutralization of acidic  streams in alkylation process  and spent dessicant clays.  The
residuals  from  other upgrading processes,  such  as  reforming,  isomerization, poly-
merization and sweetening  include wastes resulting from spent catalyst re-processing
(usually offsite), neutralized spent caustic from dimerization  operation and spent salt
or clay from drying.

Alkylation sludges from  the HP  alkylation process are  produced as a result of removal
of acid from  organic streams (isobutane recycle and  alkylate),  vent  scrubbing, tank
sludge and  HP  regenerator bottoms (acid   oils).  The wastes from the  sulfuric acid
alkylation include residuals  from  acid regeneration (usually   done  by  an  offsite
contractor),  caustic  washes  and  acid blowdown  stream.   Alkylation sludges  are
produced  as a result of direct neutralization of acidic effluents using lime or indirectly
by using  lime  to  reconstitute primary base, such as  KOH.  The sludges are usually
landfilled.  Acid soluble  oils from HP  alkylation are  either sold,  burned or recycled to
other units in the refinery.

                                   89-16

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7.4   Auxiliary Process Wastes

The amine scrubbing process,  used to remove hydrogen sulfide and carboft dioxide from
refinery gases, generates a  spent amine waste stream.  Another waste stream, which
contains spent anthraquinone  disulfonic acid (ADA) along with vanadium salts, results
from  the Stretford section of  the Beavon process that removes hydrogen sulfide from
the tail gases originating from a Claus plant.  Both of these wastes are often drummed
and disposed of in a landfill.  The wastes from auxiliary processes also include  spent
catalyst from steam reforming, Claus plant, and sulfuric  acid plant.

7.5   Equipment Cleaning Wastes

Equipment cleaning wastes are  mainly generated from heat exchanger and  storage
tank cleaning.  Heat exchanger bundles are periodically cleaned  during plant or unit
shutdown.  Scale and sediment resulting from such cleaning  is collected in sumps, from
which it is either  flushed into the process sewer system or shoveled out and disposed
on land.   The  disposal practices for spent chemical cleaning solutions could not be
ascertained.   The heat exchanger  cleaning    waste is considered  to be a RCRA
hazardous waste.
                                 •
Solid  sediment from incoming crude oil  accumulates at the  bottom  of the crude oil
storage tanks.   These  tanks are cleaned periodically to remove  the sediment.   The
cleaning  frequency  is  dependent on the sediment  content in the  crude oil.     In
refineries which  use mixers in the storage tanks, this  waste  source is non-existent.
Constituents of the crude  tank  sludge vary  with type  of  crude oil  as well as with
handling  and shipping  methods  employed prior to delivery  to the refinery.  Settled
sludge consists of a mixture of iron, rust, clay, sand,  water, sediment, and occluded oil
and wax.  Usually, this  mixture is a  tightly held emulsion which does not separate on
settling.   The frequency of sludge removal varies from  once a year to once every ten
years.

Solids from leaded or non-leaded products settle to the bottom of storage tanks, where
they remain  until  they  are  removed.  This accumulated sludge is removed whenever
the tank  service  is changed, the  sediment content of the stored product exceeds
specifications, or the tank itself needs inspection or repair.  The characteristics of the
deposited  sludge  will vary with the  type  of product  stored in the  tank.  Leaded tank

                                   89-17

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bottoms are considered RCRA hazardous and special handling methods are used when
the sludge  is removed.   It is  removed at intervals varying between once a year and
                                                                    <
once every  five to seven  years.  The sludge  is spread on special  concrete  pads for
weathering. Weathered sludge is disposed of in a Class I landfill.

7.6  Wastewater Treatment Wastes

Waste  due  to wastewater  treatment is produced  by  the API separator,  dissolved air
flotation unit, slop oil tank, vacuum filter, biological treatment system (if present),
and the stormwater settling basins.  Solids which settle in the  API separator during
primary wastewater treatment are periodically removed with a vacuum truck, water is
discharged  to the  secondary  treatment  and  oil  is recycled back  to  the  crude unit
through slop oil tank.   Refinery  API separators are usually connected to the oily water
plant sewer.  The bottoms,  therefore,  are a mixture  of settleable portions of all
sewered wastes, such as tank bottoms and desalter sludges,  and, probably contain a
certain amount  of all other  compounds  that are present in the wastewater.  These
sludges are  listed  as RCRA hazardous wastes.  In some refineries,  additional oil and
solids  are  removed from  the API  water effluent by  dissolved air flotation.  The
flotation process  takes place in a  tank  with  or  without  the  aid of chemicals.  Air
bubbles form and bring  the finely divided solids and oil particles to the surface, where
they are skimmed  off.   Oils  are  pumped to  the  slop oil tank.   Sludge is sent  to a
landfill.  The waste is classified  as RCRA hazardous.

Skimmed oil from  the API separators is usually pumped into a  slop oil tank where the
mixture is  separated into three fractions: oil, water, and emulsion.  The oil is returned
for reprocessing, and the water is recycled back  to the  API separator.  The emulsion
layer may  be disposed  as  a sludge, or it may be further  treated, i.e., de-emulsified.
De-emulsification  is carried out by chemical or  by physical treatment.  The  former
process employs the use of special chemicals or agents, heat,  and settling tanks. The
later involves removal of suspended solids by centrifugation or vacuum filtration and
the  water  and  oils are separated  in settling tanks.   In either  process, the oil is
reprocessed, the water is returned to the  wastewater treatment system, and the solids
are disposed as a solid waste.  This waste  is classified as  a RCRA hazardous waste.

In order to  reduce sludge volume, some  refineries concentrate certain waste  streams
through  use of a common  dewatering  system.   The dewatered  cake from these

                                   B9-18

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processes  is disposed  to  land,  while  the  filtrate  or  centrate  is returned  to  the
wastewater treatment system.
                                                                     «
In" the process of biological treatment  of  refinery aqueous  waste streams emerging
from the primary or secondary  treatment, excess bio-sludge  is  created  which,  for
efficient operation,  must be controlled by  wasting.  The waste bio-sludge has a very
high water content (99%) and is dewatered  prior to disposal.  This waste is generated
intermittently at a rate which is dependent upon activated sludge process variations,
the desired level of process efficiency, and the raw waste load.

Silt  which  collects in the stormwater settling basins in some  refineries is periodically
removed, de-watered, and  land disposed.  The quantity of silt is usually a function of
the amount of rainfall and/or refinery paved area rather than of  process complexity.

7.7   Utilities Production Wastes

Utility wastes are created by treatment of  raw process water or once-through cooling
water conditioning, cooling tower water  blowdown treatment,  cooling  tower sludge,
and  boiler  feedwater   treatment.    Raw  water  is usually  strained,  clarified  using
coagulation, flocculation, and sedimentation, and sometimes softened using lime treat-
ment.  Water pumped  from  a nearby source  is passed through  primary settling  tanks
prior to  usage for once-through  cooling.   Sludge is periodically removed from  these
tanks.

The  blowdown from  the recirculating cooling water system is  treated  to precipitate
chromium.   Chromium  salts are added  to  the cooling water to  inhibit corrosion  of
carbon steel.  Sludge which settles in the cooling tower basin  is  removed whenever  the
cooling tower is out of operation. It  is either  washed into the  process sewer system or
shoveled  out and land disposed. This sludge also contains chromium.

Spent lime from cold or hot  lime softening and from the clarification of boiler feed
water is  continuously discharged, de-watered in a settling basin, and disposed on land
or re-used  for neutralization of acidic waste  streams (e.g. HF alkylation spent acid).
The  quantities and composition  of  the spent lime sludges are dependent upon  the
characteristics of the raw makeup water.
                                  B9-19

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8.    WASTE GENERATION RATES

In  1976,  the EPA published a study on Hazardous Waste  Practices  in "the petroleum
refining industry (Jacobs 1976).  One of the four basic  objectives of  the  study was to
determine the source, nature, and quantity of potentially hazardous  wastes generated
by industries engaged in the business of refining crude oil.  Seventeen representative
refineries were selected  for study.   Potential  sources  of  hazardous  waste  were
identified,  sampled, and  chemically  analyzed  for a  range of  constituents.   These
analyses  served as the basis for estimates of  total waste emissions from the refining
industries.  This information was subsequently reported in a 1979 study (Jacobs 1979).
Generation rates are summarized in  Table 8-1 for various petroleum refining waste
streams.  More recent waste generation data were not in evidence at the  time  of final
report preparation.

9.    WASTE REDUCTION THROUGH SOURCE CONTROL

Generation and minimization of  waste  from petroleum refining can be initially viewed
in  the  simple context of conceptualizing the complex process  of refining  as one in
which the undesirable impurities naturally  occurring in petroleum (principally heavy
metals,  water, sulfur, oxygen and nitrogen) are removed from the hydrocarbons.  At
this general level, it is important to note that the wastes produced  due to impurity
removal  are unavoidable and can only be reduced  by  using lighter crude feedstock (an
issue of  high  economic  and political complexity) or  by  a decrease in the  use  of
petroleum (an even more controversial and complex issue); neither one is  suitable even
for a topical  exploration  in this study.   Hence, waste  minimization in  petroleum
refining  is  more readily  addressed in terms of what can be done given a current mix
and flow of refinery feedstock.   Here,  the following general areas of focus  are
distinguished.

           Maximize utilization (minimize loss) of auxiliary  materials  and supplies.
           For example, extending the catalyst's life results in less frequent catalyst
           replacement  thus reducing possible  waste associated with its disposal or
           reprocessing.
                                   89-20

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                          Table 8-1 1974 Waste Generation Rates from the Petroleum Refining Industry
DO
Waste
Kerosene filter clays
Lube oil filter clays
Neutralized alkylation sludge
Heat exchanger cleaning sludge
Crude oil tank bottoms
Leaded gas tank bottoms
API separator sludge
Slop oil emulsion solids
Biological treatment sludge
Storm water silt
Once through cooling water sludge
Cooling tower sludge
Boiler feedwater treatment sludge
Oil
(Weight %)
3.5
21.9
6.9
10.7
47.4
20.0
22.6
18.0
0.3
3.9
0.4
0.4
0.3
Water
(Weight %)
5.0
50.0
54.2
53.0
13.3
0.3
53.0
40.0
87.0
25.0
25.0
75.4
59.0
Others
(Weight %J
91.5
28.1
38.9
36.3
39.3
79.7
24.4
42.0
12.7
71.1
74.6
24.2
40.7
Total
(Metric Tons/Yr/
1,000 BPSD
Crude Capacity)
1.0
431. 2(a)
47.4
0.7
0.2
0.8
4.7
2.3
6.2
2.7
16.8
0.1
70.5
        Source:  Alternatives for Hazardous Waste Management in the Petroleum Refining Industry (Jacobs 1979).




        (a)    Metric tons per 1,000 BPSD lube capacity.

-------
           Search for less toxic substitutes.   An example of  less toxic materials
           substitution  is found  in the use of non-chromate corrosion inhibitors for
                                                                    t
           cooling water treatment.

           Maximize slop oil recovery. This pertains to oil that is lost with sludge and
           emulsion  solids leaving primary or secondary  wastewater treatment.  In
           this context, one should address the  causes of slop  oil generation and the
           ways to improve its separation efficiency from aqueous streams.

           Maximize energy and water conservation.  This reduces waste generation
           associated with  treatment of boiler  feedwater, plant water,  and cooling
           tower water.

           Reduce equipment cleaning frequency to cut down on equipment cleaning
           waste.

All of the  above practices are encountered in one form or another at virtually every
refinery.   The attempt  to  identify and characterize  waste minimization  options is
presented  below.    Most of  the principal  waste streams leaving a  refinery  were
addressed -some of  which are exempt from  federal regulations  (but not  from  state
regulations),  others'that are not considered to be hazardous, and  still others that are
listed  RCRA  wastes.  The rationale  for  including all streams was provided  in the
introduction to this appendix.

9.1   Description of  Techniques

The  list of  individual  primary  waste streams  along  with a list  of possible  source
reduction methods is presented in Table 9-1.  Sections  below deal with the description
of  the listed  methods.    All  proposed  methods appear  to be  technically feasible;
however,  the decision of whether or not to use a particular  method is  highly site
specific and  is dependent on other factors  such as economics, cost/benefits, configura-
tion of existing facility, and local regulatory constraints.

In addition to the waste reduction measures classified as being process  changes or
material/product substitutions, a variety  of  waste reducing measures titled "good
                                   B9-22

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                                M SUHWRY or SOURCE CONIROI utiHoowocr ron THE  PHROUUK REFINING INOUSIHT
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Sludge (•). 13
Bctto»s. and IS
Gasoline lank 16
Bottoms 1'; i'
II
MO

!
i
ceo!a;e f'.ltrsfon «lth hydrotreatlng)
Regenerate and recycle clay |
Use fi>ed bed city filtration process I
Overall |

fmlaite aeration and purg? sl*a» |
Overall |
Proper operation of In* process |
Use HOH to neutrtliie HF acid uaste I
Upgrade feedstock, by hydrogenat Ion I
Overall |
Cholct of oroper a«lne solution |
Prevent deterioration of jtret so'n 1
tlte-nat'.es to .V-AO» I
Seco.er products froi tne »»it»s!rta«|
Oteinatives to Stretforo process 1
Overall |
Decrease fil» teaperatjre 1
Use proper corrosion inhibitors {
Use smooth Sett eicUnqt tube surface)
Reduction of Pb In gtinline |
IrsMll storage ttnk agitators |
Use liners/corrosion resist aaterlal I
Prevent omdation of crude oil |
Refine/recycle sludge fo' orgtnlcs I
Overall |
found Documentation
Quantity | Quality
1 1
1 1
1 1
1 00 | 1

0 1
0 30 | 0
7 I
7 1
t 1
1 67 | 1
7 1
1 i
; i
i :
i i
1 33 I 1
1 1
1 1
1 1
' 1
1 1
0 1
i I
1 1
0 80 | 0


1
1
30

0
00
1
7
It
7
1
7
13
1

1
1
1
0
1
1
90
1 Naste I
1 Effectiveness |
1 - 3 |
i 3 |
1 ? I' 1

1 7|
1 7 SO |
1 3 |
1 3 |
I 3 00 |
1 3 |
J 1
1 ) 1
1 * 1
1 Ml I
1 1 1
i y \

i 1 1
i 3 |
1 3 |
1 ' 1
1 3 i
1 ? 10 1
Extent of | Future t Iractlon of |
| Potential 1 |
1 1 3 | |
n n i
71 ' 1 1
1 It | 7 00 | 0 01 |

31 1 1 1
7 00 | 1 SO | unknown |
31 1 1 1
J 1 H 1
1 1 7| |
7 00 | 1 It | 0 31 |
31 M 1
71 M 1
71 1 1 1
M I) 1
M M 1
7 00 | 1 SO | unknom |
1 1 I 1 1
J 1 II 1
M M i
ji ii i
i ' i l
i i i i
i M i
1 M 1
1 M 1
1 3 | |
1 30 1 1 30 | 0 01 I
Current |
Inden |
01 |
1 5 |
1 0 I
1 S |

' 1
1 S |
1 5 1
I 3 |
1 5 |
0 1 1
7 3 |
» 3 |
1 0 |
1 S |
0 3 |
1 « 1
J 3 |
0 S |
1 0 1
' 5 |
1 0 1
0 3 |
7 3 |
0 1 1
0 5 I
0 1 1
7 ; ;
Future 1
Probable
1
0
0
0

1
0
0
0
1
0

0
0
0
0
0
0
g
0
o
0
0
1
0
1
0
eduction Indev
| Naiiaui
t 1 1
1 1
3 I
J | 1

1 1
• 1 '
7 1
' 1
1 1 1
t 1 1

3 I
1 I
7 I
S 1
• 1 '
1 1
} |
3 1
1 1
3 1
7 I
1 1
1 1
I 1 1
5 1 -1


1
7


1
1
1


1


7
7
       (*}  Jht?$«» $tr«?a«s include listed  T* and/or "K"  RCRA wastes

-------
                   7WU I-1 continued
'

1
1
i
1
1
I
1
1
1
1
1
1
1
1
1
1
i
1
1
1
1
1


Hlitf Strps"

1
1
1
Kaste>ater treat mg|l
1FI Separator
31ud,e >•).
0«f flcat (')
Sloo Oil lank
Siudge (•).
Biosludge. and
Si!t


Utility Production
Da> Hater
treatment Sludga
Cooling lo»er
Sludge.
Cl Blo.do.n
treatment Sludge
i;
i!
II
IS
16
|7
o
1 >
1
II
i2
13
II
IS
It
1'
and 6IM treaties 13



•11 Sou'C.S
19
no
!
.
I found Dori/.n«?nl jl ton | Haste | Intent of 1 future | fraction of |

io'nroi "pinooo'OQy | • -- — • "| Deduction | Lurrent usf | Application | i&tai Haste |
1 Quantity 1 Quality I effectiveness | 1 Potential I I
Segregate aqueous and ally Hastes | ' 1 1 I 2 | 3 | 1 | I
Kcco.er oil fro* «fl tludge | 1 1 1 I 3 | 1 | 3 I I
Install 1 loll ing roof cjvei s 0.1 unit I 1 I 1 | 1 | 1 | 31 |
Use pressurised air In air 'lotatton | 1 | 1 | 1 | ? | ? | j
Oversue unit to «a« tludge rteoval I 0 ; 0 | Ij 21 1 i I
Crtoue flocculant usage/addition | 0 | 0 I 1 | 1 | 1 | |
Us* alternate cleaning techniques | 1 | 1 | 2 | 1 | 21 I
Use sludge in the production of coke I 1 | 1 | 1 | 1 | 2 I I
Better operating practices I 1 I 1 | 2 | 3 | 1 | 1
Overall I 0 71 1 0 11 I 1 1) I 1 »7 | 1 1C | 0 10 I
Irstell air coolers | 01 0 | 3 | 31 1 | |
Meat e»changer tube leak prevention I 0 I 0 | 21 2 I 1 \ \
Proper cooling lo.er oater treatwnt I ? | 21 2 i 3 I 1 I I
Ninimie cooling to.er duly 1 0| 0| 2 I 3| I I |
Die cleaner »ak»-up «ater I 01 0 I 2 | 21 2 I |
Use non-chronate vater treatment | 2| 2 | 3| l| 2 I |
Add Insulation to pipes, tanks, ect I 01 0 | 1 | 3 I 1 | I
Con.ert stea« to rebelled strippers 1 1 | 1 I 2 | 2 I 1 i 1
«t.nli« heat recovery | ) I 3 | 1 | 3 | 21 I
Getter operating practice I 2| 2 | 2| 2 | 21 |
Ove'-al! | 1 00 1 1 00 | 2 00 | 2 10 | 1 SO | 0 57 |
ill HetMxts I | 00 |
Current I future keduCt • Qf«
Keduct ton

	 -. . - —
Index | Probable I *
1 S
0 1
0 3
0 S
0 S
0 3
0 S
I 0
1 S
1 5
7 3
1 0
1 S
1 5
1
0
0
1
0
1
0 1 |
1 t |
0 6 |
0 ) |
0 1 1
0 2 |
0 1 |
' S 1
0 1 1
0 t |
0 2 |
0 5 1
0 1 |
0 1 |
0 5 |
1 1 |
0 1 |
0 3 |
0 1 1
0 5 |
2 3 | 0 1 |
J 2 | 05|
!r,de- I

— 	 1
1,1.,,,. |
	 	 4
1
1 7 |
1
1
1
1
1
I
i
1 7 |
1
1
1
1
1
1 1 |
1
,
1
1
1 1 1
' 2 I
C)  these ttreais Include  listed T and/or '«'  WS« wjstfi

-------
operating practices" have also been included.  Good operating practices are defined as
being procedural or institutional policies  which result in a reduction of waste.  The
following items highlight the scope of good operating practices:        *

     o     Waste stream segregation
     o     Personnel practices
                management initiatives
                employee training
     o     Procedural measures
                documentation
                material handling  and storage
                material tracking  and inventory control
                scheduling
     o     Loss prevention practices
                spill prevention
                preventive maintenance
                emergency preparedness

For each waste stream, good operating  practice applies whether  it is  listed  or not.
Separate listings have been provided whenever case studies were identified.

9.1.1       Separation Process Wastes

These wastes include kerosene and lube oil filter clays.  Some uses of clays inclusive
final treating of lube oil base stocks to improve color and remove acidic compounds,
copper removal from kerosene filtrate, and removal of BTX from catalytic reformate.
The following methods allowing for elimination or reduction of this waste stream were
noted:

     o     Replace clay filtration with hydrotreating.
           Where a  need  to remove color bodies and  olefins exists, hydrotreating is
           replacing  clay filtration as the method of choice.  Hydrotreating does a
           better job of improving color, increasing  stability against oxidation, and
           has no yield loss (the oil measured in the spent filter clay represents a loss
           of some  of  the  most valuable products produced in  a  refinery).   It also
           eliminates the problem of spent clay disposal.

                                   B9-25

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     o     Regenerate and recycle spent clay.
           Spent clays  from the  contact  process  may constitute one of the largest
           waste streams from major  refineries.  At least one  refinery .reported that
           it was attempting to recycle this clay (Jacobs 1979). It is not known what
           type of regeneration process was being used, but their previous attempts to
           regenerate contact  clay  by burning the residual oil with air, or by using
           roasting  kilns  or  similar  equipment,  were  not  satisfactory.    Close
           temperature control is necessary for the clay to  maintain its activity,  and
           with the variations in the amount of   residual  oil  left on the  clay,  this
           becomes  extremely   difficult.    The  Socony-Mobil  Oil  Company  has
           developed their Thermofor kiln for the regeneration  of  non-activated clay.
           The process consists of washing the spent clay with naphtha to free it from
           oil and render it mobile.  It is then dried by steam heating and fed to  the
           clay burning kiln where it is regenerated by controlled combustion of  the
           absorbed impurities.  The unit is quite complex and  a considerable amount
           of auxiliary equipment is required.   The process  has been in use for many
           years on a batch basis, but has, as yet, never been run  as  a  continuous
           operation.

                                  89-27
     o     Use fixed bed clay filtration process.
           The  fixed bed  (percolation') process uses  more  clay for  a given  duty as
           compared  to  the fluid bed  (contact) process  but the spent clays can  be
           regenerated  many times using kiln.   In  addition, clays used in  the fluid  bed
           process  must be treated with sulfuric acid before  use.  The main  advantage
           of the  fluid  bed process, however,  is that it has a  neutralizing effect on
           acid treated oils.

9.1.2       Conversion Process Wastes

Conversion  process wastes  include  spent catalysts  from  FCC, hydrotreating  and
hydrocracking.  FCC catalyst  is  continuously  regenerated  by  burning off the coke
formed  on the  catalyst  during the cracking process.  Some of the metal compounds in
the feed are adsorbed on  the catalyst.  In  the catalytic cracking unit regenerator,
where coke is burned off the spent catalyst, the organic portion of these molecules is
burned  off and the metals are  oxidized  to  an inorganic  oxide that remains on  the
                                   B9-26

-------
catalyst.   Corrosion and  erosion products  may  be mixed  with the catalyst  as  fine
particles  or may also be  deposited  on the  catalyst surface.   The  heavy  metals,
vanadium and nickel, and  to a lesser extent, iron and  copper,  act as dfthydrogenation
catalysts  and  produce  excessive  quantities  of undesirable  coke  and light gases
(especially  hydrogen).   In many cases, these metal  contaminants  are the primary
reason  for  discarding  part of  the  equilibrium  catalyst.   Fresh  (uncontaminated)
catalyst is then added  to maintain a desirable level of contamination.

The  flue gas from the regenerator passes  through  a series of cyclones that  recover
most of the catalyst which is returned  to the reactor vessel.  Fines  are recovered  in
electrostatic precipitators. Operators try to control the operation such that the fines
production  rate   about  equals  the  poisoning rate  in  order   to  avoid removal  of
equilibrium catalyst. Suggestions for reducing FCC  catalyst losses are as follows:

      o     Demetalize gas oil charged to cat cracker.
           Catalyst withdrawal rate can be reduced by decreasing the rate of catalyst
           deactivation by removal of metals  before gas oil is  charged  to the reactor.
           A  mild  hydrogenation  or hydrotreating process has been used  on  the
           catalytic cracking feed in some  units. This feed treatment removes some
           of the  metal  compounds  and provides  other  benefits  to  the  catalytic
           cracking operation, such as removing  sulfur, which  reduces the amount  of
           sulfur  emissions from the  regenerator,  and increasing yields of  desirable
           products such as gasoline.

      o     Minimize use of aeration and purge steam.
           Excess fines  will be  generated  by overuse of aeration and  steam  purges
           during cracker operation.

Minimization of spent catalysts from hydrotreating and hydrocracking operation  was
not addressed in  detail.  Generally, catalyst losses  can be reduced by  proper  loading
and pre-sulfiding  procedures, good reactor temperature control, good  flow distribution
and continuation  of research  into development of  more active, stable  and  selective
catalysts.
                                   B9-27

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9.1.3       Upgrading Process Wastes

The principal wastes of concern are the sludges resulting from neutralisation of acidic
effluents  from alkylation operation.  Wastes  associated with the alkylation process
primarily  result from carryover of acid into  the organic phase (oil)  and carryover of
organic phase into  acid.  The carryover  in both directions is attributed to physical
entrainment  (physical  carryover)  or to  the  formation  of  undesirable compounds
between components  of the  organic phase and the  acids (chemical  carryover).   The
following  methods were noted as potentially useful in reducing alkylation wastes:

     o     Proper operation of the process.
           By reducing the degree of physical and chemical carryover that occurs, a
           reduction in caustic waste can be achieved.  Physical carryover of acid can
           be caused by using excessively cold acid, improper acid settler  level, low
           reactor  pressure,  and  an  excessive  acid  recycle  rate.    Chemical  acid
           carryover can be due to low isobutane or acid concentration, high reaction
           temperature, and improper mixing.   Improvements  in operation  of the
           alkylation process were previously  discussed in more detail (NPRA 1977,
           Libberman 1980, Hammershaimb and Shah 1985).

     o     Use KOH to neutralize HF acid waste.
           In  the past, lime was used to neutralize acid carryover  and other wastes
           produced by the alkylation process directly.  The newer process alternative
           relies on potassium hydroxide (KOH) to neutralize acid; this is followed by
           reconstitution of KOH  by reacting KF with  lime outside of the neutralizer
           or  scrubber.    With  HF alkylation,   the  switch  to  KOH for initial
           neutralization has  achieved  a reduction in the overall   amount  of  lime
           required and,  thus, in  the amount of sludge produced.   Additionally, the
           overall  system  efficiency and  reliability  is improved  over  calcium  or
           sodium based solutions (Hammershaimb and Shah 1985).

     o     Upgrade feedstock by selective hydrogeneration  or hydroisomerization.
           Because of increased demands for  higher octane gasoline and the increased
           conversion of heavier crudes to  lighter products, there has been  a relative
           decrease  in the  quality  of alkylation  feed   throughout  the   industry
                                   89-28

-------
          (Hammershaimb and  Shah 1985).   By selectively hydrogenating diolefins
          (acid polymer precursors)  in the feed, acid  consuming impurities can  be
          removed and hence overall acid consumption reduced.  Hydroisomerization
          processes are commercially available, e.g. HPNIVB process.

9.1.4      Auxiliary Process Wastes

Refinery gases that contain  CO2,  H2S, and  traces of COS and  C$2, are typically
scrubbed by amines to remove  these components.  The  amines  form certain  non-
regenerable  compounds which  must be  removed  by  intermittent  bleed of amine
inventory. The following source control methods were noted:

     o    Choice of proper scrubbing solution.
          Presently,  monoethanol  amine  (MEA),  diethanol  amine  (DEA), digly-
          colamine (DGA),  diisopropanolamine (DIPA),  and  methyldiethanolamine
          (MDEA)  are  in  use.   There  are some advantages  and disadvantages
          associated with  any of these  solvents.  Typically, the waste generation
          aspect  is  addressed  in terms  of  reducing costly  amine losses due  to
          formation  of  non-regenerable  compounds.   This  aspect  usually  receives
          close attention of a process designer.  The  ultimate choice  of solvent
          depends  on specific application, therefore it  is difficult to  generalize which
          solvent is most preferable from the waste generation standpoint.  Recently
          MDEA has been more frequently applied than in the  past.   The use of non-
          amine gas treatment  processes (e.g.  Purisol, Selexol or Benfield) should be
          carefully considered from the waste generation aspect as  an alternative to
          amines.

     o    Reduction of amine loss.
          The loss of amine  solution through  degradation  can lead to many problems.
          Besides the actual loss of solution,  degradation products are corrosive and
          can lead to equipment  fouling.  Studies have shown that  the  rate of DEA
          degradation increases with increasing  temperature and  pressure (Melsen
          and Kennard  1982).   Therefore,   the rate  of DEA flowing  through the
          regenerator reboiler should be kept high and the steam or gas temperature
          kept low so as to  lower  the film temperature on the process side. Efforts
                                   B9-29

-------
           to remove the degradation products by means of carbon filtration have not
           been very successful (while the appearance of the DEA improves from dark
           brown to  light  yellow,  no major  degradation  products were   removed).
           Also,  increased pressure was shown  to accelerate degradation process.
           Examination of tradeoffs between higher amine losses and operating the
           regenerator  at  atmospheric  pressure  with  amine  gas  re-compression
           appears worthy of consideration.

           The use  of additives to inhibit amine deterioration is in common use and
           was  found   effective   in  the case  of  "Amine  Guard",  an additive
           manufactured by Union Carbide.

Tail gases  from the Glaus sulfur recovery plant are treated to remove residual sulfur
and its compounds (CS2, COS, SO2,  H2S) in order to meet sulfur emission standards.
Among the processes used to treat the tail gases  is the Beavon process which relies on
a catalytic reactor to convert all sulfur compounds to  H2S  and  a Stretford  section
where H2S is selectively scrubbed and  oxidized  to sulfur in an aqueous phase.   To
avoid  excessive  buildup  of  non-regenerable impurities  (chiefly  thiosulfate),  the
Stretford  solution inventory is bled, thus generating a potentially hazardous waste
stream  containing sodium salts  of  anthraquinone  disulfonic  acid  (ADA), vanadium
compounds, sodium bisulfite, thiosulfate, carbonate, and bicarbonate. The following
techniques are considered useful to minimization of this waste stream.

     o     Prevent excessive deterioration of  Stretford solution.
           If the absorber  is overloaded  with inlet tail  gas, excessive  amounts  of
           thiosulfate and insoluble vanadium oxysulfide are formed.  When a Claus
           plant produces big swings in  the sulfur content of the tail gas,  overloading
           of Stretford  solution  is likely, which in turn leads to excessive chemical
           losses. Adding  small quantities of sodium tartarate  to the solution helps
           prevent  the formation of vanadium  oxysulfide and hence reduces losses
           (Kohn and  Riesenfeld 1979).  The initial degradation of  2,7-ADA  during
           startup can be inhibited by adding sodium  thiosulfate  to virgin solution
           prior to startup.
                                   B9-30

-------
     o     Alternatives to 2,7-ADA.
           Since  2,7-ADA is  not  very stable, the use of more stable  substitutes is
           desireable. Proprietary formulations, such as  "Elvada" and,"Amada", have
           been offered  as possible substitutes.   Elvada  contains a mercury catalyst
           and thus  may not be an environmentally advantageous substitute.  Amada
           does not contain mercury and appears to be a better choice.

     o     Recover products from the waste stream.
           Two processes,  one developed  by  Nittetsu  Chemical  Engineering Ltd.
           (Japan) and  the other  by Peabody-Holmes  Ltd.,  are available to recover
           useful products from Stretford process wastes (Kohl and Riesenfeld 1979).
           Both processes concentrate  the waste stream  by evaporation of water,
           followed  by  combustion  of the  residue under reducing conditions,  where
           vanadium, sodium carbonate, and  hydrogen sulfide  are  recovered to be
           returned  to  the process.  Organic  compounds,  such as  ADA  and other
           additives, are destroyed in the  combustion process.  These  processes  are
           thus capable of reducing wastes from the Stretford process.

     o     Alternatives to Stretford process.
           An  alternate  process (Seiectox)  for sulfur recovery from Claus tailgas was
           developed and licensed by Ralph  M. Parsons Co. and Union Oil Co. (Beavon
           et.  al. 1979).   This  sulfur  removal  process uses a cobalt-molybdenum
           catalyst to hydrolyze and hydrogenate COS,  CS2, SO2, and elemental sulfur
           to  H2S which is then catalyticaly oxidized to SO2 using air.   The H^S and
           SO2 then form elemental sulfur  by the Claus reaction. Since no chemicals
           other  than the catalyst are used in the process, no solution purges  are
           necessary.   The  process  is  said  to  have  lower  capital  investment  and
           produce a slightly better quality  sulfur than  the Stretford process.  At least
           one industrial  unit (Wintershall AG, Lingen, West Germany)  has  been
           reported  to use this process.  New  promising developments include Unocal's
           Unisulf process which is yet to be tested on commercial scale.

Minimization of spent catalyst wastes from  the Claus plant, sulfuric acid plant and
steam reformer was not addressed.
                                   B9-31

-------
9.1.5       Equipment Cleaning Wastes

Heat  exchanger  tube  bundle cleaning sludge is a  major contributor, to equipment
cleaning wastes.  Often  these wastes are discharged into  a  pit which  is then flushed
out with water.  This sludge/water waste flows into  the chemical or oily water sewer
(OW5) and on into the API separator for primary treatment.  The following suggestions
for waste reduction were noted:

     o     Decrease  film  temperature and increase  turbulence  on  heat   transfer
           surfaces.
           A decrease in film (or surface) temperature and  an increase in turbulence
           (or velocity) will decrease the asymptotic fouling resistance, thus reducing
           the cleaning frequency.  This could be accomplished by  not oversizing the
           heat exchangers excessively or by provision of recirculation  of cooling  fluid
           in  order  to  maintain  high  velocity (Garrett-Price 1985).   On the cooling
           water side,  excessive  film  temperatures often result from low  flows of
           cooling water during turndown  operations.  Where  possible, the feasibility
           of  temperature  control using process stream bypass as  opposed to direct
           throttling of cooling water should be addressed.

     o     Reduce deposit precursors in process fluids and cooling water.
           Calcium  and  magnesium  salts present  in  crude oil  contribute  to  scale
           buildup and corrosion in crude preheat trains.  Reducing the allowable salt
           content by  water injection upstream of desalters, operating the  crude
           desalters at maximum  efficiency, and addition  of emulsifier downstream of
           desalter will minimize  the exposure of the process side of the exchanger to
           scale  forming salts (Van der Wee  and  Tritsmans 1966).  If economically
           feasible to  do so, a  softened water (i.e., clarified boiler blowdown) can be
           used   as cooling  tower makeup.   The reduced  level of calcium  and
           magnesium salts in cooling water  would reduce  the exposure of the  tubes to
           scale  forming salts.

     o     Use proper corrosion inhibitors in cooling water.
           Selection of  the proper type and dosage  of corrosion inhibitors  will cut
           down  on scale formation.  Typical corrosion inhibitors currently being used
           include chromium, zinc, phosphates, and free chlorine (USEPA 1978).  Since

                                   B9-32

-------
      these additives pose a potential pollution problem, they need to be removed
      prior to discharge or their use avoided.  The use of organic chelating agents
      as replacements for zinc and chromium compounds is a via51e  alternative
      (Gesick 1974,  Zecher  1975).  The  use of a  reacted phosphate  product
      developed by Hercules,  Inc., as a substitute for heavy metal inhibitors has
      been reported (Wilkes and  Model 1984).  Wites Chemical  Co., reports the
      use of a non-oxidizing  biocide as a similar  substitute (Hoblack and Kawlor
      1985).  A proprietary nonchromate treatment, Dianodic II, was found to be
      effective in controlling scale formation at  National Cooperative Refinery
      Association, McPherson, Kansas (Nichols et al. 1980).

      Substitute air coolers or electric heaters for heat  exchanger.
      Reduction in sludge generation due to bundle cleaning on utility side can be
      accomplished  by  replacing  heat  exchangers with  air coolers or electric
      heaters. This should be done if economically sound.

      Use smooth heat exchanger tube surfaces or on-stream cleaning devices.
      Providing  a  smooth surface  for heat transfer  will  minimize  the   sites
      available for scale formation to start. The  use of electropolished stainless
      steel tubes in a black liquor  forced circulation evaporator (paper and pulp
      industry) resulted in a drastic reduction in cleaning frequency from once-a-
      week to once-a-year (Uddeholm Co., Tubec  Tubes Brochure).  Smooth non-
      stick  surfaces can also  be provided  by  Teflon*.    Complete Teflon
      exchanger designs  are available  (Dupont 1985).   The additional advantage
      of Teflon tubes is their ease of cleaning and  corrosion resistance.

      The onstream cleaning devices generally rely on an insert propelled by the
      process  fluid through the heat exchanger tube.  Brushes propelled back and
      forth by flow  reversal accomplished with  a diverter (Water Services of
      American    Inc.)    or    sponge   balls   recirculated   by   a   special
      retrieval/reinjection device (Amertap Inc.) are both commercially available
      onstream cleaning systems.
Registered trademark of E.I. DuPont de Nemours & Co.

                              B9-33

-------
Sludge due  to  cleaning  of crude  oil,  leaded  gasoline, non-leaded gasoline,  and  other
product storage  tanks  is another major equipment  cleaning waste.   The  following
methods for reducing the generation of sludge were noted:             «

      o     Reduction of lead in gasoline.
           The current  trend of reducing the level  of lead  in gasoline, coupled with
           the possibility of a ban on leaded gasoline, will lower the toxicity of leaded
           gasoline tank sludges.

      o     Install storage tank agitators on crude oil tanks.
           Agitation of the vessel contents  will prevent the  deposit of  settleable
           solids and hence reduce the  need for cleaning.    It must be noted that
           agitation  does  not by  itself  reduce the  amount  of  waste  generated; it
           simply transfers the solids downstream to the crude unit - they eventually
           end-up either in asphalt or  coke.

      o     Use corrosion resistant materials.
           Some of the sludge generated is the  result of corrosion or  deterioration of
           the storage  tank internals.   Installation of a liner  or using  materials of
           construction which are more resistant to the corrosive elements of  crude
           oil will reduce sludge production.

      o     Prevent oxidation of crude oil.
           Gums and resins form  as the result of air oxidizing unsaturated compounds
           in the crude oil.  Air oxidation can be minimized  in crude storage tanks by
           providing a  nitrogen blanket  over the surface of the oil or, more commonly,
           by use  of floating roofs.  The floating  roof should  preferably  be of the
           double  cover type  with  liquid seals.   Many storage tanks are  already
           equipped with floating roofs as a result of air emission regulations.

      o     Refine or recycle sludge for organic content.
           Conventional cleaning  of crude tanks often relies on mechanical removal of
           sludge  and   its subsequent   land  disposal.   The  use of  warm  oil  and
           circulating  cleaning techniques reduces the  ultimate  sludge  volume  and
           allows for recovery of considerable quantities of valuable crude tied up in
           the sludge (Barnett 1980).  Here, a light gas oil, clean crude stock,  or other

                                    B9-3A

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           available  low  viscosity straight run  distillate  is  warmed,  mixed  with
           dispersant  additive, and circulated through  the  tank.   This  process re-
           suspends the sludge and dissolves the crude that is entrapped in the sludge,
           which amounts to 60 to 90 percent of oil by volume. The liquid can then be
           sent to the  refinery's slop  oil  recovery  system.   Again,  as in case of
           agitation, the solids are transfered  to the part of the process where they
           can be more efficiently separated from valuable entrained liquid.

           The sludge volume  can be  reduced at small refineries by using the Victor
           extraction  process (API-NPRA  Conference  1980).  Here,  the  sludge  is
           dumped into a container and agitated  for an extended period of time with
           steam and air.  This process separates the  residual oil trapped in the sludge
           which can  then be  taken off  from the top of the container.   The solids,
           significantly smaller in volume by comparison to the original sludge, settle
           to the bottom.  This process works well for granular type sludges but is not
           very effective for clay type sludges.

           At large refineries, the sludge volume can be reduced by concentrating  it
           using  vacuum,  gravity belt,  or   automated  plate and   frame  filters
           (centrifugal filters  were not found to  be very effective).  Also, the sludge
           volume  can be  reduced significantly by using  patented Chevron Recovered
           Oil Process.  This process is  said to be more effective than conventional
           filtration methods (API-NPRA Conference 1980).  Other methods involve
           thermal/chemical emulsion  breakup using  steam or indirect heating.  One
           such method  was  used at  Vickers Petroleum   refinery  where the  de-
           emulsifier  was added  to the sludge,  which  was  then pumped  through  a
           steam heater into  a conical bottom decanter (op. cit.).  Other techniques
           include  ultrasonic de-emulsification, solvent extraction (e.g. using B.E.S.T.
           process  available from Resources Conservation Co.), and recently patented
           electroacoustic dewatering (Battelle 1985).

9.1.6       Wastewater Treatment Wastes

Oily aqueous wastes which originate in the refinery are collected in chemical or oily-
water sewers (OW5) which usually discharge to an API  separator.   The  feed  to the
                                    B9-35

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separator can vary widely in  both  flowrate and composition.  The wastes are usually
comingled  and consist of oil,  water,  suspended  solids, and various emulsions.   The
function of the separator is to perform the initial separation of solids from liquids and
oil from water.  Virtually all dilute  aqueous wastes from the refinery will pass through
the API separator.

Skimmed oil  from the API separators  is usually pumped to  the slop oil tank where the
mixture is separated into three phases:  oil, water, and emulsion.  The oil is returned
for reprocessing, and  the water is recycled to the  API separator. The emulsion may be
disposed as a waste or may be processed further for recovery of oil.

Dissolved air flotation  (DAF) units  are  usually  installed after the  API  separator.
Water which  is discharged from the API separator contains emulsified oil, water, and
suspended solids.  Suspended solids  are removed in the  DAP unit either by flocculating
agents and settling, or by air  coming out of solution  and carrying the particles to the
surface along with the oil.  The froth  "float" which contains emulsified oil, water, and
solids is skimmed off  and sent to  a de-emulsifier.

Basically, the problem of reducing API sludge volume can be approached in two ways:

           Reduce the raw waste loads upstream of the API separator.

           Maximize recovery of oil from  the sludge  before disposal.

Raw  oil-containing  wastes  entering  the  API  separator  can  originate  from  heat
exchanger cleaning operations, crude tank cleaning  operations, equipment and piping
drainage and steamouts prior to maintenance, maintenance parts cleaning, and  spill
cleanup.   Generally,  most methods  mentioned  in  Section 9.1.5  apply.   Continuous
sources of aqueous streams entering  the  API separator include sour  water stripper,
desalter, boiler  blowdown, cooling  tower blowdown,  BFW treatment (ion-exchange
regeneration brine)  effluent, and  other  refinery units.  Source control  techniques
allowing  for a  decrease in  the carryover  of oil are addressed in the  appropriate
sections. Methods proposed for reducing waste associated with waste  water treatment
are as follows:
                                    69-36

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Reduce API separator inflow by waste segregation.
A major portion of the API separator load  is water that originally may or
may not have been  an  oily waste.   Efforts should be mafle to  install a
separate sewer system which would convey  oil-free aqueous wastes.  Boiler
blowdown,  some pump seal water, ion exchanger regeneration brines, and
other non-oil  containing wastes should be diverted  to  this system.  These
streams  would then by-pass the API  separator, thereby reducing its  load
and thus improve separation efficiency in the existing separators.

Recover oil from API sludge.
Most  techniques discussed in Section  9.1.5 under "refining or recycling of
sludge for organic content" for crude tank sludges also apply to API sludge.
These  methods include filtering, thermal/chemical emulsion breakup  and,
possibly,  ultrasonic separation of oil  from solids.  Solvent extraction was
found to have high effectiveness and application potential (API comments).

Install floating roof covers on API separators.
At Conoco Inc., installation of floating covers on API separators was found
to reduce the oxidation of oil that  results in the formation of heavy waste
material (API-NPRA  Conference  1980).   Floating roofs were   installed
originally to reduce air emissions.

Use pressurized air technology.
DAF units using  pressurized  air generate  less  than one half of  the  float
volume compared to induced air units for a given amount of solids removal.
New  facilities  should  incorporate   this  technology   in  the  design if
technically and economically compatible  with  the overall  refinery  plan.
Facilities currently using  induced air  systems should convert to pressurized
air systems if the economics justify this change-over.

Use sufficient overdesign  factor for new systems.
With oversized systems,  the  impact of process  upsets and flow excursions
will  be  minimized.   Reducing  the  impact  of process upsets  and  flow
excursions  leads  to  much more efficient  and  reliable operation of the
individual waste treatment units.
                         B9-37

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     o    Use proper flocculants.
          Proper   matching  of  flocculant  to  refinery  waste  will  increase  the
          separation efficiency of the process and reduce the amount of, waste that is
          carried downstream.

     o    Use alternate cleaning techniques.
          All of the methods that reduce waste due to equipment  cleaning (Section
          9.1.5)   will   reduce   waste   associated   with  wastewater   treatment.
          Additionally, removal of sludge prior to its discharge to API  separator may
          reduce organic carryover into water and reduce the resulting  biosludge.  An
          example is  an alternate design of a heat exchanger bundle  cleanup pit to
          recirculate  water through filter  to remove sludge, prior  to  discharge into
          API separator (NMERDI 1985).

     o    Use sludge in  the production of coke.
          For facilities with  cokers,  most  of  the  sludge   produced by  the  API
          separator, the DAF  unit, and the slop oil  tank  can be  injected into  the
          coker and converted to coke (API comments).

     o    Better operating practices.
          These  include  minimization  of spills of process fluids and reduction of the
          practice of hosing refinery wastes into the chemical sewer.  Because spent
          filter clays have high oil adsorption qualities it makes  them ideally suited
          for use on in-plant oil spills.  The clays are  typically from the  filtration of
          light-end distillates  and lube  oils.   Rather than  immediately  disposing of
          this spent clay, the refineries stockpile them within  the diked areas around
          the refinery  until used.  Stockpiling  of  the clay  also  allows, the hydro-
          carbons to degrade by microbial action. For additional methods, the reader
          is refered to a separate study of "good operating practices" contained in
          this appendix (Study #819).

9.1.7      Utility Production Wastes

Sludge that settles in the cooling tower basin is removed whenever the cooling tower is
out of operation.  It is either washed into  the process  sewer system or shoveled out and
                                    R9-38

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disposed to a landfill.  The sludge sources are residues from cooling tower biocides,
hardness scale from  exchanger  surfaces, cross contamination  from process  fluids,
biological materials, and airborne dirt.  Suggestions for sludge volume reduction are as
follows:

      o     Install air  coolers.
           Replacing  water-cooled exchangers, where  practical,  with air fan coolers
           will reduce contamination of cooling water with process fluid  as well as  the
           volume of  cooling water in circulation.

      o     Heat exchanger tube leak prevention.
           Cross contamination from the process side  of  heat transfer equipment is
           one of  the sources of  sludge  creating  materials.   Part  of  this  cross
           contamination is created  by leaky  exchanger  tubes.   Use of seal welded
           tube joints in some cases, or double tubesheets will minimize or eliminate
           process  fluid  leakage into  the  cooling  water  (and  vice-versa).   Tube
           vibration analysis should be performed more  routinely in the design stage.

      o     Proper cooling tower water treatment.
           Cooling  tower chemicals are  responsible for sludge  buildup.   Operators
           should refrain from  overtreatment to avoid excess buildup due to chemical
           addition.  The heavy metal content in the cooling tower  sludge  can be
           reduced  or eliminated by methods such  as the  nonchromate  treatment
           discussed in section 9.1.5.

The  cooling  tower  blowdown  treatment  sludge can  be minimized by  the  following
methods:

      o     Minimize cooling tower duty
           This is closely related to  energy  conservation in the refinery.  The waste
           (low pressure) stream, e.g.  from  leaky steam  traps,  is  condensed  using
           cooling  water which  increases  cooling  tower  duty.   Reducing  steam
           consumption helps to reduce cooling tower blowdown.

     o     Use of a  cleaner make-up water
           This will reduce the blowdown  stream and, thus,  the toxic  sludge generated
           by chromate removal. Use of boiler blowdown as a make-up stream should
           be considered.            B9-39

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     o     Use of non-chromate treatment
           As mentioned  in Section 9.1.5, this  will reduce the toxicity of the sludge
           produced by  treating  the  cooling  tower blowdown.   The* non-chromate
           corrosion  inhibitors  are reliable, except  in  services  where  water  film
           temperatures are very  high  -  in  such cases  the  design, operation, and
           controls of exchanger should be carefully re-examined anyhow.

Most refineries use a vast amount of  steam in normal operation.   Feedwater to the
boilers,  particularly the high pressure boilers, must be very clean for safety reasons as
well as  equipment longevity.  Any projects  undertaken  by the refinery  which  would
seek to  cut steam consumption  would  not  only reduce spent lime production, but also
result in operating cost savings.  Some  suggestions for reducing steam consumption are
as follows:

     o     Add insulation to pipes, tanks, valves, etc.
           Decreasing heat losses from  pipes, tanks,  valves  and other process  units
           will reduce steam consumption.  This, in turn,  will reduce the load on the
           boiler feedwater treatment system.

     o     Convert steam strippers to  reboiled strippers.
           All stripping steam eventually winds up in the waste treatment system. 3y
           converting to reboiled  strippers where possible, the spent lime required  in
           the  treatment of the water used to produce stripping steam as well as the
           wastewater load to API separator will be eliminated.

     o     Maximize  heat recovery from process.streams.
           Identify those  areas in  the  refinery for  installation  of  additional  heat
           exchanger networks to  make maximum use of available heat energy.

     o     Better operating practices.
           Many  refineries have areas where steam demand may be reduced.  It is  to
           the  advantage of the refiner to  promote  the  identification of areas and
           develop projects to  increase the overall plant thermal efficiency. Promote
           an aggressive approach to steam system preventive maintenance. Maintain
           steam traps, valves and piping runs to minimize steam or condensate  leaks.
           Provide strict guidelines  to  limit  unneeded blowdown  of  boilers  or

                                   B9-AO

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           automate  it.   Provide  rigorous  maintenance  of the  condensate return
           systems and boiler feedwater treatment systems to minimize contaminants
           which enter into the boiler feedwater.                     *

9.2        Implementation Profile

Good operating practices, while easy  to  implement, do not appear  to have as high an
impact on waste minimization  as do  process modifications, such  as replacement of
clay filtration with hydrotreating or recovery of oil from sludges.  Process modifica-
tions are expected to be considered  in the planning stages for unit replacement, major
overhaul, or  during  the  conceptual design  stage  for  any new grass-roots facility.
Considerable amount of engineering  and economic analysis is usually required before a
decision can be made because of the high capital costs involved.

9.3  Summary

The ratings  of every listed  method  shown  in the table were based  on  review of
available  literature,  engineering judgement and input  from the American Petroleum
Institute.  Each  method  was rated on a scale of zero to four  for  its  effectiveness,
extent of current use and future application potential.  The current  and  future extents
of  waste  reduction  were then  derived  using the  methodology  presented  in  the
introduction to this appendix.

A  current reduction  index of 2.2 (55 percent) is indicative of the significant level to
which  the noted wastes have  already  been  minimized (CRI  is a measure of  the
reduction of  waste  that would  have  been generated  if  none  of the  methods were
practiced at  their current level of application).  By  implementing additional waste
reduction measures,  or  by increasing  the  use of existing  measures, the amount of
waste currently being generated can be reduced to a moderate extent, as evidenced by
a future reduction index of 0.5 to 1.2 (12 to 30 percent).

The  most effective  measures currently applied to control  hazardous  (RCRA  listed)
wastes include segregation of aqueous and oily wastes, oil  recovery from sludges, re-
use of sludge  as a coker feedstock and better operating practices.
                                   B9-41

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The  most  effective  future methods  for  minimizing  hazardous wastes  are  those
characterized by high individual FRI  value.  These include oil recovery  from sludges
and use of sludge as a coker feedstock.

10.  PRODUCT SUBSTITUTION ALTERNATIVES

At this time there are no economic substitutes for petroleum products.  Alternative
sources of  energy such  as solar, nuclear, coal or shale oil cannot currently  compete
with petroleum to satisfy the energy  needs at the  level required  in the United States.
Until the world supplies of crude  oil are exhausted, or oil becomes unavailable for
other reasons, it is unlikely that it will be economically feasible for the alternatives
discussed above  to significantly displace the refining of crude oil in the near future.

One  area in which product substitution has been occurring is with the product  gasoline.
Currently,  there have been major  efforts being undertaken to reduce  and eventually
eliminate the use  of  lead in  gasoline.   Producing  a  non-leaded gasoline  requires
additional processing  to  ensure the same  level of  octane as in leaded gasoline.  Most
commonly, alkylation is employed to  boost octane levels so that  more acid  wastes are
expected to be produced per gallon of gasoline sold.  Offsetting this increase however,
is  the elimination of wastes due to tetra-ethyl lead production, leaded gasoline storage
tank sludge, and the emission of lead into  the environment by way of combustion.
Eliminating the  use of lead  in gasoline is expected to  achieve a large reduction in the
amount of toxic metal contained in a  refineries waste.

Another  alternative which  is worth  mentioning  is methanol which can be produced
from petroleum and which can be successfully used in place of gasoline (Othmer 1985).
Cited environmental advantages include low  fire hazard, absence of carcinogenic BTX
compounds  present in unleaded  gasoline,  and very  low exhaust emissions of hydro-
carbons, carbon  monoxide, nitrogen oxides and aldehydes.

11.  CONCLUSIONS

While  the  petroleum refining industry has significantly reduced  its  waste volume
generation, it appears that  further reduction is possible.  Our estimates indicate that
it  may be technically feasible to further reduce the volumes in the range  of 12 to 30
                                    B9-42

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 percent.  However, any further voluntary reduction will only be realized from in-plant

 studies which show  that  changes,  such as the  ones  suggested in this  report, are
 economical.                                                        *


 12.   REFERENCES

 Anonymous, 1981.   Novel solvent recovery  enhances residuum upgrading.   Chemical
 Engineering, 88 (24):  69.

 Anonymous, 1984. Dimersol, Hydrocarbon Processing, 63 (9):125.

 API-NPRA  Conference,  1980,  American Petroleum Institute  and National  Petroleum
 Refiners  Association.    Solid  waste  practices  under  RCRA  in  the  hydrocarbon
 processing industry, pp. 133-174. Dallas: API-NPRA.

 Barnett,  J.W.,  1980.   Better ways  to clean  crude  storage  tanks  and  desalters.
 Hydrocarbon Processing.  60 (l):82-86.

 Battele,  1985.   U.S. Patent  No. 4,561,953, issued to  Batelle,  Columbus Division,
 Columbus, OH.

 Beavon, D.J.,  Haas,  R.H., and Muke,  B.   1979.   High  Recovery, Lower  Emissions
 Promised  for Claus-Plant Tail Gas.  Oil and Gas Journal.  77(3):76-80.

 Dupont, 1985.  Chemical Processing. 48  (6):42-3.

 Garret-Price  B.A., et. al  1985.   Fouling of heat  exchangers; characteristics,  costs,
 prevention and removal.  1st ed. Noyes Publications Park Ridge, N.J.

 Gesick, J.A.  1974.   A comparative study  of non-chromate  cooling water  corrosion
 inhibitors.  Presented at  the 35th Annual  International Water Conference  of the
 Engineers' Society of  Western Pennsylvania.

 Hammershaimb, H.U. and  Shah, B.R.   1985.  Trends in HP alkylation.  Hydrocarbon
 Processing,  64(6):73-6.

 Hoblack, R. and Kawlor, L. 1985. Chemical Processing.  48(8):84-6.

 Jacobs  1976, Jacobs Engineering Co. Assessment of hazardous waste practices  in the
 petroleum refining industry.  EPA-SW-129C.  Washington, D.C.:  U.S.  Environmental
 Protection Agency.

 1979,  Alternatives  for  hazardous  waste   management  in  the  petroleum refining
 industry.  EPA-530-SW-172C.   Washington,  D.C.:  U.S.  Environmental  Protection
 Agency.

Jahnig,  C.E.   1982.    Petroleum  refinery  processes,  survey.   In  Kirk-Othmer
Encyclopedia of Chemical Technology.  3rd ed. Vol. 17, pp. 183-256.  New York, NY:
Wiley.

Kohl, L.A.,  and Riesenfeld, F.D.   1979.  Gas purification. 3rd ed.  pp. 28-90 and pp.
476-487. Houston, TX: Gulf Publishing Company.

                                   B9-43

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Libberman, N.  1980.  Basic decision key  to alky problems.  Oil and Gas Journal.  78
(June 23): 141-4.

Melsen, A. and  Kennard, M.L.   1982.  DEA  degradation  mechanism.  Hydrocarbon
Processing, 61(10):105-8.

Nichols, J.D.,  Clavin, J.S., and Blasdel, J.E. 1980.  Nonchromate treatment performs
well.  Hydrocarbon Processing, 59(lQ):75-8.

NMERDI 1985. New Mexico Energy Research  and Development  Institute.   Water use,
conservation and wastewater treatment alternatives for oil refineries in New Mexico.
Prepared by Jacobs Engineering Group Inc.  Albuquerque, NM.

NPRA.  1977.  National Petroleum Refiners Association Q&A-5.  Experience with alky
units  traded. Oil and  Gas Journal. 75 (May 23):66-75.

Othmer,  D.F.  1985, Methanol:  fuel for automobiles, Chemical Engineering Progress.
Robitaille, D.R.,  and Bilek,  J.G.   1976.   Molybdate  cooling  water  treatments.
Chemical Engineering, 83(27): 77-82.

Shreve, R.N. 1967. Chemical  process industries.  3rd ed.  New York, NY:  McGraw-
Hill Book Co.

Uddeholm Corporation (Sweden), Technical Brochure on Tubec Tubes.

USCD,  1985.   U.S. Department  of  Commerce, Bureau of the Census.   Petroleum
refining.  In  1982 Census of Manufacturers.   MC-82-I-28F.  Washington, D.C.:  U.S.
Governmental Printing Office.

USEPA,  1978.  U.S. Environmental Protection Agency, Effluent Guidelines Division.
Draft development document  for effluent  limitations guidelines (batea), new  source
performance standards, and pretreatment standards for the petroleum refining point
source category.  Washington D.C.:  U.S. Environmental Protection Agency.

Van  der  Wee,  P.,  Tritsmans,  P. A.   1966.  Crude limit  preheat exchanger fouling
Hydrocarbon Processing,  45(8):141-4

Van  Matre,  J.   1977.   Clean  heat  exchange  equipment on-stream.   Hydrocarbon
Processing, 56(7):115-7.

Wilkes, T. and Hodel, A.E.  1984.  Non-heavy metal inhibitor protects at pH 6.5-7.0.
Chemical Processing,  47(9):38-9.

Zecher, D.C.  1975.  Corrosion inhibition by surface active chelants.  The International
Corrosion Forum, Toronto, Canada.
 13.   INDUSTRY CONTACTS

 P.J. Tussey, American Petroleum Institute, Washington, D.C.



                                    B9-44

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1.    PROCESS:  PHENOLIC RESINS MANUFACTURE
2.    SIC CODE:   2821(8)
3.    INDUSTRY DESCRIPTION

Manufacturers of phenolic  resins are included as part of the plastic materials and
resins industry.  Large phenolic resin producers tend to produce the resins for sale to
other users. Smaller producers tend to produce resins for captive use.

3.1   Company Size Distribution

Relative  to   many   other   chemical  producing  industries,  the   phenolic   resin
manufacturing industry contains a large number  of producers.  This may  be because
the manufacturing processes involved  are not highly capital intensive and because of
the large variety  of final products.

In 1980, there were 50 companies producing phenolic resins at 102 establishments.  Of
the 50 companies, 6 produced more  than 100  million pounds of phenolic resins during
the year, 14 produced between 10 and  100 million pounds, and 31 produced less than 10
million  pounds.   Each  establishment  produced  an average  of  30 million pounds  of
phenolic resins in 1980.  The employment figures by EPA regions for the phenolic  resin
industry were  not available.

3.2   Principal Producers

The  following principal producers  manufacture  in  excess  of  100 million pounds  of
phenolic resins annually:

      Borden Incorporated             Occidental Petroleum Corporation
      Georgia-Pacific Corporation      Owens-Corning Fiberglass Corporation
      Monsanto Company              Reichhold Chemicals Corporation
                                  B10-1

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3.3  Geographical Distribution

Table 3-1 displays the number of phenolic resin manufacturing establishments by EPA
Region.  Region V contains 28 establishments, or over 25 percent of the establishments
in the  U.S.   However, relative  to other chemical  manufacturing industries,  the
phenolic resins  industry  is  geographically  widespread.    Figure  3-1 displays  the
geographical distribution of phenolic resin facilities located in the U.S.

       Table 3-1 Geographical Distribution of Phenolic Resins Manufacturing
                          Establishments by EPA Region
EPA Region
I
II
III
IV
V
VI
VII
VIII
IX
X
National
Number of Establishments
5
14
5
15
28
10
3
1
6
15
102
A.   PRODUCTS AND THEIR USE

The binding quality of phenolic resins make them very versatile.  Thus, they  are used
in a wide variety of products including:

                Molding Compounds              Plywood
                Insulation                       Fibrous or Granulated Wood
                Foundry Binders                 Laminates
                                  B10-2

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o
I
PO
          0
Figure
                               I 2-5
                                   d 6-10
                   Roman numerals show EPA regions

              3-1  Phenolic Resins Plants in the U.S.

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                Brake Linings
                Abrasives
                Protective Coatings
Clutch Facings
Rubber
For  1985,  phenolic resin production  was estimated  to be  2.5 billion pounds  (Greek
1985).  Table 4-1 gives the use pattern for phenolic resins.
                  Table 4-1 1985 Use Pattern of Phenolic Resins
                   Use
              Consumption
     Bonding plywood and wood fiber board
     Other adhesives
     Molded items
     All others
                    60%
                    28%
                    10%
                     2%
     Source: Chemical and Engineering News (Greek 1985).
5.    RAW MATERIALS

Reactants     Formaldehyde  (solution  or solid),  phenol, calcium  hydroxide, sulfuric
              acid,  paraformaldehyde,  hexamethyl  tetramine,  sodium  hydroxide,
              substituted phenols.

Solvents       Cellosolve   acetate,    butanol,   ethanol,   methyl   ethyl  ketone,
              cyclohexanone, xylene.

Additives      Wood flour, amino resins, oils, plasticizers.
                                 R10-4

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6.   PROCESS DESCRIPTION

Phenolic resins  are a broad  variety of  materials, all  of  which are based upon  the
reaction between phenol,  or a substituted phenol, such as cresol or resorcinol, and an
aldehyde, such as formaldehyde or acetaldehyde.  Most significant resins  are  based
upon the reaction of phenol with formaldehyde.  By proper control of the reaction, a
wide variety of phenol-formaldehyde resins can be manufactured.

In general,  phenolic  resins are produced batchwise  in a  batch  kettle  arrangement
schematically depicted in Figure 6-1.   The  batch reactor typically has a size varying
from 2,000  to 10,000 gallons.  The reactor  is equipped with  a  jacket  to  facilitate
cooling or heating  at  different phases  of reaction.  The following sections deal with
the manufacture of two principal types of phenolic resins: Resols and Novolacs.

6.1  Manufacture of Resols

Resols are  thermoset phenolic resins  used for  making bonding resins, varnishes, or
thermosetting molding powders. Resols are formed by the condensation of phenol  and
formaldehyde  present in   a  molecular  ratio  of  1.0:1.5.  An alkali,  such as sodium
hydroxide, is used as a catalyst.

Phenol, in molten form,  is charged to  the  kettle followed by  addition  of 37 percent
formaldehyde  solution which  washes away  any  residual phenol present in  the lines
leading to   the kettle.   After  the  catalyst  is charged to  the reactor,  the  reactor
contents are heated to about 1AO°F by steam to start the condensation reaction.  Once
initiated, the  reaction generates heat,  which is  removed by the  water-cooled kettle
jacket  and  a  water-cooled  overhead  condenser.  These  are  used to  maintain  the
temperature at 140-175°F for 1 to 5 hours, depending on the required properties of  the
final product.  The  reaction is stopped at  the desired point by  cooling  the  reactor
contents to  95°F.  At this point,  the  caustic may be neutralized by the addition of
sulfuric  acid.   The  reactor  contents  are then  heated  to  remove water and  other
volatiles from the resin.  The removed water contains unreacted phenol, formaldehyde,
and low molecular weight resins.  This  stream can be processed in a variety of ways
                                  B10-5

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      FORMALDEHYDE
                         PHENOL
                                                                   RECEIVER
CRUSHINI
ANfi
•RIHDINS






                                                                                               SOLID
                                                                                              PRODUCT
                                                                                               RESIN
                                                                                              LUC/ID
                                                                                              PRODUCT
                                                                                              RESIN
I
!  PROCESS HASTE CATEIORIES:
|  0   OFF-SHADE PRODUCTS
:  0   RECEIVER CONTENTS
!  _
   3}   VASTEVATER
  7)   EQUIPMENT CLEANINS HASTES
         Figure 6- i   Process Flo* Diagrai for the Manufacture  of Phenolic Resins
                                   R10-6

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 including re-use  in  compatible  batches,  phenol  recovery followed  by treatment,
 dilution followed by treatment, incineration and land disposal.

 The product resin  may be  washed several  times,  resulting in a  waste water stream.
 The solid products are dried and ground to a specific size prior to  packaging.   The
 liquid products are filtered prior to packaging.  This filtration produces a solid waste
 of oversize  resin particles which is disposed of by landfill or incineration.

 By  proper control of the reaction, three classes of products can be produced.  If the
 reaction is stopped when the polymer is still water-soluble, the product can be used for
 bonding resins.  If the reaction proceeds till the polymer precipitates,  the product can
 be used to manufacture a varnish. If the reaction  is carried out till the resin reaches
 the  brittle  stage,  "one-stage" solid resin  is  produced and can be used  as molding
 powder.   In the  last case,  the molten resin  must  be  quickly discharged  in order to
 prevent solidification in the reactor.

 6.2  Manufacture of Novolacs

 The manufacture of Novolacs  is similar to  that of  resols except that  an acid such as
 sulfuric acid is used as a catalyst.  The ratio of  phenol to formaldehyde  is normally
 1.0:0.75-0.9.  The deficiency of formaldehyde produces a stable, low molecular weight,
 thermoplastic.

 Vapors generated by the heat of reaction are condensed and returned to the reactor in
 order to  maintain  the reaction temperature  at  185-195°F.   After  3 to 6 hours  of
 reaction,  the condensate is  sent to a receiver instead of being returned to the reactor.
 When the temperature rises to 250-300°F,  vacuum is  applied to  remove water and
 unreacted phenol.  At this  point, the receiver contains water,  phenol,  formaldehyde
 and  methanol, which is used  as a stabilizer  for formaldehyde.   This stream can  be
processed in a variety of ways including re-use in compatible batches, phenol recovery
 followed by  treatment, dilution followed by treatment, incineration and land disposal.

 The  reactor contents need not be cooled as the polymerization is complete.  The  final
product is purified by dehydration under vacuum before being dumped on cooling pans.
                                    B10-7

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The reactors are periodically cleaned with caustic  solution,  generating an additional
waste stream.

7.   WASTE DESCRIPTION

Table  7-1  shows  the  primary  waste streams  associated  with the  manufacture  of
phenolic resins.  The off-grade  products, which amount to 0.8 percent of total resin
production (Snell 1978),  are  the result of bad batches.  This waste  stream contains
unreacted  phenols,  formaldehyde,  methanol,  and  resins   at  various  degrees  of
polymerization.   This waste may  be drummed  and  landfilled  or  stored onsite  in
concrete-lined  lagoons.  The  material can  also  be  incinerated  using  a fluid-bed
combustor (Lanouette 1977).

Losses from  grinding,  screening, packaging,  and filtering  are routinely collected and
reworked at  most  of the facilities.  In a  few cases, these handling losses generate a
waste stream which  is disposed of along with  the off-grade products.

The liquid in the condensate  receiver amounts to 67 percent  of total  resin production
(Snell 1978).  However, according  to more recent information, this stream constitutes
30  percent  of total resin production*.   The  stream  is  generated  from  product
dehydration in the case of resols,  or in the case of Novolacs, the water is removed in
the final phase  of  reaction  to accelerate polycondensation.  This stream  contains
water, phenol, formaldehyde, methanol,  and  low molecular weight resins.  The stream
may be land disposed or may  undergo recovery of phenol (hence producing a less toxic
and more easily treatable wastestream),  controlled incineration, chemical  or biological
oxidative treatment.

A wastewater stream, which amounts  to 8 percent of total resin  production  (Snell
1978), is also generated when the final resin product  is washed to remove traces of the
unreacted phenol,  formaldehyde, and salts produced by neutralization of  the reaction
mixture.  This stream is usually filtered  to remove any solids and then discharged to
the  sewer,  or combined  with  the receiver effluents,  or  treated  separately  using
chemical or biological oxidation, depending on the final organics content.
*Reichhold Chemicals Inc. 1985: Private communication.
                                    B10-8

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                                          Table 7-1 Phenolic Resins Manufacturing Wastes
2
o
I
No.
1.



2.


3.

Waste
Description
Off-grade
products


Receiver
contents

Wash water
waste
Process Origin
Grinding, screening
and packaging.
Filtration of the
liquid resin
Reaction water with
organics

Washing and/or neu-
tralization of the
Composition
Unreacted phenols,
low molecular weight resins


5-7 wt.% phenol
5-8 wt.% formaldehyde
5-7 wt.% methanol
Unreacted
phenol and salts
RCRA Codes




—


	

4.
            5.
Spills
            Equipment
            cleaning
            waste
product resin

Reactor, storage
tanks, valves,
pumps

Washing Novolak
reactor
Phenol and
formaldehyde, etc.
                                      Na2SO4 and NaOH
                                      in water

-------
Spills and leaks are  inadvertent discharges  occurring at various plant locations.  The
liquid discharges are usually  mixed with the  receiver  contents  for  disposal.   It  is
expected that the waste resulting from spills and leaks will be small.

A  caustic solution  is used  to wash the  reactor  for  the manufacture of  novolacs,
generating a waste stream.  This stream contains sodium sulfate, sodium hydroxide,
and traces of phenol and formaldehyde in water.  A similar, but acidic waste stream
from  resol  manufacture  is  mixed  with  the receiver contents  and  disposed  of as
described previously.

8.    WASTE GENERATION RATES

The  recent  nationwide  waste generation rates from phenolic resins  manufacturing
process were not in  evidence at the time of final document preparation.  The  most
recent estimates found  through literature  search give  fractional  waste generation
rates for 1974 (Snell 1978).  Since the  phenolic resin industry has  made many process
improvements in the last decade, the current waste generation figures are expected to
be much lower than the 1974 figures.  The 1974  estimates correspond to about 0.6
pounds of waste per pound of product, whereas current waste generation  is estimated
at less than 0.2 pounds of waste per pound of product*.  The relative waste generation
rates expressed as weight  fractions of the  total waste  stream were computed  based
upon the 1974 data (Snell 1978) and other available, more current  information.  These
relative rates are given in Table 8-1 and also in Table 9-1.

9.    WASTE REDUCTION THROUGH  SOURCE CONTROL

9.1  Description of Techniques

The  summary  of all  the  waste  streams  together with source reduction methods  is
shown  in  Table 9-1.  The  discussion of each method is given below along with the
rationale for its inclusion and application cases, if known.
      Reichhold Chemicals 1985:  Private communication.
                                   B10-10

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  Table 8-1 Fractional Waste Generation Rates from Phenolic Resins Manufacturing
Waste
Off-grade Products
Receiver Contents
Resin Wash-water
Spills
Equipment cleaning wastes
Total
Percent of Total(a)
(excludes added water)
1
64
15
1
19
100
Percent of TotaKb)
(includes added water)
> 1
10
36
> 1
52
100
Source: estimated by project staff.

^a'   Water used for resin wash and equipment cleaning is excluded; only the organics
     and salts present in these streams are counted.

(°)   Includes water added for resin wash anrd equipment cleaning.
                                  R10-11

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In addition to the  waste reduction  measures classified as being process changes or
material/product substitutions, a variety of waste reducing measures labeled as "good
operating practices"  are defined  as  being  procedural  or  institutional policies  which
result  in a  reduction  of waste.  The  following  items highlight the  scope of good
operating practice:

     o     Waste stream segregation
     o     Personnel practices
                management initiatives
                employee training
     o     Procedural measures
                documentation
                material handling and storage
                material tracking and inventory control
                scheduling
     o     Loss  prevention practices
                spill prevention
                preventive manintenance
                emergency preparedness

For each waste  stream, good operating practice applies  whether it  is listed or not.
Separate listings have been provided whenever case studies were identified.

9.1.1   Off-Grade Products

Off-grade  products containing traces  of  unreacted  phenol  and  formaldehyde  are
obtained from bad batches  and are usually landfilled offsite  or  stored  on-site in
concrete lined lagoons. The following source reduction  methods were noted:

     o     Proper control of reactor temperature.
           In most  cases,  bad batches are the result  of  the  reactor contents being
           cooled too rapidly.  This  leads  to the formation of an insoluble, infusible
           mass. This can be prevented by  proper control  of the reactor temperature,
           along with prompt attention   to  any rapid  decreases in  temperature.
           Temperature excursions can be minimized by:
                                   B10-12

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                 Frequent  calibration  checks  of temperature  sensors,  and  more
                 frequent maintenance of temperature control systems.
                 Frequent monitoring of set point drift.
                 Use of reactors with separate jackets or coils for cooling water and
                 steam. Such reactors are  commercially available and will avoid the
                 deposition  of  dissolved cooling  water solids  on the heat transfer
                 surfaces when steam is applied.  Buildup of these deposits leads  to
                 inefficient heat transfer and subsequently poor temperature control.

      o    Increased automation.
           Bad  batches may also  result from  failure to charge proper quantities  of
           various reactants.  This can be prevented  by  double-checking  the quantity
           of input materials to the reactor.   Usually,  feed  materials  are weighed
           before being sent to the  reactor.  Weighing  errors can be  decreased by
           using  an  automated batching  system  properly  maintained  by  frequent
           calibration.   If  installation  of  automated  batching  controls  proves
           impractical, manual batching can be improved by  closer supervision, better
           documentation procedures, better operator training, and frequent checks  of
           weighing equipment.

      o    Re-use of off-grade products.
           Off-specification  products can  sometimes be blended with  high-grade
           product to yield an intermediate-grade  resin  which meets  the  required
           specification.  This practice is not always possible; however, it  appears  to
           be widely  used in the industry.

9.1.2   Receiver Contents

In  resols  manufacture, water is removed  from  the  reactor  to  favor  the poly-
condensation reaction.  This water stream  carries phenol, formaldehyde,  and other
soluble organics and is stored in drums for land disposal, or treated  to recover phenol.

In  Novolaks  manufacture,   the   reactor   contents   are  maintained  at  constant
temperature  in  the  initial  phases  by  condensing  water vapor  and  returning  the
condensate to the kettle.  Late  in  the  reaction, the slowing polymerization  rate  is
                                   810-13

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increased by diverting the condensate to a receiver rather than to the reactor.  The
receiver contents  are  sent  to  waste  storage.   The  following  source  reduction
techniques were noted:

     o     Use of improved catalyst.
           The  phenol  and formaldehyde content in  the  receiver  effluent  can be
           minimized by obtaining higher conversion yields for  the polycondensation
           reaction.  This  can be facilitated by use  of more active catalysts (Brode
           1982).  One patented catalyst  which  is a combination of a divalent  metal
           and  an  acidic  material,  is  an  alternative to  presently  used  catalysts
           (Culbertson 1978).   The use of improved catalysts should be examined for
           their environmental advantages along with their potential ability  to reduce
           waste through better yields.

     o     Lower water content in the reactor.
           A  patented  process  for  high  molecular  weight  Ortho  Novolaks  using
           exotherm  control  allows  the  use  of  higher  concentration  of aqueous
           formaldehyde  (Culberston 1978).   In  this  process,  50  weight  percent
           formaldehyde can  be  used as  opposed  to 37  weight  percent formaldehyde
           used in  conventional processes (Brode 1982).  The lower  water content in
           the reactor should subsequently produce a smaller aqueous waste stream
           and also should improve reactant's conversion.  This process is claimed to
           have  an  improved  reaction   rate  because  of less  water  and  easier
           temperature control.

     o     Use of azeotropic solvents.
           Since phenol  and water are totally miscible under reaction conditions, the
           water which  is removed  carries phenol  with it.   Use of  an azeotropic
           solvent,  such  as  xylene, can decrease  the  phenol  content  in water
           (Culberston  1978,  Brode  1982).   As  water is  continually  removed,  the
           organic  phenol-rich  phase can be separated and recycled.  The environ-
           mental advantages and disadvantages of this suggested technique will  have
           to be fully assessed, since introduction of entrainer or azeotropic  solvent,
           such as xylene,  may not always be  desirable.
                                    BJO-14

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Re-evaluation of current temperature trajectory.
As explained earlier, in the final stage  of reaction, water is removed from
the reactor to promote the equilibrium shift toward novolac products.  In
the first stage of reaction, a vacuum reflux is used to maintain the reactor
at 185-195°F.  After 3-6 hours of reaction time, the condensate from the
overhead condenser is sent to a receiver instead of being returned  to the
reactor.   This  switch-over  point  is  crucial  from the  standpoint  of
phenol/formaldehyde losses through the overhead  vapor.   If  this switch-
over is  made too early, the losses of organic reactants will be high because
of their higher concentration in the reactor.

In addition to the cost of  lost reactants, another factor to be considered in
the optimization is the cost of disposal and  treatment of liquid waste.  If
the organics content in the liquid is more  than 12%,  the fuel requirements
for incineration are minimal and phenol recovery by solvent extraction is
less  costly.   If  the  organics  content  is  lower,  then solvent extraction
becomes costly and the fuel requirements to support incineration may  be
substantial (Snell 1978).

It is  suggested  that  reassessment  of the  currently  used  temperature
trajectory  may lead to the overall  lowering of waste generation rates in
certain  cases.

Re-evaluation of reactant and/or catalyst addition strategy.
Addition of reactants (phenol and/or formaldehyde)  or  catalyst  (sodium
hydroxide,  sulfuric  acid)  can be done  in  one step, in  increments,  or
continuously following a  schedule designed  for maximum  conversion and
minimum  losses during  the  evaporative  mode  of  reactor operation.
Development of such a strategy can be assisted using a reactor modeling
approach.  For example, staged addition of remaining  formaldehyde before
switching to an evaporative mode from  isothermal operation, reduces the
free phenol content in the reactor, which reduces phenol losses through the
vapor stream.   As before, it is suggested  that  reconsideration of  the
reactant or catalyst addition strategy may lead to the overall decrease of
waste generation in certain cases.
                         B10-15

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Inversion of dispersion mode.
The  process  involves a primary  reaction cycle under  basic conditions at
194-220°F and a  secondary reaction  cycle,  at  176-194°F  under neutral
conditons in the  presence  of  a protective colloid used  to stabilize  the
dispersion (Brode 1982, Brode et al. 1974, Harding 1977).  In  the  primary
cycle,  condensation  of formaldehyde and phenol  occurs.  In  the secondary
cycle,    inversion   from    a    water-in-phenolic   dispersion    to    a
phenolic-in-water dispersion takes place speeding up the poly-condensation
to the desired end point.  Based upon preliminary review, the  process seems
to offer a  potential for higher conversion  and  thus lower  waste loads
compared to the more conventional route.

Internal phenol recycle with treatment of receiver contents.
Recovery of phenols from aqueous streams and its recycle to  the process
has been  practiced.   Phenol separation  from water  can be  achieved by
several liquid solvent-extraction processes  (Brode 1982,  Lanouette 1977),
adsorption processes, or critical fluid extraction.  A  discussion of these
processes follows:

The  benzene-caustic pherplization process  uses benzene  as the extraction
solvent in a packed tower with countercurrent flow. The  caustic is used to
wash the phenols from  benzene, converting  them to  sodium phenolates.
Using  steam,  carbonic  acid,  and  additional  caustic,  phenols  can  be
separated from the aqueous phase to be  recycled  to the process.  Removal
efficiency of 92-93% can be achieved.  In some  plants, it has been shown
that the removal efficiency can be improved to 95% by using a Podbielniak
centrifugal  countercurrent solvent extractor  instead of a packed  column.
Efficiencies  of  98.6-98.8%  can be  achieved by using  a pulsed packed
column which improves scrubbing.

The  Lurgi  Phenosolvan process  uses  isopropyl ether  as the  solvent in a
multi-stage solvent extractor.  This solvent has a lower boiling point than
phenol  and  can be distilled from  phenol  for further  reuse.   The Ifawol
dephenolization  process uses  a countercurrent  packed  column  with  a
solvent that  has a boiling point higher  than that of phenol and is practically
                         B10-16

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      insoluble in water.   The phenol  can be recovered  from  the  dewatered
      solvent  by  vacuum distillation.  After passing through a  separator, the
      solvent can be recovered for reuse.

      Activated carbon adsorbent, in the form of granules, has a  finite capacity
      for  removing  phenol  from waste  water.   Phenol  can be  removed  from
      activated carbon by chemical  regeneration (Lanouette 1977).   The waste
      stream has to be  filtered prior to contact with  activated  carbon.   The
      disadvantage  of  this process is  that carbon removes other organics  present
      in  the  waste  stream, thus  the regenerated  stream  may  contain other
      organics besides phenol.  In addition to carbon, some polymeric  adsorbents
      are  found to  be effective in  removing phenol  from aqueous waste (Fox
      1975, 1978).   The phenolic waste  stream is passed through one or more
      polymeric adsorbent  columns   yielding  an effluent containing  less than
      1 ppm phenol.  Column loadings of  0.6 to 11 Ibs of phenol per cubic foot of
      this adsorbent are possible at  raw waste  phenol concentrations of 100 to
      50,000 ppm, respectively.  Regeneration  of  the resin  with concentrated
      formaldehyde  allows   convenient   recycle   of   the   resulting   phenol
      formaldehyde eluate directly to the polymerization reactor.
                        *
      A critical fluid extraction method  for recovering phenol from waste water
      is commercially  available*.   The  method uses  a  condensed gas,  such as
      carbon  dioxide in  the vicinity  of  its critical  point.  Critical fluids have
      highly favorable  solvent properties and they behave as a liquid in dissolving
      significant amounts of organic substance.  At  the same time, they  behave
      like gases in that the rate of extraction is  extraordinarily high compared to
      normal  liquid  solvents.  Commercial systems  are available  for  capacities
      ranging from 1 to 100  gallons per minute.

      Each of the methods  listed above  has to  be  individually evaluated for  a
      specific application.  General environmental attributes of  each   method
      were not evaluated.
Critical Fluid Systems Inc. 1985:  Personal communication.
                              B10-17

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     o    Altering resin  molecular weight distribution and  functionality  to  reduce
          wastes.
          Phenolic resins have different  molecular weight distributions depending on
          their end  use.    By making  small  changes  in  their  molecular  weight
          distributions, the  change in their  properties may not be significant,  but
          could contribute toward waste reduction (Brode 1982).  By  increasing  the
          conversion slightly, the quantity of unreacted phenol and formaldehyde  can
          be decreased. Though this does not result in lowering the quantity of waste
          water generated, it reduces the toxicity of this stream.

     o    Use of excess formaldehyde to  reduce free phenol content.
          Free phenol content in  the  reactor  can be  decreased by using  higher
          quantity of formaldehyde feed  to the reactor.  Excess  formaldehyde can be
          removed from the resin by  stripping.  Lower free phenol results in lower
          phenol in the waste water stream, reducing its toxicity.

     o    Isolating the wash-water stream from receiver contents.
          The wash  water is  sometimes mixed with  the  receiver  contents  before
          treatment.  If the wash water contains only traces of phenol, mixing it with
          the receiver contents results in a larger and more dilute waste stream.  By
          isolating the wash water and treating it separately, the receiver contents
          will not be diluted.  This could facilitate their disposal by incineration or
          use of phenol recovery options.

9.1.3   Resin Wash Water

In the manufacture of liquid resols,  the final product may  be  washed with water
several times  to  remove  inorganic  salts  and  traces of   unreacted  phenol  and
formaldehyde.  This washwater is usually  filtered to remove any solids present prior to
discharge  to the sewer or treatment as a separate stream or in combination  with other
aqueous streams.  The following  source  reduction methods  were considered for  this
waste stream:

     o    Use of counter-current washing.
           The  amount of  wash  water  necessary to  remove a certain amount of
           unreacted phenol  or formaldehyde  is lowest  when  counter-current washing
                                   B10-18

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              HASTEMATER


                   RESIN
                                               
-------
           is  used.  Counter-current washing  may be more favorable in a continuous
           operation where washing  can be done in counter-current extractors (e.g.
           rotating  disk  type)  if the  viscosity  of  the liquid  resin permits  such an
           operation.   In batch  operation,  the liquid resin could  be allowed to
           accumulate in tanks and counter-current  washing can be done periodically.

           When the product resin needs to be washed several  times, counter-current
           washing (e.g. similar to the  scheme shown in Figure 9-1) will generate  low
           quantities of waste water.  Counter-current rinsing may offer a substantial
           improvement over sequential rinse-decant sequences  used to achieve the
           same washing  efficiency.    It is possible   that  due  to the  increased
           concentration  of organics  in the wash-water  stream,  it  may  then be
           suitable for phenol recovery.

      o     Re-use of resin wash water.
           The  purpose of washing the resin  with water is to  remove inorganic salts
           and residual water-soluble organics.  In priciple, it is possible  to re-use the
           wash-water until  the dissolved impurity concentration reaches prohibitive
           levels. This type  of  wash-water re-use is common in  the synthetic rubber
           industry  where the  inhibitors present in  monomers  are  washed  using  a
           caustic solution (Snell  1978).  If wash-water is reused for the  first rinse,
           the second (or consecutive)  rinsing may require clean  water to efficiently
           remove  the contaminants.   The  wash-water accumulated  from the first
           rinse  may  eventually be treated along with receiver  contents to  recover
           phenol.

9.1.4   Spills and Leaks

Spills are  due  to  accidental  discharges  of  liquids during  transfer  operations or
equipment  leaks.  The spill cleanup  wastes are  stored  in  drums and are considered
hazardous.  Only the implementation of better operating practices is suggested for this
waste  stream, especially  in the  area  of  better operator  training  and  preventive
maintenance.
                                   B10-20

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9.1.5  Equipment Cleaning Wastes

After each batch,  the reactors for resols and novolacs are cleaned with dilute acid or
caustic solution  to remove resin  particles that  remain  on  the reactor walls.   This
intermittent waste stream  is filtered to remove the particles and the filtrate is mixed
with  the receiver contents prior  to disposal.   The filtered particles  are often mixed
with  other  non-recyclable  off-grade  products and  disposed  of in  a  landfill.   The
equipment  cleaning waste  generated  by  the  washing procedure  contains  traces  of
phenol and formaldehyde.  On occassions, it is necessary to use solvent for equipment
cleaning.  In such cases, the resulting waste is generally incinerated,  however, it may
be  landfilled by facilities  which  do not use  an  incinerator.  The  following  source
reduction  techniques have a  potential for  reducing the amount of aqueous waste
produced:

      o     Reduction of resin buildup on the reactor walls.
            The use of Teflon*  coated reactors or reactors equipped with wipers that
            continually  clean the  walls  will  reduce  polymer  buildup  on  the walls.
            Teflon is known to possess low adhesion characteristics which may help to
            relieve  buildup  and help drainage. It  is  also suitable for use  in process
            environments  at temperatures  up  to  400°F  which adequately covers  the
            range involved  in production of phenolic resins.  Teflon  coating must  be
            closely  scrutinized if there is  an occasional need for  mechanical cleaning
            that involves  chipping off  accumulated  material.    However, the use  of
            Teflon may eliminate the need for mechanical  cleaning  altogether.  The
            designs  of  double shaft mixers equipped with wall and bottom  wipers are
            commercially  available and are routinely used  in  applications requiring
            mixing of high viscosity resins.

      o     More complete drainage of process lines.
           Prior to rinsing  with water, the equipment, along with process lines should
           be properly drained.  Such  drainage can be accomplished by proper piping
           layout (e.g. no pockets, sloping toward equipment) and also  by "pigging" the
           lines,  which is an encountered practice  in the paint manufacturing industry.
           There, a plastic slug is propelled by an inert gas  through  the lines which
* Registered trademark of E.I. du Pont de Nemours & Co.
                                     B10-21

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cleans them while increasing  product yield.  For phenolic  resin process
piping it may be possible to use a similar approach.

Maximizing equipment dedication.
The  frequency  of equipment  cleaning  can be  reduced  by maximizing
equipment dedication to a  single  formulation.    In  the  limit,  a  total
dedication  is accomplished  by  conversion  from  batch to  a continuous
process.   Continuous  processes for the production of phenolic resins have
been  developed  (Euleco  1975,  Anon. 1965).  Since  the market calls  for a
large  diversity of products, it appears unlikely  that these processes can be
used universally.  Proper production scheduling, e.g., maximizing  the size
of the product  obtained  from a single campaign,  or scheduling compatible
batch campaigns adjacent to each other is probably  a much  more widely
practiced  technique to lower  the cleaning frequency and  the associated
waste.

Filter resin recovery.
Prior  to shipping,  liquid  resins  are usually filtered.  The resin  remaining in
the filter  casing can be easily recovered by blowing the resin  out with the
use of plant air prior to screen  cleanup.  This procedure was effectively
used by  Borden Chemical Company (Huisingh et. al. 1985).

Use of a two step rinse with  recycle of the first rinse.
Some  facilities use a "fill-and-empty" reactor cleaning  technique,  where
the reactor  is  filled with  water,  which  is  subsequently  dumped  after
agitation.  This produces a large  amount of wastewater contaminated with
phenolic  resins.   As an  alternative, an initial low-volume rinse (e.g.
employing spray nozzles) can remove the bulk  of the resins to  produce a
small quanity of wastewater with a  high concentration of phenol.  This
material can be reused in the next compatible batch of resin.  The tank can
then be washed  with  a full volume rinse  to generate  a waste  with a  much
lower resin  content.    This  procedure,  used   at  Borden  Chemical Co.,
contributed to a 93 percent reduction in the amount of discharged organics
(Huisingh  et. al. 1985).
                         B10-22

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9.2   Implementation Profile

While  some of the  methods proposed  or  identified  require  installation of additional
equipment,  substantial  reductions  can  be  made   through  changes  in  operating
procedures. The use of a two step rinse method with the recycle of the first rinse, and
an  increased awareness of waste  on the part of plant personnel, contributed to a
significant reduction in the organics lost with equipment  cleaning wastes at Borden
Chemicals Co.   The procedure  appears easy to implement at many  phenolic  resin
manufacturing facilities.

The use  of countercurrent  product washing  and the  recovery of phenol from  aqueous
wastes  for recycling  to   the  process usually  requires  installation  of  additional
equipment.  These options  may  not be  implementable at all facilities. Recovery of
phenol using polymeric adsorbents  or solvent extraction techniques  was found  feasible
by some  manufacturers.

Because  different manufacturers produce  different grades  of resin, great variation in
wastestream composition is encountered.  Each  facility must therefore  choose the
control measures compatible  with its  own  specific requirements.    For facilities
already having suitable  waste treatment plants or incinerators, many of the proposed
methods cannot  be economically justified.  Implementation will ultimately depend on
economic feasibility, which should  take  into  account  avoided treatment costs,  avoided
disposal costs for treatment residuals, and  raw material savings.

9.3  Summary

The summary of  all noted source control techniques  is given in Table 9-1.   Each
technique was rated for its effectiveness, extent of current  use, and future  application
potential on scale of 0 to 4. The ratings were derived by project staff based on review
of the available data.  The estimates of  current level  of  waste  reduction achieved
(current  reduction index) and possible future reduction (future reduction index)  were
obtained from  the  ratings in accordance with  the methodology  presented  in the
introduction to  this appendix.   Fractional waste generation rates (including water)
were taken from  Table 8-1.  Current reduction and future reduction indices were also
                                   R10-23

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                         TABLE 9-1 StMUftr OF SOURCE CONTROL METHODOLOGY FOR THE PHENOLIC RESINS MANUFACTURING INDUSTRY
DO
l—>
O
1
Haste Stream |
1
Off -Grade Products |1.
|2.
|3.
1
Receiver Contents 1 1.
12.
I'-
ll.
15
16
IT.
l«
19.
|10
1
Resin Hash Hater |1.
|2.
*"
1
Spills and Leaks |1.
1
Equipment Cleaning |t.
Hastes |2.
13.
I*.
15.
1
All Sources |

Control Methodology

Proper control reactor temperature
Increase use of automation
Re-use in product
Overall
Use improved catalyst
Lower water content In the reactor
Use of aieotropic solvents
Re-evaluate temperature trajectory
1
1-
1
1
1
1
1
1
1
1
1
Re-evaluate react/cat addition method|
Inversion of dispersion mode
Internal phenol recycle
1
1
Alteration of resins molecular weight]
Use excess formaldehyde
.Isolate washwater from rec. contents
Overall
Use counter-current rinse
Re-use of resin wash water
Overall
Better operating practices
Overall
1
1
1
1
1
1
1
1
Reduce resin build-up on reactor wall)
Use of a two-step rinse with recycle
Maximiie equipment dedication
Filter resin for recovery
More complete drainage/process Mnes
Overall
All Methods
1
1
1
1
1

Found Documentatior

Quantity 1 Quality
1 1
1 1
1 1
1 00 | 1
1 1
1 1
1
1
1
!
1
1
1
1
1.10 | 1
i 1
i 1
t.OO | 1
1 1
1.00 | 1
1 1
1 1
1 1
1 1
1 1
1.00 | 1

1
— 1
1
1 1
1 1
2 1
33 |
1 i
' 1
' 1
1 1
1 1
2 1
2 1
1 1
' 1
' 1
20 |
1 1
1 1
00 |
1 1
00 |
1 1
2 1
1 1
1 1
1 1
20 |

Haste | Extent of | Future | Friction of |
Reduction | Current Use | Application | Total Haste |
Effectiveness | | Potential | |
3 1 3| 1 | |
3 1 2| 2| |
31 3| 1 | |
3.00 | 2.67 | 1.33 | 0.01 |
21 2| 2| |
1 1 'I ' 1 1
2 1 1 I 2| |
' 1 3 | 1 | |
'1 3| 1 | I
21 H M 1
3 1 2| 3| |
2 1 2 | 1 | |
1 1 2| 1 | |
21 3| 1 | |
1.70 | 2.00 | 1.10 | 0.10 |
31 1 1 1 1 1
21 0 | 1 | |
2.50 | 0.50 | 1.00 | 0.36 |
2 1 3 | 3 | |
2.00 | 3.00 | 3.00 | 0.01 |
2 | 1 | 2 | !
3 1 1 1 3 | |
3 I 3 | 3| |
2 1 1 1 3 | |
21 2| 2| |
2.40 | 1.60 | 2.60 | 0.52 |
I 1.00 i
Current
Reduction
Index
2
1
2
2
1
0
0
0
0
o
1
1
0
1
1
0
0
0
1
1
0
0
2
0
1
z
1
1

1
1
3 1
5 1
3 I
3 1
0 1
3 1
5 1
8 1
8 1
5 1
5 1
0 1
5 1
5 1
5 1
8 1
0 1
8 1
5 1
5 1
5 I
8 1
3 I
5 1
0 1
3 1
8 1
Future Reduction Index


Probable
0
0
0
0
0
0
0
0
0
0
t
0
0
0
0
0
o
0
0
0
o
1
o
1
0
0
0



2
1
2
4
5
2
1
1
1
4
1
3
1
1
4
5
5
S
4
|
1
7
6
1
5
9
7


| Maximum
1
1 0
1
1 0
1
1
1
1
1
1
1 1
1
1
1
1 '
1 o
1
1 o
1 o
1 o
1
1 1.
1
1
1
1 1
1 1
1
	 1
1
1
1
1 1
1
8 1
1
1
1
1
1
1
1 1
1
1
1
1 1
6 1
1
« 1
4 1
< 1
1
7 1
1
1
1
7 1
2 1
      (') These streams  Include  listed 'f and/or '1C RCRA wastes.

-------
computed using  fractional waste generation rates that excluded water and the overall
results were very similar.

The  current reduction index (CRI) is a measure of reduction of waste that would be
generated if  none of the methods listed were implemented to  their current level of
application.   For the   phenolic resin  industry,  CRI is 1.8 (45 percent) which  is
indicative of the significant level of waste minimization that already has taken place.

The  future reduction index (FRI) is an indication of the  level to which the currently
generated waste can be  reduced if  all  of the  techniques  noted  were implemented
according to their rated potential.  The FRI value of 0.7 to 1.2 (18 to 30 percent) is
indicative of the moderate extent of future waste  reductions.  Among  the  techniques
that were found most effective and applicable (as evidenced by high  FRI value) for
control of wastes were the use of a two-step rinse  with recycle,  the use of a counter-
current rinse, and recycling of waste phenol.

10.  PRODUCT SUBSTITUTION ALTERNATIVES

In 1980,  about 27 percent of the phenolic  resins  were used as a binder  for making
plywood.   This  demand  depends on  the  extent  of  use of pine from the Pacific
Northwest  instead of southern  pine.  Southern pine, due  to  its higher absorbency,
requires almost 20 percent more resin than northwest pine (SRI  1981). Phenolic resins
are  also  used as  binders  for  fibrous and granulated wood to make waferboards.
Injection molded thermoplastics can be  effectively used to  make waferboards, thus
avoiding the use of phenolic resins.

In 1980,  about  7  percent of phenolic resins were used  for making  decorative and
commercial laminates.  Use of  thinner boards for  vertical  use  as opposed  to thicker
horizontal  boards will  lower the amount  of phenolic resin per square foot of the
decorative  laminate.  Low-pressure  polyester and  melamine laminates, which do not
use phenolic resins, or epoxy or silicone resin substitutes are some other possibilities.
                                  B10-25

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11.   CONCLUSIONS


Since  phenolic resin manufacturing  produces  a relatively high quantity of  waste,

waste reduction  by  source control  deserves  special  attention.   Our qualitative

estimates indicate  that the possible waste reductions range from  18  to 30  percent.

Several methods that appear to be quite effective for the industry as a whole are the

two-step rinse method with the  recycle of the first rinse, recovery and recycle of

phenol from  aqueous wastes, segregating of wash water from the receiver  contents,
and reuse of wash water.


12.   REFERENCES

AESI. 1981. American Electroplater's society, Inc.  Conference of advanced pollution
control for the metal finishing industry (3rd) held at Orlando Hyatt House Kissimmee,
Florida on  April 14-16, 1980.  EPA-600-2-81-028.  Cincinnati,  Ohio:  U.S.   Environ-
mental Protection Agency.

Anonymous. 1965. Planning it cool pays off.  Chem. week. 97(19):  35-40.

Brode, G.L.  1982.    Phenolic  resins.   In Kirk-Othmer  encyclopedia  of  chemical
technology.   3rd. ed. Vol. 17, pp.  384-416. New York, N.Y.: Wiley.

Brode, G.L., Harding, J. Marrion,  T. et al. 1974.  Synthesis of phenolic dispersions. U.S.
Pat. 3,823,103 (July 9, 1974) to UCC.

Cameron, J.B., Lundeen, A.J., and McCulley, Jr., J.H. 1980. Trends  in suspension PVC
manufacture.  Hydrocarbon Processing (3):  39.
                         	BTO-27
Culberston, H.M. 1978.  U.S. Pat.  4, 113,700 (Sept. 12, 1978) to Monsanto Co.

Euleco.  1975. Euleco continuous process:   technical bulletin.   Milan, Italy:  Euleco,
S.P.S.

Fox, C.R.  1975. Remove and recover phenol.   Hydrocarbon processing  54 (7):  109-
11.

         . 1978. Plant uses prove phenol recovery with resin.  Hydrocarbon Processing
57 (11): 269-73.

Froment, G.F., and Bischoff, K.B. 1979.  Chemical reactor analysis and design.  New
York, N.Y.:  John  Wiley and Sons.

Gleason, M.N.,  Gosselin, R.E,  Hodge,  H.C.,  et. al. 1984.   Clinical toxicology of
commercial  products;  acute poisoning.  4th ed.  Baltimore:  The William and Wilkins
Co.

Greek, B.F.  1985.  Chem. Enq. News  63 (22):  38.
                                  B10-26

-------
Harding, J. 1977. U.S. Pat. 4,026,848. (May 31, 1977) to UCC.

Hoshika, Y., and Muto, G. 1978.  J. Chromato 157: 277-78.

Huisingh, D., Martin  L.,  Hilger,  H.,  et.  al. 1985.  Proven profit  from  pollution
prevention.  Washington, D.C.:  The Institute for Local Self- Reliance.

Johnson, H.  1973.   A  study of hazardous  waste  materials,  hazardous effects  and
disposal  methods.    Vol. 2.  Booz-Allen Applied Research,  Inc.   EPA-670-2-73-15.
Washington, D.C.:  U.S.  Environmental Protection Agency.

Lanouette, K.S. 1977. Treatment of phenolic waste.  Chem. Eng.  84 (22): 99-106.

Radian  Corp. 1977.  Industrial process profiles for  environmental use;  Chapter 10.
Plastics  and  resin  industry.  EPA - 600-2-77-023.  Cincinnati, Ohio:  U.S.  Environ-
mental Protection  Agency.

Sax, N.I.   1984.   Dangerous properties of industrial materials.  6th ed.  New York,
N.Y.: Van Nostrand Reinhold.

Snell, Inc.    1978.   Assessment of  industrial hazardous waste practices;  rubber  and
plastics industry.  Plastic  materials and synthetics  industry.  EPA-530-SW-163C-2.
Washington, D.C.:  U.S.  Environmental Protection Agency.

SRI. 1981.   Stanford Research Institute. Chemical economics handbook. Menlo Park,
Calif.: Stanford Research Institute.

Steiner,  T.E. 1984.   Modern plastics  encyclopedia.   New  York,  N.Y.:   Plastics
Catalogue Corp.
USEPA. 1974a.  U.S. Environmental Protection Agency, Effluent Guidelines Division.
Addendum  to  the  development document for the  proposed effluent limitation guide-
lines and new  source performance standards for the synthetic resins segment of the
plastics and  synthetic  manufacturing point source  category.   EPA-440-l-74-036a.
Washington, D.C.:  U.S.  Environmental Protection Agency.

_ . 1974b.  U.S.  Environmental Protection Agency, Effuent guidelines Division.
Development and new source performance standards for the synthetic resins segment
of the  plastics and synthetics materials manufacturing point source category.  EPA -
440-l-74-010a. Washington, D.C.: U.S. Environmental Protection Agency.

Wynstra, J., and Schultz, S.J. 1980.  U.S.  Pat. 4,206,295 (June 3, 1980) to UCC.

13.  INDUSTRY CONTACTS

M.J. Kowalski.    Manager, Environmental  Compliance,  Reichhold Chemicals,  Inc.,
White Plains, NY.
                                   B10-27

-------

-------
     1.    PROCESS:  PRINTED CIRCUIT BOARD MANUFACTURE

     2.    SIC CODE:  3679 (052)

     3.    INDUSTRY DESCRIPTION

     Manufacturers of printed circuit boards (PCB's) are included as part of the electronic
     component manufacturing industry.

     3.1   Company Size Distribution

     As of 1984, the PCS manufacturing  industry included a total  of 585 plants* with a
     total employment of 435,100 (NCO 1984).   The industry consists  of large facilities
     which are totally involved  with PCB's,  large and small captive facilities, small job
     shops doing  contract work,  and specialty shops doing low-volume and high-volume
     precision  work.    Approximately half of the  PCB's produced are  by independent
     producers, while the rest are by captive producers.  Table 3-1 lists  company size
     distribution in the U.S.

                           Table 3-1 Company Size Distribution

            	Number of Employees per Facility	
              Total    1-50   51-100   101-500   501-1000     1001-2500   2501-5000   5000+

No. of
establish-
ments             585    177     109        151         42            49         14       43
No. of
employees     435,100  4,425   8,175     37,750     31,500       85,750     52,500  215,000


     Source:    Electronic Marketing Directory (NCO 1985).
     * Industry contacts indicate that the actual number may be closer to 1000 plants.
                                       Bll-1

-------
3.2  Principal Producers
The ten major PCB producers in the U.S. are listed below (PEI 1983):
                TRW Cinch Graphite
                Texas Instruments
                Motorola Semiconductor
                Microtran
                GTE Sylvania
                                Western Electric
                                Rockwell International
                                Syn-thane-Taylor
                                Cincinnati Millacron
                                Chicago Etching
3.3  Geographical Distribution

Over 65% of all PCB manufacturing sites are located in the northeastern states and in
California.  The remaining plants are scattered throughout the country as represented
by Figure 3-1 and Table 3-2 below.
     Table 3-2 Geographical Distribution of Printed Circuit Board Manufacturing
                            Facilities by EPA Region
EPA Region

1-50
I 16
II 39
III 12
IV 18
V 42
VI 11
VII 2
VIII 1
IX 33
X 3
Number of Employees per
51-
100
12
14
8
13
37
4
1
1
18
1
101-
500
23
19
12
11
43
10
5
2
23
3
501-
1000
3
7
3
5
10
2
1
1
9
1
1001-
2500
7
8
4
4
12
2
2
0
8
2
Facility
2501-
5000
4
1
0
3
2
1
0
1
2
0


5001+
4
3
2
2
15
4
4
0
8
1


Total
69
91
41
56
161
34
15
6
101
11
National
177
109
151
42
49
14
43
585
Source:    Electronic Marketing Directory (NCO 1985).
                                  Bll-2

-------
                           VIII
i
C/J
                       11-20
TV^J 2-5

   21-50
6-10

51-100
                    Roman numerals show EPA regions

   Figure   3-1  Printed Circuit  Board Plants in the U.S.

-------
4.   PRODUCTS AND THEIR USE

PCB's can be classified into 3 basic types: single-sided, double-sided, and multilayered.
The  total board production in 1983 was estimated at 14  million square meters  (PEI
1983).   Double-sided boards accounted for about 55 percent of the PCB's produced,
while the percentage of multi-layer board production was 26 percent (PEI 1983).  The
type of board produced  depends on the spatial and  density requirement, and on the
complexity of the circuitry.  PCB's  are used mainly  in  the  production of  business
machines, computers, communication equipment, and  home entertainment equipment.

5.   RAW MATERIALS

The  following raw materials are used by the industry (Stintson 1983, PEI 1983, Cox and
Mills 1985):
Board materials
glass-epoxy, ceramics, plastic, phenolic paper, copper foil
Cleaners
sulfuric  acid,  fluoroacetic  acid,  hydrofluoric  acid,  sodium
hydroxide,   potassium  hydroxide,  trichloroethylene,   1,1,1-
trichloroethane, perchloroethylene, methylene chloride
Etchants
sulfuric  and  chromic  acid,  ammonium  persulfate,  hydrogen
peroxide, cupric chloride, ferric chloride, alkaline ammonia
Catalysts
stannous tin, palladium chloride
Electroless copper
bath
copper sulfate, sodium carbonate, sodium gluconate, Rochelle
salt, Versene-T, sodium hydroxide, formaldehyde
Screen
silk, polyester, stainless steel
Screen ink
composed of oil, cellulose, asphalt, vinyl or other resins
Resists
polyvinyl  cinnamate,  allyl  ester,  resins,  isoprenoid  resins,
methacrylate derivatives, poly-olefin sulfones
                                   Bll-4

-------
Sensitizers
thiazoline compounds, azido compounds, nitro compounds, nitro
aniline  derivatives,  anthones,  quinones,   diphenyls,  azides,
xanthone, benzil
Resist solvents
xylenes,   toluene,  benzene,   chlorobenzene,  celiosolve  and
cellosolve   acetate,   butyl   acetate,   1,1,1-trichoroethane,
acetone, methyl ethyl ketone, methyl isobutyl ketone.
Electroplating baths
copper  pyrophosphate  solution,  acid-copper  sulfate solution,
acid-copper fluoroborate solution,  tin-lead, gold, and  nickel
plating solutions
Resist stripping
solutions
sulfuric-dichromate,    ammoniacal     hydrogen    perioxide,
metachloroperbenzoic acid, methylene chloride, methyl alcohol,
furfural,  phenol,  ketones,  chlorinated  hydrocarbons,  non-
chlorinated organic solvents, sodium hydroxide
6.   PROCESS DESCRIPTION

Three  principal production methods  have been employed by the industry to produqe
printed circuit boards. These include:

           The conventional subtractive process
           The fully additive process
           The semi-additive process

Detailed descriptions of the process sequences are given elsewhere (Yapoujian 1982,
Coombs  1979,  USEPA 1979, PEI  1983).  Because of the limitations of  the  additive
processes,  the  subtractive method is currently the  most widely used method.  Figure
6-1  illustrates the procedure  for the  production  of  double-sided  panels using  the
subtractive method (Yapoujian 1982).  Most of the operations shown are also  common
to the production of other types of printed circuit boards such as single-sided or multi-
layered boards.
                                   Bll-5

-------
















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Figure 6-1    Substractive Process  for the Production of  Double-sided  Printed Circuit Boards
                                  Bll-6

-------
The  conventional  subtractive  process starts  with  a copper-cladded laminate board,
composed  of  a  non-conductive  material  such  as glass  epoxy  or  plastic.    PCB
manufacturers often purchase panels of board that are already copper cladded from
independent laminators  to  use as the starting material  for  the  PCB's.  The manu-
facturing process consists of the following operations:

Board preparation -  The  process sequence begins with a baking step to ensure that the
copper laminated  boards are  completely cured.  Holes for the components are  then
drilled through stacks of boards or panels, often 4 layers thick.  The drilling operation
results in burrs being formed  on  one or both sides of the panel.  These are removed
mechanically  through sanding and  deburring steps to create an even surface.

Electroless copper   plating  - The  smooth  copper-cladded  board  is  subsequently
electroless plated with copper to  provide a conducting  layer through the drilled holes
for  circuit connections between  the  copper-cladded board surfaces.  Electroless
plating  involves the  catalytic reduction of  a  metallic  ion in  an aqueous  solution
containing a  reducing agent.   The  metal  is  therefore deposited  without  the use of
external electrical energy.   The circuit board  must be thoroughly cleaned before it  is
electroless plated. The  typical steps for electroless plating are:

           Mechanically scrub and alkaline  clean the  boards  to remove soil  and
           fingerprints.   This  is followed by  a rinsing step usually involving spray or
           counter flow rinsing with water.

           Etch the copper-cladded  surface.  The board is immersed in  ammonium
           persulfate or a  peroxide-sulfuric  acid  mixture  to  remove  the oxidation
           inhibitor  in  the copper  foil.  This provides for  better adhesion of the
           electroless plating  catalyst. After etching, the board is again rinsed.

           Catalyst  application.   This step  is required for through-hole plating.   A
           catalyst must be applied for the initial metal deposition to  occur on non-
           metal  surfaces,  such  as the interiors of the holes.  Catalysis is done by a
           stabilized  reaction product of stannous chloride  and palladium  chloride
           which  is often  sold as concentrated solution in hydrochloric  acid.   The
           resulting board  will consist  of a  surface  layer of palladium nuclei, and
                                    Bll-7

-------
           stannous and stannic hydrous oxides and oxychlorides.  Following catalyst
           application, the board is rinsed with water.

           Surface activation.  The catalyzed board  is immersed  in a  solution that
           dissolves away the excess tin, exposing the molecular  layer  of  palladium
           metal  on the board surface.   The palladium  then acts as  the  base for
           electroless copper deposition.   Following surface  activation, the board is
           rinsed.

           Electroless plating.  The board is immersed in an electroless copper plating
           bath.   The  plating bath usually consists of a  copper salt such  as  cupric
           chloride or copper sulfate.  The reducing agents most often used  to reduce
           the metal  to its  base state  are  formaldehyde  and  hypophosphate.   In
           addition, chelating agents are also added to the plating bath to hold the
           metal  in solution, preventing plate-out on  the  tank wall. The four  most
           common  types of chelating agents used are amino  acids, carboxylic  acids,
           hydroxy  acids, or amines.  Following plating, the  board  is rinsed  and
           mechanically scrubbed.

Pattern printing  and masking - After the board is electroless-plated with  copper to
provide a uniform conducting layer over  the  entire surface,  the board  can  be  panel
plated or pattern plated to  produce the desired circuitry. Panel plating consists of
copper electroplating the entire board area, including holes, immediately  following the
electroless copper plating.  A metal etching resist is then plated onto the copper board
in a pre-determined pattern.  The board is subsequently etched to provide the desired
circuitry.  Pattern plating, on the other  hand, consists of copper electroplating only
the holes and circuitry.  Since pattern plating is more  commonly used in the industry,
the steps involved in this operation are described below.

In pattern plating, a plating resist is applied to produce the  circuit image  on the board.
The resist  is  a resin whose function  is to provide a protecting layer over areas of a
substrate  that are not  to be  affected by a  subsequent  etching or plating process.
There are two main ways in which a  resist can be applied onto the board.  These are
screen-printing and photolithography.
                                    611-8

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In the screen-printing method, ink is forced through unblocked spaces in  a stainless
steel  mesh or synthetic  fabric screen and  onto  the  board.  The ink  is then cured  by
heating or by exposing the board to UV light, and thus produces the desired image of
the circuit pattern on the board.

The  second  method  relies  on exposing a light-sensitive  resist to  light  through  a
patterned glass or  a photographic  film master called  a phototool (or photo  mask).
There are many types of photoresist on the market.  These include liquid or dry film,
which can be either negative or positive resists.  A negative resist  is a resin whose
solubility in  the developer is greater for the areas which are unexposed to light.  This
will lead to the formation of a pattern by  the  removal of unexposed  zones when  the
board is dipped into a developing solution.  The common types of negative  resist used
are epoxy, vinyl polymers, or halogenated aromatics.

A positive resist is more soluble in the developing solution in the light-exposed areas.
Therefore, a  pattern will  be  formed  by  the  removal  of  the exposed  areas.  The
different types of  positive resist are: methacrylates,  halogenated  methacrylates,
cross-linked methacrylates, or  polyolefin sulfones.

To transfer a circuit image onto the board, the board must  be coated either with a
liquid  resist  or a  dry  film resist.   Liquid  resist  can be applied  to  the panel  by
immersing it into the solution and withdrawing it at a controlled rate.  The  coated
board is then dried, and the pattern is printed onto the board by exposing it to UV light
through a photo mask.  Dry film  resist is a photo-sensitive resin, sandwiched between
a polyethylene and a polyester  layer. To apply the dry film resist, a polyethylene layer
is peeled off and the bare resin  surface is  laminated onto the board. The  printing of
the circuit image can then  be done by exposing the board to UV light with  a photo
mask. The remaining polyester film is then peeled off before developing.

After the photoresist-coated surface has been printed by exposure  to  UV  light,  the
desired circuit pattern can be produced through a developing process. The developer
can be an organic solvent, or an alkaline aqueous-based solution, depending on the type
of resist being used.  The developing solution will dissolve away the resist in unwanted
areas, leaving behind a pattern of copper-exposed areas for subsequent plating.  This
operation is usually done by immersing the  panels  in a still developer solution, a spray
tank,  or a conveyorized system.

                                    Bll-9

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Electroplating - After  a  pattern  is developed onto  the  board, the circuit is built  up
through a copper  electroplating process.  The steps involved  in  the  copper electro-
plating operation include:

           Alkaline clean to  remove  any residual from  the developing operation and
           then rinse.

           Light etch to ensure the removal of any residual photoresist not already
           removed in the developing of the  image.  The board is usually immersed in
           a  light  etching  solution,  such  as  peroxide-sulfuric  acid  or  sodium
           persulfate.  Following this  step, the board is rinsed.

           Acid dip to remove oxides and then rinse.

           Copper electroplating.  The boards are immersed in a copper plating bath.
           The bath contains copper salts dissolved in alkaline cyanide, acid sulfate,
           pyrophosphate, or fluroborate solutions.   The pattern or circuitry is thus
           built up to the desired thickness.   This step is  then followed by rinsing.

After the circuit is copper electroplated, tin/lead is  used as a resist for the subsequent
etching process.  The procedure  for  tin/lead electroplating is  similar  to  the copper
electroplating process described previously.  However, the tin/lead electrolyte is very
sensitive  to  contamination by  sulfates.  Therefore, care must  be taken  to prevent
drag-in from the pre-cleaning operations.   After  the  board  is  tin/lead  plated, the
original  plating resist  is stripped  off by immersing the  boards in resist  stripping
solutions  such as caustic,  methylene  chloride,  glycol ethers  with caustic,  or  glycol
ethers with  amines/ammonia. The boards are then thoroughly rinsed  with water.

Etching  - The  removal  of the  original plating resist results  in exposed  areas of
unwanted copper. In batch etching, which is rarely used now, the  panels are immersed
in a still tank containing an  etching  solution until  all the  unwanted copper  is etched
away.  In etching using a conveyorized system, panels are  placed on a conveyor, and
etchant is sprayed on them.  The most common types of etchant  are:  ferric chloride,
cupric chloride,  chromic  acid,  ammonium  persulfate, peroxide-sulfuric  acid,  and
ammoniacal  etchants.   Chromic acid  used  to  etch  tin/lead  plated  panels  has been
virtually eliminated due to effluent guidelines; however, it is still used to etch  epoxy
smears following the drilling of multilayer boards.
                                    Bll-10

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Copper etching represents the  last major operation involved in  the  manufacturing of
printed circuit boards.  The boards are subsequently cleaned  and electroplated with
different  types of  metals, such  as  nickel and  gold,  to provide  solderability  and
corrosion protection. The procedures for these  operations, however, are similar  to the
one described previously for copper electroplating.

The fully additive  method differs from  the subtractive method  described above in that
it involves the deposition of the plating material onto the board in the pattern dictated
by the  circuit, as opposed to the removal of  the  metal  already deposited  through
etching.  The  process begins with an uncladded board.  Plating  resist is then applied
onto the board in  non-circuit areas.   Electroless copper is subsequently deposited to
build up the circuit  to the desired  thickness. Since the board doesn't  initially have any
copper in non-circuit areas, a copper etching step is thus eliminated.

7.    WASTE DESCRIPTION

There  are  5 principal operations common  to the production  of all  types of printed
circuit boards. These include:

           Cleaning and surface preparation
           Catalyst application and electroless plating
           Pattern printing and masking
           Electroplating
           Etching

Typical waste  streams generated from the unit operations in the printed circuit board
manufacturing industry are listed in Table 7-1.

Airborne particulates generated from the cutting, sanding, routing, drilling, beveling,
and slotting operations during board preparations are normally  collected and separated
using bag-house and cyclone separators.  They are then disposed of, along with other
solid wastes, at landfills.

Acid fumes froTi  acid cleaning and organic vapors from vapor degreasing  are usually
not contaminated  with other materials, and  therefore  are often kept  separate for
subsequent treatment.  The acid fume air stream is collected via  chemical  fume hoods,
                                    Bll-11

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                               Table 7-1 Waste Streams from Printed Circuit Board Manufacturing
Waste Source
Waste Stream
Description
Waste Stream
Composition
RCRA
Code
   Cleaning/Surface preparation
oo
   Catalyst application/
   Electroless plating
   Pattern printing/masking
   Electroplating
   Etching
1. Airborne participates
2. Acid fumes/organic vapors
3. Spent acid/alkaline solution
4. Spent halogenated solvents
5. Waste rinse water

1. Spent electroless copper bath
2. Spent catalyst solution
3. Spent acid solution
4. Waste rinse water

1. Acid fumes/organic vapors
2. vinyl polymers,
3. Spent resist removal solution
4. Spent acid solution
5. Waste rinse water

1. Spent plating bath
2. Waste rinse water
1. Spent etchant
2. Waste rinse water
board materials,
sanding materials,
metals, fluoride,
acids, halogenated
solvents, alkali

acids, stannic
oxide, palladium,
complexed metals,
chelating agents.
F003, F005
chlorinated
hydrocarbons, organic
solvents, alkali

Copper, nickel, tin,
tin/lead, gold,
fluoride, cyanide,
sulfate.

ammonia, chromium,
copper, iron, acids.
F001, F002
F006, F007,
F008, F009

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and sent to a scrubber where it is contacted with water.  The scrubbed air then passes
on to the atmosphere, and  the spent absorbing  solution is  treated  along  with  other
acidic waste streams.  Similarly, organic fumes are often collected and passed through
a bed of activated carbon.  The carbon bed is then regenerated with  steam.  In  many
cases, the regenerative vapor  is condensed  and  the  condensate containing water  and
solvents is drummed and land disposed.   In  a few cases,  the regenerative  vapor is
combusted.

The  spent  acid  and alkaline  solutions from the cleaning  steps are either  contract
hauled for  offsite disposal  or pH-treated  to  precipitate out the contaminants.   The
precipitates are  removed by  clarification, filtration, or flotation, and  the  resulting
sludge is hauled  away for  disposal or  recovery. Spent chlorinated organic solvents are
often gravity separated, and are recovered in-house or hauled away for reclaiming.

The  remaining majority of  the  wastes produced are liquid  waste  streams containing
suspended solids, metals,  fluoride, phosphorus, cyanide, and chelating agents.  Low pH
values are often the characteristic of the wastes  due to acid cleaning operations.  The
liquid wastes may be controlled using end-of-pipe treatment  systems, or a combination
of in-line  treatment  and  separate  treatment  of  segregated waste  streams.   A
traditional  treatment  system for the wastes generated is often based  on  pH adjust-
ment, or on the  addition  of chemicals that will  react with the soluble pollutants to
precipitate out  the dissolved  contaminants in  a form  such  as metal  hydroxide or
sulfate.  The solids are removed as  a  wet sludge by filtration or flotation,  and  the
water is discharged to the sewer.   The  diluted sludge is  usually  thickened before
dumping into landfills. Recent improvements in in-line treatment technologies such as
reverse  osmosis, ion exchange, membrane filtration, and advanced rinsing techniques
increase the possibility for the  recovery and reuse of water and  metals.

8.   WASTE GENERATION RATES

Very little data was available  on specific  waste generation  rates  from the printed
circuit  board  manufacturing industry.   Typical concentration  values of  principal
pollutants present  in wastewater were reported previously  (USEPA  1979).   Principal
pollutants included suspended solids, cyanide, copper, nickel, lead, chromium, fluoride,
phosphorus, and  several noble metals.  While no  specific waste generation rates were
                                  B1J-13

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reported,  fractional rates were estimated by  project  staff based  on the available
information and engineering judgement. These values are shown in Table 9-1.

9.   WASTE REDUCTION THROUGH SOURCE CONTROL

9.1  Description of Techniques

A summary of the  waste sources and the corresponding source reduction  methods is
given in Table 9-1.  This section deals with the description of the listed  techniques.

In addition  to  the  waste  reduction  measures classified as being process changes  or
material/product substitutions, a variety of waste reducing  measures labeled as "good
operating  practices" has also been included. Good operating practices are defined  as
being procedural  or institutional policies which result  in a reduction  of waste.  The
following items highlight the scope of good operating practice:

     o     Waste stream segregation
     o     Personnel practices
                management  initiatives
                employee training
     o     Procedural  measures
                documentation
                material handling and storage
                material tracking and inventory control
                scheduling
     o     Loss prevention practices
                spill prevention
                preventive maintenance
                emergency preparedness

For  each  waste stream, good  operating practice applies whether it is listed or not.
Separate listings have been provided  whenever case studies were identified.
                                  Bll-14

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9.1.1       Cleaning and Surface Preparation

The majority  of  the waste generated by  this operation comes from  various  rinsing
steps.    Since a substantial  amount  of  water  is  often  required,  treatment  of
contaminated  rinse water presents a major problem in waste disposal  for the printed
circuit board  manufacturing industry.  The rinse water is often pH treated, and the
resulting sludge hauled away for disposal or recovery.  The less contaminated water is
then discharged.

Source reduction methods for the minimization of wastes generated from  different
cleaning  operations have been described in a separate study of metal parts cleaning
practice  included in  this appendix.  Since a very high water  usage rate is a  major
characteristics of the printed circuit board manufacturing industry, reduction of the
amount of water used  will greatly improve the waste  treatment process along with
reducing  the  precipitated calcium and magnesium  salts  which are  present  in  the
treatment  sludges together with  heavy metal precipitates.  The reader is referred to
the study mentioned above for appropriate source reduction methods for the cleaning
and surface preparation operations  in the manufacturing  of PCB's.

9.1.2       Catalyst Application and Electroless Plating

The waste  streams generated from this operation are liquids which are either spent
process solutions  or  waste rinse water.  Generally, pH adjustment and clarification are
used to precipitate out the contaminants. The source reduction techniques include:

     o     Use combined sensitization and activation solution to eliminate one extra
           rinsing step.

           Some  PCS manufacturers are  using  this technique  in the manufacturing
           process.   Others  prefer to use  separate  application and activation steps
           since  it seems to  improve the  activity of the catalyst.  The reduction of
           waste  resulting from  the elimination of one extra rinsing  step, however,
           should outweigh  the disadvantage  of reduced catalyst activity.   The
           opinions on the technical merit of this technique appear to be split.

     o     Use lower concentration plating bath to reduce the  degree of subsequent
           rinsing required.
                                   Bll-15

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This approach has been  tried mostly by  large companies in the electro-
plating industry.  No available  information has been reported from  PCS
manufacturers on the use of plating baths with lower concentrations.

Use  differential  plating instead of the  conventional  electroless plating
process.
By controlling the concentration of certain stabilizers in the electroless
copper bath, copper will  be deposited  three  to  five times  faster on the
through-hole walls  than on  the copper cladded  surface  (Poskanzer  and
Davis 1982).  This process will reduce the amount of copper which must be
subsequently etched away  in  the  subtractive  method.    The  use of
differential   electroless   plating   has  not   been  reported   by   PCB
manufacturers and it may require  significant  developmental work before
commercialization is possible.

Use weak or biodegradable  chelating agents.
The  use  of  weak agents  will  allow  more  effective  metal  removal  in
subsequent  metal recovery  operations, and  thus  reduce  the amount of
waste  discharged.   Only  a small number of  PCB manufacturers   have
reportedly been  using weak chelating agents  such  as hydroxy acids in the
electroless plating bath.

Use in-line techniques for metal recovery.
Metal recovery units, such as an ion-exchange columns, should be installed
in-line to  remove metals from  spent plating baths  and  waste rinse waters.
The ion-exchange resin  can be  periodically regenerated to provide plating
solutions which  can then  be recycled  to the plating  bath.  Large  PCB
manufacturing plants have  begun to install metal recovery units  on-site to
recover  metals   from  wastewaters.   However,  since  these  units  are
generally used to remove different  metals from a combined  waste stream,
regeneration of the plating bath solution is not being practiced.

Use computerized/automated control systems.
Computerized process-control systems can be used for board handling and
process bath monitoring  to  prevent  unexpected  decomposition of  the
plating bath.  Since the use of a  computerized control system  not  only

                        311-16

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           requires a large capital outlay for initial installation but also increases the
           demand for skilled operations and maintenance personnel, only very large
           companies which manufacture both PCB's and other electronic components
           are incorporating this change in their manufacturing process.  For example,
           Hewlett-Packard  in  Sunnyvale,  California reported  its successful  use of
           computers for plating operations on PCB's (Anonymous 1983).  The majority
           of PCS manufacturing plants, however, are  small and therefore  can only
           utilize automated handling of the boards in the  plating operations.

     o     Better operating practices.
           Due to their  simplicity and low cost,  good operating  practices are  widely
           used  in the  industry  as the  first effort  to  reduce the waste generated.
           Some  of the methods  used are frequent inspection of plating racks for loose
           insulation to prevent excessive dragout of process  solution, distributing the
           work  load  evenly  to  avoid  dense  loading   which  can  cause localized
           instability of the process solution, and stripping copper out  of  the plating
           tank regularly to prevent continuous deposition of copper and palladium on
           the tank walls.

           Another  approach is  to segregate  all waste  streams.   Chelated waste
           streams should be separated from other streams  to  prevent problems in
           precipitating   out  the  metals  during   subsequent  waste  treatment.
           Segregation  of  complexed  copper  streams is widely practiced  in  the
           industry to reduce the volume of waste generated.

9.1.3       Pattern Printing and  Masking

Depending  on the chemicals used, air emissions consist of various organic compounds.
The fumes are usually collected  and passed through an  activated carbon bed.   The
remaining  liquid  waste  streams  are spent chlorinated solvents,  spent resist solution,
and waste  rinse  water.   The organic solvents and resists are gravity  separated  and
collected  for disposal  or recovery. The following source reduction  techniques were
noted:
                                  Bll-17

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           Use aqueous processable resist instead of solvent processable resist.
           Aqueous processable resists, such as the Du Pont Riston photopolymer film
           resists which allow for  the use of caustic and carbonates as developer and
           stripper*, can  be  used  in  place  of solvent processable resists whenever
           possible to eliminate the generation  of toxic spent solvents.  Hundreds of
           facilities  are  now  using these aqueous  processable  films  for the  manu-
           facturing of PCB's.

           Use screen-printing  instead of photolithography to eliminate the need for
           developers.
           Screen-printing has conventionally been used only to produce PCB's which
           require  very low  resolution in  the  width  and spacing  of the circuit  lines.
           Some  companies have recently developed screen-printing techniques which
           can provide higher  degrees of  resolution.   For  example, General Electric
           has developed a method for screen-printing down to  0.01  inch  resolution
           which can be used to manufacture PCB's for appliances (Greene 1985).  The
           majority of PCB  manufacturers, however,  are  still using  the photolitho-
           graphic  technique for PCB's  having circuitry finer than 12 mil lines and
           spaces.

           Use Asher dry photoresist removal  method  to eliminate the use of organic
           resist  stripping solutions.
           Although  this  method  is  increasingly  being used  in  the  semiconductor
           industry, its use has not been reported by  PCB manufacturers,   probably
           because the PCB  resists are  usually  much  thicker than the corresponding
           semi-conductor resist layers.  Additional exploration is suggested.
* E.I. Du Pont de Nemours & Co. 1985:  Personal communication.
                                   Bll-18

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9.1.A       Electroplating

Electroplating waste streams consist mainly of rinse water and contaminated or spent
dumps of plating solutions.  The dissolved metals are often precipitated  out  by pH
adjustment,  and are  contract  hauled  for metal recovery or disposal.   Cyanide-
containing waste must  be oxidized using chlorine or other strong  oxidants.  The  source
reduction  techniques  which  are used to  minimize the  wastes generated from  the
electroplating operation are given in a separate process study on electroplating (B3).
The source reduction method considered  specific to the manufacturing  of PCB's is the
use of pattern plating instead of panel plating:

      o     Use pattern instead of panel plating.
           Since panel plating consists of  copper plating the entire board area, while
           pattern plating  requires copper electroplating  only the holes and circuitry,
           the use of the latter technique will reduce  the amount  of  non-circuit
           copper which  must  be  subsequently  etched   away.    This practice  can
           therefore   reduce  the  amount  of  waste  generated  from  the etching
           operation.  The switch from panel to pattern  plating has been  made by  a
           large number of PCB  manufacturers.  Customers  demanding applications
           for a uniform cross section of circuitry in computer and microwave  PCB's,
           however, may  dictate  the use of panel plating to provide  highly uniform
           copper thickness.

9.1.5       Etching

Spent  etchant  and  rinse  water are  the  main  waste streams  generated  from  this
operation. As with electroplating, the metals are precipitated out of the waste stream
by pH adjustment. The following source reduction techniques were noted:

      o     Use dry plasma etching techniques.
           The  need   for  toxic  etching  solutions can  be eliminated by using  a  dry
           etching  technique (Till  and  Luxon  1982).   Etching can be done  either
           chemically  using reactive gaseous radicals, or physically using non-reactive
           ion bombardment.  Radio-frequency  sources can be used to ionize gaseous
           molecules to create plasma.  The etching products can then be removed by
           vacuum pumps. The use of dry etching techniques has not been reported by

                                   Bll-19

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          PCB manufacturers.  A separate study can to examine the applicability of
          this technique in removing thick copper layers (1.4 mil) which are used in
          PCB manufacture.

          Use additive instead of subtractive method.
          This change will eliminate the copper etching step, and therefore eliminate
          the generation of substantial volumes of spent etchant as  well  as reduce
          the amount of metal hydroxide sludges generated. Although subtractive is
          still the  most widely used  method in  the  manufacturing of PCB's,  the
          additive method is gaining in popularity since its use results in less waste
          and  lower manufacturing costs (Brush 1983).   A noted  drawback to  the
          additive method, however, lies in the fact that additive processing requires
          the  use  of  solvent  processable instead  of  aqueous processable photo-
          resists*.  Futhermore, spent  additive  plating bath often contains heavily
          complexed copper which may result in  waste treatment problems.

          Use less toxic etchant.
          Non-chromium  etching   solution  has  reportedly  been  used   by  PCB
          manufacturers in an effort to  reduce the toxicity of the waste generated.

          Use in-line techniques for metal recovery.
          Bend Research,  Inc., has  recently  developed a metal recovery  technique
          using liquid  membranes, which  can be used to remove copper from PCB
          etching solution  (Basta 1983).

          Use thinner copper foil to  clad the laminated board.
          This change  will reduce the amount of copper  which must be  etched,  and
          thus will reduce the amount of  waste  generated from the etching process.
          PCB manufacturers are switching to boards cladded with thinner copper as
          their starting materials.
* E.I. Du Pont de Nemours &. Co. 1985: Personal communication.
                                  Bll-20

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9.2  Implementation Profile

The  amount  of hazardous waste generated by the printed circuit board industry  has
been and can be  further  reduced through implementation of the source  reduction
techniques outlined  above.  Many of these techniques are currently practiced, which
demonstrates their technical and economic feasibility.

Basic  improvements in  operating  practices  can yield  substantial  savings in  raw
material disposal  and treatment costs at little  expense  to  the  manufacturer.  For
example,  frequent rack  equipment inspection for loose insulation can  prolong  the
integrity of process solutions, thereby reducing  the  rate at which the solutions  are
replaced. Segregating chelating agents from solutions containing  metals enhances the
feasibility  of recovery of  these  metals  from the solutions.  Improvements  in  the
process itself may  require significant outlays of capital and  increases in  operating
cost.  The economic feasibility of such proposed improvements  should be  examined
carefully and should include proper consideration of avoided costs.

Specific to the PCB  manufacturing industry, implementation of major source reduction
techniques such as the use of the additive instead of the subtractive  method, or the
substitution of materials and/or techniques associated with the  electroless plating and
electroplating processes,  might be promoted effectively through  guidelines, technical
assistance, and information programs.  A majority  of the PCB manufacturers are small
companies who may have difficulties  in conducting extensive research and  testing to
assure the performance of modifications in the manufacturing process.

9.3  Summary

The  summary of  all noted source  control techniques  is given  in Table 9-1.  Each
technique was rated for its  effectiveness, extent of current use and future application
potential on scale of 0 to 4. The ratings were derived by project staff based on review
of the  available data and  in consultation with the industry.  The  estimates of current
level of  waste  reduction  achieved  (current reduction  index)  and   possible  future
reduction (future reduction index) were obtained  from the ratings in accordance  with
the methodology presented in  the introduction to this appendix.
                                  Bll-21

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                    TABLE 9-1 SUWARY OF  SOURCE  CONTROL HETHOOOLOGY FOR THE PRINTED CIRCUIT BOARD NANUFACTURIN6 INDUSTRY
                                                                  Found  Documentation      f     Waste     f    Extent of   f    future     f'Tracffon'of "f   Current"  "f     Fufure~Reduc£fon~fndex    f
                                                                                                                                                                                                       -I
                                                                                                                                                                                                        I
1 | | Quantity | Quality | Effectiveness | Potential
Cleaning/Surface |1. See study on Ketal Parts Cleaning | — | — | — |
I Overall | — | — | — |
Catalyst Activation|l. Use combined sensitization/activation| 2 | I | 2 | 2 2
| and Electroless |2. Use tower concentration plating bath | 1 | 1 | 2 | 1 2
Plating |3. Use differential electroless plating | 0 | 0 | 3 | 0 3
|4. Use weak/biodegrade chelating agents | 1 | II 2 | 2 2
|5 Use in-line metal recovery techniquesl 31 3 | 3 | 2 2
| |6. Use computerized/automated control | 1 | 1 | 2 | 2 3
|7. Better operating practices | 3 | 3 | 3 | 2 2 |
1 | Overall | 1 57 | 1 43 | 2 43 | 1.57 2 29
Pattern Printing/ |1. Use aqueous processable resists | 2 | 1 | 2 | 1 3
| Masking (») |2. Use screen print instead of photolith| 1 | 1 | 2 | 3 1
|3. Use Asher dry resist removal method | 1 j 1 | 1 | 0 I
1 Overall | 1.33 | 1.00 | 1.67 | 1 33 1.67
Electroplating (') |1 See study on Electroplating I — | — | --- |
|2. Use pattern instead of panel plating | 1 | 1 | 3 | 3 1
| | Overall | — | — | — |
Etching |1. Use dry plasma etching techniques | 01 0 | 3 | 0 2
|2 Use additive in place of sub method I 2 | 2 | 3 | 1 1
|3. Use less toxic etchants 1 1 | 1 | 2 | 2 i 2
|4. Use in-line metal recovery techniques] 3 | 3 | 3 | 2 2
|5. Use thinner copper foil for cladding | 1 | 1 | 2 | 2 1
| | Overall I 1 40 | 1.40 I 2 60 I 1 40 1 60
All Sources | All Methods
waste Keaucnon 	
Index Probable
2 0 1.2
0 15 2.0 1.2
1.0 0.5
0.5 0.8
0.0 2.3
1.0 0.5
1.5 0 8
1 0 0.8
1.5 0.8
0.21 1 5 0.9
0.5 1.1
1.5 0.1
0.0 0.3
0 05 1.5 0.5
1,3 0.3
2.3 0.2
0 44 2.3 0.5
0 0 1.5
0.8 0.6
1 0 0.5
1.5 | 0.8
1.0 0.3
0.15 1.5 0.7
1 00 2.0 0.7
Maximum
1 9
1 9
2.3
2 3
1 1
1.1
1 9
1.9
1 5
1.5
1 S
(*}  These streams  include  listed T" and/or 'K" RCRA wastes

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Based  on these ratings, it is  estimated  that the currently  achieved  level of waste
minimization is significant, as evidenced  by the current reduction index (CRI) of 2.0
(50 percent).  CRI is a measure of reduction of the potential waste that would  have
been generated,  if none  of the techniques  listed  in Table  9-1 were used at  their
present levels.

By  additional implementation of the techniques listed, it is estimated  that the extent
of  future  waste  reductions  can be  characterized as  moderate to  significant,  as
evidenced by the future reduction index (FRI) of 0.7  to 1.9 (18 to 48 percent).

The techniques that offer most promise to contribute significantly to waste reduction
in the  future are the ones characterized by a high FRI. It appears that  the use  of  more
efficient  cleaning techniques  (see study  on  metal  parts cleaning),  along  with
differential electroless plating,  use  of aqueous processable  resist, source control in
electroplating operation (see study on electroplating), and  use of dry  plasma  etching
are the most promising for the entire  industry. However, each installation is unique
and will evaluate only  those  options that have the highest application  potential for
their specific needs.

-lO.  PRODUCT SUBSTITUTION ALTERNATIVES

Improvements  in  the techniques used  in the packaging of  microchips can alter the
design of PCB's significantly  and result in  a decrease of waste  associated with PCB
manufacturing.   Presently, the  dual-in-line  package (DIP) accounts  for 80% of  all
packaging of integrated circuits (Bowlby 1985).  More efficient packages, however, are
being developed which utilize a relatively new method of attaching packages  to  PCB.
One important  me,thod  is  called  surface  mounting.  The use  of surface mounting
instead of the conventional through-hole  insertion mounting allows for closer  contact
areas  of chip  leads,  and  therefore  reduces the size of  PCB's required for  a given
number of packages or DIPS.  For a fixed number  of packages,  the  PCB needs to be
only 35% to 60% as large  as  a PCB designed for the old style package (Bowlby 1985).
As the metal area on  which cleaning, plating  and photoresist operations are performed
is decreased, the wastes associated with these operations will also undergo a decrease.

In  addition, the  development  of high-temperature, high-performance thermoplastics
has introduced the use  of  injection molding into the manufacturing of PCB's.   In this

                                   Bll-23

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process,  heated liquid polymer  is injected  under high  pressure into precision molds.
Since the molded substrates are unclad, semiadditive or fully additive plating is used
to produce metalized  conductor patterns.  (Eugelmaier and  Frisch  1982).  Injection
molding, coupled with a fast-rate electrodeposition (FRED)  technique, such as that
developed by Batelie (LWVM  1985), can therefore be  used to  manufacture  complex
three-dimensional PCB's with possible reduction in hazardous  waste generation due to
the elimination of spent toxic etchants.

11.  CONCLUSIONS

Waste reduction in  the printed circuit board manufacturing industry  has already been
accomplished to a significant extent  through the implementation of the source control
techniques listed in Table 9-1.   Additional waste  reduction  in the 18 to 48 percent
range,  can be  expected  by  wider adoption  of  such   techniques  as more  efficient
cleaning,  differential  electroless plating,  use of aqueous  processable resist, source
control of the electroplating operation, and use of dry plasma etching.  In  the area of
product substitution, the use of surface  mounting technology  and the use  of injection
molding coupled with fast-rate electrodeposition  appear to offer high future potential
for waste reduction.

12.  REFERENCES
AESI.  1981.  American Electroplater's Society, Inc. Conference on advanced pollution
control for the  metal finishing industry (3rd) held at Orlando Hyatt House,  Kissimmee,
Florida  on April 14-16,  1980   EPA-6QQ-281-Q28.  Cincinnati, Ohio:  U.S.  Environ-
mental Protection Agency.
Anonymous.   1983.  California-style  circuit  manufacturing using  computerization.
Plat. Surf. Finish. 70:26-9.
Basta,  N. 1983. Total metals recycle  is metal finishers' goal.  Chem. Enq. August 8.
pp.16-19.
BRSRTF.   1984. Boston Regional Source  Reduction  Task Force.   Hazardous waste
source reduction potentials in the semi-conductor manufacturing industry.
Bowlby, R. 1985.  The DIP may take its final bows! IEEE  Spectrum. June 1985.  pp.
37-42.
Brush, P.M. 1983. Fast track for PCBs.  Prod. Finish. November 1983, pp.  84-5.
Coombs, C.F.   1979.  Printed  circuit handbook.  2nd ed.  New York, N.Y.:  McGraw-
Hill Book Co.
                                  Bll-24

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Cox, D.5., and  Mills, A.R. 1985. Electronic chemicals:  a growth market for the 80's.
Chem. Enq. Prog. 81(1): 11-15.

Engelmaier, W., and Frisch, D.C.  1982.  Injection molding shapes new dimensions for
boards. Electronics. December 15. pp 155-158.

Engles, K.O.,  and Hamby, J.T.   1983.  Computerized controller for  electroplating
printed wiring boards. Met. Finish. 81:95-100.

Greene, R., ed.  1985.  Biotechnology  and pollution control.  Chem. Enq.  March 4.
pp.85

Gunderson,  R.,  and  Holden,  H.   1983.   CAM techniques improve  circuit  board
production.  Control. Eng.  30:141-2.

Harper, C.A. 1970.  Handbook of materials and processes for electronics.  New York,
N.Y.:  McGraw Hill Book Co.

LWVM. 1985.  The League of Women  Voters in Massachussetts.  Waste reduction the
untold story.  Seminar Proceeding at the National Academy of Science, Conference
Center on  June 19-21,  1985.  Wood Hole, Mass.:   the League of Women Voters in
Massachussetts.

Lyman, J.  1984. Surface mounting alters the PC board scene.  Electronics. February
9, 1984.

NCO.  1984.   National Credit Office.  Electronic marketing directory.   New York:
National Credit Office.

PEL  1983.   Pedco-Environmental, Inc.  Industrial process profiles for  environmental
use. Chapter 30.  The electronic component manufacturing industry.  EPA-600-2-83-
033. Cincinnati, Ohio. U.S. Environmental Protection Agency.

Poskanzer, A.M.  1983.  Plating  printed circuit substrates: circuit topics.  Plat.  Surf.
Finish.  70:10.

Poskanzer, A.M., and Davis, S.C.  1982.   An efficient electroless plating system for
printed circuitry. Plat. Surf.  Finish. 69:95-7.

Stintson, S.C.  1983.  Chemicals for  electronics:  new growth in competitive field.
Chem. Enq.  News. 61(30):7-12.

Tills,  W.C.,  and Luxon,  J.T.   1982.   Integrated  circuit;   materials,  devices and
fabrication. Englewood Cliffs, N.J.: Prentice-Hall, Inc.

USDC.   1985.   U.S. Department of Commerce, Bureau of the Census.  Electronic
components  and accessories.    In  1982  Census of  manufacturers.   MC82-I-36E.
Washington, D.C.: U.S. Government Printing Office.

USEPA.  1979.  U.S. Environmental Protection Agency, Office of Water  and Hazardous
Materials.   Development document for existing source pretreatment standards for the
electroplating point source category.   EPA-440-1-79-003.   Washington,  D.C.:  U.S.
Environmental Protection Agency.
                                  Bll-25

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	.  1983. U.S. Environmental Protection Agency. Office of Water
Regulation and Standard.   Development document for effluent limitation  guidelines
and  standards  for  the  metal finishing point  source category.   EPA-440-1-83-091.
Washington, D.C.:  U.S. Environmental Protection Agency.

WAPORA.   1977.  Wapora, Inc.  Assessment of industrial hazardous waste  practices;
electronic component manufacturing industry.  PB-265532.  Washington, D.C.:   U.S.
Environmental Protection Agency.

Wynschenk,  J.  1983.  Electroless copper plating chemistry and maintenance.  Plat.
Surf. Finish.  70:28-9.

Yapoujian, F.  1982.  Overview of printed circuit  board technology.  Met. Finish.
80:21-5.
13.  INDUSTRY CONTACTS


Dr. G.J. Hollod, Senior Environmental Engineer, E.I. Du Pont de Nemours & Company,
Wilmington, DE.

W.G.   Vaux,  P.E.,  Chemical  and  Process  Engineering,  Westinghouse  Electric
Corporation, Pittsburgh, PA.
                                  Bll-26

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1.    PROCESS: PRINTING OPERATIONS
2.    SIC CODE: 27
3.    INDUSTRY DESCRIPTION

As defined in the Standard Industrial Classification Manual (USDC 1972), Major Group
27 - the printing,  publishing, and  allied  industries include "establishments  engaged in
printing  by one or more of the common processes, such as letterpress,  lithography,
gravure, or screen; and those establishments which perform services for the  printing
trade, such as bookbinding, typesetting, engraving, photoengraving, and electrotyping.
This major group also includes establishments engaged in publishing newspapers, books,
and  periodicals, regardless of whether  or not  they do their  own printing".  Of the
seventeen SIC subgroups under  major group 27, about fifteen would involve  substantial
printing operation activities.

The  graphic  arts industry, as SIC  27 is otherwise referred  to in this report, is one of
the  biggest  in the  United States,  ranking highly  among the  twenty major manu-
facturing groups included in the SIC system.  This is evidenced by the statistics shown
in Table 3-1.

               Table 3-1  1982 Ranking of the Graphic Arts Industry
Rank
First
Sixth
Seventh
Eighth
Tenth
Tenth
Eleventh
Criteria Value,
in number of establishments
in number of employees
in total dollar payroll
in value added by manufacturing
in value of shipments
in dollars reinvested in capital expenditures
in average hourly earnings


$
$
$
$
$
U.S. dollars
53,500
1.3 million
22.7 billion
49.4 billion
85.8 billion
3.2 billion
8.58 per hour
Source:    Printing Industries of America 1985:  Personal communication.
                                  B12-1

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3.1   Company Size Distribution

Of the 53,356 printing facilities located in  the  U.S., 80 percent employ less than 20
people each.  Overall, the Bureau of the Census (USDC 1985a, 1985b,  1985c) estimated
that 1,291,000 people were employed by the printing industry in 1982.  Table 3-2 lists
company size distribution as a function of total number of employees at a given site.

                    Table 3-2  1982 Company Size Distribution
No. of employees per

No.
No.

of establishments
of employees (x 1,000)
1-19
42,485
231
20-49
6,145
187
50-99
2,525
175
facility
100+
2,201
698

Total
53,356
1,291
Source:    1982 Census of Manufactures (USDC 1985a, 1985b, 1985c).

3.2  Principal Producers

The printing industry  is composed  of a small number of multi-plant firms and a large
number of single plant firms.  The six  largest firms, in  terms of sales and number  of
employees, are  listed in Table 3-3 below.

             Table 3-3 Principal Producers in the Graphic Arts Industry
Company
R.R. Donnelley & Sons
(Chicago, IL)
Hallmark Cards
(Kansas City, MO)
Moore Business Forms
(Glenview, IL)
American Greetings
(Cleveland, Ohio)
Deluxe Check Printers
(St. Paul, Minnesota)
Sales
(1984)
$1.8 billion
$1.5 billion
$1.4 billion
$945 million
$682 million
No. of Plants
17
1
38
7
61
Number of
Employees
17,700
20 , 100
15,000
23,000
10,900
Source:    American Printer (Anonymous 1985).

                                  B12-2

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3.3   Geographical Distribution

Graphic arts establishments are scattered  all over the United States, with the largest
concentrations in California and New York.  These two  states share about 12 and 11
percent  of  the  industry, respectively.    Illinois,  Texas,  Florida,   New  Jersey,
Pennsylvania, and Ohio each share about 5 percent of the total.  Distributions by EPA
region  are shown  in Table 3-4 and Figure 3-1.  About 20  percent  of  the  firms are
located in Region V, and about 15 percent in Regions II and IX.

                  Table 3-4 Location of Facilities by EPA Region
EPA
Region
I
II
III
IV
V
VI
VII
VIII
IX
X
Total No.
of Facilities
3,458
8,203
4,359'
7,305
10,586
4,985
3,153
1,827
7,530
1,800
Number of employees
1-19
2,625
6,420
3,203
6,097
8,174
4,111
2,485
1,514
6,237
1,519
per facility
20+
833
1,783
1,156
1,208
2,412
874
668
313
1,293
281
Source:    1982 Census of Manufactures (USDC 1985d).

4.    PRODUCTS AND THEIR USES

The graphic  arts industry produces a large number of products such  as newspapers,
paper packaging containers,  business forms, books,  posters etc.  (printed matter), and
printing  plates which  serve  various needs.   These products fall under  any  one of the
seventeen  SIC subgroups.  Table 4-1 lists the major  sub-industries and the  value  of
product shipments.
                                   B12-3

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                             VIII
DO
r-o
i
            0
                      0-500

                      2501-5500
501-1500

over 5500
1501-2500
                      Roman numerals show EPA regions


     Figure    3-1  Printing Establishments in the U.S.

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           Table 4-1  Graphic Arts Industry: Value of Shipments in 1984
SIC
27
2711
2721
2732
2741
275
2761
2771
2795
-
Industry
Printing and allied products
Newspaper publishing and printing
Periodical publishing and printing
Book printing
Miscellaneous publishing and printing
Commercial printing
Manifold business forms
Greeting card publishing and printing
Lithographic platemaking services
Other printing and publishing
Value of Shipments^3'
(in millions of dollars)
40,256
9,890
5,932
3,585
2,310
11,600
2,318
1,228
830
2,308
Source:    1984 U.S. Industrial Outlook (USDC 1984).

(a)
  Forecast estimate.


5.   RAW MATERIALS


The principal raw materials used by the graphic arts industry are inks and substrates.
A substrate is any material upon which ink is impressed, such as paper, plastic, wood,

or metal.  Table 5-1 shows the recent usage of ink and paper by the industry.

         Table 5-1 Paper and Printing Ink used by the Graphic Arts Industry

                                                                         Volume
                  Material                                              (short tons)
   Commercial printer                                                  5,300,000
   Magazines and other periodicals
       (other periodicals include catalogs and
       directories                                                       4,000,000
   Book                                                                 900,000
Printing Ink^b)
   Lithographic and offset                                                190,150
   Gravure                                                              179,750
   Letterpress                                                           119,250
   Flexographic                                                           91,150


Source: 1984 U.S. Industrial Outlook (USDC 1984); American Paper Institute 1985:
        Personal communication.
(a) Data are for 1984.
(b) Data are for 1982.
                                  B12-5

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6.    PROCESS DESCRIPTION

In  the  graphic  arts  industry,  there  are  three  major  printing  processes (offset
lithography,  gravure,  and flexography).  Two  additional methods, letterspace and
screen,  are also important but represent a much smaller share of the market.  Table 6-
1 presents current  and future trends in the distribution  of printing processes.   Since
offset lithography and gravure are the most popular printing processes used, they will
be discussed  in greater detail in this report. Detailed discussion of the other printing
processes may be found in the  literature (USEPA 1976).  Figure  6-1 is  a  block flow
diagram of offset lithography and gravure printing operations.
          Table 6-1  Trends in Distribution of Printing Processes in the U.S.
Process

Lithography
Gravure
Letterpress
Flexography
Screen printing and other processes
Year
1977
38%
14%
32%
11%
5%
1985
45%
18%
15%
16%
6%
1990
47%
20%
8%
18%
7%
1995
46%
21%
4%
21%
8%
Source:    Profit  from  Pollution Prevention  (Campbell and Glenn  1982); Status  of
           Printing in the USA (Bruno 1985).

Except for the use of a plate or cylinder to transfer ink to a substrate (such as paper)
both off-set lithography  and gravure  are conceptually very similar.  Art work  or copy
is prepared and the image is transferred to the plate or cylinder.  This operation makes
certain areas of the plate or cylinder receptive to ink (the image area).  The substrate
is then passed by  the  plate (i.e. the  ink is first tranferred from the plate to  a rubber
blanket, and then  onto the substrate) or cylinder.  The substrate absorbs the ink,  thus
reproducing the image.   The substrate is then processed mechanically (cut, folded,
bound, etc.) to produce  the final  product.  Since the  only major difference  between
lithography and  gravure  lies in the manner in  which the plates  or cylinders are made
and subsequently  operated, the  following  discussion  will be  general except where
further details are warranted.
                                   R12-6

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    INK

SUBSTRATE
 (PAPER)
                                ARTWORK
                                /TEXT
                            IMAGE
                         PROCESSIN6
                    [ON-SITE OR OFF-
                                FILM
                      PLATE OR CYLINDER
                           MAKING
                    (ON-SITE OR OFF-SITE]
                                FINISHED
                                PLATE/CYLINDER
                           DRYING
FINISHING


                             V
                           PRINTED
                           PRODUCT
                                                           PROCESS HASTE CATEGORIES!

                                                           (l)  TRASH

                                                           (2)  KASTEKATEH

                                                           (?)  EQUIPMENT CLEANING
    Figure 6-1   Block Flow Diagram for  Offset  Lithography/ Gravure Printing Operations
                                 B12-7

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Most  printing operations begin  with  art  and copy  (or text) preparation.   Once  the
material is properly arranged, it is photographed to produce transparencies and color
separations.  Color separations are required to provide a single-color  image or record
which can then be used to produce the single-color printing  plate for lithography or the
cylinder for  gravure (multi-color printing is done  by passing  the substrate  through
several single-color printing operations).  Once the  film has been  developed, checked,
and rephotographed (if necessary),  it is sent  on  to the plate-  or  cylinder-making
operation.

Plate making consists  of cleaning or counter-etching the surface of an aluminum plate
and then applying a photosensitive coating. Counter-etching  involves the use of dilute
acid solutions such as phosphoric, acetic, hydrochloric, and sulfuric acids, although
alkaline counter-etches are  sometimes  employed.   The  solution is poured   on  the
surface and agitated  with  a bristle  brush.   The plate is  then copiously rinsed  with
water.  The metal surface is then coated in the whirler with a photosensitive  solution
consisting  of  an  aqueous  solution  dichromate,  ammonium  hydroxide,  and colloidal
protein.

The image from  a photolithographic negative is transferred to the photosensitive plate
by exposure to light, and the coating \sf covered with a developing  ink to increase  the
affinity of the image area for ink during printing.  The plate is  developed by removing
the unhardened  non-image  areas  of the  coating  with dilute  ammonium  hydroxide
solution and is then washed with water and dried. An  acidified solution  of gum arabic,
which may also contain ammonium dichromate, is subsequently used to desensitize the
developed plate.   Finally, the plate is again washed with water,  a plain solution of gum
arabic is applied, and the plate is allowed to dry.

Cylinder  making begins  with a steel cylinder plated with copper.  The  cylinder  is
machined and polished so as to remove any imperfections in the copper  plating. Next,
the surface is either engraved using a diamond stylus or chemically etched using ferric
chloride.   Use of ferric  chloride requires that a resist (in the form  of the negative
image) be transferred to the cylinder before etching.  The resist protects the non-
image  areas of  the  cylinder  from the  etchant.   After  etching, the  resist  may be
subsequently  stripped  off.   This operation  is  analagous to  the manufacturing of
                                    B12-8

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printed  circuit boards.  Following this operation, the cylinder is proofed or tested, re-
worked  if required, and then chrome plated.

Following  the  plate-  or cylinder-making  operation,  the  next step  is printing.   In
lithographic printing, the plate  is mounted to  a rotating cylinder.   As the cylinder
rotates, a dampening solution followed by ink  is transferred to the plate's image area.
The inked image repels the solution and accepts the printing ink, while the non-image
area accepts the dampening solution and repels the ink.  As the cylinder continues to
rotate,  the inked image is transferred to a rubber roller or blanket and then onto the
substrate.  The two major forms of substrates used in lithography  are single sheets of
paper, (sheet-fed lithography) and continuous rolls of paper (web lithography).

In gravure printing, the cylinder is placed in the press and partially immersed in an ink
bath or  fountain.  Solvent is  added to the ink to maintain the proper level and viscosity
of the bath.   As the cylinder is rotated, ink coats  the entire surface.  Next,  a metal
wiper (doctor blade) presses against the surface of the cylinder and removes ink from
the non-etched (non-image)  areas.  The substrate is then pressed  against the rotating
cylinder and the ink is transferred.

After printing, the substrate  may  pass  through a  drying  operation  depending on the
type of ink used.  Lithography  can use  heat-set and  non-heat-set inks.   In heat-set
lithography,  the substrate is passed through a  tunnel or floater dryer which  utilizes
hot air  or direct flare.  With non-heat-set  lithography, the ink is normally air dried.
Gravure uses heat-set  inks, so a drying operation  is  required.  Following this drying
operation, the  printed substrate can be finished by slitting, cutting, trimming, folding,
binding, laminating, or  embossing.

7.    WASTE DESCRIPTION

Listed  in  Table 7-1 are  the  principal  wastes associated with lithographic  printing
operations. Gravure printing operations have been excluded since the major difference
between the two processes, from a waste  generation viewpoint,  is  in  the plate- and
cylinder-making operation.  Gravure  cylinder  making  is very similar  to  other metal
                                  B12-9

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                                         Table 7-1 Offset Lithography Printing Process Wastes
Waste
Stream
No

Waste
Description


Process Origin


Composition


RCRA Codes
              1.
03
h-•
hO
              2.
              3.
Trash           Image Processing


                Plate Making


                Printing


                Finishing

Wastewater     Image Processing

                Plate Making
Equipment
Cleaning
Wastes
Printing


Printing
Empty containers, packages,
used film, out-dated materials

Damaged plates, developed film,
out-dated materials

Test production, bad printings,
empty ink containers, used blankets

Damaged products, scrap

Photographic chemicals, silver

Acids, alkali, solvents, plate
coatings (may contain dyes
photopolymers, binders, resins
pigments, organic acids),
developers (may contain
isopropanol, gum arable,
lacquers, caustics), and
rinsewater.

Spent fountain solutions (may
contain chromium).

Lubricating oils, waste ink,
clean up solvent (halogenated
and non-halogenated), rags.
                                                                                                            F002
                                                                                                            E003
                                                                                                            F005
F002
F003
F005

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processing operations; therefore, the reader is referred to the process studies on metal
parts cleaning, electroplating, and metal surface treatment elsewhere in this appendix
for information regarding the types  of waste that would be encountered. Additionally,
the inks used by the gravure industry tend to contain solvent and heavy metals, unlike
the inks used by the lithographic industry*.  While this would affect the ways in which
certain wastes are classified, regulated, handled, and disposed,  the  nature of the inks
used for lithography does not detract from the desirability of minimizing all non-paper
waste.

The  major wastestream encountered in the  lithographic  industry is trash.  Almost 98
percent of the total waste generated by this segment of the industry is spoiled paper
and paper  wrap*.  This paper is normally recycled, incinerated, or disposed of.  Other
trash,  such as scrap  photographic  material, is sold for  metal recovery.   Empty
containers are normally scraped clean of ink (to an economically feasible  extent) and
discarded.

Wastewater from image processing  is normally treated  to recover silver  and  is then
discharged. Plate-making wastes, such as acids and alkalis used to clean  the  plates,
must be either sent to wastewater treatment  or drummed for disposal.  For facilities
that use pre-sensitized plates, this waste is avoided (though the supplier  of the pre-
sensitized  plates  would be producing this waste).  Currently, only large-volume users
of plates  (i.e.  newspapers) still produce their own  plates*.   Photochemical  wastes
would  be   handled  in  the same manner as  image processing  wastes.   Wastewater
containing spent fountain solutions may go  to  a waste  treatment unit but  is normally
discharged into the  sewer.

The final  wastestream, equipment cleaning wastes, consists of dirty rags soaked with
solvent and waste  ink.  Dirty  rags  are  laundered,  are disposed  as  trash,  or  are
incinerated.  If a facility employs a professional laundry, then the rags  are picked up,
laundered,  and returned. The fate of the solvent and ink contained in these rags would
depend on how the laundry is designed and operated (e.g. water vs. dry cleaning). Most
waste inks  are either incinerated or discarded with the trash.
* Graphic Arts Technical Foundation 1985: Personal communication.
                                 B12-11

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8.    WASTE GENERATION RATES

The  only  published  estimates  of the nationwide  waste generation rates from the
graphic arts  industry were  given for  1972 (Bohn 1976).   It was estimated that the
industry as a whole generated 7,300 short tons  of waste excluding  waste paper and
photoprocessing  chemicals.  Separate listings by  type of operation analyzed were not
provided  and more  recent estimates  have not  been reported.   Fractional  waste
generation rates for  the lithographic printing industry were estimated by project staff
based  on  the  available  information,  engineering judgement,  and  input from the
industry.  These values,  excluding trash attributable to scrap  or  waste paper, are
shown in Table 9-1.

9.    WASTE REDUCTION THROUGH SOURCE CONTROL

9.1  Description of  Techniques

The list of individual primary lithographic waste  streams and their sources along with
a list of source reduction methods is presented  in Table 9-1.   Recommended  waste
reduction  methods and  identified procedures are  discussed in  the following sections.
The basis  for identification  came from published accounts in the open literature and
industry contacts.

In  addition to the waste  reduction  measures classified as being process changes or
material/product substitutions, a variety of waste reducing measures labeled as "good
operating  practices" has also been included. Good operating practices are defined as
procedures or institutional policies which result in a reduction of waste.  The following
items highlight the scope of good operating practices:

     o     Waste stream segregation
     o     Personnel practices
                Management initiatives
                Employee training
     o     Procedural measures
                Documentation
                Material handling and storage
                Material tracking and inventory control
                Scheduling

                                  B12-12

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      o     Loss prevention practices
                Spill prevention
                Preventative maintenance
                Emergency preparedness

For each waste stream,  good operating practice applies whether it is listed  or not.
Separate listings have been provided whenever case studies were identified.

9.1.1   Trash

Even  excluding spoiled paper, trash represents a major wastestream in the lithographic
industry.   This  wastestream  includes used photographic film, empty  containers  and
packages,  and  out-dated  materials.   The  following waste  reduction  measures were
noted:

      o     Recycle empty containers.
           Most ink containers are  scraped  free of ink and discarded  in  the trash.
           Since the degree of cleanliness is a function of operator effort, the  amount
           of ink  discarded  can vary widely.  By  purchasing ink in recyclable bulk
           containers, the container can be returned to  the  ink supplier  for refilling
           instead of being thrown away.  In addition, the use of bulk containers also
           cuts down on the amount of cleaning required  since the surface area of the
           container per unit  volume of  ink stored is reduced.

      o     Recycle spoiled photographic film  and paper.
           It is already a current practice of the industry to  send used and/or  spoiled
           film to professional recyclers for recovery of silver*.  However, this option
           might not be practical  to small scale producers  or available to facilities
           located far away from recyclers.

      o     Electronic imaging and laser  platemaking.
           Since all text and  photos are  edited  on a video terminal, the need for
           photographing,  editing, and  re-shooting is  reduced.  In addition, color
           separations can be produced electronically and therefore may eliminate the
           need for the many  photoprocessing steps  currently  employed.
* R.R. Donnelley & Sons 1985:  Personal communication.

                                   B1Z-13

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     o     Installation of web break detectors.
           The Oxy-Dry Corporation  manufactures an electronic system  that detects
           web breaks in a non-contact fashion that will neither smear ink nor crease
           the web, thereby reducing waste from  these sources.  Both McGraw-Hill
           Publications in New York, New York, and the St. Petersburg  Times in  St.
           Petersburg,  Florida have installed web  break detection systems  and have
           reduced waste (Campbell and Glenn 1982).

     o     Monitoring press performance.
           Crosfield  in Chicago,  Illinois,  markets  the Pressdata  190 waste  system
           which provides a means of monitoring press performance.

     o     Better operating practices.
           Photosensitive  film  and  paper  storage areas  should  be  designed  for
           economical and efficient use.  Some shops waste up to one-fourth of these
           materials due to  improper storage (op. cit.)

9.1.2   Wastewater

Wastewater  comes  from  two  main  sources:    image processing  (including  plate
developing) and the platemaking process.   Other  sources are clean-up operations and
spent  formation  solutions.    Since  these wastes  are  produced  by  many  different
processes and therefore require  different  minimization procedures,  each operation is
discussed separately.

Image  processing (and plate developing)   The  photographic industry  has made great
strides in pollution abatement and many of the methods developed by this industry  are
applicable to the  printing industry. The waste reduction methods are as follows:

     o     Use silver-free films.
           Napp  Systems,  among  several  other  companies, is marketing silver free
           films for lithography  (Campbell and Glenn 1982).

     o     Use water-developed lithographic  plates.
           3M is marketing its Hydrolith  plate which requires only water to process
           aluminum  off-set plates (op. cit.).
                                 B12-14

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           Electronic imaging and laser platemaking.
           Text and photos are read by an  electronic scanner,  edited with  a  display
           monitor, and non-silver plates  are made using laser beams*.   Due to the
           expense of this system,  it is currently being tried by  only the largest of
           printers, e.g. newspapers. USA Today currently employs this system.

           Recover silver and recycle spent chemicals.
           Basically, photoprocessing chemicals consist of developer, fixer,  and rinse
           water.  Keeping the  individual process baths as uncontaminated as possible
           is a prerequisite to the successful recycling of these chemicals. Silver is a
           component in most  photographic films and paper  and is  present  in  the
           wastewaters  produced.   Various  economical methods of  recovering silver
           are  available  (e.g.    metallic  replacement,   chemical  precipitation,
           electrolytic  recovery) and a number of companies market equipment that
           will suit the needs of even the smallest printing shop. Technologies  for re-
           use of developer and fixer are  available.  These technologies make use of
           various methods such as ozone oxidation, electrolysis, and ion exchange.

           Employ counter-current washing.
           Counter-current washing, as opposed to the parallel tank system, reduaes
           processing solution contamination thereby increasing  the ease of  recycling
           process baths and reducing the  quantity of make-up chemicals required. In
           a parallel system,  fresh  water  enters each wash  tank and effluent  leaves
           each wash tank. In counter-current  rinsing, water from previous rinsings is
           used in the initial film-washing  stage.  Fresh water  enters the process at
           the final rinse stage, at which point  much of the contamination has already
           been rinsed  off the  film.   The  main consideration  in a  counter-current
           system is availability of space.

           Use of squeegees.
           Squeegees  in  non-automated  processing  systems  can  reduce  chemical
           carry-over typically by 50 percent on film and paper from one process bath
           to   the next  by  wiping off  excess  liquid.       Minimizing   chemical
* Printing Industries Association 1985: Personal communication.
                                  B12-15

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           contamination of process baths increases ease of recycling, enhances the
           lifetime of the  process baths, and  substantially  reduces  the amount of
           replenisher chemicals  required.   Most  firms, however,  use automated
           processors*.

     o     Better operating practice.
           Taking  care  to  accurately  add and  monitor chemical  replenishment of
           process baths will cut down chemical wastage.   Some process chemicals
           have expiration  dates.   If  there are not enough  orders to consume these
           chemicals  before they  expire,  these  would  go  to  waste.    Pre-mature
           expiration  of  light-sensitive chemicals may be  prevented by keeping them
           in the dark.

           Easily  oxidizable process  baths  may  be protected  from  quickly  losing
           potency by reducing their exposure to air.  Small-scale photo developers
           store their chemicals in closed plastic containers and use glass marbles to
           bring the liquid level to the brim each time liquid is  used.  This way, the
           amount  of oxygen available  to the  chemical  is  reduced  to  a minimum,
           thereby extending the chemical's useful life.

Wastewater from platemakinq   Only the  newspaper sector of lithography still widely
employs  platemaking.   Waste  reduction can be accomplished  using the  following
technique:

     o     Removal of heavy metals from wastewater.
           Hexavalent chromium can be  reduced  to the less toxic trivalent form by
           lowering pH to about 2 with a strong mineral acid and then adding a strong
           solution of reducing  agent such as ferrous sulfate or sodium bisulfite. Upon
           addition of caustic  soda or lime, the heavy  metals will precipitate out as
           hydroxides (Latus 1976).  This is applicable to older technologies that are
           being phased  out but would not apply to newer systems**.  Moreover,
           hooking up holding tanks to the sink and whirler will prevent the pollutants
           from reaching the municipal sewage system without prior treatment.
*  R.R. Donnelley and Sons 1985:  Personal communication.
**  Printing Industries Association 1985: Personal communication.
                                  B12-16

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9.1.3   Clean-up Solvents and Waste Ink

The clean-up solvent waste stream consists of waste ink, ink solvents, lubricating oil,
and solvent.  In  many printing establishments, excess ink and solvent is collected in a
drip pan underneath the press.  This waste is typically drummed and hauled away to a
landfill area. The following waste reduction methods are noted:

     o    Recycle waste ink and clean-up solvent.
           Ink recovery machines are commercially available  in  a  number of  sizes.
           For firms which choose not to recycle waste ink onsite, it can be sent back
           to the  ink  manufacturer  who may  turn   it  into black  newspaper ink
           (Campbell and Glenn 1982, Huisingh et al. 1985).

           If waste  cleaning  solvent is generated in substantial quantity, it may  be
           recycled  on-site or sent to  a professional solvent recycler.  In many cases,
           however, a printing shop  does  not generate enough solvent waste to justify
           onsite  recycling.  Waste solvent can be reclaimed through simple  batch
           distillation or can be incinerated with recovery of heating value.

           Clean-up is  usually done  by wetting  a piece of rag with solvent and wiping
           the equipment to be  cleaned, or by pouring some solvent on the equipment
           and wiping it.  Drip pans are placed  underneath equipment to collect  waste
           solvent.  The dirty rags are then sent to professional cleaners for cleaning
           or drummed for disposal.  In many cases, the nature of the waste does not
           lend  itself readily  to  recycling efforts.  However, as  indicated by  the
           example   of better  operating  practice'  given  below,  waste  handling
           procedures can often be changed to facilitate recycling.

     o    Use of automatic cleaning  equipment  can promote a more efficient use of
           cleaning solvent*. However, this equipment  is very expensive to purchase
           and maintain.
* R.R. Donnelly and Sons 1985:  Personal communication.
                                  B12-17

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     o     Use of an automatic ink leveller.
           Oxy-Dry Corporation  is one company  that produces this equipment which
           maintains  the  desired  ink level  in  the fountain  for optimum  inking
           conditions.   This  prevents ink  waste and ink  spoilage around  the  press
           (Campbell and Glenn 1982).

     o     Substitution with less toxic solvent.
           In  some  cases it  may be possible  to  substitute highly toxic aromatic
           solvents,  such  as  benzene or  toluene,  with  less toxic  straight  chain
           paraffinic solvents, e.g. hexane.

     o     Better operating practices.
           Rexham  Corporation   of  Matthews,  N.C.,  does high-tech  printing  and
           coating, including film  substrate, for the  photographic industry.  Toluene is
           used to  clean  the  ink  from the press, and runoff toluene  is collected as
           waste.  Rexham has nearly eliminated  its  toluene waste by segregating
           used clean-up  toluene  according to the color and type  of ink contaminant
           and then reusing the collected wastes to thin future batches of the  same
           ink.  The procedure has no effect on product quality  and has resulted in
           almost 100% reuse of the toluene solvent (Huisingh et al. 1985).

9.2  Implementation Profile

Most  of  the measures  undertaken by  the  printing industry to  reduce waste center
around recycling of  materials and the implementation  of good operating practices.
The  technical  and commercial viability of recycling waste ink is evidenced by  the
commercial availability of ink recovery machines.  Portable and non-portable models
are available to suit the  different needs and preferences of printers.   For waste ink
that  is contaminated, turning  it into black  newspaper ink may be more  practical than
preserving  the original color.  Implementation  of  good  operating practices either
assures that materials can be more readily recycled or  avoids the need  for recycling
altogether.
                                   B12-18

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The  installation  of  silver,  ink,  and/or solvent recovery  equipment  (among other
methods)  requires significant capital  outlays  and entails possible  increases in labor
costs.   The economic feasibility  of making these changes  depends in  large measure
upon the quantity of recoverable/recycleable material generated by a facility.  Small-
volume waste ink generators may find internal or on-site  recycling less  economical
than sending their ink runoff to ink  manufacturers who  can convert  it into black
newspaper ink  or  to  recyclers who collect from groups of small-volume  generators.
Large-volume generators,  who comprise approximately  20  percent of all waste ink
generators,  will likely find on-site recovery systems to be  more cost-effective.  The
availability  of greater  financial  and  personnel  resources serves  to  enhance  the
potential   for  cost-effective  on-site  recovery  and   recycling  for  large-volume
generators.

9.3  Summary

The  sources of waste from  the  conventional  lithographic  printing  process and the
associated source control techniques are summarized in Table 9-1.  Spoiled paper and
paper  wrap  were excluded from this summary  so as to provide a better focus on the
wastes of concern.  The  ratings listed in the  table are based on a scale of 0 to 4 and
are used to evaluate each technique for its waste reduction effectiveness, extent of
current use  and future application potential.  The ratings  were derived by project staff
from the available information and from industry comments.

It  appears that the current level of waste minimization in  the lithographic printing
industry  is  high.   This  is  evidenced  by  the current reduction index  (CRI)  of 2.5
(63 percent) which measures the extent of reduction in the waste that otherwise would
be generated if none of the listed methods were applied as they  are currently.

The potential for future  reductions appears modest to significant, as evidenced by the
future  reduction  index (FRI)  of  0.7 to  1.4 (18 to 35 percent).  The  future reduction
index  is  the measure  of waste  reduction achievable through  implementation  of the
listed techniques to their full rated potential.

Ways   in which  these reductions  can  be  achieved  would   be  to  recycle empty ink
containers  and  increase  the use  of  counter-current  rinsing  and good operating
practices.   Measures  that  have  helped the  industry  to achieve  a high degree of
                                 812-19

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                              TABLE  9-1 SUNNUtr OF SOURCE  CONTROL HETHOOOL06Y FOR THE PRINTING OPERATIONS INDUSTRY

Haste Stream


Trash






Hastewater








Clean-Up Solvent
and Haste Ink (<





All Sources
1 1
1 Control Methodology |-

i i
|t. Recycle empty containers 1
|2. Recycle spoiled photographic film |
|3. Electronic Imaging/laser platemaking |
|4. Install web break detectors |
|5. Monitor press performance |
|6. Better operating practices |
| Overall |
|1. Use silver free films |
|2. Use water developed litho plates |
|3. Electronic imaging/laser platemaking |
|4. Recover silver and recycle chemicals |
| 5. Use counter-current washing sequence |
| 6. Use of squeegees I
|7. Better operating practices |
|8. Remove heavy metals from Hastewater I
| Overall |
|t. Recycle waste ink and solvent I
)|2. Use of automatic cleaning equipment |
|3. Recovery of heating value from waste |
|4. Use of an automatic ink leveller |
|5. Use less toxic solvent |
|6. Better operating practices |
| Overall |
| All Methods
Found Documentation


Quantity | Quality
0 I
1 1
1 I
1 1
1 1
1 I
0 83 | 0
1 I
' 1
1
1
1
1
1
1 I
1.00 | 1
2 I
1 I
1 1
1 1
0 1
2 1
	 4 	
1.17 | 1

1
— !
1
I
o l
1
1
1
1
1
83 |
1 1
t I
1 1
t 1
2 1
1 1
t 1
2 1
	 4.
25 I
2 1
1 1
1 1
1 I
0 I
2 I
n |

Haste |
Reduction 1

Effectiveness |
3 1
3 1
2 1
' 1
1 1
2 1
2.00 |
1
1
1
1
1
1
2 1
3 I
2.63 |
2 1
2 1
« 1
1 I
0 I
• I
2 17 |

Extent of |
- .. i
current use |
1
0 1
3 1
1 I
1 1
1 1
1 1
1.17 |
1 1
3 1
1 I
3 I
2 I
1 1
2 1
1 I
1.75 |
2 1
1 1
1 1
1 I
2 I
2 I
1.50 |

Future | Fraction of I
11. ..J ITfclut 1
Application [ total waste |
Potential | |
2 1 1
1 1 1
2 1 1
2 1 1
2 1 1
« 1 1
2.17 | 0.36 |
' 1 1
2 1 1
2 1 1
' 1 1
2 1 1
1 1 1
3 1 1
2 1 1
1.75 | 0.24 |
3 1 1
1 1 1
1 1 1
2 1 1
2 1 1
3 1 1
2 00 | 0.40 |
1 i.oo |
Current |
n J
Reduction |--
Index |
0.0 |
2.3 I
0.5 i
0.3 |
0.3 |
0.5 |
2.3 |
0.3 |
3.0 |
0.5 |
3.0 |
2.0 |
0.3 |
1.0 I
0.8 |
3.0 |
1 0 |
0.5 |
1.0 |
0.3 |
0.0 |
2.0 |
20 |
2.5 |
Future Reduction Index


Probable | Maximum
1.5 | 1
0.2 |
0.8 |
0.4 |
0.4 I
1.5 | t
0.8 | 1
0 2 |
0.5 |
0.8 |
0.3 |
1.0 |
0.2 |
0.8 |
1.1 | 1
0.6 | t
0.8 |
0 4 |
0.8 |
0.4 |
0.0 |
1.5 | 1
	 	 	 1 	 	 	 	 	
0.6 | 1
0.7 | 1
1


1
	 4.
•5 1

1

|
5 1
5 1
,
|
I

1
1
1
.1 1
	 4-
•1 1
	 4
1
1
1
1
1
5 1
5 1
	 1
< 1
CD
(—>
NJ
I
         (*) These waste streams include listed "F" and/or  "K" RCRA wastes.

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reduction (but  appear to have limited potential  for further implementation) include
recovery of silver from  film and process solutions and  switching to water-developed
lithographic plates.

10.  SUBSTITUTION ALTERNATIVES

10.1 Ink Substitution

Conventional inks used  in lithography are heat-set solvent-base  inks  which contain
coloring pigments and about 30 to 60 percent low boiling organic solvents.  Most of the
solvent is removed during the drying step  and  is either emitted into the air, recycled,
or incinerated.  New types of ink are described below.  These were formulated  with air
pollution reduction (particularly solvent emissions reduction) and energy conservation
as a goal.

     o    Water-base inks.
           Also called water-borne inks, these inks are usually pigmented suspensions
           in water.  These inks find their  greatest application in flexographic printing
           on  paper  substrates  (Campbell  and  Glenn 1982) and  their  use is also
           recommended fos gravure*  (water-base  inks are not  available  yet for
           lithography).

           One factor stifling the development of water-base  inks is that they require
           more  energy  to dry than do solvent-borne  inks.  Another difficulty results
           from  the necessity  to shut presses down for short periods of time. During
           this period the ink dries, and since  water is not a solvent for the dried ink,
           more  frequent equipment cleaning is  required.  Other problems besetting
           water-borne inks are low gloss and paper curl.

     o    UV-cured  inks.
           These inks consist of one  or more monomers  and  a  photosynthesizer that
           selectively absorbs  energy.  Benefits of  using UV inks are that  the inks
           contain no solvent.   The paper is not  heated above 50° C, and a minimum
           of moisture is lost in the process (Carpenter and Milliard 1976, Shahidi and
    National Printing Ink Research Institute 1985: Personal communication.
                                   B12-21

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Rowanda 1975, Bassemir 1974).  Since the inks do not "cure" until exposed
to UV light, and  may therefore be allowed to remain in  the ink  fountains
(and plates) for long periods of time, the need for clean-up is reduced. UV
inks are particularly attractive for letterpress and lithography applications.
The following  have been cited as advantages of using UV  inks for sheet-fed
lithography (Carpenter and Milliard 1976):

-   Elimination of "set-off",  the unintentional  transfer of ink to adjacent
    sheets before  the ink has dried up completely.

    Elimination of the use of powders  that  are  applied to protect an ink
    film that is "set" but not "dry".

    Elimination of the storage of printed sheets for  ventilation required in
    oxidative drying processes.

The disadvantages of the UV-cured  inks include:

    Cost  (75  to  100 percent  more  expensive than  conventional heat-set
    inks).

    Hazards of UV to operating personnel.

    Formation  of ozone by  the action of UV light on oxygen.

    Conventional  commercial paper  recycling process will not remove the
    UV-cured ink  which  hinders recyclability  of the paper printed  with this
    method.

    Some chemicals used to formulate the ink are  toxic.

Electron-beam-dried (EB) inks.
The "low-energy" EB system was  developed by Energy  Sciences Inc.,  of
Bedford, Massachusetts.  Electri Graphics markets the Electricure system
                       B12-22

-------
           which is  claimed to operate at  a  much lower energy than the EB system.
           Many advantages are claimed over the use of conventional heat-set ink and
           other curing systems (Perino 1976, De Young 1976).  Like UV curing, EB
           curing causes  resins to crosslink.  Inks can be  applied as fluid monomers
           and rapidly converted to  tough, solid polymers.  The fluidity  of  the resin
           eliminates the need  for solvent.  UV  ink can be converted  to  EB-curable,
           but little has been done to develop EB-curable  coatings for use where UV
           does not appear practicable.   The  disadvantage in EB systems  is  the
           degradation  of  paper  and  the  generation  of  x-rays  that  necessitates
           elaborate and  expensive operator  protection (Carpenter and Hillard 1976,
           Anonymous 1975).

           Heat-reactive  inks.
           These inks contain a pre-polymer, a cross-linking resin, and a catalyst. The
           catalyst activates at 350°F in the dryer and converts the liquid into a solid
           polymeric film via  condensation polymerization reactions.  Reaction by-
           products  are principally C^-C^  alcohols,  moisture,  and  small  amounts of
           formaldehyde.   Overall volatile  content of these inks is 20 percent or less
           of  that  of  the conventional heat-set inks.   The  smoking tendency was
           reported  to be practically nil.   Because heat is required for drying, these
           inks cannot be used on sheet-fed presses.  Moreover, they are  reported to
           permit build up of static electricity in the folding operation (Carpenter and
           Hillard, 1976).
10.2 Equipment Substitution
           Electrostatic screen printing process.
           Also  known  as pressureless printing,  this process was developed by  the
           Electrostatic Printing Corporation of America and therefore  is called  the
           EPC  process (USEPA 1979b).   A thin,  flexible  printing element, with  a
           finely screened opening  defining the  image to  be  printed, is used.   An
           electric field is established between the image element and the surface to
           be printed.  Finely divided "electroscopic" ink particles, metered  through
           the image openings, are attracted to  the printing surface, where  they  are
           firmly held by electrostatic forces until they have been fixed by heat or by
           chemical means.
                                  B12-23

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           Other alternatives  to  conventional printing  include "desk-top" publishing
           using  micromputers  with  laser printers - development seen by  some  as
           presenting a serious future competition to small printing shops.


11.  CONCLUSIONS


The  industry has significantly reduced  non-paper waste as  evidenced by a current
reduction index of 2.5 (63 percent). Estimates indicate that  future waste  reductions
are expected to be moderate as characterized by a future reduction index of 0.7 to 1.4

(18 to 35 percent). Several methods that appear to be quite effective  for the industry
as a whole include implementation of better operating practices, recycling of empty
ink containers, and the continued  or increased  recycling of silver, solvent, and waste

ink.  For those waste reduction measures that could be used by the gravure  industry to
reduce waste  due to their  electroplating  operations, the reader  is  referred to  the
process studies on electroplating, metal parts cleaning, and metal surface finishing.


12.  REFERENCES

Anonymous. 1973. UV cure cuts pollution, energy use.  Envr. Sci. Tech. 7(6).

	.  1975.   Curing ink with  electron beams.   Business Week.
March 24, 1975.
                         1977.   Electronic ink curing can  reduce costs improving
quality. Inland Printer/American Lithographer.  March 1977.
                        1985.  American Printer's top one hundred plus.   American
Printer.  194(4): 61-76.

Bassemir, R.W. 1974.   UV  ink chemistry: paper  and paperbook.  Amer.  Ink. Maker.
December 1974.

Berustein,  M. 1977.  From  splitting atoms to curing inks.  Screen Printing.  August
1977.

Bohon,  R.L.  1976.  Lithography:  laboratory evaluation  of  environmental risk.   In
Environmental  aspects  of chemical use  in printing  operations.   EPA-560-1-75-005.
Washington D.C.:   U.S. Environmental Protection Agency.

Bruno,  Michael H.  1985.  Status of  printing in the  U5A--1985.   IARIGAI,  18th
International Conference. Williamsburg, Virginia, U.S.A. (June 2-8, 1985).

Campbell, M.E., and Glenn, W.M.  1982.  Profit from pollution prevention; a guide to
industrial  waste   reduction  and  recycling.    Toronto,   Canada:    Pollution  Probe
Foundation.
                                   B12-24

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Carpenter, B.H., and Milliard, G. 1976.  Overview of printing processes and chemicals
used.  In Environmental aspects of chemical use in printing operations. EPA-560-1-75-
005. Washington D.C.: U.S. Environmental Protection Agency.

De Young, S. 1976. Electricure vs. ultraviolet printing.  Amer. Ink. Maker.  February
1976.

Huisingh, D., et al. 1985.  Proven profit from pollution prevention.  Washington, D.C.:
the Institute for Local Self-Reliance.

Latus,  S.  1976.  Platemaking  and  its effect  on the  environment.  In Environmental
aspects of chemical use in printing operations.  EPA-560-1-75-005.  Washington D.C.:
U.S. Environmental Protection Agency.

Magee, B.  1985.   Environmental control report.  Graphic Arts Technical Foundation.
55:1-4.

Perino, D.A.  1976. Nonscanning thermoionic  emission—what?. Paper, Film, and  Foil
Converter. March 1976.

Shahidi, I.K., and  Powanda, T.M.  1975. Ultraviolet curing: a review of the technology.
Amer.  Ink. Maker. January 1975.

Stevenson, G.A., ed. 1968.  Graphic art encyclopedia.  New  York, N.Y.:  McGraw Hill
Book Co.

USDC.   1972.   U.S.  Department of Commerce.   Standard industrial  classification
manual.  Washington, D.C.:  U.S. Government Printing Office.

	_.   1985a.  U.S. Department  of  Commerce.  Bureau of the
Census.   Commercial Printing and manifold  business  forms.   In 1982  Census of
manufacturers. MC82-I-27B.  Washington, D.C.: U.S. Government Printing Office.

	.  1985b.  U.S. Department of Commerce, Bureau of the Census.
Greeting cards, bookbinding, printing trade services.  In 1982 Census of manufacturers.
MC82-I-27C. Washington, D.C.: U.S. Government Printing Office.

	.  1985c.  U.S. Department of Commerce, Bureau of the Census.
Newspapers,  periodicals, books,  and  miscellaneous  publishing.   In 1982  Census of
manufacturers. MC82-I-27A. Washington, D.C.: U.S. Government Printing Office.

	_	.   1985d.   U.S.  Department of Commerce, Bureau  of  the
Census.  In 1982  Census of  manufacturers, geographic area series (various states).
Washington, D.C.:  U.S. Government Printing Office.

USEPA 1976.   U.S. Environmental  Protection Agency.   Environmental aspects of
chemical  use  in  printing operations.   EPA-560-1-75-005.   Washington, D.C.:  U.S.
Environmental Protection Agency.

		.  1979a. U.S. Environmental Protection Agency.  Compilation
of air  pollutant factors.  3rd ed. Research Triangle Park, N.C.:  U.S.  Environmental
Protection Agency.
                                  B12-25

-------
	•  1979b.  U.S. Environmental Protection Agency.  Graphic arts;
an  AP-42  update.   EPA-450-4-79-014.    Research  Triangle  Park,  N.C.:    U.S.
Environmental Protection Agency.

Zborowsky, J.L. 1976. Current status of Web heat set emission control technology. In
Environmental  aspects of chemical use in printing  operations.   EPA-560-1-75-005.
Washington D.C.: U.S. Environmental Protection Agency.


13.  INDUSTRY CONTACTS

G.J. Bender,  Technical Director, Manufacturing  Engineering, R.R. Donnelley & Sons
Co., Chicago, IL.

Dr. W.D. Schaeffer,  Research  Director,  Graphic  Arts Technical Foundation,  Inc.,
Pittsburgh, PA.

H.F. George.  Exec. Vice-President  & Research Director.  Gravure Research Institute,
Inc., Port Washington, NY.

Dr. J.W.  Vanderhoff, National Printing Ink Research Institute, Lehigh University,  PA.

B. Ryerson, Printing Industries Association,  Los Angeles, CA.

S. Marshall, Printing Industries of America,  Arlington, VA.
                                  R12-26

-------
1.    PROCESS: SYNTHETIC FIBERS MANUFACTURE
2.    SIC CODE:  2824
3.    INDUSTRY DESCRIPTION

By definition, SIC 2824 includes establishments involved in the production of synthetic
(or more commonly called man-made) noncellulosic organic fibers.   Cellulosic fibers
such as  acetate  and  rayon and  the noncellulosic inorganic fibers  such as boron,
fiberglass, and graphite are excluded. Included in SIC 2824 are acrylic and modacrylic
fiber, nylon, olefin (such  as polyethylene and polypropylene), and polyester. These four
fiber types comprise more than 99 percent of the  total man-made  fiber produced in
the United States (Farr 1977).

The  manner  in which fiber production  is carried out  involves a  small  degree of
integration between  fiber  producer and  user.   Fiber production begins with  the
production of a polymer solution and ends with the packaging and shipment of the fiber
to a converter or downstream processor.  It is the converter or  downstream processor
who twists the fiber into cord, dyes it, weaves it, and knits it.  Fiber manufacturers
who do not produce their own polymer purchase  it in flake or pellet form  from a
supplier. - Hdwever, the  majority of fiber producing  operations are fully  integrated
with the polymerization operation.

3.1  Company Size Distribution

In the  U.S., synthetic  fibers are currently produced by 28 companies  which  own and
operate a total of 71 facilities.  The synthetic fiber industry employs approximately
60,000 people (USDC 1985).

3.2  Principal Producers

Table 3-1 lists the ten largest producers of synthetic  fibers and their major products.
These ten companies account for about  85 percent of the  total capacity of organic
man-made fibers in the United  States.
                                  B13-1

-------
      Table 3-1 Major U.S. Producers of Man-Made Organic in Fibers in (1981)
Major Products and Capacities (millions Ib/yr.)
Producer
Akzona Inc.
Allied Chemical Corp.
American Hoechst Corp.
Badische Corp.
E.I. du Pont de Nemours
& Co., Inc.
Eastman Kodak Co.
Fiber Industries Inc.
Hercules Incorporated
Monsanto Co.
Standard Oil Co. (Indiana)
Total
Acrylic

--
--
70

317
40
--
--
315
--
742
Nylon
210
455
--
145

1375
--
--
--
560
--
2745
Olefin
15
--
--
--

--
--
--
130
__
215
360
Polyester
147
80
460
--

1623
540
1406
-_
120
--
4376
Source:    Chemical Economics Handbook (SRI 1982).

3.3  Geographical Distribution

Of the 71 plants in operation in 1982, 44 were located in the states of North Carolina,
South Carolina, Virginia, and Tennessee (USDC 1985).  The remaining 27 plants were
located in several adjoining states such as Georgia, Alabama, and Maryland.  These
fiber producers are mostly concentrated in EPA regions III and IV.  Figure 3-1 depicts
a geographical distribution of these producers.

4.   PRODUCTS AND THEIR USE

Man-made fibers are broken into two major categories which can be further subdivided
as shown below:
                                           acetate
                           cellulosic        rayon
              Man-made
                           noncellulosic  -  inorganic
                                           organic
                                  B13-2

-------
                           VIII
CO
1—"
CO

oo
           0
                izzu o-
2-5
6-10
11-20
                    Roman numerals show EPA regions

      Figure   3-1 Synthetic Fiber Plants in the U.S.

-------
Noncellulosic organic fibers (SIC 2824) include acrylic  and modacrylic  fiber,  nylon,
olefin,  and polyester.   Modacrylic  fiber is composed  of  at least 85%  by  weight
acrylonitrile.  Nylon is a polyamide in which less than 85% of the amide linkages are
attached directly to two aromatic rings. Olefin is composed of at least  85% by weight
ethylene, propylene, or other olefins.    Polyester  is composed  of  at least 85% by
weight  of an ester  of  a substituted aromatic  carboxylic  acid (including  but not
restricted  to substituted  terephthalate units and  parasubstituted hydroxy-benzoate
units).

Fibers are generally marketed as yarn, staple, or tow.  Other forms are  monofilament,
split film, fiberfill, and nonwoven fabrics.  The major end uses of  man-made fibers are
shown in Table 4-1.  About half of  the synthetic fiber produced  goes into the making
of knit and  woven  apparel, about  30 percent  goes for home  furnishings, and the
remainder for  various  industrial  uses.  Over 80 percent of  the  fiber used in home
furnishings is for rugs, carpets, and carpet backing.  Most of the remainder is used for
draperies and  upholstery.   The  major  industrial  use  of  man-made fibers  is for
automobile tire cord.  Other uses  of these fibers are automobile  seat covers, belting,
electrical wire insulation, hose, recreational surfaces, roofing, rope and twine, sewing
thread, tents, parachutes, sails, tarps,  and webbing for outdoor furniture.

5.            RAW MATERIALS

Relatively pure raw materials are required to produce man-made  fibers  because  of the
deleterious  effect  of impurities  on  the  properties  of  the  fiber.  The  monomers
(described  above) are derived from  basic petrochemicals such as benzene, butadiene,
ethylene,  propylene,  and  xylene.  Table 5-1 presents  a  list of monomers and other
intermediate products from which  the  fiber-forming polymers are  produced.

Many additives are blended with the polymer before fiber  production.  Examples are
delustrants,  pigments,  dyeing  assistants,  dye receptors,  optical brighteners,  heat
stabilizers, antioxidant stabilizers, and light  stabilizers.  Ordinarily, the total amount
of additives does not exceed  five percent.  Materials added  to the  fiber to enhance
product  utility  include  lubricating  agents, bacteriostats,  humectants,  anti-static
agents,  and other additives. Table 5-2 contains a list of some additives  added to man-
made fibers to increase their usefulness.
                                   B13-4

-------
                                                      Table 4-1 Synthetic Fiber Product and Their Use in million tt>s./yr.
CD
i
vn
Acrylic/
Modacrvlic



Apparel
Knit
Woven
Home Furnishing
Carpets/Rugs
Curtains arid
Draperies
Upholstery
Other
Industrial
Rubber Industry
Nonwovens
Rope and Cordage
Fiberfill
Other
Total
Staple
and
Tow
467
461
6
111
n.a.

14
9
88
7
1
--
1
5
585

Filament,
Monofilament
383
324
59
740
715

1
24
1
366
232
1
28
„.
105

Nylon

Textured
Yard
149
147
2
12



12
6
2
1
..
3


Stable
and
Tow
17
3
14
659
632

25
2
35
13

--
33




Total
549
474
75
1,411
1,347

1
49
15
407
234
14
29
--
130
2,367

Filament,
Texturized
Yarn
1,667
1,054
613
152
--

62
13
77
310
191
1
13
--
105

Polyester
Stable
and
Tow
1,096
318
778
513
120

48
10
335
461
150
2
205
309




Total
2,763
1,372
1,391
665
120

110
23
412
771
191
150
15
205
414
4,199
Polyolefin
Yarn, Mono Stable
filament and and
Fiber Film Tow
11
11
-- - -
326 77
287 62

39 15
_ — — —
275 38
1
31 35
84
--
159 3




Total
11
11
*" ~
403
349

54

313
1
66
84
~~
162
727
        Source:    Chemical Fconomics Handbook (SRI 19B2).

-------
  Table 5-1  Input Raw Materials for Production of Organic Man-Made Fibers in 1982
 Raw  Material
                                                              Consumption
                                                              million Ib/yr
Acrylonitrile
Caprolactam (nylon 6)
Adipic acid + hexamethylenediamine (nylon 6,6)
Glycols (ethylene, propylene, etc.)
Dimethyl terephthalate (DMT)
Terephtalic acid (TPA)
                        743
                        840
                       1860
                       1362
                       1560
                       1386
Source:    1982 Census of Manufacturers (USDC 1985).
      Table 5-2  Typical Additives Used in Organic Man-Made Fiber Production
Delustrants

Optical brighteners


Antioxidant stabilizers




Light stabilizers


Dyeing assistants




Lubricants and other finishes
Usually titanium dioxide

Stilbene
Phenyl coumarin derivatives

Alkylated phenols
p-cresols mixed with sulfides
Thio compounds such as dilauryl or
 distearyl thio dipropionate

Long-chain alkyl derivatives of
 hydroxybenzophenones

2-methyl 5-vinyl pyridine
2-vinyl pyridine
p-vinyl-benzene sulfonic acid
sulphocinamic acid

Polyoxyethylene attached to
 aliphatic hydrocarbon
Long-chain alkyl quartenary ammonium
 salts
Hydroxyalkyl amine salts of fatty
 acids
Aliphatic esters
Hydrocarbons
Fluid silicones
Source:    Industrial Process Profiles for Environmental Use (Farr 1977).
                                  B13-6

-------
For some fibers,  solvents are mixed with the polymer in order to obtain a liquid
solution amendable to fiber formation.  These solvents invariably are recovered and
recycled.   Solvent  is  almost exclusively  used  for the production  of  acrylics and
modacrylics.       The   most   widely   used   solvents   are   dimethylacetamide,
dimethylformamide,  acrylonitrile,   acetone,  aqueous   ZnCl£,  aqueous  NaSCN,
tetramethylene sulfane.

6.   PROCESS DESCRIPTION

Man-made  fibers  are formed  primarily by  three different  processes:  melt spinning,
wet solution spinning, and dry  solution spinning. Wet and dry solution spinning are used
for producing acrylic and modacrylic fibers.  Melt spinning is used for producing nylon,
polyester,  and   polyolefin   fibers.    A  summary   of   production   methods   for
acrylic/modacrylic fibers is given in  Tables 6-1 and 6-2.

                        Table 6-1  Acrylic Fiber Processes
Spinning
process
Dry
Wet
Wet
Wet
Wet
Wet
Wet
Wet
Solvent
Dimethylformamide
Dimethylformamide
Dimethylacetamide
Aqueous NaSCN
Aqueous HNO3
Aqueous ZnCl2
Dimethyl sulfoxide
Ethylene carbonate
World
capacity, %
22
11
23
23
12
4
3
2
Source: Kirk-Othmer Encyclopedia of Chemical Technology, 3rd. Ed. (Roberts 1980)
                                    B13-7

-------
                                      Table 6-2 Acrylic and Modacrylic Fiber Production Routes
Company
Acrylic Fibers
American Cyanamid
Company
Dow Badische Company
E.I. du Pont de Nemours
& Company, Inc.
Monsanto Company
2 Modacrylic Fibers
OJ
i
00 E.I. du Pont de Nemours
& Company, Inc.
Eastman Chemical
Products, Inc.
Monsanto Company^8)

Typical Chemical
Registered Composition of
Trade Name Fiber
Cresland 89-90% Acrylonitrile
8% Methyl Methacrylate
Zefran 87-90% Acrylonitrile
8% Methyl Acrylate
2-5% Other
Orion 88-91% Arcylonitrile
7% Methyl Acrylate
2-5% Other
Acrilan 88-91% Acrylonitrile
8-10% Vinyl Acetate
2-4% Other
Orion FLR 66-70% Acrylonitrile
30% Vinyl Chloride
0-4% Other
Verel 37% Acrylonitrile
40% Vinylidene Chloride
20% Isopropylarcylamide
3% Methyl Acrylate
Elura 76-78% Acrylonitrile
20% Vinyl Acetate
2-4% Other
SEE 79-81% Acrylonitrile
8% Vinylidene Chloride
9% Vinyl Bromide
2-4% Other
Polymerization
Medium
Solution
Solution
Suspension
Suspension
Suspension
Solution
Suspension
Suspension
Type of Type of
Polymerization Spinning
Operation Process
Continuous Wet
Continuous Wet
Continuous Dry
Batch Wet
Continuous Dry
Batch Dry
Batch Wet
Batch Wet
Spinning
Solvent
Aqueous
NaSCM
Aqueous
ZnCl?
DMF
DMAc
DMF
Acetone
DMAc
DMAc
Source:    (SRI 1982).
(a'In addition, Monsanto also has two other modacrylic fibers, known as type 65 and type 67.

-------
Fiber production begins  with  the  production of polymer in a polymerization reactor.
This reactor can be operated  either in a batch or continuous mode depending  on the
type of polymer being produced. The major route  for polymerization of acrylonitrile is
as a  water  emulsion.   Most  of  the water  formed is  subsequently  used  in  other
operations.   By-products of polymerization also occur with the manufacture of nylon
6,6 and polyester.   Most of  these  by-products  also find use  in  other  parts  of the
process. For many  other polymers, no by-products are formed.

The choice of spinning method employed depends  primarily on polymer characteristics
such as melting point, melt stability, and solubility in different  solvents.  The  fiber
formation step is accomplished by  the extrusion of polymer in liquid form through fine
orifices called spinnerets.   The manner in which the polymer is liquefied determines
the manner  in  which the  extruded filaments are  solidified.   Figure  6-1 shows  a
simplified  pictorial representation  of man-made  fiber manufacturing operations,
excluding the polymerization reaction.

In keeping with its name, melt spinning begins with molten polymer.  This  process is
used  for  polymers which  can  be  melted  under reasonable   conditions  without
degradation, such as nylon, polyester, and olefin filaments.

Most  melt spinning is integrated  with polymerization  units  that  supply the spinning
operation with molten polymer.   The molten  polymer  is  metered through accurately
machined gear pumps to  filter assemblies consisting of either a series of  metal gauzes
or layers of graded sand.   The filtered polymer  is then extruded  under high pressure
and at  a constant  rate  through a nickel or stainless steel  spinneret.  The extruded
liquid  polymer streams  are cooled  using  an air  stream  and the  solid filaments thus
formed converge at a guide  to yield spun yarn.   For  fibers such as nylon 6,6, the
filaments pass through a steam conditioning tube before converging.

Wet solution spinning is  used  to produce filaments from polymer  by extrusion into  a
liquid  coagulation   bath.    This  production  method   is  usually  reserved  for the
manufacture of heavy  tow,  which  requires slower spinning and  processing speeds than
in  melt or  dry  spinning.    This  method is  used  primarily  to produce  acrylic and
modacrylic tow.
                                   B13-9

-------
MELT
SPIN

TRANSFER

MAAA/W\





©



1 HEATER '
DRY
SPIN
                                                  SPINNERET —
                                              AIR STREAM
                                               COOLINE
MET
SPIN
\
SOLVENT
>
DISSOLVER



FILTER
               MAKE-UP
               SOLVENT
OISSOLVER
                             FILTER
                                                           STEAM,HOT  MATER
                                                            OR HOT INERT
                                                               LIQUID
                                                                  LUBRICANT
•ASHING
©


LUBHICA -
TION


DRAWING
©


                                                                          SOLVENT LEAN
                                                                             VAPOR
                                                                          SOLVENT RICHt
                                                                             VAPOR
                                                                     PROCESS  HASTE  CATEGORIES

                                                                     ©    SOLID  KASTE
                                                                     (5)    KASTEHATER
                                                                     (7)    SPENT  SOLVENT
                            Figure 6- 1  Synthetic  Fiber Hanufacturing Block Flow Diagram
                                          B13-10

-------
Equipment required for wet spinning includes a  solution vessel, a metering  pump, a
filter, a spinneret,  and  a coagulant tank. Aging of the polymer solution (a mixture of
polymer and  organic or inorganic solvent) before  spinning requires a holding tank. All
wet spinning  processes  include a washing step immediately after extrusion  to remove
solvent  and other  impurities,  and a recovery system to separate the coagulant and
solvent.  Four specific methods of wet solution  spinning have been described in the
literature (Monorieff 1975).  As  an example, one of the four methods presented by
Monorieff is listed below:

           An 18 percent  solution of polymer  in dimethylacetamide  is spun into a
           mixture  of  2  parts  dimethylacetamide  and  1 part  water;  as the  yarn
           emerges from  the bath  it  is washed with water, which  flows  counter-
           currently into the spinning bath at such a rate that the bath composition is
           kept  constant;  dimethylacetamide  is  continually  being  added  by the
           polymer as it is extruded; water is being added from the wash.

Dry  solution  spinning  is the  third  process  for  converting  polymer   into filament.
Polymer is dissolved in  solvent and the polymer solution is then extruded into a zone of
heated  gas or vapor.   The volatile solvent  readily  evaporates,  leaving a  solidifed
filament which is then further processed.   This  process is used  for easily dissolved
polymers such as acrylonitrile, polyvinyl chloride,  or polyurethane.

Gear pumps,  filter packs, and spinnerets are used  in much the same fashion as  they are
in melt spinning.   After leaving the spinneret, the solution passes through a  spinning
cell  which consists of a cabinet about 25 feet long.   Hot, solvent-lean, gas  or  vapor
enters at  one end and solvent-rich gas or vapor emerges from the other.  An  efficient
solvent recovery  system is required.

The  three  basic finishing steps after fiber spinning are lubrication, drawing, and fiber
modification.  The application of a lubricant immediately after  filament formation
improves  subsequent handling and processing.  The three main functions of lubrication
are  surface  lubrication, plasticizing action, and static protection.   Lubricants are
generally   aqueous  solutions, emulsions, or  organic  liquids.   From a holding  tank,
lubricant is circulated into feeding traps where it wets ceramic wheel applicators that
coat the fiber surfaces.
                                  B13-11

-------
Drawing introduces  molecular  orientation to the fiber (this causes crystalization and
increases density), thus producing  a stronger fiber.  Fibers are drawn by  stretching
between pairs of rolls, with the second set moving faster than the first in order to
collect  the drawn fiber.  Drawn lengths are from 2-7 times spun length.  Many fibers
are drawn as an integral part  of the  spinning process.   The drawing process may be
aided by heating the fibers either through direct metal-to-fiber contact, by passing the
fibers through  a bath containing a heated liquid, or by passing  the fibers  through a
steam jet.  In  some  cases, drawing may  be combined  with other processes such as
cleaning or lubrication.

The  function  of  the  fiber modification  step is to  add attributes necessary for a
marketable product.  Modifications include twisting  to produce interfilament cohesion,
heat setting or heat relaxation  to produce dimensional stability, crimping to add bulk
and resilience,  or cutting to produce staple products similar to natural fibers.  Other
processing steps sometimes utilized are treating  with water-repellant, fire  retardant,
or other finishes.

7.   WASTE DESCRIPTION

The primary specific wastes associated with the  manufacturing of synthetic fibers are
listed in Table 7-1.  Relatively  little data was available  on the environmental impact
of the  man-made fibers industry (Farr 1977).   The  same remains  true  today.   The
polymer materials are not toxic or otherwise hazardous  unless heated to temperatures
at which  decomposition  can occur.  Wastes  from the fiber industry usually  arise from
mechanical  treatment of the polymer or are associated  with auxiliary materials used
in processing such as solvents,  additives, lubricants, or finishes.  Companies which use
integrated  polymerization spinning  systems also  produce  waste  which  contains
unreacted monomer.

Most  of the solid waste  is waste fiber that  is generated during startup of the process
or during times of upset.  This waste fiber can be generated  at the spinning, drawing,
and  fiber modification  steps.   In the past, much of this waste was  incinerated or
landfilled. Currently, much of  this waste is reprocessed  either on-site (converted back
into  polymer and respun) or off-site (production of plastic bottles, for example). When
waste fiber contains highly degraded polymer or has become  heavily contaminated
with machine oil or dirt, then it is incinerated or  landfilled.
                                 B13-12

-------
                                          Table 7-1  Synthetic Fibers Manufacturing Process Wastes
      No.
  Waste Description
      Process Origin
    Composition
RCRA
Codes
CO
      1.
      2.
      3.
      4.
Solid wastes
Solvent vapor
Contaminated solvent
Contaminated coagulant
bath
Filtration; pump seals; waste
fiber; incineration residue
Evaporation from fiber;
scrubber loss

Solvent purification and
recovery

Wet spinning
Polymer, filter sand;
fiber finishers; Ti
others

Solvents (see Section 5)
Solvents (see Section 5)
Water; glycerol; CaCl2;
dimethylacetamide;
others
      5.


      6.


      7.


      8.

      9.
Contaminated drawing
bath

Polymerization by-
products

Wastewater
Spills/leaks

Air emissions
Wet drawing
Nylon 6,6 polymerization,
polyester from TPA

Coagulant bath treatment;
polymerization by-product

Undefined

Scrubber; steam jets; tank
breathers; evaporation from
fiber
Water; glycerol; CaCl2;
dimethylacetamide; others

Contaminated water
Contaminated water
Water

Mostly solvent and in-
cineration products

-------
Wastewater  is  generated whenever  the level of  contaminants  in the  inorganic
coagulant, washing, or drawing batch becomes an unacceptable and purging is required.
Usually, drawing bath purges can be treated and used as make-up to the washing bath.
In addition, washing  bath  purges can also be treated and  used  as make-up to the
coagulant bath provided a water-based coagulant is being used.  Many of the impurities
(solvent carried into  the washing bath by the fiber, for example)  can be recovered
during treatment and be  recycled  to  the  appropriate operation.  When the need for
water  in a previous step  does not exist,  the wastewater can be used to formulate
finishes.   Since the  fiber absorbs some  water  during  processing, there  is usually a
constant demand for water in the finishing operation.  Only  the  purging  of the
inorganic coagulant bath produces a major wastewater  steam that requires treatment
and subsequent disposal.

Wastewater ia also  generated as a by-product of certain polymerization reactions.
With the production of nylon  or the polymerization of acrylonitrile, most  of the water
produced is used elsewhere in the facility. With polyester, the by-products depend on
the starting  monomer.  If terephtalic acid  is used,  the by-products  are  water and
glycol.  If dimethyl terephthalate  is used, the  by-products  are methanol and glycol.
Glycol is recycled within the  polymerization process while  methanol  is usually sold for
reprocessing back into DMT or used as  fuel.

Fiber manufacturers try to limit  the escape of organic solvent  from their processes to
the fullest degree practical  because of economic,  safety  and  regulatory compliance
considerations.  For this reason,  most solvent losses are either accidental or occur at
very low levels of concentration (scrubber exhausts), where further  recovery becomes
unfeasible.   Bottoms from  the  solvent recovery operation used in  wet  spinning  is
usually incinerated.   When inorganic solvents are used, the contaminated solvent  is
discharged to the facilities wastewater treatment system.

8.    WASTE GENERATION RATES

As  stated earlier, very little data was  available on specific waste generation rates
from synthetic fiber production facilities.  Waste stream information was  given mainly
in the form  of general comments related  to  production of  a  particular fiber.   It
appears that  aqueous emissions from wet  spinning processes  (coagulation  bath purges)
represent the largest potential source of  emissions.  Next,  is  by-product water from
polymerization.
                                  B13-14

-------
To a great extent, purge rates from coagulation baths depend on the type of bath and
the age of the manufacturing plant.  Glycol baths are less likely  to be discarded than
calcium chloride baths, due to the greater value of the glycol.  The age of the plant
comes  into  play because  early  designs  did  not incorporate  features  for  reusing
coagulation baths to the extent that those  features would be incorporated today.

By-product  water  from  polymerization,  by  its   nature,   must  contain  organic
contaminants.  These contaminants  would conist of the monomers used in producing
the polymer.  Table 8-1 gives wastewater generation  rates for nylon 6,6 and polyester
from TPA. The values are based on the stoichiometry  of the chemical reactions.  A
fair amount of this water is used where water containing small quantities of organic
matter is not objectionable (n some finishes, for example).

                   Table 8-1 Stoichiometric By-Product Water

                                                       By-Product Water
                  Fiber                                 (gal/10-5 Ibs fiber)

           Nylon 6,6                                             9.5
           Polyester from TPA                                  22.7
                *

Wastewater emissions from some operations have been classified according to waste
load and  treatability (Farr  1977).   This  information  is  summarized  in  Table  8-2.
Analysis of samples  from  a settling pond  at  an acrylic fiber production facility
indicated  the presence of acrylonitrile (100  mg/1), 2,3-dibromo-l-propanol (0.5 mgl/1),
an isomer of dibromopropene, and 2,4-dimethyl-diphenylsulfone.

            Table 8-2 Summary of Wastewater Data for Selected Fibers

                             Wastewater       Raw Waste Loads (Ib 103 product)
                                                                    Suspended
Fiber                      (gal/103 Ib fiber)      BOD        COD      Solids

Nylon                        0.16-3.71          0.1-60      0.2-90    0.1-6.0
Olefin (polypropylene)         1.00-1.71          0.4-1.1     1.8-2.6   0.2-2.2
Source: Industrial Process Profiles for Environmental Use (Farr  1977).
                                  B13-15

-------
Overall current waste generation rates for the fiber manufacturing industry were not
in evidence at the  time of final  document preparation.  Fractional waste generation
(the fraction each waste represents of the  total waste generated) was estimated by the
project staff based  on the available data and engineering judgement.  These values are
shown in Table 9-1.

9.    WASTE REDUCTION THROUGH SOURCE CONTROL

9.1   Description of Techniques

A summary of the  waste sources and the corresponding source reduction methods is
given in Table 9-1.  This section deals with  the description of the  listed methods,
including known application cases.

In addition  to  the  waste reduction  measures  classified as being process changes or
material/product substitutions, a  variety of waste reducing measures labeled as "good
operating practices" has also been included.  Good operating practices are defined as
being procedural or institutional  policies which result  in  a reduction of waste.  The
following items highlight the scope of good operating practice:

      o     Waste stream segregation
      o     Personnel practices
                management  initiatives
                employee training
      o     Procedural measures
                documentation
                material handling and storage
                material tracking and inventory control
                scheduling
      o     Loss prevention practices
                spill prevention
                preventive maintenance
                emergency preparedness

For each  waste stream, good  operating practice applies  whether it is  listed or  not.
Separate listings have been provided whenever case studies were identified.
                                 B13-16

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9.1.1   Solid Wastes

Fiber spinning operations generate solid wastes including filter residues  and waste
fibers. The filter residue wastes are generally minor compared to waste fiber.  Waste
fiber  comes  mostly  from  process  upsets or  during  spinning  machine  startups.
Mechanical fiber modification operations, such as twisting, crimping, or cutting, also
produce solid  waste in the form of particulates and waste fiber.  Several methods for
waste reduction through  source control were noted:

     o     Recycle waste fiber.
           Waste fiber that does not contain surface finish materials is relatively easy
           to   reprocess.   In the  case  of polyester,   it can  be  sold  to  a  PET
           (polyethylene terephthalate) bottle reprocessor.  In the case of all thermo-
           plastics, this fiber  can be  remelted and  respun,  but  a loss  of  quality
           generally  results  due  to  thermal degradation.   At  least  one company
           markets a processor for chopping up thermoplastic waste and pelletizing it.
           Clean acrylic waste is easily redissolved and respun; the economics of this
           are so clearly in favor of it, in fact, that it is widely practiced.

           Waste fiber containing surface finishes is often reprocessed by washing the
           fiber in detergents,  chopping the wet fiber,  and flash drying it.  In  those
           cases where  waste fiber cannot  be recycled due to surface contamination,
           the causes for surface contamination should be identified and eliminated.

      o    Increased automation
           The revolution now  underway  in electronics has spawned a new generation
           of  instruments such  as  tenacity  gauges,   optical   inspection  devices,
           differential thermal analysers, etc. that can be employed to catch process
           upsets at an early  stage.

      o    Good operating practices
           Good operating practices  include determination of the causes for process
           upsets  and  their  subsequent  minimization,  examination  of  start up
           procedures,  identification  of devices and  methods  that will  cut  waste
           production, and commitment to an effort to develop additional methods of
                                  B13-17

-------
           salvaging  off-grade  fiber.    An  accounting  system  (or  checklist)  for
           identifying origins of waste fiber appears worthy of consideration.

9.1.2       Wastewater

Fiber spinning  also  results in  the generation of liquid wastes, primarily from wet
spinning. A large portion of liquid waste occurs when the coagulation bath is entrained
on fiber surfaces into subsequent wash stages.  Liquid wastes are also generated in the
drawing and chemical fiber modification operations  and  during the polymerization
reaction of the polymer.  For ways in which aqueous wastes associated with equipment
cleaning can be  minimized,  the reader is referred to the study on equipment  cleaning
contained in this appendix.  Methods for minimizing aqueous waste include:

     o     Redesign of washers.
           The greatest potential for improved water  economy stems  from the use of
           better washing methods (Masselli 1973).  Washers should be designed to use
           only  the  amount of water  necessary  for  a  particular  step  or operation.
           Rodney-Hunt,  manufacturers  of  the  tersitrol washer, compared  their
           washer to two  tight-strand  washers and suggested that up to 85 percent
           less water use may be achievable (USEPA 1974).   •

     o     Use multistage counter-current wash system.
           By using  a multistage  counter-current wash  system,  a  large  reduction in
           the  amount of  water  required for washing  can be achieved.  Since  the
           system produces a  much more concentrated effluent stream, it  is  often
           practical to concentrate the stream (by means of evaporation) and recycle
           the  material.   In the wet spinning process, coagulant is entrained on  the
           fiber and carried over into subsequent wash  baths.  By producting a wash
           water wastestream as concentrated as  possible, the feasibility of recycling
           this waste back  to the coagulation bath can  be improved.

     o     Use oil and lubricant substitutes.
           Carding oils and antistatic  lubricants  can be  replaced by mineral oils with
           nonionic emulsifiers and other low-BOD substitutes (Masselli and Burford
           1956).   This  change  improves the treatability of  the lubricant  waste
           generated.   In  addition, this  method  improves the treatability  of  the
                                  B13-18

-------
In dry spinning, the recycled solvent does not build up objectionable impurities so that
it can  be  reused  indefinitely.   Solvent  losses occur  almost  exclusively  through
evaporation.    These  losses can  be  minimized  by  reducing  the  leakage of  non-
condensibles during spinning.

In wet  spinning, contaminated solvent becomes a  problem only  in  isolated cases.
Usually, the preferred method  for dealing with this material is to sell it back to the
solvent  supplier or to install on-site distillation equipment.

9.2  Implementation Profile

Reduction of the waste load generated by  fiber manufacturers can be accomplished to
a  large  extent  through  the  employment  of  modern instruments  and  equipment,
advanced processing techniques, and  careful identification of the  origins of waste.
Water   usage  control techniques have been extensively  studied  and  documented;
manufacturers of synthetic fibers are  expected to have applied these to a high degree
methods to reduce their wastewater load.  Additional waste reduction will come  from
improvements in  operating practices -these are the easiest to apply.

9.3  Summary

A summary of the  source  reduction  techniques along with the associated ratings is
given in Table 9-1.  The ratings represent  the assessment of the relative usefulness of
the proposed  techniques.  Each method is  rated on  an  integral scale  of 0 to 4 with
respect  to  its  waste  reduction effectiveness, extent of  current use,  and  future
application  potential.  Based  on these ratings, current and  future  waste reduction
indices  are  derived  to provide  a  measure of current and future extent of  waste
reduction for each technique, each waste stream, and the entire process.

A current reduction index (CRI) of 2.3 (58 percent)  is indicative of the high  level of
waste reductions achieved by the synthetic fibers  industry. CRI represents the  ratio
of the amount of waste that was reduced  to the amount that  would be  generated if
none  of the  measures listed  were used  at their current  level of application.   By
implementing additional source reduction  techniques,  the amount of waste currently
being generated can be reduced to a modest extent, as evidenced by a future reduction
index of 0.5  to 0.8  (13 to 20 percent). As seen from Table 9-1, the most effective
                                    B13-19

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                    TABLE 9-1  SIMWRY  OF SOURCE COHTROL HETHODOL06Y FOR THE SYNTHETIC FIBERS MNUFACTURIN6 INDUSTRY
'J3
. . ^
ho
1 I Found Documentation | Waste | Cxtent of future [ fraction of 1 Current
1 1 Quantity | Quality | Effectiveness | | Potential i I Index
Solid Wastes |1. Recycle waste fiber | 2| 2| 21 3 | 1| | 1
|2. Increased automation | 1 | 1| 3| 2 3| | 1
|3 Better operating practices 1 | 1| 3| 3 | 3 | | 2
I Overall 1.33 I 1 33 I 2 67 | 2 67 | 2.33 1 0.10 | 2
— +_
1
r
1
5 1
5 1
3 1
3 1
Wastewster |1. Redesign of washers 2 | 1 | 2 | 1 | 2 | | 0.5 |
|2. Use counter-current wash system | 2| 11 3 | 2 2| | 15|
|3. Use oil and lubricant substitutes 1 | 1 | 1 | 2 I t I | 0.5 |
|4 Fractionate by-product water | 0 i 0| t| 1 1 | | 03|
|5. Increased automation ! 1 | l| 2| 2| 21 | 10|
|6. Better operating practices | 1 | 1 | 3 | 3 3 I | 2.3 |
| Overall | 1 17 | 0.83 I 2.00 | 1.83 | 1 S3 | 0.85 | 2
Contaminated |1. Maintain solvent recovery / recycling) II !| t \ 3| 1| | 3
I Overall t.OO ( 1.00 I 4.00 I 3.00 1 1 00 1 0.05 1 3
All Sources | All Methods ' I 1.00 | 2
	 + 	 + 	 1 	 + 	 . 	 . 	 . 	 . 	
3 1
0 1
0 1
3 1
Future
Probable
0
1
0
0
0
0
0
0
0
0
0
0
0
0
	
Deduction Index
| Maximum
.' i
,ii 11
.6 1 1
6 | 1.1 |
3 | 0 8 |
8 | OS
1 1 1
2 1
.5 1 1
.6 1
.5 | 0.8
.3 | 03|
3| 03|
5 | 0.8 1
{*) These streams  include  listed  T' and/or  "K"  RCRA wastes

-------
measures  that can  be  used to  achieve  this reduction include better water usage e.g.
through redesign of washers, use of multistage  counter-current  washing,  increased
automation, and implementation of better operating practices.  Current measures that
have been very  effective include  recycling of waste  fiber,  recycling of solvent, and
good operating procedures.

10.  PRODUCT SUBSTITUTION ALTERNATIVES

From the earliest  days of  rayon, the  demand  for  man-made  fibers has continually
increased. Combined  production of polyester, nylon,  and  acrylic fibers was up about
14% from 1982 to 1983 (Greek 1983). This is a clear indication that man-made fibers
will continue to  increase in demand.
                                                    v

No viable alternatives to man-made fibers have been identified; that is  to say, man-
made fibers  possess certain physical  properties  (e.g. wear and  wrinkle resistance)
which have enabled them  to compete effectively with certain natural fibers  such  as
cotton and wool. Presently, it would be  unrealistic to assume that this trend will  ever
reverse.

11.  CONCLUSIONS

Generally, very  little documentation was found concerning the extent  to which  fiber
producers  have  implemented waste  reduction  measures.   Estimates  indicate  that
solvent recovery, waste reprocessing, and wastewater reductions are practiced widely
for economic reasons.  It should be noted that each individual fiber production  facility
may have  its own  specific production  and finishing  steps.  Therefore,  the extent  of
reduction possible in one facility may differ greatly from that in another facility.  For
the synthetic fiber  industry,  it is estimated that modest future  reduction in waste
volumes are possible. The largest reductions in waste will center on ways of decreasing
wash water use.  The industry has done  much in the area of  reducing solid and solvent
waste by recycling these materials.

12.  REFERENCES
Dixit, M.D.  1972.  Practical  Reuse of  Water in the Textile Industry. Colourage  I-IV.
April 20, 1972.
                                   B13-21

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Fair,  J.L.  1977.  Industrial process profiles for environmental use;  chapter 11.  the
synthetic fiber industry.  Radian  Corp.  EPA-600-2-77-023k.  Cincinnati, Ohio:   U.S.
Environmental Protection Agency.

Greek, B.F. 1983. Chem. Enq. News.  May 30, 1983.  p.11.

Huisingh,  D.,  Martin,  L.,  Hilger, H., et al.   1985.  Proven profit  from pollution
prevention. Washington,  D.C.: The Institute for Local Self-Reliance.

Masselli, J.W.  1973.  Textile Waste Treatment, Past, Present, and  Future.  AATCC
Symposium. Washington, D.C.:  AATCC.

Masselli, 3.W., and Burford, M.G.  1956.  Pollution sources from finishing of synthetic
fibers. Boston, Mass.:  New England Interstate Water Pollution Control Commission.

Monorieff, R.W.  1975.  New  Jersey Department of Environmental Protection, Division
of Waste Management.  Source reduction of hazardous waste.  Seminar Proceeding at
Douglas College,  Rutgers University on August 22,  1985.  New Jersey: N.J.  Depart-
ment  of Environmental Protection.

Roberts, W.J.  1980.  Fibers:  Chemicals.  In  Kirk-Othmer Encyclopedia of Chemical
Technology.  3rd ed.  Vol. 10, pp. 148-66.  New York, NY: Wiley.

SRI, 1982.  Stanford  Research Institute.  Synthetic  Fibers.  In Chemical Economic
Handbook.  Menlo Park, Calif. Stanford Research Institute.

USDC.   1985.   U.S.  Department of Commerce,  Bureau of the  Census.   Plastic
Materials,  Synthetic Rubber,  and  Man-made Fibers.  In 1982 Census of manufacturers.
MC82-I-286. Washington, D.C.: U.S. Government Printing Office.

USEPA.  1974. U.S. Environmental Protection Agency, Office  of Technology Transfer.
Upgrading  textile operation to reduce Pollution.  Vol. 1.  In-plant control of pollution.
EPA-625-3-74-004.  Cincinnati, Ohio:  U.S. Environmental Protection Agency.

13.   INDUSTRY CONTACTS

Dr. G.J. Hollod, Senior Environment Engineer, Petrochemical Department, E.I. du Pont
Nemours and Co., Wilmington, DE.
                                    BJ3-22

-------
1.    PROCESS: SYNTHETIC RUBBER MANUFACTURE
2.    SIC CODE: 2822
3.    INDUSTRY DESCRIPTION

The industry  consists of establishments primarily engaged in manufacturing synthetic
rubber by polymerization or copolymerization of monomeric  feedstock. An elastomer,
for the purpose of  this classification,  is a rubber material  capable of vulcanization,
such as copolymers  of butadiene and styrene, or butadiene and acrylonitrile, polybuta-
diene,  chloroprene  rubbers, and isobutylene-isoprene copolymers.  Butadiene copoly-
mers containing less than  50 percent butadiene are classified  in SIC 2821.   Natural
chlorinated rubbers and cyclized rubbers are considered as semi-finished  products and
are classified in SIC 3069.

3.1  Company Size Distribution

The synthetic rubber industry consists of five major producers accounting for about 75
percent of the total production in the United States.  More than 55 percent of the 77
synthetic rubber  plants employ less than 20 employees each.   Table 3-1 shows the
company size distribution of the synthetic rubber industry for 1982.

                       Table 3-1 Company Size Distribution

                        	No. of employees per facility	
                          Total     1-19    20-49     50-99     100-999   1000+
No.  of establishments       77     43        4        6            22     2
No of  employees         11,800    200     600     no data     11,000   no data

Source: 1982 Census of Manufacturers (USDC 1985).

3.2  Principal Producers

Table  3-2  lists the  major producers  of synthetic rubber  along  with  their  annual
capacity.   The  types  of  rubber  considered  are styrene-butadiene rubber  (SBR),
polybutadiene rubber (PBR), neoprene  or chloroprene rubber (CR), ethylene-propylene
                                  B14-1

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                   Table 3-2 Principal Producers of Synthetic Rubber
Company and          	Annual Capacity (Thousands of Tons)
Plant Location                  SBR   PBR    CR    EPR    IIR     IR     NBR

American Synthetic Rubber Co.
    Louisville, KY                70     50
Cities Service Co., Inc.
    Lake Charles, LA                                         38
Copolymer Rubber & Chemical Co.
    Baton Rouge, LA            125                                          5
    Addis, LA                                        33
Denka Chemical Co.
    Houston, TX                               27
E.I. du Pont de Nemours Co.
    Laplace, LA                               36
    Louisville, KY                              134
    Beaumont, TX                                     77
Exxon Co.
    Baton Rouge, LA                                  60     85
    Bayton,  TX                                              105
The Firestone Tires Rubber Co.
    Pottstown, PA               3
    Akron, OH                   50
    Lake Charles, LA            310
    Orange,  TX                  45     110
The B.F. Goodrich Co.
    Orange,  TX                         74     22
    Port Noches, TX             152
    Akron, OH                                                              14
    Louisville, KY                                                           28
The General  Tire & Rubber Co.
    Borger,  TX                  40
    Mogadore, OH                15
    Odessa,  TX                  83
The Goodyear Tire & Rubber Co.
    Calhoun, GA                 7
    Houston, TX                395                                         16
    Beaumont, TX                       115                           60
    Akron, OH                                                       3
Philips Petroleum Co.
    Borger,  TX                  96     68
Polysar Resins, Inc.
    Chattanooga, TN             30
Texas - U.S.  Chemical Co.
    Port Noches, TX             183
U.S. Steel Co.
    Scotts Bluff, LA              15
Uniroyal, Inc.
    Geismar, LA                                      44
    Paineville, OH                                                          16

    ToT^I17624     420     197    236    228    125      82

Source:    Chemical Economics Handbook (SRI 1980).
(a)        Plant not operating at present.
                                      B14-2

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rubber (EPR),  butyl  or isobutylene-isoprene rubber  (IIR),  polyisoprene  or  isoprene
rubber (IR), and nitrile or acrylonitrile-butadiene rubber (NBR).

3.3   Geographical Distribution

Since  most  synthetic  rubber  is  used  for tires  and tire products,  the industry  is
concentrated near automobile  assembly plants  in Michigan  or close to raw  material
sources in Texas.  There are twelve establishments in Texas, six each in Michigan and
Louisiana,  and four  each  in New  York,  New Jersey  and  Ohio.   The  location  of
establishments in the  U.S. is shown in Figure 3-1 and Table 3-3 below.

                  Table 3-3  Location of Facilities by EPA Region
EPA Region
I
II
III
IV
V
VI
VII
VIII
IX
Number of
Establishments
--
8
1
8
10
18
--
--
—
           National                                        77
Source: 1982 Census of Manufacturers (USDC 1985).
4.   PRODUCTS

In 1977, it was estimated that about 65 percent of the synthetic rubber produced was
used for  tires and  tire  products (Parr,  Parson, and  Phillips 1977).    The  annual
production  rates  for  some significant types  of rubber  are listed  in Table  4-1.
Table 4-2 shows the use pattern of these same types of rubber.
                                  B14-3

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                      VIII
      0
              0-1
2-5
4 6-10
11-20
               Roman numerals show EPA regions
Figure   3-1  Synthetic Rubber Plants in the U.S.

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      Table 4-1 Annual Production Rates (TRY) of Various Synthetic Rubbers
Type
Styrene-Butadiene
Rubber
Polybutadiene
Rubber
Neoprene/Polychloroprene
Rubber
Ethylene-Propylene
Rubber
Butyl Rubber
Nitrile Rubber

Abbreviation
SBR

PBR

CR

EPR

IIR
NBR

Production
TPY
1,420,000
958,000
378,000
359,000
109,900
130,000
187,400
215,000
142,000
76,000
67,000
Year
1978
1984
1978
1984
1975
1984
1983
1984
1979
1979
1984
Source:   Chemical Economics Handbook (SRI 1980), Chemical and Engineering News
         (Stimson 1985).
               Table 4-2 Use Pattern of Various Synthetic Rubbers
    Application
 Total
                  Percent Consumption
                      SBR
         PBR
        CR
                 IIR
100
100
100
100
100
                  IR
                NBR
Tires and tire
products
Automotive
application
Mechanical goods
Latex applications
Seals and gaskets
Hoses
Footwear
Wire and cable
insulation
Impact modifier
Others

63

7
18
10
--
--
--

__
--
2

84

28
5 35
__
__
__
-_

13
11
24

9

34
3
--
3
6
1

7
13
24

75

--
--
--
10
--
_-

__
--
15

55

--
13
--
3
5
10

—
--
14

--

--
--
10
25
25
5

	
--
35
100    100
Source:    Chemical Economics Handbook (SRI 1980).
                                B14-5

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5.
RAW MATERIALS
     Monomers
                        Styrene,  butadiene, chloroprene, isobutylene, isoprene,
                        acrylonitrile, ethylene,  propylene, 1,5-cyclo octadiene,
                        dimethyl  siloxane,  diisocyanates,  ethylene   glycols,
                        ethylidene norborene, 1,4-hexadiene, dicyclopentadiene,
                        methylene norborene, etc.
     Initiators
                        Potassium  peroxy disulfate, benzoyl  peroxide,  azobis
                        isobutyronitrile,  cumene  hydroperoxide,   p-menthane
                        hydroperoxide,  butyl lithium,  nitrogen hepta  sulfuri-
                        mide, formamidine sulfinic acid, potassium persulfate.
      Chain transfer agents
                        N-dodecyl    mercaptan,    tert-dodecyl    mercaptan,
                        thiuranes,  xylene   solution  of  tetraethyl  thiuram
                        disulfide.
      Emulsifiers
                        Aqueous  solutions of sodium stearate, sodium  rosinate,
                        disodium salt of ethylene diamine tetracetic, acid, zinc
                        stearate, sodium formaldehyde sulfoxylate.
      Terminators
      Solvents
                        Sodium   dimethyl  dithio-carbamate,   sodium  nitrite,
                        sodium polysulfide, hydroquinone.

                        N-hexane, pentane, heptane, methyl chloride, naphtha,
                        cyclohexane, benzene, toluene, xylene, chlorobenzene,
                        propylene.
      Catalysts
                        Butyl lithium,  vanadium  tetrachloride,  vanadium  oxy-
                        trichloride,   diethyl   aluminum  chloride,   diisobutyl
                        aluminum chloride, ethyl aluminum sesquichloride, tri-
                        ethyl   or  triisobutyl  aluminum,  TiCl4,  Til4, CoCl2,
                        A1C13, BF3.
                                   B14-6

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     Activators              Ferrous sulfate  heptahydrate, disodium salt of ethylene
                             diamine tetracetic acid, sodium formaldehyde  sulfoxy-
                             late, zinc stearate.

     Fillers                  Carbon black,  sulfur,  aromatic  (staining)  oils,  naph-
                             thenic (nonstaining) oils, paraffin wax,  clay,  whiting,
                             titanium  dioxide,  silica, hydrated alumina,  polyvinyl
                             chloride.

     Curing agents           Tetramethyl thiuram disulfide,  mercaptobenzothiozole,
                             zinc dibutyl diltuis carbamate,  ferric dimethyl dithyio
                             carbamate, sulfur, dicumyl  peroxide, zinc  oxide,  cal-
                             cined magnesia, etc.

     Reagents               Potassium chloride, potassium hydroxide, brine, sulfuric
                             acid, chlorine.

6.    PROCESS DESCRIPTION

Synthetic rubber is  manufactured mostly by  emulsion polymerization, solution poly-
merizations, or slurry polymerization. Table 6-1 lists some  synthetic rubbers and their
corresponding monomers along  with  the polymerization schemes used.  Butyl rubbers
are produced by a slurry process which is considered to be similar to  the solution poly-
merization process from  a waste generation standpoint.   For this reason, the slurry
process is not considered separately in this study.  The following sections deal with the
emulsion and solution polymerization  processes.

6.1  Emulsion  Polymerization Process

In  1979, the emulsion polymerization process was used to produce 90% of  the styrene-
butadiene rubber and almost all nitrile  and neoprene rubber.   Since styrene-butadiene
rubber accounts for more than 60 percent of all synthetic rubber produced in the U.S.,
emulsion polymerization is the most widely used method.

In  emulsion polymerization, the monomers  are emulsified in a  medium,  such as water,
along  with emulsifying   agents  such   as  soaps  and  synthetic emuisifiers.    The
                                     B14-7

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                                     Table 6-1 Production Methods for Various Synthetic Rubbers
oo
I—'
.p-
I
00
Rubber
SBR
PBR
CR
EPR

I1R
IR
NBR
Monomers
Styrene,
butadiene
Butadiene
Chloroprene
Ethylene,
propylene,
and dienes

Isobutylene,
Isoprene
Isoprene
Acrylonitrile,
butadiene
Polymerization
Scheme
Emulsion (90%)
Solution (10%)
Solution
Emulsion
Solution

Slurry
Solution
Emulsion
Temperature
<°F)
112 or 41
112
--
104
95

148
4
112 or 41
Percent
Conversion
60-75
98
70-90
91
--

70-95
--
75-90
Product
Composition
23%
styrene
98% cis
--
40-50%
Ethylene
3-9%
diene
--
98% cis
30-40%
Acrylonitrile
Residence Pressure
Time (atm)
8-15 hrs 4-5
1-2
--
..
--

30-60 min. 2-4
-.
5-12 hrs 8-9
    Source:    Kirk-Othmer Encyclopedia of Chemical Technology (McGrath et. al. 1979) and Assessment of Industrial Hazardous Waste

               Practices: Rubber and Plastics Industry (Kushnir and Nagy 1978).

-------
polymerization reaction is started by the addition of a water soluble initiator, and can
be  stopped  at  a desirable point by  the  addition of  chemicals called  shortstops (or
terminators).

The first step  in emulsion polymerization, as shown  in Figure 6-1, is the removal of
inhibitors.   Inhibitors   are   added  to   some   monomers  to  prevent  premature
polymerization during transport and storage.  This removal is achieved by washing the
monomer with a caustic solution.   The  caustic  solution is usually  recycled  to the
washing  process until it becomes saturated with  inhibitors and is then  transferred to
settling pits where it is mixed with other process effluents.  The settling pits are used
to remove suspended solids present in some effluent streams. After sufficient settling
time, this stream is further treated to reduce its biological oxygen demand (BOD).

The uninhibited monomers are fed to a polymerization reactor containing water and
emulsifying  agents.  Typical reactors have sizes varying from 5,000 to 30,000 gallons.
The emulsion  is  created  by  agitators  or  by  recirculating the  mixture  through
centrifugal pumps, as in the case of neoprene rubber production.  Initiators, catalysts,
activators,  and stabilizers are  added to  the reactor  to  start  the  polymerization
reaction. The  polymerization reaction is highly  exothermic and proper temperature
control is achieved  by  heating/cooling  coils  through  which a heat transfer fluid is
circulated.  Additional cooling is achieved by condensing the vapors emitted  from the
reactor and returning the condensate to the reactor.

Polymerization  is stopped at  the  desired  degree of conversion by  the  addition  of
chemicals, called short stops,  in aqueous solution. The polymerized monomer of latex
is then sent to a vacuum flash unit where light monomer, along  with water  vapor, is
separated out as overhead.  This vapor stream is condensed and the light monomer is
recovered by decantation to be recycled to the polymerization process.   The water
stream generated is  sent to wastewater treatment.  The noncondensible  impurities are
sent to a flare.

Unreacted heavy monomer present  in the latex from the vacuum flash unit is removed
by steam stripping the latex.  Again, the vapor stream from the stripper is condensed
to  remove the  heavy monomer by  decantation, which is  recycled  to the process.
Another aqueous waste stream is generated in this separation step.
                                  B14-9

-------
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                 Figure 6-1   Eaulsion Polyserization R'ocess for Synthetic Rubber Manufacture
                                        814-10

-------
The  latex,  thus  freed  of monomers, is mixed with antioxidants and sent  to  latex
storage, where it can be sold as a product. When the product is to be sold  as bales, the
rubber particles dispersed  in  the latex need to  be  solidified.   This  is  done  by
coagulating the rubber particles,  which causes them  to  settle faster due  to  their
increased size.  To  achieve  this separation,   the  latex is  sent to  a coagulation tank
where it  is mixed with brine.  The brine causes the  latex to "cream," which is  a partial
flocculation of the rubber particles.  This flocculation is caused by the breaking of the
emulsion, resulting from  the  altered ionic interaction between emulsion  components.
The  emulsifiers are  thus  separated from the rubber particles, though the  particle size
of the rubber  is still too small for rapid settling.   Addition of  dilute  sulfuric acid
causes these particles to agglomerate.  Sometimes extender  oils in aqueous  emulsion
and  carbon black in slurry form are added to  the  latex  prior to coagulation.   The
particles from the coagulation liquid are separated on a shaker screen.  The liquor is
recycled with  fresh  brine and acid  make-up.   The liquor overflow (blowdown) is a
significant  waste stream and is  sent  to settling ponds before being sent to waste
treatment.  The screened rubber particles from the coagulation  tank  are slurried  in
water and sent for further processing.

The  screened rubber particles slurried  in water are  rinsed with more water and are
then filtered and dewatered in rotary vacuum filters.  The filtrate  is sent  to a reslurry
tank where some of  the liquid is discharged to waste treatment and the  remainder is
recycled  to  the rinsing  unit.   The dewatered crumbs are  dried using hot  air  in
continuous or screen dryers.  The dry product is weighed and  formed  into bales using
hydraulic balers and sent  to product storage.

6.2   Solution Polymerization Process

Solution  polymerization is the other major process for  synthetic rubber manufacture,
used  mostly for the production  of polybutadiene,  polyisoprene,  ethylene-propylene
rubbers,  and part of styrene-butadiene rubbers.  The use of solution polymerization for
SBR (the  major synthetic rubber produced), is  expected  to  grow because SBR made by
solution  polymerization  has  better  rolling  resistance  and other  desirable  qualities
(McNaughton 1983).

In solution polymerization,   the  monomers are dissolved  in  a solvent,  such as  an
aromatic,  aliphatic,  or alicyclic hydrocarbon.  Addition of catalysts  of  the Zeigler-
                                  B14-11

-------
Natta  or  Friedel-Crafts type  starts the polymerization reaction.  As  the polymer
forms, it  precipitates out since it  is insoluble in the solvent.   The reaction can be
stopped at any time by the addition of shortstops.

The  solution polymerization  process  is  shown  schematically  in Figure  6-2.   The
removal of any  inhibitor present in the monomer is achieved in a manner similar to
that used  in the emulsion polymerization process. The uninhibited monomers are then
mixed  with the  solvent  and the mixture is dried in  a  desiccant  column.   The solid
desiccant  used for drying is regenerated or discarded.   The regeneration  step may
produce some aqueous waste and the discarded desiccant  is a solid waste.

The  dried  monomer is sent to  the polymerization reactor where a catalyst, which can
be a complex alkyl  of  metals such as titanium or  aluminum,  is  added  to start the
polymerization.   The reaction produces heat,  which  is  removed by cooling coils  in
which  a suitable refrigerant is circulated.  The reaction is terminated at the desired
point by the addition of shortstops.

The  polymer slurry  from the  reactor  is then  treated  with  liquids such as aqueous
alcohol.  The alcohol allows the transfer of  the catalyst  to  the aqueous phase, leaving
the  now catalyst-free  polymer slurried in the  solvent.  The aqueous alcohol/catalyst
solution is treated to precipitate the catalyst as metallic oxides, and recover solvent
and  alcohol to be recycled  to the process.  The metal oxides, suspended in water, are
mixed  with other effluents and sent to waste treatment.  The polymer slurry is mixed
with antioxidants and  extender oil and is  stored in a suspension form called  rubber
cement.

The  rubber cement  is  sometimes  mixed with carbon  black slurry and then  contacted
with hot water (for butyl rubbers) or steam  (for others).  This operation removes the
solvent and unreacted  monomers while coagulating the rubber at the same time. The
vapor stream from this process is distilled to recover solvents and monomers which are
recycled to the polymerization process. Distillation  produces an  aqueous waste stream
and  an organic stream containing oily slops.  The aqueous stream  is either sent directly
to wastewater treatment or is steam-stripped before discharge.  The oily  wastes are
used as a fuel or processed for further purification.  The  polymer crumb  slurry thus
generated is dewatered, screened,  dried,  and baled by processes similar to those used
for producing bales in the emulsion polymerization process.
                                  B14-12

-------
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                Figure 6-2   Solution Polynerization Process for Synthetic Rubber Manufacture
                                       B14-13

-------
7.    WASTE DESCRIPTION

Table 7-1  lists  the  primary wastes  associated  with  synthetic rubber  manufacturing
both by  emulsion and solution polymerization.

Off-grade products, which amount to 1 to 3 percent of total production, are the result
of bad  batches  and product changes.   This stream  contains rubber  particles with
different  degrees of  contamination suspended in water (in the case  of  emulsion
polymerization), or a  solvent (in  the  case of solution  polymerization).  This stream is
usually  mixed with other effluents and sent to settling pits where the solid particles
separate out.  These  solids are  removed  periodically and are reused, landfilled, or
incinerated depending  on the degree of contamination.

Periodic cleaning of the equipment results in aqueous and organic  wastes.  The solid
particles suspended in water are usually recovered at the settling ponds, as are the
heavy ends and  waste  oils present in the waste water.  Since solution polymerization
involves the  use of solvents (and hence requires a  water-free  environment) very little
water would  be  used for cleaning equipment used in the solution  process.  Solvents
used for cleaning can be collected and reused in the process.

Other aqueous wastes  result from  inhibitor  removal,  monomer and solvent recovery,
coagulation dewatering,  rinsing,  screening and carbon black slurry  preparation opera-
tions.  The inhibitor removal achieved by  caustic  wash generates an aqueous  stream
containing  phenols.  As this stream is usually  reused  until it is completely saturated,
its  discharge is  intermittent.  Solvent and  monomer recovery  operations consist of
condensation, decantation,  and distillation of  the  vapor overheads from  the reactor.
Since this  aqueous stream contains a significant amount of dissolved  organics, it  is
usually  steam-stripped  to remove  the  volatiles before  being  mixed with  other
effluents.  Coagulation of the latex in emulsion schemes is achieved by  the addition of
brine and sulfuric acid solutions. The coagulation  overflow is the major portion  of all
the aqueous  wastes.   Overflow  from carbon black slurry preparation  is an  aqueous
waste containing suspended carbon particles.   All the above streams  are mixed and
sent to  settling pits where the solids and oils are removed. The aqueous effluent from
these pits  is sent to  treatment  plants where  the  biological oxygen demand (BOD) is
lowered to acceptable  levels.
                                   814-14

-------
                                            Table 7-1 Synthetic Rubber Manufacturing Wastes
            Waste
         Description
           Process
            Origin
        Composition
RCRA
Codes
   Off-grade products
   Equipment cleaning
   wastes

   Other aqueous waste
03
   Heavy ends and waste
   oils
   Spent catalyst


   Spent adsorbent


   Spills


   Gaseous emissions
Bad batches, production
changes
Washing operations on
various equipment

Monomer solvent separations,
rinsing, filtering, de-
watering, coagulation,
screening, inhibitor removal,
carbon black slurry making
operations

Monomer and solvent recovery
operations  in solution
polymerization,  oils
separated from aqueous
wastes

Catalyst removed in solution
polymerization

Feed drying in solution
polymerization

Various process equipment
and piping

Leaks, drying and stripping
operations, adsorbent
regeneration in solution
polymerization
rubber particles containing
traces of unreacted monomers,
solvents, catalysts and
other additives

rubber particles in water
containing organics

rubber particles, carbon
black, and various
organics in water
Monomers, solvents,
extender oils, etc.
Oxides of titanium, aluminum
Traces of monomers, solvent
in solid adsorbent

Monomers, solvents, oils, etc.
Monomers, solvents, etc.

-------
Heavy ends  and waste  oils  are  generated by  the solvent and  monomer  recovery
operations, and by the entrainrnent of extender oils in the coagulation overflow.  The
heavy  ends generated  in  the distillation  operations  contain significant hazardous
organic materials.  This  stream is mixed with  waste oils recovered from the settling
pits and incinerated or drummed for land disposal.

Solution  polymerization  requires the  removal  of catalyst.   This  catalyst is usually
removed by an undisclosed process in the form of metallic oxides suspended  in water.
This stream is expected to be small and is probably mixed with other  aqueous streams
and sent  to  settling  pits,  where  the catalyst particles along with  other suspended
material settle out.  The solids are periodically removed and disposed of as described
previously.

The  monomer  and  solvent  dehydration operations in  solution polymerization  are
accomplished by using solid desiccant.  This adsorbent is regenerated  periodically and
discarded eventually  as a solid  waste.  This  waste  is expected to  be small and
information on  the disposal methods was not found.

Spills that occur in various parts of  the plant due to accidental discharges  generate
another waste stream.  This  stream is usually  mixed with other streams and disposed
of as  explained before.  The gaseous waste streams are generated by fugitive emissions
at various parts of the plant, air drying of rubbers, and non-condensables vented from
flashing  and stripping  operations.   The  gas  streams  are generally vented  to  the
atmosphere in high-level stacks or sent to a flare  for incineration.

8.    WASTE GENERATION RATES

Current  waste  generation  rates were not  in evidence at the time  of final document
preparation.   Table  8-1 lists 1974  nationwide  waste  generation  rates for various
synthetic rubbers.  Based  on a review of the  other process studies,  it  is likely that
these rates have changed dramatically due to RCRA.
                                    B14-16

-------
                   Table 8-1 1974 Nationwide 1984 US. Waste Generation
                 Rates for Various Synthetic Rubbers in metric tons per year
to.
1)
2)
3)
4)
5)
6)
7)
8)
Waste Source
Off-grade products
Equipment cleaning wastes
Other aqueous wastes
Heavy ends and waste
oils
Spent catalyst
Spent adsorbent
Spills
Fugitive emissions
Emulsion
SBR
28,600
5,700
incl.(2)
2,900
NA
NA
incl .(4)
NA
Solution
SBR
2,200
2,200
incl.(2)
2,200
NA
NA
incl. (4)
NA
PBR
1,000
NA
NA
50
NA
50
incl .(4)
NA
CR
5,300
NA
NA
10,600
NA
NA
incl. (4)
NA
EPR
Q(a)
NA
NA
Q(b)
30
100
incl. (4)
NA
IIR
O(b)
NA
NA
NA
NA
100
NA
NA
IR
NA
NA
NA
NA
NA
NA
NA
NA
Source:  Assessment of Industrial Hazardous Waste Practices (Kushnir and Nagy 1978) and
         Industrial Process Profiles for Environmental Use (Parr, Parson, and Phillips 1977).

(a)       Material was sold for special use.

(b)       Use was found for the material at the production site.
                                      B14-17

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9.    WASTE REDUCTION THROUGH SOURCE CONTROL

9.1  Description of Techniques

The list of individual waste streams and their sources along with the source reduction
methods  are presented in  Table 9-1.   In addition to the waste  reduction measures
classified as being process changes  or material/product  substitutions, a  variety  of
waste reducing measures labeled as "good operating practices" has also been included.
Good  operating practices  are defined  as being  procedural  or  institutional policies
which result in a reduction of waste.   The following items highlight the scope of good
operating practice:

     o     Waste stream segregation
     o     Personnel practices
                management initiatives
                employee  training
     o     Procedural measures
                documentation
                material handling and storage
                material tracking and inventory control
         •  -    scheduling
     o     Loss prevention practices
                spill prevention
                preventive maintenance
                emergency preparedness

For each waste stream, good operating practice applies whether it  is listed or not.
     •
Separate listings have been provided whenever case studies were identified.

9.1.1   Off-Grade Products

Off-grade  products  are the  result of  operator  error or system malfunction.  The
product lost due to this waste stream  amounts to  1-3 percent of the total production.
This solid waste is either sold as an off-grade product or buried in landfills, depending
on the degree of contamination.  These solids contain traces of unreacted  monomers
                                 B14-18

-------
and other additives and may pose  an  environmental hazard.  The  following source
reduction methods are noted:

     o     Reduction of polymer buildup on the reactor walls.
           During the polymerization reaction, the polymer that forms may  build up
           on  the  reactor  walls.   This impairs  heat transfer  resulting  in  poor
           temperature control  and  thus contributes to lower product quality.  It may
           even result  in production of a bad batch.  Preventing polymer buildup on
           the reactor wall can  be done by spraying or rinsing the  reactor walls with
           certain chemicals as  is done with polyvinyl chloride reactors (Wilkins 1977),
           using  Teflon* liners  on the  reactor walls to reduce adhesion, or installing
           mechanical wall wipers inside the reactor (Wilkins 1977).

           Teflon* liners are suggested because the anticipated low adhesion between
           Teflon and  the  polymeric  material should reduce buildup.  Tank  designs
           employing dual shaft  mixers, one serving the mixer and another one for the
           wiper blade, are available commercially and have been used  extensively for
           viscous fluid mixing applications.

     o     Using continuous versus batch  operation.
           From a  waste generation standpoint, continuous operation is preferable to
           batch operation because  it  requires less equipment  cleaning, and because
           the probability  is operator error  leading to production of  a bad  batch  is
           lower. This is due to the higher degree of human involvement required for
           a batch operation.  Neoprene  rubber is usually made by  a batch operation
           and  its manufacture  suffers from  3 percent product  loss.   Continuous
           operation for Neoprene rubber and for SBR,  have been  developed and can
           cut down both product loss and waste generation (Huisingh et. al. 1985; Aho
           1958; SIR  1968). Most SBR is already produced by continuous operation.
           Application  of a continuous  process concept to Neoprene rubber can be re-
           examined in the context of waste generation and reduction.
^Registered trademark of E.I. du Pont de Nemours & Co.
                                 814-19

-------
Increased automation.
By increasing the degree of automation, operator errors that result in bad
batches could be avoided.  Automation  is typically simpler and less costly
in a continuous process as opposed to a batch, or discrete, process.

Backup systems.
Emergencies, such  as power failures  or  equipment  failures,  should be
considered  in  the design or production planning  stage  and contingency
procedures should be worked out.  An  interruption of cooling  water flow
can cause a run-away reaction which, in addition  to being a safety  hazard,
may  generate  large  waste quantities.  By using diesel or steam  turbine-
driven pumps to provide  cooling water during a power failure,  this can be
avoided.  Automatic  back-up power  systems and chemical injection systems
that  spray short stops to  stop polymerization are some alternatives.  Such
systems are used in the manufacture of polyvinyl chloride (Wilkins 1977).

Finding use for off-grade products.
By blending off-grade products  with other  rubbers  or  rubber wastes, a
useful rubber product can be made  (Zimmerman 1981; Anonymous  1982a).
This  is done extensively for both butyl and ethylene-propylene rubber.

French  researchers  report a  procedure  whereby  raw  materials  can be
recovered from  the  off-grade products (Anonymous 1982b).   The  process
consists of dissolving the off-grade  products  in an oil (primarily composed
of aromatic compounds)  at 572-716°F.  Carbon black and  rubber (free of
monomer) can be recovered from this  solution.

In  another process, off-grade products  are  depolymerized  in  a liquid
hydrocarbon medium by  means of  agitation,  heat, free radical  initiators
and molecular oxygen (Scott  1972 and USEPA 1975).  The rubber-modified
hydrocarbon that results can be vulcanized to produce a moisture barrier or
insulation  coating.    It  can  also  be  blended with  asphalt  to  provide
rubberized  asphaltic composition,  or thermally  decomposed  to  produce
carbon black.
                       814-20

-------
9.1.2   Equipment Cleaning Wastes

Equipment cleaning wastes are the result of various washing operations performed on
the reactors and other process equipment.  The reactors in the emulsion scheme are
usually washed with water, thereby generating an aqueous waste. In solution schemes,
since the reactors should be kept free of water,  organic solvents are used to wash the
reactors.  This organic stream can be treated to remove the solvent and  the dissolved
rubber  can be precipitated to be  reused  or discarded  as a  waste.  The following
techniques for reducing wastes from equipment washing operations were noted:

     o     Reduction of polymer build-up on the reactor walls.
           Reduction of polymer build-up on the reactor walls by using Teflon*  liners
           or spraying chemicals on the walls reduces the required equipment washing
           frequency  and therefore results in less wastewater being produced. Use of
           reactors equipped with wipers that continuously clean the walls is another
           practical alternative.

     o     Altering product composition.
           Changing  the  product  composition  can reduce   the  concentration  of
           contaminants in the aqueous waste.  For example, SBR typically contains
           23 percent styrene and  the increasing cost of styrene has  prompted  some
           manufacturers  to lower the  styrene content  to  15 percent  (Anonymous
           1985). This results in a lower styrene content in the waste wash water.

           By increasing the degree of polymerization allowed, rubbers  with higher
           molecular  weights could be  produced.   This higher  degree of conversion
           would result in  less unreacted  monomer ending  up in the  wastewater
           (McGrath et. al. 1979).  While  these rubbers would be harder  to process,
           their  processability could be  improved  by  adding  extender   oils.    This
           practice is widespread in the  industry.

     o     Increased automation.
           Increased  use of  automation results in the reduction of  errors and bad
           batches. This means a lower  wash frequency  and thus less waste.
''Registered trademark of E.I. du Pont de Nemours &. Co.
                                  B14-21

-------
     o     Increase batch size to minimize cleaning frequency.
           Reducing equipment cleaning  frequency by  increasing batch  size  would
           result in less  cleanup wastes.  Expansion of production capacity is usually
           done by  adding more batch reactors.  By using a larger batch  reactor, as
           opposed  to  two  smaller  batch reactors, the  amount of waste generated
           from cleaning would be reduced.  This trend, observed  in  the polyvinyl-
           chloride  (PVC) industry,  might prove economical in the synthetic  rubber
           industry  (Cameron, Lundeen, and McCulley Jr.  1980).

     o     Better operating  practices.
           Usually,  equipment  is rinsed   with  large  volumes  of  water  to  remove
           residual  rubber.  By initially rinsing the reactors with a small volume of
           water (about  5 percent  of  equipment volume), waste water with  a high
           concentration of rubber particles is  generated.  This stream can then be
           recycled to the  process.   The  equipment can then  be washed  with  a full
           volume rinse  and generate  wastewater  with  a lower solid content.   This
           two-step rinsing  procedure was adopted  by Borden  Chemical Co.  and
           reduced  off-product waste by 95 percent (Sittig 1975b).

           A similar procedure was  adopted by  a plant for cleaning latex  tanks.  The
           plant used a rinse procedure that generated a  rinse water containing more
           than 2 percent solids.  This stream was  then used for latex blending (Riley
           1974). Rinse  water containing less  than 2 percent solids is  not useful for
           blending.

9.1.3   Other Aqueous Wastes

These aqueous  wastes  are the  result of inhibitor removal, coagulation  and screening,
rinsing and dewatering, carbon black slurry preparation, and monomer, solvent, and
catalyst recovery steps.  The removal of inhibitors from the monomers by caustic wash
generates a waste containing traces of phenol.  Since this stream is usually  recycled to
the washing  process until it becomes  saturated, the volume of this waste stream is
quite  small.  The overflow from  carbon  black  slurry preparation is  also small and
contains only the suspended carbon particles.
                                 B14-22

-------
The bulk of the aqueous wastes are the result of coagulation and screening, rinsing and
dewatering, and monomer,  solvent, and catalyst recovery operations.   All  of  these
streams  are  usually sent to settling pits  where suspended  solids and heavy oils are
removed.   Since  some  of  these  aqueous streams  contain significant  amounts  of
organics (unreacted  monomers, etc.),  they may be steam stripped to remove volatile
organics, incinerated,  or  stored in drums  for land disposal.   The following  methods
could reduce the generation of these aqueous wastes:

      o     Use of  alternate coagulation procedures.
           Usually, coagulation of the latex  produced by emulsion polymerization is
           achieved by the  addition of brine  and sulfuric acid solution.  The  overflow
           from the coagulation  tank  contains solid particles which  are recovered  in
           settling pits.   This waste stream can be  reduced by using alternate means
           of coagulation such as spraying  the  latex  into  a heated  chamber and
           thereby  accomplishing  coagulating and  drying the  latex  in one  step.
           Another approach is to  deposit the latex as a frozen film on rolls kept  at
           low temperature followed by washing, using ultrasonic sound, or by forcing
           the latex through jets for emulsion breaking (Riley 1974).  Since all of the
           above alternatives achieve coagulation without using  increased quantities
           of water (brine and sulfuric acid solutions),  less aqueous waste is produced.

           Using acid  polyamide, a coagulation procedure that reduces the quantity  of
           total dissolved solids in the overflow has been developed. This procedure
           was  adopted  by a  synthetic   rubber  plant  which reduced  coagulation
           overflow wastes  significantly. Also reported was a process used by another
           plant that  converted rubber  cement from solution polymerization directly
           into  baleable  crumbs  using an extruder.    This  process  was used for
           polybutadiene  and reduced  waste significantly since  the traditional method
           of coagulation (using hot water  or steam) was not required.

      o     Recycling of vacuum pump  seal water.
           Vacuum  pumps  are  used  for  generating  vacuum   in  the light monomer
           recovery operation. The water used to seal the vacuum pump accumulates
           organics  and  is usually  discharged  as a waste stream.  Studies have  been
           done on recycling  this  aqueous waste to the polymerization process (op.
           cit.).  Though  the quantity of this stream is not known, this procedure could
           contribute  to overall waste reduction.

                                 B14-23

-------
     o    Different mode of carbon black slurry preparation.
          Usually, carbon black  (in the form of a  water slurry)  is added to the
          polymer latex from  the reactor.   The overflow  from the slurry mixer
          results  in a wastewater stream.   3y using a different slurrying procedure,
          some plants have effectively reduced this loss (Riley 1974).

     o    Altering product composition.
          As discussed  in section 9.1.2,  changing the product  composition  could
          reduce  the concentration of contaminants in the aqueous wastes.

     o    Alternatives to solution polymerization.
          Polyisoprene  and  polybutadiene  are produced  mostly  by  solution  poly-
          merization. Enoxy Chimica  5.P.A. of Italy has developed  a polymerization
          process  which does not use solvents (Zimmerman 1981,  Lipowicz 1982).
          The  process  uses  a  rare  earth-based catalyst system  at conventional
          temperatures  and pressures.   Currently, a  pilot plant  is  in operation  in
          Italy.  The process has the advantage  of eliminating the need for steam
          stripping the  product which  reduces the amount of wastewater generated.
          Additional advantages  include  energy savings up  to 80  percent,  a  much
          smaller reactor, and reduction of heavy slops formation.

9.1.4   Heavy Ends and Waste Oils

Heavy  ends are removed  by the various distillation operations used  for the recovery of
monomers and solvents.    This stream,  sometimes referred  to  as "heavy  slops",  is
usually  disposed  of  by   drumming for  landfill  or  incineration.    This  potentially
hazardous stream can be  reduced by the following methods:

     o    Replace the slurry process for butyl rubber with a solution process.
          The slurry process  for  butyl rubber  synthesis uses toxic  methyl chloride  as
          a carrier fluid, which ends up in  the heavy  slops (Parr, Parson and Philips
          1977).  Though it was  suggested that a use could  be found for this  waste
          stream  (Kushnir and  Nagy  1978),  this has not  been supported by  other
          sources.  By employing a solution process using a solvent such as  hexane or
          pentane, the  toxicity  of this stream could be  reduced.  A solution process
          of this type is believed to be  in commercial operation  in the USSR  (Parr,
           Parson and Phillips 1977).
                                   B14-24

-------
      o     Alternatives to solution polymerization processes.
           As mentioned  in Section 9.1.3, a non-solvent process developeed by Enoxy
           Chimica S.P.A. can reduce  formation of  heavy slops in production  of
           polyisoprene and polybutadiene.

      o     Avoiding the use of aromatic solvents.
           Aromatic solvents  are usually  more  volatile and toxic in comparison  to
           aliphatic solvents.   By using  aliphtic solvents, the  toxicity of the heavy
           slops could be  reduced (Parr, Parson, and Phillips 1977).

9.1.5   Spent Catalyst and Adsorbent

The catalysts used  in emulsion polymerization usually stay in the final rubber product.
In solution polymerization, the catalysts are removed by contacting the polymer slurry
with an alcohol solution  and then precipitating the catalyst from the alcohol (Kushnir
and Nagy  1978). The separated catalyst, present as a suspension in an aqueous stream,
is usually  mixed with other aqueous wastes and sent to settling ponds.  In these ponds,
the catalyst (in the form  of oxides of titanium or aluminum), separates out along with
other suspended particles (rubber, carbon black, etc.).  All of these solids are removed
periodically and disposed of in a landfill.  Since the spent catalyst waste is reported  to
be equal to about 0.01 percent of the total product, and since reducing this waste will
not have  a  significant  impact on  overall  waste  generation,  no  waste  reduction
measures  are proposed.

In solution polymerization processes, care is taken to keep water  out of the system.
This is accomplished by  drying the monomer-solvent mixture with  a  solid desiccant.
After several regeneration cycles, the desiccant  is discarded  as a waste.  The  actual
disposal methods  for this solid waste were not reported.  Elimination  of this stream
can be accomplished, in principle, by using a distillation of the feed to remove  water,
as is done in  the case of EPR.  However, it is not clear that the resulting wastewater
stream is  environmentally preferable to the existing alternative.  Further exploration
of this approach is needed.
                                   B14-25

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9.1.6   Spills and Leaks

Spills and leaks are the result of accidental discharges of liquids and solids in various
parts  of  the plant.  The  exact  amount of this stream is not known.  The liquids are
usually  mixed with  the  heavy slops and  disposed of as  explained  previously.   The
following suggestions could reduce this waste stream:

      o     Use of continuous operation instead of batch operation.
           Since  there  are many sequential processing  steps  in  a  batch operation,
           chances of operator errors  that result  in inadvertent spills  and emissions
           are higher. Thus, a continuous operation is preferable.

      o     Better operating practices.
           Latex spills are  usually washed down with water and are sent to the waste
           treatment plant. Washing  with  water makes coagulation of this  stream
           difficult.  By using  alum  to coagulate  the latex in-situ and removing the
           coagulated rubber  solids  with  scrapers,  lower quantities  of water  are
           required for washing (Riley  1974). This reduces the quantity  of wastewater
           generated due to washing of latex spills.

           Losses from  loading  and  unloading  procedures can be  reduced  by  the
           following  method.  Two  hoses  are usually connected to the  track  of  a
           railroad car for  loading or unloading.  The bottom hose transfers material
           while  the  top hose maintains pressure.  Material left in the  hoses may be
           lost or spilled upon  disconnection.  This can  be avoided by more complete
           drainage and  by  purging the lines with  inert gas to  a recovery system or  a
           control device prior to disconnect.

9.2   Implementation Profile

Some of the noted source control methods appear  to be economically attractive.  For
example, by reusing off-grade products or by selling  them at a lower price, off-grade
product  waste can be reduced, thereby cutting disposal  costs  and perhaps increasing
revenue  at the same time.  Segregating wastes (e.g. keeping the spent catalyst stream
separate from the coagulation overflow) involves little  or no  cost to the facility but
                                   B14-26

-------
can  mean substantial  savings  in  disposal  costs.   Modifying  equipment  cleaning
procedures results in recycleable waste streams generated with only minor increases in
operating costs.

All other methods  identified  may require a significant expenditure of capital and an
increase in labor costs.  The economic feasibility of these methods  depends upon their
potential to  produce a savings in  disposal and  treatment costs  and  reduce future
liability  for landfilled waste.  Some of these methods may even be feasible for firms
which  have already installed  wastewater  treatment units, though  managers at these
firms are generally reluctant to consider further environmental expenditures.  Even so,
source  reduction methods  are  certainly worth considering when  planning for plant
expansions or replacements.

Because of the  diversity encountered  in the synthetic  rubber industry, source  control
methods feasible at one  facility may  not be feasible  at  another.   In  addition, one
facility may  produce many  different grades of rubber, making it difficult for a general
and  yet meaningful control scheme to be profiled.  In practice,  managers  of each
facility must independently determine  their own best course of action with regard to
waste  minimization.

9.3   Summary

The summary  of all noted source  control  techniques is  given  in  Table  9-1.   Each
technique was rated for its  effectiveness,  extent of current use and future application
potential on  scale of 0  to 4. The ratings were derived by project staff based on review
of the available. The estimates of current level of waste reduction achieved  (current
reduction  index) and possible future reduction (future  reduction  index) were obtained
from the ratings in accordance  with the methodology presented  in the introduction to
this appendix.

The current  reduction  index (CRI)  is a measure  of  reduction of waste that would be
generated if none of the methods listed were implemented to  their current  level of
application.  For the entire synthetic rubber industry, CRI is 2.1 (53 percent)  which is
indicative of the significant level of waste minimization that already has taken place.
                                   B14-27

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                              TABLE 9-1 SUMMARY OF SOURCE CONTROL METHODOLOGY  FOR  THE SYNTHETIC RUBBER MANUFACTURING INDUSTRY
1
Waste Stream |
1
Off-Grade Products |1
12.
|3
|4.
15
1
Equipment Cleaning | 1
Hastes |2.
|3
|4.
|5
1
Other Aqueous | 1 .
Hastes |2.
|3.
|4.
|5.
I
Heavy Ends and | 1 .
Waste Oils |2.
|3.
1
Spills and Leaks |1.
12.
1
All Sources |
1
Control Methodology |-
1
Reduce polymer build-up on react wal)|
Use continuous versus batch operation)
Increased automation |
Provide emergency backup systems |
Find use for off-grade product |
Overall )
Reduce polymer build-up on react wallj
Alter product composition |
Increased automation |
Increase batch size / reduce cleaning)
Better operating practices |
Overall |
Use alternate coagulation methods |
Recycle vacuum pump seal water |
Different carbon slurry preparation j
Alter product composition |
Use alternatives to solution process |
Overall |
Replace slurry process - Butyl rubber)
Use alternatives to solution process |
Avoid the use of aromatic solvents |
Overall 1
Use continuous versus batch operation)
Better operating practices |
Overall |
All Methods
Found Documentation

Quantity | Quality
1
1
1
1
1
1.00 | t
t 1
1 1
1 1
1 I
1 1
1.00 | 1
2 1
1 1
1 1
1 1
1 I
1 20 | 1
1 I
' I
1 I
1.00 | 1
1 1
1 1
t 00 | 1

1
.... 1
1
1 1
1 1
1 1
t 1
2 1
20 |
|
1
1
1
1
00 |
2 1
1 1
1 1
1 1
2 1
40 |
1 1
1 1
t 1
00 |
1 1
1 I
00 |

Waste |
Reduction I
Effectiveness |
1 1
2 1
2 1
2 1
3 1
2.00 |
2 1
1 |
1 1
2 1
3 1
1.80 |
3 1
1 |
t |
1 |
' 1
1.40 |
2 I
1 1
2 1
1.67 |
2 1
3 1
2 50 |

Extent of |
Current Use |
1
1
1 1
1
3 1
3 1
t 80 |
' 1
3 1
1 1
2 1
2 1
1.80 |
1 1
t 1
1 1
3 1
0 1
1 20 |
1 1
0 1
1 1
0.67
1 I
2 1
1 50 |

Future | Fraction of |
Application I Total Waste 1
Potential | |
2 1 1
1 1 1
2 1 1
1 1 1
2 1 1
1.60 | 0.77 |
2 I I
1 1 1
' 1 1
1 I I
3 I I
1.60 | 0 04 |
2 1 1
2 1 1
' 1 !
t 1 !
1 i I
t 40 | 0.12 |
1 1 1
' 1 i
' 1 1
1.00 | 0 06 i
1 1 1
3 1 1
2 00 ) 0 0! |
i '.DO |
Current
Reduction
Index
0
0
0
t
2
2
0
0
0
1
1
1
0
0
0
o
0
0
0
0
0
0
0
I


I
•3 I
5 !
5 I
5 I
3 I
3 I
.5 I
8 I
3 I
0 I
5 I
5 I
8 I
3 I
3 I
3 I
0 I
8 I
5
0 I
5
5 I
5 I
1.5 |
1
2
5 I
1 1
Future


Probable
0
0
0
0
0
0
0
0
0
0
1
0
,
0
0
0
0
0
0
0
0
0
0
1
o
0
deduction Index


| Maximum
.4 I
4 I
.3 | 0
•1 1
4 1
.4 | 0
•S 1
.1 1
2 1
3 1
.1 | 1
.5 | 1
, , ,
4 1
•2 1
1 1
.3 1
4 | 1
4 | 0
3 1
.4 | 0
3 | 0
4 1
' 1 1
8 | 1
4 | 0
1


1

1
8 1
1
1
.3 1
1

1
1
1 1
1 1
1
1
1
1
1
1 1
4 i
1
4 1
4
1
1
1
8
03
 I
hO
CD
          (*)  These  streams  Include listed "F*  and/or  'IT  RCRA wastes.

-------
The future reduction index (FRI) is an indication of the level to  which the currently
generated waste  can be  reduced  if all of  the  techniques noted  were implemnted
according to their rated potential.  The FRI value  of 0.4  to  0.8 (10 to 20 percent) is
indicative of  a  low to  moderate  extent  of future waste reductions.  Among the
techniques that were found most effective and applicable (as evidenced by high FRI
value) for the control of waste generation were increased automation, use of alternate
coagulation  methods, and further implementation  of better  operating practices.

10.  PRODUCT SUBSTITUTION ALTERNATIVES

Synthetic rubbers are  predominantly used  in  the  manufacture  of tires and  tire
products. It is estimated that tire  replacement amounts to about  75 percent  of total
tire sales (Zanetti  1984a).   By increasing the  lifetime of passenger  car  tires, the
demand for  synthetic rubber can be decreased. This could  be  done by better consumer
tire maintenance (e.g. by  preventing  tire  under-inflation  and by maintaining proper
wheel-alignment), and by increasing car-pool use.

It  is estimated that  92% of the passenger  tires made in 1990 will be radial tires, up
from  61% in  1980.   Since  radial   tires use more  natural rubber,  the demand  for
synthetic rubber could decrease.

Natural rubber is an accepted substitute for  synthetic rubber  (the roles were reversed
prior to  1940).  Most of the natural rubber  is imported;  however,   domestic rubber
production from guayule plants (found in  the southwestern U.S.)  has received recent
attention (McNaughton  1983, Lipowicz 1982).  The concept  of guayule rubber was
explored in the U.S.  during the Second World War  when natural rubber imports declined
drastically.   Though guayule  rubber lacks  economic  feasibility at  present,  it  is
expected  to be economical by the end of this decade.

The increasing cost of styrene prompted manufacturers to  investigate possible substi-
tution of SBR  by  medium vinyl polybutadiene rubbers (Parr, Parson, and Phillips 1977).
The waste reduction  implications of this substitution are not clear.

EPR can be used  for tire-making purposes, replacing other synthetic  rubbers. Various
problems  associated with  using EPR  for  tire applications have  been  solved  (Parr,
                                  B14-29

-------
Parson, and Phillips 1977).  The apparent  low waste  loads associated with EPR makes
this substitution worthy of exploration.

11.  CONCLUSIONS

While the synthetic rubber industry has done much to reduce wastes,  it appears that
moderate reductions characterized by a future reduction index of 0.4  to 0.8 (10 to 20
percent) are possible. Several methods that appear to be quite effective  would be to
expand the reuse or recycle of off-grade products, increase the use of automation,  use
alternate coagulation  procedures,  and  extend  the  application  of  good  operating
practices.  Source  reduction methods already in application at some plants need to be
examined at others.

One  area that can have an impact is  improved tire maintenance  by consumers which,
in turn, could increase passenger car tire life and thus reduce the demand for synthetic
rubber.  By increased use of radial tires, the amount of synthetic rubber used  per  tire
could be  lowered  since radials  use more  natural rubber than other  types of tires.
Natural rubber is the best substitute for synthetic rubber; however, full environmental
assessment  of such a  substitution  must be  made,  along   with  an  evaluation  of
socioeconomic impacts, before its desirability is fully established.

12.  REFERENCES
Aho, C. E.  1958.   U.S.  Pat. 2,831,842. (Apr. 22, 1958) to E.I. duPont de Nemours &
Co., Inc.
Anonymous.  1982a. Chementator.  Chem. Eng. 89 (2): 17.
	.   1982b. Chementator. Chem. Enq. 89 (14): 17-8.
	.   1985. Chem. Enq. News. 63 (23): 26.
Cameron, J.B., Lundeen, A.J., and McCulley Jr., J.H. 1980.  Trends in  suspension PVC
manufacture.  Hydrocarbon Processing.  59 (3): 39.
Greeme, R. 1981.  Chem. Enq. 88 (17): 101.
Huisingh, D. et. al. 1985.   Proven profit from pollution prevention. Washington, D.C.:
The  Institute for Local Self-Reliance.
Johnson,  H. 1973.  A  study of hazardous  waste materials, hazardous effects  and
disposal methods.   Vol.  2,  Booz-Allen  Applied  Research,   Inc.  EPA-670-2-73-15.
Washington, D.C.:  U.S. Environmental Protection Agency.
                                   B14-30

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Kushnir,  J.M.,  and  Nagy,  S.F. 1978.  Assessment  of industrial hazardous  waste
practices; rubber and plastics industry.  Snell (Foster D.), Inc.  EPA-530-SW-163C-2.
Washington, D.C.: U.S. Environmental Protection Agency.

Lipowicz, M. 1982.  Organic and inorganic chemicals see major advances. Chem. Enq.
89 (3): 109.

McGrath, J.E.,  Vial, T.M., Baldwin,  P.P., et.  al. 1979.   Elastomers, synthetic  in
Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed. Vol. 8, pp. 446-640.  New
York, N.Y.: Wiley.

McNaughton, K.J. 1983. Surge in search for synfuels.  Chem. Eng. 90 (2): 108.

Parr, J.,  Parson,  T.B.,  and Phillips,  N.P.  1977.   Industrial  process profiles  for
environmental use: chapter 9.  the synthetic rubber industry.  Radian  Corp.  EPA-600-
2-77-023L  Cincinnati, Ohio: U.S. Environmental Protection Agency.

Riley, J.E. 1974. Development  document for effluent limitations guidelines and New
source performance  standards   for  the  tire and  synthetic  segment  of the rubber
processing; point source  category.   EPA-440-l-74-013a.   Washington, D.C.:   U.S.
Environmental Protection  Agency.

Scott, C.E. 1972. U.S. Pat. 3,700,615.  (Oct. 24, 1972)  to Cities Service Co.

SIR. 1968.  Shell International Research.  Brit. Pat. 1,136,189 (Dec. 11, 1968) to Shell
International Research.

Shreve, R.N., and Brink, J.A. 1977.  Chemical process industries.  4th  ed. New York,
N.Y.: McGraw Hill Books Co.

Sittig, M. 1975a. Environmental sources and emission handbook. New Jersey:  Noyes
Data Corp.

	. 1975b.  Pollutant removal handbook. New Jersey: Noyes Data Corp.
SRI. 1980.  Stanford Research Institute.  Chemical economics handbook, 1978.  Menlo
Park, CA: Stanford  Research Institute.

Stimson, S.C. 1985.  Chem. Eng. News. 63 (15): 33-60.

USDC.  1972.  U.S.  Department  of Commerce,  Office of Management  and Budget.
Standard industrial classification manual. Washington, D.C.: U.S. Government Printing
Office.

	.  1985.  U.S.  Department of Commerce, Bureau of the Census.  Plastics
materials, synthetic rubber, and man-made fibers.  In  1982 Census of manufacturers.
MC 82-I-28B.  Washington, D.C.: U.S. Government Printing Office.

USEPA. 1975. U.S. Environmental Protection  Agency,  Office of Air  Quality  Planning
and Standards.  Standard support environmental  impact document.  Vol. 2.  Research
Triangle Park, N.C.: U.S. Environmental Protection Agency.
                                  B14-31

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Wilkins, G.E.   1977.  Industrial process profiles  for environmental  use,  chapter 10;
plastics and resin industry.  Radian Corp. EPA-6QO-2-77-023; Cincinnati, Ohio:  U.S.
Environmental Protection Agency.

Zanetti, R. 1984a.  Battles for tire markets  feature two SBR types. Chem. Enq.  91
(12): 29-33.

          _. 1984b.  Guayule makes progress toward commercialization. Chem.  Enq.
91 (9): 27-31.

Zimmerman, A. 1981.  U.S. rubber - flat growth is buoyed by specialities.  Chem.  Enq.
88 (24): 34-5.
                                  B14-32

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1.   PROCESS:      1,1,1 -TRICHLOROETHANE MANUFACTURE

2.   SIC CODE:      2869(2)

3.   INDUSTRY DESCRIPTION

Manufacturers of 1,1,1-trichloroethane (1,1,1-TCE) are included as part of the organic
chemicals manufacturing industry. The industry is composed of relatively large plants
producing a wide variety of chlorinated compounds.  The manufacturing processes are
often interrelated, since  products from  one  process  can be used as  feedstock for
another.

Three major companies are responsible for all  of the U.S. production  of 1,1,1-TCE.
Dow Chemical  is  the largest producer of 1,1,1-TCE,  with  two plants providing  57
percent of  the  total  U.S. production capacity.   PPG  Industries Inc.  and Vulcan
Materials Co., each with one plant, account for 27 percent  and 16 percent of the  total
production  capacity, respectively.

Three of the plants producing 1,1,1-TCE are located in  Louisiana.  The  remaining
operational site, owned by Dow, is located in Texas.

4.   PRODUCT AND THEIR USE

Annual  U.S. production  of  1,1,1-TCE  was  334,000  short tons  per  year in  1984
(Anonymous 1985a).  1,1,1-TCE is primarily used as solvent for oils,  grease, and wax in
metal cleaning operations.   Commercial  grades of  1,1,1-TCE are  available with  or
without oxidation  inhibitors  added.   Solvent  degreasing  grades  often  contain  trace
amounts of organic inhibitors, such as acid acceptors  or metal stabilizers,  which are
used to neutralize any HC1 formed during  solvent  use,  and  to  deactivate  metal
surfaces  for  the   prevention  of adverse  reactions  during the  cleaning process.
1,1,1-TCE  is also used as raw  material  for  the manufacture  of other chlorinated
chemicals,  in aerosol propellant formulations,  and as a solvent in  adhesive and coating
formulations.  The relative consumption  rates of 1,1,1-TCE are given  in  Table 4-1
based on 1977 data.  The relative distribution of 1,1,1-TCE among the different end
uses appears to have remained unchanged since that date.
                                      B15-1

-------
               Table 4-1 End-Use Profile for 1,1,1-TCE in the U.S.
         End Use                       Relative Consumption Rate
                                                  Percent
     Metal Cleaning                                67.0
     Chemical Intermediate                          2.0
     Miscellaneous                                 31.0
     Total                                        100.0

Source: Organic Chemicals  Manufacturing (Key et al. 1980).

5.    RAW MATERIALS

The  raw materials used to produce  1,1,1-TCE are summarized  below (Van Gemert
1982, Stevens 1979, Key et al. 1980):

     Reactants      hydrogen chlorine, chlorine, vinyl chloride, 1,1-dichloroethylene
                (VCM route).
                ethane, vinylidene chloride (ethane route).
     Catalysts       FeCl3
     Inhibitors     •  butylene  oxide,  dioxane, nitro  methane,  tert-amyl  alcohol,
                     methyl ethyl ketone, isopropyl nitrate
     Neutralizes    ammonia, sodium hydroxide

6.    PROCESS DESCRIPTION

Production of  1,1,1-TCE in  the  United  States is based  primarily  on the two-step
chlorination process using vinyl chloride as a raw material.  This method accounts for
85 percent of total production.  An alternative production method, based on the direct
chlorination of ethane,  is  responsible  for  the remaining  15 percent.   The ethane
process, however,  is also capable of using ethylene dichloride derivatives as feedstock.
Detailed descriptions  of the two processes mentioned are  given  elsewhere (Boozalis
and Ivy 1978, Berrie,  Chaler,  and  Chuffart  1978, Key et al. 1980).   Due to its wider
applicability, only  the vinyl chloride route will be discussed.
                                      B15-2

-------
In  this  process,  vinyl   chloride  is  first  catalytically  hydrochlorinated  to  give
1,1-dichloroethane   (1,1-DCE).    The  1,1-DCE  intermediate  is   then   thermally
chlorinated  to give  1,1,1-TCE as the final product.   Yield from vinyl chloride often
exceeds 95 percent.  The overall reactions include:
      1.    Hydrochlorination of vinyl chloride to 1,1-DCE
                              FeCl3
                              catalyst
           CH2  = CHC1 + HC1	^CH3-CHC12
      2.    Chlorination of 1,1-DCE to 1,1,1-TCE:
           CH3-CHC12 + Cl2	>CH3CCl3 + HC1
Figure 6-1 represents the flow diagram  for the production of 1,1,1-TCE  from vinyl
chloride.  For this process, vinyl chloride, HC1, and recycled chlorinated  hydrocarbons
are fed into a hydrochlorination reactor, operating  at 95°F-105°F.  The  reaction is
homogeneously catalyzed by dissolved ferric chloride.  Ammonia  is then added to the
reactor effluent stream  to form a solid complex with the residual HC1 and the FeCl3
catalyst.*  The complex  is removed through a spent catalyst filter as solid waste.  The
filtered hydrocarbon stream then passes through a heavy ends column.  Bottoms from
this column, containing  tars and  heavy chlorinated  hydrocarbons,  are  removed  as  a
liquid waste.  The overhead is  transferred to a light ends column for the separation of
1,1-DCE.  Overhead from the light  ends column,  containing  mostly unreacted vinyl
chloride, is recycled to  the hydrochlorination reactor.  The 1,1-DCE intermediate is
removed as bottom from the distillation column and is stored for further processing.

In the second stage of the process, 1,1-DCE and chlorine  are  combined and fed to  a
non-catalytic fluidized bed chlorination reactor, operating  at 750°F.  The  exothermic
reaction is  thermally  induced  and subsequently self-sustaining. The reactor effluent
then passes through an HC1 column, where HC1 and light chlorinated hydrocarbons are
removed  as overhead.   This  stream  can be  used  directly  to  supply  HC1  for  the
manufacturing of other chlorinated chemicals, or is further purified to recover HC1 as
a by-product.
*   Other means of  FeCl3 removal,  which  do not involve NH3  addition, are also
    practiced.
    Dow Chemical Co. 1985:  Personal  communication.
                                      B15-3

-------
                   HCL	

                  VINYL
                 CHLORIDE^
                  FECL3

                 CATALYST
                               HYDRO-
                             CHLORINATION
                               REACTOR
CD
                     NH-q
                                   SPENT
                                  CATALYST
                                   FILTER
HVY
ENDS
COL
                                                I
                                                      HCL  TO
                                                      RECOVERY
                                                       A
LIGHT
 ENDS
 COL
CHLOHINATION
  REACTOR

HCL
COL.
1,1,1-
TCE
 COL
                                                                                           CHLORINE
                                                                Cg CHLORINATED
                                                                FEEDS  TO  OTHER
                                                                  PROCESSES
                                                                                              PROCESS WASTE CATEGORIES

                                                                                              0   HEAVY ENDS
                                                                                              0   SPENT CATALYST

                                                                                              (3)   VENT GASES
                                               Figure  6-1    Production  of  \\\\ i-TCE from Vinyl Chloride

-------
The bottom stream from the HC1 column is fed to the 1,1,1-TCE column,  where the
purified  1,1,1-TCE is removed as overhead.   Inhibitors  are then added  to provide
different  commercial grades of  the  final product.   The  bottom stream from the
1,1,1-TCE column,   containing  mostly  C2  -  chlorinated  hydrocarbons,  is  often
transferred as feed to other chlorination processes.  Storage tanks and light ends off
distillation column overheads are vented to a  scrubber to  remove residual HC1 and
chlorinated hydrocarbons, although alternate means of processing are also used.

7.   WASTES DESCRIPTION

The primary specific  wastes associated with the 1,1,1-TCE manufacturing industry are
listed in Table 7-1.   The waste streams generated from  this industry include  liquid
organic wastes, semi-solid spent catalyst, and scrubbing system wastewater.

Since liquid organic effluents, such as heavy tars,  are often used  as  a feedstock to
other processes  in a highly  integrated chlorohydrocarbon facility, the term  "waste" is
not applicable universally.   Organic  heavy ends  account  for a large  portion  of the
residuals  generated.    This liquid  stream   comes   from   the  distillation  of  the
hydrochlorination  reactor effluent stream to remove  heavy chlorinated hydrocarbons
that cannot be  directly  recycled  or further processed. The resulting  tars are often
oxidized for recovery of  HC1 and heat or sent to land disposal.

Another major source of waste comes from  the removal of spent catalyst which is used
for the  hydrochlorination reaction. Ammonia is added to  the reactor effluent stream
to form a solid complex with the catalyst.   The solid is then filtered out,  and the
resulting sludge  is sent to land disposal.  Again, it  must be  noted that certain facilities
use alternate methods of catalyst removal which do not rely on NH3 addition.

The  scrubber  effluent,  containing   mostly   water   with  condensed   or   dissolved
halogenated organics, is  normally sent  to a central wastewater treatment  system for
the entire facility.
                                      B15-5

-------
                Table 7-1  1,1,1-TCE Manufacturing Process Wastes
No.
1.
Waste
Description
Heavy ends
Process Origin
Hydrochlorination
reactor
Composition
tars, heavy
chlorinated
hydrocarbons
RCRA
Code
K096
  2.
  3.



  4.


  5.
     Spent catalyst   Spent catalyst
                     filter
     Scrubber
     effluent
     waste
Emission control
operations
     Equipment      Tanks, towers,
     cleaning wastes heat exchangers

     Spills & leaks
FeCl3, ferric    K028
ammonium chloride
complex,
dichloroethene

chlorinated
hydrocarbons,
water

                F024
8.
WASTE GENERATION RATES
The survey of the available literature did not yield waste generation rates' from the

production of 1,1,1-TCE.   Fractional waste generation (the  percentage each  stream

represents of the total waste generated)  was estimated by the report authors based on

the available information  and industry comments.  These values are shown in Table 9-

1.
9.
WASTE REDUCTION THROUGH SOURCE CONTROL
9.1  Description of Techniques


In addition to the waste reduction  measures classified as being process changes or

material/product substitutions, a variety of waste reducing measures labeled as "good

operating practices" have also been included.  Good operating practices are defined as

procedural or institutional policies which result in a reduction of waste.  The following

items highlight the scope of good operating practice:
                                      B15-6

-------
     o     Waste stream segregation
     o     Personnel practices
                     Management initiatives
                     Employee training
     o     Procedural measures
                     Documentation
                     Material handling and storage
                     Material tracking and inventory control
                     Scheduling
     o     Loss prevention practices
                     Spill prevention
                     Preventive maintenance
                     Emergency preparedness

For each waste stream,  good operating practice applies  whether it  is listed or not.
Separate listings  have  been  provided  whenever case studies were identified.    A
summary of the waste sources and the corresponding source reduction  methods is given
in Table 9-1.  This section describes the  listed methods,  including known  specific
applications.

9.1.1  Heavy Ends

A major portion of the waste generated  from the manufacturing of 1,1,1-TCE comes
from the distillation operation required  for the removal of chlorinated   compounds
containing  more  than  two  carbon  atoms.  These compounds are formed by various
polymerization reactions during_the hydrochlorination of vinyl chloride  to form  the
1,1-DCE intermediate.  Since these compounds cannot be  directly recycled, or readily
used as  feedstock  to  other  manufacturing processes,  they  must be  chemically
converted prior to reuse  or produced in  minimum quantities prior  to disposal.  The
following minimization techniques were noted:

     o     Heavy ends hydrocracking.
           Similarly to  the method  proposed  in  the process study for  TCE/PCE
           manufacturing,  an additional  reactor  might be  used to hydrocrack  the
           heavy  chlorinated hydrocarbons into lighter products. The  light chlorinated
                                      B15-7

-------
           organics  generated from this  step  can  then  be recycled  to  the  hydro-
           chlorination  reactor.    The  experiments  at  the  Illinois  Institute  of
           Technology revealed severe catalyst fouling problems.  Further research is
           planned  to  explore  other  operating  conditions  such  as  the  effect  of
           increasing H2/feed ratios to alleviate the fouling problem*.

     o     Lowering hydrochlorination reactor temperature.
           It is possible that the heavy ends formation reaction has a higher activation
           energy than the principal 1,1-DCE formation reaction.  If this is true,  then
           the selectivity ratio would increase  with  a decrease in temperature.  This
           would lead to higher yields of 1,1-DCE and, consequently, lower generation
           of heavies.  Examination of the  reaction kinetics along with the economic
           feasibility of this proposed method appears worthwhile.

     o     Thermal oxidation with recovery of HC1 and heat.
           This  technique is used by at least one facility**.    The heavy ends are
           combusted and both heat and HC1 are recovered. Recovered hydrochloric
           acid  can either be sold or used  to generate anhydrous HC1 for  use in other
           processes.

9.1.2   Hydrochlorination Catalyst Waste

Waste  is  produced  from the disposal  of  spent catalyst  from the  hydrochlorination
reactor.   For the facilities  where  FeCl3  catalyst (dissolved in the 1,1-DCE liquid
effluent  from the reactor)  is treated with  ammonia to form  solid complexes, the
following source reduction methods were noted:

     o     Elimination of filter aid.
           The type of filters used to separate  the precipitated salts from the organic
           stream was not described in the available literature.  In cases where pre-
           coat type pressure filters are being used, a filter aid is first  deposited to
           improve the filtration rate.  Waste volumes can be significantly reduced by
           switching  to bag or leaf type filters  which do not require the use of  a filter
           aid (LWVM 1985).
*  Illinois Institute of Technology 1985:  Personal communication.
** Dow Chemical Co. 1985:  Personal communication.
                                       B15-8

-------
     o     FeCl3 catalyst precipitation and recycle.
           Decreasing the temperature of the  1,1-DCE liquid effluent  stream may
           cause FeCl3  to precipitate because  of the decrease in solubility.   The
           precipitated catalyst can then be separated, redissolved, and recycled back
           to  the reactor.   Residual  catalyst in  the  1,1-DCE  stream can  then  be
           removed conventionally using ammonia.

9.1.3  Equipment Cleanup Wastes

Usually, the wasteloads associated with equipment cleaning are small and periodic in
nature (once every 1 or 2 years). Further reductions may be obtained through:

           o     More complete drainage of process  piping or equipment prior to
                cleaning.

           o     Lower process film temperatures and increase turbulence at the heat
                exchange surfaces to reduce fouling  rates. This can be accomplished
                by avoidance of overdesign and using recirculation during turndown
                operations.

           o     Use  of  electropolished or Teflon*  heat  exchanger tubes to  reduce
                deposit clingage (Anonymous 1985c).

           o     Use  of in-process heat exchanger tube cleaning devices (Anonymous
                1985b).

The reader is  also referred  to  the study of process  equipment cleaning contained in
this appendix.

9.1.4  Spills and Leaks

As mentioned  before, spills and  leaks constitute  a  very  minor waste stream owing to
the extensive implementation of preventive maintenance measures in facilities dealing
  Registered trademark of E.I. Du Pont de Nemours & Co.
                                      B15-9

-------
with hazardous materials.   Further  source reduction is possible, in principle, through
better  operating  practices  (see   also  process   study   entitled   "Good  Operating
Practices"). Additionally, some consideration should be given to:

           o    Replacing  single mechanical seals with double mechanical  seals on
                punnps or using canned seal-less pumps.

           o    Using leak detection systems and portable monitors.

           o    Using enclosed sampling and analytical systems.

           o    Using  vapor-recovery  systems for loading, unloading, and equipment
                cleaning.

9.2   Implementation Profile

The  facilities  that currently combust their organic wastes with attendant recovery of
HC1  and  heat value  will  probably have  little  or  no  incentive to  pursue  waste
minimization options, some of which may require considerable investment of effort for
engineering and economic analyses before implementation.

9.3   Summary

Table 9-1 represents  a  summary  of  source  control methodologies  for the 1,1,1-
trichloroethane  manufacturing industry.   Based on the measures  currently  taken to
minimize waste,  it is estimated  that waste generation has been reduced  to the level
characterized  by a   current  reduction   index  of  3.0  (75  percent),  due  to   the
implementation  of methods listed in this section (the 75 percent value represents the
amount of waste that current waste  reduction measures have reduced compared to the
waste volumes  that  currently  would  be generated  without  these  measures.)   By
implementing  additional  waste  reduction  measures,  it  appears that the  amount of
waste currently being generated can be further reduced to a level characterized  by an
index of 0.7 to 0.8 (18 to 20 percent reduction from current waste generation levels.)
The most effective potential measures for achieving this reduction are those with high
future reduction  index shown in  Table  9-1.  These include:  hydrocracking the heavy
chlorinated hydrocarbons,  precipitation and  recycling of the FeCl3 catalyst.  Among
the measures that do  have current industrial precedent, thermal oxidation of the heavy
ends with attendant HC1 and heat recovery has the highest application potential.
                                      315-10

-------
                                   TABLE 9-1 SUHURY OF SOURCE CONTROL METHODOLOGY FOR THE 1,1.1  - TRICHLOROCTHANE MANUFACTURIN6 INDUSTRY
1


1
I Heavy Ends (*)
1
1
i
1
I Spent Catalyst (*)
1
1
1
| Equipment Cleaning
1 Wastes («)
1
1
i
1
| Leaks and Spills
1
1
1
1
1
| All Sources
1
1

1
|1
It-
|3.
1
|1.

I
I'-
|2.
|3-

I
11.
|2
|3.
|4.
I
I




Hydrocrack heavy chlor. hydrocarbons
Use lower hydrochlor. reaction temp.
Recover HCl/heating values
Overall
Eliminate use of filter aid
Precipitate & recycle FeC13 catalyst
Overall
Increase equipment drainage time
Lower heat exchanger film temperature
Electropollsh heat exchanger tubes
Use in-process H.X. cleaning devices
Overall
Use double mechanical seals on pumps
Use leak detectors
Enclosed sampling and analy. systems
Use of vapor recovery systems
Overall
All Hethods
Found Documentation


Quantity | Quality
1 I
0 1
2 1
1.00 | 1
0 1
0 1
0.00 | 0
1 1
1 1
2 1
2 1
1.50 | 1
1 I
3 I
3 I
2 I
2.25 | 2

I

" I
I
n
o I
2 I
00 |
o I
o I
00 |
1 I
1 1
1 1
1 1
00 |
1 I
3 I
2 I
2 I
00 |

Waste I


Effectiveness |
3 I
2 I
4 l
3.00 |
2 1
3 1
2 50 1
3 1
2 1
3 1
2 1
2.50 |
3 1
2 1
2 1
4 1
2.75 |

Extent of |


1
0 1
0 1
3 1
1.00 |
1 1
0 1
0.50 1
3 1
1 I
0 I
1 1
1.25 |
4 I
3 I
3 I
4 I
3.50 |

Future | Fraction of |


Potential | [
' i i
' i i
3 1 1
1.67 | 0 89 |
1 1 1
' 1 1
1.00 | 0.05 I
2 I I
' 1 1
2 1 1
2 1 1
1.75 | 0.05 |
2 I I
1 1 1
1 1 1
1 1 1
1.25 | 0.01 |
1 '.oo |
Current I


Index |
0.0 |
0.0 |
3.0 |
3.0 |
0.5 |
0.0 |
0.5 |
2.3 I
0.5 |
0.0 |
0.5 |
2.3 I
3 0 |
1.5 |
1.5 |
3.9 |
3.9 |
3.0 |
Future Reduction Index


Probable I Maximum
0.8 |
0.5 |
0.8 |
0.7 |
0.4 I
0.8 |
0.6 |
0.» |
0.4 I
1.5 |
0.8 |
0.8 |
0.0 |
0.1 |
0.1 I
0.0 |
0.1 |
0.7 I




0

0
0

0
0


1

1

0
0

0
0
1

1
1
8 1
1
8 1
8 1
1
8 1
8 1
1
1
5 1
1
5 1
1
1 1
1 |
I
1 1
8 1
CD
               (*) These waste streams include listed T"  and/or  "K" RCRA wastes.

-------
10.   PRODUCT SUBSTITUTION ALTERNATIVES

The  growth in industrial use of 1,1,1-TCE as a solvent for vapor degreasing and cold
cleaning operations has been substantial in the 1970's and the early  1980's. Due to  its
relatively low toxicity, low level of photochemical  reactivity, its adequate solvency,
and  the  absence  of the  need  for  equipment changeover,  1,1,1-TCE  was  used
extensively to replace the more highly  criticized  trichloroethylene as a solvent for
metal cleaning operations. Environmental concerns over the fact that 1,1,1-TCE may
threaten the earth's stratospheric ozone layer, however, has placed  the use of  1,1,1-
TCE under stricter scrutiny (SRI 1982).

Substitution  of  water-soluble  synthetic cleaners for  organic  solvents has  also  been
practiced in industry.  Improvement in cleaning techniques  can enhance the ability  of
weaker  cleaning  substances,  such  as  alkaline  solutions   or soaps,  to  remove oily
residues.  These less toxic cleaners can then be used to replace chlorinated  organic
solvents such as  1,1,1-TCE.

Production  demand  for  solvents (including  1,1,1-TCE) is  largely  controlled by the
consumers' effort for conservation and the extent of solvent recovery being employed.
Increasing  costs of waste disposal,  coupled with stricter  air emission regulations, are
likely to result in increased recycling and tighter control of  solvent evaporation losses.
Conservation and  recovery, together with  availability of  less toxic substitutes, may
result in a future reduction of the production rate of 1,1,1-TCE.

11.  CONCLUSIONS

The  principal waste  stream  from the  1,1,1-TCE  production   process  consists  of
chlorinated  organic by-products (heavy ends),  which are  formed  during the synthesis
stage.  Past modifications of the manufacturing process to  eliminate the  formation  of
by-products were not in evidence; instead the trend has been to reprocess  this  stream.
In facilities  where  heavy ends are  currently  dealt  with  satisfactorily  by  thermal
oxidation combined with HC1 and heat  recovery, manufacturers  of 1,1,1-TCE do not
have the incentive to change their manufacturing process.  Further extension of this
option (thermal  oxidation) appears to be a  major practical step  toward minimizing
waste  disposal.    Nevertheless, source  reduction  techniques,   such  as heavy end
hydrocracking with  recycle,  may  deserve  further investigation  primarily  as   yield
promoters and not  necessarily as waste minimizers.

                                     B15-12

-------
It  appears that,  in  the  case of 1,1,1-TCE, the issue  of  reducing  wastes related  to
manufacturing  process is  subordinate  to the  issue of product  substitution or use

alteration relying on more  extensive use of improved cleaning techniques, employment

of less toxic cleaning substitutes and increased  recovery and conservation efforts  by

the users.  This conclusion is based on  the observation that nearly two-thirds of the

total 1,1,1-TCE produced is consumed in cleaning operations  and subsequently disposed

of as cleaning sludges  or lost as atmospheric emissions. By comparison, the amount  of

wastes produced during the manufacturing process is very minor.
12.  REFERENCES

Anonymous.  1979.  Key chemical: 1,1,1-Trichloroethane.  Chem. Eng. News. 57(40):
130.

Anonymous.  1980a.  Clean-up for solvents market.  New Scientist. 86:  315.

	.  1980b.  ICI commissions safer solvent plant.  Chem & Ind.
June~21, 1980.  p.A72.

	.   1980c.   Solvent  processing gets a second look.  Textile
World.  130;  67-76.

	f	.  1983.  Solvent switch cuts cost of vapor degreasing. Met.
Prog. 123:  17.

	.   1985a.   Aliphatic  hydrocarbon  output.   Chem. Market.
Rep.  July 15, 1985.  p.15.

	.  1985b.  Chemical  Engineering Progress, 81(7):7.

	.  1985c.  Chemical  Engineering Progress, 81(7):104-5.

Archer,  W.L., and  Simpson, E.L.   1977.   Chemical  profile of  polychloroethanes and
polychloroalkenes.  Ind. Eng. Chem. Product Res. &  Dev. 16:  158-62.

Archer, W.L., and Stevens, V.L.  1977. Comparison  of chlorinated, aliphatic,  aromatic,
and oxygenated  hydrocarbon as  solvents.  Ind. Eng. Chem.  Product  Res. &  Dev.   16:
319-25.

Berrie,   J.S.,  Charles,  R.,  and  Chuffant,  H.    1978.    Manufacture   of  1,1,1-
Trichloroethane.  Brit. Pat.  1,500, 136. (Feb.  8, 1978).

Boozalis, T.S., and Ivy, J.B.  1978.  Process for production of 1,1,1-Trichloroethane and
vinylidene chloride.  U.S. Pat. 4,119,674 (Oct.  10, 1978).  To Dow Chemical Co.
                                     B15-13

-------
Clark, J.B.,  Steven,  J.C.,  and Pevetti,  D.J.   1984.   Laser initiated  free-radical
reaction.  Proc. SPIE - Int. Soc. Opt. Enq.  458:  82-8.

Emig,  G.,  Hoffman,  V.,  and  Ruppert,  W.    1979.   Investigation  of kinetics  for
photosynthesis of methyl chloroform.  Chem. Eng. Sci. 34(6):  801-9.

Forsht, E.H.  1983.  Development document for proposed  effluent limitation guidelines
and  new  source  performance  standards  for  the  organic  chemicals,  plastics, and
synthetic  fibers  industries.  EPA-440-1-83-009B.  Washington, D.C.:   U.S.  Environ-
mental Protection Agency.

Johnson,  J.C., and Wedmore, L.K.  1983.   Metal cleaning by vapor degreasing.  Met.
Finish. 81(9):  59-63.

Key,  J.A., Stuewe, C.W.,  Standifer,  R.L., et al.   1980.   Organic chemicals  manu-
facturing,  Vol.  8.    selected  processes.   IT Enviroscience.    EPA-450-3-80-028C.
Research Triangle Park, N.C.: U.S. Environmental Protection Agency.

Khan, Z.S., and Hughes, T.W.  1979.   Source  assessment;   chlorinated hydrocarbons
manufacture.   Monsanto Research Corp.  EPA-600-2-79-019G.   Research  Triangle
Park, N.C.:  U.S. Environmental Protection Agency.

LWVM.  1985. The League of Women Voters in Massachusetts.  Waste  reduction, the
untold story.  Meeting materials, National Academy of Science Conference Center on
June 18-21, 1985. Woods Hole,  Mass.:  The League of Women Voters of Massachusetts.

Monahan,  R. 1977. Vapor degreasing with chlorinated solvents.  Met. Finish.  75: 26-
31.

PACE.  1983.  PACE Company Consultants &  Engineers, Inc.  Solvent recovery in the
United States; 1980 - 1990.  Houston,  Tex.: PACE Co.

SRI.  1982.   Stanford  Research  Institute.   C2-Chlorinated  solvents.   In Chemical
economic  handbook, 1982.  Menlo Park, Calif.:  Stanford Research Institute.

Stevens, V.L.  1979.   1,1,1-Trichloroethane.  In Kirk-Othmer encyclopedia of chemical
technology. 3rd ed. Vol. 5, pp.  728-31.  New York, N.Y.:  Wiley.

Stevens, V.L., and Hansen,  T.F. 1982.  Non VOC solvents  for air quality  compliance.
Met. Finish. 80:  41-2.

Van  Gemert, B.  1982.  Role of stabilizer: aluminum reaction in methyl  chloroform
stabilization.  Ind. Enq. Chem. Product Res. &  Dev.  21:  296-9.
13.  INDUSTRY CONTACTS

S.L.  Arnold, Manager, Environmental Information Clearinghouse, Dow Chemical Co.,
Midland, MI.

R. Samelson, PPG Industries, Pittsburgh, PA.
                                     815-14

-------
1.    PROCESS:      TRICHLOROETHYLENE/PERCHLOROETHYLENE
                    MANUFACTURE

2.    SIC CODE:     2869(2)

3.    INDUSTRY DESCRIPTION

Manufacturers of trichloroethylene (TCE) and perchloroethylene (PCE) are included as
part of the organic chemicals industry. A variety of feedstocks and processes are used
to manufacture TCE and PCE as co-products.

3.1   Company Size Distribution

Four major manufacturers are  currently  responsible for all of the U.S.  production of
TCE  and PCE.  These  are  large chemical companies producing a great variety  of
organic  compounds at each of  their manufacturing plants.  A company usually owns
one or two plants, with combined annual production capacity of TCE and  PCE between
25 to 200 thousand short tons/year (TPY).

3.2   Principal Producers

The five principal producers of TCE  and/or PCE are listed below*:
     Diamond Shamrock Corp. - PCE only
     Dow Chemicals USA - TCE/PCE
     E.I. du Pont de Nemours & Company, Inc. - shut down
     PPG Industries - TCE/PCE
     Vulcan Materials Company - PCE only

3.3   Geographical Distribution

Nationwide,  there  is a total  of six plants producing TCE and/or PCE (SRI 1982).
Among these,  one plant is  located in Texas, three in Louisiana, one in Kansas,  and one
in California.
  PPG Industries 1985: Personal communication.
                                     B16-1

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4.    PRODUCTS AND THEIR USE:

TCE and  PCE  are used mainly as solvents  for  dry-cleaning and  metal degreasing
operations. PCE is also used as  an  intermediate for the production of other chemicals
such as C2-fluorocarbons.  The end-use profile of TCE and PCE in 1981-1982 is  given
in  Table 4-1.  Due  to  stricter government regulations on the use  of toxic  solvents,
consumption of TCE in metal cleaning was expected to drop by an average of 3%
annually in the 1980's.  While annual production rates of TCE in recent years could not
be found,  significant reduction from  the  value of 133,100 TPY produced in 1975 is
expected due to the effect of increasing application of solvent re-use, recovery,  and
recycling.   Demand for PCE peaked in 1979, but has been declining since.  Annual U.S.
production of PCE was  254,364 TPY in 1984 (Anonymous 1985).

           Table 4-1.  1981-82  End-Use Profile for TCE/PCE in the U.S.

                                           Relative Consumption Rates, %
           End Use                          TCE                    PCE
                                            (a)                      (b)
Metal Cleaning
Dry Cleaning/Textile Processing
Chemical Intermediate
Miscellaneous
66
--
7
27
21
59
6
14
       Total                                100.0                   100.0

     Source:    Hughes, et al., 1985
5.   RAW MATERIALS

The raw materials used in the production process (Liepins et. al., 1977) are:

Reactants           ethylene  chloride,  ethylene  dichloride,  Ci~Cj  hydrocarbons,
                    C2-chlorinated hydrocarbons, chlorine, hydrochloric  acid,  oxygen
                    (air)
Catalysts           CuCl2, BaC^, KC1, Aid}, graphite, activated carbon.
Stabilizers          trimethylamine,  pyrrole-based compounds, hydroquinone mono-
                    methyl ether, p-tertiary annyl phenol.
                                      B16-2

-------
Neutralizes         sodium hydroxide, ammonia
Drying materials     sulfuric  acid, molecular sieves,  activated  carbon,  alumina gel,
                    silica gel, and others

6.   PROCESS DESCRIPTION

A variety of feedstocks and  processes can  be  used to produce TCE and PCE.  The
principal processes of current  commercial importance in the U.S.  are:

           The coproduction of PCE and carbon tetrachloride (CC^) from the thermal
           chlorination of  Ci  to C4 paraffinic  hydrocarbons,  or  their partially
           chlorinated derivatives.

           The  coproduction  of  TCE and  PCE  from the  thermal  chlorination  of
           ethylene  dichloride (EDC), or other C2~chlorinated hydrocarbons.

           The coproduction  of TCE  and  PCE  from  the  oxychlorination of EDC,  or
           other C2-chlorinated hydrocarbons.
                                *
ThesS  processes allow for  re-use  of C3 and  higher chlorinated  hydrocarbon by-
products, and thus enable the upgrading  of chlorinated hydrocarbon  residuals from
other processes, with the exception of  chlorinated  tars*.

The thermal  chlorination process can be performed  either with or  without  a catalyst,
and results in an  output of HC1 as  a co-product.  The catalytic oxychlorination process,
on  the other hand, avoids a net  production  of  HC1 and  even provides an  outlet  for
unwanted HC1  from other  processes.  The  oxychlorination reaction produces water
along with TCE/PCE and hence requires the removal of water from  the final  product.

Descriptions  of  the  above manufacturing  processes have been given in the literature
(McNeill Jr., 1979; Key et al., 1980;  Liepins et. al., 1977).   In this report, only the
oxychlorination route will be described and discussed in detail.
  E.I. Du Pont de Nemours & Co. 1985:  Personal communication.
                                      B16-3

-------
TCE  and  PCE  are  coproduced  from  the  oxychlorination  of  EDC  or  other
C2-chlorinated hydrocarbons.  The raw  material ratios  determine  the  proportions of
TCE and PCE being produced.  Conversion  of  chlorinated hydrocarbons to TCE  and
PCE was reported as 75-85%, with 10-15% chlorinated by-products, and 5-10% loss as
CO and CC>2 (McNeill 1979). The overall reaction for this process is given by:
C2-chlorinated hydrocarbons + C>2 + C12         TCE + PCE + H2O                (1)

HC1 can also be used as a feedstock since C12 can be produced from HC1 by a Deacon
reaction:
                     2HC1 + 1/202       > C12 + H20                           (2)

Figure 6-1  represents  the  flow diagram  for  the production of  TCE  and PCE  by
oxychlorination.  In  this process, EDC, recycled chlorinated hydrocarbons, chlorine,
and oxygen are fed  into a fluidized bed  reactor.  For this  process, C2-chlorinated
hydrocarbon wastes from other processes can also be consumed by introducing them
into the organic recycle storage tank which feeds the fluid bed reactor.  The reactor
operates at slightly  above  atmospheric pressure and about 800°F (Keil 1979).   The
most common catalyst used is CuCl2.

The reactor effluent  gas, containing chlorinated organics, water,  a  small  amount of
HC1, CO, CO2, and traces  of other inert  gases, is condensed using water-cooled and
refrigerated condensers.  The  condensed  crude product stream is drained through a
decanter to remove entrained catalyst fines.  The non-condensed  vent gas stream is
sent through a HC1 recovery unit where the gas stream is water scrubbed  to remove
HC1 as by-product.

The  crude hydrocarbon stream is separated in the decanter.  This stream is then
azeotropically distilled to remove  water. Waste water from the azeotropic  distillation
is combined with the aqueous phase containing  catalyst fines from the decanter.  The
combined stream is sent to waste  water treatment.  An  alternative approach relies on
concentrated sulfuric acid  (98% H?SO4) to  remove water from the  crude  TCE/PCE.
The acid and crude TCE/PCE are contacted and then allowed  to separate.  The acid is
then sent to a vacuum flash unit where  the absorbed  water is  removed. The water can
then be  steam- or  air-stripped of organics  (which  are  recycled  to  the reactor),  pH
                                     B16-4

-------
                                         VENT BAS
                                                                                                  TCE
C2 CHLORINATED
ORCANICS  FROM
OTHER PROCESSES
             PROCESS HASTE CATEGORIES!

             (7)   HEAVY ENDS

             (7)   SPENT CATALYSTS

             (7)   SPENT ALKALINE SOLUTION

             0   SPENT ORYINB  MATERIALS

             (T)   NAETENATER
                      Figure 6-1   Production of  TCE  and  PCE  by Oxychlorination
                                                  B16-5

-------
adjusted  and discharged to NPDES  permitted  outfall.   The recovered sulfuric  acid
(*> 80%  h^SO^)  is then used  in other processes or sold, e.g.  as a raw  material to
produce fertilizer.

The  crude  chlorinated hydrocarbon mixture is  further  separated  into TCE and  PCE
crude streams in a TCE/PCE  column.  The TCE crude  is purified  in a TCE column.
Overhead from this distillation column  is sent to an organic recycle storage tank.  The
bottom stream is neutralized with dilute  caustic, ammonia or washed  with water, and
subsequently dried to give the desired TCE product.  Wastes from the neutralization
and drying operations are sent  to waste-water treatment or disposal.

The  bottom stream from  the  TCE/PCE column is separated  in a heavy-ends column.
The PCE-rich overhead stream from the heavy-ends column is sent to  the PCE column
where  final PCE purification takes place.  The overhead from the PCE column is
recycled to  the process  and the  purified PCE  is  withdrawn  as  bottoms,  then
neutralized, washed and dried.

The  bottom stream from the  heavy-ends column is flashed to  separate  the  tars and
carbon in the organic recycle system.  The flash overhead stream  is recycled back to
the process.   The separated heavies, called "hex-waste", contain  hexachlorobenzene,
hexachlorobutachrene plus various chlorinated  G£ compounds in addition to  tars and
carbon.

7.   WASTE DESCRIPTION

The  primary  specific  wastes associated  with TCE/PCE  manufacturing using  the
oxychlorination  process are listed in Table 7-1.  Organic  heavy ends account for  a
large portion of  the waste generated.  This liquid stream comes from the distillation of
the  hydrochlorination  reactor  effluent   stream   to   remove   heavy  chlorinated
hydrocarbons  that cannot  be  recycled or  further processed.  The resulting tars are
often oxidized for recovery of HC1 and heat or sent  to land disposal.

A second  source of waste  involves spent catalyst.   Entrained catalyst  fines are
removed from the reactor effluent stream when the condensed   stream is  drained
through the decanter.  The liquid waste stream  is then combined with wastewater  from
                                      B16-6

-------
 the azeotropic distillation or sulfuric acid drying operation, and is sent to wastewater
 treatment. Spent sulfuric acid is then used elsewhere in the facility or sold.


 Neutralization  and drying  operations  produce streams  containing  aqueous caustic
 solutions and spent absorbents.  The  aqueous waste  streams are sent  to waste  water
 treatment, and the spent absorbent is  regenerated  (if a  regenerable type is used) or
 land disposed.
 The remaining  portion of the waste is the scrubber effluent wastewater.  This liquid
 waste stream is generated from the  use  of emission control equipment to  limit the
 amount of gases being released  to the atmosphere.  The main  sources for emission

 include  vents from drying and neutralizing columns,  vents  from the HC1 absorbent
 unit, and vents from organic  storage tanks.  The gas streams are  often water scrubbed

 to remove hazardous materials.  The resulting aqueous waste streams are combined
 and sent to wastewater treatment.


Table 7-1.  TCE/PCE Manufacturing Wastes from the Oxychlorination TCE/PCE Process
No.
1.
2.
Waste
Description
Heavy ends
Spent catalyst
Process
Origin
Distillation from
organic recycle
system
Decanting of
entrained
catalyst
Composition
Tars, heavy
chlorinated
hydrocarbons
Metals, tars,
chlorinated
hydrocarbons
RCRA
Code
K030

   3.     Spent caustic
          solution
   4.     Drying waste

   5.     Spent scrubber
          wastewater
   6.     Equipment
          cleanup
          wastes

   7.     Spills &. leaks
Neutralization
Chlorinated
hydrocarbons,
spent caustic
solution
Drying operations    Spent absorbents
Emission control
operations
Cleaning of tanks,
towers, and heat
exchangers
Chlorinated hydro-
carbons, acids,
water
                   F024
                                       B16-7

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8.   WASTE GENERATION RATES

Very little data was available on waste generation rates from TCE/PCE manufacturing
facilities.  In 1975, Catalytic Inc. reported waste generation rates for the production
of PCE from a generalized model plant.  These values, however, were given for  the
manufacturing of PCE based on the direct chlorination  process alone.  Due to the lack
of  information,  estimation  of current  annual  waste  generation  volumes  by  the
TCE/PCE  manufacturing  based  on  oxychlorination  process  could  not  be  made.
Fractional waste  generation (weight fraction each waste represents as compared to all
waste  generated)  was  estimated by  the  project  staff. These  values  are  shown  in
Table 9-1.

9.   WASTE REDUCTION THROUGH SOURCE CONTROL

9.1  Description of Techniques

In addition to the waste  reduction measures  classified as being process changes or
material/product  substitutions, a variety of waste reducing measures labeled as "good
operating practices" has  also been included.  Good operating practices are defined as
being procedural  or institutional policies  which result  in a reduction of waste.  The
following items highlight  the scope of good operating  practices:

     o     Waste Stream Segregation
     o     Personnel Practices
                Management Initiatives
                Employee Training
     o     Procedural Measures
                Documentation
                Material Handling and Storage
                Material Tracking and Inventory Control
                Scheduling
     o     Loss Prevention Practices
                Spill Prevention
                Preventive and Corrective Maintenance
                Emergency Preparedness
                                     316-8

-------
For each  waste stream, good  operating practice applies  whether it is listed or not.
Separate  listings  have been  provided whenever case  studies  were  identified.   A
summary of the waste sources and the corresponding source reduction methods is given
in Table 9-1.  This section deals with  the description of the listed methods, including
known application  cases.

9.1.1  Heavy Ends

A major portion of the waste generated  from the manufacturing of  TCE and PCE
comes from distillation and flashing operations required for the removal of chlorinated
hydrocarbon heavy ends. Since only light chlorinated hydrocarbons can be recycled to
give TCE and PCE as products, reduction of the waste load can be done either  through
modifications  of the existing  manufacturing process to  minimize the formation  of
heavy  chlorinated  hydrocarbons,  or  from the upgrading of these  heavy  by-products.
The following source reduction  methods are noted:

      o     Rapid cooling of reactor effluent gas.
           It is postulated that the  extent to which the formation of the undesirable
           byproducts can be inhibited depends,  in part,  on how quickly  the  reactor
           offgas is  cooled. This postulate is based on the  argument that after leaving
           the  fluid bed,  the  gas  mixture is no longer in  intimate contact with the
           catalyst.   Therefore, side reactions can now take place without the benefit
           of selectivity control of the catalyst.

           Rapid quench of the reactor offgas leaving  catalytic reactors  is a  feature
           often encountered in chemical processes, such as acrylonitrile  or  TCE/PCE
           production through thermal chlorination.  It is suggested that the control of
           cooling (or quench) rate be examined in the  context  of reducing formation
           of  the  compounds  found in  the  "hex-waste",  along with the effects on
           TCE/PCE distribution.

     o     Control of chlorine-to-hydrocarbon ratio in the  feed.
           Formation  of  03 and  heavier compounds  is  strongly dependent  on the
           chlorine-to-hydrocarbon ratio in the  feed, as chlorine presence moderates
           carbon-to-carbon  radical reactions responsible  for the formation  of C3+
           byproducts.  Examination of  Cl2/hydrocarbon ratio  as a waste generation
           control parameter is suggested.
                                     B16-9

-------
           Re-examination of fluidization conditions.
           In the fluidized beds operating in a bubbling regime, the effective size of
           bubbles  controls  the degree  of mixing,  which,  in turn,  influences  the
           catalyst-gas  contacting,   represented   by  an  interchange  coefficient
           (Froment & Bischoff 1979). It is postulated that by decreasing the bubble
           size (e.g. by decreased tube pitch of the cooling coil bundle) the catalyst-
           gas  contacting is improved resulting  in  a lower  rate of formation  of
           undesirable byproducts.  It is suggested that this aspect be examined for its
           waste minimization potential.

           Application of improved catalysts.
           Use  of  the  oxychlorination  catalysts with  higher selectivity  toward
           TCE/PCE is an effective method of minimizing waste due to formation of
           undesirable  byproducts.   Research  efforts have  been  made  to  improve
           currently used catalysts.

           Heavy ends hydrocracking.
           An  additional reaction  may  be  used  to  break  the  heavy  chlorinated
           hydrocarbons into lighter  products.    The cracking  can be  done  using
           catalytic hydrogenation processes.  The light hydrocarbons generated from
           this operation can then be combined with other light chlorinated  organic
           streams  to  be  recycled to the reactor.   Research work at the Illinois
           Institute  of  Technology  indicates  that  the  process  remains,   so  far,
           technically  infeasible due  to severe fouling of the catalyst*.   However,
           further research  is planned to explore the effect of increasing  H2/feed
           ratio on reactor performance.

           Replacement of oxychlorination with a combination of direct chlorination
           and an HC1  oxidation unit.
           Since the product yields from oxychlorination process (r>> 80%) are usually
           much lower than  those from direct  chlorination processes (^95%), the use
           of chlorination instead  of  oxychlorination to manufacture TCE and  PCE
           should reduce the amount of byproducts formed.  Also, subsequent  product
           purification operations are simpler  because of  the absence of water being
           formed as byproduct  in an organic environment in oxychlorination step.
* Illinois Institute of Technology 1985:  Personal communication
                                     316-10

-------
           A major disadvantage in using the chlorination process is the large amount
           of HC1  that is  formed as a byproduct.  The HC1 stream, however,  can be
           electrolytically oxidized into H2 and Cl£.  The chlorine generated in this
           process can then be recycled to the  feed.  Conversely, HC1 can be directly
           oxidized using  oxygen  to H£O and C\2  (Kel-chlor  process).   Both  HC1
           oxidation routes have been applied  commercially.  A big problem  is  that
           the direct HC1 oxidation route  is very costly and,  at the present, cannot
           compete with the  conventional  oxychlorination route.  The  only operating
           unit in  the U.S. (Du  Pont's  Kel-Chlor  facility in Corpus Christi, TX.)  is
           planned  to be  shut  down  and  replaced with  oxychlorination  due to
           unacceptably high  cost.   However, the  electrolytic route is  still  under
           consideration*.

      o     Thermal oxidation  with recovery of HC1 and heat.
           The heavy ends are often incinerated and both heat and HC1  are recovered.
           Recovered  hydrochloric  acid  can  either  be sold   or  used to  generate
           anhydrous HC1 for  use in the oxychlorination process.

9.1.2   Spent Catalyst

Hazardous waste can be produced from the periodic disposal of  spent catalyst, or from
the loss  of catalyst due to entrainment.   To reduce  the waste load  generated, the
following steps can be taken:

      o     Use dry dust collectors or filters.
           High temperature  ceramic fiber** or sintered metal  can be used as filter
           elements to remove entrained catalyst fines from  the effluent gas.   The
           catalyst  can  be  partially  recycled back  to  the   process  or collected
           separately  from other  waste streams.    The advantages  include  nearly
           complete  removal  of solids  in the dry  phase,  which  decreases  waste
           generation associated  with liquid filtration.  The disadvantages may include
           longer residence time of reactor offgas in the stand-alone filter as opposed
           to currently used cyclones and the potential for plugging.
* Du Pont 1986: Personal communication.
**  Acurrex Corporation 1985:  Personal communication.
                                     B16-11

-------
      o     Use of a tougher catalyst support.
           In fluidized bed  catalytic reactors, it is evident that the catalyst particles
           break into smaller fragments due to attrition and are consequently  swept
           out  of the reactor  with the  effluent gas.   This  results in the  loss of
           expensive  catalyst  material and additional  waste  residual that must be
           disposed of.  A substantial reduction in these losses might be obtained using
           a tougher  catalyst support and/or  by reducing the velocity of gas jets out
           of the distributor.

9.1.3   Spent Caustic Solution

Caustic wastes are generated in the  TCE  and PCE neutralization process where large
amounts of water and ammonia are  used.  A  method  to reduce the toxicity  of  this
stream as opposed to its volume was identified*:
     o     Use of NaOH instead of
           The usual method of  treating the spent caustic  stream is to neutralize  it
           using  spent  sulfuric  acid  and to then  send it  to  wastewater  treatment.
           Depending  on the type of  treatment system  employed,  the  presence of
           copper in the stream  can have adverse effects.  Facilities using  copper
           chloride  catalysts would  be advised against  using  ammonia since  it  will
           solubilize  copper  from   the  catalyst   and  create  potential  upsets
           downstream.  This effect  also  points  out the  importance, of  efficient
           catalyst  recovery back at the reactor and decanter units.  According to
           industry contacts, most facilities are already using NaOH.

9.1.4   Drying Waste

The waste generated from  the disposal of spent absorbent from  the drying operation
can be reduced by using regenerabie drying  materials  which include activated carbon,
aluminum gel, and silica.  Regenerabie drying agents are currently in wide use*.
* E.I. Du Pont de Nemours & Co. 1985:  Personal communication.
                                     B16-12

-------
9.1.5   Equipment Cleanup Wastes

Usually, the wasteloads associated with equipment cleaning are small and  periodic in
nature (once every 1 or 2 years).  Further reductions may be obtained through:

      o     More complete drainage of process piping or equipment prior to cleaning.

      o     Lower  process film temperatures  and increased turbulence at the  heat
           exchange surfaces to reduce fouling rates.

      o     Use of electropolished or Teflon* heat exchanger tubes to reduce deposit
           clingage (Anonymous 1985b).

      o     Use of in-process heat exchanger tube cleaning devices (Anonymous 1985a).

All suggestions listed above  will have only a minor impact on overall waste generation,
since equipment cleaning wastes are but a small fraction of th'e total waste.

9.1.6  Spills and Leaks
                                             «
As  mentioned  before, spills  and leaks constitute a rather minor waste stream owing to
extensive implementation of preventive maintenance  measures  in  facilities dealing
with  hazardous materials.  Further source reduction is possible,  in principle,  through
better operating  practices (see practice study  entitled "Good  Operating Practices").
Additionally, some consideration should be  given to:

      o     Replace single mechanical seals with double mechanical seals on pumps or
           use canned seal-less pumps.

      o     Use of leak detection systems and portable monitors.

      o     Enclosed sampling and analytical systems.
      o     Use  of vapor-recovery  systems  for  loading,  unloading, and  equipment
           cleaning.
* Registered trademark of E.I. Du Pont Co.

                                      B16-13

-------
9.2   Implementation Profile

Since the current common practice for the disposal of organic waste by incineration is
environmentally  viable  and successfully  complies  with  government  standards  and
regulations,  most  manufacturers  do  not have a  strong  incentive  to  investigate
alternative waste reduction techniques.  However, current permit difficulties to site,
build and operate an  on-site hazardous waste incinerator,  combined with  increasing
land  disposal costs  and  restrictions, could induce  source  control efforts in  those
facilities which currently landfill their waste.

9.3   Summary

A  summary of the source reduction  techniques, along with the associated ratings  is
given in  Table 9-1.  The ratings represent the assessment of the relative  usefulness
among the proposed  techniques.  It is estimated that the potential waste that could be
generated has been reduced  to a level characterized by a current reduction index of
2.3  (58  percent).    By  implementing the  proposed  source reduction techniques or
expanding the use of  those  already  in place,  the amount of  waste  currently  being
generated can be reduced to a level characterized by a future reduction index of 0.4 to
0.9 (10 to 22 percent).  Among the  most effective measures are  the increase  in the
recovery of HC1  and heating values  from the  heavy ends and,  potentially,  control of
the quench rate to reduce the byproduct formation.

10.   PRODUCT SUBSTITUTION ALTERNATIVES

TCE  and PCE have  been  the  principal  solvents  used  for  cleaning due to their
outstanding ability to  dissolve  a  great variety  of oily substances.  TCE is used mainly
in  the vapor degreasing process for metal surface preparation operations. PCE is more
widely used in dry-cleaning, textile processing,  or cold cleaning of metal surfaces.

TCE  can  be  replaced  by  other  solvents  such  as   1,1,1-trichloroethane   or
chlorofluorocarbons  (CFC)  in  metal   degreasing   operations.     In  dry-cleaning
applications,  petroleum-based  Stoddard solvent is  used  as  an alternative to PCE.
Chlorofluorocarbons,  such  as  l,l,2-trichloro-l,2,2-trifluoroethane,  which are both
non-flammable and  very low in toxicity, are  not  used  widely mainly due to cost.
                                     816-14

-------
                                   TABLE 9-1 SUWARY OF  SOURCE CONTROL METHODOLOGY FOR THE TCE/PCE HMHIFACTURIK6 IHDUSTRY
1
Waste Stream
1
| Heavy Ends (*)
1
1

1
1

1
| Spent Catalyst

1
I Spent Caustic

1
| Drying Waste
1
i
| Equipment Cleaning
| Wastes (»)
1
1
I

| Leaks and Spills
1
1
1
1
I All Sources
1
1
11
12
13
14
15.
16.
|7
I

|2.
1
M

I

I
|1-
12.
13.
|4
1
I'.
12
13.
14
1
1
1
Control Methodology I 	
Found Documentation I Waste | Extent of 1 future | Fraction of | C
	 	 __ Deduction I Current Use | Application | Total Waste | Re
| Quantity | Quality | Effectiveness |
Cool reactor effluent gas rapidly |
Control chlorine/hydrocarbon ratio |
Improve fluidization conditions |
Improve catalyst |
Hydrocrack heavy chlor hydrocarbons |
Replace Oxychlorination w/HCl oxid. . |
Oxidize waste w/HCl and heat recovery!
Overall |
Use dry dust collectors and filters |
Use of a tougher catalyst support I
Overall |
Use NaOII in place of NH3 |

Overall |
Use regenerable drying materials |
Overall |
Increase equipment drainage time I
Lower heat exchanger film temperature!
Electropolish heat exchanger tubes |
Use in-process H.X. cleaning devices 1
Overall |
Use double mechanical seals on pumps I
Use leak detectors [
Enclosed sampling and analy systens 1
Use of vapor recovery systems |
Overall |
All Methods
2 1
1 1
1 1
1 1
1 1
2 1
3 1
1 57 |
1 I
1 1
1.00 |
2 1

2 00 |
1 1
1 00 |
1 1
1 1
2 1
2 1
1.50 |
1 1
3 1
3 1
2 1
2.25 |

1
1

1

2 1
2 I
1 29
1 I
1 I
1.00 |
2 1

2 00 |
1 I
1.00 |
1 1
t 1
1 1
1
1.00 I
1 1
3 1
2 1
2 1
2 00 |

3 I
2 1
1 |
2 1
2 1
3 1
4 1
243 |
1 1
3 1
2 00 |
2 1

2.00 |
3 1
3.00 I
3 1
2 1
3 1
2 1
2 50 |
3 I
2 1
2 1
4 1
2.75 |

| Potential | |
2 1
3 1
0 1
3 1
0 i
1 I
2 I
1 57 I
0 1
3 1
1 50 I
4 1

4.00 I
3 1
3.00 !
3 1
1 1
0 1
1 I
1.25 |
4 1
3 1
3 1
4 !
3 50 |

2 1 1
1 1 1
1 1 1
3 1 1
1 1
1 1 1
2 1 1
1.57 I 0.73
2 1 1
1 I I
1.50 | 0.01 |


0.00 ! 0.10 |
1 1 1
1.00 | 0.05 |
2 1 1
1 I I
2 I I
2 I I
1 75 I 0 05 |
2 1 1
' 1 1
' 1 1
1 I I
1.25 | 0 81 |
1 LOO |
jrrent | Future Reduction


Index | Probable
1.5 |
1-5 1
0.0 I
1.5 |
0 0 |
0 8 |
2.0 |
2.0 I
0.0 I
23 |
2.3 |
2.0 I

2 0 |
2.3 |
2.3 |
2.3 |
0.5 |
0.0 |
0.5 |
2.3 |
3.0 |
1.5 |
1.5 |
3.9 |
3.9 |
2.3 |
0
0
0
0

Index I
	 -|
| Maximum |
8 1
J |
3 1
4 I
1
1
1
1
0.5 | |
0
1
0
0
0
0
0

0
0
0
0
0
1
0
0
0
0
0
0
0
0
6 1
0 1
5 1
5 1
2 1
3 1
0 1

0 1
2 1
2 1
4 1
4 I
5 1
8 1
8 1
0 1
t 1
1 1
0 1
t 1
» 1
1
1.0 I
1 0 I
0.5 !
1
0.5 |
1

0.0 |
0.2 |
0 2 |
1
1
1.5 |
1
1.5 1
1
0.1 |
0.1 |
1
0.1 |
0 9 !
CD
h-'

 I
t—i
\-n
               (*)  These  waste  streams  include  listed "F' and/or "K" RCRA wastes

-------
Improvement  in  equipment  and  techniques  which  make  emission  control more
effective, may contribute to an increased use of these solvents to replace  TCE or PCE
in the future. However, it must be noted that since PCE is used as a raw material in
the manufacture of several CFCs, their substitution for TCE/PCE may have a limited
impact on TCE/PCE production.

Changes in cleaning techniques can be  adopted to allow  for the use of less powerful
cleaning substances in place of  TCE and PCE. For example, a combined ultrasonic-
alkaline cleaning step would greatly improve the ability of alkaline cleaning solution to
remove oily residues, and thus  would eliminate the need for using  organic solvent
cleaners (the reader is also referred to the study  of metal parts cleaning  contained in
this appendix).

The dominant factor controlling the production demand for any solvent (including TCE
and PCE) is the extent of the recovery and conservation effort  by the  users.   The
increasing costs  of  waste disposal coupled with tougher and more  vigorously enforced
air emission standards are likely to result  in  increased recycling and  tighter control
of solvent evaporation losses.   These, in turn, may lead to the decrease of production
demand.
                                                          i
In summary,  the  likelihood  of future decreases in the production rate of TCE/PCE
remains strong in  view of such  factors as   the  enhanced solvent  conservation  and
recovery efforts by  consumers and the availability of less toxic substitutes.

11.   CONCLUSIONS

Those  TCE/PCE  manufacturers  who use the  oxychlorination route appear to have
minimized their  waste generation considerably. The reduction is  on the  order of 60
percent with  respect to the waste that would have been produced if none  of the noted
methods were implemented.   Further reductions  appear  possible, albeit  low,  on  the
order of 10 to 20 percent with  respect to current waste.

The most effective techniques identified  were oxidation  of  heavy chlorinated  waste
with attendant HC1 recovery  and, potentially, control of quench rate to reduce  the
byproduct formation.
                                     B16-16

-------
 Waste generation  from TCE/PCE manufacturing is directly related to the demand for

 these solvents which,  in turn, is influenced by consumer conservation  and recycling

 efforts and substitution of  TCE/PCE with other media in cleaning applications.


 12.   REFERENCES

 Anonymous. 1985.  Aliphatic hydrocarbons output.  Chem. Market Rep.  July 15, 1985.
 p. 15.

 	.  1985a.  Chemical Engineering Progress, 81(7):7.

 	. 1985b.  Chemical Engineering Progress. 81(7):104-5.
Arcoya, A., Cortes, A., and Seoane, X.L.  1980a.  Tri- and perchloroethylene 1.  fluid
catalytic  oxyhydrochlorination of ethylene. Ind. Eng. Chem. Prod. Res. Dev.  19: 77-
82.

	.  1980b.  Tri- and perchloroethylene 2. fluid catalytic oxy hydro-
chlorination of dichloroethane. Ind. Eng. Chem. Prod. Res. Dev. 19: 82-6.

Catalytic, Inc.  1975.  Water pollution  abatement  technology;   organic chemicals
industry.  PB 244544. Springfield, VA.:  National Technical Information Service.

Forsht, E. H. 1983.  Development document for proposed effluent  limitation guidelines
and new source performance standard for the organic chemicals, plastics and synthetic
fibers  industries.   EPA-440-1-83-009B.   Washington, D.C.:   U.S.   Environmental
Protection Agency.       '

Froment,  G.F., Bischoff,  K.B., 1979.  Chemical reactor analysis  & design, J.Wiley  &
Sons, 1 ed.

Genser, J. M., Zipperstein, A. H., Klosky, S. P., et al 1977. Alternatives for hazardous
waste  management  in the organic  chemicals, pesticides, and explosives  industries.
Process Research, Inc. EPA-530-SW-151C.  Washington,  D.C.:  U.S.   Environmental
Protection Agency.

Gruber, G.I. 1975.   Assessment of  industrial hazardous waste  practices;  organic
chemicals, pesticides, and explosives industries.   TRW Systems Group EPA-530-SW-
118C.  Washington, D.C.:  U.S. Environmental Protection Agency.

Hughes, T.H.,  et. al. 1985. A  descriptive survey of selected solvents, Open file report
No. 1,  Environmental Institute for Waste Management Studies,  University of Alabama,
Tuscaloosa, Alabama.

Keil,  S.  L. 1979. Tetrachloroethylene.   In  Kirk-Othmer  Encyclopedia of Chemical
Technology. 3rd ed. Vol. 5, pp. 754-62.  New York, N.Y.: Wiley.

Key,   J.A.,  Stuewe,  C.W.,   Standifer,  R.L.,  et  al.  1980.    Organic  chemicals
manufacturing,  vol.  8. selected processes.  IT Enviroscience.  EPA-450-3-80-028C.
Research  Triangle Park, N.C.:  U.S. Environmental Protection Agency.
                                     816-17

-------
Khan,  Z.S., and  Hughes, T.W.  1979.   Source assessment;  chlorinated hydrocarbon
manufacture.  Monsanto  Research Corp. EPA-600-2-79-019G.  Research Triangle Park,
N.C.:  U.S. Environmental Protection Agency.

Liepins,  R., Mixon,  F., Hudak,  C, et. al. 1977.   Industrial process  profile  for
environmental use:  chapter 6.   the industrial organic chemicals industry.  Research
Triangle  Institute.  EPA-600-2-77-023f.    Cincinnati,  Ohio:    U.S.  Environmental
Protection Agency.

Marsman, C. J.,  and Bleich,  B.  J.  1982.  Pollution  control practice:   HC1 emission
reductions from reactor vent system. Chem. Eng. Prog. 78(6): 40-2.

McNeill, Jr., W.C. 1979.  Trichloroethylene.  In Kirk-Othmer encyclopedia of chemical
technology.  3rd ed. Vol.  5, pp. 745-53.  New York, N.Y.: Wiley.

Miller,  S. 1983.   Chlorinated hydrocarbon  waste.   Environmental Sci.  Tech.   17(7):
290A-1.

Payer, S. 1974. Recover  chlorine from HC1.  Hydrocarbon Processing. 53(11):  147-50.

PPG  Industries,   Inc. 1981.    Perchloroethylene-trichloroethylene.    Hydrocarbon
Processing.  60(11): 195.

Reich, D.A., and  Cormany, C.L. 1979.  Dry cleaning.  In Kirk-Othmer encyclopedia of
chemical technology.  3rd ed. Vol. 8, pp. 50-68. New York, N.Y.:  Wiley.

Scharein,  G. 1981.  Recover  products from chlorohydrocarbon residues.  Hydrocarbon
Processing.  60(9): 193-4.

Schneiner, W.C.,  Cover,  A.E., Hunter, W.D.,  et al. 1974.  Oxidize HC1 for chlorine.
Hydrocarbon Processing.  53(11):  151-6.

SRI. 1982.   Stanford Research Institute.    C2~chlorinated  solvents.   In Chemical
economic  handbook, 1982. Menlo Park, Calif.: Stanford Research Institute.

Vail,  S.L.  1983.   Textiles:   finishing.   In  Kirk-Othmer encyclopedia of  chemical
technology.  3rd ed. Vol.  22, pp. 769-802.  New York, N.Y.: Wiley.


13.   INDUSTRY  CONTACTS

S.L. Arnold, Manager Environmental Information Clearinghouse, Dow Chemical Co.,
Midland, MI.

G.J. Hollod, Sr. Environmental Engineer, Petrochemical  Department, E.I. Du Pont de
Nemours & Co., Wilmington, DE.

R. Samelson, PPG Industries,  Pittsburgh, PA.
                                    816-18

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1.    PROCESS: VINYL CHLORIDE MONOMER MANUFACTURE

2.    SIC CODE:  2869

3.    INDUSTRY DESCRIPTION

Because  the  manufacture  of vinyl chloride involves a  capital-intensive  process,
virtually all of the  U.S. vinyl chloride manufacturing capacity is provided by a small
number of producers with  14 plant locations (see Table 3-1).  Individual plant annual
production capacities of major vinyl chloride manufacturers range from 150 million
pounds to 1,250 million pounds.   In 1984, U.S. plants produced 7,513 million pounds of
vinyl chloride  (Anonymous 1985a).

Vinyl  chloride production  units  are  generally  part  of  large  integrated  chemical
production facilities.  Of the 14  major vinyl  chloride  producing plants, eight  are
located in Louisiana and  four are located  in Texas.   California  and Kentucky each
contain one plant.

4.    PRODUCTS AND THEIR USE

Most vinyl chloride production is consumed in the  manufacture of polyvinyl chloride
(PVC)  and its  copolymers.   The small remainder  is either exported or used  in  the
manufacture of adhesives  and specialty chemicals.

5.    RAW MATERIALS

Chemical Feedstocks;  ethylene  route -  ethylene, chlorine, air, or oxygen; acetylene
route - acetylene (C2H2),  hydrogen chloride (HC1).

Drying  Agents and  Absorbents:    silica  gel,   solid   potassium  hydroxide  (KOH),
concentrated sulfuric acid (H2SO4), activated  charcoal,  bauxite, methanol.

Catalysts:   FeCl3 (direct  chlorination),  KC1  or CuCl2 (oxychlorination),  HgCl2
(acetylene hydrochlorination), on various supports and promoters.
                                       B17-1

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               Table 3-1 U.S. Producers of Vinyl Chloride Monomer
                                                              Annual Capacity
Company and Plant Location                                     (million pounds)
Borden Chemical Divison
   Geismar, LA                                                     610

Dow Chemical U.S.A.
   Freeport, TX                                                    150
   Oyster Creek, TX                                                750
   Plaquemine, LA                                                1,250 (a)

Ethyl Corporation
   Baton Rouge, LA                                                 330 (°)

Formosa Plastics Corporation
   Baton Rouge, LA                                                 300

Georgia-Gulf Corporation
   Plaquemine, LA                                                1,000
B.F. Goodrich Company
   Calvert City, KY
   La Port, TX                                                   1-,000
   Calvert City, KY                                               1,000
PPG Industries
   Lake Charles, LA                                                500

Shell Chemical Co.
   Deer Park, TX                                                   840
   Norco, LA                                                       700

Stauffer Chemical Co.
   Carson, CA                                                      174

Vista Chemicals Company
   Lake Charles, LA                                                700
   Total                                                         9,304


Source:   Chemical Economics  Handbook (SRI 1982); PPG Industries 1985:  Personal
          communication.

(a-   Source at Dow Chemicals indicates that capacity is lower.

(b)   Plant not operating at present.
                                     B17-2

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6.   PROCESS DESCRIPTION

Detailed process  descriptions for vinyl chloride monomer (VCM) production have been
presented in open literature (Cowfer and Magistro 1983, McPherson, Starks, and Fryar
1979, Sittig 1978, Liepins et al. 1977). The following paragraphs are based on a review
of the literature  and  on  industry comments.  The two main  methods of production of
vinyl chloride, the  acetylene  route  and  the  ethylene  route,  are discussed.   The
descriptions presented  below  are  general and  may not account for all  different
configurations encountered in the actual plant design.

Prior to the 1950's, the acetylene process for the manufacture of VCM  was dominant.
As ethylene  became plentiful  and the demand  for  VCM increased, the  commercial
processes shifted to  the ethylene route.   Currently, most of VCM production  in  the
U.S. is from ethylene.   The acetylene route is still practiced only in one installation
owned by Borden  Chemicals.

In the first route, the acetylene feed is reacted with HC1. The acetylene  feed is first
dried by  passing  it  through a bed containing silica gel,  KOH solid or concentrated
H2SO4.   The HC1 feed is  dried by  contacting  it  with  concentrated h^SO^.   The
dehydrated feed  streams are  mixed  in a chamber containing activated  charcoal to
adsorb  small  quantities of  Cl2 present   in HC1;  this is done  to prevent  explosive
chloroacetylene formation.  The drying  agents and activated carbon are  periodically
regenerated and discarded eventually as wastes.

The mixture is  then passed  through  packed  tubes  containing  mercuric  chloride  on
activated  charcoal  as   a  catalyst.    Thorium, cerium,  cadmium, and/or potassium
chlorides are  used in conjunction with  mercuric  chloride.    The  products  are vinyl
chloride,  ethylidene  chloride,  acetaldehyde,  unreacted  HC1 and  C-2^2-   The  spent
catalyst containing  mercuric chloride is  a potentially  hazardous waste stream.   The
inorganic impurities  from the product are removed  by alkaline and water scrubbing.
Water is removed by freezing the scrubbed gas stream or passing it  through a methanol
column or a bauxite  drier.  Secondary drying of VCM is accomplished by contact with
solid KOH.   The first  distillation  column removes low molecular  weight gaseous
impurities at low pressure.  In  the second column  VCM is further  purified.  Yields as
high as 99 percent are possible.
                                      B17-3

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The more predominant ethylene route, shown schematically  in the block  flow diagram
in Figure 6-1, consists of 3 basic reaction steps:

      1.    Direct chlorination of ethylene to ethylene dichloride (EDC):
           CH2 =  CH2 + C12	»CH2C1  -  CH2C1

      2.    Oxychlorination of ethylene to EDC using  HC1 and O2:
           CH2 = CH2 + 2HC1 + i 02	} CH2C1 - CH2C1 +  H2O

      3.    Pyrolysis of EDC to VCM and HC1:
           2 CH2C1 - CH2 Cl  neat> 2CH2  = CHC1 + 2 HC1

Direct chlorination  is conducted by passing ethylene and chlorine gas through  liquid
EDC at 80-250°F (depending on whether a sub-cooled  or boiling  reactor is used) and at
pressures close to  atmospheric or higher. The  reaction is homogeneously catalyzed by
ferric chloride dissolved in EDC. The  heat  of  reaction is dissipated either by cooling
with water  coils or by the vaporization of EDC,  with the  reactor operating  at  the
boiling point.

EDC is produced at very high yield and can  be  withdrawn either as a liquid (sub-cooled
reactor) or as a vapor (boiling reactor).  Where liquid withdrawal  is used, FeCl3 must
be removed  from EDC using an acid wash, or by adsorption on a  solid such as activated
carbon. With vapor withdrawal, no FeCl3 separation step is necessary.

Oxychlorination also produces  EDC  for use  in pyrolysis,  except that it uses HC1
recycled from the pyrolysis step, thus resulting in  zero net  HC1 production from  the
entire  process.  This was precisely the reason why Oxychlorination was  added to  the
direct  ethylene chlorination step in  the 1950's, when  HC1 produced by  the  direct
chlorination and pyrolysis  steps could  not be marketed.  Oxychlorination is typically
conducted at 430-490°F and 20-270 psig in fluid bed reactors, or at 450-570°F  and  20-
200 psig in  tubular  fixed bed  reactors  in  the presence of cupric chloride catalysts.
Temperature control of this highly exothermic  reaction is of  paramount importance to
waste generation, as temperatures in excess of 620°F result  in an increased byproduct
formation.   Other penalties for excessive temperatures include catalyst deactivation
and loss of ethylene through burning.
                                     B17-4

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CL,
     DIRECT
  CHLORINATION
     REACTOR
A.  SUBCOOLEO
B.  BOILINS
                                                                                                              VCM
ETHYLENE
Oa OR AIR
-=
OXYCHLORINATION
 A. FIXED BED
 B. FLUID BED
                                EDC
                                                   HCL
                                                                         EDC
                                                                     PROCESS HASTE CATEgORIES!
                                                                     (T)    LIBHT/ HEAVY  ENDS  FROM EDC PURIFICATION

                                                                     (?)    HEAVY  ENDS  FRON  VCN PURIFICATION
                                                                     (3)    PYROLYSIS COKE /TARS
                                                                     (7)    SPENT  CATALYST
                                                                     ©    AQUEOUS STREANS

                                                                     (?)    VENT BASES
                           Figure 6- 1   Vinyl  Chloride Manufacture via Ethylene Route
                                                      B17-5

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The excellent temperature control characteristics of fluid beds led to the development
of the fluid bed reactor, which successfully competed with the older fixed bed tubular
design.  Fluid beds offered improved EDC yield over the fixed bed reactor.  In recent
years, however,  the introduction of  new catalysts  increased the yields and  made the
fixed bed reactor technology  more competitive with the fluid bed reactors.

Either  air or  oxygen can be used in oxychlorination; however,  the trend has  been
toward use of oxygen which drastically reduces vent gas volume and associated losses.
The  hot oxychlorination reactor  effluent  gas  is  condensed  and  the condensate
containing EDC  and water is sent to the EDC treating and purification section.   The
offgas  is treated with chlorine to convert unreacted ethylene to EDC, which then  is
removed through solvent absorption or refrigerated condenser.  For the oxygen-blown
reactor, it  is possible for excess ethylene to be recycled  back to the  oxychlorination
unit.

Comparison between direct  chlorination  and  oxychlorination shows that the latter
produces more impurities.   These  include ethyl  chloride,  vinylidene  chloride,   1,1-
dichloroethane, chloral  and others.  EDC from  direct chlorination, oxychlorination and
pyrolysis (after treatment) is washed with water and caustic  to remove water soluble
impurities (e.g., chloral), and then distilled in  two steps to yield 98-99.9 percent  p'ure
EDC for pyrolysis.  Distillation also yields light and heavy end waste streams.

The endothermic pyrolysis step is conducted at 900-1025°F and usually  in the 50-500
psig  pressure  range.  After pyrolysis,  the products are rapidly  quenched  to  avoid
increased heavy ends and tars formation.  HC1 is recycled back to the  oxychlorination
section.  The VCM product is then separated from the unreacted EDC via distillation
and EDC is recycled back to the purification section, usually  following chlorination to
convert chloroprene and trichloroethylene. The pyrolysis step produces a large portion
of byproducts, most of which are  removed  when unconverted  EDC is washed and
distilled in the EDC purification/treatment section ahead of pyrolysis.

7.   WASTE DESCRIPTION

The primary wastes associated with  VCM production are shown  in Table 7-1.   The
wastes consist of  liquid, solid, and gaseous streams and, when economically  feasible,
are processed on-site  to recover  some of  the  chemicals.   In highly integrated
                                      B17-6

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          Table 7-1. Process Wastes from VCM Manufacturing Process
No.
   Waste
Description
Process Origin
                                                                         RCRA
                                                                         Codes
          Light and heavy ends
          from EDC purification
 2        Heavy ends from VCM
          purification

 3        Pyrolysis coke/tars

 4        Spent catalyst


 5        Aqueous streams


 6        Vent streams

 7        Leaks & spills

 9        Equipment cleaning
                       Direct chlorination reactor           K019*
                       Oxychlorination reactor
                       Pyrolysis reactor

                       Pyrolysis reactor                    K020
                        Pyrolysis reactor                    K024

                        Direct chlorination (FeCl3)
                        Oxychlorination

                        Oxychlorination water
                        EDC wash  solutions

                        Misc. equipment

                        Misc. equipment & piping

                        Tanks, towers, heat exchangers,      F024
                        piping
 RCRA code covers heavy ends only.
                                     B17-7

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manufacturing  facilities,  some  of  these streams  are used  as  feedstocks to  other
manufacturing  units, and hence are not classified as "wastes".  The wastes shown in
Table 7-1 can be further grouped into the following categories.

Organic Liquid  Wastes

The EDC purification step yields light and heavy ends chlorinated hydrocarbons which
are removed in two consecutive distillation steps prior  to  pyrolysis.   Both streams
undergo reprocessing in many facilities in the following ways (USC 1983):

           High efficiency thermal oxidation followed by water or caustic scrubbing
           of the flue gas (SCC 1981).  This process may be preceded by an additional
           distillation step to effect further recovery of useful chemicals.

           Catalytic oxidation with heat recovery and direct recycle of HCl-bearing
           flue gas to oxychlorination (Benson 1979).

           Chlorination  at elevated temperature and pressure.  The process ultimately
           yields carbon tetrachloride and/or perchloroethylene.
                                                                    •
Other disposal  methods include landfilling, deep  well injection and at-sea incineration,
which is currently practiced on  a developmental basis (Benson  1979, Scharein 1981).
Land  disposal  is practiced  only by  a  few  manufacturers; others  use  the recycling
techniques mentioned above. Ocean dumping was discontinued in the United States.

Crude VCM is purified, yielding a bottoms stream which contains heavy  ends from the
pyrolysis section.  In an integrated plant, VCM heavies can be routed to  the EDC still;
in non-integrated  plants,  they  are  stripped of  EDC  which  is recycled to pyrolysis.
Ultimately, this stream  is expected  to be  disposed  of  by incineration,  landfill or
subjected to further chlorination to yield other chlorinated organic products.

Solid Wastes

Pyrolysis tars  and coke  form as a result of thermal reactions inside the tubes of the
cracking (pyrolysis)  furnace and are periodically  removed to restore heat transfer and
to  lower  the  hydraulic resistance  of  the equipment.   The  solids  can  be  either
incinerated or landfilled.

                                       B17-8

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Spent  catalyst  waste  stream  is  comprised  of  FeCl3 catalyst  from  the direct
chlorination section and spent CuCl2-based catalyst from the oxychlorination section.
In direct  chlorination, the  subcooled  reactor generates a considerably  larger FeCl3
stream compared to the boiling reactor, owing to the  withdrawal and subsequent wash
of the liquid  EDC stream  containing dissolved catalyst (by comparison,  the boiling
reactor generates a vapor EDC stream with virtually all FeCl3 'e^*- behind).

In oxychlorination, the  catalyst  is CuCl2  on  various supports (e.g., alumina  or silica-
alumina).  The catalyst  waste is generated due to deactivation and due to attrition (in
the fluidized beds only).

Aqueous Wastes

Aqueous  streams originate  from various EDC washing  and  vent scrubbing operations
involving  alkaline  solutions and from  the formation  of  water  in the oxychlorination
reaction.   The  wastewater  is typically steam-stripped to  remove  volatile  organics,
neutralized  and  treated in an activated sludge system prior to discharge.

Vent Streams

Vent streams  originate mainly  from the non-condensibles present in the offgas from
the  direct  chlorination  and  oxychlorination.   The  air-blown  process  generates a
considerable  vent  stream.   The  treatment  includes high efficiency incineration or
catalytic  combustion and scrubbing with alkaline solutions.

Spills & Leaks

Leaks  and spills along with equipment cleanup are minor effluents in comparison with
the waste streams  mentioned above.  Due to  the highly  toxic nature of process fluids
and  the  resulting  regulation  of emissions, the  quantity  of leaks and spills  from  the
VCM process has been greatly reduced in the last ten years.

Equipment Cleaning Wastes

The equipment  cleaning  wastes include periodic  wastestreams originating  from  the
steamout of  process vessels  and  the  chemical or  mechanical cleaning  of  heat
exchangers  and  piping.  These  do not include  pyrolysis coke  and  tars  from the cracking

                                       B17-9

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furnace,  which were considered separately.  Disposal methods for equipment cleaning
wastes probably vary from facility  to  facility  and  it is likely that land disposal  is
practiced.

8.    WASTE GENERATION RATES

The  current  waste generation rates were not  in evidence at the time  of the  final
document preparation. The 1974 specific waste generation rates found (Liepins et. al.
1977,  USEPA  1975);  however,  according to  industry  contacts  these  rates  have
undergone a substantial decrease and are outdated.

The  approach  used  to  estimate  the  achieved  and projected reductions in waste
generation  requires  that  relative (or fractional)  waste  generation rates be known.
Such were  compiled  by the project staff using information obtained from the industry
and are shown in Table 8-1.

         Table 8-1 Waste Generation Profile for the Vinyl Chloride Industry

                Waste/                                   Total
                Residual                                Percent  (by weight)

                Organic Liquids                             10
                Spent Catalyst                              1
                Solids                                       1
                Aqueous Streams                           87
                Leaks and Spills                             1
                Equipment Cleaning                          1

                Total                                      100

Source: Estimated by project staff
9.    SOURCE REDUCTION TECHNIQUES

9.1  Description of Techniques

In  addition to  the waste reduction  measures classified  as being  process changes or
material/product substitutions, a variety of waste reducing measures  labeled as "good
operating practices"  have also been included.  Good operating practices are defined as
                                     B17-10

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being procedural or institutional changes which result in a reduction of waste.  The
following items highlight the scope of good operating practice:

      o     Waste stream segregation
      o     Personnel practices
                management initiatives
                employee training
      o     Procedural measures
                documentation
                material handling and storage
                material tracking and inventory control
                scheduling
      o     Loss prevention practices
                spill prevention
                prevention maintenance
                emergency preparedness

For  each  waste stream,  good operating practice applies whether it is listed or not.
Separate  listings  have  been  provided  whenever  case  studies  were  identified.
The  primary  waste streams and  their source  reduction  methods are  summarized  in
Table 9-1.   The following is a description of the source control techniques considered
for  each of the  waste sources.

9.1.1  Liquid Organic Wastes

As mentioned previously, these wastes are composed of distillation light and heavy
ends separated out during  EDC and VCM purification processes in separate distillation
steps.  At highly integrated manufacturing facilities, these streams are often used  as
feedstocks  to other  units and, as such, are not classified as wastes.   The primary
process origins  of liquid organic waste include oxychlorination and pyrolysis reactors.
Direct chlorination is not  a significant byproduct generator, as catalyst selectivity is
excellent.    Sections  below describe source  control methods  that have  actual  or
potential application to reduce byproduct formation.
                                      B17-11

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9.1.1.1     Oxychlorination Step

Minimization of waste generation from the oxychlorination step could conceptually be
approached in two ways.  First,  improvements to the oxychlorination process could be
made  to   reduce  the   formation  of  the  undesirable   byproducts.    Second, the
oxychlorination step can be avoided altogether by replacing it with an alternative low-
waste process.  Byproduct generation  is related to the following  five main aspects of
the oxychlorination reaction:  temperature uniformity and control, feed purity, use of
oxygen versus air, catalytic selectivity, and gas-catalyst contact.

The following practiced and proposed source reduction methods have been identified:

     o     Use of fluidized bed reactors as opposed to fixed bed reactors.
           Fluid bed reactors are characterized by better temperature uniformity and
           lower operating pressures  and temperatures  in comparison  to  fixed bed
           designs.  Fluidized bed reactors are more widely used  than older fixed bed
           designs (Leddy et al. 1983).  However,  recent  improvements in the catalyst
           performance make the  fixed  bed  technology  competitive again with the
           fluid bed designs.

     o     Modifications to tubular fixed  bed reactor design.
           Currently practiced  modifications  include:    an  increase  in  catalyst
           concentration along  the reaction path to avoid hot spotting; minimization
           of radial temperature gradient by optimizing tube diameter;  and  staging  of
           consecutive  oxygen or air injection.

     o     Use of oxygen instead of air.
           This decreases EDC vent  losses and byproduct formation.   The  EDC
           obtained from the  C^-based oxychlorination can be comparable in purity  to
           EDC obtained  from  direct chlorination*.  The  manufacturers have  been
           shifting to the oxygen-based process for oxychlorination because of product
           purity  and lower  vent  gas loads  (Leddy et  al.  1983).   The opinions on
           whether  the  C>2-based process is economically advantageous  over  the air-
           based process are split.
                                      817-12

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     o     Selective hydrogenation of acetylene in the feed.
           This has been practiced to reduce subsequent byproduct formation in  the
           oxychlorination reactor (Leddy et al. 1983).

     o     Use of improved catalysts.
           The efforts to improve the selectivity, stability and attrition resistance of
           oxychlorination catalysts yielded improvements, especially  for  the  fixed
           bed applications.   New  fixed  bed  catalysts  offer  significant lifetime
           improvements; one catalyst offered by a Japanese manufacturer since 1983
           can extend the lifetime from 9 to 18 months*.

     o     Re-examination of reactor conditions.
           Additional  means of  improving the  oxychlorination  process to reduce
           byproduct formation  can  be  postulated.    These  include:   a  thorough
           investigation  of the effects of reducing the effective bubble  size in fluid
           beds (e.g., using shorter pitch of the cooling coil bundle) to promote  gas-
           catalyst contact; variations  of  the ethylene recycle rate; a  decrease in
           operating pressure; and quick post-reactive cooling.

The identified alternatives to oxychlorination include an HC1 oxidation step, the use of
an ethylene/acetylene route, and the use of the Akzo-Zout Chemie process.

     o     Replacement of oxychlorination with an HC1 oxidation step.
           In  this  scheme,  the   formation of  the  undesirable byproducts  due  to
           oxychlorination is avoided  by oxidation of the purified  pyrolysis HC1  and
           subsequent C12  recycle back to the direct chlorination EDC production unit
           (see Figure  9-1).

           HC1 oxidation can be accomplished in one of two ways:
                     Direct oxidation (Schreiner et al. 1974, Bostwick 1976)
                             2HCl+iO2	>C12+H2O
                     Electrolytic oxidation (Payer 1974)
                                 2HC1
* Conoco Inc. 1986:  Private communication.
                                     B17-13

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ETHYLENE
                DIRECT
             CHLORINATION
                REACTOR
           A.  SUBCOOLED
           B.  BOILINS
                                                                                                              VCM
CL,
   FOR
OXIDATION
HCL OXIDATION
     OR
 ELECTROLYSIS
                                                   HCL
             HATER OR H,
                                                                        EDC
                                                        PROCESS  MASTE  CATE60RIES.

                                                        (T)   LIGHT/ HEAVY ENDS  FROM EDC PURIFICATION

                                                        (D   HEAVY  ENDS  FRON  VCN  PURIFICATION

                                                        ©   PYROLYSIS COKE /TARS

                                                        (7)   SPENT  CATALYST

                                                        (?)   AQUEOUS  STREAMS

                                                        (T)   VENT BASES
                   Figure 9-1   Vinyl  Chloride Manufacture via an Alternate Process Scheie
                                       with   HCL   Oxidation Replacing Oxychlorination
                                                    817-14

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           Both schemes  employ commercially  proven processes such as the Deacon,
           Shell, or Kel-Chlor process for direct oxidation, or the Westvaco or Bayer-
           Hoechst-Uhde  process for electrolytic oxidation (Leddy et al. 1983, Versar
           1979).   Shell  Oil  operates a 19,000  TPY pilot plant  at Pernis in  the
           Netherlands using  a  modified Deacon  process  for direct oxidation (Versar
           1979).  Du Pont operates  a  200,000  TPY  plant at Corpus Christi, Texas
           using the  Kel-Chlor  process  (Versar 1979).  The Hoechst-Uhde process is
           practiced  at 14 plants in various countries with a  total capacity of 1400
           tons  per day using electrolytic oxidation*.  Mobil  Chemical has operated
           two electrolytic HC1 oxidation units in their toluene diisocyanate  facility
           in Baytown, Texas.

The  postulated  advantages  of  the  HC1  oxidation  route over  the currently  used
oxychlorination route  include:

           Waste byproducts  of oxychlorination are totally avoided;  instead,  a  high-
           quality EDC stream  from  direct chlorination  can  be further purified  at
           minimum expense.

           Purer EDC feed  to  pyrolysis  results in   a  decreased waste byproduct
           generation during the pyrolysis step.

           Waste water is produced  outside of the organic phase, thus avoiding  costly
           waste  treatment  and  the  disposal  of  ultimate  treatment  residuals
           associated with organics carryover.

           Reaction water generation  can be largely avoided in an electrolytic step.

The  principal  disadvantages are  the  current  high   capital   and  operating  costs.
Numerous examinations of  the  HC1 oxidation processes indicate that they were  not
economically competitive with oxychlorination*.  Excessive costs are the reason  for
the planned shutdown  of the only U.S. installation of the direct HC1 oxidation process
*  Hoechst-Uhde Corporations 1986:  private communication.
** Dow  Chemical  Company  1985:   Personal communication; PPG Industries  1985:
   Personal communication.
                                    817-15

-------
(Kel-Chlor)  at  Du Pont's Corpus Christi facility*.  The economics of these processes
was discussed in  detail (Versar 1979).   The Kel-Chlor process is economical only for
large  scale  units (600-1000 TPD of HC1  loads) using  the oxygen-based process.  The
high capital cost of the Kel-Chlor process is partly due to the tantalum construction
required because of the corrosive process environment.   The Hoechst-Uhde process,
though suitable for  any capacity due  to modular construction of electrolysis units, may
not be  economically competitive with oxychlorination even though  the  electricity
requirements were  reduced from 1900 kWh per metric ton  of Cl2 in 1964 to 1400 kWh
presently.  Further reductions in electricity consumption can be explored in the area
of H2 fuel cell technology.  Even if  the HC1 oxidation alternative is viable  for a grass
roots  plant, it  may not be affordable  to  existing plants which are currently handling
their wastewaters in an environmentally acceptable manner.

     o     Mixed feedstock option.
           Another process option  is the use  of a mixed  feedstock of ethylene and
           acetylene (Cowfer and Magistro 1983). HC1 produced in the pyrolysis step
           can  be  reacted   with  acetylene  to  produce  VCM,   thus  avoiding
           oxychlorination of ethylene.   The  mixed  feed  stock  option  depends on
           economic and  geographic conditions, and  the development of  lower cost
           routes to the production of acetylene.  At the present, acetylene  routes
           generally lack economic feasibility.  The environmental disadvantage of
           this process is the  generation of  spent  catalyst (mercuric chloride on
           activated carbon) which is potentially hazardous.

     o     Akzo-Zout Chemie  process.
           An  alternate  route  to  VCM,  which is still in its experimental stages,
           converts ethylene, sodium chloride,  oxygen, and carbon dioxide to EDC and
           sodium bicarbonate  (Anonymous 1983).  EDC can then be pyrolyzed to yield
           VCM,  and sodium bicarbonate can  be calcined to soda ash.   This  route
           eliminates  the  direct chlorination  and  oxychlorination routes to produce
           VCM.   This process  is being patented by  Huls  (Germany)  and  Akzo-Zout
*  Du Pont 1986:  Personal communication.
                                    817-16

-------
           Chemie B.V. (Hengelo, the Netherlands).  The process uses a homogeneous
           catalyst  of complexed  ions  of  trimethylamine  hydrochloride,  copper
           chloride and iodine  in adiponitrile  solvent.  The development  work on this
           process was halted*.  The advantages and disadvantages of the process
           over the conventional routes from  a waste  minimization  point of view
           could not be assessed due to the lack  of available data.

9.1.1.2     Pyrolysis Step

Generation of byproducts  from the pyrolysis reaction has been an area of considerable
investigative effort.   The  following  is a listing  of both practiced and  postulated
techniques for reducing byproduct formation:

      o     A laser-induced EDC cracking technique.
           Under development by the Max Planck Institute in West Germany, laser-
           induced EDC cracking is  claimed  to have a considerably lower byproduct
           yield than  thermal cracking  (Wolfrom 1979,  1980).  At  the  present, the
           process  is  not a  commercially proven  technology; the problem of the
           availability of  a large size laser still  persists.

      o     Use of additives to EDC feed.
           Additives such as  chlorine or carbon tetrachloride, have been reported  in
           patent literature  to  suppress methyl chloride  formation  (Cowfer and
           Magistro 1983).   According to Dow Chemical, methyl chloride is  only a
           minor impurity (less than  40 ppm in  VCM).  The presence of nitromethane
           was reported  to increase EDC- conversion  to 92.5 percent (McPherson,
           Starks and Fryar 1979).

      o     More stringent control of  EDC feed purity.
           This widely practiced  technique reduces  fouling and byproduct  formation
           during pyrolysis.
*  Vinyl Chloride Institute 1985:  Personal communication.
                                     B17-17

-------
     o     Rapid quench rate.
           Byproduct  formation depends  to a  large  measure on  how  quickly  the
           pyrolysis offgas is cooled.  If cooling is done  too slowly,  the VCM yield is
           substantially decreased with attendant formation of undesirable byproduct.
           The technique of direct  quench of  the  hot pyrolysis  offgas using cold
           recycled EDC condensate is widely practiced.

9.1.2   Solid Wastes

Solid wastes from the  manufacture of VCM consist of pyrolysis tars and coke produced
in the cracking furnace, spent catalysts, catalyst fines from oxychlorination, and spent
drying  reactants. Possible measures to reduce these wastes are:

     o     Modification and/or proper control of the pyrolysis process.
           Coking  can be   reduced  through a  reduction of the  trichloroethylene
           concentration in the feed to the cracking furnace (opinions  are split on this
           issue*), temperature profile  monitoring along the  pyrolysis path, and the
           use of an  alternate laser-induced  EDC cracking  process  (Wolfrom 1979,
           1980).   Of  these  measures, only temperature monitoring appears to have
           the largest  immediate utility for further application.

     o    Convert pyrolysis tars into valuable byproducts.
           Chlorinated tars and coke can be blended with other chlorocarbon streams
           and treated in  a  combination of thin-film  evaporators and decomposition
           screws to produce HC1, carbon black (low in chlorine), and some useful low
           boiling  chlorohydrocarbons.  This process  is in commercial operation at
           Chemische  Werke Huls AG, West Germany (Scharein 1981).

     o    Reduction of the  oxychlorination catalyst attrition  rate.
           The oxychlorination catalyst  fines generation  rate can be  decreased by
           reducing the  attrition rate through use of a more  stable catalyst support.
           Catalyst attrition  can  largely  be  avoided  by  using fixed bed  reactors,
           though  they  may suffer  from temperature maldistribution  (hot-spotting)
           problems.
   Vinyl Chloride Institute 1985:  Personal communication.

                                     B17-18

-------
     o     Prevention of oxychlorination catalyst deactivation.
           Excessive temperatures result  in volatilization and  subsequent loss of
           CuCl2 from the catalyst leading to its deactivation.  Avoidance  of upsets
           resulting in excessive temperature episodes will contribute to curtailment
           of the  catalyst loss and the  associated  generation  of  waste.  Also, as
           discussed  previously, new  fixed bed  catalysts  offer significant lifetime
           improvement over older ones.

9.1.3   Aqueous Wastes

Process related aqueous waste streams originate mainly from:

           Water produced in oxychlorination.
           Miscellaneous washing operations.

Oxychlorination water is a necessary reaction product and cannot be avoided without
drastic  revamping  of  the  entire process scheme.  A process  option where water  is
produced outside of the  organic  phase—or is  not  produced at  all—is to  substitute the
oxychlorination step with an HC1 oxidation step as discussed before. In concept, the
elimination of oxychlorination  water  formation by  electrolytic HC1 oxidation  is
possible, but  the attendant  reduction  in  the hazardous  waste loads attributable to
water will  probably be very small (possibly through avoidance of organics carryover
into wastewater treatment   and an associated  reduction  of the treatment  sludge
volume).

Other  sources  of   wastewater  are  washing  operations  to  remove  water-soluble
impurities.  Washing operations are performed on EDC to  remove FeCl^ when using a
subcooled reactor for direct  chlorination and  on EDC  from oxychlorination, to remove
water soluble impurities (mainly chloral).  The washing operations are often performed
on combined EDC feed to  the pyrolysis section prior to distillation and  drying.  Water
use and the associated treatment waste can  be minimized by the following  practiced
source reduction techniques:

     o     Use of solid absorbent for FeCl3 catalyst removal from EDC liquid effluent
           from the direct chlorination reactor.
                                       817-19

-------
      o     Use of boiling vs. subcooled reactors.
           As explained in sections 6 and 7, the boiling reactor for direct chlorination
           produces EDC  in vapor form, thus obviating the need for  continuous FeCl3
           removal in large quantities from the effluent.  The original catalyst charge
           is replaced much less frequently by comparison to the subcooled reactor
           design.

           Boiling reactors, pioneered by Stauffer Chemical Company,  are already in
           widespread use.  Boiling reactors eliminate the need to wash FeCl3 out °f
           the  EDC produced and thus eliminate the generation of related treatment
           residuals (McNaughton  1983).   Also,  steam  consumption  is  drastically
           reduced, which results in limiting the boiler feedwater treatment wastes.

      o     Use  of  multi-stage  countercurrent  contactor  for EDC pyrolysis  feed
           washing.  When washing is  to be performed, a multi-stage countercurrent
           contactor will produce  a  smaller,  more  concentrated  wash-water stream
           than will a single stage.

9.1.4  Spills and Leaks

Due to the toxic/carcinogenic nature of VCM, a great deal of attention has been paid
to reducing fugitive emissions from VCM plants.   In 1974, EPA estimated that  a
typical VCM plant lost through leakage 0.1215 kg of VCM per 100 kg of VCM produced.
The EPA  formulated various  regulations to reduce  these  emissions by  94  percent.
Since  1974, the VCM industry  has reduced leakage by a factor of ten*.  The following
source reduction  techniques  are  considered as  good  operating practices,  with  many
being  actually mandated by the 1976 VCM standards (NESHAP 1984):

      o     Replace  single mechanical  seals with double mechanical seals on pumps or
           use canned seal-less pumps.

      o     Use of bellows sealed valves to limit leakage around stem  packing.

      o     Use of leak detection systems and portable monitors.
  Dow Chemical Co. 1985: Personal communication.

                                     817-20

-------
     o    Enclosed sampling and analytical systems.

     o    Use of vapor-recovery  systems for  VC loading,  unloading and  equipment
          cleaning.

9.1.5   Equipment Cleaning Wastes

Generation of this minor waste stream can be minimized by:

     o    More complete drainage of process piping or equipment prior to cleaning.

     o    Lower  process  film  temperatures  and  higher  turbulence  at  the  heat
          exchange surfaces to reduce fouling rates.

     o    Use  of  non-stick  (electropolished or  Teflon*) heat  exchanger tubes to
          reduce deposit clingage (Anonymous 1985c).

     o    Use of in-process heat exchanger tube cleaning devices (Anonymous 1985b).

All the suggestions, listed above  will  have  only  a  minor impact  on overall  waste
generation,  since  equipment cleaning  wastes are  but a small fraction  of the  total
waste.

9.2  Implementation Profile

VCM plants  tend to be an integral part of large chlorohydrocarbon production facilities
where  significant capital has been  invested to handle process wastes and effluents in
an  environmentally  acceptable manner.  This  makes waste minimization  infeasible,
unless  significant economic benefits  can be demonstrated.  In this context, a  basic
process modification requiring  substantial capital investment  would  need  extensive
economic evaluation, including  consideration of the  incremental profit due  to  the
increased VCM yield, the incremental decrease in waste treatment and disposal costs,
and  the  avoidance  of  future  costs  associated  with  liability for  environmental
impairment.
* Registered trademark of E.I. Du Pont de Nemours Co.

                                     B17-21

-------
Most waste minimization  measures identified in this work  are capital-intensive, hence
their  implementation  appears  more  likely  for the  grass-roots plants than  for  the
existing  ones.   Other measures identified in this  report are  still developmental in
nature (laser-induced pyrolysis,  mixed feed operation, or Akzo-Zout  Chemie process),
lack economic feasibility  at their current stage of development (HC1 oxidation route),
or  would have  only a relatively  small  impact  (use of  non-stick  heat  exchanger
surfaces).

9.3  Summary

The summary of all noted source control techniques is  given in Table 9-1.  Each
technique was rated for its effectiveness, extent of current use and future application
potential on scale of 0 to  4.  The ratings were derived by project staff based on review
of the  available  data and  in consultation with the  industry.  The estimates of current
level  of  waste   reduction  achieved  (current reduction  index) and possible future
reduction (future reduction index) were obtained from the ratings  in accordance  with
the methodology presented in the introduction to this appendix.

The current reduction index (CRI) is  a measure of reduction of waste that would be
generated if  none of the  methods  listed were implemented to their  current  level of
application. For the entire VCM process, CRI is 1.5 (38 percent) which is indicative of
the moderate level  of waste minimization that already has taken place.  It  must be
noted,  however, that reduction  of waste was not  a primary objective behind  most of
these measures;  rather, it was the effort to increase VCM yield or energy efficiency of
the process.

The future reduction index (FRI) is an indication of the level to which the currently
generated waste can be  reduced if  all of  the techniques noted  were  implemented
according to their  rated  potential.  The  FRI value  of  0.1 to 0.3  (2  to  8 percent) is
indicative of low extent of future waste reductions.  Among the techniques  that  were
found  currently  most  effective and  applicable (as  evidenced by high FRI  value) for
control of liquid organic wastes was selective hydrogenation of C2H2 in the feed, use
of  improved  catalysts and fluid beds in oxychlorination,  and  use  of  additives to the
EDC feed  to  pyrolysis.   Use of  boiling  reactors for direct chlorination  was  found
effective in reduction of solid waste  (FeCl3  catalyst), washwater and  water  treatment
sludges.
                                     B17-22

-------
                                    TABLE 9-1 SUMMARY OF SOURCE CONTROL METHODOLOGY FOR THE VINYL CHLORIDE MONOMER MANUFACTURING  INDUSTRY
f
Waste Stream

Liquid Organics
Oxychlorlnatlon
Reactor (•)






1
I Liquid Organ (cs
I Pyrolysis
1 Reactor (»)
1

| Solid Waste
I Pyrolysis Coke
I and Tars (*)
1
1 Solid Waste
| Spent Catalysts
I
1
| Aqueous Haste
1
I Aqueous Waste
EDC Washing
1
1
| Spills and Leaks

1
1
1
1
1
Equipment Cleaning
| Wastes (')
1
1
I All Sources
1 1
I Control Methodology |-
1
|1 Use fluid-bed over fixed bed reactor |
|2. Modify fixed bed reactor design |
|3. Use oxygen Instead of air |
II. Selective hydrogenatfon, C2H2 in feed|
1 5 Use Improved catalysts |
|6. Re-examine reaction conditions |
|7 Replace OxychloMnation w/HCl oxld. |
|8. Use mixed C2H4/C2H2 feed option |
19. Use Akzo-Zout Chemie process |
1 Overall |
|1. Use of laser Induced pyrolysis |
|2. Use of additive to EDC pyrolysis feed]
|3. Tighter control of EOC purity |
|4. Quench products rapidly |
| Overall |
|). Proper control of pyrolysis |
|2 Recover products from solid waste |
| Overall |
|1. Reduce oxychlor cat attrition rate |
|2. Prevent catalyst deactlvatlon |
1 3. Use boiling versus sub-cooled reactor |
| Overall |
|1 Use electrolytic IIC1 oxld vs oxychlor|
I Overall |
|t. Use solid FeC13 absorbent |
|2 Use boiling versus sub-cooled reactor |
|3. Use multistage countercurrent wash |
I Overall |
|1. Use double mechanical seals on pumps |
|2. Use bellows seal valves |
|3. Use leak detectors and monitors |
|4. Enclosed sampling and analy. systems |
|5 Use of vapor recovery systems I
| Overall |
1 1 Increase equipment drainage time |
|? ElectropoHsh heat exchanger tubes 1
|3 Lower heat exchange film temperature |
| Overall |
1 All Methods
Found Documentation

Quantity | Quality
3 1
1 1
3 1
1
1
1
1
1
1
1.56 | 1
2 I
t I
1 1
1 1
1.25 | 1
' 1
3 i
2.00 | 2
1 1
1 1
2 I
1.33 | 1
2 1
2.00 | 2
1 1
2 1
1 1
1.33 | 1
1 1
3 1
3 1
3 1
2 !
2.40 | 2
1 1
2 1
1 1
1 33 | 1

1
— -1
1
3 1
1 1
3 1
1 1
1 1
1 I
3 I
1 1
2 1
78 I
2 1
1 1
1 I
1 1
25 |
1 1
3 1
00 |
1 1
1 1
3 1
67 |
2 1
00 I
' 1
3 1
1 1
67 |
1 I
3 I
3 1
2 1
2 1
20 |
1 1
1 1
1 1
50 1

Waste |
Reduction |
Effectiveness I
2 1
2 1
1
i

1
1
1
0 1
1 89 |
2 1
1
2 1
3 1
2.00 |
^»
3 I
2.50 |
2 1
1 1
3 1
2 00 |
3 1
3 00 I
' 1
2 1
2 1
• ^
1.67 |
3 1
2 1
0 1
3
0 1
1 60 |
2 1
2 1
1 i
1 67 |

Extent of I
Current Use |
1
2 1
3 1
3 1
3 1
2 1
3 1
0 1
' 1
0 1
1 39 |
0 1
2 1
3 1
4 1
2.25 |
3 1
0 1
1.50 |
3 1
3 1
3 I
3 00 |
0 1
0 00 |
o 1
2 1
4 1
2.00 |
3 1
1 1
3 1
3 1
4 1
2.30 |
3 1
0 1
3 1
2 00 |

Future I
Application |
Potential |
1 I
1 1
1 1
3 1
2 1
1 1
0 1
1 1
0 1
1 11 |
Q j
2 1
1 1
0 1
0 75 |
t 1
1 I
1.00 |
1 I
1 1
2 1
1.33 |
1 1
0 00 |
1 1
3 1
0 1
1.33 |
3 1
1 1
3 1
3 1
4 1
2 80 |
« I
2 1
1 1
J 33 |
1
Fraction of I
Total Waste I
1
I
1
1
1
1
1
1
1
1
0.05 |
1
1
!
1
0 05 |
1
1
0.01 |
1
1
1
0.01 |
I
0 60 |
1
1
1
0.26 |
1
1
1
1
!
0.01 |
1
1
1
0.01 |
t 00 |
Current |
Reduction |-
Index |
1 0 I
1.5 |
0 8 |
30 |
05 |
1.5 |
0.0 |
0 3 |
0.0 |
3.0 |
0.0 |
0.5 |
1 5 |
3.0 |
3.0 |
1.5 |
0 0 |
1 5 |
1.5 |
0 8 |
2.3 |
2.3 |
0.0 |
0.0 |
0.0 |
1.0 |
2.0 |
2 0 |
2 3 |
0 5 |
0.0 |
2 3 |
0 0 |
2 3 |
1.5 |
0 0 |
0 8 |
1.5 |
1.5 1
Future Reduction Index


Probable
0
0
0
0
0
0
0
o
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
0


| Maximum
3 1
t 1
1 1
8 ! 08
3 1
1 1
0 I
2 1
0 1
2 | 0.8
0 1
3 | 0.3
' 1
0 I
1 | 0.3
1 1
8 | 08
4 | 0.8
1 1
1 1
4 | 04
2 | 0.4
0 1
0 | 0.0
3 1
8 I 0.8
0 1
3 | 0.8
6 | 0.6
4 1
0 1
6 | 0.6
0 1
3 | 0.6
5 1
0 | 1.0
1 1
5 | 10
1 | 03
1
-I
1
1
1
1
1
1
1
1
1
1
1
I
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
CD
ro
               (')  These waste streams Include listed T  and/or  'K1  RCRA hastes.

-------
Among the techniques that were  found potentially most  effective were the use of
electrolytic HC1 oxidation  in  place  of  oxychlorination and the use of  laser-induced
pyrolysis.   Both will probably require  substantial  development  effort  before  both
economic and technical feasibility are fully established.

10.   PRODUCT SUBSTITUTION ALTERNATIVES

Since  most VCM output  is  consumed  by  PVC production,  the  principal  product
substitution routes must be explored primarily in the area of PVC applications. Long-
term demand  for PVC  is expected to remain stable, although in the short term the
operating capacity has steadily been decreasing.  In 1981, about 50 percent of PVC was
consumed in construction-related uses (SRI 1982).  Clay, cast iron, or ductile steel can
replace PVC in piping uses.  This  substitution is economical  only for pipe diameters
larger than 16 inches.  Aluminum is an  effective substitute for PVC in the irrigation
pipe market.

Other PVC uses include consumer goods, electrical,  and  packaging uses.   Product
substitution in these  areas, even if possible,  would  have only  a minor impact on the
total PVC demand.

11.   CONCLUSIONS

While the VCM manufacturing industry  appears  to  have appreciably minimized their
waste (current reduction index  of  1.5),  it is  also apparent that very modest further
reductions are possible  (future reduction index  of  0.1  to  0.3).  The most effective
control  methods appear to be selective hydrogenation  of  acetylene  in  the  ethylene
feed  to  oxychlorination,   use  of  fluid  bed  reactors and   improved  catalyst  in
oxychlorination, use  of  additives  to the  EDC  feed to pyrolysis and  use of  boiling
reactors.

The  technical and  economic  details of replacing oxychlorination  with  direct  or
electrolytic HC1 oxidation appear to be  worth exploring, since the  measure would  be
very  effective in eliminating  the  organic liquid wastes from oxychlorination.  The
currently prohibitive economics of the HC1 oxidation route  is a problem;  however, the
potential benefits may justify the search for  cost-effective solutions.  Laser-induced
pyrolysis,  while in the developmental stage, offers a  substantial potential  for reduction
in pyrolysis byproduct formation.

                                     817-24

-------
The identified PVC product substitution alternatives include clay, cast iron, steel or
aluminum piping.


12.    REFERENCES


Anonymous, 1983. Chemical Engineering, 90(5):10.

             , 1984.  Output makes a strong  recovery.  Chemical Engineering News,
62(24):34.
           , 1985a.  Production increased only weakly in 1984.  Chemical Engineering
News, 63(23):27.

	, 1985b. Chemical Engineering Progress, 81(7):7.

	, 1985c. Chemical Engineering Progress, 81(7):104-5.

Benson, J.S.,  1979.   Catoxid for chlorinated  byproducts.   Hydrocarbon Processing,
59(10):107-8.

Bostwick,  L.E.,  1976.   Recovering  chlorine  from  HC1., Chemical  Engineering,
83(21):86-7.

Cowfer, J.A., and Magistro,  A.J. 1983.  Vinyl chloride.  In  Kirk-Othmer Encyclopedia
of Chemical Technology.  3rd ed., Vol. 23, pp. 865-85. New York, N.Y.: Wiley.

Hardie, D.W.F.,  1964.   Vinyl chloride.  In Kirk-Othmer Encyclopedia  of  Chemical
Technology.  2nd  ed. Vol. 5, pp. 171-8. New York, N.Y.:  Wiley.


Johnson,  H.,  1973.   A study of hazardous waste  materials, hazardous effects and
disposal  methods.   Vol. 2, Booz-Allen  Applied  Research, Inc.  EPA-670-2-73-15.
Washington, D.C.: U.S. Environmental Protection Agency.

Leddy, J.J., Jones, Jr., I.C.,  Lewry, B.5., et al., 1983. Alkali and chlorine products.  In
Kirk-Othmer encyclopedia of chemical technology.  3rd ed.,  Vol. 1, pp. 826-7, 844-5.
New York, N.Y.:  Wiley.

Liepins,  R.,  Mixon,  P.,  Hudak, C.,  et  al.,  1977.   Industrial  process profiles  for
environmental use;  Chapter 6.  The industrial  organic  chemical industry.  Research
Triangle  Institute.   EPA-600-2-77-023f.   Cincinnati,  Ohio:    U.S.  Environmental
Protection Agency.

McNaughton,  E.J.,  1983.   Ethylene  dichloride  process.   Chemical  Engineering.
90(25):54-8.

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