EPA-450/3-73-005a
   JANUARY 1974
                   SURVEY REPORTS
     ON ATMOSPHERIC  EMISSIONS
      FROM THE PETROCHEMICAL
                             INDUSTRY
                             VOLUME I
~
          U.S. ENVIRONMENTAL PROTECTION AGENCY
               Office of Air and Water Programs
           Office of Air Quality Planning and Standards
          Research Triangle Park, North Carolina 27711

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                                  EPA-450/3-73-005a
        SURVEY REPORTS


ON ATMOSPHERIC EMISSIONS


 FROM  THE PETROCHEMICAL


              INDUSTRY



              VOLUME I



                 Prepared by

       J. W. Pervier, R. C. Barley, D. E. Field,
    B. M. Friedman, R. B. Morris, and W. A. Schwartz

                Houdry Division
          Air Products and Chemicals, Inc.
                P.O. Box 427
          Marcus Hook , Pennsylvania 19061


             Contract No. 68-02-0255


         EPA Project Officer:  Leslie B. Evans
                 Prepared for


        ENVIRONMENTAL PROTECTION AGENCY
          Office of Air and Water Programs
       Office of Air Quality Planning and Standards
         Research Triangle Park, N .C .  27711


                 January 1974

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This report is issued by the Environmental Protection Agency to report
technical data of interest to a limited number of readers.  Copies are
available free of charge to Federal employees, current contractors and
grantees, and nonprofit organizations - as supplies permit - from the
Air Pollution  Technical Information Center, Environmental Protection
Agency,  Research Triangle Park, North Carolina 27711, or from the
National Technical Information Service, 5285 Port Royal Road, Springfield,
Virginia  22151.
This report was furnished  to the Environmental Protection Agency by
Houdry Division,  Air  Products  and Chemicals, Inc., Marcus Hook,
Pennsylvania,  in  fulfillment of  Contract No.  68-02-0255.   The contents
of this report are reproduced herein  as received  from the Houdry
Division,  Air Products and Chemicals, Inc. The opinions, findings,
and conclusions expressed  are  those  of the author and not necessarily
those of the Environmental  Protection Agency.   Mention of company  or
product names is  not  to be considered  as  an endorsement by  the
Environmental  Protection Agency.
                     Publication No.  EPA-450/3/73/005a
                                    11

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                    PETROCHEMICAL AIR POLLUTION STUDY
                         INTRODUCTION TO SERIES

     This document is one of a series of four volumes prepared for the
                            T
Environmental  Protection Agency (EPA) to assist it in determining the
significance of air pollution  from the petrochemical  industry.
    A total of 33 distinctly different processes which are used to
produce 27 petrochemicals have been surveyed, and the results  are
reported in these four volumes numbered EPA 450/3-73-005-a, -b, -c, and -d.
The Tables of Contents of these reports list the processes that have been
surveyed.
    Those processes which have a significant impact on air quality
are being studied in more detail by EPA.  These in-depth studies will  be
published separately in a series of volumes entitled Engineering and
Cost Study of Air Pollution Control for the Petrochemical  Industry
(EPA-450/3-73-006-a, -b, -c, etc.)  At the time of this writing, a total
of seven petrochemicals produced by 11 distinctly different processes has
been selected for this type of study.  Three of these processes, used to
produce two chemicals (polyethylene and formaldehyde), were selected
because the survey reports indicated further study was warranted.  The
other five chemicals (carbon black, acrylonitrile, ethylene dichloride,
phthalic anhydride and ethylene oxide) were selected on the basis of
expert knowledge of the pollution potential of their production processes.
One or more volumes in the report series will be devoted to each of these
chemicals.

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                               ACKNOWLEDGEMENTS

      Survey and study work such as that described in this report have value
only to the extent of the value of the imput data.  Without the fullest
cooperation of the companies involved in producing the petrochemicals that
have been studied, this report vould not have been possible.  Air Products
wishes to acknowledge this cooperation by commending:

                       The U.  S. Petrochemical Industy
                       Member Companies of the Industry
                    The Manufacturing Chemists Association

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                              Table of Contents

Section                                                       Page Number

      Summary                                                     i

I.    Introduction                                                1
II.   Discussion                                                  2
III.  Results                                                     8
IV.   Conclusions                                                 9

Appendicies

      Acetaldehyde via Ethylene                                   ACD
      Acetaldehyde via Ethanol                                    AC
      Acetic Acid via Methanol                                    HAG
      Acetic Acid via Butane                                      ACA
      Acetic Acid via Acetaldehyde                                ACE
      Acetic Anhydride                                        •    ANA
      Adipic Acid                                                 AA
      Adiponitrile via Butadiene                                  AN
      Adiponitrile via Adipic Acid                                AL

      Mailing List                                                I
      Example Questionnaire                                       II
      Questionnaire Summary                                       III
      Significance of Pollution                                   IV
      Efficiency Ratings                                          V

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                          List of Tables and Figures

Table Number                      Title

     I                            Emissions Summary (3 pages)
     II                           Total Emissions, All Pollutants, by 1980*
     III                          Total Annual Weighted Emissions, by 1980*
     IV                           Significant Emission Index*
     V                            Number of New Plants (1973-1980)*

*Fifteen highest ranks from Table !„
NOTE:  There are numerous tables and figures in the Survey Reports that are
       included in the appendicies of this report.  These tables and figures
       are separately listed in each appendix.

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                                   SUMMARY

       A study of air pollution as caused by the petrochemical industry has
been undertaken in order to provide data that the Environmental Protection
Agency can use in the fulfillment of their obligations under the terms of
the Clean Air Amendments of 1970,,  The scope of the study includes most
petrochemicals which fall into one or more of the classifications of (a)
large production, (b) high growth rate, and (c) significant air pollution.
The processes for the production of each of these selected chemicals have
been studied and the emissions from each tabulated on the basis of data
from and Industry Questionnaire.  A survey report prepared fcr each process
provides a method for ranking the significance of the air pollution from
these processes.  In-depth studies on those processes which are considered
to be among the more significant polluters either have been or will be
provided.

       To date, drafts of in-depth studies on seven processes have been
submitted.  In addition, two further processes have been selected for
in-depth study and work on these is in progress.  All of these in-depth
studies will be separately reported under Report Number EPA-450/3-73-006
a, b, c, etc.

       A total of 33 Survey Reports have been completed and are reported
here, or in one of the other three volumes of this report series.

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                                    - 1 -
I.  Introduction

    A study has been undertaken to obtain information about selected pro-
duction processes that are practiced in the Petrochemical Industry.  The
objective of the study is to provide data that are necessary to support
the Clean Air Ammendments of 1970.

    The information sought includes industry descriptions, air emission
control problems, sources of air emissions, statistics on quantities and
types of emissions and descriptions of emission control devices currently
in use.  The principal source for these data was an industry questionnaire
but it was supplemented by plant visits, literature searches, in-house
background knowledge and direct support from the Manufacturing Chemists
Association.

    A method for rating the significance of air emissions was established
and is used to rank the processes as they are studied.  The goal of the
ranking technique is to aid in the selection of candidates for in-depth
study.  These studies go beyond the types of information outlined above
and include technical and economic information on "best systems" of emission
reduction, the economic impact of these systems, deficiencies in petrochemical
pollution control technology and potential research and development programs
to overcome these deficiencies.  These studies also recommend specific plants
for source testing and present suggested checklists for inspectors.

    This final report presents a description of the industry surveys that
have been completed, as well as a status summary of work on the in-depth
studies.

    The Appendicies of this report include each of the 33 Survey Reports
that were prepared during the course of the study.

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                                    - 2 -
II.   Discussion

     A.   Petrochemicals to be Studied

         There are more than 200 different petrochemicals in current
     production in the United States.  Many of these are produced by tvo
     or  more processes that are substantially different both with respect
     to  process techniques and nature of air emissions.  Although it may
     eventually become necessary to study all of these, it is obvious
     that the immediate need is to study the largest tonnage, fastest growth
     processes that produce the most pollution.

         Recognizing this immediate need, a committee of Air Products'
     employees and consultants reviewed the entire list of chemicals and
     prepared a list of thirty chemicals which were recommended for primary
     consideration in the study and an additional list of fourteen chemicals
     that should receive secondary consideration.  Since this was only  a
     qualitative evaluation it was modified slightly as additional information
     was received and after consultation with the Environmental Protection
     Agency (EPA).

         The final modified list of chemicals to be studied included all
     but three from the original primary recommendations.   In addition,  four
     chemicals were added and one was broken into two categories (namely low
     and high density polyethylene) because of distinct differences in  the
     nature of the final products.  This resulted in thirty-two chemicals
     for study and fourty one processes which are sufficiently different to
     warrant separate consideration.   Hence,  the following list of petro-
     chemicals is the subject of this study.
     Acetaldehyde (2 processes)
     Acetic Acid (3 processes)
     Acetic Anhydride
     Acrylonitrile
     Adipic Acid
     Adiponitrile (2 processes)
     Carbon Black
     Carbon Disulfide
     Cyclohexanone
     Ethylene
     Ethylene  Bichloride  (2  processes)
     Ethylene  Oxide (2  processes)
     Formaldehyde (2 processes)
     Glycerol
     Hydrogen  Cyanide
     Maleic Anhydride
Nylon 6
Nylon 6,6
"Oxo" Alcohols and Aldehydes
Phenol
Phthalic Anhydride C2 processes)
Polyethylene (high density)
Polyethylene (low density)
Polypropylene
Polystyrene
Polyvinyl Chloride
Styrene
Styrene - Butadiene Rubber
Terephthalic Acid (1)
Toluene Di-isocyanate (2)
Vinyl Acetate (2 processes)
Vinyl Chloride
     (1)   Includes  dimethyl  terephthalate,
     (2)   Includes  methylenediphenyl  and  polymethylene  polyphenyl  isocyanates,

     B.   Preliminary Investigations

         Immediately upon completion  of the  preliminary study  lists,  a
     literature  review was begun on those chemicals  which  were considered
     likely candidates for study.  The purpose  of  the review was to  prepare
     an  informal "Process Portfolio"  for  each chemical.  Included  in  the
     portfolio are  data concerning processes for producing the chemical,
     estimates of growth in  production, estimates  of production costs,  names,

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                               - 3 -
locations and published capacities of producers, approximations of
overall plant material balances and any available data on emissions
or their control as related to the specific process.

    The fundamental purpose of these literature revievs vas to obtain
background knowledge to supplement vhat vas ultimately to be learned
from completed Industry Questionnaires.  A second and very important
purpose vas to determine plant locations and names of companies
producing each chemical.  This information vas then used to contact
responsible individuals in each organization ("usually by telephone) to
obtain the name and address of the person to vhom the Industry Question-
naire should be directed.   It is believed that this approach greatly
expedited the completion of questionnaires.  The mailing list that vas
used is included as Appendix I of this report.

C.  Industry Questionnaire

    Soon after the initiation of the petrochemical pollution study, a
draft questionnaire vas submitted by Air Products to the Environmental
Protection Agency.  It had been decided that completion of this
questionnaire by industry vould provide much of the information
necessary to the performance of the study.  The nature and format of
each question vas revieved by EPA engineers and discussed vith Air
Products engineers to arrive at a modified version of the originally
proposed questionnaire.

    The modified questionnaire vas then submitted to and discussed
vith an Industry Advisory Committee (IAC) to obtain a final version for
submission to the Office of Management and Budget <"OMB) for final
approval, as required prior to any U.  S. Government survey of national
industries.  The folloving listed organizations, in addition to the
EPA and Air Products, vere represented at the IAC meeting:

    Trade Associations

    Industrial Gas Cleaning Institute
    Manufacturing Chemists Association

    Petrochemical Producers

    B. F. Goodrich Chemical Company
    E. I. duPont deNemours and Company
    Exxon Chemical Company
    FMC Corporation
    Monsanto Company
    Northern Petrochemical Company
    Shell Chemical Company
    Tenneco Chemicals, Inc.
    Union Carbide Corporation

    Manufacturers of Pollution Control Devices

    John Zink Company
    UOP Air Correction Division

    State Pollution Control Departments

    Nev Jersey
    Texas

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                               - 4 -
    The questionnaire, along with a detailed instruction sheet and
an example questionnaire (which had been completed by Air Products
for a fictitious process that was "invented" for this purpose) were
submitted to the OMB for approval.  In due course, approval was
received and OMB Approval Number 158-S-72019 was assigned to the
questionnaire.  Copies of the approved instruction sheet, example
questionnaire are included as Appendix II of this report.
    The questionnaires were mailed in accordance with the mailing
list already discussed and with a cover letter that had been prepared
and signed by the EPA Project Officer.  The cover letter was typed in
a manner that permitted the insertion of the name and address of the
receipient at the top of the first page and the name of the process,
the plant location and an expected return date at the bottom of the
first page.  A copy of this letter of transmittal is also included in
Appendix II.

    Understandably, because of the dynamic nature of the petrochemical
industry, about 10 percent of the questionnaires were directed to plants
which were no longer in operation, were still under construction, were
out-of-date processes or were too small to be considered as typical.
This did not present a serious problem in most cases because (a) 100
percent of the plants were not surveyed and (b) the project timing per-
mitted a second mailing when necessary,,  Appendix III tabulates the
number of questionnaires incorporated into each study.

    One questionnaire problem that has not been resolved is confiden-
tiality.  Some respondents omitted information that they consider to
be proprietary.  Others followed instructions by giving the data but
then marked the sheet (or questionnaire) "Confidential".  The EPA is
presently trying to resolve this problem, but until they do the data
will be unavailable for inclusion in any Air Products' reports.

D.  Screening Studies

    Completed questionnaires were returned by the various respondents
to the EPA's Project Officer, Mr. L. B. Evans.  After reviewing them
for confidentiality, he forwarded the non-confidential data to Air
Products.  These data form the basis for what has been named a "Survey
Report".  The purpose of the survey reports being to screen the various
petrochemical processes into the "more" and "less - significantly
polluting processes".  These reports are included as appendicies to
this report.

    Obviously, significance of pollution is a term which is difficult
if not impossible to define because value judgements are involved.
Recognizing this difficulty, a quantitative method for calculating a
Significant Emission Index (SEI) was developed.  This procedure is
discussed and illustrated in Appendix IV of this report.  Each survey
report includes the calculation of an SEI for the petrochemical that
is the subject of the report.  These SEI's have been incorporated into
the Emissions Summary Table that constitutes part of this report.  This
table can be used as an aid when establishing priorities in the work
required to set standards for emission controls on new stationary
sources of air pollution in accordance with the terms of the Clean Air
Amendments of 1970,

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                               - 5 -
    The completed survey reports constitute a preliminary data bank on
each of the processes being studied.  In addition to the SEI calculation,
each report includes a general introductory discussion of the process,
a process description (including chemical reactions), a simplified
process (Block) flow diagram, as well as heat and material balances.
More pertinent to the air pollution study, each report lists and
discusses the sources of air emissions (including odors and fugitive
emissions) and the types of air pollution control equipment employed.
In tabular form, each reports summarizes the emission data (amount,
composition, temperature, and frequency); the sampling and analytical
techniques; stack numbers and dimensions; and emission control device
data (types, sizes, capital and operating costs and efficiencies).

    Calculation of efficiency on a pollution control device is not
necessarily a simple and straight-forward procedure.  Consequently,
two rating techniques were established for each type of device, as
follows:

    1.   For flares, incinerators, and boilers a Completeness of Combustion
        Rating (CCR) and Significance of Emission Reduction Rating  (SERR)
        are proposed.

    2.   For scrubbers and dust removal equipment, a Specific Pollutant
        Efficiency (SE)  and a SERR are proposed.

    The bases for these ratings and example calculations are included
in Appendix V of this report.

E.  In-Depth Studies

    The original performance concept was to select a number of petro-
chemical processes as "significant polluters", on the basis of data
contained in completed questionnaires.  These processes were then to
be studied "in-depth".  However, the overall time schedule was such
that the EPA requested an initial selection of three processes on the
basis that they would probably turn out to be "significant polluters".
The processes selected in this manner were:

    lo   The Furance Process for producing Carbon Black,

    2.   The Sohio Process for producing Acrylonitrile.

    3,,   The Oxychlorination Process for producing 1,2 Dichloroethane
        (Ethylene Bichloride) from Ethylene.

    In order to obtain data on these processes, the operators and/or
licensors of each were approached directly by Air Products' personnel.
This, of course, was a slow and tedious method of data collection because
mass mailing techniques could not be used, nor could the request for
data be identified as an "Official EPA Requirement".  Yet, by the time
that OMB approval was given for use of the Industry Questionnaire, a
substantial volume of data pertaining to each process had already been
received.  The value of this procedure is indicated by the fact that
first drafts of these three reports had already been submitted to the
EPA, and reviewed by the Industry Advisory Committee, prior to the
completion of many of the survey reports.

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                               - 6 -
    In addition, because of timing requirements, the EPA decided that
three additional processes be "nominated" for in-depth study.  The
chemicals involved are phthalic anhydride, formaldehyde and ethylene
oxide.  Work on these indicated a need for four additional in-depth
studies as follows:

    1.  Air Oxidation of Ortho-Xylene to produce Phthalic Anhydride.

    2.  Air Oxidation of Methanol in a Methanol Rich Process to
        produce Formaldehyde over a Silver Catalyst.

    3.  Air Oxidation of Methanol in a Methanol-Lean Process to
        produce Formaldehyde over an Iron Oxide Catalyst.

    4o  Direct Oxidation of Ethylene to produce Ethylene Oxide.

    Drafts of these have been submitted to the EPA and reviewed by the
Industry Advisory Committee.  The phthalic anhydride report also includes
a section on production from naphthalene by air oxidation, a process
which is considered to be a significant polluter in today's environment
but without significant growth potential.

    These seven in-depth studies will be separately issued in final
report form, under Report Number EPA-450/3-73-006 a, b, c, etc.

    An in-depth study, besides containing all the elements of the
screening studies, delves into questions such as "What are the best
demonstrated systems for emission reduction?", "What is the economic
impact of emission control on the industry involved?", "What deficiencies
exist in sampling, analytical and control technology for the industry
involved?".

    In striving to obtain answers to these questions, the reports
include data on the cost effectiveness of the various pollution control
techniques source testing recommendations, industry growth projections,
inspection procedures and checklists, model plant studies of the
processes and descriptions of research and development programs that
could lead to emission reductions.

    Much of the information required to answer these questions came
from the completed Industry Questionnaires and the Process Portfolios.
However, the depth of understanding that is required in the preparation
of such a document can only be obtained through direct contact with the
companies that are involved in the operation of the processes being
studied.  Three methods for making this contact were available to Air
Products.  The first two are self-evident, as follows:  Each
questionnaire contains the name, address and telephone number of an
individual who can provide additional information.  By speaking with
him, further insight was obtained into the pollution control problems
that are specific to the process being studied; or through him, a
visit to an operating plant was sometimes arranged, thus achieving a
degree of first hand knowledge.

    However, it was felt that these two techniques might fall short of
the level of knowledge desired.  Thus, a third, and unique procedure was
arranged.  The Manufacturing Chemists Association (MCA) set up, through

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                               - 7 -
its Air Quality Committee (AQC), a Coordinating Technical Group
(CTG) for each in-depth process.  The role of each CTG was to:

    1.  Assist in the obtaining of answers to specific questions.

    2.  Provide a review and commentary (without veto power) on
        drafts of reports.

    The AQC named one committee member to provide liaison.  In
several cases, he is also one of the industry's specialists for the
process in question.  If not, one other individual was named to
provide CTG leadership.  Coordination of CTG activities was provided
by Mr. Howard Guest of Union Carbide Corporation who is also on the
EPA's Industry Advisory Committee as the MCA Representative.  CTG
leadership is as follows:

     Chemical                   AQC Member                  Other

Carbon Black                 C. B. Beck                 None
                             Cabot Corporation

Acrylonitrile                W. R. Chalker              R. E. Farrell
                             Du Pont                    Sohio

Formaldehyde                 W. B. Barton               None
                             Borden

Ethylene Bichloride          W. F. Bixby                None
                             B. F. Goodrich

Phthalic Anhydride           E. P. Wheeler              Paul Hodges
                             Monsanto                   Monsanto

Ethylene Oxide               H. R. Guest                H. D. Coombs
                             Union Carbide              Union Carbide

F.  Current Status

    Survey Reports on each of the 33 processes that were selected for
this type of study have been completed, following review of the drafts
by both the EPA and the Petrochemical Industry.  These reports constitute
the subject matter of this report.

    In-depth studies- of the seven processes mentioned above have been
completed in draft form, submitted to the EPA for initial review,
discussed in a public meeting with the Industry Advisory Committee and
re-submitted to the EPA in revised form.  They are currently receiving
final EPA review and will be issued as final reports, following that
review.

    The EPA has now selected two additional processes for in-depth study
and work on these is currently in progress.  They are:

    1.  High Density Polyethylene via the Low and Intermediate Pressure
        Polymerization of Ethylene.

    2.  Low Density Polyethylene via the High Pressure Polymerization
        of Ethylene.

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                                    - 8 -
III.  Results

      The nature of this project is such that it is not possible to report
any "results" in accordance with the usual meaning of the word.   Obviously,
the results are the Survey Reports and In-Depth Studies that have been
prepared.  However, a tabulation of the emission data collected  in the
study and summarized in each of these reports will be useful to  the EPA
in the selection of those processes which will be either studied in-depth
at some future date, or selected for the preparation of new source standards.
Such a tabulation, entitled "Emissions Summary Table",  is attached.

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                                    - 9 -
IV.  Conclusions

     As was stated above under "Results", the conclusions reached are
specific to each study and, hence, are given in the individual reports.
Ultimately, some conclusions are reachable relative to decisions on
processes which require future in-depth studies or processes which warrant
the promulgation of new source standards.

     A firm basis for selecting these processes is difficult to achieve,
but the data contained in the Emissions Summary Table can be of value in
setting a basis, or selecting processes.

     It is imperative, when using the table, to be aware of the following
facts.

     1.  The data for some processes are based on 100 percent survey of
         the industry, while others are based on less than 100 percent
         with some as few as a single questionnaire.

     2.  Some of the reported data are based on stack sampling, others on
         continuous monitoring and still others on the "best estimate" by
         the person responsible for the questionnaire.

     3.  Air Products attempted to use sound engineering judgement in
         obtaining emission factors, industry capacities and growth
         projections.  However, other engineering firms, using the same
         degree of diligence would undoubtedly arrive at somewhat different
         final values.

     Thus, the tabulation should be used as a guide but not as a rigorous
comparison of process emissions.

     Furthermore, data on toxicity of emissions, odors and persistence of
emitted compounds are not included in the tabulation.  In addition, great
care must be used when evaluating the weighted emission rates because of
the wide range in noxiousness of the materials lumped together in the two
most heavily weighted categories.  For example, "hydrocarbons" includes
both ethane and formaldehyde and "particulates" includes both phthalic
anhydride and the permanent hardness of incinerated water.

     Bearing all of these qualifications in mind, several "top 15" rankings
of processes can be made, as in Tables II through V.  Obviously, one of
these tables could be used to select the more significant polluters directly.
Of course, other rankings could be made, such as leading emitters of NOX or
particulates, etc.  Using these four tables, however, one analysis might be
that the number of times a process appears in these tables is a measure of
its pollution significance, or in summary:
     Appear in 4 Tables

     Carbon Black
     Low Density Polyethylene
     High Density Polyethylene
     Cyclohexanone
     Polypropylene
     Polyvinyl Chloride
     Ethylene Oxide
Appear in 3 Tables

Acrylonitrile
Adiponitrile (Butadiene)
Ethylene Dichloride (Oxychlorination)
Dimethyl Terephthalate
Ethylene Dichloride (Direct)
Ethylene

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                                    - 10 -
     Appear in 2 Tables                          Appear in 1 Table

     Maleic Anhydride                            Phthalic Anhydride
     Isocyanates                                 Formaldehyde (Iron Oxide)
     Phenol                                      Polystyrene
     Formaldehyde  (Silver)                       Nylon 6
                                                 Nylon 6,6
                                                 Vinyl Chloride

     Thus, on this basis and in retrospect, it could be concluded that four
of the selected in-depth studies (carbon black, ethylene oxide, and both
low and high density polyethylene)  were justified but that three of them
(phthalic anhydride and both formaldehyde processes) were of lesser importance.

     On the same basis, seven processes should be considered for future
in-depth studies, namely:

     Cyclohexanone
     Polypropylene
     Polyvinyl Chloride
     Adiponitrile (Butadiene Process)
     Dimethyl Terephthalate (and TPA)
     Ethylene Bichloride (Direct)
     Ethylene

     Obviously, many alternative bases could be established.   It is not
the function of this report to select a basis for initiating future studies
because the priorities of the EPA are unknown.  The most apparent of these
bases are the ones suggested by Tables II through V, namely the worst total
polluters, the worst polluters on a weighted basis, the greatest increase
in pollution (total or weighted) or the largest numbers of new plants.  In
addition, noxiousness of the emissions (photo-chemical reactivity, toxicity,
odor, persistence) could be considered in making a selection.

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                                                                                       TABLE I
Acetaldehyde via Ethylene
             via Ethanol
Acetic Acid via Methanol
            via Butane
            via Acetaldehyde
Acetic Anhydride via Acetic Acid
Acrylonitrile (9)
Adipic Acid
Adiponitrile via Butadiene
             via Adipic Acid
Carbon Black
Carbon Disulfide
Cyclohexanone
Dimethyl Terephthalate  (+TPA)
Ethylene
Ethylene Dichloride via Oxychlorination
                    via Direct  Chlorination
Ethylene Oxide
Formaldehyde via Silver Catalyst
             via Iron Oxide Catalyst
Glycerol via Epichlorohydrin
Hydrogen Cyanide Direct Process
Isocyanates
Maleic Anhydride
Nylon 6
Nylon 6,6
Oxo  Process
Phenol
Phthalic Anhydride via  0-Xylene
                   via  Naphthalene
High Density Polyethylene
Low  Density Polyethylene
Polypropylene
Polystyrene
Polyvinyl  Chloride
Styrene
Styrene-Butadiene Rubber
Vinyl Acetate via Acetylene
              via Ethylene
Vinyl Chloride
                              Totals
EMISSIONS SUMMARY
ESTIMATED C1) CURRENT AIR EMISSIONS,
Hydrocarbons ' '
1.1
0
0
40
6.1
3.1
183
0
11.2
0
156
0.15
70
91
15
95.1
29
85.8
23.8
25.7
16
0.5
1.3
34
0
0
5.25
24.3
0.1
0
79
75
37.5
20
62
4.3
9.4
5.3
0
17.6
Particulates CO
0
0
0
0
0
0
0
0.2
4.7
0.5
8.1
0.3
0
1.4
0.2
0.4
0
0
0
0
0
0
0.8
0
1.5
5.5
0.01
0
5.1
1.9
2.3
1.4
0.1
0.4
12
0.07
1.6
0
0
0.6
Oxides of Nitrogen
0
0
0.01
0.04
0
0
5.5
29.6
50.5
0.04
6.9
0.1
0
0.1
0.2
0
0
0.3
0
0
0
0.41
0
0
0
0
0.07
0
0.3
0
0
0
0
0
0
0.14
0
0
TR
0
Sulfur Oxides
0
0
0
0
0
0
0
0
0
0
21.6
4.5
0
1.0
2.0
0
0
0.1
0
0
0
0
0.02
0
0
0
0
0
2.6
0
0
0
0
1.2
0
0
0.9
0
0
0
MM LBS./YEAR
Page 1 of 3
Carbon Monoxide Total
0
27
0
14
1.3
5.5
196
0.14
0
0
3,870
0
77.5
53
0.2
21.8
0
0
107.2
24.9
0
0
86
260
0
0
19.5
0
43.6
45
0
0
0
0
0
0
0
0
0
0
1.1
27
0.01
54
7.4
8.6
385
30
66.4
0.54
4,060
5.1
148
146.5
17.6
117.3
29
86.2
131
50.6
16
0.91
88
294
1.5
5.5
24.8
24.3
51.7
47
81.3
76.4
37.6
21.6
74
4.5
12
5.3
TR
18.2

Total Weighted <5
86
27
1
3,215
490
253
15,000
1,190
3.200
30
17,544
120
5,700
7,460
1,240
7,650
2,300
6,880
1,955
2,070
1,280
56
231
2,950
90
330
440
1,940
422
160
6,400
6,100
2,950
1,650
5,700
355
870
425
TR
1.460
                                                  1,227.6
                                                                          49.1
                                                                                                94.2
                                                                                                                  33.9
                                                                                                                            4,852.6
                 6,225.9
                                                                                                                                                                  110,220 (7>
 (1)
 (2)
 (3)
 CO
 (5)
 (6)
 (7)
 (9)
In most instances numbers are based on less than 1007. survey.  All based on engineering judgement of best current control.
Assumes future plants will employ best current control techniques.
Excludes methane, includes H2S and all volatile organics.
Includes non-volatile organics and inorganics.
Weighting factors used are:  hydrocarbons - 80, particulates - 60, NOX - 40, SOX - 20, and CO - 1.
Referred to elsewhere in this study as "Significant Emission Index" or "SEI".
Totals are not equal across and down due to rounding.
Emissions based on what is now an obsolete catalyst.  See Report No. EPA-450/3-73-006 b for up-to-date information.
Probably has up to 10% lov bias.

-------

Hydrocarbons ^ '
1.2
0
0
0
12.2
0.73
284
0
10.5
0
64
0.04
77.2
73.8
14.8
110
34.2
32.8
14.8
17.6
8.9
0
1.2
31
0
0
3.86
21.3
0.3
0
210
262
152
20
53
3.1
1.85
4.5
0
26.3
1,547.2

Part iculates
0
0
0
0
0
0
0
0.14
4.4
0.5
3.3
0.07
0
1.1
0.2
0.5
0
0
0
0
0
0
0.7
0
3.2
5.3
0.01
0
13.2
0
6.2
5
0.5
0.34
10
0.05
0.31
0
0
0.9
55.9
TABLE I
EMISSION SUMMARY
ESTIMATED ADDITIONAL (2)
' ' Oxides of Nitrogen
0
0
0.04
0
0
0
8.5
19.3
47.5
0.04
2.8
0.03
0
0.07
0.2
0
0
0.15
0
0
0
0
0
0
0
0
0.05
0
0.8
0
0
0
0
0
0
0.1
0
0
TR
0
79,5
AIR EMISSIONS IN
Sulfur Oxides
0
0
0
0
0
0
0
0
0
0
8.9
1.1
0
0.84
61.5
0
0
0.05
0
0
0
0
0.02
0
0
0
0
0
6.8
0
0
0
0
1.13
0
0
0.18
0
0
0
80.5
1980, MM LBS./YEAR
Carbon Monoxide
0
0
0
0
2.5
1.42
304
0.09
0
0
1,590
0
85.1
42.9
0.2
25
0
0
66.7
17.0
0
0
85
241
0
0
14.3
0
113
0
0
0
0
0
0
0
0
0
0
0
2,588
Page 2 of 3
Total
1.2
0
0.04
0
14.7
2.15
596
19.5
62.4
0.54
1,670
1.24
162
118.7
77
136
34.2
33
81.5
34.6
8.9
0
87
272
3.2
5.3
18.2
21.3
134
0
216
267
152.5
21.47
63
3.25
2.34
4.5
TR
27.2
4,351.9

Total Weighted O>6)
96
0
2
0
980
60
23,000
779
3,010
30
7,200
30
6,260
6,040
2,430
8,800
2,740
2,650
1,250
1,445
700
0
225
2,720
194
318
325
1,704
1,100
0
17,200
21,300
12,190
1,640
4,840
225
170
360
TR
2.170
134,213 (7)
Acetaldehyde via Ethylene
             via Ethanol
Acetic Acid via Methanol
            via Butane
     4      via Acetaldehyde
Acetic Anhydride via Acetic Acid
Aerylonitrile (9)
Adipic Acid
Adiponitrile via Butadiene
             via Adipic Acid
Carbon Black
Carbon Disulfide
Cyclohexanone
Dimethyl Terephthalate  (4-TPA)
Ethylene
Ethylene Dichloride via Oxychlorination
                    via Direct Chlorination
Ethylene Oxide
Formaldehyde via Silver Catalyst
             via Iron Oxide Catalyst
Glycerol via Epichlorohydrin
Hydrogen Cyanide Direct Process
Isocyanates
Maleic Anhydride
Nylon 6
Nylon 6,6
Oxo Process
Phenol
Phthalic Anhydride via  0-Xylene
                   via  Naphthalene
High Density Polyethylene
Low Density Polyethylene
Polypropylene
Polystyrene
Polyvinyl  Chloride
Styrene
Styrene-Butadiene Rubber
Vinyl Acetate via Acetylene
              via Ethylene
Vinyl Chloride

                           Totals

(1)   In most instances  numbers are based  on  less  than  100%  survey.  All based on engineering  judgement of best current control.
(2)  Assumes future plants will employ best  current  control  techniques.
(3)   Excludes methane,  includes H2S and all  volatile organics.
(4)   Includes non-volatile organics and inorganics.
(5)  Weighting  factors  used are:  hydrocarbons  -  80, particulates  - 60, NOX  - 40,  SOX  - 40, and CO  -  1.
(6)   Referred to elsewhere in  this study  as  "Significant  Emission  Index"  or  "SEI".
(7)  Totals are not equal across and down duw to  rounding.
(9)   See sheet  1 of 3.
Probably has up to 107. low bias.

-------
                                                                                        TABLE I
Acetaldehyde  via  Ethylene
              via  Ethanol
Acetic  Acid via Methanol
            via Butane
            via Acetaldehyde
Acetic  Anhydride  via Acetic Acid
Acrylonitrile (9)
Adipic  Acid
Adiponitrile  via  Butadiene
              via  Adipic Acid
Carbon  Black
Carbon  Disulfide
Cyclohexanone
Dimethyl Terephthalate (+TPA)
Ethylene
Ethylene Dichloride via Oxychlorination
                     via Direct Chlorination
Ethylene Oxide
Formaldehyde  via  Silver Catalyst
              via  Iron Oxide Catalyst
Glycerol via  Epichlorohydrin
Hydrogen Cyanide  Direct Process
Isocyanates
Maleic  Anhydride
Nylon 6
Nylon 6,6
Oxo Process
Phenol
Phthalic Anhydride via 0-Xylene
                    via Naphthalene
High Density  Polyethylene
Low Density  Polyethylene
Polypropylene
Polystyrene
Polyvinyl Chloride
Styrene
Styrene-Butadiene Rubber
Vinyl Acetate via Acetylene
               via Ethylene
Vinyl Chloride
Emissions
Total by 1980
2.3
27
0.05
54
22
10.8
980
50
128.8
1.1
5,730
6.3
310
265
94
253
63
120
212.5
85
25
0.5 (10)
175
566
4.7
10.8
43
46
186
47
297
343
190
43
137
7.4
14
9.8
TR
45
EMISSIONS SUMMARY
(2>, MM Lbs. /Year
Total Weighted (5) by 1980
182
27
3
3,215
1,470
313
38,000
1,970
6,210
60
24,740
150
11,960
13,500
3,i70
16,450
5,040
9,530
3,205
3,515
2,000
28 (10)
456
5,670
284
650
765
3,640
1,522
160
23 , 600
27,400
15,140
3,290
10,540
610
1,040
785
TR
3.630
                                                                                                                                    Page 3 of 3
                                Totals
                                                   10,605
                                                          (7)
                                                                                                          Estimated Number  of New Plants
                                                                                                          	(1973 - 1980)	
                                                                                                                   0
                                                                                                                   4
                                                                                                                   0
                                                                                                                   3
                                                                                                                   3
                                                                                                                   5
                                                                                                                   7
                                                                                                                   4
                                                                                                                   3
                                                                                                                  13
                                                                                                                   2
                                                                                                                  10
                                                                                                                   8
                                                                                                                  21
                                                                                                                   8
                                                                                                                  10
                                                                                                                  15
                                                                                                                  40
                                                                                                                  12
                                                                                                                   1
                                                                                                                   0
                                                                                                                  10
                                                                                                                   6
                                                                                                                  10
                                                                                                                  10
                                                                                                                   6
                                                                                                                  11
                                                                                                                   6
                                                                                                                   0
                                                                                                                  31
                                                                                                                  41
                                                                                                                  32
                                                                                                                  23
                                                                                                                  25
                                                                                                                   9
                                                                                                                   4
                                                                                                                   1
                                                                                                                   4
                                                                                                                  10
                                                                                                                                            Total Estimated Capacity
                                                                                                                                                     MM Lbs./Year
                                                                                                                                            Current       By 1980  '
1,160
966
400
1,020
875
1,705
1,165
4,430
435
280
3,000
871
1,800
2,865
22,295
4,450
5,593
4,191
5,914
1,729
245
412
1,088
359
486
1,523
1,727
2,363
720
603
2,315
5,269
1,160
3,500
4,375
5,953
4,464
206
1,280
5,400
2

' 1

2
2
3
2


5
1
3
5
40
8
11
6
9
3


2

1
3
3
4
1

8
21
5
6
8
10
5

2
13
,460
966
,800
500
,015
,100
,700 (8)
,200
845
550
,000 (8)
,100
,600
,900
,000
,250 (8)
,540
,800 (8)
,000
,520 (8)
380
202
,120
720
,500
,000
,000
,200
,800 (8)
528
,500
,100
,800
,700
,000
,000
,230
356
,200
,000
                                                                       244,420
 (1)
 (2)
 (3)
 (4)
 (5)
 (6)
 (7)
 (8)
 (9)
(10)
In most instances numbers are based on less than 1007, survey.  All based on engineering judgement of best current control.
Assumes future plants will employ best current control techniques.
Excludes methane, includes t^S and all volatile organics.
Includes non-volatile organics and inorganics.
Weighting factors used are:  hydrocarbons - 80, particulates - 60, NOX - 40, SOX - 20, and CO - 1.
Referred to elsewhere in this study as "Significant Emission Index" or "SEI".
Totals are not equal across and down due to rounding.
By 1985.
See sheet 1 of 3
Due to anticipated future shut down of marginal plants.
Probably has up to 107. low bias.

-------
                            TABLE II




TOTAL ANNUAL EMISSIONS, ALL "POLLUTANTS". BY 1980  (MM LBS./YR.)*




Carbon Black                                            5,730




Acrylonitrile                                             980




Maleic Anhydride                                          566




Low Density Polyethylene                                  343




Cyclohexanone                                             310




High Density Polyethylene                                 297




Dimethyl Terephthalate                                    265




Ethylene Dichloride                                       253




Phthalic Anhydride (Total)                                233




Formaldehyde (Silver)                                     212




Polypropylene                                             190




Isocyanates                                               175




Polyvinyl Chloride                                        137




Adiponitrile (Butadiene Process)                          129




Ethylene Oxide                                            120







''"Fifteen highest numbers, as summarized in Table I, for this category.

-------
                      TABLE III

TOTAL ANNUAL WEIGHTED EMISSIONS BY 1980  (MM LBS./YR.)*

Acrylonitrile                                38,000

Low Density Polyethylene                     27,400

Carbon Black                                 24,740

High Density Polyethylene                    23,600

Ethylene Bichloride (Oxychlorination)        16,450

Polypropylene                                15,140

Dimethyl Terephthalate                       13,500

Cyclohexanone                                11,960

Polyvinyl Chloride                           10,540

Ethylene Oxide                                9,530

Adiponitrile (Butadiene Process)              6,210

Maleic Anhydride                              5,670

Ethylene Dichloride (Direct)                  5,040

Ethylene                                      3,670

Phenol                                        3,640
*Fifteen highest numbers, as summarized in Table I, for
 this category.

-------
                       TABLE IV

             SIGNIFICANT EMISSION INDEX*

Acrylonitrile                                 23,000

Low Density Polyethylene                      21,300

High Density Polyethylene                     17,200

Polypropylene                                 12,190

Ethylene Dichloride (Oxychlorination)          8,800

Carbon Black                                   7,200

Cyclohexanone                                  6,260

Dimethyl Terephthalate                         6,040

Polyvinyl Chloride                             4,840

Adiponitrile (Butadiene)                       3,010

Ethylene Dichloride (Direct)                   2,740

Maleic Anhydride                               2,720

Ethylene Oxide                                 2,650

Ethylene                                       2,430

Vinyl Chloride                                 2,170
^Fifteen higest numbers, as summarized in Table I, for
 this category.

-------
                       TABLE V

          NUMBER OF NEW PLANTS  (1973-1980)*

Low Density Polyethylene                             41

Formaldehyde (Silver)                                40

Polypropylene                                        32

High Density Polyethylene                            31

Polyvinyl Chloride                                   25

Polystyrene                                          23

Ethylene                                             21

Ethylene Oxide                                       15

Carbon Black                                         13

Formaldehyde (Iron Oxide)                            12

Phenol                                               11

Cyclohexanone                                        10

Isocyanates                                          10

Nylon 6                                              10

Nylon 6,6                                            10

Ethylene Dichloride (Direct)                         10
*Fifteen highest numbers, as summarized in Table I, for
 this category.

-------
Acetaldehyde via Ethylene

-------
                              Table of Contents

Section                                                         Page Number

I.    Introduction                                                  ACD-1
II.   Process Description                                           ACD-2
III.  Plant Emission                                                ACD-4
IV.   Emission Control                                              ACD-6
V.    Significance of Pollution                                     ACD-7
VI.   Acetaldehyde Producers                                        ACD-8

                       List of Illustrations and Tables

      Flow Diagram                                              Figure ACD-I
      Material Balance                                          Table ACD-I
      Cross Heat Balance                                        Table ACD-II
      Emission Inventory                                        Table ACD-III
      Catalog of Emission Control Devices                       Table ACD-IV
      Number of New Plants by 1980                              Table ACD-V
      Emission Source Summary                                   Table ACD-VI
      Weighted Emission Rates                                   Table ACD-VII

-------
                                    ACD-1
I.   Introduction

    Acetaldehyde, C^CHO, is a mobile, colorless, inflammable liquid with a
pungent, choking odor.  It was first noticed by Scheele in 1774 and recognized
as a new compound by Foucroy and Vaughelin in 1880.

    Most acetaldehyde is used as an intermediate in the manufacture  of
other organic compounds.  The largest single outlet accounting for more than
half of the acetaldehyde use is the manufacture of acetic acid.  Other
processes which utilize it as a raw material are the production of butyl
alcohol, butyraldehyde, chloral and pyridine. (1)

    There are four ways acetaldehyde can be made industrially.  They are
oxidation or dehydrogenation of ethanol, oxidation of ethylene in one or
two stages, propane-butane oxidation and acetylene hydration.  The oxidation
or dehydrogenation of ethanol and ethylene oxidation are the major processes
currently used.  Ethylene oxidation is a relatively new method which is
more attractive financially than ethanol oxidation because it utilizes a
cheaper raw material.  Although acetaldehyde via ethanol plants constitute
about 4470 of the current capacity no new plants of this type have been built
in the last five years or are expected to be built in the future.

    The decision as to which of the ethylene processes to use breaks down to a
choice between lower initial investment costs for the one-stage process and
lower raw material (air opposed to oxygen) costs for the two-stage process.
The availability of cheap high grade oxygen is the prime determining factor.
Currently the two-stage process is more popular in the U.  S.  but world wide
both processes are being used extensively.

    Air emission data presented in this report are from one respondent who
uses the two-stage process.   Because of the similarities of yields, catalyst
type and separation techniques between the tvo processes,  it is believed
that air emissions for the one-stage method should be of the same order of
magnitude as the two-stage method.

    Air pollution released by a plant using the two-stage ethylene oxidation
process can best be described as low.  The main sources of air emissions are
gases vented from the two scrubbers employed in the process.
(1)  According to the Chemical Marketing Reporter for August 20, 1973, the
     current uses for acetaldehyde are:

     Acetic Acid and Anhydride                  5070
     n-Butanol                                  1470
     2-Ethyl Hexanol                            11%
     Other                                      25%

-------
                                      A CD-2
II.  Process Description

     The oxidation of ethylene  to acetaldehyde  is  based  on  the  reaction of
aqueous palladium chloride with ethylene.

     C2H4  +  PdCl2  +  H20   -• ••••  -      >   CH3CHO  +   Pd   +  2  HCl

     There are two versions of  the  process.  In the  'two stage' version,
ethylene is fed into a reactor  with an aqueous  solution  of  palladium  chloride
and cupric chloride.  Ethylene  is oxidized to acetaldehyde,  and cupric
chloride is reduced to cuprous  chloride as a result of its  oxidation  of
palladium back to palladium chloride.  The actual  reaction  scheme is  quite
complex but the basic reaction  reduces to:

     C2H4  +  2 CuCl2  +  H20   -£-£-2	^   CH3CHO  +   2  CuCl   + 2 HCl

     In another reactor, which  constitutes the  second stage,  cuprous  chloride
is oxidized back to cupric chloride with  air completing  the  cycle

     2 CuCl  +  2 HCl  -f  \ 02	>   2 CuCl2  + HO

     In the 'one stage' version oxygen is fed into a reactor  with ethylene.
Both chlorides become catalytic for the reaction and the  total process  takes
place in one reaction vessel.

     C0H.  +  \ 09   PdP12.	>  CHoCHO
      24        ^
     The one stage process requires high purity ethylene and oxygen which could
be a disadvantage depending on the availability of oxygen.
     The following is a description of the tvo-stage ethylene oxidation technique.
The separation methods for the single stage process are quite similar to the
process described below.  The only major difference between the two overall
processes is the method of catalyst regeneration used,and the need for ethylene
recycle in the one stage process.

     (See Figure ACD-I)
     Ethylene is reacted at 10 atm. with a palladium chloride-cuprous chloride
solution in a titanium lined tubular reactor.  Conversion is about 99°/,.  The
acetaldehyde yield is around 9570; 1% of the ethylene does not react and the
remainder forms by-products.  The by-products include chloroacetaldehydes,
ethyl chloride, chloroethanol, acetic and oxalic acids, crotonaldehyde and
chlorocrotonaldehyde.

     The reactor effluent is sent to a flash tower where the pressure is
reduced to atmospheric and the heat of reaction is used to vaporize acetaldehyde
and some water.  The flash tower bottoms containing reduced catalyst solution
is sent to an oxidizing reactor where the catalyst is regenerated by air
oxidation.  Unreacted oxygen, nitrogen and various other organics are purged
off to a scrubber where some product and by-product are recovered and sent to
distillation, while gases leaving the scrubber are vented to the atmosphere.
Regenerated catalyst is returned to the reactor.

-------
                                    ACD-3
     Flashed gas passes to a crude acetaldehyde still where acetaldehyde is
distilled to 60 - 90%.  Light ends are removed next, in another column.  Gas
exiting from the top of this tower is water scrubbed and then vented to the
atmosphere.   The acetaldehyde leaves the bottom of the light ends column and
enters a finishing column where chloroaldehydes, water and other undesirables
are removed.  Finished acetaldehyde is taken overhead and sent to storage.

     A  material balance and information on the heat liberated by reaction can
be found in Tables I and II, respectively.

-------
                                    ACD-4
III.  Plant Emissions

      A.  Continuous Air Emissions

          1.  Regenerator Off-Gas Scrubber Vent

              After the catalyst is regenerated with air the gaseous stream is
          purged from the reactor system and scrubbed to recover vater
          soluble organics, while the solution of regenerated catalyst is
          returned to the reactor.  The stream leaving the scrubber is
          vented to the atmosphere.  Since nitrogen in the air does not
          react, it is the primary component present in the vent gas.
          Quantities of argon,  unreacted oxygen,  vater,  carbon dioxide and
          smaller amounts of methyl and ethyl chloride also enter the atmosphere
          through this vent.  Total hydrocarbon emissions are reported to be
          .00045 Ibs./lb. acetaldehyde from this  source.

          NOTE:   Calculations made by Houdry shov that it is possible that
                 the average flov rate of this stream could be tvice as
                 high as that claimed by the respondent.

          2.  Light Ends Scrubber Vent

              Light ends consisting of nitrogen,  carbon dioxide, ethylene,
          methyl and ethyl chloride and vater soluble oxygenated hydrocarbons
          including acetaldehyde and acetic acid  are removed from the
          system by crude distillation and light  ends distillation and are
          sent to a vater scrubber.  Water soluble vapors are removed in the
          scrubber and the insoluble gas is vented to the atmosphere.   The
          air pollutants released through this vent are methyl chloride,
          ethyl  chloride and ethylene.  Hydrocarbon emissions are usually
          around .00047 Ibs./lb. acetaldehyde from this source but emissions
          could  vary because the flov rate can change by 500%.

      B.  Intermittent Air Emissions

              No sources of intermittent air emissions vere reported by the
          respondent.

      C.  Continuous Liquid Wastes

              Approximately 150 GPM of waste vater is discharged.   The
          effluent is  treated in biological aerated ponds vith solar
          evaporation.

      D.  Solid  Waste

              About one ton  of solid vaste, consisting mainly of spent
          catalyst,is  disposed  of in a sanitary land fill, per day.

      E.  Odor

              In general the ethylene process for the production of acetaldehyde
          does not appear to present an odor problem.   No community complaints
          have been reported.

-------
                              ACD-5
F.  Fugitive Emissions and Storage Losses

    The respondent reports that losses due to leaks and spills are
too small to measure.

    Acetaldehyde storage tanks are vented to a scrubber so no
acetaldehyde enters the atmosphere from the storage area.

-------
                                    ACD-6
IV.  Emission Control

     Usually efficiencies are calculated for any emission control device
reported, but since the only respondent to the questionnaire failed to supply
information about the composition and flow of the inlet streams to the devices
employed, it was impossible to do so.  A brief description of these devices
follows:  Details concerning the emission control equipment employed can be
found in Table IV - Catalog of Emission Control Devices.

     Scrubbers

     A.   Off Air Scrubber

         This scrubber removes any soluble organics such as acetaldehyde,
     acetic acid and chloroaldehydes which may be present in the nitrogen
     and unreacted oxygen stream which is purged from the reaction area.  Since
     no acetaldehyde, acetic acid or chloroacetaldehyde are present in the
     vent gas, the efficiency of removal for these components is 1007«.  The
     liquid outlet from this scrubber is sent to the purification system.

     B.   Light Ends Scrubber

         Light components from the crude still, light ends column and product storage
     tanks are sent to this scrubber for soluble organics recovery.   The
     liquid effluent is returned to the purification system.  Almost all
     soluble components are removed by this scrubber.

     C.   Water Insolubles

         Both of the above vent streams contain traces  of methyl and ethyl
     chlorides and the light ends scrubber vent also contains unreacted
     ethylene.  All three of these chemicals are only slightly soluble in
     water so the efficiency relative to each is near zero percent.

-------
                                     ACD-7
V.  Significance of Pollution

    It is recommended that no in-depth study of the ethylene process for
acetaldehyde be made at this time.  The reported emission data indicate
that the ouantity of pollutants released to the atmosphere as air emissions
is less for the subject process than for processes currently under in-depth
study.

    The methods outlined in Appendix IV of this report have been used to
estimate the total weighted annual emissions from new plants.  This work is
summarized in Tables V, VI and VII.  The growth projection is based on the
assumption that all new acetaldehyde plants will use the ethylene process.

    On a weighted emission basis a Significant Emission Index of 96  has
been calculated in Table VII.   Hence, the recommendation to exclude the
subject process from the in-depth portion of the work for this project.

    However, it should be noted that reported emissions, especially of ethylene,
do not agree with literature reports on the ethylene conversion of 9970.
Since the process is "once-through" with respect to ethylene, one volume
percent of unconverted ethylene would be equivalent to nearly 0.007 Ibs. of
ethylene vented/lb.  of acetaldehyde product (at 95% yield).   On this basis,
the calculated  SEI would increase to about 780.

-------
VI.  Acetaldehyde Producers
     The following tabulation of acetaldehyde producers indicates production capacity by company, location
and process.
Celanese
Commercial Solvents

Du Pont

Eastman


Goodrich

Hercules

Monsanto

Publicker

Union Carbide
                                                    Butane
                                                    Propane
Bay City, Texas
Bishop, Texas
Pampa, Texas
Clear Lake, Texas

Agnev, California

Belle, W. Va.

Kingsport, Tenn.
Longviev, Texas

Calvert, City

Parlin, N. J.

Texas City, Texas

Philadelphia, pa.

Institute, W. Va.       )
South Charleston, W. Va.)
Texas City, Texas       )
By-Product    Ethanol
                                                                    10
    10
                                                                   Ethylene
                                                                   1 Stage
                200
                 35
                 80
                                                                                650
Ethylene
2 Stage

   210
                                                                                                            500
                                             450
                                                    8
                                                    oo
                                               Total MM Lbs./Yr.
    26
                                                         966
  1,160

-------
PAGE NOT
AVAILABLE
DIGITALLY

-------
Stream I. D. No.
Stream
Component
Ethylene
Air
1) Nitrogen
2) Oxygen
3) Argon
Make-Up HCl
Ace t aldehyde
Carbon Dioxide
Water
Methyl Chloride
Ethyl Chloride
Chloroaldehydes
Acetic Acid
i 2 :
Ethylene Feed Air Make-Up

.6570
1.3739
.4209
.0233
.0100
.0323






                      .6570            1.8181

                     Total  In =  2.5174
                                                          (2)
                                                                                 TABLE ACD-I
                                                                               MATERIAL  BALANCE
                                                                               T/T ACETALDEHYDE
                                                                                     VIA
                                                                               ETHYLENE  PROCESS

                                                                                 45                       6

                                                                        Off-Air Scrubber Vent ' '  Light  Ends Scrubber  Vent ^ ' By-Products
                                                                        1.3739
                                                                         .0086
                                                                         .0233
                                                                                                    .0013
                                                                         .0166

                                                                         .0001

                                                                         .0008

                                                                         .0001
.0423                 1.4234

Total Out T 2.5174
                                                .0230

                                                .0001

                                                .0004

                                                .0008
                                                .0256
.0187

.0015

.0202
                                                                                         Water  to V'apte  fl)      Product
                .0482
                .0482
                                                                                                                                                                     1.0000
                                     1.0000
(1)   Water formed by side combustion reactions  and water from make-up HCl  solution  only;  recycled water and other process water introduced into the system not
     included;  contains some hydrocarbon.

(2)   Contained  in recycled water used as HCl diluent.

(3)   Vent streams show emissions somewhat greater than reported in the single questionnaire.

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                                   TABLE AGO-II
                                  HEAT BALANCE
                                  ACETALDEHYDE
                                      VIA,
                                ETHYLENE PROCESS

      There is insufficient information available on which to base an overall
heat balance for this process.
      Overall Heat of Reaction for Reaction and Regeneration Steps

      C2H4 (g) + \ 02 (g) 	>   CH3CHO (g)


       H =  2,210  BTU/lb. acetaldehyde

-------
                                                                                   TABLE ACD-III
                                                                            NATIONAL EMISSIONS INVENTORY
                                                                                    ACETALDEHYDE
                                                                                        VIA
                                                                                  ETHYLENE PROCESS
EPA Plant Code No.
Capacity - Tons of Acetaldehyde/Yr.
Production - Tons of Acetaldehyde/Yr.
Emissions to the Atmosphere
   Stream I. D. No.
   Stream
   Flov - Lbs./Hr.
   Flov Characteristic - Continuous or Intermittent
       if Intermittent - Hrs./Yr.
   Composition - Tons/Ton of Acetaldehyde
       Ethylene
       Methyl Chloride
       Ethyl Chloride
       Carbon Dioxide
       Vater
       Nitrogen
       Argon
       Oxygen
   Analysis
       Sample Tap Location
       Frequency of Sampling
       Type of Analysis
       Odor Problem
   Vent Stacks
       Number
       Height - Ft.
       Diameter - Inches
       Exit Gas Temperature - F°
       SCFM
   Emission Control Devices
       Type
   Summary of Air Pollutants
       Hydrocarbons - Ton/Ton of Acetaldehyde
       Particulates - Ton/Ton of Acetaldehyde
       NOX - Ton/Ton of Acetaldehyde
       SOX - Ton/Ton of Acetaldehyde
       CO  - Ton/Ton of Acetaldehyde
                             1-2
                           225,000
                           220,000
Regenerator Off-Gas
Scrubber "ent

40,871 (1)
Continuous
 .00041
 .00004
 .00828
 .00040
 .74524
 .01288
 .00430
Yes
 In stream
C2H^ & C02 Continuous - Others Weekly
CjH4 Infrared - Others Chromatograph
No
Yes
2 (3)
 100
 16
59
4500
Yes
Scrubber

                             .00092
                                0
                                0
                                0
                                0
Light Ends
Scrubber "ent

2675 d)
Continuous
 00025
 00007
.00015
.00459

.00502 (2)
Yes
In stream
C^HA & C02 Continuous - Others Weekly
C.2^b & C02 Infrared - Others Chromatograph
No
Yes
2 (3)
80
4
59
50
Yes
Scrubber
 (1)  Plant has two identical systems so actually two identical scrubbers of this type are employed.
 (2)  From acetaldehyde storage tank purge.
 (3)  For each scrubber.
                                                                                                     Flow is total for each scurbber.

-------
ABSORBERS /SCRUBBERS
   EPA Code No. for plant using
   Flow Diagram (Fig. ACT-I) Stream I. D.
   Control Emission of
   Scrubbing/Absorbing Liquid
   Type - Spray
          Packed Column
          Column w/Trays
   Scrubbing/Absorbing Liquid Rate - GPM
   Operating Temperature - F°
   Gas Rate - SCFM
   T-T Height - Ft.
   Diameter - Ft.
   Washed Gases to Stack
          Stack Height - Ft.
          Stack Diameter - Inches
   Installed Cost - Mat'l. 6, Labor - $
   Installed Cost based on "year" - $
   Installed Cost - c/lb. of Acetaldehyde/Yr.
   Operating Cost - Annual - $ - 1972
   Value of Recovered Product - $/Yr.
   Net Operating Cost - c/lb. of Acetaldehyde
   Efficiency - "I, - SE
   Efficiency - % - SERR
                                                                                      TABLE  ACD-IV
                                                                        CATALOG OF EMISSION CONTROL DEVICES
                                                                                    ACETALDEHYDE
                                                                                        VIA
                                                                                  ETHYLENE PROCESS
(D
1-2
 A
Organic Vapors (2)
Water

Yes
62.5 - 140
4500 - 8000
90
5
Yes
100 (3)
16
410,000     490,000
1965        1969
       .20
45,000
Unknown
       .01
(D
1-2
 B
Organic Vapors (2)
Vater

Yes
     - 140
     250
62.5
50 -
70
3
Yes
80 (3)
4
255.000
1965
      .12
26,500
Unknown
      .006
            275,000
            1969
(1)  Two identical scrubbers of each type are employed.  Specifications are for each scrubber; a total of four scrubbers are used for emission control in the
     process.  Cost figures are the combined costs for two identical scrubbers.

(2)  Acetaldehyde, acetic acid and some chlorohydrocarbons.

(3)  Each scrubber has two stacks, each stack has specifications shown.

-------
TABLE ACD-VI
Emission

Hydrocarbons
Participates
NOX
sox
CO
EMISSION SOURCE SUMMARY
ACETALDEHYDE
VIA
ETHYLENE PROCESS
Source
Regenerator Off-Gas
Scrubber Vent
. 00045
0
0
0
0

Light Ends
Scrubber Vent
.00047
0
0
0
0
Total

.00092
0
0
0
0

-------
1160
                                                TABLE ACD-V
Current Marginal
Capacity Capacity
NUMBER OF NEW PLANTS BY
ACETALDEHYDE
VIA
ETHYLENE OXIDATION
Current
Capacity
on-stream Demand
in 1980 1980
1980
Capacity
1980
Capacity
to be
Added
Economic
Plant
Size
Number
of Nev
Plants
1160
2460 (1)
2460
1300 (2)
250
5-6
(1)   For ethylene process.




(2)   Based on studies prepared for the EPA by  Process Research,  Inc.

-------
TABLE ACD-VII
Chemical
Process
Increased Capacity
Pollutant
Hydrocarbons
Participates
NOX
S°x
CO
WEIGHTED EMISSION RATES
Acetaldehyde
Ethylene
1300 MM Lbs./Year
Emissions Ib./lb. Emissions MM 11
.00092 1.2
0 0
0 0
0 0
0 0
                               Weighting         Weighted Emissions
                               Factor            MM Ibs./yr.	

                               80                     96

                               60                      0

                               40                      0

                               20                      0

                                1                     _0

                         Significant Emission Index = 96

-------
Acetaldehyde via Ethanol

-------
                              Table of Contents

Section                                                           Page  Number

I.    Introduction                                                  AC-1
II.   Process Description                                           AC-2
III.  Plant Emissions                                               AC-3
IV.   Emission Control                                              AC-5
V.    Significance of Pollution                                     AC-6
VI.   Acetaldehyde Producers                                        AC-7

                        List of Illustrations  and  Tables
      Flow Diagram                                                Figure AC-I
      Net Material Balance                                        Table AC-I
      Gross Heat Balance                                          Table AC-II
      Emission Inventory                                          Table AC-III
      Catalog of Emission Control Devices                          Table AC-IV
      Number of New Plants by 1980                                Table AC-V
      Emission Source Summary                                     Table AC-VI
      Weighted Emission Rates                                     Table AC-VII

-------
                                     AC-1
I.   Introduction

    Acetaldehyde (CH3CHO) is a mobile, colorless, inflammable liquid with
a pungent, choking odor.  It was first noticed by Scheele in 1774 and rec-
ognized as a new compound by Foucroy and Vaughelin in 1880.

    Most acetaldehyde is used as an intermediate in the manufacture of other
organic compounds.   The largest single outlet accounting for more than half
of the acetaldehyde use, is the manufacture of acetic acid.   Other processes
which utilize it as a raw material are the production of butyl alcohol,
butyraldehyde, chloral and pyridine.

    There are four ways that acetaldehyde can be made industrially.  They
are the oxidation or dehydrogenation of ethanol, oxidation of ethylene in
one or two stages,  propane-butane oxidation and acetylene hydration.   The
oxidation or dehydrogenation of ethanol and ethylene oxidation are the major
processes currently used.  Ethylene oxidation is a relatively nev method
which is more attractive financially than ethanol oxidation because it
utilizes a cheaper raw material.  Although acetaldehyde via ethanol plants
constitute 43.8% of the current capacity of 2.4 billion Ibs./year no new
plants of this type have been built in the last five years or are expected
to be built in the future.

    Atmospheric emissions generated by the ethanol process are associated
primarily with the absorber vent gas stream.   All other sources of emissions
are minimal.

    It should be noted that this report is based on the responses of one
questionnaire.  The only respondent was a plant using ethanol oxidation and,
therefore, the straight dehydrogenation of ethanol is covered only briefly in
Section V.

-------
                                      AC-2
II.   Process Description

     Acetaldehyde is produced by passing ethanol vapors and preheated air
over a suitable catalyst, preferably silver, at 300 - 575° C.

     Two possible reactions occur to varying degrees depending on the
reactor environment.

     (1)  C2H50H + \ 02 -••  ->  CH3CHO + H20    H = -40.55 kcal./g-mole

     (2)  C2H5OH •••	>  CH3CHO + H2           H = +17.28 kcal./g-mole

     Industrially oxidation, a combination of oxidation and dehydrogenation
and straight dehydrogenation (which is not covered in this report) are used.
The reactor temperature depends on the air-ethanol-steam ratio and the
velocity of the gas over the catalyst.  Overall alcohol conversion varies
from 25 - 45% and yields are 85 to 95%.  Small amounts of acetic acid and
1-butanol are also formed.  Many times dilute acetic acid is recovered as
a by-product.

     The gases leaving the reactor, after passing through a condenser, go to
a phase separator.   The vapor phase is absorbed in refrigerated water, and
the wash is combined with the liquid phase.   The combined stream is fractionated
into acetaldehyde and a water-ethanol mixture, which is further separated into
ethanol, which is recycled,  and waste acetic acid can be recovered from the
waste.

-------
                                     AC-3
III.   Plant Emissions

      A.  Continuous Air Emissions

          1.  Absorber Vent

              The emissions from this vent constitute the most important
          source of air pollution associated with the production of
          acetaldehyde by oxidation.  In comparison, all other sources of
          air pollution are minimal.

              The vent stream is composed primarily of nitrogen.  Small
          quantities of water, carbon dioxide, carbon monoxide, hydrogen
          methane and oxygen are also present.  Plant 1-1 reports the
          following emissions from the scrubber vent stream.

          Component                            Lbs./Lb. Acetaldehyde

            Water                                     .00088
            CO                                        .00271
            C02                                       .00934
            H2                                       1.12450
            CH4                                       .01950
            02                                        .02240

              A more complete description of emissions can be found in
          Table III.

      B.  Intermittent Air Emissions

          1.  Combustion of Fuel for Reactor Start-Up

              The respondent reports that 480,000 CF/year of natural gas with
          sulfur content of 2.0 grains/100 CF are needed to start the reactors,
          If the sulfur content of this fuel is fully converted into sulfur
          dioxide, it would produce 2.8 Ibs of S02 per year, which is
          1.6 x 10~8 Ibs. S02/lb. product.  This quantity is considered
          negligible.

          2.  Ethanol Storage Tank Vent

              Inert gases are periodically purged from the ethanol storage
          tank.  During venting small amounts of ethanol are released to the
          atmosphere.  Lack of data prevents the calculation of emission
          rates, but this vent could not be considered a significant emission
          source.

      C.  Continuous Liquid Wastes

              16,000 gallons per hour of waste water is produced.  The
          respondent reports that waste water is treated on-site.

      D.  Solid Wastes

              No solid wastes are produced by this process.

-------
                               AC-4
E.  Odor

        No odor problems were reported for the ethanol oxidation
    process for the production of acetaldehyde.

F.  Fugitive Emissions

        No sources of fugitive emissions were reported.  If they
    exist, they are probably due to minor losses of acetaldehyde
    and/or ethanol due to pump seals and occasional piping leaks.
    The actual amount is considered negligible.

-------
                                     AC-5
IV.  Emission Control

     The only emission control device reported is a scrubber system.  It is
summarily described in Table IV of this report.  Two types of efficiencies
have been calculated.

     1)  SE - Specific Efficiency

         SE = specific pollutant in - specific pollutant out   ,„„
                           specific pollutant in

     2)  SERB. - Significance of Emission Reduction. Rating
         SERR = (pollutant x weighting factor)in - (pollutant x weighting
                                             	factor*)out	
                            (pollutant x weighting factor)in
x 100
     A more complete description of the rating system can be found in Appendix V
of this report.

     ^weighting factor same as Table VII weighting factor.

     Absorbers

       Although the respondent lists the two scrubbers as emission control
     devices their primary function is the recovery of acetaldehyde and
     ethanol.  Alcohol and acetaldehyde recovery is 100 percent while
     practically no CO is removed.   However, the SERR is greater than 99.9
     percent because of the relatively small quantity of CO present as well
     as its low weighting factor.

-------
                                     AC-6
V.  Significance of Pollution

    It is recommended that no in-depth study of this process be undertaken
at this time.  This conclusion is drawn for two reasons.

    1)  The reported emission data indicate the quantity of pollutants
        released as air emissions is less for the subject process than
        for other processes that are currently being surveyed.

    2)  No new plants are expected to be built using ethanol as the starting
        material„  New production will probably rely on the ethylene oxidation
        processes which are already taking a large role in acetaldehyde
        production.  Some of the advantages of using the ethylene oxidation
        processes are listed below:

        a)  Uses a less expensive starting material - ethylene.

        b)  Utilizes a shorter route from hydrocarbon to acetaldehyde.

        c)  Products yields of approximately 95 percent.

        d)  Operates at lov; temperatures and pressures.

    The outlook is for acetaldehyde capacity to grow to three to five billion
pounds per year by 1980, which will require four or five new plants which are
expected to be of the ethylene oxidation type.

    The methods outlined in Appendix IV of this report have been used to
estimate the total weighted annual emissions from new plants.  This work is
summarized in Tables V, VI and VII.

    On a weighted emission basis a Significant Emission Index of zero has
been calculated in Table VII, due to the fact that no new ethanol oxidation
plants are expected to be built.  Since the total emissions from this process
are small and no growth is anticipated, it is recommended to exclude
acetaldehyde production via ethanol oxidation for an in-depth study.

    In passing, something should be said about the straight ethanol dehydro-
genation process which is not covered in this report.  Due to the fact that
no oxygen is introduced in the system it appears that the total amount of
emissions released to the atmosphere should be minimal.  This prediction is
confirmed by limited data made available by the EPA, Raleigh, N. C.  Emissions
from a typical ethanol dehydrogenation plant are;  A once/week vent for one
minute at a rate of 50,000 CFH of a stream whose typical composition is:

                 Component                    Volume %

                 Hydrogen                       98.5
                 Methane                          .8
                 Carbon Monoxide                  .3
                 Ethane                           .1
                 Carbon Dioxide                   .3

        The plant mentioned produced 27,190 Ibs./hr. of acetaldehyde.  The
quantity of emission is quite small in comparison to other processes studied.

-------
VI.  Acetaldehyde Producers
     The following tabulation of acetaldehyde producers indicates published production capacity by company,
location and process.
      Company

Celanese
Commercial Solvents

Du Pont

Eastman


Hercules

Monsanto

Publicker

Union Carbide
        Location

Bay City, Texas
Bishop, Texas
Pampa, Texas
Clear Lake, Texas

Agnew, California

Belle, W. Va.

Kings port, Tenn.
Longview, Texas

Parlin, N. J.

Texas City, Texas

Philadelphia, pa.

Institute, W. Va.       )
South Charleston, W. Va.)
Texas City, Texas       )
Butane -
Propane
By-Product    Ethanol
                                                                    10
                10
                           200
                            35
                            80
                                                                               650
Ethylene
1 Stage
Ethylene
2 Stage

210 (1962)
                                                                                                         500
                                                     500  (1970)
                                                Total MM Lbs./Yr. = 25

                                                    7o Grand Total =1.3
                                                        966

                                                        43.8
                                                     1,210

                                                     54.9

-------
PAGE NOT
AVAILABLE
DIGITALLY

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                                                 TABLE AC-I
Stream I.  D. No.




Ethanol

Acetaldehyde

Water/Steam

Oxygen

Carbon Monoxide

Methane

Carbon Dioxide

Hydrogen

Nitrogen

Acetic Acid

Oxygenatic Organics

    Total
Fresh
Feed
1.1066
               Water
               .0592
               .0897
ACETALDEHYDE
VIA
ETHANOL OXIDATION
MATERIAL BALANCE - T/T OF ACETALDEHYDE
23 4
Recycle Gross
Ethanol Air Feed
.0592 1.1658

.0897
.3575 .3575




1.1769 1.1769


5
Reactor
Effluent
.0592
1 . 0000
.4920
.0224
.0027
.0020
.0093
.0149
1.1769
.0032
.0073
1.1066
               .0897
                             .0592
                                             1.5334
                                                            2.7899
                                                                           2.7899
                                                                                           Off-Gas
                                                                                             .0009

                                                                                             .0224

                                                                                             .0027

                                                                                             .0020

                                                                                             .0093

                                                                                             .0149

                                                                                           1.1769
                                                                                           1.2291
                                                                                                          Product
                                                                                                          1.0000
By-Product
5% Acid        Waste
                                                                                                                        .0638
                                                                                                                        .0032
                                                                                                          1.0000        .0670
                                                                                                                                       .4273
                                                                                                                                       .0073
                                                                                                                                       .4346

-------
                                  TABLE AC-II
                                 ACETALDEHYDE
                                     VIA.
                              ETHANOL OXIDATION

      There are not sufficient data to permit the construction of an overall
heat balance for this process.

                          Heat Generated by Reaction

      C2H5OH  +  % 02 	>  CH3CHO  + H20      H - -44.55 kcal./mole

      C2H5OH   	   •*» CH3CHO  +  H20           H » +17.28 kcal./mole


      97.8% Oxidation
       2.2% Dehydration

      Heat evolved by reaction •» J.,763 BTU/lb. acetaldehyde

-------
EPA Plant Code No.
Capacity, Tons of Acetaldehyde/Yr.
Range in Production - 7. of Max.
Emissions to Atmosphere
   Stream

   Flov - Lbs./Hr.
   Flov Characteristic - Continuous or  Intermittent
      if Intermittent - Hrs./Yr.
   Composition - Tons/Ton of AccraIdehyde
      Methane
      Carbon Monoxide
      Carbon Dioxide
      Hydrogen
      Nitrogen
      Oxygen
      Water
   Sample Tap Locations
   Frequency of Sampling
   Type of Analysis
   Odor Problem
Vent Stacks
   Flov - SCFM/Stack
   Number
   Height - Feet  (elev. (? tip)
   Diameter - Inches
   Exit Gas Temperature - F°
Emission Control Devices
   Type
Summary of Air Pollutants
   Hydrocarbons - Ton/Ton AcetaIdehyde
   Particulates - Ton/Ton Acetaldehyde
   NOX - Ton/Ton Acetaldehyde
   SOX - Ton/Ton Acetaldehyde
   CO  - Ton/Ton Acetaldehyde
        TABLE AC-III
NATIONAL EMISSIONS INVENTORY
        ACETALUEIIVnE
            VIA
     ETIIAN'OL OXIDATION

            1-1
            90,000
            Not Specified

            Absorber Vent

            24,42fa
            Continuous
            .00195
            .00276
            .00934
            .01491
           1.12450
            .02239
            .00934
            Not Specified
            Three times per week
            Gas Chromatography
            No

            6,500
            3
            75
            792
            45

            Two water scrubbers

            0
            0
            0
            0
            .00276

-------
ABSORBER/SCRUBBER
   EPA Code No. for plant using
   Flow Diagram (Fig. I) Stream I. D.
   Control Emission of
   Scrubbing/Absorbing Liquid
   Type - Spray
          Packed Column
          Column w/trays*
             Number of trays
             Tray type
          Other
   Scrubbing/Absorbing Liquid Rate - CPM
   Design Temp. (Operating Temp.) F°
   Gas Rate - SCFM
   T-T Height-, Ft.
   Diameter - Inches
   Washed Gases to Stack**
          Stack Height - Feet
          Stack Diameter - Inches
   Installed Cost - Mat'1. & Labor - $
   Installed Cost based on - "year" - $
   Installed Coat c/lb. of acetaldehyde/Yr.
   Operating Cost - Annual - $ -  1972
   Value of Recovered Product - $/Yr.
   Net Operating Cost - c/lb. of Acetaldehyde
   Efficiency - % - SE
   Efficiency - 7. - SERR
                                                                                    TABLE AC-IV
                                                                        CATALOG OF EMISSION CONTROL DEVICES
                                                                                    ACETALDEHYDE
                                                                                        VIA
                                                                                 ETHANOL OXIDATION
           1-1
            6
Water Soluble Organics
          Water
       29
       Bubble Cap
25
Bubble Cap
       170         170
       45°         45°
       6,500       6,500
       Not Specified
       96          60
       No          Yes
                   75 ft.
                   3 at 66 each
       80,000      95,000
       1938        1940
             .102
             55,330
           2,275,000
          (2,219,670)
             100
             99.9+

-------
Current
Capacity
(1)
   2,402
              (2)
                                             TABLE AC-V
                                    NUMBER OF NEV PLANTS BY 1980
                                  ACETALDEHYDE VIA ALL PROCESSES


Marginal
Capacity
Current
Capacity
on-stream
in 1980


Demand
in 1980

Capacity
to be
Added

Economic
Plant
Size

Number
of Nev
Plants
2,202 (3)
3,500 (4)
1,298
                      ACETALDEIIYDE ETHANOL OXIDATION AND/OR DEHYDROGENATION
   200
Current
Capacity

966 (5)

Marginal
Capacity
Current
Capacity
on-stream
in 1980

Demand
in 1980

Capacity
to be
Added

Economic
Plant
Size

Number
of Nev
Plants
               '2)
966
966 (6)
   0
100
0
(1)   All capacities in MM Ibs./year.
(2)   No data is available.
(3)   Assumed 0 marginal capacity - it is possible that all plants using the ethanol process will be  operating
     since many manufacture acetic acid directly from the acetaldehyde produced.
(4)   C & E News, May 17, 1971.
     The Petrochemical Industry Markets & Economics, 1970.
(5)   Include acetaldehyde produced by straight dehydrogenation.
(6)   Assumes no nev ethanol plants will be built and no capacity will be lost.

-------
TABLE AC-VI
Emission

Hydrocarbons
Participates
NOX
sox
CO
EMISSION SOURCE SUMMARY
T/T OF ACETALDEHYDE
Source
Absorbent Vent Fuel for Reactor
0
0
0
0
.00276

Start-Up
3
fl>
OQ
H-
(TO
cr
t-1
R>



Ethanol Storage Vent
2!
n
OQ
H-
IK
cr1
i-*
«t)



-------
                                            TABLE AC-VII
Chemical
Process
WEIGHTED EMISSION RATES
Acetaldehyde
Ethanol Oxidation

Increased Capacity* 0.0 Lbs./Yr.
Pollutant
Hydrocarbons
Particulates
NOX
SOX
CO
Increased Emissions
Emissions Lbs./Lb. MM Lbs. /Year
None
None
None
Negligible
.00276 0.0
Weighting Weighted Emissions
Factor MM Lbs. /Year
80
60
40
20
1 0.0
                                                                    Significant Emissions Index *• 0.0 MM Lbs./Yr.
NOTE
••-No new ethanol oxidation or dehydration plants are expected to be built.

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Acetic Acid via Methanol

-------
                              Table of Contents

Section                                                          Page Number

I.    Introduction                                                  HAC-1
II.   Process Description                                           HAC-2
III.  Plant Emissions                                               HAC-3
IV.   Emission Control                                              HAC-5
V.    Significance of Pollution                                     HAC-6
VI.   Acetic Acid Producers                                         HAC-7

                       List of Illustrations and Tables

      Flow Diagram                                               Figure HAC-1
      Net Material Balance                                       Table EAC-I
      Gross Heat Balance                                         Table HAC-II
      Emission Inventory                                         Table HAC-III
      Catalog of Emission Control Devices                        Table HAC-IV
      Number of New Plants by 1980                               Table HAC-V
      Emission Source Summary                                    Table HAC-VI
      Weighted Emission  Rates                                   Table HAC-VII

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                                   MAC - 1
I.   Introduction

    Acetic acid passed the billion Ib./year mark ten years ago and has
continued to be one of the fastest growing of all chemicals.   All of the
grovth in acetic acid production for the past 20 years has been via nev
synthetic routes.   Destructive distillation of vood to give acetic acid,
methanol and by-products is a dying process and has been on a steady
decline since 1950.  There are three main synthetic processes currently
in use for acetic acid production in the United States.

                                                             Approximate 70
               Process                    Raw Materials      of 1972 Production

1.   Oxidation of hydrocarbons (LPG)       mainly butane               43
2.   Oxidation of acetaldehyde             acetaldehyde                31
3.   Carbonylation of methanol             CF^OH and CO                16

    The largest single use for acetic acid is in the production of acetic
anhydride which, in turn, goes into the production of cellulose acetate for
fibers.  A second large use is the production of vinyl acetate used in vinyl
plastics, paints,  adhesives and textile finishes.  Acetate esters, chloroacetic
acid, nylon and acrylic fibers (chain terminator), and pharmaceuticals make
up the rest of the major uses of acetic acid.

    This report covers acetic acid made from the newest of the synthetic
routes, carbonylation of methanol.  Reactants for this process are methanol
and a "synthesis gas" composed mainly of Ho, CO, COo and hydrocarbons.  Two
variants of the process are in use; both are moderate temperature (480° F)
liquid phase reaction but pressures range from comparatively low to near
10,000 PSI.  A brief scanning of the reactants used shows that this process
could be a large source of air pollution if excess snythesis gas were vented
directly to the air.  However, since reactants and products are hydrocarbons
or oxygen containing organics only, proper flaring or incineration of
vented gases will produce only C02 and water with no NOX or SO .   This
appears to be the case for the data supplied by the respondents indicating
little or no pollutants emitted from these plants.  Of course, since
atmospheric air is required in the flaring operation, some NOX is probably
produced by oxidation of the atmospheric nitrogen.

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                                   MAC - 2


II.  Process Description

     The main reaction involved in the carbonylation of methanol is-

                                     ,0
     CH3OH + CO 	>•  CH3 C/
                                    XOH
     a by-product reaction also gives

     CO + H20  	>   COo + H2

     Other by-products formed are methyl acetate, dimethyl ether, formic
acid, propionic acid and vater.  All secondary reactions are reversible,
fortunately, and can be minimized or eliminated by proper choice of operating
conditions.  The first successful process involving the carbonylation of
methanol in the U. S. vas the BASF process vhich uses temperatures around
500° F and pressures of 7500 to 10,000 PSI.   It is a liquid phase reaction.
Choice of catalyst is highly critical for good yields.   Cobalt Iodide is
one such catalyst.  Monsanto uses a similar process but their catalyst,
reportedly a "Rhodium and Iodine containing system" from the literature,
enables them to carry out the reactions at a much lower pressure than the
BASF process.

     Reacted products are stripped of light ends, scrubbed and vented to
the air via a flare or incinerator.  There is a recycle stream back to the
reactor.  Crude acetic acid is then purified by distillation.  Either
conventional rectification vith a "vet acid" recycle stream or azeotropic
distillation is used.  Most by-products are returned to the reaction system
v?here they become recycled to extinction.  A "heavy" SLream of mixed acetic
and propionic acids is   removed from the distillation section and incinerated.
Ultra pure (99.8+7,,) acetic acid is the main product.

     Yields of 99+% of acetic acid on methanol and over 907 on CO are reported
in the literature and data from the respondents confirm these figures.   Only
small amounts of by-products are produced.

-------
                              HAC - 3


III.   Plant Emissions

      A.   Continuous Air Emissions

          1.   Purification Section Vents

              Light ends and unreacted (or excess) synthesis gases are
          scrubbed and flared or incinerated by both respondents.   No data
          are available on the composition of the combusted gases.   However,
          analyses are available for the gas streams as they go to incineration.
          If the incinerator (flare) is operating properly and is  well designed
          for complete combustion, there is no reason to believe that these
          gases will not be converted completely to CC>2 and water.  No
          nitrogen or sulfur compounds are present.  Possibly some CO could
          be emitted but this should be minimal with a good incinerator or  flare.
          As a result, we have assumed pollutant emissions from this source as
          nil, except  for 20 to 40  ppm of NOX generated by the oxidation  of
          atmospheric  nitrogen.
      B.   Intermittent Air Emissions

          1.   Catalyst System Purge Gas

              One respondent reports an intermittent purging of his catalyst
          make-up system with air.  Some iodine vapor (0 - 1000 PPM) escapes
          with the air.  This is reported as completely removed by a sodium
          carbonate absorber and, hence, emissions from this source are nil.

      C.   Continuous Liquid Wastes

              A stream of mixed acetic and propionic acid is removed from the
          purification section and  sent to incineration.  No data  are available
          on the incinerated gases  from this stream.  Apparently,  both
          respondents  sent this stream to a plant incinerator along vith other
          waste streams.  There is  nothing about this stream that  would
          preclude it being burned  completely to C02 and water only.  Once
          again, emission of pollutants would be nil.

      D.   Solid Wastes

              There were no solid waste reported for this process.

      E.   Odors

              When operating properly, there does not seem to be an odor
          problem associated with this process.  All vent gases are incinerated
          to C02 and water.  Only one respondent indicated a possible odor
          problem.  In this plant ("presumably the other plant has  a similar
          vent) there  is an emergency vent in the purification system which
          vents pure acetic acid vapor to the atmosphere for 10 -  15 minutes
          in the event of a total power failure.  In this emergency condition,
          the odor of acetic acid was obviously evident in and around the plant
          but no complaints were reported.  This appears to be only isolated
          instances so in general,  the plant seems to be relatively clean and
          free of atmospheric pollutants.  Some emergency vents are flared.

      F.   Fugitive Emissions

              No fugitive emissions are mentioned.  Since both plants handle gas
          streams containing CO, one would imagine that any leaks  whatsoever

-------
                            HAG - 4


    would receive prompt attention, if only for operator safety.

G.  Other Emissions

        One respondent has a vapor conservation system consisting of
    a nitrogen blanket and conservation vents on all product and raw
    material storage tanks.  They vent to the atmosphere during
    filling or from solar heating.  No estimate of emissions was
    made, but some must occur.

-------
                                   HAC - 5


IV.  Emission Control

     Emission control devices employed in this process are summarized in
Table IV.  Unfortunately, there are very little data available on these
devices, as is true with most incineration systems.   As mentioned previously,
composition of the streams going to incineration or flaring are such that
complete combustion would lead to only CC>2 and water.  Calculation of any
efficiencies or emission indices for these devices in the absence of flue
gas composition becomes meaningless for one can only assume 100% combustion
and, therefore, 100% efficiency, except for some formation of NOX.

     One respondent uses a sodium carbonate absorber to remove iodine vapor
from purge air from his catalyst preparation system.  This is an intermittent
stream and is reported as 100% absorbed in the sodium carbonate.   Its  efficiency
is, therefore, 100%.

-------
                                   HAC  -  6
V.  Significance of Pollution

    We recommend that no in-depth study of this process be made.  Present
technology is more than adequate to give a virtually air pollutant free
plant if the devices are used properly.  All vaste streams are capable of
incineration to C02 and water.   Assuming that any new plant using this
process would employ similar pollution control devices, there should be no
atmospheric emissions from this process other than emergency venting due
to power failures and the like.

-------
                                    HAG - 7
 VI.  Producers of Acetic Acid - All Routes Shovn
         Company
 Borden, Inc.

 Celanese
 Eastman Chemical Prod.
 FMC, Organic Chem. Div.
 Forest Prod.
 Hercules, Inc.
 Kingsford Chem. Co.
 Monsanto

 Publicker Industries
 Sonoco Prod. Co.
 Union Carbide
 Mobil Chemical
      Location

Geismar, La.

Bayport, Texas
Bishop, Texas
Pampa, Texas
Kingsport, Tenn
Bayport, Texas
Memphis, Tenn.
Parlin, N. J.
Iron Mtn., Mich.
Texas City, Texas

Philadelphia, Pa.
Hartsville, S. C.
Brownsville, Texas
Taft, La.
Texas City, Texas
Beaumont, Texas
MM Lbs./Yr.           Route

   100        Carbonylation of
              Methanol
   300        Acetaldehyde
   150             "
   500        Oxidation of butane
   325        Acetaldehyde
    45        Glycerine by-product
   N. A       Wood Distillation
    40*       By-product
   N. A.       Wood Distillation
   300        Carbonylation of
              Methanol
    80        Fermentation by-product
   N. A.       Extraction
   500        Oxidation of butane
    90        Caprolactone by-product
   100*       Acetaldehyde
    30        Terephthallic acid
 	        By-product
                                                  2,420** on stream

 *140 on stand-by
**400 from Carbonylation of methanol or 17% of installed capacity.

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PAGE NOT
AVAILABLE
DIGITALLY

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                                 TABLE  HAG-I
                       ACETIC ACID FROM METHANOL AND CO

Of the two respondent questionnaires, only one had sufficient data to construct
a material balance.  The other had apparently a large excess of snythesis gas,
only a portion of which was used in the process and the excess flared.
Material In
      Raw CO -
      CH3OH
CO
N2
CH4
                       Balance - in Ib./lb. acetic acid
                                                    Total In
Lb./Lb.

0.512
0.004
0.004
0.540
1.060
Material Out
      Acetic Acid - CH3COOH
      Heavy Liquids (Cl^COOH
         (Mixed)    (CH3CH2COOH

      Tail Gas -  CO
                  C02
                  H2
                  Others
                                                   1.000
                                                   0.003
                                                   0.001

                                                   0.040
                                                   0.013
                                                   0.001
                                                   0.001
      Unaccounted for
                                                    Total Out
                                                   0.001
                                                   1.060

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                                TABLE HAC-II
                       ACETIC ACID FROM METHANOL AND CO

Very little data are available for construction of a detailed heat balance.
for this process.  Literature reports the liquid phase reaction as mildly
exothermic with only preheaters required to bring the reactants up to
temperature.

HEAT' IN                                                      BTU/Lbs. HAG

Preheat reactants to 480° F                                      213
Exothermic heat of reaction                                      984*
                                                               1,197

HEAT OUT

Enthalpy of products leaving reactor                           1.197


60° temperature base and no external losses assumed.


*Literature reports heat release of 1.9 x 10^ BTU/ton acid vs calculated
 1.968 x 106 BTU/ton HAC (984 BTU/lb. HAC).

-------
                                                                                   TABLE  HAC-III
                                                                            NATIONAL EMISSIONS INVENTORY
                                                                          ACETIC ACID FROM MET11ANOL AND CO
Plant EPA Code No.
Capacity, Tons HAC/Yr.
Range of Production, 7. of Max.
Emissions to Atmosphere - Stream
   Flov - Lbs. /Hi".
   Flov Characteristic
Composition, Ton/Ton HAC
   HAC
(A)
36,480 (!)
Continuous
N. A.
                     2-3
                     50,000
                       0
                     'Bl
                   CC1
                   2,209 (1)
                   Continuous
                   N  A.
                     3,085
                     Continuous
                     N. A.
                   2-6
                   150,000
                   0
                   (B)
                   Nil
                   Open only in emergency

                   1.000
                              (C)
                              297 CD
                              Continuous
                              N. A.
Vent Stacks
   Number
   Height - Feet
   Diameter - Inches
   Exit Gas Temp.
   SCFM/Stack
Emission Control Devices
   Flare/Incinerator
   Absorber/Scrubber
   Condenser/K. 0. Drum
   Other
Analysis
   Date or Frequency of Sampling
   Sample Tap Loaction
   Type of Analysis
   Odor Problem
Summary of Air Pollutants
   Hydrocarbons, Ton/Ton HAC
   Aerosols and Particulates, Ton/Ton HAC
   NOX, Ton/Ton HAC
   SOX, Ton/Ton HAC
   CO  , Ton/Ton HAC
1
100
48
3600° F
7300 (1)

Incinerator
Never
None
None
None
No Data
1
100
4
90° F
1
10
96
3400° F
426 (D

Incinerator
                   Spot
                    ?
                   None
                   No
                   No  Data
1
199
16
N. A.
475

Flare
                     Yes
1
10
8
Ambient
1090

None
                                        Never
                                        None
                                        None
                                                                                0.0000
                                                                                1.0000
                                                                                0.0000
                                                                                0.0000
                                                                                0.0000
                                                                                                              N. A
                                                                                                              Incinerator
                                                                                                              N. A.
                                                                                                              No data
(1)  Calculations from composition and Ibs./hr. of feed to incinerator or flare, an estimate.

-------
                                                                                    TABLE HAC-IV
                                                                       CATALOG OF EMISSION CONTROL DEVICES
                                                                          ACETIC ACID FROM METHANOL AND CO
INCINERATION DEVICES
   EPA Code for plant using
   Flov Diagram (Fig. HAC-11 Stream I. D,
   Device I. D. No.
   Type of Compound Incinerated
   Type of Device
   Material Incinerated, SCFM (Ib./hr.)
   Auxilliary Fuel Ren'd. 'Excl. pilot)
         Type
         Rate, BTU/Hr.
   Device or Stack Height, Ft.
   Installed Cost - Mat'l. & Labor - S
   Installed Cost based on "year" dollars
   Installed Cost, c/lb. Acetic Acid/Yr.
   Operating Cost. Annual - $ (1972)
   Operating Cost, c/lb. Acetic Acid

   Efficiency - % - CCR (3)
   Efficiency - 7. - SERR  (3)
2-3
(C)
F-101
Mixed Organic Acids
Incinerator
(1020)

Natural gas

10
210,000
1972
0.21
28,000
0.028

No Data
No Data
2-3
(A)
F-102
Hydrocarbons & Organic Gases
Incinerator
7000

None

too
100.000
1965
0.10
4,000
.004

No Data
No Data
2-6
(C)
F-101
Mixed Organic Acids
Incinerator
(137)
No Data
No Data
2-6
(A)
F-102
Hydrocarbons & Organic Gases
Flare
475
                            199
                            No Data
                            No Data
ABS ORBER/S CRUBBERS
   EPA Code No. for plant using
   Flow Diagram (Fig. HAC-1) Stream I. D.
   Control of
   Scrubbing/Absorbing Liquid
   Type
   Scrubbing/Absorbing Liquid Rate - GPM
   Operating Temp., °F
   Gas Rate - SCFM
   T-T Height, Feet
   Diameter, Feet
   Washed gases to stack
         Stack Height - Ft.
         Stack Diameter - Inches
   Installed Cost - Mat'l. & Labor - $
   Installed Cost based on "year" dollars
   Installed Cost, c/lb. Acetic Acid/Yr.
   Operating Cost - Annual - (1972)
   Value of Recovered Product, $/Yr.
   Net Operating Cost - c/lb. Acetic Acid

   Efficiency - % - SE  (3)
   Efficiency - % - SKRR  (3)
                                      2-6
                                      (D)
                                  Iodine Vapor
                                Sodium Carbonate
                                   Static bed
                                 175 gal. -static
                                    Ambient
                                     13  (D
                                         6
                                       2.5
                                        Yes
                                      10,000
                                      1970
                                     0.003
                                     $2,625
                                        0
                                     0.0009

                                      100
                                      100
(1)  Average flow is intermittent at  1090 SCFM  for 2 hrs./week

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                                 TABLE  HAG-IV
                     CATALOG OF EMISSION CONTROL DEVICES
                                    NOTES
1.  Incinerators and Flares.  No data on combusted gases given.  There are
    no nitrogen or- sulfur compounds in the gases and complete combustion
    should give only CC>2 and water.

2.  Absorber is for recovery of  iodine vapors from catalyst preparation and
    activation section.  Flov is intermittent.  Recovery of 12 is given as
    100%.  Therefore, the SE and SERR based on iodine are 1007».  Effluent gas
    to atmosphere is air only.

3.  See Appendix V for definition and explanation.

-------
                                               TABLE HAC-V
NUMBER OF NEW PLANTS BY 1980
Process
Methanol
Acetaldehyde
Butane
Others
Current
Capacity
400
875
1,000
285
2,560
Marginal
Capacity
0
100
500
100
700
ACETIC ACID
Current
Capacity
on- stream Demand*
in 1980 1980
400 "\
775 1
;4,000

1,860
Capacity
1980
1,800
2,015
500
185
4,500
Capacity-"-'" Economic Number
to be Plant of Nev
Added Size Units
1,400 400 4
1 , 240 400 3
0
0
NOTE:  All capacities in MM Ibs./year.

 *From Final Report prepared by Processes Research, Inc., August 15,  1971.
**Assumes 50 - 55% of new capacity will be by methanol process.

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Emission
      TABLE HAOVI
EMISSION SOURCE SUMMARY
  TON/TON ACETIC ACID

         Source

   Purification Section
Total
                                                                       Acid  Recovery
Hydrocarbons

Particulates & Aerosols

NOX

SOX

CO
                    - See Belov -
0.00003
Note:

All waste gas streams leaving this process are flared or incinerated.   No data on combusted gases are
available.  Hovever, these gases contain no NOX °r SOX or particulates and if incinerated properly
should give only C02 and H^O as off gas, except about 20 - 40 ppm of NOX from atmospheric nitrogen, as
indicated in the total column.

-------
TABLE HAC-VII
WEIGHTED EMISSION RATES
Chemical Acetic Acid
Process Carbonylation of
Increased Capacity by 1980 1400 MM

Methanol
Ibs. /year
Pollutant Emissions, Lb./Lb.
Hydrocarbons
Aerosols & Participates
NOX
SOX
CO
0*
0
0.00003
0
0*



Increased Emissions
MM Lb. /Year
0
0
0.042
0
0
                                   Weighting
                                   Factor

                                      80

                                      60

                                      40

                                      20

                                       1
                                                                                                 Weighted Emissions
                                                                                                 MM Lb./Year	

                                                                                                        0

                                                                                                        0

                                                                                                        2

                                                                                                        0

                                                                                                        0
                           ^-^Significant Emission Index =» 2
 •-In lieu of any data to the contrary, complete combustion of the vent gases to C02
**See Appendix IV for explanation.
                                              assumed.

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Acetic Acid via Butane

-------
                              Table of Contents

Section                                                          Page Number

I.    Introduction                                                  ACA-1
II.   Process Description                                           ACA-2
III.  Plant Emissions                                               ACA-3
IV.   Emission Control                                              ACA-6
V.    Significance of Pollution                                     ACA-7
VI.   Acetic Acid Producers                                         ACA-8

                       List of Illustrations and Tables

      Flov Diagram                                               Figure ACA-I
      Net Material Balance                                       Table ACA-I
      Gross Heat Balance                                         Table ACA-II
      Emission Inventory                                         Table ACA-III
      Catalog of Emission Control Devices                        Table ACA-IV
      Number of New Plants by 1980                               Table ACA-V
      Emission Source Summary                                    Table ACA-VI
      Weighted Emission Rates                                    Table AQA-VII

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                                    ACA-1
I.  Introduction

    Acetic acid is an important chemical used to produce acetic anhydride
for cellulose acetate, vinyl acetate monomer for vinyl polymer, acetate
esters for use as commercial solvents and chloroacetic acid for use in
the leather and textiles industry.  The manufacture of cellulose acetate
and vinyl acetate monomer account for 44% and 3170 of the acetic acid
produced.

    Acetic acid was first produced commercially by vood distillation.  A
concerted effort was made during World War I to make synthetic acetic acid
because of its use in acetone synthesis.  Today, almost all acetic acid is
made by synthetic methods.   The major routes are oxidation of n-butane,
acetaldehyde oxidation and carbonylation of methanol.   The first tvo processes
account for 44% and 327, of the acetic acid capacity, respectively.  The
methanol carbonylation process is new and growth is expected in that area.

    The oxidation of butane is used in two large acetic acid installations.
Large quantities of by-products are produced by the process, the more
useful  of which are recovered.  The economic success  of such a plant is
tied  to a source of cheap butane and a high market value for by-products.

    Acetic acid production is expected to grow to 4.5  billion lbs./yr.* by
1980, which is an increase of about 2 billion Ibs./yr. Because butane has
become more useful for other purposes and by-product formation is undesirable,
future plants are expected to be built using either acetaldehyde oxidation
or methanol carbonylation process.

    Emissions from a butane oxidation plant can best be described as moderate.
Since no growth is expected, however, annual emissions are not significant.
NOTE:  This report is based on the data supplied by one respondent and
       information found in literature.
 *More recent estimates indicate that growth may be to 3.2 billion Ibs./year
  by 1980, or only about 1 billion Ibs./year increased capacity.

-------
                                    ACA-2
II.  Process Description

     (See Figure ACA-1)

     The commercial oxidation of n-butane produces acetic acid along vith a
large number of by-products.  Some of the useful by-products vhich are
usually recovered and sold or used in captive processes include ethyl acetate,
ethanol, methyl-ethyl ketone, formic acid and propionic acid.  Product and
by-product separation is extremely difficult because azeotropes are formed
between many of the components and a large percentage of the capital and
operating costs are tied up in the recovery area.  The large number of by-
products produced by butane oxidation (up to 70 components could be present
in the reactor effluent stream) are the chief drawback to the process.

     The oxidation of butane is carried out in recycle reactors due to low
butane conversion.  Typical reaction conditions described for a plant built
by Chemische Werke Huls in Germany are as follows: oxidation is carried out
in stainless steel towers at a temperature of 170 - 200° C and a pressure
of 65 atmospheres.  The reaction takes place in the presence of a large
excess of reaction products and is considered a liquid phase reaction even
though butane is above its critical temperature.

     There is a considerable heat of reaction,  9,000 BTU/lb. butane oxidized,
which must be removed mainly by evaporation of products and feed preheating.
Oxidation can be carried out using air or oxygen.  If air is used nitrogen
must be removed from the system.   Reaction products are separated from un-
reacted butane and combustion products such as carbon dioxide, carbon monoxide,
etc.  Butane is recycled, C02, CO and some hydrocarbons are vented and/or
flared and the crude mixutre of products and by-products is sent to the
purification system.

     There are many schemes to carry out the difficult purification steps
necessary.  The following is a general description of a typical process.   In
the first step a crude separation is made between alcohols, acetates, aldehydes,
ketonej& light components and acids plus acid residues.  The alcohols, acetates,
etc., undergo another distillation whereby the heavy components, 04*5, are
removed to incineration, the light solvent? including acetone and methyl
acetate are partially recycled to the reactor with the rest being burned, and
the useful by-products, ethyl acetate, methyl ethyl  ketone and ethanol are sent
to further purification.  Ethyl acetate is usually recovered and refined
first, followed by ethanol and finally the ketone.  The purification of these
components involves either extractive distillation or azeotrope breakers or
both.

     The acids and residues passing from the bottoms of the crude separation
column are sent to another column for removal of heavy residues, which are
burned, and water which is sent to treatment.  The mixture of acids leaving
the column goes to further azeotropic distillation steps where the acids are
separated and purified.  Formic acid is recovered and purified first followed
by acetic acid and then propionic acid.

     Large amounts of liquid waste products (about .4 Ib./lb. acetic acid) are
produced by the process and they are burned in boilers to recover heat.   The
aqueous waste is usually sent to treatment.

-------
                                    ACA-3


III.   Plant Emissions

      A.   Continuous Air Emissions

          1.  Reactor Section Emissions

              The respondent shows a large number of streams outletting from
          the process section described as "stripping recycle reactors".   To
          avoid possible inaccuracies it feemed wise to assign these streams
          to the general category "reaction section" and not attempt to guess
          the individual sources from which they originate.   Emissions to the
          atmosphere from this section are described below without further
          clarification.

              a.  Flare Stack Emissions

                  Hydrocarbon liquids and gases from each of the two reactor
              sections are burned in a flare prior to release to the
              atmosphere.  The liquid stream consists of 75  - 100 Ibs./hr.
              of all types of acids, alcohols,acetates and ketones.   The
              gaseous stream contains mainly carbon dioxide  (approximately
              80 wt. %) with smaller amounts of butane, ethane,  methane
              and inert argon.  Since no sulfur or nitrogen  compounds are
              present in the incinerated streams and no smoke or odor is
              reported by the respondent it is assumed that  nearly complete
              combustion takes place and the only emissions  are  carbon
              dioxide, water and traces of NOX and unburned  hydrocarbons.

              b.  Vent No. 1

                  One or two streams composed mainly of carbon dioxide with
              large nuantities of butane and smaller amounts of  ethane and
              methane are vented to the atmosphere from each of  the reactor
              sections.  Carbon monoxide, nitrogen and argon are also present
              in the stream.  Total hydrocarbon emissions for all vents in this
              category are .03824 Ibs./lb. acetic acid.  Carbon  monoxide
              emissions are .01354 Ibs./lb. acetic acid from this source.

              c.  Vent No. 2

                  Each reactor section has a small vent (.21 SCFM) for light
              gases.  Small amounts of hydrocarbons (.00001  Ibs./lb. acetic
              acid) are emitted.

          2.  Liquid Waste Boiler - Flue Gas

              The large quantity of organic liquid waste described in Section
          III-C-1 of this report,  is  burned in boilers.  No sulfur or nitrogen
          is present in any of the components so combustion  is assumed to be
          complete.  NOX composition is estimated to be 30 PPM which is
          .00004 Ibs./lb. acetic acid for the quantity of liquid burned.

          3.  Storage Tank Losses

              The respondent estimates that .00087 Ibs. of product and by-product
          per Ib. of acetic acid, is lost due to storage tank venting.

-------
                               ACA-4
B.  Intermittent Air Emissions

    1.  Topping Column and Crude Separation Column Venturi Scrubbers -
        Accumulator Relief Vent  .

        Both the crude separation column and the topping column have two
    Venturi scrubbers to absorb organic vapors, which are assumed to
    originate from the reflux accumulators.  The accumulator on the
    scrubber exhaust is covered with a methane pad.  Infrequent pressure
    release allows methane along with some acetone, methyl acetate,
    acetaldehyde and other light alcohols, acetates, aldehydes and
    ketones to enter the atmosphere.  The total quantity vented is
    considered insignificant on a yearly basis.

    2.  Purification Section Pressure Relief Vents

        Small amounts of methane along with hydrocarbons are released by
    pressure relief on columns in the purification section.  The total
    amount emitted to the atmosphere is described by the respondent as small,

C.  Continuous Liquid Wastes

    1.  Liquid Waste to Incineration

        Large quantities of unrecovered by-products produced by the
    process are burned.  The source and composition of these streams is
    described below.

        a.  Acid Purification Section

            Approximately 19,000 Ibs./hr. of C^ - C,  acids and water
        are released from the acid purification section to boilers or
        incinerators.

        b.  Topping Column Bottoms

            About 6,000 Ibs./hr. of butyl esters and alcohols exit from
        the topping column to boilers.

        c.  Light Solvents from Topping Column

            Unrecycled acetone, acetaldehyde,  methyl acetate, etc., are
        burned.

    2.  Waste Water

        An estimated flow of 200 GPM of waste  water from the process is
    treated in an anaerobic lagoon.

D.  Solid Waste

        Acid residue is burned in boilers.

E.  Odor Problem

        The respondent reports that odors of acetone,  acetic acid and
    methyl acetate are infrequently detectable off of the plant property.

-------
                              ACA-5
F.   Fugitive Emissions

        No other sources of emissions were mentioned although losses
    due to leaks and spills probably do occur.

-------
                                    ACA-6
IV.  Emission Control

     The emission control devices that have been reported as being employed
by the respondent are summarily described in Table  IV of this report.  An
efficiency has been assigned each device vherever data sufficient to calculate
it have been made available.  Three types of efficiencies have been calculated.*

     (1)  "CCR" - Completeness of Combustion Rating

          CCR = Ibs. of 02 reacting (vith pollutant in device feed)
                     Ibs. of On that theoretically could react

     (2)  "SE" - Specific Efficiency

          SE = specific pollutant in - specific pollutant out
                           specific pollutant in              x

     (3)  "SERR" - Significance of Emission Reduction Rating
          SERR =  (pollutant x veighting factor)in -  (pollutant x weighting
                 	factor)out	
                              (pollutant x weighting factor*)in

          *Weighting factor same as Table VII weighting factor.

     Emission Control Devices Employed

     Flares (with steam rings for emergency smokeless operation)

     The respondent claims flares are smokeless so complete combustion is
     assumed to the extent possible with flares.

     Venturi Scrubbers

     Since the only emission from the scrubbers is infrequent pad gas vents
     the "SE" and "SERR" efficiencies are near 1007,.
x 100
*For complete description, see Appendix V of this report.

-------
                                    ACA-7
V.  Significance of Pollution

    It is recommended that no in-depth study be made of the butane oxidation
process for acetic acid.  This conclusion is drawn because no growth is
expected in the process between now and 1980.  The reasons for this are as
follows:

    1.  Butane is becoming important for other purposes.

    2.  The methanol carbonylation process is growing in  favor.

    3.  Large quantities of by-products are undesirable.

    Since no new capacity is anticipated, the Significant Emissions Index
(SEI) for the oxidation of butane route to acetic acid is zero.   For explanation
of SEI, see Appendix IV of this report.

-------
VI.  Synthetic Acetic Acid Producers

                                                   Butane
      Producer                 Location            Oxidation       Acetaldehyde       Methanol & CO       By-Product

Borden Inc.                Geismar, La.                                                    100

Celanese Corp.             Bayport, Texas                              300
                           Bishop, Texas                               150
                           Pampa, Texas               500

Eastman Kodak              Kingsport, Tenn.                             325

FMC Corp.                  Bayport, Texas                                                                     45
(peracetic acid)

Monsanto Co.               Texas City. Texas                                               300
                                      '                                                                                  >
                                                                                                                        £
Publicker Ind.,  Inc.       Phi la., Pa.                                                                        80        '

Union Carbide              Brownsville, Texas         520
(peracetic acid)           Taft, La.                                                                          90
                           Texas City, Texas        	              100                 	               	

                                           Total  - 1,020              875                 400               210

                               Percentage  Total  -    41               35                  16                 8

-------
PAGE NOT
AVAILABLE
DIGITALLY

-------
                                  TABLE ACA-I
                               MATERIAL BALANCE
                                 ACETIC ACID
                                     VIA
                               BUTANE OXIDATION
MATERIAL IN

BUTANE

1)  n-butane           1.130
2)  iso-butane          .017
3)  lights and heavies   .006
OXYGEN
1)
2)
3)
oxygem
nitrogen
argon
1.578
 .097
 .003
                                             MATERIAL OUT CLB./LB. ACETIC ACID)
99% acetic acid            1.000
98% formic acid             .030
95% propionic acid          .003
99.5% methyl-ethyl ketone   .159
85% ethanol                 .031
99% ethyl acetate           .119
waste liquid and gases     1.489
Total In - 2.831 Ib./lb. 99% acetic acid
                                             Total Out - 2.831 Ib./lb.
                                                         99% acetic acid

-------
                                  TABLE ACA-II
                              GROSS HEAT BALANCE
                                 ACETIC ACID
                                     VIA
                               BUTANE OXIDATION

     There is insufficient data available for a complete energy balance on
this process.

     Heat of Reaction

     9,000 BTU/lb. butane oxidized*
*1)  Includes all products and by-products.

 2)  Reported for Chemische Werke Huls1 n-butane oxidation process in
     Chemistry and Industry, May 28, 1966.  Different relative amounts of
     products and by-products are produced by this process than were reported
     by the only respondent in the study, so the heat of reaction might vary
     somevhat.

-------
Capacity - Tons of Acetic Acid
Production - Tons of Acetic Acid
Emissions to Atmosphere
    Stream No.
    Stream
Flow - Lbs./Hr.
Flow Characteristic - Continuous or Intermittent
    if Intermittent - Hrs./Yr.
Composition
    Ethane
    Methane
    Butane
    Carbon Dioxide
    Carbon Monoxide
    Oxygen
    Nitrogen
    Nitrogen Oxides
    Water
    Argon
    Hydrocarbons (assorted)
    Acetone
    Acetaldehyde
    Methyl Acetate

Analysis
    Sample Tap Location
    Date or Frequency of Sampling
    Type of Analysis
    Odor Problem
Vent Stacks
    Number
    Height - Ft.
    Diameter - Inches
    Temp. - F°
    Flow Rate - SCFM per stack
Emission Control Device
    Type - Incinerator
           Scrubber
Summary of Emissions
    Total Hydrocarbon Emissions - Ton/Ton of Acetic Acid
    Total Particulate Emissions - Ton/Ton of Acetic Acid
    Total NOX Emissions - Ton/Ton of Acetic Acid
    Total SOX Emissions - Ton/Ton of Acetic Acid
    Total CO  Emissions - Ton/Ton of Acetic Acid
              —
NATIONAL EMISSIONS INVENTORY
        ACETIC ACID
            VIA
      BUTANE OXIDATION

            2-1
          260,000
          260,000
                                                                                                                                      Page  1  of  3
                                                                   Reactor I
                                                                   Section vent 1

                                                                   14,065
                                                                   Continuous
                                                                   .00367
                                                                   .00245
                                                                   .01743
                                                                   .15289
                                                                   .00685

                                                                   .00499
                                                                   .02076
                                                                   .00409
                                                                   Yes
                                                                   Side of Units
                                                                   3 times a week
                                                                   Mass Spectrometer
                                                                   No
                                                                   Yes
                                                                   1
                                                                   90
                                                                   10
                                                                   100
                                                                   2023
                                                                   No
              Reactor I '
              Section Vent 2

              1.4
              Continuous
              .00001
                 +
                 +
                 +
                 +
              .00001
              Yes
              None
              On request
              Mass Spectrometer
              No
              Yes
              1
              20
              2
              SO
              .2
              No
Reactor II
Section Vent IA

8005
Continuous
                                     .00149
                                     .00075
                                     .00136
                                     .10954
                                                                                                                 .00230
.00585
. 00348
Yes
Side of Unit
3 times a veek
Mass Spectrometer
No
Yes
1
100
10
90
1,154
No
Reactor II
Section Vent IB

6720
Continuous
                        00134
                       .00185
                       .00274
                        05790
                       .00669

                       .00750
.02120
 00262
Yes
Side of Unit
3 times a veek
Mass Spectrometer
No
Yes.
1
100
10
86
1,043
No
Reactor III
Section Vent 2
1.4
Continuous
                        00001
                          +
                          +
                          +
   +
 00001
Ye?
None
On repueft
Mass Spectrometer
No
Yes
1
12
.5
80
 2
No
                                                                                                           Continued

-------
                                     or Intermittent
EPA  Code No.
Capacity - Tons of Acetic Acid
Production - Tons of Acetic Aeid
Emissions to Atmosphere
    Stream No.
    Stream
Flov - Lbs./Hr.
Flov Characteristic - Continuous
    if Intermittent - Hrs./Yr.
Composition
    Ethane
    Methane
    Butane
    Carbon Dioxide
    Carbon Monoxide
    Oxygen
    Nitrogen
    Nitrogen Oxides
    Water
    Argon
    Hydrocarbons (assorted)
    Acetone
    Acetaldehyde
    Methyl Acetate
    Analysis
        Sample Tap Location
        Date or Frequency of Sampling
        Type of Analysis
        Odor Problem
    Vent Stacks
        Number
        Height -  Ft.
        Diameter  - Inches
        Temp. - F°
        Flow Rate - SCFM per stack
    Emission Control Devices
        Type - Incinerator
               Flare
               Scrubber
    Summary of Emissions
        Total Hydrocarbon Emissions - Ton/Ton of Acetic Acid
        Total particulates and Aerosols - Ton/Ton of Acetic Acid
        Total NOX - Ton/Ton of Acetic Acid
        Total SOX - Ton/Ton of Acetic Acid
        Total CO  - Ton/Ton of Acetic Acid
                                                                                  TABLE ACA-III
                                                                        NATIONAL EMISSIONS INVENTORY
                                                                                ACETIC ACID
                                                                                    VIA
                                                                              BUTANE OXIDATION

                                                                                    2-1
                                                                                  260,000
                                                                                  260,000
         1A
Flare Stack Emissions
Reactor Section I Flare (1)

3380 (2)
Continuous
                                                                            .03875
                                                                           Negligible
                                                                           .01245
                                                                           .00041
                                                                       (2)
                                                                       No
                                                                       Yes
                                                                       1
                                                                       210
                                                                       24
                                                                       Unknown
                                                                      -660
                                                                       Yes

                                                                       Yes
                                                                                                                                       Page 2 of 3
        IB
  Flare Stack Emissions
  Reactor Section II Flare  (3)

^6700  (2)
  Continuous
                                                                                                                  .08691
                                       Negligible
                                       .01433
                                       .00082
                                                                                                                  None
                                       C2)
                                       No
                                       Yes
                                       1
                                       210
                                       24
                                       Unknown
                                       Yes

                                       Yes


                                    Continued
                                                                                                                                                           3A
                                                                                                                                                    Topping Column
                                                                                                                                                    Venturi Scrubber Vent
                                                                                                                                                        Intermittent
                                                                                                                                                        Not Specified
                                                                                                                                                                              (4)
                                                                                                                                                        None
                                        Yes
                                        Yes
                                        2
                                        58
                                        3
                                        90
42
6
86
 (1)  Approximately 2825  Ibs./hr.  of  light hydrocarbons and 75  Ibs./hr.  of  liquid alcohols, acids and ketones are incinerated in this flare.
 (2)  Combustion  products estimated by  Houdry assuming complete conversion  to C02 and H20 and 30 PPM NO* formation.
 (3)  Approximately 3610  Ibs./hr.  of  light hydrocarbons and 100 Ibs./hr.  of liquid alcohols, acids and ketones are incinerated in this flare.
 (4)  Infrequent  pressure release  of  methane pad.
 (5)  Mostly methane.

-------
EPA Code No.
Capacity - Tons of Acetic Acid
Production - Tons of Acetic Acid
Emissions to Atmosphere
    Stream No.
    Stream
                          Continuous or Intermittent
                          Hrs./Yr.
Flov - Lbs./Hr.
Flow Characteristic
    if Intermittent
Composition
    Ethane
    Methane
    Butane
    Carbon Dioxide
    Carbon Monoxide
    Oxygen                                      -     ,
    Nitrogen
    Nitrogen Oxides
    Water
    Argon
    Hydrocarbons (assorted)
    Acetone
    Acetaldehyde
    Methyl Acetate

Analysis
    Sample Tap Location
    Date or Frequency of Sampling
    Type of Analysis
    Odor Problem
Vent Stacks
    Number
    Height - Ft.
    Diameter - Inches
    Temp. - F°
    Flow Rate - SCFM per stack
Emission Control Devices
    Type - Incinerator
           Flare
           Scrubber
Summary of Emissions
    Total Hydrocarbon Emissions - Ton/Ton of Acetic Acid
    Total particulate and Aerosols - Ton/Ton of Acetic Acid
    Total NOX - Ton/Ton of Acetic Acid
    Total SOX - Ton/Ton of Acetic Acid
    Total CO  - Ton/Ton of Acetic Acid
                                                                                  TABLE ACA-III
                                                                        NATIONAL EMISSIONS INVENTORY
                                                                                ACETIC ACID
                                                                                    VIA
                                                                              BUTANE OXIDATION

                                                                                    2-1
                                                                                 260,000
                                                                                 260,000
                                                                        Crude Separation Column,
                                                                        Venturi Scrubber Vent (4)
Intermittent
Not Specified
                                                                          (5)
                                                                           +
                                                                           +
                                                                           +

                                                                        None
                                                                        Yes
                                                                        Yes
                                                                        2
                                                                        55
                                                                        3
                                                                        98

                                                                        Yes
                                                                        Yes
       55
       3
       98
                                                                                                                                       page  3  of 3
                                 Flue Gas
                                 Liquid Waste Boilers

                                 49,267 (2)
                                 Continuous
                                                                                                         .46192
                                                                                                         .00004
                                                                                                         .26356
Storage
Tank Vents

57.8
Purification
Relief Valve

T'O
Intermittent
Not Specified
                                                                                                         None
                                   (2)
                                 No
                                 Not Specified
                                                                                                         No
                                                                                                         .03911
                                                                                                            0
                                                                                                         .00004
                                                                                                            0
                                                                                                         .01354
                                                                                                                                      .00087
                                                                                                                                      None
                                                                                                                                      Calculated
                                                                                                                                      No
                                                                                                                                      No
                                                                                                                                                              None
                        No
                        No
                                                                                                                                                              NO
 (1)  Approximately 2825  Ibs./hr. of  light hydrocarbons and  75  Ibs./hr.  of  liquid alcohols, acids and ketones are incinerated in this flare.
 (2)  Combustion products estimated by Houdry assuming complete  conversion  to CO. and HoO, and 30 PPM NOX formation.
 (3)  Approximately 3610  Ibs./hr. of  light hydrocarbons and  100  Ibs./hr.  of liquid alcohols, acids and ketones are incinerated in this flare
 (4)  Infrequent pressure release of  methane pad.
 (5)  Mostly methane.

-------
                                                                                     TABLE ACA-IV
                                                                        CATALOG OF EMISSION CONinOL DEVICES
                                                                                    ACETIC ACID
                                                                                        VIA
                                                                                  BUTANE OXIDATION
FLARE
   EPA Code No.  for plant using
   Flov Diagram CFig. ACA-I) Stream I. D.
   Device I.  D.  No.
   Types of Compounds Flared
   Amount Flared - Ibs./hr.
   Device or Stack Height - Ft.
   Stack Diameter (3 Tip - Inches
   Installed Cost - Mat'l. 6, Labor - $
   Installed Cost - Mat'l. & Labor - c/lb. Acetic Acid
   Installed Cost - based on - "year" - $
   Operating Cost - Annual - (1972)
   Operating Cost Annual - c/lb. Acetic Acid
   Efficiency - CCK - %
   Efficiency - S ERR - "/.
             2-1
             Al
             FL-I
             Assorted HC Liquids & Vapors
             2790
             210
             24
             84,760
             .016
             34,760 - 1971     50,000 - 1961
                                               16,560
                                                .003
                                               Near 1007.
                                               Near 100%
       2-1
       A2
       FL-I I
       Assorted HC Liquids & Vapors
       3450
       210
       24
       84,760
       .016
       34,760 - 1971     50,000 - 1964
SCRUBBERS
   EPA Code No. for plant using
   Stream I. D. No.
   Device I. D. No.
   Control Emission of
   Scrubbing Liquid
   Type - Venturi
          Absorber
   Scrubbing Liquid Rate - GPM
   Design Temp. - F°
   Gas Rate - SCFM (Ib./hr.)
   Washed Gases to Stack
   Stack Height - Ft.
   Stack Diameter - Inches
   Installed Cost - Mat'l. 6. Labor - $
   Installed Cost - c/lb. of Acetic Acid
   Installed Cost - based on - "year" - $
   Operating Cost - Annual - (1972)
   Value of Recovered Product - $/Yr.
   Net Operating Cost - Annual - $
   Net Operating Cost - c/lb, of Acetic Acid
   Efficiency - 7. - SE
   Efficiency - 7. - SERR
2-1
 B
SC-I & SC-II
Acetaldehyde, Acetone, Methyl Acetate
Water
Yes

9.2 each
Yes
55 each
3 each
4,000
.0008
1964
200
0
200
.00004
99.9+
99.9+
2-1
 B
SC-III & SC-IV
Acetaldehyde. Acetone. Methyl Acetate
Water
Yes
    Ye
58
3
2,000
.0004
1964
     200
      0
     200
    . 00004
     99.9+
     99.9+
42
6
2,000
.0004
1968

-------
1020
                                              TABLE ACA-V
Current (1)
Capacity
NUMBER OF NEW PLANTS BY
ACETIC ACID
VIA
BUTANE OXIDATION
Current
Capacity
Marginal on-stream Demand
Capacity in 1980 1980
1980
Capacity
1980
Capacity
to be
Added
Economic
Plant
Size
Number
of Nev
Units
0
1020
1020
1020
0
(1)   MM Ibs./year.




(2)   No new butane oxidation plants are expected to be built.
300
                                                                                                                (2)

-------
TABLE ACA-VI
EMISSION SOURCE SUMMARY
TON/TON OF ACETIC ACID
Emission
Source
Total
Venturi Scrubber
Reactor Stripping Liquid Waste and Purification Section Tank Vents &
Section Incineration Relief Valves Fugitive Emissions
Hydrocarbons
Particulates
NOX
SOX
CO
.03824
0
0
0
; 01354
0
0
. 00004
0
0
Negligible
0
0
0
0
.00087
0
0
0
0
.03911
0
.00004
0
.01354

-------
TABLE ACA-VII
Chemical
Process
Increased Capacity
Pollutant
Hydrocarbons
Participates
NOX
sox
CO
WEIGHTED EMISSION RATES
Acetic Acid
Butane Oxidation
by 1980 0
Increased Emissions
Emissions Lb./Lb. MM Lbs./Year
.03911 0
0 0
. 00004 0
0 0
.01354 0
Weighting
Factor
80
60
40
20
1
Weighted Emissions
MM Lbs./Year
0
0
0
0
0
                         Significant Emission Index ° 0

-------
EPA Plant Code No.
Capacity - Tons of Acetic Acid/Yr.
Production - Tons of Acetic Acid/Yr.
Emissions to Atmosphere
    Stream

    Flow - l.bs./Hr.
    Flov Characteristic - Continuous or Intermittent
        if Intermittent - Hrs./Yr.
    Composition - Tons/Ton of Acetic Acid
        Acetaldehyde
        Ethyl Acetate
        Carbon Dioxide
        Carbon Monoxide
        Water
        Oxygen
        Nitrogen
    Analysis
        Sample Tap Location
        Frequency of Sampling
        Type of Analysis
        Odor Problem
    Vent Stacks
        Number
        Height -  Ft.
        Diameter  - Inches
        Exit Gas  Temp. - F°
        Flov - SCFM/Stack
    Emission Control Devices
        Type
    Summary of Air Pollutants
        Hydrocarbons - Ton/Ton Acetic Acid
        Particulates - Ton/Ton Acetic Acid
        NOX - Ton/Ton Acetic Acid
        SO  - Ton/Ton Acetic Acid
        CO  - Ton/Ton Acetic Acid
       TABLE ACE-III
NATIONAL EMISSIONSTNVENTORY
        ACETIC ACID
            VIA
   ACETALDEHYDE OXIDATION

            2-5
         162.500 (1)
          72,000

       Scrubber Vent

          22,457
         Cont inuoue
           .00481
           .00502
           .02089
           .00202
           .00077
           .04529
          1.26869
            Yes
 On-stream to control room
       3 times/veek
  Gas Chromatograph - Orsat
             No
            Yes
              1
             75
             66
             45
           5000
            Yes
       Tvo Absorbers

           .00983
              0
              0
              0
           .00202
     (1)   Published  capacity.

-------
Acetic Acid via Acetaldehyde

-------
                                 TABLE ANA-I
                      ACETIC ANHYDRIDE FROM ACETIC ACID
             OVERALL MATERIAL BALANCE - TON/TON ACETIC ANHYDRIDE
MATERIAL IN                                                      MATERIAL OUT
Pure Acetic Acid
Misc. Carboxylic Acids
   and Water
1.2000
0.0011

1.2011
Acetic Anhydride       1.0000
Low Boiling Liquids    0.0010
Tars                   0.0005
Water                  0.1760
Flare Gas*             0.0206
Acetic Acid            0.0030
                       1.2011
     Hydrocarbons, N2, 02, C02 CO

-------
                                  TABLE ANA-II
                      ACETIC ANHYDRIDE FROM ACETIC ACID
                                 HEAT BALANCE

There is not enough data to calculate a detailed heat balance for this
process.  An estimate of the heat flovs around the preheater, vaporizers
and cracking furnace is:

HEAT IN                                          BTU/LB.  ACETIC ANHYDRIDE

Sum of steam, heat exchange and
fired heaters                                             2240

HEAT OUT

Endothermic heat of reaction                              1158
Differential enthalpy (Reaction products - feed)            1082
                                                          2240

-------
                                                                                     TABLE ANA-III
                                                                             NATIONAL EMISSIONS INVENTORY
                                                                   ACETIC ANHYDRIDE FROM ACETIC ACID (KETENE ROUTE)
 Plant - EPA Code No.
 Capacity,  Tons Acetic Anhydride/Yr.
 Range in Production,  7. of Max.
 Emissions  to Atmosphere

..^   Stream
     Flov,  Lb./Hr.
     Flow Characteristic. Continuous or Intermittent

     Composition, Lb./Lb. Acetic Anhydride
        Particulate
        Carbon Dioxide
        Carbon Monoxide
        Propodiene
        Ethylene
        Methane
        Water
        Ethane
        Diketene
        Acetic Anhydride
        Oxygen
        Nitrogen
        Acetic Acid
        Hydrogen
        Propane
     Vent Stacks
        Number
        Height, Ft.
        Diameter, Inches
        Exit Gas Temp. °F
        SCFM/Stack

 Emission Control Devices
     Flare/Incinerator
     Absorber/Scrubber
 Analysis
     Date or Frequency of Sampling
     Sample Tap Location
     Type of Analysis
     Odor Problem
 Summary of Air Pollutants
     Hydrocarbons - Lb./Lb. Aceric Anhydride
     Aerosols & Particulates - Lb./Lb. Acetic Anhydride
     NOX - Lb./Lb. Acetic Anhydride
     SOX - Lb./Lb. Acetic Anhydride
     CO  - Lb./Lb. Acetic Anhydride
30,000 Est.
None (liven
Final Scrubber Off-Gas

Stream goes to flare
no comp. of flared
gas given
180
Continuous
   -f-
0.00405
0.00975
0.00112
0.00368
0.00279
0.00241
0.00010
0.00007
0.00050
0.00034
0.00136
No Data
Incinerator
Never

Calculated
No
No Data
3-2
30,000 Est.
None Given
Tar Incinerator Flue Gas
1458 Est.
Continuous
30,000 Est.
None Given
Vaporizer Emergency Rupture Disc
Unknovn
Open only in emergencies
                             0.27-
                                                          99.87.
                                                           None
                              1400° F
                              Unknovn
                              Incinerator
Never
Stack Top
None
No
No Data
                                                           Normally Closed
                                                           None
                                                           Never
                                                           Not App.
3-1
425,000
None Given
Final Scrubber Off-Gas
1800
Continuous
                                     0.002907
                                     0,008144
                                     0.000021
                                     0.003113
                                     0.002660

                                     0.00008?
                                                                  0.000433
                                                                  0.001856
                                                                  0.000000?
                                                                  0.000144
                                                                  0.001258

                                                                  2
                                                                  90    75
                                                                   8     6
                                                                     100
                                                                 300    60
                                                                                                None
                                     Annually
                                     Sump
                                     G.C.
                                     No

                                     0.004474
                                        0
                                        0
                                        0
                                     0.008144

-------
                                                                                    TABLE ANA-IV
                                                                        CATAI.OC- OF EMISSION CONTROL DEVICES
INCINERATION DEVICES
   EPA Code No.  for plant using
   Flov Diagram 'Fig.  II Stream
   Device No.
   Type of Compound Incinerated
   Type of Device
   Material Incinerated SCFM db./hr.)
   Auxilliary Fuel Reo'd.
   Type
   Rate BTU/Hr.
   Device or Stack Height, Ft.
   Installed Cost - Mat'l. & Labor - $
   Installed Cost based on "year" - dollars
   Installed Cost, c/lb. of Acetic Anhydride - Year
   Operating Cost - Annual - $
   Operating Cost - c/lb. of Acetic Anhydride
   Efficiency - 7. - CCR
   Efficiency - % - SERR
3-2
 A
F-101
Hydrocarbons
Flare
40
Not Given
3-2
 B
1-101
Organic Tars
Inci nerator
1458
                                     Not Civen
3-1
 C
1-10?.
Organic?, Hydrocarbons
Incinerator
(83)
                                                                          Not Given

-------
                                             TABLE ANA-V

Current
Capacity

Marginal
Capacity
NUMBER
Current
Capacity
on-stream
in 1980
OF NEW PLANTS BY 1980

Demand
1980

Capacity
1980

Capacity*
to be
Added

Economic
Plant
Size

Number
of Nev
Units
 1705**            0           1705            2050         2100           267             100            2-3
 NOTE:   All capacities in millions of Ibs./year.




 *Capacity using pyrolysis of MAC route only.




**Excludes U. S. Army Munitions Report

-------
                                                TABLE  ANA-VI
Emission

EMISSION SOURCE SUMMARY
TON/TON ACETIC ANHYDRIDE
Source
Total
Absorber-Scrubber
Tail Gas Tar Incinerator Gas Fugitive Emissions
Hydrocarbons
Particulates & Aerosols
NOX
sox
CO
0.002729
0
0
0
0.004968
0
TR
0 None Given
0
+
0.002729
TR
0
0
0.004968
NOTE:  (+) Compound present but no analysis available.

-------
    TABLE ANA-VII
WEIGHTED EMISSION RATES
Chemical
Process
Increased Capacity
Pollutant
Hydrocarbons
Aerosols
NOX
SOX
CO
Acetic Anhydride
Pyrolysis of Acetic
by 1980 267 MM Ibs
Emissions Ib./lb.
0.002729
TR
0
0
0.004968

Acid
., assume 1133 MM Ibs. in 1973
Emissions MM Ib./yr.
0.73
TR
0
0
1.42
Weighting
Factor
80
60
40
20
1
Weighted Emissions
MM Ib./yr.
58.4
0
0
0
1.42
                              Significant Emission Index =  59.87

-------
Adipic Acid

-------
                              Table of Contents

Section                                                        Page Number

I.    Introduction                                                AA-1
II.   Process Description                                         AA-2
III.  Plant Emissions                                             AA-4
IV.   Emission Control                                            AA-7
V.    Significance of Pollution                                   AA-10
VI.   Adipic Acid Producers                                       AA-11

                        List of Illustrations  and  Tables

      Flow Diagram                                             Figure  AA-I
      Net Material Balance                                     Table AA-I
      Gross Heat Balance                                       Table AA-II
      Emission Inventory                                       Table AA-III
      Catalog of Emission Control Devices                      Table AA-IV
      Emission Source Summary                                  Table AA-V
      Number of New Plants by 1980                             Table AA-VI
      Weighted Emission Rates                                  Table AA-VII

-------
                                    AA-1
I.  Introduction

    Ninety percent of all adipic acid produced is used in the manufacture of
nylon 6,6.  Adipic acid is condensed with hexamethylene-diamine to form
nylon salt; this requires 0.7 Ibs. of adipic acid/lb. of nylon 6,6.
Additionally some hexamethylene-diamine is derived from adipic acid; this
requires 1.05 Ibs. of adipic acid/lb. of nylon 6,6.  Thus, the current
demand and the future growth of adipic acid is closely bound to the nylon
6,6 market.  Of lesser importance is adipic acid's use in the production of
plasticizers, synthetic lubricants and urethanes.

    Practically all commercial production of adipic acid is based on oxidizing
cyclohexanone/cyclohexanol with nitric acid.  The various oxides of nitrogen
produced during the oxidation constitute the principal source of air pollution
for this process.  The separation of adipic acid from its various by-products-
primarily glutaric and succinic acid - and the purification of adipic acid
contribute only slightly to the overall air pollution.  Likewise; the
pneumatic conveying, drying and melting of the purified adipic acid crystals
contribute relatively little to the total air emissions produced by the
process as a whole.  Air pollution resulting from the production of adipic acid
can be characterized as being moderate.

    The current U. S. capacity for the production of adipic acid is 1.43 x 10
Ibs./yr.  1980 production capacity, based on an annual growth rate of 5.570(*-),
is estimated at 2.20 x 109 Ibs./yr.
 (1)  Chemical Marketing Reporter, April 24, 1972

-------
                                     AA-2
II.   Process Description

     Cyclohexanone and cyclohexanol are oxidized to adipic acid by reaction
with nitric acid.  The following two equations illustrate the gross  chemistry:

          0
          II

(A)    H2 C C H2
         ! !       + (a) HNO- 	^  H2C - CH  - COOH
         HP P u              -3             UP. PU  — ppdPtu   v ^ /   v   \ **/  no w
       9 L L. no                           no L* " brio   UUUrl         A        ^
         V
          Ho

   Cyclohexanone   + Nitric Acid 	^-  Adipic Acid      + Nitrogen  Oxide + Water


(B)   H OH
      "c
  H2 C C H?                              H2C - CH0 - COOH
     ||      +  (x) HN03  	*•   H2C - CH2 - COOH + (y) N0x  +  (z> H2°
  H2 C C H2
      c'
      H2

  Cyclohexanol+Nitric Acid 	>*•  Adipic Acid       + Nitrogen Oxide  + Water

     The nitrogen compounds formed, shown above as NO , are predominately NO,
N02  and N20.  Additionally, various organic acid by-products are produced,
chief among these are acetic acid, glutaric acid and succinic acid-j  in larger
plants some of these may be recovered and sold.

     The following process description may more easily be followed by  referring
to Figure I - a process flow diagram:

     In commercial practice a mixture of cyclohexanone/cyclohexanol  is
oxidized in a series (generally two) of stirred tank reactors.   Feed to the
reactors is approximately one part alcohol-ketone and five parts 50  wt. %
nitric acid.  Pressure is about 30 psig and temperature is maintained  at
170° to 180° F by water cooling or heat exchange.  Standard catalyst for the
oxidation is a mixture of cupric nitrate and ammonium vanadate.

     Subsequent to the oxidation the dissolved NOX gases plus any light
hydrocarbon by-products are stripped from the adipic acid/nitric acid  solution
with air and steam.  NO and N02 are recovered by absorption in nitric  acid.

     The stripped adipic acid/nitric acid solution is then chilled and sent
to the No. 1 crystallizer, where crystals of adipic acid are formed.   The
crystals are separated from the mother liquor in the No. 1 centrifuge  and
transported to the adipic acid drying and/or melting facilities.  The  mother
liquor is separated from the remaining uncrystallized adipic acid in the
product still and recycled to the reactors.

     The bottoms from the product still are diluted with water, rechilled and
pumped to the No. 2 crystallizer.  The slurry from the No. 2 crystallizer is
pumped to the No. 2 centrifuge where the remaining adipic acid crystals are

-------
                                     AA-3
separated from the diluted residual mother liquor.  The crystals are
combined with the product from the No. 1 centrifuge.  The mother liquor
is distilled to recover the nitric acid; the residual material  is sent to
waste disposal.

-------
                                    AA-4


III.  Plant Emissions

      A.  Continuous Air Emissions

          1.  Reactor Off-gas

              All adipic acid plants tha-t oxidize cyclohexanone/cyclohexanol
          mixtures with nitric acid produce NO .   Much of the NO  formed
          is recovered as nitric acid, but a significant portion is emitted
          to the atmosphere.   The NOX emissions reported varied from .03 to
          .34 Ibs. of NOX per Ib. of adipic acid produced.   This tenfold
          variation in emission rates is apparently the result of two
          factors; (1) the difference in the performance of NOX recovery
          systems and (2) the variation in the percentage of N20 in the NOX -
          this is a factor because N£0 cannot be  easily recovered as nitric
          acid.  (^O/NO  ratio is dependent to some extent on cyclohexanol/
          cyclohexanone ratio).   Reactor off-gas  emissions  are summarized
          in Table III.  Note, however, that ^0 is not considered a pollutant.

          2.  Adipic Acid Purification and Nitric Acid Recovery Vents

              Because of the  variation in processing schemes and the inter-
          relationship of the two above named operations it is difficult to
          make generalized distinctions between the subject streams.  Air
          emissions from these two sources share  a similarity in composition -
          they are predominantly NOX.  In most instances, nitric acid recovery
          operations succeed  in minimizing emissions.   One  operator (EPA Code
          5-2); however, does report venting significant amounts (.03 Ib./lb.)
          of NOX from these facilities.  These emissions are summarized in
          Table III.

          3.  Vents from Adipic Acid Conveyors, Driers and  Melters

              The drying, conveying and general handling of adipic acid
          crystals presents the same problems that most dry solids present.
          The 'handling' produces 'fines'  and the fines generate dust.   The
          respondents report  utilizing a variety  of dust control equipment;
          cyclones, bag filters and wet scrubbers.   In general, the
          particulate emissions from this source  are low.  The highest rate
          of particulate emissions reported - by  EPA Code No. 5-4 - was
          .0005 Ibs./lb. of adipic acid.  Table III contains a complete
          summary of all reported emissions in this category.

          4.  Plant Flare and Incinerator Flue Gases

              Most petrochemical plants employ flares, 'thermal oxidizers'  or
          some type of incineration devices to burn waste hydrocarbons; either
          on a continuous basis, or intermittently, during  plant emergencies.
          Adipic acid plant operators are no different, in  this respect, than
          operators of other  types of petrochemical plants.   They have reported
          the use of various  incineration devices;  however,  in order to "burn"
          NOX containing gases in such a way that the  'combustion' products
          are less offensive  than their 'uncombusted'  precursors, the
          incineration devices must be specially  designed to decompose NOX
          into N2 and §•£.  At least one respondent has indicated that such a
          special incinerator is indeed utilized  (EPA  Code  No.  5-3, Device
          AA-8).  Flue gases  from less specialized devices  must be suspected
          of containing practically all of the NOX that was fed to them.
          This information is summarized in Table IV.

-------
                               AA-5
    5.  Storage Losses

        No respondent has offered an estimate of storage losses.  They
    should be quite low for two reasons, (1) final product is a solid
    and not subject to evaporation and (2) the hydrocarbon feed fre-
    quently comes direct from a previous processing step, and hence is
    not subject to normal storage losses.  Both operators EPA Code 5-2
    and 5-4 report using absorbers/scrubbers on nitric acid storage tank
    vents, thus minimizing emissions from that source.  Therefore,
    although no quantitative data are available it seems safe to surmise
    that air emission from adipic acid plant storage facilities are low.

B.  Intermittent Air Emissions

        Start-up and Emergency Vents

        This type of emission is universally encountered in the
    pertochemical industry and will vary from process-to-process,
    from operator-to-operator and even from year-to-year.  One operator
    (EPA Code No. 5-2) estimates that he vents his reactors to the
    atmosphere - on an emergency basis - six to twelve times per year.
    Taking the higher figure this still amounts to less than one ton
    per year of NOX - an insignificant amount.   This information is
    detailed in Table III.

C.  Continuous Liquid Wastes

        Waste Water

        All respondents report the production of waste water:

        Operator EPA Code 5-1 reports 90 GPM, which is disposed of by
    deep well injection.

        Operator EPA Code 5-2 reports 600 GPM,  containing 0.5 wt. %
    succinic acid and 1.2 wt. % glutaric acid.   Its method of disposal
    is not discussed.

        Operator EPA Code 5-3 reports the production of about 350 GPM,
    containing 0.9 wt. % HN03 and 2.3 wt. °L organics.   Deep well
    injection is used for disposal.

        Operator EPA Code 5-4 reports the production of about 40 GPM
    of waste water.

D.  Intermittent Liquid Wastes

        No intermittent liquid wastes were reported.

E.  Solid Wastes

        No solid wastes were reported.

F.  Fugitive Emissions

        Only one operator (EPA Code No.  5-1) has made  a quantitative
    estimate of fugitive emissions.   His estimate is 150 SCFH (of NOX?).

-------
                              AA-6
    Other operators state that emissions of this type are either non-
    existent or very low.  Considering that the adipic acid process
    is low pressure, and that fugitive emissions would probably be
    fairly easy to detect because of their odor or their visibility,
    it is probable that fugitive emissions are quite low.
G.  Odors
        In general, the production of adipic acid via nitric acid
    oxidation of cyclohexanol/cyclohexanone does not appear to be a
    process that has an odor problem.

        None of the respondents reported an odor complaint in the past
    year.   Most of the reported odors  are said to be detected only on
    the plant property and only at intermittent intervals.  The odiferous
    materials are usually identified as NOX.

        All NOX containing vent streams are potential sources of odors.
    However, according to the questionnaire these streams are  well
    enough controlled to prevent odor  problems.

-------
                                     AA-7


IV.  Emission Control

     The emission control devices that have been reported as being employed
by operators of adipic acid plants are. summarily described in Table IV of
this report.  An efficiency has been assigned each device whenever data
sufficient to calculate it have been available.  Three types of efficiencies
have been calculated:

(1)  "CCR" = Completeness of Combustion Rating

     CCR = Ibs. of 02 reacting (with pollutants in device feed)
                Ibs. of 02 that theoretically could react

(2)  "SE" - Specific Efficiency

     SE = specific pollutant in - specific pollutant out
                      specific pollutant in

(3)  "SERR" - Significance of Emission Reduction Rating
                                                                           x 100
     SERR =   (pollutant x weighting factor*) in -  (pollutant x weighting
            	factor*) out	
                               (pollutant x weighting factor*) in

^Weighting factor same as Table VII weighting factor.

     Normally a combustion type control device (i.e., incinerator, flare, etc.)
will be assigned both a "CCR" and a "SERR" rating, whereas, a non-combustion
type device will be assigned an "SE" and/or an "SERR" rating.  A more complete
description of this rating method may be found in Appendix V of this report.

     Although efficiency ratings for most devices are shown  in Table IV, a
few general comments  regarding adipic acid pollution control device per-
formance seems  in  order:

     Absorbers
        Adipic acid plant operators reported the use of five absorbers.  They
     are  identified in Table IV as devices AA-1, AA-2, AA-3, AA-4, and AA-7.
     The  specific efficiencies (with regard to NOX, but excluding ^0 since
     it is not regarded as a pollutant) range from 487» to 98.870.  Information
     sufficient to determine the cause of device AA-7's unusually low
     efficiency (i.e., 48%) is not available.  Three of the other four devices
     have specific efficiencies greater than 957,, while insufficient data
     precluded the calculation of an efficiency for the third.  Thus, based
     on the data reported in the questionnaires, absorbers  in adipic acid
     'NOX service1 appear capable of removing 95 + 7, of NO  and N02-

     Scrubbers
        The operator of  plant EPA Code No. 5-2, reports the use of two
     scrubbing devices,  AA-5 and AA-6, to control the emission of adipic
     acid dust.  His estimates  of adipic acid concentrations lead to cal-
     culated specific efficiencies of about 907, for both devices.  This is
     probably typical for this service, but variations in particle size
     distribution and device energy input will alter efficiency.

-------
                                     AA-8
     Cyclones

        The use of two cyclone separators has been reported by questionnaire
     respondents.  Particle size information is lacking for both installations.
     Based on the scant information available on these devices it seems safe
     to say only that adipic acid dust collection efficiencies in excess of
     90% are feasible with single stage cyclones.

     Bag Filters

        The operator of plant EPA Code No. 5-3 provides the only information
     on the use of bag filters in the control of adipic acid dust emissions.
     Although he does not report particle  size, he states dust collection
     efficiency is 100%.

     Incineration Devices

        Pollution reduction via the incineration of nitrogen oxides requires
     the use of devices specifically designed for this duty.  These special
     burners reduce NOX to elemental nitrogen by providing a reducing
     atmosphere through the use of at least 10% excess fuel.  NOX reductions
     of 75 to 90% have been reported for this method in the literature.
     The operator of plant EPA Code No. 5-3 reports utilizing such a device
     for "burning" the NOX fumes vented from his nitric acid storage facilities,
     Data provided by that respondent show that his NOX burner, identified
     as device AA-8 in Table IV, operates with an efficiency (CCR & SERR)
     of 70%.  However, the same respondent reports sending another NOX
     bearing stream - the effluent from device AA-7 - to the boiler house,
     where he states "an indeterminate amount of NO and N02 are reduced to
     N2 in the burner flame".  It seems extremely unlikely that the proper
     conditions for NOX reduction exist within a boiler firebox.

        Operator EPA Code No. 5-4 reports burning about 25 gallons an hour
     of various waste organic acids.  His analysis of incinerator flue gases
     show his device to be 100% efficient in this duty.

     It is unlikely that any change in operating conditions, per se, will
lead to a significant decrease in air pollution.  However, many adipic acid
plants would benefit through more extensive use of pollution control
equipment currently in use by some segments of the industry.  As previously
pointed out, with few exceptions, most of the devices that are employed have
efficiencies in excess of 907» and better utilization of them could reduce
the industry wide pollution average significantly.

     Developmental work directed toward reductions in emissions from this
process falls into the following general categories:

     (1)  One-step oxidation of cyclohexane to adipic acid - thereby reducing
          the number of pollution generating steps in the overall process
          by 50%.

     (2)  Substitution of air or preferably oxygen for nitric acid - as the
          oxidant.  Although this has been studied and found uneconomic,
          further investigation of the overall environmental impact might  be
          warranted.

     (3)  Devise method for economically recovering ^0.  Although not a

-------
                               AA-9
     pollutant,  N£0 recovery  might  lead  to  an  overall  reduction  in
     nitric acid production if  it could  be  re-oxidized and  recycled.

(4)   More efficient design and  operation of devices  currently being
     utilized.

-------
                                    AA-10
V.  Significance of Pollution

    It is recommended that no in-depth study of this process be undertaken at
this time.  The reported emission data indicated that the quantity of pollutants
released as air emissions is less for the subject process than for other
processes that are currently being surveyed.  However, one must be cognizant
of the fact that although the production of adipic acid a   the production
of cyclohexanol/cyclohexanone were surveyed as two separate and individual
processes, current practice is to integrate the production facilities into
one plant.  Therefore, the emissions accompanying 'one process' co-exist with
the emissions from the other.  This may give rise to consideration of an
in-depth study of the entire process (cyclohexane to adipic acid) at some
later date.

    The methods outlined in Appendix IV of this report have been used to
forecast the number of new plants that will be built by 1980 and to estimate
the total weighted annual emissions from these new plants.  This work is
summarized in Tables V, VI and VII.

    The Table V forecast of new plants is based on a predicted annual capacity
growth of 5.5%.  This is in agreement with the estimate published in the
Chemical Marketing Reporter, April 24th,  1972.

    On a weighted emission basis a Significant Emission Index of 780 has been
calculated in Table VII.  This is less than the SEI's for some of the other
processes in the study.  Hence, the recommendation to exclude adipic acid
production from the in-depth study portion of the overall scope of work.
However, due to the fact that most of the SEI results from NOX emissions,
any effort to reduce this type of pollution should certainly consider new
source standards on adipic acid production.

-------
                                    AA-11
VI.  Adipic Acid Producers

     The following tabulation of producers of adipic acid indicates  published
production capacity by company and location:
 Company

Allied

Celanese

DuPont


El Paso

Monsanto
     Location

Hopewell, Va. (2)

Bay City, Texas (3)

Orange, Texas (3)
Victoria, Texas (3)

Odessa, Texas (3)

Luling, La.  (2)
Pensacola, Fla. (3)
Capacity
                                                                          (1)
                                                  Total
     20

    130

    300
    300

     80

     60
    540

  1,430
Notes

(1)  Capacity in MM Lb./Yr.

(2)  Cyclohexanone/cyclohexanol derived from phenol.

(3)  Cyclohexanone/cyclohexanol derived from cyclohexane.

-------
 PAGE NOT
AVAILABLE
DIGITALLY

-------
                                                    TABLE AA-I
Stream No. (Fig. I)











Cyclohexanone




Cyclohexanol




Cyclohexyl Esters  (as formate)




Adipic Acid




Dicarboxylic Acids (as succinic)




Monocarboxylic Acids (as acetic)




Water




Nitric Acid (100%)




Nitrogen  Oxides




Total
TYPICAL ADIPIC ACID PLANT
MATERIAL BALANCE
T/T OF ADIPIC ACID
1 2
Organic Feed Acid Feed
to Oxidizer to Oxidizer
.3402
.2778
.1399



1.8434
2.0813

.7579 3.9247


3 (A & B) 4 (A & B)
Oxidizer Nitric Acid to
Effluent Recycle & Concen. '



1.0000
.0624
.0357
2.0130 2.0130
1.2193 1.2193
.3522
4.6826 3.2323


5 6 (A & B) 7
Light Heavy Adipic
Ends Ends Acid



1.0000
.0624
.0357


.3522
.3522 .0981 1.0000

-------
                                 TABLE AA-II
                            ADIPIC ACID PRODUCTION
                                     VIA
                            NITRIC ACID OXIDATION
                                      OF
                         CYCLOHEXANONETCYCLOHEXANOL
                          GROSS REACTOR HEAT BALANCE
Heat In
   Exothermic Heat of Reaction
BTU/LB. OF ADIPIC ACID PRODUCED

            1390*
Heat Out

   Reactor Temp. Control (@ 180° F)
   NOX Vapor Vent
   Sensible Heat Removal - Heat Exchange
   Sensible Heat Removal - Cooling (to 60° F)
            1030
              20
             170
             170

     Total  1390
*Based on feed, conversions, etc. shown in Table 5.

-------
Plant - EPA Code No.
Capacity, Tons of Adipic Acid/Yr.
Average Production, Tons of Adipic Acid/Yr.
Range in Production - 7. of Max.
Emissions to Atmosphere
   Stream
                   TABLE AA-III
            NATIONAL  EMISSIONS  INVENTORY
               ADIPIC ACID PRODUCTION
                        VIA
NITRIC ACID OXIDATION OF CYCLOHEXANOL/CYCLOHEXANONE

                                        5-1
                                      65,000
                 Reactor Vent
                                                                                                                                  Page  1  of  4
Combined
HN03 One  &
Prod  Purification Vent
   Flow - Ibs./hr.
   Flow Characteristic, Continuous or Intermittent
        if Intermittent, hrs./yr. flow
   Composition, Ton/ton of Adipic Acid
        Nitric Oxide
        Nitrogen Dioxide
        Nitrous Oxide
        Nitrogen
        Oxygen
        Carbon Monoxide
        Carbon Dioxide
        Water
        Adipic Acid
        Nitric Acid
                 7796
                 Continuous
                 .00363

                 .33846
                 .06726
                 .01539

                 .05286
                 .00215
Unknown
Continuous
.00008
   Vent Stacks
        Number
        Height -  Ft.
        Diameter  -  Inches
        Exit Gas  Temp.  - F°
        SCFM/Stack
   Emission Control Devices
        Ab sorber/S crubber
        Incinerator/Flare
        Condensor/K.  0. Drum
        Other
   Analysis
        Date or Frequency  of Sampling
        Tap Location
        Type of Analysis
        Odor Problem
   Summary of Air Pollutants
        Hydrocarbons, Ton/Ton  of Adipic Acid
        Particulates, Ton/Ton  of Adipic Acid
        NOX  -  Ton/Ton of Adipic Acid
        SOX  -  Ton/Ton of Adipic Acid
        CO   -  Ton/Ton of Adipic Acid
                 Yes
                 1
                 140
                 42
                 70
                 1260
                 Yes - AA-1
                 Varies

                 Phenoldisulfonic Acid
                 No
                                         0
                                         0
                                       •00371
                                         0
                                         0
Yes
1
63
8
110
Unknown
Yes - AA-2
Never
None
Estimate
No

-------
                                                                                    TABLE AA-III
Plant - EPA Code No.
Capacity, Tons of Adipic Acid/Yr.
Average Production, Tons of Adipic Acid/Yr.
Range in Production - 7, of Max.
Emissions to Atmosphere
    Stream
    Flov - Lbs./Hr.
    Flow Characteristic, Continuous or Intermittent
       if Intermittent, Hrs./Yr. Flow
    Composition, Ton/ton of Adipic Acid
       Nitric Oxide
       Nitrogen Dioxide
       Nitrous Oxide
       Nitrogen        '
       Oxygen
       Carbon Monoxide
       Carbon Dioxide
       Water
       Adipic Acid
       Nitric Acid
    Vent Stacks
       Number
       Height - Ft.
       Diameter - Inches
       Exit Gas Temp. - F°
       SCFM/Stack
    Emission Control Devices
       Absorber/Scrubber
       Incinerator/Flare
       Condenser/K. 0. Drum
       Other
    Analysis
       Date or Frequency of Sampling
       Tap Location
       Type of Analysis
       Odor Problem
    Summary of Air Pollutants
       Hydrocarbons, Ton/Ton of Adipic Acid
       Participates, Ton/Ton of Adipic Acid
       NOX, Ton/Ton of Adipic Acid
       SOx, Ton/Ton of Adipic Acid
       CO  , Ton/Ton of Adipic Acid



NITRIC



Reactor
Emergency
Vent
>-i2,500
Intermittent
-"0.1
•^.00001
t-. 00001
.£.00001
•^.00001

^.00001
•^.00001
/". 00001

Yes
2
100
24
170
1000
No
Never
None
Calc.
No





NATIONAL EMISEIONT INVENTORY
ADIPIC ACID PRODUCTION
VIA
ACID OXIDATION OF CYCLOHEXANOL/CYCLOHEXANONE Pag.
5-2
270,000
0
Adipic Acid
Reactor Off-Gas Prod. Purification Drier
Vent Vent
5567 2903 80.963
Continuous Continuous Continuous

. 00005 . 00003
. 00008 . 00005

). 07564 ). 03954 ) 1 . 12003
) ) )


.00376 .00185 .03659
.00014
Yes Yes No
2 3
80 90
12 12
120 120
^ 625 ^220
Yes - AA-3 Yes - AA-4 Yes - AA-5
Never Never Never
None None
Calc. Calc. Calc. or Est.
No No No
0
.00014
.0300
0
0
 Adipic Acid
  Melter
  Vent

  2220
  Continuous
  .03171
^.00001
*£. 00001
  Never
  None
  Calc.
  No
Nitric" Acid
Recovery
Vent

58,550
Continuous
                        .0110
                        .0169
                        .2971
                        .4521
                        .0141

                        .0451
Yes
2
85
8
180
•"390
Yes - AA-6
Yes
1
75
4
80

No
Accessible
Various
No

-------
Plant - EPA Code No.
Capacity - Tons of Adipic Acld/Yr.
Average Production, Tons of Adipic Acid/Yr.
Range in Production - % of Max.
Emissions to Atmosphere
    Stream
    Flow - Lbs./Hr.
    Flow Characteristic, Continuous or Intermittent
        if Intermittent, Hrs./Yr. Flow
    Composition - Ton/Ton of Adipic Acid
        Nitric Oxide
        Nitrogen Dioxide
        Nitrous Oxide
        Nitrogen
        Oxygen
        Carbon Monoxide
        Carbon Dioxide
        Water
        Adipic Acid
        Nitric Acid

    Vent Stacks
        Number
        Height - Ft.
        Diameter - Inches
        Exit Gas Temp. F°
        SCFM/Stack
    Emission Control Device
        Absorber/Scrubber
        Incinerator/Flare
        Condenser/K. 0. Drum
        Other
    Analysis
        Date or Frequency of Sampling
        Sample Tap Location
        Type of Analysis
        Odor Problem
    Summary of Air Pollutants
        Hydrocarbons, Ton/Ton of Adipic Acid
        Particulates, Ton/Ton of Adipic Acid
        NOX, Ton/Ton of Adipic Acid
        EOX, Ton/Ton of Adipic Acid
        CO , Ton/Ton of Adipic Acid
                                                                                    TABLE AA-III
                                                                            NATIONAL EMISSION? INVENTORY
                                                                               ADIPIC'ACID PRODUCTION
                                                                                        VIA
                                                                KTTP.TC ACID OXIDATION OF CYCLOHEXANOL/CYCLOHEXANONE
                                                                                                                                  Page 3 of 4


Reactor
Vent
30,000
Continuous
5-3
150,000
0
HN03 Recovery
Vent
5,000
Continuous
5-4 '
40,000
40,000

Prod. Purif.
Vent
2.6,000
Continuous

Pneumatic
Conveyor
Vent
13,500
Continuous
0
Process (B)
Vent
Header
5597
Continuous

Adipic Acid
Drier
Vent
45,169
Continuous

Heavy Ends
Incinerator
Flue Gas
8866
Continuous
. \J£.J?
.2464
.45155
.05218
.14650
.01204
). 00010
)
)1. 00334
>


No
Yes - AA-7



+ steam boiler

Infrequently

Mass Spec.
No
                 Yes AA-8
                 Never
                 None
                 Calc.
                 No
                        0
                     .00009
                     .026
                        0
                        0
                        0
                                  ). 86957
                                   .00009
                                   Yes - AA-9
+ bag filter

Never
None
Calc.
No
                                                   ). 45155
Yes
1
64
36
1832°
Yes
1
64
36
150°
Yes
1
64
36
150'
Yes - AA-10



+ cyclone sep.

Never

Estimate
No
                                    ,06834
                                    .36274
                                    .08299
                                    .00046
                                    .04514
                                                                       No  (C)
                                                                       Yes  (C)
                                                                       Infreauent
GLC
No
14.43000
1

.08640
.00050
Yes
1
33
18
160
10,200
Yes - AA-11
.65516
.04047
.11130
.07968

Yes
1
34
48
1400
2,000
Yes - AA-12
+ cyclone sep

Never
None
Estimate
No
                                                                                   0
                                                                                .00050
                                                                                .003
                                                                                   0
                                                                                .00046
Never
None
Calc
No

-------
                                 TABLE AA-IH               page 4 of 4
                             EXPLANATION OF NOTES
                         NATIONAL EMISSIONS INVENTORY

                            ADIPIC ACID PRODUCTION
                                     VIA
             NITRIC ACID OXIDATION OF CYCLOHEXANONE/CYCLOHEXANOL
A)  Operator states that this stream is sent to boiler house and used as
    'air' for burners, where upon an unknown amount of NOX    »  N2 + 02-
    Composition reported in Table III (ton/ton) is based on assumption
    that NOX is reduced by 20% by this treatment.  Actual NOX concentration
    may increase or (under special conditions) be reduced by up to 907».

B)  Operator states that this stream is sent to HMD plant 'thermal oxidizer'
    It is assumed that this device is especially designed for NO  reduction.
    Consequently, a NO  reduction of 707o (which is reported performance of
    device AA-8) has been assumed and the  NO  concentration reported in
    this column is correspondingly decreased.

C)  No vent stack for this stream in adipic acid plant.  Stream sent to
    thermal oxidizer in HMD plant.

-------
                                                                                     TABLE AA-IV
ABSORBERS/ECRUBBEFS
   EPA Code No. for plant, using
   Flov Diagram (Fig.   ID Stream  T.U.
   Device I.D No.
   Controls Emission ot -
   Scrubbing/Absorbing  Liquid
   Type - Spray
          Packed Column
          Column v/trays
                 Number of trays
                 Kind of  tray
          Plenum Chamber
          Other
   Scrubbing Absorbing  Liquid Rate  -  i PM
   Design Temp. (Operating Temp.1  F°
   Gas Rate, SCFM  (Ib./hr.1
   T-T Height, Ft.
   Diameter, Ft.
   Vashed Gases to Stack  -
          Stack Height  -  Ft.
          Stack Diameter  - Inches
   Installed Cost  - Mat'l. & Labor -  S
   Installed Cost  Based on - "year" - dollars
   Installed Cost  -  c/lb. of Adipic .\cid/Yr.
   Operating Cost  -Annual (1972)
   Value of Recovered Product;  $/yr.
   Net Operating Cost - Annual, $
   Net Operating Cost - c/lt>- of Adipic Acid
   Efficiency  - V  SE
 INCINERATION DEVICfcb
   EPA Code No.  for  plant using
   Flow Diagram  (Fig. II) Stream  I.D.
   Device I.D. No.
   Type of Compound  Incinerated
   Type of Device  -  Flare
                     Incinerator
                     Other
   Material Incinerated,  TCFM  (Ib./hr.)
   Auxilliary  Fuel Req'd.  'excl.  pilot)
                     Type
                     Rate  - BTU/hr.
   Device or Stack Height  -  Ft.
   Installed Cost  -  Mat'l. & Labor -  S
   Installed Cost  Based on "vear"  dollars
   Installed Cost  -  c/lb. of Adipic Acid/Yr.
   Operating Cost  -  Annual - $  (1972)
   Operating Cost  -   /Ib. of Adipic Acid
   Efficiency  - CCP  - 7.
   Efficiency  - SEPR  -  7,

CATALOG OF EMISSION CONTROL DEVICES

I'MPIC ACID PRODUCTION VIA NITRIC ACID OXIDATION OF CYCLOHEXANOL/CYCLOHEXANONE F


5-1
AA-1
NOX
Vater
Kot Specified
4
100
1204


Yes
140
42
360,000
1965-1970
.2769
57,000
74,000
- 17,000

95.9% (NOX)




Reactor Vent

-------
                                                                                      TABLE  AA-IV
                                                                         CATALOG OF EMISSION  CONTROL DEVICES
                                                    ADI PIC ACID  PRODUCTION' VIA "ITRIC ACID  OXIDATION OF  CYCLOHEXANOL/CYCLOHEXANONE       page 2 of 4

                                                                                "Finished1  Product  Operations
                                                                                 Conveying, Drying, Melting, etc.
ABSORBERS /SCRUBBERS
   EPA Code No. for plant using
   Flow Diagram (Fig. II) Stream T.I),
   Device I.D. No.
   Controls Emission of -
   Scrubbing/Absorbing Liquid
   Type - Spray
          Packed Column
          Column w/trays
                 Number of trays
                 Kind of tray
          Plenum Chamber
          Other
   Scrubbing Absorbing Liquid Rate - GPM
   Design  Temp,  (operating Temp.) F°
   Gas Kate, SCFM  (Ib./hr.)
   T-T Height, Ft.
   Diameter, Ft.
   Washed Gases to Stack -
          Stack Height -  Ft.
          Stack Diameter - Inches
   Installed Cost  - Mat'l. & Labor - S
   Installed Cost  - Based on - "year" - Dollars
   Installed Cost  - C/lb. of Adipic Acid/Yr.
   Operating Cost  - Annual, S (1972)
   Value of Recovered Product, $/Yr.
   Net Operating Cost - Annual, $
   Net Operating Cost - c/lb. of Adipic Acid
   Efficiency  - %   SE

INCINERATION DEVICES
   EPA Code No. for plant using
   Flow Diagram (Fig. II) Stream T.D.
   Device I.D. No.
   Type of Compound Incinerated
   Type of Device  - Flare
                    Incinerator
                    Other
   Material Incinerated, SCFM (Ib./hr.)
   Auxilliary  Fuel Req'd (excl. pilot)
                    Type
                    Rate - BTU/hr.
   Device or Stack Height - Ft.
   Installed Cost  - Mat'l. & Labor - $
   Installed Cost  Based on "year" Dollars
   Installed Cost  - C/lb. of Adipic Acid/yr.
   Operating Cost  - Annual - S (1972)
   Operating Cost  - c/lb. of Adipic Acid
   Efficiency  - CCR - If,
   Efficiency  - SERR - 7.
                                                                       'T
5-2
_E,
AA-5
Adipic Acid Dust
Water
5-2
Jfc,
AA-6
HN03 & Adipic Acid
Water
5
120
18,000
15
10
No
25,000
1960

3500
0
3500

90
3
200
425
5.25
2
Yes
85
8
15,000
1967

1500
0
1500

90+

-------
                                                                                   TABLE AA-IV
                                                                        CATALOG OF EMISSION CONTROL DEVICES
                                                   ADIPIC ACID  PRODUCTION VIA NITRIC ACID OXIDATION OF  CYCLOHEXANONE/CYCLOHEXANOL
                                                                                                                                        Page 3 of 4
CYCLONES

   EPA Code No.  for plant using
   Flow Diagram (Fig. II) Stream I
   Device I.D. No.
   Controls Emission of
   T-T Height - Ft.
   Diameter - Ft.
                                                                    Adipic Acid
                                                                    Puri fication
                                                                                                          'Finished'  Product Operations
                                                                                                          Drying,  Conveying, Melting, etc.
   No. of Stages
   Installed Cost - Mat'l.
                           & Labor
                                D.
                                   - $
                                   1 - $
Installed Cost hased on - "year"
Installed Cost - c/lh. of Adipic Acid/Yr.
Operating Cost - Annual - $ (1972)
Value of Recovered Product, $/Hr.
Net Operating Cost, $/Yr.
Net Operating Cost, r/Lb. of Adipic Acid
Efficiency - % SE
 -3

AA-10
Adipic Acid Dust
63,000
1964 — 1966
.0210
                                                                                                        100
5-4
.JK
AA-11
Adipic Acid Dust
18
5.5

30,000
1967
.0375
2000
3300
- 1300

93.8
BAG FILTERS

   EPA Code No. for plant using
   Flov Diagram (Fig.  II) Stream  I.D.
   Device I.D. No.
   Controls Emissions  of
   Number of Compartments
   Number of bags per  compartment
   Bag Cloth Material
   Total Bag Area - Ft2
   Design (operating)  Temp.  -  F°
   Design (operating)  press  -  psig
   Installed Cost - Mat'l. {< Labor,  S
   Installed Cost Based on - "Year"  -  Dollars
   Installed Cost, c/lb. of  Adipic Acid/Yr.
   Operating Cost - Annual - $  (1972)
   Value of recovered  product  - $/yr.
   Operating Cost - Annual - S  (1972)
   Value of Recovered  product  - $/yr.
   Net Operating Cost  - S/Yr.
   Net Operating Cost  - c/lb.  of  Adipic Acid
   Efficiency  - "L SE
                                                                  5-3
                                                                 AA-9
                                                                 HN03 + Adipic  Acid  Dust
                                                                  28,000
                                                                  1967
                                                                  .0093
                                                                     HN03  -  90%,  Dust  -  1007.

-------
                                 TABLE AA-IV                  Page 4 of 4
                             EXPLANATION OF NOTES
                     CATALOG OF EMISSION CONTROL DEVICES
                            ADIPIC ACID PRODUCTION
  I  This device consists of two identical scrubbers.   Costs reported are
     total costs.

 II  No note.
Ill  This device consists of three identical scrubbers.   Costs reported are
     total costs.

 IV  Device consists of dust scrubber and cyclone but no description given
     of either.

-------
                                                TABLE AA-V



Current
Capacity



Marginal
Capacity

Current
Capacity
on-stream
in 1980
NUMBER OF NEW


Demand
1980
PLANTS BY 1980


Capacity (1)
1980


Capacity
to be
Added


Economic
Plant
Size


Number
Of
New Units
1430            160             1270           1900           2200              930             150            6-7
Note:

General - All capacities in MM Lbs./Yr.

(1)  1980 capacity based on growth rate of 5.5% per year as predicted
     by Chem. Marketing, April 24, 1972.

-------
                                               TABLE AA-VI
EMISSION SOURCE SUMMARY
Pollutant Source
"Finished" Product-
Product Purification Operations -
Reactor and Conveying, Fugitive
Off-Gas Nitric Acid Recovery Drying, etc. Emissions
Hydrocarbon x
Particulate .00005 .00010
NO,, .0037 .017 Negligible
X.
SOK j
CO .00010 ""
Total
0
.00015
.0207
0
.00010
Note:   Pollutant quantities in Ib./lb.  of adipic acid.

-------
TABLE AA-VII
WEIGHTED EMISSION RATES
deal: Adipic Acid
ess: HNC>3 Oxidation
eased Capacity by 1980: 930 MM Lbs./Yr.
Pollutant Emissions Lb./Lb.
Hydrocarbon 0
Particulate .00015
NOX .0207
sox o
CO .00010
Increased Emissions Weighting
MM Lbs./Yr. Factors
0 80
. 140 60
19.25 40
0 20
.093 1
Weighted
Emissions
MM Lbs. /Yr.
0
8.4
770
0
0.1
                            Significant Emissions Index     778.5

-------
Adiponitrile via Butadiene

-------
                              Table of Contents

Section                                                          Page Number

I.    Introduction                                                 AN-1
II.   Process Chemistry                                            AN-2
III.   Plant Emissions                                              AN-4
IV.   Emission Control.                                             AN-7
V.    Significance of Pollution                                    AN-9
VI.   Adiponitrile Producers                                       AN-10

                        List of Illustrations & Tables

      Block Flow Diagram                                         Figure AN-I
      Net Material Balance                                       Table AN-I
      Gross Heat Balance                                         Table AN-II
      Emission Inventory                                         Table AN-III
      Catalog of Emission Control Devices                        Table AN-IV
      Number of New Plants by 1980                               Table AN-V
      Emission Source Summary                                    Table AN-VI
      Weighted Emission Rates                                    Table AN-VII

-------
                                     AN-1
I.  Introduction

    Adiponitrile is an intermediate in the synthesis of nylon 6, 6; with this
use alone accounting for over 907o of all adiponitrile production.  Several
routes to adiponitrile are available, but (in the U. S.) only three are
utilized at the present time.  Primary raw materials for the three routes are:

    (1)  Butadiene
    (2)  Adipic Acid
    (3)  Acrylonitrile

    In terms of process capacity, the process utilizing butadiene is pre-
eminent - and is the subject of this survey report.

    Nitrogen oxides comprise the bulk of the air pollutants associated with
the butadiene process; with the major portion of them arising from the
incineration of nitrogenous waste materials.  Of less importance, but still
significant, are the various hydrocarbon emissions generated by the chlorination
section of the plant.   Additionally, several waste liquid streams are produced,
the most  important of these being the waste brine produced by the chlorobutene
cyanation reaction.  In general, air emissions from the subject process can
be characterized as moderate.

    The current U. S.  adiponitrile production capacity - for the butadiene
process - is estimated at 4.35 x 10° Ibs./yr.  1980 capacity is estimated to be
8.45 x 108 Ibs./yr.; assuming that the process maintains its present share of the
industry!s total capacity.   However, the butadiene process operates from a
narrow base, with only one producer utilizing it, and the premise upon which
the 1980 estimate is based, may best be described as - tenuous.

-------
                                      AN-2
 In most  of  the  petrochemical  industry survey reports there is a brief 'process
 description1  section.   However,  data  sufficient  to permit the provision of
 such information in  this  report  are not  availabe,  most probably because a
 sole producer has better  control over the  dissemination of process information.
 Consequently, the following discussion of  process  chemistry  is substituted.

 II.   Process  Chemistry

      The production  of  adiponitrile from butadiene involves four distinct
 reaction steps.   They are:

 I.   Chlorination

      CH2 =  CH-CH = CH2  +  C12  '"•'^    CH2  Cl - CHCl  -  CH = CH2

      Butadiene          Chlorine      3, 4 - Dichloro-1-Butene

 Mol.  Wt.  54.09           70.91                 125.00

      This reaction will procede  readily  in either  the  liquid  or gas  phase and
 with or  without  a catalyst.   It  is believed that current commercial  practice
 is  restricted to a copper chloride catalyzed vapor phase process,  with
 temperatures  in  the  range of  150 to 350° C.   Yields  as  low as 75% are reported
 by  some  of  the earlier  (Circa 1962) references available.   A  (perhaps)  more
 realistic representation  of commercial experience  shows  a  (catalyzed) yield of
 987»*, with  the following  distribution of useable isomers:
             3, 4  - Dichloro  -  1  - Butene
     Cis     1, 4  - Dichloro  -  2  - Butene
     Trans - 1, 4  - Dichloro  -  2  - Butene
II.  Cyanation

     CH2 Cl - CHCl - CH
           CH2 + 2 NaCN
                             42%
                             157.
                             417,
                             987»
             NC - CH2 - CH(CN)-CH = CH2 + 2 NaCl
     3, 4 - Dichloro-1-Butene
Mol. Wt.
125.00
Sodium
Cyanide

  49.01
                              3,  4 - Dicyano-1-Butene
106.13
Sodium
Chloride

 58.45
     The cyanation can be effected with either hydrogen cyanide or sodium
cyanide, with the latter preferred.  The reaction takes place in an aqueous
media, and may be catalyzed with a cuprous cyanide complexing agent.  The
yield for this step, including extraction and distillation losses, is about 9570.
III.  Isomerization

A     NC-CH2-CH(CN)-CH = CH2 —

       3, 4 - Dicyano-1-Butene

Mol. Wt.       106.13
                     NC-CH2-CH=CH-CH2-CN

                     1,  4 - Dicyano-2-Butene

                         106.13
     The above isomerization  'step' (III-A) apparently takes place more-or-less
simultaneously with the cyanation  'step1.  (Of course only about 4070 of the
dicyanobutenes formed undergo this re-arrangement since the other 607« were derived
*Excluding processing losses.

-------
                                    AN-3
from dichlorobutenes of the 'proper1 configuration - see Step I product
distribution).  The 1, 4 dicyano-2-butene so formed exists in both the cis
and trans form.  The trans form is a solid at processing conditions and some
sources report that is is "partially isomerized to a liquid isomer".  That
reaction is shown below:

B     NC-CH2-CH = CH-CH2-CN        n >     NC-d^-Cfi^-CH - CH-CN

   (Trans only) 1, 4 - Dicyano-2-Butene         1, 4 - Dicyano-1-Butene

Mbl.  Wt.             106.13                             106.13

     Information regarding the process conditions  favoring this isomerization
(III-B) has not been found.

IV.  Hydrogenation

     NC-CH2-CH = CH-CH2-CN         + H2         V    NC-(CH2)4 - CN

     1, 4 - Dicyano-2-Butene        Hydrogen         Adiponitrile

Mol.  Wt.     106.13                    2.02             108.15

     The mixture of 1, 4 dicyano-1-butene and 1, 4 dicyano-2-butene is
hydrogenated over a palladium catalyst at 100° C to 300° C.  An early reference
states that at 25 atmospheres the yield is 96%.

-------
                                     AN-4


III.  Plant Emissions

      A.  Continuous Air Emissions

          1.  Chlorination Section Process Vents

              The respondent reports three streams in this category.  All
          contain butadiene and/or various chlorinated hydrocarbons.  All
          three are relatively insignificant - with total emissions of
          approximately .002 Ib./lb. of hydrocarbon.

          2.  Chlorination Section Storage Tank Vents

              The two tank vents reported for this plant section are both
          nearly 100 percent nitrogen, and thus, essentially non-polluting.

          3.  Cyanide Snythesis Section Process Vents

              This source contributes over 70 percent (on a weighted basis)
          of all the air emissions produced by the process.  The vent consists
          of the combustion products from three incinerators and a boiler.
          In lieu of information to the contrary it has been assumed, that,
          upon combustion, 10 percent of the nitrogen in nitrogen containing
          compounds, is oxidized to NOX.  Emissions from this source are
          .0379 Ibs./lb. of NOX.

          4.  Cyanation and Isomerization Section Process Vents

              Table IV summarizes the twelve streams  reported by the
          respondent that fall into this category.  Of the twelve, one
          contains a relatively small amount of NOX (.021 Ibs./lb.) and
          five contain varying (small) amounts of benzene, with a total
          benzene emission from this source of .008 Ibs./lb.  The other six
          streams contain only non-polluting substances;  generally nitrogen,
          air or water vapor.

          5.  Cyanation and Isomerization Section Tank Vents

              The two tank vents reported for this section of the plant both
          contain small amounts benzene.  Total benzene from this source is
          approximately .0002  Ibs./lb.

          6.  Hydrogenation Section Process Vents

              The tv?o vents reported from this section of the plant contain
          only insignificant amounts of ammonia and non-polluting compounds.

          7.  Boiler House Emissions

              Waste liquids from the cyanation and isomerization section and
          from the hydrogenation section are burned as fuel.  2100 Ibs./hr.
          of liquid containing 23.4 wt.  percent nitrogen  and 1.6 wt.  percent
          chlorine and 11,000  Ibs./hour of liquid containing 21.2 percent
          N£ and 0.6 wt.  percent chlorine are thus disposed of from these two
          sections.  Emissions resulting from this operation amount to .00688
          pounds aerosols  (HC1)  per pound and .05686  pounds NOX per pound
          (assuming 10 percent of the nitrogen is oxidized to NOX).

-------
                               AN-5


B.  Intermittent Air Emissions

    The respondent reports no intermittent air emissions.

C.  Continuous Liquid Wastes

    1.  Waste Brine

        1200 GPM of waste brine is produced.  Disposal is by on-site
    deep well injection.

    2.  Spent Caustic

        Although not reported as a liquid waste, it would appear that
    a small amount of spent caustic would be produced through the
    operation of several gas scrubbing devices, which the operator has
    indicated do use caustic.

D.  Solid Wastes
   >
    The operator reports disposal of 58,000 Ib./month of waste solids
via his plant land fill area.  The solid waste includes 40,000 Ib./month
of miscellaneous trash such as packing material, waste paper etc. and
18,000 Ib./month of 'chemical' waste such as filter aid, coke, polymer,
etc.

E.  Odors

    In general the butadiene process for the production o(f adiponitrile
does not appear to be a process that has an odor problem.

    The respondent reported no odor complaints in the past year.  Most
of the reported odors are said to be detectable only on the plant
property and only at intermittent intervals.  The materials contributing
to odors in this category have been identified as ammonia, chlorobutenes,
chlorine, butadiene, benzene and triethylamine.  However, according to
the questionnaire, these emissions are well enough controlled to prevent
odor problems.

F.  Fugitive Emissions

    In addition to storage tank vents, which have been listed elsewhere,
two sources of fugitive emissions have been reported.  The first is
the chlorination section refrigeration unit, which  'lopes'  1,700,000
Ibs./yr. of propane.  This is equal to .00531 Ibs. of propane/lb. of
adiponitrile.  The second source, described as butadiene losses due to
overloading the chlorination section recovery systems during start-ups
and shut-downs, amounts to 3,400,000 Ibs./yr. or .01062 Ib./lb.  No
other significant source of fugitive emissions is thought to exist.

G.  Other Emissions

    The respondent reports that unknown quantities of emissions are
associated with the following:

    (1)  Power House stacks.

-------
                           AN-6
(2)   Cooling tower.

(3)   Steam exhaust from flash tanks,  turbines and reciprocating
     pumps.

(4)   Exhuast from natural gas engines  used to drive compressors,

-------
                                     AN-7


IV.  Emission Control

     The emission control devices that have been reported as being employed by
the operator of the butadiene process adiponitrile plant are summarily described
in Table IV of this report.  An efficiency has been assigned each device
whenever data sufficient to calcualte it have been available.  Three types of
efficiencies have been calculated.

     (1)  "CCR" - Completeness of Combustion Rating

          CCR = Lbs. of C>2 reacting (with pollutants in device feed)
                          Ib. of 02 that theoretically could react   x

     (2)  "SE" - Specific Efficiency

          SE = specific pollutant in - specific pollutant out
                          specific pollutant in

     (3)  "SERR" - Significance of Emission Reduction Rating
                                                                             x 100
          SERR = j;_(pollutant x weighting factor)in -^(pollutant x weighting
                  	factor*) out	
                               2L(pollutant x weighting factor*)in

     *Weighting factor same as Table VII weighting factor.

     Normally, a combustion type control device (i.e. incinerator, flare, etc.)
will be assigned both a "CCR" and an "SERR" rating, whereas a non-combustion
type device will be assigned an "SE" and/or an "SERR" rating.  A more complete
description of this rating method may be found in  Appendix V of this
report.

     Although efficiency ratings for most devices are ehovn in Table IV, a few
general comments regarding adiponitrile pollution control device performance
seems in order:

     Absorbers

        Two thirds of the control devices reported consisted of, at least in
     part, some type of absorber.  They are identified in Table IV as devices
     AN-4 to AN-12.  With the exception of devices AN-5 and AN-7, all have
     calculated SE and SERR efficiencies of 1007,.   Absorber AN-5 is used in
     conjunction with a chiller and K.  0. Drum.  Its  reported efficiency
     of 56.6% is the combined efficiency of both pieces of equipment.   The
     specific efficiency, with regard to butadiene, is only 6570.  Since
     butadiene is quite easy to absorb (efficiencies  of 98 + % being common),
     one must assume that the particular device is either under-sized or was
     designed to perform at some economic optimum - rather than at much higher,
     though practical, hydrocarbon recovery rates.  The other device vith a
     low efficiency (AN-7 w/SE of 757.,)  appears to suffer from a poor choice of .
     absorbents.  More specifically, spent caustic does not seem to be the
     ideal absorbent for a mixture of butadiene, chloroprene and vinyl-
     cyclohexane - there may be other process considerations for this seemingly
     strange choice, but they have not been presented.

        In summary, the performance of absorbers in adiponitrile pollution control
     applications is excellent, and in most instances their SE and SERR
     efficiencies approach 1007,.

-------
                                     AN-8
     Incinerators

        With one exception, the composition of flare or incinerator flue
     gases has not been reported.  Consequently, efficiencies for these
     devices have been estimated (by Houdry) rather than calculated from
     actual performance data.  This is necessary in order that an SEI  (see
     Table VII) may be calculated.  The estimated efficiencies are based
     on two assumptions:

      I  All hydrocarbons are completely combusted, producing only CC>2 and
         H20.

     II  Ten percent of the nitrogen in the combusted material is oxidized
         to NOX, with a mol. wt. of 40.

     The true efficiencies of these devices remain unknown.

     It is extremely unlikely that a change in operating conditions will lead
to a significant decrease in air pollution - considering the source of the
major portion of the pollutants.

     Development work directed toward reductions in emissions from this process
falls into the following general categories.

     (1)  Substitute alternate disposal method for current practice of
          burning nitrogenous materials.

     (2)  More efficient design and operation of devices currently being
          utilized.

-------
                                     AN-9
V.  Significance of Pollution

    It is recommended that no in-depth study of this process be undertaken at
this time.  The reported emission data indicate that the quantity of pollutants
released as air emissions is less for the subject process than for other
processes that are currently being surveyed.

    The methods outlined in Appendix IV of this report have been used to
estimate the total weighted annual emissions from these new plants.  This
work is summarized in Tables V, VI and VII.

    Published support for the Table V forecast of new plants has not been
found.  The forecast is based on two assumptions:

    (1)  The butadiene process will account for 55.5 percent of 1980
         adiponitrile capacity.

    (2)  Adiponitrile capacity in 1980 will be 111 percent of demand.

    Unless there is a technological breakthrough it is believed that errors
inherent in these assumptions will not significantly alter the SEI.

    On a weighted emission basis a Significant Emission Index of 3,007 has
been calculated in Table VII.  This is less than the SEI's of many of the
other processes in the study.  Hence, the recommendation to exclude an
in-depth study of adiponitrile production via the butadiene process from
the in-depth study portion of the overall scope of work.

-------
                                    AN-10
VI.  Producers of Adiponitrile ex Butadiene

     Apparently there is some question as to the location and capacity of the
few plants utilizing the subject process.  The capacities quoted below are,
in part, based on assumptions outlined elsewhere in this report.  Plant
locations are based on published and private information.

                                                                  1972 Capacity
     Company                       Location                         MM Lb./Yr.

     Du Pont                    Victoria, Texas                        320
                                La Place, Louisiana                    !L15

                                                           Total       435

-------
PAGE NOT
AVAILABLE
DIGITALLY

-------
                                  TABLE AN-I
                                 ADI PONI TRUE
                                      EX
                                  BUTADIENE

                    MATERIAL BALANCE - T/T OF ADIPONITRILE

      There are not sufficient published data available to permit the
presentation of a meaningful material balance.  The reader is referred to
Section II - Process Chemistry - for more generalized information of this
type.

-------
                                 TABLE AN-II
                                 ADIPONITRILE
                                      EX
                                  BUTADIENE

                              GROSS HEAT BALANCE

      There are not sufficient published data available to permit the
construction of a heat balance for this process.

-------
                                                                                     TABLE AN-III
                                                                            NATIONAL EMISSIONS INVENTORY
                                                                                    ADIPONITRILE
                                                                                         EX
                                                                                     BUTADIENE
                                                                                                                              Page  1  of 6
Plant EPA Code No.
Capacity, Tons of Adiponitrlle/Yr.
Range in Production - 7, of Maximum
Emissions to Atmosphere
   Stream

    Flow - Lbs./Hr.
    Flow Characteristic, Continuous or Intermittent
       if Intermittent, Hrs./Yr. - Flow
    Composition, Tons/Ton of Adiponltrile
       Propane
       Nitrogen
       Oxygen
       Carbon Monoxide
       Carbon Dioxide
       Water
       NOX
       Misc. Lt. HC
       Butadiene
       Chloroprene
       Vinyl Cyclohexane
       Benzene
       Hydrogen Chloride
       Hydrogen
       Methane
       Ammonia
    Vent Stacks
       Number
       Height - Ft.
       Diameter -  Inches
       Exit Gas Temp. - F°
       SCFM/Stack
    Emission Control Devices
       Flare/Incinerator
       Refrig. Cond/K. 0. Drum
       Absorber/Scrubber
       Other
    Analysis
       Date or Frequency of Sampling
       Sample Tap Location
       Type of Analysis
       Odor Problem
    Summary of Air Pollutants
       Hydrocarbons, Ton/Ton of Adiponitrile
       Particulates, Ton/Ton of Adiponitrile
       NOX, Ton/Ton of Adiponitrile
       SOX, Ton/Ton of Adiponitrile
       CO , Ton/Ton of Adiponitrile
Fugitive Emiss.
    from
Refrig. Unit
1,700,000/Yr.
Intermittent
.00531
No
None
None
No
                                         6-3
                                       160,000
                                          0
Cyanide Sect.
Vent Inciner.
Flue Gas
                      Chlorination
                      Sect.  By-Product
                      Vent
                                                      Chlorination
                                                      Sect   Process
                                                      Vent
259,933
Continuous
                           4.88321
                            .54403
                           1.33472
                            .37903
Yes
4
164
16
140
 30
175
6.5
               90
                6
               95
                           AN-1  AN-2  AN-3  Yes
None
Calc'd.
No
                                      See  Continuation
                      650
                      Continuous
                                                           .01356
                                                           .00069

                                                           .00362
                                                           Yes
                                                           1
                                                           65
                                                           2
                                                           95
                                                           144
                                                           AN-4
                                                           Calcd.
                                                           No
                                                      82
                                                      Continuous
                                                                                      .00071
                                                                                      .00070
                                                                                      .00083
Yes
1
90
1.5
122

AN-5
                                                                                      No

-------
                                                                                     TABLE AN-III
                                                                            NATIONAL EMISSIONS INVENTORY
                                                                                    ADIPONTTRILE
                                                                                         EX
                                                                                     BUTADIENE
                                                                                                                              Page 2 of 6
Plant EPA Code No.
Capacity, Tons of Adiponitrile/Yr.
Range In Production - 7, of Maximum
Emissions to Atmosphere
   Stream

   Flow - Lbs./Hr.
   Flow Characteristic, Continuous or Intermittent.
      if Intermittent, Hrs./Yr. Flow
   Composition, Tons/Ton of Adiponitrile
      Propane
      Nitrogen
      Oxygen
      Carbon Monoxide
      Carbon Dioxide
      Water
      NOX
      Misc. Lt. HC
      Butadiene
      Chloroprene
      Vinyl Cyclohexane
      Benzene
      Hydrogen Chloride
      Hydrogen
      Methane
      Ammonia
   Vent Stacks
      Number
      Height - Ft.
      Diameter - Inches
      Exit Gas Temp. - F°
      SCFM/Stack
   Emission Control Devices
      Flare/Incinerator
      Refrig. Cond/K. 0. Drum
      Absorber/Scrubber
      Other
   Analysis
      Date or Frequency of Sampling
      Sample Tap Location
      Type of Analysis
      Odor Problem
   Summary of Air Pollutants
      Hydrocarbon, Ton/Ton of Adiponitrile
      Particulates,  Ton/Ton of Adiponitrile
      NOX, Ton/Ton of Adiponitrile
      SO^, Ton/Ton of Adiponitrile
      CO , Ton/Ton of Adiponitrile
                                   6-3
                                 160,000
                                    0
Chlorinat ion
Sect. Fugitive
Emissions & Emergency Vents
3,400,000 Yr.
Intermittent
.01062
No
No
Calc'd.
No
Chlorination
Sect.  Storage
Vent
100
Continuous
                                          .00275
                                          Yes
                                          1
                                          90
                                          8
                                          120
                                          23
                                          AN-6 (B)
Calc'd.
No
                                See Continuation
Chlorination
Sect.  Vac.
Ejector Disch.
124
Continuous
                                                                         .00284
                                                                         .00008
                                                                         .00015
                                                                         .00022
                                                                         .00008
                               Yes
                               1
                               90
                               8
                               120
                               26
                               AN-7 CB)
Calc'd.
No

-------
                                                                                      TABLE AN-III
Plant EPA Code No.
Capacity, Tons of Adiponitrile/Yr.
Range in Production - % of Maximum
Emissions to Atmosphere
   Stream

   Flow - Lbs./Hr.
   Flow Characteristic, Continuous or Intermittent
      if Intermittent, Hrs./Yr. Flow
   Composition, Tons/Ton of Adiponitrile
      Propane
      Nitrogen
      Oxygen
      Carbon Monoxide
      Carbon Dioxide
      Water
      NO
      Misc. Lt. HC
      Butadiene
      Chloroprene
      Vinyl Cyclohexane
      Benzene
      Hydrogen Chloride
      Hydrogen
      Methane
      Ammonia
   Vent Stacks
      Number
      Height - Ft.
      Diameter - In.
      Exit Gas Temp. - F°
      SCFM/Stack
   Emission Control Devices
      Flare/Incinerator
      Refrig. Cond./K. 0. Drum
      Absorber/Scrubber
      Other
   Analysis
      Date or Frequency of Sampling
      Sample Tap Locaton
      Type of Analysis
      Odor Problem
   Summary of Air Pollutants
      Hydrocarbons, Ton/Ton of Adiponitrile
      Particulates, Ton/Ton of Adiponitrile
      N0x, Ton/Ton of Adiponitrile
      SOX> Ton/Ton of Adiponitrile
      CO , Ton/Ton of Adiponitrile
NATIONAL EMISSIONS INVENTORY
ADIPONITRILE
EX
BUTADIENE
6-3
160,000
0
Chlor inat ion
Section Storage
Tank Vent
67
Cont inuous
Cyanation &
1 someri zat ion
Process Vent
781
Continuous
C & I
Process Vent
92
Continuous
C & I
Process Vent
6429 fA)
Continuous
Page 3
C & I
Ejector Effl,
35
Conti nuous
of 6
C i I C & I
Process Vent Process Vent
? 36
Continuous Continuous

C & I
Process

Vent
36
Continuous
.00184
No
AN-8 (C)
                  .02101
                  .00045
                  Infrequently
                  Wet
                                  .00022
                                  .00230
Never
None
Calc'd.
No
                                                     (A)
                .12583
                .02576
                .02120
                                                  .00381
                                                                  00094
Never
None
Calc'd.
No
                                                                 No
                                       SEE CONTINUATION
                                                                                 .00006
                                                                                                 .00013
                                                                                                 .00086
                                                                                                                 .00013
                                                                                                                 .00086
Yes
1
70
6
140
115
No
Yes
1
55
3
158

No
Yes
1
175
6.5


AN-3
Yes
1
90
6
95
8
AN- 9
Yes
1
65
2
95
0.6
AN- 10
Yes
1
90
1.5
122
3.6
No
Yes
1
90
1.5
122
3.6
No

-------
                                                                                     TABLE AN-III
Plant EPA Code No.
Capacity, Tons of Adiponitrile/Yr.
Range in Production - /„ of Maximum
Emissions to Atmosphere
   Stream

   Flow - Lbs./Hr.
   Flow Characteristic, Continuous or Intermittent
      if Intermittent, Hrs./Yr. - Flow
   Composition, Tons/Ton of Adiponitrile
      Propane
      Nitrogen
      Oatygen
      Carbon Monoxide
      Carbon Dioxide
      Water
      NOX
      Misc. Lt. HC
      Butadiene
      Chloroprene
      Vinyl Cyclohexane
      Benzene
      Hydrogen Chloride
      Hydrogen
      Methane
      Ammonia
   Vent Stacks
      Number
      Height - Ft.
      Diameter - Inches
      Exit Gas Temp. - F°
      SCFM/Stack
   Emission Control Devices
      Flare/Incinerator
      Refrig. Cond./K. 0. Drum
      Absorber/Scrubber
      Other
   Analysis
      Date or Frequency of Sampling
      Sample Tap Location
      Type of Analysis
      Odor Problem
   Summary of Air Pollutants
      Hydrocarbons, Ton/Ton of Adiponitrile
      Particulates, Ton/Ton of Adiponitrile
      N0x, Ton/Ton of Adiponitrile
      SO , Ton/Ton of Adiponitrile
      CO , Ton/Ton of Adiponitrile

C & I
Vac. Ejector
Disch.
115
Continuous
NATIONAL EMISSIONS INVENTORY
ADIPONITRILE
EX
BUTADIENE
6-3
160,000
0
C & I C & I
Process Vent Process Vent
58 92
Continuous Continuous
Page 4 of 6
C & I C & I
Process Vent Process Vent
1353 92
Continuous Continuous

C & I C & 1
Tank Vents Tank Vents
5 7
Continuous Continuous
.00316
No
No
                    .00159
                                                       .03718
                   No
                   AN-11 (D)
                                     .00022
                                     .00230
                                     Yes
                                     1
                                     25
                                     3
                                     158

                                     No
Yes
1
30
2
104
306
AN-12 (D)
                                                                                             .00009
                                                                          .00022
                                                                           00?30
Yes
1
25
3
158

No
                                                                                             .00003
                                                                                             No
                                                                                            No
                                                                                                              .0000?
                                                                                                              .00016
No
                                                                                                             No
                                           SEE  CONTINUATION

-------
                                                                                    TABLE AN-III
                                                                            NATIONAL EMISSIONS INVENTORY
                                                                                    APT PONT TRI1.E
                                                                                         EX
                                                                                     BUTAPTENE
                                                                                                                              Page 5 of b
Plant EPA Code No.
Capacity, Tons of Adiponi tri le./Yr.
Range in Production - I. of Maximum
Emissions to Atmosphere
   Stream

   Flov - Lbs./Hr.
   Flov Characteristic, Continuous or Intermittent
      if Intermittent, Hrs./Yr. - Flow
   Composition, Tons/Ton of Adiponitrile
      Propane
      Nitrogen
      Oxygen
      Carbon Monoxide
      Carbon Pioxide
      Water
      NOX
      Misc. Lt. HC
      Butadiene
      Chloroprene
      Vinyl Cyclohexane
      Benzene
      Hydrogen Chloride
      Hydrogen
      Methane
      Ammonia
   Vent Stacks
      Number
      Height - Ft.
      Diameter -  Inches
      Exit Gas Temp.  - F°
      SCFM/Stack
   Emission Control Pevices
      Flare/Incinerator
      Re frig.  Cond./K. 0.  Prum
      Absorber/Scrubber
      .Other
   Analysis
      Pate or  Frequency  of Sampling
      Sample Tap  Location
      Type of Analysis
      Odor Problem
   Summary of Air  Pollutants
      Hydrocarbons, Ton/Ton of Adiponitrile
      Particulates, Ton/Ton of Adiponitrile
      N0x, Ton/Ton  of Adiponitrile
      SO   Ton/Ton  of Adiponitrile
                           fa-3
                         160,000
                            0
llydrogenation
Unit
Process Vent
241
Cont i nuous
Hydropenation
Unit
Ejector Pischarpe
384
Continuous
                                               ,01054
.00180
.00477
.00004
No
No
                                               No
                                               No
                          .02564
                          .00385
                          .40023
      CO
           Ton/Ton of Adiponitrile

-------
                                 TABLE AN-III
                         NATIONAL EMISSIONS INVENTORY
                                 ADIPONITRILE
                                      EX
                                  BUTADIENE

                             EXPLANATION OF NOTES         Page 6 of 6

(A)   Respondent reported composition of stream prior to combustion.   Combustion
     products estimated by Houdry.

(B)   Devices AN-6 and AN-7 both consist of three identical scrubbers.

(C)   Device AN-8 consists of six identical scrubbers.

(D)   Devices AN-11 and AN-12 consist of tvo identical scrubbers.

-------
ABSORBERS/s CRUBB ERS
   EPA Code No. for plant using
   Flow Diagram (Fig. I) Stream I. 0.
   Device I. D. No.
   Control Emission of
   Scrubbing/Absorbing Liquid
   Type - Spray
          Packed Column
          Column w/trays
                 Number of Trays
                 Tray Type
          Other
   Scrubbing/Absorbin Liquid Rate - GPM
   Design Temp. (Operating Temp.) F°
   Gas Rate, SCFM  (Lb./Hr.)
   T-T Height, Ft.
   Diameter, Ft.
   Washed Gases to Stack
          Stack Height - Ft.
          Stack Diameter - Inches
   Installed Cost  - Mat'l. & Labor -  $
   Installed Cost  Based on - "year" - dollars
   Installed Cost  -  c/lb. of Adiponitrile  - Yr.
   Operating Cost  - Annual, $  (1972)
   Value of Recovered Product,  $/Yr.
   Net Operating Cost - Annual, $
   Net Operating Cost - c/lb.  of Adiponitrile
   Efficiency  - %  - SE
   Efficiency  - 7,  - SERR
                                                                                     TABLE AN-IV
                                                                        CATALOG OF EMISSION  CONTROL  DEVICES
                                                                             ADIPONITRILE EX BUTADIENE
                                                                                         CYANIDE SYNTHESIS
                                                                    Page 1 of It
                                                                                            CHLORI NATION
                                                                                           6-3
                                                                                           /fis.
                                                                                           AN-4
                                                                                           Chlorinated HC
                                                                                           Vater
                                                                                           Shell & Tube
                                                                                              - 27
                                                             200
                                                             144
                                                             25
                                                             6-7
                                                             Yes
                                                             65
                                                             2
                                                             4,120,000
                                                             1963 - 1972
                                                             1,?8750
                                                             776.000
                                                             925.000
                                                            -149.000
                                                             N'e ga t i ve
                                                             100
                                                             100
INCINERATION  DEVICES
   EPA  Code No.  for plant  using
   Flov Diagram  (Fig.  I) Stream  I.  D.
   Device  I.  D.  No.
   Type of Compound Incinerated
   Type of Device  - Flare
                    Incinerator
                    Other
   Material Incinerated, SCFM (Ib./hr.)
   Auxilliary Fuel Req'd.  (excl.  pilotl
                    Type
                    Rate - BTU/Hr.
   Device  or  Stack Height  -  Ft.
   Installed  Cost  - Mat'l.  & Labor  -  $
   Installed  Cost  Based on - "year" - dollars
   Installed  Cost  - c/lb.  of Adiponitrile  -  Yr.
   Operating  Cost  - Annual - S (1972)
   Operating  Cost  - c/lb.  of Adiponitrile
   Efficiency -  %  - CCR
   Efficiency -  7.  - SERR
6-3

AN-1
Lt. HC, NH3, HCN
833
Yes
Nat. Gas
75 CFH
164
12,770
1950
.00399
100
^ 95  (I)
6-3

AN-2
Lt. HC, NH3, HCN
5833
Yes
Nat. Gas
350 CFH
140
48,900
1958
.01528
160,700
.05021
100
~95 (I)
6-3

AN-3
Lt. HC, NH-. HCN
5833
Yes
Nat. Gas
5000 CFH
175
386,700
1950 - 1968
.12084
                                                            100
                                                                                                                                 (I)
 an
 6-3

 AN-4
 Chlorinated HC
 Yes
 Hydrogen
 672 CFH
 65
 4,120,000
 1963 - 1972
 1.2875
-149.000 CNet)
 Ne ga t i ve
 100
 100

-------
                                                                                     TABLE AN-IV
                                                                         CATALOG  OF  EMISSION CONTROL DEVICES
                                                                              ADIPONITRILE  EX  BUTADIENE
                                                                                                        CHLORINATION
                                                                                                                                   Page 2 of 4
ABSORBERS/SCRUBBERS
   EPA Code No. for plant using
   Flow Diagram (Fig.  I) Stream 1. D.
   Device I. D. No.
   Control Emission of
   Scrubbing/Absorbing Liquid
   Type - Spray
          Packed Column
          Column w/trays
                 Number of Trays
                 Tray Type
          Other
   Scrubbing/Absorbing Liquid Rate -  CPM
   Design Temp. (Operating Temp.) F°
   Gas Rate, SCFM  (Lb./Hr.)
   T-T Height, Ft.
   Diameter, Ft.
   Washed Gases to Stack
          Stack Height - Ft.
          Stack Diameter - In.
   Installed Cost  - Mat'l. & Labor -  $
   Installed Cost  Based on - "year"  - dollars
   Installed Cost  - r/lb. of Adiponitrile  -  Yr.
   Operating Cost  - Annual, $  (1972)
   Value of Recovered  Product,  $/Yr.
   Net Operating Cost  - Annual, S
   Net Operating Cost  - c/lb. of Adiponitrile
   Efficiency  - %  - SE
   Efficiency  - 7.  - SERR
ft-3

AN-5
Butadiene & l.t .  HC
Oil
Not Specified
 Yes
 90
 1.5
 50,000
 1950 - 1971
 .01562
 5,500
 425.000
-419,500
 Negative
 56.6
 56.6
                                   6-3
                                   Zfi^
                                   AN-6
                                   Chlorinated HC
                                   Spent Caustic
                                   Not Specified
 C120)
 22. 7
,.14
•• ?
 Yes
 90
 8
 14,500
 1953
 .00453
 1,300
   0
 1,300
 .00040
 •T-lOO
 A/100
                              6-3
                              ^B\
                              AN-7
                              Chlorinated HC
                              Spent Caustic
                              Not Specified
 020)
 26
 ,.-14
^/2
 Yes
 90
 8
 14,500
 1953
 .00453
 1,300
   0
 1,300
 .00040
 74.6
 74.6
                              OV)
                              6-3
                              ^
                              AN-8
                              Chlorinated HC
                              Water
                                                                                             12
                                                                                             ''Ambient)
                                                                                             15

                                                                                             V;
                                                                                             No
                                                                                            12,000
                                                                                            1962
                                                                                            .00375
                                                                                            14.600
                                                                                              0
                                                                                            14,600
                                                                                            .00456
                                                                                            100
                                                                                            100

-------
                                                                                     TABLE AN-IV
                                                                         CATALOG OF EMISSION CONTROL DEVICES
                                                                              AD1PONITRILE EX BUTADIENE
                                                                    page 3 of A
ABSORBERS/SCRUBBERS
   EPA Code No. for plant using
   Flow Diagram (Fig. I) Stream  T. D.
   Device I. D. No.
   Control Emission of
   Scrubbing/Absorbing Liquid
   Type - Spray
          Packed Column
          Column v/trays
                 Number of  trays
                 Tray type
          Other
   Scrubbing/Absorbing Liquid Rate -  GPM
   Design Temp. (Operating  Temp.)  F°
   Gas Rate, SCFM  (Lb./Hr.')
   T-T Height, Ft.
   Diameter, Ft.
   Washed Gases to Stack
          Stack Height - Ft.
          Stack Diameter -  In.
   Installed Cost  - Mat'l.  & Labor -  $
   Installed Cost  Based on  - "year"  - dollars
   Installed Cost  -  c/lb. of Adiponitrile - Yr.
   Operating Cost  - Annual,  1007.
 (V)
 6-3
 .CN.
 AN-11
 HCN
 127, NaOH
 167
 9.8
 0.7
 No
 3,000

 .00093
 9030
 0
 9030
 .00282
,-^1007
  (V)
  6-3
  _C^
  AN-12
  HCN
  127. NaOH
  f!04)
  306
  8
  0.7
  Yes
  30
  2
  3.000

  .00093
  9030
  0
  9030
  .00282
/V1007

-------
                                 TABLE AN-IV
                     CATALOG OF EMISSION CONTROL DEVICES
                                 ADIPQNITRILE
                                      EX
                                  BUTADIENE

                             EXPLANATION OF NOTES         page 4 of 4

  I.  When respondent does not report composition of combustion products, it
      is assumed that ten percent of the nitrogen in all nitrogenous
      compounds is oxidized to NOX.

 II.  Device AN-4 is a combination incinerator/absorber/scrubber.  Operating
      and installed cost figures shown are for the entire device.  Performance
      efficiencies also refer to the overall performance of the device.

III.  Device AN-5 used in conjunction with propane chiller.

 IV.  Device AN-8 consists of six identical scrubbers.

  V.  Device consists of two identical scrubbers.

-------
  435
0
                                               TABLE AN-V



Current
Capacity



Marginal
Capacity
NUMBER
Current
Capacity
on-stream
in 1980
OF NEW PLANTS


Demand*
1980
BY 1980


Capacity
1980


Capacity
to be
Added


Economic
Plant
Size


Number
of Nev
Units
435
760
845
410
100
Note:  All capacities in MM Lbs./Yr.




*Based on assumption that butadiene process will account for 55.57» of adiponitrile production.







 Total adiponitrile demand based on C. E.  H. and Chem.  Systems estimates of HMDA demand.

-------
                                                   TABLE AN-VI
                                            EMISSION SOURCE SUMMARY
                                            TON/TON OF ADIPONITRILE
Emission
Source*
Total
Cyanide
Chlorination Synthesis
Hydrocarbons .01791
Particulates & Aerosols
NO,, .0379
Cyanation
and
Isomerization
.00773
.00381
.02120
Boiler House
Combustion
Hydrogenation of Liquid Waste
.02564
.00004 .00688 .01073
.05686 .11596
SO,
CO
*Emissions from individual sections include fugitive emissions.

-------
TABLE AN-VII

WEIGHTED EMISSION RATES


Chemical Adiponitrile
Process Butadiene
Increased Capacity
Pollutant
Hydrocarbons
Aerosols
NOX
S0x
CO
by 1980 410 MM Lb./Yr.
Increased Emissions
Emissions, Lb./Lb. MMLbs./Yr.
.02564 10.51
.01073 4.40
.11596 47.54
0 0
0 0
Weighting
Factor
80
60
40
20
1
Weighted Emissions
MM Lbs./Yr.
841
264
1,902
0
0
                       Significant Emission Index  = 3,007

-------
Adiponitrile via Adipic Acid

-------
                              Table of Contents

Section                                                           Page Number

I.    Introduction                                                    AL-1
                                                                      Ai —9
II.   Process Description                                             AJ" ^
                                                                      AT _T
III.  Plant Emissions                                                 AL J
                                                                      A T _ C
IV.   Emission Control                                                ttlj D
V.    Significance of Pollution                                       AL~7
VI.   Adiponitrile Producers                                          AL-8

                        List of Illustrations & Tables

      Flow Diagram                                                Figure AL-I
      Net Material Balance                                        Table AL-I
      Gross Heat Balance                                          Table AL-II
      Emission Inventory                                          Table AL-III
      Catalog of Emission Control Devices                         Table AL-IV
      Number of Nev Plants by 1980                                Table AL-V
      Emission Source Summary                                     Table AL-VI
      Weighted Emission Rates                                     Table AL-VII

-------
                                   AL-1
I.  Introduction

    Adiponitrile is an intermediate in the synthesis of nylon 6,6; with this
use alone accounting for over 90% of all adiponitrile production.  Several
routes to adiponitrile are available, but (in the U. S.) only three are
utilized at the present time.  Primary raw materials for the three routes are;

    (1)  Butadiene
    (2)  Adipic Aicd
    (3)  Acrylonitrile

    In terms of production capacity, the adipic acid process is pre-eminent
in Europe and second ranked in the United States.  That process is the subject
of this report.

    Nitrogen compounds, more specifically NHo and NOX,  comprise the sum total
of air pollutants associated with the adipic acid process.   Some tars are
produced, but they are disposed of by land fill methods and do not contribute
to air pollution.  Additionally,  several waste water streams are produced.  In
general, air emissions from the subject process - based on information supplied
by the petrochemical questionnaire respondents - are very low.

    The current U. S. adiponitrile ex adipic acid production capacity is 2.80 x
108 Ibs./yr.  1980 capacity is estimated to be 5.50 x 108 Ibs./yr. - assuming
that the subject process maintains  its present share of the industry's total
capacity.

-------
                                    AL-2
II.   Process Description

     Adipic acid, in the presence of a dehydrating catalyst, reacts vith
ammonia to form adiponitrile.  The chemical reaction is:

     HOOC (CH2)4 COOH + 2 NH3        »    NC (CH2)4 CN -f 4 H20

     Adipic Acid      + Ammonia      »    Adiponitrile + Water

Mol. Wt.  146.14         17.03                108.15   +  18.02

     Standard commercial practice is to conduct the reaction in the vapor
phase, utilizing a phosphorous containing compound as the catalyst.

     Adipic acid is melted, heated to between 500 - 600° F and sparged into
the bottom of the number one reactor.  In the reactor, the molten adipic acid
vaporizes and mixes with an excess of ammonia, which has also been sparged in.
The vapors pass up through reactor tubes packed with a mixture of phosphoric
acid and bone particles.  The reactor effluent is cooled 75 - 100 F° and sent
to a vapor/liquid separator.  The liquid from the separator is sent to reactor
No.  2, where it is revaporized and contacted with additional  ammonia.  The
tars and heavy ends formed in reactor No. 2 are rejected and the remainder
of the reaction products are combined with the vapor phase effluent from
reactor No.  1.  The combined effluents pass on to the ammonia still where
ammonia, carbon dioxide and water are taken overhead; crude adiponitrile is
taken as a 'middle cut1 and unreacted adipic acid is taken as a bottoms product.
The ammonia overhead product is purified and recycled.  The bottoms are
returned to reactor No. 1.

     The crude adiponitrile, from the ammonia still 'middle cut', is processed
in a series of columns which dehydrate it and remove light and heavy ends.
Product adiponitrile is sent to storage, where it is maintained at 105 - 110° F
until it is used.

-------
                                     AL-3


III.  Plant Emissions

      A.  Continuous Air Emissions

          1.  Ammonia Recovery Section Vent

              Both respondents report atmospheric emissions from this source.
          The operator of plant EPA Code No. 6-1 burns these materials in
          his plant flare.  Estimated noxious emissions, based on the
          assumption that ten percent of N becomes NOX, amount to .00027
          Ibs.  N0x/lb. of adiponitrile and constitutes the total amount of
          air pollutants emitted by the plant.  The operator of plant EPA
          Code No. 6-2 reports the use of an absorber/scrubber (device AL-2,
          Table IV) on this stream.  This device operates with an efficiency
          approaching 100 percent and pollutant emission is essentially nil.

          2.  Product Fractionation Vent

              Both respondents report atmospheric emissions from this source.
          The operator of plant EPA Code No. 6-1 burns these materials in a
          "thermal oxidizer" (device AL-1, Table IV)  and reports only trace
          emissions of NOX in the flue gas.  The operator of plant EpA Code
          No. 6-2 reports only "trace" flow from this source, with 99 percent
          of the "trace" flow - water and 'trace1 amounts of NOX.

          3.  Product Recovery Vent

              Plant operator 6-2 reports discharging  .0036 Ibs./lb of ammonia
          from vacuum ejectors located in this area of his plant.  According
          to his report this emission constitutes his only significant release
          of atmospheric pollutants.  All reported streams are summarized in
          Table III.

      B.  Intermittent Air Emissions

              No intermittent air emissions were reported.

      C.  Continuous Liquid Wastes

              Waste water in the amount of 16 GPM is  'treated and disposed1 by
          plant 6-1.  Plant 6-2 allocates its waste water production as follows:

              NH3 Recovery                             250 GPM
              Purification                              30 GPM
              Product Recovery & Refining              	5_ GPM
                                               Total  - 285 GPM

              All 285 GPM are subject to "in-plant treating and processing".

              No other liquid waste streams were reported.

      D.  Solid Wastes

              The operator of plant EPA Code No.  6-1  reports  the production of
          10,400 Ibs./day of solid wastes.   The wastes  are 'disposed1  of by
          "piling  them" on the plant site.  Plant 6-2  operator reports disposing
          of 12,000 Ibs./day of waste solids by landfill on plant property.  The
          solid wastes consist, in part, of spent catalyst.  Other components
          were not identified.

-------
                                AL-4
E.  Odors

    In general, the adipic acid process for the production of adiponitrile
does not appear to be a process that has an odor problem.

    Both respondents reported no odor complaints in the past year.  In fact,
neither respondent admitted to the detection of any odors, at  any time -
even on plant property.  Despite this fact, it seems only reasonable to
expect the occassional presence of ammonia odors - at least on the plant
site.

F.  Fugitive Emissions

    Neither respondent offers an estimate of fugitive losses.   The
operator of plant 6-2 summarizes the situation thusly:  "NH_ handling has
the highest potential for possible emissions due to leaks.  Since ammonia
is readily detectable, leaks are promptly corrected and do not represent
any appreciable loss".

G.  Other Emissions

    The only candidate for inclusion in this category would be the 0.02%
sulfur in the natural gas reported by operator 6-2.  However,  this amounts
to only one ton/yr. of sulfur, and is,  therefore,  insignificant.

-------
                                     AL-5
IV.  Emission Control

     The emission control devices that have been reported as being employed
by the operators of the adipic acid process adiponitrile plants are summarily
described in Table IV of this report.  An efficiency has been assigned each
device whenever data sufficient to calculate it have been available.  Three
types of efficiencies have been calculated.

     (1)  "CCR" - Completeness of Combustion Rating

           CCR = Ibs. of Oo reacting (with pollutants in device feed)
                      Ibs. of 02 theoretically capable of reacting    x

     (2)  "SE" - Specific Efficiency

           SE = specific pollutant in - specific pollutant out  x ^QQ
                            specific pollutant in

     (3)  "SERR" - Significance of Emission Reduction Rating

           SERR =^(pollutant x weighting factor*)in --^(pollutant x weighting
                   	factor*)out	
                             •^(pollutant x weighting factor*) in

     *Weighting factor same as Table VII weighting factor.

     Normally a combustion type control device (i.e. incinerator, flare, etc.)
will be assigned both a "CCR" and an "SERR" rating, whereas a non-combustion
type device will be assigned as "SE" and/or an "SERR" rating.  A more
complete description of this rating method may be found in Appendix V of
this report.

     Although efficiency ratings for all (both) devices reported are shown in
Table IV, a few general comments regarding adiponitrile pollution control device
performance seems in order:

     Absorbers/Scrubbers

        Device AL-2 is a combination absorber/scrubber.   It is the only device
     reported that belongs in the subject category.  It is used to prevent
     the emission of ammonia.   Based on the  infomation supplied by the operator
     utilizing the device its efficiency (SE & SERR) is 100%.

     Incinerators

        The operator of plant EPA Code No.  6-1 utilizes two combustion devices
     for pollution control; the plant flare and an incinerator.   The incinerator,
     a John Zink Thermal Oxidizer, is identified as device AL-1 in Table IV.
     Based on flue gas analyses, this device is capable of converting all
     contained nitrogen to N2, and hence, its efficiency (CCR & SERR) is 100%.
     On the other hand,  no information is given on the performance of the flare.
     However-; in order to calculate an SEI (see Table VII).its performance or
     efficiency must be estimated.  The efficiency estimate is based on two
     assumptions:

        I   All hydrocarbons are completely combusted, producing only C02 and


        II  The nitrogen in the combusted material is oxidized to NO ,  with a
                                                                    X

-------
                                     AL-6
            mol. wt.  of 40.

        Thus, the effluent composition of the device vas calculated and
     listed in Table III.

     Based on the information supplied by the two respondents,  emissions are
already so lov that further  work in emission control seems unnecessary at
this time.

-------
                                     AL-7
V.  Significance of Pollution

    It is recommended that no in-depth study of this process be undertaken.
The reported emission data indicate that the quantity of pollutants released
as air emissions is less for the subject process than for many other processes
studied to date.

    The methods outlined in Appendix IV of this report have been used to
estimate the total weighted annual emissions from these new plants.  This
work is summarized in Tables V, VI and VII.

    Published support for the Table V forecast of new plants has not been
found.  The forecast is based on two assumptions:

    (1)  The adipic acid process will account for 36 percent of 1980
         adiponitrile capacity.

    (2)  Adiponitrile capacity in 1980 will be 111 percent of demand.

    Errors inherent in these assumptions, unless they are several orders of
magnitude in size, cannot significantly alter the SEI.

    On a weighted emission basis, a Significant Emission Index of 30 has been
calculated for the subject process.  This is substantially lower than the SEI
of most of the processes studied.  Hence, the recommendation to exclude an
in-depth study of adiponitrile production via the adipic acid process from the
in-depth study portion of the overall scope of work.

-------
                                    AL-8
VI.  Producers of Adiponitrile ex Adipic Acid

     The capacities and plant locations listed belov are based on information
provided in the questionnaires and in the literature.

                                                               Capacity
         Company                     Location                1967    1972

Celanese Corp.                  Bay City, Texas               45       ?

El Paso Products                Odessa, Texas                         27.5

Monsanto                        Pensacola, Florida                   180
                                                   Est. Total        280
Note:

(1)  Capacities in MM Lbs./Yr.

(2)  Estimated 1972 capacity based in part on assumptions outlined in
     Section V of this report.

-------
PAGE NOT
AVAILABLE
DIGITALLY

-------
                                  TABLE AL-I
                                 ADIPONITRILE
                                      EX
                                 ADIPIC ACID

                    MATERIAL BALANCE - T/T OF ADIPONITRILE
     There are not sufficient published  data  available  to permit  the  pre-
sentation of a meaningful material  balance.

-------
                                 TABLE AL-II
                                 ADIPONITRILE
                                      EX
                                 ADIPIC ACID
                          GROSS REACTOR HEAT BALANCE
   There are not sufficient published data available to permit the construction
of a detailed heat balance for this process.   An estimate of the total reactor
heat flow shows:
Heat In*

   Sum of steam, fired heaters
and heat exchange

Heat Out

Endothermic heat of reaction
Differential enthalpy
    (Reaction products - feed)
BTU/Lb. of Adiponitrile
          1490
           434

          I9JL6
          1490
-w/60° temperature base.

-------
Plant EPA Code No.
Capacity, Tons of Adiponitr i le/Yr .
Range in Production - 7, of Max.
Emissions to Atmosphere
   Stream

   Flow - Lbs. /Hr.
   Flow Characteristic, Continuous or Intermittent
      if Intermittent, Hrs./Yr. Flow
   Composition, Tons/Ton of Adiponitrile
      Ammonia
      Nitrogen
      Oxygen
      Carbon Dioxide
      Water
      Nitrogen Oxides

   Vent Stacks
      Number
      Height - Ft.
      Diameter -  Inches
      Exit Gas Temp. - F°
      SCFM/Stack
   Emission Control Devices
      Flare /Incinerator
      Absorber /Scrubber
      Condenser/K. 0. Drum
      Other
   Analysis
      Date or Frequency of Sampling
      Sample Tap  Location
      Type of Analysis
      Odor Problem
   Summary of Air Pollutants
      Hydrocarbons, Ton/Ton of Adiopnitrile
      Aerosols       "   "   "     "
      SOX
      CO
NHj Recovery
Sect ion
Purge
20
Cont inuous

   (A)
.00185
.000274

(Flare)
Yes
          TABLE AL-III
  NATIONAL EMISSIONS INVENTORY
          ADIPONITRILE
               EX   -
          ADIPIC ACID

 6-1
13,750
  0
           Light Ends
           Incinerator
           Flue Gas
           49,510
           Cont inuous
                       10.97706
                        2.33098
                         .60096
                         .49169
                       Yes
                       1
                       13
                       57
                       1800
                       11.000
                       Yes AL-1
1968
Vent Line
<;LC
No









0
0
.000274
0
0
Never

C»lc'd
No





NHj Recovery
Section
Vent
209
Continuous
                                              .00928
                                  Yes
                                  1
                                  77
                                  4
                                  77°
                                 A/30
                                  Yes AL-2
                                              Never
                                              None
                                              Estimate
                                              No
 6-2
90,000
  0
 Product
 Purification
 Vent
 "Trace"
 Continuous
                      Yes
                      1
                      77
                      5
                      212C

                      No
                                                                    Never
                                                                    None
                                                                    Estimate
                                                                    No

                                                                       0
                                                                    .00356
                                                                       0
                                                                       0
                                                                       0
                                                                                             Product
                                                                                             Recovery Elector
                                                                                             Discharge
                                                                                             1380
                                                                                             Continuous
                                                                                             .00356
                                                                                            ).0133
                                                                                             .04444
                                                                                             Yes
                                                                                             1
                                                                                             120
                                                                                             2
                                                                                             212
                                                                                             420
                                                                                             No
                                                                                 Never
                                                                                 None
                                                                                 Estimate
                                                                                 No
  .A)  Assumed combustion products.  Reapo: dent report.' d    v and composition of str'^arv prior to combustion (in flare).
       by assuming 100 percent combustion and ten percent conversion of contained nitrogen to NOX with mol. vt.  of 40.
                                                          Combustion products  were estimated

-------
                                                                                      TABLE AL-IV
                                                                         CATALOG OF EMISSION  CONTROL DEVICES
                                                                             ADIPONITRn.E  EX  ADTPIC ACID
ABSORBER/SCRUBBERS
   EPA Code No. for plant using
   Flow Diagram (Fig. I) Stream T.D.
   Device I. D. No.
   Control Emission of
   Scrubbing/Absorbing Liquid
   Type - Spray
          Packed Column
          Column w/Trays
                 Number of Trays
                 Tray Type
          Other
   Scrubbing/Absorbing Liquid Rate - GPM
   Design Temp. (Operating Temp.) F°
   Gas Rate, SCFM  (Ib./hr.)
   T-T Height, Ft.
   Diameter, Ft.
   Washed Gases to Stack
          Stack Height -  Ft.
          Stack Diameter  - In.
   Installed Cost  - Mat'l. & Labor - $
   Installed Cost  Based on - "year" - dollars
   Installed Cost  -  c/lb. of Adiponitrile/Yr.
   Operating Cost  - Annual, $  (1972)
   Value of Recovered Product, $/Yr.
   Net Operating Cost - (fib.  of Adiponitrile
   Efficiency  - 7.  - SE
   Efficiency  - 7.  - SERR

INCINERATION DEVICES
   EPA Code No. for  plant using
   Flov Diagram (Fig. I)  Stream I.D.
   Device I. D. No.
   Type of Compound  Incinerated
   Type of Device  -  Flare
                     Incinerator
                    Other
   Material Incinerated,  SCFM  (Ib./hr.)
   Auxiliary Fuel  Req'd.  (Excl. pilot)
                    Type
                    Rate  BTU/Hr.
   Device or Stack Height - Ft.
   Installed Cost  - Mat'l. & Labor - $
   Installed Cost  Based on - "year" - dollars
   Installed Cost  -  c/lb. of Adiponitrile  -  Yr.
   Operating Cost  - Annual - $  (1972)
   Operating Cost  -  (fib. of Adiponitrile
   Efficiency  - 'I,  -  CCR
   Efficiency  - "I,  - SERR
AMMONIA RECOVERY SUCTION

            o-2
            . A^
            AL-2 (I)
            Ammon i a
            Water
                                                                                                                 PRODUCT FRACTIONATION SECTION
            40
            (77)
            14
            6.5
            2
            Yes
            77
            4
            20,000
            1953 6, 1956
            .0111
            2,000
            0
            .0011
            100
            100
                                                                6-1
                                                                /&.
                                                                AL-1
                                                                Nitriles & Imines
                                                                (50)
                                                                Yes
                                                                Nat. Gas
                                                                130 MMCF/Yr.
                                                                13
                                                                80,000 (II)
                                                                1965
                                                                .2909
                                                                67,000
                                                                .2436
                                                                100
                                                                100
 (I)   Device  AL-2  consists  of five identical scrubbers.   Indicated costs  are total costs.

(II)   Installed cost estimated by Houdry.   Rcspondci t  reported cost, excluding labor,  of $41,265.

-------
  280
                                              TABLE AL-V
Current
Capacity
Marginal
Capacity
NUMBER
Current
Capacity
on-stream
in 1980
OF NEW PLANTS
Demand*
1980
BY 1980
Capacity
1980
Capacity
to be
Added
Economic
Plant
Size
Number
of
Nev Units
280
495
550
270
100
2-3
Note:  All capacities in MM Lbs./Yr.




•'•Based on assumption that adipic acid process will account for 367n of adiponitrile production.






 Total adiponitrile demand based on C.E.H. and Chem. Systems estimates of HMDA demand.

-------
Emission
                                          TABLE AL-VI
                                    EMISSION SOURCE SUMMARY
                                    TON/TON OF ADIPONITRILE
          Source
                                   Ammonia
                                   Recovery
                                   Section
                   Product
                   Fractionation
                   Section
Fugitive
Emissions
                      Total
Hydrocarbons

Particulates & Aerosols

NO
  x

SO,,
                    .00178
.000137
Negligible
.00178

.000137
CO

-------
TABLE AL-VII
Chemical
Process
Increased
Pollutant
WEIGHTED EMISSION RATES
Adiponitrile
Adipic Acid
Capacity by 1980 270 MM Lb./Yr.
Emissions Increased Emissions
Lb./Lb. MM Lbs./Yr.
Hydrocarbons 0 0
Aerosols
N0x
S0x
CO
.00178 .5
.000137 .04
0 0
0 0
Weighting
Factor
80
60
40
20
1
Weighted Emissions
MM Lbs./Yr.
0
28.8
1.5
0
0
                         Significant Emission Index = 30.3

-------
Appendix I, II, & III

-------
                              APPENDIX I
                          FINAL ADDRESS LIST
Air Products & Chemicals, Inc.
P. 0. Box 97
Calvert City, Kentucky

Attention:. Mr. Howard Watson

Allied Chemical Corp.
Morristown, New Jersey

Attention:  Mr. A. J. VonFrank
            Director Air & Water
            Pollution Control

American Chemical Corp.
2112 E. 223rd
Long Beach, California  90810

Attention:  Mr. H. J. Kandel

American Cyanamid Company
Bound Brook, New Jersey

Attention:  Mr. R. Phelps

American Enka Corporation
Enka, North Carolina  28728

Attention:  Mr. Bennet

American Synthetic Rubber Corp.
Box 360
Louisville, Kentucky  40201

Attention:  Mr. H. W. Cable

Amoco Chemicals Corporation
130 E. Randolph Drive
Chicago, Illinois

Attention:  Mr. H. M. Brennan, Director
            of Environomental Control Div.

Ashland Oil Inc.
1409 Winchester Ave.
Ashland, Kentucky  41101
Borden Chemical Co.
50 W. Broad Street
Columbus, Ohio  43215

Attention:  Mr. Henry Schmidt

Celanese Chemical Company
Box 9077
Corpus Christi, Texas  78408

Attention:  Mr. R. H. Maurer

Chemplex Company
3100 Gulf Road
Rolling Meadows, Illinois  60008

Attention:  Mr. P. Jarrat

Chevron Chemical Company
200 Bush Street
San Francisco, California  94104

Attention:  Mr. W. G. Toland

Cities Service Inc.
70 Pine Street
New York City, NY  10005

Attention:  Mr. C. P. Goforth

Clark Chemical Corporation
Blue Island Refinery
131 Kedzie Avenue
Blue Island, Illinois

Attention:  Mr. R. Bruggink, Director
            of Environmental Control

Columbia Nitrogen Corporation
Box 1483
Augusta, Georgia  30903

Attention:  Mr. T. F. Champion
Attention:  Mr. 0. J. Zandona

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Continental Chemical Co.
Park 80 Plaza East
Saddlebrook, NJ  07662

Attention:  Mr. J. D. Burns

Cosden Oil & Chemical Co.
Box 1311   .
Big Spring, Texas  79720

Attention:  Mr. W. Gibson

Dart Industries, Inc.
P. 0. Box 3157
Terminal Annex
Los Angeles, California  90051

Attention:  Mr. R. M. Knight
            Pres. Chemical Group

Diamond Plastics
P. 0. Box 666
Paramount, California  70723

Attention:  Mr. Ben Wadsworth

Diamond Shamrock Chem. Co.
International Division
Union Commerce Building
Cleveland, Ohio  44115

Attention:  Mr. W. P. Taylor, Manager
            Environ. Control Engineering

Dow Badische Company
Williamsburg, Virginia  23185

Attention:  Mr. L. D. Hoblit

Dow Chemical Co. - USA
2020 Building
Abbott Road Center
Midland, Michigan  48640

Attention:  Mr. C. E. Otis
            Environmental Affairs Div.
E. I. DuPont de Nemours & Co.
Louviers Building
Wilmington, Delaware  19898

Attention:  Mr. W. R. Chalker
            Marketing Services Dept.

Eastman Chemicals Products, Inc.
Kingsport, Tennessee

Attention:  Mr. J. A. Mitchell
            Executive Vice President
            Manufacturing

El Paso Products Company
Box 3.986
Odessa, Texas  79760

Attention:  Mr. N. Wright,
            Utility and Pollution
            Control Department

Enjay Chemical Company
1333 W. Loop South
Houston, Texas

Attention:  Mr. T. H. Rhodes

Escambia Chemical Corporation
P. 0. Box 467
Pensacola, Florida

Attention:  Mr. A. K. McMillan

Ethyl Corporation
P. 0. Box 341
Baton Rouge, Louisiana  70821

Attention:  Mr. J. H. Huguet

Fibre Industries Inc.'
P. 0. Box 1749
Greenville, South Carolina  29602

Attention:  Mr. Betts

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Firestone Plastics Company
Box 699
Pottstown, Pennsylvania  19464

Attention:  Mr. C. J. Kleinart

Firestone Synthetic Rubber Co.
381 W. Wilbeth Road
Akron, Ohio  44301

Attention:  Mr. R. Pikna

Firestone Plastics Company
Hopewell, Virginia

Attention:  Mr. J. Spohn

FMC - Allied Corporation
P. 0. Box 8127
South Charleston, W. VA  25303

Attention:  Mr. E. E. Sutton

FMC Corporation
1617 J.F.K. Boulevard
Philadelphia, PA

Attention: Mr. R. C. Tower

Foster Grant Co., Inc.
289 Main Street
Ledminster, Mass.  01453

Attention. Mr. W. Mason

G.A.F. Corporation
140 W. 51st Street
New York, NY  10020

Attention:  Mr. T. A. Dent, V.P.
            of Engineering

General Tire & Rubber Company
1 General Street
Akron, Ohio  44309
Georgia-Pacific Company
900 S.W. 5th Avenue
Portland, Oregan  97204

Attention:  Mr. V. Tretter
            Sr. Environmental Eng.

Getty Oil Company
Delaware City, Delaware  19706

Attention:  Mr. Gordon G. Gaddis

B. F. Goodrich Chemical Co.
6100 Oak Tree Blvd.
Cleveland, Ohio  44131

Attention:  Mr. W. Bixby

Goodyear Tire & Rubber Co.
1144 E. Market Street
Akron, Ohio  44316

Attention:  Mr. B. C. Johnson, Manager
            Environmental Engineering

Great American Chemical Company
650 Water Street
Fitchburg, Mass.

Attention:  Dr. Fuhrman

Gulf Oil Corporation
Box 1166
Pittsburgh, Pennsylvania

Attention:  Mr. D. L. Matthews
            Vice President -
            Chemicals Department

Hercules Incorporated
910 Market Street
Wilmington, Delaware

Attention:  Dr. R. E. Chaddock
Attention:  Mr. R. W. Laundrie

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Hooker Chemical Corporation
1515 Summer Street
Stamford, Conn.  06905

Attention:  Mr. J. Wilkenfeld

Houston Chemical Company
Box 3785
Beaumont, Texas  77704

Attention:  Mr. J. J. McGovern

Hystron Fibers Division
American Hoechst Corporation
P. 0. Box 5887
Spartensburg, SC  29301

Attention:  Dr. Foerster

Jefferson Chemical Company
Box 53300
Houston, Texas  77052

Attention:  Mr. M. A. Herring

Koch Chemical Company
N. Esperson Building
Houston, Texas  77002

Attention:  Mr. R. E. Lee

Koppers Company
1528 Koppers Building
Pittsburgh, Pennsylvania  15219

Attention:  Mr. D. L. Einon

Marbon Division
Borg-Warner Corporation
Carville, Louisiana  70721

Attention:  Mr. J. M. Black
Mobay Chemical Corporation
Parkway West & Rte 22-30
Pittsburgh, Pennsylvania  15205

Attention:  Mr. Gene Powers

Mobil Chemical Company
150 E. 42nd Street
New York, NY  10017

Attention:  Mr. W. J. Rosenbloom

Monsanto Company
800 N. Lindbergh Boulevard
St. Louis, Missouri  63166

Attention:  Mr. J. Depp, Director of
            Corp. Engineering

National Distillers & Chem. Corp.
U.S. Industrial Chem. Co. Div.
99 Park Avenue
New York, NY  10016

Attention:  Mr. J. G. Couch

National Starch & Chem. Co.
1700 W. Front Street
Plainfield, New Jersey  07063

Attention:  Mr. Schlass

Northern Petrochemical Company
2350 E. Devon Avenue
Des Plaines, Illinois  60018

Attention:  Mr. N. Wacks

Novamont Corporation
Neal Works
P. 0. Box 189
Kenova, W. Virginia  25530
                                        Attention:  Mr.  Fletcher

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Olin Corporation
120 Long Ridge Road
Stamford, Conn.

Attention:  Mr. C. L. Knowles

Pantasote Corporation
26 Jefferson Street
Passaic, New Jeresy

Attention:  Mr. R. Vath

Pennwalt Corporation
Pennwalt Building
3 Parkway
Philadelphia, PA  19102

Attention:  Mr. J. McWhirter

Petro-Tex Chemical Corporation
Box 2584
Houston, Texas  77001

Attention:  Mr. R. Pruessner

Phillips Petroleum Co.
10 - Phillips Bldg.
Bartlesville, Oklahoma  74004

Attention:  Mr. B. F. Ballard

Polymer Corporation, Ltd.
S. Vidal Street
Sarnia, Ontario
Canada

Attention:  Mr. J. H. Langstaff
            General Manager
            Latex Division

Polyvinyl Chemicals Inc.
730 Main Street
Wilmington, Mass.  01887

Attention:  Mr. S. Feldman, Director of
            Manufacturing - Engineering
PPG Industries Inc.
One-Gateway Center
Pittsburgh, Pennsylvania  15222

Attention:  Mr. Z. G. Bell

Reichold Chemicals Inc.
601-707 Woodward Hts. Bldg.
Detroit, Michigan  48220

Attention:  Mr. S. Hewett

Rohm & Haas
Independence Mall West
Philadelphia, PA  19105

Attention:  Mr. D. W. Kenny

Shell Chemical Co.
2525 Muirworth Drive
Houston, Texas  77025

Attention:  Dr. R.L. Maycock
            Environ. Eng. Div.

Sinclair-Koppers Chem. Co.
901 Koppers Building
Pittsburgh, Pennsylvania  15219

Attention:  Mr. R. C. Smith

Skelly Oil Company
Box 1121
El Dorado, Kansas  67042

Attention:  Mr. R. B. Miller

Standard Brands Chem. Industries
Drawer K
Dover, Delaware  19901

Attention:  Mr. E. Gienger, Pres,

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Stauffer Chemical Co.
Westport, Connecticut

Attention:  Mr. E. L. Conant

Stepan Chemical Company
Edens & Winnetka Road
Northfield, Illinois  60093

Attention:  Mr. F. Q. Stepan
            V.P. - Industrial Chemicals

Tenneco Chemicals Inc.
Park 80 Plaza - West 1
Saddlebrook, NJ  07662

Attention:  Mr. W. P. Anderson

Texas - U.S. Chemical Company
Box 667
Port Neches, Texas  77651

Attention:  Mr. H. R. Norsworth

Thompson Plastics
Assonet, Mass.  02702

Attention:  Mr. S. Cupach

Union Carbide Corporation
Box 8361
South Charleston, W. Virginia  25303

Attention:  Mr. G. J. Hanks, Manager
            Environ. Protection
            Chem. & Plastics Division

Uniroyal Incorporated
Oxford Management &
Research Center
Middlebury, Conn.  06749
The Upjohn Company
P. 0. Box 685
La Porte, Texas

Attention:  Mr. E. D. Ike

USS Chemicals Division
U.S. Steel Corporation
Pittsburgh, Pennsylvania  15230

Attention:  Mr. Gradon Willard

W. R. Grace & Company
3 Hanover SquarNew York, NY  10004

Attention:  Mr. Robt. Goodall

Wright Chemical Corporation
Acme Station
Briegelwood, North Carolina  28456

Attention:  Mr. R. B. Catlett

Wyandotte Chemical Corp.
Wyandotte, Michigan  48192

Attention:  Mr. John R. Hunter

Vulcan Materials Company
Chemicals Division
P.O. Box 545
Wichita, Kansas  67201

Attention:  H.M. Campbell
            Vice-President, Production
Attention:  Mr. F. N. Taff

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               ENVIRONMENTAL PROTECTION AGENCY

                     Office of Air Programs
          Research Triangle Park, North Carolina 27711
Dear Sir:

     The Environmental Protection Agency,  Office of Air Programs is
engaged in a study of atmospheric emissions from the Petrochemical
Industry.  The primary purpose of this study is to gather information
that will be used to develop New Stationary Source Performance Standards
which are defined in Section 111 of the Clean Air Act as amended
December 31, 1970 (Public Law 91604).   These new source standards will
not be set as part of this study but will  be based (to a large extent)
on the data collected during this study.

     A substantial part of the work required for this study will be per-
formed under contract by the Houdry Division of Air Products and Chemicals.
Several other companies not yet chosen will assist in the source sampling
phase of the work.

     Very little has been published on atmospheric emissions from the
petrochemical industry.  The first part of this study will therefore
rank the most important petrochemical  processes in their order of importance
in regard to atmospheric emissions. The Petrochemical Emissions Survey
Questionnaire will be the primary source of data during the first phase.
This ranking will be based on the amount and type of emissions from the
process, the number of similar processes and the expected growth of the
process.  A second in-depth phase of the study to document emissions more
completely will be based on information obtained through actual stack
sampling.

     Attached you will find a copy of  the  petrochemical questionnaire
which you are requested to complete and return to the Enviromental
Protection Agency within forty-two (42) calender days.

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                                  -2-
     You are required by Section 114 of the Clean Air Act to complete
each applicable part of this questionnaire except for question II.4. and
II.5.  These two questions are concerned with the water and solid waste
generated by the process itself not with that generated by the emission
control equipment.  This information would be of a value to the EPA and
your answers will be appreciated.

     This questionnaire is to be completed using the information presently
available to your company.  We are not asking that you perform special
non-routine measurements of emissions streams.  We are asking for results
of measurements that you have made or for estimates when measurements have
not been made.  Where requested information is not available, please mark
sections "not available".  Where the requested information is not appli-
cable to the subject process, mark the questionnaire sections "not
applicable".  A sample questionnaire, filled out for a fictitious process
is enclosed for your guidance.

     It is the opinion of this office that for most processes it should
be possible to answer all survey questions without revealing any
confidential information or trade secrets.  However, if you believe that
any of the information that we request would reveal a trade secret if
divulged you should clearly identify such information on the completed
questionnaire.  Submit, with the completed questionnaire, a written
justification explaining the reason for confidential status for each item
including any supportive data or legal authority.  Forward a duplicate
of your claim and supporting material, without the questionnaire data, to
our counsel, Mr. Robert Baum, Assistant General Counsel, Air Quality and
Radiation Division, Environmental Protection Agency, Room 17B41,
5600 Fishers Lane, Rockville, Maryland 20852.  Emission data cannot be
considered confidential.

     Final authority for determining the status of the information resides
with the Enviromental Protection Agency.  A reply describing the decision
reached will be made as soon as possible after receipt of the claim and
supporting information.  During the period before the final determination
this office will honor any request to treat the questionnaire information
as confidential.

     Information declared to be a trade secret is subject to protection
from being published, divulged, disclosed or made known in any manner
or to any extent by Section 1905 of Title 18 of the United States Code.
The disclosure of such information, except as authorized by law, shall
result in a fine of not more than $1,000 or imprisonment of not more
than one year, or both; and shall result in removal of the individual
from his office or employment.

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                                  -3-
     Although it should be noted that Section 114, Subsection C of the
Clean Air Act allows such information to be disclosed "to other officers,
employees, or authorized representatives of the United States concerned
with carrying out the Act or when relevant in any proceeding under this
Act," no confidential information will be revealed to any private concern
employed by the Environmental Protection Agency to assist in this study.

     The handling and storage of information for which the determination
is pending or information which has been determined to be of a confidential
nature is carefully controlled.  Preliminary control procedures require
that the material be labeled confidential and stored in a locked file.

     The complete form should be mailed to:

          Mr. Leslie B. Evans
          Environmental Protection Agency
          Office of Air Programs
          Applied Technology Division
          Research Triangle Park, NC  27711

     It is possible that additional copies of this questionnaire which
will request information covering other petrochemical processes or
other plants using the same process and operated by your organization
will be sent to you in the course of this study.  Clarification of items
contained in the questionnaire may be obtained from Mr.  Evans by tele-
phone at 919/688-8146.  Thank your for your help in this matter.

                                   Sincerely,
                                   Leslie B. Evans
                              Industrial Studies Branch

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                      Petrochemical Questionnaire

                             Instructions


I.     Capacity.   Describe capacity of process by providing the following:

       1.    Process capacity.   Give capacity in units per year and units
            per hour.   An "actual" capacity is preferred but "published"
            or "name plate" capacity will be satisfactory if such capa-
            city is reasonably correct.   Do not give production.

       2.    Seasonal variation.   Describe any significant seasonal
            variations in production.

            As example an ammonia plant might produce more during
            spring and winter  quarters:

            quarter   Jan-Mar    April-June   July-Sept   Oct-Dec    Year
                                                                   Total
            %            40         20          10          30     100%

II.     Process.  Describe the  process used to manufacture the subject
       chemical by providing the following:

       1.    Process name.  If  the process has a common name or description,
            give this.  If any portion of the process (e.g., product
            recovery method) has a common name, give this.

       2.    Block Diagram.  Provide a block diagram of the process showing
            the major process  steps and stream flows.

            (a)  Show on block diagram all streams described below.
                 Identify each required stream by letter.  (A,B,C, etc.)
                 In general the streams  that must be identified are
                 (1) the gaseous emissions streams before and after
                 any control device and  (2) the gaseous or liquid
                 streams which,  after leaving the process site, produce
                 gaseous emissions during further processing or com-
                 bustion.

                 (1)    Any gaseous waste streams before and after any
                        pollution device should be shown and identified.

                 (ii)    Streams from rupture disks or pressure relief
                        valves which protect equipment from operating
                        upsets but discharges less than once every year
                        need not be shown.

                 (iii)  Emissions from pressure relief systems that
                        normally discharge during power failures  or
                        other  emergencies should be shown, identified
                        by letter and labeled "emergency".

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                           -2-
          (iv)   Emissions from fueled heaters such as "heat
                 transfer medium" heaters, steam generators,
                 or cracking furnaces need not be shown if
                 they are fueled completely by fuels listed in
                 Question VII and are not used to incinerate by-
                 products or off gases.

          (v)    Emissions from Claus units associated with
                 process need not be shown.  Stream to Claus
                 unit should be shown and identified with letter.

          (vi)   Emissions from a central power plant (or steam
                 plant) which burns a liquid fuel produced as a
                 by-product of this process need not be shown.
                 Such liquid fuel should be shown and identified
                 by letter.

          (vii)  Emissions from a central power plant (or steam
                 plant) which burns a gaseous fuel produced as
                 a by-product of this process need not be shown.
                 Such gaseous fuel should be shown and identified
                 by letter.

     (b)  Show all gaseous emission control devices.  Identify
          each control device on the block diagram by a three
          digit number (101, 102, 103, etc.)

     (c)  Show all stacks or vents that vent streams listed in
          (a) and (b) above.  It a stack to vent discharges
          emissions from more than one source, label this stack
          or vent with a letter in sequence started in II.2.a.
          (D,E,F, etc.)  If a stack or vent discharges emissions
          from only one source label the stack with the same
          letter as the emission stream.

3.    Raw material and product.  Give approximate chemical com-
     position and approximate amount (on yearly basis and at
     capacity given in I.I) of all raw-materials, products
     and by-products.  If composition or amounts vary, give
     ranges.  Composition may be given in commonly accepted
     terms when a chemical analysis would be inappropriate.
     The description "light straight-run naphtha" would be
     adequate.

4.    Waste water.  Is there a waste water discharge from this
     process which is (eventually) discharged to a receiving
     body of water?  Is this waste water treated by you or
     by others?  Give the approximate volume and indicate
     whether this is measured or estimated.

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                                  -3-


       5.   Waste solids.   Is there a waste solids discharge from this
            process?  How is it disposed of?  Give the approximate
            daily total of waste solids and indicate if this is mea-
            sured or estimated.

III.   Emissions (composition and flow) ;  For each stream requested in
       II. 2. a.  and shown on the block diagram by letter provide the
       following:  (Use separate sheets for each identified location - 6
       copies are provided) .  All of the questions will not be appli-
       cable  for each stream.

       As an  example, question 10, odor problem, applies only to streams
       which  are emitted to the atmosphere.

       1.   Chemical composition and flow.   Give composition as completely
            as  possible from information you have available.  Do not omit
            trace constituents if they are known.  If anything (e.g. fuel)
            is  added upstream of any emission control devices, give the
            chemical composition and flow prior to the addition, and give
            the quantity and composition of the added material.  If liquids
            or  solids are  present (in gas stream) provide the composition
            and amount of  these also.  Give flow volume (SCFM) , temperature
            (F°) and pressure (psig or inches
       2.    Variation in chemical composition and flow.   If average stream
            composition or flow varies significantly over some period of
            time during normal or abnormal operation, discuss this varia-
            tion and its frequency.   Relate this to the  average and range
            of composition given in  III.l.

            As examples :

            "During start-up (once a month) the benzene  is about 12% by
            volume for one hour" or  "the benzene can be  expected to go
            from 5% to 9% by volume  during life of catalyst,  the 'average'
            figure given is about average over the catalyst life" or
            "power failures occur about once each winter causing stream
            A to increase from 0 to  (initially) 50,000 Ibs/hr. , and about
            8,000 Ibs is vented over a 15 minute period."

       3.    Production rate during sampling.   If stream  composition and
            volume flow rates given  in answer to questions III.l. and
            III. 2.  were measured at  a plant production rate different
            than the capacity of the plant given in I.I.  give the rate
            at which the measurements were made .

            As example :

            Figures given for this stream (A)  were made  when  plant was
            operating at 90% of capacity given in I.I.

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                           -4-
 4.   Methods used to determine composition and flow.  Is information
     from material balance, from sample and analysis, or other?
     Describe briefly.

 5.   Sampling procedure.  If samples have been taken, give summary
     description of sampling procedure or give reference if
     described in open literature.

 6.   Analytical procedure.  If samples have been taken, give sum-
     mary description of analytical procedure or give reference if
     described in open literature.

 7.   Sampling frequency.  How often is the stream sampled?

     As Examples:

     "continuous monitor" or "twice a shift for last 18 months"
     or "once in the fall of 1943".

8.   Confidence level.   Give some idea how confident you are in
     regard to compositions in III.l.

     As examples:

     "probably correct + 20%" or "slightly better than wild guess".

9.   Ease of sampling.   How difficult is it to sample this stream?

     As examples:

     "sample line runs into control room" or "sample port provided
     but accessible only with 20-ft.  ladder."

10.  Odor problem.   Is the odor of this emission detectable at
     ground level on the plant property or off the plant property?
     If odors carry beyond the plant property are they detectable
     frequently or infrequently?  Have you received a community
     odor complaint traceable to this source in the past year?
     Has the odorous material been chemically identified?  What
     is it?

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                                  -5-
IV.    Emission control device.   Supply the following information for each
       control device shown on the  block diagram.   (Use separate sheets
       for each - 3 copies are provided).

       1.    Engineering description.   Give brief description and process
            sketch of the control device.   Attach print or other des-
            cription if you prefer.   Show utilities used,  steam produced,
            product recovered, etc.   Give manufacturer, model number and
            size (if applicable).   Give complete (applicable) operating
            conditions,  i.e.  flows,  temperatures,  pressure drops, etc.

       2.    Capital cost of emission control system.

            (a)   Give capital cost  for the emission control device as it
                 is described in  IV.1.  above;  i.e., if equipment has been
                 modified or  rebuilt  give your best estimate of capital
                 cost of equipment  now in service.   For the total installed
                 cost give the approximate breakdown by year in which cost
                 was incurred.

                 As example:

                 Major equipment  cost    $155,000
                 Total installed  cost    $250,000
                 Year      Cost
                 1963      $160,000
                 1964        40,000
                 1971        50,000
                           $250,000

            (b)   On the  check list  given  mark  whether the  items listed  are
                 included in  total  cost as given above.  Give one sentence
                 explanation  when required but do not give dollar amounts.

            (c)   Was outside  engineering  contractor used and was cost
                 included in  capital  cost?

            (d)   Was in-house engineering  used and  was  cost included in
                 capital cost?

            (e)   Was emission control  equipment installed  when plant was
                 built?

       3.    Operating cost of emission  control system.   Give the best
            estimate of  cost  of operating  emission  control system in
            dollars per  year  with process  operated  at capacity given
            in I.I.   Other disposal  (g) would  include,  as  example,
            the  cost of  incinerating  a  by-product stream which has  no
            value.

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                                  -6-
V.     Stack or vent description.  Each stack or vent should have been
       identified by letter on the block diagram.  Provide the requested
       information for each stack.  Stack flow, V.A. should be entered
       only when it is not possible to calculate this number by adding
       gas flows given in III.l.

       An example would be when an off gas from the process is discharged
       into a power plant stack.

VI.    Tankage.  Give information requested for all tankage larger than
       20,000 gallons associated with the process and normally held at
       atmospheric pressure (include raw material, process, product and
       by-product tankage).  Method of vapor conservation (3.) might
       include, as examples:

       "none, tank vents to air"
       "floating roof"
       "vapor recovery by compression and absorption".

VII.   Fuels.  If fuels are used in the process give the amount used on
       a yearly basis at capacity given in I.I.  Do not include fuel used
       in steam power plants.   Give sulfur content.  Identify each fuel
       as to its source (natural gas pipeline, process waste stream,
       Pennsylvania soft coal).   Is the fuel used only as a heat source
       (as with in-line burner)?

VIII.  Other emissions.  If there is a loss of a volatile material from
       the plants through system leaks, valve stems, safety valves,
       pump seals, line blowing, etc., this loss is an emission.  In a
       large complex high pressure process this loss may be several per-
       cent of the product.  Has this loss been determined by material
       balance or other method?   What is it?  Give best estimate.

IX.    Future plans.  Describe,  in a paragraph, your program for the
       future installation of air pollution control equipment for this
       unit or for future improvements in the process which will reduce
       emissions.

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                                              OMB Approval Number 158 S 72019
This example questionnaire has been
completed for a fictitious company
and process.
                                Example
                             Questionnaire
Air Pollution Control Engineering and Cost Study of the Petrochemical Industry
Please read Instructions before completing questionnaire.
Subject chemical:	Pyrrole	•

Principal by-products ;   Pyrrolidone	

Parent corporation name; Orivne Petrochemical Co.	__

Subsidiary name:	Noissime Division	

Mailing address:	P.O. Box 1234	

               	Rianaelc, North Carolina. 27700
Plant name:	Rianaelc Plant	

Physical  location:	30 miles N.W. Durham. North Carolina	

(include  county  and
air  quaility  control
region)   Orange County; Eastern Piedmont Intrastate (Region IV)	

Person EPA should contact  regarding  information  supplied  in  this  questionnaire

Name:	John Doe	

Title:	Supervisor of Process Development	

Mailing address:_	Noissime Division of P.P.C.	

               	P.O. Box 1234	

               	Rianaelc, North Carolina. 27700	

Telephone number:	919  XXX  XXXX	

Date questionnaire  completed:	May 30, 1972	

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                                  -2-
I.  Capacity.

    1.  Process capacity,  (not production)

          80.000.000 Ibs.   	per year

        	10.000 Ibs.	per hour

    2.  Seasonal variation,  (of production)

        quarter               1         2
                                                                      year
                                                                      total
                              30        20        20        30         100%

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                           STACK:
                        A
     AIR
COMPRESSION
                          •v— — -  -
                FUEL
 PYRROLIDINE
   STORAGE
 PYRROLE
 STORAGE
PYRROLIDONE
  STORAGE
                 HEAT EXCHANGERS
                     &
              FLUID BED  CATALYTIC
                    REACTORS
                                 RECYCLE
   PRODUCT
  RECOVERY
     &
PURIFICATION
                                    HEAVY
                                     ENDS

                                    -0
                                               PRODUCT
                                                 DRUM
FILTER
                                                     L
                                              WATER RECYCLE
                                             EMERGENCY VENT TO
                                             INCINERATOR 102
                                                                       ©
                                 STACK
                                 *—
                                  C
                                                                             SCRUBBER
                                                                                101
                                                                  DISCHARGED
                                                                  WATER - WASHED
                                                                     SOLIDS
                                                                STACK
                                                                                               IS)
                                                                                               W
                                                                                               8-
                                                        WATER
                                                        DISCHARGE-
                                             INCINERATOR
                                                 102
                                                                         D
                                                                         •o
                                                                         O
                                                                         O
                                                                         9
                                                                         IB
                                                                         IB
                                                                                                   O
                                                                                                   X
0.
I
M
O
00
B
                                                o

                                                o
                                                m
                                                •o
                                                M
                                                O
                                                t->
                                                I*
                                                O.
                                                H-
                                                (D
                                                    o
                                                    o
                                                    o
                                                    IB
                                                    IB
                                                    9
                                                    §
                                                    m
                                                        o
                                                        o
                                                                                                           so
                                                                                                           IB

-------
                                  -4-
II.
     Process.   (Continued)




     3.   Raw materials and  products




         Raw materials




          Name                Quantity




          Pyrrolidine        130.000.000 Ibs/yr.
                                                       Composition
pyrrolidine
other amines
98%
2%






Product and by-products



          Name                Quantity                 Composition




          Pyrrole             80.000.000 Ibs/vr.       pyrrole	99.5%
          Pyrrolidone
20.000.000 Ibs/yr.
pyrrolidone
                                                                        99.5%

-------
                                  -5-
II.  Process.  (Continued)




     4.   Waste water.
          750 gal/hr.  treated  by us,  measured  in treatment  unit,
     5.   Waste solids.




         200  Ibs/hr.  catalyst dust  from  filter.   Estimated  average




         quantity hauled away by  solids  waste disposal  contractor.

-------
                                                        T3T
III. 1.Emissions (composition and flow).
                                                        Six copies provided
                                                        this section
      Stream flow shown on block diagram by letter	A_

  1.  Flow     ?      Temperature     ?      Pressure
      Component
        Name
      Particulate
Formula
State
                  Solid
Average amount
or composition
Composition
   Range
      Depending upon cause of  emergency,  emissions  could range from contaminated feed to contaminated product.

      Upset durations seldom exceed  15 minutes during which time incinerator operation would be modified.  For

      initial 1-2 minutes  after  upset pollutants might leave incinerator stack.  Following that, stack gases will

      be nearly 100% C02,  H20  &  N2.   On average, such upsets occur two or three times per year.  Particulates are

      possible,  depending  upon cause of upset.  One such upset occurred in 1969.
      * Particulate matter should be described as fully as possible.

-------
                                  -7-
                                  (a)
III.  Continued   For stream flow shown on block diagram by letter	A



      2.  Composition variation.

           See III-l
      3.  Production rate during sampling.

           Never Sampled                '
      A.  Method used to determine composition and flow.

           Not applicable

-------
III.  Continued  For stream flow shown on block diagram by letter	A
      5.  Sampling procedure.




           Not Applicable
      6.  Analytical procedure.




           Not Applicable
      7.  Sampling frequency.



           Never

-------
                                  -9-
                                  (a)
III.  Continued  For stream flow shown on block diagram by letterA
      8.  Confidence level.
           Not Applicable
      9.  Ease of sampling.

           Impossible
     10.  Odor problem.   (Circle yes or no or mark "not applicable")

          Is the odor of this emission ever detectable at ground level

          on the plant property?  Yes/no  Off the plant property?  Yes/no

          If odors carry beyond the plant property are they detectable

          Infrequently?  Yes/no Frequently?  Yes/no  Have you received a

          community odor complaint traceable to this source in the past

          year?  Yes/no  Has the odorous material been chemically identified?

          Yes/no  What is it?	

                Not Applicable

-------
Ill.1.Emissions (composition and flow),
Six copies provided
this section
      Stream flow shown on block diagram by letter
Flow lOjOOO SCFHTemperature
Component
Name
Particulate
Nitrogen
Oxygen
Carbon Monoxide
Carbon Dioxide
Hydrogen
Water
Various Amines
Nitrogen Oxides
Formula
*
N2
°2
CO
COj
H2
H20
**
NOX
* Particulate matter should be
contains cobalt and chromium
less than 5 microns;
5% less
110°F Pressure 25 PSIG
State
Solid
Gas
Gas
Gas
Gas
Gas
Vapor
Vapor
Gas
described as fully as possible.
on alumina base. 1002 lea
-------
                                  fb7)-
III.  Continued   For stream flow shown on block diagram by letter     B	.








      2.  Composition variation.




           During 2nd and  3rd  quarter when  plant  is  operated below capacity,




           nitrogen is at  high end  of range and all  other materials  near  low




           end.   During start-up or plant upset  (average about  50 hours/year)




           nitrogen is near low end of  range and  all other materials near high



           end.
      3.  Production rate during sampling.



           Average composition based on-rated capacity.
      A.  Method used to determine composition and  flow.




           Engineering  calculation and plant material balance (flow).




           Composition  calculated on  basis of stream "C" analysis and  estimated



           amine losses  prior to installation of  scrubber.

-------
III.  Continued  For stream flow shown on block diagram by letter	B
      5«  Sampling procedure.




          Never sampled.
      6.  Analytical procedure.



          Never Analyzed.
      7.  Sampling frequency. •••»



           See  (5) above.

-------
                                  (I)
III.  Continued  For stream flow shown on block diagram by letter	B
      8. "Confidence level.
      9.  Ease of sampling.




          No sample taps are available,  but one could be easily installed




          in readily accessible location.   However,  it would not be 8 pipe



          diameters from a disturbance.
     10.  Odor problem.  (Circle yes or no or mark "not applicable")




          Is the odor of this emission ever detectable at ground level




          on the plant property?  Yes/no  Off the plant property?  Yes/no




          If odors carry beyond the plant property are they detectable




         "Infrequently?  Yes/no Frequently?  Yes/no  Have you received a




          community odor complaint traceable to this source in the past




          year?  Yes/no  Has the odorous material been chemically identified?




          Yes/no  What is it?	



                  No applicable -  this  stream is no longer




                  emitted to the atmosphere.

-------
III.1.Emissions (composition and flow).
Six copies provided
this section
      Stream flow shown on block diagram by letter	C
Flow lO.OOOSCFM Temperature 100°F Pressure 0 PSIG
Component
Name
Particulate
Nitrogen
Oxygen
Carbon Monoxide
Carbon Dioxide
Hydrogen
Water
Various Amine
Nitrogen Oxides
Formula
*
N2
°2
CO
C02
H2
H20
**
NOX
* Particulate matter should be described as
5 microns; 60% less than 1 micron.
State
Solid
Gas
Gas
Gas
Gas
Gas
Vapor
Vapor
Gas
fully as possible.
Average amount
or composition
10 Ibs./hour
83.9 Vol. %
1.4 "
4.1 "
1.4 "
2.1 "
7.1 "
50 YPPMV
300 YPPMV
Composition
Range
5-20 Ibs./hour
80-85%
1-2%
3-5%
1-2%
2-2.5%
6.5-7.5%
30-100 PPMV
200-500 PPMV
See "B". Size distribution 100% less than


    **  See "B".

-------
III.  Continued   For stream flow shown on block diagram by letter

      2.  Composition variation.
           See "BY
      3.  Production rate during sampling.
           See "B"
      4.  Method used to determine composition and flow.
           See "B" for flow.  Specific analysis methods are given in III-6(C)

-------
                                  -8-
                                  Cc)
III.  Continued  For stream flow shown on block diagram by letter
      5.  Sampling procedure.

          a.  Particulates and moisture collected in sampling train as detailed
              in Federal Register, Dec. 23,  1971 (Method 5).

          b.  NO  sampled by EPA Method 7.
                X

          c.  Other constituents collected using grab sampling procedures for
              collection of gas.  Sample size 10 liters in stainless steel tank.
      6.  Analytical procedure.

          a.   Particulates and moisture determined gravimetrically as detailed
              in Federal Register,  Dec. 23,  1971.   (Method 5)

          b.   NOX determined by EPA method 7.

          c.   Hydrogen,  oxygen,  and nitrogen determined  by mass  spectrometer
              analysis at local university.

              Amine,  CO  and C02 determined by  infra-red  analysis.
      7.  Sampling frequency.

          Once,  - one  month after  scrubber was put  on  stream.

-------
                                  -9-
                                  (c)
III.  Continued  For stream flow shown on block diagram by letter
      8.  Confidence level.

          Oxygen, C02, CO and H may be + 10%.

          Nitrogen would be better than this,  perhaps + 5%

          Amines are near limit of detection - + 50%.
      9.  Ease of sampling.

          Difficult - only sample tap is six feet above top of scrubber

          tower - approximately 65 feet in air - reached by caged ladders.
     10.  Odor problem.  (Circle yes or no or mark "not applicable")

          Is the odor of this emission ever detectable at ground level

          on the plant property?  Yes/no  Off the plant property?  Yes/no

          If odors carry beyond the plant property are they detectable

          infrequently?  Yes/no Frequently?  Yes/no  Have you received a

          community odor complaint traceable to this source in  the past

          year?  Yes/no  Has the odorous material been chemically identified?

          Yes/no  What is it?    Amine compounds.     	

-------
III.I.Emissions (composition and flow).
                                                        Six copies provided
                                                        this section
      Stream flow shown on block diagram by letter	D_
  1.  Flow 300 GPH    Temperature   300°F     Pressure  10 PSIG
      Component
        Name
      Particulate

      Heavy Amines
Formula
State
Solid
Liquid
Average amount
or composition
Trace
100%
Composition
Range

      * Particulate matter should be described as fully as possible.   Very  fine catalyst dust - never sampled

         or analyzed - estimated to be 1-5 Ibs./hour.        	        		

-------
                                  -7-
                                  (d)
III.  Continued   For stream flow shown on block diagram by letter  D
      2,  Composition variation.


           Not applicable - unknown - never analyzed.
      3.   Production rate during sampling.


           See "B"
      4.   Method used to determine composition and flow.

           Rotameter in liquid line for flow.  Composition unknown.

-------
                                  -o-
III.  Continued  For stream flow shown on block diagram by letter     D
      5.  Sampling procedure.



          Not applicable.
      6.  Analytical procedure.




          Not applicable.
      7.  Sampling frequency.




          Not applicable.

-------
                                  -9-
                                  (d)
III.  Continued  For stream flow shown on block diagram by letter	D
      8.  Confidence level.
          Not applicable.
      9.  Ease of sampling.

          Liquid drain line is available at ground level.   Could be used

          for sample tap.
     10.  Odor problem.   (Circle yes or no or mark "not applicable")

          Is the odor of  this emission ever detectable at ground level

          on the plant property?  Yes/no  Off the plant property?  Yes/no

          If odors carry  beyond the plant property are they detectable

          infrequently?   Yes/no Frequently?  Yes/no  Have you received a

          community odor  complaint traceable to this source in the past

          year?  Yes/no   Has the odorous material been chemically identified?

          Yes/no  What is it?	

                    Not applicable - not an emitted stream.

-------
III. 1 Emissions (composition and flow).
            Six copies provided
            this section
      Stream flow shown on block diagram by letter
  1.   Flow 10,OOOSCFM Temperature   450°F    Pressure 0 PSIG
Component
Name
P articulate
Nitrogen
Oxygen
Carbon Dioxide
Water
Nitrogen Oxides
Formula
*
N2
°2
co2
H20
NOX
State
Solid
Gas
Gas
Gas
Vapor
Gas
Average amount
or composition
Trace
77.0 Vol. %
9.2 Vol. %
6.4 Vol. %
7.4 Vol. %
150 VPPM
Composition
Range

76.5-77.5%
9-9.5%
6-7%
7-8%
100-300 VPPM
      * Particulate matter  should be  described  as  fully  as  possible,
See "Dr

-------
III.  Continued   For stream flow shown on block diagram by letter
      2.  Composition variation.
           Random variation depending on many variables  such as production
           rate,  ambient air temperature and humidity, catalyst age,  etc.,
           all within limits shown.
      3.  Production rate during sampling.
           See "B"
      A.  Method used to determine composition and flow.
           Calculation based on incinerator vendor's specifications, guarantees
           and laboratory tests.

-------
                                  —o—
                                  (e)
III.  Continued  For stream flow shown on block diagram by letter	F_
      5.  Sampling procedure.

          Never sampled.
      6.  Analytical procedure.

           Never analyzed
       7.   Sampling  frequency.

           See (5) above

-------
                                  -9-
                                  (e)
III.  Continued  For stream flow shown on block diagram by letter	E
      8.  Confidence level.

          + 10%
      9.  Ease of sampling.


          No sample tap, very hot stream, no access ladders, minimal insulation.
     10.  Odor problem.   (Circle yes or no or mark "not applicable")


          Is the odor of  this emission ever detectable at ground  level


          on the plant property?  Yes/no  Off the plant property?  Yes /no


          If odors carry  beyond the plant property are they detectable


          infrequently?*  Yes/no Frequently?  Yes/no  Have you  received  a


          community odor  complaint traceable to  this source in the past


          year?  Yes/jjo   Has the odorous material been chemically identified?


          Yes/no  What is it?
          * Only during start-up or upset of the incinerator and then only


            if atmospheric conditions are favorable for ground level detection.

-------
                                 -10-
                                 (a)
            3  copies  provided
            this  section.
IV.  Emission control device

     For device shown on block diagram by number    101
     1.  Engineering description.


                        . GAS TO
                       T STACK
         GAS
     DISTRIBUTOR
                               MIST
                               ^ELIMINATOR
Multi-nozzle spray tower manu-
factured by Rebburcs Corp.
Model No. 10,000-W
Water rate:  100 GPM
Gas rate:    10,000 SCFM
Temperature: 100°F.
Pressure:  Atmospheric
Gas AP:    8 in, H20
Water Pump Head:  150 Ft.
Discharge Pump Head:  100 Ft.

Diameter of Tower:  6 Ft.
T-T Length:        60 Ft.
                                       WATER PUMP


                                 \ DOWNCOMER
    DISCHARGE
      PUMP
Utilities:

   35 HP for Pumps
-,
   10,000,000 BfU/Hr.  Additional steam in product recovery section.

   1500 GPM   Additional cooling water circulation in product recovery section.

-------
                                 ctf-
IV.  Continued  For device shown on block  diagram by number	101




     2.  Capital cost of emission control  system.




         (a)  Capital cost








          Major equipment cost     $ 160,000	
          Total installed cost     $ 350.000
          Year                Cost



          1968               $350,000

-------
                                 -12-
                                 (a)
IV.  Continued  For device shown.on block diagram by number    101
     (b)  Check list.  Mark whether items listed are included in total


          cost included in IV.2.a.  Do not give dollar value -
Yes
Cost
               Facilities outside


               battery limits*
Explanation
X
X
X
X
X
X
X
X
X
X
Site development Additional foundation required fo
scrubber .
Buildings
Laboratory equipment
Stack
Rigging etc.
Piping
Insulation
Instruments
Instrument panels
Electrical
               Storage tanks, spheres


               drums, bins, silos
               Catalysts
               Spare parts and


               non-installed parts
*Such as - process pipe  lines  such as  steam,  condensate, water,  gas,  fuel,


 air, fire,  instrument and  electric  lines.

-------
                                   -13-
                                    (a)
   IV.   Continued  For device  shown on block diagram by  number  101
  Yes
No
                      Was  outside  engineering  contractor used?

                      Was  cost  included in capital cost?

                      Was  in-house engineering used?
          X	       Was  cost  included  in capital  cost?
         _X	      Was  emission control  equipment installed
                      and  constructed  at  the time  plant (process)
                      was  constructed?

   3.   Operating costs of control  system.

   Give 1972  dollar  values  per  year at  capacity given in I.I.

   (a)   Utilities                                              $ 68.000

   (b)   Chemicals*                                               10.000

   (c)   Labor (No Additional Operators')                         _j;	
   (d)   Maintenance  (labor  & materials)                           14,000

   (e)   Water  treatment  (cost of treating any waste
        water  produced by this control system) **                 -	
   (f)   Solids remmoval  (cost  of removing any waste
        solids produced  by this control system)                   20,000

   (g)   Other disposal                                           -	
   (h)   By-product  or product recovery     CREDIT               $89,000 )

        Total operating costs                                  $ 23.000
*  Additional cooling water treatment included in utility costs -
   this cost is for corrosion inhibition in scrubber.

** Water waste is produced by process.  It is treated at cost of
   $30,000/year.  This treatment was required before scrubber was
   installed.

-------
                                                                      3 copies provided
                                                                      this section.
          IV.  Emission control device

               For device shown on block diagram by number	102
      WATER
    BURNERS
               1.  Engineering description.
                      t
TO STACK

 CONVECTIVE
       CTION
                   RADIANT
                   SECTION
                                              STEAM
                                      SECONDARY
HEAVY ENDS
                AIR
             BLOWER
Steam Generator/Waste Incinerator

Manufactured by:  Xoberif Corp.
Model No.:        40-H
Heavy Ends Rate:  300 GPH
Air Rate:   9,500 SCFM
Steam Rate: 20,000 Ibs./hour
Vessel Diameter:  15 Ft.
Height:     40 Ft.
Tube Diameter:   3 in. nominal
Tube Length:     (Material)
  Convective  (mild steel): 6,000 Ft,
  Radiant  (304 stainless): 2,000 Ft,
               Utilities:

                   Heavy Ends Pump:    20 HP

                   Blower:            100 HP

-------
                                 -11-
                                 (10
IV.  Continued  For device shown-on block diagram by number	102


     2.  Capital cost of emission control system.


         (a)  Capital cost




          Major equipment cost     $ 350,000	
          Total installed cost     $1,000,000
          Year                Cost


           1960              $1,000,000

-------
                                 -12-
                                 (b)
IV.  Continued  For device shown on block diagram by number
                                                         102
Yes
     (b)  Check list.  Mark whether items listed are included in total

          cost included in IV.2.a.  Do not give dollar value -
No
        X
Cost
        Storage tanks, spheres

        drums, bins, silos
Explanation
X
X
X
X
X
X
X
X
X
X
X
Site development Cost prorated from total plant
site costs.
Buildings
Laboratory equipment
Stack
Rigging etc.
Piping
Insulation
Instruments
Instrument panels
Electrical
Facilities outside
battery limits*
               Catalysts
        X
        Spare parts and

        non-installed parts
*Such as - process  pipe  lines  such  as  steam,  condensate,  water,  gas,  fuel,

 air, fire,  instrument and  electric lines.

-------
                                 -13-
                                 (b)
IV.  Continued  For device shown on block diagram by number  102
Yes
X
X

X
x
No

X


                    Was outside engineering contractor used?

                    Was cost included in capital cost?

                    Was in-house engineering used?

                    Was cost included in capital cost?

                    Was emission control equipment installed
                    and constructed at the time plant (process)
                    was constructed?

3.  Operating costs of control system.

Give 1972 dollar values per year at capacity given in I.I.

(a)  Utilities                                              $	

(b)  Chemicals
                         5,000
(c)  Labor  (^ man per shift -  excludes supervision &
                                        overhead)
(d)  Maintenance  (labor & materials)

(e)  Water treatment  (cost of treating any waste
     water produced by this control system)

(f)  Solids remmoval  (cost of removing any waste
     solids produced by this control system)
                         7,000
                        40,000
(g)  Other disposal

(h)  By-product or product recovery

     Total operating credit
CREDIT- STEAM
($100,
                    $   48 , 000

-------
                                 -14-
V.  Stack or vent description.
For stack or vent shown on block diagram by letter
     1.  Stack height                             	100ft




     2.  Stack diameter                           	2ft




    ' 3.  Gas temperature stack exit               	100 °F




     4.  Stack flow   *                           	SCFM(70°F & 1 Atra.)






For stack or vent shown on block diagram by letter	E	.
     1.  Stack height                                  60 Ft.




     2.  Stack diameter                                 3 Ft.
     3.  Gas temperature stack exit                   450 F




     4.  Stack flow   *
For  stack or vent  shown on block diagram by letter




      1.  Stack height




      2.  Stack diameter




      3.  Gas temperature  stack  exit




      4.  Stack flow   *
 For  stack or  vent  shown on block diagram by  letter




      1.   Stack height




      2.   Stack diameter



      3.   Gas  temperature stack exit




      4.   Stack flow   *






 * See instructions

-------
VI.  Tankage.
No. of
tanks
3
4
composition
Pyrrolidine

-------
                                 -16-
VII.   Fuels.

        800,000 gal./year fuel oil for fired air heater 3% sulfur.
VIII.  Other emissions.
        No other known emissions although minor leakages probably occur.

        Engineering estimate of average losses is 0.01% of throughput or
        13,000 Ibs./year of amines.
 IX.     Future plans.
         1.   Current  research  on heavy  amine  stream  indicates  further
             processing will produce  a  marketable product  -  if so,
             incinerator will  be shut down.

         2.   We  are currently  negotiating  a long term contract to purchase
             1%  sulfur fuel oil from  the Plused Oil  Company.

-------
                                 APPENDIX  III
                         FINAL QUESTIONNAIRE  SUMMARY
                 Chemical

Acetaldehyde via Ethylene
             via Ethanol
Acetic Acid via Methanol
            via Butane
            via Acetaldehyde
Acetic Anhydride
Acrylonitrile
Adipic Acid
Adiponitrile via Butadiene
             via Adipic Acid
Carbon Black
Carbon Bisulfide
Cyclohexanone
Dimethyl Terephthalate (+TPA)
Ethylene
Ethylene Dichloride via Oxychlorination
                    via Direct Chlorination
Ethylene Oxide
Formaldehyde via Silver Catalyst
             via Iron Oxide Catalyst
Glycerol
Hydrogen Cyanide
Isocyanates
Maleic Anhydride
Nylon 6
Nylon 6,6
Oxo Process
Phenol
Phthalic Anhydride via o-xylene
                   via naphthalene
Polyethylene (High Density)
Polyethylene (Low Density)
Polypropylene
Polystyrene
Polyvinyl Chloride
Styrene
Styrene - Butadiene Rubber
Vinyl Acetate via Acetylene
              via Ethylene
Vinyl Chloride
Number of Questionnaires
used as Basis for Report

             1
             1
             2
             1
             1
             2
             4
             4
             1
             2
             7
             4
             7
             6
            13
            10
             3
             7
            12
             6
             2
             1
            10
             7
             4
             3
             6
             8
             5
             3
             5
             7
             7
             4
             7
             6
             3
             1
             8

-------
Appendix IV & V

-------
                      INTRODUCTION TO APPENDIX IV AND V

       The following discussions describe techniques that were developed for
the single purpose of providing a portion of the guidance required in the
selection of processes for in-depth study.  It is believed that the underlying
concepts of these techniques are sound.  However, use of them without sub-
stantial further refinement is discouraged because the data base for their
specifics is not sufficiently accurate for wide application.  The subjects
covered in the Appendix IV discussion are:

       1.  Prediction of numbers of new plants.

       20  Prediction of emissions from the new plants on a weighted
           (significance) basis.

       The subject covered in the Appendix V discussion is:

       Calculation of pollution control device efficiency on a variety of
bases, including a weighted (significance) basis.

       It should be noted that the weighting factors used are arbitrary,,
Hence, if any reader of this report wishes to determine the effect of
different weighing factors, the calculation technique permits changes in
these, at the reader's discretion.

-------
                                 APPENDIX IV

                         Number of New Plants by 1980

       Attached Table 1 illustrates the format for this calculation.
Briefly, the procedure is as follows:

       1.  For each petrochemical that is to be evaluated, estimate what
           amount of today's production capacity is likely to be on-stream
           in 1980.  This will be done by subtracting plants having marginal
           economics due either to their size or to the employment of an
           out-of-date process.

       2.  Estimate the 1980 demand for the chemical and assume a 1980
           installed capacity that will be required in order to satisfy
           this demand.

       3.  Estimate the portion of the excess of the 1980 required capacity
           over today's remaining capacity that will be made up by
           installation of each process that is being evaluated.

       4.  Estimate an economic plant or unit size on the basis of today's
           technology.

       5»  Divide the total required new capacity for each process by the
           economic plant size to obtain the number of new units.

       In order to illustrate the procedure, data have been incorporated
into Table I, for the three processes for producing carbon black, namely
the furnace process, the relatively non-polluting thermal process, and
the non-growth channel process.

-------
                                      Table 1.  Number of New Plants by 1980
                                                           Current
Chemical
Carbon Black


Process
Furnace
Channel
Thermal
Current
Capacity
4,000
100
200
Marginal
Capacity
0
0
0
Capacity
on-stream
in 1980
4,000
100
200
Demand
1980
4,500
100
400
Capacity
1980
5,000
100
500
Capacity
to be
Added '
1,000
0
300
Economic
Plant
Size
90
30
150
Number
New
Units
11 -
0
2
of
12


                                                                                                                            I
                                                                                                                           M
Notes:  1.  Capacity units all in MM Ibs./year.


        2.  1980 demand based on studies prepared for EPA by Processes Research, Inc. and MSA Research Corporation.

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                                     IV-3
                    Increased Emissions (Weighted) by 1980

       Attached Table 2 illustrates the format for this calculation.
However, more important than format is a proposal for a weighting basis.
There is a wide divergence of opinion on which pollutants are more noxious
and even when agreement can be reached on an order of noxiousness, dis-
agreements remain as to relative magnitudes for tolerance factors.  In
general pollutants from the petrochemical industry can be broken down into
categories of hydrogen sulfide, hydrocarbons, particulates, carbon monoxide,
and oxides of sulfur and nitrogen.  Of course, two of these can be further
broken down; hydrocarbons into paraffins, olefins, chlorinated hydrocarbons,
nitrogen or sulfur bearing hydrocarbons, etc,, and particulates into ash,
catalyst, finely divided end products, etc.  It is felt that no useful
end is served by creating a large number of sub-groupings because it will
merely compound the problem of assigning a weighting factor.  Therefore,
it is proposed to classify all pollutants into one of five of the six
categories with hydrogen sulfide included with hydrocarbons„

       There appears to be general agreement among the experts that carbon
monoxide is the least noxious of the five and that NOX is somewhat more
noxious than SOX»  However, there are widely divergent opinions concerning
hydrocarbons and particulates - probably due to the fact that these are
both widely divergent categories.  In recent years, at least two authors
have attempted to assign tolerance factors to these five categories„
Babcock (1), based his on the proposed 1969 California standards for
one hour ambient air conditions with his own standard used for hydrocarbons.

       On the other hand, Walther (2), based his ranking on both primary
and secondary standards for a 24-hour period.  Both authors found it
necessary to extrapolate some of the basic standards to the chosen time
period„  Their rankings, on an effect factor basis with carbon monoxide
arbitrarily used as a reference are as follows:
                 Babcock
                          Walther
       Hydrocarbons
       Particulates
       NOX
       SOX
       CO
  2.1
107
 77o9
 28.1
  1
Primary

  125
   21.5
   22.4
   15.3
    1
                                                                 Secondary
125
 37,
 22,
 21.5
  1
       Recognizing that it is completely unscientific and potentially subject
to substantial criticism it is proposed to take arithmetic averages of the
above values and round them to the nearest multiple of ten to establish a
rating basis as follows:
       Hydrocarbons
       Particulates
       NOX
       sox
       CO
          Average

            84.0
            55o3
            40.9
            21.6
             1
                   Rounded

                      80
                      60
                      40
                      20
                       1

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Table 2.  Weighted Emission Rates
Chemical
Process
Increased Capacity
Increased Emissions
Pollutant Emissions, Lbs./Lb. Lbs=/Year
Hydrocarbons
Particulates
NOX
sox
CO
Weighting
Factors
80
60
40
20
1
Weighted Emissions
Lbs./Year





                                           Total

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                                     IV-5


              Increased Emissions (Weighted) by 1980 (continued)

       This ranking can be defended qualitatively, if not quantitatively for
the following reasons:

       1.  The level of noxiousness follows the same sequence as is obtained
           using national air quality standards.

       20  Approximately two orders of magnitude exist between top and bottom
           rankings.

       30  Hydrocarbons should probably have a lower value than in the
           Walther analysis because such relatively non-noxious compounds
           as ethane and propane will be included.

       4.  Hydrocarbons should probably have a higher value than in the
           Babcock analysis because such noxious (or posionous) substances
           as aromatics, chlorinated hydrocarbons, phenol, formaldehyde, and
           cyanides are included,

       5.  Particulates should probably have a higher value than in the
           Walther analysis because national air standards are based mostly
           on fly ash while emissions from the petrochemical industry are
           more noxious being such things as carbon black, phthalic anhydride,
           PVC dust, active catalysts, etc.

       6.  NOX should probably have a higher value than in the Walther
           analysis because its role in oxidant synthesis has been neglected.
           This is demonstrated in Babcock's analysis.

       Briefly, the procedure, using the recommended factors and Table 2, is
as follows:

       1.  Determine the emission rate for each major pollutant category in
           terms of pounds of pollutant per pound of final product.  This
           determination is to be made on the basis of data reported on
           returned questionnaires.

       2.  Multiply these emission rates by the estimate of increased production
           capacity to be installed by 1980 (as calculated while determining
           the number of new plants), to determine the estimated pounds of
           new emissions of each pollutant.

       3.  Multiply the pounds of new emissions of each pollutant by its
           weighting factor to determine a weighted pounds of new emissions
           for each pollutant.

       4.  Total the weighted pounds of new emissions for all pollutants to
           obtain an estimate of the significance of emission from the process
           being evaluated.  It is proposed that this total be named
           "Significant Emission Index" and abbreviated "SEI".

       It should be pointed out that the concepts outlined above are not
comp'letely original and considerable credit should be given to Mr. L. B. Evans
of the EPA for setting up the formats of these evaluating procedures.

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                                     IV-6
              Increased Emissions (Weighted)  by 1980 (continued)

(1)   Babcock,  L.  F.,  "A Combined Pollution Index for Measurement of Total
     Air Pollution,"  JAPCA,  October,  1970; Vol. 20,  No.  10;  pp 653-659

(2)   Walther,  E.  G.,  "A Rating of the Major Air Pollutants and Their Sources
     by Effect",  JAPCA, May,  1972;  Vol.  22, No. 5;  pp 352-355

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                                  Appendix V
                   Efficiency of Pollution Control Devices

Incinerators and Flares

       The burning process is unique among the various techniques for
reducing air pollution in that it does not remove the noxious substance
but changes it to a different and hopefully less noxious form.  It can be,
and usually is, a very efficient process when applied to hydrocarbons,
because when burned completely the only products of combustion are carbon
dioxide and water.  However, if the combustion is incomplete a wide range
of additional products such as cracked hydrocarbons, soot and carbon
monoxide might be formed.  The problem is further complicated if the
hydrocarbon that is being burned is halogenated, contains sulfur or is
mixed with hydrogen sulfide, because hydrogen chloride and/or sulfur oxides
then become products of combustion.  In addition, if nitrogen is present,
either as air or nitrogenated hydrocarbons, oxides of nitrogen might be
formed, depending upon flame temperature and residence time.

       Consequently, the definition of efficiency of a burner, as a pollution
control device, is difficult.  The usual definition of percentage removal of
the noxious substance in the feed to the device is inappropriate, because
with this definition, a "smoky" flare would achieve the same nearly 100
percent rating, as a "smokeless" one because most of the feed hydrocarbon
will have either cracked or burned in the flame.  On the other hand, any
system that rates efficiency by considering only the total quantity of
pollutant in both the feed to and the effluent from the device would be
meaningless.  For example, the complete combustion of one pound of hydrogen
sulfide results in the production of nearly two pounds of sulfur dioxide, or
the incomplete combustion of one pound of ethane could result in the
production of nearly two pounds of carbon monoxide.

       For these reasons, it is proposed that two separate efficiency rating
be applied to incineration devices.  The first of these is a "Completeness
of Combustion Rating" and the other is a "Significance of Emission Reduction
Rating", as follows:

       I.  Completeness of Combustion Rating (CCR)

           This rating is based on oxygen rather than on pollutants and is
       the pounds of oxygen that react with the pollutants in the feed to
       the device, divided by the theoretical maximum number of pounds that
       would react:  Thus a smokeless flare would receive a 100 percent
       rating while a smoky one would be rated somewhat less, depending upon
       how incomplete the combustion.

           In utilizing this rating,  it is clear that carbon dioxide and water
       are the products of complete combustion of hydrocarbons„   However, some
       question could occur as to the theoretical completion of combustion
       when burning materials other than hydrocarbons.   It is recommended
       that the formation of HX be considered complete combustion of halogenated
       hydrocarbons since the oxidation most typically does not change the
       valence of the halogen.   On the other hand, since some incinerators will
       be catalytic in nature it is recommended that sulfur trioxide be
       considered as complete oxidation of sulfur bearing compounds.

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                              V-2
            Efficiency of Pollution Control Devices

1.  Completeness of Combustion Rating (CCR) (continued)

    Nitrogen is more complex, because of the equilibria that exist
between oxygen, nitrogen, nitric oxide, nitrogen dioxide and the
various nitrogen radicals such as nitrile.  In fact, many scientists
continue to dispute the role of fuel nitrogen versus ambient nitrogen
in the production of NOX.  In order to make the CCR a meaningful
rating for the incineration of nitrogenous wastes it is recommended
that complete combustion be defined as the production of N2, thus
assuming that all NOX formed comes from the air rather than the fuel,
and that no oxygen is consumed by the nitrogen in the waste material.
Hence, the CCR becomes a measure of how completely the hydrocarbon
content is burned, while any NOX produced (regardless of its source)
will be rated by the SERR as described below.

2„  Significance of Emission Reduction Rating  (SERR)

    This rating is based primarily on the weighting factors that
were proposed above.  All air pollutants in the feed to the device
and all in the effluents from the device are multiplied by the
appropriate factor.  The total weighted pollutants in and out are
then used in the conventional manner of calculating efficiency
of pollutant removal, that is pollutants in minus pollutants out,
divided by pollutants in, gives the efficiency of removal on a
significance of emission basis.

    Several examples will serve to illustrate these rating factors.
as follows:

    Example 1 - One hundred pounds of ethylene per unit time is burned
                in a flare, in accordance with the following reaction:
    3C2H4
7 02
C  +  2 CO  +  3 C02  +  6 H20
    Thus, 14.2 Ibs. of particulate carbon and 66.5 Ibs. of carbon
monoxide are emitted, and 265 Ibs. of oxygen are consumed.

    Theoretical complete combustion would consume 342 Ibs. of oxygen
in accordance with the following reaction:
            3 02  • •     >   2 C02  +  2 H20

    Thus, this device would have a CCR of 265/342 or 77.57=,

    Assuming that one pound of nitric oxide is formed in the reaction
as a result of the air used for combustion (this is about equivalent to
100 ppm) , a SERR can also be calculated.  It should be noted that the
formation of this NO is not considered in calculating a CCR because it
came from nitrogen in the air rather than nitrogen in the pollutant
being incinerated.  The calculation follows:

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                              V-3
            Efficiency of Pollution Control Devices
2o Significance of Emission Reduction Rating (SERR) (continued)
Pollutant
Hydrocarbons
Particulates
NOX
SOX
CO
Total
SERR = 8000 -
Weighting
Factor
80
60
40
20
1
958.5
Pounds in
Actual Weighted
100 8000
0
0
0
0
8000
O Ooy
Pounds out
Actual Weighted
0
14.2 852
1 40
0
66,5 66.5
958.5

           8000      x iuu - 00/°

    Example 2 - The same as Example 1, except the hydrocarbons are
                burned to completion.  Then,
                CCR = 342
                      342
x 100 = 100%
                and
                SERR = 8000 - 40
                          8000
       = 99.5%
    Example 3 - One hundred pounds per unit time of methyl chloride is
                incinerated, in accordance with the following reaction.
                2 CH3C1  +  3 02
                 2 C02  +  2 H20 +  2 HC1
    This is complete combustion, by definition, therefore, the CCR is
100%o  However, (assuming no oxides of nitrogen are formed), the SERR
is less than 100% because 72.5 Ibs. of HC1 are formed.  Hence,
considering HC1 as an aerosol or particulate;
    SERR = 100 x 80 - 72.5 x 60
                  100 x 80
       x 100 = 45.5%
    The conclusion from this final example, of course, is that it is
an excellent combustion device but a very poor pollution control device,
unless it is followed by an efficient scrubber for HCl removal.

    Example 4 - The stacks of two hydrogen cyanide incinerators, each
burning 100 pounds per unit time of HCN are sampled.  Neither has any
carbon monoxide or particulate in the effluent.  However, the first is
producing one pound of NOX and the second is producing ten pounds of
NOX in the same unit time.  The assumed reactions are:

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                                     V-4


                   Efficiency of Pollution Control Devices

           Significance of Emission Reduction Rating  (SERR)  (continued)

           4 HCN  +  5 02  ' '    »    2 H20  +  4 C02  +  2 N2

                       N2  (atmospheric) -I- X02 •-•  •>. 2 NOX

           Thus, CCRi = 1007=  and  CCR2 = 100% both by definition.
           However, SERR-, = 100 x 80 - 1 x 40
                         1       100 x 80

           and SERR2 = 100 x 80 - 10 x 40
                          100 x  80

           Obviously, if either of these were "smoky" then both the CCR  and
       the SERR would be lower, as in Example 1.

Other Pollution Control Devices

       Most pollution control devices, such as bag filters, electrostatic
precipitators and scrubbers are designed to physically remove one or more
noxious substances from  the stream being vented.  Typically, the efficiency
of these devices is rated relative only to the substance which they are
designed to remove and for this reason could be misleading.  For example:

       1.  The electrostatic precipitator on a power house stack might be
           99% efficient relative to particulates , but will remove little
           or none of the SOX and NOX which are usually present.

       2.  A bag filter on a carbon black plant will remove 99 + °L of the
           particulate but will remove none of the CO and only relatively
           small amounts of the compounds of sulfur that are present.

       3.  A water scrubber on a vinyl chloride monomer plant will remove
           all of the hydrogen chloride but only relatively small amounts
           of the chlorinated hydrocarbons present.

       4.  An organic liquid scrubber on an ethylene dichloride plant will
           remove nearly all of the EDC but will introduce another pollutant
           into the air due to its own vapor pressure.

       For these reasons, it is suggested again that two efficiency ratings be
applied.   However, in this case, the first is merely a specific efficiency as
is typically reported, i.e., "specific to the pollutant (or pollutants) for
which it  was designed", thus:

       SE = specific pollutant in - specific pollutant out
                        specific pollutant in               x

       The second rating proposed is an SERR, defined exactly as in the case
of incinerators.

       Two examples will illustrate these ratings.

-------
                   Efficiency of Pollution Control Devices

Other Pollution Control Devices (continued)

       Example 1 - Assume that a catalytic cracker regenerator effluent
                   contains 100 pounds of catalyst dust, 200 Ibs. of
                   carbon monoxide and 10 pounds of sulfur oxides per unit
                   time.  It is passed through a cyclone separator where
                   95 pounds of catalyst are removed.  Therefore,

       SE = 100 - 5    ._„
              100    X 95/°

       and SERR = (100 x 60 + 10 x 20 + 200 x 1) - (5 x 60 + 10 x 20 + 200 x 1) x 100
                                  (100 x 60 + 10 x 20 + 200 x 1)

                = 6400 - 700 x 100 = 89%
                     6400

       Example 2 - Assume that an organic liquid scrubber is used to wash a
                   stream containing 50 pounds of S02 per unit time.  All
                   but one pound of the S02 is removed but two pounds of
                   the hydrocarbon evaporate into the vented stream.  Then
                        = 98%
       and SERR = (50 x 20) - (1 x 20 + 2 x 80)
                            (50 x 20)           x 1UU

                = 1000 - 180
                     1000

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                                   TECHNICAL REPORT DATA
                            (Please read Instructions on the reverse before completing)
 1. REPORT NO.
EPA-450/3-73-005-a
4. TITLE AND SUBTITLE
 Survey Reports on Atmospheric  Emissions from the
 Petrochemical Industry, Volume 1
                                                          5. REPORT DATE
                                                           March 1974  (date  of issue)
                                                          6. PERFORMING ORGANIZATION CODE
                                                           3. RECIPIENT'S ACCESSION-NO.
7. AUTHOR(S)
J.  W.  Pervier, R. C. Barley,  D.  E.  Field, B. M. Friedman
R.  B.  Morris, and W. A. Schwartz
                                                           8. PERFORMING ORGANIZATION REPORT NO
9. PERFORMING ORGANIZATION NAME AND ADDRESS
 Houdry Division/Air Products  and Chemicals
 P.O.  Box 427
 Marcus Hook, Pennsylvania   19061
                                                           10. PROGRAM ELEMENT NO.
                                                          11. CONTRACT/GRANT NO.
                                                             68-02-0255
 12. SPONSORING AGENCY NAME AND ADDRESS
 EPA,  Office of Air Quality  Planning & Standards
 Industrial  Studies Branch
 Research Triangle Park,  N.C.   27711
                                                           13. TYPE OF REPORT AND PERIOD COVERED
                                                           Final Report
                                                          14. SPONSORING AGENCY CODE
 15. SUPPLEMENTARY NOTES
 16. ABSTRACT

      This document is one of  a  series of four volumes prepared  for the Environmental
 Protection Agency (EPA) to  assist it in determining the significance of air
 pollution from the petrochemical  industry.  A total of 33  distinctly different
 processes which are used to produce 27 petrochemicals have been surveyed, and the
 results are reported in four  volumes numbered EPA-450/3-73-005-a,  -b, -c, and -d.

      This volume covers the following processes:  acetaldehyde  via ethylene,
 acetaldehyde via ethanol, acetic  acid via methanol, acetic acid via butane,
 acetic acid via acetaldehyde, acetic anhydride, adipic acid,  adiponitrile via
 butadiene, and adiponitrile via adipic acid.  For each process  the report includes
 a  process description, a process  emission inventory, a catalog  of  emission control
 equipment, a list of producers, and an evaluation of the significance of the air
 pollution from the process.   Also included is a summary table of emissions to the
 atmosphere from all the processes studied.
17.
                               KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
                         Acetic  Anhydride
                         Adipic  Acid
                         Adiponitrile
                                             b.IDENTIFIERS/OPEN ENDED TERMS  C. COS AT I Field/Group
Air Pollution
Carbon Monoxide
Hydrocarbons
Nitrogen Dioxide
Sulfur Dioxide
Acetaldehyde
Acetic: Acid
Petrochemical  Industry

Particulates
 7A
 7B
 7C
13B
13H
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