Industrial Chemicals Solid Waste Generation - The Significance Of Process Resource Recovery And Improved Disposal


EPA-670/2-74-078
November 1974
Environmental Protection Technology Series
    Hi

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                                          EPA-670/2-74-078
                                          November 1974
 INDUSTRIAL  CHEMICALS SOLID WASTE GENERATION


     THE  SIGNIFICANCE OF PROCESS CHANGE,

  RESOURCE RECOVERY,  AND IMPROVED DISPOSAL
                      By

                James C. Saxton
                  Marc Kramer
    International  Research and Technology
         Arlington,  Virginia  22209
         Program  Element No.  1DB063
                Project  Officer

              Richard A.  Carnes
Solid and Hazardous  Waste Research Laboratory
   National Environmental  Research Center
           Cincinnati,  Ohio  45268
   NATIONAL ENVIRONMENTAL  RESEARCH CENTER
     OFFICE OF RESEARCH  AND DEVELOPMENT
    U.S. ENVIRONMENTAL PROTECTION AGENCY
           CINCINNATI, OHIO  45268
      For sale by the Superintendent of Documents, U.S. Government
            Printing Office, Washington, D.C. 20402

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                   REVIEW NOTICE


      The National Environmental Research Center-
Cincinnati has reviewed this report and approved
its publication.  Approval does not signify that
the contents necessarily reflect the views and
policies of the U.S. Environmental Protection
Agency, nor does mention of trade names or com-
mercial products constitute endorsement or
recommendation for use.

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                         FOREWORD
    Man and his environment must be protected from the
adverse effects of pesticides, radiation, noise and other
forms of pollution, and the unwise management of solid
waste.  Efforts to protect the environment require a
focus that recognizes the interplay between the com-
ponents of our physical environment—air, water, and
land.  The National Environmental Research Centers
provide this multidisciplinary focus through programs
engaged in

         studies on the effects of environmental
         contaminants on man and the biosphere, and

      *  a search for ways to prevent contamin-
         ation and to recycle valuable resources.

    The study described here characterizes the process-related
wastes produced during manufacture of industrial chemicals, SIC
Group 281.  Thirty-three chemicals were selected that:  possess
significant resource value, pose a difficult solid waste dis-
posal problem, and/or have markedly deleterious properties, e.g.
toxicity.
                              A.  W.  Breidenbach, Ph.D.
                              Director
                              National Environmental
                              Research Center, Cincinnati

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                                ABSTRACT
        The objective of the study was to characterize the process-related
solid wastes produced during the manufacture of industrial chemicals,
SIC Group 281.  Thirty three chemicals were identified that suffice to
represent the entire Group in terms of solid waste generation.   The
criteria for selection were that the resulting solid waste:  possess
significant resource value, pose a difficult waste disposal problem,
and/or have markedly deleterious properties,  e.g., toxicity.   The
presence of toxic components is particularly significant in that they
inhibit resource recovery and necessitate greater care and expense  in
disposal.  The selected chemicals composed 40% of the 1971 Group output
(149 x 10° tons), and are estimated to account for over 95% of  the  Group's
solid waste.

        Factors leading to a change in solid waste generation  include:
market growth or decline, process substitutions, process modifications,
and raw material changes.  The latter refers to those cases in  which the
production process remains essentially unchanged even though the raw
materials change, e.g., ore grades.  Fifteen of the 33 selected chemicals
were found to be undergoing process substitutions, and in every case the
newer process generates less solid waste.  A five year projection to 1977
indicates that process and raw material changes reduce the overall  solid
waste quantity 7.3%, and if phosphorus and phosphoric acid are  excluded,
the reduction is 13.6%.

        The resource value of the solid waste stream from the  33 chemicals,
if all contained chemicals could be sold at market value, is 11.9%  of  the
$7.2 billion production value of the primary chemicals.  Most  of these
resources are of low value, however, and cannot compete in the  commercial
market.  A case study of sodium sulfate illustrates the way in  which the
supply of a ubiquitous byproduct increases beyond its market demand.
Another case study, of phosphorus and phosphoric acid, depicts  a situation
in which a scarce resource (fluorine) is presently discarded with process
waste.  In this instance, resource recovery is important, even  though  the
waste volume is not reduced thereby.

        Disposal costs were estimated for the solid wastes from each of
the 33 chemicals.  Inorganics account for over 90% of the total cost,
with Industry 2819 alone accounting for more than 71%.  The latter  is
due to the large waste volume from the ore-related processes,  such  as
alumina and phosphoric acid.  In terms of disposal, the organics appear
to pose little problem.  The elimination of water discharge as  a disposal
alternative was found to double the disposal cost of the 33 chemicals.
                                    IV

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                          TABLE OF CONTENTS

                                                                   PAGE

Abstract                                                            iv
List of Figures                                                     vi
List of Tables                                                      vii
Acknowledgements                                                    ix
SECTIONS
I     Conclusions                                                    1
II    Recommendations                                                2
III   Introduction                                                   3
IV    Industrial Chemical Solid Waste Generation                    18
V     Industrial Chemical Solid Waste Data Base                     41
VI    Market and Process Change Effects on Solid Waste
        Generation                                                  64
VII   Resource Recovery Needs and Opportunities                     95
VIII  Waste Treatment and Disposal                                 111
IX    Governmental Opportunities to Influence the Management
        of Industrial Chemical Solid Wastes                        124
X     References                                                   132
XI    Pending Publications                                         138
XII   Appendix                                                     138

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                               FIGURES

No.                                                             Page
 1      Manufacture of Toluene, Benzene, and Xylene from
       Coal Gas and Tar Light Oil by Acid Washing                19

 2      Manufacture of Phosphoric Acid from Phosphate Rock
       by the Wet Process                                        22

 3      Scenario Results for Sodium Sulfate                       7^

 4      Solid Waste Generation from Ti02 Production               79
                                                                  87
 5     Process Change Effect on Ethylene Oxide Solid Waste

 6     Process Change Effect on Percentage of Perch! oroethylene
       Produced Via the Acetylene Process
       Process Change Effect on Percentage of Soda Ash (NapCOg)
       Produced Via the Solvay Process                            ™
 8     Process Network Leading to PVC Bottles
                                                                 108

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                               TABLES

No.                                                               Page
 1     Significant Solid Waste Producers Among Industrial
       Chemicals                                                  25

 2     Chemicals Selection Criteria and Solid Waste Origin        27

 3     Characterization of Principal Chemical's Production        29

 4     Character of Solid Wastes                                  44

 5     Resource Recovery Potential of Waste Streams               51

 6     Solid Waste Treatment and Disposal Costs                   58

 7     Mannheim Furnace Participation in Hydrogen Chloride        67
       Production

 8     Titanium Dioxide Scenario Data and Results                 78

 9     Projections of Solid Waste Generation (Dry Weight)         82

10     Summary Data from Projections of Solid Waste Genera-
       tion                                                       84

11     Resource Value and Composition of Solid Waste from the
       33 Selected Chemicals                                      97

12     Unit Processes Participating in PVC Bottle Manufacture     109

13     Treatment Disposal Costs                                   113
                                  vii

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                          TABLES (cont'd.)

No.                                                            Page
14     Summary of Solid Waste Treatment and Disposal  Costs
       for 33 Selected Chemicals                                115

15     Land Use for Solid Waste Disposal                         117

16     Land Use for Solid Waste Disposal  in Absence of
       Water Discharge                                          ^

17     Process Change Among the 33 Selected Chemicals           126
                                 vm

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                            ACKNOWLEDGEMENTS

The authors wish to acknowledge the contributions of a number of other
International Research and Technology staff members.  Helpful in develop-
ing concepts explored in the study were:  Bruce Everling, George Foster,
Narayan Thadani, and Dale Schmidt.  Performing vital roles  in publica-
tion of the report were:  Patty Pearce, Fran Calafato, Sandy Thomas,
Barbara Schwartzman, and Carolyn Cummings-Saxton.
                                   IX

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                               I.  CONCLUSIONS

The findings of this study are that:

     (1)   ongoing process substitutions are acting to produce a significant
           reduction in quantity of wastes generated—by  1977,  process
           substitutions will reduce solid wastes from the selected chemicals
           by 7.3%;
     (2)   the viability of resource recovery as a method of waste reduction
           is hampered in Sector 281 by the intrinsically low economic  value
           of most waste materials produced;
     (3)   constraints on disposal of solid wastes to water bodies are
           already being translated into economic decisions by the industry.

These findings lead us to conclude that the emphasis of Federal action
should be upon the promulgation of environmentally based  regulations for
solid waste disposal.   Action is presently being undertaken in the areas
of sanitary landfill and hazardous waste disposal.  Similar steps should be
taken for disposal via lagoons and subsurface injection.   In each case, an
important aspect is the establishment of a monitoring and data assessment
system to evaluate the immediate and long term effects of the disposal
method.  Subsurface injection monitoring is particularly  critical  due to
the difficulty in correcting the situation if leakage develops.  In all
modes the significance of even small quantities of toxic  material  must  be
carefully assessed.

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                           II.  RECOMMENDATIONS

This study has developed the context within which more detailed assessments
of resource recovery and waste disposal  can be carried out.   In addition,
our method of evaluation of the effect of process substitution on pollutant
generation can be fruitfully extended from solid wastes to air and water
borne wastes.  Specifically, we recommend:

      (1)   an equivalent assessment of the effect of process substitution
            on the air and water borne wastes from Sector 281;
      (2)   the extension of such analysis to all wastes from other large
            waste producing economic sectors;
      (3)   the identification of the flow paths of valuable materials,
            such as scarce metals, through Sector 281, starting with
            their purchase by that sector; then an evaluation of the
            potential for recovery of these materials at that point at
            which they enter the waste stream;
      (4)   a regional analysis of the synergistic effect of use and gener-
            ation of hazardous materials by contiguous industries;
      (5)   a detailed economic study of the waste handling alternatives,
            including resource recovery, for the more burdensome wastes,
            such as those from phosphoric acid;
      (6)   the placing of documentation requirements on the producers of
            solid waste, such that the quantity and chemical composition of
            the waste generated at each production facility is identified.

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                           III.  INTRODUCTION

PROJECT SCOPE

This project has considered:
       •  The amount and composition of the solid wastes generated
          during industrial chemicals manufacture;
       t  The present means for handling and disposing of these wastes;
       t  The manner in which these wastes evolve with time due to
          process substitutions and modifications;
       •  The opportunities for resource recovery and/or improved
          treatment and disposal of these wastes; and
       t  The governmental strategy options for affecting solid waste
          management in the industrial chemicals sector.

Industrial chemicals manufacture forms Sector 281 in the Standard
Industrial Classification; included are the following six major sub-
groups:
       2812  Alkalies and Chlorine
       2813  Industrial Gases
       2815  Cyclic Crudes and Intermediates, Dyes, and Organic Pigments
       2816  Inorganic Pigments
       2818  Industrial Organic Chemicals, NEC*
       2819  Industrial Inorganic Chemicals, NEC*

In 1970 industrial  chemicals were manufactured at 2034 plants employ-
ing 252,200 people.   The value of shipments in that year was  $14.3
billion, which represents over one-third that of the entire Chemicals
and Allied Products Major Group (#28).
*NEC, Not Elsewhere Classified.

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The wastes generated at an industrial  chemical  production facility are
of two distinct types:  process related and non-process related.   The
latter are those wastes generated in any production facility that are
due to 'overhead'  activities not directly attributable to the production
process.   For example, cafeteria trash, sewage, used computer paper,
etc., are all in the latter classification*  The former, on the other
hand, relate directly to the primary production process.  If plant out-
put is increased,  these wastes are also generated in proportionally
greater measure.  This study has considered only process related  wastes,
and has further restricted its attention to those wastes unique to the
chemical  industry.  Thus, proper management of flyash from power  genera-
tion and activated sludge from waste water treatment has not been
addressed.  On the other hand, liquid/solid mixtures, such as slurries
and sludges, have been included because they are inherently associated
with the production process and are often handled together with dry
solid wastes.
PROJECT OBJECTIVES

The purpose of the present investigation was four-fold:
       (1)  to delineate the extent and nature of the solid wastes
            generated during industrial chemicals manufacture in
            sufficient detail that the significance of these wastes to
            the nations economy and environment can be properly
            appraised;
       (2)  to assemble a data base appropriate to an evaluation of the
            potential for and importance of resource recovery from in-
            dustrial chemical solid wastes; to consider a number of
            examples illustrating the dimensions of the resource reco-
            very opportunities associated with industrial chemical
            solid wastes;
*These do not usually contain toxic or hazardous materials.

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       (3)  to identify present waste disposal practices in the indus-
            try and to indicate areas in which this practice could or
            should be improved; and
       (4)  in line with the foregoing, to consider the appropriateness
            of alternative courses of governmental  action in the devel-
            opment of sound solid waste management practices for the
            industrial chemicals group.
PROJECT BACKGROUND

The IR&T study is a follow-on to a prior study of industrial  chemical
solid wastes by The Research Company (TRC) of New England.  That work
was sponsored by the Industrial and Agricultural  Data Section, Division
of Technical Operations, EPA National Environmental  Research Center,
Cincinnati, Ohio.  The TRC report titled, "Solid  Waste Management in
the Industrial Chemical Industry,"2 was completed in early 1971.  TRC
considered both process and non-process wastes.

TRC grouped process wastes in six categories:
       (1)  sludges,
       (2)  filter residues,
       (3)  tars,
       (4)  flyash,
       (5)  off-quality product, and
       (6)  all other.
Using a survey technique, TRC gathered data on the generation of these
various waste types within the industrial chemical  industry.   They also
explored the methods employed for solid waste management and described
the production processes for a number of representative chemicals, in-
cluding a discussion of the sources of solid waste generation and gene-
ral nature of the resulting waste.

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 While  the TRC study offers a useful orientation regarding the general
 nature of industrial chemical solid wastes, it is not helpful in iden-
 tifying areas for potential resource recovery.  Nor does it offer
 insight into the manner in which the solid waste streams can be expected
 to change in the future.  For both these purposes it is necessary to
 identify the specific waste streams from each process, in terms of quan-
 tity and chemical composition.  Knowing the stream content and the geo-
 graphic location of its generation, it is possible to speculate on the
 potential for resource recovery.  Knowing the manner in which the pro-
 duction processes are evolving, it is possible to determine the chang-
 ing character of the overall industrial  solid  waste output,  including
 toxid  hazards.*

 Another factor that has played a role in shaping the form of the IR&T
 study  is an extensive investigation of the treatment and disposal of
 hazardous chemicals undertaken by EPA.  This  investigation was conducted
 in compliance with Section 212 of the Resource Recovery Act of 1970.
 That act dictated that a  technologic and economic evaluation be carried
 out regarding the establishment of a system   of National Disposal Sites
 for hazardous wastes.  Over 1.5 million dollars has been expended by
 five contractors** to develop a data base describing toxic wastes gener-
 ation; explore resource recovery, treatment,  and disposal options; con-
 duct economic assessments of a system of National Disposal Sites and
 of alternative approaches; and survey citizen opinions regarding
 community acceptance of a Disposal Site.  IR&T has incorporated rele-
 vant findings of the hazardous waste effort into this study, and, where
 *Data of the type assembled  by  TRC  is  somewhat helpful  in overall con-
  sideration of treatment and alternate disposal requirements.  Even
  here, however, specific characterization  of  the waste  streams is
  necessary before detailed evaluations can be undertaken.   Toxic
  hazards were not considered.
**Booz Allen Applied Research Inc.;  TRW:, Battelle Memorial  Institute,
  Pacific Northwest Laboratories; Arthur D. Little  Inc.; and HumRRO.

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appropriate, we have adjusted the direction of our effort to avoid an
unproductive overlap of the two studies.   For example, less emphasis
was placed on waste treatment and disposal than originally planned,
while the manner in which the waste stream is evolving received greater
emphasis.

Although the hazardous waste effort forms an important complement to
the IR&T study, there are significant differences between the two
efforts.  Our study focuses on the whole range of process-generated
solid wastes unique to the industrial chemical industry, whereas the
hazardous waste study considers only toxic wastes, while encompassing
all industrial sources and including air and water pollutants in addi-
tion to solid wastes.  (In fact, 90% of the toxic wastes were found to
be water borne.)  In extending beyond toxic wastes, IR&T considered
those solid wastes that contain significant resource value or pose
difficult treatment/disposal problems.
PROJECT METHODOLOGY

The conduct of the project can be described in terms of six consecu-
tive phases:
       (1)  develop data base for present solid waste quantities and
            chemical composition;
       (2)  identify present solid waste management practice for select-
            ed wastes;
       (3)  identify ongoing or planned industrial  process changes and
            assess their effect on the solid waste stream;

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       (4)  evaluate potential  for resource recovery from candidate
            waste streams;
       (5)  explore alternatives for improved waste treatment and dis-
            posal ;  and
       (6)  utilize the foregoing information to assess governmental
            strategy options for influencing industrial chemical  solid
            waste management.
In the following sections each  phase is discussed in terms of the prin-
cipal decisions affecting the structure and content of this study.

Develop Data Base

The initial phase of the project involved selecting representative
chemicals from among the several thousand inorganic and organic chemi-
cals produced by the industrial  chemicals sector.  A manageable subset
of representative chemicals was  needed to characterize the sector as
a whole in terms of its solid waste stream.  The criteria for selection
arise naturally from the objective of the study, namely to identify
needs and opportunities for improved waste resource recovery, treatment,
and ultimate disposal.  To qualify for inclusion on the list, the waste
chemicals had to satisfy the following requirements, viz.
       (1)  possess significant resource value,
       (2)  pose a  difficult waste disposal problem, and/or
       (3)  have markedly deleterious properties, e.g., toxicity,
            combustibility.
Using these criteria, 33 specific chemicals were chosen to provide a
reasonable characteristic sample of the entire sector.  These 33
chemicals accounted for 40% of the 149 million short tons of product
output by Sector 281 in 1971.  In terms of solid waste, we estimate
that production of the selected chemicals accounts for more than 95%  of
the entire sector's solid waste.  The emphasis of the present study was
not specifically upon toxic wastes.  Since some of the smaller production
processes may contribute a disproportionate share of the toxic waste, a

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a follow up to the present study which focus upon toxic wastes is in
order.

Having selected the chemicals to be studied, initial estimates for the
solid wastes from each were refined.' In doing so, information was ob-
                                    •3  4  5 *
tained from the published literature '  '  '  EPA publications and
     fi-i ?                       1 ^  i d.
data     , Bureau of Mines data   '    trade associations, industrial
        **
concerns  , and IR&T industrial process files.  From these diverse
data sources, estimates were made and cross checked for the solid
wastes generated by each production process.  Then, the participation
of each process in the production of the marketed chemical was deter-
                    15                       *•*•,*
mined from SRI data   , published information   , and trade association
information.  Knowing the participation of each process and its associ-
ated solid waste, the overall solid waste associable with each chemical
and with the entire set of 33 chemicals was directly determined.

Appraise Present Solid Waste Management

The nature of the solid waste treatment presently afforded the 33 repre-
sentative chemicals was identified via literature search, plant visits,
and discussions with governmental and industrial representatives.  The
costs of such treatment were estimated based on knowledge of the waste
composition and rough guidelines for such costs as furnished in the
literature.  The emphasis in this portion of the study was to formulate
*The published literature contains primarily process information.  Waste
data must be calculated or inferred.  References 3 to 5 are the primary
texts employed.  Other references are given in the subsequent discussion
of the solid waste data base.
**Dr. Joan Berkowitz of Arthur D. Little, who was working on a companion
  study to establish a solid waste classification system, was of partic-
  ular assistance.  She arranged for IR&T staff to discuss our project
  with those Arthur D. Little Staff members familiar with the chemicals
  of interest.
***Individual sources employed are referenced in the chapter on the
   solid wastes data base.

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an approximate, but consistent, estimate of solid waste management costs.
This information was then used as a point of departure for the consider-
ation of improved disposal.
Assess Change in Solid Waste Stream

The amount of solid waste generated by production of a specific chemical
varies with time.  There are four major determining influences:  market
growth or decline, process substitutions, process modifications, and raw
material changes.*  In overall terms, the market for industrial chemi-
cals has been continually expanding since the construction of a sulfuric
acid plant in Philadelphia in 1793.  From 1958 to 1967 value added by manu-
facture in the Chemical and Allied Products Sector (SIC Sector 28) grew
by 90%, and that of Industrial Chemicals (Sector 281) by 83.5%. 16
Superimposed on the overall growth, however, competition among chemicals
led to a decline in demand for some chemicals and an accelerated growth
for others.  For example, since 1945 ethylene has progressively dis-
placed acetylene in nearly all applications.  In the four-year period
from 1964 to 1968 .annual production of ethylene increased by 52% as
contrasted with a minor 8.6% increase in acetylene production. ^7

Process substitution relates to the competition between alternative pro-
duction processes for a given chemical.  Benzene offers an  interesting
illustration of this type of substitution.  Benzene was originally pro-
duced as a byproduct of  steel manufacture.  Coal tars given off during
the production of coke were distilled to produce a number of chemical
products, including benzene, toluene, xylene, and butadiene.  Such pro-
*Raw material changes could be considered within the general category of
 process changes.  We discuss them separately because frequently the pro-
 cess operations remain the same, even though the raw material may change.
 An example is the processing of various grades of ore.
                                   10

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ducts, called coal tar derivatives, are included in SIC Sectors 2815
and 2818.  Since the mid 50's, however, benzene and the other coal de-
rivatives have been produced in increasing quantity with petroleum as
feedstock.*  Today, 90% of benzene is produced from petroleum, and this
feedstock continues to increase its share of the market.  Coal tar pro-
                                                            is
duction of benzene actually declined 22.2% from 1964 to 1968  .  As pro-
duction shifts from one process to the other, the amount and nature of
the solid wastes produced correspondingly shift.   (As it happens,
petroleum based production of benzene is classified in SIC Sector 2911,
and so is not included within the purview of our study.**)  In the case
of benzene, it is anticipated that with the advent of large scale coal
                            1 g
conversion processes in 1987  , or so, that coal will again offer a com-
petitive alternative to petroleum as a benzene feedstock, and hence
another change to the solid waste stream will occur.
The third major factor acting to produce a change in the solid waste
stream is process modification.  The principal modifications affecting
solid waste generation are:  changing the process operating conditions,
adding process steps for resource recovery and general  waste reduction,
and upgrading process air and water pollution control capability.  The
first two modifications tend to reduce the solid waste load while the
*In this case the process substitution is related directly to a raw
 material change.  There are distinct differences between the processes
 utilizing the two feedstocks, however.  We consider Category 4 - raw
 material-related changes to solid wastes generation - to apply to
 those situations in which the process remains essentially unchanged,
 e.g., a change in ore grade.
**If coal tars are not used in the production of benzene and other
  chemical products, they will presumably be burned.  They then pose a
  waste disposal  problem attributable to steel production  (Sector 3313)
                                   11

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last tends to increase it.  Examples of changing the process operating
conditions without changing the basic process include:   changing reac-
tion temperature or pressure; replacement of a fixed by a  fluidized  bed;
increasing the amount of material  recycled to the reactor;  introducing
on-line process computer control;  or replacing the present catalyst  with
another that allows higher or lower temperature operation,  increases
reaction rates, or is easier to regenerate.  Such process  changes are
normally introduced in order to increase yield, and therefore are
judged on an economic basis.*  An  accompanying benefit, however, is  that
the process waste load is usually  concurrently reduced  as  process effi-
ciency increases.  Because of its  economic significance, information
regarding the details of process modifications is frequently regarded
as proprietary.

Process modification via the addition of process steps  for resource  re-
covery and general waste reduction is in fact the focus of our study.
Such additional steps can be carried out either at the  production faci-
lity, by an independent processor, or at a municipal facility   such
as a National Disposal Site (whether privately or governmentally oper-
ated).  In all cases, the waste is presently being disposed of in some
way, so these additional steps represent an upgrading of the solid waste
management process.

Another type of process modification affecting the solid waste stream is
the transformation of air and water borne wastes into solid wastes.   This
transformation is already underway due to recent legislation, and will
come to nearly complete fruition over the next decade and a half.
*Environmental regulations will play an increasing role in all  process
 modifications (and initial process designs or selections) as these
 regulations are translated into economic terms and hence are accounted
 for in process management decisions.
                                    12

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The amount of material so transformed will increase as the legislative
constraints on air and water pollution tighten.  By 1977 "best practi-
cable technology" will be required for water treatment, and by 1983 the
standards will be raised to "best available technology" with  the ex-
press goal of reaching zero discharge.   In effect, all pollutants now
released  into the air and water will eventually be treated as solid
wastes unless otherwise eliminated by the factors discussed above, e.g.,
process substitution and/or modification.

The last major factor to be considered regarding solid waste generation
is the selection and treatment of raw materials (without process change),
This factor may lead to either an increase or decrease in process solid
wastes.  On the one hand, for political, economic, or environmental
reasons, raw materials of lower grade, such as some types of domestic
ores, may take the place of higher grade feedstocks, and these lower
grade materials will impose a greater solid waste burden.  On the other
hand, higher grade materials may become available or raw materials may
be more highly beneficiated at the mining (or extraction) site.   It
should be noted that the pretreatment of raw materials is directly
equivalent to adding later process steps, merely occurring as a  precur-
sor rather than a postcursor to the process.  The solid waste load is
shifted from the production facility to an earlier stage (and location)
in the materials conversion sequence.

It is revealing to consider the significance of resource recovery in
light of the foregoing discussion.  That is, the need for and nature of
the additional process steps must be interpreted within the context of
overall market considerations, ongoing technological substitutions, and
modifications of existing processes introduced to achieve greater effi-
ciency.  The economic leverage of each of these three factors is consi-
derably greater in most instances than that offered by increased reco-
very of resource value or otherwise optimum disposal of the waste.
                                   13

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Only legislative constraints can rearrange these relative priorities.
For this reason a great deal of emphasis was placed in our study on
identification of the trends in regard to market and process technology
and interpretation of their significance to solid waste generation.
Three case studies were conducted to illustrate these considerations.

In order to develop  a framework within which the need for and nature
of additional process steps for resource recovery and improved treatment/
disposal can be evaluated, the solid wastes attributable to the 33
selected chemicals were projected forward five and ten years.  In doing
this, account was taken of market considerations, process substitutions,
and process modifications.  Least-squares fits to historical time trends
and specific knowledge of industrial plans were employed in making the
projections.  Greater knowledge of actual industry capacity expansion
plans would permit increased accuracy in this projection, of course,
but it is felt that a reasonable and meaningful projection has been
achieved.  The legislative factors affecting air and water pollutant
contributions were reviewed, but quantitative evaluation of these con-
tributions was beyond the scope of this study.
Consider Need and Potential for Resource Recovery

The need for resource recovery was addressed within the context of the
resource value presently discarded through existing waste management
practice.  It was considered of central importance to determine whether
scarce resources are being dissipated.  An upper limit estimate was
made for the commercial value of the wastes from each of the 33 chemi-
cals based on the market value of the contained chemicals.  Present
market size was used as a  gauge of the ability of the commercial market
to absorb the waste chemical if recovered.  A case study was made of
the possibility for resource recovery from the wastes of the two
                                   14

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chemicals-phosphorus and phosphoric acid - which together generate more
solid waste than the other 31 chemicals combined.
Explore Needs and Capabilities for Improved Treatment and Disposal

To reiterate, the principal mode for improved disposal  is to adjust the
production process in such a manner as to reduce the amount of solid
waste generated.  Once this is done, the most significant problem
associated with the solid waste load is that of toxicity.  The detailed
studies of hazardous waste disposal recently made under EPA sponsorship
were reviewed in terms of their applicability to the industrial  chemi-
cals sector.  Aspects of present disposal practice for the 33 repre-
sentative chemicals that require modification were identified and
potential alternative approaches indicated.  Estimates were made of the
revised disposal costs.  The demands on land use were considered within
the context of the present waste load and that projected for 1977.   It
was assumed that little ocean dumping or subsurface injection will  be
practiced in 1977.
Assess Governmental Strategy Options
          \
The emphasis in our approach was to determine whether there are areas
in which governmental  action would be clearly beneficial.   The alter-
natives for governmental action considered were:
       (1)  regulation,
       (2)  tax incentives,
       (3)  subsidy,
       (4)  preferential procurement,
       (5)  research and development, and
       (6)  public education.
                                  15

-------
In approaching the study it was assumed that economic  self-interest
of the industry will, in nearly all  cases,  operate to  encourage  resource
recovery and waste reduction.  The study sought to identify marginal
instances in which additional incentive or  disincentive may produce a
desirable change, yet will  not disrupt the  industry.   Alternative
governmental actions were evaluated  using such criteria as:   the impor-
tance of the problem, the size and character of the alleviation  govern-
ment action would accomplish, its cost, what sector would  bear the  cost,
whether disruption to the industry would result, and the time required
to accomplish the change.
                                   16

-------
            IV.   INDUSTRIAL CHEMICAL SOLID WASTE GENERATION

In this chapter we consider the mechanisms for generation of process
solid waste and the types of waste that result.  Using the criteria
described previously, a subset of representative chemicals that char-
acterize the solid wastes of SIC Sector 281  is identified.
SOLID HASTE ORIGINS AND CHARACTER

Within the category of solid waste (as we have defined it for purposes
of this study) are materials ranging from slurries to dry solid  cake;
from combustible organic tars to inert inorganic salts;   from toxic
materials, such as chromates, to common salt.   These wastes arise from
three principal sources:
     (1)  unreacted raw materials,
     (2)  contaminants of the raw materials,  or
     (3)  by-products of the chemical  reaction.*
The contribution from unreacted inputs can be expressed  in terms of
overall reaction yield:  a yield of 80% means that 20% of the limiting
reactant and a somewhat greater percentage of the other  reactants
remain unconverted.  By-products, the third category, can be further
differentiated into coproducts of the main reaction or products  of an
undesired side reaction.  An example of the latter is NO  generation
                                                        X
in combustion processes.  Again, not all  of the wastes will  be solid
wastes.  However, even airborne and waterborne wastes may be subse-
quently converted to solid form, i.e., in the course of  air and  water
*To some extent the principal  product also enters the waste stream  as
a result of inadequate separation.   It may appear as a solid waste.
                                  17

-------
treatment.  Hence, participates and water-soluble salts are considered
here with other solid wastes.

An example of a solid waste traceable to material entering in the raw
                                    20
material stream is shown in Figure 1.  This figure depicts the process-
ing sequence for the manufacture of benzene, toluene, and x/lene (BTX)
from coal tars.  In this process the crude oil  contaminants are sepa-
rated from the desired products by acid washing and alkali  neutral-
ization.  An acid and an alkali sludge result.   Subsequently, the
desired products are mutually separated by fractional distillation,
and the still bottoms are removed as waste tars.

A primary distinction between the chemicals composing Sector 281  is
whether they are organic or inorganic.  For the most part the solid
wastes associated with the two chemical types are quite different.
The BTX example considered above is interesting because it is an
exception to the general rule.  For the most part, the production of
organic chemicals involves the use of a petroleum feedstock whose
contaminants have been stripped away during the prior refining
process (SIC Sector 2911).  In this event the principal solid wastes
from production of the organic product are organic tars formed as
undesired products of side reactions.  These tars may be furthur
stripped of chemical value by subsequent processes.  For example, one
of the alternatives for production of carbon tetrachloride and
perchloroethylene is called the "garbage can" process because it
accepts waste tars formed during earlier chlorination steps.  In
effect, this process serves as a resource recovery step.  Alternatively,
waste tars can be incinerated with or without heat recovery.  For the
most part, disposal of organic tars is not difficult, however, the
cost of incinerating corrosive halogen-containing tars is significant,
and frequently leads to their disposal through landfill.
                                   18

-------
Spent catalysts are an important component of the solid  waste from
organic chemical production.   These materials are of interest due to
their metallic content and because they are frequently of a  toxic
nature.  They were not studied in detail  during this project because
we found the chemical industry fully aware of their resource value,
and acting accordingly.  For  example, spent nickel  catalysts are con-
                                                            pi
ventionally shipped to Europe for their metallic value there,  and
Union Carbide sells spent catalyst from phthalic anhydride production
                          22
for its vanadium content.
The BTX example represents a deviation from the general  rule that the
raw materials for organic chemicals are relatively uncontaminated.
In this instance, the production process is one step closer to the
initial step in the materials processing sequence than is  normally
the case for organic chemicals.  The processes by which  chemicals are
produced occur on a number of levels, the first being the  beneficiation
of the extracted ore or refinement of the basic oil  or gas.  Only the
raw materials associated with the initial conversion steps carry
unwanted material with them.

As a more typical example, consider phosphate rock processing.
Phosphate rock is washed at the mining site to remove material un-
desired in later processing steps.*  The resulting sand  tailings
and phosphate slurries (classified here as sol id waste) account for
sixty-eight percent of the weight of the mined rock, or  2.1 Ibs. waste
per Ib. product.  The slime is a particularly voluminous and undesir-
able waste having a low solids content (:5%) which settles out very
slowly over a period of years.  At the next stage in materials con-
version, phosphoric acid is produced.  The earlier beneficiation
*The beneficiation of phosphate rock falls within SIC Sector 1475.
                                  20

-------
step greatly reduces the waste that would otherwise be attributable
to phosphoric acid production.*  Nevertheless, a certain amount of
mineral contaminants are given off as sludge waste, 0.21 Ibs/lb
product.  The use of phosphoric acid in subsequent processing steps,
such as fertilizer production or sugar refining, entails essentially
no ore-related solid wastes.

Although there are ore-related wastes involved in phosphoric acid
production, the principal solid waste from the "wet process" is an
economically undesired coproduct—calcium sulfate dihydrate or "gypsum"--
produced in the main chemical reaction.   The "wet process"  sequence is
                 23
shown in Figure 2.  The chemical reaction, with 95% yield,  is:

     Ca10F2 (PV6 + 10H2S04 + 20 H2° "" 10CaS04 * 20H2°  + 2HF  + 6H3P04
In this reaction, 3.36 Ib of gypsum is produced for every Ib of
phosphoric acid.  The gypsum is separated through filtration, and
normally is sent to lagoons for temporary storage with later release
to a river body during periods of high flow.  The gypsum is "discarded"
in this manner because in the United States gypsum from natural deposits
is available in abundant quantity and at low price.  Thus,  whether
gypsum—like many other coproducts--is a desired material  or a waste
is a question of geochemistry and economics.

For the most part, the nature of the waste relates to its origin and
those generated by inorganics differ from those output from organic
reactions.  Raw-material-related wastes and undesired coproducts are
generally attributable to inorganic reactions.   Tars (by definition)
and spent catalysts can usually be related to organic reactions.  In
*The discussion here pertains to the "wet process"  for phosphoric  acid
manufacture.  In the dry process, the phosphate rock is employed
directly, without prior beneficiation.
                                   21

-------
the following section, a subset of representative chemicals are
selected  in order to permit specific consideration of the options
available  in industrial chemical solid waste management.
SELECTION OF REPRESENTATIVE CHEMICALS

As  stated  in the  introduction,  the  principal criteria employed in
selecting representative chemicals to characterize Sector 281's solid
waste load were that the waste:
     (1)  possess significant resource value,
     (2)  pose a difficult waste disposal problem, or
     (3)  have markedly deleterious properties, e.g., toxicity.
There were also a number of secondary criteria employed in order to
achieve general balance in our selections.  These secondary criteria
were that:
     (4)  at least one representative be considered from each SIC 281
          subgroup,
     (5)  a roughly equivalent number of inorganic and organic
          chemicals be included, and
     (6)  all  of the leading commercial  chemicals from 281* be
          considered as candidates.
We will now discuss the manner in which these criteria were utilized
in the selection process, and identify the chemicals selected.

Roughly 200 production processes associated with industrial  chemical
manufacture were reviewed from the perspective of their production
of solid wastes.  The level of detail  employed is exemplified by
standard chemical  engineering reference works,  e.g., Faith,  Keyes,
         24                    25
and Clark  and  Kirk and Othmer.   Inorganic reactions were examined
*In terms of value of shipments.
                                 23

-------
for production of a non-economic coproduct,  use of  crude  raw materials,
or low reaction yields.   Organic reactions  were primarily examined
                                                pc_OQ
for low reaction yield.   In addition,  EPA reports ~ on  the industries
of interest were reviewed.   An initial  designation  of toxic wastes
was made based on the process review.   The  estimates for  toxic  waste
loads were later correlated with those made in the  concurrent EPA
                         29-32
study of hazardous wastes.     The solid wastes associated with  mineral
ores were checked against information  presented in  Bureau of Mines
             33 34
publications.  '   On the basis of such an  assessment and extension
of available literature, fifty-two chemicals were initially selected.
Following discussions with  industry personnel  and our own appraisal
of the relative significance of wastes, fifteen chemicals were  dropped
from further consideration  leading to  a final  subset of 33 chemicals,
of which 16 are inorganic and 17 arc inorganic. These  are listed by
SIC category in Table 1.*  Their solid wastes are   felt to be
sufficiently representative of the Sector 281  solid waste load  as to
permit the formulation of meaningful conclusions regarding proper
solid waste management for  the entire sector.   In Table 2 the selected
chemicals are delineated in terms of the mechanism  by which they
generate solid wastes and the criteria under which  they were chosen.
In the following paragraphs, examples are given that illustrate use
of the various selection criteria.
* All chemicals and groups of chemicals contained in Sector 281  are
given in Table Al   of   the Appendix.
                                 24

-------
                               TABLE 1

      SIGNIFICANT SOLID HASTE PRODUCERS AMONG INDUSTRIAL CHEMICALS

       (Grouped by Standard Industrial  Classification Category)



281   Industrial Inorganic and Organic Chemicals

     2812  Alkalies and Chlorine

           Chlorine
           Sodium carbonate (soda ash)
           Sodium hydroxide (caustic soda)

     2813  Industrial  Gases

           Acetylene

     2815  Cyclic Intermediates, Dyes,  Organic Pigments, and Cyclic Crudes

           Aniline
           Benzene
           Benzene hexachloride
           Chlorobenzene
           Phenol
           Phthalic Anhydride
           Styrene

     2816  Inorganic Pigments

           Titanium dioxide
           Zinc oxide

     2818  Industrial  Organic Chemicals, Not Elsewhere Classified

           Chloroform
           Ethylene dichloride
           Ethylene glycol
           Ethylene oxide
           Formic acid
           Glycerine
           Perchloroethylene
           Propylene oxide
           Tetraethyl  and tetramethyl  lead
                                    25

-------
                     TABLE 1  (contd.)

2819  Industrial Inorganic Chemicals. Not Elsewhere Classified

      Aluminum oxide (alumina)
      Aluminum sulfate
      Ammonium chloride
      Boric acid
      Chromium trioxide (chromic acid)
      Hydrochloric acid
      Hydrofluoric acid
      Phosphorus
      Phosphoric acid
      Sodium chromate and dichromate
      Sodium sulfite
                             26

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-------
As discussed in the Introduction,  changes to  the  sol id.wastes generated
during production of a particular  chemical  can  arise  from any of  four,
not wholly independent, factors:   market growth and decline, process
substitution, process modification,  and  raw material  changes.   In
most instances the change in solid waste can  be related to more than
one of these factors.  For example,  the  substitution  of petroleum for
coal tar in the production of "coal  tar  derivatives"  like benzene,  as
discussed in the Introduction, is  a  process substitution motivated
by a raw material change.  Likewise, there are  two distinct  processes
for handling the various grades of titanium dioxide ores (rutile  and
ilmenite).  The so-called chloride process is used for  the high grade
ore, while the sulfate process is  employed for  the lower grades.   Use
of the chloride process has been increasing,  reaching 47% of the  market
in 1972.  One of the motivations for use of the chloride process  is its
avoidance of acid sludge wastes through  chlorine  recover} and recycling^
Steps to modify the sulfate process  so that it  includes sulfuric
acid reclamation are now underway.
*Toxic metals content in the chloride  waste  prevents use in some
 applications, e.g. waste treatment.
                                   36
-------
An example of market considerations playing a role in determining the
type of solid wastes generated is the decrease in production of alky1
leads due to an environmentally motivated drop in demand.  The wastes
from alkyl lead production are highly toxic, and are frequently stored,
in lieu of an acceptable disposal alternative.  Another market-
related example is the displacement of sodium carbonate by sodium
hydroxide as a source of sodium oxide for some uses, e.g., in the
aluminum industry.  This decline in demand for the chemical, when com-
bined with its waste disposal problems, has contributed to the shutdown
of a number of Solvay plants for sodium carbonate production.  Since
the Solvay process is one of the largest solid waste producers in
terms of quantity, the shift away from this process to use of natural
soda-ash deposits (trona) has a significant effect on the volume of
solid waste generation from Sector 281.

The increasing importance of the "Oxirane" process as an alternative
to the "chlorohydrin" process for propylene oxide manufacture is an
example of an ongoing process substitution.  At present, the Oxirane
                                       oc
process accounts for 27% of the market   and its prospects for future
growth are buoyed by its ability to avoid the solid waste problems -
waste calcium chloride brine - associated with the chlorohydrin pro-
cess.  Dow Chemical  Company, which currently has 48% of total industry
capacity for propylene oxide, is seeking to integrate their chloro-
hydrin process with electrolytic chlorine regeneration to get around
present waste problems.   Since Dow is the nation's largest chlorine
producer, it has significant economic incentive for solving the waste
problems of the chlorine-based chlorohydrin process.   Direct oxidation
has already completely displaced the chlorohydrin process for the
manufacture of ethylene oxide.  Another example of ongoing process
substitution is the recent, environmentally motivated move away from
the mercury cell electrolysis process to the diaphragm process for
chlorine manufacture.  This counteracts the gains made by the mercury
                                  37
-------
process since its domestic introduction.  It is anticipated that all
future growth in electrolysis capacity will  be allocated to the dia-
phragm process.

In considering resource recovery, emphasis was placed on wastes pre-
sently causing difficulty or for which recovery processes have been
tentatively proposed.  Calcium chloride falls in the former category
because the extremely large volumes of waste produced by the Solvay
process for sodium carbonate appear to be causing the disappearance
of that process in the United States.  Phosphoric acid belongs to both
categories because the present volume of waste is large and also con-
tains significant potential resource value.   Several processes have
                                                            OC  Q O
been proposed to abstract hydrofluoric acid from the waste,   ~   and
                                        39
use as a fertilizer has been suggested.    Alumina production (Bayer
process) also generates extremely large waste volumes but over several
decades no one has yet been successful in abstracting the significant
resource value contained therein.  Presently, efforts are underway to
modify the process itself as a means of avoiding the resource value
loss currently suffered.  Other instances in which resource recovery
can eventually be expected to be introduced (for environmental
reasons) have already been mentioned:  chlorine recovery from the
chlorohydrin process for propylene oxide, and sulfuric acid recovery
from the sulfate process for titanium dioxide manufacture.  The
principal resource potential of the organic wastes seems to be
recovery of the Btu content of the waste tars.  Alternatively,
chlorinated hydrocarbons can be converted to hydrochloric acid, to
carbon tetrachloride and perchlorethylene, or to vinyl chloride
monomer.

The criterion of difficulty was taken to be that the waste be of ex-
ceptionally large and irreducible volume or that the unit cost of
disposal significantly exceed  the average.  Calcium chloride is an
                                  38
-------
example of a large volume waste, being produced in large quantity by
both the Solvay process for sodium carbonate and the chlorohydrin pro-
cess for propylene oxide, as already noted.  Likewise, the carbide
process for acetylene manufacture produces large quantities of calcium
hydroxide waste.  In the urban areas where acetylene is typically pro-
duced for industrial purposes the disposal of this waste poses some-
thing of a problem.  The other major large volume wastes produced in
the sector are those associated with chlorine, alumina, hydrofluoric
acid, titanium dioxide, phosphorus, and phosphoric acid manufacture.

The cases where disposal costs are exceptionally high tend to coincide
with particularly undesirable properties, and are discussed in that
context.  The most important deleterious property is toxicity.  In the
later stages of this project information became available from EPA's
study of hazardous wastes, although by that time most of our deter-
minations had been made.*  The largest class of toxic wastes produced
in the industrial chemical sector is the chlorinated hydrocarbons.  The
pesticide benzene hexachloride (trade name lindane) is one example.
This is but one of six isomers concurrently produced and the others,
having no market, pose a difficult disposal problem.  Chlorobenzene
is another example.  The principal commercial market is for mono-
chlorobenzene, with a lesser market existing for dichlorobenzene.
However, the more highly chlorinated products simultaneously produced
have little market, and must be discarded.  Ethylene dichloride (EDC)
is a third example, but here process modification is tending to reduce
the problem.  In addition to the chlorinated hydrocarbons, there are
a number of other producers of toxic wastes in the sector.  The alkyl
* Our data was checked, however, against that EPA  data applicable to
  toxic solid wastes generated during industrial  chemical  manufacture.
                                  39
-------
leads have already been mentioned.  Mercury loss from electrolytic
chlorine production in the mercury cell is a well known problem.
Although nearly all mercury loss has been curtailed, concern over
this problem appears to have eliminated the mercury cell from
participation in future growth in chlorine production capacity.
Sodium chromate and dlchrornate production and chromic acid manufacture
release toxic chromates in their solid wastes.

In the foregoing we have identified the chemicals selected as repre-
sentative of Sector 281 in solid waste generation, and have discussed
the criteria under which these chemicals were selected.  In the next
chapter we present the data base developed for the selected chemicals.
                                  40
-------
              V.   INDUSTRIAL  CHEMICAL SOLID HASTE DATA BASE

 In  this chapter we present the data base assembled for each of the 33
 selected chemicals.  In subsequent chapters we draw upon this data base
 to  address the significance of process change; to project the solid
 waste estimates to 1977 and 1982; to consider the need and potential for
 resource recovery; and to assess the need for improved waste treatment
 and disposal.  The data base  is organized under four headings:
     (1)  characterization of the production of the principal chemical;
     (2)  identification of the quantity and chemical composition of
          the solid waste generated (when more than one production pro-
          cess participates, each is individually assessed);
     (3)  assembly of information bearing upon the potential for re-
          source recovery; and
     (4)  characterization of present waste treatment and disposal,
          and identification of the differential costs associated with
          improved treatment and disposal.
 In the following sections we describe each of these four sets of data.
CHARACTERIZATION OF THE PRINCIPAL CHEMICAL'S PRODUCTION
To characterize production of the principal chemicals data were assembled
on the economic value of the annual production, the diversity of pro-
cesses participating, the geographic location of production, and the
rate of change in the quantity produced via each process route.
Economic worth is presented in terms of annual  quantity output (million
short tons produced in 1971); present unit value U/lb.); and rank
among chemicals of a particular category, viz.  principal  organics  (PO),
organic intermediates (01), organic end products (OE), and inorganics
                                     41
-------
Breadth of process participation was appraised by identifying the major
production processes and their percentage of annual  production.*

Geographic diversity of manufacture was assessed by determining the
number of participating companies, number of plant sites employed, and
number of states in which production occurs.  This varied widely from
one company with one plant producing benzene hexachloride to 51 com-
panies with 79 plants in 18 states producing benzene.   The top four
companies were identified for each chemical, and the fraction of indus-
try capacity attributable to them was determined.  For each company the
geographic location of its plants was given (by state) with capacity
and production process identified.

Rates of market growth or decline were ascertained for the decade
1961-19/1.  Kates of change in process participation were estimated, so
that changes in the character or waste load could be predicted.**  In
making these estimates, use was made where possible, of market and pro-
cess appraisals appearing in the trade journals, such as Chemical
           41                               42               4~3
Engineering  , Chemical Engineering Progress  , Chemical Week  ,
                             __
Chemical and Engineering News  , and others.  Information gleaned from
informal contacts with industry personnel was also employed.

The data gathered to characterize production of the 33 chemicals are
given in Table 3.
* In instances for which the process participation could not be directly
  determined, an estimate was made based on installed plant capacity
  for each process.
**The changes in process participation are presented in the chapter on
  process change.
                                   42
-------
IDENTIFICATION OF THE SOLID WASTES GENERATED

The solid waste associated with each production process has been
identified in terms of its physical form, chemical composition, and
annual domestic production.  Terms such as acid sludge, brine, or dry
powder are employed to describe physical form. Chemical composition is
expressed in terms of tons of each identified waste component per ton
of product.  We are aware that in many instances trace contaminants are
present, and that frequently these contaminants exert a disproportionate
influence in determining the economics of resource recovery and waste
disposal.  Where possible we have identified such contaminants, however,
they are often related to proprietary aspects of the process and con-
sequently little information is available regarding them.   Also, they
may vary among the various users of the process, e.g., different
catalysts may be employed to accomplish the same end.  Our emphasis
has been on identifying the primary components of the waste.  Annual
waste production  attributable to a particular process alternative is
derived from the fraction of the primary chemical produced by that
process.

The data gathered to identify the wastes generated by the  33 chemicals
are given in Table 4.
                                   43
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                                                                   49
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APPRAISAL OF THE POTENTIAL FOR RESOURCE RECOVERY
Data gathered to serve as a basis in appraising resource recovery
potential included:  commercial value of the waste chemical  components;
present market size for the waste chemicals; identification  of resource
options; and an approximate index of recovery potential  based on market
and technology considerations.  Resource recovery options are presented
in the form of descriptive phases.

The indices of market, technology, and net potential  are intended as a
partial quantization of the impressions gained by the authors in their
process reviews.  The index of market potential represents a weighting
of the ability of the commercial market to accept that quantity of
material and the capability to market the recovered material at a com-
petitive price.  Technology potential refers to the present  technological
capability to carry out the indicated recovery: L means that the
technology for recovery is not presently available, M means  that the
recovery technology is at the pilot plant stage of development, and H
means that commercial processes are available.  Net potential is an overall
average of of the two considerations.  In some cases, even though little
market demand exists, the net potential is judged medium if  other considera-
tions, e.g., environmental, motivate recovery.

The data pertaining to resource recovery from the waste streams of the
33 chemicals are given in Table 5.
                                     50
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CHARACTERIZATION OF PRESENT AND POTENTIAL FUTURE DISPOSAL PRACTICE

The manner of present treatment and disposal is depicted by identifying
waste quantity per plant, potential environmental affects of the solid
waste, conventional practice, and resulting costs.  The waste quantity
per plant was estimated by identifying a typical plant size (for the
principal chemical) and normalizing the waste production to this
throughout.  Conventional treatment and disposal practice is presented in
descriptive terms, such as lagooning, slag piling, ocean dumping.  The
environmental effects of such practice are described in a similar manner.
For instance we might note that a given waste increases the turbidity
of water body and has a threshold limiting value of X PPM (for toxic
wastes).  The costs of the various treatment and disposal practices
were estimated using values given in the literature.  Waste quantity
per plant was used as a rough guide tp waste treatment throughput.
This tends to be an underestimate since each process waste is nearly
always combined with other wastes prior to treatment.  For this reason,
a throughput of four times the typical plant-size process waste was
assumed if the treatment or disposal cost seemed sensitive to scale.*
Where improvements in disposal practice appear advisable, the differen-
tial costs to achieve such improved treatment and disposal were
estimated.

The data for solid waste treatment and disposal for the 33 chemicals
are given in Table 6.
* Total  costs attributable to that process were based on the actual
  throughput, of course, with only unit costs being based on large
  flows.
                                    57
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62
-------
SUMMARY

The data given in the preceding sections represents the basic data
gathered for the selected chemicals.  In subsequent chapters this data
is amplified in the context of discussing the effects of process
change, forecasting solid waste generation in 1977 and 1982, appraising
resource recovery possibilities, and evaluating improved waste treat-
ment and disposal options.
                                  63
-------
    VI.  MARKET AND PROCESS CHANGE EFFECTS ON SOLID HASTE GENERATION

In this chapter we consider the role played by market and process sub-
stitutions in determining the quantity and composition of the industrial
chemical waste load.  In so doing we address those aspects of waste
generation that bear upon the needs and opportunities for resource recovery.
Two specific case studies are discussed.   In the first, alternative
ways of producing sodium sulfate are considered.  In addition to being
mined in its naturally occurring form, sodium sulfate is generated as
a byproduct in production of eight SIC 281 chemicals and during rayon
manufacture.  The questions addressed in  the case study are whether a
suitable market can be found for this material, now and in the future,
and what effect changes in the ten production processes will  have in
its generation.  The second case study concerns the production of tita-
nium dioxide.  Here, the effect process and raw material changes can
have on solid waste generation is examined.

In each case study, time trends were constructed from historical data
for market and process change.  These time trends were formed by extra-
polation of production data since 1950*.   Both a linear and an expo-
nential fit were attempted using a least-squares approximation.

In the final section of the chapter, five and ten year projections are
made for the solid wastes associable with each of the 33 chemicals.
The more provocative examples are individually discussed.  These pro-
jections are important from the standpoint of placing considerations
of resource recovery and treatment and disposal in perspective.
*If the process was commercially employed in 1950.  Otherwise, the year
 of process introduction served as the initial  point for the time series,
                                    64
-------
CASE STUDY OF SODIUM SULFATE

In both case studies the order of presentation is to provide relevant
background information, briefly describe the scenarios to be considered,
then discuss the scenarios results.
Background

Sodium sulfate is produced by mining the naturally occurring ore and
as a byproduct in rayon manufacture and in production of the following
chemicals:
     (1)  hydrogen chloride (from the Mannheim furnace)
     (2)  phenol (via the benzene sulfonate method)
     (3)  sodium sulfite (by reaction of S02 with sodium carbonate)
     (4)  sodium chromate
     (5)  chromic acid
     (6)  boric acid
     (7)  ammonium chloride
     (8)  formic acid

Process substitution is occurring among the production alternatives for
hydrogen chloride, phenol, and sodium sulfite.  Ammonium chloride is
produced by two processes but no change is underway or anticipated.
The other chemicals are produced by only one process.  The preponder-
ance (73.8%) of commercial  sodium sulfate is produced by mining and
rayon manufacture, with the other processes playing a minor role.
Excess production of sodium sulfate is discarded as solid waste.

Though sodium sulfate is not a toxic substance or rare commodity, it
is of interest because of the large volume produced, the diversity of
its sources of production, and its being representative of diverse
                                   65
-------
 manner in which  wastes  are  produced  in  the  industry.   In  this case
 study we focus upon  two questions:   how will  normally  occurring  process
 changes effect the volume of sodium  sulfate produced?   Secondly,  how
 much sodium sulfate  can the future commercial market be expected  to
 accomodate,  i.e.,  what  is the potential for resource recovery?

The changes occurring among  processes producing sodium sulfate as a by-
product are:
      (1)  HC1 from Mannheim furnace  -
           This is  the only  process for  HC1  which  generates  sodium
           sulfate, and  historically  it  has  been an  important  source
           for the  sulfate.   However, HC1  is being increasingly produced
           as a byproduct of other reactions, and  the Mannheim furnace
           is being phased out.   The  projected variation of  Mannheim
           participation in  HC1  manufacture  is shown in Table  7.
      (2)  Phenol via Benzene Sulfonation  -
           Although there are five processes for producing phenol, only
           one yields sodium sulfate  as  a  byproduct.  In 1970  the sul-
           fonation process  accounted for  about 16.2% of the phenol  pro-
           duced.  The process is phasing  out, however, with one  of  the
           major  producers expected to close down  soon. For purposes
           of projection we  assumed that by  1980 no  benzene  sulfonation
           plants will be in operation.
      (3)  Sodium Sulfite from Soda Ash  -
           Sodium sulfite is produced as a byproduct of resorcinol and
           of phenol  via the benzene  sulfonation process.   It  is  also
           produced synthetically by  the reaction:
                Na2 C03   +  S0£   ->•  Na2  S03   +  C02
           A parallel reaction leading  to  sodium sulfate occurs,  such
           that  for every Ib. of sulfite produced  6.25  Ib. of  sulfate
           is generated.   Presently, only 7.5% of commercial  sodium
           sulfite  is produced by the synthetic process.  However, the
                                   66
-------
                            TABLE 7



MANNHEIM FURNACE PARTICIPATION IN HYDROGEN CHLORIDE PRODUCTION
YEAR
1952
1954
1956
1958
1960
1962
1964
1966
1968
1970
HC1 PERCENT VIA MANNHEIM
FURNACE PRODUCTION
23.7%
19.6
16.4
12.9
9.3
10.0
11.0
9.2
7.1
5.6
                              67
-------
           benzene sulfonation process, is decreasing in importance as
           discussed above.  Under these circumstances, the amount of
           sulfite produced by the synthetic route may increase.
Scenarios
The amount of sodium sulfate produced as waste equals the deficit of
market demand to the amount produced.  That is,
     W(t) = -D(t) + N(t) + R(t) + £-PCi(t) fi(t) coi
where W(t):    waste sodium sulfate
      D(t):    commercial demand for sodium sulfate
      N(t):    amount of sodium sulfate mined
      R(t):    sodium sulfate produced as rayon byproduct
      Pc-(t):  amount of chemical i produced
      f-j(t):   fraction of chemical i produced by a process* that gen-
               erates sodium sulfate as waste
and   u>j:      amount of sodium sulfate produced per unit of chemical i
All production is expressed on an annual basis and, as indicated, all
quantities other than ui vary with time.  The sum, £ Pc.(t) « f-j(t) w-j,
is the total amount of sodium sulfate produced as a byproduct in the
production of the eight chemicals listed previously.  The demand for
sodium sulfate, amount produced by mining and as rayon byproduct, and
the production rates for the other chemicals, Pc-, were projected for-
ward in time by extension of least squares fits to historical data, as
described previously.  The variation of the fraction fj of HC1, phenol,
and sodium sulfite produced by processes generating sodium sulfate as
byproduct was also projected from time trends.
*If more than one process for chemical i were to generate sodium sul-
 fate as waste, they would have to be considered separately as their
 u's would probably differ.  No instances of this occur, however.
                                   68
-------
Three scenarios were considered.  The waste equation was solved  for
each.

     t  Scenario 1
        To serve as a baseline, the product mix existing in 1965 is
        projected into the future with increases in production taken
        into account.  This scenario is intended for purposes  of com-
        parison in illustrating the effect process changes have had,
        and will have, on the generation of sodium sulfate as  waste.

     t  Scenario 2
        It is assumed that increases in sodium sulfate demand  are met
        through processes which do not involve sodium sulfate  genera-
        tion.  Synthetic production is held at its 1972 level.

     •  Scenario 3
        It is assumed that lags in sodium sulfite production caused  by
        phasing out the benzene sulfonation process are met by increas-
        ing sulfite production via the synthetic (soda ash) process.
Results

Closest correspondence to historical  data for sodium sulfate demand  was
achieved using a linear least-squares fit.  The demand  from 1950  to  1971
and its projection to 1984 is shown in Figure 3.  Also  shown are  equi-
valent data for sodium sulfate mined  and that disposed  as  waste,  as
determined in the three scenarios.  A number of points  can be made
regarding the scenario results:
     (1)  Scenario 2 indicates that with synthetic production of  sodium
          sulfite held at its present value ongoing process changes
          effectively countervail against an increase in solid waste
                                  69
-------
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                                                  70
-------
           generation with market growth.  A modest increase over the
           1965 waste load occurs:  34% by 1972 and 50% by 1982.
      (2)   In  the  absence of  process changes, the amount of waste sodium
           sulfate produced in  1972 would be double that produced in 1965>
           and by  1982  the quantity of waste would increase an additional
           67%.
     (3)   In  Scenarios 1 and 2 the amount of sodium sulfate discarded
           is  less than that mined.   Thus, if sufficient motivation
           existed, reduction of sodium sulfate mining could enable
          market accomodation of the excess  sulfate.
     (4)   In  Scenario 3,in which additional  sulfite requirements are
          met through increasing synthesis process  participation, sodium
           sulfate waste generation becomes excessive.  Within four  years
           the amount of sodium sulfate discarded  as waste  becomes equal
           to  the entire market demand.  Such a course of events can be
          modified by employing another alternative for sodium sulfite
          manufacture or finding ways  to  increase the sodium sulfate
          market demand.

The conclusion to be drawn from the results  of the  three scenarios  is
that resource recovery does not seem to be the answer for  reducing  so-
dium sulfate waste since market demand will  not support such a course
of action.  To penetrate the market,  recovered sodium sulfate must  be
sold at a price competitive with its mined counterpart.  Recovery is
justified only if:
     (1)  advantage can be taken of geographic location to minimize
          transportation costs, or
     (2)  recovery costs are slight due either to a  relatively pure
          waste  stream or a market  being  found for  low purity products,
          or
     (3)  the disposal  costs  are sufficiently  high  that product
          recovery and  sale at a loss  becomes  preferrable.
                                   71
-------
Since sodium sulfate and the materials for manufacturing it abound,
there is minimal need for conservation of this resource.  Rather,  atten-
tion should be focused upon proper disposal practice.   The benign  nature
of sodium sulfate presents little difficulty in the achievement of safe
disposal through sanitary landfill.

Sodium sulfate is typical of the majority of the wastes produced in  the
industrial chemical sector.   They frequently have slight intrinsic
value, and pose little disposal  problem.  In the next case study we
consider a situation in which the wastes do present an awkward disposal
problem and the most convenient method of alleviating present difficul-
ties appears to be via resource recovery.
                                   72
-------
CASE STUDY OF TITANIUM DIOXIDE

Background

A significant quantity of solid waste is generated during titanium
dioxide production.  A prevalent method for disposal  of the wastes
has been through discharge into the ocean or a large  body of water.
American Cyanimid has recently received criticism regarding such dis-
position of the wastes from its plant in Savannah, Georgia, and the
South Carolina legislature has asked EPA to determine whether the
water bodies receiving such wastes are being harmed.

•  Production Process Alternatives

There are presently two alternatives for producing titanium dioxide:
the chloride and the sulfate method.  Of the two the  chloride process
                                                                    45
produces solid waste in less volume and of a less  hazardous   nature.
There are two basic steps to the process:
     (1)  separation of titanium from its ore via chlorination
     (2)  oxidation of the titanium
For ore of high purity, termed rutile, the chemical reactions are:
     (a)  Ti02 (+ impurities) + 2C + 2C12 •* TiCl4 + 2C02 + ... *
     (b)  TiCl4 + 02 -»• Ti02 + 2C12
In ore of lesser purity, termed ilmenite, the corresponding reactions
are:
     (a)  TiFe03 + C + Cl2 -»• TiCl4 + FeCl3 + C02 + CO + FeCl2 + ...*
     (b)  TiCl4 + 02 -»• Ti02 + 2C12
In both cases the chlorine is recovered and recycled.

The sulfate process is traditionally employed for the lower grade ores.
The reactions that take place are the following:
     (a)  TiFe03 + 2^804 -> FeS04 + TiOS04 + 2H20
*Coke is used as the source of carbon.
                                 73
-------
     (b)  TiOS04 + 2H20 •> TiO(OH)2
     (c)  TiO(OH)2 •* Ti02 + H20
The sulfuric acid produced in the second reaction is quite dilute and
is not recovered at  present.  It is the disposal of acid sludge that
has recently been criticised.

•  Ores

Three categories of ores are utilized in titanium dioxide production:
     rutile                      > 96% Ti02
     high grade ilmenite         - 64% Ti02; 30% iron oxides
     low grade ilmenite         *° 44% Ti02; 45-50% iron oxides
Historically, only rutile has been used in the chloride process, i.e.,
all ilmenite has been processed using the sulfate method.  Recently
DuPont opened a plant capable of processing high grade ilmenite using
the chloride process; the ilmenite must contain 50% or more Ti02.  This
extension of the chloride process offers a significant opportunity for
reduction of the solid waste associated with titanium dioxide produc-
tion.

•  Process Modifications

Numerous attempts are being made to modify the present manner of tita-
nium dioxide production. The National Materials Advisory Board recently
reviewed the relevant technology.    One approach is to recover resource
value presently lost in sulfate process wastes.  Another is to upgrade
low grade ilmenite ore for use in the chloride process.

An example of moves toward recovering resource value from sulfate pro-
cess wastes is the work of American Cyanimid.  In response to regula-
tory pressure, two alternatives to present handling of their sulfate
process wastes are being considered.    A process which enables them
                                   74
-------
to recover gypsum following neutralization of the acid sludge appears
to be favored.  The other process neutralizes the acid, and then dis-
cards the waste into the Savannah River.  This alternative represents
a solution of limited duration in light of the increasing stringency of
water pollution regulations.

Attempts to produce a synthetic high grade ore are spurred by a short-
age of natural rutile.  Such ore offers tremendous processing advantages.
One of the more interesting approaches is that of the Benilite Corpora-
tion of America.  In their process, ilmenite is partially reduced
through use of carbonaceous material to convert most of the ferric oxide
to ferrous oxide:
     (a)  (FeO, Fe203)-Ti02 + C -> FeO-Ti02 + CO + C02
The reduced ilmenite is leached with 18-20% HC1:
     (b)  FeO-Ti02 + 2HC1 + FeCl2 + 2H20 + Ti02
The leached solid is then separated, washed, and  calcined.  They call
the resulting beneficiated ore, "Benilite."  The  leachate containing
ferrous chloride is meanwhile treated to regenerate hydrochloric acid,
with iron oxide obtained as byproduct:
     (c)  2FeCl2 + H20 + 2FeO + 2HC1
The technology for carrying out rutile upgrading  in this manner has
now been developed.  Its implementation is a matter economics, with the
cost of rutile being the principal  variable.
Scenarios

As described, there are at present two production processes and three
types of ores.  Rutile and high grade ilmenite are processed by the
chloride process and low grade ilmenite is processed by the sulfate
process.  Therefore, three waste coefficients are needed to determine
the solid waste produced during titanium dioxide manufacture:
                                  75
-------
     A-j:  the quantity of waste produced by the  chloride  process
          employing rutile;
     A2:  the quantity of waste produced by the  chloride  process
          employing high grade ilmenite;
 and A3',  the quantity of waste produced by the  sulfate process
          employing low grade ilmenite.
The values of the waste coefficients per pound of ore are:
     AT* 0
     A2^ 0.611 FeCl3
          0.032 Ti02
          0.064 inerts
          0.707 total
     A3^ 0.96 H2S04
          0.86 FeS04
          0.14 Ti02
          0.12 inerts
          2.08 total
The waste equation is then:
          W(t)  =  ArR(t) + A2-H(t) + A3L(t)
    where W(t):  total waste produced
          R(t):  rutile ore utilized
          H(t):  high grade ilmenite utilized
      and L(t):  low grade ilmenite utilized

Three scenarios were considered:

     Scenario 1
     This scenario was compiled as a baseline  in comparing  the past and
     future effects of process change.  Rutile participation and  the
     fractional production by the chloride process were maintained  at
     their 1965 levels.  A linear fit was employed for titanium dioxide
     demand.
                                   76
-------
     Scenario 2

     Present trends in titanium dioxide production were assumed to con-
     tinue in the future.  In 1965 rutile composed 9.8% of the ore used
     in Ti02 production.  By 1970 its participation had increased to
     14.4%.  A linear least squares fit to this trend in rutile parti-
     cipation indicates that by 1977 rutile will  compose approximately
     20.8% of mined titanium ore.  Since the reserves for rutile are
     diminishing, a further increase in rutile participation seems un-
     likely. Therefore,  beyond 1977  rutile participation was assumed
     to remain constant at 20.8%.

     Scenario 3

     In this scenario we made the optimistic assumption that for econo-
     mic and environmental  reasons there will be a rapid introduction of
     the Benilite process (or an equvalent ilmenite beneficiation tech-
     nique).  Specifically, we assumed that by 1977 50% of the ore
     being utilized in Ti02 production will be rutile or Benilite, and
     that by 1982 the percentage will have risen  to 80%.  All  such high
     grade, or upgraded, ore is presumed to be processed via the chlo-
     ride method.*  Chloride process participation is thus taken to be
     73.5% in 1977 and 90.5% in 1982.
Results

The data employed and the scenario results for solid waste generation
are presented in Table 8.  These results are plotted Figure 4,  together
*Alternatively, the sulfate method may be improved  to an  equivalent
 status (in terms of waste reduction)  by that time.
                                  77
-------
                            TABLE 8


             TITANIUM DIOXIDE SCENARIO DATA AND RESULTS
Scenario 1 1965 1972
Chloride process 20.6* 20.6
participation (%)
Rutile 9.8 9.8
participation (%)
Total SW (103S.T.) 2232 2606
Scenario 2
Chloride process 20.6* 50.0
participation (%)
Rutile 9.8 16.4
participation (%)
Total SW (103S.T.) 2232 2080
Scenario 3
Chloride process 20.6* 50.0
participation (%)
Rutile 9.8 16.4
participation (%)
Total SW (103S.T.) 2232 2080
1 977 1 982
20.6 20.6
9.8 9.8
2891 3177
67.0 80.0
20.8 20.8
.1877 1664
73.5 80.0
50.0 80.0
1510 707
*This percentage was inferred from information presented by the National
 Materials Advisory Board   regarding rutile use.   It was assumed that in
 1965 only rutile was used in the chloride process.
                                  78
-------
                                               FIGURE  4
                           SOLID  WASTE GENERATION  FROM  Ti02  PRODUCTION
 oo
 z
 o
CO
 o
4000
3800
3600
3400
3200
3000
2800
2600
2400
2200
2000
1800
1600
1400
1200^,
1000
 800
 600
 400
 200
   0_
  1965
                      1967  1969  1971   1973  1975  1977   1979  1981   1983  1985
                                                   YEAR

                              Assume 1965 process mix  & rutile percentage projected into  the future.
                              Projection into future,  no major benelite  capacity.
                              Projection into future assuming major benelite production.
                              Ore use
                                              79
-------
with the time trend in rutile (or equivalent)  ore use.   Two main  points
can be made regarding the scenario results:
     (1)  Clearly, process substitution and  changes  in  raw material
          usage have a marked impact upon solid  waste generation.   If
          present trends continue, the quantity  of solid waste in  1982
          will have been reduced 25% relative  to its 1965 level.   This
          is in marked contrast to the 44% increase  that would have
          occurred in the absence of process change.
     (2)  The introduction of a process like that employed in  Benilite
          production can make a significant contribution to reduction
          of the solid waste load.  By 1982 the  projected use  of  Beni-
          lite would enable a 57% reduction in solid waste load over
          that anticipated by present trends,  and a  78% reduction  over
          that produced if no process substitution or raw material
          change had occurred.  To some extent the solid waste load  is
          merely shifted to the location at which ilmenite is  upgraded
          to Benilite.  However, resource recovery can  be employed,
          both through recovery and sale of the  iron oxide and through
          regeneration and recycling of the hydrochloric acid. This
          enables the avoidance of wastes that would be generated  during
          sulfate processing of such lower grade ores.   It should  be
          noted that attempts are also underway  to improve the sulfate
          process in terms of its waste generation properties.

The significance of the trends observed in the titanium dioxide case
study is that to a large extent these process  substitutions  have  been
encouraged by environmental pressures.  The resource value lost in the
sulfate process, while significant, was not sufficient  by itself  to
bring about a switch to the chloride process.  The environmental  advan-
tages of the chloride process  have provided an  added lure to  its  uti-
                                    80
-------
lization, and have added further stimulation to attempts to upgrade
ilmenite.  The stimulus toward resource recovery has come in this in-
stance from industry's transmutation of environmental regulations into
economic decisions.
FIVE- AND TEN-YEAR SOLID HASTE PROJECTIONS

Considerations similar to those presented in the case studies were
employed in making five and ten year projections for solid wastes of
the 33 selected chemicals.  Time trends were constructed for the market
growth (or decline) of each chemical and the participation of each pro-
cess and raw material  alternative.  Resource recovery was not taken
into account.  For example, all sodium sulfate byproduct was
considered to be a potential solid waste, whereas in our case study we
saw that a considerable portion of this material  is commercially sold.
Likewise, all undesired solids were considered to be solid wastes, even
though present disposal practice may be via dilution in air or water
streams, e.g., river disposal  of salts such as calcium chloride.  By
1977 such practices will have  been severely curtailed.

Projections were made for the  years 1977 and 1982.   For comparison, a
baseline value was determined  for 1977 by assuming  no process or raw
material  changes.
Projection Results

The projections are presented by individual  chemical  in Table 9,  and
are summarized from various viewpoints in Table 10.   As in the case
studies, the effect of process change can be clearly  seen.  Overall,
a 7.3% reduction in the projected 1977 waste load  can be attributed to
                                  81
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-------
                               TABLE  10

                     SUMMARY  DATA  FROM PROJECTIONS
                       OF  SOLID WASTE GENERATION
                1972
               1977*
               1977
               1982
Inorganics
2812
2813
2816
2819
8578.7
589.0
2691.5
43164.5
10859.6
589.0
3605.4
65062.6
9585.3
589.0
2531.6
61909.4
11728.3
589.0
2355.0
86448.4
 Total
55023.7
80116.6
74615.3
101120.7
Organics
2815
2818
554.6
973.7
701.0
1118.5
561.8
797.2
625.7
903.1
 Total
 1528.3
 Ore Based**   45272.6
 Non-Ore Based 11279.4
 All but       23847.8
 Phos.  Acid
 1819.5

68029.9
13906.2
30722.7
 1359.0

63669.9
12304.4
26539.9
  1528.8

 87218.3
 15431.2
 29221.0
 *Waste quantity in 1977 in absence  of  changes  to 1972 process participation,

**Alumina, aluminum sulfate, sodium  chromate  &  dichromate,  titanium dioxide,
  zinc oxide, phosphoric acid,  phosphorus,  hydrofluoric acid.
                                     84
-------
process and raw material changes.  Among the organics and the non-ore-
based materials the reduction is more dramatic, being 25.2% and 11.5%
respectively.  Even among ore-based materials significant redaction
occurs if the masking effect of phosphorus and phosphoric acid waste
generation is removed.  All other ore-based solid wastes have been
reduced 15.5% through process and raw material changes that will  have
occurred by 1977.  The net effect among all 33 chemicals, excluding
phosphorus and phosphoric acid, is a 13.6% reduction.  In the remainder
of this chapter we present the general projection results and individually
discuss the more interesting chemicals.
Our projections indicate that after 1977 the growth rate of solid waste
production increases.  This can be primarily attributed to a diminished
influence of presently ongoing process and raw material changes toward
alleviation of SW generation.  It is to be expected that additional
process and raw material utilization changes will  be invoked during
intervening years, and  as a result the projected  increased growth rate
after 1977 may not occur.  We anticipate that changes to the ore-based
processes will be of the sort already underway for titanium dioxide.
Continuing improvement in the extraction of resource value from the
organic raw materials is to be expected.  However, in view of the
increasing demand for petroleum as an energy source, the shift from
coal and inorganic raw materials to petroleum or natural gas feedstocks
can be expected to slow, and perhaps be reversed.

Process change, along with product mix changes, will decrease the frac-
tional amount of hazardous waste in the total waste stream as accounted
for by the 37 selected chemicals.  The recent decline of the mercury cell
process for chlorine produce will result in a decrease in the expected
mercury waste stream.  The limitations placed on some pesticides are
reducing the demand for benzene hexachloride and chlorobenzene.  Both
of these hydrocarbons are toxic.
                                    85
-------
Significant Process Changes

•  Past Changes

   Ethylene oxide:
The two commercial  methods for production of ethylene  oxide  have  been
the chlorohydrin and direct oxidation methods.   Direct oxidation  of
                                                                      AO
ethylene is the cleaner process,  producing essentially no  solid waste.
The chlorohydrin method, on the other hand, produces a great deal  of
solid waste.  For each pound of ethylene oxide,  1.26 Ibs.  of calcium
chloride and approximately 0.038 Ibs. of chlorinated hydrocarbons are
produced as undesired byproducts.  Since the 1950's use of the chloro-
hydrin method has been declining, culminating in its total elimination
in early 1972. The effect on solid waste is shown in  Figure  5.

   Perchloroethylene:
Perchloroethylene production has been growing rapidly  due  to its  use
in dry cleaning, which accounts for around 75% of its  sales.  Initially,
Perchloroethylene was produced from acetylene and chlorine by way of
trichloroethylene.   Today, however, most is made by chlorination  or
oxychlorination of other hydrocarbons.  The acetylene  route  produced
large quantities of calcium chloride, 0.670 Ibs. of CaCl2  per Ib.
of product.  The effect of process change on perch!oroethylene's  solid
waste generation is shown in Figure 6.

   Chloroform:
There are two process for making chloroform:  direct chlorination of
methane and reaction of acetone with bleaching powder.  The  reaction
sequences  are:
   1.  (a)  CH4 + C12 -»• r.H3Cl + HC1
       (b)  CHsCl + C12 + CH2C12 + HC1
       (c)  CH3C12 + Cl2 -»• CHC13 + HC1
                                    86
-------
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FIGURE 6
PROCESS CHANGE EFFECT ON
PERCENTAGE OF PERCHLOROETHYLENE PRODUCED VIA THE
ACETYLENE PROCESS
s,
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 1950   52   54    56    58    60    62    64    66    68    70
                              YEAR
                             88
-------
   2.
       2CH3COCH3 + 6CaOCl2-H20 -> 2CHC13 + Ca(CH3COO)2 + 2Ca(OH)2 +
       3CaCl2 + 6H20
The chlorination of methane produces byproduct hydrogen chloride, but
essentially no solid waste.  In contrast, the acetone and bleaching
powder  method produces 0.63 Ib. calcium hydroxide, 1.4 Ib.  calcium
chloride, and 0.67 Ib. calcium acetate per Ib. of product.   Although
the bleaching powder method used to manufacture a significant fraction
of the chloroform, it is now nearly extinct.   Only one small  plant
(as of 1968) still made chloroform by the acetone bleaching  process.

   Hydrochloric Acid:
Hydrochloric acid is primarily produced as a  byproduct from  chlorinated
hydrocarbon manufacture (chloroform being one example) or a  principal
product from the reaction of sodium chloride  and sulfuric acid (Mann-
heim furnace):
   (a)  NaCl + H2S04 -> NAHS04 + HC1
   (b)  NaCl + NaHS04 + Na2S04 + HC1
As the reaction sequence indicates, manufacture of HC1 via  the Mannheim
furnace produces byproduct sodium bisulfate and sodium sulfate.  As
discussed in the sodium sulfate case study, these byproducts end up as
waste if the market conditions do not permit  their sale.  HC1  production
via the Mannheim process has steadily decreased over the last twenty
years.  This is shown in Table 7 of the case  study.
t  Ongoing Changes

   Sodium Carbonate (Soda Ash):
This is one of the most striking process changes presently occurring,
It can be directly related to difficulties in waste product disposal,
   "By the end of the month PPG's 600,000 tons/day Solvay process
   plant at Barberton, Ohio, will be added to the growing list of
                                   89
-------
       shuttered synthetic soda ash units.   The high cost of finding
       ways to dispose of byproduct calcium chloride and competition
       from lower cost western U.S. natural soda ash generation forced
       PPG to throw in the towel."49
Synthetic production of Na2C03 is by the Solvay process:
   (a)  NH4OH + C02 •»• NH4HC03
   (b)  NH4HC03 + NaCL + NaH 0)3 + NH4C1*
   (c)  2NaHC03 + Heat -> Na2C03 + C02 + H20
   (d)  2NH4C1 + Ca(OH)2 -*• 2NHs + CaCl2 + 2H20
This process produces about 1.2 Ib. CaCl2 and .045 Ib. other inerts for
every Ib. of soda ash.  Alternative production methods are mining from
Trona deposits and extraction from salt lake brine evaporation.   Trona
(Na2C03'NaHC03-2H20) contains only about 6% insolubles.  Thus the waste
problem with Trona is far less severe than with the Solvay process.
Natural lake brines are frequently carbonated and contain burkeite
(Na2C03'2Na2S04).  The burkeite is processed to form Na2C03 and
Na2S04-10H20 (Glauber's salt) plus a number of other byproducts.   The
Glauber's salt can be sold and disposal of the remaining  salts poses
no problem since the lake itself is highly saturated.  The decline of
the synthetic process for producing Na2CC>3 is illustrated in Figure 7.
   Chlorine:
Chlorine is primarily manufactured by electrolysis in either a mercury
cell or a diaphragm cell.  The diaphragm cell tends to use brine as
raw material while the mercury cell uses rock salt, thus the solid
wastes from the former are slightly greater.  However, the essential
difference between the two wastes is that the mercury cell creates highly
toxic, mercury containing wastes.  The primary problem has been elimi-
*Some of the ammonium chloride is sold as byproduct.
                                   90
-------
o
CO
                                       FIGURE 7

                              PROCESS  CHANGE EFFECT ON

                  PERCENTAGE OF SODA  ASH  (NAgCOg) PRODUCED VIA

                                 THE SOLVAY PROCESS
              60   61   62   63   64    65    66    67   68   69   70   71    72
                                          Year
                                                                                 JC
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                                        91
-------
nating the mercury wastes to water.   This has  been essentially accom-
plished but the cost is high, averaging about  10%  of  the  cost of  the
original plant.  Continuing uncertainty in regulations  regarding  mer-
cury waste emissions and the high cost of clean up have caused the mer-
cury cell process to fall into disfavor.
   "The Chlorine Institute, which is surveying the U.S. chlorine
    industry this month, says that in '68, 28.6% of chlorine capa-
    city was mercury cells and 68.1% diaphragm cells.   This com-
    pares with 24.2% mercury cells and 72.4% diaphragm  cells in  '72.
    However, with U.S. chlorine in tight supply, a 22%  increase in
    capacity is now on the drawing boards.  And, with the exception
    of the modernization of a few existing mercury-cell plants, all
    of the new capacity probably will be diaphragm cells."

   Acetylene:
Prior to 1951, all acetylene was derived from  calcium carbide.  Since
then, nine companies have built hydrocarbon acetylene plants and  one
carbide plant has closed down.  No new carbide  plants  have been con-
structed in the U.S. within the last three years.   By 1966 acetylene
produced via the hydrocarbon method had risen  to about  60% of total pro-
duction.  In the calcium carbide process large quantities  of Ca(OH)2
are produced as a byproduct.  About 2.88 Ib. Ca(OH)2  (dry weight) is
produced for every Ib. of acetylene.  As waste, the hydroxide poses a
disposal problem since many of the acetylene plants are located  in
populated areas where land value is high.  An  effort  has  been made  to
market the hydroxide.    Increased water treatment requirements may
boost demand for it.

   Propylene Oxide:
Propylene oxide is primarily produced by the chlorohydrin process,  as
ethylene oxide used to be.  However, Oxirane Chemical Co. has installed
a plant in Bayport, Texas that produces propylene  oxide via direct  oxi-
                     52
dation of propylene.
                                   92
-------
   "Halcon-Arco (Oxirane) say that the process is a closed-loop,
    essentially pollution-free system.  To some extent the companies
    are counting on the anti-pollution movement for an economic
    booster shot for their process".
The chlorohydrin method produces about 0.950 Ib. of CaCl2 for every
pound of propylene oxide produced.  Our projections assume that 50%
of new propylene oxide capacity will employ the Oxirane method.
•  Potential Change

   Alumina:
Alumina is one of the major solid waste producing chemicals.  About one
pound of dry weight (2.5-4.0 Ibs. wet weight) waste are generated per
pound of alumina.  At present, nearly all alumina is extracted from its
ore (bauxite) via the Bayer process.  In this process, bauxite contain-
ing 30-55% A1203 is finely ground and reacted with lime in a caustic
soda solution.  The sodium aluminate (Na2Al204) formed is separated,
seeded with alumina, and decomposed into aluminum hydroxide.  The
hydroxide is drawn off and calcined to alumina
The Applied Aluminum Research Corporation (AARC) has developed an alter-
native process, the  "Toth"  process.  This process begins by chlorinat-
ing the bauxite.  The aluminum chloride formed is separated and reacted
with manganese metal to produce manganese chloride plus aluminum.  The
manganese chloride is then processed to regenerate manganese metal  and
chlorine.  Both elements are reused.  Besides regenerating the chemicals
used in the separation process (manganese and chlorine), the  Toth
                                                                 ro
process has the potential for recovering resources from the waste.
                                   93
-------
   "In a subsequent step, fractional  condensation separates the metal
    chlorides.  Iron chlorides can be converted to oxides,  thereby
    recovering chlorine.  The oxides  can be sold.  Titanium tetra-
    chloride, a liquid, could be sold for conversion to either metal
    or oxide.  Silicon tetrachloride  also could be sold or  recycled to
    limit chlorination of silica".

Work is proceeding on the Toth  process.  AARC is raising 2 million
dollars to design a pilot plant scheduled to begin operation in 1974.

Besides having the potential to reduce alumina waste, some  of the
titanium oxide demand could be supplied as byproduct from the Toth

process, thus reducing titanium dioxide waste generation.
                                  94
-------
             VII.   RESOURCE  RECOVERY NEEDS AND OPPORTUNITIES

At the onset of the project it was found that essentially no organized
data base exists for industrial chemical solid wastes.   Without such
a data base it is impossible to formulate meaningful  conclusions
regarding the needs and opportunities for resource recovery.  Therefore,
a primary objective of this project was taken to be the assembly of a
base set of solid waste data for industrial  chemicals.   Emphasis was
placed upon the collection and assessment of data pertaining most
directly to total sector waste management.  That is, attempts were not
made to identify a host of innovative resource recovery pos'sibilities,
but rather to construct a framework within which the importance of such
opportunities can be considered.  These were identified in Table 5
and/or are discussed below in the course of considering the overall
context of sector resource recovery.
PERSPECTIVE

The assumption has been made in this study that only in the event a
scarce resource is being discarded should resource recovery be con-
sidered an end in its own right.   Otherwise,  resource recovery performs
a role comparable to other market and process changes wherein they act
to reduce the solid waste load.  An example of resource recovery as
a form of waste reduction is the recovery of gypsum from titanium
dioxide (sulfate process) wastes, as discussed previously.  Regulatory
imposition of waste disposal controls has sufficed, in this case, to
set in motion economic forces that are encouraging recovery of (low
value) resources.
                                  95
-------
As stated in the Introduction, emphasis was not placed upon  the  identi-
fication of valuable trace materials present among the solid wastes,
e.g., spent catalysts.  While such a catalog of valuable materials
would be useful, it was necessary first to delineate the bulk composition
of the waste.  Four points should be made in this regard:
     (1)  trace components frequently vary from company to
          company, with their exact composition often a
          closely held secret; therefore, it is difficult
          to draw general conclusions regarding their presence;
     (2)  we found the industry adept at taking advantage of
          specific, valuable commodities present in the waste
          stream;
     (3)  a number of computerized indexing schemes are being
          developed   "   to correlate generation and use of
          intrinsically valuable commodities; and finally,
     (4)  trace materials frequently pose waste disposal problems
          and as such their identification to pollution regula-
          tory bodies is necessary, but was beyond the scope of
          this study.

The primary resource content of the wastes associated with the 33  select-
ed chemicals is listed in Table 11.  As can-be seen in this  table,  the
waste chemicals are mainly very low value materials.  However, their  total
commercial value, if a market were found for them, is 11.9%  of the  $7.20
billion production value of the 33 principal chemicals.*  Considering them
individually:
*The 854 million dollars contained in the solid wastes of the 33 chemi-
 cals can be compared with an estimate of 2 billion dollars for wastes of
 all types from the entire sector.56
                                    96
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                                                97
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     Titanium Dioxide
The titanium dioxide content of the waste streams  practically  equals
the total titanium dioxide market demand (1970).   As  indicated in Table
5, most of the Ti02 is contained in alumina waste.  Efforts  have been
made for over 50 years to extract this resource.   So  far  they  have  been
unsuccessful.  As indicated in the discussion of  process  change, the
Troth process for producing alumina may enable titanium dioxide recovery.

     Calcium Chloride
Generation of calcium chloride exceeds its market  demand, so that even
if processors wish to sell their byproduct calcium chloride  at a low
price, the present market cannot accomodate the available quantity. As
a result, processes generating calcium chloride are having economic
difficulties, e.g., the Solvay process for soda ash and the  chlorohydrin
process for ethylene oxide.

     Acetylene
As indicated in the previous chapter, generation  of large quantities of
waste calcium hydroxide within an urban setting has caused disposal
difficulties foracetylene manufacturers.  Use of  calcium  hydroxide  in
water treatment may increase demand for it,enabling its sale as a bypro-
duct.

     Sodium Sulfate
Refer to the first case study on process change effects on solid waste
generation.

    Sulfuric Acid
Environmental considerations are increasing interest in regenerating  sul-
furic acid from waste sludges.  The sulfate process for titanium  dioxide,
which produces the majority of the acid sludge in Table 11,  is a  specific
example of this.
                                   98
-------
     Hydrofluoric Acid
Discussed in the phosphorus and phosphoric acid case study (next section),
     Iron Compounds
There has been little effort to regenerate iron from waste streams.
Process changes occurring in titanium dioxide and alumina may generate
iron oxide as a byproduct.  This is primarily done to recapture the
chlorine.
     Calcium Sulfate
Discussed in the phosphorus and phosphoric acid case study (next section),
     Tars
Tars can be burned on site, and thus do not pose a solid waste disposal
problem.  In addition, their heat of combustion can be recovered, and so
they have (at least potential) resource value.  Halogenated tars are
less likely to be incinerated because they produce HC1, which is highly
corrosive.
     Hazardous Substances
Resource recovery of hazardous materials is highly dependent upon
economics.  For example, the lead content in the waste from production
of TEL, TML is recovered to make the process more economic, however,
recovery of arsenic from copper smelting is not economic since there is
a glut of arsenic on the market.
In the remainder of this chapter we consider the possibilities for re-
source recovery from the voluminous wastes generated during phosphorus
and phosphoric acid production, and discuss general approaches being
taken toward facilitation of resource recovery.
CASE STUDY OF PHOSPHORUS ACID
Background
In 1972 phosphorus and phosphoric acid production generated about 57%
of the total  (dry weight) solid waste from the 33 selected chemicals.
Because of the preponderance of this waste, it is important to ascertain
                                    99
-------
whether either resource recovery or process change can be expected to
significantly reduce the volume of waste or the associated environmental
problems.

All phosphoric acid produced .in the world today is derived from phosphate
rock (Caio(P04)5F2).  There are two processes for converting the rock into
phosphoric acid:  a wet process involving its acidulation; and a two step
thermal reduction-oxidation process that first produces phosphorus, then
phosphoric pentoxide (Pads), and finally phosphoric acid.

The wet process involves the following chemical reactions:
     3Caio(P04)6F2 + 30H2S04 + Si02 + 58H20 •*•
         30CaS04-2H20 + 18H3P04 + H2$iF6
Impurities such as aluminum, silicon, iron and sulfur add to the volume
of solid waste from this process.  The resulting solid waste stream can
be dissaggregated into the following components (per Ib. of 100% H3P04)  :
     3.360 # CaS04
     0.034 # CaF2 (from abatement of HzSiFe)
     0.091 # P04
     0.085 # Silicon, A1. Fe
     3.470 # Total

In the dry process phosphate rock is smelted with coke and silica in an
electric  (or blast) furnace to produce elemental phosphorus.  Most of the
phosphorus is converted to high purity phosphoric acid by oxidation to
PzOs vapor, which is then absorbed in water.  A simplified version of the
reaction is:
     (a)  Ca3(P04)2 + 5C + 3Si02 -»• 2P4 + 3CaSi03 + SCO
     (b)  2P + 5CO + 502 •* P205 + 5C02
The dry process generates more waste per unit product  (100% H3P04) than
the wet process:
                                    100
-------
     2.30 # CaSi03
     3.43 # inerts (FeO,
     0.006 # Pa
     5.637 # Total
The greater solid waste load from the dry process  is partially the result
of its using a lower grade ore.   Also, the higher  grade ore used  in the
wet process is further upgraded  through beneficiation to relatively
pure (Caio(P04)6Fz) fluorapatite.  The waste associated with the  benefi-
cation process is not included within the chemical  industry, but of
course must be environmentally accommodated.

Process change has been occurring in the phosphorus/phosphoric acid
industry over the last thirty years.
     Year                     % thermal (dry)/total
     1940                             45%
     1945                             50%
     1950                             49.6%
     1955                             41%
     1960                             36.5%
     1965                             26.2%
     1970                           - 20%
The wet process achieved its predominance in the market by exploiting
economies of scale, particularly in fertilizer production.  As a  result
of this process substitution, the unit volume of waste produced in the
chemical  industry has been reduced.  As noted above, this is primarily a
change in waste bookeeping.
Resource Recovery

Since process change is not acting to reduce the solid  waste  load,  other
alternatives should be examined.   Resource recovery would  be  the  preferred
                                   101
-------
method.  The two largest wastes are gypsum (CaSO^I^O)  and  slag

In 1972 about 18.69 x 10& S. T. of CaSCty-Z^O and  6.897  x 106  S.  T.  of

CaSiOs were generated from phosphoric acid and phosphorus production

alone.  Unfortunately, both gypsum and slag are plentiful  in nature  and
as a result their sales price is low.

     "Other than for road building and fill, it [slag] is
      generally a worthless waste product, and can not be
      counted on to return a credit to the phosphorus opera-
      tion.  Places like Florida, where natural  aggregate is
      scarce, may be an exception, and a limited market  for
      both regular and expanded slag exists"


Gypsum, the  other  major  byproduct,  is usually placed in sanitary landfill or

simply piled  up.   In  1970  9.436 x 10  short tons of gypsum were mined and

another 6.128  x  10 S.T. were  imported.  Although this  market potential

exists, the  sales  price  of  $3.72  per  ton is too low for phosphoric acid

manufacturers  to sell except in  local markets.  However, this is not

true  in Japan  where a shortage of natural gypsum leads  to a higher market

price.

     "These Japanese companies offer processes based on  the
       initial formation of calcium sulfate in the  semihydrate
      form (CaS04-l/2 HgO) which is ultimately hydrated  to pro-
      duce an especially high quality gypsum.  Simultaneously,
       a high P2®5  recovery, from 97-98.5%, is achieved.   The
       byproduct gypsum thus produced may be used in wall  board
      manufacture, and reportedly sets the government standard
       for the Japanese plasterboard industry.  This type of  pro-
       cess was originally developed in Japan because of  the  lack
       of high quality natural gypsum resources in  that  country,
       and also to  effect some economic recovery of the  sulfur
       required for phosphoric acid manufacture."58


Even  if the  byproduct gypsum could displace the naturally mined  gypsum

there  would  still  be a significant solid waste load since byproduct  pro-

duction of gypsum  from all chemical processes [19.92 x  106 S.T.]  exceeds the

total market demand [15.5 x 10  S.T.].  Furthermore, phosphoric acid demand

is growing at a rapid rate while gypsum demand has remained  steady for the

last 6 years.  Thus, the gap between byproduct production and  demand is  going
                                    102
-------
to widen.  Also, known reserves of natural gypsum contain about 20 billion tons
                                                          59
or approximately 2000 years supply at current usage rates.    Consequently, the
recovery of gypsum from U.S. phosphoric acid plants is not going to be mo-
tivated by resource conservation considerations.

Production of hydrofluoric acid as a byproduct of phosphorus and phospho-
ric acid manufacture is presently being investigated as a resource reco-
very possibility.  0  Interest has been stimulated by a projected shortage
of hydrofluoric acid.  It is produced by reaction of high grade fluor-
spar (CaF2) with sulfuric acid:
     CaF2 + H2S04 -»• CaS04 + H2F2
 Demand for hydrofluoric acid has grown at a rapid rate,  11% annually  for
 the decade of the 1960's,  and this growth is expected to continue  indefi-
 nitely.   The accelerating  demand is depleting domestic fluorspar supplies.
 (According to the Bureau of Mines, all fluorspar will have been utilized
 by 1993-1995.)  Although phosphate rock contains only 3% fluorine, rock
 reserves are so large that development of an economic process  for  recovering
 its fluorine content will  increase U.S. fluorine reserves fifty-fold.

Two processes  have been examined for recovering hydrofluoric acid from
phosphoric acid and phosphorus wastes.  Silicon fluoride  (SiF4) is pro-
duced in both  processes.  Once formed,  the SiF4 vapors are captured in
water to produce fluorsilicic acid.
     3SiF4 + 2H20 -> 2H2SiFe + Si02
In one of the methods, the fluorsilicic acid is reacted with ammonia to
form ammonia fluoride.
     H2SiFe +  6NH3 + 2H20 + 6NH4F + Si024-
The ammonia fluoride is heated with calcium hydroxide to produce synthe-
tic fluorspar  (CaF2).
     6NH4F + 3Ca(OH)2 + 3H20 ->•  3CaF2 + 9H20 + 6NH3t
which then is  treated in the conventional manner to generate hydrofluoric
acid.  The second method involves a one step conversion from fluosilicic
                                       103
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acid to calcium fluoride, but according to a Bureau of Mines  study the
                                     CO
process is more difficult to perform.
The reduction in solid waste volume which accompanies the recovery of
fluorine is slight, and, the synthetic fluorspar produces large quanti-
ties of gypsum when converted to hydroflouric acid.   Thus, this process
serves as an example of a case in which market conditions are acting  to
bring about resource recovery for its own sake.
GENERAL APPROACH

In the foregoing discussion we have considered the overall  perspective
for resource recovery in the industrial  chemical  sector and addressed
a prominent candidate for such recovery.  In general  terms, our assess-
ment indicates that resource recovery should be considered  as  one facet
of solid waste management, not necessarily  preferable to proper waste
disposal.  Economic considerations appear to act as a sufficient screen-
ing device for insuring that a valuable resource is not discarded.  There
are instances in which resource recovery should and will  be employed
for its own sake, however, and in the following sections we consider two,
not independent, devices for assisting such recovery.
"Junkie" Dealers
Junkie dealers are those commercial enterprises which serve as middle
men in waste recovery - receiving waste from its originator, recovering
the desired resource value, and selling the recovered material, perhaps
back to the original source.  There are many such dealers in the United
                                   104
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States, but their numbers are thinning*,  with competitive  forces favoring
the larger enterprises such as International  Mills  Service and  Heckett
Engineering.  At a recent AIChE meeting,  an excellent review was presented
of the opportunities and pitfalls associated with operation as  a junkie
dealer.63  The primary difficulty lies in insuring  continuity in both
the raw material, i.e., waste supply and  the market demand for  the re-
covered resource.  Process or raw material changes, such as those  we have
discussed, may act to curtail waste generation by the originating  pro-
cessor.  Faced with such uncertainty in supply, the dealer must neverthe-
less be able to provide assurances of product delivery to his customers.
Clearly, there is an advantage where the  waste being regenerated can be
returned to the original processor.  And, of course, some processes or
participating materials, such as catalysts, are less subject to change.

In spite of the difficulties, there is a  function to be provided by such
junkie dealers.  The larger companies are frequently not geared to either
processing or selling the recovered resource, which is usually  produced
in much smaller quantity than the primary product.   The higher  overhead
usually associated with a large company hinders effective competition
against contenders to the recovered material, the sales staff is not
geared to low quantity sales, and there are frequently alternative invest-
ment opportunities which afford a higher  return.  Thus, it is frequently
in the interest of the large company to cooperate with'the junkie  dealer,
however, not to the extent that it interferes with  the main process or
its modification.

The question arises as to whether it is appropriate for the government  to
provide assistance to junkie dealers.  In line with our previously stated
conclusion that economic forces appear sufficient to prevent scarce
*We were unable to obtain a meaningful  estimate of  the  number  of  junkie
 dealers.  Most are small, having a $50,000 annual  profit  or so.   Tonnage
           variable.
                                   105
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resource loss, our answer tends to be in the negative.  The issues to be
addressed in consideration of the junkie industry are those appropriate
to any small business, and are not specific to industrial  chemical manu-
facture.  As such, it would seem that steps to provide a healthful cli-
mate for small business while not unduely interfering with the normal
course of business would be useful.  Such steps include support of
research on fundamental recovery operations, such as sludge reduction and
treatment, and development of enhanced data handling schemes.   The gov-
ernment is already acting in both these areas.  The latter is  discussed
next.
Improvements in the Data Base

This report represents one step toward improvement of available informa-
tion on industrial chemical wastes.  There are a number of complementary
efforts underway.  The work of A. D. Little to develop a classification
scheme for industrial solid wastes is one example.64 The 16 month ADL
study was sponsored by the same EPA project office-The Solid and Hazardous
Waste Research Laboratory, National Environmental Research Center, Cincinnati,
Ohio-and was performed  in  parallel with the present study.  The
classification scheme attempts to provide a waste designation containing
sufficient  information  to  enable identification of resource recovery
opportunities.   Data of the following type are included:
     (1)  plant data - SIC code,  value added,  waste treatment
     (2)  waste properties - form, physical  properties, economic and
          planning data
     (3)  ultimate waste composition (if wastes combined) - material  codes
     (4)  intermediate wastes (each process) - water content, recovery
                                                   •
          value
     (5)  chemical classification - atomic number, density
From such data, detailed planning for solid waste management can be con-
ducted.  Since information of this level of detail is beginning to be
                                     106
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collected for air and water released wastes, its provision for solid
wastes will enable construction of overall  process (and industry)  material
balances.  It seems  realistic to expect that such an information  system
will be assembled in the next decade.

Under contract to the National Science Foundation, IR&T has developed  a
Materials-Process-Product (MPP) model which conducts material, energy, and
                                             55
economic balances over entire process chains.    A "process chain" is
the sequence of material conversion steps that leads from the primary raw
materials to the finished product.  For example, a process chain leading
to production of vinyl chloride monomer (VCM) might include:  chlorine
production via diaphragm cell electrolysis, ethylene production via
ethane pyrolysis, ethylene dichloride (EDC) production by direct chlori-
nation of ethylene,  and VCM production by EDC pyrolysis.  Another chain
might employ mercury cell electrolysis for chlorine manufacture, and
another replace ethane by naphtha as an ethylene feedstock.  A network
of process chains for polyvinyl chloride (PVC) bottles is shown in Figure
8, with the processes identified in Table 12.  The objective of construct-
ing such networks is to relate economic variables, such as market  demand
for PVC bottles, to materials and energy usages.  When the entire  economy
has been so described, it will be possible to determine net requirements
for a given material, e.g., sulfuric acid,  and,  likewise, net material
wastes.  At present, it is not feasible to gather the quantity and detail
of information required for the entire economy,  but the necessity  to
assemble such information for material planning  purposes is rapidly
increasing.  The detail suggested by the ADL classification scheme is
actually greater than required by the MPP model.

Another activity relevant to solid waste information management is work
on an "Effluent Management Information System (EMIS) at Development
Sciences Inc.    Like the IR&T model, EMIS employs a materials flow point
of view.  A regional data base for this model is now being established
                                   107
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     o
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tn
     LU
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     ae
-------
                            TABLE 12
      UNIT PROCESSES  PARTICIPATING IN  PVC BOTTLE  MANUFACTURE

   1.   Chlorine via salt  electrolysis  -  mercury cell
   2.   Chlorine via salt  electrolysis  -  diaphragm cell
 * 3.   Chlorine via HC1 oxidation  using  HNO,  (Kel-Ch!or)
   b.   Ethylene from  ethane  pyrolysis
 * 5.   Ethylene via autothermic  cracking
   6.   Acetylene/ethylene via Wulff  process  (naphtha  feed)
 * 7.   Acetylene/ethylene from naphtha by partial  oxidation
   8.   Acetylene from methane by partial  oxidation
   9.   EDC via  ethylene chlorination (vapor)
 *10.   EDC via  ethylene oxychlorination  (vapor)
  11.   EDC via  ethylene chlorination/oxychlorination  (vapor)
 *12.   EDC via  ethylene chlorination (liquid)
    .   EDC via  ethylene oxychlorination  (liquid)
    .   EDC via  ethylene chlorination/oxychlorination  (liquid)
  15.   VCM from EDC pyrolysis
  16.   VCM from EDC pyrolysis with waste  treatment
  17.   VCM from concentrated acetylene
*18.   VCM from ethane oxychlorfnatlon (Transcat)   - part waste
       feed
  19.   PVC from VCM - bulk process.
 23.   PVC bottle manufacture
     *Processes not presently In domestic production.
                             109
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for Southeastern  Massachusetts.   The objective of EMIS is  to identify
firms within and among industries which could benefit from  resource
recovery and shared capital  investment in treatment centers.   EMIS is
designed to pose three questions:
     (1) "Are there any chemicals or materials being captured in pollu-
          tion control which can be used as raw materials by other pro-
          cesses?
     (2)  Are there any materials captured in pollution controls which
          can share treatment with other wastes?
     (3)  Are there any classified land ecosystems which can accumulate
          wastes with specified characteristics?"
Obviously, EMIS, like the MPP model, is limited by the extent of its data
base.
                                   110
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             VIII.   WASTE TREATMENT AND DISPOSAL

This chapter considers the final  stage in the materials  processing
sequence-waste treatment and disposal-in terms of present practice,
environmental  implications, and expectations for improved performance.
The 33 selected chemicals are again used as a focus  for  discussion.
PRESENT DISPOSAL PRACTICE

Seven methods predominate among the alternatives  for solid  waste dispo-
sal.  Considering each briefly:
     (1)  Incineration:   This involves oxidative  conversion of combus-
          tible solid material  to harmless gases  suitable for atmospheric
          release.  Undesired gaseous products, such as  HC1,  S02, NOX,
          must be removed prior to release.   Heats  of combustion may
          sometimes be recovered, and occasionally  additional  combustible
          material must be added to insure adequate combustion.   Resi-
          dual solids, i.e., ash, are landfilled.  To the extent that
          residual solids remain, incineration is a waste reduction step
          rather than an ultimate disposal.
     (2)  Dispersal into contiguous water bodies:  Historically, this
          practice has been widely employed,  but  EPA action has  now
          curtailed it in many industries.  Usually, the waste solid
          is temporarily stored in a lagoon,  wherein it  is  treated to
          minimuze environmental  impact.   For example, acids  and bases
          are neutralized and suspended solids are  permitted  to  settle.
          In the case of river discharge, attempts  are made to release
          the waste during periods of high flow.
     (3)  Ocean dumping:   This  practice involves  transporting the mater-
          ial out to sea, then releasing it.   Usually the material is
          conveyed by barge; it may be released directly or within con-
          tainers.  Costs depend upon the distance  of transport, and
                                   111
-------
           whether the material  can  be  loaded  in-plant or must be inter-
           mediately transported.
      (4)   Lagooning:   Lagoons  may be employed for  either temporary or
           permanent storage.   As  previously mentioned,  lagoons are fre-
           quently employed  for interim storage and water treatment
           prior to release  to  contiguous  water bodies.  Permanent stor-
           age occurs  when the  solid material  tends not  to  settle, e.g.,
           phosphate slimes, or would have undesirable properties if
           water cover were  not maintained, e.g., red mud (blows) from
           alumina and phossy   water (burns) from phosphorus.
      (5)   Sanitary landfill:   This  pertains to the burial  of non-hazar-
           dous solid  wastes under controls sufficient to preclude de-
           gradation of the  surrounding environment.  Controls include:
           proper site selection,  exclusion of hazardous materials,
           periodic provision  (usually  daily)  of soil cover, etc.
                            •ju-ii.-
      (6)   Chemical landfill:   This  is  the extension of  sanitary landfill
           to enable acceptance of hazardous materials.  Included are:
           the provision of  careful  material identification, adequate
           safety standards  (firefighting, etc.,),  surface  water channel-
           ing, leachate collection  and treatment,  materials recycling, etc.
      (7)   Subsurface  injection:   In this  case the  solid material is
           slurried and then pumped  into underground cavities.  The
           implications of many aspects of this practice are not yet
           clearly understood.   Subsurface injection of  hazardous
           waste should only occur when the leachate can be fully
           contained.

 The unit costs of treatment via each of the seven  techniques were as-
 certained from the literature.  Actual costs  vary  widely depending upon
 waste quantity, geographic  location, company  size  and expertise, etc.
 The values shown in Table 13  were employed in estimating the disposal
 *
  Phossy water is water which contains particles  of phosphorus  metal.
  The metal  burns into flames when exposed to oxygen;  thus  water cover
  is required.
**
  Termed Class 1  landfill  in California—no connection with groundwater.
                                     112
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                              TABLE  13
                       TREATMENT  DISPOSAL  COSTS
      METHOD
(1)  Incineration
(2)   Dispersal  to  contiguous
       water
(3)   Ocean dumping
(4)   Lagooning
       neutralization/
        precipitation
(5)   Sanitary landfill

(6)   Chemical landfill
(7)   Disposal fee
COST ($/T)
  067
                                   15
                                     68
 9569


 1-370'71
 1-3
 1072
 3-573'74

 4075
 19-82
       QUALIFICATIONS
HC still bottoms, slight
inorganic content.
high water, ash, sulfur,
or chlorine content
hazardous waste
storage costs attributed
to lagooning
excluding containment
and transport
excluding inplant collec-
tion and storage
quote from Rollins
                                 113
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 costs for the 33 selected  chemicals.*   It  was assumed  that slurries and
 sludges are temporarily stored  in lagoons  pending final disposal, and
 that acids and bases are neutralized at that point.  Hazardous wastes
 were relegated to chemical  landfill.   The  disposal cost estimates are
 presented for each chemical  in  Table 6. This data has been  aggregated
 by SIC Sector in Table 14.   Two striking aspects of  present  disposal
 costs are:
      (1)  Sector 2819 accounts  for 71% of  total costs.  As discussed
           below, our estimate may not  fully account  for the  scale eco-
           nomics available with such large volume wastes.
      (2)  Organics do not pose  a significant solid waste  problem.  Their
           disposal cost is less than 9% of the  total.
 The costs are lowest for Sector 2813.   This is  because there is  only
 one solid waste producer in the sector- acetylene via  the carbide pro-
 cess.

 It is useful to place the disposal figures for  the 33  chemicals  in per-
 spective.  The total waste quantity from the 33 chemicals is calculated
 to be 55.9 million tons.  This  compares with an estimate of  140  million
 tons for all industrial solid wastes.   The correspondence seems  reason-
 able, in view of the high contribution from phosphorus and phosphoric
 acid solid wastes.     In terms of disposal cost, the  estimated  $70.7
 million for the 33 chemicals exceeds  the $45.3  million**  attributed to
 all chemical manufacture (Sectors 281  and  282)  by the  137 corporate
 members of the Manufacturing Chemists  Association.     There are four
 sources from which the discrepancy between these two estimates may arise:
 *Subsurface injection is not included since this is not the  predominate
  disposal method for any of the wastes considered.
**IR&T estimate based on MCA data; includes all  operating and maintenance
  costs plus 10% of original capital  investment.
                                    114
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                               TABLE 14
      SUMMARY OF SW TREATMENT AND DISPOSAL COSTS FOR 33 CHEMICALS
                  Waste      Present
                 Amount   Disposal Cost
                (103 S.T.)    ($1000)
      Improved         Cost
   Disposal Cost       Ratio
      ($1000)
Inorganics
2812
2813
2816
2819
Organics
2815
2818

Total
55,024
8,579
589
2,692
43,164
1,491
554
937
*
56,515
64,963
8,709
1,178
4,841
50,235
5,750
1,896
3,854

70,713
                                              121,501
                                               38,528
                                                2,945
                                               22,192
                                               57,836

                                               19,967
                                                3,165
                                               16,802
                                              141,468
                          .87
                          .42
                          .50
                          .58
                          .15

                          .47
                          .67
                        4.36
                        2.00
*Includes material  sold as byproduct;
 is not included in cost estimates.
such material  (584 x 10  S.T.)
                                 115
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     (1)   the Manufacturing  Chemists  Association estimate only  includes
          expenditures by its  members;  these are the  largest  producers,
          however,  and probably account for 99% of  production;
     (2)   inaccuracies in our  estimations  of waste  quantities are  passed
          on in the estimation of disposal costs;
     (3)   some of the expense  we have allocated to  solid wastes may  be
          considered within  the category of water treatment by  the MCA,
          e.g., acid neutralization;  it is extremely  difficult  to  eli-
          minate such bookeeping type discrepancies;
     (-1)   we have probably not fully  accounted for  existing scale  eco-
          nomies; for example, $32.7  million of our estimate  is trace-
          able to phosphorus and phosphoric acid treatment, and opera-
          tion at this level can probably  be conducted  at less  than  the
          $l/ton assumed; to illustrate, disposal of  phosphate  slurries
          at a Florida phosphate plant costs $0.245/ton  ;
          if this figure is  assumed to also apply to  the phosphorus  and
          phosphoric acid wastes*, our cost estimate  is reduced by $24.7
          million;  this single change suffices to bring our estimate in
          line with that of  the MCA.
It is felt that when the four  factors are  considered  the correspondence
between the two estimates is reasonable.  Also, the manner  in which  our
individual chemical estimates  have been made is clearly evident, and so
they furnish useful first estimates for use  in further  consideration of
industrial chemical solid waste management costs.

Land usage requirements for  disposal  of solid wastes  from the 33 chemi-
cals are estimated in Table  15.  This table accounts  for the  disposition
of over 99% of the solid wastes.  The remainder are incinerated or sold
*Such low cost solid waste management was observed by the author  (JCS)
 during a visit to Freeport Chemical's Uncle Sam (wet process)  phospho-
 ric acid plant.
                                  116
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                                 TABLE 15
                     LAND USE FOR SOLID WASTE DISPOSAL
  Storage or
  Disposal Mode

  Temporary
  Lagooning

  Permanent
  Lagooning

  Sanitary
  Landfill

  Chemical
  Landfill
Waste Quantity
 (ID3 S.T.)

    12,064


    29,460


    14,930


       217
Waste Volume*
(1Q6 cu. yd.)

      161
      393
       60
                             56,671
                         615
Land Area**
 (acres)

  2,080


  5,075


    769


     11
                    7,935
                                                                     ***
  *Based on 504 Ib./yd.^ and 30% solids content in  lagoon.

 **Based on 48 ft. depth for lagoons and landfills.

***This represents land used during the year.   The  2080 acres  employed
   for temporary lagooning can be reused.   The remaining  5855 acres
   are added to permanent inventory.
                                   117
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as byproduct.*   Lagooning accounts for 90% of the land  use.   This  is
traceable to its use in control  of ore residuals,  such as  red  mud,  and
for storage of large volume inorganic byproduct salts prior  to their
dispersal to water bodies.  As noted in the table, 2080  acres  are
available for reuse and 5855 acres are added to permanent  inventory.
In comparison, 5 x 10^ acres of land are presently occupied  by the
extractive industries, and roughly 5% of this figure, i.e.,  250,000
acres, is consumed each year.'78  Industrial chemical annual  land usage
is, therefore, less than 3% that of the extractive industries. A
significant factor is that, like the extractive industries,  most indus-
trial chemical facilities producing large quantities of  solid  waste are
located in rural areas, e.g., phosphorus and phosphoric  acid plants.
When this is not the case, as for carbide-process  acetylene  manufacture,
solid waste disposal land requirements do pose a problem.
ENVIRONMENTAL CONSIDERATIONS

The environmental problems associated with present disposal  methods can
be described in terms of the seven techniques which now predominate.
Considering the environmental implications of each:
     (1)  Incineration:  Unless adequate controls are exercised,  incin-
          eration can lead to atmospheric release of undesired materials.
          The increasing stringency of air pollution regulations  is
          leading to more expensive, environmentally acceptable practice
          in most instances.  For example, hydrogen chloride generated
          during incineration of chlorinated hydrocarbons is now  being
          removed through absorption in water.  The hydrochloric  acid
          so formed is then either neutralized or is concentrated for
*The estimate for chemical landfill assumes most tars are handled in this
 manner.  Since tars are incinerated whenever possible, the land requirements
 for chemical landfill may be overestimated.  However, Union Carbide's
 Institute, West Virginia plant, alone allocates 24,000 cu. yds. per year
 to chemical landfill.
                                     118
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     plant use.
(2)   Dispersal  into  contiguous water  bodies:  If water salinity
     is  unduely increased, water  biota are endangered and ulti-
     mately agricultural  land is  harmed.  Interim water pollution
     regulations are acting  to curtail discharge of dissolved
     solids.  Most firms  are preparing to lagoon material previously
     discharged.
(3)   Ocean dumping:   There have been  a number of instances of fish
     kill   and  beach spoilages due  to ocean dumping.  The Marine
     Protection, Research, and Sanctuaries Act of 1972 establishes
     a  permit system for  control  of future ocean dumping.  In
     addition,  the Secretary of Commerce has been instructed to
     conduct and encourage a broad  effort aimed at minimizing or
     ending all  dumping of materials  within five years of the
     effective  date  of the act (23  October 1973).
(4)   Lagooning:   Potential environmental problems that may result
     from  lagooning  relate to subsurface transport of the leachate
     and surface water runoff.  For example, during the rainy
     season lagoons  may overflow, and occassionally the containment
     dikes are  breached.  Such an instance is reported in EPA's
     Report to  Congress on Hazardous  Waste Disposal:
       "Phosphate Slime Spill.  On  December 7, 1971, at a
        chemical plant site  in Fort Meade, Florida, a portion
        of a  dike forming a  waste pond ruptured releasing an
        estimated two billion gallons (7.58 billion liters) of
        slime composed of phosphatic  clays and insoluble halides
        into  Whidden Creek.  Flow patterns of the creek led
        to subsequent contamination of Peace River and the estuarine
        area  of Charlotte Harbor.   The water of Charlotte Harbor
        took  on a thick milky white appearance.  Along the river,
        signs of life were diminished, dead fish were sighted and
        normal  surface fish  activity  was absent.  No living orga-
        nisms were found  in  Whidden Creek downstream of the spill
        or in Peace  River at a point  eight miles downstream of
        Whidden Creek.  Clam and  crab gills were coated with the
        milky substance and  in general all benthic aquatic life was
        affected in  some
                              119
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     (5)  Sanitary landfill:   Sanitary landfill  protects  against surface
          runoff but the concern remains that the leachate  may  cause
          environmental  damage.   For this reason, hazardous wastes  cannot
          be accommodated in  such a facility.  The potential  duration
          of danger from leachate is illustrated by the following exper-
                80
          lence.
            "As a result of arsenic burial  30 years ago on  agricultural
             land in Perham,  Minnesota, several  people who  recently con-
             sumed water contaminated by the deposit were hospitalized.
             The water came from a well that was drilled near this  30
             year old deposit of arsenic material.  Attempts to correct
             this contamination  problem are now being studied."
     (6)  Chemical landfill:   If properly managed, this method  of dis-
          posal poses no environmental hazard.  Care must be taken  to
          contain contaminated surface runoff and leachate.
     (7)  Subsurface disposal:  The dangers with this technique are that
          large quantities of material may be emplaced before difficul-
          ties arise.  EPA opposes such disposal practice for hazardous
          wastes,
            "unless all  other alternatives have been found  to be
             less satisfactory in terms of environmental protec-
             tion, and unless extensive  hydraulic  and geologic
             studies are made to insure that ground water conta-
             mination will be minimized".
The overall effect of environmental considerations for the  seven dis-
posal techniques is to identify  incineration, sanitary landfill, and
chemical landfill as the preferred modes of disposal. Those alternatives
which lead to dispersal  in water bodies will be increasingly curtailed.
Lagooning will be continued for  temporary storage and in  those  cases
in which it is not possible to convert the waste to a form  suitable for
ultimate emplacement or destruction.      Subsurface disposal may ulti-
mately become established as  a viable alternative for non-hazardous
wastes as more experience is  gained in this technique.   In  the  next
section we consider the effect of increased land disposal on the costs
of waste disposal for Sector 281.
                                    120
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IMPROVED DISPOSAL PRACTICE

The treatment and disposal costs were re-evaluated in light of the ex-
pected changes in solid waste management.  The costs of such improved
treatment are given by chemical in Table 6 and by SIC Sector in Table 14.
The costs for the 33 chemicals were determined to be double those of
present treatment.  In effect, it can be said that the solid waste dis-
posal  portion of the "costs of clean water" for these chemicals is $70.7
million.  The inorganics continue to account for over 90% of the total
cost, with Sector 2819 remaining the largest contributor*.   Sector 2819's
contribution diminishes from 72% to 41%, however.  This because disposal
techniques will not change greatly for this sector, the principal  differ-
ence being more rapid utilization of low cost, rural land for permanent
lagooning.

The cost ratios in Table 14 serve to highlight areas in which non-typical
changes occur.  The absence of significant change in Sector 2819 has
already been discussed.   In contrast, sectors 2812, 2816, and 2818
exhibit higher than average cost increases.  In Sector 2812 all of the
chemicals exhibit a significant cost increase.  Principal sources of
increase are the chemical landfill ing of treated mercury-containing
sludges (from chlorine-caustic production) and the sanitary landfill ing
of the Solvay plant calcium chloride waste (due to inadequate market
demand for this byproduct).  In Sector 2816 the increased rate stems
directly from the necessity for improved treatment of acid sludges from
the sulfate process for titanium dioxide.  To the extent that resource
recovery and process change occur, as discussed in the case study, this
cost increase may be reduced.  In Sector 2818 the high cost increase is
again  attributable to a single source - the necessity to provide ulti-
mate disposal for alky!  lead wastes.  Market decline (for environment-
related reasons) is causing a reduction of alky! lead wastes.  Present
                                   121
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considerations regarding hazardous waste handling will  determine the
disposition of such wastes.  Land usage for solid wastes from the 33
chemicals following curtailment of water discharge is shown in Table
16.  At present, material temporarily stored in lagoons is subsequently
discharged to the river, ocean dumped, or sent to sanitary landfill.
About 760 x 10-3 S.T. are estimated to fall  into the latter category,
with the remaining 11,300 S.T. discharged to water bodies.  It was
assumed that when discharge to water bodies is curtailed, half the mate-
rial now temporarily stored in lagoons will be retained in permanent
lagoons and the remainder will be consolidated in landfill.  Comparing
Tables 15 and 16 we see that land use actually decreases.  This is due
to the consolidating effect of solids transfer from lagoons to sanitary
landfill.  Land consumption increases by 22%, however,  since the land
becomes the final repository of material previously released to the
water bodies.  Nevertheless, land consumption remains a small percentage
of that for the extractive industries.
                                   122
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                                TABLE 16



     LAND USE FOR SOLID HASTE DISPOSAL IN ABSENCE OF WATER DISCHARGE
  Storage or             Waste Quantity     Waste Volume*     Land Area**
  Disposal Mode           (TO3 S.T.)        (1Q6 cu.  yd.)     (acres)

  Permanent                 35,110                468           6053
  Lagooning

  Sanitary                  20,580                 82           1062
  Landfill

  Chemical                     217                  1              n
  Landfill

  Other                         24                	           	
                            55,931***             551            7126
  *Based on 504 lb./yd.3 and 30% solids  content in  lagoon.

 **Based on 48 ft. depth for lagoons and landfills.

***Another 584 x 103 S.T. are sold as byproduct (refer  Table  11.)
                                   123
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         IX.  GOVERNMENTAL OPPORTUNITIES TO INFLUENCE THE
           MANAGEMENT OF INDUSTRIAL CHEMICAL SOLID WASTES
In previous chapters we have addressed present practice for resource
recovery and waste disposal  of industrial  chemical  solid wastes.   We
have predicted changes to the solid waste stream that will  result from
ongoing and anticipated process changes, and evaluated the effect of
changes in waste disposal that have been motivated  by constraints on
water disposal.  In this chapter we consider in what way the government
might contribute to improved waste management in the industrial  chemi-
cals sector either in the form of increased resource recovery or en-
hanced disposal methods.  First we place such opportunities in perspec-
tive by considering the industry's capability and responsiveness to
improved waste management, and the activity already being pursued by
the government.  We then consider additional opportunities for govern-
mental action.
PERSPECTIVE

The character of the industry itself is the most important factor bear-
ing upon the need for and appropriate extent of governmental  incursion
into the workings of a commercial sector.  When changes to present prac-
tice are sought, the specific factors to be considered are the industry's
capability to accomplish the desired change and its responsiveness to
the need for the change.  Industrial chemical manufacturers have
demonstrated their capability to institute changes when economic condi-
tions dictate.  Further, to date they have been relatively responsive to
the increasingly stringent controls being placed upon their interaction
with the environment.  Although there have been notable exceptions,
industry has generally succeeded in meeting the deadlines set for pro-
cess waste control.  The desire to maintain good public relations serves
                                   124
-------
as an important prod for heeding rather than hindering calls  for im-
proved environmental practice.

The industrial chemical industry is highly competitive, and as  a result
individual companies must be adaptive to market forces.  A reflection
of this adaptability can be seen in the many process substitutions  which
occur.  Those pertaining to the 33 selected chemicals are summarized in
Table 17.*  As indicated, nearly half of the selected chemicals are
undergoing process substitutions.   In every instance the process substi-
tution leads to a reduction in solid waste genration.  Although other
economic factors play a role, it is evident that the industry is already
responding to pollution reduction constraints.   In addition to  display-
ing a capability for realignment,  the financial  capacity to completely
eliminate product lines, such as chlorinated pesticides, has  been
demonstrated.

The foregoing discussion leads to the conclusion that the industry
possesses a capability at least equal to that of government to  trans-
late environmental prerequisites into economic  decisions.  In light of
this it seems most appropriate for the governmental  strategy  to center
around the identification and regulation of environmental prerequisites.
In the area of solid wastes this means the preservation of scarce
resources and the insurance of proper residuals disposal.

Government intervention to preserve scarce resources seems justified
only when market forces fail to do so.  We have not identified  any
instances in which industry has failed to attempt recovery of a scarce
resource.  Two examples are the steps being taken to recover  the
*These process substitutions were discussed in the chapter on market
 and process changes.  Their effect on solid waste was appraised.   Pro-
 jections were made for the years 1977 and 1982.
                                  125
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                                 TABLE 17

              PROCESS CHANGE AMONG THE 33 SELECTED CHEMICALS
SIC
CODE
CHEMICAL
PRODUCED
2812   Chlorine/Sodium
         hydroxide
       Sodium Carbonate

2813   Acetylene
SUBSTITUTION*
  TIMING       SUBSTITUTES     SUBSTITUTOR
                    0
2815

2816
2818




2819


Benzene
Phenol
Titanium dioxide
Chloroform
Ethyl ene oxide
Glycerine
Perchl oroethyl ene
Propylene oxide
Alumina
Hydrochloric acid
Hydrofluoric acid
0
0
0
P
P
0
0
0
F
0
F
             mercury cell

             Solvay process

             carbide process

             coal  tar
             benzene sulfon.
diaphragm cell

natural ore

hydrocarbon conv.

petroleum
cumene oxidation
                                      sulfate process   chloride process

                                      acetone bleaching chlorination
                                      chlorohydrin      direct oxidation
                                      natural           synthetic
                                      acetylene         hydrocarbon chlor.
                                      chlorohydrin      Oxirane process
                                      Bayer Process
                                      acid/salt
                                      fluorspar
                                              Troth process
                                              byproduct
                                              phosphoric acid
                                                waste
*Timing of Substitution:  past (P), on going (0), future (F)
                                    126
-------
fluorine from phosphoric acid sludges and the alumina, titanium
dioxide, and iron content of the red mud from bauxite.  Fluorine
reserves are low and both aluminum and titanium are valuable metals.
In both cases, the government has conducted extensive research pro-
grams, but it is not clear to what extent the government's program
has been synergistic with that of industry.  One particular aspect to
be considered in the preservation of scarce resources is that wastes
be discarded in such a manner that future resource recovery is neither
precluded nor made unresonably difficult.  An obvious step in this direc-
tion is the curtailment of waste disposal through dilution in large
water bodies, i.e., rivers and oceans.  Action toward this end is
already being taken from the standpoint of maintaining proper water
quality.  It will have the corollary effect of maintaining the potential
for resource recovery from industrial chemical solid wastes even after
they are allocated to (land) disposal.


The government is already active in  the insurance of proper residuals
disposal.  Water discharge controls  have motivated the process substi-
tutions shown in Table 17 for chlorine, sodium hydroxide, sodium car-
bonate, and titanium dioxide.  Similar regulation of solid waste dispo-
sal is now receiving attention.  EPA's Office of Solid Uaste Management
Programs has in 1973 promulgated proposed guidelines for sanitary land-
fill and reported to Congress on alternatives for hazardous waste dis-
      co
posal.    The results achieved in the amelioration of air and water
pollution demonstrate the  efficiencyof such a regulatory approach.
This is recognized as the most important step the government can take
to ensure proper environmental management.  In the following section,
additional opportunities for  the governmental insurance of proper
management of industrial  chemical solid wastes are discussed.
APPRAISAL OF GOVERNMENTAL STRATEGY OPTIONS
We consider governmental strategy options as falling within six general
                                   127
-------
categories:  regulations, tax incentives, subsidies, preferential  pro-
curement, research and development, and public education.   In the  follow-
ing paragraphs we present steps the government might take  in control
of industrial chemical solid wastes that go beyond the current effort
related to sanitary landfill and hazardous waste disposal.
Regulation

The two steps that we recommend be undertaken in the regulation of in-
dustrial chemical solid wastes are:
     (1)  require documentation of the quantity and chemical  composi-
          tion of the process-related solid waste load from each pro-
          duction facility, and
     (2)  impose and enforce standards for disposal via lagoons and sub-
          surface injection comparable to those being prepared  for sani-
          tary landfill and hazardous waste disposal.

Documentation of the content of water borne wastes is already required
for critical components, e.g., phosphates, prior to the issuance of a
discharge permit.  Similar information on solid wastes would enable the
assurance of proper disposal, assist in the planning of future disposal
modes,and permit the monitoring of significant resources.   Plant-wide
identification of waste stream content may be all that is  required,
although as indicated in this report process-specific identification
of wastes is necessary in order to predict future changes  to the waste
stream.

There is already governmental activity in the area of improved  lagooning
and subsurface injection practice.  For example, the Bureau of  Mines
                                                                83
has investigated various modes of sludge dewatering:  chemical.
                        84
mechanical, vegetative,     etc.  The Bureau has also investigated
                                 128
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various aspects of subsurface disposal.   We recommend that EPA place
emphasis on understanding the basic prerequisites of each of these
waste management techniques from the standpoint of avoiding both short
and long term environmental degradation.

Alternative opportunities for regulation of industrial  chemical solid
wastes which we have considered include:  legislation of a particular
resource recovery technique, outlawing of production processes that
generate excessive amounts of pollutants, or imposition of import re-
strictions to motivate use or recovery of domestic resources.  At this
stage in the imposition of solid waste controls, none of these specific
constraints on the commercial process seems appropriate.  Rather, proper
environmental constraints are required, with the development of an in-
formation system and enforcement machinery to insure compliance with
these constraints.
Tax Incentives

Tax incentives that might be employed could range from accelerated
depreciation of equipment intended for enhanced resource recovery or
residuals disposal to impositions of graduated tax penalties for
failure to achieve specified norms of disposal.  Alternatively, a
deadline could be set for achieving a specific discharge standard, and
tax incentives offered for earlier achievement of the given standard.
We do not recommend such tax strategies.   Processes that produce
disproportionately large wastes may be inexpensive precisely
because waste disposal practices are inadequate.   When this
is true, tax incentives will be ineffective unless calibrated with
greater precision than taxing procedures  permit.   Direct regulation
                                   129
-------
seems preferable.
Subsidy

It is our premise that only in the event a specific resource needs to
be conserved should direct or indirect subsidies be provided.   Otherwise,
the government ends up paying for a change that would ultimately be made
at no cost via economic adjustments.  In our study of the 33 selected
chemicals we have identified no instances in which subsidies should be
provided.

Temporary subsidies were considered directed toward the recovery or
disposal process itself.  For example, part of the start-up cost of
improved disposal might temporarily be subsidized by the government.
However, we have not encountered evidence that such subsidies are
necessary.  The existence of companies, such as Rollins Environmental
Services, that provide disposal service at a fee would seem to offer an
interim solution for a firm needing time to develop its own technology.
Preferential Procurement

Three variations of preferential procurement have been considered:
Selective purchase of recovered materials from U.S. firms or purchase
of primary products only from firms that have been actively complying
with feasibly established solid waste disposal standards.  In the first
case, the need for action to promote resource recovery has not been
identified among the chemicals of Sector 281.  In terms of reward or
penalty to ameliorate unsatisfactory disposal procedures, selective
procurement seems an administratively cumbersome substitute for direct
regulation.
                                   130
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Research and Development

This is an area in which the government is already active.   Programs
are underway in a number of areas:  sludge dewatering,  appraisal  of
deep well disposal, assessment of long,term environmental  implications
of present practice.  The emphasis here, as in other areas,  should  be
in the definition of the standard to be met, while leaving  to industry
the development of the technology to meet the standard.  Work to  be
supported is that necessary to permit regulation of lagooning and
subsurface disposal and to complete the ongoing definition  of ocean
dumping, sanitary landfill, and hazardous waste disposal  standards.
Public Education

Two areas of public education might be amplified:
     (1)  if, as seems presently the case, industry is  cooperating  with
          government in the attainment of environmental  objectives,
          this cooperation should be brought to public  attention, and
     (2)  when consumer pressure can be used to motivate more rapid
          achievement of a particular goal, public  education  could  be
          usefully employed to elucidate the alternatives.
To summarize the foregoing, the principal  action of the government in
the area of industrial  chemical solid wastes should be toward  improved,
environmentally based,  regulation of disposal  methods.  This conclusion
is based on the premise that this highly competitive industry  is  itself
best suited to judging  the paths whereby the environmental  objectives
are to be achieved.
                                  131
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                     X.  LIST OF REFERENCES


I.   INTRODUCTION

    1.   Annual  Survey of Manufactures,  U.S.  Bureau of the Census, 1970.

    2.   "Solid  Waste  Management in the  Industrial Chemical  Industry",
        The Research  Corporation of New England [SW-33c] for EPA,
        1971.   [Draft]

    3.   Faith,  W.L.,  Keyes, D.B., and Clark, R.L., Industrial
        Chemicals, 3rd ed., John Wiley and Sons, New York,  1965.

    4.   Kirk, R.E., and Othmer, D.F., Encyclopedia of Chemical Technology,
        Volume  1-25,  John Wiley & Sons, New York, 1963-1972.

    5.   Shreve, R.N.,  "The Chemical Process Industries", 2nd ed.,
        McGraw-Hill Book Company, New York, 1956.

    6.   "Inorganic Chemicals Industry Profiles", Datagraphics Inc.
        for EPA [#12020  EJI], Gov't. Printing Office, July 1971.

    7.   "Projected Wastwater Treatment Costs in the Organic Chemical
        Industry", Datagraphics Inc. for EPA [#12020 GWD],  Gov't.
        Printing Office, July 1971.

    8.   "Industrial Waste Study of Inorganic Chemicals, Alkalies and
        Chlorine", General Technologies Corp. for EPA [#68-01-0020],
        23 July 1971.  [Draft]

    9.   "A Study of Hazardous Waste Materials, Hazardous Effects and
        Disposal Methods". Booz Allen Applied Research Inc. for EPA
        [#68-03-0032], June 1972.

   10.   "Recommended  Methods of Reduction, Neutralization, Recovery
       and Disposal of Hazardous Waste", TRW for EPA [#68-03-0089],
        Feb.  1973  [Draft]

   11.   "Program for  the Management of  Hazardous Wastes", Battelle
        Memorial  Institute for EPA [#68-01-0762] March 1973.

   12.   "Alternatives to the Management of Hazardous Wastes at National
        Disposal Sites", ADL for EPA [#68-01-0556], May 1973. [Draft]

   13.   Mineral Facts and Problems, U.S. Dept. of the Interiors, 1970.


                                  132
-------
    14.  Minerals Yearbook (Vol. II), U.S.  Dept.  of  the  Interior,  1970.
    15.  "1971 Directory of Chemical  Producers, USA",  Stanford Research
         Institute, Calif., 1971.
    16.  Backman, 0- "The Economics of the  Chemical  Industry", Manu-
         facturing Chemists Association,  Washington, D.C.,  Feb.  1970.
    17.  "Chemical Statistical  Handbook", 7th  ed., Manufacturing Chem-
         ists Association, Washington, D.C.,  1971.
    18.  Ibid.
    19.  Brownstein, A.M., Spitz,  P.M., Springborn,  R.C.,  "Changes
         in Technology and Products Anticipated by 1985",  in The
         Changing World Chemical Industry.  .  .Its Outlook  & Problems
         to 1985.Manufacturing Chemists Association, Washington, D.C.,
         WTT.
IV.  INUDSTRIAL CHEMICAL SOLID WASTE GENERATION
    20.  Op. cit., reference 3.
    21.  Op. cit., reference 2.
    22.  George Hanks, Union Carbide, personnel communication.
    23.  Op. cit., reference 3.
    24.  Ibid.
    25.  Op. cit., reference 4.
    26.  Op. cit., reference 6.
    27.  Op. cit., reference 7.
    28,  Op. cit., reference 8.
    29.  Op. cit., reference 9.
    30.  Op. cit., reference 10.
    31.  Op. cit., reference 11.
    32.  Op. cit., reference 12.
                                  133
-------
    33.  Op. cit., reference 13.

    34.  Op. cit., reference 14.

    35.  Chemical and Engineering News, 22 January 1973,  pp.  8-9.

    36.  "Utilization of Waste Fluosilicic Acid", U.S.  Dept.  of the
         Interior [RI 7502], April 1971.

    37.  "Phosphate-Plant Waste Looms As Hydrofluoric-acid  Source",
         Chem. Eng.. May 4, 1970, pp. 46-48.

    38.  "At the ready:  New Routes to Hydrofluoric Acid",
         Chemical Week, Vol. 108 No. 1 (Jan.  6, 1971)  pp.47-50.

    39.  G. G. Brown and D. C. Harper, Patent No. 1,179,246
         (Jan. 28, 1970).

 V.  INDUSTRIAL CHEMICAL SOLID WASTE DATA BASE

    40.  "Chemical Origins and Markets" Stanford Research Institute,
         California, 1969.

    41.  Chemical Engineering .  McGraw-Hill  Publication  (bi-weekly).

    42.  Chemical Engineering Progress.  Published by  American Institute
         of Chemical Engineers (monthly).

    43.  Chemical Week.  Published by McGraw-Hill, Inc. (weekly).

    44.  Chemical and Engineering News.  Published by  the American
         Chemical Society,  (weekly)

IV.  MARKET AND PROCESS CHANGE EFFECTS ON SOLID WASTE GENERATION

    45.  "Processes for Rutile Substitutes",  National  Materials
         Advisory Board [NMAB-293] for the National Academy for Science,
         June 1972. p. 28

    46.  Ibid.

    47.  "Cyanamid Proposes Alternative to Ocean Dumping  of Waste
         Water", Chemicology  (Published by Manufacturing  Chemists
         Association), Feb. 1973.

    48.  Op. cit., reference 22.
                                   134
-------
      49.  Chemical Week. March 7, 1973, p. 40
      50.  Chemical Meek. August 9, 1973, p. 32
      51.  Op. cit., reference 2, p. 164.
      52.  Chemical and Engineering News, August 3, 1970.
      53.  Chemical and Engineering News, Feb. 26, 1973, p. 11.
VII.  RESOURCE RECOVERY NEEDS AND OPPORTUNITIES
      54.  "Exploratory Study on Alternative  Pollution  Abatement Techniques
            Through Continued Development  of  the  Ecosystem of  Machines
            Information System", Development  Sciences  Inc.  for NSF
            (c-673),  July 17, 1972.
      55.  "Industrial  Solid Waste  Classification"  Arthur D.  Little, Inc.,
           for EPA (#68-03-0123), December 1972 [Draft]
      56.  Frantz, J.   "Byproduct processing,  Theres Gold  on Them Thar
           Streams" presented to the American  Institute  of Chemical
           Engineers,  March 12,  1973.
      57.  "Phosphoric  Acid:  Electrothermal vs.  Wet Process"   The
           Sulfur Institute, Washington  D.  C., April 1969,  p.  11.
           [723.0000-762.9999]
      58.  Chemical Economic Handbook, Stanford Research Institute,
           1969,  p. 761.5020 D
      59.  Op.  cit., reference 13,  p. 1044.
      60.  Ibid.
      61.   Ibid.
      62.   Op.  cit., reference 36.
      63.   Op.  cit., reference 56.
      64.   Op.  cit., reference 55.
      65.  Ayres,  R., Saxton,  J., Stern, M. "Materials-Process-Product
          Model  for the  Bottle Manufacturing  Industry for  NSF  [NSF-C 652],
          Dec. 1972.
                                    135
-------
      66.  Op. cit., reference 54.

VIII. WASTE TREATMENT AND DISPOSAL

      67.  Op. cit., reference 55.

      68.  Ibid.

      69.  "Report to Congress on Hazardous Waste", Office of Solid Waste
           Management Programs,   EPA Hazardous WasteSection s Washington,
           D. C., June 30, 1973.

      70.  Ibid.

      71.  Chemical Engineering Deskbook, August 1972.

      72.  Op. cit., reference 69.

      73..  ibid.

      74.  Op. cit., reference 71.

      75.  Slover,  Edwin E., "Solid Waste Disposal in a Multi-Product
           Chemicals Plant", for the American Association of Textile
           Chemists and Colorists Symposium; The Textile Industry and
           the Environment-!973, Washington, D.C., May 22-24, 1973.

      76.  "Environmental Commitment-1972", Manufacturing Chemists
           Association,  1972.

      77.  "Waste Disposal Costs of a Florida Phosphate Operation",
           Bureau of Mines Information Circular 8404, 1969.

      78.  Stern, Martin,  "S.E.A.S. Test Model:  Land Use Forecasts  "
           Prepared for  EPA, 1973, IRT-314-R.


      79.   Op. cit., ref. 69.

      80.   ibid.

      81.   Ibid.
                                   136
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IX.   GOVERNMENTAL OPPORTUNITIES TO INFLUENCE THE  MANAGEMENT  OF
     INDUSTRIAL CHEMICAL SOLID WASTES
     82.  Op. cit., reference  69.
     83.  "Chemical Stabilization  of the Uranium Tailings at Tuba City,
         Arizona" Bureau of Mines report of Investigation 7288, 1969.
     84.  "Chemical and Vegetative Stabilization of a Nevada Copper
         Porphysy Mill Tailing" Bureau of Mines REport of Investigation,
         7261, May 1969.
                     XI.   PENDING PUBLICATIONS
          The report has been submitted to Chemical  Engineering.   A
     review of the study will be published.
                                   137
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                              XII.    APPENDIX


94                  STANDARD INDUSTRIAL CLASSIFICATION

 Major  Group  28.—CHEMICALS AND ALLIED  PRODUCTS

                           The Major Group as a Whole

    This major group includes establishments producing  basic chemicals, and  establish-
ments manufacturing products by  predominantly chemical processes.   Establishments
classified in this major group manufacture three  general classes of products:  (1)  basic
chemicals such as acids, alkalies, salts, and organic chemicals; (2) chemical products to be
used  iu further manufacture such as synthetic fillers,  plastics materials, dry colors, and
pigments;  (3)  finished chemical  products to  be  used  for ultimate consumption such as
drugs, cosmetics, and soaps ;  or to be used as materials or supplies in other industries such as
paints, fertilizers, and explosives.  The mining of natural rock salt is classified  in mining
industries.   Establishments  primarily engaged in manufacturing nonferrous metals and
high  percentage  ferroalloys are classified in  Major Group  33;  silicon carbide  in Major
Group 32;  baking powder, other  leavening compounds and  starches in Major Group 20;
and embalming fluids and artists' colors in Major Group 30.  Establishments  primarily
engaged  in packaging, repackaging, and bottling of purchased chemical products, but not
engaged  in manufacturing chemicals and allied products, are classified iu trade industries.
Group Indnstrv
 No.     No.
281          INDUSTRIAL INORGANIC AND ORGANIC  CHEMICALS
               This  group  includes  establishments primarily engaged in manufacturing
             basic industrial inorganic  and organic chemicals.   K>tablishments primarily
             engaged in manufacturing formulated agricultural pesticides are classified in
             Industry  2STl>;  organic   and inorganic medicinal  chemicals, drugs and
             medicines in Industry 2833; wood distillation  products and naval stores  in
             Group 286; and soap, glycerin (except synthetic), and cosmetics in Group2S4.
       2812  Alkalies and Chlorine
               Establishments primarily engaged in manufacturing alkalies and chlorine.
                   Alkalies                              Potassium hydroxide
                   Carbonates, potassium and sodium       Sal soda
                   Caustic potash                         Soda ash
                   Caustic soda                          Sodium bicarbonate
                   Chlorine,  compressed or liquefied          Sodium carbonate (soda  ash)
                   Potassium carbonate         '           Sodium hydroxide (caustic soda)
       2813  Industrial Gases
               Establishments primarily engaged in manufacturing gases for sale in com-
             pressed, liquid, and  solid forms.  Establishments primarily engaged in manu-
             facturing fluorine, ammonia, and sulfur dioxide  are classified in Industry
             2819; and  chlorine  iu  Industry  2S12.  Distributors of industrial  gases and
             establishments primarily  engaged in shipping liquid oxygen are classified in
             trade.
                   Acetylene                            Helium
                   Argon                               Hydrogen
                   Carbon dioxide                         Neon
                   Dry ice (solid carbon  dioxide)           Nitrogen
                   Gases, industrial: compressed,  lique-       Nitrous oxide
                     fled,  or   solid—not  made  in       Oxygen, compressed and  liquefied
                     petroleum refineries  or in natural       Refrigerant gases, except ammonia
                     gasoline plants
                                        138
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                                    MANUFACTURING
                                                                                  95
Group
  No.

281
Industry
   No.
      INDUSTRIAL  INORGANIC AND ORGANIC CHEMICALS—Continued

2815   Cyclic Intermediates,  Dyes,  Organic  Pigments  (Lakes and Toners), and
           Cyclic (Coal Tar) Crutles

         Establishments primarily engagtxl in manufacturing cyclic organic  inter-

       mediates, dyes, color lakes  aud  toners, and coal  tar  crudes.    Important

       products  of  this  industry  include: (3)  derivatives of  benzene, toluene,
       naphthalene,  anthracene,  pyridine,  carbazole, and  other  cyclic chemical
       products;  (2) synthetic organic  dyes;   (3)  synthetic organic pigments: and
       (4) cyclic  (coal tar)  crudes, such as light oils and lif,rht  oil products; coal tar

       acids; and products of medium and heavy oil such as creosote oil, naphthalene.

      anthracene, aud their higher komologues, and tar.  Establishments primarily
      engaged  in manufacturing coal tar crudes in chemical recovery  ovens are
       classified  in  Industry  3312,  and petroleum refineries  which produce such

      products in Industry 2011.
                    Acid dyes, synthetic
                    Acids, coal tar:  derived from  coal
                      tar distillation
                    Alkylated  dtphenylamines,  railed
                    Alkylatcd  phenol, mixed
                    Aminoanthraquinone
                    Aoinoazobenzenc
                    Amlnoazotolucne
                    Aminopbenol
                    Aniline
                    Aniliue oil
                    Anthracene
                    Anthraquiuonc dyes
                    Azine dyes
                    Azobcnzene
                    Azo dyes
                    Azoic dyes
                    J»eijZ<\lueH.v ut'
                    Benzene bexuehlorlde
                    Benzene,  product of  coal  tar  dis-
                      tillation
                    Renzoic acid
                    Benzol, product of coal  tar dlstliia-
                      tion
                    Biological  stains
                    Chemical  indicators
                    Chips and flakes, naphthalene
                    Chloroben/ene
                    Culoronaphthalene
                    Chloropoenol
                    Chlorotoluene
                    Coal  tar  acids, derived from coal
                      tar distillation
                    Coal  tar crudes, derived from coal
                      tar distillation
                    Coal tar distillates
                    Coal tar intermediates
                    Color lakes and toners
                    Color  pigments,  organic:  except
                      animal black and bone black
                    Colors,  dry: lakes,  toners, or full
                      strength organic colors
                    Colors, extended (color lakes)
                    Cosmetic dyes,  synthetic
                    Cresols, product of coal tar distilla-
                      tion.
                    Creosote oil. product of coal tar dis-
                      tillation
                    Cresylic acid,  product  of  coal  tar
                      distillation
                   Cyclic crudes,  coal tar:  product of
                      coal tar distillation
                   Cyclic intermediates
                   Cyclobeiane
                   Diphenylamine
                   Drug dyes, synthetic
                   Dyes, synthetic organic
                    Kosine toners
                   Ethylbenzene
                                                     Kood dyes .and colors, synthetic
                                                     Hydroquinone
                                                     Isocyanatcs
                                                     Lake red C  toners
                                                     I/lthcl rubine lakes and toners
                                                     Maleic anhydride
                                                     Methyl violet toners
                                                     Naphtha,  solvent: product of coal
                                                       tar distillation
                                                     Naphthalene, product  of  coal tar
                                                       distillation
                                                     Naphthol, alpha and beta
                                                     Naphtholsulfonic  acids
                                                     NItroanillne
                                                     Nitrobenzene
                                                     Nitro dyee
                                                     Nitropbenol
                                                     Nlrroso  dyes
                                                     Oils: light,  medium,  and heavy—
                                                       product of coal tar distillation
                                                     Orthodichlorobenzeue
                                                     Paint pigments, organic
                                                     Peacock blue lake
                                                     Pcntachlorophenol
                                                     Persian  orange lake
                                                     Phenol
                                                     Pbloxlne toners
                                                     Phosphomolybdic  acid  lakes  and
                                                       toners
                                                     Phosphotungstlc   acid  lakes  and
                                                       toners
                                                     Phthallc anhydride
                                                     Phthalocjanine toners
                                                     Pigment scnrlet lake
                                                     Pigments,  organic:  eicept animal
                                                       black and  bone black
                                                     Pitch, product of coal  tar distilla-
                                                       tion
                                                     Pulp colors, organic
                                                     Quinoline dyes
                                                     Resorclnol
                                                    Scarlet 2 R lake
                                                    Stilbene dyes
                                                     Styrene
                                                    Styrene  monomer
                                                    Tar. product of coal tar distillation
                                                    Toluene, product of coal tar distilla-
                                                      tion.
                                                    Toluol, product  of coal tar  distil-
                                                      lation
                                                    Toluidine*
                                                    Toners  (reduced  or  full  strength
                                                      organic colors)
                                                    Vat dye«. s-ynthetlc
                                                    Xylene.  product of coal tar  distil-
                                                      lation
                                                    Xylol. product of coal  tar distilla-
                                                      tion
                                              139
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96                   STANDARD INDUSTRIAL CLASSIFICATION

Group  Industry
  No.     No.
281          INDUSTRIAL INORGANIC AND ORGANIC CHEMICALS-Continued
       2816  Inorganic Pigments
               Establishments primarily engaged in manufacturing inorganic pigments.
             Important products of this indu>try  include black  pigments (except carbon
             black, Industry 289,")), white pigments and color pigments.   Organic color pig-
             ments, except animal black and bone black, are classified in Industry 2815.
                    Animal black                           Llthopone
                    Barium sulfato, precipitated  (blauc       Metallic pigments. Inorganic
                     (5x6)                                Mineral colors and pigments
                    Baryles pigments                       Minium (pigment;
                    Blanc fixe  (barium sulfate, preclpi-       Ochert-
                     tatcd)                               Palm pigments, inorganic
                    Bone black                             Pearl oscnce
                    Chrome  pigments:  chrome  green,       Pigments, inorganic
                     chrome  jellow.  chrome  orange.       Pru«-ian blue pigments
                     zinc yellow                           Red lead pigment
                    Color pigments, inorganic                Satin white pigment
                    Inorganic pigments                      Slenua'
                    Iron blue pigment                       Titanium pigments
                    Iron culor-                             Ultramarine pigment
                    Iron oxide, black                        Umber-
                    Iron oxide, magnetic                     Vermilion pigment
                    Iron oxide, yellow                       Whit" lead pigments
                    Lamp black                            Whit ins
                    I^ead oxide pigments                     Xinc o\ide pigments
                    Lead pigments                         Zinc pigments : zinc .\ellow and zinc
                    Litharge                                 sulfide
       2818  Industrial Organic Chemicals, Not Elsewhere Classified
                Establishments  primarily engaged in  manufacturing  industrial  organic
             chemicals, not elsewhere classified.   Important pmducts of this industry in-
             clude: (1)  non-cyclic organic chemicals such as acetic, chloroacetic, adipic,
             formic, oxalic and  tartaric acids and their metallic salts;  chloral, formalde-
             hyde and methylamine; (2) solvents such as amyl, butyl, and ethyl alcohols;
             methanol; amyl, butyl and ethyl acetates; ethel ether, ethylene glycol ether
             and diethylene glycol ether ; acetone, carbon disulfide and chlorinated solvents
             such  as  carbon tetrachlorido,  perchloroethylene and  tricholoethylene;  (3)
             polyhydric  alcohols such as ethylene plycol, sorbitol. pentaerythritol, synthetic
             glycerin;  (4)  synthetic perfume and flavoring materials such as coumarin,
             methyl  salicylate,  saccharin, citral. cltronellnl, synthetic geraniol, ionone.
             terpineol, and synthetic vanillin ; (.">) rubber processing chemicals such as ac-
             celerators and  antioxidants, both cyclic and  acyclic;  (6) plasticizers, both
             cyclic and acyclic, such as esters of phosphoric acid, pbthalic anhydride, adipic
             acid, lauric acid, oleic acid, s-ebacic acid, and stearic acid;  (7) synthetic tan-
             ning  agents such  as naphthalene sulfonic  acid condensates: (8) chemical
             warfare  gases; and (9)  esters, amines, etc. of polyhydric  alcohols ami fatty
             and other acids.  Establishments primarily engaged in manufacturing plastic
             materials and  nonrulcauizable elastomers  are  classified in Industry  2S21;
             synthetic rubber in Industry 2*22: essential oils in Industry 2809; wood dis-
             tillation  products,  naval  stores, and natural dyeing and  tanning materials
             in  Group 28G: rayon and other synthetic fibers in Industries 2S23 and 2S24:
             specialty cleaning,  polishing and sanitation preparations  in Industry 2842:
             and paints in Industry  28ol;  organic pigments in Industry 2815:  and in-
             organic pigments in Industry 2810.   Distilleries engaged in the manufacture
             of grain alcohol for beverage purpOM?s are classified in Industry 20S3.
                    Accelerators,   rubber   processing:        Acetone, synthetic
                      cyclic and acyclic                     Acids, organic
                    Acetaldehyde                            Aerolein
                    Aetates, except natural acetate of        Acrylonitrile
                      lime                                 Adipic acid
                    Acetic acid, synthetic                     Adiponitrile
                    Acetic anhydride                        Alcohol, aromatic
                    Acetin                                 Alcohol, fatty : powdered
                                            140
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                                      MANUFACTURING
                                                                                             97
Group  Industry
  No.      No.
2.S1           INDUSTRIAL INORGANIC AND ORGANIC CHEMICALS—Continued

       2818   Industrial Organic Chemicals, Not Elsewhere Classified—Continued
                    •Alcohols,   inilustri.il :   denatured
                       (noli beverage)
                     .Algin products
                     Amines  of polOiydrie alcohols, anil
                       of fatty and  other  acid?
                     Am.il acetate and alcohol
                     Antluxidants,   rubber  processing:
                       cyclic and acyclic
                     P'romochloromethaue
                     Butadiene, from alcohol
                     Butjl  acetate,   alcohol, and  pro-
                       pionate
                     Butyl ester  solution  of 2.  4-D
                     Calcium ovalate
                     Camphor, synthetic
                     Carbon  bisulfide (disulnde)
                     Carbon tetracbloride
                     Casing  fluids,  for  curing   fruits,
                       spices, tobacco, etc
                     Cellulose acetate, unplasticized
                     Chemical warfare gases
                     Chloral
                     Chlorinated solvents
                     Chloroacetlc acid and metallic salts
                     Chloroform
                     Chloropicrin
                     Citral
                     Citrates
                     Citric acid
                     Citronellol
                     Coumarin
                     Cream of tartar
                     Cyclopropane
                     ]>DT. technical
                     PeCrihj dronaphthalene
                     IMchlorodlfluoromethane
                     Dletliyleyclohevane (mixed isomers)
                     Dicthylene glycol ether
                     Dimethyl  divinyl  acetjlene  (di-
                       isopropenyl acetylene)
                     Dimethylhydrazlue, unsyminetrical
                     Enzymes
                     Ksters of phthalic anhydride:  and
                       of  phosphoric,   adipic,    lauric,
                       oleic,  sebacic, and  stearic acids
                     Esters of pobhydric  alcohols
                     Ethanol, industrial
                     Ether
                     Ethyl acetate, synthetic
                     Ethyl  alcohol,   industrial   (non-
                       beverage)
                     Ethjl butyrate
                     Ethyl cellulose,  unplasticized
                     Ethyl chloride
                     Ethyl ether
                     Ethyl formate
                     Ethyl nitrite
                     Ethyl perhydropheuanthrene
                     Ethylcne
                     Ethylene glyeol
                     Ethylene glycol  ether
                     Ethylene glycol. inhibited
                     Ethylene oxide
                     Ferric ammonium oxalatc
                     Flavors  and  flavoring  materials,
                       synthetic
                     Fluorlnated hydrocarbon gases
                     Formaldehyde (formalin)
                     Formic acid and metallic salts
                     Freon
                     Fuel  propellants. solid, organic
                     Fuels, high energy, organic
                     Gases, fluoriuated hydrocarbon
                     Geraniol, synthetic
                     Glycerin, except  from  fats  (syn-
                       thetic)
                     Grain  alcohol,   industrial   (non-
                       beverage)
                     Hexamethylenediamine
                     Hexamethylei.etetramine
                     High purity  grade chemicals,  or-
                       ganic :  refined  from  technical
                       grades
 Hydraulic fluids,  synthetic base
 Ilydrazine
 Industrial organic cyclic cornpound;-
 lonone
 Jsopropyl alcohol
 Ketone, methyl ethyl
 Ketone, methyl isobutyl
 Laboratory chemicals, organic
 I^aurit acid esters
 Lime citrate
 Malononitrile, technical grade
 Metallic  salts  of  acyclic organic
   chemicals
 Metallic stearare
 Methanol. sj nthetic  (methyl  alco-
   hol)
 Methyl chloride
 Methjl perliydrofluorine
 Methjl salicylate
 Metln laminc
 Methylene chloride
 MouochlorodifUiorqni ethane
 Slonomethylporaminopheuol sulfate
 Monosodiuni glutamate
 Muptard pas
 Nitrous' ether
 Normal hexyl decaliu
 Nuclear fuels, organic
 Oleic acid enters
 Organic adds, except Ciclic
 Organic chemicals, acyclic
 Oxalates
 Oxalic acid and metallic salt*
 Pentaerythritol
 Perchloroethylene
 Perffnne materials,  synthetic
 Phosgene
 Phthalates
 Plasticlzers,  organic: cyclic   and
   acyclic
 Polyhydric alcohols
 Potassium bitartrate
 Propellants for missiles,  solid, or-
   ganic
 Propylene
 Propylene glycol
 Quinuclidinol  ester  of benzylic acid
 Reagent  grade chemicals, organic :
   refined  from  technical grades
 Rocket engine fuel, organic
 Rubber  processing  chemicals,  or-
   ganic:  accelerators and antioxi-
   dants—-cyclic and acyclic
 Saccharin
 Sebacic acid
 Sillcones
 Soaps, naphthenle acid
 Sodium acetate
 Sodium alginate
 Sodium benzoate
 Sodium glutamate
 Sodium pentachlorophenate
 Sodium sulfoxalate  formaldehyde
 Solvents,  organic
 Sorbltol
 Stearic acid esters
 Stearic acid salts
 Sulfonated naphthalene
 Tackifiers. organic
Tannic acid
Tanning  agents, synthetic organic
Tartaric  acid nnd metallic salts
Tart rates
Tear gas
Terpineol
Tert-butylated    bis   (p-phenoxy-
   phenyl) ether fluid
Tetrachloroethylene
Tetraethyl lead
 Thloglycolic  acid,  for  permanent
  wave lotions
Trlchloroethylenc
                                                   141
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98
               STANDARD  INDUSTRIAL  CLASSIFICATION
Group
  No.

281
Industry
   No.
       2S18
      INDUSTRIAL INORGANIC AND ORGANIC  CHEMICALS—Continued

      Industrial Organic Chemicals, Not Elsewhere Classified—Continued

                              stabilized,
                    Trichloroethylenc   stabilized,   de-
                      greasing
                    Trichlorophenoxyaeetic acid
                    Trirhlorotriftuoroethane tetrachloro-
                      difiuoroethane isopropyl alcohol
                    Tricresyl phosphate
                    Triclec.vl alcohol
Trlmcthyltrithio phosphite
  propellants)
Triphenyl phosphate
Urea
Vanillin, synthetic
Vinyl acetate
                                                                                    (rocket
       2819   Industrial Inorganic Chemicals, Not Elsewhere  Classified

                Establishments primarily  engaged in  manufacturing industrial inorganic

              chemicals, not  elsewhere  classified.  Important  products  of  this  industry

              include inorganic salts of sodium (excluding refined sodium chloride), potas-

              sium, aluminum, calcium, chromium, magnesium, mercury, nickel, silver, tin;

              inorganic compounds such as  alurns,  calcium carbide,  hydrogen peroxide,

              phosphates, sodium silicate,  ammonia compounds and anhydrous ammonia;

              rare earth metal salts and elemental bromine, fluorine, iodine, phosphorus, and

              alkali  metals (sodium, potassium, lithium, etc.)   Establishments primarily

              engaged in mining, milling, or otherwise preparing natural potassium, sodium.

              or boron compounds (other than common salt) are classifies)  in Industry  1474.

                                                           Dlammoniura phosphate
                                                           Dichromates
                                                           Ferric chloride
                                                           Ferrocyanldes
                                                           Fissionable material production
                                                           Fluorine, elemental
                                                           Fuel  propellants solid, inorganic
                                                           Fuels, high energy, inorganic
                                                           (letters
                                                           Glauber's salt
                                                           Heavy water
                                                           High purity  grade  chemicals, in-
                                                             organic : refined  from  technical
                                                             grades
                                                           Household bleaches, dry or liquid
                                                           Hydrnted alumina silicate powder
                                                           Hydrochloric acid
                                                           Hydrocyanic add
                                                           Hydrofluoric acid
                                                           Hydrogen peroxide
                                                           Hydrogen bulf
                                                           Hydrosulfites
             Activated carbon and charcoal
             Alkali metals
             Alumina
             Aluminum chloride
             Aluminum compounds
             Aluminum  hydroxide   (alumina
               trihydrate)
             Aluminum oxide
             Aluminum sulfate
             Alums
             Ammonia alum
             Ammonia liquor
             Ammonium chloride, hydroxide, and
               molybdate
             Ammonium compounds
             Ammonium perchlorate
             Ammonium thiosulfate
             Anhydrous ammonia
             Anhydrous nitrogen tetroxlOe
             Aqua ammonia, made in ammonia
               plants
             Barium compounds
             Beryllium oxide
             Bleaches, household : liquid or dry
             Bleaching powder
             Borax (sodium  tetraborate)
             Boric acid
             Boron compounds, not produced at
               mines
             Borosilicate
             Brine
             Bromine, elemental
             Caesium metal
             Calcium   carbide,  chloride,  and
               hypochlorite
             Calcium compounds, inorganic
             Calcium metal
             Calomel
             Carbide
             Catalysts, chemical
             Cerium salts
             Charcoal,  activated
             Chemical catalysts
             Chlorosulfonic acid
             Chromates and  bichromates
             Chromic acid
             Chromium compounds, Inorganic
             Chromium salts
             Cobalt chloride
             Cobalt GO  (radioactive)
             Cobalt sulfate
             Copper chloride
             Copper iodide and oxide
             Copper sulfate
             Cyanides
             Deslecants, activated : silica  gel
                                                           Hypyphosphite*
                                                           Indium chloride
                                                           Inorganic acids
                                                           Iodides
                                                           Iodine, elemental
                                                           Iodine, resubliined
                                                           Iron sulphate
                                                           Isotopes, radioactive
                                                           Laboratory chemicals, inorganic
                                                           Lead oxides, other than pigments
                                                           Lead silicate
                                                           Lime bleaching compounds
                                                           Lithium compounds
                                                           Lithium metal
                                                           Magnesium carbonate
                                                           Magnesium chloride
                                                           Magnesium compounds, inorganic
                                                           Manganese dioxide powder, synthetic
                                                           Mercury chlorides (calomel, corro-
                                                             sive sublimate), except C.S.P.
                                                           Mercury compounds, inorganic
                                                           Mercury oxides
                                                           Mercurv. redistilled
                                                           Metals." liquid
                                                           Mixed  acid
                                                           Muriate of potash, not produced at
                                                             mines
                                                           Xickel ammonium sulfate
                                                           Xlekel  carbonate
                                                           Nickel  compounds. Inorganic
                                                           Xickel sulfate
                                                           Xltric  acid
                                                           Xuclear cores, Inorganic
                                                           Xuclear fuel reactor cores, inorganic
                                             142
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                                   MANUFACTURING
                                                                                      99
 Group
  No.

 2S1
Industry
  Xo.
      INDUSTRIAL INORGANIC AND ORGANIC CHEMICALS—Continued

2819  Industrial Inorganic Chemicals, Not Elsewhere Classified—Continued
282
       2821
                    Nuclear fuel scrap reprocessing
                    Oleum (fuming suJfuric acid;
                    Oxydation   cataljst  made   from
                      porcelain
                    Perchloric acid
                    Phosphates, except defluorir.aled
                    Peroxides, inorganic
                    Phosphoric acid
                    Phosphorus  aud  phosphorus oxy-
                      chloride
                    Potash alum
                    Potassium aluminum sulfate
                    Potassium bichromate and chromate
                    Potassium bromide
                    Potassium chlorate
                    Potassium chloride and cjanide
                    Pola^ium compounds, inorganic, ex-
                      crept  potassium   hydroxide  and
                      carbonate
                    Potassium cyanide
                    Potassium hypochlorate
                    PotasMum iodide
                    Potassium metal
                    Potassium nitrate and sulfato
                    Potassium permanganate
                    Propellants for missile",  solid, in-
                      organic
                    Radium chloride
                    Radium luminous compounds
                    Rare earth metal salts
                    Reagent grade chemicals, inorganic :
                      refined, from technical prades
                    Refrigerants, ammonia Upe
                    Rubidium metal
                    Salt cake (sodium sulfate)
                    Salts  of rare earth  metals
                    Senndiu'm
                    Silica, amorphous
                    Silica pel
                    SiUcoQuorides
                    Silver bromide, chloride, and nitrate
                    Silver compounds, Inorganic
                    Soda  alum
                    Sodium aluminate
                    Sodium aluminum sulfate
                    Sodium antimoniate
                    Sodium bichromate and chromate
                    Sodium berates
                                                   Sodium borohydride
                                                   Sodium  bromide, not produced ct
                                                     mines
                                                   Sodium chlorate
                                                   Sodium compound*.  Inorganic
                                                   Sodium cyanide-
                                                   Sodium hydrosulfito
                                                   Sodium hjpochloritc
                                                   Sodium, metallic
                                                   Sodium molybdate
                                                   Sodium perborate
                                                   Sodium peroxide
                                                   Sodium phosphate
                                                   Sodium polyphospliate
                                                   Sodium silicate
                                                   Sodium silieofluorlde
                                                   Sodium stannate
                                                   Sodium sulfate—bulk or tablets
                                                   Sodium tetraborate,  not produced at
                                                     mines
                                                   Sodium thiosulfate
                                                   Sodium tuugstate
                                                   Sodium uranate
                                                   Solid fuel propellants, inorganic
                                                   Stannic and stnnnous chloride
                                                   Strontium  carbonate,  precipitated,
                                                     and oxide
                                                   Strontium nitrate
                                                   Sublimate, corrosive
                                                   Sulfate of potash and potash  mag-
                                                     nesia, not produced at mines
                                                   Sulfides and sulfites
                                                   Sulfoeyanides
                                                   Sulfur chloride
                                                   Sulfur dioxide
                                                   .Sulfur hexafiuoride gas
                                                   Sulfur,  recovered or refined, except
                                                     from  sour gas
                                                   Sulfuric acid
                                                   Tanning agents, synothetlc Inorganic
                                                   Thiocyanates,  inorganic
                                                   Tin chloride
                                                   Tin compounds. Inorganic
                                                   Tin. oxide
                                                   Tin salts
                                                   Uranium slug, radioactive
                                                   Water glass
                                                   '/.lac chloride
      PLASTICS MATERIALS AND SYNTHETIC RESINS, SYNTHETIC RUB-
          BER,  SYNTHETIC  AND  OTHER  MAN-MADE  FIBERS,  EXCEPT
          GLASS

        This group includes chemical establishments  primarily engaged in manu-
      facturing'  plastics materials  and  synthetic  resins,  synthetic  rubbers,  and
      cellulosic and  man-made organic  fibers.   Establishments primarily engaged
      in the manufacture of rubber products, nnd  those primarily engaged in the
      fabrication of  miscellaneous plastics products, are classified in Major Group
      30; and  textile mills primarily engaged in throwing, spinning, weaving, or
      knitting  textile products from manufactured fibers  are classified in Major
      Group 22.

      Plastics  Materials, Synthetic  Resins, and  Nonvulcanizable  Elastomers

        Establishments primarily  engaged  in   manufacturing  synthetic resins,
      plastics  materials, and  nonvulccnizable elastomers.  Important products of
      this industry include: cellulose plastic materials : phenolic and other tar acid
      resins: urea and melamine resins:  vinyl resins; styreue resins: alkyd resins:
      acrylic  resins: polyethylene  resins;  polypropylene  resins;  rosin  modified
      resins: couroarone-indene and petroleum polymer resins; and miscellaneous
                                              143
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                                   TECHNICAL REPORT DATA
                            (Please read Instructions on the reverse before completing)
1. REPORT NO.
  EPA-67Q/2-74-078
                             2.
                                                           3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
  Industrial  Chemicals Solid Waste  Generation—The
  Significance  of Process Change, Resource Recovery,
  and Improved  Disposal
                                                           5. REPORT DATE
               November 1974; Issuing  Date
             6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)

  James C.  Saxton and Marc Kramer
                                                           8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS

  International  Research and Technology
  1501 Wilson  Boulevard
  Arlington, Virginia  22209
             10. PROGRAM ELEMENT NO.
               1DB063; ROAP-24AIO; Task  01
             11. CONTRACT/GRANT NO.
               68-03-0138
12. SPONSORING AGENCY NAME AND ADDRESS
  National Environmental Research  Center
  Office of  Research and Development
  U.S. Environmental Protection Agency
  Cincinnati,  Ohio   45268
             13. TYPE OF REPORT AND PERIOD COVERED
               Final
             14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
  The study  characterizes the process-related solid wastes  produced during manufacture
  of industrial  chemicals, SIC Group  281.   Thirty three chemicals  were selected that:
  possess significant resource value,  pose a difficult solid waste disposal problem,
  and/or have  markedly deleterious  properties, e.g., toxicity.   The selected chemicals
  composed 40% of 1971 group output (149  x 106 tons) and an estimated 95% of the
  group's solid waste.  Fifteen of  the chemicals are undergoing  process substitutions;
  in every case the newer process generates less solid waste.   Projection to 1977
  indicates  that process and raw material  changes reduce the overall  solid waste
  quantity 7.3%.   Most of wastes are  of intrinsically low value, so resource recovery
  is seldom  economic.  Inorganics account for over 90% of total  disposal  cost, due to
  large waste  volume from ore-related  processes, such as alumina and  phosphoric acid.
  Organics appear to pose little disposal  problem.  Elimination  of water discharge
  doubles the  disposal cost of the  33  chemicals.
17.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS  C. COSATI Field/Group
  Toxicity
 *Sodium sulfates
 *Phosphorus
  Waste disposal
 *Reclamation
  Fluorine
 Industrial chemicals
 SIC Group 281
*Case studies
 Process change
 Market change
13B
18. DISTRIBUTION STATEMENT
  Release  to  public
19. SECURITY CLASS (This Report)
  Unclassified
                                                                         21. NO. OF PAGES
                                                                           154
                                              20. SECURITY CLASS (Thispage)

                                              	Unclassified	
                                                                         22. PRICE
EPA Form 2220-1 (9-73)
                                            144
                                                  •&U.S. GOVERNMENT PRINTING OFFICE: 1971»-&57-587/53l8  Region No. 5-11
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