atmospheric emissions from the petrochemical industry_volume iv
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VOLUME IV
u.s. ENVIRONMENTAL PROTECTION AGENCYOffice of Air and Water Programs
Office of Air Quality Planning and StandardsResearch Triangle Park, North Carolina 27711
REPRODUCED BY -- '"
NATIONAL TECHNICAL IiINFORMATION SERVICE II
u. s. DEPARTMENTOF COMMERCE .1 1,SPR!NGFIE~D. VA, 22161 •
SURVEY REP'ORTS
ON ATMOSPHERIC EMISSIONS
FROM THE PETROCHEMICAL
INDUSTRY
PB·2456301111111111111111111111111111 ~I
EPA-450/3~73'()05.d .
APRIL 1974
TECHNICAL REPORT DATA(Please read IIIUf.Uctions on tlte reverse before completing)
~==':"7.-;::--------"':"'r::--------~--:;..--=-r::--==:==~~=~~~---' -1. REPORT NO. 12. 3.':'1E •... IW·S(.AC~Sl}LO~O"EPA-450/3-73-005-dLl .~ I. ~" ~r I
4. TITLE AND SUBTITLE
Survey Reports on Atmospheric Emissions from thePetrochemical Industry, Volume IV
I5IRE_ .. "'" V -' \JAoril 1974 (date of issue)6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S) F . d B. PERFORMING ORGANIZATION REPORT NO.J. W. Pervier, R. C. Barley, D. E. Field, B. M. rle rnaR. B. Morris, and W. A. Schwartz
9. PERFORMING OR~ANIZATIONNAME AND ADDRESS
Houdry Division/Air Products and ChemicalsP.O. Box 427Marcus Hook, Pennsyl~?nia 19061
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Air Quality Planning &StandardsIndustrial Studies BranchResearch Triangle Park, N.C. 27711
15. SUPPLEMENTARY NOTES
16. ABSTRACT
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-02-025513. TYPE OF REPORT AND PERIOD COVERED
Fin;ll {PnI
14. SPONSORING AGENCY CODE
This document is one of a series of four volumes prepared for the EnvironmentalProtection Agency (EPA) to assist it in determining the significance of airPOllution from the petrochemical industry. A total of 33 distinctly differentprocesses which are used to produce 27 petrochemicals have been surveyed, and theresults are reported in four volumes numbered EPA-450j3-73-005-a, -b, -c, and -d.
This volume covers the following processes: Polypropylene, Polystyrene,Polyvinyl Chloride, Styrene, Styrene-Butadiene Rubber, Vinyl Acetate via Acetylene,Vinyl Acetate via Ethylene, and Vinyl Chloride. For each proce~s the reportincludes a process description, a process emission inventory, a catalog of emissioncontrol equipment, a list of producers, and an evaluation of the significance ofthe air pollution from the process. Also included is a summary table of emissionsto the atmosphere from all the processes studied. ,
17. KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORSa.
Air PollutionCarbon MonoxideHydrocarbonsNitrogen DioxideSulfur DioxidePolypropylenePo lys tyrene
Polyvinyl ChlorideStyreneSynthetic ElastomersStyrene-Butadiene ResinVi nyl AcetateVinyl Chloride
h.IDENTIFIERS/OPEN ENDED TERMS
Petrochemical IndustryParticulates
c. COSATI Field/Group
IA7B7C
13Bl3H
\-
'_3._D__IS_T_R_13_U.-T_1O_N_S_T_A_T_EM_E_N_T ...J_19.,:. .;.S;.:EC..;,U.;.R,;:"IT,;:"Y.;..;..CL,;,.;A;,.S;..S_(I_'''_i.t_R_rp_ii_rt_T~...121 __' _N,O_'_'OF,=AGJ]~ S _ _Release Unlimited Un~!assified20. SECURITY CLASS (TlJis page)
UnclassifiedEPA Form 2220·119'731:;;;0'" .~
PORTIONS OF THIS REPORT ARE NOT LEGIBLE.
HOWEVER, IT IS mE BEST REPRODUCTION
AVAILABLE FROM TI-IE COpy SENT 10 NTIS
EPA-450/3-73~5-d
SURVEY REPORTSON ATMOSPHERIC EMISSIONS
FROM THE PETROCHEMICAL
INDUSTRY
VOLUME IVby
J. W. Pervier, R. C. Ba:dey, D. E. Field,B. M. Friedman, R. B. Morris, W. A. Schwartz
Houdry DivisionAir Products and Chemicals, Inc.
P. O. Box 427Marcus Hook, Pennsylvania 19061
Contract No. 68-02-0255
EPA Proj ect Officer: Leslie B. Evan~
Prepared for
ENVIRONMENTAL PROTECTION AGENCYOffice of Air and Water Programs
Office of Air Quality Planning and StandardsResearch Triangle Park, N. C. 27711
April 1974
I a
This report is issued by the Environmental Protection Agency to report technicaldata of interest to a limited number of readers. Copies are available free of chargeto 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 for afee, from the National Technical Information Service 5285 Port Royal Road, Springfield, Virginia 22151.
This report was furnished to the Environmental Protection Agency by Air P:r:oductsand Chemicals, Inc. , Marcus Hook, Pennsylvania, in fulfillment df ContractNo. 68-02-0255. The contents of this report are reproduced herein as receivedfrom Air Products and Chemicals, Inc. The opinions, findings, and conclusionsexpressed are those of the author and not necessarily those of the EnvironmentalProtection Agency. Mention of company or product names is not to be consideredas an endorsement by the Environmental Protection Agency.
Publication No. EPA-450/3-73-005-d
ii
PETROCHEMICAL AIR POLLUTION STUDY
INTRODUCTION TO SERIES
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 these four volumes numbered EPA 450/3-73-005-a, -b, -c, ~nd -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.
iil
ACKNOWLEDGEMENTS
Survey and study work such as that described in this report have valueonly to the extent of the value of the imput data. Without the fullestcooperation of the companies involved in producing the petrochemicals thathave been studied, this report would not have been possible. Air Productswishes to acknowledge this cooperation by commending:
The U. S. Petrochemical IndustyMember Companies of the Industry
The Manufacturing Chemists Association
iv
Table of Contents
Page Number
SummaryIntroductionDiscussionResultsConclusions
Survey Reports (Located by tabs)
PolypropylenePolystyrenePolyvinyl ChlorideStyreneStyrene-Butadiene RubberVinyl Acetate via AcetyleneVinyl Acetate via EthyleneVinyl Chloride via EDC Pyrolysis
Appendicies (Located by tabs)
viI289
AppendixAppendixAppendixAppendixAppendix
Table Number
IIIIIIIVV
I - Mailing ListII - Example Questionnaire
III - Questionnaire Summa~y
IV - Significance of PollutionV - Efficiency Ratings
List of Tables anq Figures
Title
Emissions Summary (3 pages)Total Emissions, All Pollutants, by 1980*Total Annual Weighted Emissions, by 1980*Significant Emission Index*Number of New Plants (1973-1980)*
*Fifteen highest ranks from Table I.
NOTE: There are numerous tables and figures in the Survey Reports that areincluded in the appendicies of this report. These tables and figuresare separately listed in each appendix.
v
SUMMARY
A study of air pollution as caused by the petrochemical industry hasbeen undertaken in order to provide data that the Environmental ProtectionAgency can use in the fulfillment of their obligations under the terms ofthe Clean Air Amendments of 19700 The scope of the study includes mostpetrochemicals 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 havebeen studied and the emissions from each tabulated on the basis of datafrom and Industry Questionnaire. A survey report prepared for each processprovides a method for ranking the significance of the air pollution fromthese processes. In-depth studies on those processes which are consideredto be among the more significant polluters either have been or will beprovided.
To date, drafts of in-depth studies on seven processes have beensubmitted. In addition, two further processes have been selected forin-depth study and work on these is in progress. All of these in-depthstudies will be separately reported under Report Number EPA-450/3-73-006a, b, c, etc.
A total of 33 Survey Reports have been completed and are reportedhere, or in one of the other three volumes of this report series.
vi
I. Introduction
A study has been undertaken to obtain information about selected production processes that are practiced in the Petrochemical Industry. Theobjective of the study is to provide data that are necessary to supportthe Clean Air Ammendments of 1970.
The information sought includes industry descriptions, air emissioncontrol problems, sources of air emissions, statistics on quantities andtypes of emissions and descriptions of emission control devices currentlyin use. The principal source for these data was an industry questionnairebut it was supplemented by plant visits, literature searches, in-housebackground knowledge and direct support from the Manufacturing ChemistsAssociation.
A method for rating the significance of air emissions was establishedand is used to rank the processes as they are studied. The goal of theranking technique is to aid in the selection of candidates for in-depthstudy. These studies go beyond the types of information outlined aboveand include technical and economic information on '~est systems" of emissionreduction, the economic impact of these systems, deficiencies in petrochemicalpollution cDntrol technology and potential research and development programsto overcome these deficiencies. These studies also recommend specific plantsfor source testing and present suggested checklists for inspectors.
This final report presents a description of the industry surveys thathave been completed, as well as a status summary of work on the in-depthstudies.
The Appendicies of this report include each of the 33 Survey Reportsthat were prepared during the course of the study.
1
II. Discussion
A. Petrochemicals to be Studied
There are more than 200 different petrochemicals in currentproduction in the United States. Many of these are produced by twoor more processes that are substantially different both with respectto process techniques and nature of air emissions. Although it mayeventually become necessary to study all of these, it is obviousthat the immediate need is to study the largest tonnage, fastest growthprocesses that produce the most pollution.
Recognizing this immediate need, a committee of Air Products'employees and consultants reviewed the entire list of chemicals andprepared a list of thirty chemicals which were recommended for primaryconsideration in the study and an additional list of fourteen chemicalsthat should receive secondary consideration. Since this was only aqualitative evaluation it was modi~ied slightly as additional informationwas received and after consultation with the Environmental ProtectionAgency (EPA).
The final modified list of chemicals to be studied included allbut three from the original primary recommendations. In addition, fourchemicals were added and one was broken into two categories (namely lowand high density polyethylene) because of distinct differences in thenature of the final products. This resulted in thirty-two chemicalsfor study and fourty one processes which are sufficiently different towarrant separate consideration. Hence, the following list of petrochemicals is the subject of this study.
Acetaldehyde (2 processes)Acetic Acid (3 processes)Acetic AnhydrideAcrylonitrileAdipic AcidAdiponitrile (2 processes)Carbon BlackCarbon DisulfideCyc lohexanoneEthyleneEthylene Dichloride (2 processes)Ethylene Oxide (2 processes)Formaldehyde (2 processes)GlycerolHydrogen CyanideMaleic Anhydride
Nylon 6Nylon 6,6"Oxo" Alcohols and AldehydesPhenolphthalic Anhydride (2 processes)Polyethylene (high density)Polyethylene (low density)PolypropylenePolystyrenePolyvinyl ChlorideStyreneStyrene - Butadiene RubberTerephthalic 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, aliterature review was begun on those chemicals which were consideredlikely candidates for study. The purpose of the review was to preparean informal "Process Portfolio" for each chemical. Included in theportfolio are data concerning processes for producing the chemical,estimates of growth in production, estimates of production costs, names,
2
locations and published capacities of producers, approximations ofoverall plant material balances and any available data on emissionsor their control as related to the specific process.
The fundamental purpose of these literature revievs vas to obtainbackground knowledge to supplement vhat vas ultimately to be learnedfrom completed Industry Questionnaires. A second and very importantpurpose was to determine plant locations and names of companiesproducing each chemical. This information was then used to contactresponsible individuals in each organization (usually by telephone) toobtain the name and address of the person to whom the Industry Questionnaire should be directed. It is believed that this approach greatlyexpedited the completion of questionnaires. The mailing list that wasused is included as Appendix I of this report.
C. Industry Questionnaire
Soon after the initiation of the petrochemical pollution study, adraft questionnaire was submitted by Air Products to the EnvironmentalProtection Agency. It had been decided that completion of thisquestionnaire by industry would provide much of the informationnecessary to the performance of the study. The nature and format ofeach question was reviewed by EPA engineers and discussed with AirProducts engineers to arrive at a modified version of the originallyproposed questionnaire.
The modified questionnaire was then submitted to and discussedwith an Industry Advisory Committee (lAC) to obtain a final version forsubmission to the Office of Management and Budget rOME) for finalapproval, as required prior to any U. S. Government survey of nationalindustries. The following listed organizations, in addition to theEPA and Air Products, were represented at the IAC meeting:
Trade Associations
Industrial Gas Cleaning InstituteManufacturing Chemists Association
Petrochemical Producers
B. F. Goodrich Chemical CompanyE. I. duPont deNemours and CompanyExxon Chemical CompanyFMC CorporationMonsanto CompanyNorthern Petrochemical CompanyShell Chemical CompanyTenneco Chemicals, Inc.Union Carbide Corporation
Manufacturers of Pollution Control Devices
John Zink CompanyUOP Air Correction Division
State Pollution Control Departments
Ne~ JerseyTexas
3
The questionnaire, along with a detailed instruction sheet andan example questionnaire (which had been completed by Air Productsfor a fictitious process that was "invented" for this purpose) weresubmitted to the OMB for approval. In due course, approval wasreceived and OMB Approval Number 158-8-72019 was assigned to thequestionnaireo Copies of the approved instruction sheet, examplequestionnaire are included as,Appendix II of this report.
The questionnaires were mailed in accordance with the mailinglist already discussed and with a cover letter that had been preparedand signed by the EPA Project Officer. The cover letter was typed ina manner that permitted the insertion of the name and address of thereceipient 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 thefirst page. A copy of this letter of transmittal is also included inAppendix II.
Understandably, because of the dynamic nature of the petrochemicalindustry, about 10 percent of the questionnaires were directed to plantswhich were no longer in operation, were still under construction, wereout-of-date processes or were too small to be considered as typical.This did not present a serious problem in most cases because (a) 100percent of the plants were not surveyed and (b) the project timing permitted a second mailing when necessaryo Appendix III tabulates thenumber of questionnaires incorporated into each study.
One questionnaire problem that has not been resolved is confidentiality. Some respondents omitted information that they consider tobe proprietary. Others followed instructions by giving the data butthen marked the sheet (or questionnaire) "Confidential". The EPA ispresently trying to resolve this problem, but until they do the datawill be unavailable for inclusion in any Air Products' reports.
D. Screening Studies
Completed questionnaires were returned by the various respondentsto the EPA's Project Officer, Mr. L. B. Evans. After reviewing themfor confidentiality, he forwarded the non-confidential data to AirProducts. These data form the basis for what has been named a "SurveyReport". The purpose of the survey reports being to screen the variouspetrochemical processes into the "more" and "less - significantlypolluting processes". These reports are included as appendicies tothis report o
Obviously, significance of pollution is a term which is difficultif not impossible to define because value judgements are involved.Recognizing this difficulty, a quantitative method for calculating aSignificant Emission Index (SEI) was developedo This procedure isdiscussed and illustrated in Appendix IV of this report. Each surveyreport includes the calculation of an SEI for the petrochemical thatis the subject of the report. These SEIls have been incorporated intothe Emissions Summary Table that constitutes part of this report. Thistable can be used as an aid when establishing priorities in the workrequired to set standards for emission controls on new stationarysources of air pollution in accordance with the terms of the Clean AirAmendments of 1970 0
4
The completed survey reports constitute a preliminary data bank oneach 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 simplifiedprocess (Block) flow diagram, as well as heat and material balances.More pertinent to the air pollution study, each report lists anddiscusses the sources of air emissions (including odors and fugitiveemissions) 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 analyticaltechniques; stack numbers and dimensions; and emission control devicedata (types, sizes, capital and operating costs and efficiencies).
Calculation of efficiency on a pollution controlnecessarily a simple and straight-forward procedure.two rating techniques were established for each typefollows:
device is notConsequently,
of device, as
1. For flares, incinerators, and boilers a Completeness of CombustionRating (CCR) and Significance of Emission Reduction Rating (SERR)are proposed.
2. For scrubbers and dust removal equipment, a Specific PollutantEfficiency (SE) and a SERR are proposed.
The bases for these ratings and example calculations are includedin Appendix V of this report.
Eo In-Depth Studies
The original performance concept was to select a number of petrochemical processes as "significant polluters", on the basis of datacontained in completed questionnaires. These processes were then tobe studied "in-depth". However, the overall time schedule was suchthat the EPA requested an initial selection of three processes on thebasis that they would probably turn out to be "significant polluters".The processes selected in this manner were:
1 0 The Furance Process for producing Carbon Black,
2. The Sohio Process for producing Acrylonitrile.
30 The Oxychlorination Process for producing 1,2 Dichloroethane(Ethylene Dichloride) from Ethylene.
In order to obtain data on these processes, the operators and/orlicensors of each were approached directly by Air Products' personnel.This, of course, was a slow and tedious method of data collection becausemass mailing techniques could not be used, nor could the request fordata be identified as an "Official EPA Requirement". Yet, by the timethat OMB approval was given for use of the Industry Questionnaire, asubstantial volume of data pertaining to each process had already beenreceived. The value of this procedure is indicated by the fact thatfirst drafts of these three reports had already been submitted to theEPA, and reviewed by the Industry Advisory Committee, prior to thecompletion of many of the survey reports.
5
In addition, because of timing requirements, the EPA decided thatthree additional processes be "nominated" for in-depth study. Thechemicals involved are phthalic anhydride, formaldehyde and ethyleneoxide. Work on these indicated a need for four additional in-depthstudies as follows:
1. Air Oxidation of Ortho-Xylene to produce Phthalic Anhydride.
2. Air Oxidation of Methanol in a Methanol Rich Process toproduce Formaldehyde over a Silver Catalyst.
3. Air Oxidation of Methanol in a Methanol-Lean Process toproduce Formaldehyde over an Iron Oxide Catalyst.
40 Direct Oxidation of Ethylene to produce Ethylene Oxide.
Drafts of these have been submitted to the EPA and reviewed by theIndustry Advisory Committee. The phthalic anhydride report also includesa section on production from naphthalene by air oxidation, a processwhich is considered to be a significant polluter in today's environmentbut without significant growth potential.
These seven in-depth studies will be separately issued in finalreport form, under Report Number EPA-450!3-73-006 a, b, c, etc.
An in-depth study, besides containing all the elements of thescreening studies, delves into questions such as r~hat are the bestdemonstrated systems for emission reduction?", ''What is the economicimpact of emission control on the industry involved?", ''What deficienciesexist in sampling, analytical and control technology for the industryinvolved?".
In striving to obtain answers to these questions, the reportsinclude data on the cost effectiveness of the various pollution controltechniques source testing recommendations, industry growth projections,inspection procedures and checklists, model plant studies of theprocesses and descriptions of research and development programs thatcould lead to emission reductions.
Much of the information required to answer these questions camefrom the completed Industry Questionnaires and the Process Portfolios.However, the depth of understanding that is required in the preparationof such a document can only be obtained through direct contact with thecompanies that are involved in the operation of the processes beingstudied. Three methods for making this contact were available to AirProducts 0 The first two are self-evident, as follows: Eachquestionnaire contains the name, address and telephone number of anindividual who can provide additional information. By speaking withhim, further insight was obtained into the pollution control problemsthat are specific to the process being studied; or through him, avisit to an operating plant was sometimes arranged, titUS achieving adegree of first hand knowledge.
However, it was felt that these two techniques might fall short ofthe level of knowledge desired. Thus, a third, and unique procedure wasarranged. The Manufacturing Chemists Association (MCA) set up, through
6
its Air Quality Committee (AQC), a Coordinating Technical Group(CTG) for each in-depth processo 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) ondrafts of reports.
The AQC named one committee member to provide liaison. Inseveral cases, he is also one of the industry's specialists for theprocess in question. If not, one other individual was named toprovide CTG leadership. Coordination of CTG activities was providedby Mr. Howard Guest of Union Carbide Corporation who is also on theEPA's Industry Advisory Committee as the MCA Representative. CTGleadership is as follows:
Chemical
Carbon Black
Acrylonitrile
Formaldehyde
Ethylene Dichloride
Phthalic Anhydride
Ethylene Oxide
F. Current Status
AQC Member
C. B. BeckCabot Corporation
W. R. ChalkerDu Pont
W. B. BartonBorden
W. F. BixbyB. F. Goodrich
E. P. WheelerMonsanto
H. R. GuestUnion Carbide
Other
None
R. E. FarrellSohio
None
None
Paul HodgesMonsanto
H. D. CoombsUnion Carbide
Survey Reports on each of the 33 processes that were selected forthis type of study have been completed, following review of the draftsby both the EPA and the Petrochemical Industry. These reports constitutethe subject matter of this report.
In-depth studies of the seven processes mentioned above have beencompleted in draft form, submitted to the EPA for initial review,discussed in a public meeting with the Industry Advisory Committee andre-submitted to the EPA in revised form. They are currently receivingfinal EPA review and will be issued as final reports, following thatreview.
The EPA has now selected two additional processes for in-depth studyand work on these is currently in progress. They are:
10 High Density Polyethylene via the Low and Intermediate PressurePolymerization of Ethylene.
2. Low Density Polyethylene via the High Pressure Polymerizationof Ethylene.
7
III. Results
The nature of this project is such that it is not possible to reportany "results" in accordance with the usual meaning of the word. Obviously,the results are the Survey Reports and In-Depth Studies that have beenprepared. However, a tabulation of the emission data collected in thestudy and summarized in each of these reports will be useful to the EPAin the selection of those processes which will be either studied in-depthat some future date, or selected for the preparation of new source standards.Such a tabulation, entitled "Emissions Summary Table", is attached.
8
IV. Conclusions
As was stated above under "Results", the conclusions reached arespecific to each study and, hence, are given in the individual reports.Ultimately, some conclusions are reachable relative to decisions onprocesses which require future in-depth studies or processes which warrantthe 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 insetting a basis, or select~ng processes.
It is imperative, when using the table, to be aware of the followingfacts.
1. The data for some processes are based on 100 percent survey ofthe industry, while others are based on less than 100 percentwith some as few as a single questionnaire.
2. Some of the reported data are based on stack sampling, others oncontinuous monitoring and still others on the "best estimate" bythe person responsible for the questionnaire.
3. Air Products attempted to use sound engineering judgement inobtaining emission factors, industry capacities and growthprojections. However, other engineering firms, using the samedegree of diligence would undoubtedly arrive at somewhat differentfinal values.
Thus, the tabulation should be used as a guide but not as a rigorouscomparison of process emissions.
Furthermore, data on toxicity of emissions, odors and persistence ofemitted compounds are not included in the tabulation. In addition, greatcare must be used when evaluating the weighted emission rates because ofthe wide range in noxiousness of the materials lumped together in the twomost heavily weighted categories. For example, "hydrocarbons" includesboth ethane and formaldehyde and "particulates" includes both phthalicanhydride and the permanent hardness of incinerated water.
Bearing all of these qualifications in mind, several "top 15" rankingsof processes can be made, as in Tables II through V. Obviously, one ofthese tables could be used to select the more significant polluters directly.Of course, other rankings could be made, such as leading emitters of NOx orparticulates, etc. Using these four tables, however, one analysis might bethat the number of times a process appears in these tables is a measure ofits pollution significance, or in summary:
Appear in 4 Tables
Carbon BlackLow Density PolyethyleneHigh Density PolyethyleneCyc1ohexanonePolypropylenePolyvinyl ChlorideEthylene Oxide
Appear in 3 Tables
AcrylonitrileAdiponitri1e (Butadiene)Ethylene Dichloride (Oxych1orination)Dimethyl TerephthalateEthylene Dichloride (Direct)Ethylene
9
Appear in 2 Tables
Maleic AnhydrideIsocyanatesPhenolFormaldehyde (Silver)
Appear in 1 Table
Phthalic AnhydrideFormaldehyde (Iron Oxide)PolystyreneNylon 6Nylon 6,6Vinyl Chloride
Thus, on this basis and in retrospect, it could be concluded that fourof the selected in-depth studies (carbon black, ethylene oxide, and bothlow 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 futurein-depth studies, namely:
CyclohexanonePolypropylenePolyvinyl ChlorideAdiponitrile (Butadiene Process)Dimethyl Terephthalate (and TPA)Ethylene Dichloride (Direct)Ethylene
Obviously, many alternative bases could be established. It is notthe function of this report to select a basis for initiating future studiesbecause the priorities of the EPA are unknown. The most apparent of thesebases are the ones suggested by Tables II through V, namely the worst totalpolluters, the worst polluters on a weighted basis, the greatest increasein pollution (total or weighted) or the largest numbers of new plants. Inaddition, noxiousness of the emissions (photo-chemical reactivity, toxicity,odor, persistence) could be considered in making a selection.
10
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TABLE II
TOTAL ANNUAL EMISSIONS. ALL "POLLUTANTS", BY 1980 (MM LBS. /YR.) *
Carbon Black 5,730
Acry lonitrile
Maleic Anhydride
Low Density Polyethylene
Cyclohexanone
High Density Polyethylene
Dimethyl Terephthalate
Ethylene Dichloride
Phthalic Anhydride (Total)
Formaldehyde (Silver)
Polypropylene
Isocyanates
Polyvinyl Chloride
Adiponitrile (Butadiene Process)
Ethylene Oxide
980
566
343
310
297
265
253
233
212
190
175
137
129
120
*Fifteen highest numbers, as summarized in Table I, for this category.
14
TABLE III
TOTAL ANNUAL WEIGHTED EMISSIONS BY 1980 (MM LBS. /YR. )*
Acrylonitrile
Low Density Polyethylene
Carbon Black
High Density Polyethylene
Ethylene Dichloride (Oxychlorination)
Polypropylene
Dimethyl Terephtha1ate
Cyclohexanone
Polyvinyl Chloride
Ethylene Oxide
Adiponitri1e (Butadiene Process)
Maleic Anhydride
Ethylene Dichloride (Direct)
Ethylene
Phenol
38,000
27,400
24,740
23,600
16,450
15,140
13 ,500
11,960
10,540
9,530
6,210
5,670
5,040
3,670
3,640
*Fifteen highest numbers, as summarized in Table I, forthis category.
15
TABLE IV
SIGNIFICANT EMISSION INDEX*
Acrylonitrile
Low Density Polyethylene
High Density Polyethylene
Polypropylene
Ethylene Dichloride (Oxychlorination)
Carbon Black
Cyclohexanone
Dimethyl Terephthalate
Polyvinyl Chloride
Adiponitrile (Butadiene)
Ethylene Dichloride (Direct)
Maleic Anhydride
Ethylene Oxide
Ethylene
Vinyl Chloride
23,000
21,300
17,200
12,190
8,800
7,200
6,260
6,040
4,840
3,010
2,740
2,720
2,650
2,430
2,170
*Fifteen higest numbers, as summarized in Table I, forthis category.
16
TABLE V
NUMBER OF NEW PLANTS (1973-1980)*
Low Density Polyethylene
Formaldehyde (Silver)
Polypropylene
High Density Polyethylene
Polyvinyl Chloride
Polystyrene
Ethylene
Ethylene Oxide
Carbon Black
Formaldehyde (Iron Oxide)
Phenol
Cyc1ohexanone
Isocyanates
Nylon 6
Nylon 6,6
Ethylene Dichloride (Direct)
41
40
32
31
25
23
21
15
13
12
11
10
10
10
10
10
*Fifteen highest numbers, as summarized in Table t, forthis category.
17
Polypropylene
Table of Contents
Section Pa~ Number
I.II.III.IV.V.VI.
IntroductionProcess DescriptionPlant EmissionsEmission ControlSignificance of pollutionPolypropylene Producers
List of Illustrations and Tables
Flow DiagramNet Material BalanceGross Heat BalanceNational Emissions InventoryCatalog of Emission Control DevicesNumber of New Plants by 1980Emission Source SummaryWeighted Emission Rates
18
PP-1PP~2
PP.,.5PP-8PP-10PP-11
Figure PP-ITable PP-ITable PP-UTable PP-IIITable PP-IVTable PP-VTable PP-VITab 1e PP-VII
I. Introduction
Polypropylene has 1) made significant inroads on polyethylene in someproduct categories such as blow-molded plastic containers. film and sheet,injection molded items, pipe and tubing and coatings; and it has 2) enteredin its own right a burgeoning market in polypropylene monofilaments andfibers. In addition, polypropylene is a participant in copolymer materialssuch as rubber-like elastomers and may have appreciable use in terpolymers;for example, from ternary mixtures like ethylene, propylene and butadiene.
The present polypropylene capacity is predominantly for isotactic homopolymer with copolymer filling out the remainder of the picture. The screeningeffort in this report is based on questionnaires returned by seven polypropylenemanufacturers.
As of mid-1972, approximately 2,050,000,000 lbs./yr. of PP capacityexisted in domestic facilities. Emissions arising from these facilities stemprimarily from operations concerned with reaction, recovery, drying, purificationof materials for recycle, materials handling, storage and packaging; inaddition, there is a significant contribution from "fugitive" or "other"emissions. The pollutants are mostly hydrocarbon vapors and polypropylenefines. Relative to pollution significance, PP projections to the year 1980indicate a weighted SEI of about 12,190 units. This index places polypropylenein the ranks of petrochemicals which may qualify for in-depth studies.
19
II. Process Description
This is a simplified description of a modern process for the productionof isotactic polypropylene.
A simplified composite flo~ diagram jF attached. please see fold-outdrawing No. R-212. A Net Material Balance is presented in Table I. pleasesee Table II relative to a Gross Heat Balance.
Polypropylene resins (PP) are thermoplastics resins containing, predominantly, the following repeating units:
r-~-~JH CH;/ n- -
The polymerization of propylene, 6==~
I IH CH3
can yield several isomeric
polymers, two of which are stereoregu1ar. These are, in simplified form:
(1) Isotactic po1xpropylene
CH3I
i C
i lir\i /\
".J1
iHI I' \ H
~ \.ICCI I ILH H
(2) Sxndiotactic polypropylene
n
" H\19H n
Both types of stereoregu1ar polypropylene are crystalline and may occuras "left-handed" or "right-handed" helix chains, or as combinations of both.
In addition to these stereoregu1ar polymers, nonstereoregu1ar, atacticpolypropylene can be formed:
(3) Atactic polxpropxlene
Atactic polymers are amorphous and must, in general, be removed from thepolymerization product to obtain the desired product specifications, althougha small amount is usually required for certain physical properties.
To improve the impact resistance, particularly at low temperatures,propylene is often copolymerized with a small amount of ethylene. Two generaltypes of propylene copolymers are produced: random copolymers and block orimpact copolymers. The random copolymers (produced by copolymerizing in arandom manner) are more flexible and ductile than homopolymers and are usedextensively in film applications. The block or impact copolymers are crystalline copolymers containing alternate segments of polymerized propyleneand polymerized ethylene. They exhibit crystallinity normally associatedonly with stereoregular homopolym~rs of polypropylene and polyethylene.
Propylene copolymers offer lower brittleness temperatures, higher impactstrength and lower notch sensitivity than propylene homopolymers and also offerbetter moldability, stress crack resistance, stiffness, and tensile strengththan polyethylene homopolymers. They are used extensively in molding application where maximum toughness and impact resistance are required.
Polypropylene is produced by heterogeneous polymerization of propylenedissolved in hydrocarbons. Stereospecific catalysts used include systems ofthe Ziegler-Natta type, e.g., titanium trichloride with aluminum alkyl asco-catalyst, as well as other catalyst systems.*
In most processes used for the manufacture of polypropylene, purifiedpropylene, catalyst slurry and dilution solvent are charged to an agitatedreactor. Diluents used include normal and isoparaffins in the CS-CS range,as well as naphthenes such as cyclohexane. However, some processe~ (e.g., thosedeveloped by Eastman Yodak Company, Phillips Petroleum Company and others)do not require a dilution solvent.
During the polymerization reaction, most of the polypropylene formed isprecipitated from the solution. The reactor slurry, containing 20-30% solids,is transferred to a flash tank where unreacted propylene and part of the solventare removed for recycle to the reactor system. The solid material (mostlyisotactic polypropylene) and the solvent phase (containing atactic and lowmolecular-weight polypropylene) are separated. The isotactic polypropylenecan be further purified by reslurrying with a purification solvent andcentrifuging, after which it is washed, dried, and stored.
Polypropylene resins and propylene copolymers are produced in manygrades and formulations. Molding and extrusion grades are available withlow-, medium-, and high-melt flows. Also included are FDA grades, moderate-or high-impact formulations, heat-resistant grades, highly UV-stablilizedresins, controlled-crystallinity resins, etc. Controlled crystallinity,obtained by means of nucleating agents, leads to improved clarity and stiffnessof the polymer. Resins for the manufacture of films and fibers are alsoproduced in various grades.
*Because the processes and catalyst systems are similar to those used for highdensity polyethylene, some plants are equipped to make both products in the samefacilities.
21
Atactic polymer, and some reject polypropylene fines and chunks areburied, incinerated, consigned to landfill, or handled by some other suitablemeans such as contract disposal.
The PP is extruded and pelletized (or other~ise mechanically prepared) sothat it can be fed to the materials handling and finishing system v'hich follovs.
The most common form of materials handling system for the pellets isairveying. This type of system permits intermediate and pre-shipment storagein an effectively deployed net~ork of silos.
22
III. Plant Emissions
A. Continuous Air Emissions
1. Flue-Gas
No process fuel usage is reported.the amount of fuel and the quantity of802 emissions are negligible.
2. Purification and Recovery Vents
Where non-process fuel is used,sulfur are such that NOx and
All producers recycle unreacted monomer. The recycle streamsrequire purification. The light and heavy ends from the purificationprocess are either vented, flared, sent to another process or topollution control. These operations can be one of the sources ofair pollution in the production of PP. The reported vent streamsin this category, along vith their pollution control devices, aresummarized in Tables III and IV.
3. Drying and Materials Handling Losses
PP solids are dried, and the semi-finished and finished solidsare most often transported in-plant via pneumatic conveying systems.The various atmospheric vents that are associated v'i th these systemsare a source of particulate emissions. Vith suitable retentionmeans such as cyclones and bag filters, continuous particulateemissions are present, but relatively small in amount compared tohydrocarbon vapor emissions. Emission and control device data aresummarized in Tables III and IV.
B. Intermittent Air Emissions
1. Routine In-Process Venting
Routine in-process venting is reported by some respondents as ausual occurrence, and present during normal on-stream steady-stateoperation. One example is in the case of batch operat'ons whereeach of several reactors goes through a cycle, part of vhich includesventing. This venting can be directed into a collection systemleading to a smokeless flare.
2. Start-Up and Emergency Vents
According to the auestionnaire responses received, these ventsare normally tied into flare systems. The products of combustion arecarbon dioxide and \-later, except in certain emergencies ~--hen theflares receive entrained liquids or excessive gas flov's, and maybriefly shov' smoky effluents.
The PP respondents' reports indicate that smokeless flare designscontain adenuate safety margin for most situations. Ho~ever. extremesvings in design parameters occasionally lead to upset conditions;e.g., pilot flame-out; excessive turndovn demands; lov or zero steampressure.
NOx formation resulting from the above start-up and emergency ventflaring is considered inappreciable relative to the national emissionsinventory.
23
IV. Emission Control
The various emission control devices that have been reported as beingemployed by operators of polypropylene plants are summarized in the catalogof Emission Control Devices, Table IV. In general, no Quantitative informationon the device performance has been made available. Never-the-less, certaingeneralizations about the performance of the devices utilized can be made.
Water Scrubbers
A water scrubber device is used by one respondent (25-5) to absorb PPfines and "organometal catalyst" from process vents prior to atmosphericentry.
Cyclones
In polypropylene production, these devices are used to remove or reducethe amount of PP dust emitted from the pneumatic conveyor and silo ventsystems. The device efficiencies cannot be calculated from the datareported. But the conclustion may be tentatively drawn that in the futuresome cyclone installations may be teamed up with or displaced by bagfilters.
Bag Filters
For retention of fines, bag filters appear to be the ultimate final-stepdevice for the PP plant of the future. A properly chosen device, according to published literature, will remove substantially all of any PPparticulate dust. The bag filters could be used alone, or as back-up
. for other devices such as cyclones, depending on the specific processreouirements.
Flares and Incinerators
All future PP plant operators are presumed to make use of a flare system.Data necessary to calculate combustion efficiencies of existing flareshave not been reported. Where specified, flares are mainly associated yliththe purification and recovery sections. Halogen or sulfur bearing compoundspotentially entering the flare systems of the future are not significantrelative to the national emissions inventory.
Future operators are presumed to employ incinerators for the (relativelysmall) combustible liquid waste effluents. Existing incinerators, wherereported, appear to make no contribution to the national emissionsinventory.
Future operators (and those present operators reporting such devices) arepresumed to have flares and incinerators with CCR ratings near 100% andSERR ratings over 99.5%.
The reason for the high presumed CCR rating is that the flares andincinerators of the future (utilizing existing designs) can be of "smokeless" or clear "stack-gas" design 'V'ith completeness of combustion closeto theoretical. Those questionnaire responses reflecting such combustionresults (from PP process wastes such as hydrocarbons) sho~J, in general,no indication of incomplete or partial oxidation (for example, no CO).
The above conclusion is based on the definition of "CCR":
26
CCR = 1bs. of 02 reacting (with pollutants in control device feed) x 1001bs. of 02 that theoretically could react
The reason for the relatively high presumed SERR ratings is that thehighly effective flare and incinerator designs as applied to futurePP process pollutant-bearing streams would emit substantially zeroparticulates and CO, and only the complete-combustion amount of NOx •There is no pollutant present to form SOx.
The above conclusion pertaining to the SERR rating is based on thedefinition of "SERR":
SERR = (weighted pollutants units in) - (weighted pOllutant units out)x 100(weighted pollutant units in)
Please see Appendix V of this report for a more detailed explanation.It is demonstrated therein that, for a hydrocarbon pollutant (withcomplete thermal combustion - as compared to complete catalyticoxidation) the assumption of one pound of nitric oxide formed foreach 100 1bs. of HC pollutant, leads to an SERR value of 99.5%. That is
SERR (100 x 80 - 1 x 40) x 100 = 99.5%( 100 x 80 )
Compression and/or Cooling or Equivalent
Several respondents (25-1, -2, -3) report as emission control devicessystems based on compression and/or cooling to condense and retaincomponents of process vent which would otherwise reach the atmosphere.One respondent (25-3) reports a total net credit of $647,000 per yearfrom such systems.
Screens
Screens with or without felt back-up are reported by one respondent (25-6)to release storage silo conveying air to atmosphere.
27
V. Significance of pollution
It is recommended that polypropylene be placed, at present, in a stand-bycategory relative to the petrochemicals which may qualify for in-depthstudies. This recommendation is made because the impact of emissions fromnew capacity is contingent upon an uncertain projected growth rate: Ifpolypropylene capacity requirements continue to increase at an annual ratecloser to the actual figures experienced in recent years (rather than atthe lower extrapolated rate of 15% per year used in this report), theproduction quantity influence (on the SEI)* could be much greater at year1980. This point is stressed here because published accounts indicate thata few industry observers consider polypropylene to be a "dark horse ' ! comparedto polyethylene. That is, polypropylene may not experience as much drop onits future d2C/dt2 curve (or rate of decrease in the annual capacity growthrate) as polyethylene has in an equivalent time interval.
A further factor which would couple with the above possibility of highgrowth rate is the emissions ratio. The emissions ratio for polypropyleneis estimated to be 0.032 ton emissions/ton of PP capacity, whereas theemissions ratio for Low Density Polyethylene, for example is about 0.016T/T LDPE capacity (ref. Survey Report on Low Density Polyethylene see Report No.EPA450/3-73-005c). Thus, for a given installed tonnage of polypropylenecapacity, the estimated emissions are about twice the emissions for anequal tonnage of LD polyethylene.
The methods outlined in Appendix IV of this report have been used toforecast the number of new plants that will be built by 1980, and to estimatethe total weighted annual emissions from these new plants. This work issummarized in Tables V and VI, respectively.
The Table V forecast of new plants is based on the assumption that thepolypropylene growth rate experienced through the year 1972 will project asan annual capacity increase of 15% through 1980. (Reference is made to"Chemical Profile, Polyproplyene, May 22, 1972".) A Significant EmissionsIndex (SEI) of 12,190 has been calculated. See Table VII. Of this total,12,160 units stem from hydrocarbon vapors, equivalent to increased emissions(by 1980) of 152,000,000 lbs./year.
If polypropylene qualifies later for an in-depth study, a further pointappears to warrant consideration: The respondents "in toto" cover a widespectrum with respect to assignment of emissions to 1) fugitive sources,and 2) all other sources. Almost all of the reported emissions (to atmosphere)may be shown under "Fugitive" or "Other" labelling in one instance, whereas"Fugitive Emissions" may appear to account for only a small portion of thetotal in another instance. As a constituent of an in-depth study, it wouldseem that further definition and resolution of this picture is required.
*See Appendix IV for definition.
, 28
VI. Polypropylene Producers
The following tabulation of polypropylene producers indicates publishedproduction capacity:
Company
Amoco ChemicalsDart IndustriesDiamond ShamrockEastman KodakEnjay ChemicalHercules, rnc.
Novamont Corp.Shell Chemical Co.
Location
Ne~' Castle, Del.Odessa, TexasDeer park, TexasLongview, TexasBayto~'n, TexasLake Charles, La]Parlin, N. J.Neal, W. Va.v.'oodbury, N. J
Total
CapacityMM Lbs./Yr.Estimated as ofAugus t, 1969'''''
200507090
150
37080
150
1,160
*For the 3rd quarter of 1972, the estimated total capacity is 2,050 MM lbs./yr.,based on figures submitted by questionnaire respondents and published projections.
29
30
TABLE PP-I=COMPOSITE POLYPROPYLENENET MATERIAL BALANCE
(TONS/TON OF PP CAPACITY)
Stream No.on SimplifiedFlow Diagram
INPUT
PolymerIngredients Other
Polymer grade propylenecatalystSolventsAntioxidants, stabilizer~ additivesPolymer grade ethylene (comonomer)
Total Input
OUTPUT
Crystalline PP and copolymerPolymer separation, drying
ReclaimResidue from reclaim operations
Semi-liquid amorphousFugitive emissions (monomer leaks)
Total Output*
1 1.0800234 0.00625 0.0035---
1. 0897
6 1.0000PP fines 7 0.0057Propylene 0.0084Propylene 8 0.0020Propylene 9 0.0101Propane 0.0019CatalystSolventsPropylene 0.0319
10 0.0200
1.0800
0.006130.01077
0.01690
0.00210.0074
0.0095
*Exclusive of losses from storage tanks.
31
TABLE PP-IIPOLYPROPYLENE
GROSS HEAT BALANCE
The exothermic heat of propylene homopo1ymerization is order-ofmagnitude 960 BTU/Lb. (1)
(1) The equivalent figure for polyethylene is reported as 1,450 BTU/lb. in"Chern. Eng.", 11 (16) 68-August 1, 1966. As a crude approximation,the propylene value, assuming equal monomeric molar heats of homopo1ymerization, is 1,450 times (28.05)/(42.08) or 966.6, which is roundeddown to 960 BTU/lb. A log-log plot for heats of homopo1ymerizationfor ethylene, 1,3-butadiene and styrene indicates, by interpolation,a value of approximately 840 for polypropylene.
32
TAB
LEP
P-I
IIN
ATI
ON
AL
EM
ISSI
ON
SIN
VEN
TORY
POLY
!.'R
0l'Y
LEN
E
pag
e1
of
4
Co
nd
ense
rC
on
den
ser
Co
nd
ense
r25
-1
.102
25-
2.1
03
25-
3.1
04
-T
on/T
onPP
0.0
22
90
.00
36
0.0
21
20
.01
94
0.0
00
8E
mis
sio
ns
-T
on/T
onPP
Non
eN
one
Non
eN
one
Non
eN
one
Non
eN
one
Non
eN
one
Non
eN
one
NO
neN
one
Non
eN
one
Non
eN
one
Non
eN
one
Com
pany
Lo
cati
on
EPA
Cod
eN
o.cap
acit
y-
Ton
so
fP
oly
pro
py
len
e/Y
r.A
vera
geP
rod
uct
ion
-T
ons
of
PP
/Yr.
Sea
son
alR
ange
inP
rod
uct
ion
-%
of
Max
.E
mis
sio
ns
toA
tmos
pher
eS
trea
m-
Lett
er
onF
low
Dia
gram
Desc
rip
tio
nF
low
-L
b./
Hr.
of
Po
llu
tan
tsF
low
Ch
ara
cte
rist
ic-
Co
nti
nu
ou
so
rIn
term
itte
nt
ifIn
term
itte
nt
-H
rs./
Yr.
Flo
wC
om
po
siti
on
-T
on/T
ono
fPP
Hy
dro
carb
on
sP
art
icu
late
sNO
xS
ampl
eL
oca
tio
nD
ate
or
Fre
auen
cyo
fS
amp
lin
gT
ype
of
An
aly
sis
Odo
rP
rese
nt
ven
tS
tack
s
Flo
w-
SCFM
per
stack
Num
ber
Hei
gh
t-
Fee
tD
iam
eter
-In
ches
Ex
itG
asT
emp
erat
ure
-F
aE
mis
sio
nC
on
tro
lD
evic
eT
ype
-F
lare
Bag
Fil
ters
Cyc
lone
Wat
erS
cru
bb
erO
ther
cata
log
I.D
.N
umbe
rT
ota
lH
yd
roca
rbo
nE
mis
sio
ns
To
tal
Part
icu
late
-A
ero
sol
To
tal
NOx
-T
on/T
onPP
To
tal
SOx
-T
on/T
onPP
To
tal
CO-
Ton
/Ton
PP
t.;.l \,JJ
25
-12
5-2
25
-36
0,0
00
15
0,0
00
62
.50
06
0,0
00
15
0,0
00
62
,50
00
0°
HI
H2
GB
G
Rec
laim
Ven
tP
uri
ficati
on
Ven
tF
ug
ativ
eR
eco
ver
yV
ent
Fu
gat
ive
344
54N
otq
uan
tifi
ed
729
303
Co
nti
nu
ou
sC
on
tin
uo
us
Co
nti
nu
ou
sC
on
tin
uo
us
0.0
22
90
.00
36
0.0
21
20
.01
94
"Dis
char
ge
Op
enin
g"
Not
sam
ple
dN
otsa
mp
led
Not
sam
ple
dO
nce
Ch
rom
ato
gra
ph
Non
eN
one
Yes
Non
eY
esy
es
Not
ind
icate
dY
es
120
991
tota
l1
120
3575
161~
24
Am
bien
t60
0F
150
max
.Y
esN
oY
es
25
-47
5,0
00
75
,00
0o
B Rec
ov
ery
Ven
t15 C
on
tin
uo
us
0.0
00
8
Not
sam
pled
Not
ind
icate
dY
es
754
1 42 8 212
No
G Fu
gati
',eN
otau
an
tifi
ed
Com
pany
Lo
cati
on
EPA
Cod
eN
o.cap
acit
y-
Ton
so
fP
oly
pro
py
len
e/Y
r.A
vera
geProdu~tion
-T
ons
of
PP
/Yr.
Sea
son
alR
ange
inP
rod
uct
ion
-%
of
Max
.E
mis
sio
ns
toA
tmo
sph
ere
Str
eam
-L
ett
er
onF
low
Dia
gra
m
Desc
rip
tio
nF
low
-L
b./
Hr.
of
Po
llu
tan
tsF
low
Ch
ar.
acte
rist
ic-
Co
nti
nu
ou
so
rIn
term
itte
nt
ifIn
term
itte
nt
-H
rs./
Yr.
Flo
wC
om
po
siti
on
-T
on/T
ono
fPP
Hy
dro
carb
on
sp
art
icu
late
sNO
xS
ampl
eL
oca
tio
nD
ate
or
Fre
qu
ency
of
Sam
pli
ng
WT
ype
of
An
aly
sis
~O
dor
Pre
sen
tV
ent
Sta
cks
Flo
w-
SCFM
per
stap
kN
umbe
rH
eig
ht
-F
eet
Dia
met
er-
Inch
esE
xit
Gas
Tem
per
atu
re-
FOE
mis
sio
nC
on
tro
lD
evic
eT
ype
-F
lare
Bag
Fil
ters
Cyc
lone
Wat
erS
cru
bb
erO
ther
cata
log
I.D
.N
umbe
rT
ota
lH
yd
roca
rbo
nE
mis
sio
ns
-T
on/T
onPP
To
tal
Part
icu
late
-A
ero
sol
Em
issi
on
s-
Ton
/Ton
PPT
ota
lNO
x-
Ton
/Ton
PPT
ota
lSO
x-
Ton
/Ton
PPT
ota
lCO
-T
on/T
onPP
TABL
EP
P-I
IIN
ATI
ON
AL
EMIS
SIO
NS
INV
ENTC
J.YPO
LYPR
OPY
LEN
E
B Scr
ub
ber
Ven
t2
5.3
Co
nti
nu
ou
s
0.0
08
5
Not
sam
ple
d
Non
eY
es
21 4 90 4 130
Yes
Scr
ub
ber
25-
5.1
01
,-
10
2,
-1
03
,-
104
0.0
08
5N
one
Non
eN
one
Non
e
25
-55
0,0
00
50
,00
0o
Pag
e2
of
4
D Incin
era
tor
Sta
ck
23 Co
nti
nu
ou
s
0.0
01
80
.00
01
Not
sam
pled
Non
eY
es
5,9
00
1 20 84 1,8
00
.In
cin
era
tor
25-
5.1
05
0.0
01
80
.00
01
Non
eN
one
G Fu
git
ive
238
Co
nti
nu
ou
s
0.0
20
0
0.0
20
0
TABL~
PP
-Hl
~TTOKAt.!:ms~!.<~~n:\'E~T"RY
f.Qbl
:.!'R
OPY
I,EX
EPa~e
'3(,r
!.;
Com
pany
Lo
cati
on
EPA
Cod
eN
o.cap
acit
y-
Ton
so
fP
oly
pro
py
len
e/Y
r.A
vera
geP
rod
uct
ion
-T
ons
of
PP
!Yr.
Sea
son
a1
Ran
gein
l't"
od
uct
ion
-%
of
Max
.E
mis
sio
ns
to.A
tm08
pher
eS
trea
m-
Lett
er
onF
low
Dia
gram
AB
B
25-0
140,
00(,
11
40
.00
0o
CE
&F
G
l(X
25
-.6
.10
5
Fu~ativc
~ot
Qu
anti
fted
POl
P-2
16
MT
ota
l1
14
0IS
13x
1310
110
14
0V
eFYl
'1f:
N-3 1 8
553
ll4
111
0Y
es
N-l
N·2
22M
l'o
tsl
11
8585
1229
x29
110
lWV
UY
ee
Scr
een
s2
5-6
.10
4
L-1
L-2
3HT
ota
l1
185
8512
Z9x
2912
012
0Vo~
ves
Scr
een
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Polystyrene
Table of Contents
Section Page Numbe!:.
I.II.III.IV.V.VI.
IntroductionProcess DescriptionPlant EmissionsEmission ControlSignificance of PollutionPolystyrene Producers
List of Illustrations and Tables
Flo,,) DiagramNet Material BalanceGross Heat BalanceEmission InventoryCatalog of Emission Control DevicesNumber of New Plants by 1980Emission Source SummaryWeighted Emission Rates
43
PS-IPS-2PS-3PS-6pS-8PS-9
Figure PS-ITable PS-ITable PS-IITable PS-IIITable PS-IVTable PS-VTable PS-VITable PS-VII
I. Introduction
The post~ar (WW II) development of the polystyrene industry in the U. S.is due, in no small part, to the extensive efforts of the CPI to develop andproduce synthetic rubber (GR-S) for the war effort. Less than 1 millionpounds of styrene based plastic was produced in 1937, today, over 2,500million pounds are produced annually. About t~enty years ago, ~hen the 100million pounds/year mark was achieved, general purpose styrene accounted forthe bulk of the production. Today, rubber-modified polymers (high impactpolystyrene, etc.) are, at least, of equal importanc~. The lo~ cost, easeof fabrication, and ease of modification are all responsible for the dramaticgro~th of this industry.
The prime air pollutant associated with the production of polystyrene isstyrene. It is emitted during feed preparation (if any), from the reactionsection and from the devo1ati1ization process. Additionally, polystyrenedust is discharged to the atmosphere by the pneumatic conveying systemsgenerally used. Also, varying quantities of ~aste ~ater are produced. Ingeneral, ho~ever, the production of polystyrene generates relatively littleair pollution.
The current U. S. polystyrene production capacity is approximately3.5 x 109 lbs./yr. This includes general purpose polystyrene, high impactpolystyrene and various co-polymers, but excludes SBR rubber and SiB latex.Production capacity will nearly double by 1980, increasing to 6.7 x 109lbs./yr.
44
II. Process Description
Styrene polymerizes Guite readily ~ith the addition of either heat oran initiator (catalyst), such as benzoyl peroxide or ditertiary butylperbenzoate. Styrene ~ill homopolymerize in the presence of diverse inertmaterials and copolymerize with a variety of monomers. Pure polystyrenehas the follo~ing structure:
H H H H/ '/
1-C - CH2 - C. -CH -C -CH-C -CH -~.). • 2 i 2. 2 ~
(1 ~ ~ "~'-1I II 1 II .II .• •_~# ~ , •• ;::J : ..,,~J i ~/
Although polymers ~ith molecular weights in the millions can be made,those most useful for molding have mol. v'ts. of about 125,000, v'hile those usedin the surface coating industry average arout 35,000.
Several techniques are empolyed to polymerize styrene. In order ofdecreasing commercial importance they are: (1) solution polymerization,(2) suspension polymerization and (3) emulsion polymerization. The firsttwo are the most important, and the subject of this report ~ as shown (Fig. FS -1).
Solution Polymerization
A mixture of styrene and solvent (such as ethylbenzene) is fed intoa series of tubular, agitated polymerization reactors. The reactorsare normally constructed of aluminum or stainless steel. Each reactorcontains several heat exchange zones to remove the large heat ofreaction generated during the polymerization. The mixture flows fromtop to bottom of each reactor, entering the first reactor at about250 0 F and leaving the last reactor at about 3400 F. The solventmaintains the viscosity of the polymerizing mass within manageablelimits and facilitates heat removal.
The solvent containing polymer is pumped from the last reactor intoa low pressure high temperature devolatilizer, where unreacted monomerand solvent are flashed off. These vapors are condensed and recycledto monomer feed. The polymer (polystyrene) is extruded, cooled, cut andconveyed to product storage.
Suspension PolYmerization
In suspension polymerization, small droplets of styrene fO.l to 1 MM)are dispersed in water. The polymerization is carried out batchv'ise instirred, jacketed reactors. Polymer is produced in the form of smallbeads or pearls. The v,ater, at a v1ater/monomer ratio of from 1 to 3,acts as a heat transfer agent and keeps the monomer/polymer droplets ata uniform temperature. The result is a product more uniform than from anyother (styrene polymerization) proce~R. Generally, reaction initiatorsand suspending agents are reouired.
The water/polymer bead mixture is pumped from the reactor to a washtank, where the suspending agents and initiators are removed. HOv'ever,polymer contamination by residual amounts of these materials normallyresults and polymer purity is lower than for other processes.
The washed beads are separated from the wash water by centrifuge, afterwhich they are dried and extruded. At this stage the polymer is treatedas it is in the solution process.
45
III. plant Emissions
A. Continuous Air Emissions
1. Feed Preparation Section Purge
Only one respondent (EPA Code No. 26-4) has reported an emissionfrom this source. Said respondent is the sole reporting employerof the solution polymerization process, vhich reputedly is Guitesensitive to catalyst poison~... i.e. feed contaminants. The naturalinference is that this type emission is to be expected of plantsutilizing solution polymerization whereas it is atypical of thesuspension process plants. The actual emissions reported aresummarized in Table III.
2. Reactor Vent
Respondent 26-1, having observed reactor li~uid level decrementduring reaction, has calculated and reported the correspondingemissions. They amount to over 700,000 lbs./yr. of styrene and300,000 lbs./yr. of water. Other operators have reported neitheremissions from this source, nor devices to prevent them. However,respondents 26-2 and 26-3 offer no ~uantitative data on pollutingemissions from any source, so lack of supportive information shouldnot deter one from surmising that reactor vapors are normallyvented to the atmosphere, and that they represent a significant portion of the total emissions for the process .
.3. Solvent Recovery Section Vent
As would be expected, only the solution polymerization plant(EPA Code No. 26-4) has reported emissions from this source Forthis plant those emissions constitute the single largest source ofatmospheric pollution, contributing nearly 75% of the total hydrocarbons emitted. On a lb./lb. basis they equal .00184 lbs. ofhydrocarbon (styrene) per pound of polystyrene.
4. Polymer Drying Vents
Both plants 26-2 and 26-3 report emissions from streams in thiscategory. With one minor exception, the contaminants in thesestreams are only identified, with no information given on theirconcentration. In general, these vents are air streams containingsmall amounts of polystyrene (plant 26-3) or pentane and hydrochloricacid (plant 26-2). Other available information is summarized inTable III.
5. Pneumatic Conveyor Exhaust
After polymerization, polystyrene undergoes a number of finishingoperations - extrusion, pelleting, coloring, packaging, etc. Therequisite polystyrene transportation is provided by a system ofpneumatic conveyors. There are always a number of conveyor exhauststreams (vents) associated with such a system. The components ofthe vents are normally air and polymer dust, occasionally the ventwill contain some water (vapor) or traces of volatile hydrocarbons.The respondents have provided no ouantitative emission data onthese streams.
46
6. Extruder Exhaust
Respondents 26-2 and 26-3 both report emissions from this source.Again, no quantitative data is available, but apparently the exhaustair contains small amounts of styrene.
B. Intermittent Air Emissions
1. Emergency vents - Reactor Section
Only respondent 26-3 mentions emissions in this category. Itseems reasonable to assume that other plants encounter emergenciessimilar to those described by 26-3 - "depending on the emergency,emissions could range from steam vented for pressure reduction tostyrene monomer vapor released from emptying the entire contentsof a reactor containing semi-polymerized styrene. Emergencies suchas power failure or loss of suspension may necessitate emptyingthe entir~ contents of a reactor".
2. Feed Preparation Purge
Respondent 26-4 reports a small styrene vent «.00001 lbs./lb.)arising from the cyclic filling and venting of a feed prep. tank.As discussed in Section III-A-l, no other respondents have feedprep. sections.
c. Continuous Liquid Wastes
The only liquid 'tI7aste reported was 'tI7aste 'tI7ater. HO'tl,ever, therewas considerable variation in the quantities reported:
Plant
26-126-226-326-4
QuantityGal. /Hr.
8,33358,200
1,240120 to 180
Contaminants
Not SpecifiedNot SpecifiedNot SpecifiedEt. Bz & Styrene
Treatment
Aeration - ClarificationYesYesNo
D. Intermittent Liquid Vastes
None reported.
E. Solid Vastes
All respondents report the disposal of solid wastes, specifically,scrap polystyrene or waste 'resin'.
Operator 26-1 reports 2 x 10 6 lbs./yr. waste polystyrene - all ofwhich is disposed of in sanitary land fills.
Operator 26-2 reports disposing of 26,000 lbs./day of wasteresin. Half is taken directly to land fill areas and half is dischargedinto settling ponds from waste water streams.
Operator 26-3 reports only 100 lb./day of waste polystyrene. Thisis disposed of by the municipal waste department .
. 47
F. Odors
In general, the production of polystyrene does not appear tohave an associated odor problem.
The respondents reported no odor complaints in the past year.All of the reported odors are said to be detectable only on theplant property and only at intermittent intervals. The materialcausing odors in this category has been identified as styrene.However, according to the questionnaires, these emissions arewell enough controlled to prevent odor problems.
,G. Fugitive Emissions
Fugitive emissions for the subject process appear to benegligible. Operator 26-2 summarizes the reasons: "Process isbasically a low pressure/atmospheric operation predominantlyhandling solids --- (Hydrocarbon) ---- piping is minimal andpumps are equipped with mechanical seals. Leakage is nil".
H. Other Emissions
Two operators (26-3 and 26-4) report using a sulfur containingfuel. SOx emissions on a Ib./lb. basis are .00033 and ~.OOOOI
respectively. No other sources of significant emissions have beenreported.
48
V. Significance of pollution
It is recommended that no in-depth study of this process be undertaken atthis time. The reported emission data indicate that the quantity of pollutantsreleased as air emissions is less for the subject process than for otherprocesses that are currently being surveyed. However, the presented appraisalof the quantity of polluting emissions is subject to error from more sourcesthan usual. They are:
A. The data from two processes (suspension and solution) have beenintegrated and presented as a whole.
B. There is no quantitative data to support the estimate of particulateemissions, they could be considerably higher.
C. The difference between 1980 capacity and demand (see Table V) is quitelarge. If this is unrealistic (and the 1980 capacity should be closerto demand) then the SEI* would be appreciably lower.
Never-the-less, because A and B (above) tend to be self-compensating andbecause the SEI* is quite low, it is believed that the characterization of theprocess as a relatively low air polluter is accurate.
The methods outlined in Appendix IV of this report have been used toestimate the total weighted emissions from new plants. This work is summarizedin Tables V, VI and VII.
Published support for the Table V forecast of new plants may be found inAppendix C of Process Research's final report on Task Order No. 14 for theEPA (August 13, 1971).
On a weighted emission basis a Significant Emission Index of 1,641 hasbeen calculated in Table VII. This is substantially less than the SEIls thatare anticipated for Some of the other processes in the study. Hence, therecommendation to exclude polystyrene from the in-depth study portion of theovera1f scope of work.
*Significant Emission Index - see Appendix IV.
51
VI. Polystyrene Producers:*
The following tabulation of polystyrene producers indicates publishedproduction capacity by company and plant location:
Plant
Alabama Binder & Chern. Co.American Petrofina
BASFBeatrice FoodsBorden
Dart Industries
Diamond plasticsDow
Foster Grant
Carden Chern.
Howard IndustriesS. C. Johnson & SonMonsanto
Morton Chern.O'Brien Co.Fuller - O'Brien Co.Pennsylvania Indust. Chern.Philip MorrisPolymeric ResinspolysarPurex
ReichholdRichardson Co.Scholler Bros.ShellSinclair KoppersSouthern PetrochemicalsStaley Chern.
Standard Oil of Indiana
Location
Tuscaloosa, Ala.Big Spring. TexasCalumet City, Ill.Jamesburg N. J.Wilmington, Mass.Illiopolis, Ill.Bainbridge, N. Y.Compton, Calif.Demopolis. Ala.Leominster, Mass.Holyoke, Mass.Joliet, Ill.Ludlow, Mass.Santa Ana, Calif.Long Beach Calif.Gales Ferry, Conn.Ironton, OhioMidland, Mich.Riverside, Mo.Torrance, Ca li f .Leominster, Mass.peru, Ill.Oxford, Mass.Worcester, Mass.Hicksville, N. Y.Racine, Wise.Addyston, OhioLong Beach, Calif.Springfield, Mass.RingY7ood. 111.South Bend, Ind.South San Francisco Calif.Clairton, Pa.Springfield, Conn.Wilmington, MassLeominster, Mass.Bristol, pa.Carson, Calif.Chicago Ill.Elizabeth, N. J.West Haven, Conn.Eh7ood, N. J.Belpre, OhioKobuta, Pa.Channelview, TexasKearney, N. J.Lemont, Ill.Marlboro Mass.Joliet, Ill.Medina, OhioTorrance, Calif.Willow Spring, Ill,Leominss~r, Mass.
Capacity - MM Lbs./Yr.
150150
80
5040302060
150270250
10130120
803050
375375375
60
50
60300
60
7025255020
Sybron CorporationUnion Carbide
U. S. Steel
Location
Haledon, N. J.Bound Brook, N. JMarietta, OhioHaver Hill, Ohio
Total""-
Capacity - MM Lbs./Yr.
65100200
3,130
*Of knovn capacities, 1971.**Straight and rubber modified, may include certain styrene co-polymer resins
and elastomers.
53
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--,IIIII
TABLE PS-IPOLYSTYRENE PRODUCTION
MATERIAL BALANCE - T/T OF POLYSTYRENE
There are not sufficient published data available to permit thepresentation of a meaningful material balance.
55
TABLE PS-IIPOLYSTYRENE PRODUCTION
GROSS REACTOR HEAT BALANCE
The exothermic heat of polystyrene homopolymerization is 290 BTU/Lb.of monomer.
There are not sufficient published data available to permit theconstruction of a typical commercial reactor section gross heat balancefor this process.
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ht·
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onde
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ther
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lly
lie
Dat
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requ
ency
of
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plin
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ampl
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of
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aly
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ary
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nt
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ity
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ons
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pher
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ient
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NO
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Non
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c!.
Cd
c'c!
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'd.
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c'c!
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No
Nil
NON
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.002
49 + 0 0 0
Flo
w-
Lb••
/Hr.
Flo
wC
hlr
.cte
ri.t
ic,
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or
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tten
tif
Inte
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tten
t.H
rl./
Yr.
Flo
wC
ompo
siti
on.
Ton
i/T
ono
fP
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lty
ren
eS
tyre
ne
Po
ly.t
yre
ne
lIat
erP
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neN
itro
gen
Eth
yl
Ilen
zene
Hyd
roch
lori
c!A
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on
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nd
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dor
Pro
blem
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ry
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ir·
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llu
t.n
ts.
Ilyd
roca
rbon
s.T
on/T
ono
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oly
ety
ren
ep
art
icu
late
s.'f
on/T
ono
fP
oly
sty
ren
eN
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Ton
/Ton
of
Po
lyst
yre
ne
so".
Ton
/Ton
of
Po
lyst
yre
ne
CO•
Ton
/Ton
of
Po
lyst
yre
ne
Ple
atEP
AC
ode
No.
Cep
ac1t
y,T
one
of
Po
lyet
yre
ne/
Yr.
Ren
gein
Pro
du
ctio
n-'X
.o
fMI
l".Em
1••i
on
.to
Atm
o.ph
ere
Str
ee.
V1
ID
TABLE PS-IIINATIONAL EMISSIONS INVENTORY
POLYSTYRENE PRODUCTIO~
VIASUSPENSION AND SOLUTION PROCESSES
EXPLANATION OF NOTES
(A) Ten separate streams comprise this entry, some are continuous and someare intermittent. Flow rates and pollutant concentrations are basedon the average total flow.
(B) The exhausts from six driers comprise this entry. Flow rates andpollutant concentrations are based on the average total flow.
(C) The discharges from seventeen blender/check bin purge 'exhausters'comprise this entry. Flow rates and pollutant concentrations arebased on the average total flow.
(D) The exhausts from twenty 'airveying' systems comprise this entry, someare continuous and some are intermittent. Flow rates and pollutantconcentrations are based on the average total flow.
(E) The discharges from two rotoclones comprise this entry. Flow ratesand pollutant concentrations are based on the combined flow.
(F) The exhausts from seven 'airveying' systems comprise this entry, someare continuous and some are intermittent. Flow rates and pollutantconcentrations are based on the average total flow.
(G) The exhausts from three driers comprise this entry. Flow rates andpollutant concentrations are based on the combined flow.
(H) The exhausts from three pneumatic transfer systems comprise this entry.Conveyor operation is intermittent, but flow rates and pollutantconcentrations are based on total flow, averaged over twenty-fourhour period.
60
TAB
LEP
S-I
VCA
TALO
GO
F.E
litS
SlO
llfC
OllT
lOL.
PE
nC
Ill'O
LY
ST
YU
RI
PIO
DU
CT
ION
!!!
SUSP
ENSI
ON
&SO
LU
TIO
NP
RO
ClS
SlS
CYC
LON
ESEP
AC
ode
No.
for
pla
nt
usi
ng
Flo
wD
iag
ram
(Fig
.II
)S
trea
mI.
D.
Dev
ice
I.·D
.N
o.C
on
tro
lE
mis
sio
no
fT
.TH
eig
ht.
Ft.
Dia
met
er-
Ft.
No.
of
Sta
gea
Inst
all
ed
Co
st-
Mat'
!.&
Lab
or
-$
Inst
aU
ed
Co
stb
ased
on-
''year'
'-
do
llara
Inata
lled
Co
st.
(;/l
b.
of
J111
,.t'.
.../
Yr.
Op
er.
tin
gC
ost
.A
nn
ual
-$
(197
2)V
alu
eo
fR
eco
ver
edP
rod
uct
,$/
Y'f:
.N
etO
per
atin
gC
ost
,$
/Yr.
Net
Op
eraU
ng
Co
st,
C/l
b.
of
Po
lyst
yre
ne
Eff
icie
ncy
-SE
-%
Eff
icie
ncy
-SE
RR
-%
So
lven
tR
e_
a!
Sactl
on
26-3
I1'
9-1
(A)
Po
lr-e
rD
ust
1',6
2519
58to
'197
0.0
0138
14
099
8,75
0-9
98,_
18(N
egat
ive)
96
(of
16
up
art
.)
Ilctr
uaio
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lon
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et't
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-l
1IAG
FIL
TE
RS
EPA
Cod
eN
o.fo
rp
lan
tuB
1ng
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wD
iag
ram
(Fig
.II
)S
trea
mI.
D.
Dev
ice
I.D
.N
o.C
on
tro
lE
mis
sio
no
fN
umbe
ro
fC
ompa
rtm
ents
Num
ber
of
:sag
s/C
om
par
tmen
tT
ota
lB
agA
rea
-F'
1'2B
agC
loth
Mate
rial
Des
ign
(op
era
tin
g)
tem
p.
-F
aD
esig
n(o
pera
tin
g)
pre
s.-
PSIG
Inst
all
ed
Co
st-
Mat'
l.&
Lab
or
-$
Inst
all
ed
Co
stB
ased
on
-"y
ear"
-d
oU
ars
Inst
aU
ed
Co
st.
c/lb
,.'o
fP
oly
sty
ren
e/Y
r.O
per
atin
gC
ost
-A
nn
ual
-'$
(19
72
)V
alu
eo
fR
eco
ver
edP
rod
uct
-$
/Yr.
Net
Op
eraU
ng
Co
st-
$/Y
r.N
etO
per
atin
gC
ost
-c/l
o.,
of
Po
lyst
yre
ne
Eff
icie
ncy
-5
E-
%E
ffic
ien
cy
-SE
RR
-%
26-3
I PS-2
(B)
Pol~r
Du
st
(130
)
37.0
0019
58to
19
69
.03
14
918
,580
14
9.8
00
-13
1,2
20
(Neg
ativ
e)
26-3
II
PI-
3(C
)P
ol,
.er
Du
et
(130
)
2,6
00
1958
to19
62.0
0221
260
20
.00
0-1
9,74
0(N
esaU
ve)
~.
TABLE PS-IVCATALOG OF EMISSION CONTROL DEVICES
POLYSTYRENE PRODUCTIONVIA
SUSPENSION & SOLUTION PROCESSES-----EXPLANATION OF NOTES
(A) Three similar cyclones comprise device PH-I. Costs detailed in TableIV are total costs.
(B) Twenty-four "flo-tronics bin vent filter assemblies" comprise devicePS-2. Costs detailed in Table IV are total costs for all 24 assemblies.
(C) Seven filter units comprise device PS-3. Costs detailed in Table IVare total costs.
62
TAB
LEPS
-VNU
MBE
ROF
NEV
PLA
NTS
BY19
80
Cu
rren
tC
apac
ity
Cap
acit
yE
cono
mic
Num
ber
of
Cu
rren
tM
arg
inal
on
-str
eam
Dem
and
Cap
acit
yto
be
Pla
nt
Nev
'G
.apa
city
Cap
acit
yin
1980
1980~'<
1980
Add
edS
ize
Un
its
3,5
00
225
3,2
75
5,5
00
6,7
00
3,4
25
150
22-
230
') w
Not
e:A
llcap
acit
ies
inM
ML
bs.
/Yr.
*198
0de
man
db
ased
onp
roce
ssre
searc
hre
po
rt.
TABL
EP
S-V
IEM
ISSI
ON
SOU
RCE
SUM
MAR
YTO
N/T
ON
OF
POLY
STY
REN
E
So
urc
e
Fir
ed
Hea
ter
Fu
git
ive
1<'11
1IB
r:9~
Em
issi
on
sT
ota
l
.00
58
3
.000
10
Neg
lig
ible
0
\.0
00
33
.000
33 0
.00
01
0
Con
veyi
ng,_
_-e
:.°.<
;.2_e
ratio
ns_
----
---
.00
18
4
So
lven
tR
eco
ver
yS
ecti
on
.003
34
Rea
cto
rV
ent
.000
65
Fee
dP
rep
ara
tio
nS
ecti
on
NOx
Hyd
roca
rbon
Part
icu
late
COTyp
e
SOx
0">
-I::"
TABL
EP
S-V
IIW
EIG
HTE
DEM
ISSI
ON
RATE
S
Po
lyst
yre
ne
Che
mic
al_
__
..::..
.:..::
:J...:
::....:
...L.::
..::..
:::..:
::..-
_
Pro
cess
Hom
opo1
ymer
izat
ion
Incr
ease
dC
apac
ity
by
1980
3,4
25
MM
Lb
s./Y
r.
Em
issi
on
sIn
crea
sed
Em
issi
on
sW
eig
hti
ng
Wei
ghte
dE
mis
sio
ns
Po
llu
tan
tLb./~
MM
Lbs
./Y
r.F
acto
rMM
Lbs
./Y
r.
0'>
Hyd
roca
rbon
s.0
0583
19
.97
801
59
7.6
VI
Part
icu
late
s.0
00
10
.34
602
0.6
NOx
00
400
SOx
.000
331
.13
202
2.6
CO0
01
0
Sig
nif
ican
tE
mis
sio
nIn
dex
..1
64
0.8
Polyvinyl Chloride
Table of Contents
Section page Number
I.II.III.IV.V.VI.
IntroductionProcess DescriptionPlant EmissionsEmission ControlSignificance of pollutionPolyvinyl Chloride Producers
List of Illustrations and Tables
Flow DiagramNet Material BalanceGross Heat BalanceEmission Inventorycatalog of Emission Control DevicesNumber of New Plants by 1980Emission Source SummaryWeighted Emission Rates
66
PV-lPV-3PV-7PV-9PV-10PV-ll
Figure PV-ITable PV-ITable PV-IITable PV-IIITable PV-IVTable PV-VTable PV-VITable PV-VII
I. Introduction
The term "polyvinyl chloride (PVC) resins" is meant to include vinylchloride homopolymers with the repeating unit -CH2CHC1- and copolymers ofvinyl chloride with minor amounts of vinyl acetate, ethylene, propylene,vinylidene chloride or acrylates. Most are available in the form of whitepowders that, after compounding with a number of auxiliary ingredients,are converted into a large variety of plastic or resinous end productsthrough several types of processes. Because PVC resins are thermoplastic,all but one of these processes for converting PVC powders employ heat tomake the end product (coating resins are processed by dissolving the resinand applying it from solution).
Industrial development of PVC resins began some 40 years ago. Productionon a full commercial scale began in Germany in 1931 and in the United Statesin the later 1930s, after the discovery that polyvinyl chloride, when heatedin the presence of a suitable high-boiling liquid (a plasticizer), formeda flexible plastic material that resembled rubber or leather. Becauseplasticized PVC showed itself to be a good insulator, resistant to theweather, and nonflammable, it was put to military uses in World War II.Diversified compounding and processing technology, which developed particularlyin the later 1940s and early 1950s, quickly led to many broad-scale commercialuses.
The processing and performance characteristics of PVC resins can bevaried with the molecular weight, which for most commercial PVC resins liesbetween 50,000 and 120,000. Equally important to the characteristics of theresins is the presence or absence of plasticizer. Most PVC plastics producedin past decades were flexible types, containing plasticizer. While the manyprocesses for plasticized PVC are relatively easy to carry out, the processingof PVC compounds containing essentially no plasticizer (for the production ofrigid PVC plastics) is technically more demanding. The properties ofplasticized PVC plastics depend greatly on the exact amounts and chemicaltypes of plasticizers used; it is common to employ mixtures to achieve thedesired properties.
Although the great majority of PVC resins used in the various processesto manufacture PVC plastics are homopolymers of vinyl chloride, copolymers arestill essential in some processes, where they are used alone or in admixturewith homopolymers.
The most important commercial copolymers of vinyl chloride are those withvinyl acetate. The higher molecular weight resins with an acetate content ofabout 2-8% are used for calendering and extrusion, where somewhat fasterprocessing is possible because of their better flow properties compared withthose of conventional homopolymers. Copolymers containing over 8% vinylacetate flow even more readily under the application of heat and pressure andare, therefore, favored in the production of phonograph records. The copolymersalso are capable of binding particularly large amounts of mineral fillers andpigments, a capability utilized in the production of vinyl-asbestos floor tile.Because the solubility in esters and ketones of vinyl chloride copolymers withan acetate content of 10-20% is much greater than that of homopolymers, theseresins are used in solution coating.
The commercial copolymers of vinyl chloride with ethylene and propylenecontain 1-8% of ethylene or propylene and are predominantly used in the man-
67
ufacturing of unp1asticized (rigid) PVC products. Such copolymers can beprocessed faster and have better impact strenght than comparable homopo1ymers,without any sacrifice in dimensional stability and other important performanceproperties.
Copolymers of vinyl chloride with viny1idene chloride are more soluble insolvents than homopo1ymers and they are good film formers. The few resins ofthis type that are on the market today are, therefore, mostly used in specialtycoatings (in solution and, in Some applications, in latex or emulsion form).
A few latex PVCs or copolymers of vinyl chloride and ethyl, n-buty1, or2-ethy1hexy1 acrylate are used in the production of wall coverings, nonwovens,and house paint. The latexes are 50 percent solid colloidal dispersions inwater.
Postch10rinated PVC homopolymer resins have long been in existence butwere of little commercial importance until recently. Products made from themhave better heat resistance (and higher densities) than products made fromordinary PVC resins. The main application for these resins is in residentialhot water pipe.
The present polyvinyl chloride capacity is mainly for various structuralforms of the homopolymer (see under "Process Description"), with copolymerfilling out the remainder of the picture. The survey activity represented inthis report is based on questionnaires returned by seven polyvinyl chloridemanufacturers.
As of February, 1972, approximately 4,375,000,000 1bs./year of PVC capacityexisted in domestic facilities. Emissions arising from these facilities stemprimarily from operations concerned with monomer storage; reaction and"stripping"; centrifugation; vinyl chloride monomer reclaim; materials handling;PVC storage; and product bagging or bulk loading. In addition, there is asignificant contribution from "fugitive" or "other" emissions. The pollutantsare mostly hydrocarbon vapors and PVC fines. Relative to pollution significance,PVC projections to the year 1980 indicate a weighted SEI of about 4,840 units.
If PVC is considered for inclusion in the group of petrochemicals whichmay qualify for in-depth studies, a further factor should be considered. Thisfactor has to do with the increasing prominence of the "bulk polymerization"process. The present report herewith does not reflect the possible influenceof appreciable "bulk polymerization" capacity on the projected SEI. It may bedetermined that questionnaires should be issued to "bulk polymerization" PVCmanufacturers if a decision is made to study PVC in-depth.
68
II. Process Description
This is a simplified description of four modern processes used to producepolyvinyl chloride. A simplified composite flow diagram is attached. pleasesee fold-out drawing No. R-225. A Net Material Balance is presented inTable I. Please see Table II ,relative to a gross heat balance.
1. Suspension Polymerization
About 78% of all PVC resins (both homopolymers and copolymers)produced in the United States in 1971 were produced by suspensionpolymerization. The polymerization is carried out in an aqueoussystem in which monomer droplets are maintained in suspension bymeans of a protective colloid in conjunction with brisk agitation.Typical protective colloids are polyvinyl alcohol, gelatin andsubstituted celluloses (e.g., carboxymethyl cellulose).
Generally, suspension polymerization is operated as a batchprocess employing glass-lined reactors (having a capacity of 2-6thousand gallons in older plants and larger in newer plants). Thereactor is first charged with deionized water, and then a protectivecolloid (0.05 to 2% of the weight of the monomer), a buffer (e.g.,sodium acetate) and an initiator (e.g., lauryl peroxide, azobisisobutyronitrile, or isopropyl peroxydicarbonate) are added. The vinylchloride and, in the case of copolymer production, the second monomer(e.g., vinyl acetate, propylene, or vinylidene chloride) are thenintermittently introduced in controlled tatios. The mixture isthen brought to the polymerization temperature (about 500 C) and,after variable induction periods depending on the initiator used,the polymerization starts. The heat of polymerization is removedfrom the system to maintain the desired reaction temperature.When lauryl peroxide is used as the initiator, the polymerizationis substantially complete after a period of about 16 hours.
A dispersion of relatively large polymer particles in water isobtained by the suspension polymerization process. After unreactedmonomer is driven out of the slurry and recovered, the slurry iscentrifuged and the polymer is dried in a flash dryer, in which itis subjected to an air stream at about 800 C, complete drying usuallyrequired more than one passage. The dry polymer is screened,generally through a 40-mesh screen, and shipped in bulk or packed inmultiwall paper bags.
2. Emulsion Polymerization
About 13% of the PVC resins produced in the United States in 1971were produced by emulsion polymerization which is basically verysimilar to the suspension P~~f~sS except that relatively large amountsof emulsifying agents are us'~, usually in pairs where one agent issoluble in the monomer and the other in water. Such systems, combinedwith powerful agitation, very effectively prevent the coalescence ofpolymer particles and, as a result, resins of a very small particlesize are obtained. The drying methods are also designed to maintaina small particle size; spray dryers are frequently used. Completeremoval of emulsifiers is never achi'e~d in resins produced by thisprocess, so that articles of high clarity (as needed in packagingfilm) or of very low water absorption (as needed in wire insulation)
69
cannot be produced from such resins. The generally higher price ofemulsion-polymerized resins compared to that of suspension-polymerizedresins is, nevertheless, accepted by users who need compounds inliquid form (fluid dispersions of PVC resins in plasticizers, calledplastisols) for the manufacturing of end products. In the UnitedStates, all resins produced by emulsion polymerization are used forplastisols (and, to a minor extent, in latex form). In Europe,emulsion polymerization processes have been refined further than inthe United States so that general purpose resins (useful for calendering and extrusion) are also produced there by variations ofthe emulsion process.
3. Bulk Polymerization
In this relatively new process, which was used to make 6% of thePVC resin produced in the United States in 1971, vinyl chloride ispolymerized without the addition of other liquids. A two-stageversion of the process is so attractive that it has been licensedallover the world (ECN, April 3, 1970, pa. 14).
In the two-stage bulk polymerization process, a suitably shapedreactor is provided for the initial liquid phase of the reaction, anda differently designed autoclave is then used to agitate the dry,powdery mass effectively until the conversion from monomer to polymerreaches a level of about 90%. Heat exchange is provided by thedistillation of monomer and its recondensation within the reactorand external condensers. The rate of out-put of the t"70-stage bulkpolymerization plants is said to be more than twice as high asthat of a good suspension process plants of comparable size (i.e.,with a comparable number and size of reactors). It is generallyexpected that two-stage bulk polymerization of vinyl chloride ~ill
be ~idely used world-wide in the next several years.
Bulk polymerized PVC resins resemble the suspension resins inappearance and are characterized by high particle uniformity and purity.This results in end products of unusually good optical clarity(important for packaging uses). Also, these resins have remarkablygood heat stability and improved fusion properties, i.e., they can beprocessed with the ease of conventional vinyl chloride-vinyl acetatecopolymers.
4. Solutioa Polymerization
Although solutio~ polymerizatio~ is over 40 years old, only about3% of the PVC resins produced in the United States in 1971 were producedby this method. In this process, the moaomers are first dissolved inan organic solvent (such as n-butane or cyclohexane) in an autoclave.After the a1dition of a peroxide initiator and heating of the stirredsolution to 40° C, polymerization begins and the polymer precipitatesas the reaction proceeds.
Solution polymerization is used exclusively for the production ofco?~lymers of vinyl chloride with vinyl acetate (usually thosecontaining 10-25% acetate). These solution-polymerized copolym~Ts areremarkably pilre and uniform and their chief value lies in theirunique solubility and film-forming characteristics. A greatlyimproved form of the original process is used for the productionof these specialty coating resins.
70
5. Structure
In principle, addition of the vinyl chloride monomer units duringpolymerization can occur either in head-to-tail fashion, resultingin 1,3 positions for the chlorine atoms
~H2CHClCH2CHC~·n
or head-to-head, tail-to-tail, placing the chlorine atoms in 1,2positions as follows:
-··F~iI2CHClCHClC~2-+n
Three categories of end groups are possible in the polymer.Saturated groups are formed by ctain transfer with monomer andpolymer and by termination through disproportionation:
Unsaturated chain ends are due to termination by disproportionationand to chain transfer to monomer:
-CH2CHClCH= CHCl; -CCL =CH2 ; -CH2CHClCH-=. CH2
Initiator or solvent (chain-transfer agent) fragments, representedby R, can be incorporated in the terminal group:
-CH2R; ---CHClR
Due to the high transfer activity of the monomer, about 60;' ofthe polymer molecules are estimated to have unsaturated end groups.For the same reason, the percentage of chain ends containing initiatorfragments is low; the amount of solvent fragments depends upon itstransfer activity.
Long-chain branching can be caused by the incorporation of theterminal double bond of a polymer molecule into a growing chain:
CHCl = CH---'VVv --+- tJN-CH2CHClCHCHCl'
~or by intermolecular chain transfer to polymer:
V\N'- CH2CHCl---J\Nv
Intramolecular chain transfer (back-biting) leads to the formationof short side chains:
ClHC
"
~CH2CHClCH2CHClCH2
ICHCl
//
CH2
71
6. PVC Product
Compounded PVC resins are converted to end products by severalprocesses. Extrusion (employing mostly mu1tip1e-scre~machines inEurope and mostly sing1e-scre~ machines in the United States) is usedto produce both rigid extrusions (e.g., pipe and conduit, siding andwindow sashes) and flexible extrusions (e.g., electrical ~ire
insulation, garden hose, and packaging film). To feed a large extruder,preheated, mixed compound in chip form may be conveyed from storageor directly from a mixing extruder.
Extrusion lines are engineered for the types of product~ to beextruded, from electrical wire insulation to pipe of 18 inches diameter.The extruders are continuously fed ~ith compound, ~hich is eitherpurchased or prepared in an on-site compounding plant. The approximatecost of a single extrusion line varies considerably depending on thesize of the extruder, its type and the auxiliary equipment.
Rigid and flexible vinyl sheets are generally produced on four-rollcalenders. The sheets may be combined with a fabric as it leaves thecalender, or this may be done subsequently in a separate laminatingstep.
Todays calenders run widths usually to 72 inches and some as broadas 92 inches, and they produce film and sheet at rates averaging morethan eight million pounds per year of compound (equivalent to 5.5-6million pounds of resin), depending on thickness (e.g., 2.5 millionpounds per year for light gauge rigid film, 4.5 million pounds peryear for heavier flexible film and higher rates for flexible sheeting).
Dispersions or plastisols are used for fabric coating (either onknife machines, roller coaters, or casting machines), and in theproduction of a low-cost type of vinyl floor tile where plastisol iscast on a felt base. Plastisols are also used in rotational molding(e.g., for toys and traffic cones) and in the dipping and hot-sprayingof tool handles and appliance parts.
The use of compression molding for PVC resins is restricted to theproduction of phonograph records. Injection molding of rigid PVC hasbeen developed largely in the 1960s and is mostly employed in theproduction of pipe fittings, and to a much smaller extent in theproduction of parts for communications equipment, business machines andtoys.
A complex and still emerging technology in the processing ofcompounded PVC resins is the blow-molding of containers.
72
III. plant Emissions
A. Continuous Air Emissions
1. Reclaim Vents
All producers reclaim unreacted monomer. These operationscan be one of the sources of air pollution in the production ofPVC. The reported vent streams in this category, along withtheir pollution control devices, are summarized in Tables IIIand IV.
2. Drying and Materials Handling Losses
After the PVC solids are dried, they are most often transportedin-plant via pneumatic conveying systems. The various atmosphericvents that are associated with these systems are a source ofhydrocarbon and particulate emissions. With suitable retentionmeanS such as cyclones and bag filters, continuous particulateemissions are present, but relatively small in amount. Emissionand control device data are summarized in Tables III and IV.
B. Intermittent Air Emissions
1. Routine In-Processing Venting
Some routine in-process venting is implicit where, for example,several batch-type reactors are operated in parallel. This ventinghas no significance relative to the SEI.
2. Start-Up and Emergency Vents
According to the questionnaire responses received, these ventsgo to atmosphere. The contribution to the SEI stemming from thesesources is negligible.
C. Waste Water
Process waste water arises from sources such as centrifugingand VCM stripping. The used water is 1) given treatment in-house,or 2) is sent out for handling by others, off-site.
One respondent (27-4) reports the system in use as developed incooperation with the U.S. EPA for demonstration of treatment methodsfor PVC waste waters. Reference - U. S. Government Printing Office,Project No. 12020 DJI.
D. Solid Wastes
1. Spent catalysts
PVC catalysts do not pose a solid waste problem. Although theliterature indicates numerous variations and nuances relative toPVC catalysts, the following explanation represents, in principle,the reason these catalysts pose no solid waste problem.
73
V. Significance of Pollution
Based on the comments below, it is recommended that polyvinyl chloridebe placed, at present, in a stand-by category relative to the petrochemicalswhich may qualify for in-depth study.
The methods outlined in Appendix IV of this report have been used toforecast the number of new polyvinyl chloride plants that will be built by1980, and to estimate the total weighted annual emissions from these newplants. This work is summarized in Tables V, VI and VII.
The Table V forecast of new plants is based on the assumption that thePVC growth rate will project on average ae an annual capacity increase ofabout 10 percent through 1980. A Significant Emission Index (SEI) of 4,840has been calculated. See Table VII. Of this total, 4,240 units stem fromhydrocarbon vapors. Total increased emissions (by 1980) of 63,000,000lbs./year are envisioned, based on the Table VII figures of 53 MM lbs./yearHC plus 10 MM lbs./year particulates.
If PVC qualifies later for an in-depth study, a further point appears towarrant consideration. The respondents "in tota" cover a wide spectrum withrespect to assignment of emissions tq 1) fugitive sources, and 2) all othersources. A significant portion of the reported emissions (to atmosphere) maybe shown under "Fugitive" or "Other" labelling in one instance, whereas"Fugitive Emissions" may appear to account for only a small portion or "none"of the total in another instance. As a constituent of an in-depth study,it would seem that further definition and resolution of this picture isrequired.
Factors for consideration in nominating PVC for a future in-depth studyinvolves the nature of the emitted particulates. The first of these is thefact that the material is inert. The second is the particle size distribution.One producer of PVC reports data indicating that the bulk of the particles infour separate samples of a suspension resin range between 100 and 250 microns,with only about 2 percent being smaller than 75 microns and 20 PPM (one sampleonly) being smaller than 15 microns. However, another producer, who admits hehas no data, has estimated the drier dust to be "very fine - perhaps less than20 microns".
76
VI. Polyvinyl Chloride Producers
The following tabulation of polyvinyl chloride producers indicatespublished production capacity.
Air Products &Chemicals, Inc.(Plastics Division)
Allied Chemical Corp.
American Chemical Corp.(jointly owned by ARCOChemical Company, divisionof Atlantic Richfield Co.and Stauffer Chemical Co.
Borden Inc.Borden Chemical, division
Continental Oil Co.Conoco Plastics Div.
Diamond Shamrock Corp.Diamond Shamrock ChemicalCo. subsidiary plasticsDivision
Ethyl Corp.Industrial Chemicals Div.
The Firestone Tire &Rubber CompanyFirestone Plastics Co.Division
The General Tire &Rubber Company,Chemical!Plastics Division
The B. F. Goodrich Co.B. F. Goodrich ChemicalCompany, Division
The Goodyear Tire &Rubber Company ChemicalDivision
Location
calvert City, Ky.pensacola, Florida
painesville, Ohio
Long Beach, Calif.
Illiopolis, Ill. )Leominster, Mass.)
Aberdeen, Miss.Oklahoma City, Oka.
Delaware City, Del.)Deer park, Texas )
Baton Rouge, La.
perryville, MarylandPottstown, Pa.
Ashtabula, Ohio
Long Beach, Calif.Henry, IllinoisLouisville, KentuckyAvon Lake, Ohiopedricktown, N. J.
plaquemine, La.Niagara Falls, N. Y.
77
Capacity - MM Lbs.!Year
12.050
no
125
240
220,80
250
180
130140
100
125125275125130
100100
Company
Great American ChemicalCorp.
Keysor-Century Corp.
Monsanto CompanyMonsanto Polymers &Petrochemicals Co.
National Starch &Chemical Corp.
Occidental Petroleum Corp.Hooker Chemical Corp.,subsidiaryRuco Division
Olin Corp.Thompson plastics Co.Division
pantasote Company
Stauffer Chemical Co.plastics Division
Tenneco Chemicals, Inc.(a major component of
Tenneco Inc.)Tenneco plastics Div.
Union Carbide Corp.Chemicals & Plastics Div.
Uniroya 1, Inc.Uniroyal Chemical,Division
Total capacity
Location
Fitchburg, Mass.
Saugus, Calif.
Springfield, Mass.
Meredosia, Ill.
Burlington, N. J.Hicksville, N. Y.
Assonet, Mass.
passaic, N. J. )Point pleasant, W. Va.)
Dela~are City, Del.
Burlington, N. J.Flemington, N. J.
Texas City, TexasSouth Charleston, W. Va.
Painesville, Ohio
78
capacity - MM Lbs.!Year
40
35
150
10
18010
150
120
160
16560
200120
140
4,375
rt:.-J.--.--IJ
79
TABLE PV-ICOMPOSITE POLYVINYL CHLORIDE
NET MATERIAL BAlANCE(TONS /TON OF PVC CAPACITY)
INPUT
Vinyl chloride monomer (VCM)Vinyl acetate monomer (VAM)PropyleneInitiators (catalysts)Suspending agentsSurface active agentsplasticizers, where used
Total Input
OUTPUT
PVC homopolymer and copolymerWaste solidsFugitive emissionsMonomer reclaim vent condenserResidual VCM from vinylChloride still bottoms streamEffluent from dryer collectorsFines from silo collectorsFines from baggers collectorsFines from bulk loading collectorsMonomer storageTotal Output
Stream No.on SimplifiedFlow Diagram
1234444
5678
910111213
80
PolymerIngredients Other
0.97000.08000.0038
0.00090.00050.0003
0.0001
1. 0539 0.0017
1.00000.03880.00200.0010
0.00020.01200.00030.00010.00030.00091.0556
TABLE PV-IIPOLYVINYL CHLORIDEGROSS HEAT BALANCE
The homopolymerization of vinyl chloride monomer occurs commerciallyaccording to four separate and distinct processes. There is one main reactionstep in each of the four processes in which initiators (via free radicalformation) induce the metamorphesis from monomer to polymer. ~Jing to thepaucity of published information on the. reaction thermal phenomena, however,there is no way to estimate suitably a gross heat balance from processinformation sources found in the public domain. However, the heat ofpolymerization is reported to be 650 BTU/lb.
81
TABL
EP
V-I
IIN
ATI
ON
AL
EM
iSSI
ON
SIN
VEN
TOR
YPO
LYV
INY
LC
HLO
RID
EP
age
1o
f8
::0 :-..l
Com
pany
Lo
cati
on
EPA
Cod
eN
o.ca
pac
ity
-T
ona
of
Po
lyv
iny
lC
hlo
rid
e/Y
r.A
vera
geP
rod
uct
ion
-T
ons
of
PV
C/Y
r.S
easo
nal
Ral
l.ge
inP
rod
uct
ion
-i.
of
Max
.E
mis
sion
sto
Atm
osph
ere
Str
eam
-l~tter
onFl
owD
iagr
amD
escr
ipti
on
Flow
-L
bs.
/Hr.
of
Po
llu
tan
tsFl
owC
hara
cte
rist
ic-
Co
nti
nu
ou
so
rIn
term
itte
nt
if
Inte
rmit
ten
t-
firs
.!Y
r.F
low
Com
posi
tion
-T
on/T
ono
fPV
CH
ydro
carb
ons
part
icu
late
sCO
Sam
ple
Lo
cati
on
Dat
eo
rF
requ
ency
of
Sam
plin
gT
ype
of
An
aly
sis
Odo
rP
rese
nt
Ven
t'S
tack
s
Flo
w-
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per
stac
kN
umbe
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eigh
t-
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eter
-In
ches
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itG
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ure
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mis
sion
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ntr
ol
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ice
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Fla
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rsC
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ater
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ber
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erca
talo
gI.
D.
Num
ber
To
tal
Hyd
roca
rbon
Em
issi
on
s~
Ton
/Ton
PVC
To
tal
Part
icu
late
-T
on/T
onPV
CT
ota
lNO
x-
Ton
/Ton
PVC
To
tal
sax
-T
on/T
onPV
CT
ota
lCO
-T
on/T
onPV
C
27
-13
7,5
00
37
,50
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inyl
Ch
lori
de
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tC
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nser
8 Can
tin
uo
ua
0.0
00
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ampl
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one
No 17
.2I 6
93 65 N
one
Ind
icat
ed
0.0
00
8
D Vin
yl
Ch
lori
de
'!~~~
~gnrt=ni;i'
12 Con
t.in
uous
0.0
01
0
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ampl
edN
one
No
Not
Ind
icat
ed1 50 1
.530 Y
es
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27
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01
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yl
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lori
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ll*
27
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x24
130
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sen
try
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ance
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.**
From
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gin
eeri
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Cal
cula
tio
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and
Pla
nt
Mat
eria
lB
alan
ce".
TABL
EP
V-I
IIN
ATI
ON
AL
EMIS
SIO
NS
INV
ENTO
RYPO
LYV
INY
LCH
LORI
DE
Pag
e2
of
8
co w
Com
pany
Lo
cati
on
EPA
Cod
eN
o.C
apac
ity
-T
ons
of
Po
lyv
iny
lC
hlo
rid
e/Y
r.A
vera
geP
rod
uct
ion
-T
ons
of
PVC
/Yr.
Sea
son
alR
ange
inP
rod
uct
ion
-%
of
Max
.E
mis
sion
sto
Atm
osph
ere
Str
eam
-L
ett
er
onF
low
Dia
gram
Des
crip
tio
n
Flow
-L
bs.
/Hr.
of
po
llu
tan
tsFl
owC
hara
cte
rist
ic-
'co
nti
nu
ou
so
rIn
term
itte
nt
ifIn
term
itte
nt
-H
rs./
Yr.
Flo
wC
ompo
siti
on-
Ton
/Ton
of
PVC
Hyd
roca
rbon
sp
art
icu
late
sCO
Sam
ple
Lo
cati
on
Dat
eo
rF
req
uen
cyo
fS
amp
lin
gT
ype
of
An
aly
sis
Odo
rP
rese
nt
Ven
tS
tack
s
Flow
-SC
FMp
erst
ack
Num
ber
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gh
t-
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eter
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ches
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itG
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Typ
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Fla
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ilte
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yclo
neW
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Scr
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log
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umbe
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ydro
carb
onE
mis
sio
ns
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on/T
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CT
ota
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art
icu
late
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on/T
onPV
CT
ota
lNO
x-
Ton
/Ton
PVC
To
tal
SOx
-T
on/T
onPV
CT
ota
lCO
-T
on/T
onPV
C
***4
,500
SCFM
tota
lfl
owfr
om12
silo
sth
rou
gh
22d
ust
co
llecto
rs.
27
-35
0,0
00
50
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GH
JK
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oB
agg
erB
ulk
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itiv
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ines
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llecto
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Em
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s
41
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tin
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on
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0.0
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00
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10
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03
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eN
one
Non
eN
otS
ampl
edN
otS
ampl
edN
otS
ampl
edN
one
Non
eN
one
No
No
No
***
500
1.5
00
***
32
7530
308
88
9595
95Y
esY
esY
es
XX
X
27
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04
27
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05
27
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06
0.0
02
00
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03
0.0
00
10
.00
03
DE
Vin
yl
Ch
lori
de
Dry
erV
ent
Con
dens
erC
oll
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rE
fflu
ent
12
Con
tinu
ous
Con
tinu
ous
0.00
020.
0003
Non
eN
one
Not
Sam
pled
Not
Sam
pled
Non
eN
one
No
No
0.0
12
5,0
00
11
5756
126
x4
645
150
Non
eIn
dic
ated
Yes
00~
Com
pany
Lo
cati
on
EPA
Cod
eN
o.ca
pac
ity
-T
ons
of
Po
lyv
iny
lC
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e/Y
r.A
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geP
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uct
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-T
ons
of
PVC
/Yr.
Sea
son
alR
ange
inP
rod
uct
ion
-%
of
Max
.E
Bt•
•io
ns
toA
tmos
pher
eS
trea
m-
Lett
er
onF
low
Dia
gram
Des
crip
tio
n
Flow
-L
bs.
/Hr.
of
Po
llu
tan
tsFl
owC
hara
cte
rist
ic-
Con
tinu
ous
or
Inte
rmit
ten
tif
Inte
rmit
ten
t-
Hrs
./Y
r.F
low
Com
posi
tion
-T
on/T
ono
fPV
CH
ydro
carb
ons
part
icu
late
sCO
Sam
ple
Lo
cati
on
Dat
eo
rF
requ
ency
of
Sam
plin
gT
ype
of
An
aly
sis
Odo
rP
rese
nt
Ven
tS
tack
s
Flow
-SC
FMp
erst
ack
Num
ber
Hei
ght
-F
eet
Dia
met
er-
Inch
esE
xit
Gas
Tem
pera
ture
-OF
Em
issi
onC
on
tro
lD
evic
eT
ype
-F
lare
Bag
Fil
ters
Cyc
lone
Wat
erS
cru
bb
erO
ther
Cat
alo
gI.
D.
Num
ber
To
tal
Hyd
roca
rbon
Em
issi
ons
-T
on/T
onPV
CT
ota
lP
art
icu
late
-T
on/T
onPV
CT
ota
lNO
x-
Ton
/Ton
PVC
To
tal
SOx
-T
on/T
onPV
CT
ota
lCO
-T
on/T
onPV
C
0.00
02
TABL
EP
V-I
IIN
ATI
ON
AL
EM
ISS
ION
SIN
VEN
TOR
YPO
LYV
INY
LCH
LORI
DE
U.O
.P.
Dus
tC
oll
ecto
r2
7-4
.10
1
0.00
03
27
-43
0,0
00
30,0
00o N
one
''Day
Sto
rag
e"C
oll
ecto
rF
ines
0.0
3C
onti
nuou
s
Neg
lig
ible
Non
eN
otS
ampl
edN
one
No
3,7
50
1 56 13x
1410
0Y
es x
27
-4.1
02
Neg
lig
ible
Page
3o
f8
G Bul
kS
tora
ge
Co
llec
tor
Fin
es
0.0
2C
onti
nuou
s
Neg
lig
ible
Non
eN
otS
ampl
edN
one
No 1,6
00
1 70 9 100
Yes x
27
-4.1
03
Neg
lig
ible
H Bag
ger
Co
llec
tor
Fin
es
0.0
2C
onti
nuou
s
Neg
lig
ible
Non
eN
otS
ampl
edN
one
No
2,2
00
1 29 10
x10
85 Yes x
27
-4.1
04
Neg
lig
ible
Com
pany
Lo
cati
on
EPA
Cod
eN
o.ca
pac
ity
-T
ons
of
Po
lyv
iny
lC
hlo
rid
e/Y
r.A
vera
geP
rod
uct
ion
-T
ons
of
PVC
/Yr.
Sea
son
alR
ange
inP
rod
uct
ion
-%
of
Max
.E
mis
sion
sto
Atm
osph
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Str
eam
-L
ett
er
onF
low
Dia
gram
Des
crip
tio
nB S
lurr
yT
ank
Ven
t
TABL
EP
V-I
IIN
ATI
ON
AL
EM
rstf
lON
SIN
VE
NT
lEY
POLY
VIN
YL
CH
LlE
IDE
C Cen
trif
ug
eV
ent
27
-54
7,5
00
47
,50
0o E D
ryer
Co
llecto
rE
fflu
ent*
***'
*-
Pag
e4
of
8
D Vin
yl
Ch
lori
de
Ven
tC
onde
nser
K Fu
git
ive
Em
issi
on
s
0.0
13
4
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59
90;
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pra
yD
rJer
38
,00
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es
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Flow
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bs.
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of
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llu
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rist
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nti
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ou
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rIn
term
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nt
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nt
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rs./
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ompo
siti
on-
Ton
/Ton
of
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roca
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sp
art
icu
late
sCO
Sam
ple
Lo
cati
on
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eo
rF
requ
ency
of
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plin
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ype
of
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aly
sis
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rP
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tack
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ber
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met
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Inch
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xit
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per
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OF
Em
issi
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ters
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ther
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icu
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Ton
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tal
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CT
ota
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C
****
Inte
rmit
ten
t
3 f 12 2 160
Non
e
Neg
lig
ible
****
Inte
rmit
ten
t
15 1 35 4 150
Non
e
Neg
lig
ible
823
Co
nti
nu
ou
s
0.0
59
90
.00
22
0.0
13
4N
one
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pled
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oR
ota
ryK
iln
33
,00
01 10
030
x36
180
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tC
oll
ecto
r
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nti
nu
ou
s
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03
4
Non
eN
otS
ampl
edN
one
No
Non
e
0.0
03
4
86
.1C
on
tin
uo
us
0.0
07
5
0.0
07
5
****
The
com
bin
atio
no
fst
ream
flo
wra
tean
dv
iny
lch
lori
de
com
po
siti
on
ran
ge
(of
0.0
to0
.5v
ol.
%)
ind
icate
dby
the
resp
on
den
tg
ive
neg
lig
ible
emis
sio
ns
eff
ects
.**
***R
espo
nden
t27
-5re
fers
to"c
ycl
on
es"
onpa
ge6
(a)
and
to"d
ust
co
llecto
r"on
page
6(f
),b
ut
un
der
''Sec
tio
nIV
,E
mis
sio
nC
on
tro
lD
evic
e",
hesa
ys.
"No
emis
sio
nco
ntr
ol
dev
ices
".If
anin
-dep
thst
ud
yen
sues
rela
tiv
eto
the
27-5
dat
a.,
the
defi
nit
ion
of
"em
issi
on
sco
ntr
ol
dev
ice"
sho
uld
be
rev
iew
edw
ith
the
resp
on
den
tan
dth
eq
ues
tio
nn
aire
dats
amen
ded
ifn
eces
sary
.F
urt
her,
itsh
ou
ldb
en
ote
dth
at
the
l~ryer
Co
llec
tor
Eff
luen
t"em
issi
on
data
are
calc
ula
ted
(to
the
excl
usi
on
of
sam
plin
gsn
dte
st
met
ho
ds)
.
h••
5o
fI
No
n'
No
tS..
.,le
dN
oni
No
ntI
nd
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ed
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04
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02
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12
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.11
22
1-6
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:0
.00
10
Com
pany
Lo
c.ti
on
EPA
Cod
.N
o.C
.p.c
ity
-T
On.
of
Po
lyv
iny
lC
hlo
rid
./Y
r.A
ver
ag.
Pro
du
ctio
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Ton
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fPV
C/Y
r.5
.48
on
l1R
Ing
'in
Pro
du
ctio
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'X.o
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ud
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pher
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tatt
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i'g
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crip
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n
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of
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nta
Plow
Ch
ar.
cte
rist
ic-
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nti
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t.rm
itt.
nt
ifIn
term
itte
nt"
Hr•
./Y
r.F
low
Com
posl
tio
n-
Ton
/Ton
of
PVC
HY
droc
'rbO
n.P
art
icu
l.te
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S'm
ple
Lo
c.ti
on
D.t
eo
rF
requ
ency
of
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nal
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Pr••
ent
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ent
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ck
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umet
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Tem
per
ltu
te..
lip'fli!'h~l
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ntn
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ypE
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iare
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tera
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ther
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alo
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umbe
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ota
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ns
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aU1
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icu
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ota1
NO
"-
Ton
lTon
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To
tdSO
x-
Ton
/Ton
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a1CO
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on/T
onPV
C
D Vin
yl
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Con
d.n•
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09
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eede
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r.It
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ain
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3'l.S
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Co
U'c
tor
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tS
tr•••
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r:: fUg
itiv
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ai.
do
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nti
nu
ou
.
0.0
01
0
****
**R
espo
nden
t2
7-6
incl
ud
esno
st.c
kin
form
atio
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rth
ese
atr
ea.
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and
po
llu
tan
tfl
ov
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ind
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at••
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thec~oI1UolI'
're
b..
...
OD.P
VC10
a4In
&••
ndIr
en
ot
qu
.nti
fied
.
TABL
EP
V-I
IIN
ATI
ON
AL
IMIS
SIiJL
i15IM
lfrO
RY
POLY
VIN
YL
CH
L<ll.
IDZ
l'lIg
e6
of
8
ex>
-...J
Com
pany
Lo
cati
on
EPA
Cod
eN
o.ca
pac
ity
-T
ons
of
Po
lyv
iny
lC
hlo
rid
e/Y
r.A
vera
geP
rod
uct
ion
-T
ons
of
PVC
/Yr.
Sea
son
alR
ange
inP
rod
uct
ion
-%
of
Max
.E
mis
sion
sto
Atm
osph
ere
Str
eam
-L
ett
er
onFl
owD
iagr
amD
escr
ipti
on
Flo
w-
Lb
s./H
r.o
fp
oll
uta
nts
Flow
Ch
ara
cte
rist
ic-
Con
tinu
ous
or
Inte
rmit
ten
tif
Inte
rmit
ten
t-
Hrs
./Y
r.F
low
Com
posi
tion
-T
on/T
ono
fPV
CH
ydro
carb
ons
Par
ticu
late
'sco
Sam
ple
Lo
cati
on
Dat
eo
rF
requ
ency
of
Sam
plin
gT
ype
of
An
aly
sis
Odo
rP
rese
nt
ven
tS
tack
s
Flo
w·
SCFM
per
stack
Num
ber
Hei
ght
-F
eet
Dia
met
er·-
Inch
esE
xit
Gas
Tem
pera
ture
•OF
Em
issi
onC
on
tro
lD
evic
eT
ype
-F
lare
Bag
Fil
ters
Cyc
lone
Wat
erS
cru
bb
erO
ther
Cat
alo
gI.
D.
Num
ber
To
tal
Hyd
roca
rbon
Em
issi
ons
-T
on/T
onPV
CT
ota
lp
art
icu
late
-T
on/T
onPV
CT
ota
lNO
x-
Ton
/Ton
PVC
To
tal
SOx
-T
on/T
onPV
CT
ota
lCO
-T
on/T
onPV
C
E Dry
erC
oll
ecto
rE
fflu
en
t
9 Co
nti
nu
ou
s
0.0
00
7
Non
eN
otS
ampl
edN
one
Non
eIn
dic
ated
54
,00
01 90 32
x42
130
-15
0Y
es**
****
*
"Dus
tC
oll
ecto
r"**
****
*0.
0007
27
-76
2.5
00
61
.70
0(E
stim
ated
)7
.7
G Sil
oC
oll
ecto
rE
fflu
en
t
0.3
Con
tinu
ous
Heg
lig
ible
Non
eN
otS
ampl
edN
one
Non
eIn
dic
ated
1,5
00
3(g
ues
s)"6
5-
82
""2
0-
31
""A
bout
Am
biel
lt"
yes*
****
**
''Dus
tC
oll
ecto
r"**
****
*
F ''Str
ipp
blg
Ven
t"
10 Con
tinu
ous
0.0
00
7
Non
eN
otS
ampl
edN
one
Non
eIn
dic
ated
"1,0
00
Lbs
./D
ay(7
5%H
20,
bab
nce
VC
M)"
1 38 3 21
2
0.0
00
7
****
***F
orin
-dep
thst
ud
yu
sin
g27
-7in
form
atio
n,
"Em
issi
on
Co
ntr
ol
Dev
ice"
defi
nit
ion
,,'ou
ldre
qu
ire
cla
rifi
cati
on
toth
eth
ere
spo
nd
ent.
sin
cehe
rep
ort
sfo
rth
isca
teg
ory
onth
e,q
ues
tio
nn
aire
:"N
otA
pp
lica
ble
".
TABL
EP
V-I
IIN
ATI
IX1I
AL
mass
l.IN
VE
lmlI
YPO
LYV
INY
LCH
LORI
DE
Pag
e7
of
8
Com
pany
Lo
cati
on
EPA
code
No.
Cap
acit
y-
Ton
so
fP
oly
vin
yl
Ch
lori
de/
Yr.
Ave
rage
Pro
du
ctio
n-
Ton
so
fPV
C/Y
r.S
easo
nal
Ran
gein
Pro
du
ctio
n-
%o
fM
ax.
Em
issi
ons
toA
tmos
pher
eS
trea
m-
Lett
er·
onF
low
Dia
gram
Des
crip
tio
n
Flow
-L
bs.
/Hr.
of
Po
llu
tan
tsF
low
Ch
ara
cte
rist
ic-
Co
nti
nu
ou
so
rIn
term
itte
nt
ifIn
term
itte
nt
-H
rs./
Yr.
Flo
wC
ompo
siti
on-
Ton
/Ton
of
PVC
Hyd
roca
rbon
sP
art
icu
late
sCO
Sam
ple
Lo
cati
on
Dat
eo
rF
requ
ency
of
Sam
plin
gT
ype
of
An
aly
sis
Odo
rP
rese
nt
COV
ent
Sta
cks
COF
low
-SC
FMp
erst
ack
Num
ber
Hei
gh
t-
Fee
tD
iam
eter
-In
ches
Ex
itG
asT
emp
erat
ure
-OF
Em
issi
on
Co
ntr
ol
Dev
ice
Typ
e-
Fla
reB
agF
ilte
rsC
yclo
neW
ater
Scr
ub
ber
Oth
erca
talo
gI.
D.
Num
ber
To
tal
Hyd
roca
rbon
Em
issi
on
s-
Ton
/Ton
PVC
To
tal
part
icu
late
-T
on/T
onPV
CT
ota
lNO
x-
Ton
/Ton
PVC
To
tal
SOx
-T
on/T
onPV
CT
ota
lCO
-T
on/T
onPV
C
A Vin
yl
Ace
tate
Sto
rag
eV
ent
it;A
ve.
Inte
rmit
ten
tN
otIn
dic
ate
d
0.0
00
9
Non
eN
otS
ampl
edN
one
Not
Ind
icate
dN
one
Non
e
0.0
00
9
27
-'7
0,0
00
70
,00
0o
B Rea
cto
ran
dB
len
dT
ank
Are
aE
mis
sio
ns
281
Con
tinu
ous*
****
***
0.0
17
6
Non
eN
otS
ampl
edN
one
Not
Ind
icate
d
"1,6
81
Lb
s./H
r."
1 60 "0.6
Ft,
"21
2N
one
0.0
17
6
(AS8
U11
18d)
E Dry
erC
oll
ecto
rE
fflu
en
t
8 Co
nti
nu
ou
s
0.0
00
5
Non
eN
otS
ampl
edN
one
Not
Ind
icate
d
"125
,883
Lb
s./H
r."
1 20 24 104
Yes x 27
-8.1
03
0.0
00
5
E Dry
erC
oll
ecto
rE
fflu
en
t
10 Co
nti
nu
ou
s
0.0
00
6
Non
eN
otS
ampl
edN
one
Not
Ind
icate
d
"13
2,0
10
Lb
s./H
r."
1 20 30 104
Yes x 27
-8.1
02
0.0
00
6
****
****
Ifre
spo
nd
ent
27
-8in
form
atio
nbe
com
esa
co
ntr
ub
tio
nto
in-d
ep
thst
ud
yacti
vit
ies,
this
stre
amsh
ou
ldb
ere
vie..d
.T
hefi
gu
res
sup
pli
edin
the
~uestionnaire
are
det
erm
ined
by"e
ng
inee
rin
gcalc
ula
tio
ns
and
des
ign
flo
wsh
eet,
pla
nt
mate
rial
bal
ance
sco
nfi
rm".
TABL
EPV
MII
IN
ATI
ON
AL
EMIS
SIO
NS
INV
EN
T<F
lPO
LYV
INY
LCH
LORI
DE
page
8o
f8
Com
pany
Lo
cati
on
EPA
Cod
eN
o.ca
pac
ity
~T
ons
of
Po
lyv
iny
lC
hlo
rid
e/Y
r.A
vera
geP
rod
uct
ion
~T
ons
of
PVC
/Yr.
Sea
son
alR
ange
inP
rod
uct
ion
-%
of
Max
.E
mis
sion
sto
Atm
osph
ere
Str
eam
-L
ett
er
onFl
owD
iagr
amD
escr
ipti
on
B Rea
cto
rA
rea
Em
issi
on
s
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EPV
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POLY
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27
-6.1
12
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.
27
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1965
100M
1970
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27
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1970
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27
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27
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num
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nd
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~
TABL
EPV
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MBE
RO
F~W
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1980
Cu
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ort
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ause
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Styrene
Table of Contents
Section
I.II.III.IV.V.VI.
IntroductionProcess DescriptionPlant EmissionsEmission ControlSignificance of pollutionStyrene Producers
List of Illustrations and Tables
Flow DiagramNet Material BalanceGross Heat BalanceEmission Inventorycatalog of Emission Control DevicesNumber of New Plants by 1980Emission Source SummaryWeighted Emission Rates
96
ST-lST-2ST-3ST-6ST-7ST-8
Figure ST-1Table ST-1Table ST-IITable ST-IIITable ST-IVTable ST-VTable ST-VITable ST-VII
Table of Contents
Section
I.II.III.IV.V.VI.
IntroductionProcess DescriptionPlant EmissionsEmission ControlSignificance of pollutionStyrene Producers
List of Illustrations and Tables
Flow DiagramNet Material BalanceGross Heat BalanceEmission InventoryCatalog of Emission Control DevicesNumber of New Plants by 1980Emission Source SummaryWeighted Emission Rates
97
ST-lST-2ST-3ST-6ST-7ST-8
Figure ST-ITable ST-ITable ST-IITable ST-IIITable ST-IVTable ST-VTable ST-VITable ST-VII
I. Introduction
Styrene is an important intermediate for the manufacture of polymericmaterials. It is used extensively in the manufacture of plastics includingpolystyrene, rubber modified impact polystyrene, acrylonitrile-butadienestyrene terpolymer, styrene-acrylonitrile copolymer and for the productionof styrene-butadiene synthetic rubber.
Commercial production began on a small scale shortly before World War II.Today over five and one half billion pounds are produced a year. Styrenecapacity is expected to grow to ten billion lbs./year by 1980.
The only commercial process to make styrene, which is in use today, iscatalytic dehydrogenation of ethylbenzene. The styrene produced is of ahigh quality and can be polymerized into high grade polymer.
Emissions from styrene production are lo~ in comparison ~ith other processessurveyed. The emissions result from distillation column vents, fuel consumption,storage tank losses and miscellaneous leaks and spills.
II. Process Description
Direct dehydrogenation is the only commercial process currently employedfor the manufacture of styrene. There are two major routes used to producethe monomer. The major one is the adiabatic process developed by DovChemical Company. Ethylbenzene is preheated with steam and by heat interchangeto 5200 C. Superheated steam, 7100 C, and ethy1benzene vapors are fed intoan adiabatic reactor at 6500 C with a steam to ethylbenzene ratio of 2-3 to 1.Both ethylbenzene and styrene are subject to thermal decomposition at temperatures in excess of 6100 C, but it is desirable to maintain temperaturesapproaching this figure to maximize conversion. The reactor contains aselective dehydrogenation catalyst such as zinc, chromium, iron or magnesiumoxide. The catalyst operates continuously and has a long life (about oneyear). The steam serves the dual purpose of supplying heat to the reaction,which is endothermic by 540 - 570 BTU/lb. ethylbenzene converted and actingas a dilutant to bolster conversion, which would otherwise be low due to thevolume change caused by the reaction. Conversion per pass is about 35 - 40%ethylbenzene reacted with yields of 90 - 92%. (See Figure ST-I)
The major diffe~ence between the isothermal reactor and the processdescribed above lies in the means of supplying heat for the reaction. Theisothermal process uses either heat exchange systems or flue gas to keep thereactants at a suitable temperature, about 585 0 C. It does have the advantagesof lower steam consumption and less chance of thermal cracking. Conversions,yields and catalyst type are similar to the adiabatic process.
The reactor effluent is cooled first by incoming ethylbenzene and then bysteam in heat exchangers. A condenser liquifies the steam, styrene, toluene,benzene and heavy products while the vent gases containing hydrogen, carbondioxide and methane are sent to a recovery system. The non-condensables fromthis gas stream are used as fuel. The condensed material passes to a settlingtank where the hydrocarbons are decanted and water is discharged to a disposalsystem.
The crude styrene is passed through a sulfur pot (sulfur acts as a polymerization inhibitor) and is then ready for vacuum distillation. vacuumdistillation is used to keep temperatures lov and minimize polymerization ofstyrene. In most cases, the first distillation separates benzene, tolueneand residual v,ater as overhead product. The benzene and toluene are redistilledin a small column and stored. The ethylbenzene-styrene mixture from the firsttover is then separated with ethylbenzene going overhead and recycled to thedehydrogenation step. The styrene bottoms containing about one percentethylbenzene is ready for final finishing. This can be done either in batchstills or more often in a continuous distillation column. The overhead fromthis column is styrene and the bottoms tar, polymer and sulfur. Tert-butylcatecholis usually added to the styrene during final finishing and 8torage to retardpolymerization.
The main reaction is:
ethylbenzene styrene
but there is Some "cracking" to benzene and toluene plus ethane, ethylene andmethane.
Material and heat balances are giv€n~in Tables I and II, respectively.
99
III. plant Emissions
A. Continuous Air Emissions
1. Distillation Vents
Non-condensibles and small amounts of condensible organicvapors are released from each of the three distillation columnsemployed in the process. Almost all respondents reported Some kindof condensible vapor conservation system in use to recover valuablerecycle materials and products. Since the type of system in usevaries, the quantity of air emissions released would vary accordingly.More than half of the plants reported negligible pollutants fromthese vents.
Typically, light gases such as hydrogen, carbon dioxide andmethane as well as small amounts of benzene, toluene and water arereleased from the benzene-toluene recovery column vent. Water andethy1benzene are vented from the ethy1benzene recovery column vent.Small amounts of styrene and water were reported from the finishingcolumn vent. A plant which listed no vapor recovery system hadtotal hydrocarbon emissions of .00417 lbs./1b. styrene from thedistillation section. The best operated recovery system reportedzero emissions to the atmosphere from the columns.
2. Furnace Flue Gas
Fuel gas containing hydrogen, methane, C02 and organic vaporsproduced by the process is combined with natural gas and burned toprovide the heat necessary to superheat the steam. Combustion isalmost totally complete to C02 and H20. Only one plant reportedany particulate products and the amount mentioned was small .000091bs./1b. styrene. NOx formation is estimated to be 30 PPM, whichis approximately .00002 1bs./1b. styrene. Low sulfur or zerosulfur natural gas is used in all cases~
3. Hydrogen Scrubber Vent
One plant 28-5 sells part of the hydrogen in the fuel gas aseconomics dictates. They employ a scrubber for this purpose. Onlycarbon dioxide and water are released from the scrubber vent.
4. Stripper Vent
Respondent 28-2 reports that a stripper is used before primarydistillation, and emits .00096 1bs. of toluene/lb. of styrene, and.0032 lbs. of ethy1benzene/lb. of styrene, as well as water into· theatmosphere through the stripper vent.
5. Storage Tank Vent
Losses due to storage vents are estimated to be 370,000 1bs./yearby respondent 28-6. This amounts to .00067 1bs. of hydrocarbons/lb.styrene. Respondent 28-8 estimates his losses to be .00003 1bs.of hydrocarbons per lb. styrene. Obviously, the method of storagetank vapor conservation is the prime determining factor whenstudying tank losses.
100
B. Intermittent Air Emissions
1. Start-Up and Emergency Vents
During start-up or emergency conditions, gas from the reactorand/or the fuel gas stream are vented. These emergencies arereported to occur about two times a year for 2 - 36 hours.Emissions from the fuel gas emergency vent are reported on ayearly basis by respondent 28-9 to be .00003 lbs. of C02/lb. ofstyrene, negligible amounts of H2 and methane and and .00051 lbs.of benzene, toluene and styrene/lb. of styrene. About half of theplants reported Some kine of flare system to handle emergency emissions.In that case, carbon dioxide and water would be essentially the onlyemissions released under emergency conditions.
Reported air emissions and emission control data are summarizedin Tables III and IV.
Co Waste Water
A large quantity of water is needed for process steam and forcooling purposes. In all cases the waste water is either treatedon-site and reused or treated and discharged. Water requirementsare summarized below.
EPA Code
28-228-3 (1)
28-6 (1)28-728-8
Discharge Flow (GPM)
No discharges0.54.5
73535065
Treatment
Neutralization,filtrationUntreated (cooling towerblowdown)
Treated and reusedTreatedUsed in another processthen treated.
(1) Combined waste water from benzene to ethylbenzene process andethylbenzene to styrene process.
D. Solid Wastes
1. Spent catalyst
About 500 Ibs. of catalyst is disposed of for every millionpounds of styrene capacity. The waste is usually sent to land fill.
2. Filter Aid
Respondent 28-5 reported disposal of 14,000 lbs./year of filteraid in sanitary land fill.
E. Odors
The production of styrene does not appear to present an odorproblem. No respondent reported any odor complaints or seriousodor problems.
101
F. Fugitive Emissions
Only respondent 28-3 provided any estimate of emissions dueto pipe leaks and spills •. The estimate provided is for a combinedprocess making styrene directly from benzene. .00015 lbs. ofhydrocarbons per lb. of styrene are emitted by the entire process.
G. unreported Emissions
None of the respondents reported air emissions resulting fromthe disposal of the tarry residue from the styrene finishing column.It is believed that this stream contains most, if not all, of thesulfur added as a polymerization inhibitor, and that it might beincinerated. The emission of sulfur dioxide resulting from thisoperation has been estimated to be about 0.014 lbs./lb. of styrenewhich is equivalent to 140 million lbs. of sulfur dioxide per yearby 1980. If this emission were to be considered in the calculationof a Significant Emission Index, it would increase the SEI by about1200 units.
102-/
IV. Emissions Control
The emission control devices that have been reported as being employed bystyrene producers are summarily described in Table IV of this report. Anefficiency has been assigned each device whenever data sufficient to calculateit have been made available. Three types of efficiencies have been calculated.
(1) "CCR" - Completeness of Combustion Rating
CCR = lbs. of 02 reacting (with pollutant in device feed) x 100lbs. of 02 that theoretically could react
(2) "SE" - Specific Efficiency
SE = specific pollutants in - specific pollutan~ut x 100specific pollutant in
(3) "SERR" - Significance of Emission Reduction Rating
SERR = (pollutant x weighting factor)in - (pollutant x weightingfactor)out
(pollutant x weighting factor*)inx 100
*Weighting factor same as Table VII weighting factor
Normally a combustion type device (i.e., incinerator, flare, etc) will beassigned both a "CCR" and a "SERR" rating, whereas a non-combustion typedevice will be assigned an "SE" and/or an "SERR" rating. A more completedescription of this rating method may be found in Appendix V.
Condensible vapor Recovery
All respondents except for one report some vapor recovery system fororganic vapors vented from the distillation columns. Their primary purposeis to recover valuable benzene, toluene and styrene but since these componentswould be vented to the atmosphere if not for the system, these devices areincluded in Table IV - Catalog of Emission Control Devices and described below.
Respondents 28-3, 28-7 and 28-8 use a combination condenser, steam ejectorand hotwell system. Vapors vented from the overhead accumulator are condensedby heat exchange with cooling water. Most of the unrecovered vapors from thecondenser are then recovered in the hotwell through steam ejection. Only smallamounts of hydrocarbons vent from the hotwell. Efficiencies are high near 100%in most cases. Respondent 28-6 uses three condensers only. Although thedetails are not spelled out, no emissions are reported from the distillationarea.
Flares
Flares are employed in a number of different areas in the various styreneplants reporting. Flares are used to burn gas vented from the reactor or fuelgas line in an emergency condition in plant 28-3, to burn irritating styrenevapors from the storage area in plant 28-5 and to burn unrecovered fuel gas inplant 28-6.
103 ;
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 releasedas air emissions is less .for the subject process than for other processesthat are currently being surveyed.
The methods outlined in Appendix IV of this reporthave been used to forecast the number of new plants that will be built by1980 and to estimate the total weighted annual emission of pollutants fromthese new plants.
The Table V forecast of 1980 U. S. capacity is based upon informationreceived from a Process Research Inc. report for the EPA. The expected growthrate for styrene is eight'percent a year.
On a weighted emission basis a Significant Emission Index of 255 hasbeen calculated in Table VII. This is substantially lower than the SEIlsof other processes currently being surveyed. Hence, the recommendation toexclude an in-depth study of the subject process from the overall scope ofwork for this project.
VI. Styrene Producers
Producers (1)
AmocoCos-MarDowDowEl pasoFoster GrantGulfMonsantoShell (2)Sinclair-KoppersSinclair-KoppersSuntideUnion carbideCosden (3)
Location
Texas City, TexasCarville, La.Freeport, TexasMidland, MichiganOdessa, TexasBaton Rouge, La.Donaldsville, La.Texas City, TexasTorrance, Calif.Houston, TexasKobuta, PatCorpus Christi, TexasSeadrift, TexasBig Spring, Texas
capacity MM Lbs./Yr.
800530693.5350120720500
1,300240110200
80310
-.LlOO)
Total = 5,953.5
(1) Chern. Profiles, February 21, 1972(2) Currently not operating(3) Stand-by
11_~_--_---1--~]J
106
~~:;!I.~ ~ ~
'rA'BL
ES
T-I
lfATE
R:J:A
LBA
LAN
CEST
YRE
NE
PRO
DU
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N
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eam
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(2)
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et.•
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ne
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48
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98
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15
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lfu
r'.0
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.00
70
I,
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ren
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00
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)'I
i}
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00
()
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zen
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34
5(
).0
31
4,!
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0.0
001
II,
(.0
00
2)
II
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~j
(1)
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ad
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(2)
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and
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.
TABLE ST-IIHEAT BALANCE (REACTOR SECTION) (1)
STYRENE PRODUCTION
Heat In
1) Enthalpy of ethy1benzenevapor (6500 C) (2)
2) Enthalpy of steam (6500 C)
Heat Out
1) Endothermic heat of reaction
2) Residual enthalpy of product~
(5900 C) and steam
Total
1,681
13 ,452
15,133 BTU/Lb. of Ethy1benzene
570
14,563
(1) For an adiabatic reactor.(2) Base temperature - 25 0 C.
108
Total = 15,133 BTU/Lb. of Ethy1benzene
TA
BL
E.S
T-I
III
NA
TIO
NA
LEM
ISSI
ON
SIN
VEN
TOR
YS
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llE
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lle
1o
f7
o 1.0
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ing
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HO
hlti
UV
altt
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D Fu
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a.)'
lue
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1 in 111.
648
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(1)
Em
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ency
Fla
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Ul!
1(2
)
1 275
24 Unk
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l
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No
++ + + +
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on
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t
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e
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aN
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nu
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s
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Cd
c'd
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o
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( I
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01
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08
5.5
Co
nti
nu
ou
s
1 16 2 135
1.6
I ~es
28·1
250,
000
250,
000
.000
54o o o o
Non
e
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Calc
'd.
No
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08
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nd
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Yes
No
ne
CsI
c'd
.N
o
A Pri
mar
yD
isti
llati
on
Hot
we1
1v
ent
82 Co
nt1
nu
ou
sF
low
-L
bs./
Hr.
Flo
wC
hara
cte
rist
ic-
Co
nti
nu
ou
so
rIn
term
itte
nt
ifIn
term
itte
nt
-H
rs./
Yr.
of
Flo
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om
po
siti
on
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on
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on
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Sty
ren
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ydro
gen
Met
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Eth
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ne
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Cer
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Mon
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arb
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Dio
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To
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thy
lb'''
'zen
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lne
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mat
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Su
Hu
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ater
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nera
tor
Refr
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Co
nd
ense
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rber
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ub
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An
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Dat
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req
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orP
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lem
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uta
nts
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dro
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Ton
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late
s,T
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so
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Pro
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D.
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(1)
f'j
:=
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are
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(2)
Info
rmati
on
ab
ou
tth
ese
stre
am
slV
asl
ah
ele
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nfi
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tial.
AB
(1)
DP
rim
ary
Sac
on
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trip
per
Fu
r"'c
eD
isti
llati
on
Ven
tD
i.li
tiU
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on
Ven
tv
ent
flu
eG
n
950
100
400
472,
000
Con
tinu
ous
Co
nti
nu
Ou
8C
on
tin
uo
u.
Co
nti
nu
ou
,
•
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10
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UL!
;:S
T-n
IN
AT
lON
AtE
mS
SIO
NS
INV
ENTO
RYSY
TREN
E
28-2
650,
000
650.
000
... ... 0,
EPA
CQ
deN
o.C
apac
ity
-T
ons
of
Sty
Ten
e/Y
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ver
age
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./U
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rist
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nti
nu
ou
so
rIn
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nt
ifIn
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nt
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rs./
Yr.
of
Flo
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om
po
siti
on
-T
on
lTo
no
fS
tyre
ne
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dro
sen
Met
h8ll
eE
thy
len
eE
than
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ide
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bon
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ene
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on
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mat
ics
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lfu
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ide
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ide
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rog
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ater
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gen
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itGa
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nd
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ate
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qu
ency
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ng
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ple
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tern
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mar
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oll
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e
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31
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ied
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eN
otS
pecif
ied
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ecH
iee!
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e
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cula
tee!
No
.004
27 o.0
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.000
03 o
Pag
e2
of
7·
.000
96.0
0032
.001
28
Not
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ed
fiee!
110
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e
Calc
ula
ted
No
.198
72
.000
032.
2506
.000
35.4
6154
.110
92
2 170
120
540
65,2
00N
o 6-9-
12In
Str
ea.
.U
nkno
....
No
(1)
Str
ipp
er
no
tsh
o"m
infl
ow
dia
gra
m,
itpreceed~
pri
mary
dis
till
ati
on
colu
mn
.
EPA
Cod
eN
o.cap
.cit
y-
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ao
fS
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ne/V
r.A
vera
geP
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uct
ion
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ona
of
Sty
ren
e/Y
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mis
sio
ns
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tmoa
pher
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mI.
D.
Str
eam
Fu
git
t'"
E.h
aiQ
rl,
9.6
(3)
Inte
r,.i
tten
t8
70
0
DF
ura
nce
Flu
ee.
.
24
,02
5C
on
tin
uo
u,
Non
eN
one
()
(.0
00
11
)(
)
,calc
".'U
)~lculated
No
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oN
o
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e
Ye.
+
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ec1
fied
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rmit
ten
tN
ot
Sp
ecif
ied
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ecif
ied
a
+Fl
Em
erg"
ncy
Fu
elee.
,lare
pag
e3
of
7
IER
dcto
rlm
erg
ency
Vei
lt
Unk
now
nIn
term
itte
nt
.02 ++ + +
No
No
Yea
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y(2
)In
Str
....
Li".~ea.
Chr
....
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1
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ted
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t
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IC
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ult
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j"Ii
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uid
Sam
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ng
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e
!,j
TAB~"ST~lIl
"N
ATI
ON
AL
EM
1jIO
NS
tllV
llIIT
OR
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t
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calc
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at..d
No
Yes
No
neA
Pri
mar
yD
isti
lI.U
on
,K
otw
ell
Ven
t
1 10 120
)0;::'0 C
on
tin
uo
us
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..•
J.b
a./H
r.Fl
o,",
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.-ra
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isti
c..
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nti
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OU
Bo
rIn
term
itte
nt
ifIn
term
itte
nt
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ra./
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Flo
.'C
om
po
siti
on
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on
s/T
on
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Sty
ren
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gen
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hane
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yle
pe
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ane
carb
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oxid
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arbo
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iox
ide
Be
nze
ne
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luen
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thy
le"e
ben
,.en
eS
tyre
ne
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rom
atic
sS
ulf
ur
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xid
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ydro
gen
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lfid
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itro
gen
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ater
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ticu
hte
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nn
ald
ehy
de
Ven
tS
tack
s~U
filb
et',
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gh
t,-
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llia
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tet
-lo
tlld
Ex
itca
.T
e",p
.•
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fM/S
tael
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mlu
tMeM
tt"l
Del
/ltU
Fla~e/Incinerator
Refr
igera
tor
/co
nd
ense
rA
bso
rber
IScr
ub
ber
Oth
er
An
aly
sis
Dat
eo
rFre~ueney
of
S.m
pli
ng
Sam
ple
Tap
Lo
cati
on
Typ
eo
fA
nal
ysi
sO
dor
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bIe
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umm
ary
of
Air
po
llu
tan
tsll
yd
'ro
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on
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ono
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ne
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icu
late
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on
/To
no
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tyre
ne
NOx
...T
on
/To
no
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tyre
ne
50•
•T
on/T
ono
f5
tyre
ne
CO..
To
n/T
on
of
Sty
ren
e
... ... ......
(I)
Res
pond
ent
use
dp
ub
lic
healt
hse
rvic
ep
ub
licati
on
No.
999-
1.1'
-42.
(2)
Sam
ple
du
nd
ern
on
-em
erg
ency
co
nd
itio
ns
on
ly.
(J)
Est
imat
edb
yH
oudr
yh
ased
onre
spo
nd
en
tsin
form
ati
on
.
TAg!
'!::
.ST
-III
NA
TIO
NA
LE
"S
ION
SIN
VE
NT
llI\Y
!..~
"'.~8·5
t!l~.
750
34
6,7
50
pege
4o
f7
.
EPA
code
No.
Cap
acit
y-
Ton
so
fSty~ene/Yr.
Ave
rage
Pro
du
ctio
n-
Ton
so
fS
tyre
ne/
Yr.
Em
issi
on
sto
Atm
osp
her
eS
trea
m1
.D
,St~eam
ER
.«ct
or
Em
erg.
ncy
V.n
t~
Scr
ub
ber
Ven
t(3
)
oF
ur.
ec.
Flu
eC
is(5
)S
tora
ge
to..
..to
Fla
re-
l'ro
du
ctf
... ... N
No
w-
Lbs
./H~.
Flo
wC
hara
cte
rist
ic-
Co
nti
nu
ou
so
rIn
ter-
mit
ten
tif
Inte~mitte
nt
-M
rs.N
r.F
low
Co
mp
osi
tio
n-
To
n/t
on
Sty
ren
eH
ydro
gen
Met
hane
Eth
yle
ne
Eth
ane
Ca~bon
Mon
oxid
eC
arbo
nD
iox
ide
Be
nze
ne
To
luen
eE
thy
lB
enze
neS
tyre
ne
Non
-Aro
mat
ics
Sulfu~
Dio
xid
eH
ydro
gen
Su
lfid
eN
itro
gen
NO
x~Bter
part
icu
late
Ven
tS
tsck
sN
umbe
rH
eig
ht
-F
t.D
iam
eter
-In
ches
Ex
itG
8S
Tem
p.-
FO
SC
rM/S
tack
I!m
is.i
on
Co
ntr
ol
Dev
ices
flare
/In
ein
era
tor
Ref
rig
erat
or/
Co
nd
ense
rA
bso
rber
/Scr
ub
ber
Oth
ar.
An
ely
sis
Oat
"o
rfr
equ
ency
of
Sam
pli
ng
Sam
ple
tap
Lo
cati
on
Typ
eo
fA
naly
sis
Odo
rP
rob
lem
Su,
""",
ryo
fA
irP
oll
uta
nts
Hyd
roca
rbon
s-
Ton
/Ton
of
Sty
ran
eP
art
icu
late
s-
Ton
/Ton
of
Sty
ren
eNO
x•
Ton
/Ton
of
Sty
ren
eSO
x-
Ton
/Ton
of
Sty
ren
eCO
•T
on/T
ono
fS
tyre
ne
(1)
Inte
rmit
ten
tN
otS
pec
1f1
ad
.000
004
+ +.0
00
00
9.0
0000
2
.000
007
.000
004
.000
0074
'
4 75 20 50 380
No Yes
(2)
Infr
eq
uen
tly
Com
pres
sor
tin
e'C
hrom
atog
raph
No
•
1,3
99
Co
nti
nu
ou
s
.00
37
8
.01
39
0
1.3
0 3 100
429
Yea
Non
e
No
.00
00
2o
Neg
1l.
g1
U.
o o
(6)
Co
nti
nu
ou
s
(7) ... +
(7)
27 67 36 500
1350
No
Non
e
No
(8)
Co
nti
nu
ou
s
(9)
(9)
Non
e
y..
YU
Con
tln\
loue
Chr
omat
ogra
phN
o(1
1)
(1)
23
.%2
Ibs/y
r.(2
)S
ampl
edu
nd
erno
rmal
op
era
tin
gco
nd
itio
ns.
0)
From
112
scru
bb
er,"
hie
his
bef
ore
dis
till
ati
on
syst
em(n
ots
ho
wo
on
flo
wdtag~am).
\"'I
flo~.
isv
ari
ah
led
epen
din
go
nH
2cu
sto
mer
nee
ds
(av
erag
efl
ow
rate
giv
en
).t5
)Furna<:,~s
bu
rnbo
t.h
fuel
gas
and
li~uid
,"'8
stee.
(6)
(7)
(8)
(9)
(0
)(1
1)
Fu
elco
nsu
mp
tio
nis
co
nfi
den
tial
no
ten
ougb
info
rmet
ion
giv
ento
calc
ule
te"u
en
tity
of
com
bu
stio
np
rod
uct
s,07
.su
lfu
rfu
el
use
d.
tbere
fore
,co
mp
lete
cOll
bu
stio
nto
CO2
and
"20
..s
umed
.R
ele
tiv
eel
DO
unts
of
CO2
and
"20
dep
end
son
fuel
nau
irem
en
ts.
vari
ab
led
epen
din
go
n~ate
of
tan
kfH
Hn
g.
Com
plet
eco
mb
ust
ion
toH
20an
dCO
2es
sum
ed.
Co
nti
nu
ou
ssa
mp
lin
gfo~
sty
ren
evapo~s,
Cou
ld.p
rese
nt
eye
irrttet1onp~(,blemif
sty
ren
eto
no
tm
anit
Dre
dcare
full
y.
..... ..... W
EPA
Cod
eN
o.cap
acit
y-
Ton
so
fS
tyre
ne/Y
r.A
vera
geP
rod
uct
ion
-T
ons
of
Sty
ren
e/Y
r.E
mis
sio
ns
toA
tmos
pher
eS
trea
m1
.D
.S
trea
m
Flo
w-
Lb
s./H
r.F
low
Ch
ara
cte
rist
ic-
Co
nti
nu
ou
so
rIn
term
itte
nt
ifIn
term
itte
nt
-H
rs./
Yr.
Flo
wC
om
po
siti
on
-T
on
s/T
on
of
Sty
ren
eH
ydro
gen
Met
hane
Eth
yle
ne
Eth
ane
Car
bon
Mon
oxid
eC
arbo
nD
iox
ide
Ben
zene
To
luen
eE
thy
lB
enze
neS
tyre
ne
No
n-A
rom
atic
sS
ulf
ur
Dio
xid
eH
ydro
gen
Su
lfid
eN
itro
gen
NOx
Wat
erV
ent
Sta
cks
Num
ber
Hei
gh
t-
Ft.
Dia
met
er-
Inch
esE
xit
Gas
Tem
p.-
FO
SC
FM/S
tack
Em
issi
on
Co
ntr
ol
Dev
ices
Fla
re/I
ncin
era
tor
Refr
igera
tor/
Co
nd
en
ser
.Ab
sorb
er/S
cru
bb
erO
ther
An
aly
sis
Dat
eo
rF
req
uen
cyo
fS
amp
lin
gS
ampl
eT
apL
oca
tio
nT
ype
of
An
aly
sis
Odo
rP
rob
lem
Sum
mar
yo
fA
irP
oll
uta
nts
Hy
dro
carb
on
s-
Ton
/Ton
of
Sty
ren
eP
art
icu
late
s-
Ton
/Ton
of
Sty
ren
eNO
x-
Ton
/Ton
of
Sty
ren
eSO
x-
Ton
/Ton
of
Sty
ren
eCO
-T
on/T
ono
fS
tyre
ne
TAB
LES
T-I
IIN
ATI
ON
AL
EMIS
SIO
NIN
VEN
TORY
STY
REN
E-
28
-62
65
,00
02
65
,00
0
Incin
era
tio
nP
rod
ucts
,U
nre
cov
ered
Fu
elG
asF
lare
855
(1)
Co
nti
nu
ou
s
.00
94
3
.00
33
9(2
)1 17
516 U
nkno
wn
636
(3)
Yes
Yes
Non
e
Cal
cula
ted
Non
e
DF
urn
ace
Flu
eG
as
19
,77
9C
on
tin
uo
us
,13
51
0
.00
00
2.1
61
50
Not
Sp
ecif
ied
No
Non
e
Non
e
.00
06
7o
.00
00
2o o
Pag
e5
of
7
Tan
kL
oss
es
44
.6C
on
tin
uo
us
) ).0
00
67
) ) )
Non
e
Non
e
Est
imat
eN
one
(1)
Bas
edon
tota
lco
nv
ersi
on
of
un
reco
ver
edfu
el
gas
toCO
2an
dH
20.
(2)
Fla
reis
use
dfo
rin
cin
era
tio
no
fv
apo
rsfr
omo
ther
pro
cess
es
als
o.
(3)
To
tal
from
all
pro
cess
es.
(4)
Com
plet
eco
mb
ust
ion
toC
02an
dH
20,
NOx
co
ncen
trati
on
isap
pro
xim
atel
y30
PPM
.
..... ..... .+:
EPA
Cod
eN
o.C
aoac
ity
-T
ons
of
Sty
ren
e/Y
r.A
vera
geP
rod
uct
ion
-T
ons
of
Sty
ren
e/Y
r.E
mis
sio
ns
toA
tmos
pher
eS
trea
mI.
D.
Str
eam
Flo
..'-
Lb
s./H
r.Flo~
Ch
ara
cte
rist
ic-
Co
nti
nu
ou
so
rIn
term
itte
nt
ifIn
term
itte
nt
-H
rs./
Yr.
Flo~
Co
mp
osi
tio
n-
Ton
/Ton
of
Sty
ren
eH
ydro
gen
Met
hane
Eth
yle
ne
Eth
ane
Car
bo
nM
onox
ide
Car
bo
nD
iox
ide
Ben
zen
eT
olu
ene
Eth
yl
Ben
zene
Sty
ren
eN
on
-Aro
mat
ics
Su
lfu
rD
iox
ide
Hyd
roge
nS
ulf
ide
Nit
rog
enNO
xW
ater
ven
tS
tack
sN
umbe
rH
eig
ht
-F
t.D
iam
eter
-In
ches
Ex
itG
asT
emp.
-FO
SC
FM
/Sta
ckE
mis
sio
nC
on
tro
lD
evic
esF
lare
/In
cin
era
tor
Refr
igera
tor/
Co
nd
en
ser
Ab
sorb
er/S
cru
bb
erO
ther
An
aly
sis
Dat
eo
rF
req
uen
cyo
fS
amp
lin
gS
ampl
eT
apL
oca
tio
nT
ype
of
An
aly
sis
Odo
rP
rob
lem
Sum
mar
yo
fA
irp
oll
uta
nts
Hy
dro
carb
on
s-
Ton
/Ton
of
Sty
ren
eP
art
icu
late
s~
Ton
/Ton
of
Sty
ren
eNO
x-
Ton
/Ton
of
Sty
ren
esa
x-
Ton
/Ton
of
Sty
ren
eCO
-T
on/T
ono
fS
tyre
ne
AD
isti
llati
on
Ho
h>
ell
Ven
t
>0 Co
nti
nu
ou
s
+ + + +
1 30 6 10
0
yes
Non
e
No
TABL
ES
T-I
IINATIONA~EMISSIONS
INV
ENTO
RY
STY
REN
E
28
-71
00
,00
01
00
.00
0
Atm
osp
her
icD
isti
llati
on
Bre
ath
er
Ven
ts
:::>0 C
on
tin
uo
us
+ + +
2 40,
603,
210
0,10
0
No
Non
e
No
.00
00
2.0
00
02
o o o
Pag
e6
of
7
Fu
git
ive
Em
issi
on
s;A
.P.I
Sum
pS
ecti
on
.5 Co
nti
nu
ou
s
()
()
("0
00
02
)
()
No No
Non
e
NO
DF
urn
ace
Flu
eG
as
10
,65
6C
on
tin
uo
us
.18
92
4
.00
00
2.2
37
00
Not
Sp
ecif
ied
No
Non
e
No
TABL
ES
T-I
IIN
ATI
ON
AL
EM
ISSI
ON
SIN
VEN
TOR
YST
YR
ENE
28
-81
55
,00
01
55
,00
0
DF
urn
ace
Sto
rag
eF
lue
Gas
Lo
sses
11
.55
5(1
)1
,33
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on
tin
uo
us
Co
nti
nu
ou
s
()
(.0
00
94
)
,10
64
4
.00
00
3
.00
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2
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6.5
48 835
30
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......
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fS
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om
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ane
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idde
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ide
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zen
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ene
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y1
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zen
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ne
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atic
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ur
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itG
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FM
/Sta
ckE
mis
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cin
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tor
Refr
igera
tor/
Co
nd
en
ser
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sorb
er/S
cru
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ther
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aly
sis
Dat
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req
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lin
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of
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aly
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lem
Sum
mar
yo
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uta
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dro
carb
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s-
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/Ton
of
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ren
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late
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of
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of
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ono
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ne
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CD
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Vac
uum
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hau
st
30
00
Co
nti
nu
ou
s
+ + + +
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3
1 13
7.6
96 690
60
,00
0
Yes
Non
e
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mer
genc
yF
uel
Gas
Ven
t
6,8
00
Inte
rmit
ten
t25
+ +
.000
02.0
00
30
.00
00
4.0
00
D.0
00
04
Not
Sp
ecif
ied
No
Ap
pro
xim
atel
y2
tim
es/
year
Not
Sp
ecif
ied
Ch
rom
ato
gra
ph
&M
ass
Sp
ectr
om
ete
rY
es
.00
05
4o
.00
00
2o o
page
7o
f7
Non
eN
one
TAB
LES
T-I
VCA
TALO
GO
FE
MIS
SIO
NCO
NTR
OL
DEV
ICES
STY
REN
EPR
OD
UC
TIO
NP
age
1o
f2
.... .... P'l
VAPO
RC
ON
SER
VA
TIO
ND
EVIC
ES---
EPA
Cod
eN
o.fo
rp
lan
tu
sin
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low
Dia
gra
m-
Str
eam
I.L
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evic
e1
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.N
o.C
on
tro
lE
mis
sio
no
fU
nit
sin
Sy
stem
Co
mp
ress
or
Co
nd
ense
rN
umbe
rC
oo
lin
gL
iqu
idC
oo
lan
tF
low
Rat
eT
emp.
toC
on
den
ser
-F
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ou
to
fC
on
den
ser
-Fa
K.
O.
Dru
mS
team
Eje
cto
rS
tag
es
Hot
we1
1L
iqu
idR
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ver
ed-
GPM
No
n-C
on
den
sib
les
-SC
FMIn
stall
ed
Co
st-
Mat'
l.&
Lab
or
-$
Inst
all
ed
Co
stb
ased
on-
"year"
-d
oll
ars
Inst
all
ed
Co
st-
¢/l
b.
of
Sty
ren
eO
per
atin
gC
ost
-A
nn
ual
-$
-(1
97
2)
Val
ue
of
Rec
ov
ered
Pro
du
cts
-$
/Yr.
Net
Op
erat
ing
Co
st-
An
nu
al-
$N
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per
atin
gC
ost
-c/
1b
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fS
tyre
ne
Eff
icie
ncy
-%
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Eff
icie
ncy
-%
-SE
RR
28
-19
,10
&11
VC
-IO
rgan
icV
apo
rsN
otS
pecif
ied
28
-39 V
C-I
IA
Org
anic
Vap
ors
Yes
1 Wat
erN
otS
pecif
ied
142
Not
Sp
ecif
ied
Yes
1 Yes
Not
Sp
ecif
ied
.70
17
,38
019
70.0
03
5N
otS
pecif
ied
1N
ear
10
0/ 0
Nea
r10
0%
28
-310 v
c-n
BO
rgan
icV
apo
rs
Yes
3 .Tat
erN
otS
pecif
ied
136
Not
Sp
ecif
ied
Yes
1 Yes
Not
Sp
ecif
ied
.00
01
14
,60
019
70.0
02
9N
otS
pecif
ied
1N
ear
100/
0N
ear
100%
28
-311 V
C-I
IC
Org
anic
vap
ors
Yes
3 Fate
rN
otS
pec
ifie
d11
5N
otS
pecif
ied
Yes
1 Yes
Not
Sp
ecif
ied
.00
04
19
,20
019
70.0
03
8N
otS
pecif
ied
1N
ear
100%
Nea
r10
0%
28
-59
,10
&11
VC
-III
Org
anic
Vap
ors
Co
nfi
den
tial
100%
100%
Inte
rmit
ten
t:>
0::
:-0
Co
nfi
den
tial
(3)
No
No
No
150
Not
Sp
ecif
ied
Not
Sp
ecif
ied
(4)
Co
nfi
den
tial
Co
nfi
den
tia
1
11
110
0/0
1007
010
0/0
10
0/ 0
100%
100%
INC
INER
ATI
ON
DEV
ICES
EPA
Cod
eN
o.fo
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sin
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low
Dia
gra
m(F
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trea
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D.
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I.D
.N
o.T
ype
of
Com
poun
dIn
cin
era
ted
Typ
eo
fD
evic
e-
Fla
reIn
cin
era
tor
Oth
erM
ate
rial
Incin
era
ted
-SC
FM(l
b./
hr.
)A
ux
illi
ary
Fu
elR
eq'd
.(e
xcl.
pil
ot)
Typ
eR
ate
-B
TU
/hr.
Dev
ice
or
Sta
ck
Hei
gh
t-
Ft.
Inst
all
ed
Co
stM
at'
l.&
Lab
or
-$
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all
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Co
stb
ased
on-
"year"
-d
oll
ars
Inst
all
ed
Co
st-
¢/l
b.
of
Sty
ren
eO
per
atin
gC
ost
-A
nn
ual
-$
-(1
97
2)
Op
erat
ing
Co
st-
¢/l
b.
of
Sty
ren
eE
ffic
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cy
-%
-CC
RE
ffic
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cy
-%
-SE
RR
28
-1'I
tF
L-I
Org
anic
vap
ors
(2)
+
28
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L-I
IF
uel
Gas
Ven
t(E
mer
genc
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on
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s)...
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FL
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+
28
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-IV
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eth
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(2)
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stly
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Info
rmat
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imp
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of
2
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for
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1.
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onde
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for
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nt
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ate
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ted
SCFM
(lb
./h
r.)
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xil
llary
Fu
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pil
ot)
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ate
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/hr.
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or
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ck
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at'
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Lab
or
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base
don
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lied
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st..
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b.o
fS
tyre
ne
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ing
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st-
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ual
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(19
72
)O
per
atin
gC
ost
-c/l
b.
of
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ren
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rrle
ten
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lete
ncy
·1,
-SE
lll{
28
-69
,10
&11
VC
-IV
Org
anic
Vap
ora
(1)
Yes
3 Wat
er1
40
(To
tal)
35
0
4 13SC
FM8
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019
68.0
01
51
16
04
4,7
00
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.
28
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on
den
sib
leR
eco
Jery
fro
mS
trea
m8
(3)
VC
-VO
rgan
icv
ap
ou
Yes
Yes
2 Wlt
er
534
(To
tell
10
0
Yes
Not
Sp
ecif
ied
45
0SC
FM3
75
,00
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68.0
71
18
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) 1
28
-79
,10
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ra
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ater
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eC
ifie
d
Yes
3 Yes
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Sp
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'" I
28
-89
,10
&11
lie-
VII
Org
enic
vap
ara
Yes
4 Bri
ne
642
(To
tal)
14
0
Yea
3 Yee
16 13
SCFM
59
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64.0
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00
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28
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on
den
sib
leae
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yer
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a.
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eam
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Org
anic
Vap
on
Yes
Yes
2 WSte
l'-B
rin
e2
80
wat
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120
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1,5
73
1964
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211
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0,0
00
(45
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)(.
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.67.
97
.'7
.
(1)
nen
zen
e.to
luen
e,
cth
vlh
en
zen
e8
nd
sty
ren
e.
(2)
AC
CllT
di.n
gto
Info
rrn
atio
nrc
ce
ived
.(3
)R
esp
on
den
tcl
aim
sti
lls
asan
em
issi
on
co
ntr
ol
dev
ice,
actu
all
yh
eis
JUB
tre
co
veri
ng
ve1
usb
lec!o
nd
en
sib
h.
from
IIIll
tth
mth
et
wou
14b
eco
mb
u.t
edIn
y"a
y.
(4)
Fla
reals
.ou
sed
fOt"
oth
er
pro
cess
es,
no
bre
akd
ow
ng
iven
.
TABL
ES'
T-V
NU
MBE
RO
FNE
WP
lAN
TS
BY
19
80
Styrene-Butadiene Rubber
Table of Contents
Section Page Number
I.II.III.IV.V.VI.
IntroductionProcess DescriptionPlant EmissionsEmission ControlSignificance of pollutionSBR Producers
List of Illustrations and Tables
Flo,,) DiagramTypical Styrene Butadiene Rubber RecipesCross Heat BalanceList of Original Government Owned SBR PlantsEmission InventoryCatalog of Emission Control DevicesEmission Source SummaryNumber of New Plants by 1980Weighted Emission Rates
119 "
SB-ISB-2SB-3SB-7SB-lOSB-ll
Figure SB-ITable SB-IATable SB-IBTable SB-IITable SB-IIITable SB-IVTable SB-VTable SB-VITab Ie SB-VII
I. Introduction
Rubber is one of the most important basic raw materials of industry.Prior to World War II nearly all the rubber used in the U. S. came from thegreat rubber tree planations of the Far East, located mainly in BritishMalaya and the Dutch East Indies. With the advent of ~~J II these sources ofnatural rubber became unavailable and the U. S. Government inaugurated aGovernment Synthetic Rubber Program, which quickly established a vast industryfor the manufacture of synthetic rubber from styrene and butadiene (SBR).The plants, which were built under the auspices of this progra~have constitutedthe backbone of the rubber industry to this day. (A list of the originalplants and related pertinent data is presented in Table II of this report.)
The old government rubber plant technology was based on emulsion polymerization, and that is still the dominant method of producing SBR. Othermethods (and other rubbers) are assuming ever greater importance, but theyhave not yet surpassed that method upon which the industry was founded.
There are five main sources of air pollution associated with the subjectprocess. They are~
(1) Butadiene absorber vent gases.
(2) Dryer exhaust gases.
(3) Carbon black emissions from masterbatching operations.
(4) Talc from rubber bale dusting (during final packaging operations).
(5) Fugitive emissions.
Additionally, fairly large quantities of waste water are produced.in general, the process may be characterized as a low (air) polluter.due in part to the very low growth rate of the industry.
However,This is
Today's estimated U.S. SBR production capacity is 4.5 x 109 lbs./yr. 1980capacity is predicted to be 5.2 x 109 Ibs./yr.
120
II. Process Description
Although most of the SBR made today is still produced in the rubberplants built in the 1940's, the production methods have undergrone almostcontinual evolution. The 'original' process involved batch polymerizationat 122 0 F. Most of the SBR made today is 'cold rubber' ••• po1ymerized at41 0 F, with the polymerization being carried out continuously. Modern oiland carbon black masterbatching techniques provide synthetic rubbers thatare, in most respects, significantly better than natural rubber. Thefollowing process description may be more easily followed by referring tothe flow diagram presented in Figure I: .
Fresh styrene is stored in 30,000 gallon horizontal steel tanks, orin larger (and more modern) floating roof tanks of up to 650,000 gallonscapacity. Butadiene may be stored in tanks or spheres of from 30,000 to600,000 gallon capacity, although many plants receive butadiene by pipelineand have no storage facilities for it. Fresh styrene is mixed with recyclestyrene, cooled and pumped into the bottom of the first of a series ofstirred polymerization reactors. Fresh butadiene is mixed with recyclebutadiene, sometimes caustic washed (to remove polymerization inhibitorsfrom the fresh butadiene), chilled and pumped to the bottom of the firstpolymerization reactor. Additionally, soap, water and various modifyingand activating agents are also pumped into the first reactor simultaneouslywith the addition of styrene and butadiene. The flow rates of all componentsmust be carefully regulated to assure that the proper proportioning of 'recipe'components is achieved. (See Table I for typical recipes.) All componentsare added continuously.
Most plants still use modified versions of the original 3,750 gallonglass-lined batch reactors. The reactors are now connected in series withthe inlets in the bottom and the outlets at the top. Agitation is providedby suspended, three bladed impellors. Heat removal and temperature control(at 41 0 F) is accomplished thru refrigerated jacketing. Following thebattery of agitated reactors is a 'displacement reactor' section, which isessentially a long, large diameter pipe, possibly 18" x 300' long, usuallysubdivided into a series of shorter sections. Polymerization is haltedby the addition of a 'shortstopping' agent, which may be introduced atvarious points along the displacement reactor. The conversion normallyvaries between 60% and 70%, and is controlled by the location at which theshortstop is added and by small variations in the temperature of the lastfew reactors. Viscosity measurements indicate the extent of reaction.Reactor residence time depends on the particular formulation or 'recipe'being used, but it usually ranges between six and 12 hours.
The latex emerging from the displacement reactor is heated and thenpressured into a series of two flash tanks, operating at about 3 PSIG in thefirst and 4 PSIA in the second, where butadiene and other 'light ends' aretaken overhead. The butadiene vapors are compressed, cooled and condensed,and recycled back to the reactor section via recycle storage tanks. Noncondensibles are vented to the atmosphere thru the butadiene absorber tower.The liquid from the second flash tank, partially stripped latex, is pumpedto the top of a steam stripping tower. The latex flows down thru the strippingtower and is pumped out of that tower to the coagulation and drying section.Live steam flows counter-current to the latex (in the tower) and vaporizesthe ·::ontained styrene. Styrene vapors, steam, small amounts of butadieneand entrained particles of latex are taken overhead. The vapors are condensed,the hydrocarbon and water are separated, and the styrene is recycled to theprocess.
. 121
The stripped latex is coagulated by the addition of salt, followed byacid addition. If the SBR is to be masterbatched, extended by the additionof carbon black and/or oil, either or both of the additives are mixed inwith the latex and co-currently coagulated. The coagulation is effectedby adding brine to the latex, this partially flocculates or agglomerates therubber particles and changes the latex consistency from a mobile liquid toa heavy cream. The coagulation is completed by the addition of dilute acid,which converts the layer of soap molecules on the surface of each particleto a fatty acid. This 'breaks' the emulsion and the SBR globules agglomerateto form 'crumbs' of rubber.
The crumbs are washed to remove soluble impurities and dewatered on ascrew-type water expeller or a rotary vacuum filter. The dewatered crumbsare broken up in a hammer mill and the SBR particles are blown into the topof a hot air, conveyor type dryer. The dried crumb rubber is compacted into75 pound bales, dusted with talc and packaged in kraft paper bags.
122
III. Plant Emissions
This section of the survey report is based primarily on informationprovided by respondents 29-1, 29-2, 29-4, and 29-5.
A. Continuous Air Emissions
I. Butadiene absorber Vent
Following polymerization, unreacted butadiene is flashedoff, compressed, condensed, and recycled. The non-condensiblecontaminants - mostly air - are vented to atmosphere through anabsorption column. Small amounts of butadiene (about .0001 lbs.butadiene/lb. of SBR) are vented along with the non-condensibles.The pertinent data are summarized in Table III.
2. Carbon Black Operations
Most styrene-butadiene rubbers are 'extended' by the additionof oil and/or carbon black, which simultaneously imparts variousdesirable characteristics to the rubber, and decrease the perpound cost of the finished product. These two componentsconstitute an average of 40 wt. % of extended rubbers. If theoil or carbon black is added to the SBR latex prior to coagulation(see flow diagram) the operation is called masterbatching. Morethan two thirds of all styrene butadiene rubbers are masterbatched.The handling of carbon black during masterbatching results in theemission of carbon black particles to the air. Three respondentshave reported these emissions and it may be assumed that alloperators involved in carbon black masterbatching generate similaremissions. Based on three replie these emissions amoun~ to about.001 lbs. of carbon black/lb. of SBR.
3. Dryer Vent
The predominant method for drying the dewatered SBR crumbs isin a perforated apron type, hot air, continuous dryer. Dryerresidence time is about two hours. The crumbs may contain upto 30 percent moisture prior to drying. The dried crumbs willcontain less than 0.50 percent volatile matter. The exhaust gasesfrom the dryer contain water, styrene, and fine particles of SBR.A comparison of the reported composition of this stream is shownbelow:
Respondent SBR Styrene Water
29-1 ("A" train) .00058 .0846129-1 (liB" train) .00058 .0846129-2 (Conveyor
dryer) .00002 .0569229-2 (Extruder
dryer) .00002 .0189729-3* .00001 to .0007 to
.00009 .000180,b'( .021 to .038
*Composition range of various unspecified streams that havetentatively been identified as drier vent streams
**Identified only as hydrocarbons.123
In addition to the components tabulated above, there are otheremissions associated with the operation of the dryero Operator29-4 reports that his dryers are gas fired, burning 459.3 MM ft. 3 /yro of gas containing .0625 wt. % sulfur o This results in theemission of .00005 lbs. S02/lb. of SBRo Presumably some of theother plants utilize direct fired heaters, but none reportedemissions from this source.
Extruder driers are also used to dry some types of SBR. Inthese devices, water and other volatile materials are vaporized,mainly by energy transferred from the screw which forces therubber through the barrel.
Other techniques, such as the formation of thin sheets ofrubber on a paper maker's type of dewatering screen permits shortdrying times to be utilized. But, whatever the type of dryingapparatus, it seems reasonable to assume that most operators willdischarge some amount of hydrocarbons to the atmosphere duringdrying.
4. Engine Exhausts
Respondents 29-1 and 29-6 both indicate that internal combustionengines burning natural gas, are used to drive certain processequipment. Respondent 29-1 reports that his seven engines burn260 MM ft. 3 /yr. of gas containing less than 40 grains of sulfur/Mft. 3 ; this represents less than .00001 lbs. of S02/lb. of SBR.Data on unburned hydrocarbons, NOx and CO were not furnished byeither respondent.
B. Intermittent Air Emissions
Talc Dusting Operations
The crumb rubber product from the SBR plant is normally formedinto 75 lb. bales and packaged in multi-layer paper bags. Talc isapplied to the exterior of the bale to prevent the rubber fromsticking to the inside of the bag. The dusting is accomplished byair blowing the talc onto the bales as they pass through a 'dustchamber' on a conveyor belt. Respondent 29-1 states that his isan intermittent operation and that 12,000 lbs. a year of talc(.00003 lbs./lb. of SBR) is discharged to the atmosphere. Respondent29-3 reports an emission of .00001 lbso of talc/lbo of SBRo
C. Continuous Liquid Wastes
1. Waste Water
The following waste water rates were reported by the respondents:
Plant
29-129-229-329-429-529-6
Water Rate
1,050 GPM1,330 GPM1,350 GPM2,900 GPM
450 GPM<: 1 GPM (7)
! 124
Water Treatment
Yes - In plant facilitiesYes - In plant facilitiesYes - In plant facilitiesYes - In plant facilitiesYes - In plant facilitiesYes - In plant facilities
Several plants report, and probably most plants are similar inthis respect, that certain of their waste water stream containsuspended particles of carbon black and rubber. These streams aresent to settling ponds, which are periodically dredged. The'recovered' sediment is normally disposed of in sanitary land fillareas.
20 Waste Caustic
Butadiene, prior to being charged to the polymerization reactors,is sometimes caustic washed to remove polymerization inhibitors.This results in the generation of some liquid wastes, however,no respondents reported such a waste stream.
D. Intermittent Liquid Wastes
No waste streams in this category were reported.
E. Solid Wastes
Respondents 29-1, 29-2, and 29-3 all report the use of landfill areas for the disposal of solid wastes. The operator ofplant 29-4 utilizes the services of a local disposal contractorwhereas plants 29-5 and 29-6 report incinerating solid wastes(emissions from the incinerators were not reported).
F. Odors
In general, questionnaire responses seem to indicate that theproduction of SBR is not a process that has an odor problem.
No respondent reported any odor complaints in the past year.Most, however, did report that odors are occasionally detectableat the plant site. Although the odoriferous materials were notidentified, the odor itself is described as the "typical rubberplant smell". This odor is most commonly associated with therubber drying operation. Lack of community complaints impliesthat odor control is currently adequate.
G. Fugitive Emissions
Only operator 29-1 has offered an estimate of fugitive emissions •.If it is assumed that this estimate is both (1) reasonably accurateand (2) typical of the industry as a whole, then one must concludethat fugitive emissions account for about half of all the atmosphericpollutants released as a result of the production of SBR via emulsionpolymerization. Operator 29-l's estimate of fugitve emissions is:
Plant Area
Reactor SectionMonomer RecoveryTank FarmCompressor House
Total
Stryene
.00004<. 000001
000004
000008
125
Component - Lb./Lbo of SBRButadiene Ammonia
000034 .00030.00034.00017
000046----.00085 .00076
H. Other Sources
A very large number of chemicals with potential for producingair and water pollution are utilized in varying amounts by SBRproducers. These include nitrogen and sulfur containing compounds,metallic salts, numerous organics and several powder-form solids.Fortunately, the potential is, for the most part, unrealized andthese compounds are 'locked-up' in the SBR polymer without beingemitted. All reported emissions are summarized in Table III National Emissions Inventory.
126
IV. Emission Control
The few emission control devices that were reported as being employed,by respondents to the questionnaire pertaining to the subject process, aresummarily described in Table IV of this report o An efficiency has beenassigned each device when data sufficient to calculate it have beenavailable. Three types of efficiency are normally calculated:
(1) "CCR" - Completeness of Combustion Rating
CCR = 1bso of 02 reacting (with pollutants in device feed) x 1001bs. of 02 that theoretically could react
(2) "SE" - Specific Efficiency
SE = 1bso of specific pollutants in - 1bso of specific pollutant out x 1001bs. of specific pollutant in
(3) "SERR" - Significance of Emission Reduction Rating
SERR* =t(lbs. of pollutant x wf) in - ~lbs. of pollutant x wf) out x 100~(lbso of pollutant x wf) in
*where wf = weighting factor designated in Table SB VII of this report.
Usually a combustion type control device (ioe., incinerator, flare, etc.)will be assigned both a "eCR" and a "SERR" rating, whereas a non-combustiontype device will be assigned an "SE" and/or an "SERR" rating. A more completedescription of this rating method may be found in Appendix V of this report.
Since data sufficient to permit device efficiency calculation areavailable for only three of the fourteen devices summarized in Table IV(Catalog of Emission Control Devices), a few general comments regardingdevice performance are in order:
Absorbers
Most respondents chose to classify their butadiene absorbers as airpollution control deviceso They do minimize air pollution but that isnot their primary function. (See Section II)
Of the five absorbers reported, data sufficient to calculate efficiencieswere available on only two, SB-6 and SB-9; their efficiencies were reportedas 9605% and 98% respectively.
However, a comparison of the economic data pertaining to these twodevices (in Table SB-IV) discloses some inconsistencies. This resultsfrom the fact that the operator of device SB-6 is crediting recoveredbutadiene at 2-3¢/lb. whereas the operator of device SB-9 is creditingit at 10-11¢/lb. (The current selling price of pure butadiene is10-11¢/lb.)
Absorbers were not employed as pollution abatement devices elsewhere inthe respondents' SBR plants~
Scrubbers
Four respondents reported using scrubbers to control pollution, the
127
devices used are listed in Table SB-IV as SB-5, 7, 10, and 12 0 All areemployed to minimize the emission of carbon black particleso All usewater as the scrubbing liquid. Devices SB-7 and SB-lO are identifiedas spray type scrubbers while 29~6 is designated as a 'high energy'scrubber. Only one respondent provides sufficient data for the calculation of scrubber efficiency; device SB-lO has a calculatedefficiency of 95%0 Respondent 29-3 reports visible emissions fromdevice SB-7. Because of the extremely small size of the carbon blackused by the rubber industry, (grades HAF, SAF, ISAF, etco, with averagesize around 0.2 microns), high energy type scrubbers are required forhigh recovery efficiencies. Venturi and flooded disc scrubbers wouldprobably be quite effective and should give efficiencies in the 99+range.
Cyclones
The two cyclones (SB-2 and SB-13) listed in Table SB-IV are both used tominimize talc losses from the bale dusting operationo Data sufficient tocalculate the efficiencies of these devices were not reported. DeviceSB-2 is described as a IDustex Microclone' and was installed when thegovernment owned the planto Device SB-13 is a single stage device, butis 'backed-up' by a bag filter •• oso it's efficiency is not critical.Standard low resistance cyclones, as these two devices are though to be,could be expected to recover particles in the size range associated withtalc (1 to 20 microns) at an efficiency no higher than about 75%0
Bag Filters
Two bag filters are reported by the respondenb~ device SB-4 and SB-14(SB-13 listed under cyclones, see note IV, Table IV). No collectionefficiencies are indicated, but the device in the more difficult carbonblack service (SB-4) should be capable of 99+ %, as indicated by anextensive study of devices in this particular service. (See ReportNumber EPA-450/3-006a)
Incineration Devices
Two flares are listed in Table IV, they are identified therein asdevices SB-8 and SB-14. Unfortunately, none of the (3) respondentssupplying information about these two flares provided any descriptionof their location or exactly what they are burning. Most probably theyare 'plant flares' and are used to burn materials from pressure reliefvalves, emergency vents, etc. Due to the great variety of raw materialsused in the production of SBR (respondent 29-5 lists 39 different rawmaterials), the composition of the material being burned by the flarecould vary considerably. Flare efficiency would vary accordingly,probably being greater than 90% CCR for 'straight' hydrocarbons, with aproportionately lower SERR for compounds containing nitrogen, sulfur,metals, etc o
Changes in operating conditions, or more specifically changes in emulsionpolymerization conditions, would have a negligible effect on atmosphericemissions. The emissions from the process result primarily from fugitivelosses, masterbatching, talcing operations and monomer recovery; and thus willnot be directly affected by such changes.
12&
Changes in polymerization techniques, such as a change from emulsionpolymerization to solvent polymerization, could have an affect on overallemissions. For example, solvent polymerization could result in increasedemissions due to solvent losses (see Table SB-III, plant 29-4, I~ryer
Exhaust" - of .006 lbs. of hexane emission/lb. of SBR, which are losses froma solvent polymerization train). However, a lack of questionnaire baseddata on this subject probably places it outside the scope of this particularsurvey report. To include it would involve mailing additional questionnairesto operators of non-emulsion type SBR plants.
Developmental work (some of which has either been tried or is in progress)directed toward reducing emissions from this process might be directed alongthe following lines:
(1) Devise technique, whereby no monomer is recycled, that is, wherepolymerization is complete. This would do away with butadieneabsorber and associated emissions, although earlier work hasresulted in lower quality rubber when striving for higherconversions.
(2) Devise method for recycling dryer exhaust gases.
(3) Develop non-polluting substitute for talcing operation.
(4) Utilization of best available technology in carbon black recoveryoperations.
(5) Develop substitute method of handling coagulated latex, one wheresmall crumbs or SBR fines are not generated and subseuqentlyemitted to the atmosphere during drying and packaging operations.Extruder driers have resulted in some progress in this direction.
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 releasedas air emissions is less for the subject process than for other processesthat are currently being surveyed.
The methods outlined in Appendix IV of this report have been used toforecast the number of new plants that will be built by 1980 and to estimatethe total weighted annual emissions of pollutants from these new plants. Itshould be noted that the low predicted growth rate of the industry isresponsible, in part, for the very low SEI. Additionally, it is assumedthat all new plants will employ emulsion polymerization. This is mostprobably a false assumption, however, since the SEI is so low, it is verydoubtful that the utilization of other polymerization techniques in the newplants could increase the SEI to the extent that the industry would beconsidered other than a low polluter.
The Table V forecast of 1980 U.S. capacity is based on a 1971 capacityof 1,954 MM long tons/yr. and a growth rate of 2%/year. The predicted growthrate is an average of the various growth rates that have appeared in theliterature. The July 12th, 1971 issue of Oil Plant & Drug Reporter (nowChemical Marketing) predicts a l%/year growth rate, whereas other sourcespredict up to 3%/year.
On a weighted emission basis a Significant Emission Index of 170 hasbeen calculated in Table VIIg This is substantially lower than the anticipatedSEIls of other processes in the study. Hence, the recommendation to excludean in-depth study of the subject process from the overall scope of work forthis project
136
VI. Styrene Butadiene Rubber Producers (Domestic)
Producer
American Synthetic RubberBo F. GoodrichAshlandCopolymerFirestoneGeneral TireGoodyearPhi llipsPolymer CorporationShellStandard BrandsTexas - U. S.UniroyalOther (2)
NOTES:
(1) Long tons of net polymer. (1971 capacity)
125,000193,000
60,000125,000360,000110,000403,000
77,00050,000
116,00040,000
148,00028,000
119,0001,954,000 (3)
(2) Eight producers with annual capacity of 20,000 tons or less.
(3) Includes 407,000 tons of latex.
131.(----4"
132
r
TABLE SB-I-ATYPICAL STYRENE BUTADIENE RUBBER RECIPES
The following recipes are typical of the formulations used in theproduction of cold (41 0 F) rubber. (Hot SBR now constitutes only a minorportion of total SBR production.)
peroxamine Recipe
This type formulation is used when rosin soap is tpbe avoided, inwhich case potassium fatty acid soap is used as th~ ~mulsifier and'peroxamine' as the activator.
Component
WaterButadieneStyrenePotassium fatty acid soapTrisodium phosphate - 12 H20Tamol NDiethylene triaminep-menthane hydroperoxideFerrous sulfate - 7 H20Versene Fe-3Tert-dodecyl mercaptan
Sulfoxylate Recipe
Parts by v-Teight
20072284.70.80.150.150.120.0020.020.02
This type formulation has the advantage of (1) easily prepared activators, (2) non-slurry activator, (3) uniform polymerization rates(4) 'revivable' polymerization and (5) relativ~ly low cost components.
Component
WaterButadieneStyrenePotassium soap of dis proportionated rosinTrisodium phosphate - 12 H20Tamol NSodium formaldehyde sulfoxylate - 2 H20Ferrous sulfate - 7 H20Versene Fe-3P-menthane hydroperoxideTert-dodecyl mercaptan
/
133
Parts by Weight
20070304.50.80.150.150.050.070.100.20
TABLE SB-I-BSTYRENE BUTADIENE RUBBER
VIAEMULSION POLYMERIZATION
APPROXIMATE GROSS HEAT BALANCEPOLYMERIZATION REACTOR SECTION ONLY
HEAT OUT TOTAL SYSTEM BTU/LB. OF SBR PRODUCED (1)
Cool feed from ambient topolymerization temperature(75 0 to 41 0 F)
Maintain reactants at temperature
HEAT IN
82
217
Total Heat Out (3) (4) 299
Heat of polymerization (2) 217
Steam-heat latex and unreactedmono~ers (to 75 0 for purposeof heat balance) 82
Total Heat In (3) (4) 299
(1) Polymer only - does not include carbon black and oil (which if consideredwould lower reactor heat req'ts./lb. of extended rubber).
(2) Based on 60% conversion. (Actual heat is about 500 BTU/lb. polymerized.)
(3) Does not account for energy input of agitators.
(4) Assumes no butadiene condensation or vaporization.
134
TAB
LES
B-I
I
~L
IST
OF
OR
IGIN
AL
GO
VER
NM
ENT
OWNE
DSB
RPL
AN
TSAN
DPE
RTI
NEN
TD
ATA
Est
imat
edP
lan
tIn
ves
tmen
t
Rat
edcap
acit
y,
Dat
eD
ate
Pro
du
ctio
n*
Lon
gT
ons
Co
nst
ructi
on
Op
era
tio
nN
ame
of
Com
pany
Lo
cati
on
of
pla
nt
per
Yea
rS
tart
ed
Sta
rted
$19
45
Fir
est
on
eT
ire
&R
ubbe
rC
o.A
kro
n,
Ohi
o1
5,0
00
7-2
8-4
14
-26
-42
30
,97
61
5,0
00
1-2
1-4
37
,30
0,0
00
Fir
est
on
eT
ire
&R
ubbe
rC
o.L
ake
Ch
arl
es,
La.
30
,00
09
-14
-42
9-
1-4
36
6,3
06
30
,00
04
-19
-44
14
,00
0,0
00
Fir
est
on
eT
ire
&R
ub
ber
Co.
Po
rtN
ech
es,
Tex
as3
0,0
00
6-
4-4
21
1-2
8-4
36
3,5
05
30
,00
03
-15
-44
16
,40
0,0
00
B.
F.
Go
od
rich
Co.
Lo
uis
vil
le,
Ky.
22
,50
02
-15
-42
11
-27
-42
22
,50
02
-19
-43
62
,21
31
5,0
00
6-
4-4
31
1,2
00
,00
0
B.
F.
Go
od
rich
Co.
Bo
rger
,T
exas
30
,00
09
-15
-42
7-2
7-4
34
8,5
24
15
,00
01
1-1
8-4
38
,90
0,0
00
B.
F.
Go
od
rich
Co.
Po
rtN
ech
es,
Tex
as3
0,0
00
6-
4-4
28
-22
-43
63
,43
03
0,0
00
3-
3-4
41
6,4
00
,00
0
Goo
dyea
rsy
nth
eti
cR
ub
ber
Co
rp.
Ak
ron
,O
hio
15
,00
06
-1
-41
5-1
8-4
22
9,6
97
15
,00
06
-8
-43
8,4
00
,00
0
Goo
dyea
rS
yn
theti
cR
ub
ber
Co
rp.
Ho
ust
on
,T
exa
s3
0,0
00
8-
8-4
21
0-2
6-4
36
3,9
97
30
,00
04
-9
-44
13
,50
0,0
00
Goo
dyea
rS
yn
theti
cR
ub
ber
Co
rp.
Los
An
gel
es,
Cali
f.3
0,0
00
9-
1-4
26
-15
-43
29
.73
03
0,0
00
10
-25
-43
11
,34
0,0
00
U.
S.
Ru
bb
erC
o.N
aug
atu
ck,
Con
n.1
0,0
00
9-3
1-4
19
-4
-42
30
,35
72
0,0
00
9,0
00
,00
0
U.
S.
Rub
ber
Co.
Insti
tute
,W
.v
a.3
0,0
00
6-1
8-5
23
-31
-43
97
.84
53
0,0
00
7-2
8-4
33
0,0
00
9-1
5-4
31
8.7
50
,00
0
U.
S.
Ru
bb
erC
o.L
osA
ng
eles
,C
ali
f.3
0,0
00
9-
1-4
21
0-1
3-4
35
,67
0,0
00
33
,80
5
Cop
olym
erC
orp
.**
Bat
on
Ro
ug
e,L
a.3
0,0
00
10
-29
-42
3-3
1-4
37
,85
0,0
00
32
,84
9
Gen
eral
Tir
e&
Rub
ber
Co.
***
Bay
tow
n,T
exas
30
,00
09
-24
-42
7-2
1-4
38
,00
0,0
00
32
,66
0
Nat
ion
alS
yn
theti
cR
ubbe
rC
orp
.1'"'
"<*
Lo
uis
vil
le,
Ky.
30
,00
01
2-1
5-4
29
-30
-43
~Q,OOO
31
,79
41
64
,34
0,0
00
71
7,6
88
*Exc
1ude
sm
ate
rials
ble
nd
edin
toth
ela
tex
.*
*O
per
ated
by
Cop
olym
erC
orp
.co
mp
rise
do
f:
Arm
stro
ng
Ru
bb
erC
o.,
Wes
tH
aven
,C
on
n,:
Day
ton
Ru
bb
erM
anu
fact
uri
ng
Co
.,D
ayto
n,
Oh
io;
Gat
esR
ub
ber
Co
.,D
env
er,
Co
lo.;
Lak
eS
ho
reT
ire
&R
ub
ber
Co
.,D
esM
oin
es,
Ia.;
Sears
,R
oebu
ck&
Co
.,C
hic
ago
,Ill
.(i
nclu
din
gA
rmst
ron
gT
ire
&R
ub
ber
Co
,N
atch
ez,
Mis
s"in
wh
ich
Sears
.R
oebu
ek&
Co.
owns
50p
erce
nt
of
the
vo
tin
gst
ock
);M
ansf
ield
Tir
e&
Ru
bb
erC
o.,
Man
sfie
ld,
Oh
io;
pen
nsy
lvan
iaR
ub
ber
Co
.,Je
an
nett
e,
pa.
**
*O
per
ated
byG
ener
alT
ire
&R
trnb
erC
o.(G
ener
alL
atex
&C
hem
ical
Co
.,C
amb
rid
ge,
Mas
s.A
sso
cia
tes)
.*
k*
*O
per
ated
byN
atio
nal
Sy
nth
eti
cR
ub
ber
Co
rp.
com
pri
sed
of:
Go
od
all
Ru
bb
erC
o.,
Tre
nto
n,
N.
J.;
Hew
itt
Ru
bb
erC
o.,
Bu
ffalo
,N
.Y
.;L
eeR
ub
ber
&T
ire
Co
.,C
on
sho
ho
cken
,P
a.;
Min
nes
ota
Min
ing
&M
anu
fact
uri
ng
Co
.,S
t.p
au
l,M
inn.
(in
clu
din
gIn
lan
dR
ub
ber
Co
rp.,
asu
bsi
dia
ry).
TAB
LES
B-I
IIN
ATI
ON
AL
EM
ISSI
ON
SIN
VEN
TORY
STY
REN
EB
UTA
DIE
NE
RUBB
ERV
IAEM
ULS
ION
POLY
MER
IZA
TIO
Np
age
1o
f8
Pla
nt
EPA
Cod
eN
o.C
apac
ity
,T
ons
of
SB
R/Y
r.R
ange
inP
rod
uct
ion
-%
of
Max
.E
mis
sio
ns
toA
tmos
pher
eS
trea
m
Flo
y'
-L
bs.
/Hr.
Flo
vC
hara
cte
rist
ic,
Co
nti
nu
ou
so
rIn
term
itte
nt
ifIn
term
itte
nt,
Hrs
./Y
r.-Flo~
Co
mp
osi
tio
n,
To
ns/
To
no
fSB
RS
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Car
bon
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ane
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00
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00
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Calc
'd.
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29
-12
19
,00
05
.7
Tra
in"A
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rea
Fu
git
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s
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01
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No
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No
SEE
CO
NTI
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ON
Bu
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Ab
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No
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+
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No
TAB
LES
B-I
IIN
ATI
ON
AL
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ON
StN
VEN
TORY
STY
REN
EB
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DIE
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29
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19
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05
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Pag
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Tra
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21
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B-I
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TAB
LES
B-I
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11
14
04
1.5
41
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1'
30 20 470
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fA
nal
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-......1
j.•
t=Pi_
....
TABLE SB-IIINATIONAL EMISSIONS INVENTORY
STYRENE BUTADIENE RUBBERVIA
EMULSION POLYMERIZATION
EXPLANATION OF NOTES
I. Respondent reported emissions during period of lo~ plant thru-put(25 - 50% of design), normally_~hen appropriate.. emissions are adjustedas follows:
actual emissions reported emissions x~l_O~O~~~__reported plant thru-put as % of design
Ho~ever, after comparing reported emissions ~ith data from otherrespondents, no adjustment ~as made.
II. This emission results from solution polymerization unit, v'hich respondentoperates in tandem with emulsion process.
III. Respondent did not claim device SB-ll as pollution control device,however, as all other respondents did, device ~as listed here and inTable IV for purposes of comparison.
144
fill
/-j
1>
(lll·1 '"
90 2.8
00
1911
1961
-19
11.0
0041
3.0
00
5.1
15
-2.1
15
Neg
.95 95
30 160
360
3.2
51
.0
13
.18
819
66
.00
38
18
.30
0o
18
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0.0
052
+D
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13
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59.0
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B-I
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TALO
GO
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MIS
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NCO
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DEV
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STY
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EB
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DIE
NE
RUBB
ERV
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ULS
ION
POLY
MER
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TIO
N
f IP
rod
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3 29
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lack
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tray
sN
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per
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b./
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tack
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met
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all
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l.&
Lab
or
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all
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ased
on-
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all
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of
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R/Y
r.O
per
atin
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-A
nn
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-$
(197
2)V
alu
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fR
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ver
edP
rod
uct
,$
/Yr.
Net
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erat
ing
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st-
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ual
-$
Net
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b.
of
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RR
:77,
500
19
67
.003
8
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------
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NES
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tu
sin
gF
low
Dia
gram
(Fig
.I)
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ased
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(III
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V)
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alc
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gle
15
,00
01
96
6.0
02
1
__
...
J-..J
TABL
ES
B-I
VCA
TALO
GO
FE
MIS
SIO
NCO
NTR
OL
DEV
ICES
STY
REN
EB
UTA
DIE
NE
RUBB
ERV
IAEM
ULS
IONPOLYMERIZ~
page
3o
f3
._..."
._.
IU
nsp
ecif
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Are
asI
j I I---~_._--
_._..-
(V)
29
-1A SB
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ntr
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on
of
Num
ber
of
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part
men
tsN
umbe
ro
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ags/
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mp
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thM
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rial
To
tal
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all
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l.&
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or
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all
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ased
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per
atin
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97
2)
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per
atin
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ost
-$
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st-
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R+=
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J
15
01
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84
0,0
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(VII
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19
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01
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00
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30
II
J
INC
INER
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tu
sin
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low
Dia
gra
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ig.
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trea
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ice
1.
D.
No.
Typ
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fC
ompo
und
Incin
era
ted
Typ
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fD
evic
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reIn
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tor
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era
ted
,SC
FM(l
b./
hr.
)A
ux
illi
ary
Fu
elR
eq'd
.-
Ex
clu
din
gP
ilo
tT
ype
Rat
e-
BT
U/H
r.D
evic
eo
rS
tack
Hei
gh
t-
Ft.
Inst
all
ed
Co
st-
Mat'
l.&
Lab
or
-$
Inst
all
ed
Co
stB
ased
on-
"year"
-d
oll
ars
Inst
all
ed
Co
st-
c/l
b.
of
SB
R/Y
r.O
per
atin
gC
ost
-A
nn
ual
-$
(19
72
)V
alu
eo
fH
eat
or
Pow
erR
eco
ver
y-
$/Y
r.N
etO
per
atin
gC
ost
-$
/Yr.
Net
Op
erat
ing
Co
st-
¢/l
b.
of
SBR
Eff
icie
ncy
-%
-CC
RE
ffic
ien
cy
-%
-SE
RR
29
-1(V
I)
SB
-8 +
29
-6
SB
-14 +
29
-3(V
I)
SB
-8 +
TABLE SB-IVCATALOG OF EMISSION CONTROL DEVICES
STYRENE BUTADIENE RUBBERVIA
EMULSION POLYMERIZATION
EXPLANATION OF NOTES
I Estimated by Houdry, respondent reported eauipment (only) cost of $6,788.
II Device SB-7 consists of four identical units, costs given are total forall units.
III. Device SB-2 consists of t~o identical units, costs given are total forboth units.
IV Device SB-13 consists of a cyclone separator ~ith a bag filter on theatmospheric discharge.
V Unit ~as acquired at unkno~n cost, respondent reconditioned it in 1969 atcost of $5,067.
VI Device SB-8 is used jointly by respondents 29-1 and 29-3, costs sho~n
are respondents 50% share of total.
VII Respondent indicates cost is for "flare tip" only.
148
TAB
LESB
-VN
UM
BER
OF
NEW
PLA
NTS
BY19
80
Cu
rren
tC
apac
ity
Cap
acit
yE
cono
mic
Num
ber
+:-
Cu
rren
tM
arg
inal
on
-str
eam
Dem
and
Cap
acit
yto
be
pla
nt
of
Ne~'
c..o
Cap
acit
ycap
acit
yin
1980
1980
1980
Add
edS
ize
Un
its
4,4
64
112
4,3
52
3,5
87
5,2
31
879
250
3-
4
NO
TE:
(1)
All
cap
acit
ies
inM
M1
bs.
/yr.
(2)
Cu
rren
tcap
acit
y19
80ca
pac
ity
Mlo
ng
ton
s
""
"1
,99
3.
=2
,33
5.
(3)
1980
rate
sb
ased
onas
sum
ed2
%/y
r.gro~th
rate
.
U1 o
Em
issi
on
TAB
LES
B-V
IE
MIS
SIO
NSO
URC
ESU
MM
ARY
TON
/TO
NO
FSB
R
So
urc
e
Mon
omer
Po
lym
erE
xtr
usi
on
Car
bo
nB
lack
Rec
ov
ery
and
Dry
ing
Han
dli
ng
pac
kag
ing
Fu
git
ive
Em
issi
on
sH
eat
and
Po"
Jer
Cen
.T
ota
l
Hy
dro
carb
on
Part
icu
late
s&
Aer
oso
ls
NOx
SOx
CO
.00
01
0.0
01
00
.00
00
2.0
00
10
.00
00
2
.00
10
0
.00
02
1
.00
02
0
.00
21
0
.00
03
5
o
.00
02
0
o
Ch
emic
al:
Pro
cess
:
TAB
LES
B-V
IIW
EIG
HTE
DE
MIS
SIO
NRA
TES
Sty
ren
e-B
uta
die
ne
Ru
bb
er
Em
uls
ion
Po
lym
eri
zati
on
(Jl ...
Incre
ase
dC
apac
ity
by19
8087
9M
Mlb
s./
yr.
po
llu
tan
t
Hy
dro
carb
on
s
Part
icu
late
&A
ero
sols
NOx
SOx
CO
v,T
eigh
ted
Em
issi
on
Incre
ase
dE
mis
sio
ns
v,T
eigh
ting
Em
issi
on
sL
b./L
b.
MM
Lb
s./Y
r.F
acto
rM
ML
bs.
/Yr.
.00
21
01
.85
801
47
.7
.00
03
5.3
160
18
.5
00
400
.00
02
0.1
820
3.5
00
10
Sig
nif
ican
tE
mis
sio
nIn
dex
=1
69
.7
Vinyl Acetate via Acetylene
Table of Contents
Section Page Number
I.II.III.IV.V.VI.
IntroductionProcess DescriptionPlant EmissionsEmission ControlSignificance of pollutionVinyl Acetate Producers
List of Illustrations and Tables
Flo'to7 DiagramNet Material BalanceGross Heat BalanceEmission Inventorycatalog of Emission Control DevicesNumber of New plants by 1980Emission Source SummaryWeighted Emission Rates
152
VI-lVI-2VI-3vr-sVI-6VI-7
Figure VI-ITable VI-ITable VI-IITable VI-IIITable VI-IVTable VI-VTable VI-VITable VI-VII
VI-l
I. Introduction
Vinyl acetate is an important petrochemical used to produce polymer.Most of the vinyl acetate manufactured is polymerized into polyvinyl acetatewhich is used in latexes, emulsion paints, adhesives and various textilecoatings or futher processed into polyvinyl alcohol or polyvinyl butyral.About 10% is co-polymerized with vinyl chloride, ethylene and other monomers.
Vinyl acetate is currently produced by three processes. The newer twoutilize ethylene, oxygen and acetic acid in a vapor or liquid phase reaction.The old~stprocess, which presently accounts for 30% of vinyl acetate production,uses acetylene and acetic acid in a vapor phase reaction. Because of thehigh acetylene raw material costs, little, if any, growth is expected in theacetylene based vinyl acetate industry. Older plants are currently beingphased out. Total capacity of acetylene based plants is expected to dropwhile overall growth of vinyl acetate will be about 10% a year through 1980.
Air emissions arising from vinyl acetate produced using acetyleneand acetic acid stem primarily from the venting of light by-products. Othersources are incineration of liquid waste and storage tank vent losses. Sincethe process is not expected to grow, total emission through 1980 will beinsignificant compared to other processes being surveyed.
153
II. Process Description
Vinyl acetate can be produced by the chemical combination of acetic acidand acetylene. The catalyzed reaction is carried out in the vapor phase
Zinc Acetate------;.;,0.;...-.............-----...)0,. CH3COOCH = CHZ'
Glacial acetic acid and recycle acid are blended in a charge vaporizer.Recycle plus fresh acetylene enters the tank through a sparger and passup through the acid. Typical operating conditions for the vaporizer are4 to 5 PSIG and 160 to 1800 F.
The charge is then preheated first by exchange with the reactor effluentand finally with steam. The reaction takes place in a vertical tubular reactorof stainless steel. Typically, the tubes are 12 feet long with a two inchdiameter. The packing is composed of granular activated carbon with a 20 to30 wt. % zinc acetate catalyst. The reactor operates at 3500 F with freshcatalyst and the temperature is gradually increased to 400 0 F as the catalystages. Typical space velocities are 300 to 400 hours~l Excess heat due to theexothermic heat of reaction is removed by heat transfer in the shell side ofthe reactor.
Yields areon acetic acid.of acetylene to
quite good, 92 to 98% based on acetylene andAcetic acid conversion is usually about 80%.
acetic acid is usually about 4-5 to one.
95 to 99% basedThe molar ratio
The effluent gases are cooled in two stages, first by exchange with feedvapors and finally by exchange with a coolant. A mixture of crude vinylacetate and unreacted acetic acid is condensed in this step, while non-condensibles, primarily acetylene, pass overhead and recycle to the reactor. Inthe first column, light ends such as residual acetylene, acetone and acetaldehydeare separated, the acetylene can be separated and returned to the reactor, whileother light ends are generally vented to the atmosphere. The bottoms from thiscolumn passes to another distillation column ~here a sharp separation is madebetween vinyl acetate and acetic acid plus v'aste. Heavy reaction products areremoved from the system in a heavy ends column. The acetic acid recovered fromoverhead is recycled to the charge vaporizer.
The finished vinyl acetate has a purity of 99.5'% or better. The BordenChemical plant in Geismar, Louisiana, is using a modified process developedjointly with Blaw-Knox. The process is the first to make vinyl acetate directlyfrom raw acetylene produced in a partial oxidation process. The operating costsare said to be about 30% less than for a conventional vinyl acetate process.The key to the lower operating costs is in the purification of ra~ acetyleneand recycle acetylene.
154
III. plant Emissions
A. Continuous Air Emissions
1. Light Ends vent
The emissions from this vent constitute the most importantsource of air pollution associated with the production of vinylacetate from acetylene.
The stream consists of acetaldehyde, acetylene, acetone, vinylacetate and acetic acid. The relative composition of components andflow rate from this vent varies greatly between respondents. Factorsinfluencing the flow are 1) amounts of light by-products produced,2) efficiency of product and recycle gas recovery systems. Totalhydrocarbon emissions were .0400 lbs./lb. vinyl acetate in the worstcase and .0082 lbs./lb. vinyl acetate in the best case. Plant 13-2plans in the future to either recover this stream in the system orpipe it to the incinerator~
2. Heavy Ends Column Vent
Only respondent 30-3 reported a vent of this type. Acetic acidvapors are the only noxious emission associated with this stream andits flow rate is sufficiently small so that only .0002 lbs./lb. vinylacetate are released to the atmosphere.
3. Incineration of Liquid Waste
Plant 30-2 reports that heavy organic wastes removed from thesystem are burned continuously in an incinerator. The liauidseparated from acetic acid in the heavy ends column, containsacetaldehyde, acetic anhydride, crotonaldehyde and polymer. Due tothe fact that no nitrogen or sulfur is present in the compounds,combustion to C02 and H20 is almost totally complete.
4. Vinyl Acetate Storage Tank Vents
The auantity of vapors released to the amosphere through tankventing was significant for 30-3, the sole plant to supply detailedinformation. .00754 lbs. of hydrocarbons per lb. vinyl acetate arecontinuously vented. Other facilities blanketed the liquid withpads of nitrogen or methane to reduce losses. .
5. Acetic Acid Storage Tank Vents
Negligible amounts of acetic acid are vented to the amosphere.
B. Intermittent Air Emissions
1. Incineration of Liquid Waste
Some plants store their hea'~7 organic liquid and burn it for afew hours weekly or monthly. The waste is identical in composition tothat described in Section A-3. The auantity of flow varies dependingon the system. Organic liquid is either burned in open air or in
155
an atmospheric liquid waste burner. As in the case of the continuousincinerator, combustion is almost totally complete and only smallamounts of particulates are produced.
2. Reactor Emergency Vent
In case of a compressor breakdown or system malfunction, vinylacetate converters are equipped with an emergency blow~off system.Failure is said to occur about five times a year and lasts from onehour to one day. Light hydrocarbons of all types are released tothe atmosphere under these conditions.
3. Reactor Purge Gas
Respondent 30-3 reports that approximately ten times a year for aduration of six hours the reactor is purged with acetic acid andnitrogen when preparing for catalyst change. Emissions on a yearlybasis are small, .0001 lbs. of acetic acid per lb. vinyl acetate.
C. Continuous Liquid Wastes
1. Heavy Organic Liquid Waste
Residue from the heavy ends column is burned as described above.
2. Waste Water
plants 30-3 and 30-4 report waste water streamS.
plant GPH % Organic Treatment---30-2 030-3 4,400 10% Primary30-4 150 Not Specified Off-site
D. Intermittent Liquid Waste
No waste streams in this category were reported.
E. Solid Waste
Spent catalyst and residue carbon are removed to land fill.
F. Odors
All respondents reported that acetic acid and acetaldehyde odorswere present on plant property but they claim the odor does not carryoff plant property. On this basis, it is concluded that the productionof vinyl acetate does not present a community odor problem.
G. Fugitive Emissions
No sources of fugitive emissions were mentioned.
156
LV. Emission Control
The only emission control devices reported as being empLoyed by respondentswas liquid waste incinerators whose function can be described as water pollutioncontrol. Never~the-less, since their overall purpose is that of reducingharmful pollutants they are summarily described in Table IV. An efficiency hasbeen assigned each device.
(1) CCR - Completeness of Combustion Rating
CCR = lbs. of 02 reacting (with pollutants in device feed) x 100lbs. of 02 that theoretically could react
A more complete description of this rating method may be found inAppendix, V of this report.
Incineration Methods Employed
1) Incinerator2) Atmospheric Liquid Waste Burner3) Open Air Burning
157
V. Significance of Pollution,
It is recommended that no in-depth study of this process be undertakenfor the following reasons:
1. The reported emissions data indicate that the quantity of pollutantsreleased as air emissions is less for the subject process than forother processes that are currently being surveyed.
2. Due to the high cost of acetylene, new plants are expected to be builtusing one of the ethylene processes. Ethylene is presently sellingat about 3¢ per pound while acetylene is difficult to obtain at 9¢per pound. Many companies (USI, celanese, DuPont) have already builtnew plants using ethylene as the starting material. Monsanto andseveral other companies have phased out their acetylene based vinylacetate production. Union Carbide plans to follow suit by putting its225 MM 1bs/year Texas City plant on a stand-by basis by 1974, due tohigh acetylene costs and old equipment. Borden Chemical and NationalStarch and Chemical will be the only acetylene based producers in 1974.Bordern uses the B1aw-Knox acetylene process which is more economicalthan the older method. One new acetylene type vinyl acetate plant isprojected to be built on the possibility that lower acetylene rawmaterial costs and other factors could make such a project economical.The growth forecast is summarized in Table V.
On a weighte~ basis, a Significant Emission Index of 360 has been calculatedin Table VII. The low number is attributed to the fact that little or no growthof this process is expected. Hence, the recommendation to exclude an in-depthstudy of the subject process from the overall scope of work for this project.For a complete explanation of the Significant Emission Index, see Appendix IVof this report.
158
VI. VinXl Acetate Producers
Borden Chemical Company
Celanese Chemical Company
1) Clear Lake, Texas2) Bay City, Texas
DuPont
National Starch & Chemical
Union Carbide
U. S. Industrial Chemical
Capacity MM Lbs./yearAcetxlene Ethxlene
150
300*350,,,,
300
56
225*Ok
330
''''Estimated.**P1ant to be phased out by 1974.
159 ;
Total 431 1,280
160
Ace
tyle
ne
Ace
tic
Aci
d
Vin
yl
Ace
tate
Ace
ton
e
Ace
tald
ehy
de
Ace
tic
An
hy
dri
de
Cro
ton
ald
ehy
de
Pol
ymer
Wat
er
..........
.~ --..
...
TABL
EV
I-I
VIN
YL
ACE
TATE
FRO
MA
CET
YLE
NE-
AC
ETIC
AC
ID
MA
TER
IAL
BALA
NCE
-T
ITV
INY
LA
CET
ATE
Fre
shF
eed
Rec
ycl
eA
cety
len
eR
ecy
cle
Aceti
cA
cid
Gro
ssF
eed
Rea
cto
rE
fflu
en
tP
rod
uct
Lig
htEn~
Hea
vyE
nds
.31
01
1.
2699
1.
5800
1.2
702
.00
03
.74
40
.17
05
.91
45
.17
37
.00
32
1.0
22
01
.00
00
.02
20
.00
02
.00
02
.01
68
.(n
68
.00
16
.00
16
.00
07
.00
07
.00
06
.00
06
.00
87
.00
87
1.0
541
1.
2699
.17
05
2.4
94
52
.49
45
1.0
00
.04
80
.00
61
TABLE VI-aVINYL ACETATE
FROMACETYLENE :-ACETIC ACID
GROSS HEAT BALANCE - CONVERTER SECTION ONLY
Heat In (1)
vaporizer and PreheaterExothermic Heat of Reaction
Heat Out
Total Heat In
638 (2)577
= 1,215 BTU/lb. of Vinyl Acetate
Maintain Reactants @ Temperature 577Enthalpy Residual (above base temperature) 638
Total Heat Out = 1,215 BTU/lb. of Vinyl Acetate
NOTE:
(1) Base temperature - 25 0 C.
(2) Part of preheat generated by exchange ~ith reactor effluent.
162
01
W
Pla
nt
EPA
Cod
eN
o.cap
acit
y-
Ton
so
fV
iny
lA
ceta
te/Y
r.P
rod
uct
ion
-T
ons
of
Vin
yl
Aceta
te/Y
r.R
ange
inP
rod
uct
ion
-%
of
Max
.E
mis
sio
ns
toA
tmo
sph
ere
Str
eam
Flo
w-
Lbs
./H
r.F
low
Ch
ara
cte
rist
ic,
Co
nti
nu
ou
so
rIn
term
itte
nt
ifIn
term
itte
nt
-H
rs./
Yr.
Flo
wC
om
po
siti
on
-T
on
s/T
on
Vin
yl
Aceta
teA
cety
len
eA
ceto
ne
Ace
tald
ehy
de
Ace
tic
Aci
dV
iny
lA
ceta
teN
itro
gen
C02
H2
0NO
xV
ent
Sta
cks
Num
ber
Hei
gh
t-
Ft.
Dia
met
er-
Inch
esE
xit
Gas
Tem
p.-
FOE
mis
sio
nC
on
tro
lD
evic
esF
lare
/In
cin
era
tor
An
aly
sis
Dat
eo
rF
req
uen
cyo
fS
amp
lin
gS
ampl
eT
apL
oca
tio
nT
ype
of
An
aly
sis
Odo
rP
rob
lem
Sum
mar
yo
fA
irP
oll
uta
nts
Hy
dro
carb
on
s,T
on/T
onV
iny
lA
ceta
tep
art
icu
late
s,T
on/T
onV
iny
lA
ceta
teNO
xT
on/T
onV
iny
lA
ceta
teCO
Ton
/Ton
Vin
yl
Aceta
te
TABL
EV
I-II
IN
ATI
ON
AL
EMIS
SIO
NS
INV
ENTO
RYV
INY
LA
CET
ATE
VIA
ACE
TYLE
NE
=-A
CE
TIC
AC
ID
Ab
sorb
erV
ent
600
Co
nti
nu
ou
s
.02
68
0.0
03
00
.00
12
6.0
01
90
3 80 1 90 No
Ap
ril,
1972
Not
Sp
ecif
ied
Gas
Ch
rom
ato
gra
ph
No
30
-27
5,0
00
75
,00
0o ,02
99
6o o o
page
1o
f4
Incin
era
tio
no
fL
iqu
idW
aste
(7)
1,2
40
Co
nti
nu
ou
s
.04
67
2.0
18
53
1 10 96 3400
Yes
No
Pla
nt
EPA
Cod
eN
o.cap
acit
y-
Ton
so
fV
iny
lA
ceta
te/y
r.P
rod
uct
ion
-T
ons
of
Vin
yl'
Aceta
te/Y
r.R
ange
inP
rod
uct
ion
-%
of
Max
.E
mis
sio
ns
toA
tmo
sph
ere
Str
eam
TAB
LEV
I-II
IN
ATI
ON
AL
EM
ISSI
ON
SIN
VEN
TOR
YV
INY
LA
CET
ATE
.V
IAA
CE
TY
LE
NE
-=-A
CE
TIC
AC
ID
30
-31
1,2
50
11
,25
0o
pag
e2
of
4
See
Co
nti
nu
ati
on
c:r>
-1:=
Flo~'
-L
bs.
/Hr.
Fl~'
Ch
ara
cte
rist
ic-
Co
nti
nu
ou
so
rIn
term
itte
nt
ifIn
term
itte
nt,
Hrs
./Y
r.Flo~
Co
mp
osi
tio
n-
Ton
/Ton
Vin
yl
Aceta
teA
cety
len
eA
ceto
ne
Ace
tald
ehy
de
Aceti
cA
cid
Vin
yl
Aceta
teN
itro
gen
C02
H20
Met
hy
lA
cety
len
eP
rop
yle
ne
Pro
pan
eM
etha
neE
than
eE
thy
len
eV
ent
Sta
ck
sN
umbe
rH
eig
ht
-F
t.D
iam
eter
-In
ches
Ex
itG
asT
emp.
-FO
Em
issi
on
Co
ntr
ol
Dev
ices
Fla
re/I
ncin
era
tor
Ab
sorb
erA
nal
ysi
sD
ate
or
Fre
qu
ency
of
Sam
pli
ng
Sam
ple
Tap
Lo
cati
on
Typ
eo
fA
naly
sis
Odo
rP
rob
lem
Sum
mar
yo
fA
irp
oll
uta
nts
Hy
dro
carb
on
s,T
on/T
onV
iny
lA
ceta
teP
art
icu
late
s,T
on
/To
nV
iny
lA
ceta
teNO
x'
Ton
/Ton
Vin
yl
Aceta
teCO
,T
on/T
onV
iny
lA
ceta
te
Co
nv
erte
rP
urg
eG
as69
4In
term
itte
nt
60 .00
01
0
00
00
9
No
No
No
ne
Calc
ula
ted
Yes
(1)
Reacto
rE
mer
genc
yV
ent
1470
Inte
rmit
ten
tN
otS
pecif
ied
+ + + + + + + +Y
es3 SO 3 1
10
No
On
ce/.
leek
Mas
sS
pectr
om
ete
rY
es(1
)
Hea
vyE
nds
Col
umn
Ven
t6
.3C
on
tin
uo
us
.000
21
.00
00
7
) ).0
02
27
) ) ) )N
o
No
Non
e
Liq
uid
Sam
pli
ng
Yes
(1)
(4)
Lig
ht
End
sC
olum
nV
ent
214
1C
on
tin
uo
us
.001
O?
.00
18
5.0
07
85
) )
.00
17
8) ) ) )
No
No
3ti
mes
ay
ear
Rec
ov
ery
colu
mn
feed
stre
am
Ch
rom
ato
gra
ph
Yes
(1)
TABL
EV
I-II
IN
ATI
ON
AL
EM
ISSI
ON
SIN
VEN
TORY
VIN
YL
AC
ETA
TE--
VIA
--
ACETYLENE-:-A~TIC~IQ
Pag
e3
of
4
CT\
U1
Pla
nt
EPA
Cod
eN
o.cap
acit
y-
Ton
so
fV
iny
lA
ceta
te/Y
r.P
rod
uct
ion
-T
ons
of
Vin
yl
Aceta
te/y
r.R
ange
inP
rod
uct
ion
-%
of
Max
.E
mis
sio
ns
toA
tmo
sph
ere
Str
eam
Flo
w-
Lb
s./H
r.F
low
Ch
ara
cte
rist
ic-
Co
nti
nu
ou
so
rIn
term
itte
nt
ifIn
term
itte
nt,
Hrs
./Y
r.F
low
Co
mp
osi
tio
n-
Ton
/Ton
Vin
yl
Aceta
teA
cety
len
eA
ceto
ne
Ace
tald
ehy
de
Aceti
cA
cid
Vin
yl
Aceta
teN
itro
gen
CO2
H20
Met
hy
lA
cety
len
eP
rop
len
eP
rop
ane
Met
hane
Eth
ane
Eth
yle
ne
ven
tS
tack
sN
umbe
rH
eig
ht
-F
t.D
iam
eter
-In
ches
Ex
itG
asT
emp.
-FO
Em
issi
on
Co
ntr
ol
Dev
ices
Fla
re/I
ncin
era
tor
Ab
sorb
erA
nal
ysi
sD
ate
or
Fre
qu
ency
of
Sam
pli
ng
Sam
ple
Tap
Lo
cati
on
Typ
eo
fA
nal
ysi
sO
dor
Pro
ble
mSu
mm
ary
of
Air
po
llu
tan
tsH
yd
roca
rbo
ns,
Ton
/Ton
Vin
yl
Aceta
tep
art
icu
late
s,T
on/T
onV
iny
lA
ceta
teNO
x,
Ton
/Ton
Vin
yl
Aceta
teCO
,T
on/T
onV
iny
lA
ceta
te
Cru
deV
iny
lA
ceta
teS
tora
ge
Tan
kV
ents
19
2.3
Co
nti
nu
ou
s
.00
04
7.0
02
84
.00
20
8
No
No
Upo
nR
equ
est
Liq
uid
Sam
ple
Ch
rom
ato
gra
ph
Yes
(1)
30
-31
1,2
50
11
,25
0o
Ref
ined
Vin
yl
Aceta
teS
tora
ge
Tan
kV
ents
35
.7(5
)C
on
tin
uo
us
.00
37
No
No
Non
e
Est
imat
edY
es(1
)
.01
36
6o o o
Aceti
cA
cid
Sto
rag
eT
ank
Ven
ts1
6.9
(6)
Co
nti
nu
ou
s
.00
00
7
No
No
Non
e
Est
imat
edY
es(1
)
Incin
era
tio
no
fL
iau
id\<
18ste
Not
Sp
ecif
ied
(3)
Inte
rmit
ten
tN
otS
pecif
ied
.04
08
1.0
18
00
No
Yes
Ope
na
irb
urn
ing
Non
e
Est
imat
edN
o
en en
Pla
nt
EPA
Cod
eN
o.cap
acit
y-
To
ns
ofViny~
Aceta
te/Y
r.P
rod
ucti
on
-T
ons
of
Vin
yl
Aceta
te/Y
r.R
ange
inP
rod
ucti
on
-%
of
Max
.E
mis
sio
ns
toA
tmo
sph
ere
Str
eam
Flo
,"'
-L
bs.
/Hr.
Flo
wC
ha
ra
cte
ris
tic,
Co
nti
nu
ou
so
rIn
term
itte
nt
ifIn
term
itte
nt,
Hrs
./Y
r.F
lat.
·C
om
po
siti
on
-T
on
/To
nV
iny
lA
ceta
teM
eth
ane
Ace
tyle
ne
Eth
yle
ne
Ace
ton
eA
ceta
ldeh
yd
eA
ceti
cA
cid
Vin
yl
Aceta
teH2
0CO
2NO
xp
art
icu
late
ven
tS
tack
sN
umbe
rH
eig
ht
-F
t.D
iam
eter
-In
ch
es
Ex
itG
as
Tem
p.-
Fa
Em
issi
on
Co
ntr
ol
Dev
ices
Fla
re/I
ncin
era
tor
An
aly
sis
Dat
eo
rF
req
uen
cyo
fS
amp
lin
gS
amp
leT
apL
ocati
on
Typ
eo
fA
naly
sis
Odo
rP
rob
lem
Sum
mar
yo
fA
irp
oll
uta
nts
Hy
dro
carb
on
s,T
on
/To
nV
iny
lA
ceta
teP
art
icu
late
s,
To
n/T
on
Vin
yl
Aceta
teNO
x'
To
n/T
on
Vin
yl
Aceta
teCO
,T
on/T
onV
iny
lA
ceta
te
TAB
LEV
I-II
IN
ATI
ON
AL
EM
ISSI
ON
SIN
VEN
TOR
YV
INY
LACET~
VIA
AC
ETY
LEN
E:-
AC
ET
ICA
CID
Reacto
rE
mer
genc
yV
ent
790
Inte
rmit
ten
t3
0
.00
00
4.0
00
14
.00
00
5
1 43 1.5
185
Dail
yIn
stre
am
Gas
Ch
rom
ato
gra
ph
Yes
Pag
e4
of
4
30
-42
8,0
00
28
;00
0o
Lig
ht
End
eC
olum
nv
en
t2
69
Co
nti
nu
ou
s
.00
02
5
.00
07
0.0
17
37
.02
26
0
1 43 15
12
0
Onc
eV
ent
pip
eG
asC
hro
mat
og
rap
hY
es
.040
65.0
00
02
.00
00
6a
Incin
era
ted
W~fte
100
Inte
rmit
ten
t15
6
.00
36
0.0
1100
.000
06.0
00
02
Not
Sp
ecif
ied
Yes
Nev
er
No
TABLE VI-IIINATIONAL EMISSIONS INVENTORY
VINYL ACETATEFROM
ACETYLENE - ACETIC ACID
EXPLANATION OF NOTES
(1) Odor problem limited to plant property.
(2) Average number of emergency situations a year was not specified.
(3) 804 1bs./hr. of liquid waste burned weekly in open air.
(4) In stream sample taken under ordinary conditions.
(5) 93% air.
(6) 95/0 air.
(7) Estimated by Houdry assuming total conversion of organics to carbondioxide and water.
167
O"l
00
INC
INER
ATI
ON
DEV
ICES
EPA
Cod
eN
o.fo
rp
lan
tu
sin
gF
lov
Dia
gram
(Fig
.I)
Str
eam
I.D
.D
evic
e1
.D
.N
o.T
ype
of
Com
poun
dIn
cin
era
ted
Typ
eo
fD
evic
e-
Fla
reIn
cin
era
tor
Oth
erM
ate
rial
Incin
era
ted
-L
b./
Hr.
Au
xi1
liary
Fu
elR
eq'd
.-
Ex
clu
din
gP
ilo
tT
ype
Rat
e-
BT
IJ/H
r.D
evic
eo
rS
tack
Hei
gh
t-
Fee
tIn
stall
ed
Co
st-
Mat'
l.&
Lab
or
-$
Inst
all
ed
Cos
tb
ased
on"y
ear"
-d
oll
ars
Inst
all
ed
Co
st-
¢/l
b.
of
Vin
yl
Aceta
teO
per
atin
gC
ost
-A
nn
ual
-$
(19
72
)v
alu
eo
fH
eat
or
pow
erR
eco
ver
y-
$/Y
r.N
etO
per
atin
gC
ost
-$
/Yr.
Net
Op
erat
ing
Co
st-
c/1
b.
of
Vin
yl
Aceta
teE
ffic
ien
cy
-%
-CC
R
TABL
EV
I-IV
CATA
LOC
OF
EMIS
SIO
NCO
NTR
OL
DEV
ICES
VIN
YL
ACE
TATE
FROM
ACE
TYLE
NE
:-A
CE
TIC
AC
ID
14
-29 V
A-l
Hea
vyL
iqu
idO
rgan
icW
aste
x
450
No Not
Sp
ecif
ied
21
0,0
00
1971
.14
28
,00
0o 2
8,0
00
.07
99
9.9
+
®
14
-49 V
A-2
Hea
vyL
iqu
idO
rgan
icW
aste
Atm
osp
her
icL
iqu
idW
aste
Bu
rner
804
No
6 16
,00
019
62.0
11
2.5
00
o 2,5
00
.001
79
9.9
+
TAB
LEV
I-V
NU
MBE
RO
FA
CET
YLE
NE
BASE
DV
INY
LA
CET
ATE
PLA
NTS
BY19
80
F~
0')
1..0
Cu
rren
tC
apac
ity
(1)
431
NO
TE:
--
Mar
gin
alcap
acit
y
225
(2)
Cu
rren
tC
apac
ity
on
-str
eam
in19
80
20
6
Dem
and
1980
35
6
Cap
acit
yE
cono
mic
Num
ber
Cap
acit
yto
be
Pla
nt
of
Ne\<
'19
80A
dded
Siz
ep
lan
ts
35
615
015
01
(3)
(1)
All
cap
acit
ies
inM
Mlb
s.(2
)U
nio
nC
arb
ide
isclo
sin
git
s22
5M
MIb
s./
yr.
pla
nt.
Itis
po
ssib
leth
at
Nati
on
al
Sta
rch
and
Ch
emic
alC
ompa
ny's
50M
Mp
lan
t~ill
be
ab
leto
stan
dp
rice
pre
ssu
re,
(3)
One
ne~
pla
nt
of
this
typ
eis
pro
jecte
don
the
po
ssib
ilit
yth
atra~
mate
rial
co
sts
cou
ldm
ake
are
vis
ed
acety
len
eb
ased
pla
nt
eco
no
mic
ally
feasi
ble
.
Em
issi
on
TAB
LEV
I-V
IE
MIS
SIO
NSO
URC
ESU
MM
ARY
TON
/TO
NO
FV
INY
LA
CET
ATE
So
urc
eT
ota
l
Lig
ht
End
sV
ent
Incin
era
tio
no
fL
iou
idW
aste
"H
yd
roca
rbo
ns
.02
99
60
.02
99
60
part
icu
late
s0
Neg
lig
ible
0
NOx
0N
eg
lig
ible
0
SOx
00
0
CO0
00
Ch
emic
alV
iny
lA
ceta
te
TAB
LEV
I-V
II~~IGHTED
EM
ISSI
ON
RATE
S
Pro
cess
Ace
tyle
ne
-A
ceti
cA
cid
Incre
ase
dcap
acit
y.~1~5~0~
__
'-I ....
Incre
ase
dE
mis
sio
ns
Feig
hti
ng
Poll
uta
nt
Em
issi
on
sL
b./
Lb
.M
ML
bs.
IYe
ar
Facto
r
Hy
dro
carb
on
s.0
29
96
4.5
80
Part
icu
late
s0
060
NOx
00
40
SOx
00
20
CO0
01
Feig
hte
dE
mis
sio
ns
MML
bs.
/Year
360 o o ° o
Sig
nif
ican
tE
mis
sio
nIn
dex
~3
60
Vinyl Acetate via Ethylene
Table of Contents
Section Page Number
I.II.III.IV.V.VI.
IntroductionProcess DescriptionPlant EmissionsEmission ControlSignificance of PollutionVinyl Acetate Producers
List of Illustrations and Tables
Flow DiagramMaterial BalanceGross Heat BalanceEmission InventoryCatalog of Emission Control DevicesNumber of New Plants by 1980Emission Source SummaryWeighted Emission Rates
172
VAC-lVAC-2VAC-3VAC-4VAC-SVAC-6
Figure VAC-ITable VAC-ITable VAC-IITable VAC-IIITable VAC-IVTable VAC-VTable VAC-VITable VAC-VII
VAC-l
I. Introduction
Vinyl acetate is an important pertochemical used to produce polymer.Most of the vinyl acetate manufactured is polymerized into polyvinyl acetatewhich is used in latexes, emulsion paints, adhesives and various textilecoatings or further processed into polyvinyl alcohol or polyvinyl butyral.About 10 percent is co-polymerized with vinyl chloride, ethylene and othermonomers.
Vinyl acetate is currently produced by three processes. The newer twoutilize ethylene, oxygen and acetic acid in a vapor or liquid phase reaction.The oldest process, which presently accounts for 30 percent of vinyl acetateproduction, uses acetylene and acetic acid in a vapor phase reaction.Because of high acetylene raw material costs, little, if any, growth isexpected in the acetylene based vinyl acetate industry.
Of the ethylene processes, the vapor phase method is the most popularand future growth is expected in that area. The liquid phase process wastried by Celanese at Bay City, Texas with a 100 MM lbs./year plant. Corrosionproblems interrupted produ~tion for a while until extensive rebuilding solvedthese problems.
Currently, there are two patented vapor phase processes available; theU. S. I. Process and the Bayer-Hoechst Process. They both rely on the samereaction scheme, similar catalysts and similar separation techniques. Emissionsdata found in this report are for a plant using the USI technique. There aretwo other vinyl acetate plants in the U. S. which rely on ethylene feed, oneis operating today and one is in the start-up phase. Both use the BayerHoechst method.
The only emissions ~eported for the ethylene process were from the flaringof light hydrocarbons and from the incineration of liquid waste. Assumingthat complete combustion is achieved the only emissions to the atmosphereare trace amounts of NOx '
VAC-2
II. Process Description
The following is a description of the USI Vapor Phase Process for vinylacetate from ethylene, acetic acid and oxygen. The Bayer-Hoechst Process isquite similar and any description of that method would merely be repetitious.(See Fig. VAC-l)
Ethylene, acetic acid and oxygen can react in the vapor phase to producevinyl acetate and water.
place in a fixed bed tubular reactor with a supportedThe reactor operates at 15 to 100 PSIG and below
is exothermic and heat is removed on the shell side by
The reaction takesnoble metal catalyst.3500 F. The reactioncooling water.
Aside from vinyl acetate the reactor effluent consists of water, carhondioxide, unreacted feed and small auantities of oxygenated hydrocarbons. Carbondioxide is produced by side combustion reactions, the most important of whichis the oxidation of ethylene. The yield is about 91% for vinyl acetate. Ofthe other 9%, 8% is lost to CO2 formation and 1% is lost to all other by-products.Conversion is low due to the explosion limit of the ethylene/oxygen mixture.
Prior to introduction in the reactor, acetic acid and ethylene pass toan acid vaporizer where ethylene is saturated with acetic acid to give therequired ethylene/acetic acid ratio. The acid tower also serves the purposeof removing any heavy impurities present. Ethylene and acetic acid aresuperheated upon leaving the vaporizer and mixed with oxygen. This combinedstream is fed into the reactor.
Reactor effluent is cooled and sent to an absorber where uncondensed vinylacetate is absorbed in acetic acid. The absorber off-gas is then water scrubbedto remOve any excess acetic acid. The scrubber overhead containing ethylene,carbon dioxide and water is sent to a carbon dioxide absorber where carbondioxide is removed by potassium carbonate. The overhead contains ethylene,which is recycled to the acid tower. Carbon dioxide is stripped from thepotassium carbonate solution and vented to the atmosphere.
Crude vinyl acetate leaving the acetic acid absorber is sent to primarydistillation. This system consisting of a distillation column and twoauxilliary strippers removes water from the product. Dry vinyl acetate passesto two distillation columns where light ends and heavy ends are removed. Thefinished vinyl acetate is of a high quality suitable for polymerization.
174
III. Plant Emissions
A. Continuous Air Emissions
1. Carbon Dioxide Vent
Carbon dioxide, absorbed by potassium carbonate from thenon-condensible gas stream is subsequently stripped and vented tothe atmosphere. A small amount of water (2.3 vol. %) is carriedwith the carbon dioxide. No pollutants enter the atmosphere fromthis vent.
2. Light Ends Flaring
Light hydrocarbons and some inerts, vhich are purged from thesystem (from the vater scrubber and the light ends distillationcolumn) are mixed 'to,i th fuel gas and flared. The stream enteringthe flare consists of ethylene, fuel gas and smaller amounts ofoxygen, oxygenated hydrocarbons and inerts such as argon and nitrogen.The respondent claims that the f 1 are is smokeless so it is assumedthat combustion is complete to carbon dioxide and v'ater. The onlypollutant entering the atmosphere vould, therefore, be trace amountsof NOx and possibly some unburned hydrocarbons.
3. Heavy Ends Incineration
Heavy components removed from the acid vaporization tower and theheavy ends column are burned in an incinerator. The inlet to theincinerator contains acetic acid, mixed glycol diacetates, vinylacetate, polyvinyl acetate and ethyl acetate. Since no nitrogen orsulfur is present in any of the components burned, the combustionproducts are carbon dioxide and water. The only air pollutantreleased is NOx ' which is present in trace amounts.
4. Storage Losses
Vinyl acetate is stored under a blanket and the respondent reportsfloating roofs will be installed by 1973. Acetic acid is allowed tovent to the atmosphere. On a whole, storage losses should be small.
B. Intermittent Air Emissions
No sources of intermittent air emissions were reported.
C. Continuous Liquid Waste
226 GPM of v7aste water are produced by the process. The 'to'aste istreated on-site.
D. Odor
Thereprocess.prior to
does not seem to be an odor problem associated vith thisAll vent gases are incinerated to carbon dioxide and water
release to the atmosphere.
F. Fugitive Emissions
No emissions due to leaks, spills, etc. were reported.
175
VAC-4
IV. Emission Control
The emission control devices that have been reported as being employed byvinyl acetate producers using the ethylene process are summarily describedin Table IV of this report. An efficiency has been assigned each devicewherever data sufficient to calculate it have been made available. Twotypes of efficiencies have been calculated.*
(1) "CCR" - Completeness of Combustion Rating
CCR - lbs. of 02 reacting (with pollutant in device feed)x 100lbs. of O2 that theoretically could react
(2) "SERR" - Significance of Emission Reduction Rating
SERR = (pollutant x weighting factor)in - (pollutant x weightingfactor)out
(pollutant x weighting factor*)in x 100
*Weighting factor same as Table VII weighting factor.
Emission Control Devices
1) Light Ends Flare
The respondent reports that the flare is smokeless, therefore,complete combustion is assumed and efficiencies are near 100%.
2) Liquid Waste Thermal Oxidizer
This device is included in the Catalog of Emission Control Devices,Table IV even though it releases gases to the atmosphere because it servesthe purpose of destroying harmful liquid waste.
*See Appendix V for a complete explanation of these ratings.
176
VAC-5
V. Significance of pollution
It is recommended that no in-depth study be made of the ethylene processfor vinyl acetate. The only pollutant reported as being released to theatmosphere from this process are trace amounts of NOx ' Assuming that any newplant will employ modern technology to control emissions, there should be noneed for further study of the subject process.
The methods outlined in Appendix IV of this report havebeen used to forecast the number of new plants by 1980 and to estimate theweighted annual emissions from these new plants. This work is summarized inTables V, VI and VII.
177
VAC-6
VI. Vinyl Acetate Producers
Borden Chemical Co.
Celanese Chemical Co.
du Pont
Nat. Starch & Chemical Co.
Union Carbide
U. S. Industrial Chemicals
Location
Geismar, La.
Clear Lake, TexasBay City, Texas
La Porte, Texas
Long Matt, Texas
Texas City, Texas
La Porte, Texas
capacity (MM Lbs.!Year)Ethylene Acetylene
150
300*350"~
300
56
330
Total
~'(Estimated
**Plant to be phased out by 1974
178
1,280 431
17Q
""--~
~
Str
eam
1.
D.
No.
12
34
TAB
LEV
AC
-IM
ATE
RIA
.LBA
.LA
NCE
VINYi:ACE~
VIA
ETHYLE~PROCESS
56
78
9
Str~
Com
pone
nt
Fre
shF
eed
Rec
ycl
eT
ota
lF
eed
Rea
cto
rE
fflu
en
t----------
CO2
Pu
rge
Lig
ht
End
s&
Inert
s!!~'::LEn~
Was
teW
ater
Pro
du
ct
Eth
yle
ne
Ace
tic
Aci
d
Oxy
gen
'Arg
on
Nit
rog
en
Vin
yl
Aceta
te
Car
bon
Dio
xid
e
Wat
er
Met
hyl
Aceta
te
Acr
ole
in
Ace
tald
ehy
de
Gly
col
Po
lyv
iny
lA
ceta
te
Eth
yl
Aceta
te
Mis
cell
aneo
us
Org
anic
s
.36
72
.71
52
.28
35
.00
10
.00
04
1.3
67
3
3.3
04
8
2.8
60
4(1
)
(3)
(3)
(3)
(3)
6.1
65
2
3.6
72
0
3.5
75
6
.28
35
.00
10
.00
04
7,5
32
5
3.3
22
0.0
17
2
2.8
62
2.0
01
8
.00
13
.00
13
.00
10
.00
10
.00
04
.00
04
1.00
17.0
00
2.0
01
51
.00
00
.10
16
.10
16
(4)
2390
.00
09
(4)
.23
81
.00
01
.00
01
()
()
(.0
00
1)
(.0
00
1)
()
()
.00
15
.00
15
.00
09
.00
09
.00
02
.00
02
.00
05
.00
05
(2)
7,5
32
5.1
02
5.0
20
3.0
05
9.2
38
61
.00
00
(1)
Ap
pro
xim
ate
recy
cle
rate
bas
edon
10%
eth
yle
ne
con
ver
sio
nan
d20
%aceti
cacid
co
nv
ers
ion
.
(2)
Est
imat
ed.
(3)
Rec
ycl
eactu
all
yco
nta
ins
som
eo
fth
ese
gase
s,am
ount
has
no
tb
een
est
imate
d.
(4)
Scr
ub
ber
pu
rge
als
oco
nta
ins
som
eo
fth
ese
gase
s.
TABLE VAC-IIGROSS HEAT BALANCE (REACTOR SECTION ONLY)
VINYL ACETATEVIA
ETHYLENE PROCESS
Heat In
Enthalpy of reactants at 177 0 C(above base temperature*)
Exothermic heat of reaction**
Heat Out
Heat removed by coolant
Residual enthalpy(above base temperature)
BTU/Lb. Vinyl Acetate
1,544
1,600
3,144
BUT/Lb. Vinyl Acetate
1,600
1,544
3,144
*Base temperature = 25 0 C.**Includes vinyl acetate reaction and the combustion reactions ~~ich form
C02 and H20.
181
TABL
EV
AC
-III
NA
TIO
NA
LE
MIS
SIO
NIN
VEN
TORY
--
VIN
YL
AC
ET
AT
E--
--
VIA
--
ETHYLE~PROCESS
pla
nt
EPA
Cod
eN
o.cap
acit
y-
Ton
so
fV
iny
lA
ceta
te/Y
r.R
ange
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uct
ion
-%
of
Max
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mis
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toA
tmo
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1.
D.
No.
Str
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+N
one
Co
nti
nu
ou
s
Calc
ula
ted
No01
480
.00
88
1.0
4715 +
7 1 Incin
era
tio
no
fL
iou
idV
aste
1 50 48 1600
Yes
+N
one
Calc
ula
ted
No6 1 Lig
ht
End
sF
lam
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om
bu
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ases
14
,12
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a o + o o1 100
14 1000
Yes
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51
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55
34
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31
1+
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0
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e
30
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15
,00
0o
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Pu
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62
7.0
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92
3985
Co
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nu
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s
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teA
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lo
fV
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om
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Part
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Gas
Tem
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mis
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rber
/Scr
ub
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reA
nal
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ate
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qu
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of
Sam
pli
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Sam
ple
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Typ
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fA
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Pro
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Ton
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Ton
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(Fig
.I)
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.D
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Incin
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./H
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yl
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atin
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ual
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alu
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b.
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yl
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tate
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TAB
LEV
AC
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CATA
LOG
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--
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30
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67
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uid
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500
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1970
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100%
TAB
LEV
AC
-VNU
MBE
RO
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WPL
AN
TSBY
1980
USI
NG
ETH
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NE
TOPR
OD
UCE
VIN
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AC
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Cu
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Cap
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Num
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in19
8019
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280
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2,2
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2,2
00
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00
300
4
(1)
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Ibs.
/year.
(2)
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and
for
eth
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pro
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assu
min
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SOx
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TAB
LEV
AC
-VI
EM
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SOU
RCE
SUM
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yl
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te
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yle
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TAB
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AC
-VII
WEI
GH
TED
EM
ISSI
ON
RA
TES
Incre
ase
dcap
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y19
801
,20
0M
ML
bs.
/Year
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Po
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tan
t
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s
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late
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b./
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Incre
ase
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mis
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ns
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s./Y
ear
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gh
tin
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acto
r
80 60 40 20
1
Wei
gh
ted
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issi
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bs.
/Year
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Sig
nif
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tE
mis
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dex
=0
Vinyl Chloride via EDC Pyrolysis
Table of Contents
Section page Number
1.II.III.IV.V.VI.
IntroductionProcess Descriptionplant EmissionsEmission ControlSignificance of pollutionVCM Producers
List of Illustrations & Tables
Flow DiagramNet Material BalanceGross Heat BalanceEmission InventoryCatalog of Emission Control DevicesNumber of New Plants by 1980Emission Source SummaryWeighted Emission Rates
187
VC-lVC-2VC-3VC-6VC-8VC-9
Figure VC-ITable VC-ITable VC-IITable VC-IIITable VC-IVTable VC-VTable VC-VITable VC-VII
VC-l
I. Introduction
About 90 percent of the vinyl chloride monomer in the United States isproduced by cracking dichloroethane. The older process using acetyleneand hydrogen chloride feed has been or shortly will be completely replacedby the dichloroethane process because of the high cost of acetylene. Thedichloroethane feedstock is produced by either direct chlorination ofethylene, oxychlorinationof ethylene or a combination of the two processes.Most of the air emissions associated with production of vinyl chloride monomeroriginate in the production of dichloroethane and are covered under separatestudies of that chemical. vapor emissions from the cracking operation aresmall provided that the hydrogen chloride by-product can be recycled to adichloroethane plant (which is usually the case) or has value for Someother operation. In addition to the vapor emissions, a heavy chlorinatedhydrocarbon tar is produced which will add to the air pollution problem ifthis material has to be burned.
A new process has been offered by Lummus Co. (Hydrocarbon Processing,March, 1971, p 11) which produces VCM from ethane, chlorine and air. Thisprocess, "Transcat" , is reported to have a l¢/lb. lower VCM manufacturingcost, primarily because of the use of ethane in place of ethylene feedstock.In addition, tar and other chlorinated hydrocarbons are recycled to thecracking reactors so that the process is "free of any known pollutionproblems", (C & EN, March 1, 1971). A search of the Hydrocarbon Processingworld wide boxscore and plant construction does not shown any new vinylchloride plants presently being built which use the Lummus technology.However, if the process has the reported economic advantage it will probablybe incorporated into future VCM construction.
188
VC-2
II. Process Description
Dry dichloroethane which is often known as ethylene dichloride, isdehydrochlorinated to vinyl chloride as it passes through the packed tubesof a cracking furnace.
H H HThe chemical reaction is: CI-C-C-Cl----). H-C
I •H H
~C-Cl + HCl
The tubes are normally packed with pumice, charcoal or Some otherIIcontact ll type catalyst. At 900 to 9500 F and 50 PSIG, DCE conversion isabout 50 percent and yield to vinyl chloride is 94 to 97 mole percent. Thehot effluent gases are then quenched, and partially condensed, by directcontact with cold dichloroethane in a quench tower.
Effluent fractionation and product purification are generally accomplishedin three additional towers. However, each producer of VCM has his own minormodifications in the fractionation section. The following description and theFlow Diagram provide generalities about what is achieved by this furtherprocessing.
Hydrogen chloride and light chlorinated hydrocarbons are rejectedoverhead in the IIHCL" and IILight Ends" towers. The hydrogen chloride isnormally recovered by water scrubbing and recycled to the dichloroethaneplant. Trichloroethane, chlorinated C4 's and other hea\ry ends are rejectedfrom the bottom of either the IIquench tower" or the "vinyl tower ll • Containeddichloroethane is recovered by fractionation and the light and heavy endsare either further processed or disposed of by incineration and othermethods. Dichloroethane from the bottom of either the IIquench" tower orthe IIv inylll tower is recycled to both the quench tower and the feed storagetank. If the DCE is taken from the bottom of the quench tower it is purifiedbefore it is recycled. Vinyl chloride monomer is taken overhead in the"vinyl" column, generally caustic washed, and then sent to the productstorage facilities,
A "typical ll overall material balance is shown in Table I and anestimated cracking furnace heat balance is shown in Table II.
189
III. Plant Emissions
A. Continuous Air Emissions
1. Cracking Furnace Combustion Stack
All reported operators of plants producing VCM by the pyrolysisof DCE use "sweet" natural gas to fire the cracking furnace. Thereported sulfur contents vary between "less than 10 ppm" and "zero".The unit reporting the highest sulfur consumes 60 rom lb/year ofgas in the production of 700 rom lb/year of VCM. Therefore, theemission rate is less than 600 lbs/year of sulfur. As S02, thisis less than 1.7 x 10-6 tons/ton of VCM.
2. By-Product Recovery Systems
All producers of VCM employ scrubbers to recover by-product HCLwhich is either recycled or used in some other plant process. Thenon-condensible streams from the HCL recovery sections plus theother light ends from the vinyl chloride purification are eithervented, flared, or sent to another process or a pollution controldevice on another process. This is the main source of air pollutionfrom the process and the reported vent streams, as, treated by thevarious producers, are summarized in Table III.
3. Drier Vent
The pyrolysis process requires the use of dry dichloroethane.The oxychlorination process produces wet dichloroethane. Inaddition, some reported storage systems employ water seals orwater blanketing. Therefore it is presumed that a drying stepwill be required by some, if not all, process operators. One suchoperator (EPA Code No. 31-2) reports vent losses from a dryingcolumn and these are included in Table III. Since this emission is lessthan 0.005 tons per ton of VCM, an effort has not been made tocontact the other operators to determine if they have a similar vent,or if not, how the DCE is dried. Realistically, the drying stepmight be considered part of the DCE production process and, therefore,rightfully should be studied in connection with oxychlorination.
4. Storage Losses
Vinyl chloride is stored under pressure, so has no continuousvent losses. Dichloroethane feed is typically stored at atmosphericpressure so that some continuous losses will be experienced. Suchdevices as nitrogen blanketing, storage under water, or low pressurebreather valves are reported with no estimate of actual loss ratesgiven. Presumably, these losses are minimal.
B. Intermittent Air Emissions
1. Cracking Furnace Decoking
Periodically, the process side of the cracking furnace requiresdecoking. One operator (EPA Code No. 31-8) reported emissionsfrom this operation and they are summarized in Table III. It shouldbe presumed that all operators of dichloroethane cracking furnacesrequire a similar operation.
190
2. Start-Up and Emergency Vents
This type of emission is universally encountered in thepetrochemical industry and will vary from process-to-process,from operator-to-operator and even from year-to-year. Thosewhich have been reported are included in Table III.
3. Vinyl Chloride Storage
One operator (EPA Code No. 31-8) reports an estimated vinylchloride loss of 150,000 lbso/year resulting from depressurizingVCM storage for maintenance or relief valve lifting. This isabout 0.0002 tons/ton of VCM.
C. Continuous Liquid Wastes
1. Process Tar
All operators report the formation of heavy chlorinated hydrocarbons. These are all reported as going to further processingbut might ultimately end up as a waste disposal problem. Ifincinerated, the problem would be one of air emissions. Oneoperator (EPA Code Noo 31-6) reports about one ton per day ofthis material as "solid" waste. The disposal method is notreported.
2 0 Drier Column Water
The one operator who reported a drier column included acontinuous 0.3 gpm of waste water. Presumably, this iscurrently discarded but it will eventually go to an overallplant DCE recovery system that is under construction.
3. Vent Scrubbers
One operator (EPA Code No. 31-1) reported 190 gpm of wastewater from a vent scrubber. However, the main gas stream tothis scrubber is from an oxychlorination unit.
4. Cuastic Washing
One operator (EPA Cdoe No. 31-3) reported a continuous flow ofwaste caustic from the vinyl chloride washing step. It goes toa pond where it is used to neutralize HCL from other processvents. The quantity of caustic is unreported as is the ultimatepond disposal method. Presumably, all operators must wash thefinal VCM product with caustic, so all will have spent causticfor disposal.
50 Light Ends
Some operators condense a portion of this material and disposeof it as liquid waste o
D. Intermittent Liquid Wastes
The only reported intermittent water wastes are from emergencyand start-up scrubbers, or inte;qni ttent spills.
191
VC-5
E. Solid Wastes
Solid wastes from the process, are spent catalysts, spentdesiccants and broken tower packing. Only one operator (EPA CodeNo. 31-1) made an estimate of these. However, the questionnairealso covered oxychlorination and direct chlorination processes forthe production of DCE so the reported numbers are probably higherthan for DCE pyrolysis alone. 425,000 lbs./year of spent materialsand 550 cubic yards per year of broken materials were reported.Both are used as land fill within the plant. An estimate of 200cubic yards per year of miscellaneous trash which is disposed ofby a local contractor, was also reported by this operation.
Presumably, disposal of waste salts from vinyl chloride washingwith caustic will also be required, especially in the plant thatponds this material.
F. Odors
The questionnaire replies indicate that the cracking of ethylenedichloride is a process with little or no odor problems. Allreports on odors indicate that they occur infrequently and (withone exception) only on the plant property. Various chlorinatedcompounds account for the odors, among these are hydrogen chloride(but only when a scrubber malfunctions), vinyl chloride and ethylenedichloride.
The one report of odors reaching beyond property limits is theflare pond (EPA Code No. 31-3), that is used to incinerate off-gases.This odor has not resulted in any recent complaints, none beingreported in the last year.
G. Fugitive Emissions
All respondents report that fugitive emissions are minor. Onlyone gives an estimate of their magnitudes and that is based on theentire vinyl chloride production facility, including the productionof ethylene dichloride by two separate processes. The estimate,having been made by overall material balance is probably notreliable (small difference of large numbers). Thus, there seemslittle point in reporting'it here.
The logical conclusion is that due to the nature of chlorinatedhydrocarbons, the operators of this process are careful in theirmaintenance and sampling and, therefore, achieve minimal fugitivelosses.
192
VC-6
IV. Emission Control
The various emission control devices that have been reported as beingemployed by operators of vinyl chloride monomer plants are summarized inTable IV of this report, which is entitled Catalog of Emission ControlDevices. The control devices may be divided into two broad categories:(1) Combustion Devices - those devices which depend on thermal or catalyticoxidation of combustibles for emission control, and (2) Non-combustionDevices - devices that do not depend on combustion for emission control.In Table IV, all combustion devices will be assigned two efficiency ratings(when data are available), they are:
(1) CCR - Completeness of Combustion Rating
CCR = Lbs. of 02 that react with pollutants in feed to device x 100Lbs. of 02 that theoretically could react with these pollutants
(2) SERR - Significance of Emission Reduction Rating
SERR = weighted pollutants in - weighted pollutants out x 100weighted pollutants in
A more detailed discussion of these ratings may be found in Appendix V.Whenever data are available, the non-combustion pollution control devices alsohave been assigned two efficiencies. The first, is merely a calculation ofefficiency in the usual sense, that is percent removal of a specific pollutant(or pollutants) for which the device has been designed. However, as alsodescribed in Appendix V, many devices do not remOve any significant amountsof some pollutants. Thus, a more realistic efficiency rating is the SERR asdescribed above, because it is a measure of the reduction in total pollutantsweighted by their noxiousness. In all cases this will either be less than orequal to the efficiency that is usually reported.
One operator (EPA Code No. 31-5) reports scrubber data which areinconsistent. Part III of the questionnaire for streams A & B reports anaverage removal of 28,600 lbs./hr. of HCL. Yet, Part IV of the questionnairefor device 101 (coded VC-2 in this report), indicates only 200,000 lbs./daytotal gas flow (8,333 lbs./hr.). The later number is probably correct becauseit is consistent with the 300 gpm of water to the scrubber and the 8% RCLsolution outlet that are reported.
It is unlikely that any change in process operating conditions can bemade that will reduce air emissions. Overall selectivities in excess of94% are reported by all of the process operators, thus it is safe to assumethat either a change in catalyst or the use of less severe cracking conditionscould only achieve minimal if any improvement in selectivity. Furthermore,most of the non-selective products (light and heavy chlorinated hydrocarbons)are reported to go to other processes where they presumably are convertedto marketable or recycleable products. Obviously, any increased severity wouldresult in a lower selectivity and more potential pollution.
There is a possibility that some minor reduction in air emissions could beachieved by the use of a purer raw material. One operator (EPA Code No. 31-3)reports using 497 rom 1bs./year of 99.95% DCE as feed, while another (EPA CodeNo. 31-2) reports using 545 rom 1bs./year of 98% DCE as feed. Obviously, thesecond of these units is required to dispose of more than 10 rom 1bs./year of
1~
VC-7
additional organic material. However, since both units have associated sideproduct recovery systems, this is probably not a pertinent observation,especially since the unit with the more pure feed also reports a greater quantityof air emissions.
Development work directed toward further reductions in emissions from thisprocess falls into the following general categories:
1) Condensation of intermittent releases.
2) Use of vent or waste streams in other processes.
3) More efficient incineration.
4) HCL recovery from incineration.
19~.
VC-8
v. Significance of pollution
It is recommended that an in-depth study of this process ~~£ b~ undertakenat this time. Although the growth rate of vinyl chloride monomer productionby pyrolysis is forecast to be significant, the emission data indicate thatthe quantity of pollutants from the air emissions is less significant thanfrom many of the other processes that are currently being surveyed.
The methods outlined in Appendix IV of this report have been used t~
forecast the number of new plants that will be built by 1980 and to estimatethe total weighted annual emissions of pollutants from these new plants.This work is summarized in Tables V, VI, and VII.
Support for the Table V forecast of new plants has appeared in print asrecently as May 10, 1972 (Chemical Week, pp 13-14). This article indicatesthat one new 700 to 800 MM 1bs./year plant every 14-18 months from now until1980 is a reasonable estimate. Thus, the number of new units to be built,especially when the size of each unit is considered, is certainly significant.
However, on a weighted emission basis, a Significant Emission Index (SEI)of 2,159 has been calculated in Table VII. This is substantially lessthan the SEI's that are anticipated for other processes in the study. Hence,the recommendation to exclude an in-depth study on vinyl chloride monomerproduction from the scope of work.
195
VC-9
VI. VCM Producers
The following tabulation of producers of vinyl chloride monomer indicatespublished production capacity by process and location.
Company
Allied ChemicalAmerican ChemicalContinental OilDow Chemical
Ethyl Corporation
B. F. GoodrichPPC Industries
Shell Chemical
Monochem, Inc.Tenneco Chemicals
1£.cation
Baton Rouge, La.Long Beach, Cal,Lake Charles, La.Freeport, TexasPlaquemine, La.Oyster Creek, TexasBaton Rouge, La.Pasadena, TexasCalvert City, Ky.Lake Charles, La,Guayanilla, P. R.Deer Park, Texas
Geismar, La.Pasadena, Texas
300165 - 170
600180
300 - 340800270150
875 - 1000300
500 - 575700
Sub-Total - 5,140 - 5,385 (1)
300225 - 250
Sub-Total - 525 - 550 (2)
Grand Total - 5,665~~
(1) All by pyrolysis of idchloroethane.
(2) All by hydrochlorination of acetylene.
196
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Fre
shL
igh
tH
eavy
End
sV
iny
lC
hlo
rid
eC
ompo
nent
Fee
dB
y-P
rod
uct
Hy
dro
carb
on
sP
rod
uct
Pro
du
ct
HCL
.58
35
Lig
ht
Hyd
roca
rbon
s.0
01
5(a
)
-D
ich
loro
eth
ane
1.6
495
~ 00
1.0
000
(b)
Vin
yl
Ch
lori
de
Hea
vyE
nds
.06
45
1.6
495
.58
35
.00
15
0.0
64
5(c
)1
.00
00
(a)
Pro
bab
lyin
clu
des
eth
yl
ch
lori
de,
eth
yle
ne,
acety
len
ean
dch
lori
ne;
po
ssib
lyas
larg
eas
4ti
mes
val
ue
show
n.
(b)
Incl
ud
eslo
adin
g,
un
load
ing
and
sto
rag
elo
sses
of
app
rox
imat
ely
0.1%
.
(c)
Incl
ud
esv
iny
lch
lori
de
loss
es;
stre
amp
rob
ably
als
oco
nsi
sts
of
tric
hlo
roeth
an
e,
ch
lori
nate
dC
4's
and
cok
e.
Heat Out----
TABLE VC-IIVINYL CHLORIDE MONOMER
VIADICHLOROETHANE PYROLYSIS
GROSS HEAT BALANCE*
of VCM produced11 11 11
Endothermic heat of reactionQuench (to 2000 F)
**Heat losses & inefficiencies
Heat In
Total
468 BTU!LB.531 11
946 11
l'9'45" " "
Fuel to cracking furnaceTotal
* Basis
1945 BTU/LB. of VCM produced1945 " "" "
199
Conversion (DCE) per pass 50%
Selectivity (Moles VCM produced)(Moles DCE converted) 96%
Furnace outlet temperature 9000 F
** Some portion of the heat in thiscategory is most probably recoveredby steam economizer type devices.
TAB
LEV
C-l
llE
MIS
SIO
NS
INV
ENTO
RY
FOR
PRO
DU
CTI
ON
OF
VIN
YL
CH
LOR
IDE
MON
OMER
BYPY
RO
LYSI
SO
FD
ICH
LOR
OET
HA
NE
Pag
e1
of
6
31
-2
16
5,0
00
No
ne
Not
Ap
pli
cab
le(e
)
0.0
00
20
Fla
reP
ond
o14
2
Non
e(f
)
VC-
9
8,4
43
Co
nti
nu
ou
s
0.0
28
Non
e
Nev
erC
alc
ula
ted
Yes
0.0
58
0.0
00
09
0.0
58
04
31
-3
33
Non
e
14
7,5
00
Que
nch
Tow
erV
ent
686
Inte
rmit
ten
t
0.0
00
04
3
No
ne
t:ev
erC
alc
ula
ted
No
1 175
4 125
8256 0.0
00
02
2'0
.00
00
65
VC-
10
Nev
erC
alc
ula
ted
No
VC-
Sta
rt-u
pan
dE
mer
genc
yV
ent
2,3
50
Inte
rmit
ten
t0
.5
1 120
12 Ver
yH
ot50
0
~O.OOOOI
'.0
.00
00
1
"-0
.00
00
1N
one
"-0
.00
00
1
o
0.0
04
65
~0
.00
00
1
Non
e
Dri
erV
ent
200
Co
nti
nu
ou
s
0.0
00
24
'8
flo
ors
abo
ve
gra
de
Infr
eq
uen
tly
GLC
No
1 96
.53 10
0-
120
170.0
01
37
0.0
02
59
0.0
00
49
Non
e
Nev
erC
alc
ula
ted
No
Refr
igera
nt
Lea
kag
e8
(av
g.)
Vari
ab
le
0.0
00
1
1 120
8 80 2.4
o
31
-1
30
0,0
00
VC-
4
0.0
14
40
0.0
06
11
0.5
49
99
0.0
24
44
0.0
03
93
3fe
et
abo
ve
gra
de
Wee
kly
GLC
&W
etY
es(e
)
1 148
36 90 11
,00
0(e
)
0.0
01
72
0.0
07
56
0.0
01
09
0.0
06
34
0.0
00
40
0.0
01
86
0.0
06
24
Scr
ub
ber
Eff
luen
t4
6,9
80
(e)
Co
nti
nu
ou
sF
low
-L
bs.
/Ho
ur
Flo
wC
hara
cte
rist
icif
Inte
rmit
ten
t,H
rs./
Yr.
Co
mp
osi
tio
n,
To
ns/
To
nVC
MD
ich
loro
eth
an
eV
iny
lC
hlo
rid
eE
thy
lC
hlo
rid
eA
cety
len
eH
yd
rog
enC
hlo
rid
eC
hlo
rin
eE
thy
len
eP
rop
yle
ne
Met
han
eM
isc.
Ch
lori
nate
dH
yd
roca
rbo
ns
Car
bo
nD
iox
ide
Car
bo
nM
onox
ide
Nit
rog
en
Oxy
gen
Wat
erS
ampl
eT
apL
oca
tio
n
Dat
eo
rF
req
uen
cyo
fS
amp
lin
gT
ype
of
An
aly
sis
Odo
rP
rob
lem
Ven
tS
tack
sN
umbe
rH
eig
ht,
Ft.
Dia
met
er,
Inch
esE
xit
Gas
Tem
p.o
fSC
FMP
erS
tack
Em
issi
on
Co
ntr
ol
Dev
ices
(b)
Wat
erS
cru
bb
erIn
cin
era
tor
Refr
igera
ted
Co
nd
ense
rF
lare
Oth
ero
rN
one
Sum
mar
yo
fA
irP
oll
uta
nts
Hy
dro
carb
on
s(c
)P
art
icu
late
(d)
NOx
SOx
CO
Com
pany
Lo
cati
on
EPA
Cod
eN
umbe
rD
ate
on
-str
eam
cap
acit
y,
Ton
sV
CM
/Yr.
Av
erag
eP
rod
ucti
on
,T
on
s/Y
r.R
ange
inP
rod
ucti
on
,%
of
Max
.(a
)E
mis
sio
ns
toA
tmo
sph
ere
Str
eam
""o o
TAB
LEV
c-ll
1EMISSlu~S
INV
ENTO
RY
FOR
PRO
DU
CTI
ON
OF
VIN
YL
CH
LOR
IDE
MON
OMER
BYPY
RO
LYSI
SO
FD
ICH
LOR
OET
HA
NE
Pag
e2
of
6
Tra
ce
0.0
00
10
.00
00
65
Bal
ance
96.5
%B
alan
ce
Satu
rate
dN
one
Non
eN
on
eN
on
e
Nev
er
Nev
er
Nev
erN
ever
Nev
erC
alc
ula
ted
Calc
ula
ted
Pu
rge
Rat
eE
stim
ated
Est
imat
edE
stim
ated
No
No
No
No
No
No
Non
e(h
)1
21
11
110
110
115
40(g
)12
64
8(g
)10
0-
120
Am
bien
tA
mbi
ent
Am
bien
tA
mbi
ent
Am
bien
t1
290
.33
Unk
now
nU
nkno
wn
Unk
no,,'
l1
VC-
2VC
-5
VC-
6
No
ne
Non
eN
on
e
0.0
00
12
0.0
05
5
N o -'
Com
pany
Lo
cati
on
EPA
Cod
eN
umbe
rD
ate
on
-str
eam
Cap
acit
y,
Ton
sV
CM
/Yr.
Av
erag
eP
rod
uct
ion
,T
on
s/Y
r.R
ange
inP
rod
uct
ion
,%
of
Max
.(a
)E
mis
sio
ns
toA
tmo
sph
ere
Str
eam
Flo
w-
Lb
s./H
ou
rF
low
Ch
ara
cte
rist
icif
Inte
rmit
ten
t,H
rs./
Yr.
Co
mp
osi
tio
n,
To
ns/
To
nVC
MD
ich
loro
eth
ane
Vin
yl
Ch
lori
de
Eth
yl
Ch
lori
de
Ace
tyle
ne
Hyd
roge
nC
hlo
rid
eC
hlo
rin
eE
thy
len
eP
rop
yle
ne
Met
hane
Mis
c.C
hlo
rin
ate
dH
yd
roca
rbo
ns
Car
bon
Dio
xid
eC
arb
on
Mon
oxid
eN
itro
gen
Oxy
gen
Wat
erS
ampl
eT
apL
oca
tio
n
Dat
eo
rF
req
uen
cyo
fS
amp
lin
gT
ype
of
An
aly
sis
Odo
rP
rob
lem
Ven
tS
tack
sN
umbe
rH
eig
ht,
Ft.
Dia
met
er,
Inch
esE
xit
Gas
Tem
p.o
fSC
FMP
erS
tack
Em
issi
on
Co
ntr
ol
Dev
ices
(b)
Wat
erS
cru
bb
erIn
cin
era
tor
Refr
igera
ted
Co
nd
ense
rF
lare
Oth
ero
rN
one
Sum
mar
yo
fA
irp
oll
uta
nts
Hy
dro
carb
on
s(c
)P
art
icu
late
(d)
NOx
SOx
CO
31
-4
(g)
31
-5
21
6,0
00
o
HCL
Tow
.er
No
n-c
on
den
sib
le6 C
on
tin
uo
us
0.0
00
04
1
0.0
00
08
2
Tan
kV
ent
280
Co
nti
nu
ou
s
0.0
05
5
Safe
tyR
eli
ef
3(i)
Co
nti
nu
ou
s
31
-6
20
0,7
50
o
Scr
ub
ber
&S
tack
Sea
lU
nkno
wn
Em
erge
ncy
Ven
tU
nkno
wn
Inte
rmit
ten
tU
nkno
wn
3.5%
Lo
adin
gV
ent
Unk
now
nIn
term
itte
nt
GU
KIl
UW
U
Tra
ce
31
-7
(g
)
Pag
e3
of
6
31
-7
85
,00
0"
NQ
0000
5
'Hea
vyE
nd
s'V
ent
5 Co
nti
nu
ou
s
0047
8
'o.S
"7E
nd
e'V
ent
516
Co
nti
nu
ou
s
.00
03
7.0
00
37
.00
11
1
HO
neN
on.
Non
..N
.ver
N.v
.rN
lv.r
Calc
'd.
Cd
c'd
.C
_Ic
'dN
o11
0N
oV
eaV
etY
es1
11
14
04
44
43
34
lOS
120
120
No
No
No
.00
03
7.0
00
37"
31-4
I~\r
',iii.
43
2,0
00
,410'~OO
to4
75
,00
0
'Lig
ht
lnd
a,
'L,I
Bht
En
ds'
Ven
tV
ent
200
200
Co
nti
nu
us
CQ
nti
nu
ou
s
!
See
Co
nti
nu
atiQ
n
9 Co
nti
nu
ou
s
EDC
vap
ori
zer
Ven
t
1 1.00
008
.00
06
8
206
Co
nti
nU
QU
B
.00
11
1
.00
01
21
.00
00
3N
an'
Ho
n.
Hon
e".
v.r
£.t1
l111
t.C
ll.'
4.
Cd
c'd
.NQ
No
No
Vea
Ves
Ves
11
18
08
014
01
.51
.53
9012
010
5
V'C
-ll
NQNQ
+
EDC
Dri
er
Ven
t
~!\
r
•
lll'
j
.~l
I Dia
tUla
tiQ
R:v
ent
Gas
ille
ader
6080
.Co
nti
nu
ou
s
I I I \.01
056
1.21
465
,05
06
6.0
0115
8N
on.
One
il·
1964
VlIH
oua
No
VI'
S1 40 30 80 13
50y
es-
V'C
-18
+
o o 0, o o n
<0
00
01
""i\1
lHe
v"I.
Hll
iUa
No No
VCM
Dri
er
Ven
t
15Ib
./m
Q.
lnte
rmit
ten
t
£.0
00
01
Inte
rmit
toln
t
Com
pany
Lo
cati
on
EPA
cod
eN
o.D
ate
on
-atr
eam
Cap
adty
,,T
ona
VC
H/V
r.A
vera
geP
rod
uct
ion
.T
ons
VC
M/V
r.R
ange
inP
rod
uct
ion
,%
of
Ma
x.<
a)E
mis
sio
ns
toA
tmo
sph
ere
Str
eam
Flo
w-
Ibs.
/hr.
Flo
wC
hara
cte
rist
ic)
'::on
tlnu
OU
8o
rif
Inte
rmit
ten
t.h
rs./
yr.
£low
Co
mp
osi
tio
n,
To
ns/
To
no
fV
CHD
ich
loro
eth
ane
Vin
yl
Ch
lori
de
Eth
yl
Ch
lori
de
Ace
tyle
ne
Hyd
roge
nC
hlo
rid
eC
hlo
rin
eE
thy
len
eP
rop
yle
ne
Met
hane
Mis
c.C
nlo
rin
ated
Hy
dro
carh
on
sC
arbo
nD
iox
ide
Car
bon
Mon
oxid
eN
itro
gen
Oxy
gen
Wat
erI,
,SIo
mpr
eT
apL
oca
tio
n!l
llte
or
Fre
quel
lcy
III~8PlpUnll
ii
'l'yl'@
ofA
cn.ly
BI.
"O
dor
Pto
bIe
",V
eMS
tack
sI
Num
ber
Hei
gh
t.,
Ft.
Dia
met
er•
Inch
esE
"it
Gas
Tem
p.F
aI
SCFM
per
atac
kE
mis
sio
nC
on
tro
lD
evic
es(b
)W
ater
Scr
ub
ber
Incin
era
tor
Ref
rig
erat
ed'C
onde
nser
Oth
erSU
ll1ll\
ary
of
Air
Po
llu
tan
tsH
ydro
c,a
rbo
ns
Pat'
ticu
late
NO
xS
O"
CO
...., o ....,
N o W.
Com
pany
Lo
cati
on
EPA
Cod
eN
o.D
ate
on
-str
eam
cap
acit
y,
Ton
sV
CM
/Yr.
Av
erag
eP
rod
uct
ion
,T
ons
VC
M/Y
r.R
ange
inP
rod
ucti
on
,%
of
Max
.(a
)E
mis
sio
ns
toA
tmos
pher
eS
trea
m
Flo
w-
lbs./
hr.
Flo
wC
hara
cte
rist
ic,
Co
nti
nu
ou
so
rIn
term
itte
nt
ifIn
term
itte
nt.
hrs
./y
r.fl
ow
Co
mp
osi
tio
n-
To
ns/
To
no
fVC
MD
ich
loro
eth
ane
Vin
yl
Ch
lori
de
Eth
yl
Ch
lori
de
Ace
tyle
ne
Hyd
roge
nC
hlo
rid
eC
hlo
rin
eE
thy
len
eP
rop
yle
ne
Met
hane
Mis
c.C
hlo
rin
ate
dH
yd
roca
rbo
ns
Car
bon
Dio
xid
eC
arbo
nM
onox
ide
Nit
rog
enO
xyge
nW
ater
Sam
ple
Tap
Lo
cati
on
Dat
eo
rF
req
uen
cyo
fS
amp
lin
gT
ype
of
An
aly
sis
Odo
rP
rob
lem
Ven
tS
tack
sN
umbe
rH
eig
ht
-F
t.D
iam
eter
-In
ches
Ex
itG
asT
emp.
-FO
SCFM
per
stack
Em
issi
on
Co
ntr
ol
Dev
ices
(b)
Wat
erS
cru
bb
erIn
cin
era
tor
Refr
igera
ted
Co
nd
ense
rO
ther
Sum
mar
yo
fA
irp
oll
uta
nts
Hy
dro
carb
on
sp
art
icu
late
NOx
SOx
CO
TABL
EV
C-I
IIN
ATI
ON
AL
EM
ISSI
ON
SIN
VEN
TORY
VIN
YL
CH
LOR
IDE
MON
OMER
PRO
DU
CTI
ON
VIA
PYRO
LYS
ISO
FDIC
HLO
RO
ETH
AN
E
31
-4
43
2,0
00
40
0,0
00
to4
75
,00
0o
To
pp
ing
Col
umn
Off
-Gas
30 Co
nti
nu
ou
s
.00
00
6
.00
01
6
Nev
erC
alc
'd.
No
Yes
1 46
2 1200
VC-1
2
Hea
vyE
nds
Rec
ov
ery
ven
t5 C
on
tin
uo
us
.00
00
5
Nev
erC
alc
'd.
No
Yes
1 58 3 90
0
No
.00
95
6.0
00
07
Pag
e4
of
6
Fla
reF
lue
Gas
Not
Sp
ecif
ied
Co
nti
nu
ou
s
,..1
0000
7
+ + + +
Nev
erC
alc
'dN
oY
es1 15
024 V
C-1
6
Fla
re
!'.J o .J::'
Com
pany
Lo
cati
on
EPA
Cod
eN
umbe
rD
ate
on
-str
eam
Cap
acit
y,
Ton
sV
CM
/Yr.
Ave
rage
Pro
du
cti
on
,T
on
s/Y
r.R
ange
inP
rod
ucti
on
,%
of
Max
.(a
)E
mis
sio
ns
toA
tmo
sph
ere
Str
eam
Flo
w-
Lb
s./H
ou
rF
low
Ch
ara
cte
rist
icif
Inte
rmit
ten
t,H
rs./
Yr.
Co
mp
osi
tio
n,
To
ns/
To
nVC
MD
ich
loro
eth
ane
Vin
yl
Ch
lori
de
Eth
yl
Ch
lori
de
Ace
tyle
ne
Hyd
roge
nC
hlo
rid
eC
hlo
rin
eE
thy
len
eP
rop
yle
ne
Met
hane
Mis
c.C
hlo
rin
ate
dH
yd
roca
rbo
ns
Car
bon
Dio
xid
eC
arb
on
Mon
oxid
eN
itro
gen
Oxy
gen
Wat
erSamp~e
Tap
Lo
cati
on
Dat
eo
rF
req
uen
cyo
fS
amp
lin
gT
ype
of
An
aly
sis
Odo
rP
rob
lem
Ven
tS
tack
sN
umbe
rH
eig
ht,
Ft.
Dia
met
er,
Inch
es
Ex
itG
asT
emp.
OF
scnl
Per
Sta
ckE
mis
sio
nC
on
tro
lD
evic
es(b
)W
ater
Scr
ub
ber
Incin
era
tor
Refr
igera
ted
Co
nd
ense
rF
lare
Oth
ero
rN
one
Sum
mar
yo
fA
irp
oll
uta
nts
Hy
dro
carb
on
s(c
)P
art
icu
late
(d)
NOx
SOx
CO
Var
iou
sT
ower
Ov
erh
ead
s19
8(j)
Co
nti
nu
ou
s
0.0
02
3
Non
e
Nev
erC
alc
ula
ted
No
1 11
03
0 60-
100
20(j)
VC-
3
TABL
EV
C-I
IIE
MIS
SIO
NS
INV
ENTO
RYFO
RPR
OD
UC
TIO
NO
FV
INY
LC
HLO
RID
EM
ONOM
ERBY
PYR
OLY
SIS
OF
DIC
HLO
RO
ETH
AN
E
31
-8
35
0.0
00
o
Sto
rag
eV
ent
18(a
vg
.)In
term
itte
nt
Unk
now
n
0.0
00
21
Non
e
Nev
erC
alc
ula
ted
No
1 75 7 Am
bien
t2
(av
g.)
Non
e
0.0
02
51
Tra
ce
Tra
ce
Pag
e5
of
6
Ma
inte
na
nce
Ven
t1
,00
0(l
bs./
yr.
)In
term
itte
nt
Unk
now
n
6% Tra
ce
Tra
ce
Bal
ance
Non
e
Nev
erE
stim
ated
1 40
8 Am
bien
t7
,00
0-
1400
0(C
FY)
Non
e
Fu
rnac
eD
eco
kin
g3
0.0
00
Inte
rmit
ten
t50
-10
0
Tra
ce
Unk
no'to
rnU
nkno
"'"
"' ~M
ost
ly_
I
Non
e
Nev
erA
ir&
Str
eam
Met
ers
1 40 12 212
6,0
00
VC-
1
TABLE VC- IIIEXPLANATION OF NOTESEMISSIONS INVENTORY
FOR PRODUCTION OF VINYL CHLORIDE MONOMER BYPYROLYSIS OF DICHLOROETHANE Page 6 of 6
(a) Difference between maximum & minimum quarterly production divided bymaximum quarterly production.
(b) See Table IV, Catalog of Emission Control Devices for details.
(c) Includes HZS. Excludes CH4 & HZ'
(d) Includes aerosols such as HCI and C1Z'
(e) Unspecified portion of this stream results from dichloroethane production.
(f) Stream is vented below surface of pond, combustibles burn at pond surface.
(g) No data received.
(h) Vents from top of 14 foot scrubber tower.
(i) Purged Header - pollutants will increase during emergencies or reliefvalve lifitng.
(j) Minor portion of a combined vent from other process.
205
~ATER
SCR
UllB
ERS
-·F
low
dia
gra
mst
ream
I.D
evic
et.
D.
Num
ber
EPA
Cod
eN
o.
for
pls
nt
usi
ng
Pu
rpo
se·
-C
on
tro
lE
mis
sio
no
fT
ype
-S
pra
yP
ack
edC
olum
nT
ray
s-
Typ
eN
um
ber
Ple
num
Cha
mbe
rO
ther
Wat
erR
ate
-GP
MD
esig
nT
emp.
(op
ers
tin
gte
mp
.)-
poG
ssR
ate
-SC
FM(l
b./
hr.
)T
-TH
eig
ht
-F
t..
Dia
met
er-
Ft.
Was
hed
Ga.
esto
Sta
ck
Sta
ck
Hei
gh
t-
Ft.
Sta
ck
Dia
met
er-
Ft.
Inst
all
ed
Co
st-
Mate
rial
&L
abo
r-
$In
stall
ed
Co
st-
c/l
b.
of
VC
M/Y
r.::
;O
per
atin
gC
ost
-A
nn
ual
-$
0"1
Op
erat
ing
Co
st-
c/l
b.
of
VCM
Eff
icie
ncy
1-E
ffic
ien
cy
·SE
RR
%
"-'
o -...J
REF
RIG
ERA
TED
CON
DEN
SER
&K
.O
.DR
UM-
Flo
wD
aigr
amS
trea
mI.
D.
Dev
ice
I.D
.N
umbe
rEP
AC
ode
No.
for
pla
nt
usi
ng
Pn
rpo
seP
rim
ary
Refr
igera
tio
nL
iqu
idC
apac
ity
of
Refr
igera
tio
nU
nit
-To
ns
Gas
Rat
e-
SCFM
Tem
per
atu
reto
co
ole
r-
OF
Tem
per
atu
re-
K.
O.
Dru
m-
OFL
iqu
idR
eco
ver
ed-
GPM
No
n-c
on
den
sib
ies
-SC
FMIn
stall
ed
Co
st-
Mate
rial
&L
abo
r-
$In
stall
ed
Co
st-
¢/l
b.
of
VCM
Op
erat
ing
Co
st-
An
nu
al-
$O
per
atin
gC
ost
-¢
/lb
.o
fVC
ME
ffic
ien
cy
%SE
RR
%
TAB
LEV
C-I
VCA
TALO
GO
FE
MIS
SIO
NCO
NTR
OL
DEV
ICES
CURR
ENTL
YU
SED
INTH
EPR
OD
UC
TIO
NO
FV
INY
LC
HLO
RID
EM
ONOM
ERV
IATH
EPY
RO
LYSI
SO
FD
ICH
LOR
OET
HA
NE
HCL
Tow
erOV
HD
(VC
-8
)3
1-1
Rec
ov
erD
eE(B
)P
rop
yle
ne
230
11,4
00
95-1
0 1011
,00
05
25
,00
0
-1
,05
2,0
00
80 72
.5
Pag
e2
of
6
N o CIO
.
INC
INER
ATI
ON
DEV
ICES
-F
low
Dia
gram
Str
eam
I.D
.D
evic
eI.
D.
Num
ber
EPA
Cod
eN
o.fo
rp
lan
tu
sin
gT
ypes
of
Com
poun
dsIn
cin
era
ted
Typ
eD
evic
e-
Fla
reIn
cin
era
tor
Oth
erM
ate
rials
Incin
era
ted
SCFM
(lb
./h
r.)
Ati
xi1
liar
yF
uel
Req
'd(e
xcl
ud
ing
pil
ot)
Au
xi1
liary
Fu
elT
ype
Au
xi1
liary
Fu
elR
ate
-B
TU
/Hr.
Dev
ice
Ele
vati
on
-F
t.ab
ov
eg
rad
eIn
stall
ed
Co
st-
Mate
rial
&L
abo
r-
$In
stall
ed
Co
st-
cll
b.
of
VC
M/Y
r.O
per
atin
gC
ost
-A
nn
ual
-$
Op
erat
ing
Co
st-
c/l
b.
of
VCM
Eff
icie
ncy
-CC
R-
%E
ffic
ien
cy
-SE
RR
-%
TAB
LEV
C-I
VCA
TALO
GO
FE
MIS
SIO
NCO
NTR
OL
DEV
ICES
CURRE~7LY
USE
DIN
THE
PRO
DU
CTI
ON
OF
.V
INY
LC
HLO
RID
EM
ONOM
ERV
IATH
EPYROLYSIS~HLOROETHANE
(VC
-9
)3
1-3
Lt.
H.
C.
X (22)
No °65,
00
0.0
22
01
4,5
00
.00
49
10
05
3.8
(H)
Pag
e3
of
6
(VC
-10
)3
1-2
Lt.
H.
C.
X (36
0)
Non
e
120
Not
Sp
ecit
ied
10
05
6.0
REF
RIG
ERA
TED
CON
DEN
SER
&K
.O
.DR
UM
TABL
EV
C-I
VCA
TALO
CO
FE
MIS
SIO
NCO
NTR
OL
DEV
ICES
CURR
ENTL
YU
SED
INPR
OD
UC
TIO
N--
OF
VIN
YL
CH
LOR
IDE
MON
OMER
--
VIA
THE
PYR
OLY
SIS~LOROETHANE
Pag
e4
of
6
Flo
wD
iagr
amS
trea
m1
.0.
Dev
ice
1.D
.N
o.EP
AC
ode
No.
for
pla
nt
usi
ng
Pu
rpo
se-
Co
ntr
ol
emis
sio
no
fP
rim
ary
Refr
igera
tio
nL
iqu
idC
apac
ity
of
Refr
igera
tio
n,
Un
it-T
on
sG
asR
ate
SCFM
(lb
./h
r.)
Tem
per
atu
reto
co
ole
r-
FT
emp
erat
ure
ou
to
fco
ole
r-
Fa
Liq
uid
Rec
ov
ered
-GP
M(l
b./
hr.
)N
on
-Co
nd
ensi
ble
s-
SCFM
(lb
./h
r.)
Inst
all
ed
Co
st-
Mat'
l.&
Lab
or
-$
Inst
all
ed
Co
st-
Mat'
l.&
Lab
or
-c/l
b.
of
VC
M-Y
r.O
per
atin
gC
ost
-A
nnua
l-
$O
per
atin
gC
ost
-c/
1b
.o
fVC
ME
ffic
ien
cy
and
SER
R%
INC
INER
ATI
ON
DEV
ICES
Flo
wD
iag
ram
Str
eam
I.D
.D
evic
e1
.D.
No.
EPA
Cod
eN
o.fo
rp
lan
tu
sin
gT
ypes
of
Com
poun
dsIn
cin
era
ted
Typ
eD
evic
e-
Fla
reIn
cin
era
tor
Oth
erM
ate
rials
Incin
era
ted
SCFM
(lb
./h
r.)
Au
xil
liary
Fu
elR
eq'd
.(e
xcl
ud
ing
pil
ots
)A
ux
il1
iary
Fu
elT
ype
Au
xil
liary
Fu
elR
ate
-B
TU
/ilr
.D
evic
eE
lev
ati
on
-F
t.ab
ov
eg
rad
eIn
stall
ed
Co
st-
Mat'
l.&
Lab
or
-$
Inst
all
ed
Co
st-
Mat'
l.&
Lab
or
-¢
/lb
.o
fVC
MO
per
atin
gC
ost
-A
nnua
l-
$O
per
atin
gC
ost
-¢
/lb
.o
fVC
ME
ffic
ien
cy
-CC
R-
%E
ffic
ien
cy
-SE
RR
-%
t~
34
45
VC
-ll
VC
-12
vc-1
3V
C-1
4V
C-1
53
1-4
31
-43
1-4
31
-43
1-4
(F)
EDC
Ch
lori
nate
dHC
Ch
lori
nate
dHC
Ch
lori
nat
edHC
VCM
Wat
erB
rin
eW
ater
Wat
erW
ater
(36
9)
(20
0)
900
500
900
900
102
0
(23
6)
of
EDC
(170
).(
11
6)
(30
)40
0045
0040
0040
0066
000
.00
04
6.0
00
52
.00
04
t)
.00
04
6.0
07
64
-44
,50
090
0(E
)10
00E
1000
(E)
-4
5.5
00
.00
01
0.0
00
12
.00
01
28
5.3
85
.0
3 VC
-16
31
-4M
isc.
HC+
30
0,0
00
.03
47
28
.00
0.0
00
93
100
L10
0
N ..... o
WAT
ERSC
RU
BB
ERS
Flo
wD
iagr
amS
trea
mI.
D.
Dev
ice
1.D
.N
o.EP
AC
ode
No.
for
pla
nt
usi
ng
Pu
rpo
se-
Co
ntr
ol
emis
sio
no
fT
ype
-S
pra
yP
acke
dC
olum
nT
ray
s-
Typ
eN
umbe
rP
lenu
mC
ham
ber
Oth
erW
ater
Rat
e-
GPM
Des
ign
Tem
p.(O
per
atin
gT
emp.
)FO
Gas
Rat
eSC
FM(l
b./
hr.
)T
-TH
eig
ht
-F
t.D
iam
eter
-F
t.W
ashe
dG
ases
toS
tack
Sta
ck
Hei
gh
t-
Ft.
Sta
ckD
iam
eter
-F
t.In
stall
ed
Co
st-
Mat'
l.&
Lab
or
-$
Inst
all
ed
Co
st-
Mat'
l.&
Lab
or
-c/
Lb
.V
CM
-Yr.
Op
erat
ing
Co
st-
An
nu
al-
$O
per
atin
gC
ost
-c/l
b.
of
VCM
Eff
icie
ncy
-%
(D)
TABL
EV
C-I
VCA
TALO
GO
FEMISSI~NTROL
DEV
ICES
CURR
ENTL
YU
SED
INPR
OD
UC
TIO
NO
F.
VIN
YL
CH
LOR
IDE
MON
OMER
VIA
THE
PYR
OLY
SIS~LOROETHANE
2-3
-4-5
VC
-18
31
-7C
hlo
rin
ate
dH
yd
roca
rbo
ns
+
+(G
)2
5-5
0(8
0)
1350
40 4.5
Yes
40 2.5
15
0,0
00
.05
55
51
5,6
00
.00
57
8
Pag
e5
of
6
2 VC
-17
31
-4H
CL +(P
ond)
Am
bien
t
No
40
,00
0.0
0463
16
,00
0.0
01
85
TABLE VC-IVCATALOG OF EMISSION CONTROL DEVICES.CURRENTLY USED IN THE PRODUCTION OF
VINYL CHLORIDE MONOMERVIA THE
PYROLYSIS OF DICHLOROETBANE Page 6 of 6
(A) Treats effluents from direct chlorination, oxychlorination and "variousrelief systems in plant" in addition to indicated stream.
(B) Recovers DCE from oxychlorination process.
(C) All plant waste streams pumped to waste pond. Flammable materials burntat pond's surface.
(D) Defined as percent removal of total air pollutants in stream being treated.
(E) In addition to listed operating cost, respondent added $139,325/year foroff-site disposal (incineration).
(F) This device consists of a compressor and oondensor, for recovery of VCMvapors from tank cars.
(G) This complex device consists of:
(1) Two Parallel Vent Gas Scrubbers
@ 35' T-T, 24" dia., packed with raschig rings and intalox saddles,5 - 10 GPM caustic eire.
(2) Waste Gas Boiler
10,000 lbs./hr., 250 psig steam6000 F operating temperature
(3) Final flue gas scrubber - See Table IV
Costs listed are for all equipment.
(R) 53.8% = SERR efficiency for combustion process only, for pond & flareSERR = 66.5% (assumes pond absorbs all RCL in feed to flare).
211
t:: \S.
TABL
EV
C-V
NUM
BER
OF
NEW
PLA
NTS
BY19
80
Cu
rren
tC
apac
ity
Cap
acit
yE
cono
mic
Num
ber
Cu
rren
tM
arg
inal
on
-str
eam
Dem
and
Cap
acit
yto
be
Pla
nt
of
New
Che
mic
alP
roce
ssC
apac
ity
Cap
acit
yin
1980
1980
1980
Add
edS
ize
Un
its
VCM
DCE
Py
roly
sis
5,4
00
500
4,9
00
12
,00
01
3,0
00
8,1
00
800
10A
cety
len
e55
055
00
00
00
0
Not
e:A
llcap
acit
ies
inrn
mlb
s./y
ear.
TAB
LEV
C-V
ISU
MM
ARY
OF
EM
ISSI
ON
SOU
RC
ES*
Sou
Lce
N ..... wP
oll
uta
nt
Hy
dro
carb
on
s
Part
icu
late
s
NOx
SOx
CO
EDC
Dri
er
and
Vap
ori
zer
plu
sVC
MD
rier
.00
10
0
Cra
ckin
gF
urn
ace
TR TR
Que
nch
Tow
er
.00
00
5
.00
00
1
HCL
Tow
er
,00
01
0
,00
01
0
"Lig
ht
En
ds"
Reje
ct
:00
10
0
"Hea
vyE
nds"
Reje
ct
.00
10
0
Sto
rag
eL
oss
esan
dF
ug
itiv
eE
mis
sio
ns
.00
01
0
To
tal
.00
32
5
.00
01
1
TR TR
*P
oll
uta
nt
co
ncen
trati
on
sin
lbs./
lb.
of
VCM
.
TABL
EV
C-V
IIW
EIG
HTE
DEM
ISSI
ON
RATE
S
Che
mic
alVC
M
Pro
cess
DCE
Py
roly
sis
____
8,1
00
MML
bso
/Yea
rIn
crea
sed
Cap
acit
yby
lQR
O~
__
_i'
.) ..r:=
Po
llu
tan
tE
mis
sio
ns
Lb
so/L
b.
Incr
ease
dE
mis
sio
ns
MML
bso
/Yea
rW
eig
hti
ng
Facto
rW
eig
hte
dE
mis
sio
ns
MM
Lbs
0!Y
ear
Hy
dro
carb
on
s00
0032
52
6.3
380
2,1
06
Part
icu
late
s0
00
00
11
0089
6053
NOx
TR
40
SOx
TR
20
CO1
Sig
nif
ican
tE
mis
sio
nIn
dex
=2
,15
9
Appendix I, II, & III
APPENDIX I
FINAL ADDRESS LIST
Air Products & Chemicals, Inc.P. O. Box 97Calvert City, Kentucky
Attention: Mr. Howard Watson
Allied Chemical Corp.Morristown, New Jersey
Attention: Mr. A. J. VonFrankDirector Air & WaterPollution Control
American Chemical Corp.2112 E. 223rdLong Beach, California 90810
Attention: Mr. H. J. Kandel
American Cyanamid CompanyBound Brook, New Jersey
Attention: Mr. R. Phelps
American Enka CorporationEnka, North Carolina 28728
Attention: Mr. Bennet
American Synthetic Rubber Corp.Box 360Louisville, Kentucky 40201
Attention: Mr. H. W. Cable
Amoco Chemicals Corporation130 E. Randolph DriveChicago, Illinois
Attention: Mr. H. M. Brennan, Directorof Environomental Control Div.
Ashland Oil Inc.1409 Winchester Ave.Ashland, Kentucky 41101
Attention: Mr. O. J. Zandona
215
Borden Chemical Co.50 W. Broad StreetColumbus, Ohio 43215
Attention: Mr. Henry Schmidt
Celanese Chemical CompanyBox 9077Corpus Christi, Texas 78408
Attention: Mr. R. H. Maurer
Chemplex Company3100 Gulf RoadRolling Meadows, Illinois 60008
Attention: Mr. P. Jarrat
Chevron Chemical Company200 Bush StreetSan Francisco, California 94104
Attention: Mr. W. G. Toland
Cities Service Inc.70 Pine StreetNew York City, NY 10005
Attention: Mr. C. P. Goforth
Clark Chemical CorporationBlue Island Refinery131 Kedzie AvenueBlue Island, Illinois
Attention: Mr. R. Bruggink, Directorof Environmental Control
Columbia Nitrogen CorporationBox 1483Augusta, Georgia 30903
Attention: Mr. T. F. Champion
Continental Chemical Co.Park 80 Plaza EastSaddlebrook, NJ 07662
Attention: Mr. J. D. Burns
Cosden Oil & Chemical Co.Box 1311Big Spring, Texas 79720
Attention: Mr. W. Gibson
Dart Industries, Inc.P. O. Box 3157Terminal AnnexLos Angeles, California 90051
Attention: Mr. R. M. KnightPres. Chemical Group
Diamond PlasticsP. O. Box 666Paramount, California 70723
Attention: Mr. Ben Wadsworth
Diamond Shamrock Chern. Co.International DivisionUnion Commerce BuildingCleveland, Ohio 44115
Attention: Mr. W. P. Taylor, ManagerEnviron. Control Engineering
Dow Badische CompanyWilliamsburg, Virginia 23185
Attention: Mr. L. D. Hoblit
Dow Chemical Co. - USA2020 BuildingAbbott Road CenterMidland, Michigan 48640
Attention: Mr. C. E. OtisEnvironmental Affairs Div.
216
E. I. DuPont de Nemours & Co.Louviers BuildingWilmington, Delaware 19898
Attention: Mr. W. R. ChalkerMarketing Services Dept.
Eastman Chemicals Products, Inc.Kingsport, Tennessee
Attention: Mr. J. A. MitchellExecutive Vice PresidentManufacturing
El Paso Products CompanyBox 3986Odessa, Texas 79760
Attention: Mr. N. Wright,Utility and PollutionControl Department
Enjay Chemical Company1333 W. Loop SouthHouston, Texas
Attention: Mr. T. H. Rhodes
Escambia Chemical CorporationP. O. Box 467Pensacola, Florida
Attention: Mr. A. K. McMillan
Ethyl CorporationP. O. Box 341Baton Rouge, Louisiana 70821
Attention: Mr. J. H. Huguet
Fibre Industries Inc.P. 0, Box 1749Greenville, South Carolina 29602
Attention: Mr. Betts
Firestone Plastics CompanyBox 699Pottstown, Pennsylvania 19464
Attention: Mr. C. J. Kleinart
Firestone Synthetic Rubber Co.381 W. Wilbeth RoadAkron, Ohio 44301
Attention: Mr. R. Pikna
Firestone Plastics CompanyHopewell, Virginia
Attention: Mr. J. Spohn
FMC - Allied CorporationP. O. Box 8127South Charleston, W. VA 25303
Attention: Mr. E. E. Sutton
FMC Corporation1617 J.F.K. BoulevardPhiladelphia, PA
Attention: Mr. R. C. Tower
Foster Grant Co., Inc.289 Main StreetLedminster, Mass. 01453
Attention. Mr. W. Mason
G.A.F. Corporation140 W. 51st StreetNew York, NY 10020
Attention: Mr. T. A. Dent, V.P.of Engineering
General Tire & Rubber Company1 General StreetAkron, Ohio 44309
Attention: Mr. R. W. Laundrie
217
Georgia-Pacific Company900 S.W. 5th AvenuePortland, Oregan 97204
Attention: Mr. V. TretterSr. Environmental Eng.
Getty Oil CompanyDelaware 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 StreetAkron, Ohio 44316
Attention: Mr. B. C. Johnson, ManagerEnvironmental Engineering
Great American Chemical Company650 Water StreetFitchburg, Mass.
Attention: Dr. Fuhrman
Gulf Oil CorporationBox 1166Pittsburgh, Pennsylvania
Attention: Mr. D. L. MatthewsVice President Chemicals Department
Hercules Incorporated910 Market StreetWilmington, Delaware
Attention: Dr. R. E. Chaddock
Hooker Chemical Corporation1515 Summer StreetStamford, Conn. 06905
Attention: Mr. J. Wilkenfeld
Houston Chemical CompanyBox 3785Beaumont, Texas 77704
Attention: Mr. J. J. McGovern
Hystron Fibers DivisionAmerican Hoechst CorporationP. O. Box 5887Spartensburg, SC 29301
Attention: Dr. Foerster
Jefferson Chemical CompanyBox 53300Houston, Texas 77052
Attention: Mr. M. A. Herring
Koch Chemical CompanyN. Esperson BuildingHouston, Texas 77002
Attention: Mr. R. E. Lee
Koppers Company1528 Koppers BuildingPittsburgh, Pennsylvania 15219
Attention: Mr. D. L. Einon
Marbon DivisionBorg-Warner CorporationCarville, Louisiana 70721
Attention: Mr. J. M. Black
218
Mobay Chemical CorporationParkway West & Rte 22-30Pittsburgh, Pennsylvania 15205
Attention: Mr. Gene Powers
Mobil Chemical Company150 E. 42nd StreetNew York, NY 10017
Attention: Mr. W. J. Rosenbloom
Monsanto Company800 N. Lindbergh BoulevardSt. Louis, Missouri 63166
Attention: Mr. J. Depp, Director ofCorp. Engineering
National Distillers & Chern. Corp.U.S. Industrial Chern. Co. Div.99 Park AvenueNew York, NY 10016
Attention: Mr. J. G. Couch
National Starch & Chern. Co.1700 W. Front StreetPlainfield, New Jersey 07063
Attention: Mr. Schlass
Northern Petrochemical Company2350 E. Devon AvenueDes Plaines, Illinois 60018
Attention: Mr. N. Wacks
Novamont CorporationNeal WorksP. O. Box 189Kenova, W'. Virginia 25530
Attention: Mr. Fletcher
Olin Corporation120 Long Ridge RoadStamford, Conn.
Attention: Mr. C. L. Knowles
Pantasote Corporation26 Jefferson StreetPassaic, New Jeresy
Attention: Mr. R. Vath
Pennwalt CorporationPennwalt Building3 ParkwayPhiladelphia, PA 19102
Attention: Mr. J. McWhirter
Petro-Tex Chemical CorporationBox 2584Houston, 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 StreetSarnia, OntarioCanada
Attention: Mr. J.H. LangstaffGeneral ManagerLatex Division
Polyvinyl Chemicals Inc.730 Main StreetWilmington, Mass. 01887
Attention: Mr. S. Feldman, Director ofManufacturing - Engineering
219
PPG Industries Inc.One-Gateway CenterPittsburgh, Pennsylvania 15222
Attention: Mr. Z. G. Bell
Reichold Chemicals Inc.601-707 Woodward Hts. Bldg.Detroit, Michigan 48220
Attention: Mr. S. Hewett
Rohm & HaasIndependence Mall WestPhiladelphia, PA 19105
Attention: Mr. D. W. Kenny
Shell Chemical Co.2525 Muirworth DriveHouston, Texas 77025
Attention: Dr. R.L. MaycockEnviron. Eng. Div.
Sinclair-Koppers Chern. Co.901 Koppers BuildingPittsburgh, Pennsylvania 15219
Attention: Mr. R. C. Smith
Skelly Oil CompanyBox 1121El Dorado, Kansas 67042
Attention: Mr. R. B. Miller
Standard Brands Chern. IndustriesDrawer KDover, Delaware 19901
Attention: Mr. E. Gienger, Pres.
Stauffer Chemical Co.Westport, Connecticut
Attention: Mr. E. L. Conant
Stepan Chemical CompanyEdens & Winnetka RoadNorthfield, Illinois 60093
Attention: Mr. F. Q. StepanV.P. - Industrial Chemicals
Tenneco Chemicals Inc.Park 80 Plaza - West 1Sadd1ebrook, NJ 07662
Attention: Mr. W. P. Anderson
Texas - U.S. Chemical CompanyBox 667Port Neches, Texas 77651
Attention: Mr. H. R. Norsworth
Thompson PlasticsAssonet, Mass. 02702
Attention: Mr. S. Cupach
Union Carbide CorporationBox 8361South Charleston, W. Virginia 25303
Attention: Mr. G. J. Hanks, ManagerEnviron. ProtectionChern. & Plastics Division
Uniroyal IncorporatedOxford Management &Research CenterMiddlebury, Conn. 06749
Attention: Mr. F. N. Taff
220
The Upjohn CompanyP. O. Box 685La Porte, Texas
Attention: Mr. E. D. Ike
USS Chemicals DivisionU.S. Steel CorporationPittsburgh, Pennsylvania 15230
Attention: Mr. Gradon Willard
W. R. Grace & Company3 Hanover SquarNew York, NY 10004
Attention: Mr. Robt. Goodall
Wright Chemical CorporationAcme StationBriege1wood, North Carolina 28456
Attention: Mr. R. B. Catlett
Wyandotte Chemical Corp.Wyandotte, Michigan 48192
Attention: Mr. John R. Hunter
Vulcan Materials CompanyChemicals DivisionP.O. Box 545Wichita, Kansas 67201
Attention: H.M. CampbellVice-President, Production
ENVIRONMENTAL PROTECTION AGENCY
Office of Air ProgramsResearch Triangle Park, North Carolina 27711
Dear Sir:
The Environmental Protection Agency, Office of Air Programs isengaged in a study of atmospheric emissions from the PetrochemicalIndustry. The primary purpose of this study is to gather informationthat will be used to develop New Stationary Source Performance Standardswhich are defined in Section III of the Clean Air Act as amendedDecember 31, 1970 (Public Law 91604). These new source standards willnot 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 performed under contract by the Houdry Division of Air Products and Chemicals.Several other companies not yet chosen will assist in the source samplingphase of the work.
Very little has been published on atmospheric emissions from thepetrochemical industry. The first part of this study will thereforerank the most important petrochemical processes in their order of importancein regard to atmospheric emissions. The Petrochemical Emissions SurveyQuestionnaire will be the primary source of data during the first phase.This ranking will be based on the amount and type of emissions from theprocess, the number of similar processes and the expected growth of theprocess. A second in-depth phase of the study.to document emissions morecompletely will be based on information obtained through actual stacksampling.
Attached you will find a copy of the petrochemical questionnairewhich you are requested to complete and return to the EnviromentalProtection Agency within forty-two (42) calender days.
221
You are required by Section 114 of the Clean Air Act to completeeach applicable part of this questionnaire except for question 11.4. and11.5. These two questions are concerned with the water and solid wastegenerated by the process itself not with that generated by the emissioncontrol equipment. This information would be of a value to the EPA andyour answers will be appreciated.
This questionnaire is to be completed using the information presentlyavailable to your company. We are not asking that you perform specialnon-routine measurements of emissions streams. We are asking for resultsof measurements that you have made or for estimates when measurements havenot been made. Where requested information is not available, please marksections "not available". Where the requested information is not applicable to the subject process, mark the questionnaire sections IInotapplicable". A sample questionnaire, filled out for a fictitious processis enclosed for your guidance.
It is the opinion of this office that for most processes it shouldbe possible to answer all survey questions without revealing anyconfidential information or trade secrets. However, if you believe thatany of the information that we request would reveal a trade secret ifdivulged you should clearly identify such information on the compl~ted
questionnaire. Submit, with the completed questionnaire, a writtenjustification explaining the reason for confidential status for each itemincluding any supportive data or legal authority. Forward a duplicateof your claim and supporting material, without the questionnaire data, toour counsel, Mr. Robert Baum, Assistant General Counsel, Air Quality andRadiation Division, Environmental Protection Agency, Room l7B4l,5600 Fishers Lane, Rockville, M~ryland 20852. Emission data cannot beconsidered confidential.
Final authority for determining the status of the information resideswith the Enviromental Protection Agency. A reply describing the decisionreached will be made as soon as possible after receipt of the claim andsupporting information. During the period before the final determinationthis office will honor any request to treat the questionnaire informationas confidential.
Information declared to be a trade secret is subject to protectionfrom being published, divulged, disclosed or made known in any manneror to any extent by Section 1905 of Title 18 of the United States Code.The disclosure of such information, except as authorized by law, shallresult in a fine of not more than $1,000 or imprisonment of not morethan one year, or both; and shall result in removal of the individualfrom his office or employment.
222
Although it should be noted that Section 114, Subsection C of theClean Air Act allows such information to be disclosed "to other officers,employees, or authorized representatives of the United States concernedwith carrying out the Act or when relevant in any proceeding under thisAct," no confidential information will be revealed to any private concernemployed by the Environmental Protec'tion Agency to assist in this study.
The handling and storage of information for which the determinationis pending or information which has been determined to be of a confidentialnature is carefully controlled. Preliminary control procedures requirethat the material be labeled confidential and stored in a locked file.
The complete form should be mailed to:
Mr. Leslie B. EvansEnvironmental Protection AgencyOffice of Air ProgramsApplied Technology DivisionResearch Triangle Park, NC 27711
It is possible that additional copies of this questionnaire whichwill request information covering other petrochemical processes orother plants using the same process and operated by your organizationwill be sent to you in the course of this study. Clarification of itemscontained in the questionnaire may be obtained from Mr. Evans by telephone at 919/688-8146. Thank your for your help in this matter.
Sincerely,
Leslie B. EvansIndustrial Studies Branch
223
Petrochemical Questionnaire
Instructions
I. Capacity. Describe capacity of process by providing the following:
1.· Process capacity. Give capacity in units per year and unitsper hour. An "actual" capacity is preferred but "published"or "name plate" capacity will be satisfactory if such capacity is reasonably correct. Do not give production.
2. Seasonal variation. Describe any significant seasonalvariations in production.
As example an ammonia plant might produce more duringspring and winter quarters:
quarter
%
Jan-Mar
40
April-June
20
July-Sept
10
Or.t-Dec
30
YearTotal100%
II. Process. Describe the process used to manufacture the subjectchemical 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., productrecovery method) has a common ~ame, give this.
2. Block Diagram. Provide a block diagram of the process showingthe 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 afterany control device and (2) the gaseous or liquidstreams which, after leaving the process site, producegaseous emissions during further processing or combustion.
(1) Any gaseous waste streams before and after anypollution device should be shown and identified.
(ii) Streams from rupture disks or pressure reliefvalves which protect equipment from operatingupsets but discharges less than once every yearneed not be shown.
(iii) Emissions from pressure relief systems thatnormally discharge during power failures orother emergencies should be shown, identifiedby letter and labeled "emergency".
224
(iv) Emissions from fueled heaters such as "heattransfer medium" heaters, steam generators,or cracking furnaces need not be shown ifthey are fueled completely by fuels listed inQuestion VII and are not used to incinerate byproducts or off gases.
(v) Emissions from Claus units associated withprocess need not be shown. Stream to Clausunit should be shown and identified with letter.
(vi) Emissions from a central power plant (or steamplant) which burns a liquid fuel produced as aby-product of this process need not be shown.Such liquid fuel should be shown and identifiedby letter.
(vii) Emissions from a central power plant (or steamplant) which burns a gaseous fuel produced asa by-product of this process need not be shown.Such gaseous fuel should be shown and identifiedby letter.
(b) Show all gaseous emission control devices.each control device on the block diagram bydigit number (101, 102, 103, etc.)
Identifya three
(c) Show all stacks or vents that vent streams listed in(a) and (b) above. It a stack to vent dischargesemissions from more than one source, label this stackor vent with a letter in sequence started in II.2.a.(D,E,F, etc.) If a stack or vent discharges emissionsfrom only one source label the stack with the sameletter as the emission stream.
3. Raw material and product. Give approximate chemical composition and approximate amount (on yearly basis and atcapacity given in 1.1) of all raw-materials, productsand by-products. If composition or amounts vary, giveranges. Composition may be given in commonly acceptedterms when a chemical analysis would be inappropriate.The description "light straight-run naphtha" would beadequate.
4. Waste water. Is there a waste water discharge from thisprocess which is (eventually) discharged to a receivingbody of water? Is this waste water treated by you orby others? Give the approximate volume and indicatewhether this is measured or estimated.
225
5. Waste solids. Is there a waste solids discharge from thisprocess? How is it disposed of? Give the approximatedaily total of waste solids and indicate if this is measured or estimated.
III. Emissions (composition and flow): For each stream requested inII.2.a. and shown on the block diagram by letter provide thefollowing: (Use separate sheets for each identified location - 6copies are provided). All of the questions will not be applicable for each stream.
As an example, question 10, odor problem, applies only to streamswhich are emitted to the atmosphere.
1. Chemical composition and flow. Give composition as completelyas possible from information you have available. Do not omittrace constituents if they are known. If anything (e.g. fuel)is added upstream of any emission control devices, give thechemical composition and flow prior to the addition, and givethe quantity and composition of the added material. If liquidsor solids are present (in gas stream) provide the compositionand amount of these also. Give flow volume (SCFN), temperature(FO) and pressure (psig or inches H20).
2. Variation in chemical composition and flow. If average streamcomposition or flow varies significantly over some period oftime during normal or abnormal operation, discuss this variation and its frequency. Relate this to the average and rangeof composition given in 111.1.
As examples:
"During start-up (once a month) the benzene is about 12% byvolume for one hour" or "the benzene can be expected to gofrom 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 streamA to increase from 0 to (initially) 50,000 lbs/hr., and about8,000 Ibs is vented over a 15 minute period."
3. Production rate during sampling. If stream composition andvolume flow rates given in answer to questions 111.1. and111.2. were measured at a plant prod~ction rate differentthan the capacity of the plant given in 1.1. give the rateat which the measurements were made.
As example:
Figures given for this stream (A) were made when plant wasoperating at 90% of capacity given in 1.1.
226
4. Methods used to determine composition and flow.from material balance, from sample and analysis,Describe briefly.
Is informationor other?
5. Sampling procedure. If samples have been taken, give summarydescription of sampling procedure or give reference ifdescribed in open literature.
6. Analytical procedure. If samples have been taken, give summary description of analytical procedure or give reference ifdescribed 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 inregard to compositions in 111.1.
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 providedbut accessible only with 20-ft. ladder."
10. Odor problem. Is the odor of this emission detectable atground level on the plant property or off the plant property?If odors carry beyond the plant property are they detectablefrequently or infrequently? Have you received a communityodor complaint traceable to this source in the past year?Has the odorous material been chemically identified? Whatis it?
221
IV. Emission control device. Supply the following information for eachcontrol device shown on the block diagram. (Use separate sheetsfor each - 3 copies are provided).
1. Engineering description. Give brief description and processsketch of the control device. Attach print or other description if you prefer. Show utilities used, steam produced,product recovered, etc. Give manufacturer, model number andsize (if applicable). Give complete (applicable) operatingconditions, i.e. flows, temperatures, pressure drops, etc.
2. Capital cost of emission control system.
(a) Give capital cost for the emission control device as itis described in IV.I. above; i.e., if equipment has beenmodified or rebuilt give your best estimate of capitalcost of equipment now in service. For the total installedcost give the approximate breakdown by year in which costwas incurred.
As example:
MajorTotalYear196319641971
equipment costinstalled cost
Cost$160,000
40,00050,000
$250,000
$155,000$250,000
(b) On the check list given mark whether the items listed areincluded in total cost as given above. Give one sentenceexplanation when required but do not give dollar amounts.
(c) Was outside engineering contractor used and was costincluded in capital cost?
(d) Was in-house engineering used and was cost included incapital cost?
(e) Was emission control equipment installed when plant wasbuil t?
3. Operating cost of emission control system. Give the bestestimate of cost of operating emission control system indollars per year with process operated at capacity givenin 1.1. Other disposal (g) would include, as example,the cost of incinerating a by-product stream which has novalue.
221k
V. Stack or vent description. Each stack or vent should have beenidentified by letter on the block diagram. Provide the requestedinformation for each stack. Stack flow, V.4. should be enteredonly when it is not possible to calculate this number by addinggas flows given in 111.1.
An example would be when an off gas from the process is dischargedinto a power plant stack.
VI. Tankage. Give information requested for all tankage larger than20,000 gallons associated with the process and normally held atatmospheric pressure (include raw material, process, product andby-product tankage). Method of vapor conservation (3.) mightinclude, 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 ona yearly basis at capacity given in 1.1. Do not include fuel usedin steam power plants. Give sulfur content. Identify each fuelas 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 fromthe plants through system leaks, valve stems, safety valves,pump seals, line blowing, etc., this loss is an emission. In alarge complex high pressure process this loss may be several percent of the product. Has this loss been determined by materialbalance or other method? What is it? Give best estimate.
IX. Future plans. Describe, in a paragraph, your program for thefuture installation of air pollution control equipment for thisunit or for future improvements in the process which will reduceemissions.
229
OMB Approval Number 158 S 72019
This example questionnaire has beencompleted for a fictitious companyand process.
ExampleQuestionnaire
Air Pollution Control Engineering and Cost Study of the Petrochemical Industry
Please read instructions before completing questionnaire.
Subj ect chemical : --'P=-yL;r!:..:r~o,."l=:.:e"__ __'__. _
Principal by-products:_.__P~y~r~r~o~l~i~d~o~n~e __
Parent corporation name: Orivne Petrochemical Co.,--------'-~::.;;.;;:=-....;;;.,.;;-=---------------
Subsidiary name : N_o_i...;;s_s_i_m_e_D_i..;..v.;;;:i.;;;;.s.;;;.i.;.on;.:;.... _
Mailing address: P.O. Box 1234
__. .__..Rianae1c, North Carolina , 27700
Plant name:---- Rianae1c Plant
Physical location: ..30 miles N.W. Durham, North Carolina
(include county andair quaility controlregion) Orange County;. Eastern Piedmont Intrastate (Region IV)
Person EPA should contact regarding information supplied in this questionnaire
John DoeName:-------------------------------------------Title: Supervisor of Process Development
Mailing address : .:.:N.:.o.;:i.::,s.;:;.s;;:im..::e.::....;D;;;.;i=.v:..;i=.;:s::;i=.;:o;.:n:....:o;.:f;.-::O;..:.•.,:.P..:,•..::C..:,. _
P.O. Box 1234
Rianae1c, North Carolina, 27700
Telephone number: ~9=1~9~XXX~~~XXXX==~ ~ _
Date quest ionnaire completed : -=Ma=.:Ly....::,3.::,0.Lp_1::::.9:;..7.:..,:2=-- _
230
1. Capacity.
l. Process capacity. (not production)
80.000.000 lbs. per year
10.000 lbs. per hour
2. Seasonal variation. (of production)
quarter 1 2 3 4
yeartotal
% 30 20 20 30 100%
231
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II. Process. (Continued)
3. Raw materials and products
Raw materials
Name
Pyrrolidine
Quantity
130,000,000 lbs/yr.
Composition
pyrrolidine 98%
Product and by-products
Name Quantity
other amines 2%
Composition
Pyrrole
Pyrrolidone
80,000,000 lbs/yr.
20,000,000 lbs/yr.
pyrrole
pyrrolidone
99,5%
99,5%
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.
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III. Continued For stream flow shown on block diagram by letter A
2. Composition variation.
See III-l
3. Production rate dur~ng samp1ina.
Never Sampled
4. Method used to determine composition and flow.
Not applicable
236
,.
III. Continued For stream flow shown on block dipgram by letter A------
5. Sampling procedure.
Not Applicable
6. Analytical procedure.
Not Applicable
7. Sampling frequency.
Never
237
III. Continued For stream flow shown on block diagram by letter A_o-U. _
8. Confidence level.
~ot Applicable
9. Ease of sampling.
Impossible
of
10. Odor probl~m. (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
238
III.
I.E
Mis
sio
ns
(com
posi
tion
~nd
flo
w).
Str
eam
flow
show
non
blo
ckdi
agra
mb
yle
tter
B
1.
Flo
w10
*OQ
OS
CP
Hre
mp
erat
ure
1l0~F
Pre
ssu
re25BST~
•
•
.,S
ixco
pie
spr
ovid
edth
isse
ctio
n
Com
pone
ntN
ame
.F
orm
ula
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te
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ticu
late
*S
oli
d
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rog
enN 2
Gss
f:.JO
Xyg
en°2
Gae
\,;-1~
Car
bon
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oxid
eCO
Gas
'
carb
onD
ioxi
deCO
2G
ae
Hydto~en
~~s
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el'
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Vap
or
Var
ious
Am
ines
••V
apor
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roge
nO
xide
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xG
as
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rage
amou
nto
rco
mpo
siti
on
150
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/ho
ur
83
.8V
ol.
%
1.4
It
4.1
Gl
1.4
II
2.1
II
7.1
"0
.1..
300
Vl'P
M
Com
posi
tion
Ran
/te
10
0-2
00
,lb
s./h
ou
t
80-8
5%
1-2%
3-5%
1-2%
2"2.
51
6.5-
1.5%
0.05
-0.2
%
200-
500
VPP
K
*P
art
icu
late
mat
ter
sho
uld
bed
escr
ibed
asfu
lly
asro
ssib
le.
Cata
lyst
Du
et(c
C>'
ft'".S
!!H1o
nh
prp
SJr
jeq
r;,)
con
tain
sco
balt
and
chro
miu
mon
Alu
min
Ab
ase,
10.DU~68
thaD
15m
iccO
BI.
6Q%
leu
than
10
"l1c
TO
OS
I20
%
less
than
5m
icro
ns;
5%le
ssth
an1
mic
ron.
**C
ompo
siti
onun
know
n-
mix
ture
of
feed
,p
rod
uct
san
do
ther
amin
es•
•.•._
_..
._-'
....,q
....
....
..·:a
t·.....
ai:I.
.."lIili~l'\i.mM..
.{"
·Iiil!
tI_
*.....
1al
iiI
.'.Q
i.•
...
•..
...'
.;4
....
._..
....
...~.
BIII. Continued For stream flow shown on block diagram by letter-----
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.
4. Method used to determine composition an~ 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 •
. 240
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.
- 241
III. Continued For stream flow shown on block diagram by letter B
8. -·Confidence level.
±.. .l~%
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.
242
III.
l.E
mis
sio
ns
(co
mp
osi
tio
nan
dfl
ow
).
Str
eam
flo
wsh
own
onb
lock
dia
gra
mb
yle
tter
C~
_
1.
Flo
w10
,000
SCFM
Tem
per
atu
re10
00F
Pre
ssu
re0
PSIG
~ j
Six
co
pie
sp
rov
ided
this
secti
on
Com
pone
ntA
ver
age
amou
ntC
om
po
siti
on
Nam
eF
orm
ula
Sta
teo
rco
mp
osi
tio
nR
ange
Part
icu
late
*S
oli
d1
0lb
s./h
ou
r5-
Z0
Ibs.
/ho
ur
Nit
rog
enNZ
Gas
83
.9V
ol.
%80
-85%
Oxy
gen
°zG
as1
.4"
l-Z
%N
Car
bon
Mon
oxid
eCO
Gas
4.1
"3-
5%~ w
Car
bon
Dio
xid
eCO
ZG
as1
.4"
l-Z
%
Hyd
roge
nHZ
Gas
Z.l
"Z
-Z.5
%
Wat
erHZ
OV
apor
7.1
"6
.5-7
.5%
Var
iou
sA
min
e**
Vap
or50
YPPM
V3
0-1
00
PPM
V
Nit
rog
enO
xide
sNO
xG
as30
0YP
PMV
ZO
O-5
00PP
MV
*P
art
icu
late
matt
er
sho
uld
be
desc
rib
ed
asfu
lly
asp
oss
ible
.S
ee"B
".S
ize
dis
trib
uti
on
100%
less
than
5m
icro
ns;
60%
less
than
1m
icro
n.
**S
ee"B
".
III. Continued For stream flow shown on block diagram by letter C _
2. Composition variation.
See "B~'
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 1II-6(C)
244
III. Continued For stream flow shown on block diagram by letter C~ __
5. Sampling procedure.
a. Particulates and moisture collected in sampling train as detailedin Federal Register, Dec. 23, 1971 (Method 5).
b. NO sampled by EPA Method 7.x
c. Other constituents collected using grab sampling procedures forcollection of gas. Sample size 10 liters in stainless steel tank.
6. Analytical-procedure.
a. Particulates and moisture determined gravimetrically as detailedin Federal Register, Dec. 23, 1971. (Method 5)
b. NOx determined by EPA method 7.
c. Hydrogen, oxygen, and nitrogen determined by mass spectrometeranalysis at local university.
Amine, CO and CO2 determined by infra-red analysis.
7. Sampling frequency.
Once, - one month after scrubber was put on strewn.
245
III. Continued For stream flow shown on block diagram by letter C---..;;..---
8. Confidence level.
Oxygen, CO2, 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.
246
III.
l.E
mis
sio
ns
(co
mp
osi
tio
nan
dfl
ow
).
.. .S
ixco
pie
sp
rov
ided
this
secti
on
Str
eam
flo
wsh
own
onb
lock
dia
gra
mby
lett
er
D~
.
1.
Flow
300
GPH
Tem
per
atu
re300~
Pre
ssu
re1
0PS
IG
Com
pone
ntN
ame
For
mul
aS
tate
Ave
rage
amou
nto
rco
mp
osi
tio
nC
om
po
siti
on
Ran
ge
Part
icu
late
*S
oli
dT
race
N ti··, "t
Hea
vyA
min
es{C
Hx}
yNH
zL
iqu
id10
0%
--
_.--
---.
Ver
vfi
ne
catC
ily
stcl
1Jst
-Ile:v~amtlled
*P
art
icu
late
mat
ter
sho
uld
be
desc
rib
ed
asfu
lly
aspn~~ihlP.!
--F---
or
ar.a
lyze
ci-
esti
mat
edto
be1
-5Ib
s./h
ou
r..
---
.:..
:...
::.:
...:
.;:;
.-::
..-.
...-
----
._--
--_
.•_-_._._~.-.
.-
III. Continued For stream flow shown on block diagram by letter D-----
2. Compo~!~ion variation.
Not applicable - unknown - never analyzed.
3. Produc!~£n rate during sampling.
See liB"
4. Method used to determine composition and flow.
Rotameter in liquid line for flow. ,Composition unkno~~.
24.8 ,
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.
249
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? Ye~/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.
2&0
III.
l.E
mis
sio
ns
(co
mp
osi
tio
nan
dfl
ow
).
Str
eam
flo
wsh
own
onb
lock
dia
gra
mby
lett
er
~E_
1.
Flow
10,0
00S
CF
MT
empe
ratu
re45
00
FP
ress
ure
0PS
IG
Six
cop
ies
pro
vid
edth
isse
cti
on
Com
pone
ntA
vera
geam
ount
Nam
eF
orm
ula
Sta
teo
rco
mp
osi
tio
n
Part
icu
late
*S
oli
dT
race
Nit
rog
enN
2G
as7
7.0
Vo
l.%
Oxy
gen
O2
Gas
9.2
Vo
l.%
.JfN
itJ
1'
Car
bon
Dio
xid
eCO
2G
as6
.4V
ol.
%.....
.'
Wat
erH 2O
Vap
or7
.4V
oL
%
Nit
rog
enO
xide
sNO
xG
as15
0V
PPM
Co
mp
osi
tio
nR
ange
76
.5-7
7.5
%
9-9.
5%
6-7%
7-8%
10
0-3
00
VPP
M
*P
art
icu
late
mat
ter
sho
uld
be
des
crib
edas
full
yas
po
ssib
le.
~S=e
=e__
"~D~
"_
_
EIII. 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 liB"
4. Method used to determine composition and flow.
Calculation based on incinerator vendor's specifications, guarantees
and laboratory tests.
III. Continued For stream flow shown on block diagram by letter -ME __
5. Sampling procedure.
Never sampled.
6. Analytical procedure.
Never analyzed
7. Sampling frequency.
See (5) above
253.
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/~ Has the odorous material been chemically identified?
Amines
* Only during start-up or upset of the incinerator and then only
if atmospheric conditions are favorable for ground level detection.
254
3 copies providedthis section.
IV. Emission control device
For device shown on block diagram by number__~l~O~l _
1. Engineering description.
• GAS TOI STACK
Multi-nozzle spray tower manufactured by Rebburcs Corp.Model No. 10,000-WWater rate: 100 GPMGas rate: 10,000 SCFMTemperature: 1000 F.Pressure: AtmosphericGas AP: 8 in, H20Water Pump Head: 150 Ft.Discharge Pump Head: 100 Ft.
GASIN .
\).....----.-....DISCHARGE
PUMP
Utilities:
35 HP for Pumps
Diameter of Tower:T-T Length:
EIR
4--iQWATER PUMP
OOWNCOMER
6 Ft.60 Ft.
10,000,00Q BTU/Hr. Additional steam in product recovery section.
1500 GPM Additional cooling water circulation in product recovery section.
255 ,$,1
IV. Continued For device shown'on block diagram by number ~l~O~l~ _
2. Capital cost of emission control system.
(a) Capital cost
Major equipment cost
Total installed cost
$ 160,000
$ 350,000
Year
1968
Cost
$350,000
256 '
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
x
x
x
x
x
x
x
No
x
x
x
x
x
x
x
Cost
Site development
Buildings
Laboratory equipment
Stack
Rigging etc.
Piping
Insulation
Instruments
Instrument panels
Electrical
Facilities outside
battery limits*
Storage tanks, spheres
drums, bins, silos
Catalysts
Spare parts and
non-installed parts
Explanation
Additional foundation required forscrubber.
*Such as - process pipe lines such as stearn, condensate, water, gas, fuel,
air, fire, instrument and electric lines.
-;~57
IV. Continued For device shown on block diagram by number 101------Yes No
X Was outside engineering contractor used?
X Was cost included in capital cost?
X 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 1.1.
(a) Utilities
(b) Chemicals *
(c) Labor (No Additional Operators)
(d) Maintenance (labor & materials)
(e) Water treatment (cost of treating any wastewater produced by this control system)**
(f) Solids remmoval (cost of removing any wastesolids produced by this control system)
(g) Other disposal
$ 68,000
10,000
14,000
20,000
(h) By-product or product recovery
Total operating costs
CREDIT G89,OOO )
$ 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,OOO!year. This treatment was required before scrubber wasinstalled.
3 copies providedthis section.
IV. Emission control device
For device shown on block diagram by number 102
1. Engineering description.
RADIANTSECTION
WATER
BURNERS
t TO STACK
CONVECTIVE~CTION
STEAM
Steam Generator/Waste Incinerator
Manufactured by: Xoberif Corp.Model No.: 40-HHeavy Ends Rate: 300 GPHAir Rate: 9,5QO SCFMSteam Rate: 20,000 lbs./hourVessel Diameter: 15 Ft.Height: 40 Ft.Tube Diameter: 3 in. nominalTube Length: (Material)
Convective (mild steel): 6,000 Ft.Radiant (304 stainless): 2,000 Ft.
-E7PUMP
HEAVY ENDS
Utilities:
SECONDARY
AIRBLOWER
Heavy Ends Pump: 20 HP
Blower: 100 HP
2
IV. Continued For device shown'on block diagram by number 102
2. Capital cost of emission control system.
(a) Capital cost
Major equipment cost
Total installed cost
$350,000
$ 1,000,000
Year
1960
Cost
$1,000,000
IV. Continued For dev;ce shown on block diagram by number 102----------(b) Check list. Mark whether items listed are included in total
cost included in TV~2,a. Do not give dollar value -
Yes Explanation
_~ ~.Lr_~'~~~'::':.:~_~:_~~(:.I1_r. --"C:.:::o:.:::s"-,t::-;p<=..r"-'o~r"",a-"t-"e,",,d,-,,f....r...,Q....m_.kt~Q...t~a...l'---4p...l...a....n....t__
site costs.x 3:~ t__' (! j ng'?- .. _
x Stack
_X ._. R_'~r,i!:'1.._e.!_.~_. __. _. . _
x ___F_-il'J:.~~ _
--------_. --_._--_._-------------_._---------------------InsulAtion-----x
x :nstruments
x In_~,trutn..':E..!:_~~'=-~~. . _
x Electd.r.al
F3cilitie~ outsi~e
x batte.::-y limits*
SUn c1ri(' tcmks '_ spheres
x drums, hins, silos
-------------------------_.__._--_._-----------------._---------X Catclysts
----- ------------._------------
xnon-installed parts
*Such as - process pi)c ] -Lnes such as steam, conctensate, water:, gas, fuel,.
air. fire, instrument dnd electric lin!":'s.
IV. Continued For device shown on block diagram by number 102-......;;,=..---
Yes No
X Was outside engineering contractor used?
X Was cost included in capital cost?
I X
_Xf---,
X I
Was in-house engineering used?
Was cost included in capital cost?
Was emission control equipment installedand constructed at the time plant (process)was constructed?
3. Operating costs of control system.
Give 1972 dollar values per year at capacity given in 1.1.
(a) Utilities
(b) Chemicals
(c) Labor (~man per shift - excludes supervision &overhead)
Cd) MaintenHnce (labor & materials)
(e) Water treatment (cost of treating any wastewater produced by this control system)
(f) Solids remmoval (cost of removing any wastesolids produced by this control system)
(g) Other disposal
$ 5,000-------
7,000
40,000
(h) By~product or product recovery
Total operating credit
CREDIT - STEAM ~lOO,OOq
$ 48,000
V. Stack or vent description.
For stack or vent shown on block diagram by letter C
1. .Stack height 100 ft
2. Stack diameter 2 ft
3. Gas temperature stack exit 100 of
4. Stack flow * SCFM(70°F & 1 Atm.)
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 4500 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 1etter _
1. Stack height
2. Stack diameter
3. Gas temperature stack exit
4. Stack flow *
* See instructions
VI.
Tan
kage
.
No.
of
tan
ks
com
po
siti
on
tem
p.cap
acit
y(e
ach
)
app
rox
imat
etu
rno
ver
sp
ery
ear
met
hod
of
vap
or
con
serv
atio
n
3P
yrr
oli
din
eA
mbi
ent
10
0,0
00
50N
one,
ven
tsto
air
(CH
2)4
NHg
al.
(ea)
4P
yrr
o1
eA
mbi
ent
10
0,0
00
25"
(CH
)4NH
gal.
(ea)
1P
yrr
o1
ido
ne
Am
bien
t1
00
,00
025
"(C
H)2
CH
2CO
NH
gal.
(ea)
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 occu~.
Engineeting estimate of average losses is 0.01% of throughput or13,000 lbs./year of amines.
IX. Future plans.
1. Current research on heavy amine stream indicates furtherprocessing will produce a marketable product - if so,incinerator will be shut down.
2. We are currently negotiating a long term contract to purchase1% sulfur fuel oil from the Flused Oil Company.
APPENDIX III
FINAL QUESTIONNAIRE SUMMARY
Chemical
Acetaldehyde via Ethylenevia Ethanol
Acetic Acid via Methanolvia Butanevia Acetaldehyde
Acetic AnhydrideAcrylonitrileAdipic AcidAdiponitrile via Butadiene
via Adipic AcidCarbon BlackCarbon DisulfideCyclohexanoneDimethyl Terephthalate (+TPA)EthyleneEthylene Dichloride via Oxychlorination
via Direct ChlorinationEthylene OxideFormaldehyde via Silver catalyst
via Iron Oxide CatalystGlycerolHydrogen CyanideIsocyanatesMaleic AnhydrideNylon 6Nylon 6,6Oxo ProcessPhenolPhthalic Anhydride via o-xylene
via naphthalenePolyethylene (High Density)Polyethylene (Low Density)PolypropylenePolystyrenePolyvinyl ChlorideStyreneStyrene - Butadiene RubberVinyl Acetate via Acetylene
via EthyleneVinyl Chloride
266
Number of Questionnairesused as Basis for Report
1121124412747
·61310
37
12621
107
4368535774876318
Appendix IV &V
INTRODUCTION TO APPENDIX IV AND V
The following discussions describe techniques that were developed forthe single purpose of providing a portion of the guidance required in theselection of processes for in~depth study. It is believed that the underlyingconcepts of these techniques are sound. However, use of them without sub~
stantial further refinement is discouraged because the data base for theirspecifics is not sufficiently accurate for wide application. The subjectscovered in the Appendix IV discussion are:
1. Prediction of numbers of new plants.
2 0 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 ofbases, including a weighted (significance) basis.
It should be noted that the weighting factors used are arbitraryoHence, if any reader of this report wishes to determine the effect ofdifferent weighing factors, the calculation technique permits changes inthese, at the reader's discretiono
267
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 whatamount of today's production capacity is likely to be on-streamin 1980. This will be done by subtracting plants having marginaleconomics due either to their size or to the employment of anout-of-date process.
2. Estimate the 1980 demand for the chemical and assume a 1980installed capaeity that will be required in order to satisfythis demand.
3. Estimate the portion of the excess of the 1980 required capacityover today's remaining capacity that will be made up byinstallation of each process that is being evaluated.
4. Estimate an economic plant or unit size on the basis of tOday'stechnology.
50 Divide the total required new capacity for each process by theeconomic plant size to obtain the number of new units o
In order to illustrate the procedure, data have been incorporatedinto Table I, for the three processes for producing carbon black, namelythe furnace process,the relatively non-polluting thermal process, andthe non-growth channel process.
26~
Tab
lel.
Num
ber
of
New
Pla
nts
by
1980
Cu
rren
tC
apac
ity
Cap
acit
yE
cono
mic
Num
ber
of
Cu
rren
tM
arg
inal
on
-str
eam
Dem
and
Cap
acit
yto
be
Pla
nt
New
Che
mic
alP
roce
ssC
apac
ity
Cap
acit
yin
1980
1980
1980
Add
edS
ize
Un
its
Car
bon
Bla
ckF
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2.
1980
dem
and
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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 noxiousand even when agreement can be reached on an order of noxiousness, disagreements remain as to relative magnitudes for tolerance factors. Ingeneral pollutants from the petrochemical industry can be broken down intocategories of hydrogen sulfide, hydrocarbons, particulates, carbon monoxide,and oxides of sulfur and nitrogen. Of course, two of these can be furtherbroken 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 usefulend is served by creating a large number of sub-groupings because it willmerely compound the problem of assigning a weighting factor. Therefore,it is proposed to classify all pollutants into one of five of the sixcategories with hydrogen sulfide included with hydrocarbons.
There appears to be general agreement among the experts that carbonmonoxide is the least noxious of the five and that NOx is somewhat morenoxious than SOx. However, there are widely divergent opinions concerninghydrocarbons and particulates - probably due to the fact that these areboth widely divergent categories. In recent years, at least two authorshave attempted to assign tolerance factors to these five categories.Babcock (I), based his on the proposed 1969 California standards forone hour ambient air conditions with his own standard used for hydrocarbons.
On the other hand, Walther (2), based his ranking on both primaryand secondary standards for a 24-hour period. Both authors found itnecessary to extrapolate some of the basic standards to the chosen timeperiod. Their rankings, on an effect factor basis with carbon monoxidearbitrarily used as a reference are as follows:
Babcock Walther
Primary Secondary
HydrocarbonsParticulatesNOxSOxCO
2.1107
77.928.1
1
12521.522.415.3
1
12537.322.421.5
1
Recognizing that it is completely unscientific and potentially subjectto substantial criticism it is proposed to take arithmetic averages of theabove values and round them to the nearest multiple of ten to establish arating basis as follows:
HydrocarbonsParticulatesNOxSOxCO
Average
84.055.340.921.6
1
270
Rounded
80604020
1
Tab
le2
.W
eig
hte
dE
mis
sio
nR
ates
Che
mic
al....
,.-_
Pro
cess
_
Incr
ease
dC
apac
ity
_
.J oJ ..P~~lutant
Em
issi
on
s,L
bs.
/Lb
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Hy
dro
carb
on
s
Part
icu
late
s
NOx
SO
x
CO
Incre
ase
dE
mis
sio
ns
Lb
s./Y
ear
Wei
gh
tin
gF
acto
rs
80 60 40 20 1
Wei
gh
ted
Em
issi
on
sL
bs.
/Yea
r
To
tal -
---------------
Increased Emissions (Weighted) by 1980 (continued)
This ranking can be defended qualitatively, if not quantitatively forthe following reasons:
1. The level of noxiousness follows the same sequence as is obtainedusing national air quality standards.
2. Approximately two orders of magnitude exist between top and bottomrankings.
3. Hyd·rocarbons should probably have a lower value than in theWalther analysis because such relatively non-noxious compoundsas ethane and propane will be included.
4. Hydrocarbons should probably have a higher value than in theBabcock analysis because such noxious (or posionous) substan~es
as aromatics, chlorinated hydrocarbons, phenol, formaldehyde, andcyanides are included.
5. Particulates should probably have a higher value than in theWalther analysis because national air standards are based mostlyon fly ash while emissions from the petrochemical industry aremore 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 Waltheranalysis 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, isas follows:
1. Determine the emission rate for each major pollutant category interms of pounds of pollutant per pound of final product. Thisdetermination is to be made on the basis of data reported onreturned questionnaires.
2. Multiply these emission rates by the estimate of increased productioncapacity to be installed by 1980 (as calculated while determiningthe number of new plants), to determine the estimated pounds ofnew emissions of each pollutant.
3. Multiply the pounds of new emissions of each pollutant by itsweighting factor to determine a weighted pounds of new emissionsfor each pollutant.
4. Total the weighted pounds of new emissions for all pollutants toobtain an estimate of the significance of emission from the processbeing evaluated. It is proposed that this total be named"Significant Emission Index" and abbreviated IISEI".
It should be pointed out that the concepts outlined above are notcompletely original and considerable credit should be given to Mr. L. B. Evansof the EPA for setting up the formats of these evaluating procedures.
Increased Emissions (Weighted) by 1980 (continued)
(1) Babcock, L .. F., "A Combined Pollution Index for Measurement of TotalAir Pollution," JAPCA, October, 1970; VoL 20, No. 10; pp 653-659
(2) Walther, E. G., "A Rating of the Major Air Pollutants and Their Sourcesby Effect", JAPCA, May, 1972; VoL 22, No.5; pp 352-355
Appendix VEfficiency of pollution Control Devices
Incinerators and Flares
The burning process is unique among the various techniques forreducing air pollution in that it does not remove the noxious substancebut 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 carbondioxide and water. However, if the combustion is incomplete a wide rangeof additional products such as cracked hydrocarbons, soot and carbonmonoxide might be formed. The problem is further complicated if thehydrocarbon that is being burned is halogenated, contains sulfur or ismixed with hydrogen sulfide, because hydrogen chloride and/or sulfur oxidesthen become products of combustion. In addition, if nitrogen is present,either as air or nitrogenated hydrocarbons, oxides of nitrogen might beformed, depending upon flame temperature and residence time.
Consequently, the definition of efficiency of a burner, as a pollutioncontrol device, is difficult. The usual definition of percentage removal ofthe noxious substance in the feed to the device is inappropriate, becausewith this definition, a "smoky" flare would achieve the same nearly 100percent rating, as a "smokeless" one because most of the feed hydrocarbonwill have either cracked or burned in the flame. On the other hand, anysystem that rates efficiency by considering only the total quantity ofpollutant in both the feed to and the effluent from the device would bemeaningless. For example, the complete combustion of one pound of hydrogensulfide results in the production of nearly two pounds of sulfur dioxide, orthe incomplete combustion of one pound of ethane could result in theproduction of nearly two pounds of carbon monoxide.
For these reasons, it is proposed that two separate efficiency ratingbe applied to incineration devices. The first of these is a "Completenessof Combustion Rating" and the other is a "Significance of Emission ReductionRating", as follows:
1. Completeness of Combustion Rating (CCR)
This rating is based on oxygen rather than on pollutants and isthe pounds of oxygen that react with the pollutants in the feed tothe device, divided by the theoretical maximum number of pounds thatwould react: Thus a smokeless flare would receive a 100 percentrating while a smoky one would be'rated somewhat less, depending uponhow incomplete the combustion.
In utilizing this rating, it is clear that carbon dioxide and waterare the products of complete combustion of hydrocarbons. However, somequestion could occur as to the theoretical completion of combustionwhen burning materials other than hydrocarbons. It is recommendedthat the formation of HX be considered complete combustion of halogenatedhydrocarbons since the oxidation most typically does not change thevalence of the halogen. On the other hand, since some incinerators willbe catalytic in nature it is recommended that sulfur trioxide beconsidered as complete oxidation of sulfur bearing compounds.
V-2
Efficiency of Pollution Control Devices
1. Completeness of Combustion Rating (CCR) (continued)
Nitrogen is more complex, because of the equilibria that existbetween oxygen, nitrogen, nitric oxide, nitrogen dioxide and thevarious nitrogen radicals such as nitrile. In fact, many scientistscontinue to dispute the role of fuel nitrogen versus ambient nitrogenin the production of NOx • In order to make the CCR a meaningfulrating for the incineration of nitrogenous wastes it is recommendedthat complete combustion be defined as the production of N2' thusassuming 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 hydrocarboncontent 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 thatwere proposed above. All air pollutants in the feed to the deviceand all in the effluents from the device are multiplied by theappropriate factor. The total weighted pollutants in and out arethen used in the conventional manner of calculating efficiencyof pollutant removal, that is pollutants in minus pollutants out,divided by pollutants in, gives the efficiency of removal on asignificance 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 burnedin a flare, in accordance with the following reaction:
3C2~ + 7 02 C + 2 CO + 3 C02 + 6 H2°Thus, 14.2 1bs. of particulate carbon and 66.5 1bs. of carbon
monoxide are emitted, and 265 1bs. of oxygen are consumed.
Theoretical complete combustion would consume 342 1bs. of oxygenin accordance with the following reaction:
2 C02 + 2 H20
Thus, this device would have a CCR of 265/342 or 77.5%
Assuming that one pound of nitric oxide is formed in the reactionas a result of the air used for combustion (this is about equivalent to100 ppm), a SERR can also be calculated. It should be noted that theformation of this NO is not considered in calculating aCCR because itcame from nitrogen in the air rather than nitrogen in the pollutantbeing incinerated. The calculation follows:
V-3
Efficiency of Pollution Control Devices
2. Significance of Emission Reduction Rating (SERR) (continued)
Actual WeightedWeighting Pounds in
Pollutant Factor Actual Weighted
Hydrocarbons 80 100 8000
Particulates 60 a
NOx 40 a
SOx 20 a
CO 1 a
Total 8000
SERR = 8000 - 958.58000 x 100 = 88%
Pounds out
o
85214.2
401
a
66.566.5
958.5
Example 2 - The same as Example 1, except the hydrocarbons areburned to completion. Then,
CCR = ;~; x 100 = 100%
and
SERR = 8000 - 408000 = 99.5%
Example 3 - One hundred pounds per unit time of methyl chloride isincinerated, in accordance with the following reaction.
This is complete combustion, by definition, therefore, the CCR is100%. However, (assuming no oxides of nitrogen are formed), the SERRis less than 100% because 72.5 lbs. of HCI are formed. Hence,considering HCl as an aerosol or particulate;
SERR = 100 x 80 - 72.5 x 60100 x 80
x 100 = 45.5%
The conclusion from this final example, of course, is that it isan 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, eachburning 100 pounds per unit time of HCN are sampled. Neither has anycarbon monoxide or particulate in the effluent. However, the first isproducing one pound of NOx and the second is producing ten pounds ofNOx in the same unit time. The assumed reactions are:
276
Efficiency of Pollution Control Devices
2. Significance of Emission Reduction Rating (SERR) !continued)
4 HCN + 5 02
N2 (atmospheric) + XOZ
Thus, CCRl = 100% and CCRZ = 100% both by definitioQ.
However, SERR1· = 100 x 80 - 1 x 40 100 99 5"1100 x 80 x =.. 10
and SERR2 = 100 x 80 - 10 x 40100 x 80 j x 100 = 95%
Obviously, if either of these were "smoky" then both theCCR andthe SERR would be lower, as in Example 1.
Other Pollution Control Devices
Most pollution control devi~es, such as bag filters, electrostaticprecipitators and scrubbers are designed to physically remove one or morenoxious substances from the stream being vented. Typically, thE! efficieJ:\cyof these devices is rated relative only to the substance which they aredesigned to remove and for this reason could be misleading. For example:
1. The electrostatic precipitator on a power house stack might be99% efficient relative to particulates, but will remove littleor none of the SOx and NOx which are usually present.
2. A bag filter on a carbon black plant will remove 99 + % of theparticulate but will remove none of the CO and only relativelysmall amounts of the compounds of sulfur that are present.
3. A water scrubber on a vinyl chloride monomer plant will removeall of the hydrogen chloride but only relatively small amountsof the chlorinated hydrocarbons present.
4. An organic liquid scrubber on an ethylene dichloride plant willremove nearly all of the EDC but will introduce another pollutantinto the air due to its own vapor pressure.
For these reasons, it is suggested again that two efficiency ratings beapplied. However, in this case, the first is merely a specific efficiency asis typically reported, Le., "specific to the pollutant (or pollutants) forwhich it was designed", thus:
SE = specific pollutant in - specific pollutant butspecific pollutant in x 100
The second rating proposed is an SERR, defined exactly as in the caseof incinerators •.
Two examples will il~~st.!ate these ratings.
V-5
Efficiency ofPPl,lo.t;.ion Control Devices
Other pollution Control Devices (continued)
Example 1 - Assume that a catalytic cracker regenerator effluentcontains 100 pounds of catalyst dust, 200 lbso ofcarbon monoxide and 10 pounds of sulfur oxides per unittime. It is passed through a cyclone separator where95 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 astream containing 50 pounds of S02 per unit time. Allbut one pound of the S02 is removed but two pounds ofthe 4ydrocarbon evaporate into the vented stream. Then
SE = 50 - 1)( 10050
= 98%
and SERR = (50 x 20) - (1 x 20 + 2 x 80) x 100(50 x 20)
= 1000 - 180 x 100 = 82%1000