EPA-450/3-73-005a
JANUARY 1974
SURVEY REPORTS
ON ATMOSPHERIC EMISSIONS
FROM THE PETROCHEMICAL
INDUSTRY
VOLUME I
~
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Water Programs
Office of Air Quality Planning and Standards
Research Triangle Park, North Carolina 27711
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EPA-450/3-73-005a
SURVEY REPORTS
ON ATMOSPHERIC EMISSIONS
FROM THE PETROCHEMICAL
INDUSTRY
VOLUME I
Prepared by
J. W. Pervier, R. C. Barley, D. E. Field,
B. M. Friedman, R. B. Morris, and W. A. Schwartz
Houdry Division
Air Products and Chemicals, Inc.
P.O. Box 427
Marcus Hook , Pennsylvania 19061
Contract No. 68-02-0255
EPA Project Officer: Leslie B. Evans
Prepared for
ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Water Programs
Office of Air Quality Planning and Standards
Research Triangle Park, N .C . 27711
January 1974
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This report is issued by the Environmental Protection Agency to report
technical data of interest to a limited number of readers. Copies are
available free of charge to Federal employees, current contractors and
grantees, and nonprofit organizations - as supplies permit - from the
Air Pollution Technical Information Center, Environmental Protection
Agency, Research Triangle Park, North Carolina 27711, or from the
National Technical Information Service, 5285 Port Royal Road, Springfield,
Virginia 22151.
This report was furnished to the Environmental Protection Agency by
Houdry Division, Air Products and Chemicals, Inc., Marcus Hook,
Pennsylvania, in fulfillment of Contract No. 68-02-0255. The contents
of this report are reproduced herein as received from the Houdry
Division, Air Products and Chemicals, Inc. The opinions, findings,
and conclusions expressed are those of the author and not necessarily
those of the Environmental Protection Agency. Mention of company or
product names is not to be considered as an endorsement by the
Environmental Protection Agency.
Publication No. EPA-450/3/73/005a
11
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PETROCHEMICAL AIR POLLUTION STUDY
INTRODUCTION TO SERIES
This document is one of a series of four volumes prepared for the
T
Environmental Protection Agency (EPA) to assist it in determining the
significance of air pollution from the petrochemical industry.
A total of 33 distinctly different processes which are used to
produce 27 petrochemicals have been surveyed, and the results are
reported in these four volumes numbered EPA 450/3-73-005-a, -b, -c, and -d.
The Tables of Contents of these reports list the processes that have been
surveyed.
Those processes which have a significant impact on air quality
are being studied in more detail by EPA. These in-depth studies will be
published separately in a series of volumes entitled Engineering and
Cost Study of Air Pollution Control for the Petrochemical Industry
(EPA-450/3-73-006-a, -b, -c, etc.) At the time of this writing, a total
of seven petrochemicals produced by 11 distinctly different processes has
been selected for this type of study. Three of these processes, used to
produce two chemicals (polyethylene and formaldehyde), were selected
because the survey reports indicated further study was warranted. The
other five chemicals (carbon black, acrylonitrile, ethylene dichloride,
phthalic anhydride and ethylene oxide) were selected on the basis of
expert knowledge of the pollution potential of their production processes.
One or more volumes in the report series will be devoted to each of these
chemicals.
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ACKNOWLEDGEMENTS
Survey and study work such as that described in this report have value
only to the extent of the value of the imput data. Without the fullest
cooperation of the companies involved in producing the petrochemicals that
have been studied, this report vould not have been possible. Air Products
wishes to acknowledge this cooperation by commending:
The U. S. Petrochemical Industy
Member Companies of the Industry
The Manufacturing Chemists Association
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Table of Contents
Section Page Number
Summary i
I. Introduction 1
II. Discussion 2
III. Results 8
IV. Conclusions 9
Appendicies
Acetaldehyde via Ethylene ACD
Acetaldehyde via Ethanol AC
Acetic Acid via Methanol HAG
Acetic Acid via Butane ACA
Acetic Acid via Acetaldehyde ACE
Acetic Anhydride • ANA
Adipic Acid AA
Adiponitrile via Butadiene AN
Adiponitrile via Adipic Acid AL
Mailing List I
Example Questionnaire II
Questionnaire Summary III
Significance of Pollution IV
Efficiency Ratings V
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List of Tables and Figures
Table Number Title
I Emissions Summary (3 pages)
II Total Emissions, All Pollutants, by 1980*
III Total Annual Weighted Emissions, by 1980*
IV Significant Emission Index*
V Number of New Plants (1973-1980)*
*Fifteen highest ranks from Table !„
NOTE: There are numerous tables and figures in the Survey Reports that are
included in the appendicies of this report. These tables and figures
are separately listed in each appendix.
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SUMMARY
A study of air pollution as caused by the petrochemical industry has
been undertaken in order to provide data that the Environmental Protection
Agency can use in the fulfillment of their obligations under the terms of
the Clean Air Amendments of 1970,, The scope of the study includes most
petrochemicals which fall into one or more of the classifications of (a)
large production, (b) high growth rate, and (c) significant air pollution.
The processes for the production of each of these selected chemicals have
been studied and the emissions from each tabulated on the basis of data
from and Industry Questionnaire. A survey report prepared fcr each process
provides a method for ranking the significance of the air pollution from
these processes. In-depth studies on those processes which are considered
to be among the more significant polluters either have been or will be
provided.
To date, drafts of in-depth studies on seven processes have been
submitted. In addition, two further processes have been selected for
in-depth study and work on these is in progress. All of these in-depth
studies will be separately reported under Report Number EPA-450/3-73-006
a, b, c, etc.
A total of 33 Survey Reports have been completed and are reported
here, or in one of the other three volumes of this report series.
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I. Introduction
A study has been undertaken to obtain information about selected pro-
duction processes that are practiced in the Petrochemical Industry. The
objective of the study is to provide data that are necessary to support
the Clean Air Ammendments of 1970.
The information sought includes industry descriptions, air emission
control problems, sources of air emissions, statistics on quantities and
types of emissions and descriptions of emission control devices currently
in use. The principal source for these data was an industry questionnaire
but it was supplemented by plant visits, literature searches, in-house
background knowledge and direct support from the Manufacturing Chemists
Association.
A method for rating the significance of air emissions was established
and is used to rank the processes as they are studied. The goal of the
ranking technique is to aid in the selection of candidates for in-depth
study. These studies go beyond the types of information outlined above
and include technical and economic information on "best systems" of emission
reduction, the economic impact of these systems, deficiencies in petrochemical
pollution control technology and potential research and development programs
to overcome these deficiencies. These studies also recommend specific plants
for source testing and present suggested checklists for inspectors.
This final report presents a description of the industry surveys that
have been completed, as well as a status summary of work on the in-depth
studies.
The Appendicies of this report include each of the 33 Survey Reports
that were prepared during the course of the study.
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II. Discussion
A. Petrochemicals to be Studied
There are more than 200 different petrochemicals in current
production in the United States. Many of these are produced by tvo
or more processes that are substantially different both with respect
to process techniques and nature of air emissions. Although it may
eventually become necessary to study all of these, it is obvious
that the immediate need is to study the largest tonnage, fastest growth
processes that produce the most pollution.
Recognizing this immediate need, a committee of Air Products'
employees and consultants reviewed the entire list of chemicals and
prepared a list of thirty chemicals which were recommended for primary
consideration in the study and an additional list of fourteen chemicals
that should receive secondary consideration. Since this was only a
qualitative evaluation it was modified slightly as additional information
was received and after consultation with the Environmental Protection
Agency (EPA).
The final modified list of chemicals to be studied included all
but three from the original primary recommendations. In addition, four
chemicals were added and one was broken into two categories (namely low
and high density polyethylene) because of distinct differences in the
nature of the final products. This resulted in thirty-two chemicals
for study and fourty one processes which are sufficiently different to
warrant separate consideration. Hence, the following list of petro-
chemicals is the subject of this study.
Acetaldehyde (2 processes)
Acetic Acid (3 processes)
Acetic Anhydride
Acrylonitrile
Adipic Acid
Adiponitrile (2 processes)
Carbon Black
Carbon Disulfide
Cyclohexanone
Ethylene
Ethylene Bichloride (2 processes)
Ethylene Oxide (2 processes)
Formaldehyde (2 processes)
Glycerol
Hydrogen Cyanide
Maleic Anhydride
Nylon 6
Nylon 6,6
"Oxo" Alcohols and Aldehydes
Phenol
Phthalic Anhydride C2 processes)
Polyethylene (high density)
Polyethylene (low density)
Polypropylene
Polystyrene
Polyvinyl Chloride
Styrene
Styrene - Butadiene Rubber
Terephthalic Acid (1)
Toluene Di-isocyanate (2)
Vinyl Acetate (2 processes)
Vinyl Chloride
(1) Includes dimethyl terephthalate,
(2) Includes methylenediphenyl and polymethylene polyphenyl isocyanates,
B. Preliminary Investigations
Immediately upon completion of the preliminary study lists, a
literature review was begun on those chemicals which were considered
likely candidates for study. The purpose of the review was to prepare
an informal "Process Portfolio" for each chemical. Included in the
portfolio are data concerning processes for producing the chemical,
estimates of growth in production, estimates of production costs, names,
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locations and published capacities of producers, approximations of
overall plant material balances and any available data on emissions
or their control as related to the specific process.
The fundamental purpose of these literature revievs vas to obtain
background knowledge to supplement vhat vas ultimately to be learned
from completed Industry Questionnaires. A second and very important
purpose vas to determine plant locations and names of companies
producing each chemical. This information vas then used to contact
responsible individuals in each organization ("usually by telephone) to
obtain the name and address of the person to vhom the Industry Question-
naire should be directed. It is believed that this approach greatly
expedited the completion of questionnaires. The mailing list that vas
used is included as Appendix I of this report.
C. Industry Questionnaire
Soon after the initiation of the petrochemical pollution study, a
draft questionnaire vas submitted by Air Products to the Environmental
Protection Agency. It had been decided that completion of this
questionnaire by industry vould provide much of the information
necessary to the performance of the study. The nature and format of
each question vas revieved by EPA engineers and discussed vith Air
Products engineers to arrive at a modified version of the originally
proposed questionnaire.
The modified questionnaire vas then submitted to and discussed
vith an Industry Advisory Committee (IAC) to obtain a final version for
submission to the Office of Management and Budget <"OMB) for final
approval, as required prior to any U. S. Government survey of national
industries. The folloving listed organizations, in addition to the
EPA and Air Products, vere represented at the IAC meeting:
Trade Associations
Industrial Gas Cleaning Institute
Manufacturing Chemists Association
Petrochemical Producers
B. F. Goodrich Chemical Company
E. I. duPont deNemours and Company
Exxon Chemical Company
FMC Corporation
Monsanto Company
Northern Petrochemical Company
Shell Chemical Company
Tenneco Chemicals, Inc.
Union Carbide Corporation
Manufacturers of Pollution Control Devices
John Zink Company
UOP Air Correction Division
State Pollution Control Departments
Nev Jersey
Texas
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The questionnaire, along with a detailed instruction sheet and
an example questionnaire (which had been completed by Air Products
for a fictitious process that was "invented" for this purpose) were
submitted to the OMB for approval. In due course, approval was
received and OMB Approval Number 158-S-72019 was assigned to the
questionnaire. Copies of the approved instruction sheet, example
questionnaire are included as Appendix II of this report.
The questionnaires were mailed in accordance with the mailing
list already discussed and with a cover letter that had been prepared
and signed by the EPA Project Officer. The cover letter was typed in
a manner that permitted the insertion of the name and address of the
receipient at the top of the first page and the name of the process,
the plant location and an expected return date at the bottom of the
first page. A copy of this letter of transmittal is also included in
Appendix II.
Understandably, because of the dynamic nature of the petrochemical
industry, about 10 percent of the questionnaires were directed to plants
which were no longer in operation, were still under construction, were
out-of-date processes or were too small to be considered as typical.
This did not present a serious problem in most cases because (a) 100
percent of the plants were not surveyed and (b) the project timing per-
mitted a second mailing when necessary,, Appendix III tabulates the
number of questionnaires incorporated into each study.
One questionnaire problem that has not been resolved is confiden-
tiality. Some respondents omitted information that they consider to
be proprietary. Others followed instructions by giving the data but
then marked the sheet (or questionnaire) "Confidential". The EPA is
presently trying to resolve this problem, but until they do the data
will be unavailable for inclusion in any Air Products' reports.
D. Screening Studies
Completed questionnaires were returned by the various respondents
to the EPA's Project Officer, Mr. L. B. Evans. After reviewing them
for confidentiality, he forwarded the non-confidential data to Air
Products. These data form the basis for what has been named a "Survey
Report". The purpose of the survey reports being to screen the various
petrochemical processes into the "more" and "less - significantly
polluting processes". These reports are included as appendicies to
this report.
Obviously, significance of pollution is a term which is difficult
if not impossible to define because value judgements are involved.
Recognizing this difficulty, a quantitative method for calculating a
Significant Emission Index (SEI) was developed. This procedure is
discussed and illustrated in Appendix IV of this report. Each survey
report includes the calculation of an SEI for the petrochemical that
is the subject of the report. These SEI's have been incorporated into
the Emissions Summary Table that constitutes part of this report. This
table can be used as an aid when establishing priorities in the work
required to set standards for emission controls on new stationary
sources of air pollution in accordance with the terms of the Clean Air
Amendments of 1970,
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The completed survey reports constitute a preliminary data bank on
each of the processes being studied. In addition to the SEI calculation,
each report includes a general introductory discussion of the process,
a process description (including chemical reactions), a simplified
process (Block) flow diagram, as well as heat and material balances.
More pertinent to the air pollution study, each report lists and
discusses the sources of air emissions (including odors and fugitive
emissions) and the types of air pollution control equipment employed.
In tabular form, each reports summarizes the emission data (amount,
composition, temperature, and frequency); the sampling and analytical
techniques; stack numbers and dimensions; and emission control device
data (types, sizes, capital and operating costs and efficiencies).
Calculation of efficiency on a pollution control device is not
necessarily a simple and straight-forward procedure. Consequently,
two rating techniques were established for each type of device, as
follows:
1. For flares, incinerators, and boilers a Completeness of Combustion
Rating (CCR) and Significance of Emission Reduction Rating (SERR)
are proposed.
2. For scrubbers and dust removal equipment, a Specific Pollutant
Efficiency (SE) and a SERR are proposed.
The bases for these ratings and example calculations are included
in Appendix V of this report.
E. In-Depth Studies
The original performance concept was to select a number of petro-
chemical processes as "significant polluters", on the basis of data
contained in completed questionnaires. These processes were then to
be studied "in-depth". However, the overall time schedule was such
that the EPA requested an initial selection of three processes on the
basis that they would probably turn out to be "significant polluters".
The processes selected in this manner were:
lo The Furance Process for producing Carbon Black,
2. The Sohio Process for producing Acrylonitrile.
3,, The Oxychlorination Process for producing 1,2 Dichloroethane
(Ethylene Bichloride) from Ethylene.
In order to obtain data on these processes, the operators and/or
licensors of each were approached directly by Air Products' personnel.
This, of course, was a slow and tedious method of data collection because
mass mailing techniques could not be used, nor could the request for
data be identified as an "Official EPA Requirement". Yet, by the time
that OMB approval was given for use of the Industry Questionnaire, a
substantial volume of data pertaining to each process had already been
received. The value of this procedure is indicated by the fact that
first drafts of these three reports had already been submitted to the
EPA, and reviewed by the Industry Advisory Committee, prior to the
completion of many of the survey reports.
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In addition, because of timing requirements, the EPA decided that
three additional processes be "nominated" for in-depth study. The
chemicals involved are phthalic anhydride, formaldehyde and ethylene
oxide. Work on these indicated a need for four additional in-depth
studies as follows:
1. Air Oxidation of Ortho-Xylene to produce Phthalic Anhydride.
2. Air Oxidation of Methanol in a Methanol Rich Process to
produce Formaldehyde over a Silver Catalyst.
3. Air Oxidation of Methanol in a Methanol-Lean Process to
produce Formaldehyde over an Iron Oxide Catalyst.
4o Direct Oxidation of Ethylene to produce Ethylene Oxide.
Drafts of these have been submitted to the EPA and reviewed by the
Industry Advisory Committee. The phthalic anhydride report also includes
a section on production from naphthalene by air oxidation, a process
which is considered to be a significant polluter in today's environment
but without significant growth potential.
These seven in-depth studies will be separately issued in final
report form, under Report Number EPA-450/3-73-006 a, b, c, etc.
An in-depth study, besides containing all the elements of the
screening studies, delves into questions such as "What are the best
demonstrated systems for emission reduction?", "What is the economic
impact of emission control on the industry involved?", "What deficiencies
exist in sampling, analytical and control technology for the industry
involved?".
In striving to obtain answers to these questions, the reports
include data on the cost effectiveness of the various pollution control
techniques source testing recommendations, industry growth projections,
inspection procedures and checklists, model plant studies of the
processes and descriptions of research and development programs that
could lead to emission reductions.
Much of the information required to answer these questions came
from the completed Industry Questionnaires and the Process Portfolios.
However, the depth of understanding that is required in the preparation
of such a document can only be obtained through direct contact with the
companies that are involved in the operation of the processes being
studied. Three methods for making this contact were available to Air
Products. The first two are self-evident, as follows: Each
questionnaire contains the name, address and telephone number of an
individual who can provide additional information. By speaking with
him, further insight was obtained into the pollution control problems
that are specific to the process being studied; or through him, a
visit to an operating plant was sometimes arranged, thus achieving a
degree of first hand knowledge.
However, it was felt that these two techniques might fall short of
the level of knowledge desired. Thus, a third, and unique procedure was
arranged. The Manufacturing Chemists Association (MCA) set up, through
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its Air Quality Committee (AQC), a Coordinating Technical Group
(CTG) for each in-depth process. The role of each CTG was to:
1. Assist in the obtaining of answers to specific questions.
2. Provide a review and commentary (without veto power) on
drafts of reports.
The AQC named one committee member to provide liaison. In
several cases, he is also one of the industry's specialists for the
process in question. If not, one other individual was named to
provide CTG leadership. Coordination of CTG activities was provided
by Mr. Howard Guest of Union Carbide Corporation who is also on the
EPA's Industry Advisory Committee as the MCA Representative. CTG
leadership is as follows:
Chemical AQC Member Other
Carbon Black C. B. Beck None
Cabot Corporation
Acrylonitrile W. R. Chalker R. E. Farrell
Du Pont Sohio
Formaldehyde W. B. Barton None
Borden
Ethylene Bichloride W. F. Bixby None
B. F. Goodrich
Phthalic Anhydride E. P. Wheeler Paul Hodges
Monsanto Monsanto
Ethylene Oxide H. R. Guest H. D. Coombs
Union Carbide Union Carbide
F. Current Status
Survey Reports on each of the 33 processes that were selected for
this type of study have been completed, following review of the drafts
by both the EPA and the Petrochemical Industry. These reports constitute
the subject matter of this report.
In-depth studies- of the seven processes mentioned above have been
completed in draft form, submitted to the EPA for initial review,
discussed in a public meeting with the Industry Advisory Committee and
re-submitted to the EPA in revised form. They are currently receiving
final EPA review and will be issued as final reports, following that
review.
The EPA has now selected two additional processes for in-depth study
and work on these is currently in progress. They are:
1. High Density Polyethylene via the Low and Intermediate Pressure
Polymerization of Ethylene.
2. Low Density Polyethylene via the High Pressure Polymerization
of Ethylene.
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III. Results
The nature of this project is such that it is not possible to report
any "results" in accordance with the usual meaning of the word. Obviously,
the results are the Survey Reports and In-Depth Studies that have been
prepared. However, a tabulation of the emission data collected in the
study and summarized in each of these reports will be useful to the EPA
in the selection of those processes which will be either studied in-depth
at some future date, or selected for the preparation of new source standards.
Such a tabulation, entitled "Emissions Summary Table", is attached.
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IV. Conclusions
As was stated above under "Results", the conclusions reached are
specific to each study and, hence, are given in the individual reports.
Ultimately, some conclusions are reachable relative to decisions on
processes which require future in-depth studies or processes which warrant
the promulgation of new source standards.
A firm basis for selecting these processes is difficult to achieve,
but the data contained in the Emissions Summary Table can be of value in
setting a basis, or selecting processes.
It is imperative, when using the table, to be aware of the following
facts.
1. The data for some processes are based on 100 percent survey of
the industry, while others are based on less than 100 percent
with some as few as a single questionnaire.
2. Some of the reported data are based on stack sampling, others on
continuous monitoring and still others on the "best estimate" by
the person responsible for the questionnaire.
3. Air Products attempted to use sound engineering judgement in
obtaining emission factors, industry capacities and growth
projections. However, other engineering firms, using the same
degree of diligence would undoubtedly arrive at somewhat different
final values.
Thus, the tabulation should be used as a guide but not as a rigorous
comparison of process emissions.
Furthermore, data on toxicity of emissions, odors and persistence of
emitted compounds are not included in the tabulation. In addition, great
care must be used when evaluating the weighted emission rates because of
the wide range in noxiousness of the materials lumped together in the two
most heavily weighted categories. For example, "hydrocarbons" includes
both ethane and formaldehyde and "particulates" includes both phthalic
anhydride and the permanent hardness of incinerated water.
Bearing all of these qualifications in mind, several "top 15" rankings
of processes can be made, as in Tables II through V. Obviously, one of
these tables could be used to select the more significant polluters directly.
Of course, other rankings could be made, such as leading emitters of NOX or
particulates, etc. Using these four tables, however, one analysis might be
that the number of times a process appears in these tables is a measure of
its pollution significance, or in summary:
Appear in 4 Tables
Carbon Black
Low Density Polyethylene
High Density Polyethylene
Cyclohexanone
Polypropylene
Polyvinyl Chloride
Ethylene Oxide
Appear in 3 Tables
Acrylonitrile
Adiponitrile (Butadiene)
Ethylene Dichloride (Oxychlorination)
Dimethyl Terephthalate
Ethylene Dichloride (Direct)
Ethylene
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Appear in 2 Tables Appear in 1 Table
Maleic Anhydride Phthalic Anhydride
Isocyanates Formaldehyde (Iron Oxide)
Phenol Polystyrene
Formaldehyde (Silver) Nylon 6
Nylon 6,6
Vinyl Chloride
Thus, on this basis and in retrospect, it could be concluded that four
of the selected in-depth studies (carbon black, ethylene oxide, and both
low and high density polyethylene) were justified but that three of them
(phthalic anhydride and both formaldehyde processes) were of lesser importance.
On the same basis, seven processes should be considered for future
in-depth studies, namely:
Cyclohexanone
Polypropylene
Polyvinyl Chloride
Adiponitrile (Butadiene Process)
Dimethyl Terephthalate (and TPA)
Ethylene Bichloride (Direct)
Ethylene
Obviously, many alternative bases could be established. It is not
the function of this report to select a basis for initiating future studies
because the priorities of the EPA are unknown. The most apparent of these
bases are the ones suggested by Tables II through V, namely the worst total
polluters, the worst polluters on a weighted basis, the greatest increase
in pollution (total or weighted) or the largest numbers of new plants. In
addition, noxiousness of the emissions (photo-chemical reactivity, toxicity,
odor, persistence) could be considered in making a selection.
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TABLE I
Acetaldehyde via Ethylene
via Ethanol
Acetic Acid via Methanol
via Butane
via Acetaldehyde
Acetic Anhydride via Acetic Acid
Acrylonitrile (9)
Adipic Acid
Adiponitrile via Butadiene
via Adipic Acid
Carbon Black
Carbon Disulfide
Cyclohexanone
Dimethyl Terephthalate (+TPA)
Ethylene
Ethylene Dichloride via Oxychlorination
via Direct Chlorination
Ethylene Oxide
Formaldehyde via Silver Catalyst
via Iron Oxide Catalyst
Glycerol via Epichlorohydrin
Hydrogen Cyanide Direct Process
Isocyanates
Maleic Anhydride
Nylon 6
Nylon 6,6
Oxo Process
Phenol
Phthalic Anhydride via 0-Xylene
via Naphthalene
High Density Polyethylene
Low Density Polyethylene
Polypropylene
Polystyrene
Polyvinyl Chloride
Styrene
Styrene-Butadiene Rubber
Vinyl Acetate via Acetylene
via Ethylene
Vinyl Chloride
Totals
EMISSIONS SUMMARY
ESTIMATED C1) CURRENT AIR EMISSIONS,
Hydrocarbons ' '
1.1
0
0
40
6.1
3.1
183
0
11.2
0
156
0.15
70
91
15
95.1
29
85.8
23.8
25.7
16
0.5
1.3
34
0
0
5.25
24.3
0.1
0
79
75
37.5
20
62
4.3
9.4
5.3
0
17.6
Particulates CO
0
0
0
0
0
0
0
0.2
4.7
0.5
8.1
0.3
0
1.4
0.2
0.4
0
0
0
0
0
0
0.8
0
1.5
5.5
0.01
0
5.1
1.9
2.3
1.4
0.1
0.4
12
0.07
1.6
0
0
0.6
Oxides of Nitrogen
0
0
0.01
0.04
0
0
5.5
29.6
50.5
0.04
6.9
0.1
0
0.1
0.2
0
0
0.3
0
0
0
0.41
0
0
0
0
0.07
0
0.3
0
0
0
0
0
0
0.14
0
0
TR
0
Sulfur Oxides
0
0
0
0
0
0
0
0
0
0
21.6
4.5
0
1.0
2.0
0
0
0.1
0
0
0
0
0.02
0
0
0
0
0
2.6
0
0
0
0
1.2
0
0
0.9
0
0
0
MM LBS./YEAR
Page 1 of 3
Carbon Monoxide Total
0
27
0
14
1.3
5.5
196
0.14
0
0
3,870
0
77.5
53
0.2
21.8
0
0
107.2
24.9
0
0
86
260
0
0
19.5
0
43.6
45
0
0
0
0
0
0
0
0
0
0
1.1
27
0.01
54
7.4
8.6
385
30
66.4
0.54
4,060
5.1
148
146.5
17.6
117.3
29
86.2
131
50.6
16
0.91
88
294
1.5
5.5
24.8
24.3
51.7
47
81.3
76.4
37.6
21.6
74
4.5
12
5.3
TR
18.2
Total Weighted <5
86
27
1
3,215
490
253
15,000
1,190
3.200
30
17,544
120
5,700
7,460
1,240
7,650
2,300
6,880
1,955
2,070
1,280
56
231
2,950
90
330
440
1,940
422
160
6,400
6,100
2,950
1,650
5,700
355
870
425
TR
1.460
1,227.6
49.1
94.2
33.9
4,852.6
6,225.9
110,220 (7>
(1)
(2)
(3)
CO
(5)
(6)
(7)
(9)
In most instances numbers are based on less than 1007. survey. All based on engineering judgement of best current control.
Assumes future plants will employ best current control techniques.
Excludes methane, includes H2S and all volatile organics.
Includes non-volatile organics and inorganics.
Weighting factors used are: hydrocarbons - 80, particulates - 60, NOX - 40, SOX - 20, and CO - 1.
Referred to elsewhere in this study as "Significant Emission Index" or "SEI".
Totals are not equal across and down due to rounding.
Emissions based on what is now an obsolete catalyst. See Report No. EPA-450/3-73-006 b for up-to-date information.
Probably has up to 10% lov bias.
-------
Hydrocarbons ^ '
1.2
0
0
0
12.2
0.73
284
0
10.5
0
64
0.04
77.2
73.8
14.8
110
34.2
32.8
14.8
17.6
8.9
0
1.2
31
0
0
3.86
21.3
0.3
0
210
262
152
20
53
3.1
1.85
4.5
0
26.3
1,547.2
Part iculates
0
0
0
0
0
0
0
0.14
4.4
0.5
3.3
0.07
0
1.1
0.2
0.5
0
0
0
0
0
0
0.7
0
3.2
5.3
0.01
0
13.2
0
6.2
5
0.5
0.34
10
0.05
0.31
0
0
0.9
55.9
TABLE I
EMISSION SUMMARY
ESTIMATED ADDITIONAL (2)
' ' Oxides of Nitrogen
0
0
0.04
0
0
0
8.5
19.3
47.5
0.04
2.8
0.03
0
0.07
0.2
0
0
0.15
0
0
0
0
0
0
0
0
0.05
0
0.8
0
0
0
0
0
0
0.1
0
0
TR
0
79,5
AIR EMISSIONS IN
Sulfur Oxides
0
0
0
0
0
0
0
0
0
0
8.9
1.1
0
0.84
61.5
0
0
0.05
0
0
0
0
0.02
0
0
0
0
0
6.8
0
0
0
0
1.13
0
0
0.18
0
0
0
80.5
1980, MM LBS./YEAR
Carbon Monoxide
0
0
0
0
2.5
1.42
304
0.09
0
0
1,590
0
85.1
42.9
0.2
25
0
0
66.7
17.0
0
0
85
241
0
0
14.3
0
113
0
0
0
0
0
0
0
0
0
0
0
2,588
Page 2 of 3
Total
1.2
0
0.04
0
14.7
2.15
596
19.5
62.4
0.54
1,670
1.24
162
118.7
77
136
34.2
33
81.5
34.6
8.9
0
87
272
3.2
5.3
18.2
21.3
134
0
216
267
152.5
21.47
63
3.25
2.34
4.5
TR
27.2
4,351.9
Total Weighted O>6)
96
0
2
0
980
60
23,000
779
3,010
30
7,200
30
6,260
6,040
2,430
8,800
2,740
2,650
1,250
1,445
700
0
225
2,720
194
318
325
1,704
1,100
0
17,200
21,300
12,190
1,640
4,840
225
170
360
TR
2.170
134,213 (7)
Acetaldehyde via Ethylene
via Ethanol
Acetic Acid via Methanol
via Butane
4 via Acetaldehyde
Acetic Anhydride via Acetic Acid
Aerylonitrile (9)
Adipic Acid
Adiponitrile via Butadiene
via Adipic Acid
Carbon Black
Carbon Disulfide
Cyclohexanone
Dimethyl Terephthalate (4-TPA)
Ethylene
Ethylene Dichloride via Oxychlorination
via Direct Chlorination
Ethylene Oxide
Formaldehyde via Silver Catalyst
via Iron Oxide Catalyst
Glycerol via Epichlorohydrin
Hydrogen Cyanide Direct Process
Isocyanates
Maleic Anhydride
Nylon 6
Nylon 6,6
Oxo Process
Phenol
Phthalic Anhydride via 0-Xylene
via Naphthalene
High Density Polyethylene
Low Density Polyethylene
Polypropylene
Polystyrene
Polyvinyl Chloride
Styrene
Styrene-Butadiene Rubber
Vinyl Acetate via Acetylene
via Ethylene
Vinyl Chloride
Totals
(1) In most instances numbers are based on less than 100% survey. All based on engineering judgement of best current control.
(2) Assumes future plants will employ best current control techniques.
(3) Excludes methane, includes H2S and all volatile organics.
(4) Includes non-volatile organics and inorganics.
(5) Weighting factors used are: hydrocarbons - 80, particulates - 60, NOX - 40, SOX - 40, and CO - 1.
(6) Referred to elsewhere in this study as "Significant Emission Index" or "SEI".
(7) Totals are not equal across and down duw to rounding.
(9) See sheet 1 of 3.
Probably has up to 107. low bias.
-------
TABLE I
Acetaldehyde via Ethylene
via Ethanol
Acetic Acid via Methanol
via Butane
via Acetaldehyde
Acetic Anhydride via Acetic Acid
Acrylonitrile (9)
Adipic Acid
Adiponitrile via Butadiene
via Adipic Acid
Carbon Black
Carbon Disulfide
Cyclohexanone
Dimethyl Terephthalate (+TPA)
Ethylene
Ethylene Dichloride via Oxychlorination
via Direct Chlorination
Ethylene Oxide
Formaldehyde via Silver Catalyst
via Iron Oxide Catalyst
Glycerol via Epichlorohydrin
Hydrogen Cyanide Direct Process
Isocyanates
Maleic Anhydride
Nylon 6
Nylon 6,6
Oxo Process
Phenol
Phthalic Anhydride via 0-Xylene
via Naphthalene
High Density Polyethylene
Low Density Polyethylene
Polypropylene
Polystyrene
Polyvinyl Chloride
Styrene
Styrene-Butadiene Rubber
Vinyl Acetate via Acetylene
via Ethylene
Vinyl Chloride
Emissions
Total by 1980
2.3
27
0.05
54
22
10.8
980
50
128.8
1.1
5,730
6.3
310
265
94
253
63
120
212.5
85
25
0.5 (10)
175
566
4.7
10.8
43
46
186
47
297
343
190
43
137
7.4
14
9.8
TR
45
EMISSIONS SUMMARY
(2>, MM Lbs. /Year
Total Weighted (5) by 1980
182
27
3
3,215
1,470
313
38,000
1,970
6,210
60
24,740
150
11,960
13,500
3,i70
16,450
5,040
9,530
3,205
3,515
2,000
28 (10)
456
5,670
284
650
765
3,640
1,522
160
23 , 600
27,400
15,140
3,290
10,540
610
1,040
785
TR
3.630
Page 3 of 3
Totals
10,605
(7)
Estimated Number of New Plants
(1973 - 1980)
0
4
0
3
3
5
7
4
3
13
2
10
8
21
8
10
15
40
12
1
0
10
6
10
10
6
11
6
0
31
41
32
23
25
9
4
1
4
10
Total Estimated Capacity
MM Lbs./Year
Current By 1980 '
1,160
966
400
1,020
875
1,705
1,165
4,430
435
280
3,000
871
1,800
2,865
22,295
4,450
5,593
4,191
5,914
1,729
245
412
1,088
359
486
1,523
1,727
2,363
720
603
2,315
5,269
1,160
3,500
4,375
5,953
4,464
206
1,280
5,400
2
' 1
2
2
3
2
5
1
3
5
40
8
11
6
9
3
2
1
3
3
4
1
8
21
5
6
8
10
5
2
13
,460
966
,800
500
,015
,100
,700 (8)
,200
845
550
,000 (8)
,100
,600
,900
,000
,250 (8)
,540
,800 (8)
,000
,520 (8)
380
202
,120
720
,500
,000
,000
,200
,800 (8)
528
,500
,100
,800
,700
,000
,000
,230
356
,200
,000
244,420
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
In most instances numbers are based on less than 1007, survey. All based on engineering judgement of best current control.
Assumes future plants will employ best current control techniques.
Excludes methane, includes t^S and all volatile organics.
Includes non-volatile organics and inorganics.
Weighting factors used are: hydrocarbons - 80, particulates - 60, NOX - 40, SOX - 20, and CO - 1.
Referred to elsewhere in this study as "Significant Emission Index" or "SEI".
Totals are not equal across and down due to rounding.
By 1985.
See sheet 1 of 3
Due to anticipated future shut down of marginal plants.
Probably has up to 107. low bias.
-------
TABLE II
TOTAL ANNUAL EMISSIONS, ALL "POLLUTANTS". BY 1980 (MM LBS./YR.)*
Carbon Black 5,730
Acrylonitrile 980
Maleic Anhydride 566
Low Density Polyethylene 343
Cyclohexanone 310
High Density Polyethylene 297
Dimethyl Terephthalate 265
Ethylene Dichloride 253
Phthalic Anhydride (Total) 233
Formaldehyde (Silver) 212
Polypropylene 190
Isocyanates 175
Polyvinyl Chloride 137
Adiponitrile (Butadiene Process) 129
Ethylene Oxide 120
''"Fifteen highest numbers, as summarized in Table I, for this category.
-------
TABLE III
TOTAL ANNUAL WEIGHTED EMISSIONS BY 1980 (MM LBS./YR.)*
Acrylonitrile 38,000
Low Density Polyethylene 27,400
Carbon Black 24,740
High Density Polyethylene 23,600
Ethylene Bichloride (Oxychlorination) 16,450
Polypropylene 15,140
Dimethyl Terephthalate 13,500
Cyclohexanone 11,960
Polyvinyl Chloride 10,540
Ethylene Oxide 9,530
Adiponitrile (Butadiene Process) 6,210
Maleic Anhydride 5,670
Ethylene Dichloride (Direct) 5,040
Ethylene 3,670
Phenol 3,640
*Fifteen highest numbers, as summarized in Table I, for
this category.
-------
TABLE IV
SIGNIFICANT EMISSION INDEX*
Acrylonitrile 23,000
Low Density Polyethylene 21,300
High Density Polyethylene 17,200
Polypropylene 12,190
Ethylene Dichloride (Oxychlorination) 8,800
Carbon Black 7,200
Cyclohexanone 6,260
Dimethyl Terephthalate 6,040
Polyvinyl Chloride 4,840
Adiponitrile (Butadiene) 3,010
Ethylene Dichloride (Direct) 2,740
Maleic Anhydride 2,720
Ethylene Oxide 2,650
Ethylene 2,430
Vinyl Chloride 2,170
^Fifteen higest numbers, as summarized in Table I, for
this category.
-------
TABLE V
NUMBER OF NEW PLANTS (1973-1980)*
Low Density Polyethylene 41
Formaldehyde (Silver) 40
Polypropylene 32
High Density Polyethylene 31
Polyvinyl Chloride 25
Polystyrene 23
Ethylene 21
Ethylene Oxide 15
Carbon Black 13
Formaldehyde (Iron Oxide) 12
Phenol 11
Cyclohexanone 10
Isocyanates 10
Nylon 6 10
Nylon 6,6 10
Ethylene Dichloride (Direct) 10
*Fifteen highest numbers, as summarized in Table I, for
this category.
-------
Acetaldehyde via Ethylene
-------
Table of Contents
Section Page Number
I. Introduction ACD-1
II. Process Description ACD-2
III. Plant Emission ACD-4
IV. Emission Control ACD-6
V. Significance of Pollution ACD-7
VI. Acetaldehyde Producers ACD-8
List of Illustrations and Tables
Flow Diagram Figure ACD-I
Material Balance Table ACD-I
Cross Heat Balance Table ACD-II
Emission Inventory Table ACD-III
Catalog of Emission Control Devices Table ACD-IV
Number of New Plants by 1980 Table ACD-V
Emission Source Summary Table ACD-VI
Weighted Emission Rates Table ACD-VII
-------
ACD-1
I. Introduction
Acetaldehyde, C^CHO, is a mobile, colorless, inflammable liquid with a
pungent, choking odor. It was first noticed by Scheele in 1774 and recognized
as a new compound by Foucroy and Vaughelin in 1880.
Most acetaldehyde is used as an intermediate in the manufacture of
other organic compounds. The largest single outlet accounting for more than
half of the acetaldehyde use is the manufacture of acetic acid. Other
processes which utilize it as a raw material are the production of butyl
alcohol, butyraldehyde, chloral and pyridine. (1)
There are four ways acetaldehyde can be made industrially. They are
oxidation or dehydrogenation of ethanol, oxidation of ethylene in one or
two stages, propane-butane oxidation and acetylene hydration. The oxidation
or dehydrogenation of ethanol and ethylene oxidation are the major processes
currently used. Ethylene oxidation is a relatively new method which is
more attractive financially than ethanol oxidation because it utilizes a
cheaper raw material. Although acetaldehyde via ethanol plants constitute
about 4470 of the current capacity no new plants of this type have been built
in the last five years or are expected to be built in the future.
The decision as to which of the ethylene processes to use breaks down to a
choice between lower initial investment costs for the one-stage process and
lower raw material (air opposed to oxygen) costs for the two-stage process.
The availability of cheap high grade oxygen is the prime determining factor.
Currently the two-stage process is more popular in the U. S. but world wide
both processes are being used extensively.
Air emission data presented in this report are from one respondent who
uses the two-stage process. Because of the similarities of yields, catalyst
type and separation techniques between the tvo processes, it is believed
that air emissions for the one-stage method should be of the same order of
magnitude as the two-stage method.
Air pollution released by a plant using the two-stage ethylene oxidation
process can best be described as low. The main sources of air emissions are
gases vented from the two scrubbers employed in the process.
(1) According to the Chemical Marketing Reporter for August 20, 1973, the
current uses for acetaldehyde are:
Acetic Acid and Anhydride 5070
n-Butanol 1470
2-Ethyl Hexanol 11%
Other 25%
-------
A CD-2
II. Process Description
The oxidation of ethylene to acetaldehyde is based on the reaction of
aqueous palladium chloride with ethylene.
C2H4 + PdCl2 + H20 -• •••• - > CH3CHO + Pd + 2 HCl
There are two versions of the process. In the 'two stage' version,
ethylene is fed into a reactor with an aqueous solution of palladium chloride
and cupric chloride. Ethylene is oxidized to acetaldehyde, and cupric
chloride is reduced to cuprous chloride as a result of its oxidation of
palladium back to palladium chloride. The actual reaction scheme is quite
complex but the basic reaction reduces to:
C2H4 + 2 CuCl2 + H20 -£-£-2 ^ CH3CHO + 2 CuCl + 2 HCl
In another reactor, which constitutes the second stage, cuprous chloride
is oxidized back to cupric chloride with air completing the cycle
2 CuCl + 2 HCl -f \ 02 > 2 CuCl2 + HO
In the 'one stage' version oxygen is fed into a reactor with ethylene.
Both chlorides become catalytic for the reaction and the total process takes
place in one reaction vessel.
C0H. + \ 09 PdP12. > CHoCHO
24 ^
The one stage process requires high purity ethylene and oxygen which could
be a disadvantage depending on the availability of oxygen.
The following is a description of the tvo-stage ethylene oxidation technique.
The separation methods for the single stage process are quite similar to the
process described below. The only major difference between the two overall
processes is the method of catalyst regeneration used,and the need for ethylene
recycle in the one stage process.
(See Figure ACD-I)
Ethylene is reacted at 10 atm. with a palladium chloride-cuprous chloride
solution in a titanium lined tubular reactor. Conversion is about 99°/,. The
acetaldehyde yield is around 9570; 1% of the ethylene does not react and the
remainder forms by-products. The by-products include chloroacetaldehydes,
ethyl chloride, chloroethanol, acetic and oxalic acids, crotonaldehyde and
chlorocrotonaldehyde.
The reactor effluent is sent to a flash tower where the pressure is
reduced to atmospheric and the heat of reaction is used to vaporize acetaldehyde
and some water. The flash tower bottoms containing reduced catalyst solution
is sent to an oxidizing reactor where the catalyst is regenerated by air
oxidation. Unreacted oxygen, nitrogen and various other organics are purged
off to a scrubber where some product and by-product are recovered and sent to
distillation, while gases leaving the scrubber are vented to the atmosphere.
Regenerated catalyst is returned to the reactor.
-------
ACD-3
Flashed gas passes to a crude acetaldehyde still where acetaldehyde is
distilled to 60 - 90%. Light ends are removed next, in another column. Gas
exiting from the top of this tower is water scrubbed and then vented to the
atmosphere. The acetaldehyde leaves the bottom of the light ends column and
enters a finishing column where chloroaldehydes, water and other undesirables
are removed. Finished acetaldehyde is taken overhead and sent to storage.
A material balance and information on the heat liberated by reaction can
be found in Tables I and II, respectively.
-------
ACD-4
III. Plant Emissions
A. Continuous Air Emissions
1. Regenerator Off-Gas Scrubber Vent
After the catalyst is regenerated with air the gaseous stream is
purged from the reactor system and scrubbed to recover vater
soluble organics, while the solution of regenerated catalyst is
returned to the reactor. The stream leaving the scrubber is
vented to the atmosphere. Since nitrogen in the air does not
react, it is the primary component present in the vent gas.
Quantities of argon, unreacted oxygen, vater, carbon dioxide and
smaller amounts of methyl and ethyl chloride also enter the atmosphere
through this vent. Total hydrocarbon emissions are reported to be
.00045 Ibs./lb. acetaldehyde from this source.
NOTE: Calculations made by Houdry shov that it is possible that
the average flov rate of this stream could be tvice as
high as that claimed by the respondent.
2. Light Ends Scrubber Vent
Light ends consisting of nitrogen, carbon dioxide, ethylene,
methyl and ethyl chloride and vater soluble oxygenated hydrocarbons
including acetaldehyde and acetic acid are removed from the
system by crude distillation and light ends distillation and are
sent to a vater scrubber. Water soluble vapors are removed in the
scrubber and the insoluble gas is vented to the atmosphere. The
air pollutants released through this vent are methyl chloride,
ethyl chloride and ethylene. Hydrocarbon emissions are usually
around .00047 Ibs./lb. acetaldehyde from this source but emissions
could vary because the flov rate can change by 500%.
B. Intermittent Air Emissions
No sources of intermittent air emissions vere reported by the
respondent.
C. Continuous Liquid Wastes
Approximately 150 GPM of waste vater is discharged. The
effluent is treated in biological aerated ponds vith solar
evaporation.
D. Solid Waste
About one ton of solid vaste, consisting mainly of spent
catalyst,is disposed of in a sanitary land fill, per day.
E. Odor
In general the ethylene process for the production of acetaldehyde
does not appear to present an odor problem. No community complaints
have been reported.
-------
ACD-5
F. Fugitive Emissions and Storage Losses
The respondent reports that losses due to leaks and spills are
too small to measure.
Acetaldehyde storage tanks are vented to a scrubber so no
acetaldehyde enters the atmosphere from the storage area.
-------
ACD-6
IV. Emission Control
Usually efficiencies are calculated for any emission control device
reported, but since the only respondent to the questionnaire failed to supply
information about the composition and flow of the inlet streams to the devices
employed, it was impossible to do so. A brief description of these devices
follows: Details concerning the emission control equipment employed can be
found in Table IV - Catalog of Emission Control Devices.
Scrubbers
A. Off Air Scrubber
This scrubber removes any soluble organics such as acetaldehyde,
acetic acid and chloroaldehydes which may be present in the nitrogen
and unreacted oxygen stream which is purged from the reaction area. Since
no acetaldehyde, acetic acid or chloroacetaldehyde are present in the
vent gas, the efficiency of removal for these components is 1007«. The
liquid outlet from this scrubber is sent to the purification system.
B. Light Ends Scrubber
Light components from the crude still, light ends column and product storage
tanks are sent to this scrubber for soluble organics recovery. The
liquid effluent is returned to the purification system. Almost all
soluble components are removed by this scrubber.
C. Water Insolubles
Both of the above vent streams contain traces of methyl and ethyl
chlorides and the light ends scrubber vent also contains unreacted
ethylene. All three of these chemicals are only slightly soluble in
water so the efficiency relative to each is near zero percent.
-------
ACD-7
V. Significance of Pollution
It is recommended that no in-depth study of the ethylene process for
acetaldehyde be made at this time. The reported emission data indicate
that the ouantity of pollutants released to the atmosphere as air emissions
is less for the subject process than for processes currently under in-depth
study.
The methods outlined in Appendix IV of this report have been used to
estimate the total weighted annual emissions from new plants. This work is
summarized in Tables V, VI and VII. The growth projection is based on the
assumption that all new acetaldehyde plants will use the ethylene process.
On a weighted emission basis a Significant Emission Index of 96 has
been calculated in Table VII. Hence, the recommendation to exclude the
subject process from the in-depth portion of the work for this project.
However, it should be noted that reported emissions, especially of ethylene,
do not agree with literature reports on the ethylene conversion of 9970.
Since the process is "once-through" with respect to ethylene, one volume
percent of unconverted ethylene would be equivalent to nearly 0.007 Ibs. of
ethylene vented/lb. of acetaldehyde product (at 95% yield). On this basis,
the calculated SEI would increase to about 780.
-------
VI. Acetaldehyde Producers
The following tabulation of acetaldehyde producers indicates production capacity by company, location
and process.
Celanese
Commercial Solvents
Du Pont
Eastman
Goodrich
Hercules
Monsanto
Publicker
Union Carbide
Butane
Propane
Bay City, Texas
Bishop, Texas
Pampa, Texas
Clear Lake, Texas
Agnev, California
Belle, W. Va.
Kingsport, Tenn.
Longviev, Texas
Calvert, City
Parlin, N. J.
Texas City, Texas
Philadelphia, pa.
Institute, W. Va. )
South Charleston, W. Va.)
Texas City, Texas )
By-Product Ethanol
10
10
Ethylene
1 Stage
200
35
80
650
Ethylene
2 Stage
210
500
450
8
oo
Total MM Lbs./Yr.
26
966
1,160
-------
PAGE NOT
AVAILABLE
DIGITALLY
-------
Stream I. D. No.
Stream
Component
Ethylene
Air
1) Nitrogen
2) Oxygen
3) Argon
Make-Up HCl
Ace t aldehyde
Carbon Dioxide
Water
Methyl Chloride
Ethyl Chloride
Chloroaldehydes
Acetic Acid
i 2 :
Ethylene Feed Air Make-Up
.6570
1.3739
.4209
.0233
.0100
.0323
.6570 1.8181
Total In = 2.5174
(2)
TABLE ACD-I
MATERIAL BALANCE
T/T ACETALDEHYDE
VIA
ETHYLENE PROCESS
45 6
Off-Air Scrubber Vent ' ' Light Ends Scrubber Vent ^ ' By-Products
1.3739
.0086
.0233
.0013
.0166
.0001
.0008
.0001
.0423 1.4234
Total Out T 2.5174
.0230
.0001
.0004
.0008
.0256
.0187
.0015
.0202
Water to V'apte fl) Product
.0482
.0482
1.0000
1.0000
(1) Water formed by side combustion reactions and water from make-up HCl solution only; recycled water and other process water introduced into the system not
included; contains some hydrocarbon.
(2) Contained in recycled water used as HCl diluent.
(3) Vent streams show emissions somewhat greater than reported in the single questionnaire.
-------
TABLE AGO-II
HEAT BALANCE
ACETALDEHYDE
VIA,
ETHYLENE PROCESS
There is insufficient information available on which to base an overall
heat balance for this process.
Overall Heat of Reaction for Reaction and Regeneration Steps
C2H4 (g) + \ 02 (g) > CH3CHO (g)
H = 2,210 BTU/lb. acetaldehyde
-------
TABLE ACD-III
NATIONAL EMISSIONS INVENTORY
ACETALDEHYDE
VIA
ETHYLENE PROCESS
EPA Plant Code No.
Capacity - Tons of Acetaldehyde/Yr.
Production - Tons of Acetaldehyde/Yr.
Emissions to the Atmosphere
Stream I. D. No.
Stream
Flov - Lbs./Hr.
Flov Characteristic - Continuous or Intermittent
if Intermittent - Hrs./Yr.
Composition - Tons/Ton of Acetaldehyde
Ethylene
Methyl Chloride
Ethyl Chloride
Carbon Dioxide
Vater
Nitrogen
Argon
Oxygen
Analysis
Sample Tap Location
Frequency of Sampling
Type of Analysis
Odor Problem
Vent Stacks
Number
Height - Ft.
Diameter - Inches
Exit Gas Temperature - F°
SCFM
Emission Control Devices
Type
Summary of Air Pollutants
Hydrocarbons - Ton/Ton of Acetaldehyde
Particulates - Ton/Ton of Acetaldehyde
NOX - Ton/Ton of Acetaldehyde
SOX - Ton/Ton of Acetaldehyde
CO - Ton/Ton of Acetaldehyde
1-2
225,000
220,000
Regenerator Off-Gas
Scrubber "ent
40,871 (1)
Continuous
.00041
.00004
.00828
.00040
.74524
.01288
.00430
Yes
In stream
C2H^ & C02 Continuous - Others Weekly
CjH4 Infrared - Others Chromatograph
No
Yes
2 (3)
100
16
59
4500
Yes
Scrubber
.00092
0
0
0
0
Light Ends
Scrubber "ent
2675 d)
Continuous
00025
00007
.00015
.00459
.00502 (2)
Yes
In stream
C^HA & C02 Continuous - Others Weekly
C.2^b & C02 Infrared - Others Chromatograph
No
Yes
2 (3)
80
4
59
50
Yes
Scrubber
(1) Plant has two identical systems so actually two identical scrubbers of this type are employed.
(2) From acetaldehyde storage tank purge.
(3) For each scrubber.
Flow is total for each scurbber.
-------
ABSORBERS /SCRUBBERS
EPA Code No. for plant using
Flow Diagram (Fig. ACT-I) Stream I. D.
Control Emission of
Scrubbing/Absorbing Liquid
Type - Spray
Packed Column
Column w/Trays
Scrubbing/Absorbing Liquid Rate - GPM
Operating Temperature - F°
Gas Rate - SCFM
T-T Height - Ft.
Diameter - Ft.
Washed Gases to Stack
Stack Height - Ft.
Stack Diameter - Inches
Installed Cost - Mat'l. 6, Labor - $
Installed Cost based on "year" - $
Installed Cost - c/lb. of Acetaldehyde/Yr.
Operating Cost - Annual - $ - 1972
Value of Recovered Product - $/Yr.
Net Operating Cost - c/lb. of Acetaldehyde
Efficiency - "I, - SE
Efficiency - % - SERR
TABLE ACD-IV
CATALOG OF EMISSION CONTROL DEVICES
ACETALDEHYDE
VIA
ETHYLENE PROCESS
(D
1-2
A
Organic Vapors (2)
Water
Yes
62.5 - 140
4500 - 8000
90
5
Yes
100 (3)
16
410,000 490,000
1965 1969
.20
45,000
Unknown
.01
(D
1-2
B
Organic Vapors (2)
Vater
Yes
- 140
250
62.5
50 -
70
3
Yes
80 (3)
4
255.000
1965
.12
26,500
Unknown
.006
275,000
1969
(1) Two identical scrubbers of each type are employed. Specifications are for each scrubber; a total of four scrubbers are used for emission control in the
process. Cost figures are the combined costs for two identical scrubbers.
(2) Acetaldehyde, acetic acid and some chlorohydrocarbons.
(3) Each scrubber has two stacks, each stack has specifications shown.
-------
TABLE ACD-VI
Emission
Hydrocarbons
Participates
NOX
sox
CO
EMISSION SOURCE SUMMARY
ACETALDEHYDE
VIA
ETHYLENE PROCESS
Source
Regenerator Off-Gas
Scrubber Vent
. 00045
0
0
0
0
Light Ends
Scrubber Vent
.00047
0
0
0
0
Total
.00092
0
0
0
0
-------
1160
TABLE ACD-V
Current Marginal
Capacity Capacity
NUMBER OF NEW PLANTS BY
ACETALDEHYDE
VIA
ETHYLENE OXIDATION
Current
Capacity
on-stream Demand
in 1980 1980
1980
Capacity
1980
Capacity
to be
Added
Economic
Plant
Size
Number
of Nev
Plants
1160
2460 (1)
2460
1300 (2)
250
5-6
(1) For ethylene process.
(2) Based on studies prepared for the EPA by Process Research, Inc.
-------
TABLE ACD-VII
Chemical
Process
Increased Capacity
Pollutant
Hydrocarbons
Participates
NOX
S°x
CO
WEIGHTED EMISSION RATES
Acetaldehyde
Ethylene
1300 MM Lbs./Year
Emissions Ib./lb. Emissions MM 11
.00092 1.2
0 0
0 0
0 0
0 0
Weighting Weighted Emissions
Factor MM Ibs./yr.
80 96
60 0
40 0
20 0
1 _0
Significant Emission Index = 96
-------
Acetaldehyde via Ethanol
-------
Table of Contents
Section Page Number
I. Introduction AC-1
II. Process Description AC-2
III. Plant Emissions AC-3
IV. Emission Control AC-5
V. Significance of Pollution AC-6
VI. Acetaldehyde Producers AC-7
List of Illustrations and Tables
Flow Diagram Figure AC-I
Net Material Balance Table AC-I
Gross Heat Balance Table AC-II
Emission Inventory Table AC-III
Catalog of Emission Control Devices Table AC-IV
Number of New Plants by 1980 Table AC-V
Emission Source Summary Table AC-VI
Weighted Emission Rates Table AC-VII
-------
AC-1
I. Introduction
Acetaldehyde (CH3CHO) is a mobile, colorless, inflammable liquid with
a pungent, choking odor. It was first noticed by Scheele in 1774 and rec-
ognized as a new compound by Foucroy and Vaughelin in 1880.
Most acetaldehyde is used as an intermediate in the manufacture of other
organic compounds. The largest single outlet accounting for more than half
of the acetaldehyde use, is the manufacture of acetic acid. Other processes
which utilize it as a raw material are the production of butyl alcohol,
butyraldehyde, chloral and pyridine.
There are four ways that acetaldehyde can be made industrially. They
are the oxidation or dehydrogenation of ethanol, oxidation of ethylene in
one or two stages, propane-butane oxidation and acetylene hydration. The
oxidation or dehydrogenation of ethanol and ethylene oxidation are the major
processes currently used. Ethylene oxidation is a relatively nev method
which is more attractive financially than ethanol oxidation because it
utilizes a cheaper raw material. Although acetaldehyde via ethanol plants
constitute 43.8% of the current capacity of 2.4 billion Ibs./year no new
plants of this type have been built in the last five years or are expected
to be built in the future.
Atmospheric emissions generated by the ethanol process are associated
primarily with the absorber vent gas stream. All other sources of emissions
are minimal.
It should be noted that this report is based on the responses of one
questionnaire. The only respondent was a plant using ethanol oxidation and,
therefore, the straight dehydrogenation of ethanol is covered only briefly in
Section V.
-------
AC-2
II. Process Description
Acetaldehyde is produced by passing ethanol vapors and preheated air
over a suitable catalyst, preferably silver, at 300 - 575° C.
Two possible reactions occur to varying degrees depending on the
reactor environment.
(1) C2H50H + \ 02 -•• -> CH3CHO + H20 H = -40.55 kcal./g-mole
(2) C2H5OH ••• > CH3CHO + H2 H = +17.28 kcal./g-mole
Industrially oxidation, a combination of oxidation and dehydrogenation
and straight dehydrogenation (which is not covered in this report) are used.
The reactor temperature depends on the air-ethanol-steam ratio and the
velocity of the gas over the catalyst. Overall alcohol conversion varies
from 25 - 45% and yields are 85 to 95%. Small amounts of acetic acid and
1-butanol are also formed. Many times dilute acetic acid is recovered as
a by-product.
The gases leaving the reactor, after passing through a condenser, go to
a phase separator. The vapor phase is absorbed in refrigerated water, and
the wash is combined with the liquid phase. The combined stream is fractionated
into acetaldehyde and a water-ethanol mixture, which is further separated into
ethanol, which is recycled, and waste acetic acid can be recovered from the
waste.
-------
AC-3
III. Plant Emissions
A. Continuous Air Emissions
1. Absorber Vent
The emissions from this vent constitute the most important
source of air pollution associated with the production of
acetaldehyde by oxidation. In comparison, all other sources of
air pollution are minimal.
The vent stream is composed primarily of nitrogen. Small
quantities of water, carbon dioxide, carbon monoxide, hydrogen
methane and oxygen are also present. Plant 1-1 reports the
following emissions from the scrubber vent stream.
Component Lbs./Lb. Acetaldehyde
Water .00088
CO .00271
C02 .00934
H2 1.12450
CH4 .01950
02 .02240
A more complete description of emissions can be found in
Table III.
B. Intermittent Air Emissions
1. Combustion of Fuel for Reactor Start-Up
The respondent reports that 480,000 CF/year of natural gas with
sulfur content of 2.0 grains/100 CF are needed to start the reactors,
If the sulfur content of this fuel is fully converted into sulfur
dioxide, it would produce 2.8 Ibs of S02 per year, which is
1.6 x 10~8 Ibs. S02/lb. product. This quantity is considered
negligible.
2. Ethanol Storage Tank Vent
Inert gases are periodically purged from the ethanol storage
tank. During venting small amounts of ethanol are released to the
atmosphere. Lack of data prevents the calculation of emission
rates, but this vent could not be considered a significant emission
source.
C. Continuous Liquid Wastes
16,000 gallons per hour of waste water is produced. The
respondent reports that waste water is treated on-site.
D. Solid Wastes
No solid wastes are produced by this process.
-------
AC-4
E. Odor
No odor problems were reported for the ethanol oxidation
process for the production of acetaldehyde.
F. Fugitive Emissions
No sources of fugitive emissions were reported. If they
exist, they are probably due to minor losses of acetaldehyde
and/or ethanol due to pump seals and occasional piping leaks.
The actual amount is considered negligible.
-------
AC-5
IV. Emission Control
The only emission control device reported is a scrubber system. It is
summarily described in Table IV of this report. Two types of efficiencies
have been calculated.
1) SE - Specific Efficiency
SE = specific pollutant in - specific pollutant out ,„„
specific pollutant in
2) SERB. - Significance of Emission Reduction. Rating
SERR = (pollutant x weighting factor)in - (pollutant x weighting
factor*)out
(pollutant x weighting factor)in
x 100
A more complete description of the rating system can be found in Appendix V
of this report.
^weighting factor same as Table VII weighting factor.
Absorbers
Although the respondent lists the two scrubbers as emission control
devices their primary function is the recovery of acetaldehyde and
ethanol. Alcohol and acetaldehyde recovery is 100 percent while
practically no CO is removed. However, the SERR is greater than 99.9
percent because of the relatively small quantity of CO present as well
as its low weighting factor.
-------
AC-6
V. Significance of Pollution
It is recommended that no in-depth study of this process be undertaken
at this time. This conclusion is drawn for two reasons.
1) The reported emission data indicate the quantity of pollutants
released as air emissions is less for the subject process than
for other processes that are currently being surveyed.
2) No new plants are expected to be built using ethanol as the starting
material„ New production will probably rely on the ethylene oxidation
processes which are already taking a large role in acetaldehyde
production. Some of the advantages of using the ethylene oxidation
processes are listed below:
a) Uses a less expensive starting material - ethylene.
b) Utilizes a shorter route from hydrocarbon to acetaldehyde.
c) Products yields of approximately 95 percent.
d) Operates at lov; temperatures and pressures.
The outlook is for acetaldehyde capacity to grow to three to five billion
pounds per year by 1980, which will require four or five new plants which are
expected to be of the ethylene oxidation type.
The methods outlined in Appendix IV of this report have been used to
estimate the total weighted annual emissions from new plants. This work is
summarized in Tables V, VI and VII.
On a weighted emission basis a Significant Emission Index of zero has
been calculated in Table VII, due to the fact that no new ethanol oxidation
plants are expected to be built. Since the total emissions from this process
are small and no growth is anticipated, it is recommended to exclude
acetaldehyde production via ethanol oxidation for an in-depth study.
In passing, something should be said about the straight ethanol dehydro-
genation process which is not covered in this report. Due to the fact that
no oxygen is introduced in the system it appears that the total amount of
emissions released to the atmosphere should be minimal. This prediction is
confirmed by limited data made available by the EPA, Raleigh, N. C. Emissions
from a typical ethanol dehydrogenation plant are; A once/week vent for one
minute at a rate of 50,000 CFH of a stream whose typical composition is:
Component Volume %
Hydrogen 98.5
Methane .8
Carbon Monoxide .3
Ethane .1
Carbon Dioxide .3
The plant mentioned produced 27,190 Ibs./hr. of acetaldehyde. The
quantity of emission is quite small in comparison to other processes studied.
-------
VI. Acetaldehyde Producers
The following tabulation of acetaldehyde producers indicates published production capacity by company,
location and process.
Company
Celanese
Commercial Solvents
Du Pont
Eastman
Hercules
Monsanto
Publicker
Union Carbide
Location
Bay City, Texas
Bishop, Texas
Pampa, Texas
Clear Lake, Texas
Agnew, California
Belle, W. Va.
Kings port, Tenn.
Longview, Texas
Parlin, N. J.
Texas City, Texas
Philadelphia, pa.
Institute, W. Va. )
South Charleston, W. Va.)
Texas City, Texas )
Butane -
Propane
By-Product Ethanol
10
10
200
35
80
650
Ethylene
1 Stage
Ethylene
2 Stage
210 (1962)
500
500 (1970)
Total MM Lbs./Yr. = 25
7o Grand Total =1.3
966
43.8
1,210
54.9
-------
PAGE NOT
AVAILABLE
DIGITALLY
-------
TABLE AC-I
Stream I. D. No.
Ethanol
Acetaldehyde
Water/Steam
Oxygen
Carbon Monoxide
Methane
Carbon Dioxide
Hydrogen
Nitrogen
Acetic Acid
Oxygenatic Organics
Total
Fresh
Feed
1.1066
Water
.0592
.0897
ACETALDEHYDE
VIA
ETHANOL OXIDATION
MATERIAL BALANCE - T/T OF ACETALDEHYDE
23 4
Recycle Gross
Ethanol Air Feed
.0592 1.1658
.0897
.3575 .3575
1.1769 1.1769
5
Reactor
Effluent
.0592
1 . 0000
.4920
.0224
.0027
.0020
.0093
.0149
1.1769
.0032
.0073
1.1066
.0897
.0592
1.5334
2.7899
2.7899
Off-Gas
.0009
.0224
.0027
.0020
.0093
.0149
1.1769
1.2291
Product
1.0000
By-Product
5% Acid Waste
.0638
.0032
1.0000 .0670
.4273
.0073
.4346
-------
TABLE AC-II
ACETALDEHYDE
VIA.
ETHANOL OXIDATION
There are not sufficient data to permit the construction of an overall
heat balance for this process.
Heat Generated by Reaction
C2H5OH + % 02 > CH3CHO + H20 H - -44.55 kcal./mole
C2H5OH •*» CH3CHO + H20 H » +17.28 kcal./mole
97.8% Oxidation
2.2% Dehydration
Heat evolved by reaction •» J.,763 BTU/lb. acetaldehyde
-------
EPA Plant Code No.
Capacity, Tons of Acetaldehyde/Yr.
Range in Production - 7. of Max.
Emissions to Atmosphere
Stream
Flov - Lbs./Hr.
Flov Characteristic - Continuous or Intermittent
if Intermittent - Hrs./Yr.
Composition - Tons/Ton of AccraIdehyde
Methane
Carbon Monoxide
Carbon Dioxide
Hydrogen
Nitrogen
Oxygen
Water
Sample Tap Locations
Frequency of Sampling
Type of Analysis
Odor Problem
Vent Stacks
Flov - SCFM/Stack
Number
Height - Feet (elev. (? tip)
Diameter - Inches
Exit Gas Temperature - F°
Emission Control Devices
Type
Summary of Air Pollutants
Hydrocarbons - Ton/Ton AcetaIdehyde
Particulates - Ton/Ton Acetaldehyde
NOX - Ton/Ton Acetaldehyde
SOX - Ton/Ton Acetaldehyde
CO - Ton/Ton Acetaldehyde
TABLE AC-III
NATIONAL EMISSIONS INVENTORY
ACETALUEIIVnE
VIA
ETIIAN'OL OXIDATION
1-1
90,000
Not Specified
Absorber Vent
24,42fa
Continuous
.00195
.00276
.00934
.01491
1.12450
.02239
.00934
Not Specified
Three times per week
Gas Chromatography
No
6,500
3
75
792
45
Two water scrubbers
0
0
0
0
.00276
-------
ABSORBER/SCRUBBER
EPA Code No. for plant using
Flow Diagram (Fig. I) Stream I. D.
Control Emission of
Scrubbing/Absorbing Liquid
Type - Spray
Packed Column
Column w/trays*
Number of trays
Tray type
Other
Scrubbing/Absorbing Liquid Rate - CPM
Design Temp. (Operating Temp.) F°
Gas Rate - SCFM
T-T Height-, Ft.
Diameter - Inches
Washed Gases to Stack**
Stack Height - Feet
Stack Diameter - Inches
Installed Cost - Mat'1. & Labor - $
Installed Cost based on - "year" - $
Installed Coat c/lb. of acetaldehyde/Yr.
Operating Cost - Annual - $ - 1972
Value of Recovered Product - $/Yr.
Net Operating Cost - c/lb. of Acetaldehyde
Efficiency - % - SE
Efficiency - 7. - SERR
TABLE AC-IV
CATALOG OF EMISSION CONTROL DEVICES
ACETALDEHYDE
VIA
ETHANOL OXIDATION
1-1
6
Water Soluble Organics
Water
29
Bubble Cap
25
Bubble Cap
170 170
45° 45°
6,500 6,500
Not Specified
96 60
No Yes
75 ft.
3 at 66 each
80,000 95,000
1938 1940
.102
55,330
2,275,000
(2,219,670)
100
99.9+
-------
Current
Capacity
(1)
2,402
(2)
TABLE AC-V
NUMBER OF NEV PLANTS BY 1980
ACETALDEHYDE VIA ALL PROCESSES
Marginal
Capacity
Current
Capacity
on-stream
in 1980
Demand
in 1980
Capacity
to be
Added
Economic
Plant
Size
Number
of Nev
Plants
2,202 (3)
3,500 (4)
1,298
ACETALDEIIYDE ETHANOL OXIDATION AND/OR DEHYDROGENATION
200
Current
Capacity
966 (5)
Marginal
Capacity
Current
Capacity
on-stream
in 1980
Demand
in 1980
Capacity
to be
Added
Economic
Plant
Size
Number
of Nev
Plants
'2)
966
966 (6)
0
100
0
(1) All capacities in MM Ibs./year.
(2) No data is available.
(3) Assumed 0 marginal capacity - it is possible that all plants using the ethanol process will be operating
since many manufacture acetic acid directly from the acetaldehyde produced.
(4) C & E News, May 17, 1971.
The Petrochemical Industry Markets & Economics, 1970.
(5) Include acetaldehyde produced by straight dehydrogenation.
(6) Assumes no nev ethanol plants will be built and no capacity will be lost.
-------
TABLE AC-VI
Emission
Hydrocarbons
Participates
NOX
sox
CO
EMISSION SOURCE SUMMARY
T/T OF ACETALDEHYDE
Source
Absorbent Vent Fuel for Reactor
0
0
0
0
.00276
Start-Up
3
fl>
OQ
H-
(TO
cr
t-1
R>
Ethanol Storage Vent
2!
n
OQ
H-
IK
cr1
i-*
«t)
-------
TABLE AC-VII
Chemical
Process
WEIGHTED EMISSION RATES
Acetaldehyde
Ethanol Oxidation
Increased Capacity* 0.0 Lbs./Yr.
Pollutant
Hydrocarbons
Particulates
NOX
SOX
CO
Increased Emissions
Emissions Lbs./Lb. MM Lbs. /Year
None
None
None
Negligible
.00276 0.0
Weighting Weighted Emissions
Factor MM Lbs. /Year
80
60
40
20
1 0.0
Significant Emissions Index *• 0.0 MM Lbs./Yr.
NOTE
••-No new ethanol oxidation or dehydration plants are expected to be built.
-------
Acetic Acid via Methanol
-------
Table of Contents
Section Page Number
I. Introduction HAC-1
II. Process Description HAC-2
III. Plant Emissions HAC-3
IV. Emission Control HAC-5
V. Significance of Pollution HAC-6
VI. Acetic Acid Producers HAC-7
List of Illustrations and Tables
Flow Diagram Figure HAC-1
Net Material Balance Table EAC-I
Gross Heat Balance Table HAC-II
Emission Inventory Table HAC-III
Catalog of Emission Control Devices Table HAC-IV
Number of New Plants by 1980 Table HAC-V
Emission Source Summary Table HAC-VI
Weighted Emission Rates Table HAC-VII
-------
MAC - 1
I. Introduction
Acetic acid passed the billion Ib./year mark ten years ago and has
continued to be one of the fastest growing of all chemicals. All of the
grovth in acetic acid production for the past 20 years has been via nev
synthetic routes. Destructive distillation of vood to give acetic acid,
methanol and by-products is a dying process and has been on a steady
decline since 1950. There are three main synthetic processes currently
in use for acetic acid production in the United States.
Approximate 70
Process Raw Materials of 1972 Production
1. Oxidation of hydrocarbons (LPG) mainly butane 43
2. Oxidation of acetaldehyde acetaldehyde 31
3. Carbonylation of methanol CF^OH and CO 16
The largest single use for acetic acid is in the production of acetic
anhydride which, in turn, goes into the production of cellulose acetate for
fibers. A second large use is the production of vinyl acetate used in vinyl
plastics, paints, adhesives and textile finishes. Acetate esters, chloroacetic
acid, nylon and acrylic fibers (chain terminator), and pharmaceuticals make
up the rest of the major uses of acetic acid.
This report covers acetic acid made from the newest of the synthetic
routes, carbonylation of methanol. Reactants for this process are methanol
and a "synthesis gas" composed mainly of Ho, CO, COo and hydrocarbons. Two
variants of the process are in use; both are moderate temperature (480° F)
liquid phase reaction but pressures range from comparatively low to near
10,000 PSI. A brief scanning of the reactants used shows that this process
could be a large source of air pollution if excess snythesis gas were vented
directly to the air. However, since reactants and products are hydrocarbons
or oxygen containing organics only, proper flaring or incineration of
vented gases will produce only C02 and water with no NOX or SO . This
appears to be the case for the data supplied by the respondents indicating
little or no pollutants emitted from these plants. Of course, since
atmospheric air is required in the flaring operation, some NOX is probably
produced by oxidation of the atmospheric nitrogen.
-------
MAC - 2
II. Process Description
The main reaction involved in the carbonylation of methanol is-
,0
CH3OH + CO >• CH3 C/
XOH
a by-product reaction also gives
CO + H20 > COo + H2
Other by-products formed are methyl acetate, dimethyl ether, formic
acid, propionic acid and vater. All secondary reactions are reversible,
fortunately, and can be minimized or eliminated by proper choice of operating
conditions. The first successful process involving the carbonylation of
methanol in the U. S. vas the BASF process vhich uses temperatures around
500° F and pressures of 7500 to 10,000 PSI. It is a liquid phase reaction.
Choice of catalyst is highly critical for good yields. Cobalt Iodide is
one such catalyst. Monsanto uses a similar process but their catalyst,
reportedly a "Rhodium and Iodine containing system" from the literature,
enables them to carry out the reactions at a much lower pressure than the
BASF process.
Reacted products are stripped of light ends, scrubbed and vented to
the air via a flare or incinerator. There is a recycle stream back to the
reactor. Crude acetic acid is then purified by distillation. Either
conventional rectification vith a "vet acid" recycle stream or azeotropic
distillation is used. Most by-products are returned to the reaction system
v?here they become recycled to extinction. A "heavy" SLream of mixed acetic
and propionic acids is removed from the distillation section and incinerated.
Ultra pure (99.8+7,,) acetic acid is the main product.
Yields of 99+% of acetic acid on methanol and over 907 on CO are reported
in the literature and data from the respondents confirm these figures. Only
small amounts of by-products are produced.
-------
HAC - 3
III. Plant Emissions
A. Continuous Air Emissions
1. Purification Section Vents
Light ends and unreacted (or excess) synthesis gases are
scrubbed and flared or incinerated by both respondents. No data
are available on the composition of the combusted gases. However,
analyses are available for the gas streams as they go to incineration.
If the incinerator (flare) is operating properly and is well designed
for complete combustion, there is no reason to believe that these
gases will not be converted completely to CC>2 and water. No
nitrogen or sulfur compounds are present. Possibly some CO could
be emitted but this should be minimal with a good incinerator or flare.
As a result, we have assumed pollutant emissions from this source as
nil, except for 20 to 40 ppm of NOX generated by the oxidation of
atmospheric nitrogen.
B. Intermittent Air Emissions
1. Catalyst System Purge Gas
One respondent reports an intermittent purging of his catalyst
make-up system with air. Some iodine vapor (0 - 1000 PPM) escapes
with the air. This is reported as completely removed by a sodium
carbonate absorber and, hence, emissions from this source are nil.
C. Continuous Liquid Wastes
A stream of mixed acetic and propionic acid is removed from the
purification section and sent to incineration. No data are available
on the incinerated gases from this stream. Apparently, both
respondents sent this stream to a plant incinerator along vith other
waste streams. There is nothing about this stream that would
preclude it being burned completely to C02 and water only. Once
again, emission of pollutants would be nil.
D. Solid Wastes
There were no solid waste reported for this process.
E. Odors
When operating properly, there does not seem to be an odor
problem associated with this process. All vent gases are incinerated
to C02 and water. Only one respondent indicated a possible odor
problem. In this plant ("presumably the other plant has a similar
vent) there is an emergency vent in the purification system which
vents pure acetic acid vapor to the atmosphere for 10 - 15 minutes
in the event of a total power failure. In this emergency condition,
the odor of acetic acid was obviously evident in and around the plant
but no complaints were reported. This appears to be only isolated
instances so in general, the plant seems to be relatively clean and
free of atmospheric pollutants. Some emergency vents are flared.
F. Fugitive Emissions
No fugitive emissions are mentioned. Since both plants handle gas
streams containing CO, one would imagine that any leaks whatsoever
-------
HAG - 4
would receive prompt attention, if only for operator safety.
G. Other Emissions
One respondent has a vapor conservation system consisting of
a nitrogen blanket and conservation vents on all product and raw
material storage tanks. They vent to the atmosphere during
filling or from solar heating. No estimate of emissions was
made, but some must occur.
-------
HAC - 5
IV. Emission Control
Emission control devices employed in this process are summarized in
Table IV. Unfortunately, there are very little data available on these
devices, as is true with most incineration systems. As mentioned previously,
composition of the streams going to incineration or flaring are such that
complete combustion would lead to only CC>2 and water. Calculation of any
efficiencies or emission indices for these devices in the absence of flue
gas composition becomes meaningless for one can only assume 100% combustion
and, therefore, 100% efficiency, except for some formation of NOX.
One respondent uses a sodium carbonate absorber to remove iodine vapor
from purge air from his catalyst preparation system. This is an intermittent
stream and is reported as 100% absorbed in the sodium carbonate. Its efficiency
is, therefore, 100%.
-------
HAC - 6
V. Significance of Pollution
We recommend that no in-depth study of this process be made. Present
technology is more than adequate to give a virtually air pollutant free
plant if the devices are used properly. All vaste streams are capable of
incineration to C02 and water. Assuming that any new plant using this
process would employ similar pollution control devices, there should be no
atmospheric emissions from this process other than emergency venting due
to power failures and the like.
-------
HAG - 7
VI. Producers of Acetic Acid - All Routes Shovn
Company
Borden, Inc.
Celanese
Eastman Chemical Prod.
FMC, Organic Chem. Div.
Forest Prod.
Hercules, Inc.
Kingsford Chem. Co.
Monsanto
Publicker Industries
Sonoco Prod. Co.
Union Carbide
Mobil Chemical
Location
Geismar, La.
Bayport, Texas
Bishop, Texas
Pampa, Texas
Kingsport, Tenn
Bayport, Texas
Memphis, Tenn.
Parlin, N. J.
Iron Mtn., Mich.
Texas City, Texas
Philadelphia, Pa.
Hartsville, S. C.
Brownsville, Texas
Taft, La.
Texas City, Texas
Beaumont, Texas
MM Lbs./Yr. Route
100 Carbonylation of
Methanol
300 Acetaldehyde
150 "
500 Oxidation of butane
325 Acetaldehyde
45 Glycerine by-product
N. A Wood Distillation
40* By-product
N. A. Wood Distillation
300 Carbonylation of
Methanol
80 Fermentation by-product
N. A. Extraction
500 Oxidation of butane
90 Caprolactone by-product
100* Acetaldehyde
30 Terephthallic acid
By-product
2,420** on stream
*140 on stand-by
**400 from Carbonylation of methanol or 17% of installed capacity.
-------
PAGE NOT
AVAILABLE
DIGITALLY
-------
TABLE HAG-I
ACETIC ACID FROM METHANOL AND CO
Of the two respondent questionnaires, only one had sufficient data to construct
a material balance. The other had apparently a large excess of snythesis gas,
only a portion of which was used in the process and the excess flared.
Material In
Raw CO -
CH3OH
CO
N2
CH4
Balance - in Ib./lb. acetic acid
Total In
Lb./Lb.
0.512
0.004
0.004
0.540
1.060
Material Out
Acetic Acid - CH3COOH
Heavy Liquids (Cl^COOH
(Mixed) (CH3CH2COOH
Tail Gas - CO
C02
H2
Others
1.000
0.003
0.001
0.040
0.013
0.001
0.001
Unaccounted for
Total Out
0.001
1.060
-------
TABLE HAC-II
ACETIC ACID FROM METHANOL AND CO
Very little data are available for construction of a detailed heat balance.
for this process. Literature reports the liquid phase reaction as mildly
exothermic with only preheaters required to bring the reactants up to
temperature.
HEAT' IN BTU/Lbs. HAG
Preheat reactants to 480° F 213
Exothermic heat of reaction 984*
1,197
HEAT OUT
Enthalpy of products leaving reactor 1.197
60° temperature base and no external losses assumed.
*Literature reports heat release of 1.9 x 10^ BTU/ton acid vs calculated
1.968 x 106 BTU/ton HAC (984 BTU/lb. HAC).
-------
TABLE HAC-III
NATIONAL EMISSIONS INVENTORY
ACETIC ACID FROM MET11ANOL AND CO
Plant EPA Code No.
Capacity, Tons HAC/Yr.
Range of Production, 7. of Max.
Emissions to Atmosphere - Stream
Flov - Lbs. /Hi".
Flov Characteristic
Composition, Ton/Ton HAC
HAC
(A)
36,480 (!)
Continuous
N. A.
2-3
50,000
0
'Bl
CC1
2,209 (1)
Continuous
N A.
3,085
Continuous
N. A.
2-6
150,000
0
(B)
Nil
Open only in emergency
1.000
(C)
297 CD
Continuous
N. A.
Vent Stacks
Number
Height - Feet
Diameter - Inches
Exit Gas Temp.
SCFM/Stack
Emission Control Devices
Flare/Incinerator
Absorber/Scrubber
Condenser/K. 0. Drum
Other
Analysis
Date or Frequency of Sampling
Sample Tap Loaction
Type of Analysis
Odor Problem
Summary of Air Pollutants
Hydrocarbons, Ton/Ton HAC
Aerosols and Particulates, Ton/Ton HAC
NOX, Ton/Ton HAC
SOX, Ton/Ton HAC
CO , Ton/Ton HAC
1
100
48
3600° F
7300 (1)
Incinerator
Never
None
None
None
No Data
1
100
4
90° F
1
10
96
3400° F
426 (D
Incinerator
Spot
?
None
No
No Data
1
199
16
N. A.
475
Flare
Yes
1
10
8
Ambient
1090
None
Never
None
None
0.0000
1.0000
0.0000
0.0000
0.0000
N. A
Incinerator
N. A.
No data
(1) Calculations from composition and Ibs./hr. of feed to incinerator or flare, an estimate.
-------
TABLE HAC-IV
CATALOG OF EMISSION CONTROL DEVICES
ACETIC ACID FROM METHANOL AND CO
INCINERATION DEVICES
EPA Code for plant using
Flov Diagram (Fig. HAC-11 Stream I. D,
Device I. D. No.
Type of Compound Incinerated
Type of Device
Material Incinerated, SCFM (Ib./hr.)
Auxilliary Fuel Ren'd. 'Excl. pilot)
Type
Rate, BTU/Hr.
Device or Stack Height, Ft.
Installed Cost - Mat'l. & Labor - S
Installed Cost based on "year" dollars
Installed Cost, c/lb. Acetic Acid/Yr.
Operating Cost. Annual - $ (1972)
Operating Cost, c/lb. Acetic Acid
Efficiency - % - CCR (3)
Efficiency - 7. - SERR (3)
2-3
(C)
F-101
Mixed Organic Acids
Incinerator
(1020)
Natural gas
10
210,000
1972
0.21
28,000
0.028
No Data
No Data
2-3
(A)
F-102
Hydrocarbons & Organic Gases
Incinerator
7000
None
too
100.000
1965
0.10
4,000
.004
No Data
No Data
2-6
(C)
F-101
Mixed Organic Acids
Incinerator
(137)
No Data
No Data
2-6
(A)
F-102
Hydrocarbons & Organic Gases
Flare
475
199
No Data
No Data
ABS ORBER/S CRUBBERS
EPA Code No. for plant using
Flow Diagram (Fig. HAC-1) Stream I. D.
Control of
Scrubbing/Absorbing Liquid
Type
Scrubbing/Absorbing Liquid Rate - GPM
Operating Temp., °F
Gas Rate - SCFM
T-T Height, Feet
Diameter, Feet
Washed gases to stack
Stack Height - Ft.
Stack Diameter - Inches
Installed Cost - Mat'l. & Labor - $
Installed Cost based on "year" dollars
Installed Cost, c/lb. Acetic Acid/Yr.
Operating Cost - Annual - (1972)
Value of Recovered Product, $/Yr.
Net Operating Cost - c/lb. Acetic Acid
Efficiency - % - SE (3)
Efficiency - % - SKRR (3)
2-6
(D)
Iodine Vapor
Sodium Carbonate
Static bed
175 gal. -static
Ambient
13 (D
6
2.5
Yes
10,000
1970
0.003
$2,625
0
0.0009
100
100
(1) Average flow is intermittent at 1090 SCFM for 2 hrs./week
-------
TABLE HAG-IV
CATALOG OF EMISSION CONTROL DEVICES
NOTES
1. Incinerators and Flares. No data on combusted gases given. There are
no nitrogen or- sulfur compounds in the gases and complete combustion
should give only CC>2 and water.
2. Absorber is for recovery of iodine vapors from catalyst preparation and
activation section. Flov is intermittent. Recovery of 12 is given as
100%. Therefore, the SE and SERR based on iodine are 1007». Effluent gas
to atmosphere is air only.
3. See Appendix V for definition and explanation.
-------
TABLE HAC-V
NUMBER OF NEW PLANTS BY 1980
Process
Methanol
Acetaldehyde
Butane
Others
Current
Capacity
400
875
1,000
285
2,560
Marginal
Capacity
0
100
500
100
700
ACETIC ACID
Current
Capacity
on- stream Demand*
in 1980 1980
400 "\
775 1
;4,000
1,860
Capacity
1980
1,800
2,015
500
185
4,500
Capacity-"-'" Economic Number
to be Plant of Nev
Added Size Units
1,400 400 4
1 , 240 400 3
0
0
NOTE: All capacities in MM Ibs./year.
*From Final Report prepared by Processes Research, Inc., August 15, 1971.
**Assumes 50 - 55% of new capacity will be by methanol process.
-------
Emission
TABLE HAOVI
EMISSION SOURCE SUMMARY
TON/TON ACETIC ACID
Source
Purification Section
Total
Acid Recovery
Hydrocarbons
Particulates & Aerosols
NOX
SOX
CO
- See Belov -
0.00003
Note:
All waste gas streams leaving this process are flared or incinerated. No data on combusted gases are
available. Hovever, these gases contain no NOX °r SOX or particulates and if incinerated properly
should give only C02 and H^O as off gas, except about 20 - 40 ppm of NOX from atmospheric nitrogen, as
indicated in the total column.
-------
TABLE HAC-VII
WEIGHTED EMISSION RATES
Chemical Acetic Acid
Process Carbonylation of
Increased Capacity by 1980 1400 MM
Methanol
Ibs. /year
Pollutant Emissions, Lb./Lb.
Hydrocarbons
Aerosols & Participates
NOX
SOX
CO
0*
0
0.00003
0
0*
Increased Emissions
MM Lb. /Year
0
0
0.042
0
0
Weighting
Factor
80
60
40
20
1
Weighted Emissions
MM Lb./Year
0
0
2
0
0
^-^Significant Emission Index =» 2
•-In lieu of any data to the contrary, complete combustion of the vent gases to C02
**See Appendix IV for explanation.
assumed.
-------
Acetic Acid via Butane
-------
Table of Contents
Section Page Number
I. Introduction ACA-1
II. Process Description ACA-2
III. Plant Emissions ACA-3
IV. Emission Control ACA-6
V. Significance of Pollution ACA-7
VI. Acetic Acid Producers ACA-8
List of Illustrations and Tables
Flov Diagram Figure ACA-I
Net Material Balance Table ACA-I
Gross Heat Balance Table ACA-II
Emission Inventory Table ACA-III
Catalog of Emission Control Devices Table ACA-IV
Number of New Plants by 1980 Table ACA-V
Emission Source Summary Table ACA-VI
Weighted Emission Rates Table AQA-VII
-------
ACA-1
I. Introduction
Acetic acid is an important chemical used to produce acetic anhydride
for cellulose acetate, vinyl acetate monomer for vinyl polymer, acetate
esters for use as commercial solvents and chloroacetic acid for use in
the leather and textiles industry. The manufacture of cellulose acetate
and vinyl acetate monomer account for 44% and 3170 of the acetic acid
produced.
Acetic acid was first produced commercially by vood distillation. A
concerted effort was made during World War I to make synthetic acetic acid
because of its use in acetone synthesis. Today, almost all acetic acid is
made by synthetic methods. The major routes are oxidation of n-butane,
acetaldehyde oxidation and carbonylation of methanol. The first tvo processes
account for 44% and 327, of the acetic acid capacity, respectively. The
methanol carbonylation process is new and growth is expected in that area.
The oxidation of butane is used in two large acetic acid installations.
Large quantities of by-products are produced by the process, the more
useful of which are recovered. The economic success of such a plant is
tied to a source of cheap butane and a high market value for by-products.
Acetic acid production is expected to grow to 4.5 billion lbs./yr.* by
1980, which is an increase of about 2 billion Ibs./yr. Because butane has
become more useful for other purposes and by-product formation is undesirable,
future plants are expected to be built using either acetaldehyde oxidation
or methanol carbonylation process.
Emissions from a butane oxidation plant can best be described as moderate.
Since no growth is expected, however, annual emissions are not significant.
NOTE: This report is based on the data supplied by one respondent and
information found in literature.
*More recent estimates indicate that growth may be to 3.2 billion Ibs./year
by 1980, or only about 1 billion Ibs./year increased capacity.
-------
ACA-2
II. Process Description
(See Figure ACA-1)
The commercial oxidation of n-butane produces acetic acid along vith a
large number of by-products. Some of the useful by-products vhich are
usually recovered and sold or used in captive processes include ethyl acetate,
ethanol, methyl-ethyl ketone, formic acid and propionic acid. Product and
by-product separation is extremely difficult because azeotropes are formed
between many of the components and a large percentage of the capital and
operating costs are tied up in the recovery area. The large number of by-
products produced by butane oxidation (up to 70 components could be present
in the reactor effluent stream) are the chief drawback to the process.
The oxidation of butane is carried out in recycle reactors due to low
butane conversion. Typical reaction conditions described for a plant built
by Chemische Werke Huls in Germany are as follows: oxidation is carried out
in stainless steel towers at a temperature of 170 - 200° C and a pressure
of 65 atmospheres. The reaction takes place in the presence of a large
excess of reaction products and is considered a liquid phase reaction even
though butane is above its critical temperature.
There is a considerable heat of reaction, 9,000 BTU/lb. butane oxidized,
which must be removed mainly by evaporation of products and feed preheating.
Oxidation can be carried out using air or oxygen. If air is used nitrogen
must be removed from the system. Reaction products are separated from un-
reacted butane and combustion products such as carbon dioxide, carbon monoxide,
etc. Butane is recycled, C02, CO and some hydrocarbons are vented and/or
flared and the crude mixutre of products and by-products is sent to the
purification system.
There are many schemes to carry out the difficult purification steps
necessary. The following is a general description of a typical process. In
the first step a crude separation is made between alcohols, acetates, aldehydes,
ketonej& light components and acids plus acid residues. The alcohols, acetates,
etc., undergo another distillation whereby the heavy components, 04*5, are
removed to incineration, the light solvent? including acetone and methyl
acetate are partially recycled to the reactor with the rest being burned, and
the useful by-products, ethyl acetate, methyl ethyl ketone and ethanol are sent
to further purification. Ethyl acetate is usually recovered and refined
first, followed by ethanol and finally the ketone. The purification of these
components involves either extractive distillation or azeotrope breakers or
both.
The acids and residues passing from the bottoms of the crude separation
column are sent to another column for removal of heavy residues, which are
burned, and water which is sent to treatment. The mixture of acids leaving
the column goes to further azeotropic distillation steps where the acids are
separated and purified. Formic acid is recovered and purified first followed
by acetic acid and then propionic acid.
Large amounts of liquid waste products (about .4 Ib./lb. acetic acid) are
produced by the process and they are burned in boilers to recover heat. The
aqueous waste is usually sent to treatment.
-------
ACA-3
III. Plant Emissions
A. Continuous Air Emissions
1. Reactor Section Emissions
The respondent shows a large number of streams outletting from
the process section described as "stripping recycle reactors". To
avoid possible inaccuracies it feemed wise to assign these streams
to the general category "reaction section" and not attempt to guess
the individual sources from which they originate. Emissions to the
atmosphere from this section are described below without further
clarification.
a. Flare Stack Emissions
Hydrocarbon liquids and gases from each of the two reactor
sections are burned in a flare prior to release to the
atmosphere. The liquid stream consists of 75 - 100 Ibs./hr.
of all types of acids, alcohols,acetates and ketones. The
gaseous stream contains mainly carbon dioxide (approximately
80 wt. %) with smaller amounts of butane, ethane, methane
and inert argon. Since no sulfur or nitrogen compounds are
present in the incinerated streams and no smoke or odor is
reported by the respondent it is assumed that nearly complete
combustion takes place and the only emissions are carbon
dioxide, water and traces of NOX and unburned hydrocarbons.
b. Vent No. 1
One or two streams composed mainly of carbon dioxide with
large nuantities of butane and smaller amounts of ethane and
methane are vented to the atmosphere from each of the reactor
sections. Carbon monoxide, nitrogen and argon are also present
in the stream. Total hydrocarbon emissions for all vents in this
category are .03824 Ibs./lb. acetic acid. Carbon monoxide
emissions are .01354 Ibs./lb. acetic acid from this source.
c. Vent No. 2
Each reactor section has a small vent (.21 SCFM) for light
gases. Small amounts of hydrocarbons (.00001 Ibs./lb. acetic
acid) are emitted.
2. Liquid Waste Boiler - Flue Gas
The large quantity of organic liquid waste described in Section
III-C-1 of this report, is burned in boilers. No sulfur or nitrogen
is present in any of the components so combustion is assumed to be
complete. NOX composition is estimated to be 30 PPM which is
.00004 Ibs./lb. acetic acid for the quantity of liquid burned.
3. Storage Tank Losses
The respondent estimates that .00087 Ibs. of product and by-product
per Ib. of acetic acid, is lost due to storage tank venting.
-------
ACA-4
B. Intermittent Air Emissions
1. Topping Column and Crude Separation Column Venturi Scrubbers -
Accumulator Relief Vent .
Both the crude separation column and the topping column have two
Venturi scrubbers to absorb organic vapors, which are assumed to
originate from the reflux accumulators. The accumulator on the
scrubber exhaust is covered with a methane pad. Infrequent pressure
release allows methane along with some acetone, methyl acetate,
acetaldehyde and other light alcohols, acetates, aldehydes and
ketones to enter the atmosphere. The total quantity vented is
considered insignificant on a yearly basis.
2. Purification Section Pressure Relief Vents
Small amounts of methane along with hydrocarbons are released by
pressure relief on columns in the purification section. The total
amount emitted to the atmosphere is described by the respondent as small,
C. Continuous Liquid Wastes
1. Liquid Waste to Incineration
Large quantities of unrecovered by-products produced by the
process are burned. The source and composition of these streams is
described below.
a. Acid Purification Section
Approximately 19,000 Ibs./hr. of C^ - C, acids and water
are released from the acid purification section to boilers or
incinerators.
b. Topping Column Bottoms
About 6,000 Ibs./hr. of butyl esters and alcohols exit from
the topping column to boilers.
c. Light Solvents from Topping Column
Unrecycled acetone, acetaldehyde, methyl acetate, etc., are
burned.
2. Waste Water
An estimated flow of 200 GPM of waste water from the process is
treated in an anaerobic lagoon.
D. Solid Waste
Acid residue is burned in boilers.
E. Odor Problem
The respondent reports that odors of acetone, acetic acid and
methyl acetate are infrequently detectable off of the plant property.
-------
ACA-5
F. Fugitive Emissions
No other sources of emissions were mentioned although losses
due to leaks and spills probably do occur.
-------
ACA-6
IV. Emission Control
The emission control devices that have been reported as being employed
by the respondent are summarily described in Table IV of this report. An
efficiency has been assigned each device vherever data sufficient to calculate
it have been made available. Three types of efficiencies have been calculated.*
(1) "CCR" - Completeness of Combustion Rating
CCR = Ibs. of 02 reacting (vith pollutant in device feed)
Ibs. of On that theoretically could react
(2) "SE" - Specific Efficiency
SE = specific pollutant in - specific pollutant out
specific pollutant in x
(3) "SERR" - Significance of Emission Reduction Rating
SERR = (pollutant x veighting factor)in - (pollutant x weighting
factor)out
(pollutant x weighting factor*)in
*Weighting factor same as Table VII weighting factor.
Emission Control Devices Employed
Flares (with steam rings for emergency smokeless operation)
The respondent claims flares are smokeless so complete combustion is
assumed to the extent possible with flares.
Venturi Scrubbers
Since the only emission from the scrubbers is infrequent pad gas vents
the "SE" and "SERR" efficiencies are near 1007,.
x 100
*For complete description, see Appendix V of this report.
-------
ACA-7
V. Significance of Pollution
It is recommended that no in-depth study be made of the butane oxidation
process for acetic acid. This conclusion is drawn because no growth is
expected in the process between now and 1980. The reasons for this are as
follows:
1. Butane is becoming important for other purposes.
2. The methanol carbonylation process is growing in favor.
3. Large quantities of by-products are undesirable.
Since no new capacity is anticipated, the Significant Emissions Index
(SEI) for the oxidation of butane route to acetic acid is zero. For explanation
of SEI, see Appendix IV of this report.
-------
VI. Synthetic Acetic Acid Producers
Butane
Producer Location Oxidation Acetaldehyde Methanol & CO By-Product
Borden Inc. Geismar, La. 100
Celanese Corp. Bayport, Texas 300
Bishop, Texas 150
Pampa, Texas 500
Eastman Kodak Kingsport, Tenn. 325
FMC Corp. Bayport, Texas 45
(peracetic acid)
Monsanto Co. Texas City. Texas 300
' >
£
Publicker Ind., Inc. Phi la., Pa. 80 '
Union Carbide Brownsville, Texas 520
(peracetic acid) Taft, La. 90
Texas City, Texas 100
Total - 1,020 875 400 210
Percentage Total - 41 35 16 8
-------
PAGE NOT
AVAILABLE
DIGITALLY
-------
TABLE ACA-I
MATERIAL BALANCE
ACETIC ACID
VIA
BUTANE OXIDATION
MATERIAL IN
BUTANE
1) n-butane 1.130
2) iso-butane .017
3) lights and heavies .006
OXYGEN
1)
2)
3)
oxygem
nitrogen
argon
1.578
.097
.003
MATERIAL OUT CLB./LB. ACETIC ACID)
99% acetic acid 1.000
98% formic acid .030
95% propionic acid .003
99.5% methyl-ethyl ketone .159
85% ethanol .031
99% ethyl acetate .119
waste liquid and gases 1.489
Total In - 2.831 Ib./lb. 99% acetic acid
Total Out - 2.831 Ib./lb.
99% acetic acid
-------
TABLE ACA-II
GROSS HEAT BALANCE
ACETIC ACID
VIA
BUTANE OXIDATION
There is insufficient data available for a complete energy balance on
this process.
Heat of Reaction
9,000 BTU/lb. butane oxidized*
*1) Includes all products and by-products.
2) Reported for Chemische Werke Huls1 n-butane oxidation process in
Chemistry and Industry, May 28, 1966. Different relative amounts of
products and by-products are produced by this process than were reported
by the only respondent in the study, so the heat of reaction might vary
somevhat.
-------
Capacity - Tons of Acetic Acid
Production - Tons of Acetic Acid
Emissions to Atmosphere
Stream No.
Stream
Flow - Lbs./Hr.
Flow Characteristic - Continuous or Intermittent
if Intermittent - Hrs./Yr.
Composition
Ethane
Methane
Butane
Carbon Dioxide
Carbon Monoxide
Oxygen
Nitrogen
Nitrogen Oxides
Water
Argon
Hydrocarbons (assorted)
Acetone
Acetaldehyde
Methyl Acetate
Analysis
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problem
Vent Stacks
Number
Height - Ft.
Diameter - Inches
Temp. - F°
Flow Rate - SCFM per stack
Emission Control Device
Type - Incinerator
Scrubber
Summary of Emissions
Total Hydrocarbon Emissions - Ton/Ton of Acetic Acid
Total Particulate Emissions - Ton/Ton of Acetic Acid
Total NOX Emissions - Ton/Ton of Acetic Acid
Total SOX Emissions - Ton/Ton of Acetic Acid
Total CO Emissions - Ton/Ton of Acetic Acid
—
NATIONAL EMISSIONS INVENTORY
ACETIC ACID
VIA
BUTANE OXIDATION
2-1
260,000
260,000
Page 1 of 3
Reactor I
Section vent 1
14,065
Continuous
.00367
.00245
.01743
.15289
.00685
.00499
.02076
.00409
Yes
Side of Units
3 times a week
Mass Spectrometer
No
Yes
1
90
10
100
2023
No
Reactor I '
Section Vent 2
1.4
Continuous
.00001
+
+
+
+
.00001
Yes
None
On request
Mass Spectrometer
No
Yes
1
20
2
SO
.2
No
Reactor II
Section Vent IA
8005
Continuous
.00149
.00075
.00136
.10954
.00230
.00585
. 00348
Yes
Side of Unit
3 times a veek
Mass Spectrometer
No
Yes
1
100
10
90
1,154
No
Reactor II
Section Vent IB
6720
Continuous
00134
.00185
.00274
05790
.00669
.00750
.02120
00262
Yes
Side of Unit
3 times a veek
Mass Spectrometer
No
Yes.
1
100
10
86
1,043
No
Reactor III
Section Vent 2
1.4
Continuous
00001
+
+
+
+
00001
Ye?
None
On repueft
Mass Spectrometer
No
Yes
1
12
.5
80
2
No
Continued
-------
or Intermittent
EPA Code No.
Capacity - Tons of Acetic Acid
Production - Tons of Acetic Aeid
Emissions to Atmosphere
Stream No.
Stream
Flov - Lbs./Hr.
Flov Characteristic - Continuous
if Intermittent - Hrs./Yr.
Composition
Ethane
Methane
Butane
Carbon Dioxide
Carbon Monoxide
Oxygen
Nitrogen
Nitrogen Oxides
Water
Argon
Hydrocarbons (assorted)
Acetone
Acetaldehyde
Methyl Acetate
Analysis
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problem
Vent Stacks
Number
Height - Ft.
Diameter - Inches
Temp. - F°
Flow Rate - SCFM per stack
Emission Control Devices
Type - Incinerator
Flare
Scrubber
Summary of Emissions
Total Hydrocarbon Emissions - Ton/Ton of Acetic Acid
Total particulates and Aerosols - Ton/Ton of Acetic Acid
Total NOX - Ton/Ton of Acetic Acid
Total SOX - Ton/Ton of Acetic Acid
Total CO - Ton/Ton of Acetic Acid
TABLE ACA-III
NATIONAL EMISSIONS INVENTORY
ACETIC ACID
VIA
BUTANE OXIDATION
2-1
260,000
260,000
1A
Flare Stack Emissions
Reactor Section I Flare (1)
3380 (2)
Continuous
.03875
Negligible
.01245
.00041
(2)
No
Yes
1
210
24
Unknown
-660
Yes
Yes
Page 2 of 3
IB
Flare Stack Emissions
Reactor Section II Flare (3)
^6700 (2)
Continuous
.08691
Negligible
.01433
.00082
None
C2)
No
Yes
1
210
24
Unknown
Yes
Yes
Continued
3A
Topping Column
Venturi Scrubber Vent
Intermittent
Not Specified
(4)
None
Yes
Yes
2
58
3
90
42
6
86
(1) Approximately 2825 Ibs./hr. of light hydrocarbons and 75 Ibs./hr. of liquid alcohols, acids and ketones are incinerated in this flare.
(2) Combustion products estimated by Houdry assuming complete conversion to C02 and H20 and 30 PPM NO* formation.
(3) Approximately 3610 Ibs./hr. of light hydrocarbons and 100 Ibs./hr. of liquid alcohols, acids and ketones are incinerated in this flare.
(4) Infrequent pressure release of methane pad.
(5) Mostly methane.
-------
EPA Code No.
Capacity - Tons of Acetic Acid
Production - Tons of Acetic Acid
Emissions to Atmosphere
Stream No.
Stream
Continuous or Intermittent
Hrs./Yr.
Flov - Lbs./Hr.
Flow Characteristic
if Intermittent
Composition
Ethane
Methane
Butane
Carbon Dioxide
Carbon Monoxide
Oxygen - ,
Nitrogen
Nitrogen Oxides
Water
Argon
Hydrocarbons (assorted)
Acetone
Acetaldehyde
Methyl Acetate
Analysis
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problem
Vent Stacks
Number
Height - Ft.
Diameter - Inches
Temp. - F°
Flow Rate - SCFM per stack
Emission Control Devices
Type - Incinerator
Flare
Scrubber
Summary of Emissions
Total Hydrocarbon Emissions - Ton/Ton of Acetic Acid
Total particulate and Aerosols - Ton/Ton of Acetic Acid
Total NOX - Ton/Ton of Acetic Acid
Total SOX - Ton/Ton of Acetic Acid
Total CO - Ton/Ton of Acetic Acid
TABLE ACA-III
NATIONAL EMISSIONS INVENTORY
ACETIC ACID
VIA
BUTANE OXIDATION
2-1
260,000
260,000
Crude Separation Column,
Venturi Scrubber Vent (4)
Intermittent
Not Specified
(5)
+
+
+
None
Yes
Yes
2
55
3
98
Yes
Yes
55
3
98
page 3 of 3
Flue Gas
Liquid Waste Boilers
49,267 (2)
Continuous
.46192
.00004
.26356
Storage
Tank Vents
57.8
Purification
Relief Valve
T'O
Intermittent
Not Specified
None
(2)
No
Not Specified
No
.03911
0
.00004
0
.01354
.00087
None
Calculated
No
No
None
No
No
NO
(1) Approximately 2825 Ibs./hr. of light hydrocarbons and 75 Ibs./hr. of liquid alcohols, acids and ketones are incinerated in this flare.
(2) Combustion products estimated by Houdry assuming complete conversion to CO. and HoO, and 30 PPM NOX formation.
(3) Approximately 3610 Ibs./hr. of light hydrocarbons and 100 Ibs./hr. of liquid alcohols, acids and ketones are incinerated in this flare
(4) Infrequent pressure release of methane pad.
(5) Mostly methane.
-------
TABLE ACA-IV
CATALOG OF EMISSION CONinOL DEVICES
ACETIC ACID
VIA
BUTANE OXIDATION
FLARE
EPA Code No. for plant using
Flov Diagram CFig. ACA-I) Stream I. D.
Device I. D. No.
Types of Compounds Flared
Amount Flared - Ibs./hr.
Device or Stack Height - Ft.
Stack Diameter (3 Tip - Inches
Installed Cost - Mat'l. 6, Labor - $
Installed Cost - Mat'l. & Labor - c/lb. Acetic Acid
Installed Cost - based on - "year" - $
Operating Cost - Annual - (1972)
Operating Cost Annual - c/lb. Acetic Acid
Efficiency - CCK - %
Efficiency - S ERR - "/.
2-1
Al
FL-I
Assorted HC Liquids & Vapors
2790
210
24
84,760
.016
34,760 - 1971 50,000 - 1961
16,560
.003
Near 1007.
Near 100%
2-1
A2
FL-I I
Assorted HC Liquids & Vapors
3450
210
24
84,760
.016
34,760 - 1971 50,000 - 1964
SCRUBBERS
EPA Code No. for plant using
Stream I. D. No.
Device I. D. No.
Control Emission of
Scrubbing Liquid
Type - Venturi
Absorber
Scrubbing Liquid Rate - GPM
Design Temp. - F°
Gas Rate - SCFM (Ib./hr.)
Washed Gases to Stack
Stack Height - Ft.
Stack Diameter - Inches
Installed Cost - Mat'l. 6. Labor - $
Installed Cost - c/lb. of Acetic Acid
Installed Cost - based on - "year" - $
Operating Cost - Annual - (1972)
Value of Recovered Product - $/Yr.
Net Operating Cost - Annual - $
Net Operating Cost - c/lb, of Acetic Acid
Efficiency - 7. - SE
Efficiency - 7. - SERR
2-1
B
SC-I & SC-II
Acetaldehyde, Acetone, Methyl Acetate
Water
Yes
9.2 each
Yes
55 each
3 each
4,000
.0008
1964
200
0
200
.00004
99.9+
99.9+
2-1
B
SC-III & SC-IV
Acetaldehyde. Acetone. Methyl Acetate
Water
Yes
Ye
58
3
2,000
.0004
1964
200
0
200
. 00004
99.9+
99.9+
42
6
2,000
.0004
1968
-------
1020
TABLE ACA-V
Current (1)
Capacity
NUMBER OF NEW PLANTS BY
ACETIC ACID
VIA
BUTANE OXIDATION
Current
Capacity
Marginal on-stream Demand
Capacity in 1980 1980
1980
Capacity
1980
Capacity
to be
Added
Economic
Plant
Size
Number
of Nev
Units
0
1020
1020
1020
0
(1) MM Ibs./year.
(2) No new butane oxidation plants are expected to be built.
300
(2)
-------
TABLE ACA-VI
EMISSION SOURCE SUMMARY
TON/TON OF ACETIC ACID
Emission
Source
Total
Venturi Scrubber
Reactor Stripping Liquid Waste and Purification Section Tank Vents &
Section Incineration Relief Valves Fugitive Emissions
Hydrocarbons
Particulates
NOX
SOX
CO
.03824
0
0
0
; 01354
0
0
. 00004
0
0
Negligible
0
0
0
0
.00087
0
0
0
0
.03911
0
.00004
0
.01354
-------
TABLE ACA-VII
Chemical
Process
Increased Capacity
Pollutant
Hydrocarbons
Participates
NOX
sox
CO
WEIGHTED EMISSION RATES
Acetic Acid
Butane Oxidation
by 1980 0
Increased Emissions
Emissions Lb./Lb. MM Lbs./Year
.03911 0
0 0
. 00004 0
0 0
.01354 0
Weighting
Factor
80
60
40
20
1
Weighted Emissions
MM Lbs./Year
0
0
0
0
0
Significant Emission Index ° 0
-------
EPA Plant Code No.
Capacity - Tons of Acetic Acid/Yr.
Production - Tons of Acetic Acid/Yr.
Emissions to Atmosphere
Stream
Flow - l.bs./Hr.
Flov Characteristic - Continuous or Intermittent
if Intermittent - Hrs./Yr.
Composition - Tons/Ton of Acetic Acid
Acetaldehyde
Ethyl Acetate
Carbon Dioxide
Carbon Monoxide
Water
Oxygen
Nitrogen
Analysis
Sample Tap Location
Frequency of Sampling
Type of Analysis
Odor Problem
Vent Stacks
Number
Height - Ft.
Diameter - Inches
Exit Gas Temp. - F°
Flov - SCFM/Stack
Emission Control Devices
Type
Summary of Air Pollutants
Hydrocarbons - Ton/Ton Acetic Acid
Particulates - Ton/Ton Acetic Acid
NOX - Ton/Ton Acetic Acid
SO - Ton/Ton Acetic Acid
CO - Ton/Ton Acetic Acid
TABLE ACE-III
NATIONAL EMISSIONSTNVENTORY
ACETIC ACID
VIA
ACETALDEHYDE OXIDATION
2-5
162.500 (1)
72,000
Scrubber Vent
22,457
Cont inuoue
.00481
.00502
.02089
.00202
.00077
.04529
1.26869
Yes
On-stream to control room
3 times/veek
Gas Chromatograph - Orsat
No
Yes
1
75
66
45
5000
Yes
Tvo Absorbers
.00983
0
0
0
.00202
(1) Published capacity.
-------
Acetic Acid via Acetaldehyde
-------
TABLE ANA-I
ACETIC ANHYDRIDE FROM ACETIC ACID
OVERALL MATERIAL BALANCE - TON/TON ACETIC ANHYDRIDE
MATERIAL IN MATERIAL OUT
Pure Acetic Acid
Misc. Carboxylic Acids
and Water
1.2000
0.0011
1.2011
Acetic Anhydride 1.0000
Low Boiling Liquids 0.0010
Tars 0.0005
Water 0.1760
Flare Gas* 0.0206
Acetic Acid 0.0030
1.2011
Hydrocarbons, N2, 02, C02 CO
-------
TABLE ANA-II
ACETIC ANHYDRIDE FROM ACETIC ACID
HEAT BALANCE
There is not enough data to calculate a detailed heat balance for this
process. An estimate of the heat flovs around the preheater, vaporizers
and cracking furnace is:
HEAT IN BTU/LB. ACETIC ANHYDRIDE
Sum of steam, heat exchange and
fired heaters 2240
HEAT OUT
Endothermic heat of reaction 1158
Differential enthalpy (Reaction products - feed) 1082
2240
-------
TABLE ANA-III
NATIONAL EMISSIONS INVENTORY
ACETIC ANHYDRIDE FROM ACETIC ACID (KETENE ROUTE)
Plant - EPA Code No.
Capacity, Tons Acetic Anhydride/Yr.
Range in Production, 7. of Max.
Emissions to Atmosphere
..^ Stream
Flov, Lb./Hr.
Flow Characteristic. Continuous or Intermittent
Composition, Lb./Lb. Acetic Anhydride
Particulate
Carbon Dioxide
Carbon Monoxide
Propodiene
Ethylene
Methane
Water
Ethane
Diketene
Acetic Anhydride
Oxygen
Nitrogen
Acetic Acid
Hydrogen
Propane
Vent Stacks
Number
Height, Ft.
Diameter, Inches
Exit Gas Temp. °F
SCFM/Stack
Emission Control Devices
Flare/Incinerator
Absorber/Scrubber
Analysis
Date or Frequency of Sampling
Sample Tap Location
Type of Analysis
Odor Problem
Summary of Air Pollutants
Hydrocarbons - Lb./Lb. Aceric Anhydride
Aerosols & Particulates - Lb./Lb. Acetic Anhydride
NOX - Lb./Lb. Acetic Anhydride
SOX - Lb./Lb. Acetic Anhydride
CO - Lb./Lb. Acetic Anhydride
30,000 Est.
None (liven
Final Scrubber Off-Gas
Stream goes to flare
no comp. of flared
gas given
180
Continuous
-f-
0.00405
0.00975
0.00112
0.00368
0.00279
0.00241
0.00010
0.00007
0.00050
0.00034
0.00136
No Data
Incinerator
Never
Calculated
No
No Data
3-2
30,000 Est.
None Given
Tar Incinerator Flue Gas
1458 Est.
Continuous
30,000 Est.
None Given
Vaporizer Emergency Rupture Disc
Unknovn
Open only in emergencies
0.27-
99.87.
None
1400° F
Unknovn
Incinerator
Never
Stack Top
None
No
No Data
Normally Closed
None
Never
Not App.
3-1
425,000
None Given
Final Scrubber Off-Gas
1800
Continuous
0.002907
0,008144
0.000021
0.003113
0.002660
0.00008?
0.000433
0.001856
0.000000?
0.000144
0.001258
2
90 75
8 6
100
300 60
None
Annually
Sump
G.C.
No
0.004474
0
0
0
0.008144
-------
TABLE ANA-IV
CATAI.OC- OF EMISSION CONTROL DEVICES
INCINERATION DEVICES
EPA Code No. for plant using
Flov Diagram 'Fig. II Stream
Device No.
Type of Compound Incinerated
Type of Device
Material Incinerated SCFM db./hr.)
Auxilliary Fuel Reo'd.
Type
Rate BTU/Hr.
Device or Stack Height, Ft.
Installed Cost - Mat'l. & Labor - $
Installed Cost based on "year" - dollars
Installed Cost, c/lb. of Acetic Anhydride - Year
Operating Cost - Annual - $
Operating Cost - c/lb. of Acetic Anhydride
Efficiency - 7. - CCR
Efficiency - % - SERR
3-2
A
F-101
Hydrocarbons
Flare
40
Not Given
3-2
B
1-101
Organic Tars
Inci nerator
1458
Not Civen
3-1
C
1-10?.
Organic?, Hydrocarbons
Incinerator
(83)
Not Given
-------
TABLE ANA-V
Current
Capacity
Marginal
Capacity
NUMBER
Current
Capacity
on-stream
in 1980
OF NEW PLANTS BY 1980
Demand
1980
Capacity
1980
Capacity*
to be
Added
Economic
Plant
Size
Number
of Nev
Units
1705** 0 1705 2050 2100 267 100 2-3
NOTE: All capacities in millions of Ibs./year.
*Capacity using pyrolysis of MAC route only.
**Excludes U. S. Army Munitions Report
-------
TABLE ANA-VI
Emission
EMISSION SOURCE SUMMARY
TON/TON ACETIC ANHYDRIDE
Source
Total
Absorber-Scrubber
Tail Gas Tar Incinerator Gas Fugitive Emissions
Hydrocarbons
Particulates & Aerosols
NOX
sox
CO
0.002729
0
0
0
0.004968
0
TR
0 None Given
0
+
0.002729
TR
0
0
0.004968
NOTE: (+) Compound present but no analysis available.
-------
TABLE ANA-VII
WEIGHTED EMISSION RATES
Chemical
Process
Increased Capacity
Pollutant
Hydrocarbons
Aerosols
NOX
SOX
CO
Acetic Anhydride
Pyrolysis of Acetic
by 1980 267 MM Ibs
Emissions Ib./lb.
0.002729
TR
0
0
0.004968
Acid
., assume 1133 MM Ibs. in 1973
Emissions MM Ib./yr.
0.73
TR
0
0
1.42
Weighting
Factor
80
60
40
20
1
Weighted Emissions
MM Ib./yr.
58.4
0
0
0
1.42
Significant Emission Index = 59.87
-------
Adipic Acid
-------
Table of Contents
Section Page Number
I. Introduction AA-1
II. Process Description AA-2
III. Plant Emissions AA-4
IV. Emission Control AA-7
V. Significance of Pollution AA-10
VI. Adipic Acid Producers AA-11
List of Illustrations and Tables
Flow Diagram Figure AA-I
Net Material Balance Table AA-I
Gross Heat Balance Table AA-II
Emission Inventory Table AA-III
Catalog of Emission Control Devices Table AA-IV
Emission Source Summary Table AA-V
Number of New Plants by 1980 Table AA-VI
Weighted Emission Rates Table AA-VII
-------
AA-1
I. Introduction
Ninety percent of all adipic acid produced is used in the manufacture of
nylon 6,6. Adipic acid is condensed with hexamethylene-diamine to form
nylon salt; this requires 0.7 Ibs. of adipic acid/lb. of nylon 6,6.
Additionally some hexamethylene-diamine is derived from adipic acid; this
requires 1.05 Ibs. of adipic acid/lb. of nylon 6,6. Thus, the current
demand and the future growth of adipic acid is closely bound to the nylon
6,6 market. Of lesser importance is adipic acid's use in the production of
plasticizers, synthetic lubricants and urethanes.
Practically all commercial production of adipic acid is based on oxidizing
cyclohexanone/cyclohexanol with nitric acid. The various oxides of nitrogen
produced during the oxidation constitute the principal source of air pollution
for this process. The separation of adipic acid from its various by-products-
primarily glutaric and succinic acid - and the purification of adipic acid
contribute only slightly to the overall air pollution. Likewise; the
pneumatic conveying, drying and melting of the purified adipic acid crystals
contribute relatively little to the total air emissions produced by the
process as a whole. Air pollution resulting from the production of adipic acid
can be characterized as being moderate.
The current U. S. capacity for the production of adipic acid is 1.43 x 10
Ibs./yr. 1980 production capacity, based on an annual growth rate of 5.570(*-),
is estimated at 2.20 x 109 Ibs./yr.
(1) Chemical Marketing Reporter, April 24, 1972
-------
AA-2
II. Process Description
Cyclohexanone and cyclohexanol are oxidized to adipic acid by reaction
with nitric acid. The following two equations illustrate the gross chemistry:
0
II
(A) H2 C C H2
! ! + (a) HNO- ^ H2C - CH - COOH
HP P u -3 UP. PU — ppdPtu v ^ / v \ **/ no w
9 L L. no no L* " brio UUUrl A ^
V
Ho
Cyclohexanone + Nitric Acid ^- Adipic Acid + Nitrogen Oxide + Water
(B) H OH
"c
H2 C C H? H2C - CH0 - COOH
|| + (x) HN03 *• H2C - CH2 - COOH + (y) N0x + (z> H2°
H2 C C H2
c'
H2
Cyclohexanol+Nitric Acid >*• Adipic Acid + Nitrogen Oxide + Water
The nitrogen compounds formed, shown above as NO , are predominately NO,
N02 and N20. Additionally, various organic acid by-products are produced,
chief among these are acetic acid, glutaric acid and succinic acid-j in larger
plants some of these may be recovered and sold.
The following process description may more easily be followed by referring
to Figure I - a process flow diagram:
In commercial practice a mixture of cyclohexanone/cyclohexanol is
oxidized in a series (generally two) of stirred tank reactors. Feed to the
reactors is approximately one part alcohol-ketone and five parts 50 wt. %
nitric acid. Pressure is about 30 psig and temperature is maintained at
170° to 180° F by water cooling or heat exchange. Standard catalyst for the
oxidation is a mixture of cupric nitrate and ammonium vanadate.
Subsequent to the oxidation the dissolved NOX gases plus any light
hydrocarbon by-products are stripped from the adipic acid/nitric acid solution
with air and steam. NO and N02 are recovered by absorption in nitric acid.
The stripped adipic acid/nitric acid solution is then chilled and sent
to the No. 1 crystallizer, where crystals of adipic acid are formed. The
crystals are separated from the mother liquor in the No. 1 centrifuge and
transported to the adipic acid drying and/or melting facilities. The mother
liquor is separated from the remaining uncrystallized adipic acid in the
product still and recycled to the reactors.
The bottoms from the product still are diluted with water, rechilled and
pumped to the No. 2 crystallizer. The slurry from the No. 2 crystallizer is
pumped to the No. 2 centrifuge where the remaining adipic acid crystals are
-------
AA-3
separated from the diluted residual mother liquor. The crystals are
combined with the product from the No. 1 centrifuge. The mother liquor
is distilled to recover the nitric acid; the residual material is sent to
waste disposal.
-------
AA-4
III. Plant Emissions
A. Continuous Air Emissions
1. Reactor Off-gas
All adipic acid plants tha-t oxidize cyclohexanone/cyclohexanol
mixtures with nitric acid produce NO . Much of the NO formed
is recovered as nitric acid, but a significant portion is emitted
to the atmosphere. The NOX emissions reported varied from .03 to
.34 Ibs. of NOX per Ib. of adipic acid produced. This tenfold
variation in emission rates is apparently the result of two
factors; (1) the difference in the performance of NOX recovery
systems and (2) the variation in the percentage of N20 in the NOX -
this is a factor because N£0 cannot be easily recovered as nitric
acid. (^O/NO ratio is dependent to some extent on cyclohexanol/
cyclohexanone ratio). Reactor off-gas emissions are summarized
in Table III. Note, however, that ^0 is not considered a pollutant.
2. Adipic Acid Purification and Nitric Acid Recovery Vents
Because of the variation in processing schemes and the inter-
relationship of the two above named operations it is difficult to
make generalized distinctions between the subject streams. Air
emissions from these two sources share a similarity in composition -
they are predominantly NOX. In most instances, nitric acid recovery
operations succeed in minimizing emissions. One operator (EPA Code
5-2); however, does report venting significant amounts (.03 Ib./lb.)
of NOX from these facilities. These emissions are summarized in
Table III.
3. Vents from Adipic Acid Conveyors, Driers and Melters
The drying, conveying and general handling of adipic acid
crystals presents the same problems that most dry solids present.
The 'handling' produces 'fines' and the fines generate dust. The
respondents report utilizing a variety of dust control equipment;
cyclones, bag filters and wet scrubbers. In general, the
particulate emissions from this source are low. The highest rate
of particulate emissions reported - by EPA Code No. 5-4 - was
.0005 Ibs./lb. of adipic acid. Table III contains a complete
summary of all reported emissions in this category.
4. Plant Flare and Incinerator Flue Gases
Most petrochemical plants employ flares, 'thermal oxidizers' or
some type of incineration devices to burn waste hydrocarbons; either
on a continuous basis, or intermittently, during plant emergencies.
Adipic acid plant operators are no different, in this respect, than
operators of other types of petrochemical plants. They have reported
the use of various incineration devices; however, in order to "burn"
NOX containing gases in such a way that the 'combustion' products
are less offensive than their 'uncombusted' precursors, the
incineration devices must be specially designed to decompose NOX
into N2 and §•£. At least one respondent has indicated that such a
special incinerator is indeed utilized (EPA Code No. 5-3, Device
AA-8). Flue gases from less specialized devices must be suspected
of containing practically all of the NOX that was fed to them.
This information is summarized in Table IV.
-------
AA-5
5. Storage Losses
No respondent has offered an estimate of storage losses. They
should be quite low for two reasons, (1) final product is a solid
and not subject to evaporation and (2) the hydrocarbon feed fre-
quently comes direct from a previous processing step, and hence is
not subject to normal storage losses. Both operators EPA Code 5-2
and 5-4 report using absorbers/scrubbers on nitric acid storage tank
vents, thus minimizing emissions from that source. Therefore,
although no quantitative data are available it seems safe to surmise
that air emission from adipic acid plant storage facilities are low.
B. Intermittent Air Emissions
Start-up and Emergency Vents
This type of emission is universally encountered in the
pertochemical industry and will vary from process-to-process,
from operator-to-operator and even from year-to-year. One operator
(EPA Code No. 5-2) estimates that he vents his reactors to the
atmosphere - on an emergency basis - six to twelve times per year.
Taking the higher figure this still amounts to less than one ton
per year of NOX - an insignificant amount. This information is
detailed in Table III.
C. Continuous Liquid Wastes
Waste Water
All respondents report the production of waste water:
Operator EPA Code 5-1 reports 90 GPM, which is disposed of by
deep well injection.
Operator EPA Code 5-2 reports 600 GPM, containing 0.5 wt. %
succinic acid and 1.2 wt. % glutaric acid. Its method of disposal
is not discussed.
Operator EPA Code 5-3 reports the production of about 350 GPM,
containing 0.9 wt. % HN03 and 2.3 wt. °L organics. Deep well
injection is used for disposal.
Operator EPA Code 5-4 reports the production of about 40 GPM
of waste water.
D. Intermittent Liquid Wastes
No intermittent liquid wastes were reported.
E. Solid Wastes
No solid wastes were reported.
F. Fugitive Emissions
Only one operator (EPA Code No. 5-1) has made a quantitative
estimate of fugitive emissions. His estimate is 150 SCFH (of NOX?).
-------
AA-6
Other operators state that emissions of this type are either non-
existent or very low. Considering that the adipic acid process
is low pressure, and that fugitive emissions would probably be
fairly easy to detect because of their odor or their visibility,
it is probable that fugitive emissions are quite low.
G. Odors
In general, the production of adipic acid via nitric acid
oxidation of cyclohexanol/cyclohexanone does not appear to be a
process that has an odor problem.
None of the respondents reported an odor complaint in the past
year. Most of the reported odors are said to be detected only on
the plant property and only at intermittent intervals. The odiferous
materials are usually identified as NOX.
All NOX containing vent streams are potential sources of odors.
However, according to the questionnaire these streams are well
enough controlled to prevent odor problems.
-------
AA-7
IV. Emission Control
The emission control devices that have been reported as being employed
by operators of adipic acid plants are. summarily described in Table IV of
this report. An efficiency has been assigned each device whenever data
sufficient to calculate it have been available. Three types of efficiencies
have been calculated:
(1) "CCR" = Completeness of Combustion Rating
CCR = Ibs. of 02 reacting (with pollutants in device feed)
Ibs. of 02 that theoretically could react
(2) "SE" - Specific Efficiency
SE = specific pollutant in - specific pollutant out
specific pollutant in
(3) "SERR" - Significance of Emission Reduction Rating
x 100
SERR = (pollutant x weighting factor*) in - (pollutant x weighting
factor*) out
(pollutant x weighting factor*) in
^Weighting factor same as Table VII weighting factor.
Normally a combustion type control device (i.e., incinerator, flare, etc.)
will be assigned both a "CCR" and a "SERR" rating, whereas, a non-combustion
type device will be assigned an "SE" and/or an "SERR" rating. A more complete
description of this rating method may be found in Appendix V of this report.
Although efficiency ratings for most devices are shown in Table IV, a
few general comments regarding adipic acid pollution control device per-
formance seems in order:
Absorbers
Adipic acid plant operators reported the use of five absorbers. They
are identified in Table IV as devices AA-1, AA-2, AA-3, AA-4, and AA-7.
The specific efficiencies (with regard to NOX, but excluding ^0 since
it is not regarded as a pollutant) range from 487» to 98.870. Information
sufficient to determine the cause of device AA-7's unusually low
efficiency (i.e., 48%) is not available. Three of the other four devices
have specific efficiencies greater than 957,, while insufficient data
precluded the calculation of an efficiency for the third. Thus, based
on the data reported in the questionnaires, absorbers in adipic acid
'NOX service1 appear capable of removing 95 + 7, of NO and N02-
Scrubbers
The operator of plant EPA Code No. 5-2, reports the use of two
scrubbing devices, AA-5 and AA-6, to control the emission of adipic
acid dust. His estimates of adipic acid concentrations lead to cal-
culated specific efficiencies of about 907, for both devices. This is
probably typical for this service, but variations in particle size
distribution and device energy input will alter efficiency.
-------
AA-8
Cyclones
The use of two cyclone separators has been reported by questionnaire
respondents. Particle size information is lacking for both installations.
Based on the scant information available on these devices it seems safe
to say only that adipic acid dust collection efficiencies in excess of
90% are feasible with single stage cyclones.
Bag Filters
The operator of plant EPA Code No. 5-3 provides the only information
on the use of bag filters in the control of adipic acid dust emissions.
Although he does not report particle size, he states dust collection
efficiency is 100%.
Incineration Devices
Pollution reduction via the incineration of nitrogen oxides requires
the use of devices specifically designed for this duty. These special
burners reduce NOX to elemental nitrogen by providing a reducing
atmosphere through the use of at least 10% excess fuel. NOX reductions
of 75 to 90% have been reported for this method in the literature.
The operator of plant EPA Code No. 5-3 reports utilizing such a device
for "burning" the NOX fumes vented from his nitric acid storage facilities,
Data provided by that respondent show that his NOX burner, identified
as device AA-8 in Table IV, operates with an efficiency (CCR & SERR)
of 70%. However, the same respondent reports sending another NOX
bearing stream - the effluent from device AA-7 - to the boiler house,
where he states "an indeterminate amount of NO and N02 are reduced to
N2 in the burner flame". It seems extremely unlikely that the proper
conditions for NOX reduction exist within a boiler firebox.
Operator EPA Code No. 5-4 reports burning about 25 gallons an hour
of various waste organic acids. His analysis of incinerator flue gases
show his device to be 100% efficient in this duty.
It is unlikely that any change in operating conditions, per se, will
lead to a significant decrease in air pollution. However, many adipic acid
plants would benefit through more extensive use of pollution control
equipment currently in use by some segments of the industry. As previously
pointed out, with few exceptions, most of the devices that are employed have
efficiencies in excess of 907» and better utilization of them could reduce
the industry wide pollution average significantly.
Developmental work directed toward reductions in emissions from this
process falls into the following general categories:
(1) One-step oxidation of cyclohexane to adipic acid - thereby reducing
the number of pollution generating steps in the overall process
by 50%.
(2) Substitution of air or preferably oxygen for nitric acid - as the
oxidant. Although this has been studied and found uneconomic,
further investigation of the overall environmental impact might be
warranted.
(3) Devise method for economically recovering ^0. Although not a
-------
AA-9
pollutant, N£0 recovery might lead to an overall reduction in
nitric acid production if it could be re-oxidized and recycled.
(4) More efficient design and operation of devices currently being
utilized.
-------
AA-10
V. Significance of Pollution
It is recommended that no in-depth study of this process be undertaken at
this time. The reported emission data indicated that the quantity of pollutants
released as air emissions is less for the subject process than for other
processes that are currently being surveyed. However, one must be cognizant
of the fact that although the production of adipic acid a the production
of cyclohexanol/cyclohexanone were surveyed as two separate and individual
processes, current practice is to integrate the production facilities into
one plant. Therefore, the emissions accompanying 'one process' co-exist with
the emissions from the other. This may give rise to consideration of an
in-depth study of the entire process (cyclohexane to adipic acid) at some
later date.
The methods outlined in Appendix IV of this report have been used to
forecast the number of new plants that will be built by 1980 and to estimate
the total weighted annual emissions from these new plants. This work is
summarized in Tables V, VI and VII.
The Table V forecast of new plants is based on a predicted annual capacity
growth of 5.5%. This is in agreement with the estimate published in the
Chemical Marketing Reporter, April 24th, 1972.
On a weighted emission basis a Significant Emission Index of 780 has been
calculated in Table VII. This is less than the SEI's for some of the other
processes in the study. Hence, the recommendation to exclude adipic acid
production from the in-depth study portion of the overall scope of work.
However, due to the fact that most of the SEI results from NOX emissions,
any effort to reduce this type of pollution should certainly consider new
source standards on adipic acid production.
-------
AA-11
VI. Adipic Acid Producers
The following tabulation of producers of adipic acid indicates published
production capacity by company and location:
Company
Allied
Celanese
DuPont
El Paso
Monsanto
Location
Hopewell, Va. (2)
Bay City, Texas (3)
Orange, Texas (3)
Victoria, Texas (3)
Odessa, Texas (3)
Luling, La. (2)
Pensacola, Fla. (3)
Capacity
(1)
Total
20
130
300
300
80
60
540
1,430
Notes
(1) Capacity in MM Lb./Yr.
(2) Cyclohexanone/cyclohexanol derived from phenol.
(3) Cyclohexanone/cyclohexanol derived from cyclohexane.
-------
PAGE NOT
AVAILABLE
DIGITALLY
-------
TABLE AA-I
Stream No. (Fig. I)
Cyclohexanone
Cyclohexanol
Cyclohexyl Esters (as formate)
Adipic Acid
Dicarboxylic Acids (as succinic)
Monocarboxylic Acids (as acetic)
Water
Nitric Acid (100%)
Nitrogen Oxides
Total
TYPICAL ADIPIC ACID PLANT
MATERIAL BALANCE
T/T OF ADIPIC ACID
1 2
Organic Feed Acid Feed
to Oxidizer to Oxidizer
.3402
.2778
.1399
1.8434
2.0813
.7579 3.9247
3 (A & B) 4 (A & B)
Oxidizer Nitric Acid to
Effluent Recycle & Concen. '
1.0000
.0624
.0357
2.0130 2.0130
1.2193 1.2193
.3522
4.6826 3.2323
5 6 (A & B) 7
Light Heavy Adipic
Ends Ends Acid
1.0000
.0624
.0357
.3522
.3522 .0981 1.0000
-------
TABLE AA-II
ADIPIC ACID PRODUCTION
VIA
NITRIC ACID OXIDATION
OF
CYCLOHEXANONETCYCLOHEXANOL
GROSS REACTOR HEAT BALANCE
Heat In
Exothermic Heat of Reaction
BTU/LB. OF ADIPIC ACID PRODUCED
1390*
Heat Out
Reactor Temp. Control (@ 180° F)
NOX Vapor Vent
Sensible Heat Removal - Heat Exchange
Sensible Heat Removal - Cooling (to 60° F)
1030
20
170
170
Total 1390
*Based on feed, conversions, etc. shown in Table 5.
-------
Plant - EPA Code No.
Capacity, Tons of Adipic Acid/Yr.
Average Production, Tons of Adipic Acid/Yr.
Range in Production - 7. of Max.
Emissions to Atmosphere
Stream
TABLE AA-III
NATIONAL EMISSIONS INVENTORY
ADIPIC ACID PRODUCTION
VIA
NITRIC ACID OXIDATION OF CYCLOHEXANOL/CYCLOHEXANONE
5-1
65,000
Reactor Vent
Page 1 of 4
Combined
HN03 One &
Prod Purification Vent
Flow - Ibs./hr.
Flow Characteristic, Continuous or Intermittent
if Intermittent, hrs./yr. flow
Composition, Ton/ton of Adipic Acid
Nitric Oxide
Nitrogen Dioxide
Nitrous Oxide
Nitrogen
Oxygen
Carbon Monoxide
Carbon Dioxide
Water
Adipic Acid
Nitric Acid
7796
Continuous
.00363
.33846
.06726
.01539
.05286
.00215
Unknown
Continuous
.00008
Vent Stacks
Number
Height - Ft.
Diameter - Inches
Exit Gas Temp. - F°
SCFM/Stack
Emission Control Devices
Ab sorber/S crubber
Incinerator/Flare
Condensor/K. 0. Drum
Other
Analysis
Date or Frequency of Sampling
Tap Location
Type of Analysis
Odor Problem
Summary of Air Pollutants
Hydrocarbons, Ton/Ton of Adipic Acid
Particulates, Ton/Ton of Adipic Acid
NOX - Ton/Ton of Adipic Acid
SOX - Ton/Ton of Adipic Acid
CO - Ton/Ton of Adipic Acid
Yes
1
140
42
70
1260
Yes - AA-1
Varies
Phenoldisulfonic Acid
No
0
0
•00371
0
0
Yes
1
63
8
110
Unknown
Yes - AA-2
Never
None
Estimate
No
-------
TABLE AA-III
Plant - EPA Code No.
Capacity, Tons of Adipic Acid/Yr.
Average Production, Tons of Adipic Acid/Yr.
Range in Production - 7, of Max.
Emissions to Atmosphere
Stream
Flov - Lbs./Hr.
Flow Characteristic, Continuous or Intermittent
if Intermittent, Hrs./Yr. Flow
Composition, Ton/ton of Adipic Acid
Nitric Oxide
Nitrogen Dioxide
Nitrous Oxide
Nitrogen '
Oxygen
Carbon Monoxide
Carbon Dioxide
Water
Adipic Acid
Nitric Acid
Vent Stacks
Number
Height - Ft.
Diameter - Inches
Exit Gas Temp. - F°
SCFM/Stack
Emission Control Devices
Absorber/Scrubber
Incinerator/Flare
Condenser/K. 0. Drum
Other
Analysis
Date or Frequency of Sampling
Tap Location
Type of Analysis
Odor Problem
Summary of Air Pollutants
Hydrocarbons, Ton/Ton of Adipic Acid
Participates, Ton/Ton of Adipic Acid
NOX, Ton/Ton of Adipic Acid
SOx, Ton/Ton of Adipic Acid
CO , Ton/Ton of Adipic Acid
NITRIC
Reactor
Emergency
Vent
>-i2,500
Intermittent
-"0.1
•^.00001
t-. 00001
.£.00001
•^.00001
^.00001
•^.00001
/". 00001
Yes
2
100
24
170
1000
No
Never
None
Calc.
No
NATIONAL EMISEIONT INVENTORY
ADIPIC ACID PRODUCTION
VIA
ACID OXIDATION OF CYCLOHEXANOL/CYCLOHEXANONE Pag.
5-2
270,000
0
Adipic Acid
Reactor Off-Gas Prod. Purification Drier
Vent Vent
5567 2903 80.963
Continuous Continuous Continuous
. 00005 . 00003
. 00008 . 00005
). 07564 ). 03954 ) 1 . 12003
) ) )
.00376 .00185 .03659
.00014
Yes Yes No
2 3
80 90
12 12
120 120
^ 625 ^220
Yes - AA-3 Yes - AA-4 Yes - AA-5
Never Never Never
None None
Calc. Calc. Calc. or Est.
No No No
0
.00014
.0300
0
0
Adipic Acid
Melter
Vent
2220
Continuous
.03171
^.00001
*£. 00001
Never
None
Calc.
No
Nitric" Acid
Recovery
Vent
58,550
Continuous
.0110
.0169
.2971
.4521
.0141
.0451
Yes
2
85
8
180
•"390
Yes - AA-6
Yes
1
75
4
80
No
Accessible
Various
No
-------
Plant - EPA Code No.
Capacity - Tons of Adipic Acld/Yr.
Average Production, Tons of Adipic Acid/Yr.
Range in Production - % of Max.
Emissions to Atmosphere
Stream
Flow - Lbs./Hr.
Flow Characteristic, Continuous or Intermittent
if Intermittent, Hrs./Yr. Flow
Composition - Ton/Ton of Adipic Acid
Nitric Oxide
Nitrogen Dioxide
Nitrous Oxide
Nitrogen
Oxygen
Carbon Monoxide
Carbon Dioxide
Water
Adipic Acid
Nitric Acid
Vent Stacks
Number
Height - Ft.
Diameter - Inches
Exit Gas Temp. F°
SCFM/Stack
Emission Control Device
Absorber/Scrubber
Incinerator/Flare
Condenser/K. 0. Drum
Other
Analysis
Date or Frequency of Sampling
Sample Tap Location
Type of Analysis
Odor Problem
Summary of Air Pollutants
Hydrocarbons, Ton/Ton of Adipic Acid
Particulates, Ton/Ton of Adipic Acid
NOX, Ton/Ton of Adipic Acid
EOX, Ton/Ton of Adipic Acid
CO , Ton/Ton of Adipic Acid
TABLE AA-III
NATIONAL EMISSION? INVENTORY
ADIPIC'ACID PRODUCTION
VIA
KTTP.TC ACID OXIDATION OF CYCLOHEXANOL/CYCLOHEXANONE
Page 3 of 4
Reactor
Vent
30,000
Continuous
5-3
150,000
0
HN03 Recovery
Vent
5,000
Continuous
5-4 '
40,000
40,000
Prod. Purif.
Vent
2.6,000
Continuous
Pneumatic
Conveyor
Vent
13,500
Continuous
0
Process (B)
Vent
Header
5597
Continuous
Adipic Acid
Drier
Vent
45,169
Continuous
Heavy Ends
Incinerator
Flue Gas
8866
Continuous
. \J£.J?
.2464
.45155
.05218
.14650
.01204
). 00010
)
)1. 00334
>
No
Yes - AA-7
+ steam boiler
Infrequently
Mass Spec.
No
Yes AA-8
Never
None
Calc.
No
0
.00009
.026
0
0
0
). 86957
.00009
Yes - AA-9
+ bag filter
Never
None
Calc.
No
). 45155
Yes
1
64
36
1832°
Yes
1
64
36
150°
Yes
1
64
36
150'
Yes - AA-10
+ cyclone sep.
Never
Estimate
No
,06834
.36274
.08299
.00046
.04514
No (C)
Yes (C)
Infreauent
GLC
No
14.43000
1
.08640
.00050
Yes
1
33
18
160
10,200
Yes - AA-11
.65516
.04047
.11130
.07968
Yes
1
34
48
1400
2,000
Yes - AA-12
+ cyclone sep
Never
None
Estimate
No
0
.00050
.003
0
.00046
Never
None
Calc
No
-------
TABLE AA-IH page 4 of 4
EXPLANATION OF NOTES
NATIONAL EMISSIONS INVENTORY
ADIPIC ACID PRODUCTION
VIA
NITRIC ACID OXIDATION OF CYCLOHEXANONE/CYCLOHEXANOL
A) Operator states that this stream is sent to boiler house and used as
'air' for burners, where upon an unknown amount of NOX » N2 + 02-
Composition reported in Table III (ton/ton) is based on assumption
that NOX is reduced by 20% by this treatment. Actual NOX concentration
may increase or (under special conditions) be reduced by up to 907».
B) Operator states that this stream is sent to HMD plant 'thermal oxidizer'
It is assumed that this device is especially designed for NO reduction.
Consequently, a NO reduction of 707o (which is reported performance of
device AA-8) has been assumed and the NO concentration reported in
this column is correspondingly decreased.
C) No vent stack for this stream in adipic acid plant. Stream sent to
thermal oxidizer in HMD plant.
-------
TABLE AA-IV
ABSORBERS/ECRUBBEFS
EPA Code No. for plant, using
Flov Diagram (Fig. ID Stream T.U.
Device I.D No.
Controls Emission ot -
Scrubbing/Absorbing Liquid
Type - Spray
Packed Column
Column v/trays
Number of trays
Kind of tray
Plenum Chamber
Other
Scrubbing Absorbing Liquid Rate - i PM
Design Temp. (Operating Temp.1 F°
Gas Rate, SCFM (Ib./hr.1
T-T Height, Ft.
Diameter, Ft.
Vashed Gases to Stack -
Stack Height - Ft.
Stack Diameter - Inches
Installed Cost - Mat'l. & Labor - S
Installed Cost Based on - "year" - dollars
Installed Cost - c/lb. of Adipic .\cid/Yr.
Operating Cost -Annual (1972)
Value of Recovered Product; $/yr.
Net Operating Cost - Annual, $
Net Operating Cost - c/lt>- of Adipic Acid
Efficiency - V SE
INCINERATION DEVICfcb
EPA Code No. for plant using
Flow Diagram (Fig. II) Stream I.D.
Device I.D. No.
Type of Compound Incinerated
Type of Device - Flare
Incinerator
Other
Material Incinerated, TCFM (Ib./hr.)
Auxilliary Fuel Req'd. 'excl. pilot)
Type
Rate - BTU/hr.
Device or Stack Height - Ft.
Installed Cost - Mat'l. & Labor - S
Installed Cost Based on "vear" dollars
Installed Cost - c/lb. of Adipic Acid/Yr.
Operating Cost - Annual - $ (1972)
Operating Cost - /Ib. of Adipic Acid
Efficiency - CCP - 7.
Efficiency - SEPR - 7,
CATALOG OF EMISSION CONTROL DEVICES
I'MPIC ACID PRODUCTION VIA NITRIC ACID OXIDATION OF CYCLOHEXANOL/CYCLOHEXANONE F
5-1
AA-1
NOX
Vater
Kot Specified
4
100
1204
Yes
140
42
360,000
1965-1970
.2769
57,000
74,000
- 17,000
95.9% (NOX)
Reactor Vent
-------
TABLE AA-IV
CATALOG OF EMISSION CONTROL DEVICES
ADI PIC ACID PRODUCTION' VIA "ITRIC ACID OXIDATION OF CYCLOHEXANOL/CYCLOHEXANONE page 2 of 4
"Finished1 Product Operations
Conveying, Drying, Melting, etc.
ABSORBERS /SCRUBBERS
EPA Code No. for plant using
Flow Diagram (Fig. II) Stream T.I),
Device I.D. No.
Controls Emission of -
Scrubbing/Absorbing Liquid
Type - Spray
Packed Column
Column w/trays
Number of trays
Kind of tray
Plenum Chamber
Other
Scrubbing Absorbing Liquid Rate - GPM
Design Temp, (operating Temp.) F°
Gas Kate, SCFM (Ib./hr.)
T-T Height, Ft.
Diameter, Ft.
Washed Gases to Stack -
Stack Height - Ft.
Stack Diameter - Inches
Installed Cost - Mat'l. & Labor - S
Installed Cost - Based on - "year" - Dollars
Installed Cost - C/lb. of Adipic Acid/Yr.
Operating Cost - Annual, S (1972)
Value of Recovered Product, $/Yr.
Net Operating Cost - Annual, $
Net Operating Cost - c/lb. of Adipic Acid
Efficiency - % SE
INCINERATION DEVICES
EPA Code No. for plant using
Flow Diagram (Fig. II) Stream T.D.
Device I.D. No.
Type of Compound Incinerated
Type of Device - Flare
Incinerator
Other
Material Incinerated, SCFM (Ib./hr.)
Auxilliary Fuel Req'd (excl. pilot)
Type
Rate - BTU/hr.
Device or Stack Height - Ft.
Installed Cost - Mat'l. & Labor - $
Installed Cost Based on "year" Dollars
Installed Cost - C/lb. of Adipic Acid/yr.
Operating Cost - Annual - S (1972)
Operating Cost - c/lb. of Adipic Acid
Efficiency - CCR - If,
Efficiency - SERR - 7.
'T
5-2
_E,
AA-5
Adipic Acid Dust
Water
5-2
Jfc,
AA-6
HN03 & Adipic Acid
Water
5
120
18,000
15
10
No
25,000
1960
3500
0
3500
90
3
200
425
5.25
2
Yes
85
8
15,000
1967
1500
0
1500
90+
-------
TABLE AA-IV
CATALOG OF EMISSION CONTROL DEVICES
ADIPIC ACID PRODUCTION VIA NITRIC ACID OXIDATION OF CYCLOHEXANONE/CYCLOHEXANOL
Page 3 of 4
CYCLONES
EPA Code No. for plant using
Flow Diagram (Fig. II) Stream I
Device I.D. No.
Controls Emission of
T-T Height - Ft.
Diameter - Ft.
Adipic Acid
Puri fication
'Finished' Product Operations
Drying, Conveying, Melting, etc.
No. of Stages
Installed Cost - Mat'l.
& Labor
D.
- $
1 - $
Installed Cost hased on - "year"
Installed Cost - c/lh. of Adipic Acid/Yr.
Operating Cost - Annual - $ (1972)
Value of Recovered Product, $/Hr.
Net Operating Cost, $/Yr.
Net Operating Cost, r/Lb. of Adipic Acid
Efficiency - % SE
-3
AA-10
Adipic Acid Dust
63,000
1964 — 1966
.0210
100
5-4
.JK
AA-11
Adipic Acid Dust
18
5.5
30,000
1967
.0375
2000
3300
- 1300
93.8
BAG FILTERS
EPA Code No. for plant using
Flov Diagram (Fig. II) Stream I.D.
Device I.D. No.
Controls Emissions of
Number of Compartments
Number of bags per compartment
Bag Cloth Material
Total Bag Area - Ft2
Design (operating) Temp. - F°
Design (operating) press - psig
Installed Cost - Mat'l. {< Labor, S
Installed Cost Based on - "Year" - Dollars
Installed Cost, c/lb. of Adipic Acid/Yr.
Operating Cost - Annual - $ (1972)
Value of recovered product - $/yr.
Operating Cost - Annual - S (1972)
Value of Recovered product - $/yr.
Net Operating Cost - S/Yr.
Net Operating Cost - c/lb. of Adipic Acid
Efficiency - "L SE
5-3
AA-9
HN03 + Adipic Acid Dust
28,000
1967
.0093
HN03 - 90%, Dust - 1007.
-------
TABLE AA-IV Page 4 of 4
EXPLANATION OF NOTES
CATALOG OF EMISSION CONTROL DEVICES
ADIPIC ACID PRODUCTION
I This device consists of two identical scrubbers. Costs reported are
total costs.
II No note.
Ill This device consists of three identical scrubbers. Costs reported are
total costs.
IV Device consists of dust scrubber and cyclone but no description given
of either.
-------
TABLE AA-V
Current
Capacity
Marginal
Capacity
Current
Capacity
on-stream
in 1980
NUMBER OF NEW
Demand
1980
PLANTS BY 1980
Capacity (1)
1980
Capacity
to be
Added
Economic
Plant
Size
Number
Of
New Units
1430 160 1270 1900 2200 930 150 6-7
Note:
General - All capacities in MM Lbs./Yr.
(1) 1980 capacity based on growth rate of 5.5% per year as predicted
by Chem. Marketing, April 24, 1972.
-------
TABLE AA-VI
EMISSION SOURCE SUMMARY
Pollutant Source
"Finished" Product-
Product Purification Operations -
Reactor and Conveying, Fugitive
Off-Gas Nitric Acid Recovery Drying, etc. Emissions
Hydrocarbon x
Particulate .00005 .00010
NO,, .0037 .017 Negligible
X.
SOK j
CO .00010 ""
Total
0
.00015
.0207
0
.00010
Note: Pollutant quantities in Ib./lb. of adipic acid.
-------
TABLE AA-VII
WEIGHTED EMISSION RATES
deal: Adipic Acid
ess: HNC>3 Oxidation
eased Capacity by 1980: 930 MM Lbs./Yr.
Pollutant Emissions Lb./Lb.
Hydrocarbon 0
Particulate .00015
NOX .0207
sox o
CO .00010
Increased Emissions Weighting
MM Lbs./Yr. Factors
0 80
. 140 60
19.25 40
0 20
.093 1
Weighted
Emissions
MM Lbs. /Yr.
0
8.4
770
0
0.1
Significant Emissions Index 778.5
-------
Adiponitrile via Butadiene
-------
Table of Contents
Section Page Number
I. Introduction AN-1
II. Process Chemistry AN-2
III. Plant Emissions AN-4
IV. Emission Control. AN-7
V. Significance of Pollution AN-9
VI. Adiponitrile Producers AN-10
List of Illustrations & Tables
Block Flow Diagram Figure AN-I
Net Material Balance Table AN-I
Gross Heat Balance Table AN-II
Emission Inventory Table AN-III
Catalog of Emission Control Devices Table AN-IV
Number of New Plants by 1980 Table AN-V
Emission Source Summary Table AN-VI
Weighted Emission Rates Table AN-VII
-------
AN-1
I. Introduction
Adiponitrile is an intermediate in the synthesis of nylon 6, 6; with this
use alone accounting for over 907o of all adiponitrile production. Several
routes to adiponitrile are available, but (in the U. S.) only three are
utilized at the present time. Primary raw materials for the three routes are:
(1) Butadiene
(2) Adipic Acid
(3) Acrylonitrile
In terms of process capacity, the process utilizing butadiene is pre-
eminent - and is the subject of this survey report.
Nitrogen oxides comprise the bulk of the air pollutants associated with
the butadiene process; with the major portion of them arising from the
incineration of nitrogenous waste materials. Of less importance, but still
significant, are the various hydrocarbon emissions generated by the chlorination
section of the plant. Additionally, several waste liquid streams are produced,
the most important of these being the waste brine produced by the chlorobutene
cyanation reaction. In general, air emissions from the subject process can
be characterized as moderate.
The current U. S. adiponitrile production capacity - for the butadiene
process - is estimated at 4.35 x 10° Ibs./yr. 1980 capacity is estimated to be
8.45 x 108 Ibs./yr.; assuming that the process maintains its present share of the
industry!s total capacity. However, the butadiene process operates from a
narrow base, with only one producer utilizing it, and the premise upon which
the 1980 estimate is based, may best be described as - tenuous.
-------
AN-2
In most of the petrochemical industry survey reports there is a brief 'process
description1 section. However, data sufficient to permit the provision of
such information in this report are not availabe, most probably because a
sole producer has better control over the dissemination of process information.
Consequently, the following discussion of process chemistry is substituted.
II. Process Chemistry
The production of adiponitrile from butadiene involves four distinct
reaction steps. They are:
I. Chlorination
CH2 = CH-CH = CH2 + C12 '"•'^ CH2 Cl - CHCl - CH = CH2
Butadiene Chlorine 3, 4 - Dichloro-1-Butene
Mol. Wt. 54.09 70.91 125.00
This reaction will procede readily in either the liquid or gas phase and
with or without a catalyst. It is believed that current commercial practice
is restricted to a copper chloride catalyzed vapor phase process, with
temperatures in the range of 150 to 350° C. Yields as low as 75% are reported
by some of the earlier (Circa 1962) references available. A (perhaps) more
realistic representation of commercial experience shows a (catalyzed) yield of
987»*, with the following distribution of useable isomers:
3, 4 - Dichloro - 1 - Butene
Cis 1, 4 - Dichloro - 2 - Butene
Trans - 1, 4 - Dichloro - 2 - Butene
II. Cyanation
CH2 Cl - CHCl - CH
CH2 + 2 NaCN
42%
157.
417,
987»
NC - CH2 - CH(CN)-CH = CH2 + 2 NaCl
3, 4 - Dichloro-1-Butene
Mol. Wt.
125.00
Sodium
Cyanide
49.01
3, 4 - Dicyano-1-Butene
106.13
Sodium
Chloride
58.45
The cyanation can be effected with either hydrogen cyanide or sodium
cyanide, with the latter preferred. The reaction takes place in an aqueous
media, and may be catalyzed with a cuprous cyanide complexing agent. The
yield for this step, including extraction and distillation losses, is about 9570.
III. Isomerization
A NC-CH2-CH(CN)-CH = CH2 —
3, 4 - Dicyano-1-Butene
Mol. Wt. 106.13
NC-CH2-CH=CH-CH2-CN
1, 4 - Dicyano-2-Butene
106.13
The above isomerization 'step' (III-A) apparently takes place more-or-less
simultaneously with the cyanation 'step1. (Of course only about 4070 of the
dicyanobutenes formed undergo this re-arrangement since the other 607« were derived
*Excluding processing losses.
-------
AN-3
from dichlorobutenes of the 'proper1 configuration - see Step I product
distribution). The 1, 4 dicyano-2-butene so formed exists in both the cis
and trans form. The trans form is a solid at processing conditions and some
sources report that is is "partially isomerized to a liquid isomer". That
reaction is shown below:
B NC-CH2-CH = CH-CH2-CN n > NC-d^-Cfi^-CH - CH-CN
(Trans only) 1, 4 - Dicyano-2-Butene 1, 4 - Dicyano-1-Butene
Mbl. Wt. 106.13 106.13
Information regarding the process conditions favoring this isomerization
(III-B) has not been found.
IV. Hydrogenation
NC-CH2-CH = CH-CH2-CN + H2 V NC-(CH2)4 - CN
1, 4 - Dicyano-2-Butene Hydrogen Adiponitrile
Mol. Wt. 106.13 2.02 108.15
The mixture of 1, 4 dicyano-1-butene and 1, 4 dicyano-2-butene is
hydrogenated over a palladium catalyst at 100° C to 300° C. An early reference
states that at 25 atmospheres the yield is 96%.
-------
AN-4
III. Plant Emissions
A. Continuous Air Emissions
1. Chlorination Section Process Vents
The respondent reports three streams in this category. All
contain butadiene and/or various chlorinated hydrocarbons. All
three are relatively insignificant - with total emissions of
approximately .002 Ib./lb. of hydrocarbon.
2. Chlorination Section Storage Tank Vents
The two tank vents reported for this plant section are both
nearly 100 percent nitrogen, and thus, essentially non-polluting.
3. Cyanide Snythesis Section Process Vents
This source contributes over 70 percent (on a weighted basis)
of all the air emissions produced by the process. The vent consists
of the combustion products from three incinerators and a boiler.
In lieu of information to the contrary it has been assumed, that,
upon combustion, 10 percent of the nitrogen in nitrogen containing
compounds, is oxidized to NOX. Emissions from this source are
.0379 Ibs./lb. of NOX.
4. Cyanation and Isomerization Section Process Vents
Table IV summarizes the twelve streams reported by the
respondent that fall into this category. Of the twelve, one
contains a relatively small amount of NOX (.021 Ibs./lb.) and
five contain varying (small) amounts of benzene, with a total
benzene emission from this source of .008 Ibs./lb. The other six
streams contain only non-polluting substances; generally nitrogen,
air or water vapor.
5. Cyanation and Isomerization Section Tank Vents
The two tank vents reported for this section of the plant both
contain small amounts benzene. Total benzene from this source is
approximately .0002 Ibs./lb.
6. Hydrogenation Section Process Vents
The tv?o vents reported from this section of the plant contain
only insignificant amounts of ammonia and non-polluting compounds.
7. Boiler House Emissions
Waste liquids from the cyanation and isomerization section and
from the hydrogenation section are burned as fuel. 2100 Ibs./hr.
of liquid containing 23.4 wt. percent nitrogen and 1.6 wt. percent
chlorine and 11,000 Ibs./hour of liquid containing 21.2 percent
N£ and 0.6 wt. percent chlorine are thus disposed of from these two
sections. Emissions resulting from this operation amount to .00688
pounds aerosols (HC1) per pound and .05686 pounds NOX per pound
(assuming 10 percent of the nitrogen is oxidized to NOX).
-------
AN-5
B. Intermittent Air Emissions
The respondent reports no intermittent air emissions.
C. Continuous Liquid Wastes
1. Waste Brine
1200 GPM of waste brine is produced. Disposal is by on-site
deep well injection.
2. Spent Caustic
Although not reported as a liquid waste, it would appear that
a small amount of spent caustic would be produced through the
operation of several gas scrubbing devices, which the operator has
indicated do use caustic.
D. Solid Wastes
>
The operator reports disposal of 58,000 Ib./month of waste solids
via his plant land fill area. The solid waste includes 40,000 Ib./month
of miscellaneous trash such as packing material, waste paper etc. and
18,000 Ib./month of 'chemical' waste such as filter aid, coke, polymer,
etc.
E. Odors
In general the butadiene process for the production o(f adiponitrile
does not appear to be a process that has an odor problem.
The respondent reported no odor complaints in the past year. Most
of the reported odors are said to be detectable only on the plant
property and only at intermittent intervals. The materials contributing
to odors in this category have been identified as ammonia, chlorobutenes,
chlorine, butadiene, benzene and triethylamine. However, according to
the questionnaire, these emissions are well enough controlled to prevent
odor problems.
F. Fugitive Emissions
In addition to storage tank vents, which have been listed elsewhere,
two sources of fugitive emissions have been reported. The first is
the chlorination section refrigeration unit, which 'lopes' 1,700,000
Ibs./yr. of propane. This is equal to .00531 Ibs. of propane/lb. of
adiponitrile. The second source, described as butadiene losses due to
overloading the chlorination section recovery systems during start-ups
and shut-downs, amounts to 3,400,000 Ibs./yr. or .01062 Ib./lb. No
other significant source of fugitive emissions is thought to exist.
G. Other Emissions
The respondent reports that unknown quantities of emissions are
associated with the following:
(1) Power House stacks.
-------
AN-6
(2) Cooling tower.
(3) Steam exhaust from flash tanks, turbines and reciprocating
pumps.
(4) Exhuast from natural gas engines used to drive compressors,
-------
AN-7
IV. Emission Control
The emission control devices that have been reported as being employed by
the operator of the butadiene process adiponitrile plant are summarily described
in Table IV of this report. An efficiency has been assigned each device
whenever data sufficient to calcualte it have been available. Three types of
efficiencies have been calculated.
(1) "CCR" - Completeness of Combustion Rating
CCR = Lbs. of C>2 reacting (with pollutants in device feed)
Ib. of 02 that theoretically could react x
(2) "SE" - Specific Efficiency
SE = specific pollutant in - specific pollutant out
specific pollutant in
(3) "SERR" - Significance of Emission Reduction Rating
x 100
SERR = j;_(pollutant x weighting factor)in -^(pollutant x weighting
factor*) out
2L(pollutant x weighting factor*)in
*Weighting factor same as Table VII weighting factor.
Normally, a combustion type control device (i.e. incinerator, flare, etc.)
will be assigned both a "CCR" and an "SERR" rating, whereas a non-combustion
type device will be assigned an "SE" and/or an "SERR" rating. A more complete
description of this rating method may be found in Appendix V of this
report.
Although efficiency ratings for most devices are ehovn in Table IV, a few
general comments regarding adiponitrile pollution control device performance
seems in order:
Absorbers
Two thirds of the control devices reported consisted of, at least in
part, some type of absorber. They are identified in Table IV as devices
AN-4 to AN-12. With the exception of devices AN-5 and AN-7, all have
calculated SE and SERR efficiencies of 1007,. Absorber AN-5 is used in
conjunction with a chiller and K. 0. Drum. Its reported efficiency
of 56.6% is the combined efficiency of both pieces of equipment. The
specific efficiency, with regard to butadiene, is only 6570. Since
butadiene is quite easy to absorb (efficiencies of 98 + % being common),
one must assume that the particular device is either under-sized or was
designed to perform at some economic optimum - rather than at much higher,
though practical, hydrocarbon recovery rates. The other device vith a
low efficiency (AN-7 w/SE of 757.,) appears to suffer from a poor choice of .
absorbents. More specifically, spent caustic does not seem to be the
ideal absorbent for a mixture of butadiene, chloroprene and vinyl-
cyclohexane - there may be other process considerations for this seemingly
strange choice, but they have not been presented.
In summary, the performance of absorbers in adiponitrile pollution control
applications is excellent, and in most instances their SE and SERR
efficiencies approach 1007,.
-------
AN-8
Incinerators
With one exception, the composition of flare or incinerator flue
gases has not been reported. Consequently, efficiencies for these
devices have been estimated (by Houdry) rather than calculated from
actual performance data. This is necessary in order that an SEI (see
Table VII) may be calculated. The estimated efficiencies are based
on two assumptions:
I All hydrocarbons are completely combusted, producing only CC>2 and
H20.
II Ten percent of the nitrogen in the combusted material is oxidized
to NOX, with a mol. wt. of 40.
The true efficiencies of these devices remain unknown.
It is extremely unlikely that a change in operating conditions will lead
to a significant decrease in air pollution - considering the source of the
major portion of the pollutants.
Development work directed toward reductions in emissions from this process
falls into the following general categories.
(1) Substitute alternate disposal method for current practice of
burning nitrogenous materials.
(2) More efficient design and operation of devices currently being
utilized.
-------
AN-9
V. Significance of Pollution
It is recommended that no in-depth study of this process be undertaken at
this time. The reported emission data indicate that the quantity of pollutants
released as air emissions is less for the subject process than for other
processes that are currently being surveyed.
The methods outlined in Appendix IV of this report have been used to
estimate the total weighted annual emissions from these new plants. This
work is summarized in Tables V, VI and VII.
Published support for the Table V forecast of new plants has not been
found. The forecast is based on two assumptions:
(1) The butadiene process will account for 55.5 percent of 1980
adiponitrile capacity.
(2) Adiponitrile capacity in 1980 will be 111 percent of demand.
Unless there is a technological breakthrough it is believed that errors
inherent in these assumptions will not significantly alter the SEI.
On a weighted emission basis a Significant Emission Index of 3,007 has
been calculated in Table VII. This is less than the SEI's of many of the
other processes in the study. Hence, the recommendation to exclude an
in-depth study of adiponitrile production via the butadiene process from
the in-depth study portion of the overall scope of work.
-------
AN-10
VI. Producers of Adiponitrile ex Butadiene
Apparently there is some question as to the location and capacity of the
few plants utilizing the subject process. The capacities quoted below are,
in part, based on assumptions outlined elsewhere in this report. Plant
locations are based on published and private information.
1972 Capacity
Company Location MM Lb./Yr.
Du Pont Victoria, Texas 320
La Place, Louisiana !L15
Total 435
-------
PAGE NOT
AVAILABLE
DIGITALLY
-------
TABLE AN-I
ADI PONI TRUE
EX
BUTADIENE
MATERIAL BALANCE - T/T OF ADIPONITRILE
There are not sufficient published data available to permit the
presentation of a meaningful material balance. The reader is referred to
Section II - Process Chemistry - for more generalized information of this
type.
-------
TABLE AN-II
ADIPONITRILE
EX
BUTADIENE
GROSS HEAT BALANCE
There are not sufficient published data available to permit the
construction of a heat balance for this process.
-------
TABLE AN-III
NATIONAL EMISSIONS INVENTORY
ADIPONITRILE
EX
BUTADIENE
Page 1 of 6
Plant EPA Code No.
Capacity, Tons of Adiponitrlle/Yr.
Range in Production - 7, of Maximum
Emissions to Atmosphere
Stream
Flow - Lbs./Hr.
Flow Characteristic, Continuous or Intermittent
if Intermittent, Hrs./Yr. - Flow
Composition, Tons/Ton of Adiponltrile
Propane
Nitrogen
Oxygen
Carbon Monoxide
Carbon Dioxide
Water
NOX
Misc. Lt. HC
Butadiene
Chloroprene
Vinyl Cyclohexane
Benzene
Hydrogen Chloride
Hydrogen
Methane
Ammonia
Vent Stacks
Number
Height - Ft.
Diameter - Inches
Exit Gas Temp. - F°
SCFM/Stack
Emission Control Devices
Flare/Incinerator
Refrig. Cond/K. 0. Drum
Absorber/Scrubber
Other
Analysis
Date or Frequency of Sampling
Sample Tap Location
Type of Analysis
Odor Problem
Summary of Air Pollutants
Hydrocarbons, Ton/Ton of Adiponitrile
Particulates, Ton/Ton of Adiponitrile
NOX, Ton/Ton of Adiponitrile
SOX, Ton/Ton of Adiponitrile
CO , Ton/Ton of Adiponitrile
Fugitive Emiss.
from
Refrig. Unit
1,700,000/Yr.
Intermittent
.00531
No
None
None
No
6-3
160,000
0
Cyanide Sect.
Vent Inciner.
Flue Gas
Chlorination
Sect. By-Product
Vent
Chlorination
Sect Process
Vent
259,933
Continuous
4.88321
.54403
1.33472
.37903
Yes
4
164
16
140
30
175
6.5
90
6
95
AN-1 AN-2 AN-3 Yes
None
Calc'd.
No
See Continuation
650
Continuous
.01356
.00069
.00362
Yes
1
65
2
95
144
AN-4
Calcd.
No
82
Continuous
.00071
.00070
.00083
Yes
1
90
1.5
122
AN-5
No
-------
TABLE AN-III
NATIONAL EMISSIONS INVENTORY
ADIPONTTRILE
EX
BUTADIENE
Page 2 of 6
Plant EPA Code No.
Capacity, Tons of Adiponitrile/Yr.
Range In Production - 7, of Maximum
Emissions to Atmosphere
Stream
Flow - Lbs./Hr.
Flow Characteristic, Continuous or Intermittent.
if Intermittent, Hrs./Yr. Flow
Composition, Tons/Ton of Adiponitrile
Propane
Nitrogen
Oxygen
Carbon Monoxide
Carbon Dioxide
Water
NOX
Misc. Lt. HC
Butadiene
Chloroprene
Vinyl Cyclohexane
Benzene
Hydrogen Chloride
Hydrogen
Methane
Ammonia
Vent Stacks
Number
Height - Ft.
Diameter - Inches
Exit Gas Temp. - F°
SCFM/Stack
Emission Control Devices
Flare/Incinerator
Refrig. Cond/K. 0. Drum
Absorber/Scrubber
Other
Analysis
Date or Frequency of Sampling
Sample Tap Location
Type of Analysis
Odor Problem
Summary of Air Pollutants
Hydrocarbon, Ton/Ton of Adiponitrile
Particulates, Ton/Ton of Adiponitrile
NOX, Ton/Ton of Adiponitrile
SO^, Ton/Ton of Adiponitrile
CO , Ton/Ton of Adiponitrile
6-3
160,000
0
Chlorinat ion
Sect. Fugitive
Emissions & Emergency Vents
3,400,000 Yr.
Intermittent
.01062
No
No
Calc'd.
No
Chlorination
Sect. Storage
Vent
100
Continuous
.00275
Yes
1
90
8
120
23
AN-6 (B)
Calc'd.
No
See Continuation
Chlorination
Sect. Vac.
Ejector Disch.
124
Continuous
.00284
.00008
.00015
.00022
.00008
Yes
1
90
8
120
26
AN-7 CB)
Calc'd.
No
-------
TABLE AN-III
Plant EPA Code No.
Capacity, Tons of Adiponitrile/Yr.
Range in Production - % of Maximum
Emissions to Atmosphere
Stream
Flow - Lbs./Hr.
Flow Characteristic, Continuous or Intermittent
if Intermittent, Hrs./Yr. Flow
Composition, Tons/Ton of Adiponitrile
Propane
Nitrogen
Oxygen
Carbon Monoxide
Carbon Dioxide
Water
NO
Misc. Lt. HC
Butadiene
Chloroprene
Vinyl Cyclohexane
Benzene
Hydrogen Chloride
Hydrogen
Methane
Ammonia
Vent Stacks
Number
Height - Ft.
Diameter - In.
Exit Gas Temp. - F°
SCFM/Stack
Emission Control Devices
Flare/Incinerator
Refrig. Cond./K. 0. Drum
Absorber/Scrubber
Other
Analysis
Date or Frequency of Sampling
Sample Tap Locaton
Type of Analysis
Odor Problem
Summary of Air Pollutants
Hydrocarbons, Ton/Ton of Adiponitrile
Particulates, Ton/Ton of Adiponitrile
N0x, Ton/Ton of Adiponitrile
SOX> Ton/Ton of Adiponitrile
CO , Ton/Ton of Adiponitrile
NATIONAL EMISSIONS INVENTORY
ADIPONITRILE
EX
BUTADIENE
6-3
160,000
0
Chlor inat ion
Section Storage
Tank Vent
67
Cont inuous
Cyanation &
1 someri zat ion
Process Vent
781
Continuous
C & I
Process Vent
92
Continuous
C & I
Process Vent
6429 fA)
Continuous
Page 3
C & I
Ejector Effl,
35
Conti nuous
of 6
C i I C & I
Process Vent Process Vent
? 36
Continuous Continuous
C & I
Process
Vent
36
Continuous
.00184
No
AN-8 (C)
.02101
.00045
Infrequently
Wet
.00022
.00230
Never
None
Calc'd.
No
(A)
.12583
.02576
.02120
.00381
00094
Never
None
Calc'd.
No
No
SEE CONTINUATION
.00006
.00013
.00086
.00013
.00086
Yes
1
70
6
140
115
No
Yes
1
55
3
158
No
Yes
1
175
6.5
AN-3
Yes
1
90
6
95
8
AN- 9
Yes
1
65
2
95
0.6
AN- 10
Yes
1
90
1.5
122
3.6
No
Yes
1
90
1.5
122
3.6
No
-------
TABLE AN-III
Plant EPA Code No.
Capacity, Tons of Adiponitrile/Yr.
Range in Production - /„ of Maximum
Emissions to Atmosphere
Stream
Flow - Lbs./Hr.
Flow Characteristic, Continuous or Intermittent
if Intermittent, Hrs./Yr. - Flow
Composition, Tons/Ton of Adiponitrile
Propane
Nitrogen
Oatygen
Carbon Monoxide
Carbon Dioxide
Water
NOX
Misc. Lt. HC
Butadiene
Chloroprene
Vinyl Cyclohexane
Benzene
Hydrogen Chloride
Hydrogen
Methane
Ammonia
Vent Stacks
Number
Height - Ft.
Diameter - Inches
Exit Gas Temp. - F°
SCFM/Stack
Emission Control Devices
Flare/Incinerator
Refrig. Cond./K. 0. Drum
Absorber/Scrubber
Other
Analysis
Date or Frequency of Sampling
Sample Tap Location
Type of Analysis
Odor Problem
Summary of Air Pollutants
Hydrocarbons, Ton/Ton of Adiponitrile
Particulates, Ton/Ton of Adiponitrile
N0x, Ton/Ton of Adiponitrile
SO , Ton/Ton of Adiponitrile
CO , Ton/Ton of Adiponitrile
C & I
Vac. Ejector
Disch.
115
Continuous
NATIONAL EMISSIONS INVENTORY
ADIPONITRILE
EX
BUTADIENE
6-3
160,000
0
C & I C & I
Process Vent Process Vent
58 92
Continuous Continuous
Page 4 of 6
C & I C & I
Process Vent Process Vent
1353 92
Continuous Continuous
C & I C & 1
Tank Vents Tank Vents
5 7
Continuous Continuous
.00316
No
No
.00159
.03718
No
AN-11 (D)
.00022
.00230
Yes
1
25
3
158
No
Yes
1
30
2
104
306
AN-12 (D)
.00009
.00022
00?30
Yes
1
25
3
158
No
.00003
No
No
.0000?
.00016
No
No
SEE CONTINUATION
-------
TABLE AN-III
NATIONAL EMISSIONS INVENTORY
APT PONT TRI1.E
EX
BUTAPTENE
Page 5 of b
Plant EPA Code No.
Capacity, Tons of Adiponi tri le./Yr.
Range in Production - I. of Maximum
Emissions to Atmosphere
Stream
Flov - Lbs./Hr.
Flov Characteristic, Continuous or Intermittent
if Intermittent, Hrs./Yr. - Flow
Composition, Tons/Ton of Adiponitrile
Propane
Nitrogen
Oxygen
Carbon Monoxide
Carbon Pioxide
Water
NOX
Misc. Lt. HC
Butadiene
Chloroprene
Vinyl Cyclohexane
Benzene
Hydrogen Chloride
Hydrogen
Methane
Ammonia
Vent Stacks
Number
Height - Ft.
Diameter - Inches
Exit Gas Temp. - F°
SCFM/Stack
Emission Control Pevices
Flare/Incinerator
Re frig. Cond./K. 0. Prum
Absorber/Scrubber
.Other
Analysis
Pate or Frequency of Sampling
Sample Tap Location
Type of Analysis
Odor Problem
Summary of Air Pollutants
Hydrocarbons, Ton/Ton of Adiponitrile
Particulates, Ton/Ton of Adiponitrile
N0x, Ton/Ton of Adiponitrile
SO Ton/Ton of Adiponitrile
fa-3
160,000
0
llydrogenation
Unit
Process Vent
241
Cont i nuous
Hydropenation
Unit
Ejector Pischarpe
384
Continuous
,01054
.00180
.00477
.00004
No
No
No
No
.02564
.00385
.40023
CO
Ton/Ton of Adiponitrile
-------
TABLE AN-III
NATIONAL EMISSIONS INVENTORY
ADIPONITRILE
EX
BUTADIENE
EXPLANATION OF NOTES Page 6 of 6
(A) Respondent reported composition of stream prior to combustion. Combustion
products estimated by Houdry.
(B) Devices AN-6 and AN-7 both consist of three identical scrubbers.
(C) Device AN-8 consists of six identical scrubbers.
(D) Devices AN-11 and AN-12 consist of tvo identical scrubbers.
-------
ABSORBERS/s CRUBB ERS
EPA Code No. for plant using
Flow Diagram (Fig. I) Stream I. 0.
Device I. D. No.
Control Emission of
Scrubbing/Absorbing Liquid
Type - Spray
Packed Column
Column w/trays
Number of Trays
Tray Type
Other
Scrubbing/Absorbin Liquid Rate - GPM
Design Temp. (Operating Temp.) F°
Gas Rate, SCFM (Lb./Hr.)
T-T Height, Ft.
Diameter, Ft.
Washed Gases to Stack
Stack Height - Ft.
Stack Diameter - Inches
Installed Cost - Mat'l. & Labor - $
Installed Cost Based on - "year" - dollars
Installed Cost - c/lb. of Adiponitrile - Yr.
Operating Cost - Annual, $ (1972)
Value of Recovered Product, $/Yr.
Net Operating Cost - Annual, $
Net Operating Cost - c/lb. of Adiponitrile
Efficiency - % - SE
Efficiency - 7, - SERR
TABLE AN-IV
CATALOG OF EMISSION CONTROL DEVICES
ADIPONITRILE EX BUTADIENE
CYANIDE SYNTHESIS
Page 1 of It
CHLORI NATION
6-3
/fis.
AN-4
Chlorinated HC
Vater
Shell & Tube
- 27
200
144
25
6-7
Yes
65
2
4,120,000
1963 - 1972
1,?8750
776.000
925.000
-149.000
N'e ga t i ve
100
100
INCINERATION DEVICES
EPA Code No. for plant using
Flov Diagram (Fig. I) Stream I. D.
Device I. D. No.
Type of Compound Incinerated
Type of Device - Flare
Incinerator
Other
Material Incinerated, SCFM (Ib./hr.)
Auxilliary Fuel Req'd. (excl. pilotl
Type
Rate - BTU/Hr.
Device or Stack Height - Ft.
Installed Cost - Mat'l. & Labor - $
Installed Cost Based on - "year" - dollars
Installed Cost - c/lb. of Adiponitrile - Yr.
Operating Cost - Annual - S (1972)
Operating Cost - c/lb. of Adiponitrile
Efficiency - % - CCR
Efficiency - 7. - SERR
6-3
AN-1
Lt. HC, NH3, HCN
833
Yes
Nat. Gas
75 CFH
164
12,770
1950
.00399
100
^ 95 (I)
6-3
AN-2
Lt. HC, NH3, HCN
5833
Yes
Nat. Gas
350 CFH
140
48,900
1958
.01528
160,700
.05021
100
~95 (I)
6-3
AN-3
Lt. HC, NH-. HCN
5833
Yes
Nat. Gas
5000 CFH
175
386,700
1950 - 1968
.12084
100
(I)
an
6-3
AN-4
Chlorinated HC
Yes
Hydrogen
672 CFH
65
4,120,000
1963 - 1972
1.2875
-149.000 CNet)
Ne ga t i ve
100
100
-------
TABLE AN-IV
CATALOG OF EMISSION CONTROL DEVICES
ADIPONITRILE EX BUTADIENE
CHLORINATION
Page 2 of 4
ABSORBERS/SCRUBBERS
EPA Code No. for plant using
Flow Diagram (Fig. I) Stream 1. D.
Device I. D. No.
Control Emission of
Scrubbing/Absorbing Liquid
Type - Spray
Packed Column
Column w/trays
Number of Trays
Tray Type
Other
Scrubbing/Absorbing Liquid Rate - CPM
Design Temp. (Operating Temp.) F°
Gas Rate, SCFM (Lb./Hr.)
T-T Height, Ft.
Diameter, Ft.
Washed Gases to Stack
Stack Height - Ft.
Stack Diameter - In.
Installed Cost - Mat'l. & Labor - $
Installed Cost Based on - "year" - dollars
Installed Cost - r/lb. of Adiponitrile - Yr.
Operating Cost - Annual, $ (1972)
Value of Recovered Product, $/Yr.
Net Operating Cost - Annual, S
Net Operating Cost - c/lb. of Adiponitrile
Efficiency - % - SE
Efficiency - 7. - SERR
ft-3
AN-5
Butadiene & l.t . HC
Oil
Not Specified
Yes
90
1.5
50,000
1950 - 1971
.01562
5,500
425.000
-419,500
Negative
56.6
56.6
6-3
Zfi^
AN-6
Chlorinated HC
Spent Caustic
Not Specified
C120)
22. 7
,.14
•• ?
Yes
90
8
14,500
1953
.00453
1,300
0
1,300
.00040
•T-lOO
A/100
6-3
^B\
AN-7
Chlorinated HC
Spent Caustic
Not Specified
020)
26
,.-14
^/2
Yes
90
8
14,500
1953
.00453
1,300
0
1,300
.00040
74.6
74.6
OV)
6-3
^
AN-8
Chlorinated HC
Water
12
''Ambient)
15
V;
No
12,000
1962
.00375
14.600
0
14,600
.00456
100
100
-------
TABLE AN-IV
CATALOG OF EMISSION CONTROL DEVICES
AD1PONITRILE EX BUTADIENE
page 3 of A
ABSORBERS/SCRUBBERS
EPA Code No. for plant using
Flow Diagram (Fig. I) Stream T. D.
Device I. D. No.
Control Emission of
Scrubbing/Absorbing Liquid
Type - Spray
Packed Column
Column v/trays
Number of trays
Tray type
Other
Scrubbing/Absorbing Liquid Rate - GPM
Design Temp. (Operating Temp.) F°
Gas Rate, SCFM (Lb./Hr.')
T-T Height, Ft.
Diameter, Ft.
Washed Gases to Stack
Stack Height - Ft.
Stack Diameter - In.
Installed Cost - Mat'l. & Labor - $
Installed Cost Based on - "year" - dollars
Installed Cost - c/lb. of Adiponitrile - Yr.
Operating Cost - Annual, 1007.
(V)
6-3
.CN.
AN-11
HCN
127, NaOH
167
9.8
0.7
No
3,000
.00093
9030
0
9030
.00282
,-^1007
(V)
6-3
_C^
AN-12
HCN
127. NaOH
f!04)
306
8
0.7
Yes
30
2
3.000
.00093
9030
0
9030
.00282
/V1007
-------
TABLE AN-IV
CATALOG OF EMISSION CONTROL DEVICES
ADIPQNITRILE
EX
BUTADIENE
EXPLANATION OF NOTES page 4 of 4
I. When respondent does not report composition of combustion products, it
is assumed that ten percent of the nitrogen in all nitrogenous
compounds is oxidized to NOX.
II. Device AN-4 is a combination incinerator/absorber/scrubber. Operating
and installed cost figures shown are for the entire device. Performance
efficiencies also refer to the overall performance of the device.
III. Device AN-5 used in conjunction with propane chiller.
IV. Device AN-8 consists of six identical scrubbers.
V. Device consists of two identical scrubbers.
-------
435
0
TABLE AN-V
Current
Capacity
Marginal
Capacity
NUMBER
Current
Capacity
on-stream
in 1980
OF NEW PLANTS
Demand*
1980
BY 1980
Capacity
1980
Capacity
to be
Added
Economic
Plant
Size
Number
of Nev
Units
435
760
845
410
100
Note: All capacities in MM Lbs./Yr.
*Based on assumption that butadiene process will account for 55.57» of adiponitrile production.
Total adiponitrile demand based on C. E. H. and Chem. Systems estimates of HMDA demand.
-------
TABLE AN-VI
EMISSION SOURCE SUMMARY
TON/TON OF ADIPONITRILE
Emission
Source*
Total
Cyanide
Chlorination Synthesis
Hydrocarbons .01791
Particulates & Aerosols
NO,, .0379
Cyanation
and
Isomerization
.00773
.00381
.02120
Boiler House
Combustion
Hydrogenation of Liquid Waste
.02564
.00004 .00688 .01073
.05686 .11596
SO,
CO
*Emissions from individual sections include fugitive emissions.
-------
TABLE AN-VII
WEIGHTED EMISSION RATES
Chemical Adiponitrile
Process Butadiene
Increased Capacity
Pollutant
Hydrocarbons
Aerosols
NOX
S0x
CO
by 1980 410 MM Lb./Yr.
Increased Emissions
Emissions, Lb./Lb. MMLbs./Yr.
.02564 10.51
.01073 4.40
.11596 47.54
0 0
0 0
Weighting
Factor
80
60
40
20
1
Weighted Emissions
MM Lbs./Yr.
841
264
1,902
0
0
Significant Emission Index = 3,007
-------
Adiponitrile via Adipic Acid
-------
Table of Contents
Section Page Number
I. Introduction AL-1
Ai —9
II. Process Description AJ" ^
AT _T
III. Plant Emissions AL J
A T _ C
IV. Emission Control ttlj D
V. Significance of Pollution AL~7
VI. Adiponitrile Producers AL-8
List of Illustrations & Tables
Flow Diagram Figure AL-I
Net Material Balance Table AL-I
Gross Heat Balance Table AL-II
Emission Inventory Table AL-III
Catalog of Emission Control Devices Table AL-IV
Number of Nev Plants by 1980 Table AL-V
Emission Source Summary Table AL-VI
Weighted Emission Rates Table AL-VII
-------
AL-1
I. Introduction
Adiponitrile is an intermediate in the synthesis of nylon 6,6; with this
use alone accounting for over 90% of all adiponitrile production. Several
routes to adiponitrile are available, but (in the U. S.) only three are
utilized at the present time. Primary raw materials for the three routes are;
(1) Butadiene
(2) Adipic Aicd
(3) Acrylonitrile
In terms of production capacity, the adipic acid process is pre-eminent
in Europe and second ranked in the United States. That process is the subject
of this report.
Nitrogen compounds, more specifically NHo and NOX, comprise the sum total
of air pollutants associated with the adipic acid process. Some tars are
produced, but they are disposed of by land fill methods and do not contribute
to air pollution. Additionally, several waste water streams are produced. In
general, air emissions from the subject process - based on information supplied
by the petrochemical questionnaire respondents - are very low.
The current U. S. adiponitrile ex adipic acid production capacity is 2.80 x
108 Ibs./yr. 1980 capacity is estimated to be 5.50 x 108 Ibs./yr. - assuming
that the subject process maintains its present share of the industry's total
capacity.
-------
AL-2
II. Process Description
Adipic acid, in the presence of a dehydrating catalyst, reacts vith
ammonia to form adiponitrile. The chemical reaction is:
HOOC (CH2)4 COOH + 2 NH3 » NC (CH2)4 CN -f 4 H20
Adipic Acid + Ammonia » Adiponitrile + Water
Mol. Wt. 146.14 17.03 108.15 + 18.02
Standard commercial practice is to conduct the reaction in the vapor
phase, utilizing a phosphorous containing compound as the catalyst.
Adipic acid is melted, heated to between 500 - 600° F and sparged into
the bottom of the number one reactor. In the reactor, the molten adipic acid
vaporizes and mixes with an excess of ammonia, which has also been sparged in.
The vapors pass up through reactor tubes packed with a mixture of phosphoric
acid and bone particles. The reactor effluent is cooled 75 - 100 F° and sent
to a vapor/liquid separator. The liquid from the separator is sent to reactor
No. 2, where it is revaporized and contacted with additional ammonia. The
tars and heavy ends formed in reactor No. 2 are rejected and the remainder
of the reaction products are combined with the vapor phase effluent from
reactor No. 1. The combined effluents pass on to the ammonia still where
ammonia, carbon dioxide and water are taken overhead; crude adiponitrile is
taken as a 'middle cut1 and unreacted adipic acid is taken as a bottoms product.
The ammonia overhead product is purified and recycled. The bottoms are
returned to reactor No. 1.
The crude adiponitrile, from the ammonia still 'middle cut', is processed
in a series of columns which dehydrate it and remove light and heavy ends.
Product adiponitrile is sent to storage, where it is maintained at 105 - 110° F
until it is used.
-------
AL-3
III. Plant Emissions
A. Continuous Air Emissions
1. Ammonia Recovery Section Vent
Both respondents report atmospheric emissions from this source.
The operator of plant EPA Code No. 6-1 burns these materials in
his plant flare. Estimated noxious emissions, based on the
assumption that ten percent of N becomes NOX, amount to .00027
Ibs. N0x/lb. of adiponitrile and constitutes the total amount of
air pollutants emitted by the plant. The operator of plant EPA
Code No. 6-2 reports the use of an absorber/scrubber (device AL-2,
Table IV) on this stream. This device operates with an efficiency
approaching 100 percent and pollutant emission is essentially nil.
2. Product Fractionation Vent
Both respondents report atmospheric emissions from this source.
The operator of plant EPA Code No. 6-1 burns these materials in a
"thermal oxidizer" (device AL-1, Table IV) and reports only trace
emissions of NOX in the flue gas. The operator of plant EpA Code
No. 6-2 reports only "trace" flow from this source, with 99 percent
of the "trace" flow - water and 'trace1 amounts of NOX.
3. Product Recovery Vent
Plant operator 6-2 reports discharging .0036 Ibs./lb of ammonia
from vacuum ejectors located in this area of his plant. According
to his report this emission constitutes his only significant release
of atmospheric pollutants. All reported streams are summarized in
Table III.
B. Intermittent Air Emissions
No intermittent air emissions were reported.
C. Continuous Liquid Wastes
Waste water in the amount of 16 GPM is 'treated and disposed1 by
plant 6-1. Plant 6-2 allocates its waste water production as follows:
NH3 Recovery 250 GPM
Purification 30 GPM
Product Recovery & Refining 5_ GPM
Total - 285 GPM
All 285 GPM are subject to "in-plant treating and processing".
No other liquid waste streams were reported.
D. Solid Wastes
The operator of plant EPA Code No. 6-1 reports the production of
10,400 Ibs./day of solid wastes. The wastes are 'disposed1 of by
"piling them" on the plant site. Plant 6-2 operator reports disposing
of 12,000 Ibs./day of waste solids by landfill on plant property. The
solid wastes consist, in part, of spent catalyst. Other components
were not identified.
-------
AL-4
E. Odors
In general, the adipic acid process for the production of adiponitrile
does not appear to be a process that has an odor problem.
Both respondents reported no odor complaints in the past year. In fact,
neither respondent admitted to the detection of any odors, at any time -
even on plant property. Despite this fact, it seems only reasonable to
expect the occassional presence of ammonia odors - at least on the plant
site.
F. Fugitive Emissions
Neither respondent offers an estimate of fugitive losses. The
operator of plant 6-2 summarizes the situation thusly: "NH_ handling has
the highest potential for possible emissions due to leaks. Since ammonia
is readily detectable, leaks are promptly corrected and do not represent
any appreciable loss".
G. Other Emissions
The only candidate for inclusion in this category would be the 0.02%
sulfur in the natural gas reported by operator 6-2. However, this amounts
to only one ton/yr. of sulfur, and is, therefore, insignificant.
-------
AL-5
IV. Emission Control
The emission control devices that have been reported as being employed
by the operators of the adipic acid process adiponitrile plants are summarily
described in Table IV of this report. An efficiency has been assigned each
device whenever data sufficient to calculate it have been available. Three
types of efficiencies have been calculated.
(1) "CCR" - Completeness of Combustion Rating
CCR = Ibs. of Oo reacting (with pollutants in device feed)
Ibs. of 02 theoretically capable of reacting x
(2) "SE" - Specific Efficiency
SE = specific pollutant in - specific pollutant out x ^QQ
specific pollutant in
(3) "SERR" - Significance of Emission Reduction Rating
SERR =^(pollutant x weighting factor*)in --^(pollutant x weighting
factor*)out
•^(pollutant x weighting factor*) in
*Weighting factor same as Table VII weighting factor.
Normally a combustion type control device (i.e. incinerator, flare, etc.)
will be assigned both a "CCR" and an "SERR" rating, whereas a non-combustion
type device will be assigned as "SE" and/or an "SERR" rating. A more
complete description of this rating method may be found in Appendix V of
this report.
Although efficiency ratings for all (both) devices reported are shown in
Table IV, a few general comments regarding adiponitrile pollution control device
performance seems in order:
Absorbers/Scrubbers
Device AL-2 is a combination absorber/scrubber. It is the only device
reported that belongs in the subject category. It is used to prevent
the emission of ammonia. Based on the infomation supplied by the operator
utilizing the device its efficiency (SE & SERR) is 100%.
Incinerators
The operator of plant EPA Code No. 6-1 utilizes two combustion devices
for pollution control; the plant flare and an incinerator. The incinerator,
a John Zink Thermal Oxidizer, is identified as device AL-1 in Table IV.
Based on flue gas analyses, this device is capable of converting all
contained nitrogen to N2, and hence, its efficiency (CCR & SERR) is 100%.
On the other hand, no information is given on the performance of the flare.
However-; in order to calculate an SEI (see Table VII).its performance or
efficiency must be estimated. The efficiency estimate is based on two
assumptions:
I All hydrocarbons are completely combusted, producing only C02 and
II The nitrogen in the combusted material is oxidized to NO , with a
X
-------
AL-6
mol. wt. of 40.
Thus, the effluent composition of the device vas calculated and
listed in Table III.
Based on the information supplied by the two respondents, emissions are
already so lov that further work in emission control seems unnecessary at
this time.
-------
AL-7
V. Significance of Pollution
It is recommended that no in-depth study of this process be undertaken.
The reported emission data indicate that the quantity of pollutants released
as air emissions is less for the subject process than for many other processes
studied to date.
The methods outlined in Appendix IV of this report have been used to
estimate the total weighted annual emissions from these new plants. This
work is summarized in Tables V, VI and VII.
Published support for the Table V forecast of new plants has not been
found. The forecast is based on two assumptions:
(1) The adipic acid process will account for 36 percent of 1980
adiponitrile capacity.
(2) Adiponitrile capacity in 1980 will be 111 percent of demand.
Errors inherent in these assumptions, unless they are several orders of
magnitude in size, cannot significantly alter the SEI.
On a weighted emission basis, a Significant Emission Index of 30 has been
calculated for the subject process. This is substantially lower than the SEI
of most of the processes studied. Hence, the recommendation to exclude an
in-depth study of adiponitrile production via the adipic acid process from the
in-depth study portion of the overall scope of work.
-------
AL-8
VI. Producers of Adiponitrile ex Adipic Acid
The capacities and plant locations listed belov are based on information
provided in the questionnaires and in the literature.
Capacity
Company Location 1967 1972
Celanese Corp. Bay City, Texas 45 ?
El Paso Products Odessa, Texas 27.5
Monsanto Pensacola, Florida 180
Est. Total 280
Note:
(1) Capacities in MM Lbs./Yr.
(2) Estimated 1972 capacity based in part on assumptions outlined in
Section V of this report.
-------
PAGE NOT
AVAILABLE
DIGITALLY
-------
TABLE AL-I
ADIPONITRILE
EX
ADIPIC ACID
MATERIAL BALANCE - T/T OF ADIPONITRILE
There are not sufficient published data available to permit the pre-
sentation of a meaningful material balance.
-------
TABLE AL-II
ADIPONITRILE
EX
ADIPIC ACID
GROSS REACTOR HEAT BALANCE
There are not sufficient published data available to permit the construction
of a detailed heat balance for this process. An estimate of the total reactor
heat flow shows:
Heat In*
Sum of steam, fired heaters
and heat exchange
Heat Out
Endothermic heat of reaction
Differential enthalpy
(Reaction products - feed)
BTU/Lb. of Adiponitrile
1490
434
I9JL6
1490
-w/60° temperature base.
-------
Plant EPA Code No.
Capacity, Tons of Adiponitr i le/Yr .
Range in Production - 7, of Max.
Emissions to Atmosphere
Stream
Flow - Lbs. /Hr.
Flow Characteristic, Continuous or Intermittent
if Intermittent, Hrs./Yr. Flow
Composition, Tons/Ton of Adiponitrile
Ammonia
Nitrogen
Oxygen
Carbon Dioxide
Water
Nitrogen Oxides
Vent Stacks
Number
Height - Ft.
Diameter - Inches
Exit Gas Temp. - F°
SCFM/Stack
Emission Control Devices
Flare /Incinerator
Absorber /Scrubber
Condenser/K. 0. Drum
Other
Analysis
Date or Frequency of Sampling
Sample Tap Location
Type of Analysis
Odor Problem
Summary of Air Pollutants
Hydrocarbons, Ton/Ton of Adiopnitrile
Aerosols " " " "
SOX
CO
NHj Recovery
Sect ion
Purge
20
Cont inuous
(A)
.00185
.000274
(Flare)
Yes
TABLE AL-III
NATIONAL EMISSIONS INVENTORY
ADIPONITRILE
EX -
ADIPIC ACID
6-1
13,750
0
Light Ends
Incinerator
Flue Gas
49,510
Cont inuous
10.97706
2.33098
.60096
.49169
Yes
1
13
57
1800
11.000
Yes AL-1
1968
Vent Line
<;LC
No
0
0
.000274
0
0
Never
C»lc'd
No
NHj Recovery
Section
Vent
209
Continuous
.00928
Yes
1
77
4
77°
A/30
Yes AL-2
Never
None
Estimate
No
6-2
90,000
0
Product
Purification
Vent
"Trace"
Continuous
Yes
1
77
5
212C
No
Never
None
Estimate
No
0
.00356
0
0
0
Product
Recovery Elector
Discharge
1380
Continuous
.00356
).0133
.04444
Yes
1
120
2
212
420
No
Never
None
Estimate
No
.A) Assumed combustion products. Reapo: dent report.' d v and composition of str'^arv prior to combustion (in flare).
by assuming 100 percent combustion and ten percent conversion of contained nitrogen to NOX with mol. vt. of 40.
Combustion products were estimated
-------
TABLE AL-IV
CATALOG OF EMISSION CONTROL DEVICES
ADIPONITRn.E EX ADTPIC ACID
ABSORBER/SCRUBBERS
EPA Code No. for plant using
Flow Diagram (Fig. I) Stream T.D.
Device I. D. No.
Control Emission of
Scrubbing/Absorbing Liquid
Type - Spray
Packed Column
Column w/Trays
Number of Trays
Tray Type
Other
Scrubbing/Absorbing Liquid Rate - GPM
Design Temp. (Operating Temp.) F°
Gas Rate, SCFM (Ib./hr.)
T-T Height, Ft.
Diameter, Ft.
Washed Gases to Stack
Stack Height - Ft.
Stack Diameter - In.
Installed Cost - Mat'l. & Labor - $
Installed Cost Based on - "year" - dollars
Installed Cost - c/lb. of Adiponitrile/Yr.
Operating Cost - Annual, $ (1972)
Value of Recovered Product, $/Yr.
Net Operating Cost - (fib. of Adiponitrile
Efficiency - 7. - SE
Efficiency - 7. - SERR
INCINERATION DEVICES
EPA Code No. for plant using
Flov Diagram (Fig. I) Stream I.D.
Device I. D. No.
Type of Compound Incinerated
Type of Device - Flare
Incinerator
Other
Material Incinerated, SCFM (Ib./hr.)
Auxiliary Fuel Req'd. (Excl. pilot)
Type
Rate BTU/Hr.
Device or Stack Height - Ft.
Installed Cost - Mat'l. & Labor - $
Installed Cost Based on - "year" - dollars
Installed Cost - c/lb. of Adiponitrile - Yr.
Operating Cost - Annual - $ (1972)
Operating Cost - (fib. of Adiponitrile
Efficiency - 'I, - CCR
Efficiency - "I, - SERR
AMMONIA RECOVERY SUCTION
o-2
. A^
AL-2 (I)
Ammon i a
Water
PRODUCT FRACTIONATION SECTION
40
(77)
14
6.5
2
Yes
77
4
20,000
1953 6, 1956
.0111
2,000
0
.0011
100
100
6-1
/&.
AL-1
Nitriles & Imines
(50)
Yes
Nat. Gas
130 MMCF/Yr.
13
80,000 (II)
1965
.2909
67,000
.2436
100
100
(I) Device AL-2 consists of five identical scrubbers. Indicated costs are total costs.
(II) Installed cost estimated by Houdry. Rcspondci t reported cost, excluding labor, of $41,265.
-------
280
TABLE AL-V
Current
Capacity
Marginal
Capacity
NUMBER
Current
Capacity
on-stream
in 1980
OF NEW PLANTS
Demand*
1980
BY 1980
Capacity
1980
Capacity
to be
Added
Economic
Plant
Size
Number
of
Nev Units
280
495
550
270
100
2-3
Note: All capacities in MM Lbs./Yr.
•'•Based on assumption that adipic acid process will account for 367n of adiponitrile production.
Total adiponitrile demand based on C.E.H. and Chem. Systems estimates of HMDA demand.
-------
Emission
TABLE AL-VI
EMISSION SOURCE SUMMARY
TON/TON OF ADIPONITRILE
Source
Ammonia
Recovery
Section
Product
Fractionation
Section
Fugitive
Emissions
Total
Hydrocarbons
Particulates & Aerosols
NO
x
SO,,
.00178
.000137
Negligible
.00178
.000137
CO
-------
TABLE AL-VII
Chemical
Process
Increased
Pollutant
WEIGHTED EMISSION RATES
Adiponitrile
Adipic Acid
Capacity by 1980 270 MM Lb./Yr.
Emissions Increased Emissions
Lb./Lb. MM Lbs./Yr.
Hydrocarbons 0 0
Aerosols
N0x
S0x
CO
.00178 .5
.000137 .04
0 0
0 0
Weighting
Factor
80
60
40
20
1
Weighted Emissions
MM Lbs./Yr.
0
28.8
1.5
0
0
Significant Emission Index = 30.3
-------
Appendix I, II, & III
-------
APPENDIX I
FINAL ADDRESS LIST
Air Products & Chemicals, Inc.
P. 0. Box 97
Calvert City, Kentucky
Attention:. Mr. Howard Watson
Allied Chemical Corp.
Morristown, New Jersey
Attention: Mr. A. J. VonFrank
Director Air & Water
Pollution Control
American Chemical Corp.
2112 E. 223rd
Long Beach, California 90810
Attention: Mr. H. J. Kandel
American Cyanamid Company
Bound Brook, New Jersey
Attention: Mr. R. Phelps
American Enka Corporation
Enka, North Carolina 28728
Attention: Mr. Bennet
American Synthetic Rubber Corp.
Box 360
Louisville, Kentucky 40201
Attention: Mr. H. W. Cable
Amoco Chemicals Corporation
130 E. Randolph Drive
Chicago, Illinois
Attention: Mr. H. M. Brennan, Director
of Environomental Control Div.
Ashland Oil Inc.
1409 Winchester Ave.
Ashland, Kentucky 41101
Borden Chemical Co.
50 W. Broad Street
Columbus, Ohio 43215
Attention: Mr. Henry Schmidt
Celanese Chemical Company
Box 9077
Corpus Christi, Texas 78408
Attention: Mr. R. H. Maurer
Chemplex Company
3100 Gulf Road
Rolling Meadows, Illinois 60008
Attention: Mr. P. Jarrat
Chevron Chemical Company
200 Bush Street
San Francisco, California 94104
Attention: Mr. W. G. Toland
Cities Service Inc.
70 Pine Street
New York City, NY 10005
Attention: Mr. C. P. Goforth
Clark Chemical Corporation
Blue Island Refinery
131 Kedzie Avenue
Blue Island, Illinois
Attention: Mr. R. Bruggink, Director
of Environmental Control
Columbia Nitrogen Corporation
Box 1483
Augusta, Georgia 30903
Attention: Mr. T. F. Champion
Attention: Mr. 0. J. Zandona
-------
Continental Chemical Co.
Park 80 Plaza East
Saddlebrook, NJ 07662
Attention: Mr. J. D. Burns
Cosden Oil & Chemical Co.
Box 1311 .
Big Spring, Texas 79720
Attention: Mr. W. Gibson
Dart Industries, Inc.
P. 0. Box 3157
Terminal Annex
Los Angeles, California 90051
Attention: Mr. R. M. Knight
Pres. Chemical Group
Diamond Plastics
P. 0. Box 666
Paramount, California 70723
Attention: Mr. Ben Wadsworth
Diamond Shamrock Chem. Co.
International Division
Union Commerce Building
Cleveland, Ohio 44115
Attention: Mr. W. P. Taylor, Manager
Environ. Control Engineering
Dow Badische Company
Williamsburg, Virginia 23185
Attention: Mr. L. D. Hoblit
Dow Chemical Co. - USA
2020 Building
Abbott Road Center
Midland, Michigan 48640
Attention: Mr. C. E. Otis
Environmental Affairs Div.
E. I. DuPont de Nemours & Co.
Louviers Building
Wilmington, Delaware 19898
Attention: Mr. W. R. Chalker
Marketing Services Dept.
Eastman Chemicals Products, Inc.
Kingsport, Tennessee
Attention: Mr. J. A. Mitchell
Executive Vice President
Manufacturing
El Paso Products Company
Box 3.986
Odessa, Texas 79760
Attention: Mr. N. Wright,
Utility and Pollution
Control Department
Enjay Chemical Company
1333 W. Loop South
Houston, Texas
Attention: Mr. T. H. Rhodes
Escambia Chemical Corporation
P. 0. Box 467
Pensacola, Florida
Attention: Mr. A. K. McMillan
Ethyl Corporation
P. 0. Box 341
Baton Rouge, Louisiana 70821
Attention: Mr. J. H. Huguet
Fibre Industries Inc.'
P. 0. Box 1749
Greenville, South Carolina 29602
Attention: Mr. Betts
-------
Firestone Plastics Company
Box 699
Pottstown, Pennsylvania 19464
Attention: Mr. C. J. Kleinart
Firestone Synthetic Rubber Co.
381 W. Wilbeth Road
Akron, Ohio 44301
Attention: Mr. R. Pikna
Firestone Plastics Company
Hopewell, Virginia
Attention: Mr. J. Spohn
FMC - Allied Corporation
P. 0. Box 8127
South Charleston, W. VA 25303
Attention: Mr. E. E. Sutton
FMC Corporation
1617 J.F.K. Boulevard
Philadelphia, PA
Attention: Mr. R. C. Tower
Foster Grant Co., Inc.
289 Main Street
Ledminster, Mass. 01453
Attention. Mr. W. Mason
G.A.F. Corporation
140 W. 51st Street
New York, NY 10020
Attention: Mr. T. A. Dent, V.P.
of Engineering
General Tire & Rubber Company
1 General Street
Akron, Ohio 44309
Georgia-Pacific Company
900 S.W. 5th Avenue
Portland, Oregan 97204
Attention: Mr. V. Tretter
Sr. Environmental Eng.
Getty Oil Company
Delaware City, Delaware 19706
Attention: Mr. Gordon G. Gaddis
B. F. Goodrich Chemical Co.
6100 Oak Tree Blvd.
Cleveland, Ohio 44131
Attention: Mr. W. Bixby
Goodyear Tire & Rubber Co.
1144 E. Market Street
Akron, Ohio 44316
Attention: Mr. B. C. Johnson, Manager
Environmental Engineering
Great American Chemical Company
650 Water Street
Fitchburg, Mass.
Attention: Dr. Fuhrman
Gulf Oil Corporation
Box 1166
Pittsburgh, Pennsylvania
Attention: Mr. D. L. Matthews
Vice President -
Chemicals Department
Hercules Incorporated
910 Market Street
Wilmington, Delaware
Attention: Dr. R. E. Chaddock
Attention: Mr. R. W. Laundrie
-------
Hooker Chemical Corporation
1515 Summer Street
Stamford, Conn. 06905
Attention: Mr. J. Wilkenfeld
Houston Chemical Company
Box 3785
Beaumont, Texas 77704
Attention: Mr. J. J. McGovern
Hystron Fibers Division
American Hoechst Corporation
P. 0. Box 5887
Spartensburg, SC 29301
Attention: Dr. Foerster
Jefferson Chemical Company
Box 53300
Houston, Texas 77052
Attention: Mr. M. A. Herring
Koch Chemical Company
N. Esperson Building
Houston, Texas 77002
Attention: Mr. R. E. Lee
Koppers Company
1528 Koppers Building
Pittsburgh, Pennsylvania 15219
Attention: Mr. D. L. Einon
Marbon Division
Borg-Warner Corporation
Carville, Louisiana 70721
Attention: Mr. J. M. Black
Mobay Chemical Corporation
Parkway West & Rte 22-30
Pittsburgh, Pennsylvania 15205
Attention: Mr. Gene Powers
Mobil Chemical Company
150 E. 42nd Street
New York, NY 10017
Attention: Mr. W. J. Rosenbloom
Monsanto Company
800 N. Lindbergh Boulevard
St. Louis, Missouri 63166
Attention: Mr. J. Depp, Director of
Corp. Engineering
National Distillers & Chem. Corp.
U.S. Industrial Chem. Co. Div.
99 Park Avenue
New York, NY 10016
Attention: Mr. J. G. Couch
National Starch & Chem. Co.
1700 W. Front Street
Plainfield, New Jersey 07063
Attention: Mr. Schlass
Northern Petrochemical Company
2350 E. Devon Avenue
Des Plaines, Illinois 60018
Attention: Mr. N. Wacks
Novamont Corporation
Neal Works
P. 0. Box 189
Kenova, W. Virginia 25530
Attention: Mr. Fletcher
-------
Olin Corporation
120 Long Ridge Road
Stamford, Conn.
Attention: Mr. C. L. Knowles
Pantasote Corporation
26 Jefferson Street
Passaic, New Jeresy
Attention: Mr. R. Vath
Pennwalt Corporation
Pennwalt Building
3 Parkway
Philadelphia, PA 19102
Attention: Mr. J. McWhirter
Petro-Tex Chemical Corporation
Box 2584
Houston, Texas 77001
Attention: Mr. R. Pruessner
Phillips Petroleum Co.
10 - Phillips Bldg.
Bartlesville, Oklahoma 74004
Attention: Mr. B. F. Ballard
Polymer Corporation, Ltd.
S. Vidal Street
Sarnia, Ontario
Canada
Attention: Mr. J. H. Langstaff
General Manager
Latex Division
Polyvinyl Chemicals Inc.
730 Main Street
Wilmington, Mass. 01887
Attention: Mr. S. Feldman, Director of
Manufacturing - Engineering
PPG Industries Inc.
One-Gateway Center
Pittsburgh, Pennsylvania 15222
Attention: Mr. Z. G. Bell
Reichold Chemicals Inc.
601-707 Woodward Hts. Bldg.
Detroit, Michigan 48220
Attention: Mr. S. Hewett
Rohm & Haas
Independence Mall West
Philadelphia, PA 19105
Attention: Mr. D. W. Kenny
Shell Chemical Co.
2525 Muirworth Drive
Houston, Texas 77025
Attention: Dr. R.L. Maycock
Environ. Eng. Div.
Sinclair-Koppers Chem. Co.
901 Koppers Building
Pittsburgh, Pennsylvania 15219
Attention: Mr. R. C. Smith
Skelly Oil Company
Box 1121
El Dorado, Kansas 67042
Attention: Mr. R. B. Miller
Standard Brands Chem. Industries
Drawer K
Dover, Delaware 19901
Attention: Mr. E. Gienger, Pres,
-------
Stauffer Chemical Co.
Westport, Connecticut
Attention: Mr. E. L. Conant
Stepan Chemical Company
Edens & Winnetka Road
Northfield, Illinois 60093
Attention: Mr. F. Q. Stepan
V.P. - Industrial Chemicals
Tenneco Chemicals Inc.
Park 80 Plaza - West 1
Saddlebrook, NJ 07662
Attention: Mr. W. P. Anderson
Texas - U.S. Chemical Company
Box 667
Port Neches, Texas 77651
Attention: Mr. H. R. Norsworth
Thompson Plastics
Assonet, Mass. 02702
Attention: Mr. S. Cupach
Union Carbide Corporation
Box 8361
South Charleston, W. Virginia 25303
Attention: Mr. G. J. Hanks, Manager
Environ. Protection
Chem. & Plastics Division
Uniroyal Incorporated
Oxford Management &
Research Center
Middlebury, Conn. 06749
The Upjohn Company
P. 0. Box 685
La Porte, Texas
Attention: Mr. E. D. Ike
USS Chemicals Division
U.S. Steel Corporation
Pittsburgh, Pennsylvania 15230
Attention: Mr. Gradon Willard
W. R. Grace & Company
3 Hanover SquarNew York, NY 10004
Attention: Mr. Robt. Goodall
Wright Chemical Corporation
Acme Station
Briegelwood, North Carolina 28456
Attention: Mr. R. B. Catlett
Wyandotte Chemical Corp.
Wyandotte, Michigan 48192
Attention: Mr. John R. Hunter
Vulcan Materials Company
Chemicals Division
P.O. Box 545
Wichita, Kansas 67201
Attention: H.M. Campbell
Vice-President, Production
Attention: Mr. F. N. Taff
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ENVIRONMENTAL PROTECTION AGENCY
Office of Air Programs
Research Triangle Park, North Carolina 27711
Dear Sir:
The Environmental Protection Agency, Office of Air Programs is
engaged in a study of atmospheric emissions from the Petrochemical
Industry. The primary purpose of this study is to gather information
that will be used to develop New Stationary Source Performance Standards
which are defined in Section 111 of the Clean Air Act as amended
December 31, 1970 (Public Law 91604). These new source standards will
not be set as part of this study but will be based (to a large extent)
on the data collected during this study.
A substantial part of the work required for this study will be per-
formed under contract by the Houdry Division of Air Products and Chemicals.
Several other companies not yet chosen will assist in the source sampling
phase of the work.
Very little has been published on atmospheric emissions from the
petrochemical industry. The first part of this study will therefore
rank the most important petrochemical processes in their order of importance
in regard to atmospheric emissions. The Petrochemical Emissions Survey
Questionnaire will be the primary source of data during the first phase.
This ranking will be based on the amount and type of emissions from the
process, the number of similar processes and the expected growth of the
process. A second in-depth phase of the study to document emissions more
completely will be based on information obtained through actual stack
sampling.
Attached you will find a copy of the petrochemical questionnaire
which you are requested to complete and return to the Enviromental
Protection Agency within forty-two (42) calender days.
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-2-
You are required by Section 114 of the Clean Air Act to complete
each applicable part of this questionnaire except for question II.4. and
II.5. These two questions are concerned with the water and solid waste
generated by the process itself not with that generated by the emission
control equipment. This information would be of a value to the EPA and
your answers will be appreciated.
This questionnaire is to be completed using the information presently
available to your company. We are not asking that you perform special
non-routine measurements of emissions streams. We are asking for results
of measurements that you have made or for estimates when measurements have
not been made. Where requested information is not available, please mark
sections "not available". Where the requested information is not appli-
cable to the subject process, mark the questionnaire sections "not
applicable". A sample questionnaire, filled out for a fictitious process
is enclosed for your guidance.
It is the opinion of this office that for most processes it should
be possible to answer all survey questions without revealing any
confidential information or trade secrets. However, if you believe that
any of the information that we request would reveal a trade secret if
divulged you should clearly identify such information on the completed
questionnaire. Submit, with the completed questionnaire, a written
justification explaining the reason for confidential status for each item
including any supportive data or legal authority. Forward a duplicate
of your claim and supporting material, without the questionnaire data, to
our counsel, Mr. Robert Baum, Assistant General Counsel, Air Quality and
Radiation Division, Environmental Protection Agency, Room 17B41,
5600 Fishers Lane, Rockville, Maryland 20852. Emission data cannot be
considered confidential.
Final authority for determining the status of the information resides
with the Enviromental Protection Agency. A reply describing the decision
reached will be made as soon as possible after receipt of the claim and
supporting information. During the period before the final determination
this office will honor any request to treat the questionnaire information
as confidential.
Information declared to be a trade secret is subject to protection
from being published, divulged, disclosed or made known in any manner
or to any extent by Section 1905 of Title 18 of the United States Code.
The disclosure of such information, except as authorized by law, shall
result in a fine of not more than $1,000 or imprisonment of not more
than one year, or both; and shall result in removal of the individual
from his office or employment.
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-3-
Although it should be noted that Section 114, Subsection C of the
Clean Air Act allows such information to be disclosed "to other officers,
employees, or authorized representatives of the United States concerned
with carrying out the Act or when relevant in any proceeding under this
Act," no confidential information will be revealed to any private concern
employed by the Environmental Protection Agency to assist in this study.
The handling and storage of information for which the determination
is pending or information which has been determined to be of a confidential
nature is carefully controlled. Preliminary control procedures require
that the material be labeled confidential and stored in a locked file.
The complete form should be mailed to:
Mr. Leslie B. Evans
Environmental Protection Agency
Office of Air Programs
Applied Technology Division
Research Triangle Park, NC 27711
It is possible that additional copies of this questionnaire which
will request information covering other petrochemical processes or
other plants using the same process and operated by your organization
will be sent to you in the course of this study. Clarification of items
contained in the questionnaire may be obtained from Mr. Evans by tele-
phone at 919/688-8146. Thank your for your help in this matter.
Sincerely,
Leslie B. Evans
Industrial Studies Branch
-------
Petrochemical Questionnaire
Instructions
I. Capacity. Describe capacity of process by providing the following:
1. Process capacity. Give capacity in units per year and units
per hour. An "actual" capacity is preferred but "published"
or "name plate" capacity will be satisfactory if such capa-
city is reasonably correct. Do not give production.
2. Seasonal variation. Describe any significant seasonal
variations in production.
As example an ammonia plant might produce more during
spring and winter quarters:
quarter Jan-Mar April-June July-Sept Oct-Dec Year
Total
% 40 20 10 30 100%
II. Process. Describe the process used to manufacture the subject
chemical by providing the following:
1. Process name. If the process has a common name or description,
give this. If any portion of the process (e.g., product
recovery method) has a common name, give this.
2. Block Diagram. Provide a block diagram of the process showing
the major process steps and stream flows.
(a) Show on block diagram all streams described below.
Identify each required stream by letter. (A,B,C, etc.)
In general the streams that must be identified are
(1) the gaseous emissions streams before and after
any control device and (2) the gaseous or liquid
streams which, after leaving the process site, produce
gaseous emissions during further processing or com-
bustion.
(1) Any gaseous waste streams before and after any
pollution device should be shown and identified.
(ii) Streams from rupture disks or pressure relief
valves which protect equipment from operating
upsets but discharges less than once every year
need not be shown.
(iii) Emissions from pressure relief systems that
normally discharge during power failures or
other emergencies should be shown, identified
by letter and labeled "emergency".
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-2-
(iv) Emissions from fueled heaters such as "heat
transfer medium" heaters, steam generators,
or cracking furnaces need not be shown if
they are fueled completely by fuels listed in
Question VII and are not used to incinerate by-
products or off gases.
(v) Emissions from Claus units associated with
process need not be shown. Stream to Claus
unit should be shown and identified with letter.
(vi) Emissions from a central power plant (or steam
plant) which burns a liquid fuel produced as a
by-product of this process need not be shown.
Such liquid fuel should be shown and identified
by letter.
(vii) Emissions from a central power plant (or steam
plant) which burns a gaseous fuel produced as
a by-product of this process need not be shown.
Such gaseous fuel should be shown and identified
by letter.
(b) Show all gaseous emission control devices. Identify
each control device on the block diagram by a three
digit number (101, 102, 103, etc.)
(c) Show all stacks or vents that vent streams listed in
(a) and (b) above. It a stack to vent discharges
emissions from more than one source, label this stack
or vent with a letter in sequence started in II.2.a.
(D,E,F, etc.) If a stack or vent discharges emissions
from only one source label the stack with the same
letter as the emission stream.
3. Raw material and product. Give approximate chemical com-
position and approximate amount (on yearly basis and at
capacity given in I.I) of all raw-materials, products
and by-products. If composition or amounts vary, give
ranges. Composition may be given in commonly accepted
terms when a chemical analysis would be inappropriate.
The description "light straight-run naphtha" would be
adequate.
4. Waste water. Is there a waste water discharge from this
process which is (eventually) discharged to a receiving
body of water? Is this waste water treated by you or
by others? Give the approximate volume and indicate
whether this is measured or estimated.
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-3-
5. Waste solids. Is there a waste solids discharge from this
process? How is it disposed of? Give the approximate
daily total of waste solids and indicate if this is mea-
sured or estimated.
III. Emissions (composition and flow) ; For each stream requested in
II. 2. a. and shown on the block diagram by letter provide the
following: (Use separate sheets for each identified location - 6
copies are provided) . All of the questions will not be appli-
cable for each stream.
As an example, question 10, odor problem, applies only to streams
which are emitted to the atmosphere.
1. Chemical composition and flow. Give composition as completely
as possible from information you have available. Do not omit
trace constituents if they are known. If anything (e.g. fuel)
is added upstream of any emission control devices, give the
chemical composition and flow prior to the addition, and give
the quantity and composition of the added material. If liquids
or solids are present (in gas stream) provide the composition
and amount of these also. Give flow volume (SCFM) , temperature
(F°) and pressure (psig or inches
2. Variation in chemical composition and flow. If average stream
composition or flow varies significantly over some period of
time during normal or abnormal operation, discuss this varia-
tion and its frequency. Relate this to the average and range
of composition given in III.l.
As examples :
"During start-up (once a month) the benzene is about 12% by
volume for one hour" or "the benzene can be expected to go
from 5% to 9% by volume during life of catalyst, the 'average'
figure given is about average over the catalyst life" or
"power failures occur about once each winter causing stream
A to increase from 0 to (initially) 50,000 Ibs/hr. , and about
8,000 Ibs is vented over a 15 minute period."
3. Production rate during sampling. If stream composition and
volume flow rates given in answer to questions III.l. and
III. 2. were measured at a plant production rate different
than the capacity of the plant given in I.I. give the rate
at which the measurements were made .
As example :
Figures given for this stream (A) were made when plant was
operating at 90% of capacity given in I.I.
-------
-4-
4. Methods used to determine composition and flow. Is information
from material balance, from sample and analysis, or other?
Describe briefly.
5. Sampling procedure. If samples have been taken, give summary
description of sampling procedure or give reference if
described in open literature.
6. Analytical procedure. If samples have been taken, give sum-
mary description of analytical procedure or give reference if
described in open literature.
7. Sampling frequency. How often is the stream sampled?
As Examples:
"continuous monitor" or "twice a shift for last 18 months"
or "once in the fall of 1943".
8. Confidence level. Give some idea how confident you are in
regard to compositions in III.l.
As examples:
"probably correct + 20%" or "slightly better than wild guess".
9. Ease of sampling. How difficult is it to sample this stream?
As examples:
"sample line runs into control room" or "sample port provided
but accessible only with 20-ft. ladder."
10. Odor problem. Is the odor of this emission detectable at
ground level on the plant property or off the plant property?
If odors carry beyond the plant property are they detectable
frequently or infrequently? Have you received a community
odor complaint traceable to this source in the past year?
Has the odorous material been chemically identified? What
is it?
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-5-
IV. Emission control device. Supply the following information for each
control device shown on the block diagram. (Use separate sheets
for each - 3 copies are provided).
1. Engineering description. Give brief description and process
sketch of the control device. Attach print or other des-
cription if you prefer. Show utilities used, steam produced,
product recovered, etc. Give manufacturer, model number and
size (if applicable). Give complete (applicable) operating
conditions, i.e. flows, temperatures, pressure drops, etc.
2. Capital cost of emission control system.
(a) Give capital cost for the emission control device as it
is described in IV.1. above; i.e., if equipment has been
modified or rebuilt give your best estimate of capital
cost of equipment now in service. For the total installed
cost give the approximate breakdown by year in which cost
was incurred.
As example:
Major equipment cost $155,000
Total installed cost $250,000
Year Cost
1963 $160,000
1964 40,000
1971 50,000
$250,000
(b) On the check list given mark whether the items listed are
included in total cost as given above. Give one sentence
explanation when required but do not give dollar amounts.
(c) Was outside engineering contractor used and was cost
included in capital cost?
(d) Was in-house engineering used and was cost included in
capital cost?
(e) Was emission control equipment installed when plant was
built?
3. Operating cost of emission control system. Give the best
estimate of cost of operating emission control system in
dollars per year with process operated at capacity given
in I.I. Other disposal (g) would include, as example,
the cost of incinerating a by-product stream which has no
value.
-------
-6-
V. Stack or vent description. Each stack or vent should have been
identified by letter on the block diagram. Provide the requested
information for each stack. Stack flow, V.A. should be entered
only when it is not possible to calculate this number by adding
gas flows given in III.l.
An example would be when an off gas from the process is discharged
into a power plant stack.
VI. Tankage. Give information requested for all tankage larger than
20,000 gallons associated with the process and normally held at
atmospheric pressure (include raw material, process, product and
by-product tankage). Method of vapor conservation (3.) might
include, as examples:
"none, tank vents to air"
"floating roof"
"vapor recovery by compression and absorption".
VII. Fuels. If fuels are used in the process give the amount used on
a yearly basis at capacity given in I.I. Do not include fuel used
in steam power plants. Give sulfur content. Identify each fuel
as to its source (natural gas pipeline, process waste stream,
Pennsylvania soft coal). Is the fuel used only as a heat source
(as with in-line burner)?
VIII. Other emissions. If there is a loss of a volatile material from
the plants through system leaks, valve stems, safety valves,
pump seals, line blowing, etc., this loss is an emission. In a
large complex high pressure process this loss may be several per-
cent of the product. Has this loss been determined by material
balance or other method? What is it? Give best estimate.
IX. Future plans. Describe, in a paragraph, your program for the
future installation of air pollution control equipment for this
unit or for future improvements in the process which will reduce
emissions.
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OMB Approval Number 158 S 72019
This example questionnaire has been
completed for a fictitious company
and process.
Example
Questionnaire
Air Pollution Control Engineering and Cost Study of the Petrochemical Industry
Please read Instructions before completing questionnaire.
Subject chemical: Pyrrole •
Principal by-products ; Pyrrolidone
Parent corporation name; Orivne Petrochemical Co. __
Subsidiary name: Noissime Division
Mailing address: P.O. Box 1234
Rianaelc, North Carolina. 27700
Plant name: Rianaelc Plant
Physical location: 30 miles N.W. Durham. North Carolina
(include county and
air quaility control
region) Orange County; Eastern Piedmont Intrastate (Region IV)
Person EPA should contact regarding information supplied in this questionnaire
Name: John Doe
Title: Supervisor of Process Development
Mailing address:_ Noissime Division of P.P.C.
P.O. Box 1234
Rianaelc, North Carolina. 27700
Telephone number: 919 XXX XXXX
Date questionnaire completed: May 30, 1972
-------
-2-
I. Capacity.
1. Process capacity, (not production)
80.000.000 Ibs. per year
10.000 Ibs. per hour
2. Seasonal variation, (of production)
quarter 1 2
year
total
30 20 20 30 100%
-------
STACK:
A
AIR
COMPRESSION
•v— — - -
FUEL
PYRROLIDINE
STORAGE
PYRROLE
STORAGE
PYRROLIDONE
STORAGE
HEAT EXCHANGERS
&
FLUID BED CATALYTIC
REACTORS
RECYCLE
PRODUCT
RECOVERY
&
PURIFICATION
HEAVY
ENDS
-0
PRODUCT
DRUM
FILTER
L
WATER RECYCLE
EMERGENCY VENT TO
INCINERATOR 102
©
STACK
*—
C
SCRUBBER
101
DISCHARGED
WATER - WASHED
SOLIDS
STACK
IS)
W
8-
WATER
DISCHARGE-
INCINERATOR
102
D
•o
O
O
9
IB
IB
O
X
0.
I
M
O
00
B
o
o
m
•o
M
O
t->
I*
O.
H-
(D
o
o
o
IB
IB
9
§
m
o
o
so
IB
-------
-4-
II.
Process. (Continued)
3. Raw materials and products
Raw materials
Name Quantity
Pyrrolidine 130.000.000 Ibs/yr.
Composition
pyrrolidine
other amines
98%
2%
Product and by-products
Name Quantity Composition
Pyrrole 80.000.000 Ibs/vr. pyrrole 99.5%
Pyrrolidone
20.000.000 Ibs/yr.
pyrrolidone
99.5%
-------
-5-
II. Process. (Continued)
4. Waste water.
750 gal/hr. treated by us, measured in treatment unit,
5. Waste solids.
200 Ibs/hr. catalyst dust from filter. Estimated average
quantity hauled away by solids waste disposal contractor.
-------
T3T
III. 1.Emissions (composition and flow).
Six copies provided
this section
Stream flow shown on block diagram by letter A_
1. Flow ? Temperature ? Pressure
Component
Name
Particulate
Formula
State
Solid
Average amount
or composition
Composition
Range
Depending upon cause of emergency, emissions could range from contaminated feed to contaminated product.
Upset durations seldom exceed 15 minutes during which time incinerator operation would be modified. For
initial 1-2 minutes after upset pollutants might leave incinerator stack. Following that, stack gases will
be nearly 100% C02, H20 & N2. On average, such upsets occur two or three times per year. Particulates are
possible, depending upon cause of upset. One such upset occurred in 1969.
* Particulate matter should be described as fully as possible.
-------
-7-
(a)
III. Continued For stream flow shown on block diagram by letter A
2. Composition variation.
See III-l
3. Production rate during sampling.
Never Sampled '
A. Method used to determine composition and flow.
Not applicable
-------
III. Continued For stream flow shown on block diagram by letter A
5. Sampling procedure.
Not Applicable
6. Analytical procedure.
Not Applicable
7. Sampling frequency.
Never
-------
-9-
(a)
III. Continued For stream flow shown on block diagram by letterA
8. Confidence level.
Not Applicable
9. Ease of sampling.
Impossible
10. Odor problem. (Circle yes or no or mark "not applicable")
Is the odor of this emission ever detectable at ground level
on the plant property? Yes/no Off the plant property? Yes/no
If odors carry beyond the plant property are they detectable
Infrequently? Yes/no Frequently? Yes/no Have you received a
community odor complaint traceable to this source in the past
year? Yes/no Has the odorous material been chemically identified?
Yes/no What is it?
Not Applicable
-------
Ill.1.Emissions (composition and flow),
Six copies provided
this section
Stream flow shown on block diagram by letter
Flow lOjOOO SCFHTemperature
Component
Name
Particulate
Nitrogen
Oxygen
Carbon Monoxide
Carbon Dioxide
Hydrogen
Water
Various Amines
Nitrogen Oxides
Formula
*
N2
°2
CO
COj
H2
H20
**
NOX
* Particulate matter should be
contains cobalt and chromium
less than 5 microns;
5% less
110°F Pressure 25 PSIG
State
Solid
Gas
Gas
Gas
Gas
Gas
Vapor
Vapor
Gas
described as fully as possible.
on alumina base. 1002 lea
-------
fb7)-
III. Continued For stream flow shown on block diagram by letter B .
2. Composition variation.
During 2nd and 3rd quarter when plant is operated below capacity,
nitrogen is at high end of range and all other materials near low
end. During start-up or plant upset (average about 50 hours/year)
nitrogen is near low end of range and all other materials near high
end.
3. Production rate during sampling.
Average composition based on-rated capacity.
A. Method used to determine composition and flow.
Engineering calculation and plant material balance (flow).
Composition calculated on basis of stream "C" analysis and estimated
amine losses prior to installation of scrubber.
-------
III. Continued For stream flow shown on block diagram by letter B
5« Sampling procedure.
Never sampled.
6. Analytical procedure.
Never Analyzed.
7. Sampling frequency. •••»
See (5) above.
-------
(I)
III. Continued For stream flow shown on block diagram by letter B
8. "Confidence level.
9. Ease of sampling.
No sample taps are available, but one could be easily installed
in readily accessible location. However, it would not be 8 pipe
diameters from a disturbance.
10. Odor problem. (Circle yes or no or mark "not applicable")
Is the odor of this emission ever detectable at ground level
on the plant property? Yes/no Off the plant property? Yes/no
If odors carry beyond the plant property are they detectable
"Infrequently? Yes/no Frequently? Yes/no Have you received a
community odor complaint traceable to this source in the past
year? Yes/no Has the odorous material been chemically identified?
Yes/no What is it?
No applicable - this stream is no longer
emitted to the atmosphere.
-------
III.1.Emissions (composition and flow).
Six copies provided
this section
Stream flow shown on block diagram by letter C
Flow lO.OOOSCFM Temperature 100°F Pressure 0 PSIG
Component
Name
Particulate
Nitrogen
Oxygen
Carbon Monoxide
Carbon Dioxide
Hydrogen
Water
Various Amine
Nitrogen Oxides
Formula
*
N2
°2
CO
C02
H2
H20
**
NOX
* Particulate matter should be described as
5 microns; 60% less than 1 micron.
State
Solid
Gas
Gas
Gas
Gas
Gas
Vapor
Vapor
Gas
fully as possible.
Average amount
or composition
10 Ibs./hour
83.9 Vol. %
1.4 "
4.1 "
1.4 "
2.1 "
7.1 "
50 YPPMV
300 YPPMV
Composition
Range
5-20 Ibs./hour
80-85%
1-2%
3-5%
1-2%
2-2.5%
6.5-7.5%
30-100 PPMV
200-500 PPMV
See "B". Size distribution 100% less than
** See "B".
-------
III. Continued For stream flow shown on block diagram by letter
2. Composition variation.
See "BY
3. Production rate during sampling.
See "B"
4. Method used to determine composition and flow.
See "B" for flow. Specific analysis methods are given in III-6(C)
-------
-8-
Cc)
III. Continued For stream flow shown on block diagram by letter
5. Sampling procedure.
a. Particulates and moisture collected in sampling train as detailed
in Federal Register, Dec. 23, 1971 (Method 5).
b. NO sampled by EPA Method 7.
X
c. Other constituents collected using grab sampling procedures for
collection of gas. Sample size 10 liters in stainless steel tank.
6. Analytical procedure.
a. Particulates and moisture determined gravimetrically as detailed
in Federal Register, Dec. 23, 1971. (Method 5)
b. NOX determined by EPA method 7.
c. Hydrogen, oxygen, and nitrogen determined by mass spectrometer
analysis at local university.
Amine, CO and C02 determined by infra-red analysis.
7. Sampling frequency.
Once, - one month after scrubber was put on stream.
-------
-9-
(c)
III. Continued For stream flow shown on block diagram by letter
8. Confidence level.
Oxygen, C02, CO and H may be + 10%.
Nitrogen would be better than this, perhaps + 5%
Amines are near limit of detection - + 50%.
9. Ease of sampling.
Difficult - only sample tap is six feet above top of scrubber
tower - approximately 65 feet in air - reached by caged ladders.
10. Odor problem. (Circle yes or no or mark "not applicable")
Is the odor of this emission ever detectable at ground level
on the plant property? Yes/no Off the plant property? Yes/no
If odors carry beyond the plant property are they detectable
infrequently? Yes/no Frequently? Yes/no Have you received a
community odor complaint traceable to this source in the past
year? Yes/no Has the odorous material been chemically identified?
Yes/no What is it? Amine compounds.
-------
III.I.Emissions (composition and flow).
Six copies provided
this section
Stream flow shown on block diagram by letter D_
1. Flow 300 GPH Temperature 300°F Pressure 10 PSIG
Component
Name
Particulate
Heavy Amines
Formula
State
Solid
Liquid
Average amount
or composition
Trace
100%
Composition
Range
* Particulate matter should be described as fully as possible. Very fine catalyst dust - never sampled
or analyzed - estimated to be 1-5 Ibs./hour.
-------
-7-
(d)
III. Continued For stream flow shown on block diagram by letter D
2, Composition variation.
Not applicable - unknown - never analyzed.
3. Production rate during sampling.
See "B"
4. Method used to determine composition and flow.
Rotameter in liquid line for flow. Composition unknown.
-------
-o-
III. Continued For stream flow shown on block diagram by letter D
5. Sampling procedure.
Not applicable.
6. Analytical procedure.
Not applicable.
7. Sampling frequency.
Not applicable.
-------
-9-
(d)
III. Continued For stream flow shown on block diagram by letter D
8. Confidence level.
Not applicable.
9. Ease of sampling.
Liquid drain line is available at ground level. Could be used
for sample tap.
10. Odor problem. (Circle yes or no or mark "not applicable")
Is the odor of this emission ever detectable at ground level
on the plant property? Yes/no Off the plant property? Yes/no
If odors carry beyond the plant property are they detectable
infrequently? Yes/no Frequently? Yes/no Have you received a
community odor complaint traceable to this source in the past
year? Yes/no Has the odorous material been chemically identified?
Yes/no What is it?
Not applicable - not an emitted stream.
-------
III. 1 Emissions (composition and flow).
Six copies provided
this section
Stream flow shown on block diagram by letter
1. Flow 10,OOOSCFM Temperature 450°F Pressure 0 PSIG
Component
Name
P articulate
Nitrogen
Oxygen
Carbon Dioxide
Water
Nitrogen Oxides
Formula
*
N2
°2
co2
H20
NOX
State
Solid
Gas
Gas
Gas
Vapor
Gas
Average amount
or composition
Trace
77.0 Vol. %
9.2 Vol. %
6.4 Vol. %
7.4 Vol. %
150 VPPM
Composition
Range
76.5-77.5%
9-9.5%
6-7%
7-8%
100-300 VPPM
* Particulate matter should be described as fully as possible,
See "Dr
-------
III. Continued For stream flow shown on block diagram by letter
2. Composition variation.
Random variation depending on many variables such as production
rate, ambient air temperature and humidity, catalyst age, etc.,
all within limits shown.
3. Production rate during sampling.
See "B"
A. Method used to determine composition and flow.
Calculation based on incinerator vendor's specifications, guarantees
and laboratory tests.
-------
—o—
(e)
III. Continued For stream flow shown on block diagram by letter F_
5. Sampling procedure.
Never sampled.
6. Analytical procedure.
Never analyzed
7. Sampling frequency.
See (5) above
-------
-9-
(e)
III. Continued For stream flow shown on block diagram by letter E
8. Confidence level.
+ 10%
9. Ease of sampling.
No sample tap, very hot stream, no access ladders, minimal insulation.
10. Odor problem. (Circle yes or no or mark "not applicable")
Is the odor of this emission ever detectable at ground level
on the plant property? Yes/no Off the plant property? Yes /no
If odors carry beyond the plant property are they detectable
infrequently?* Yes/no Frequently? Yes/no Have you received a
community odor complaint traceable to this source in the past
year? Yes/jjo Has the odorous material been chemically identified?
Yes/no What is it?
* Only during start-up or upset of the incinerator and then only
if atmospheric conditions are favorable for ground level detection.
-------
-10-
(a)
3 copies provided
this section.
IV. Emission control device
For device shown on block diagram by number 101
1. Engineering description.
. GAS TO
T STACK
GAS
DISTRIBUTOR
MIST
^ELIMINATOR
Multi-nozzle spray tower manu-
factured by Rebburcs Corp.
Model No. 10,000-W
Water rate: 100 GPM
Gas rate: 10,000 SCFM
Temperature: 100°F.
Pressure: Atmospheric
Gas AP: 8 in, H20
Water Pump Head: 150 Ft.
Discharge Pump Head: 100 Ft.
Diameter of Tower: 6 Ft.
T-T Length: 60 Ft.
WATER PUMP
\ DOWNCOMER
DISCHARGE
PUMP
Utilities:
35 HP for Pumps
-,
10,000,000 BfU/Hr. Additional steam in product recovery section.
1500 GPM Additional cooling water circulation in product recovery section.
-------
ctf-
IV. Continued For device shown on block diagram by number 101
2. Capital cost of emission control system.
(a) Capital cost
Major equipment cost $ 160,000
Total installed cost $ 350.000
Year Cost
1968 $350,000
-------
-12-
(a)
IV. Continued For device shown.on block diagram by number 101
(b) Check list. Mark whether items listed are included in total
cost included in IV.2.a. Do not give dollar value -
Yes
Cost
Facilities outside
battery limits*
Explanation
X
X
X
X
X
X
X
X
X
X
Site development Additional foundation required fo
scrubber .
Buildings
Laboratory equipment
Stack
Rigging etc.
Piping
Insulation
Instruments
Instrument panels
Electrical
Storage tanks, spheres
drums, bins, silos
Catalysts
Spare parts and
non-installed parts
*Such as - process pipe lines such as steam, condensate, water, gas, fuel,
air, fire, instrument and electric lines.
-------
-13-
(a)
IV. Continued For device shown on block diagram by number 101
Yes
No
Was outside engineering contractor used?
Was cost included in capital cost?
Was in-house engineering used?
X Was cost included in capital cost?
_X Was emission control equipment installed
and constructed at the time plant (process)
was constructed?
3. Operating costs of control system.
Give 1972 dollar values per year at capacity given in I.I.
(a) Utilities $ 68.000
(b) Chemicals* 10.000
(c) Labor (No Additional Operators') _j;
(d) Maintenance (labor & materials) 14,000
(e) Water treatment (cost of treating any waste
water produced by this control system) ** -
(f) Solids remmoval (cost of removing any waste
solids produced by this control system) 20,000
(g) Other disposal -
(h) By-product or product recovery CREDIT $89,000 )
Total operating costs $ 23.000
* Additional cooling water treatment included in utility costs -
this cost is for corrosion inhibition in scrubber.
** Water waste is produced by process. It is treated at cost of
$30,000/year. This treatment was required before scrubber was
installed.
-------
3 copies provided
this section.
IV. Emission control device
For device shown on block diagram by number 102
WATER
BURNERS
1. Engineering description.
t
TO STACK
CONVECTIVE
CTION
RADIANT
SECTION
STEAM
SECONDARY
HEAVY ENDS
AIR
BLOWER
Steam Generator/Waste Incinerator
Manufactured by: Xoberif Corp.
Model No.: 40-H
Heavy Ends Rate: 300 GPH
Air Rate: 9,500 SCFM
Steam Rate: 20,000 Ibs./hour
Vessel Diameter: 15 Ft.
Height: 40 Ft.
Tube Diameter: 3 in. nominal
Tube Length: (Material)
Convective (mild steel): 6,000 Ft,
Radiant (304 stainless): 2,000 Ft,
Utilities:
Heavy Ends Pump: 20 HP
Blower: 100 HP
-------
-11-
(10
IV. Continued For device shown-on block diagram by number 102
2. Capital cost of emission control system.
(a) Capital cost
Major equipment cost $ 350,000
Total installed cost $1,000,000
Year Cost
1960 $1,000,000
-------
-12-
(b)
IV. Continued For device shown on block diagram by number
102
Yes
(b) Check list. Mark whether items listed are included in total
cost included in IV.2.a. Do not give dollar value -
No
X
Cost
Storage tanks, spheres
drums, bins, silos
Explanation
X
X
X
X
X
X
X
X
X
X
X
Site development Cost prorated from total plant
site costs.
Buildings
Laboratory equipment
Stack
Rigging etc.
Piping
Insulation
Instruments
Instrument panels
Electrical
Facilities outside
battery limits*
Catalysts
X
Spare parts and
non-installed parts
*Such as - process pipe lines such as steam, condensate, water, gas, fuel,
air, fire, instrument and electric lines.
-------
-13-
(b)
IV. Continued For device shown on block diagram by number 102
Yes
X
X
X
x
No
X
Was outside engineering contractor used?
Was cost included in capital cost?
Was in-house engineering used?
Was cost included in capital cost?
Was emission control equipment installed
and constructed at the time plant (process)
was constructed?
3. Operating costs of control system.
Give 1972 dollar values per year at capacity given in I.I.
(a) Utilities $
(b) Chemicals
5,000
(c) Labor (^ man per shift - excludes supervision &
overhead)
(d) Maintenance (labor & materials)
(e) Water treatment (cost of treating any waste
water produced by this control system)
(f) Solids remmoval (cost of removing any waste
solids produced by this control system)
7,000
40,000
(g) Other disposal
(h) By-product or product recovery
Total operating credit
CREDIT- STEAM
($100,
$ 48 , 000
-------
-14-
V. Stack or vent description.
For stack or vent shown on block diagram by letter
1. Stack height 100ft
2. Stack diameter 2ft
' 3. Gas temperature stack exit 100 °F
4. Stack flow * SCFM(70°F & 1 Atra.)
For stack or vent shown on block diagram by letter E .
1. Stack height 60 Ft.
2. Stack diameter 3 Ft.
3. Gas temperature stack exit 450 F
4. Stack flow *
For stack or vent shown on block diagram by letter
1. Stack height
2. Stack diameter
3. Gas temperature stack exit
4. Stack flow *
For stack or vent shown on block diagram by letter
1. Stack height
2. Stack diameter
3. Gas temperature stack exit
4. Stack flow *
* See instructions
-------
VI. Tankage.
No. of
tanks
3
4
composition
Pyrrolidine
-------
-16-
VII. Fuels.
800,000 gal./year fuel oil for fired air heater 3% sulfur.
VIII. Other emissions.
No other known emissions although minor leakages probably occur.
Engineering estimate of average losses is 0.01% of throughput or
13,000 Ibs./year of amines.
IX. Future plans.
1. Current research on heavy amine stream indicates further
processing will produce a marketable product - if so,
incinerator will be shut down.
2. We are currently negotiating a long term contract to purchase
1% sulfur fuel oil from the Plused Oil Company.
-------
APPENDIX III
FINAL QUESTIONNAIRE SUMMARY
Chemical
Acetaldehyde via Ethylene
via Ethanol
Acetic Acid via Methanol
via Butane
via Acetaldehyde
Acetic Anhydride
Acrylonitrile
Adipic Acid
Adiponitrile via Butadiene
via Adipic Acid
Carbon Black
Carbon Bisulfide
Cyclohexanone
Dimethyl Terephthalate (+TPA)
Ethylene
Ethylene Dichloride via Oxychlorination
via Direct Chlorination
Ethylene Oxide
Formaldehyde via Silver Catalyst
via Iron Oxide Catalyst
Glycerol
Hydrogen Cyanide
Isocyanates
Maleic Anhydride
Nylon 6
Nylon 6,6
Oxo Process
Phenol
Phthalic Anhydride via o-xylene
via naphthalene
Polyethylene (High Density)
Polyethylene (Low Density)
Polypropylene
Polystyrene
Polyvinyl Chloride
Styrene
Styrene - Butadiene Rubber
Vinyl Acetate via Acetylene
via Ethylene
Vinyl Chloride
Number of Questionnaires
used as Basis for Report
1
1
2
1
1
2
4
4
1
2
7
4
7
6
13
10
3
7
12
6
2
1
10
7
4
3
6
8
5
3
5
7
7
4
7
6
3
1
8
-------
Appendix IV & V
-------
INTRODUCTION TO APPENDIX IV AND V
The following discussions describe techniques that were developed for
the single purpose of providing a portion of the guidance required in the
selection of processes for in-depth study. It is believed that the underlying
concepts of these techniques are sound. However, use of them without sub-
stantial further refinement is discouraged because the data base for their
specifics is not sufficiently accurate for wide application. The subjects
covered in the Appendix IV discussion are:
1. Prediction of numbers of new plants.
20 Prediction of emissions from the new plants on a weighted
(significance) basis.
The subject covered in the Appendix V discussion is:
Calculation of pollution control device efficiency on a variety of
bases, including a weighted (significance) basis.
It should be noted that the weighting factors used are arbitrary,,
Hence, if any reader of this report wishes to determine the effect of
different weighing factors, the calculation technique permits changes in
these, at the reader's discretion.
-------
APPENDIX IV
Number of New Plants by 1980
Attached Table 1 illustrates the format for this calculation.
Briefly, the procedure is as follows:
1. For each petrochemical that is to be evaluated, estimate what
amount of today's production capacity is likely to be on-stream
in 1980. This will be done by subtracting plants having marginal
economics due either to their size or to the employment of an
out-of-date process.
2. Estimate the 1980 demand for the chemical and assume a 1980
installed capacity that will be required in order to satisfy
this demand.
3. Estimate the portion of the excess of the 1980 required capacity
over today's remaining capacity that will be made up by
installation of each process that is being evaluated.
4. Estimate an economic plant or unit size on the basis of today's
technology.
5» Divide the total required new capacity for each process by the
economic plant size to obtain the number of new units.
In order to illustrate the procedure, data have been incorporated
into Table I, for the three processes for producing carbon black, namely
the furnace process, the relatively non-polluting thermal process, and
the non-growth channel process.
-------
Table 1. Number of New Plants by 1980
Current
Chemical
Carbon Black
Process
Furnace
Channel
Thermal
Current
Capacity
4,000
100
200
Marginal
Capacity
0
0
0
Capacity
on-stream
in 1980
4,000
100
200
Demand
1980
4,500
100
400
Capacity
1980
5,000
100
500
Capacity
to be
Added '
1,000
0
300
Economic
Plant
Size
90
30
150
Number
New
Units
11 -
0
2
of
12
I
M
Notes: 1. Capacity units all in MM Ibs./year.
2. 1980 demand based on studies prepared for EPA by Processes Research, Inc. and MSA Research Corporation.
-------
IV-3
Increased Emissions (Weighted) by 1980
Attached Table 2 illustrates the format for this calculation.
However, more important than format is a proposal for a weighting basis.
There is a wide divergence of opinion on which pollutants are more noxious
and even when agreement can be reached on an order of noxiousness, dis-
agreements remain as to relative magnitudes for tolerance factors. In
general pollutants from the petrochemical industry can be broken down into
categories of hydrogen sulfide, hydrocarbons, particulates, carbon monoxide,
and oxides of sulfur and nitrogen. Of course, two of these can be further
broken down; hydrocarbons into paraffins, olefins, chlorinated hydrocarbons,
nitrogen or sulfur bearing hydrocarbons, etc,, and particulates into ash,
catalyst, finely divided end products, etc. It is felt that no useful
end is served by creating a large number of sub-groupings because it will
merely compound the problem of assigning a weighting factor. Therefore,
it is proposed to classify all pollutants into one of five of the six
categories with hydrogen sulfide included with hydrocarbons„
There appears to be general agreement among the experts that carbon
monoxide is the least noxious of the five and that NOX is somewhat more
noxious than SOX» However, there are widely divergent opinions concerning
hydrocarbons and particulates - probably due to the fact that these are
both widely divergent categories. In recent years, at least two authors
have attempted to assign tolerance factors to these five categories„
Babcock (1), based his on the proposed 1969 California standards for
one hour ambient air conditions with his own standard used for hydrocarbons.
On the other hand, Walther (2), based his ranking on both primary
and secondary standards for a 24-hour period. Both authors found it
necessary to extrapolate some of the basic standards to the chosen time
period„ Their rankings, on an effect factor basis with carbon monoxide
arbitrarily used as a reference are as follows:
Babcock
Walther
Hydrocarbons
Particulates
NOX
SOX
CO
2.1
107
77o9
28.1
1
Primary
125
21.5
22.4
15.3
1
Secondary
125
37,
22,
21.5
1
Recognizing that it is completely unscientific and potentially subject
to substantial criticism it is proposed to take arithmetic averages of the
above values and round them to the nearest multiple of ten to establish a
rating basis as follows:
Hydrocarbons
Particulates
NOX
sox
CO
Average
84.0
55o3
40.9
21.6
1
Rounded
80
60
40
20
1
-------
Table 2. Weighted Emission Rates
Chemical
Process
Increased Capacity
Increased Emissions
Pollutant Emissions, Lbs./Lb. Lbs=/Year
Hydrocarbons
Particulates
NOX
sox
CO
Weighting
Factors
80
60
40
20
1
Weighted Emissions
Lbs./Year
Total
-------
IV-5
Increased Emissions (Weighted) by 1980 (continued)
This ranking can be defended qualitatively, if not quantitatively for
the following reasons:
1. The level of noxiousness follows the same sequence as is obtained
using national air quality standards.
20 Approximately two orders of magnitude exist between top and bottom
rankings.
30 Hydrocarbons should probably have a lower value than in the
Walther analysis because such relatively non-noxious compounds
as ethane and propane will be included.
4. Hydrocarbons should probably have a higher value than in the
Babcock analysis because such noxious (or posionous) substances
as aromatics, chlorinated hydrocarbons, phenol, formaldehyde, and
cyanides are included,
5. Particulates should probably have a higher value than in the
Walther analysis because national air standards are based mostly
on fly ash while emissions from the petrochemical industry are
more noxious being such things as carbon black, phthalic anhydride,
PVC dust, active catalysts, etc.
6. NOX should probably have a higher value than in the Walther
analysis because its role in oxidant synthesis has been neglected.
This is demonstrated in Babcock's analysis.
Briefly, the procedure, using the recommended factors and Table 2, is
as follows:
1. Determine the emission rate for each major pollutant category in
terms of pounds of pollutant per pound of final product. This
determination is to be made on the basis of data reported on
returned questionnaires.
2. Multiply these emission rates by the estimate of increased production
capacity to be installed by 1980 (as calculated while determining
the number of new plants), to determine the estimated pounds of
new emissions of each pollutant.
3. Multiply the pounds of new emissions of each pollutant by its
weighting factor to determine a weighted pounds of new emissions
for each pollutant.
4. Total the weighted pounds of new emissions for all pollutants to
obtain an estimate of the significance of emission from the process
being evaluated. It is proposed that this total be named
"Significant Emission Index" and abbreviated "SEI".
It should be pointed out that the concepts outlined above are not
comp'letely original and considerable credit should be given to Mr. L. B. Evans
of the EPA for setting up the formats of these evaluating procedures.
-------
IV-6
Increased Emissions (Weighted) by 1980 (continued)
(1) Babcock, L. F., "A Combined Pollution Index for Measurement of Total
Air Pollution," JAPCA, October, 1970; Vol. 20, No. 10; pp 653-659
(2) Walther, E. G., "A Rating of the Major Air Pollutants and Their Sources
by Effect", JAPCA, May, 1972; Vol. 22, No. 5; pp 352-355
-------
Appendix V
Efficiency of Pollution Control Devices
Incinerators and Flares
The burning process is unique among the various techniques for
reducing air pollution in that it does not remove the noxious substance
but changes it to a different and hopefully less noxious form. It can be,
and usually is, a very efficient process when applied to hydrocarbons,
because when burned completely the only products of combustion are carbon
dioxide and water. However, if the combustion is incomplete a wide range
of additional products such as cracked hydrocarbons, soot and carbon
monoxide might be formed. The problem is further complicated if the
hydrocarbon that is being burned is halogenated, contains sulfur or is
mixed with hydrogen sulfide, because hydrogen chloride and/or sulfur oxides
then become products of combustion. In addition, if nitrogen is present,
either as air or nitrogenated hydrocarbons, oxides of nitrogen might be
formed, depending upon flame temperature and residence time.
Consequently, the definition of efficiency of a burner, as a pollution
control device, is difficult. The usual definition of percentage removal of
the noxious substance in the feed to the device is inappropriate, because
with this definition, a "smoky" flare would achieve the same nearly 100
percent rating, as a "smokeless" one because most of the feed hydrocarbon
will have either cracked or burned in the flame. On the other hand, any
system that rates efficiency by considering only the total quantity of
pollutant in both the feed to and the effluent from the device would be
meaningless. For example, the complete combustion of one pound of hydrogen
sulfide results in the production of nearly two pounds of sulfur dioxide, or
the incomplete combustion of one pound of ethane could result in the
production of nearly two pounds of carbon monoxide.
For these reasons, it is proposed that two separate efficiency rating
be applied to incineration devices. The first of these is a "Completeness
of Combustion Rating" and the other is a "Significance of Emission Reduction
Rating", as follows:
I. Completeness of Combustion Rating (CCR)
This rating is based on oxygen rather than on pollutants and is
the pounds of oxygen that react with the pollutants in the feed to
the device, divided by the theoretical maximum number of pounds that
would react: Thus a smokeless flare would receive a 100 percent
rating while a smoky one would be rated somewhat less, depending upon
how incomplete the combustion.
In utilizing this rating, it is clear that carbon dioxide and water
are the products of complete combustion of hydrocarbons„ However, some
question could occur as to the theoretical completion of combustion
when burning materials other than hydrocarbons. It is recommended
that the formation of HX be considered complete combustion of halogenated
hydrocarbons since the oxidation most typically does not change the
valence of the halogen. On the other hand, since some incinerators will
be catalytic in nature it is recommended that sulfur trioxide be
considered as complete oxidation of sulfur bearing compounds.
-------
V-2
Efficiency of Pollution Control Devices
1. Completeness of Combustion Rating (CCR) (continued)
Nitrogen is more complex, because of the equilibria that exist
between oxygen, nitrogen, nitric oxide, nitrogen dioxide and the
various nitrogen radicals such as nitrile. In fact, many scientists
continue to dispute the role of fuel nitrogen versus ambient nitrogen
in the production of NOX. In order to make the CCR a meaningful
rating for the incineration of nitrogenous wastes it is recommended
that complete combustion be defined as the production of N2, thus
assuming that all NOX formed comes from the air rather than the fuel,
and that no oxygen is consumed by the nitrogen in the waste material.
Hence, the CCR becomes a measure of how completely the hydrocarbon
content is burned, while any NOX produced (regardless of its source)
will be rated by the SERR as described below.
2„ Significance of Emission Reduction Rating (SERR)
This rating is based primarily on the weighting factors that
were proposed above. All air pollutants in the feed to the device
and all in the effluents from the device are multiplied by the
appropriate factor. The total weighted pollutants in and out are
then used in the conventional manner of calculating efficiency
of pollutant removal, that is pollutants in minus pollutants out,
divided by pollutants in, gives the efficiency of removal on a
significance of emission basis.
Several examples will serve to illustrate these rating factors.
as follows:
Example 1 - One hundred pounds of ethylene per unit time is burned
in a flare, in accordance with the following reaction:
3C2H4
7 02
C + 2 CO + 3 C02 + 6 H20
Thus, 14.2 Ibs. of particulate carbon and 66.5 Ibs. of carbon
monoxide are emitted, and 265 Ibs. of oxygen are consumed.
Theoretical complete combustion would consume 342 Ibs. of oxygen
in accordance with the following reaction:
3 02 • • > 2 C02 + 2 H20
Thus, this device would have a CCR of 265/342 or 77.57=,
Assuming that one pound of nitric oxide is formed in the reaction
as a result of the air used for combustion (this is about equivalent to
100 ppm) , a SERR can also be calculated. It should be noted that the
formation of this NO is not considered in calculating a CCR because it
came from nitrogen in the air rather than nitrogen in the pollutant
being incinerated. The calculation follows:
-------
V-3
Efficiency of Pollution Control Devices
2o Significance of Emission Reduction Rating (SERR) (continued)
Pollutant
Hydrocarbons
Particulates
NOX
SOX
CO
Total
SERR = 8000 -
Weighting
Factor
80
60
40
20
1
958.5
Pounds in
Actual Weighted
100 8000
0
0
0
0
8000
O Ooy
Pounds out
Actual Weighted
0
14.2 852
1 40
0
66,5 66.5
958.5
8000 x iuu - 00/°
Example 2 - The same as Example 1, except the hydrocarbons are
burned to completion. Then,
CCR = 342
342
x 100 = 100%
and
SERR = 8000 - 40
8000
= 99.5%
Example 3 - One hundred pounds per unit time of methyl chloride is
incinerated, in accordance with the following reaction.
2 CH3C1 + 3 02
2 C02 + 2 H20 + 2 HC1
This is complete combustion, by definition, therefore, the CCR is
100%o However, (assuming no oxides of nitrogen are formed), the SERR
is less than 100% because 72.5 Ibs. of HC1 are formed. Hence,
considering HC1 as an aerosol or particulate;
SERR = 100 x 80 - 72.5 x 60
100 x 80
x 100 = 45.5%
The conclusion from this final example, of course, is that it is
an excellent combustion device but a very poor pollution control device,
unless it is followed by an efficient scrubber for HCl removal.
Example 4 - The stacks of two hydrogen cyanide incinerators, each
burning 100 pounds per unit time of HCN are sampled. Neither has any
carbon monoxide or particulate in the effluent. However, the first is
producing one pound of NOX and the second is producing ten pounds of
NOX in the same unit time. The assumed reactions are:
-------
V-4
Efficiency of Pollution Control Devices
Significance of Emission Reduction Rating (SERR) (continued)
4 HCN + 5 02 ' ' » 2 H20 + 4 C02 + 2 N2
N2 (atmospheric) -I- X02 •-• •>. 2 NOX
Thus, CCRi = 1007= and CCR2 = 100% both by definition.
However, SERR-, = 100 x 80 - 1 x 40
1 100 x 80
and SERR2 = 100 x 80 - 10 x 40
100 x 80
Obviously, if either of these were "smoky" then both the CCR and
the SERR would be lower, as in Example 1.
Other Pollution Control Devices
Most pollution control devices, such as bag filters, electrostatic
precipitators and scrubbers are designed to physically remove one or more
noxious substances from the stream being vented. Typically, the efficiency
of these devices is rated relative only to the substance which they are
designed to remove and for this reason could be misleading. For example:
1. The electrostatic precipitator on a power house stack might be
99% efficient relative to particulates , but will remove little
or none of the SOX and NOX which are usually present.
2. A bag filter on a carbon black plant will remove 99 + °L of the
particulate but will remove none of the CO and only relatively
small amounts of the compounds of sulfur that are present.
3. A water scrubber on a vinyl chloride monomer plant will remove
all of the hydrogen chloride but only relatively small amounts
of the chlorinated hydrocarbons present.
4. An organic liquid scrubber on an ethylene dichloride plant will
remove nearly all of the EDC but will introduce another pollutant
into the air due to its own vapor pressure.
For these reasons, it is suggested again that two efficiency ratings be
applied. However, in this case, the first is merely a specific efficiency as
is typically reported, i.e., "specific to the pollutant (or pollutants) for
which it was designed", thus:
SE = specific pollutant in - specific pollutant out
specific pollutant in x
The second rating proposed is an SERR, defined exactly as in the case
of incinerators.
Two examples will illustrate these ratings.
-------
Efficiency of Pollution Control Devices
Other Pollution Control Devices (continued)
Example 1 - Assume that a catalytic cracker regenerator effluent
contains 100 pounds of catalyst dust, 200 Ibs. of
carbon monoxide and 10 pounds of sulfur oxides per unit
time. It is passed through a cyclone separator where
95 pounds of catalyst are removed. Therefore,
SE = 100 - 5 ._„
100 X 95/°
and SERR = (100 x 60 + 10 x 20 + 200 x 1) - (5 x 60 + 10 x 20 + 200 x 1) x 100
(100 x 60 + 10 x 20 + 200 x 1)
= 6400 - 700 x 100 = 89%
6400
Example 2 - Assume that an organic liquid scrubber is used to wash a
stream containing 50 pounds of S02 per unit time. All
but one pound of the S02 is removed but two pounds of
the hydrocarbon evaporate into the vented stream. Then
= 98%
and SERR = (50 x 20) - (1 x 20 + 2 x 80)
(50 x 20) x 1UU
= 1000 - 180
1000
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-450/3-73-005-a
4. TITLE AND SUBTITLE
Survey Reports on Atmospheric Emissions from the
Petrochemical Industry, Volume 1
5. REPORT DATE
March 1974 (date of issue)
6. PERFORMING ORGANIZATION CODE
3. RECIPIENT'S ACCESSION-NO.
7. AUTHOR(S)
J. W. Pervier, R. C. Barley, D. E. Field, B. M. Friedman
R. B. Morris, and W. A. Schwartz
8. PERFORMING ORGANIZATION REPORT NO
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Houdry Division/Air Products and Chemicals
P.O. Box 427
Marcus Hook, Pennsylvania 19061
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-02-0255
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Air Quality Planning & Standards
Industrial Studies Branch
Research Triangle Park, N.C. 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final Report
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
This document is one of a series of four volumes prepared for the Environmental
Protection Agency (EPA) to assist it in determining the significance of air
pollution from the petrochemical industry. A total of 33 distinctly different
processes which are used to produce 27 petrochemicals have been surveyed, and the
results are reported in four volumes numbered EPA-450/3-73-005-a, -b, -c, and -d.
This volume covers the following processes: acetaldehyde via ethylene,
acetaldehyde via ethanol, acetic acid via methanol, acetic acid via butane,
acetic acid via acetaldehyde, acetic anhydride, adipic acid, adiponitrile via
butadiene, and adiponitrile via adipic acid. For each process the report includes
a process description, a process emission inventory, a catalog of emission control
equipment, a list of producers, and an evaluation of the significance of the air
pollution from the process. Also included is a summary table of emissions to the
atmosphere from all the processes studied.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
Acetic Anhydride
Adipic Acid
Adiponitrile
b.IDENTIFIERS/OPEN ENDED TERMS C. COS AT I Field/Group
Air Pollution
Carbon Monoxide
Hydrocarbons
Nitrogen Dioxide
Sulfur Dioxide
Acetaldehyde
Acetic: Acid
Petrochemical Industry
Particulates
7A
7B
7C
13B
13H
13. DISTRIBUTION STATEMENT
Release Unlimited
19. SECURITY CLASS (ThisReport)
Unclassified
21. NO. OF PAGES
259
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
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