EPA450/3-73-005-b
APRIL 1974
SURVEY REPORTS
ON ATMOSPHERIC EMISSIONS
FROM THE PETROCHEMICAL
INDUSTRY
VOLUME II
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-450/3-73-005-b
SURVEY REPORTS
ON ATMOSPHERIC EMISSIONS
FROM THE PETROCHEMICAL
INDUSTRY
VOLUME II
by
J. W. Pervier, R. C. Barley, D. E. Field,
B. M. Friedman, R. B. Morris, 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
April 1974
-------
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, Environ-
mental 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 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 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-450/3-73-005-b
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PETROCHEMICAL AIR POLLUTION STUDY
INTRODUCTION TO SERIES
This document is one of a series of four volumes prepared for the
Environmental Protection Agency (EPA) to assist it in determining the
significance of air pollution from the petrochemical industry.
A total of 33 distinctly different processes which are used to
produce 27 petrochemicals have been surveyed, and the results are
reported in these four volumes numbered EPA 450/3-73-005-a, -b, -c, 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
-------
Table of Contents
Page Number
Summary i
Introduction 1
Discussion 2
Results 8
Conclusions 9
Survey Reports (Located by tabs)
Carbon Disulfide
Cyclohexanone
Dimethyl Terephthalate (and TPA)
Ethylene
Ethylene Dichloride (Direct)
Formaldehyde (Silver Catalyst)
Glycerol (Allyl Chloride)
Hydrogen Cyanide (Andrussov)
Isocyanates via Amine Phosgenation
Appendicies (Located by tabs)
Appendix i - Mailing List
Appendix II - Example Questionnaire
Appendix III - Questionnaire Summary
Appendix IV - Significance of Pollution
Appendix V - Efficiency Ratings
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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 for 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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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 two
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 Bisulfide
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 (2 processes)
Polyethylene (high density)
Polyethylene (low density)
Polypropylene
Polystyrene
Polyvinyl Chloride
Styrene
Styrene - Butadiene Rubber
Terephthalic Acid Cl)
Toluene Bi-isocyanate (2)
Vinyl Acetate (2 processes)
Vinyl Chloride
(1) Includes dimethyl terephthalate,
(2) Includes methylenediphenyl and polymethylene polyphenyl isocyanates,
B. Preliminary Investigations
Immediately upon completion of the preliminary study lists, a
literature review was begun on those chemicals which were considered
likely candidates for study. The purpose of the review was to prepare
an informal "Process Portfolio" for each chemical. Included in the
portfolio are data concerning processes for producing the chemical,
estimates of growth in production, estimates of production costs, names,
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- 3 -
locations and published capacities of producers, approximations of
overall plant material balances and any available data on emissions
or their control as related to the specific process.
The fundamental purpose of these literature revievs vas to obtain
background knovledge 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 was 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 recmired 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:
1. The Furance Process for producing Carbon Black.
2. The Sohio Process for producing Acrylonitrile.
3o 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 GTG 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:
I. 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
EMISSIONS SUMMARY
ESTIMATED ^ CURRENT AIR EMISSIONS,
Hydrocarbons ^ '
1
0
0
40
6
3
183
0
11
0
156
0
70
91
15
95
29
85
23
25
16
0
1
34
0
0
5
24
0
0
79
75
37
20
62
4
9
5
0
17
1,227
.1
.1
.1
.2
.15
.1
.8
.8
.7
.5
.3
.25
.3
.1
.5
.3
.4
.3
.6
.6
Particulates (^)
0
0
0
0
0
0
0
0
4
0
8
0
0
1
0
0
0
0
0
0
0
0
0
0
1
5
0
0
5
1
2
1
0
0
12
0
1
0
0
0
49
.2
.7
.5
.1
.3
.4
.2
.4
.8
.5
.5
.01
.1
.9
.3
.4
.1
.4
.07
.6
.6
.1
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
94.2
Sulfur Oxides
0
0
0
0
0
0
0
0
0
0
21.
4.
n
1.
2.
0
0
0.
0
0
0
0
0.
0
0
0
0
0
2.
0
0
0
0
1.
0
0
0.
0
0
0
33.
6
5
0
0
1
02
6
2
9
9
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
4,852.6
1
27
0
54
7
8
385
30
66
0
4,060
5
148
146
17
117
29
86
131
50
16
0
88
294
1
5
24
24
51
47
81
76
37
21
74
4
12
5
.1
.01
.4
.6
.4
.54
.1
.5
.6
.3
.2
.6
.91
.5
.5
.8
.3
.7
.3
.4
.6
.6
.5
.3
Total
3
15
1
3
17
5
• . 7
1
7
2
6
1
2
1
2
1
6
6
2
1
5
TR
18
6,225
.2
Q ( 7 )
1
110
Weighted (5
86
27
1
,215
490
253
,000
,190
,200
30
,544
120
,700
,460
,240
,650
,300
.880
,955
,070
,280
56
231
,950
90
330
440
,940
422
160
,400
,100
,950
,650
,700
355
870
425
TR
,460
,220 <7)
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 Bisulfide
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
• 'It '; (
(1) '-Sp most instances numbers are based on less than 1007. 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 - 20, and CO - 1.
(6) Referred to elsewhere in this study as "Significant Emission Index" or "SEI".
•(7) Totals are not equal across and down due to rounding.
. (9) Emissions based on what is now an obsolete catalyst. See Report No. EPA-450/3-73-OOb b for up-to-date information.
Probably has up to 107S 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 EMI SSI (INS 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 1. US. /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 (5.6)
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
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
Ethylent 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
Poly vinyl Chloride
Styrene
Styrene-Butadiene Rubber
Vinyl Acetate via Acetylene
via Ethylene
Vinyl Chloride
Totals
(1) In most instances numbers are based on less than 10071 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, N'0X - 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 lov bias.
-------
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 Chlorinatlon
Ethylene Oxide
Formaldehyde via Silver Catalyst
via Iron Oxide Catalyst
Glycerol via Kpichlorohydrin
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
Lov Density Polyethylene
Polypropylene
Polystyrene
Polyvinyl Chloride
Styrene
Styrane-Butadiene Rubber
Vinyl Acetate via Acetylene
via Ethylene
Vinyl Chloride
Total by
2
27
0
54
22
10
980
50
128
1
5,730
6
310
265
94
253
63
120
212
85
25
0
175
566
4
10
43
46
186
47
297
343
190
43
137
7
14
9
Emissions
1980
.3
.05
.8
.8
.1
.3
.5
.5 (10)
.7
.8
.4
.8
TR
45
TABI.K 1
EMISSION'S SUMMARY
Cf), MM l.bs./Year
Total Weighted Is) bv 1980
182
27
3
3,215
1 ,470
313
38,000
1 ,970
6,210
60
24,740
150
11,960
13,500
3,670
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
l'at;il '
Totals
10,605
(7)
244,420
(7)
Ksl i ni;lt i'il Number i>| New Plants
(19/3 - 1980)
0
4
{)
3
3
5
7
4
3
13
2
10
8
21
8
10
15
40
12
1
0
10
6
10
10
(>
11
d
0
31
41
32
23
25
9
4
1
4
10
Total Ksl i mat i>il Capacity
MM I.bs./Yoar
I'.y 1980
1 . 1 (id
961)
4 00
1 ,020
87r>
I ,705
1 ,165
1 ,430
43r>
280
3,000
871
I , 800
2,865
22 ,295
4,450
5,593
4,191
5,914
1 ,729
245
412
1 ,088
359
486
1 ,523
1 ,72?
2,3t.3
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
I 1
1,
9
3
2
1
3
3
4
1
8
21
5
6
8
10
r)
2
13
,460
9t)t.
,800
500
,015
, I 00
,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
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
In most instances numbers are based on less than 1007 survey. All based
Assumes future plants will employ best current control techniques.
Excludes methane, includes h^S and all volatile organics.
Includes non-volatile organics and inorganics.
Weighting factors used are: hydrocarbons - 80, particulates - hO, NO
Referred to elsewhere in this study as "Significant Emission Index" o
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.
cnj;i neer i m- judgement of best current control. Probably has up to 107 low bias.
- 20,
-------
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 Dichloride (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.
-------
Carbon Disulfide
-------
Table of Contents
Section Page Number
I. Introduction CD-I
II. Process Description CD-2
III. Plant Emissions CD-3
IV. Emission Control CD-5
V. Significance of Pollution CD-6
VI. Carbon Disulfide Producers CD-7
List of Illustrations and Tables
Flov Diagram Figure CDS-I
Net Material Balance Table CD-I
Heat Balance Table CD-II
National Emissions Inventory Table CD-Ill
Catalog of Emission Control Devices Table CD-IV
Number of Nev Plants by 1980 Table CD-V
Emission Source Summary Table CD-VI
Weighted Emission Rates Table CD-VII
-------
CD-I
I. Introduction
Carbon disulfide is a colorless and extremely volatile and flammable
liquid. It is the basic raw material in the production of viscose rayon,
cellophane, carbon tetrachloride and certain pesticides and fungicides.
The compound was first synthesized 200 years ago. Up until the early 1950's
all commercial production was based upon the reaction of charcoal with
sulfur. Today, all carbon disulfide manufactured in the U. S. is produced
using methane feed. Alternate feed stocks including fuel oils and petroleum
coke are currently being investigated and may be a major raw material source
for carbon disulfide in the future.
U. S. capacity, at present, stands at 871 MM Ibs./year. Growth is
expected to be around 37» a year and capacity by 1980 should be in the
neighborhood of 1.1 billion Ibs./year.
Emissions from carbon disulfide production are primarily associated with
the Glaus plant used to recover sulfur. Emissions from Calus processes are
not within the scope-of-work for this project and will not be discussed here.
Other sources of emissions are: boiler flue gas, emergency flare flue gas
and storage leaks. Emissions from a carbon disulfide plant, excluding the
Glaus plant, are low in comparison to other processes currently being
surveyed. Emissions from plants using fuel oil or coke as feed should be
comparable to that of the methane process because of the vast similarities
between the two processes.
-------
CD-2
II. Process Description
Carbon disulfide is produced by the catalytic reaction of methane vith
sulfur vapor.
CH4 + 2 S2 *• CS2 + 2 H2S
Thermodynamically, the reaction is very favorable for carbon disulfide
formation with yields of over 90% per pass being typical. The reaction of
methane vith diatomic sulfur vapor is exothermic. However, vapor phase
dissociation of the octatomic molecule formed vhen sulfur is first vaporized
to the diatomic and hexatomic forms which predominate at higher temperatures
requires heat. The overall process is endothermic and care must be taken to
dissociate as many of the octatomic molecules as possible in the superheater
in order to limit the temperature drop across the adiabatic reactor.
Liquid sulfur, which is maintained at about 130° C is transferred to a
boiler where it is vaporized and heated to 575 - 650° C in order to convert
sulfur largely to the diatomic form. Methane is preheated to 550 - 650° C and
mixed with the sulfur vapors. The mixed vapors, with sulfur in 10% excess of
stoichiometric requirements, are fed into the reactor or reactors. Two types
of catalytic reactor system are employed commercially. In the first, preheated
feed at about 675° C is fed to a single fixed bed adiabatic reactor with a
silica gel catalyst. The other employs two fixed bed adabatic reactors with
reheating in between. The feed enters each reactor at about 600° C. In
either case, typical yields are from 90 - 95%.
The reactor effluent is cooled to approximately 130° C and unreacted
sulfur is separated in a gas-sulfur separator. Sulfur dust is recovered by
scrubbing with liquid sulfur. The carbon disulfide is separated from the
hydrogen sulfide by preferential absorbtion in mineral oil from vhich it is
subsequently stripped and sent to the distillation section. Hydrogen sulfide
gas is usually sent to a Glaus plant where sulfur is recovered and recycled.
Carbon disulfide is separated from impurities in tvo distillation columns.
In the first, low boiling impurities are removed overhead. In the second,
high boiling impurities are removed in the bottoms and carbon disulfide
product is produced overhead.
-------
CD-3
III. Plant Emissions
A. Continuous Air Emissions
1. Furnace Flue Gas
Natural gas is usually burned to supply the heat necessary
to heat and Superheat the reactants to the required temperature.
Respondent 8-3 calculated the amount of pollutants produced by
using EPA Emission Factor Rating B for Natural Gas Combustion.
He reports .00004 Ibs. of particulate per pound of CS2; .00014
Ibs.. of NOX per Ib. CS2 and .00009 Ibs. of hydrocarbons per Ib.
CS2.
2. Liquid Waste Incineration
One plant, 8-3 utilized a thermal oxidizer to burn heavy waste
produced by the process along with tail gas from their Glaus plant.
Since three-fourths of the liquid is carbon disulfide and dissolved
sulfur, substantial amounts of sulfur dixoide (.00662 Ibs./lb. CS2>
are produced from this source.
3. Sulfur Pit and Storage Losses
Approximately .00028 Ibs. of sublimated sulfur per Ib. CS2 are
released to the atmosphere through losses in the sulfur pit area
and storage tank vents.
4. Carbon Disulfide Storage Losses
Because carbon disulfide autoignites at 100° C storage losses
are kept to the minimum. Usually the product is stored under water
and losses are negligible.
B. Intermittent Air Emissions
1. Emergency Flares
All emergency venting, due to utility failure, compressor
failure, start-up and shutdown, etc. in carbon disulfide plants,
is done through flares. Since sulfur is present in almost all
compounds used or porudced in the process extremely high sulfur
dioxide emissions will result for a short period of time,,
Respondent 8-5 reports that 4.6 tons/month of sulfur containing
compounds are burned through the emergency flare. Other plants
report smaller but still substantial emergency emissions.
C. Continuous Liquid Wastes
The quantity of waste water produced by the process and the
method used to treat the waste is summarized below for the plants
surveyed.
EPA Code No. GPM Treatment
8-1 30 On-site
8-3 20 On-site
8-4 12 On-site
8-5 0
-------
CD-4
D. Solid Wastes
Only plant 8-3 reports any solid wastes produced by the process.
25 Ibs./day of oily sludge are disposed of in an undisclosed manner.
E. Odor
None of the respondents reported any odors associated with the
process, however, during emergency conditions large amounts of
sulfur dioxide are released to the atmosphere, and in spite of high
temperatures and tall stacks, it is possible that an odor could be
released to the surrounding area.
F. Fugitive Emissions
Fugitive emissions due to leaks, spills are estimated to be
.00007 Ibs./lb. CSo.
-------
CD-5
IV. Emission Control
The emission control devices that have been reported as being employed
by carbon disulfide producers are summarily described in Table IV of this
report. An efficiency has been assigned each device vhenever 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 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
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 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.
Flares
All carbon disulfide plants have flares to burn the components of streams
that are vented to the atmosphere in case of an emergency or shutdown.
Unfortunately since the streams flared usually consists of sulfur compounds,
including hydrogen sulfide, carbon disulfide, carbonyl sulfide and sulfur,
the net effect is to replace one harmful polluant with another. Since
the "SERR" efficiency is designed to weight this effect it has been
calculated wherever possible. Efficiencies of 53% and 187, have been
calculated for flares FL-V and FL-II, respectively.
Incineration
Thermal oxidizer IN-I is listed in Table IV even though it contributes
to air pollution, because it serves the purpose of destroying harmful
liquid waste. It would be ludicrous to assign an efficiency to this
device. It is also rather doubtful tV-at this is the best way to dispose
of highly sulfurous waste.
x 100
-------
CD-6
V. Significance of Pollution
It is recommended that no in-depth study of this process be undertaken at
this time. The most significant source of air pollution associated vith the
production of carbon disulfide is emissions from the Claus plant used to
recover sulfur. Emissions from the Glaus process are not covered in this
report. Air pollutants released as air emissions, for the process under study
are less than for other processes currently being surveyed.
The methods outlined in Appendix IV have been used to estimate the total
weighted annual emissions from new plants which will be in operation by 1980.
The work is summarized in Tables V, VI and VII.
On a weighted emission basis, a Significant Emission Index of 30 has
been calculated in Table VII. This is substantially less than the SEI's of
other processes in the study. Hence, the recommendation to exclude carbon
disulfide from the in-depth portion of the overall scope of work.
-------
CD-7
VI. Carbon Disulfide Producers
Company
FMC - Allied
Pennvalt
PPG
Stauffer
Stauffer
Location
South Charleston, W. Va.
Houston, Texas
Nev Martinsville, W. Va.
Delaware City, Del.
LeMoyne, Ala.
Capacity - MM Lbs./Year
220
10
53
350
238
Total - 871
-------
PAGE NOT
AVAILABLE
DIGITALLY
-------
TABLE CD-I
MATERIAL BALANCE
CARBON DISULFIDE FROM
METHANE & SULFUR
COMPONENT
Natural Gas
1) Methane
2) Ethane
3) Propane
4) PfcNj, C02
Sulfur
Carbon Diiulfide
Hydrogen Sulflde
Carbonyl Sulfide
Hydrogen
Nitrogen
Heavy Products
Sulfur, Oil, Etc.
Stream No. 1 & 2 3 4
Stream Fresh Feed Recycle Sulfur Total Feed Reactor Effluent
•2493 .2493 .0347
•0071 .0071 .0030
•0020 .0020 .0013
-0046 .0046
.9051 .9690(1) 1.8741 .1717
1.0116
.8967
.0078
.0078
.0008
'
.0017
1-1681 .9690 2.1371 2.1371
6
Gas to Claui
.0347
.0030
.0013
.0116
.8967
.0078
.0078
.0008
.9637
Heavy Ends
1.0000
.0017
.0017
1.0000
(1) Includes sulfur recovered from Glaus unit.
-------
TABLE CD-II
HEAT BALANCE (REACTOR SECTION ONLY)
CARBON DISULFIDE FROM METHANE AND SULFUR
Heat In (1)
Heat, vaporization and superheat
for sulfur and methane Cabove
base temperature) 755
Exothermic heat of reaction 324
1,079 BTU/LB. CS2
Heat Out
Endothermic heat of
dissociation for Sg 568
Enthalpy residual (above base temperature) 511
1,079 BTU/LB. CS2
(1) Base temperature - 130° C (inlet temperature to boiler for liquid sulfur).
-------
TABLETD-III
NATIONAL EMISSIONS INVENTORY
CARBON DISULFIDE FROM
METHANE AND SULFUR
Page 1 of 4
E.P.A. CODE.NO.
CAPACITY TONS OF CARBON DISULFIDE
AVERAGE PRODUCTION - TONS OF CARBON DISULFIDE
EMISSIONS TO ATMOSPHERE
8-1
Approx. 5,000 (1)
(1)
Steam
Flow-Lbs./Yr.
Flow Characteristics - Continuous or Intermittent
If Intermittent - Hrs./Yr.
Composition Lbs./Hr. of Component
Methane
Ethane
Propane
Sulfur
Carbonyl Sulfide
Carbon Disulfide
Thiophene
Hydrogen Sulfide
Sulfur Dioxide
Nitrogen
Nitrogen Dioxides
Carbon Dioxide
Oxygen
Water
Hydrocarbons
Analysis
Date of Frequency of Sampling
Type of Analysis
Odor Problem
Vent Stacks
Flow SCFM Per Stack
Number
Height (Elev. @ tip) - Ft.
Diameter - Inches
Exit Gas Temperature - F°
Emission Control Devices
Type - Scrubber
- Incinerator - Flare
Summary of Pollutants
Hydrocarbons Lbs./Hr. + Other Sulfur Compounds
Besides SOX
Particulates
N0y - Lbs./Hr.
SO - Lbs./Hr.
CO - Lbs./Hr.
Fumes From Sulfur Storage
Sulfur Pit Vent
Not Specified Not Specified
Continuous Continuous
Flue Gas From
Start-Up Flare
Not Specified
Intermittent
50
None
No
No
No
None
No
Yes
1
30
3
250
No
None
Yes
Yes
1
12
2
1200
Yes
+ (3)
Flare Flue Gas
Emergency Reactor Vent
18,562
Intermittent
.66
Storage
14,041
0.5
2,486
2,035
None
Yes
Yes
60 - 2000
1
150
8
3000
Yes
0.5
14,041
(1) Exact capacity and production figures are confidential
(2) Since capacity is calssified information it is not possible to represent composition in the usual manner of tons/tons product.
(3) Sublimed sulfur.
(4) Average of 3.7 SCFM.
None
No
Yes
0-12
1
30
2
Ambient
No
-------
TABLE CD-III
NATIONAL EMISSIONS INVENTORY
CARBON DISULFIDE
FROM METHANE AND SULFUR
Page 2 of 4
EPA CODE NO. 8-3
CAPACITY TONS OF CARBON DISULFIDE 119,000
AVERAGE PRODUCTION - TONS OF CARBON DISULFIDE 119,000
EMISSIONS TO ATMOSPHERE
Steam
Flow Lbs/Yr.
Flow Characteristics - Continuous or Intermittent
If Intermittent - Hrs./Yr.
Composition Tons/Ton of Carbon Disulfide
Particulates
Methane
Ethane
Propane
Sulfur
Carbonyl Sulfide
Carbon Disulfide
Thiophene
Hydrogen Sulfide
Sulfur Dioxides
Nitrogen
Nitrogen Dioxides
Carbon Monoxide
Carbon Dioxide
Water
Hydrocarbons
Analysis
Date of Frequency of Sampling
Type of Analysis
Odor Problem
Vent Stacks
Flow SCFM Per Stack
Number
Height (Elev. @ tip.) - Ft.
Diameter - Inches
Exit Gas Temperatures - F°
Emission Control Devices
Type - Scrubber
Incinerator - Flare
Summary of Pollutants
Hydrocarbons + Sulfur Containing
Compounds besides SOX - Tons/Ton Carbon Disulfide
Particulates - Tons/Ton Carbon Disulfide
NOX - Tons/Ton Carbon Disulfide
SOX - Tons/Ton Carbon Disulfide
CO - Tons/Ton Carbon Disulfide
(1) Not enough information to calculate - Incinerator burns claus tail
(2) Converts harmful liquid waste to air pollutants
(3) S02 from liquid waste only.
Boiler Fine
Gas
24,605
Cont inuous
.00004
Flue Gas - Liquid
Waste Incineration
U)
Continuous
Negligible
.00009
.00004
.00014
Negligible
Negligible
gas also.
Flue Gas
Emergency Flare
Not Specified
Intermittent
1
.00662 (3)
.00014
Negligible
.46342
.37918
.00009
None
Calc'd.
No
Yes
Not Specified
1
100
50
800
No
+
(1)
(1)
Yes
Once/Month
Chroma tagraph
No
Yes
1
150
78
1000
Yes
+
+
None
No
Yes
No
Yes (2)
0
0
.00662
. 0
Yes
Storage
Loss
20
Continuous
Negligible
Negligible
None
No
Yes
70
35-50
36
Ambient
No
Negligible
0
0
0
-------
TABLE CD-Ill
NATIONAL EMISSIONS INVENTORY
CARBON DISULFIDE FROM
METHANE AND SULFUR
Page 3 of
EPA CODE NO. 8-4
CAPACITY TONS OF CARBON DISULFIDE 175,000
AVERAGE PRODUCTION - TONS OF CARBON DISULFIDE 175,000
EMISSIONS TO ATMOSPHERE
Stream
Flow-Lbs./Hr.
Flow Characteristics - Continuous or Intermittent
If Intermittent - Hrs./Yr.
Composition Tons/Ton of Carbon Disulfide
Methane
Ethane
Propane
Sulfur
Carbonyl Sulfide
Carbon Disulfide
Thtophene
Hydrogen Sulfide
Sulfur Dioxide
Nitrogen
Nitrogen Dioxides
Carbon Dioxide
Water
Analysis
Date of Frequency of Sampling
Type of Analysis
Ordor Problem
Vent Stacks
Flow SCFM per Stack
Number
Height (elev. @ tip) - Ft.
Diameter - Inches
Exit Gas Temperature - F°
Emission Control Devices
Type - Scrubber
Incinerator - Flare
Summary of Pollutants
Hydrocarbons + Compounds Containing Sulfur
besides SO^ - Tons/Ton Carbon Disulfide
Particulates - Tons/Ton Carbon Disulfide
NOx - Tons/Ton Carbon Disulfide
SOX - Tons/Ton Carbon Disulfide
CO - Tons/Ton Carbon Disulfide
Boiler Flue
Gas
13,221
Continuous
.00001
.29025
.23750
Not Specified
No
Not Specified
No
0
.00001
0
0
Reactor Emergency
Vent Flare
20,800
Intermittent
72
.00025
.00369
Yes
Once
Chromatagraph
Yes
Yes
1
88
18
200
Yes
Yes
0
0
0
.00025
0
Emergency Storage
Tank Vent
47
Intermittent
12
Negligible
Negligible
None
No
No
No
Negligible
0
0
0
0
-------
TABLE CD-Ill
NATIONAL EMISSIONS INVENTORY
CARBON DISULFIDE FROM
METHANE AND SULFUR
Page 4 of 4
EPA CODE NO. 8-5
CAPACITY TONS OF CARBON DISULFIDE 26,500
AVERAGE PRODUCTION - TONS OF CARBON DISULFIDE 25,500
EMISSIONS TO ATMOSPHERE
Stream
Flow-Lbs./Hr.
Flow Characteristics - Continuous or Intermittent
If Intermittent - Hrs./Yr.
Composition Tons/Ton of Carbon Disulfide
Methane
Ethane
Propane
Sulfur
Carbonyl Sulfide
Carbon Disulfide
Thiophene
Hydrogen Sulfide
Sulfur Dioxide
Nitrogen
Nitrogen Dioxides
Carbon Dioxide
Water
Oxygen
Analysis
Date of Frequency of Sampling
Type of Analysis
Or dor Problem
Vent Stacks
Flow SCFM per Stack
Number
Height (elev. @ tip) - Ft.
Diameter - Inches
Exit Gas Temperature - F°
Emission Control Devices
Type - Scrubber
Incinerator - Flare
Summary of Pollutants
Hydrocarbons x Sulfur Contain Compounds
besides SOx - Tons/Ton Carbon Disulfide
Particulates - Tons/Ton Carbon Disulfide
NOx - Tons/Ton Carbon Disulfide
SOX - Tons/Ton Carbon Disulfide
CO - Tons/Ton Carbon Disulfide
Sulfur Storage
Vent
1.7
Continuous
Flue Gas
Emergency Flare
33.758
Intermittent
30
.00028
None
Calc'd.
No
No
No
0
.00028
0
0
0
.00478
.01260
.00005
.00122
.00685
None
Calc'd.
No
Yes
6780
1
110
12
1800
Yes
Yes
0
0
.00478
0
Storage Vent
Continuous
Fugitive Emissions
.42
Continuous
Negligible
Negligible
None
No
No
No
Negligible
0
0
0
0
( )
(.00007)
( )
None
No
No
No
.00007
0
0
0
0
-------
TABLE CD-IV
CATALOG OF EMISSION CONTROL DEVICES
CARBON DISULFIDE
FROM METHANE AND SULFUR
Page 1 of 2
8-1
Reactor
Start Up Flare
FL I
CS2,H2S,COS,Lt.HC
Yes
8-1
Purification Sect.
Emergy Flare
FL II
CS2,H2S,COS,Lt.HC
Yes
Incineration Devices
E.P.A. Code No. for Plant Using
Steam
Device I.D.
Type of Compound Incinerated
Type of Device - Flare
Incinerator
Other
Material Incinerated (SCFM)
Auxiliary Fuel Required (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 Carbon Disulfide
Operating Cost - Annual - $(1972)
Operating Cost - c/Lb. of Carbon Disulfide
Efficiency - % - CCR
Efficiency - 7, - SERR
(1) Devices also burns claus plant tail gas.
(2) Figures are for conbined function of incineration of liquid waste and claus plant.tailgas.
(3) Since device converts harmful liquid waste to air pollution.
8-3
Purification Sect.
Emergency Flare
FL III
CS2,H2S,COS,Lt.HC
Yes
8-3
Heavy Ends
Thermal Oxidlzer
IN I
CS2,S,Oil (1)
Thermal Oxidizer
•cified 1050
No
150
10,000
1967
1500
30% 100%
18%
Yes
Natural Gas
125 SCFH
120
135,000 20,000
1956 1969
.065
7500
.003
100%
-
. 143 Ib./hr.
Yes (1)
Natural Gas
29,200 SCFH
150
250,000 75,000 25,000
1956 1967 1969
.15
105,000
.044
100%
Not Applicable
(3)
-------
TABLE CD-IV
CATALOG OF EMISSION CONTROL DEVICES
CARBON DISULFIDE
FROM
METHANE & SULFUR
\
page 2 of 2
Incineration Devices
E.P.A. Code No. for plant using
Steam
Device I.D.
Type of compound incinerated
Type of Device - Flare
Incinerator
Other
Material Incinerated (SCFM)
Auxiliary Fuel Required (excl. pilot)
Type
Rate - Btu/Hr.
8-4
Purification Section
Emergency Flare
H2S,
FL IV
Yes
Not Specified
I
Device or Stack Height - Ft
Installed Cost - Mat'l & Labor - $
Installed Cost based on "year" - dollars
Installed Cost - c/lb of Carbon Disulfide
Operating Cost - Annual - $(1972)
Operating Cost - c/lb of Carbon Disulfide
Efficiency - % - CCR
Efficiency - 7, - SERR
100%
8-5
Reactor & Purification Section
Emergency Flare
FL-V
Hj8, CS2, 82, COS
Yes
500 - 700
No
110
50,000
1962
.094
6600
.012
100%
53Z
-------
TABLE CD-V
Current (1)
Capacity
871
Marginal
Capacity
0
NUMBER OF
Current
Capacity
on-stream
in 1980
871
NEW PLANTS BY
Demand
1980
i,ioo<2)
1980
Capacity
1980
1,100 (3)
Capacity
to be
Added
229
Economic
Plant
Size
200
Number
of Nev
Units
1-2
NOTE:
(1) MM Ibs./year.
(2) 3% per year increase - Chem. Profile, April, 1970.
(3) MSA report for Environmental Protection Agency.
-------
TABLE CD-VI
Emission
EMISSION SOURCE SUMMARY
T/T OF CARBON DISULFIDE
Source
Total
Furnace Flue Gas Sulfur Storage Emergency Flaring Fugitive Emissions
Hydrocarbons*
Particulates
N0x
S0x
CO
.0009 .00007
. 0004 . 00028
.00014
Negligible .00478
Negligible
00016
.00032
. 00014
. 00478
0
*Includes sulfur containing compounds excluding sulfur dioxides.
-------
TABLE CD-VII
Chemical
Process
Increased Capacity
Pollutant
Hydrocarbons*
Participates
NOX
sox
CO
WEIGHTED EMISSION RATES
Carbon Disulfide
Methane
229 MM Lbs./Year
Increased Emissions
Emissions, Lb./Lb. MM Lbs./Year
.00016 .0366
.00032 .0732
.00014 .0321
.00478 1.09
0
S:
Weighting
Factor
80
60
40
20
1
Lgnificant Emission
Weighted Emissions
MM Lbs./Year
3
4
1
22
_0
Index = 30
*Includes sulfur containing compounds excluding sulfur dioxides.
-------
Cyclohexanone
-------
TABLE OF CONTENTS
Section Page Number
I Introduction CO-1
II Process Description CO-2
III Plant Emissions CO-3
IV Emission Control CO-6
V Significance of Pollution CO-8
VI Cyclohexanone/Cyclohexanol Producers CO-9
LIST OF ILLUSTRATIONS & TABLES
Block Flow Diagram Figure CO-1
Process Flow Diagram Figure CO-2
Basic Chemical Reactions Table CO-I
Net Material Balance Table CO-II
Gross Heat Balance Table CO-II-A
Emission Inventory Table CO-III
Catalog of Emission Control Devices Table CO-IV
Number of New Plants by 1980 Table CO-V
Emission Source Summary Table CQ-VI
Weighted Emission Rates Table CO-VII
-------
CO-1
I. Introduction
Cyclohexanone is an important intermediate in the production of
nylon 6 and nylon 6,6. It is produced, primarily, by the oxidation of
cyclohexane; as is cyclohexanol, a chemical commonly produced in con-
junction with cyclohexanone. Most of the tables and figures included in
this report are keyed to the production of cyclohexanone— as the pen-
ultimate oxidation product of cyclohexane. However, as far as total
emissions are concerned, it makes relatively little difference whether
cyclohexanone or a mixture of cyclohexanone and cyclohexanol is produced.
Like most air oxidation processes, venting of the "spent air"
accounts for the bulk of the 'emissions' associated with the production
of cyclohexanone. The other prominent source of emissions is the
distillation train with its attendant vent streams. Also the dehydrogenation
section, where used, produces some emissions. In addition to the air
emissions, quantities of waste organic acids and spent caustic are produced.
In general, air emissions from the production of cyclohexanone could be
characterized as moderate.
The current U. S. capacity for the production of cyclohexanone/cyclo-
hexanol via the air oxidation of cyclohexane - including that material
that is never separated, stored or traded as an item of commerce, i.e.
intermediates in the production of other chemicals (primarily adipic acid) -
can be estimated at 1.8 x 109 Ibs./yr. (1) By 1980 U. S. capacity for .the
production of cyclohexanone/cyclohexanol can be expected to double to
3.6 x lO9 Ibs./yr. There is no basis for forecasting a change in emission
rate, i.e. tons emission/ton of cyclohexanone.
(1) Based on Process Research Inc. estimate of current and future nylon capacity.
-------
CO-2
II. Process Description
The air oxidation of cyclohexane to cyclohexanol/cyclohexanone mixtures
is carried out in the liquid phase. The conversion may be carried out thermally
or catalytically. The latter approach predominates. (The pertinent chemical
reactions are shown in Table I)
Either.of two catalysts are normally used; a soluble salt of cobalt
such as cobalt naphthanate or boric acid. Cobalt naphthanate is probably
the more common catalyst. It is reportedly used in concentrations of 2 to
40 parts per million (on cyclohexane).
The use of boric acid as a 'catalyst' is a relatively recent innovation
It is claimed that its use increases the reaction selectivity and raises the
yield from 70% to about 90%. This is accomplished because yield loss is due
primarily to the fact that oxidation does not stop at cyclohexanol or cyclo-
hexanone, but proceeds to various oxidation products such as dicarboxylic
acids. However, when the reaction is carried out in the presence of boric
acid, cyclohexanol is tied up as an ester as soon as it is formed, thus
precluding further oxidation. About .005 Ibs. of boric acid per pound of
eyelohexanone/cyclohexanol is consumed. Both I.F.P. and Scientific Design
license boric acid processes.
The following description is based on a boric acid process: (see also
Fig. I and Fig. II), Cyclohexane and a slurry of boric acid are pumped into
a series of stirred autoclaves that are maintained at a temperature of about
300 °F and a pressure of about 200 PSIG. Air is compressed, and sparged
into the bottom of each autoclave, where it initiates and sustains the oxidation
reaction (Reaction I - Table I). The exothermic heat of reaction is removed by
reflux condensers which are designed to (1) condense and return all hydro-
carbons to the reactors, (2) reject water (which suppreses the oxidation) and
(3) vent the "spent air" overhead. The liquid effluent from the final reactor
is then mixed and washed with water. The water soluble compounds are separated,
with the unreacted boric acid recycled and the other soluble acids rejected as
an aqueous waste. The washed mixture of naphthene ketone, alcohol, ester and
other reactants is then saponified to recover the esters formed by the reaction
of the boric acid and cyclohexanol (Reaction II and III, Table I). The
aqueous layer, containing soluble sodium salts, is rejected from the botton of
a wash column. The washed hydrocarbon mixture is then pumped to the cyclohexane
column where the unreacted cyclohexane is taken overhead and subsequently
recycled to the oxidation reactors. The bottoms from the cyclohexane column are
combined with the liquid effluent from the cyclohexanol dehydrogenation reactor
and cyclohexanol from the cyclohexanol recovery unit. The combined stream
is fractionated to reject heavy and light ends. The heart cut eyelohexanone/
cyclohexanol mixture ("K-A Oil") may then be sent to intermediate storage
prior to further processing (i.e. oxidation to adipic acid) or may be separated
into its constituent components via the "one-ol" tower. The overhead product
from the "one-ol" tower, cyclohexanone, is pumped to storage. The cyclohexanol
bottoms are generally dehydrogenated to produce additional cyclohexanone.
-------
CO-3
III. Plant Emissions
A. Continuous Air Emissions
1. Oxidizer Vent
All cyclohexane air oxidation plants vent 'spent air1 from the
oxidizer/reactor. Generally this vent stream represents the single
largest source of emissions in the plant. Within this general
frame work .there is still room for considerable variation in the
magnitude of emissions reported for this source. The variations
are primarily due to the amount of scrubbing done by the various
respondents and whether or not air recycling techniques are
utilized. All reported emissions are summarized in Table III.
2. Distillation Train Vents
Most of the emissions grouped under this heading are combustion
products from the variety of devices used by the operators to
combust the 'light ends' rejected by their distillation/purification
facilities.
Also included are the emissions resulting from the operation of
steam ejectors, as reported by the operators of EPA Coded Plants
9-1, 9-2 and 9-4. Operator 9-4 estimates losses from this source
at l-27o of production or about .015 Ib./lb. This seems extremely
high. Other emissions in this category are summarized in Table III.
3. Hydrogen Vent from Dehydrogenation Section
The three operators who indicated that they are dehydrogenating
cyclohexanol all process this vent differently. The operator of
plant 9-4 sends this stream to his boiler house, and thus reports
no emissions. Operator of plant 9-2 removes condensibles by chilling,
and then vents the non-condensibles. Operator 9-3 scrubs the stream
prior to venting. The emissions reported by the latter two operators
are summarized in Table III.
4. Plant Flares
Based on the sampling from the questionnaires about one half of
the cyclohexanone/cyclohexanol plant operators utilize a continuously
lighted plant flare or continuous service incineration device. The
type of compounds normally burned in these devices should not result
in the emission of significant amounts of pollutants. Minimal
amounts of CO and NOX can be expected during normal operation.
Reported emissions are summarized in Table III.
5. Dehydrogenation Heater Flue Gas
Of the three operators reporting dehydrogenation operations (see
Section III-A-3), all report using natural gas for heater fuel. Only
one (9-2) reports sulfur content of the fuel - 4 ppm. At that
concentration, S02 emissions from this source are entirely negligible.
They amount to considerably less than .00001 ton/ton of cyclohexanone.
-------
CO-4
6. Storage Losses
Only about one half of the liquid storage tanks used by the
respondents have vapor conservation devices. Consequently this
emission source vill contribute to the overall air pollution
resulting from the operation of the subject process. It is
imprudent to attempt to quantify this source without knoving further
details about storage operations - i.e., tank configuration, storage
temperature, average atmospheric conditions, etc. Hovever, it is
probably safe to say that relative to other cyclohexanone sources,
the emissions are small.
B. Intermittent Air Emissions
No intermittent air emissions have been reported by cyclohexanone/
cyclohexanol plant operators. Hovever, atmosphere venting during
start-ups and plant emergencies is an operation practiced universally
by the petrochemical industry. Unfortunately, there is great
variation in the rate and frequency of this type of emission and
even an estimate (other than one from the industry) of the importance
of this source relative to other tabulated sources vould be imprudent.
C. Continuous Liquid Wastes
1. Waste Acid
Various organic acids are formed during the oxidation of
cyclohexane. The water soluble acids are removed from the process
by standard water vashing techniques. Operators 9-2 and 9-3, both
report similar flow rates for this aqueous waste stream - 10,000
Ib./hr. and 14,000 Ib./hr. respectively. Operator 5-4 indicates that
this stream is neutralized, but he does not report the method of
ultimate disposal. Operators 9-3 and 9-2 both report utilizing a
combination of incineration and deep veil injection methods as
disposal techniques. Operator 5-3 uses deep well disposal.
2. Spent Caustic
The esters of cyclohexanol formed during the oxidation of
cyclohexane are recovered by saponification. A spent caustic stream
is generated by this procedure. Operators 9-3 and 9-2 report injecting
15,000 Ib./hr. and 14,000 Ib./hr. (respectively), of this material into
deep veils. Presumably all operators must dispose of similar streams,
but none report them.
3. Waste Water
Various quantities of waste vater have been reported. They range
from about 10 to 175 GPM. One operator C5-4) reports that his waste
vater stream contains 2.3 vt. 70 organics. Hovever; that, is vaste
from an entire adipic acid plant; the amount produced by the
cyclohexanone/cyclohexanol portion of the plant, if assumed to be
half of the total, is 175 GPM of water containing 2,000 Ib./hr. of
organics.
D. Solid Wastes
Three operators (EPA Code No.'s. 5-4, 9-2 and 9-3) report the
accumulation of from 120 to 250 Ib./hr. of solid waste materials
-------
CO-5
within their processing equipment. According to the latter two
named respondents, this material is cleaned from the equipment once
a year and used as in-plant land fill. Operator 5-4 does not
report his disposal method.
E. Odors
In general, the air oxidation of cyclohexane to cyclohexanone/
cyclohexanol does not appear to be a process that has an odor
"problem".
Only one operator (EPA Code 9-3) reported an odor complaint in
the last year. Most of the reported odors are said to be detectable
only on the plant property. The odoriferous materials are usually
either, cyclohexanone or unidentified organic acid combustion products.
Odor sources mentioned by two operators (9-2 and 9-3) are the
organic acid incinerator flue gases and the dehydrogenation unit
vent. Additionally operator 9-2 reported that the odor of
cyclohexanone, from the oxidizer air vent, is detectable on plant.
F. Fugitive Emissions
Only one operator (EPA Code No. 9-1) has made an estimate of
fugitive emissions - 10 SCF hr., which, if correct, is negligible. If
this process becomes one for in-depth study, further study of this point
will be required. For example, another estimate of fugitive emissions
may be derived from information provided by operators 9-4 and 9-2.
One could infer that the losses operator 9-4 assigned to his steam
ejector operation (see Section III-A-2) might also include fugitive
emissions. Operator 9-2, whose reported ejector losses are based -
at least in part - on plant measurement, estimates only l/30th the losses
from this source that operator 9-4 estimates. If 9-2's figures are
accepted then one could conclude that most of operator 9-4's estimated
ejector losses are actually fugitive emissions.
-------
CO-6
IV. Emission Control
The various emission control devices that have been reported as being
employed by operators of cyclohexanone/cyclohexanol plants are summarized
in Table IV of this report, which is entitled Catalog of Emission Control
Devices. The control devices may be divided into tvo broad categories;
(1) Combustion Devices - those devices which depend on thermal or catalytic
oxidation of combustibles for emission control, and (2) Non-combustion
Devices - devices that do not depend on combustion for emission control.
In Table IV, all combustion devices will be assigned two efficiency ratings
(when data are available), they are:
(1) CCR - Completeness of Combustion Rating.
CCR = Lbs. of Op that react with pollutants in feed to device x IQQ
Lbs. of 02 that theoretically could react with these pollutants
(2) SERR - Significance of Emission Reduction Rating
weighted pollutants in - weighted pollutants out ___
SERR = weighted pollutants in x iUU
A more detailed discussion of these ratings may be found in Appendix V
of this report.
Most non-combustion devices will be assigned an efficiency based on
percent reduction of a specific compound, with that compound defined. A
few non-combustion devices will receive SERR ratings,which rating will be
so designated.
Unfortunately, in only a few instances did the respondents to the
cyclohexanone questionnaire provide sufficient data with which to calculate
device efficiencies. Never-the-less, certain generalizations about the
performance of the devices utilized can be made:
Absorber/Scrubbers
Five of the seven absorber/scrubbers reported were employed in
recovering hydrocarbons from the oxidizer air vent. It is questionable
whether two of these devices, CO-1A and CO-IB, should be categorized
as pollution control devices. Although they prevent large amounts
of hydrocarbons from entering the atmosphere, it would seem more
appropriate to characterize them as product recovery devices. It seems
apparent (from the general plant-to-plant agreement on total emissions)
that other plants utilize such devices, but none other have included
them in their listings of pollution control devices.
In general it would be expected that absorber/scrubbers would perform
quite efficiently in removing hydrocarbons; which constitute over 98%
of cyclohexanone/cyclohexanol's SEI. Efficiencies should be 90 + %.
On the other hand, the types of absorber/scrubbers reported, would be
quite inefficient in controlling emissions of carbon monoxide. Other
information on these devices is tabulated in Table IV.
Condensers and K. 0. Drums
Operator EPA Code No. 9-2 uses an ammonia chiller to recover cyclo-
hexanone from his dehydrogenation unit vent. It is 98.5% effective.
-------
CO-7
However, since this $12,000 device recovers $460,000 worth of cyclo-
hexanone per year it seems inappropriate to categorize it - primarily -
as a pollution control device. Reported information on the two devices
in this grouping is tabulated in .Table IV.
Incineration Devices
Data sufficient to calculate device efficiencies have not been
reported. However, the lack of sulfur, nitrogen or halogen containing
compounds in the process would lead one to expect CCR's and SERR's of
close to 100%. Operator 9-2, states that odors associated with
incineration device CO-3 are a result of the incomplete combustion
of organic acids, however, considering the small amount of organic
aaterial necessary to generate an odor, this does not preclude incin-
eration efficiencies in excess of 99%. Additional information on
incinerators and flares is tabulated in Table IV.
It is unlikely that any change in operating conditions can be made that
will reduce air emissions since yield and selectivity are not directly
related to the primary source of air pollution. For the same reason, the use
of purer raw materials we^ild have entirely negligible effect on over-all
air pollution.
Development work directed toward reductions in emissions from this
process falls into the following general categories - with the first
preeminent:
(1) Substitution of oxygen for air; as the oxidizing agent.
(2) Substitution of another, non-pollution, oxidant for air (besides
oxygen).
(3) Prevention of hydrocarbon venting to atmosphere rather than to flare.
(4) More efficient design and utilization of devices currently being
utilized.
-------
CO-8
V. Significance of Pollution
It is recommended that no in-depth study of this process be undertaken
at this time. The predicted growth rate of cyclohexanone/cyclohexanol
production is 'significant1 but the absolute growth to 1980 is only moderate.
Furthermore, the 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
forecast the number of new plants that will be built by 1980 and to
estimate the total weighted annual emission of pollutants 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 ratio of cyclohexanone/cyclohexanol capacity to nylon 6 plus
nylon 6,6 capacity does not change from year-to-year.
(2) All future cyclohexanone/cyclohexanol processes will be based on
the air oxidation of cyclohexane.
A forecast based on these assumptions is most probably somewhat high,
however, not to the extend that it would significantly alter the S.E.I.
On a weighted emission basis a Significant Emission Index of 6,261 has
been calculated in Table VII. This is less than the S.E.I.'s calculated for
some of the other processes in the study. However, it may be sufficiently
high to justify an in-depth study if taken in conjunction with the processes
such as adipic acid and nylon which are usually associated with cyclohexanone.
Hence, it is probably expedient to defer a decision on the in-depth study of
this process.
-------
CO-9
VI. Cyclohexanone/Cyclohexanol Producers
Because much of the cyclohexanone/cyclohexanol produced exists only as
an intermediate rather than a final product, it is difficult to obtain
dependable data concerning production capacities. Listed belov are published
estimates of plant capacities, for the cyclohexane air oxidation process, for
the year 1967. Also a partial up-date, based on questionnaire information, is
shown under .the column entitled 1972 Capacity. Finally, an estimate of total
1972 capacity has been made based on the assumption that the relationship
shovn belov is true. (at least for the time period 1967 to 1972)
(Cyclohexanone + Cyclohexanol) capacity
(Nylon 6
+ Nylon 6,6) capacity
('time)
Thus, 1972 capacity is estimated at 1.8 x 1(T Ib./yr.
Company
Celanese
Columbia Nipro
Dov Badische
Du Pont
El Paso Products
Monsanto
Rohm & Hass
Union Carbide
Location
Bay City, Texas
August, Ga.
Freeport, Texas
Belle, W. Ma.
Orange, Texas
Victoria, Texas
Odessa, Texas
Pensacola, Fla.
Louisville, Ky.
Taft, La.
Total
1967 Capacity
(MM Lb./Yr.)
30
45
90
200
200
35
35
300
20
50
1005
1972 Capacity
MM Lb./Yr.
24
150
252
Shut Down
230
7
62
414
7
?
1,800 (Est.)
-------
PAGE NOT
AVAILABLE
DIGITALLY
-------
PAGE NOT
AVAILABLE
DIGITALLY
-------
Main Reaction
Reaction I
H2
H2 C' \ H2
H2 C C H2
C
H2
+ 0
2 ""
TABLE CO-I
MASK: CM KM is TRY
H2 C^ C H2
OK
CYC.].OHI:XA:-"O::I: PRODUCTION
Oxidation of Cvclohexane
v
H2 C C H2
H2 C ^C H2
H 0 -I- Various Organic Acids
Mol. Wt.
Cyclohexane
84.16
Air
-Cyclohexanone
98. 14
Cyclohexanol
100.16
+ Vater + Acid
Secondary Reactions
Reaction II
H
0 H
H2 f9 H2 +
C^ C H2
0
tt
R-C-OH
0
Forma'tion of Cyclohexanol Esters
R-C-OH
H C V H
"2 X 5 "2 4. HoO
H2 C p H2 ' n2v
"2 H2
Cyclohexanol + Organic Acid *• Ester 4- Vater
0
R-C-OWH
H2 d C H2
Reaction III Ho C C H,
*• \ i 2.
C
Ho
+ NaOH-
Recovery of Cyclohexanol Esters fSaponiiication)
Cyclohexanol Ester + Caustic
Y
H? 9 C H2
H2 C C H2
Cvclohexanol
0
R-C-O-NA
Sodium Salt
Reaction IV
X
H2 9 C H2
H2 C C H2
Cyclohexanol Dehydrogenation
0
M
C^
H2 C C H2
Ho C C HO
H2
Cvclo'iexanol
Cvc lohexanonc
Hydrogen
-------
TABLE CO-II
CYCLOHEXANE OXIDATION
TO
CYCLOHEXANONE/CYCLOHEXANOL
MATERIAL BALANCE - T/T OF "K-A OIL" PRODUCT
Stream No.
(Fig. II)
Stream Name
Cyclohexane
Cyclohexanone
Cyclohexanol
Heavy Organics
C4 - C5
02
N2
CO
C02
1234
Fresh Recycle Make-up Recycle
Feed Liquid Gas Gas
0.9863 6.6600
0.0187
.2257 0
.7430 .9831
.0363
.0120
Total Fd.
to Rx's
7.6463
.0187
.2257
1.7261
.0363
.0120
5
Rx "Effluent" Rx
(Btms. & Ovhd.) Btms
6.6600 6.6600
.1032 .1032
.8968 .8968
.1608 .1608
.0331
1.7261
.0638
.0213
6A & 6B
Vent
Gas
.0144
.7340
.0275
.0093
7 8
Heavy K-A
Ends Oil
.1032
.8968
.1608
Total
0.9863
6.6600
.9687
1.0501
9.6651
9.6651
7.8208
0.7942
.1608 1.0000
-------
TABLE CO-II-A
CYCLOHEXANONE/CYCLOHEXANOL PRODUCTION
VIA
AIR OXIDATION OF CYCLOHEXANE
GROSS HEAT BALANCE
The exothermic heat of reaction is 1200 - 1300 BTU/Lb. of converted
cyclohexane. (1)
There are not sufficient published data available to permit the construction
of a typical commercial reactor section gross heat balance for this process.
(1) Mod. Text. Mag., November, 1963
-------
Plant - EPA Code Number
Capacity - Tons of Cyclohexanone/Yr.
Average Production - Tons of Cyclohexanone/Yr.
Quarterly Production Variation - % of Max.
Emissions to Atmosphere
Stream
Flov - Ib./hr.
Flov Characteristic - Continuous or Intermittent
if Intermittent - hr»./yr. flov
Composition - Tons/ton of Cyclohexanone
Cyclohczane
Cyclohexanone
Cyclohexanol
Methane
Ethane
Ethylene
Nitrogen
Oxygen
Hydrogen
Carbon Monoxide
Carbon Dixoide
Water
Misc. Hydrocarbons
Sample Tap Location
Date or Frequency of Sampling
Type of AnalyBli
Odor Problems
Vent Stacks
Flov - SCFM/Stack
Number
Height - Feet
Diameter - Inches
Exit Gas Temp - F°
Emission Control Devices
•ype - Incinerator
Flare
Scrubber
Other
Catalog I.D. Number
Total Hydrocarbon Emissions - Ton/ton of Cyclohexanone
Total Partlculate & Aerosol " " " "
Total NOX " " " "
Total SOX " " " "
Total CO " " " "
TABLE CO-III
NATIONAL EMISSIONS INVENTORY
CYCLOHEXANONE PRODUCTION
5-2
207,000 <5)
Page 1 of 6
Lov Pressure
Off-gas
(Cyclohaxane
Recovery Section)
1409
Continuous
.01426
.00016
.00556
.00096
Every 2-3
GLC & Orsat
No
Yes
250
1
65
6
85
No
years
5-3
115,000
(8)
High Pressure
Off-gas
Cyclohexane
Recovery Section
Oxidizer
"Spent Air" 6,
Vent
44,115
Continuous
50,000
Continuous
.80195
.00470
.00370
.00193
.00740
Bi-*«ekly
GLC & Orsat
No
Yes
10,000
1
85
6
85
(7)
1.56815
.07527
.02927
Infrequent
GLC
No
Yes
-vflO, 000
1
160
.10
104
Yes
CO-11
.00926
.03379
.07637
Purification
Section
Vent
3000
Continuous
.09474
.00110
.0045?
Infrequent
GLC
No
Yes
1
160
24 (?)
104
Yes
CO-12
-------
Plant - EPA Code Number
Capacity - Tons of Cyclohexanone/Yr.
Average Production - Tons of Cyclohexanone/Yr.
Quarterly Production Varaltlon - % of Max.
Emission* to Atmosphere
Stream
Flov - Ib./hr.
Flov Characteristic - Continuous or Intermittent
If Intermittent - hrs./yr. flow
Composition - Tons/ton of Cyclohexanone
Cyclohexane
Cyclohexanone
Cyclohexanol
Methane
Ethane
Ethylene
Nltrogaa
Oxygen
Hydrogen
Carbon Monoxide
Carbon Dioxide
Water
Mies. Hydrocarbons
Sample Tap Location
Date or Frea>uenyc of Sampling
Type of Analysis
Odor Problem
Vent Stacks
Flow - SCFM/Stack
Number
Height - Feet
Diameter - Inches
Exit Gas Temp. - F°
Emission Control Devices
Type - Incinerator
Flare
Scrubber
Other
Catalog I.D. Number
Total Hydrocarbon Emissions - Ton/ton of Cyclohexanone
Total Partlculate & Aerosol - " " " "
Total NO " " " "
Total SOX " " "
Total CO " " " ' "
TABLE CO-III
NATIONAL EMISSIONS~TNVENTORY
CYCLOHEXANONE PRODUCTION
5-4
31,000 (5)
Oxidirer "Spent
Air" Vent
12,958
Continuous
.02355
1.52394
.02613
.05560
.02574
.01274
Stack
Infrequently
GLC
Yes
2870
1
19
8
No
Page 2 of 6
Desorbed
Gases from
Storage &
Purification
'•'SOO (6)
Continuous
Yes
Yes
+ K. 0.
CO-10
Drum
/. 03629
s. 0257*
-------
TABLE CO-III
NATIONAL EMISSIONS INVENTORY
CYCLOHEXANONE PRODUCTION
Page 3 of 6
Plant - EPA Code Number
Capacity - Tons of Cyclohexanone/Yr.
Average Production - Tons of Cyclohexanone/Yr.
Quarterly Production Variation - '/, of Max.
Emissions to Atmosphere
Stream
Flov - Ib./hr.
Flov Characteristic - Continuous or Intermittent
if Intermittent - hrs./yr. flov
Composition - Tons/ton of Cyclohexanone
Cyclohexane
Cy clohexanone
Cyclohexanol
Methane
Ethane
Ethylene
Nitrogen
Oxygen
Hydrogen
Carbon Monxide
Carbon Dioxide
Water
Misc. Hydrocarbons
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problems
Vent Stacks
Flov - SCFM/Stack
Number
Height - Feet
Diameter - Inches
Exit Gas Temp. - F°
Emission Control Devices
Type - Incinerator
Flare
Scrubber
Other
Catalog I.D. Number
Total Hydrocarbon Emissions - Ton/ton of Cyclohexanone
Total Particulate & Aerosol Emissions - Ton/ton of Cyclohexanone
Total NOX " " " " "
Total SOX " " " "
Total Co " " " " "
(4)
Oxidirer "Spent
Air" Vent
31,560
Continuous
9-3
51,000
0
(4)
Oxidizer "Spent
Air" Vent
12,400
Continuous
Distill. /Purf.
Waste Stream
Incinerator
Flue Gas
Not Specified
Continuous
Ground Flare
Flue Gas
1750 Max.
Intermittent
Cyclohexanol
Dehydrog«nation
Vent
Continuous
9-1
12 , 000
0
Not Specified
.01913
.00112
.00029
.01527
i
Irregular
GLC
Not Specified
Yes
CO-5 A&B
.04208
.00492
.00043
.01562
Irregular
GLC
Not Specified
Yes
CO- 6 A&B
Burner Stack
Yes
Yes
6814
1
36
72
1800
Yes
CO-7
.06968
.03089
Never
Not Specified
Yes
CO-8
.00071
.00081
e.. OOOOl
c. 00001
.00002
.02277
Irregular
GLC
No
Yes
846
1
12
8
70°
Yes
CO-9
-------
TABLE CO-III
Flint - EPA Code Number
Capacity - Tons of Cyclohexanone/Yr.
Average Production - Tons of Cyclohexanone/Yr.
Quarterly Production Variation - % of Max.
Emissions to Atmosphere
Stream
Flov - Ib./hr.
Flov Characteristic - Continuous or Intermittent
If Intermittent hrs./yr. flow
Composition - Tons/ton of Cyclohexanone
Cyclohexane
Cyclohexanone
Cyclohexanol
Methane
Ethane
Ethylene
Nitrogen
Oxygen
Hydrogen
Carbon Monoxide
Carbon Dioxide
Water
Misc. Hydrocarbons
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problems
Vent Stacks
Flov SCFM/Stack
Number
Height - Feet
Diameter - Inches
Exit Gas Temp. F°
Emission Control Devices
Type - Incinerator
Flare
Scrubber
Other
Catalog I.D. Number
Total Hydrocarbon Emissions - Ton/ton of Cyclohexanone
Total Particulate & Aerosol - " " " "
Total NO " "
Total SO* " "
Total CO Emissions - Ton/ton of Cyclohexanone
Unspecified
NATIONAL EMISSIONS INVENTORY
CYCLOHEXANONE PRODUCTION
9-2
75,000
0
~-
Oxidatiion Section Oxidation
Vent
Not Specified
Continuous
.00116
None
Never
Calc'd.
No
Yes
10
1
40
1.5
85°
None
"Air" Vent
76,675
Continuous
.00652
.00253
1.42762
.01445
1970
Mass Spec & GLC
•' No
Yes
6000
1
"•'IS
16
70°
Yes
+
CO-1A&B
Purification
Section Steam
Jet Discharge
69
Continuous
.00051
"-
+
+
None
Never
Estimate
No
Yes
5
3
55
1.5
150
No
Page 4 of 6
Cyclohexanol
Dehydrogenation
Vent
?00
Continuous
.00067
•*. 00001
i. 00001
^.00001
. 00002
.01088
.00014
1969
Mass Spec & GLC
No
Yes
630
1
40
3
54
Yes
Condenser
CO- 2
Flue Gas ex
Incineration of Various
Varte Streams
A/1000 (1)
Continuous
+
+
None
Never
No
Yes
-v/15,000
1
30
72
1750
Yes
CO- 3
.01141
.01459
-------
Plant - EPA Code Number
Capacity - Tons of Cyclohexanone/Yr.
Average Production - Tons of Cyclohexanone/Yr.
Quarterly Production Variation - 7. of Max.
Emissions to Atmosphere
Stream
Flov - Ib./hr.
Flov Characteristic - Continuous or Intermittent
if Intermittent hrs./yr. flow
Composition - Tons/ton of Cyclohexanone
Cyclohenne
Cyclohexanone
Cyclohexanol
Methane
Ethane
Ethylene
Nitrogen
Oxygen
Hydrogen
Carbon Monoxide
Carbon Dioxide
Vater
Misc. Hydrocarbons
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problems
Vent Stacks
Flov SCFM/Stack
Number
Height - Feet
Diameter - Inches
Exit Gas Temp. F°
Emission Control Devices
Type - Incinerator
Flare
Scrubber
Other
Catalog I.D. Number
Total Hydrocarbon Emissions - Ton/ton of Cyclohexanone
Total Particulate & Aerosol - " " " "
Total NOX " " " "
Total SOX " " " "
Total CO " " " "
TABLE CO-III
NATIONAL EMISSIONS INVENTORY
CYCLOHEXANONE PRODUCTION
9-4
75,000
Oxidation
"Air" Vent
Page 5 of 6
Purification
Section Stream
Jet Discharge
38,837
Continuous
.00383
1.88830
.00649
.10106
.04069
.02543
Calc'd.
No
Yes - 2
3750 4580
Not Specified
60
6"
70°
No
195
Yes (''
+ <2>
CO-4
.01500
None
Estimate
None
None
.04426
.10106
-------
TABLE CO-III
EXPLANATION OF NOTES
NATIONAL EMISSIONS INVENTORY
CYCLOHEXANONE PRODUCTION Page 6 of 6
(1) Prior to combustion.
(2) A portion of this stream vents through an unlit flare.
(3) No entry.
(4) The quantities listed belov are believed to be the sum of the emissions
from the two identical streams that make up this entry.
(5) Capacity calculated by Houdry based on stated cyclohexane feed. Basis -
.7673 ton cyclohexanpne per ton of cyclohexane feed; ratio from question-
naire data.
(6) Flow prior to combustion in off-site flare.
(7) Operator states flow is from scrubber but gives no details.
(8) Capacity calculated by Houdry, based on pro-ration from EPA Code No. 5-2.
-------
Absorbera/Scrubbers
EPA Code No. for Plant Using
Flov Diagram (Fig. II) Stream I.D.
Device I.D. No.
Purpose - Control Emission of
Scrubbing/Absorbing Liquid
Type - Spray
Packed Column
Trays - Type
Number
Plenum Chamber
Other
Scrubbing/Absorbing Liquid Rate - GPM
Design Temp. (Operating Temp.) F
Gas Rate - SCFM (Ib./hr.)
T-T Height - Ft.
Diameter - Ft.
Washing Gases to Stack
Stack Height - Ft.
Stack Diameter - Ft.
Installed Cost - Mat'l. & Labor - $
Installed Cost Based on - "year" - Dollars
Installed Cost - Mat'l. & Labor r/lb. of Cyclohexanone/Yr.
Operating Cost - Annual $ (1972)
Value of Recovered Product - $/Yr.
Net Operating Cost - Annual $
Net Operating Coat - c/Lb. of Cyclohexanone
Efficiency -.%
SERR - 7.
Incineration Devices
EPA Code No. for Plant Using
Flov Diagram (Fig. II) Stream I.D.
Device I.D. No.
Types of Compounds Incinerated
Type Device - Flare
Incinerator
Other
Materials Incinerated - SCFM (Ib./hr.)
Auxilllary Fuel Req'd. (Excl. Pilot)
Type
Rate - BTU/hr.
Device or Stack Height "• Ft.
Installed Cost - Mat'l. 6. Labor - $
Installed Cost Based on - "year" - Dollars
Installed Cost - Mat'l. & Labor c/lb. Cyclohexanone/Yr.
Operating Cost - Annual - $ (1972)
Operating Cost - c/lb. of Cyclohexanone
Efficiency - VCCR
Efficiency - 7.-SERR
TABLE CO-IV
CATALOG OF EMISSION CONTROL DEVICES
CYCLOHEXANONE PRODUCTION
Distillation Section
5-3
/&, + Others
CO-12
Ct to Cf, HC
Lean Oil
Page 1 of 4
(104)
Yes
160
2
21,000 W
1966
.0913 W
84.7 (H.C.'s)
84.5
9-4
CO-4
Emerg. Relief
1000 GPM Liq.,311,000 PPH Vapor
195
127,377
(5)
4000
9-3
/fi\/&
CO-8
Lt. & Hvy. Ends
+ Ground Flare
Yea
Not Specified
Dehydrogenation
Section
9-3
A
CO-9
Unspecified HC's
Water
3
(50)
846
12
.67
Yes
12
.67
1,000
1972
.0010
1200
100
1100
.0011
JN&&&
CO-3
Various H.C.
Yes
30
Not Specified
-------
CO-5A-B (1>
C6 HC's
TABLE CO-IV
CATALOT OF EMISSION COIITROL PEVICES
CYCLOHEXANONE_ PRODUCTION
Oxidation Section
Absorbers/Scrubbers
EPA Code No. for Plant Using 9-2 9-2 9-3
Flow Diagram (Fig. II) Stream I.D. /fry s£~>
Device I.D. No. CO-1A CO-IB
Purpose - Control Emission of Cyclohexane Cyclohexane
Scrubbing/Absorbing Liquid Cyclohexanone Cyclohexanone
Type - Spray
Packed Column +
Trays - Type
Number
Plenum Chamber
Other
Scrubbing/Absorbing Liquid Rate -GPM
Design Temp. (Operating Temp.) F° (100)
Gas Rate - SCFM (Ib./hr.) 5400 600
T-T Height - Ft.
Diameter - Ft.
Washed Gases to Stack Yes
Stack Height -Ft. 15
Stack Diameter - Ft. 1.3
Installed Cost - Mat'l. & Labor - $ 100,000 30,000
Installed Cost Based on - "year" - Dollars 1968 1968
Installed Cost - Mat'l. & Labor, c/lb. of Cyclohexanone/Yr. .0667 .0200
Operating Goat - Annual $ (1972) 16,200 2,600
Value of Recovered Product - $/Yr. 60,000 60,000
Net Operating Cost - Annual - $ - 43,800 - 57,400
Net Operating Cost - c/lb. of Cyclohexanone - .0292 - .0383
Efficiency - % 77.5 92.9
SERR - 7. 90.5
Incineration Devices
EPA Code No. for Plant Using
Flov Diagram (Fig. II) Stream I.D.
Device I.D. No.
Types of Compounds Incinerated
Type of Device - Flare
Incinerator
Other
Materials 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 - Mat'l. & Labor - c/lb. Cyclohexanone/Yr.
Operating Cost - Annual - $ (1972)
Operating Cost - c/J.b. of Cyclohexanone
Efficiency - T, - CCR
Efficiency - %-SERR
Page 2 of 4
9-3
Hydrolysis and
Saponlfication
CO-6A & B '• '
Unspecified HC
CO-11
Unspecified HC
Lean Oil
880 (Ib./hr.)
(28,000)
32.6
2
Yes
<2> 6200
1962
(2) .0061
(2) 6,300
0
(2) 6,300
(2) .0062
(Total)
(Total)
(Total)
(Total)
(Total)
C510)
28
1.3
Yes
<2) 1550
1962
(2) .0015
(2) 6,300
0
(2) 6,300
(2) 0062
'Total)
CTotal)
'Total)
(Total)
'Total)
Yes
156,000
(3) 1966 6. 1971
.0678
26,700
0
26,700
.0116
9-3
B & C
CO-7
Organic Waste
(15,300) Max.
Yes
Nat. Gas
/~2.7
36
30,600
1966
.0300
13,500
.013?
-------
K. 0. DRUMS
EPA Co8e No. for Plants Using
Flov Diagram (Fig. II.) Stream I.D.
Device I.D. No.
Purpose - Control Emission of
Type - Condenser 4- K. 0. Drum
Demister
Degasser
Other.
Design Pressure (Operating Pressure) PSIG
Design Temp. (Operating Temp.) F°
Flov Rate of Treated Stream
Liquid - Ib./hr. (GPM)
Gas - Ib./hr. (SCFM)
1/1 Height - Ft.
Diameter - Ft.
Vent Gases to Stack
Stack Height - Ft.
Stack Dlam. - Ft.
SCFM/Stack
Installed Cost - Mat'l. & Labor - $
Installed Cost Based on - "year" - Dollars
Installed Cost - Mat'l. & Labor - c/lb. of Cyclohexanone/Yr.
Operating Cost - Annual - $ (1972)
Value of Recovered Product - $/Yr.
Net Operating Cost - Annual $
Net Operating Cost - C/lb. of Cyclohexanone
Efficiency - %
CONDENSERS
EPA Code No. for Plant Using
Flov Diagram (Fig. II) Stream I.D.
Device I.D. No.
Purpose - Control Emission of
Primary Refrigeration Liquid
Capacity of Refrigeration Unit - Tons
Gas Rate - SCFM
Temperature to Condenser - F°
Temperature out of Condenser - F°
Liquid Recovered GPM
NontCondensibles - SCFM
Installed Cost - Mat'l. & Labor
Installed Cost Based on - "year" - Dollars
Installed Cost-Mt'l. & Labor - r/lb. of Cyclohexanone/Yr.
Operating Cost - Annual - $ (1972)
Value of Recovered Products - $/Yr.
Net Operating Cost - Annual - $
Net Operating Cost - c/lb. of Cyclohexanone
Efficiency - %
SERR - 7.
TABLE CO-IV
CATALOG OF EMISSION CONTROL DEVICES
CYCLOHEXANONE PRODUCT I OB
Distillation Section
5-4
A
CO-10
Hydrocarbons
(6)
(119)
30
6
(6)
10,000
1965
.0161
0
Page 3 of 4
Dehydrogenatlon Section
9-2
£
CO-2
Hydrocarbons
Auaonia
12,000 (7)
.0080
1100
460.000
-458,900
98.2
-------
TABLE CO-IV
EXPLANATION OF NOTES
CATALOG OF EMISSION CONTROL DEVICES
CYCLOHEXANONE PRODUCTION Page 4 of 4
(1) CO-'N'-A&B consists of two identical scrubbers - one threats 40% of stream
(2 reactors?) and the other 60% of the stream (3 reactors?).
(2) Assumed to be total for both CO-'N'-A and CO-'N'-B, but it may be amount
for each.
(3) $106,000 in 1966 and $50,000 in 1971.
(4) Excludes original cost of column - which was initially purchased for
other service.
(5) $56,377 in 1965, $48,000 in 1971 and $23,000 in 1972.
(6) K. 0. Drum is located up-stream of an off-site flare. Flare not described
in this report.
(7) Major equiptment cost specified as $6,000, installation estimated (Houdry)
as $6,000.
-------
Current
Capacity
1800 a
Marginal
Capacity
180 b
TABLE CO-V
NUMBER OF NEW PLANTS BY 1980
Current
Capacity
On-stream
in 1980
1620
Demand
1980
3600
Capacity
1980
3600 a
Capacity
to be added
1980
1980
Economic
Plant
Size
200
Number
of
Nev
Units
9-10
Notes:
General - All rates are MM Lbs./Yr.
a - See Section VI (one-ol Producers) for source.
b - Arbitrary assumption.
-------
TABLE CQ-VI
Emissions
EMISSION SOURCE SUMMARY
TON/TON OF CYCLOHEXANONE/CYCLOHEXANOL
Source
Total
Hydrolysis
and Fugitive
Oxidation Saponification Distillation Dehydrogenation Emissions
Hydrocarbons
Particulates & Aerosol
NO,,
J\
sox
CO
.037 1 .001 .001 4 .039
Negligible Negligible
.042
f .001
f .043
-------
TABLE CO-VII
WEIGHTED EMISSION RATES
Chemical - Cyclohexanone/Cyclohexanol
Process - Air Oxidation of Cyclohexane
Increased Capacity by 1980 - 1980 MM Lb./Yr.
Pollutant
Hydrocarbons
Particulates
NO
X
sox
CO
Emissions, Lb./Lb.
.039
0
0
0
.043
Increased Emissions Weighting Weighted Emissions
MM Lbs./Yr. Factor MM Lbs./Yr.
77.2 80 6176
60
40
20
85.1 1 85
Significant Emission Index = 6261 (MM Lbs./Yr.)
-------
Dimethyl Terephtalate (and TPA)
-------
Table of Contents
Section Page Number
I. Introduction DT-1
II. Process Description (All Processes) DT-2
III. Plant Emissions DT-5
IV. Emission Control DT-8
V. Significance of Pollution DT-10
VI. TPA/DMT Producers DT-11
List of Illustrations & Tables
Flov Diagram (Amoco Process only") Figure DT-I
Net Material Balance (Amoco Process only) Table DT-I
Gross Heat Balance Table DT-II
Emission Inventory Table DT-III
Catalog of Emission Control Devices Table DT-IV
Number of Nev Plants by 1980 Table DT-V
Weighted Emission Rates Table DT-VI
-------
DT-1
I. Introduction
Dimethylterephthalate and terephthalic acid are used almost exclusively
to produce polyester fibres and films. The polyester, polyethylene
terephthalate, can be produced either by the transesterification of
dimethylterephthalate (DMT) or by the direct esterification of terephthalic
acid CTPA). Until 1963, technological limitations prevented the utilization
of more desirable direct esterification route (i.e., ex TPA). Today,
about 257o of polyethylene terephthalate (PET) production is based on direct
esterification and by 1980 more than 50% will be.
The delay in the utilization of the TPA based process is attributable to
the requirement for very high purity monomer in the production of polyethylene
terephthalate. Prior to 1963, monomer produced from TPA did not meet the
required standards of purity. This resulted primarily from the difficulty in
purifying TPA itself, which is extremely insoluble in both water and most
common organic solvents. Additionally, it does not melt (it sublimes). DMT,
on the other hand, is susceptible to most common methods of purification and
thus, was the source of all PET monomer at that time.
In 1963, new methods of producing and purifying TPA were commercialized.
Today, both Amoco and Mobil are producing high purity TPA in the U. S. Amoco
is utilizing the Mid-Century oxidation process and Mobil is using Olin-Mathieson
technology. Currently, Amoco's high purity TPA capacity is about four times
Mobil's, with some observers predicting continued dominance in that field until
at least the end of the decade. DuPont, Hercules, Hystron and Tennessee Eastman
continue to utilize DMT technology (although Hercules is thought to be
constructing some capacity based on TPA).
A general characterization of the atmospheric emissions resulting from the
production of DMT and TPA is difficult, because of the variety of processes
utilized. From process to process, emissions vary considerably, both qualita-
tively and quantitatively. At best, one might characterize the emissions as
"moderate". Fortunately, Amoco's process appears to be one of the lowest
polluters and its predicted preeminence will have a suppressing influence on
total future emissions.
Current TPA and DMT capacity in the U. S. is about 2.9 x 10^ Ibs./year (of
equivalent DMT). If the industry grows at an annual rate of 9%%, 1980 capacity
will be 5.9 x 109 Ibs./year.
-------
DT-2
II. Process Description
There are currently five different processes utilized in the U. S, for
the production of TPA and DMT. All production ends up as polyethylene
terephthalate via transesterification or direct esterification as shovn
belov:
Transesterification
CH3OOC
COOCH3 + HOCH2CH2OH
DMT
Direct Esterification
HOOCCOOH + HOCH2CH2OH
TPA
HOCH0CH0OOC < > COOCH CH OH
2. 2. \ '/ 2 2
CMONOMER)
HOCH2CH2OOC
COOCH2CH2OH
''MONOMER)
PET
Brief descriptions of each of the five processes follov:
Amoco Process (TPA) (Also see Flov Diagram Figure DT-1)
This process vas originally developed by the Mid-Gentry Corporation,
now a vholly owned subsidiary of Standard Oil Company of Indiana. Previously,
the Mid-Century Corporation was a joint venture between Halcon International
and Standard Oil.
The method is based on the liquid phase oxidation of P-xylene with air.
Oxidizer operating conditions are about 400° F and 400 PSIG. The P-xylene
feed is diluted with glacial acetic acid and small amounts of manganese
acetate or cobalt acetate plus a bromide are added as catalysts.
Oxidizer conditions are highly corrosive and require appropriate high
alloy vessels.
The purification portion of the Amoco process involves the hydrogenation
of crude TPA over a palladium containing catalyst at about 450° F. High
purity TPA is recrystallized from a high pressure water solution of the
hydrogenated material,
Mobil Process (TPA)
In 1963, Mobil purchased exclusive world-vide rights to Olin-Mnthieson
high purity TPA technology. Subseouent development work lead to the
construction of Mobil's facility at Beaumont, Texas.
-------
DT-3
This process, like the Amoco process is based on the liquid phase
oxidation of P-xylene in an acetic acid media. Mobil, however, utilizes
95% oxygen, rather than air as the oxidizing agent. Another characteristic
of the process is the use of methyl ethyl ketone as the activator for the
cobalt catalyst. Oxidation takes place at about 265° F in a battery of
parallel stirred reactors.
The first stage purification involves slurrying the TPA with hot
acetic acid and charging it to a soaking chamber, where impurities are
leached from the crude product. This material is washed on a continuous
filter and dryed with hot nitrogen. This (now) technical grade TPA is
suitable for DMT manufacture, however, further purification is required
to obtain TPA of high enough purity for fiber-grade polymer manufacture
via direct esterification.
The final purification step consists essentially of a continuous
sublimation and condensation procedure. The technical grade of TPA is
combined with small quantities of hydrogen and a solid catalyst, disperesed
in steam, and transported to a furnace. There the TPA is vaporized and
certain of the contained impurities are catalytically destroyed. Catalyst
and non-volatile impurities are removed in a series of filters, after
which the pure TPA is condensed and transported to storage silos.
DuPont Process (DMT)
The Calico Printers Association in the United Kingdom developed a
polymerization process based on nitric acid oxidation to produce TPA.
The rights to this process were bought by DuPont in 1944. The process
was also formerly used by ICIj BASF and Farbwerke Hoechst.
TPA is produced by oxidizing P-xylene with air and nitric acid.
After various washing operations the TPA is dewatered and dried. DMT
is formed by the direct esterification of TPA with excess methanol.
The esterification takes place in a continuous stirred pressure vessel
below 300° F. A small amount of sulfuric acid is used as a catalyst.
After about two hours reaction time, cooling of the reactants allows
the DMT to crystallize out. The DMT is separated via filtration.
Impurities are removed from the DMT by melting it and distilling the
molten material.
Hercules Process (DMT)
This process was originally developed by Chemische Werke Witten and
engineered by Imhausen International Company. A modification of the
Witten process was developed by the California Research Corporation and is
used by both Hercules and Hystron. The bulk of world DMT production is
based on Witten-Imhausen technology.
P-xylene is oxidized with air, under relatively mild conditions of
temperature and pressure to P-toluic acid, which is then esterified to
its methyl ester. The P-methyl toluate is oxidized under more severe
conditions to monomethyl terephthalate. The monomethyl ester is again
esterified to form DMT. Oxidation and esterification both take place in
the same vessel. Chemical intermediates from the esterification step are
recycled back to the oxidative portion of the process. Note that TPA
is not an intermediate in this process
-------
DT-4
Tennessee Eastman Process (DMT)
Very little information is available on the Tennessee Eastman process.
The TPA portion of the process is thought to be similar to the Amoco
process. One source states that it involves the air oxidation of P-xylene
in acetic acid solution in the presence of a cobalt catalyst. Supposedly,
the use of an aldehyde promoter permits oxidation at lover temperatures
and pressures than employed by Amoco. One must assume that normal
esterification and DMT purification techniques would follov.
-------
DT-5
III. Plant Emissions
A. Continuous Air Emissions
1. Oxidizer Vent
This vent constitutes one of the main sources of emissions for
all processes. Noxious emissions are primarily carbon monoxide
and hydrocarbons, although the plant utilizing nitric acid also
discharges various oxides of nitrogen. Generally speaking,
there is little variation in the rate of discharge of either
carbon monoxide or hydrocarbons, as reported by the various
respondents. Carbon monoxide emissions vary from .02 to .03
(Ibs. of pollutant per pound of product"). Hydrocarbon emissions
vary from .002 to .009 Ibs./lb.
2. Purification Section Vents
Surprisingly, the emissions from this portion of the various
processes are as significant as the emissions from the oxidizing
section, despite the fact that most respondents report using air as
the oxidant. Because the methods of purification run the gamut
from distillation and crystallization to continuous leaching and
sublimation, it is difficult to summarize or even categorize them
here. The reader is referred to Table III - National Emissions
Inventory, for a complete tabular summary.
3. Solvent and Methanol Recovery
Most processes utilize either methanol during the esterification
step or some hydrocarbon solvent during TPA or DMT purification.
Generally, facilities are provided to recover and/or repurify these
relatively volatile compounds. Five sources of emissions associated
with these operations are reported, all of them relatively minor vith
the exception of one. Respondent 10-4 reports the emission of
.08 Ibs. MeOH/lb. of DMT apparently as a result of operations of
the type described. This seems exceptionally high, but details of
the exact operation involved have not been provided.
B. Intermittent Air Emissions
1. Emergency Vents
Only two respondents, plants 10-4 and 10-7, reported emissions
from this type of source. Neither made an estimate of emissions
but their expected infrequency and shortness of duration should
preclude the discharge of significant quantities of pollutants on
a Ib./lb. basis. However, instantaneous emission rates could be
quite high. It seems reasonable to surmise that most of the TPA/DMT
plants have some provision for emergency pressure relief.
2. Product Storage Silo Vents
Respondent 10-5 reports the intermittent emission of small quantities
«.00001 Ibs./lb.) of fine TPA 'povder1 during certain product
transportation operations.
-------
DT-6
3. Incinerator Flue Gas
Respondent 10-5 utilizes a residue incinerator on an intermittent
basis. According to his report, the flue gas from the incinerator
contains neither unburned hydrocarbons, NOX or SOX. However, he
does show the emission of .00012 Ibs./lb. of metal oxides from this
source.
C. Continuous Liauid Wastes
1. Waste Water
The following tabulation summarizes the Quantity and method of
treatment reported by all respondents,
Plant EPA Code No.
10-1
10-2
10-4
10-5
10-6
10-7
325 GPM
300 GPM
200-250 GPM
100 GPM
787 GPM
26 GPM
700 GPM
Disposition
Treated
Deep Well Infection
Treated
Treated
Untreated
Treated
Biologically Treated
2. Other Liquid Wastes
A moderate number of liquid waste streams were indicated on
the flow diagrams accompanying the returned questionnaires. Hovever,
because the questionnaire was directed primarily toward eliciting
information about air emissions, few details concerning these waste
liquid streams were made available. Respondents did report the
following:
Plant No.
10-2
10-5
10-6
10-7
Type of
Liquid Waste
Sludge
'Liquid Waste'
Sludge
Distillation Heels
Purification Heels
Quantity
2.3 tons/day
6,200 tons/year
1,000,000 Ibs./yr.
400 Ibs./hr.
5,000 Ibs./hr.
Disposition
Retained in pits
Incinerated
Buried
Burned in boiler
house
D. Solid Wastes
Three respondents reported the generation of solid vaste material.
The operator of plant 10-1 reported that 350 Ibs./day of solid wastes
were removed from the plant site and incinerated. 525.000 Ibs./year
of solid wastes are incinerated by plant 10-6. The operator of plant
10-4 reports that 400 Ibs./day of solid wastes are accumulated and
disposed of in a sanitary land fill area.
E. Fugitive Emissions
Only the operator of plant 10-7 has offered a quantitative estimate
of these emissions. He places these losses at 0.017 of flow or 25,800
-------
DT-7
Ibs./year of P-xylene and 18,000 Ibs./year of methanol. Perhaps
the methanol losses of operator 10-4 fas described in Section III,
A-3) should be included here, hovever, th«y are several orders of
magnitude greater than the losses estimated by respondent 10-7.
-------
DT-8
IV. Emission Control
The emission control devices that have been reported as being employed by
the operators of the various TPA/DMT plants are summarily described in Table IV
of this report. An efficiency has been assigned each device vhenever 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 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
fact or*) out x
^(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.
Data sufficient to permit calculation of control device efficiency were
available for only about 4070 of the devices reported as being employed. A few
general comments regarding their reported and expected performances seem in
order:
Absorbers and Scrubbers
Nearly half of the control devices reported consisted of, at least
in part, some type of absorber or scrubber. These devices are identified
in Table IV as items DT-2, DT-4, DT-6 through 9, and DT-12 and DT-17.
Of these, efficiencies were calculable only for DT-4, DT-6 and DT-7,
where SE's of from 93.8 to 99.4 were observed. With the exception of
item DT-17, the general similarity of duty and scrubber type would lead
one to expect that the calculated efficiencies would be representative of
the performance of all the scrubbers/absorbers listed in Table Iv.
Scrubber DT-17, however, is used to control the amount of TPA emitted
from containers of hot sludge (via sublimation). Thus, this device must
condense the sublimate and remove the condensed particles from the
transporting air stream. Scrubber efficiency for this service has not
been defined and would be difficult to estimate.
Bag Filters
Three bag filters are listed in Table IV, they are designated as
devices DT-10. DT-13 and DT-14. (A fourth device, item DT-11, is also
-------
DT-9
listed here, for convenience in cataloging.) All are used to prevent
the emission to TPA 'fines' to the atmosphere. Dust collection efficiency
or specific efficiency is listed as 100% for two of the devices and
probably at least approaches 1007o for the other. This is the type
performance one would predict for bag filters in this service.
Deviations from this figure would most probably result from mechanical
malfunctions such as bag rupture, etc.
Incineration Devices
Three different types of incineration devices are listed in Table IV.
Device DT-5 is a more-or-less standard thermal incinerator, it is reported
to combust organic acids and methanol with an efficiency of 99%. Device
DT-15 is a catalytic incinerator, which is reported to convert 85% of the
NOX in its feed gases to N£. Device DT-16 is a flare used to burn dimethyl
ether. Performance data are not available on this device but a CCR
efficiency of 90% would be expected. Thus, all three devices are
performing about as one might expect; i.e., performance is within
established ranges. No reports of NOX generation in DT-5 or DT-16 are
available.
Condensers
Devices DT-1 and DT-3 are shell and tube water condensers. They are
used to prevent the loss of xylene from xylene storage tank vents.
Considering the relatively high boiling point of P-xylene (281° F), these
simple devices should be reasonably efficient. Actual emissions would
depend on tank level change rates and temperatures.
Development work aimed at reducing atmospheric emissions should be
concentrated in the following areas:
(1) For processes utilizing air oxidation-substitute oxygen.
(2) For processes utilizing nitric acid as the oxidant-substitute
oxygen.
(3) More efficient design and fuller utilization of control devices
currently available.
-------
DT-10
V. Significance of Pollution
It is recommended that the decision, as to vhether or not an in-depth
study of this process should be made, be held in abeyance. The reported
emission data indicate that the quantity of pollutants released as air
emissions varies considerably from process to process. A veighted average of
the quantity of pollutants emitted from all TPA/DMT processes (1) is less
than that of some of the processes that are currently being studied.
However, the SEI for this process may be based on an understated capacity
grovth rate ^2) or on an inaccurate estimate of distribution of nev capacity
among the competing processes. Moderate errors in either of these assumptions
would most probably result in assigning too a low a numerical value to the
SEI. Also, because considerable incentive exists to develop new technology,
new processes may emerge and attain significant stature in a relatively short
time. The processes that might fall within this category are the Teijin Process,
a nitrile process - such as the recently announced '3) LummuS Process, or the
Henkel II Process,
The methods outlined in Appendix IV of this Report have
been used to estimate the total weighted annual emissions from the new plants.
The calculations are summarized in Tables V and VI.
Published support for the Table V forecast of 1980 capacity may be found
in the 0 & GJ of March 17, 1972. Earlier references, such as CEH report on
DMT/TPA of December, 1970, show estimates of 1980 capacity that are about 2070
lower than current projections. The Table V forecast indicates economic plant
size at 300 MM Ibs./year capacity. The 0 & GJ article predicts that by 1980
the economic plant size may well be double that figure.
On a weighted emission basis, a Significant Emission Index of 6,036 has
been calculated in Table VI. This is less than the SEI's of various other
processes under study, however, for the reasons outlined above, it is recommended
that no decision on the necessity of conducting an in-depth study of this process
be made at this time.
(1) See Table Vl footnote.
(2) Some references put DMT/TPA growth at 12%/year and high purity TPA at 23°/
per year, see CEN, April 2, 1973.
(3) CEN, March 19, 1973.
-------
DT-11
VI. Producers of TPA and DMT
The folloving tabulation shovs published information regarding plant
capacities and location. Various references shov significant variations in
their estimates of certain plant capacities.
Capacity - MM Lbs./Yr.
Plant Location TPA DMT
Amoco Joliet, 111. 150
Decatur, Ala. 412
(657)*
DuPont Old Hickory, Tenn. 360
Gibbstovn, N. J. 300**
Hercules Burlington, N. C. 100
Wilmington, N. C. 600
Hystron Spartanburg, S. C. 100
Mobil Beaumont, Texas 144 (168)*
Tennessee Eastman Kingsport, Tenn 580
Total = 2,865
*Equivalent DMT (- 1.17 x TPA).
**Believed to be shut down or shutting down vith new capacity to be picked up
at other sites.
-------
PAGE NOT
AVAILABLE
DIGITALLY
-------
Stream Nos. (e)
Component
CO
co2
N2
02
P-Xyl
M, 0-Xyl & ET Bz
HAG
Heavy Ends (a)
TPA
Impurities
H20
Xylene Feed
0.7100
0.0072
(d)
0.7172
TABLE DT-I
TYPICAL MATERIAL BALANCE
FOR TEREPHTHALIC ACID PRODUCTION
BY THE AMOCO PROCESS (T/T TPA)
Air
2.6056
0.7914
3.3970
Vent Gas
.0707 (b)
.1128 (b)
2.6056
.0348
2.8239
Distillation
Reject
.0104
.2749
.2853
Purification
Reject
+
.0050
Product
1.0000
.0050
1.0000
(a) Quinones and ketones.
(b) Assumes 9070 of non-selectivity goes to equal volumes of CO and C02-
(c) Isophthalic acid, benzoic acid, 0-toluic acid and acetophenone resulting from feed impurities.
(d) HAC/xylene ratio unknown, but there is large excess of HAG.
(e) Refer to stream numbers of Figure DT-I.
-------
TABLE DT-II
TPA AND DMT
EX
P-XYLENE OXIDATION
(AMOCO PROCESS)
GROSS REACTOR HEAT BALANCE
A reasonable estimate of the oxidizer heat balance for this process is
impossible because the acetic acid/P-xylene ratio is not available from the
literature. It is well known that the reaction is quite exothermic.
The heat of reaction for the oxidation of P-xylene to terephthalic acid
is estimated to be of the order of 3200 BTU/lb. of TPA.
-------
Plant EPA Code No.
Product
Capacity, Tons of DMT or (Eouivalent DMT)*/Yr.
Emissions to Atmosphere
Stream
Flov - Lbs./Hr.
Flov - Continuous or Intermittent
if Intermittent - Hrs./Yr. Flov
Composition - Ton/Ton DMT or CEcuivalent DMT1
TPA
Acetic Acid
Water
Carbon Monoxide
Carbon Dioxide
Oxygen
Nitrogen
Methyl Acetate
Xylene
Propyl Acetate
Acetaldehyde
Dimethyl Ether
Methyl Alcohol
Sulfur Dioxide
DMT
Metal Oxides
Benzole Acid
P-Toluic Acid
P-Carboxyl Benzaldehyde
Hydrogen
Misc. Light Hydrocarbons - as Methane
Vent Stacks
Number
Height - Feet
Diameter - Inches
Exit Gas Temp. - F°
SCFM/Stack
Type of Emission Control Device Employed
Control Device I. D. No.
Analysis
Date or Frequency of Sampling
Sample Tap Location
Type of Analysis
Odor Problem
Summary of Air Pollutants - T/T of DMT or ("Equivalent)
Hydrocarbons
Particulates or Aerosols
NOX
SOX
CO
TABLE DT-III
NATIONAL EMISSION INVENTORY
DMT AND TPA PRODUCTION
VIA
VARIOUS PROCESSES
10-1 (A)
TPA
(290,000)
Oxidlzer Vent
256,000
Continuous
(.01886)
(.11895)
(.25946)
(3.44695)
(.00308)
(.00077)
(.00077)
(.00039)
(.00980)
(.00036)
(.02017)
Page 1 of 7
Filter, Dryer.
Silo Vent
18,470
Continuous
(.00036)
(.00348)
(.00227)
(.00131)
(.00852)
(.02167)
(.24011)
(.00005)
Yes
18
31 to 64
3 to 10
None
Monthly
At Vent
GLC
No
Distillation
Section Vent
(.00028)
(.00259)
(.00068)
(. 00003)
(.00066)
Yes
4
21 to 40
2 to 4
None
Monthly
At Vent
GLC
No
(A) Plants 10-1 and 10-6 are part of the same overall facility.
-------
TABLE DT-III
NATIONAL EMISSIONS INVENTORY
DMT AND TPA PRODUCTION
VIA
VARIOUS PROCESSES
Plant EPA Code No.
Product
Capacity, Tons of DMT or (Equlvalent)*/Yr.
Emissions to Atmosphere
Stream
Flow - Lbs./Hr.
Flow - Continuous or Intermittent
If Intermittent - Hrs./Yr. Flow
Composition - Ton/Ton DMT or (Equivalent DKT)
TPA
Acetic Acid
Water
Carbon Monoxide
Carbon Dioxide
Oxygen
Nitrogen
Methyl Acetate
Xylane
Propyl Acetate
Acetaldehyde
Dimethyl Ether
Methyl Alcohol
Sulfur Dioxide
DMT
Metal Oxides
Benzole Acid
Para Toluic Acid
Para Carboxyl Benzaldehyde
Hydrogen
Misc. Light Hydrocarbons - as Methane
Vent Stacks
Number
Height - Feet
Diameter - Inches
Exit Gas Temp. - F°
Flow - SCFM/Stack
Emission Control Device
Type
I. D. Number
Analysis
Date or Frequency of Sampling
Sample Tap Location
Type of Analysis
Odor Problem
Summary of Air Pollutants T/T of DMT or (Eauivalent DMT)
Hydrocarbons
Particulates & Aerosols
NOX
S0x
CO
Oxidizer
Vent
Unknown
Yes
1
64
24
212
Yes
Scrubber
DT-12
Never
No
10-2
TPA
(84.240)
Condensation
Section
97,035
Continuous
(.00107)
(.00024)
(4.00158)
(.00482)
(.00061)
(.02485)
(.00021)
(.00003)
(.00146)
(.01182)
Yes
1
120
72
310
73,000
Yes
Bag Filter
DT-13
"As Required"
@ Platform
EPA Method No.
No
5 & Design Calc'd.
(.07757)
(.00223)
0
0
(.01007)
Page 2 of 7
Condensation
Section
105,597
Continuous
(.00116)
(.00026)
(4.35466)
( 00525)
(.00066)
Incinerator
Flue Gas
Unknovn
(.02704)
(.00023)
(.00003)
(.00159)
(.01286)
Yes
1
120
72
310
Yes
Bag Filter
DT-14
"As Reauired"
@ Platform
EPA Method No. 5 & Design Calc'd.
No
Yes
1
50
52
550
No
None
-------
Plant EPA Code No.
Product
Capacity, Tons of DMT or (Equivalent DMT)*/Yr.
Emissions to Atmosphere
Stream
Flow - Lbs./Hr.
Flow - Continuous or Intermittent
if Intermittent - Hrs./Yr. Flow
Composition - Ton/Ton DMT or (Equivalent DMT)
TPA
Acetic Acid
Water .01395 .29230
Carbon Monoxide .03096 .00223
Carbon Dioxide ) )
Oxygen )3.14856 ).67985
Nitrogen ) )
Methyl Acetate
Xylene .00938
Propyl Acetate
Acetaldehyde
Dimethyl Ether
Methyl Alcohol
Sulfur Dioxide .00255
DMT
Metal Oxides
Benzole Acid
P-Toluic Acid
P-Carboxyl Benzaldehyde
Hydrogen
Misc. Light Hydrocarbons - as Methane
Vent Stacks Yes Yes
Number 2? 1
Height - Feet 100 100
Diameter - Inches 30 60
Exit Gas Temp. - F° 85 450
SCFM/Stack 25,000 1,800
Type of Emission Control Device Employed Absorber Incinerator
Control Device I. D. No. DT-4 DT-5
Analysis
Date or Frequency of Sampling Weekly Weekly
Sample Tap Location Stack Base @ WHB
Type of Analysis GLC Various
Odor Problem No No
Summary of Air Pollutants - T/T of DMT or (Equivalent)
Hydrocarbons
Partlculates or Aerosols
NOx
SOX
CO
TABLE DT-III
«mONAL EMISSIONS INVENTORY
DMT AND TPA PRODUCTION
VIA
VARIOUS PROCESSES
10-4
DMT
300,000
Oxidizer
Vent
229,000
Continuous
Incinerator
Flue Gas
69,850
Continuous
Purification Section
Scrubber Vent
5,034
Continuous
Purification
Emergency Vent
Unknown
Intermittent
Page 3 of 7
Reactor Section
Ejector Discharge
. 00022
. 00068
)
). 06919
TR
.00031
942
Continuous
15 Sec./Incident
.00031
+ .00002
+ ).01209
.00075
+
+
Yes
1
90
12
50
600
Scrubber
DT-6
Semi -Weekly
Scrubber Outlet
GLC & Gas Partitioner
No
.09047
.00255
.03389
Not Specified
None
None
No
Purification
Vent
8
Continuous
.00001
)
).00006
.00003
Other
Emissions
5,720
Unknown
.0800
Yes
2?
60
6
85
100
Scrubber
DT-7
None
At Scrubber
Calc'd.
No
Not Specified No
None
None
Calc'd.
No
None
None
Calc'd.
-------
Plant EPA Code No.
Product
Capacity, Tons of DMT or (Eauivalent)*/Yr.
Emissions to Atmosphere
Stream
Flow - Lbs./Hr.
Flow - Continuous or Intermittent
if Intermittent - Hrs./Yr. Flow
Composition - Ton/Ton DMT or (Equivalent DMT)
TPA
Acetic Acid
Water
Carbon Monoxide
Carbon Dioxide
Oxygen
Nitrogen
Methyl Acetate
Xylene
Propyl Acetate
Acetaldehyde
Dimethyl Ether
Methyl Alcohol
Sulfur Dioxide
DMT
Metal Oxides
Benzole Acid
Para Toluic Acid
Para Carboxyl Benzaldehyde
Hydrogen
Misc. Light Hydrocarbons - as Methane
Vent Stacks
Number
Height - Feet
Diameter - Inches
Exit Gas Temp. - F°
Flow - SCFM/Stack
Emission Control Device
Type
I. D. Number
Aaalysis
Date or Frequency of Sampling
Sample Tap Location
Type of Analysis
Odor Problem
Summary of Air Pollutants T/T of DMT or (Equivalent DMT)
Hydrocarbons
Particulates & Aerosols
NC-x
SOX
CO
TABLE DT-III
NATIONAL EMISSIONS INVENTORY
DMT AND TPA PRODUCTION
VIA
VARIOUS PROCESSES
10-5
TPA
(241,000)
Oxidizer
Vent
5,720
Continuous
(.00163)
+
(.01591)
)(2.43726)
)
(.00513)
Yes
1
77
18
116
32,150
Yes
High Pressure Absorber
DT-8
Occasional
Accessible
GLC
No
Surge Tank
Vent
1,238
Continuous
(.00024)
(.00229)
)(.01823)
(.00020)
Yes
1
65
18
120
300
Yes
Scrubber
DT-9
Occasional
Accessible
GLC
No
Storage Silo
Vent
11,428
Intermittent
82
(<. 00001)
«. 00001)
)( .19346)
Yes
1
140
12
275
1,000
Yes
Bag Filter
DT-10
Never
Accessible
Calc'd
No
(.00855)
(.00012)
0
0
(.01591)
Page 4 of 7
Residue Incinerator
Flue Gas
74,508
Intermittent
7.344
) (1.13502)
Solvent
Dehydrator
15,650
Continuous
(.00025)
(. 26357)
(.00110)
(.00012)
Yes
1
125
42
600
16.550
Yes
Precipitator
DT-11
Never
Calc'd.
No
No
No
Once/Shi ft
Accessible
Titration
No
-------
Plant EPA Code No.
Product
Capacity, Tons of DMT or (Equivalent DMT)*/Yr.
Emissions to Atmosphere
Stream.
TABLE DT-III
NATIONAL EMISSIONS INVENTORY
DMT AND TPA PRODUCTION
VIA
VARIOUS PROCESSES
10-6 (A)
DMT
290,000
Reactor Vent
2
Continuous
Methanol Recovery
Vent (B)
~2
Continuous
Page 5 of 7
Methanol Recovery
Vent
415
Continuous
Flov - Lbs./Hr.
Flow - Continuous or Intermittent
if Intermittent - Hrs./Yr. Flov
Composition - Ton/Ton DKT or (Equivalent DMT)
TPA
Acetic Acid
Hater
Carbon Monoxide
Carbon Dioxide
Oxygen
Nitrogen
Methyl Acetate <. 00001 /^<. 00001 .00107
Xylene
Propyl Acetate
Acetaldehyde <. 00001 ~<. 00001 .00055
Dimethyl Ether .00002 ,+s.00002 .00433
Methyl Alcohol .00001 /v.00001 .00031
Sulfur Dioxide
DMT
Metal Oxides
Benzole Acid
P-Tolutt Acid
P-Carboxyl Benzaldehyde
Hydrogen
Misc. Light Hydrocarbons - as Methane
Vent Stacks Yes Yes Yes
Number 1 1 1
Height - Feet 50 100 50
Diameter - Inches 23 4
Exit Gas Temp. - F° 70° 70° 70°
SCFM/Stack
Type of Emission Control Device Employed None None None
Control Device I. D. No.
Analysis
Date or Frequency of Sampling One Session Never One Session
Sample Tap Location At Vent At Vent
Type of Analysis Unknown Estimate Unknown
Odor Problem No No No
Summary of Air Pollutants - T/T of DMT or (Equivalent)
Hydrocarbons
Particulates or Aerosols
NOX
SOX
CO
(A) Plants 10-1 and 10-6 are part of the same overall facility.
(B) This stream never sampled, but estimated to be essentially the same as the on preceeding it in the tabulation (10-6 reactor vent).
.00651
.00077
Crude Product
"Hold-Up" Vent
3
Continuous
.00005
Yes
1
30
3
70°
Condenser
DT-1
Never
Estimate
No
-------
TABLE DT-III
NATIONAL EMISSIONS INVENTORY
DMT AND TPA PRODUCTION
' VIA
VARIOUS PROCESSES
Plant EPA Code No.
Product
Capacity, Tons of DMT or (Equivalent DKT)*/Yr.
Emissions to Atmosphere
Stream •
|lov - Lbs./Hr.
Flov T Continuous or Intermittent
If Intermittent - Hrs./Yr. Flow
Composition - Ton/Ton DMT or (Equivalent DMT)
TPA
Acetic Acid
Water
Carbon Monoxide
Carbon Dioxide
Oxygen
Nitrogen
Methyl Acetate
Xylene
Propyl Acetate
Acetaldehyde
Dimethyl Ether
Methyl Alcohol
Sulfur Dioxide
DMT
Metal Oxides
Benzole Acid
P-Toluic Acid
P-Carboxyl Benzaldehyde
Hydrogen
Misc. Light Hydrocarbons - as Methane
Vent Stacks
Number
• Height - Feet
Diameter - Inches
Exit Gas Temp. - F°
SCFM/Stack
Type of Emission Control Device Employed
Control Device I. D. No.
Analysis
Date or Frequency of Sampling
Sample Tap Location
Type of Analysis
Odor Problem
Summary of Air Pollutants - T/T of DMT or (Equivalent)
Hydrocarbons
Particulates or Aerosols
NOX
SOx
CO
(A) Plants 10-1 and 10-6 are part of the same overall facility.
10-6 (A)
DMT
290,000
Crude Product
"Hold-Up" Vent
Continuous
Sludge
Recovery Vent
Continuous
Page 6 of 7
Methanol Stg. &
Slurry Prep. Vent
10,400
Continuous
.00077
.00602
.00875
. U086
Sludge
Recovery Vent
Unknown
Continuous
.00005
.00005
Yes
1
30
3
70°
10
Scrubber
DT-2
Never
Estimate
No
Yes
1
30
3
70°
10
Condenser
DT-3
Never
Estimate
No
SEE OTHER SHEET
No
No
Dally
Orsat
No
Yes
1
10
10
700
Yes
Scrubber
DT-17
Never
None
No
-------
Plant EPA Code No.
Product
Capacity, Tone of DMI or (Equivalent)*/Yr,
Emissions to Atmosphere
Stream
Flov - Lbs./Hr.
Flow - Continuous or Intermittent
if Intermittent - Hrs./Yr. Flow
Composition - Ton/Ton DMT or (Equivalent DMT)
TPA
Acetic Acid
Water
Carbon Monoxide
Carbon Dioxide
Oxygen
Nitrogen
Methyl Acetate
Xylene
Propyl Acetate
Acetaldehyde
Dimethyl Ether
Methyl Alcohol
Sulfur Dioxide
Dm
Metal Oxides
Benzole Acid
Para Toluic Acid
Para Carboxyl Benzaldehyde
Hydrogen
Misc. Light Hydrocarbons - as Methane
Vent Stacks
Number
Height - Feet
Diameter - Inches
Exit Gas Temp. - F°
Flow - SCFM/Stack
Emission Control Device
Type
I. D. Number
Analysis
Date or Frequency of Sampling
Sample Tap Location
Type of Analysis
Odor Problem
Summary of Air Pollutants T/T of DMT or (Equivalent DOT)
Hydrocarbons
Particulates & Aerosols
NOX
sox
CO
TABLE DT-III
NATIONAL EMISSIONS INVENTORY
DMT AND TPA PRODUCTION
VIA
VARIOUS PROCESSES
10-7
DMT
180,000
HNO- Oxidizer
Vent
52,590
Continuous
.00100
.00163
.03388
.14771
.86071
Purification
Section Vent
Unknown
Page 7 of 7
Emergency
Vent
Unknown
Intermittent
Unknown
NOX - .00021
NH3 • .00017
N20 - .05033
Yes
1
120
24
351
10,500
Yes
Catalytic Incinerator
DT-15
Weekly (NOX)
Accessible
Colorimetric
No
Yes
1
80
Yes
Flare
DT-16
Never
None
No
Yes
2
100
24
No
Never
No
.00225
.00017
.00021
.01634
Air Oxidizer
Vent
88,500
Continuous
.00446
.01471
.06938
.04538
1.6875
.00225
Yes
2
50
10
50
9,000
No
Semi-Annual
Accessible
I.R.
No
-------
ABS ORBERS/S GRUBBERS
EPA Code No. for plant using
Flov Diagram (Fig. It Stream I. D.
Device I. D. No.
Control Emission of
Scrubbing/Absorbing Liquid
Type - Spray
Packed Column
Column v/trays
No. of trays
Tray Type
Other
Scrubbing Absorbing Liquid Rate, CPM
Design Temp. (Operating Temp.), F°
Gas Rate, SCFM (Lb./Hr.)
T-T Height, Feet
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 - e/lb. of DMT/Yr. (or/equiv.
Operating Cost - Annual, $ (1972)
Value of Recovered Product, $/Yr.
Net Operating Cost - Annual - $
Net Operating Cost - c/lb. of DMT
Efficiency - 7. - SE
Efficiency - 7. - SERR
DKT)
TABLE DT-IV
CATALOG OF EMISSION CONTROL DEVICES
FOR
DMT AND TPA PRODUCTION
VIA
VARIOUS PROCESSES
10-6 (1) 10-4 (2)
10-4
DT-2 DT-4 DT-6
Aromatics Xylene Methanol &Xylene
Xylene Solid Carbon Water
X
X
Baffle
10
122
15.3
0.7
Yes
30
3
20,000
1970
.00345
300
0
300
.00005
Fixed Bed
N. A.
25,000
22
8
Yes
100
30
304,000
1968-1971
.05067
116,000
540,000
-424,000
Negative
93.8
93.8
Plus Cond.
100
(50)
1900
16
4
Yes
90
12
446,000
1970-1971
.07433
129,000
650,000
-521,000
Negative
99.4
99.4
10-4
DT-7
Xylene
Venturi Scrubbers & Condensers
180
338
N. A.
N. A.
Yes
60
6
78,000
1968-1972
.01300
10,500
769,500
-780,000
Negative
96.3
96.3
Page 1 of 3
10-5
10-5
10-2
10-6
DT-8
H. C.
X
10
120
32.150
Yes
77
18
108,000
1971
(.02241)
89,500
364.500
275,000
Negative
DT-9
H C
X
190
422
Yes
65
18
39,000
1971
(.00809)
116,900
245,300
-128,400
Negative
DT-12
Combustibles
Water
X
212
Yes
64
24
17,200
1965
(.01021)
DT-17
Particulates
Water
X
Plus Cyclone
25
(70)
7.5
2
Yes
10
10
10,000
1970
.00173
900
0
900
.00015
NOTES:
(1) Device DT-"N1 consists of two identical scrubbers, costs indicated are for one scrubber.
(2) Unit consists of four fixed bed absorbers, costs are for entire unit.
-------
CONDENSERS
EPA Code No. for plant using
Flov Diagram (Fig. I) Stream I. D.
Device I. D. No.
Control Emission of
Condenser Cooling Fluid - Type
Rate - GPM
Temp. In - F°
Controlled Stream - Temp. In - F°
Temp. Out - F°
Press. In - PSIG
Length, T-T - Feet
Diameter, Inches
Tube Area - Ft.2
Installed Cost - Mat'l. 6. Labor - $
Installed Cost - Based on "year" - dollars
Installed Cost - t/lb. of DMT/Yr. (or equiv. DMT)
Operating Cost - Annual - $ (1972)
Value of Recovered Product - $/Yr.
Net Operating Cost - $/Yr.
Net Operating Cost - c/lb. of DMT (or equiv. DMT)
Efficiency - SE - %
Efficiency - SERR - %
TABLE DT-IV
CATALOG OF EMISSION CONTROL DEVICES
FOR
DMT AND TPA PRODUCTION
VIA
VARIOUS PROCESSES
10-6
DT-1
Xylene
Water
15
158
6 (In H20)
8
16
18,000 (*)
1965-1966
.00310
1,000 (A)
0
1,000
.00017
Page 2 of 3
10-6
DT-3
Xylene
Water
15
158
6 (In H20)
8
16
9,000
1969
.00155
500
0
500
.00009
(A) Cost of two parallel units.
-------
BAG FILTERS
EPA Code No. for plant using
Flov Diagram (Ftg. I) Stream I. D.
Device I. D. No.
Contrwl Emission of
Number of Compartments
Number of Bags/Compartment
Total Bag Area - Ft.2
Bag Cloth Material
Design (Operating) Temp. - F°
Design (Operating) Press. - PSIG
Installed Cost - Mat'l. & Labor - $
Installed Coit Based on - "year" - dollars
Installed Cost, c/lb. of DMT/Yr. (or equlv. DMT)
Operating Cost - Annual - $ - (1972)
Value of Recovered Product - $/Yr.
Net Operating Cost - $/Yr.
Net Operating Cost - c/lb. of DMI (or equiv. DMT)
Efficiency - SE - 7.
Efficiency - SERR - %
TABLE DT-IV
CATALOG OF EMISSION CONTROL DEVICES
. FOR
DMT AND TPA PRODUCTION
VIA
VARIOUS PROCESSES
10-5
DT-10
TPA
275
0
29,200
1971
(.00606)
4,900
0
4,900
(.00102)
10-2
DT-13
TPA
3
(285)
(0.5)
222,300
1965-1966
(. 13194)
100
32
Page 3 of 3
10-2
DT-14
TPA
3
(285)
(0.5)
250,000
1966
(.14839)
100
32
10-5
(B)
DT-11
Metal Oxides
348.000
1971
(.07220)
90,800
Unknown
90,800
(.01884)
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 (Lb./Hr.)
Auxilliary Fuel Req'd. (excl. pilot)
Type
Rate - BTU/Hr.
Device or Stack Height - Feet
Installed Cost - Mat'l. & Labor - $
Installed Cost Based on - "year" - dollars
Installed Cost, c/lb. of DMT/Yr. (or equiv. DMT)
Operating Cost - Annual - $ (1972)
Value of Heat/Steam recovered - $/Yr.
Net Operating Cost - Annual
Net Operating Cost - c/lb. of DMT/Yr. (or eauiv. DMT)
Efficiency - 7. - CCR
Efficiency - % - SERR
10-4
DT-5
Organic Acids & Methanol
X
w/WHB
40 (GPM)
Yes
Fuel Oil
126 (GPH)
100
750,000
1971-1972
.12500
163,000
81,000
82,000
.01367
99+
10-7
DT-15
Nitrogen Oxides
X (Catalytic)
10,500
Yes
NH3
34 Ibs./hr.
120
131,563 (*)
1965-1972
-03655
114,900
0
11,400
.00317
NOTES: (A) Cost of two parallel units.
(B) Device is referred to as precipi tator, but no descriptive details or specifications are reported.
-------
2,865
300
TABLE DT-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
2,565
5,900
5,900
2,335
NOTE: All capacities in MM Ibs./yr.
*TPA and DMT, expressed as equivalent DMT.
300
7-8
-------
TABLE DT-VI
Chemical TPA and DMT
VEIGHTED EMISSION RATES
Process Xylene Oxidation
Increased Capacity by 1980 2,335
Pollutant
Hydrocarbons
Participates
NOX
SO
CO
Increased Emissions Weighting
Emissions Lb./Lb.* MMLbs./Year Factor
.03162
.00047
. 00003
.00036
.01836
73.83 80
1.10 60
.07 40
.84 20
42.87 1
Significant Emission
Weighted Emissions
Lbs./Year
5,907
66
3
17
43
Index =» 6,036
*Emissions based on assumption that 407» of nev capacity to be based on Amoco process and 157» based on each of
four other processes utilized in U. S. today, as summarized in Table DT-III.
-------
Ethylene
-------
Table of Contents
Section Page Number
I. Introduction EL-1
II. Process Description EL-2
III. Plant Emissions EL-4
IV. Emission Control EL-10
V. Significance of Pollution EL-12
VI. Ethylene Producers EL-13
List of Illustrations & Tables
Flow Diagram Figure EL-I
Net Material Balance Table'EL-I
Gross Heat Balance Table EL-II
Emission Inventory Table EL-III
Catalog of Emission Control Devices Table EL-IV
Number of New Plants by 1980 Table EL-V
Summary of Emission Sources Table EL-VI
Weighted Emission Rates Table EL-VII
-------
EL-1
I. Introduction
Ethylene is, today, the pre-eminent petrochemical in the United States;
both in terms of quantity and value. More than 20 billion pounds will have
been produced in 1972. Of this, approximately 15 billion pounds is produced
by the steam cracking process, the method which is the subject of this
report. The balance has its origin as by-product from a variety of refinery
operations and processes. Of the 15 billion pounds, about 80% is derived
from ethane and propane, the remainder from butane, field condensate, naphtha
and gas oil. Most of the air emissions associated with the production of
ethylene result from either of two "operations": (1) The removal of acid
gases (C02 & t^S) from the cracked gas and (2) Hydrocarbon venting and/or
flaring during plant start-ups and emergencies. In addition to the vapor
emissions, quanitites of waste water and spent caustic are produced. Also
some plants (generally the naphtha-crackers) produce a heavy, hydrocarbon,
tar-like substance which, if incinerated, would add to the volume of air
emissions produced. In general, however, air emissions from ethylene are
relatively low.
By 1980 it is expected that the demand for ethylene in the United States
will approach 40 billion pounds per year (1). The required new capacity will
be based increasingly on heavier feed stocks - naphthas and gas oils. As a
result proportionately greater quantities of sulfur compounds and "tar" will
have to be disposed of by the industry in the future.
(1) C.E.P. Vol. 68, No. 9.
-------
EL-2
II. Process Description
Ethylene is produced primarily by the pyrolysis of hydrocarbons. In
the United States ethane and propane currently predominate as feed stock
material. The chemical reaction for their pyrolysis is:
H g
H-C - C-H I
H d H
H H
H2
H H H H H
H-C - C - C-H • ' » *C=C/ + CH,
• it t \ 4
H H H H H
The conversion or "cracking" of the feed stock takes place within
the tubes of the cracking furnace. The reaction is initiated at about
1100° F. Normal temperatures within the cracking section of the heater
are 1500 to 1600° F with a residence time of one second or less. Yields
and conversion vary with the feed stock and the desired product mix.
Typically a unit cracking ethane might operate at a severity such that 60%
of the ethane is cracked, ultimate yield of ethylene will be about 80%.
Naphtha cracking, on the other hand, would yield only about 30%, ethylene.
The hydrocarbon feed stock, whatever its nature, is always diluted with
steam to depress coking tendencies within the furnace tubes.
In order that only the desired degree of cracking be obtained it is
necessary to control the temperature - residence time parameter very closely.
This requires that the hot effluent gases from the furnace be cooled rapidly
to a temperature which will 'quench1 the cracking reaction. Consequently
the cracked gases from the furnace are cooled in a variety of ways; but
usually at some point by direct contact with water in the "quench tower".
Increasing use is being made of transfer line waste heat boilers up-stream
of the quench tower to recover some of the large amounts of heat that are
removed from the cracked gas during the quench.
The purification and separation of the various products and by-products
constitute a major element in the manufacturing process. They are accom-
plished in a variety of ways depending on the feed stock, age of the plant,
contractor and many other factors. Accordingly it must be realized that the
following description of that section of the process pertains to only one of
many configurations extant:
Subsequent to quenching the cracked gases are compressed prior to
treatment for removal of the contained acid gases (C02 & HoS). The acid gases
are usually absorbed by some combination of systems using monoethanol amine
(MEA), caustic and water. After desorption, the contaminants are usually
vented or burned. The purified gas stream is then dried and further compressed
before fractionation.
After compression, the cracked gas is cooled to cryogenic temperatures
and hydrogen is flashed off and sent to either additional purification facilities
or to fuel. The dehyrogenated stream flows to the demethanator where
overhead methane is sent to fuel and the C-^ bottoms are pressured to the
de-ethanizer.
From the de-ethanizer the C3 bottoms are sent to the de-propanizer while the
-------
EL-3
overhead is selectively hydrogenated in the 'light acetylene converter1,
in order to remove trace amounts of acetylene. The stream then goes to
the ethylene splitter where the ethylene and ethane are separated. Ethane
is recycled to the cracking furnace. The overhead from the ethylene splitter
is final product and is sent to storage or pipeline.
The C4+ depropanizer bottoms are sent to the debutanizer while the
overhead is selectively hydrogenated in the 'heavy acetylene splitter' in
order to remove trace amounts of methyl acetylene and propadiene. It then
goes to the propylene splitter where the propane and propylene are separated.
Propane is usually recycled to the cracking furnace. The overhead from the
propylene splitter is pressured to storage spheres or pipeline.
The final tower in the described fractionation train is the debutanizer
where various C^ compounds are separated from the dripolene or pyrolysis
gasoline fraction. This €5+ material may be rejected as waste or, after
hydrogenation, may be used as gasoline blending stock or a source of aromatics.
-------
EL-4
III. Plant Emissions
A. Continuous Air Emissions
1. Cracking Furnace Combustion Stack
All ethylene plant operators report the use of "sweet" natural gas
supplemented by varing amounts of plant produced sulfur-free fuel gas
to fire their cracking furnaces. The plant produced fuel is generally
a mixture of hydrogen and methane. The sulfur content of the imported
fuel varies from "nil" to "less than 1 grain/100 SCF." The unit
reporting the highest sulfur consumes 1.0 x 10 Ib./yr. of imported fuel
in the production of 1.2 x 10 Ib./yr. of ethylene. The emission rate
is 10,000 Ib./yr. of sulfur. As SC-2, this is less than 2 x 10"5 tons/ton
of ethylene.
2. Waste Water and Spent Caustic De-Gassing
Most producers of ethylene "de-gas" waste quench water, waste wash
water (from the caustic-water wash column) and spent caustic prior to
recycling or further processing these liquid streams. The desorbed gases
are either returned to the process, vented, flared or sent to a pollution
control device. These emissions are summarized in Table III.
3. "Acid Gas Removal" Vents
So-called 'Acid Gas' (H_S & CC>2) is removed from the furnace effluent
gases by either caustic washing or contact with a regenerable absorbent
such as MEA. The spent liquor from the former method is generally
neutralized before disposal. The neutralization regenerates the hydrogen
sulfide, and results in its evolution from the neutralized liquid waste.
The hydrogen sulfide is either vented to atmosphere - as reported by
the operator of EPA coded plant 11-1 - or burned. The hydrogen
sulfide from the regenerable absorbent is reported as being generally
burned, although one operator (EPA Code 11-9) sends it to a Glaus
plant. The emissions from the acid gas removal section constitute one
of the primary sources of air pollution from the ethylene process. Of
those sulfur bearing, 'acid gas1 vent streams reported as being (eventually)
vented to the atmosphere, the highest emission rate - as SC>2 - is
.0012 ton/ton of ethylene. The vent streams reported for this section
are summarized in Table III.
4. Plant Flare
Most ethylene plants deploy a continuously lighted plant flare.
Normally only pilot fuel gas and flare sweep gases are burned and there
are no noxious emissions. However, during plant emergencies this may
not be the case - see section III - B, "Intermittent Air Emissions".
5. Storage Losses
With the exception of the relatively small amounts of Cc gasoline
and heavy tars all ethylene feed stocks and products are stored under
pressure. So there are no continuous vent losses. This does not apply,
of course, to the two operators (EPA Codes 11-9 and 11-10) who crack
naphtha, their feed stock storage tanks utilize, respectively, nitrogen
blanketing and a floating roof.
-------
EL-5
B. Intermittent Air Emissions
1. Cracking Furnace Decoking
Periodically, the process side of the cracking furnace requires
decoking. Several operators reported emissions from this operation and
they are summarized in Table III. It should be presumed that all
operators of ethylene cracking furnace require a similar operation.
2. Acetylene Converter Regeneration
Periodically, the 'Light Acetylene Converter1, or acetylene
hydrogenation reactor, and the 'Heavy Acetylene Converter', or methyl
acetylene and propadiene hydrogenation reactor, require regeneration.
Several operators reported emissions from this operation and they are
summarized in Table III. It should be presumed that nearly all ethylene
plants employ and regenerate a light acetylene converter, but some may
not utilize a heavy acetylene converter. Since acetylene can be
selectively adsorbed in solvents such as DMF*, some operators may use a
scrubbing technique for its removal.
3. Start-up and Emergency Vents
This type of emission is universally encountered in the petrochemical
industry and will vary from process-to-process, from operator-to-operator
and even from year-to-year. One operator (EPA Code No. 11-13) estimates
that 1.49% (8.9 x 106 Ibs.) of his production will be flared during 1973
due to process upsets and a major plant turnaround. Other estimates of
emissions in this category are listed in Table III.
C. Continuous Liquid Wastes
1. Process Tar
Not all operators report tar formation. Considerably higher amounts
of tar are reported by the operators who crack naphtha. Operator 11-10
reports 35,000 Ibs./hr. or 0.5 tons of tar/ton of ethylene product. The
highest amount of tar reported by a non-naphtha cracker is 100 Ibs./hr.
or .001 tons/ton of ethylene. In general the disposal method is not
specified, although one operator (EPA Code 11-2) reports that it is
used as a sanitary land fill.
2. Cracking Furnace Steam Condensate
The condensate from cracking furnace dilution steam is sent to
the waste water treatment facilities of a few operators. The amount
varies from plant to plant but is measured in hundreds of gallons per
minute.
3. Quench Water
Some operators treat their used quench water as waste; however,
the literature reports that the newer plants generate steam from the
quench water. Those operators that do report this stream as waste
indicate that its flow rate is measured in hundreds of gallons per
minute.
*di-methyl formamide
-------
EL-6
4. Boiler and Cooling Tower Blow-Down
Three operators reported a continuous boiler and cooling tower
blow-down. One large plant operator (EPA Code 11-13) reported that
the combined flow of these two waste water streams was 935 GPM. The
other two operators reported about half of that amount.
5. Spent Caustic
Several operators report the use of caustic in removing acid gases
from the cracking furnace effluent stream. One operator (EPA Code 11-13)
reports a continuous flow of waste caustic to a neutralizing pond. The
quantity of caustic is unreported as is the ultimate pond disposal
method. Operators EPA 11-5 and 11-8 report spent caustic rates of
20 and 16 GPM respectively; however, they do not specify how this waste
is treated. Presumably all operators use either caustic or MEA* (or
caustic and MEA) in their acid gas removal section; consequently many
will have spent caustic for disposal.
6. Wash Water
Three operators report the use of a water wash subsequent to the
caustic wash step in the acid gas removal section of the plant. The
quantity of wash water used and the method of its ultimate disposal are
not reported.
D. Intermittent Liquid Wastes
1. Acetylene Converter Regeneration
Several operators report the use of direct contact condensers and/or
water scrubbers on the effluent gases from the acetylene converter
regeneration. Although the flow rate may be quite high - operator
EPA Code 11-5 reports 1500 GPM, - the total volume of waste water is
relatively small because the converters require regeneration only about
twice a year. The duration of a given regeneration is normally limited
to a few days.
2. Cracking Furnace Decoking
It is presumed that all operators decoke their cracking furnaces
regularly. Three.operators water scrub the coke bearing gases discharged
during this operation. One operator (EPA Code 11-5) reports generating
1500 GPM of waste water as a result of this activity. However, again,
the total volume of waste water is relatively small due to the infrequency
of the operation.
3. Drier Column Water
It may be presumed that most or all operators dry the cracked gas
subsequent to its treatment in the acid gas removal section. It has not
been reported whether the removed water is rejected continuously or
intermittently; nor has its rate been reported. Such waste water streams,
small though they may be, most probably exist even though they have not
been reported.
*mono-ethanol amine
-------
EL-7
E. Solid Wastes
Solid wastes from the process consist primarily of desiccants and
furnace coke. Only one operator (EPA Code 11-13) made an estimate of
these. However, two operators reported quantities (@ 1000 Ib./day)
of unspecified solid waste materials. Operator EPA Code 11-13 reports
the disposal of 66,000 Ib./yr. of spent desiccants and 5000 Ib./yr. of
coke, both materials being used as sanitary land fill.
F. Odors
In general, the steam cracking of hydrocarbons to produce ethylene
does not appear to be a process that has an "odor problem".
Only one respondent (EPA Code 11-1) reported an odor complaint in
the past year and that was due to a flare failure. Most of the reported
odors are said to be detected only on the plant property and most of
those are intermittent. The odoriferous materials are usually either
hydrogen sulfide or unidentified compounds contained in the heavy
by-product streams that the process produces.
Operators of steam crackers seem to have eliminated most odors
by means of extensive use of flare systems on gaseous hydrocarbon waste
and vent streams.
The continuous sources of odors are degassing of quench water, and
disposal of spent caustic. According to the questionnaires, these
operations are typically well enough controlled to avoid odor problems.
The intermittent sources of odors are furnace decoking, steaming out of
driers, regeneration of hydrogenation catalyst and flare failure.
In the future, the increased use of heavier feedstocks will result
in increase production of odoriferous by-product hydrocarbons and
hydrogen sulfide. However, on the basis of the previous attention paid
by the industry to this kind of detail, it seems safe to assume that
except for the unavoidable occasional equipment failure, the process will
continue to be one that operates without "odor problems".
G. Fugitive Emissions
All respondents to the questionnaire reported little or no air
pollution resulting from fugitive emissions. There was fairly general
agreement that these can be and are minimized by following good
maintenance practices and procedures. In most instances, replies were
qualitative, but where quantities are given, they are usually estimates.
A few of the replies vere (in part):
"Process material balance closure averages 0.57o low but much of this
is believed to be metering error".
"Approximately 20,000 Ibs./year fugitive hydrocarbons from small leaks.
Engineering estimate".
"Approximately 80 SCFH vents to atmosphere from on-line process
analyzers in various parts of the plant. These streams contain H2,
G! - C5 hydrocarbons and
-------
EL-8
The most comprehensive leakage estimate was given by the company
with EPA Code 11-11 and it can be summarized as follows:
Source Estimated Losses, Ibs./year
Pump Seals 53,500
Control & Manual Valves 131,000
Safety Valves Vented to Atmosphere 35,000
Unit Leaks 103,500
Compressor Seals
Ejectors
Total 323,000
This unit has a capacity of 395,000,000 Ibs./year of ethylene,
giving a fugitive emission rate of about 0.0008 Ibs./lb. of ethylene.
However, it is a unit with gas oil feed so produces a wide range of
other products. Thus, if calculated on a different basis, the fugitive
emission rate is about 0.00015 Ibs./lb. of fresh feed.
The most comprehensive qualitative list of fugitive emission sources
was given by the company with EPA Code 11-3 and it can be summarized as
follows:
1. Fuel gas vent resulting from a low gas pressure automatic
shutdown of a cracking furnace.
2. Vapors from oil filter on waste water stream.
3. Vapors from decanted water.
4. Light oil storage drum vapors.
5. Heavy oil vapors from processing, storage or loading.
6. Control gas vent from flare stack, pneumatic instruments which
are fuel gas rather than air-operated.
7. Pump seal and packing leakage.
8. Vapors from engine crankcases and compressor oil reservoirs.
9. Losses while purging and filling sample containers.
10. Vents from moisture analyzers and gas chromatographs.
11. Vapors from oil drainage for maintenance.
12. Vapors from equipment purge both before and after maintenance.
In addition to these, as mentioned in other replies are:
1. Valve packing leaks.
2. Flange leaks.
3. Compressor seal leaks.
-------
EL-9
In summary, there are many potential sources of fugitive emissions
from the steam cracking process. However, it appears as if the industry
holds these to a relatively small total by means of careful design and
timely maintenance. It seems reasonable to expect that future operations
will continue to try to minimize losses because of economic considerations.
However, it must be remembered that by 1980 this will be a 40 billion
pound per year industry so that even a fugitive emission loss as low as
0.01% will result in 4,000,000 pounds per year of hydrocarbon emissions.
Consequently, constant attention to the potential problem is essential.
-------
EL-10
IV. Emission Control
The various emission control devices that are employed by operators
of ethylene plants are summarized in the Catalog of Emission Control Devices,
Table IV. Unfortunately, in only a few instances, are sufficient data
available to permit calculation of device efficiency. Never-the less, certain
generalizations about the performance of the devices utilized can be made:
Water Scrubbers
In ethylene production these devices are used to either prevent or
reduce the emission of coke particles during furnace decoking or to
prevent or reduce the emission of catalyst fines and desorbed hydro-
carbon vapors during converter regeneration. One operator (EPA Code
No. 11-13) states that his scrubber is able to remove 99% of the furnace
coke particles larger than 2 microns; the overall efficiency of that
device (EL-10) is calculated to be 98%. The scrubbers should be nearly
as effective in the direct contact condensation of the relatively heavy
hydrocarbons ("Green Oil") that are evolved during converter regeneration.
In general one would expect that properly designed and operated water
scrubbers would be 90 + °L effective in the described ethylene plant
service.
Incinerators and Flares
Most ethylene plants employ at least one flare or incinerator. When
'straight1 hydrocarbons are being burned, they are very efficient pollution
control devices. However, when sulfur or halogens are present in the
stream being flared, it is more difficult to characterize device per-
formance. Accordingly, devices in this category have been assigned two
efficiencies. One, "CCR", is a measure of completeness of combustion;
the other , "SERR", is a measure of the reduction of pollutant con-
centration on a weighted basis. These efficiencies, and other pertinent
data are tabulated in Table IV. A complete discussion of "CCR" and
"SERR" efficiencies may be found in Appendix V of this report.
Most ethylene plant operators report using John Zink smokeless flares,
ranging in size from 24" to 48". Flare capacities (smokeless) average
about double plant ethylene capacities', that is,a plant producing 75,000
Ib./hr. of ethylene has (on the average) a flare with a capacity for
burning 150,000 Ib./hr. of hydrocarbons - smokelessly. Operator EPA
Code No. 11-7 states that, for his flare system, smokeless operation
requires a steam injection rate of about 8000 Ib. of steam per MM BTU
of heat release. In addition to promoting smokeless buring, steam
injection also reduces NO emissions by lowering flame temperatures.
Unfortunately, very little quantitative information on flare and/or
incinerator efficiency was provided by the questionnaire respondents.
One would expect, however, that "CCR" efficiencies will average close
to 100% while "SERR" efficiencies will vary widely - depending on the
stream being 'treated'.
K. 0. Drums, Demisters & De-Gassers
This type of device is used primarily, in ethylene plant service, to
desorb and separate hydrocarbon gases from various waste streams -
principally spent caustic and wash water. The efficiency of the device
('De-gasser') is dependent to a very large extent on the amount of gas
-------
EL-11
'held' by the liquid; which in turn is related to operating temperatures
and pressures. These conditions are not disclosed, however, one may
speculate that relatively small amounts of gas are left in these streams
since they would directly (and adversly) affect overall plant yield.
It is unlikely that any change in operating conditions can be made that
will reduce air emissions since yield and selectivity are not directly related
to the two primary sources of air pollution. (See Section I)
Air emissions could be significantly reduced by the use of purer (less
sulfur) feed stocks. Unfortunately it is generally agreed that feed stocks
will contain increasing amount of sulfur as ethylene plant operators gradually
change to heavier feed. One operator (EPA Code No. 11-10) states that plants
using refinery gas oil as feed would produce three to six times as much
sulfur dioxide as a plant using lighter (Gulf Coast field condensate) feed.
Development work directed toward reductions in emissions from this process
falls into the following general categories:
(1) Economical sulfur recover from small sulfur bearing streams.
(2) Prevention of hydrocarbon venting to atmosphere rather than to
flare.
(3) More efficient design and operation of devices currently being
utilized.
-------
EL-12
V. Significance of Pollution
It is recommended that no in-depth study of this process be undertaken
at this time. Although the growth rate of ethylene production by pyrolysis
is forecast to be significant, the emission data indicate that the quantity
of pollutants emitted to the atmosphere is less, on a weighted basis, than
from many of the other processes that are currently being surveyed.
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 of pollutants from these new
plants. This work is summarized in Tables V, VI, and VII.
Support for the Table V forecast of new plants has appeared in print
as recently as September, 1972 (Chemical Engineering Progress, pp 92-98).
This article indicates that about 20 new billion Ibs./year plants will
have to be constructed between now and 1980 to keep up with the estimated
demand. Thus, the number of new units to be built, especially when the size
of each unit is considered, is certainly significant.
However, on a weighted emission basis, a Significant Emission Index
(SEI) of 2,431 has been calculated in Table VII. This is substantially
less than the SEl's that have been calculated for other processes in the
study- Hence, the recommendation to exclude an in-depth study on ethylene
production from the scope of work.
-------
EL-13
VI. ETHYLENE PRODUCERS
The following tabulation of producers of ethylene indicates published
production capacity:
Company
Allied/Wyandotte
Arco
Chemplex
Citgo
Conoco
Dow
Du Pont
Eastman Kodak
El Paso Products
Enjay
Goodrich
Gulf Oil
Jefferson
Mobil
Monsanto
National Distillers
Northern Petrochem.
Olin
Phillips
Phillips/Houston Nat. Gas
Shell
Sinclair-Koppers
Sunolin
Union Carbide
Columbia Carbon
Northern Natural Gas
Location
Geismar, La.
Wilmington, Calif.
Clinton, Ohio
Lake Charles, La.
Lake Charles, La.
Bay City, Mich.
Freeport, Texas
Plaquemine, La.
Orange, Texas
Longview, Texas
Odessa, Texas
Baton Rouge, La.
Baytovn, Texas
Bayway, N. J.
Calvert City, Ky.
Cedar Bayou, Texas
Port Arthur, Texas
Port Neches, Texas
Beaumont, Texas
Alvin, Texas
Texas City, Texas
Tuscola, 111.
East Morris, 111.
Brandenburg, Ky.
Sweeny, Texas
Sweeny, Texas
Deer Park, Texas
Norco, La.
Houston, Texas
Claymont, Del.
Seadrift, Texas
Taft, La.
Texas City, Texas
Torrance, Calif.
Whiting, Ind.
Lake Charles, La.
Bushton, Kansas
Capacity - MM Lb./Yr.
600
100
500
440
550
170
1,500
900
750
800
500
1,900
90
225
250
400
925
500
470
650
150
350
800
100
600
500
1,450
500
500
225
1,200
500
1,200
150
150
900
800
Total
22,295
-------
PAG E N OT
AVAILABLE
DIGITALLY
-------
Stream No.
Component
H2
H2S
C02
Cl
C2H2
TABLE EL-I
TYPICAL ETHY1.ENE UNIT
MATERIAL BALANCE. T/T OF ETHYLENE
Fresh
Feed
Recycle
Feed
Steam
to
Reactor
Condensate
and
Heavy
Reject
Hydrogen
to Acetylene
Converter
.0008
.0001
Reject
Acid Gas
(b)
.0002
.0005
Hydrogen
Vent Gas
.0589
.1154
Demeth«nizer
Overhead
.0065
.0956
Ethylene
Product
10
Propylene
Product
11
Product
.0003
12
Gasoline
C2~
C2 .9859 .5749
C3=4
C3 .4943 .0353
C "=
C4=
C4
C5/1C6
C6-C8
BZ
TOL
XYL
C9+ .0007
Sulfur .0002 (a)
H,0 0.6271 0.6271
.0020 .0030 1.0000
.0011 .0011 .0005 .0020
.0988
.0040 .0002
.0205
.0114
.0020 .0002
.0004 .0079
.0099
.0278
.0055
.0047
.0006
1.4804
.6102
0.6271
0.6278
.0009
.0007
0.1774
. 1062
1.0008
.1048
.0345
.0566
(a) Assumes feed contains 150 ppm sulfur.
(b) Assumes regenerative amine type scrubber. A caustic type removal unit can also be employed.
-------
TABLE EL-II
ETHYLENE
VIA
LIGHT HYDROCARBON PYROLYSIS
GROSS HEAT BALANCE
Heat Out
Endothermic heat of reaction
Furnace effluent quench
(including heat exchange)
Furnace effluent final condensation
and cooling
Heat to furnace economizing devices
Heat losses and inefficiencies
Heat In
Fuel to cracking furnace
Steam to cracking furnace
BTU/lb. of ethylene produced
2181*
2343
1125
1526
1129
Total 8304
Total
*Feed stock = 100% ethane w/ethane conversion @ 657»
**Depending on feed stock composition, cracking severity,
furnace design, etc. - this duty can range from
7,000 to 10,000 BTU/lb. of ethylene.
-------
TABLE EL-III
NATIONAL EMISSIONS INVENTORY
ETHYLENE PRODUCTION
Page 1 of 13
Company
Location
EPA Code Number
Date on-stream
Capacity - Tons of Ethylene/Yr.
Average Production - Ethylene. T/Yr.
Range in Production - 7, of Max. (f)
Emissions to Atmosphere
Stream
Flov - Lb./Hi'.
Flov Characteristic - Continuous/Intermittent
if Intermittent - Hrs./Yr. of Flow
Composition - Tons/Ton Ethylene
Hydrogen
Methane
Ethane
Ethene
Propane
Propene
C,"1" Hydrocarbons
Acetylene
Oxygen
Nitrogen
Carbon Monoxide
Carbon Dioxide
Nitrogen Oxide
Sulfur Oxides
Hydrogen Sulfide
Water
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problem
Vent Stacks
. Flow, SCFM Per Stack
Number
Height - Feet
Diameter - Inches
Exit Gas Temperature - F°
Emission Control Devices
Type - Flare
Water Scrubber
Refrigerated Condenser & K. 0. Drum
Other
Catalog I. D. Number
Total Hydrocarbon Emissions - Ton/Ton of Ethylene (g)
Total Particulate/Aerosol Emissions - Ton/Ton of Ethylene
Total NOX
Total SOX
Total CO
Propane Vaporizer
Vent
-1
Intermittent
340
•< .00001
•^.00001
* .00001
-^.00001
C3 Storage Tank
GLC
No
.008
1
30'
2"
- 40
No
11-1
600,000
540,000
5
Quench Water
Off-gas
2850
Continuous
^.00001
-.00001
^.00001
^ . 00001
.0208
Not Specified
1971
Not Specified
No
111
9
12'
8"
194
No
Emergency C02 v«nt Ex
Vent Gas Purif. Section
15,000 1,025
Intermittent Continuous
0.05
".00001
" . 00001
*-. 00001
*-. 00001
•^.00001
^.00001
^.00001
.£.00001
.00749
Source Stream Not Sampled
Source - 15 Min.
GLC Assumed
Yes No
7,000 146
1 1
100' 240'
30" 30"
113 Ambient
No Yes
X
EL - 22
•^ 00001
•=.00001
Flare Sveep
Gas
720 (a)
Continuous
(After Burning)
.01356
.01132
Not Specified
Every 15 Min.
GLC
No
284
-------
TABLE EL-III
NATIONAL EMISSIONS INVENTORY
ETHYLENE PRODUCTION
Page 2 of 13
Company
Location
EPA Code Number
Date on-etream
Capacity - Tons of Ethylene/Yr.
Average Production - Ethylene, T/Yr.
Range In Production - •£ of Mix. (f)
Emissions to Atmosphere
Stream
Flow - Lb./Hr.
Flow Characteristic - Continuous/Intermittent
if Intermittent - Hrs./Yr. of Flow
Composition - Tons/Ton Ethylene
Hydrogen
Methane
Ethane
Ethene
Propane
Propene
C4+ Hydrocarbons
Acetylene
Oxygen
Nitrogen
Carbon Monoxide
Carbon Dioxide
Nitrogen Oxide
Sulfur Oxides
Hydrogen Sulfide
Water
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problem
Vent Stacks
Flow, SCFM Per Stack
Number
Height - Feet
Diameter - Inches
Exit Gas Temperature - F°
Emission Control Devices
Type - Flare
Water Scrubber
Refrigerated Condenser & K. 0. Drum
Other
Catalog I. D. Number
Total Hydrocarbon Emissions - Ton/Ton of Ethylene ^'
Total Particulate/Aerosol Emissions - Ton/Ton of Ethylene
Total NOX
Total SOX
Total CO
11-2
385,000
0
Acid Gas
Vent
9,180 (a)
Continuous
(After Burning)
Distillation
Emergency Vent
800,000 (a)
Intermittent
Not Specified
(After Burning)
Not Specified
.22201
.00065
.15835
None
Calculated
No
Miscellaneous
Leaks
20,000/Yr.
Intermittent
Not Specified
.00003
None
No
None
N. A.
None
Not Specified
1
120'
42 @ Tip
1600
Yes
X
EL - 18
.00003
.00065
-------
TABLE EL-III
NATIONAL EMISSIONS INVENTORY
ETHYLENE PRODUCTION
Page 3 of 13
Company
Location
EPA Code Number
Date on-stream
Capacity - Tons of Ethylene/Yr.
Average Production - Ethylene Tons/Yr.
Range in Production - 7. of Max. (f)
Emissions to Atmosphere
Stream
Flov - Lbs./Hr.
Flov Characteristic - Continuous or Intermittent
if Intermittent - Hrs./Yr. Flov
Composition - Tons/Ton of Ethylene
Hydrogen
Methane
Ethane
Ethene
Propane
Propene
C,"1" Hydrocarbons
Acetylene
Oxygen
Nitrogen
Carbon Monoxide
Carbon Dioxide
Nitrogen Oxides
Sulfur Oxides
Hydrogen Sulfide
Hater
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problem
Vent Stacks
Flov, SCFM Per Stack
Number
Height - Feet
Diameter - Inches
Exit Gas Temperatures - F°
Emission Control Devices
Type - Flare
Water Scrubber
Refrigerated Condenser & K. 0. Drum
Other
Catalog I. D. Number
Total Hydrocarbon Emissions - Ton/Ton Ethylene (g)
Total Particulate & Aerosol Emissions Ton/Ton Ethylene
Total NOX
Total SOX
Total CO
11-4
145,000
25
Emergency Vent Emergency Vent
Prod. Fract. Prod. Fract.
(a) 36,000 (Max.) (a) 36,000 (Max.)
Intermittent Intermittent
Not Specified Not Specified
After Burning After Burning
/ .00001 A 00001
Not Specified Not Specified
.00001 .00001
Not Specified Not Specified
(coke) ^-.00001 (coke) ^.00001
Weekly Weekly
GLC GLC
No No
Yes Yes
Not Specified Not Specified
1 1
Ground Level Ground Level
Yes Yes
X X
X Smoke Suppressor X Smoke Suppressor
EL - 23 EL -23
.£.00001
.00002
.00001
11-5
450,000
0
Emergency Vent
Methanator
34 Lb./Yr.
Intermittent
Not Specified
^-.00001
e. .00001
.t. 00001
*.. 00001
.£..00001
e.. 00001
None
Calculated
No
Not Specified
i
No
^.00001
^..00001
11-7
325,000
325,000
18
Plant Flare
System
(a) 5,740 (Avg.)
Continuous
After Burning
.00373
.18298
.10466
Tvice Month
GLC
No
Yes
1500
1
225
36
400
Yes
X
EL - 20
11-8
127,500
0
Plant Flare
System
Not Specified
1
No
Yes
Not Specified
1
200
24 @ Tip
Yes
X
EL - 21
Not Specified
T
-------
Company
Location
EPA Code Number
Date on-stream
Capacity - Tons of Ethylene/Yr.
Average Production - Ethylene Tons/Yr.
Range In Production - "I, of Max. (£)
Emissions to Atmosphere
Stream
Flov - Lbs./Hr.
Flov Characteristic - Continuous or Intermittent
if Intermittent - Hrs./Yr. Flov
Composition - Tons/Ton of Ethylene
Hydrogen
Methane
Ethane
Ethene
Propane
Propene
£4 + Hydrocarbons
Acetylene
Oxygen
Nitrogen
Carbon Monoxide
Carbon Dioxide
Nitrogen Oxides
Sulfur Oxides
Hydrogen Sulfide
Water
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problem
Vent Stacks
Flov, SCFM Per Stack
Number
Height - Feet
Diameter - Inches
Exit Gas Temperatures - F°
Emission Control Devices
Type - Flare
Water Scrubber
Refrigerated Condenser & K. 0. Drum
Other
Catalog I. D. Number
Total Hydrocarbon Emissions - Ton/Ton Ethylene (g)
Total Particulate & Aerosol Emissions Ton/Ton Ethylene
Total NOX
Total SOX
Total CO
TABLE EL-III
NATIONAL EMISSIONS INVENTORY
ETHYLENE PRODUCTION
11-6
100,000
0
Page 4 of 13
Unspecified
Intermittent
Unspecified
Flare V«nt
Unspecified
Continuous
One is provided
None
None
None
Unspecified
1
12 above scrubber
6
212
Yes
EL-31
None
Unspecified
Unspecified
Yes
+
EL-32
None
None
None
None
None
-------
TABLE EL-III
NATIONAL EMISSIONS INVENTORY
ETHYLENE PRODUCTION
Page 5 of 13
Company
Location
EPA Code Number
Date on-stream
Capacity - Tons of Ethylene/Yr.
Average Production - Ethylene Tons/Yr.
Range in Production - % of Max. (f)
Emissions to Atmosphere
Stream
Flow - Lbs./Hr.
Flow Characteristic - Continuous or Intermittent
if Intermittent - Hrs./Yr. Flow
Composition - Tons/Ton of Ethylene
Hydrogen
Methane
Ethane
Ethene
Propane
Propene
C.+ Hydrocarbons
Acetylene
Oxygen
Nitrogen
Carbon Monoxide
Carbon Dioxide
Nitrogen Oxides
Sulfur Oxides
Hydrogen Sulfide
Water
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problem
Vent Stacks
Flow - SCFM Per Stack
Number
Height - Feet
Diameter - Inches
Exit Gas Temperatures - F°
Emission Control Devices
Type - Flare
Water Scrubber
Refrigerated Condenser & K. 0. Drum
Other
Catalog I. D. Number
Total Hydrocarbon Emissions - Ton/Ton Ethylene (8)
Total Particulate & Aerosol Emissions Ton/Ton Ethylene
Total NOX
Total SOX
Total CO
11-9
600,000
600,000
Q
Plant Flare
System
9,000
Continuous
After Burning
(b)
Hydrogenation
Catalyst Regeneration Vent
8,150
Intermittent
216
Not Specified
Cannot be Determined
Acid Gas
Vent
1800 - 2600
Continuous
re)
. 00504
.02374
.06799
1
None None
Not S
No
Yes Yes
300, C
1 1
360 260
60 192
1,000 260 •
Yes Yes
X
! X K.
FT - 17 EL -
.00492
.00820
. 00028
Cj to C? HC .00197
Not Specified
amp led Not Specified
Mass Spec.
No
Not Specified
100 (d)
300 f
Yes
0. Drum X Claus Unit
12 N. A.
-------
TABLE EL-III
Company
Location
EPA Code Number
Date on-stream
Capacity - Tons of Ethylene/Yr.
Average Production - Ethylene Tons/Yr.
Range in Production - °l. of Max. (f'
Emissions to Atmosphere
Stream
Flov - Lbs.-/Hr.
Flow Characteristic - Continuous/Intermittent
if Intermittent - Hrs./Yr. Flow
Composition - Tons/Ton of Ethylene
Hydrogen
Methane
Ethane
Ethene
Propane
Propene
C4+ Hydrocarbons
Acetylene
Oxygen
Nitrogen
Carbon Monoxide
Carbon Dioxide
Nitrogen Oxides
Sulfur Oxides
Hydrogen Sulfide
Water
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problem
Vent Stacks
Flow - SCFM Per Stack
Number
Height - Feet
Diameter - Inches
Exit Gas Temperatures - F° .
Emission Control Devices
Type - Flare
Water Scrubber
Refrigerated Condenser & K. 0. Drum
Other
Catalog I. D. Number
Total Hydrocarbon Emissions - Ton/Ton Ethylene (g)
Total Particulate & Aerosol Emissions Ton/Tone Ethylene
Total NOX
Total SOX
Total CO
NATIONAL EMISSIONS INVENTORY
ETHYLENE PRODUCTION Page 6 of 13
11-10
330,000
0
Vent From Acid Gas Dcnethanizer Cj Splitter
Furnace Decoking Vent Emergency Vent Emergency Vent
3,179 Not Specified 505 Ton/Yr. 358 Ton/Yr.
Intermittent Continuous Intermittent Intermittent
Not Specified Not Specified Not Specified
'
Not Specified except SOj
.00121
r *
' Cj* HC
Incinerator Feed None
1968 2 or 3 times/10 Yr.
GLC GLC, Great, Wet
No No No
Yes Yes Yes
1,000 24,000
1 1 1
200 120 160
24 36 10
200 780 200
No Yes No
X Incinerator
EL - 9
.00108
1
.00121
1 1
.00153 C2+ HC .00108
None
No
Yes
1
2)0
10
200
No
-------
Company
Location
EPA Code Number
Date on-stream
Capacity - Tons of Ethylene/Yr.
Average Production - Ethylene Tons/Yr.
Range in Production - % of Max. (f)
Emissions to Atmosphere
Stream
Flov - Lbs./Hr.
Flow Characteristic - Continuous or Intermittent
if Intermittent - Hrs./Yr. Flow
Composition - Tons/Ton of Ethylene
Hydrogen
Methane
Ethane
Ithylane
Propane
Prop?lane
C^ + Hydrocarbons
Acetylene
Oxygen
Nitrogen
Carbon Monoxide
Carbon Didcld*
Nitrogen Oxldas
Sulfur Oxides
Hydrogen Sulflde
Water
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problem
Vent Stacks
TABLE EL-III
NATIONAL EMISSIONS INVENTORY
ETHYLENE PRODUCTION
11-11
197,500
0
Page 7 of 13
Flare Stack
Unspecified (Variable)
Continuous
None
None
Safety Valve
Discharge Stack
Unspecified
Intermittent
Unspecified
frO.00006 fj)
^0.0005 (j)
JO.0011 (j)
)0.00008 (j)
Not Specified
Not Specified
Not Specified
None
Gas Turbine
Lube Oil Vent
225
Continuous
^ 0.000002
^0.000001
0.00013
*L 0.000002
0.005
Not Specified (Simple)
Once
Mass Spectronmeter
None
Compressor Oil
Reservtir Vent
78
Continuous
^ 0.000001
^0.000004
^ 0.000005
^. 0.00002
lo.0017
Not Specified (Simple)
Once
Mass Spectrometer
None
Compressor Sour
Drum K. 0. Vent
80
Continuous
0.00016
0.001
0 0005
Trace
$0.00013
Not Specified 'Simple)
Once
Mass Spectrograph
No
Flow, SCFM Per Stack Unspecified
Number 1
Height - Feet 300
Diameter - Inches 36
Exit Gas Temperatures - F° Unspecified
Emission Control Devices Yes
Type - Flare X
Water Scrubber
Refrigerated Condenser & K. 0. Drum
Other
Catalog I. D. Number EL-33
Total Hydrocarbon Emissions - Ton/Ton Ethylene (g)
Total Particulate & Aerosol Emissions Ton/Ton Ethylene
Total NOX
Total SOx
Total CO
Unspecified
1
150
20
Unspecified
None
See Continuation
49
1
50
2
80
None
17
1
60
4
80
None
17
1
60
4
80
None
-------
TABLE EL-III
NATIONAL EMISSIONS INVENTORY
ETHYLENE PRODUCTION
Page 8 of 13
Company
Location
EPA Code Number
Date on-stream
Capacity - Tons of Ethylene/Yr.
Average Production - Ethylene Tons/Yr.
Range In Production - 7, of Max. (f)
Emissions to Atmosphere
Stream
Flow - Lbs./Hr.
Flov Characteristic - Continuous or Intermittent
if Intermittent - Hrs./Yr. Flow
Composition - Tons/Ton of Ethylene
Hydrogen
Methane
Ethane
Ethylene
Propane
Propylene
fy -f Hydrocarbons
Acetylene
Oxygen
Nitrogen
Carbon Monoxide
Carbon Dioxide
Nitrogen Oxides
Sulfur Oxides
Hydrogen Sulfide
Water
Sample Tap Location
Date or Fraquency of Sampling
Type of Analysis
Odor Problem
Vent Stacks
Flow, SCFM Per Stack
Nunber
Height - Feet
Diameter - Inches
Exit Gas Temperatures - F°
Emission Control Devices
Type - Flare
Water Scrubber
Refrigerated Condenser & K. 0. Drum
Other
Catalog I. D. Number
Total Hydrocarbon Emissions - Ton/Ton Ethylene (g)
Total Particulate & Aerosol Emissions Ton/Ton Ethylene
Total NOX
11-11
197,500
0
Sour Seal
Oil Vent
150
Continuous
0.0003
0.00074
0.00148
¥
0
r
0.00053
.00028
Not Specified (Simple)
Once
Mass Spectrograph
No
26
1
50
1
80
None
Analyzer
Vent
Continuous
Uio"6
Not Specified (Simple)
Not Specified
Mass Spectrograph
No
0.1 SCFH
1
10
1/4
80
None
See Continuation
Fourth Stage Relief
Valve Vent
245 000
Intermittent
0.25 (i)
V
o.000155
Not Specified (Simple)
Not Specified
Mass Spectrometer
No
35,000
None
Total
Total
SOX
CO
-------
Company
Location
EPA Code Number
Date on-stream
Capacity - Tons of Ethylene/Yr.
Average Production - Ethylene Tons/Yr.
Range in Production - % of Max- (f)
Emissions to Atmosphere
Stream
Flow - Lbs./Hr.
Flov Characteristic - Continuous or Intermittent
if Intermittent - Hrs./Yr. Flov
Composition - Tons/Ton of Ethylene
Hydrogen
Methane
Ethane
Etbylene
Propane
Propylene
64 + Hydrocarbons
Acetylene
Oxygen
Nitrogen
Carbon Monoxide
Carbon Dlraide
Nitrogen Oxides
Sulfur Oxides
Hydrogen Sulflde
Water
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problem
Vent Stacks
Flow, SCFM Per Stack
Number
Height - Feet
Diameter - Inches
Exit Gas Temperatures - F°
Emission Control Devices
Type - Flare
Water Scrubber
Refrigerated Condenser & K. 0. Drum
Other
Catalog I. D. Number
Total Hydrocarbon Emissions - Ton/Ton Ethylene (g)
Total Particulate & Aerosol Emissions Ton/Ton Ethylene
Total NOX
Total SOX
Total CO
TABLE EL-III
NATIONAL EMISSIONS INVENTORY
ETHYLENE PRODUCTION
11-11
197,500
0
Deproparrl ser Relief
Valve Vent (Bottom)
214.000
Intermittent
0.25 (i)
)0.00003
3.000053
r
r
3.000035
0.000018
Not Specified (Simple)
Not Specified
Mass Spectrometer
No
None
46,000
^. 40
None
Depropaniser Relief
Valve Vent (Top)
230,000
Intermittent
0.5 (i)
) 0.00003
»o : 00013
\0. 00014
Not Specified (Simple)
Not Specified
Mass Spectrometer
No
None
46,000
None
See Continuation
Page 9 of 13
Depropsnizer
Overhead Relief Vent
230,000
Intermittent
0.25 (i)
)0.000015
JO 000065
10.00007
Not Specified (Simple)
Not Specified
Mass Spectrometer
No
None
45,300
None
Debutaniier
Overhead Relief Vent
36,000
Intermittent
0 25 (i)
0 000023
Not Specified (Simple)
Tvice Weekly
Gas Chromatograph
No
None
3,900
None
-------
Company
Location
EPA Code Number
Date on-stream
Capacity - Tons of Ethylene/Yr.
Average Production - Ethylene Tons/Yr.
Range in Production - '/, of Max. (f)
Emissions to. Atmosphere
Stream
Flow - Lbs./Hr.
Flow Characteristic - Continuous or Intermittent
if Intermittent - Hrs./Yr. Flow
Composition - Tons/Ton of Ethylene
Hydrogen
Methane
Ethane
Ethylene
Propane
Propylene
C, + Hydrocarbons
Acetylene
Oxygen
Nitrogen
Carbon Monoxide
Carbon Dioxide
NitfOgen Oxides
Sulfur Oxides
Hydrogen Sulflde
Water
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problem
Vent Stacks
Flow, SCFM Per Stack
Number
Height - Feet
Diameter - Inches
Exit Gas Temperatures - F°
Emission Control Devices
Type - Flare
Water Scrubber
Refrigerated Condenser & K. 0. Drum
Other
Catalog I. D. Number
Total Hydrocarbon Emissions - Tons/Ton Ethylene (g)
Total Particulate & Aerosol Emissions Ton/Ton Ethylene
Total NOX
Total SOX
Total CO
TABLE EL-III
NATIONAL EMISSIONS INVENTORY
ETHYLENE PRODUCTION
11-11
197,500
0
Remote Operated
Valve Vent
320
Continuous
0.006
0.0004
0.00013
0.00014
1.00045
Page 10 of 13
Not Specified (Simple)
Once
Mass Spectrograph
No
115
1
50
6
80
None
Lube Oil
Reservoir Vent
6,100
Continuous
0.001
^•0.00001
?• 0.00001
0.0001
134
Not Specified (Simple)
Once
Mass Spectrograph
No
1,320
1
50
6
80
None
0.00753
None
None
None
None
Seal Oil
Reservoir Vent
40
Continuous
^-0.00001
^L 0.00001
£J) 00001
^0.00001
Y
0.001
Not Specified (Simple)
Once
Mass Spectrograph
No
1
8
3
80
None
-------
TABLE EL-III
NATIONAL EMISSIONS INVENTORY
ETHYLENE PRODUCTION
Page 11 Of 13
Company
Location
EPA Code Number
Date on-stream
Capacity - Tons of Ethylene/Yr.
Average Production - Ethylene Tons/Yr.
Range in Production - 7. of Max. (O
Emissions to Atmosphere
Stream
Flov - Lbs./Hr.
Flov Characteristic - Continuous or intermittent
if Intermittent - Hrs./Yr. Flov
Composition - Tons/Ton of Ethylene
Hydrogen
Methane
Ethane
Ethene
Propane
Propene
C^+ Hydrocarbons
Acetylene
Oxygen
Nitrogen
Carbon Monoxide
Carbon Dioxide
Nitrogen Oxides
Sulfur Oxides
Hydrogen Sulfide
Water
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problem
Vent Stacks
Flov - SCFM per Stack
Number
Height - Feet
Diameter - Inches
Exit Gas Temperatures - F°
Emission Control Devices
Type - Flare
Water Scrubber
Refrigerated Condenser & K. 0. Drum
Other
Catalog I. D. Number
Total Hydrocarbon Emissions - Ton/Ton Ethylene (g)
Total Particulate & Aerosol Emissions Ton/Ton Ethylene
Total NOV
Total
Total
S°x
CO
11-12
225,000
225,000
0
Emergency Vent Emergency Vent
Prod. Fract. Prod. Fract.
50,000 (Max.) 50,000 (Max.)
Intermittent Intermittent
Not E
1
pecified Not
1
Specified
Weekly Weekly
GLC GLC
No No
Yes Yes
Not Specified Not Specified
1 1
Ground Level Ground Level
Yes Yes
X X
X Smoke Suppressor X Smoke Suppressor
EL -24 EL - 24
Not Specified
11-3
800,000
(e)
Not Specified
\
-------
TABLE .EL-III
NATIONAL EMISSIONS INVENTORY
ETHYLENE PRODUCTION
Company
Location
EPA Code Nunber
Date on-strean
Capacity - Tons of Ethylene/Yr.
Range in Production - "I, of Max. (f)
Emissions to Atmosphere
Stream
Flow - Lbs./Hr.
Flow Characteristic - Continuous or Intermittent
if Intermittent - Hi»./Yr. Flow
Composition - Tons/Ton of Ethylene
Hydrogen
Methane
Ethane
Ethene
Propane
Propene
C/+ Hydrocarbons
Acetylene
Oxygen
Nitrogen
Carbon Monoxide
Carbon Dioxide
Nitrogen Oxides
Sulfur Oxides
Hydrogen Sulfide
Water
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problem
Vent Stacks
Flow - SCFM Per Stack
Number
Height - Feet
Diameter - Inches
Exit Gas Temperatures - F°
Emission Control Devices
Type - Flare
Water Scrubber
Refrigerated Condenser & K. 0. Drum
Other
Catalog I. D. Number
Total Hydrocarbon Emissions - Ton/Ton Ethylene (g)
Total Particulate & Aerosol Emissions - Ton/Ton Ethylene
Total NOx
Total SOX
Total CO
Page 12 of 13
11-13
300,000
Vent From
Furnace Decoking
Intermittent
Acetylene Converter
Regeneration Vent
460
Intermittent
408
Caustic Neutraliz.
Vent
20,672
Continuous
Plant Flare
System
910 fa)
Continuous
'After. Burning)
Not Specified
Not Specified
.02400
Coke .00001
@ Furnace
1969
Coulter Counter
No
Yes
4,290
1
78.5
14
212
Yes
X
EL - 10
Not Specified
Not Specified
Not Specified
Not Specified
Not Specified
Not Sampled
No
Yes
1
42 •
8
140
Yes
X
EL - 15
.06693
.22406
.00017
Not Sampled
Engr. Est.
No
Y6B
4,500
1
93
8
Ambient
Yes
X Vapor Collectors 6. Dilution Device
EL - 11
.03486
.02852
Not Sampled
Calcuated
No
Yes
1
130
36
1800 - 2500
Yes
X
EL - 30
-------
TABLE EL-III
EXPLANATION OF FOOTNOTES
NATIONAL EMISSIONS INVENTORY
ETHYLENE PRODUCTION page 13 of 13
(a) The flow rate given describes the stream prior to combustion.
(b) 80,000 Ib./hr. of a 92% methane stream - most probably the demethanizer
overhead - is used to supplement the fuel to the pyrolysis furnace.
This stream and it's resultant atmospheric emissions (C02 & t^O) are
not detailed elsewhere in this report.
(c) This stream is not emitted to the atmosphere, it is sent to a Glaus
plant.
(d) Boiler stack used.
(e) Although there is a wealth of information in this report; quantitative
data on emissions are conspicuous by their absence. (with exception of
motor exhaust data)
(f) Difference between maximum and minimum quarterly production divided by
maximum quarterly production.
(g) Includes H2S. Excludes City & t^.
(h) Three identical scrubbers are provided on the acetylene converter,
propadiene converter and hydrogenation catalyst regeneration vents.
The emissions from each are essentially the same.
(i) Estimated maximum per year.
(j) Calculated on basis of total of maximum estimated releases from each
relief valve in circuit.
-------
WATER SCRUBBERS - Flow Diagram Stream I. D.
Device I. D. Number
EPA Code No. for plant using
Purpose - Control Emissions of
Type - Spray.
Packed Column
Trays - Type
Number
Plenum Chamber
Other
Water 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 - Ft.
Installed Cost - Material & Labor, $
Installed Cost - c/lb. of Ethylene
Op"tr«ttngyCost - Annual, $
Operating Cost - c/lb. of Ethylene
Efficiency (IX)
TABLE EL-IV
CATALOG OF EMISSION CONTROL DEVICES
CURRENTLY USED IN THE PRODUCTION OF
ETHYLENE
VIA THE
PYROLYSIS OF LIGHT HYDROCARBONS
Page 1 of 8
CRACKING I
(A)
EL - 1
11-9
Coke Particles
X
Not known
(560)
Approx. (45,000)
18
12
Via-Devlce EL - 12
260
16
100,000
.0083
6,000
Not Specified
TJRNACE
(A)
EL - 2 (I)
11-3
Coke Particles
X
X
Seive
5
Not Specified
450
(2,600)
19
4
Yes
25
.3
(Total) 870,000
(Total) .0544
(Total) 5,800
Not Specified
(A)
EL - 10
11-13
Coke Particles
'^
X,
w/Venturi Mixer
120
(212)
12,000
9.2
4
Yes
78.5
1.2
105,000
.0175
^-1,000
•*. . 0002
98% (Particulates)
-------
TABLE EL-IV
CATALOG OF EMISSION CONTROL DEVICES
CURRENTLY USED IN THE PRODUCTION OF
ETHYLENE
VIA THE
PYROLYSIS OF LIGHT HYDROCARBONS
Page 2 of 8
INCINERATION DEVICES - Flow Diagram Stream I. D.
Device I.D. Number
EPA Code No. for plant using
Types of Compounds Incinerated
Type Device - Flare
Incinerator
Other
Materials Incinerated SCFM (Ibs./hr.)
Auxiliary Fuel Req'd. - Excluding Pilots
Auxiliary Fuel Type
Auxiliary Fuel Rate - BTU/hr.
Device or Stack Height - Ft.
Installed Cost - Material & Labor - $
Installed Cost - c/lb. of Ethylene/Yr.
Operating Cost - Annual - $
Operating Cost - c/lb. of Ethylene
Efficiency - CCR - % - (X)
Efficiency - SERR - % - (X)
Quench Section
(B)
EL-3 (II)
11-3
Gas ex. H20 Drum
X
Not Specified
No
38
(Total) 28,000
(Total) .0018
(Total) 500
(Total) <.0001
,'wlOO
< 100
"Acid Gas" Removal Section
(C)
EL-9
11-10
"Waste" Gas
Yes
Gas
Not Specified
120
26,200
.0040
9,200
.0014
--•^100
-------
TABLE EL-IV
CATALOG OF EMISSION CONTROL DEVICES
CURRENTLY USED IN THE PRODUCTION OF
ETHYLENE
VIA THE
PYROLYSIS OF LIGHT HYDROCARBONS
Page 3 of 8
K. 0. DRUMS - Flow Diagram Stream I. D.
Device I. D. Number
EPA Code So. for plant using
Purpose - Control Emission of
Type - Condenser & K. 0. Drum
Demister
Degasser
Other
Design Press, (operating press) PSIG
Design Temp, (operating temp.) - F°
Feed Rate of Stream Treated
Liquid - Ib./hr. (GPM)
Gas - Ib./hr. SCFM)
T-T Height (length) - Ft.
Diameter - Ft.
Vent Gases to Stack
Stack Height - Ft.
Stack Diameter - Ft.
SCFM/Stack
Installed Cost - Material & Labor - $
Installed Cost - c/lb. of Ethylene - Yr.
Operating Cost - Annual - $
Operating Cost - c/lb. of Ethylene
Efficiency '(IX)
"Acid Gas" Removal Section
(C)
EL - 4
11-8
Wash H20 Off-gas
X
(15)
(100)
X (12)
6
2
Return to process
1,000
.0004
Not Specified
||
ii
(D)
EL - 5
11-8
Caustic Soln. Off-gas
X
(&2)
(100)
X (16)
6
2
Return to process
1,000
.0004
Not Specified
ii
ii
(C)
EL -6
11-5
Wash H20 Off-gas
X
(10)
(10)
X (10)
(17)
4.5
Return to process
(C)
EL - 7
11-5
Wash H20 Off-gas
X
(-5)
(110)
X (10)
8
3
Return to process
8,535
.0009
Not Specified
it it
ii T ii
(D)
EL - 8
11-5
Caustic Soln. Off-gas
X
(10)
(110)
X (20)
10
4
Return to process
3,900
.0004
Not Specified
ii
11
EL - 11
11-13
Waste Liquor Off-gas
X (III)
Atmos.
Not Specified
X
(sump) 12
(sump) 3.5
Yes
93
.7
Not Specified
29,000
.0048
Not Specified
ii
"
-------
TABLE EL-IV
CATALOG OF EMISSION CONTROL DEVICES
ACETYLENE
Page 4 of 8
WATER SCRUBBERS - Flow Diagram Stream I. D.
Device I.D. Number
EPA Code No. for plant using
Purpose - Control Emission of
Type - Spray
Packed Column
Trays - Type
Number
Plenum Chamber
Other
Water Rate - GPM
Design Temp, (operating temp.) - F°
GAS Rate - SCRM (Ibs./hr.)
T-T H«ight - Ft.
Diameter - Ft.
Washed Gases to Stack
Stack Height - Ft.
Stack Diameter - Ft.
Installed Cost - Material & Labor, $
Installed Cost - f/lb. of Ethylene - Yr.
Operating Cost - Annual - $
Operating Cost - $/lb. of Ethylene
Efficiency (IX)
CONVERSION SECTION
(e)
EL-13
11-8
Regeneration Gas
X (Multi-level)
250
Not Specified
Not Specified
20
1.3
Yes
175
.5
5,000
.0020
Not Specified
(e)
EL-14 (V)
11-5
Regeneration Gas
X
(Total) - 1500
140
Not Specified
6
4
Yes
30
1
(Total) 10,000
(Total) .0011
Not Specified
(e)
EL-16 (VI)
11-3
Regeneration Gas
X
Not Specified
4
2
Yes
31
1
(Total) 5,000
(Total) .0003
(Total) 300
(Total) >.0001
Not Specified
K. 0. DRUMS - Flow Diagram Stream I. D.
Device I. D. Number
EPA Code No. for plant using
Purpose - Control Emission of
Type - Condenser & K. 0. Drum
Demister
Degasser
Other
Design Press, (operating press.) PSIG
Design Temp, (operating temp.) F°
Feed Rate of stream treated
Liquid - Ibs./hr. (GPM)
Gas - Ibs./hr. (GPM)
T-T Height (length) - ft.
Diameter - ft.
Vent Gases to Stack
Stack Height - ft.
Stack Diameter - ft.
SCFM/Stack
Installed Cost - Material & Labor - $
Installed Cost - c/lb. of Ethylene - Yr.
Operating Cost - Annual - $
Operating Costs - c/lb. of ethylene
Efficiency '(IX)
(e)
EL-12
11-9
Regeneration Gas
(Atmos.)
Not Specified
Not Specified
23.5
13
Yes (IV)
260
16
300,000
350,000
.0292
6,000
.0005
Not Specified
(e)
EL-15
11-13
Regeneration Gas
X
(Atmos.)
(140)
Not Specified
6
2
Yes
42
.7
28,000
.0047
Not Specified
-------
TABLE EL-IV
CATALOG OF EMISSION CONTROL DEVICES
Page 5 of 8
INCINERATION DEVICES
Device I. D. Number
EPA Code No. for plant using
Types of Compounds Incinerated
Type Device - Flare
Incinerator
Other
Materials Incinerated SCFM (Ib./iir.)
Auxilliary Fuel Req'd - Excluding Pilot
Auxilltary Fuel Type
Auxilliary Fuel Rate - BTU/hr.
Device Elevation - Ft. above grade
Installed Cost - Material & Labor, $
Installed Cost - c/lb. of Ethylene - Yr.
Operating Cost - Annual
Operating Cost - r/lb. of Ethylene
Efficiency- CCR - % (X)
Efficiency - SERR - 7. (X)
INCINERATION DEVICES
Device I. D. Number
EPA Code No. for plant using
Types of Compounds Incinerated
Type Device - Flare
Incinerator
Other
Materials Incinerated SCFM (Ib./hr.)
Auxilliary Fuel Req'd - Excluding Pilot
Auxilliary Fuel Type
Auxilliary Fuel Rate BTU/Hr.
Device Elevation - Ft. above grade
Installed Cost - Material & Labor, $
Installed Cost - c/lh. af Ethylene - Yr,
Operating Cost - Annual
Operating Cost - c/lb. of Ethylene
Efficiency - CCR - 7. (X)
Efficiency - SERR - 7. (X)
FPlACTIONATION SECTION (INCLUDING MAIN PLANT SLOWDOWN & FLARE SYSTEM)
EL - 17
11-9
All
Emergency
Vents
X
Not Specified
No
360
2,934,000
.2445
199,800
.0167
\°o°o7-
EL - 24
11-12 (VII)
All
Emergency
Vents
X
Total (100,000) Max.
No
at Specified but Horiz
(Total) 81,000
(Total) .0180
(Total) 10,000
(Total) .0022
,^100
<100
EL - 18
11-2
Acid Gas &
All Emergency
Vents
X
Not Specified
120
500,000
.0649
50,000
.0065
100
53
EL - 25
11-10
Emergency
Vent
X
(1,000,000) Max.
ontal 200
329,000
.0498
142, C
.0213
^100 1
^:. 100
EL - 19
11-5
All
Emergency
Vents
X
(170,000) Max.
265
518,700
.0576
Not Specified
~100
<100
EL - 26
11-10
Emergency
Vent
X
(100,000) Max.
150
85,000
.0129
00
^100
.£100
EL - 20
11-7
All Waste Gases
& Emergency
Vents
X
1500
No
225
45,000
.0069
20,000
.0031
^>100
<100
EL - 27
11-3 (VIII)
Purge Gas
Vents and
Blowdovn
X
Not gp«clfl*d
150
(Total) 275,000
(Total) .0172
(Total) 10,000
(Total) .0006
-^100
< 100
EL - 2]
11-8
All
Emergency
Vents
X
(50,000) Msx.
No
200
78,600
.0308
5,500
.0022
sislOQ
< 100
EL - 28
11-3 (VIII)
Purge Gas
Vents and
Blowdovn
X
Not Specified
150
(Total) 150,000
(Total) .0094
(Total) 10,000
(Total) .0006
~<100
<100
El - 22
11-1
All Waste Gases
& Emergency
Vents
X
430 < Normal)
No
240 Not Spi
663.000
.0553
53,500
.0045
xv-100
< 100
EL - 29
11-3 (VIII)
Purge Gas
Vents and
Blowdovn
X
Total (560,000) Max
150
(Total) 500,000
(Total) .0313
(Total) 10,000
(Total) .0006
-~100
< 100
El - 23
11-4 '(Vtl)
All
Emergency
Vents
X
Not Specified
No
tctflMeftvt Horliem
'(Total) 73,000
(Total) .0252
(Total) 1,400
(Total) .0005
^100
< 100
EL - 30
11-13
Emergency
Vent
X
(160,000) Max.
130
Not Specified
^100
< 100
ai
-------
TABLE EL-IV
CATALOG OF EMISSION CONTROL DEVICES
CURRENTLY USED IN THE PRODUCTION OF
ETHYLENE
VIA THE
MATER SCRUBBERS - Flov Diagram Stream I. D.
Device I. D. Nunber
EPA Code No. for plant using
Purpose - Control Emissions of
Type - Spray
Packed Column
Trays - Type
Number
Plenum Chamber
Other
Water Rate - GPM
" Design Temp, (operating temp.) F°
Gas Rate - SCFM (Ib./hr.)
T-T Height - Ft.
Diameter - In.
Washed Gases to Stack
Stack Height - Ft.
Stack Diameter - Ft.
Installed Cost - Material & Labor, $
Installed Cost - c/lb. of Ethylene
Operating Cost - Annual, $
Operating Cost - c/lb. of Ethylene
Efficiency (IX)
PYROLYSIS OF LIGHT HYDROCARBONS
ACETYLENE CONVERSION SECTION
EL-31 (3 units)
11-6
Regeneration gas
Page 6 of 8
0.75 (?)
2120 F
steam 10,000 - air 900
4.5
30 IPS
Yes (3 stacks)
12
6
7,050 (total for all three)
0.0035
4,200
0.0021
100
-------
INCINERATION DEVICES - Flow Diagram Stream I.D.
Device I. .D. Number
EPA Code No. for plant using
Types of Compound! Incinerated
Type Device - Flare
Incinerator
Other
Materials Incinerated SCFM (Ib./hr.)
iuxllllary Fuel Req'd. - Excluding Pilots
Auxllllary Fuel Type
Auxllllary Fuel Rate - BTU/hr.
Device or Stack Height - Ft.
Installed Coat - Material & Labor, $
Installed Cost - c/lb. of Ethylene/Yr.
Operating Cost - Annual - $
Operating Cost - c/lb. of Ethylene
Efficiency- OCR - 7. (X)
Efficiency - SERR - t (X)
TABLE EL-IV
CATALOG OF EMISSION CONTROL DEVICES
CURRENTLY USED IN THE PRODUCTION OF
ETHYLENE
VIA THE
PYROLYSIS OF LIGHT HYDROCARBONS
MAIN PLANT FLARE SYSTEM
EL-3 2
11-6
Hydrocarbons
Unspecified
No
Unspecified
Unspecified
Unspecified
100
Page 7 of 8
EL-33
11-11
Hydrocarbons
Unspecified
No
300
310,000
0.0785
52,450
0.0133
100
<100
-------
TABLE EL-IV
EXPLANATION OF NOTES
CATALOG OF EMISSION CONTROL DEVICES
CURRENTLY USED IN THE PRODUCTION OF
ETHYLENE
VIA THE
PYROLYSIS OF LIGHT HYDROCARBONS Page 8 of 8
I There are fifty-eight (58) decoking scrubbers in plant # 11-3. One
for each furnace.
II There are five (5) waste gas flares in plant # 11-3.
Ill Device EL - 11 accomplishes the following:
(1) Strips dissolved gases from spent caustic and vents them to
atmosphere.
(2) Gather fumes from neutralization pit and vents them at elevation.
IV Utilizing boiler stack.
V Device consists of two paralled drums, used simultaneously.
VI There are three regenerating gas scrubbers.
VII There are two identical horizontal flare systems.
VIII There are two similar flares.
IX Defined as percent removal of total air pollutants in stream being
treated.
X See Appendix V for definitions.
-------
TABLE EL-V
NUMBER OF NEW PLANTS BY 1980
Current
Capacity
Marginal
Capacity
Current
Capacity
on-stream
in 1980
Demand
1980*
Capacity
1980
Capacity
to be
Added
Economic
Plant
Size
Number
of New
Units
22,295
2,800
19,495
40,000
40,000
20,505
1,000
20-21
Note: All capacities in mm Ibs./year.
*1980 demand based on study prepared for EPA
by Process Research, Inc. and C. E. P. Vol. 68, No. 9.
-------
TABLE EL-VI
Pollutant
Hydrocarbons
Particulates
NOX
S°x
CO
SUMMARY OF EMISSION SOURCES \L'
Source
Furnace Quench Acid Gas Distillation Fugitive
Decoking Tower Removal Compressors Train Emissions
.00001 .00001 .00010 .00050 .00010
. 90001
.00001
.00300 (2)
.00001
Total
.00072
.00001
.00001
. 00300
. 00001
Note
(1) Pollutant concentrations in Ib./lb. of ethylene.
(2) Adjusted for predicted trend in feedstock.
-------
TABLE EL-VII
Chemical Ethylene
Process Pyrolysis
Increased Capacity 20.5
Pollutant
Hydrocarbons
Participates
NO..
A
sox
CO
WEIGHTED
billion Ibs./yr.
Emissions, Ibs./lb.
.00072
.00001
.00001
.003 (a)
.00001
EMISSIONS RATES
Increased Emissions
MM Ibs . /year
14.8
.2
.2
61.5
.2
Weighting
Factors
80
60
40
20
1
Weighted Emissions
MM Ibs. /year
1180.8
12.0
8.0
1230.3
.2
Significant Emission Index - 2431.3 (MM Ibs./yr.)
(a) Adjusted for predicted trend in feedstock.
-------
Ethylene Dichloride (Direct)
-------
Table of Contents
Section Page Number
I. Introduction EDC-1
II. Process Description EDC-2
III. Plant Emissions EDC-3
IV. Emission Control EDC-5
V. Significance of Producers EDC-7
VI. Ethylene Bichloride Producers EDC-8
List of Illustrations and Tables
Flow Diagram Figure EDC-I
Net Material Balance Table EDC-I
Gross Heat Balance Table EDC-II
Emission Inventory Table EDC-III
Catalog of Emission Control Devices Table EDC-IV
Number of Nev Plants by 1980 Table EDC-V
Emission Source Summary Table EDC-VI
Weighted Emission Rates Table EDC-VII
-------
JiLKJ-i
I. Introduction
Ethylene dichloride (1, 2 dichloroethane) was the earliest known chlorinated
hydrocarbon, having been produced by four Dutchmen in 1795. At ordinary
temperatures it is an oily, colorless liquid with an odor resembling that of
chloroform. The vapor has an irritant effect on the respiratory tract and is
toxic.
Primarily, ethylene dichloride (EDC) is used to produce vinyl chloride
monomer by dehydrohalogenation. Over 80% of the ethylene dichloride man-
ufactured goes to this purpose. Virtually all EDC producers have vinyl
chloride plants nearby. Other uses for EDC are in solvent manufacture,
ethyleneamine production and as a lead scavenger in antiknock fluids.
Two commercial processes account for most of the ethylene dichloride
produced today. One is the direct chlorination of ethylene with chlorine.
The other is an oxychlorination process in which ethylene, hydrogen chloride
and oxygen react to form the same product. Presently almost all production
centers around large plants employing a balanced combination of these two
processes. These balanced plants use the hydrogen chloride recovered when
ethylene dichloride is dehydrohalogenated as feed to the oxychlorination
reactor. This requires about a 50/50 split between direct chlorination and
oxychlorination for a completely balanced operation.
Total ethylene dichloride capacity presently is 9.6 billion Ibs./year,
about 58% of the total is direct chlorination, and about 42% by oxychlorination.
Capacity is expected to rise by 12.5 billion Ibs./year between now and 1980
requiring around 9-10 large balanced operations.
This report directs its attention to the direct chlorination process.
The major source of air emissions from this process is the hydrogen chloride
scrubber vent. Quantities of chlorinated hydrocarbons and light hydrocarbons
are emitted to the atmosphere from this source. In general, air emissions
from ethylene dichloride production by direct chlorination can be best
described as moderate.
An intensive review of air pollution from the oxychlorination process is
provided in an in-depth study of that process, as reported in Report No. EPA-
450/3-73-006.
-------
EDC-2
II. Process Description
In the direct chlorination process, ethylene dichloride is produced by
the chemical combination of ethylene and chloride.
C2H4 + C12 > C2H4 C12
(See Figure EDC 1)
Chlorine and a substantially stoichiometric amount of ethylene are fed
into a reactor under constant temperature conditons, excesses of either
reactant result in raw material losses. The reaction usually takes place
in the liquid phase with a considerable excess of reaction product, although
depending upon design, excess reaction product may not be necessary. The
exothermic heat of reaction, 52 kcal./mole, is removed by jacketed walls,
internal cooling coils or external heat exchange. When considerable amounts
of inert gases are present in the feed, some packing might be necessary to
improve liquid-gas contact. Typical reaction conditions are temperatures
of 100-120° F and pressures in the range of 10-20 PSIG. Overall process yield
of ethylene dichloride from chlorine is generally better than 98 percent if
high purity reactants are used. However, the present of impurities in either
ethylene or chlorine will reduce the reaction yield. Usually a liquid and
a vapor stream exit from the reactor. The vapors pass through water cooled
condensers, and in some cases refrigerated exchangers where some ethylene
dichloride is recovered. The vapors are sent through an absorbing column
where dichloride is recovered. The vapors are sent through an absorbing
column where small quantities of hydrogen chloride and chlorine are removed.
The scrubbing liquid is either water or dilute caustic, depending on the
amount of chlorine that is desired to be removed.
The crude liquid ethylene dichloride that exists from the reactor must
be refined for commercial use. Frequently, in a balanced direct chlorination-
oxychlorination plant, the crude ethylene dichloride from both processes are
combined and refined together. In any case, the refining steps are similar.
The crude is washed with a dilute caustic solution. Greater than 10 percent
caustic is never used because it might cause product decomposition. Water
is removed either by coalescing and phase separation or by phase separation
and light ends distillation. The purity of the crude (amount of light
hydrocarbons present) and the desired purity of the product dictate equipment
design. Heavy ends, useful chlorinated hydrocarbons and tars are removed in
a distillation column and product passes overhead. In some plants, final
product distillation is not provided since crude ethylene dichloride purity
(98+7=) is adequate for many applications.
An overall material balance and an energy balance around the reactor
section are provided in Tables I and II respectively.
-------
EDC-3
III. Plant Emissions
A. Continuous Air Emissions
1. Scrubber Vent
The major source of air emissions from the direct chlorination
of ethylene, are gases, mainly inerts, vented from the scrubbing
column. The stream contains small amounts of ethylene, ethylene
dichloride, vinyl chloride, ethylchloride. as well as inert impurities
in the feed. Small quantities of hydrogen chloride and chlorine
may be emitted depending on the scrubbing medium (caustic or water)
and the unit's capacity. Most plants employ condensers to recover
some ethylene dichloride before the stream enters the scrubber.
The efficiency of recovery, of course, depends on the final gas
temperature. One plant which cools the gases and vapors to -10° F
prior to scrubbing showed significantly lower emissions than the
other two respondents. Unfortunately, since the inlet to the
scrubber consisted of a combined stream from oxychlorination and
direct chlorination the data may not be typical for a plant
providing ethylene dichloride by direct chlorination only.
2. Product Storage Losses
Ethylene dichloride storage tanks usually have simple vents to
the atmosphere because the vapor pressure (three PSI @ 100° F) is
low. In some cases, nitrogen pading is used to help minimize
emissions. It is estimated that EDC losses due to product storage
equal about 0.0006 Ibs./lb. EDC.
3. Decanter Vents
Small amounts of EDC are released to the atmosphere during washing
in plant 12-1. In the future, it was reported that the vapors will
be recovered by chilling.
B. Intermittent Air Emissions
No sources of intermittent air emissions were reported.
C. Liquid Wastes
Waste water is produced from the scrubbing of vented gases and
the caustic washing of crude EDC. Only plant 12-1 provides an
estimate of waste water flow. It reported 1,000 GPM of waste water
due primarily to indirect cooling.
D. Solid Waste
Tars produced in the heavy ends column are usually disposed of
by land fill or by incineration. If a catalyst is used, it too is
trucked to a disposal site. Respondent 21-2 reports .00027 Ibs./lb.
EDC of tar and catalyst sent to sanitary land fill.
-------
EDC-4
E. Odor
Reports on the production of ethylene dichloride by direct
chlorination indicate that the process does not present an odor
problem. No complaints were reported by the respondents although
odors of EDC and chlorine are detectable on-site.
F. Fugitive Emissions
Fugitive emissions due to leaks, spills and miscellaneous
causes are believed to be between .0007 and .00007 Ibs./lb. EDC.
-------
EDC-5
IV. Emission Control
The emission control devices that have been reported as being employed by
direct chlorination EDC producers are summarily described in Table IV of this
report. An efficiency has been assigned each device whenever data sufficient
to calculate it have been made available. Two types of efficiencies have
been calculated.
1) "SE" - Specific Efficiency
SE = ^pecific pollutant in - specific pollutant out -
specific pollutant in
2) "SERR" - Significance of Emission Reduction Rating
SERR ȣ(pollutant x weighting factor)in - ^(pollutant x weighting
factor*)out
]T(pollutant x weighting factor)in
*Weighting factor same as Table VII weighting factor.
A brief description of the emission control devices employed follows:
Scrubbers
A scrubber is usually employed to remove small amounts of HCl and
in some cases chlorine left in the non-condensed reactor effluent. Both
water and caustic scrubbers are used in U. S. plants. The water variety
are able to remove most if not all of the HC14but dilute caustic is
generally necessary to eliminate all the chlorine from the vent gas.
Some EDC may also be absorbed depending on the operating conditions.
Below is a brief summary of the efficiencies of some of the devices
reported.
Device I. D. No. "SE" - HCl "SE" - Cl? "SERR"
SC-I 100% 100% 257,
31-1 SC-IV 75% Small 18%
Condensers
Although condensers of some sort for the gaseous reactor effluent stream
are reported by all respondents only plant 31-1 cools the stream down low
enough (-10° F) to recover most of the EDC present. The "SE" for
removal of EDC for this device is 97.97o. Since the respondent reports
a net credit of $45,000/year as operating expenses on an initial investment
of $125,000, it would seem that this type of device would be a worthwhile
investment for future plants.
General Comments and Future Plans
Re c omme nd a t i ons
Since most future plants are expected to employ a balanced process and
undesirable components of the emissions from the direct chlorination
scrubber vent are similar to those in the vent from the oxychlorination
-------
EDO 6
scrubber, combining the two streams for further treatment seems to
be practical, economic and expedient. This is a scheme which has
already been demonstrated, so no development program will be required.
Future Plans for Plants Participating in the Survey
Respondent 12-1 reports that plans are under way to compress the
scrubbej: vent discharge and use it as feed to an existing unit.
Respondent 12-2 will have an incinerator on line for the scrubber
vent gases before the end of 1973.
-------
EDO 7'
V. Significance of Pollution
It is recommended that no in-depth study of this process be considered at
this time. The quantity of air pollutants released to the atmosphere are
considerably lower for the direct chlorination process than for the oxy-
chlorination process and are lower than several processes currently under
in-depth study.
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 emission of pollutants from these new plants. This
work is summarized in Tables V, VI and VII.
On a weighted emissions basis a Significant Emissions Index ov 2,738 has
been calculated in Table VII. This is substantially lower than the SEI's of
some other processes under in-depth study. Hence, the recommendation to
exclude an in-depth study of ethylene dichloride by direct chlorination from
the in-depth scope of the work for this project.
-------
VI. Ethylene Dichloride Producers
Company
Allied Chemical Corporation
American Chemical Company
Conoco Chemicals
Diamond Shamrock Chemical Co.
Dow Chemical Company
Dow Chemical Company
Ethyl Corporation
Ethyl Corporation
The B. F. Goodrich Company
PPG Industries, Inc.
Shell Chemical Company
Union Carbide Corporation
Union Carbide Corporation
Vulcan Materials Company
Location
Baton Rouge, La.
Long Beach, Calif
Lake Charles, La.
Deer Park, Texas
Freeport, Texas
Plaquemine, La.
Baton Rouge, La.
Houston, Texas
Calvert City, Ky.
Lake Charles, La,
Deer Park, Texas
Taft, La.
Texas City, Texas
Geismar, La.
Capacity,
MM Lbs./Yr,
645
325
968
265
1,100
1,160*
550
260
990
1,040
1,700
150
150
330
Total 9,633
%
Direct
Chlorination
430
225
476
95
628
600
290
260
330
803
1,126
150
150
- _,
5,565
Total 58%
Oxychlorination
215
100
492
170
472
560
260
660
237
574
330
4,070
42%
M
O
O
I
oo
*0xychlorination facility presently not in operation.
-------
PAGE NOT
AVAILABLE
DIGITALLY
-------
TABLE EDC-I
MATERIAL BALANCE (LBS./LB. EDC)
ETHYLENE DI CHLORIDE
VIA
DIRECT CHLORINATION
Stream I. D. No.
Stream
Ethylene
Chlorine
Inert s
co2
°2
N2
H2
Ethylene Di chloride
Ethylene Trichloride
Hydrogen Chloride
Tar
1 2 3 4 & 5
Ethylene Feed Chlorine Feed Total Feed Reactor Effluent
.2916 .2916 .0031
.7258 .7258 .0001
.0040 .0040 .0040
.0087 .0087 .0087
.0076 .0076 .0076
.0002 .0002 .0002
1.0030
.0101
.0004
.0007
6 7 8
Acid, Chlorine
& Ethylene DiihlorUe
Product Scrubber Vent in Scrubber Waste
.0031
.0001
.0040
.0087
.0076
.0002
.9990 .0022 .0018
.0010
.0004
Useful Heavy Ends
10
Tar
.2916
.7463
1.0379
1.0379
1.0000
.0258
.0023
.0091
.0091
. 0007
. 0007
-------
TABLE, EDO II
ENERGY BALANCE (REACTOR SECTION ONLY)
ETHYLENE PICHLORIDE
VIA
DIRECT CHLORINATION
HEAT IN
SOURCE
Enthalpy of feed at 110° F
(above base temperature)
Exothermic heat of reaction (110° F)
HEAT OUT
SOURCE
Reactor coolant
Enthalpy residual
(above base temperature)
BTU/LB. EDC
10
956
Total - 966
BTU/LB. EDC
956
10
Total - 966
NOTE: Base temperature = 60° F
-------
TABLE EDC-III
NATIONAL EMISSIONS INVENTORY
DICHLOROETHANE BY
DIRECT CHLORINATION
EPA Code No.
Capacity - Tons of EDC
Average Production - Tons of EDC
Emissions to Atmosphere
Stream
Flov - Lbs./Hr.
Flov Characteristic - Continuous or Intermittent
if Intermittent - Hrs./Yr. Flov
Composition - Tons/Ton of EDC
1,2 Dichloroethane
Vinyl Chloride
Ethyl Chloride
Methane
Ethylene
Oxygen
Nitrogen
Carbon Dioxide
Carbon Monoxide
Water
Air
Hydrogen Chloride
Chlorine
Hydrogen
Analysis
Sample Location
Date or Frequency of Sampling
Type of Analysis
Odor Problem
Vent Stacks
Number
Height - Feet
Diameter - Inches
Exit Gas Temperature - F°
Flov - SCFM
Emission Control Devices
Condenser
V'ater Scrubber
Spray Tover
Total Hydrocarbon Emissions - Ton/Ton EDC
Total Particulate & Aerosol Emissions - Ton/Ton EDC
Total NOX Emissions - Ton/Ton EDC
Total SOX Emissions - Ton/Ton EDC
Total CO Emissions - Ton/Ton EDC
Scrubber Vent
351
Continuous
.002675
.003789
.008658
.007579
.003965
.000325
.000184
No
Estimate
On-Plant
Yes
1
38
4
50
65
Yes
Yes
.006464
0
0
0
0
12-1
47,500
47,500
Primary Decanter Vent
100
Continuous
.000588
.000430
.007754
No
Estimate
On-Plant
Yes
3
12
1.5,
90
23
No
2.25, 2
(1)
.000588
0
0
0
0
Page 1 of 3
Secondary Decanter Vent
20
Continuous
.000118
.000086
.001550
No
Estimate
On-Plant
Yes
2
20
1.54, 1.54
80
4.7
No
.000118
0
0
0
0
Fugitive Emissions
1
Continuous
( )
( 00009)
( )
.000091
0
0
0
0
(1) Equivalent diameter.
-------
TABLE EDO-III
NATIONAL EMISSIONS INVENTORY
DICHLOROETHANE BY
DIRECT CHLORINATION
EPA Code No.
Capacity - Tons of EDC
Average Production - Tons of EDC
Emissions to Atmosphere
Stream
Flov - Lbs./Hr.
Flow Characteristic - Continuous or Intermittent
if Intermittent - Hrs./Yr. Flow
Composition - Tons/Ton of EDC
1,2 Dichloroethane
Vinyl Chloride
Ethyl Chloride
Methane
Ethane
Ethylene
Oxygen
Nitrogen
Carbon Dioxide
Carbon Monoxide
Water
Hydrogen Chloride
Chlorine
Air
Analysis
Sample Location
Date or Frequency of Sampling
Type of Analysis
Odor Problem
Vent Stacks
Number
Height - Feet
Diameter - Inches
Exit Gas Temperature - F°
Flow - SCFM
Emission Control Device
Condenser
Water Scrubber
Spray Tower
Total Hydrocarbon Emissions - Ton/Ton EDC
Total Particulate 6. Aerosol Emissions - Ton/Ton EDC
Total NOX Emissions - Ton/Ton EDC
Total SOy Emissions - Ton/Ton EDC
Total CO Emissions - Ton/Ton EDC
12-2
401,500
401,500
Scrubber Vent
422
Continuous
.000231
.000022
.000576
.000157
.000879
.000795
.000053
.001879
Yes
In Vent
Four times per week for six weeks
Chromatograph
No
Yes •
1
95
.505
Ambient
75
Yes
Yes
.001865
0
0
0
0
Page 2 of 3
Scrubber Vent
702
Continuous
.000775
.000023
.000406
.000812
.000127
.001476
.001504
.000282
.002311
Yes
In Vent
Four times per week for six veeks
Chromatograph
No
Yes.
1
120
.505
Ambient
150
Yes
Yes
.002807
0
0
0
0
-------
EPA Code No.
Capacity - Tons of EDC
Average Production - Tons of EDC
Emissions to Atmosphere
Stream
Flow - Lbs./Hr.
Flow Characteristic - Continuous or Intermittent
if Intermittent - Hrs./Yr. Flow
Composition - Tons/Ton of EDC
1,2 Dichloroethane
Vinyl Chloride
Ethyl ehloride
Methane-
Ethylene
Otygan•
Nitrogen
Carbon Dioxide
Carbon Monoxide
Water
Hydrogen Chloride
Chlorine
Analysis
Sample Location
Date or Frequency of Sampling
Type of Analysis
Odor Problem
Vent Stacks
Number
Height - Feet
Diameter - Inches
Exit Gas Temperature
Flow - SCFM
Emission Control Device
Condenser
Water Scrubber
Spray Tower
Total Hydrocarbon Emissions - Ton/Ton EDC
Total Particulate & Aerosol Emissions - Ton/Ton EDC (4)
Total NOX Emissions - Ton/Ton EDC
Total SOjj Emissions - Ton/Ton EDC
Total CO Emissions - Ton/Ton EDC
TABLE EDC-III
NATIOHit EMISSIONS INVENTORY
DICHLOROETHANE BY
DIRECT CHLORINATION
Page 3 of 3
31-1
238,000
Not Specified
(1)
Scrubber Vent
649
Continuous
(2)
,000156
.000018
.000014
.001232
.000262
.002274
.003983
.002689
.000193
.000062
.000020
Yes
In Vent
Once a week
Chromatograph titration for Cl»
Yes
Yes (3)
1
148
3
90
11,000
Yes
Yes :
Yes
.000450
.000082
0
0
0
Fugitive Emissions
42
Continuous
f )
( )
(.000706)
None
Estimate
No
.000706
0
0
0
0
(1) Approximate capacity based on total capacity for oxychlorination and direct chlorination units and approximate oxychlorination capacity.
(2) Approximate composition based on percentage of combined oxychlorination and direct chlorination feed stream to the scrubber and assumption (1).
(3) Unit used by oxychlorination process also.
(4) Classifies HC1 and C^ as aerosol because both are vapor at emitted conditions.
-------
TABLE EDG-IV
ABS ORBERS/S GRUBBERS
EPA Code No.
Device I. D. No.
Control Emission of
Scrubbing Liquid
Type - Spray
Packed Column
Column v/trays
Scrubbing/Absorbing Liquid Rate - GPM
Operating Temp - F°
Gas Rate - SCFM (Lb./Hr.)
T-T Height - Feet
Diameter - Feet
Washed Gases to Stack
Stack Height - Feet
Stack Diameter - Inches
Installed Cost - Mat'l. & Labor - $
Installed Cost based on "year" - dollars
Installed Cost - c/lb. of Dichloroethane - Yr.
Operating Cost - Annual - $ (1972)
Value of Recovered Product - $/Yr.
Net Operating Cost - Annual - $
Net Operating Cost - c/lb. of Dichloroethane
Efficiency - '/. - SE (Hydrogen Chloride)
Efficiency - 7. - SE (Chlorine)
Efficiency - % - SE (Dichloroethane)
Efficiency - % - SERR
CONDENSERS AND K. 0. DRUMS
EPA Code No.
Device I. D. No.
Control Emission of
Primary Refrigeration Liquid
Capacity of Refrigeration Liquid - Ton
Gas Rate - SCFM (Lbs./Hr.)
Temperature to Condensers - F°
Temperature out of Condensers - F°
Liquid Recovered - Lb./Hr.
Non-Condensibles - SCFM
Installed Cost - Mat'l. & Labor - $
Installed Cost based on - "year" - dollars
Installed Cost - c/lb. of Dichloroethane
Operating Cost - Annual - $ (1972)
Value of Recovered Products - $/Yr.
Net Operating Cost - Annual - $
Net Operating Cost - c/lb. of Dichloroethane
Efficiency - % - SE
Efficiency - 7. - SERR
(1) $1200 for utilities only.
(2) Scrubber serves combined streams from oxychlorination and direct chlorinatlon units.
(3) From direct chlorination only.
CATALOG
12-1
SC-I
HC1, C12
Water
Yes
3
40-60
65
9
1.5
Yes
38
4
6,300
1954
.0066
2450
1250
1200
. 00013
1007.
100%
397.
257.
OF EMISSION CONTROL DEVICES
DICHLOROETHANE
VIA
DIRECT CHLORINATION
12-2
SC-II
HC1, C12
Water
Yes
35
200
75
12
3
Yes
95
6.06
12,000
1967
.0015
Unknown C-)
12-2
SC-III
HCl, C12
Water
Yet
45
200
150
12
3
Yes
120
6.06
31-1
SC-IV
(2)
HCl, Clj
Water
Yes
Yea
11,000
150
50
10
Yes
148
36
2.900 (')
1969 & 1971
. 0006
672 (5)
0
.0001
757.
187.
31-1
CON-1
Dichloroethane
Fijeon
178
95
-10
304
150
125,000
100,000 - 1967; 25,000 1 1972
.026 .
15,800
60,800
(45,000)
(.0095)
97.97.
. 89.47.
(4) Total to unit.
(5) Calculated by multlpling total cost by fraction of In-let from direct
chlorinatlon process.
-------
Current
Capacity (1)
5,563
300
TABLE EDC-V
Marginal
Capacity
NUMBER OF DIRECT CHLORINATION
ETHYLENE BICHLORIDE PLANTS BY 1980
Current
Capacity
on-stream Demand
in 1980 1980
Capacity
to be
Added
Economic
Plant
Size
Number
of Nev
Units
5,263
11,513
6250
700
9-10
(1) All capacities in MM Ibs./year.
(2) Based on the assumption that balanced EDC plants will be built, increasing the present total EDC capacity by
12.5 billion Ibs/year.
-------
TABLE EDC-VI
EMISSION SOURCE SUMMARY
Emissions
Hydrocarbons
Particulates & Aerosols
NOX
sox
CO
TONS /TON ^OF ETHYLENE
Source
Scrubber Vent
.00416
0
0
0
0
BICHLORIDE
Storage Losses
.00060
0
0
0
0
Fugitive Emissions
.00071
0
0
0
0
Total
.00547
0
0
0
0
-------
TABLE EDC-VII
WEIGHTED
EMISSION RATES
Chemical Ethvlene Bichloride
Process Direct
New Added Capacity 5
Pollutant
Hydrocarbons
Particulates & Aerosols
NOX
sox
CO
Chlorination
250 MM Lbs./Year
Emissions Lb./Lb.
.00547
0
o
0
0
Increased Emissions
MM Lbs./Yr,
34.2
0
0
0
0
Weighting
Factor
80
60
40
20
1
Weighted Emissions
MM Lbs./Yr.
2,736
0
0
0
0
Significant Emission Index • 2,736
-------
Formaldehyde (Silver Catalyst)
-------
Table of Contents
Section
I. Introcution
II. Process Description
III. Plant Emissions
IV. Emission Control
V. Significance of Pollution
VI. Formaldehyde Producers
List of Illustrations & Tables
Flow Diagram
Net Material Balance
Gross Heat Balance
Emission Inventory
Catalog of Emission Control Devices
Emission Source Summary
Number of New Plants by 1980
Weighted Emission Rates
Page Number
FS-1
FS-2
FS-4
FS-7
FS-9
FS-10
Figure FS-I
Table FS-I
Table FS-II
Table FS-III
Table FS-IV
Table FS-V
Table FS-VI
Table FS-VII
-------
FS-1
I. Introduction
Formaldehyde was first produced in the U. S. in 1901, at that time its
chief use was as an embalming agent and disinfectant. Today, some seventy
odd years later production capacity exceeds seven and one half billion
pounds per year, with approximately two thirds of the production utilized in
the formulation of various synthetic resins.
Formaldehyde is normally marketed in aqueous solutions containing from
36 to 50 weight percent formaldehyde. The standard (USP) solution is 37
percent, although large scale industrial users prefer a nominal 50 percent
solution. Formaldehyde solutions usually contain sufficient methanol to
prevent precipitation of polymer during storage and shipping, although
precipitation may be prevented in solutions containing relatively small
amounts of methahol by keeping the solution warn.
Formaldehyde is produced principally from methanol. Two processes are
dominant in the U. S. today, the mixed oxide catalyzed process and the silver
crystal (or gauze) catalyzed process.
The primary licensors of the mixed oxide process are Reichhold and Lummus,
while ICI and Borden prevail in the licensing of the silver process. The
silver catalyzed process is the subject of this report.
A third process, based on the partial oxidation of light hydrocarbons,
had been utilized by Celanese at their large Bishop, Texas plant until
quite recently. That particular facility at Bishop has now been shutdown
and replaced by a silver process unit. With national energy source demands
escalating feedstock costs for the partial oxidation process, it is
extremely doubtful that any new facility in the U. S. will again employ
this process, in spite of rising methanol costs.
Atmospheric emissions generated by the silver catalyst process are
associated primarily with the absorber vent gas stream. Minor quantities
of hydrocarbons may be discharged by steam ejectors on the product fractionator.
Additionally, small quantities of spent caustic or waste water may be produced.
Today an estimated 77 percent of IL. S. formaldehyde capacity is based on
the silver catalyst process. This is appreciably more than its estimated
share of 61 percent in 1969. A large part of this increase is due to
Celanese switching to the silver process, but even discounting that situlation,
the capacity of the silver-catalyzed process appears to be increasing at a
faster rate than does the capacity of the mixed oxide process. If the silver
process can maintain its present share of the total formaldehyde capacity,
it will expand to 8 x 10^ pounds per year in 1980.
-------
FS-2
II. Process Description
Despite the fact that formaldehyde was produced from methanol over one
hundred years ago (in 1868 by A. W. Hofmann), the chemistry - of the silver
catalyzed process - is still in dispute. It is thought that the reaction
involves either the dehydrogenation of methanol (EQ. 1) followed by the
oxidation of hydrogen (EQ. 2A) .
(1) - CH20 + H2
(2A) H2 + h 02 - y H20
or a combination of methanol dehydrogenation (EQ. 1) and methanol
oxidation (EQ. 2B)
(1) CH3OH — *- CH20 + H2
(2B) CH3OH + h 02 - >. CH20 + H20
Regardless of this controversy, the implementation of the process is
relatively simple and quite straightforward, as evidenced by the following
brief process description (which may be more easily followed by referring
to the Figure I flow sheet):
Prior to its admixture with methanol vapors, air is caustic washed
to remove C02 and trace sulfur compounds - the latter of which will poison
the silver catalyst. The air is then heated to about 150° F.
Fresh methanol and recycle methanol are combined, vaporized and then
superheated to approximately 170° F. Heat is supplied by either exchange
with the converter effluent or medium pressure steam.
The air and methanol vapors are combined to give about a 1:4 oxygen/
methanol mole ratio. (Decreasing the percentage of methanol in the
mixture decreases conversion while increasing yield; however, methanol
must comprise more than 37 percent by volume of the mixture to avoid the
explosive area. Increasing the amount of methanol increases conversion
and decreases yield.) The air/methanol mixture is induced into a battery -
sometimes about three - of catalytic converters. Upon passing through the
silver catalyst, the net exotherm generated heats the vapors to about
1175° F. This temperature is maintained either by varying the air/methanol
ratio or by means of combination heating and cooling coils located within
the converters. The hot effluent gases must be quenched to avoid decomposing
the formaldehyde. This is generally accomplished solely within the primary
absorber, which is close-coupled with the converters, but feed vs effluent
heat exchange is utilized - in part - by some plants.
The primary absorber is a packed tower. The primary absorption liquid -
and quench - for the formaldehyde and unreacted methanol vapors is the
so-called "F-M Liquor". This liquor is an aqueous solution containing
about 28 to 30 percent formaldehyde and 20 to 22 percent methanol. Part
of the FM liquor is withdrawn from the bottom of the primary absorber,
pumped through a water cooled exchanger, and recirculated to the top of
the primary absorber. The remainder of the FM liquor is withdrawn from
the bottom of the absorber and pumped to intermediate storage. Uncondensed
vapors and non-condensibles are withdrawn from the top of the primary
absorber and 'blown1 into the secondary absorber.
-------
FS-3
The secondary absorber recovers the major portion of the uncondensed
vapors by providing the necessary contact between the vapors and cool
distilled water, which is introduced onto the top tray of the secondary
absorber. The top of the tower is maintained at about 75° F to 80° F by
providing additional cooling via secondary coolers for the upper tray
section. This minimizes hydrocarbon loss via the relatively large non-
condensible overhead vent. The weak formaldehyde/methanol solution
withdrawn from the bottom of the secondary absorber is pumped to the
primary absorber and used as make-up.
The FM liquor in the intermediate storage or surge tank is pumped to
the product fractionator - a vacuum column. Here pure (99 + 70) methanol
is taken as overhead product and recycled to either methanol storage or
to the vaporizer. The bottom product is a nominal 37 wt. °L solution of
formaldehyde, containing less than one percent methanol. This solution
may be treated for removal of trace amounts of formic acid prior to
storage. Polymer formation and precipitation in storage is prevented
either by the addition of supplemental methanol, by providing heated
storage, or by both.
Table FS-I presents a typical material balance for silver process
formaldehyde production. Absorber vent gas composition is based on a
combination of published data and questionnaire responses, whereas
the below listed yields, etc., are representative of published data only:
Mole %
Methanol in air/methanol
feed mixture- 44
Methanol conversion , 65
Formaldehyde yield (F.F. basis) 89
Table FS-II presents an estimated heat balance around the converter
section.
-------
FS-4
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 for-
maldehyde. Indeed, many respondents report it as their sole
source of noxious emissions.
The composition of the absorber vent stream varies somewhat
with catalyst age or activity. The normal range in composition
(excluding for the moment uncondensed hydrocarbons) is*:
Component Vol. % (dry basis)
C02 4.8 to 5.5
C0 0.2 to 0.6
CH4 0.3 to 0.4
02 0.3
H2 20.2 to 17.5
N2 74.2 to 75.7
These reaction by-products transport varying quantities of
hydrocarbons to the atmosphere when they are vented. Respondents
report the following hydrocarbon emissions are associated with
their absorber vents.
Amount
Component Lb./Lb. of 37% HCHO
Formaldehyde 0 to .001
Methanol 0 to .004
Methyl Formate 0 to .008
Methylal 0 to .001
A more complete summary of these emissions is listed in
Table FS-III
2. Product Fractionator Ejector Exhaust
It is believed that all product fractionators are operated at
sub-atmospheric pressures, which, therefore, requires the use of
either steam ejectors or vacuum pumps. Four respondents reported
emissions from this source, but only three (EPA Code No's. 14-4,
14-8 and 14-20) reported the emission of noxious compounds. The
emissions from the ejectors are listed in Table FS-III.
B. Intermittent Air Emissions
1. Converter Start-Up Vent
The operator of plant EPA Code No. 14-3 reported emissions
from this source and stated that, "during start-ups the feed to
to converter is vented to the atmosphere until stabilized and then
switched gradually into the reactor. Total vent time is about
30 minutes. There are about 10 start-ups per year". Data provided
*"Formaldehyde" - 3rd Edition, ASC Monograph Series, page 18
-------
FS-5
by the respondent indicate that this operation results in the
emission of .0001 Ibs. of hydrocarbons per Ib. of formaldehyde.
Start-up vents of a different nature were reported by
respondents 14-6 and 14-9, both of whom burn their absorber tail
gases in the boiler house. During start-ups, until the tail gas
composition and flow have stabilized, the tail gas is vented to
the atmosphere. After this period the tail gas is cut to the
boiler house and burned. No estimate was given of the emissions
resulting from this operation, but they should be negligible.
2. Converter Emergency Vent
Again, only operator 14-3 reported emissions from this source.
Lack of data prevents the calculation of emission rates, but the
infrequency and short duration of the emission preclude its
characterization as a significant emission source.
C. Continuous Liquid Wastes
1. Waste Water
The production of various waste water streams have been reported
as follows:
Plant 14-3 - .030 gallons/lb. of 37% formaldehyde or 360
gallons/hour. The waste is treated on plant in
an extended aeration biological treatment plant.
Plant 14-7 - 62,500 gallons/hour of cooling water. 'Treated1
on plant.
Plant 14-8 - 120 galIons/hour from the waste heat boiler blow-
down plus 4500 gallons/hour from the cooling tower
blowdown.
Plant 14-20 - 7500 gallons/hour cooling tower blowdown.
Treated on plants.
2. Spent Caustic
While no operator reported the generation of spent caustic, it
seems reasonable to surmise that most plants do produce small
quantities of this substance as a result of their air washing
operation.
D. Intermittent Liquid Wastes
1. Ion Exchange Regeneration
Presumably most operators remove formic acid from product
formaldehyde via an ion exchange resin system. Such systems are
normally regenerable by intermittent back-flushing procedures,
which would produce an intermittent waste liquid stream. Operator
14-10 reports that every six to twenty days a weak aqueous solution
containing about 0.4% formic acid and 1.5% formaldehyde is discharged
to the waste treatment plant as a result of this operation. Flow
rates are not given. Operator 14-3 shows such a waste stream on
this block flow diagram, but given no further details in the body
of his response.
-------
FS-6
2. Methyl Formate Removal
One operator reported privately that it was his practice to
remove methyl formate from stored formaldehyde. Presumably, this
would result in the production of a small intermittent liquid
waste stream. It is believed that this operation is atypical of
the industry.
3~. Tank Washings
This is another verbally reported source of intermittent liquid
wastes.
E. Solid Wastes
All respondents to the silver process questionnaire reported
that their facility produced no solid waste material.
F. Odors
None of the respondents reported receiving any odor complaints
during the past year. Half of the respondents, however, did report
that odors are occasionally detectable at the plant site. The
odoriferous materials were identified as formaldehyde and methanol.
All operators reporting odors mentioned the absorber vent
as at least one of the sources. In addition, operators 14-3 and
14-8 identified the product fractionator as a source.
G. Fugitive Emissions
Only the operator of plant 14-3 has offered a quantitative
estimate of fugitive emissions. His estimate is 30 Ibs./hr. or
.00025 Ibs./lb. All other operators state that fugitive emissions
are either nil or quite small. As operator 14-4 summarizes the
situation, "minor losses of formaldehyde and/or methanol occur
mainly due to leaks in pump seals and occasional piping leaks.
The actual amount is considered negligible and most likely will
not show in material balance calculations".
-------
FS-7
IV. Emission Control
The few emission control devices that were reported as being employed,
by respondents to the questionnaires pertaining to the subject process, are
summarily described in Table IV of this report. An efficiency has been
assigned each device when data sufficient to calculate it have been available.
Three types of efficiency are normally 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 = Ibs. of specific pollutants in - Ibs. of specific pollutant out
Ibs. of specific pollutant in x100
(3) "SERR" - Significance of Emission Reduction Rating
SERR* = (Ibs. of pollutant x wf)in - (Ibs. of pollutant x wf)out
(Ibs. of pollutant x wf)in
*where wf = weighting factor designated in Table VII of this report
Usually 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 the (revised) Appendix V of
this report.
Since data sufficient to permit device efficiency calculation are available
for only one device, a few general comments regarding formaldehyde pollution
control device performance seem in order:
Absorber/Scrubbers
The only reported scrubber (Plant 14-4) uses water as the scrubbing
medium in a bubble cap tower for methanol and formaldehyde removal. No
data are given, but the efficiencies should be near 100 percent.
Mist Eliminators
Devices FS-3, 4 and 5 have rather arbitrarily been listed under
"absorbers/scrubbers" in Table IV - Catalog of Emission Control De ices.
All are simple wire gauze mist eliminators located in the top of the
absorber. They undoubtedly are reasonably efficient in preventing the
emission of entrained liquids, however, no respondent has provided
data from which efficiencies might be calculated. Due to the diversity
and range of the parameters governing their performance, it would be
imprudent to attempt to further characterize them with an estimate of
their performance*
Incinerators
Two respondents report burning 'tail gas1 (absorber vent gas) as a
method of controlling associated noxious emissions. Since the compounds
being burned are 'straight' organics, containing no heteroatoms, one
-------
FS-8
would expect his method to be quite efficient - and it presumably is.
The operator fo EPA Coded Plant No. 14-1 utilizes an in-house designed
incinerator (Device FS-1) to burn tail gas. Data provided by him
indicate that this device has "CCR" and "SERR" efficiencies of 100
percent. Respondent 14-9 combusts tail gases in another in-house
designed device - this one a custom burner for the boiler house (Device
FS-2). The respondent considers the performance data for his boiler
house tail gas burner proprietary, but it seems reasonable to surmise
that iris highly efficient.
From a technical view point, it would seem that incineration devices
are ideally suited for minimizing the pollutant nature of the principal
atmospheric emission generated by the subject process.
Condensers
The operator of plant EPA Code No. 14-8 lists a refrigerated condenser
(Device FS-6), which is located up-stream of the product fractionator
vacuum ejector, as a pollution control device. The condenser undoubtedly
reduces the quantity of methanol discharge to the atmosphere. It would
seem, however, that this device might more properly be considered a part
of the methanol recovery equipment rather than a pollution control device,
although industry is not in full agreement on this point. The distinction
between the two is difficult, but based on data provided by other
respondents, most plants apparently employ similar conservation devices
and have chosen not to designate them pollution control devices.
Operating the 'silver catalyst1 formaldehyde process at lower air/methanol
ratios should reduce ghe quantity of hydrocarbons discharged to the atmosphere
via the absorber vent. However, as pointed out in Section I, decreasing this
ratio (i.e., increasing the methanol concentration in the feed gas) decreases
conversion. There is undoubtedly a point where the net heat of reaction would
fail to sustain the process without a supplemental heat source. This would
probably be quite unattractive to most operators. Considering the relatively
low emission rate associated with the process, and the effectiveness of tail
gas incineration, it wold seem that such manipulation of operating variables
to achieve lower levels of atmospheric emissions is unnecessary. Changing
of operating temperature and/or pressure would also be unattractive, since
current conditions are considered to be "close to optimum".
Developmental work directed toward reducing emissions from this process
might be directed along the following lines:
(1) Substitute oxygen for air and dilute with tail gas to achieve
desired heat balance.
(2) More efficient design and better utilization of control devices
currently available.
-------
FS-9
V. Significance of Pollution ^
It is recommended that the silver catalyst process be considered for an
in-depth study. Although the Significant Emission Index rating is normally
the criterion for this recommendation, in this instance there are other
factors of overriding importance. They are:
(1) A large number of new units 18-19 are expected to be on-stream
by 1980.
(2) The absorber vent gas has a wide heating value range, but normally
is able to support combustion without supplementary fuel.
(3) Although not classified as a source of odor problems, the uncombusted
tail gas is odoriferous.
(4) Only a small percentage of formaldehyde plant operators burn tail
gas.
(5) Increased emission control through tail gas combustion would
conserve national energy sources, if the heat so produced is
recovered.
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 emission of pollutants from these new plants.
This work is summarized in Tables V, VI and VII.
The 1980 production capacity estimate is based on the assumption that
the silver catalyst process will account for the same 77 percent of total
capacity that it does now - see Section VI. Published support for the
estimate of 1980 production capacity (total) may be found in the May 1st
issue of Chemical Marketing Report and the August, 1970 Chemical Economics
Handbook report on formaldehyde.
On a weighted emission basis, a Significant Emission Index of 1,251 has
been calculated in Table VII. Although this is appreciably less than the
SEI's anticipated for some of the other processes in the study, it is
believed the above listed reasons justify the recommendation for an in-depth
study of the process.
-------
FS-10
VI. Formaldehyde Producers
The following tabulation of formaldehyde producers indicates published
production capacity by company, location and process.
Company
Allied
Borden
Celanese
Commercial Solvents
Du Pont
GAP
Georgia pacific
Gulf
Hercules
Hooker
Monsanto
Silver
Location Process
Ironton, Ohio 308
Demopolis, Ala. 80
Diboll, Texas 70
Fayetteville, N. C. 200
Fremont, Calif. 80
Kent, Wash. 70
La Grande, Oregon 40
Louisville, Ky. 70
Missoula, Mont. 80
Sheboygan, Wise. 120
Springfield, Oregon 260
Bishop, Texas 1300
Newark, N. J.
Rock Hill, S. C.
Sterlington, La. 30
Seiple, pa. 80
Belle, W. Va. 485
Grasselli, N. J. 150
Healing Spring, N. C. 200
La Porte, Texas 200
Toledo, Ohio 320
Linden, N. J. 150
Calvert City, Ky.
Columbus, Ohio
Coos Bay, Oregon
Crosett, Ark. 100
Albany, Oregon
Taylorsville, Miss.
Vienna, Ga. 100
Vicksburg, Miss.
Louisiana, Mo. 170
Wilmington, N. C. 95
N. Tonawanda, N. Y. 135
Alvin, Texas 150
Addyston, Ohio 110
Eugene, Oregon 100
Springfield, Mass. 280
Metal Oxide
Process
117
117
100
100
80
60
100
100
40
-------
FS-11
Silver Metal Oxide
Company Location Process Process
Reichhold Hampton, S. C. 36
Houston, Texas 100
Moncure, N. C. 100
Tacoma, Wash. 40
Tuscaloosa, Ala. 70
Kansas City, Kans. 40
White City, Oregon 50
Malvern, Ark. 100
Rohm & Haas Philadelphia, pa. 25
Skelly Springfield, Oregon 70
Winfield, La. 70
Tenneco Fords, N. J. 105 160
Garfield, N. J. 105
Union Carbide Bound Brook, N. J. 150
Wright Acme, N. C. 75.
Total Process Capacity - MM Lbs./Year - 5,914 1,729
Number of Plants =36 18
Average Plant Size - MM Lbs./Year = 165.4 98.2
Capacity of Total Industry - MM Lbs./Year = 7,613
Percentage of Total Industry Capacity =78.2 21.9
-------
PAGE NOT
AVAILABLE
DIGITALLY
-------
TABLE FS-I
TYPICAL MATERIAL BALANCE
FOR
SILVER CATALYST PROCESS FORMALDEHYDE PLANT
Stream I. D. No. 1 (A & B) 2
Freeh Feed Total Feed
Formaldehyde
Methanol .4430 .6675
Hydrogen
Carbon Dioxide
Carbon Monoxide
Water
Oxygen . 1763 . 1763
Nitrogen .5832 .5832
Total 1.2025 1.4270
UNITS
3
Methanol
Converter Effluent
.3709
.2328
.0100
.0455
.0052
.1763
.0031
.5832
1.4270
- TON/TON OF 37% FORMALDEHYDE
45 67 8
Absorber Absorber Product Product Fractlonator
Vent Gas Make-up Water Fractionator Vent* Product Lig^ Ovhd . - Recycle**
.0006 .0003 .3700
.0025 .0008 .0050 .2245
.0100
. .0455
.0052
.0145 .4632 .6250
.0031
.5832
.6646 .4632 .0011 1.0000 .2245
*Also contains steam from ejector (when used) and water vapor and air from leakage.
**Contains unknown amount of formaldehyde.
-------
TABLE FS-II
FORMALDEHYDE PRODUCTION
VIA
SILVER CATALYST PROCESS
GROSS HEAT BALANCE - CONVERTER SECTION ONLY
Heat In BTU/Lb. of 37% Formaldehyde
Air Heater 23
Methanol Heater, Vaporizer
and Superheater 364
Exothermic Heat of Reaction 1.022
Total - 1,409
Heat Out
Converter Temperature Control 100
Endothermic Heat of Reaction 441
Converter Effluent Quench plus
Enthalpy Residual (above base temp.) 868
Total - 1,409
Note:
(1) Based on air/methanol and oxidation/dehydrogenation ratios shown in
Table I.
(2) Converter temperature - 1175° F.
(3) Base temperature - 60° F.
-------
TABLE FS-III
NATIONAL EMISSIONS INVENTORY
FORMALDEHYDE VIA SILVER CATALYST PROCESS
Page 1 of 6
EPA Code Number
Date on-stream
Capacity - Tons of 37% HCHO/Yr.
Average Production - Tons of 377. HCHO/Yr.
Range in Production - % of Max.
Emissions to Atmosphere
Stream
Flov - Ibs./hr.
Flow Characteristic - Continuous or Intermittent
if Intermittent - hrs/yr.
Composition - Tons/Ton of 37% HCHO
Formaldehyde
Methanol
Methyl Formate
Di-methyl Ether
Methylal
Oxygen
Nitrogen
Carbon Monoxide
Carbon Dioxide
Methane
Water
Hydrogen
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problem
Vent Stacks
Flow - SCFM per stack
Number
Height - Feet (elev. (? tip)
Diameter - Inches
Exit Gas Temperature - F°
Emission Control Devices
Type - Water Scrubber
Incinerator
Catalog I. D. No.
Total Hydrocarbon Emissions - Ton/Ton HCHO (37%)
Total Particulate & Aerosol Emissions - Ton/Ton HCHO (377,,)
Total NOX - Ton/Ton HCHO (37%)
Total SO,
Total CO
- Ton/Ton HCHO (37%)
- Ton/Ton HCHO (37%)
14-1
154,000
17
Absorber Vent
Not Specified
Continuous
None
Never
No
Yes
1
43.8
42
Yes
FS-1
Not Specified
Converter Emergency Vent
Not Specified
Intermittent
0.10
None
Never
Not Specified
>5000
No
14-3
47,500
47,500
0
Converter Start-up Vent
2620
Intermittent
5
.00011
.00003
None
Never
Not Specified
No
.00489
0
0
0
.00159
Absorber Vent
Not Specified
Continuous
.00114
.00364
-f-
+
.00159
.01193
.00755
Yes
718
1
6
.67
82°
No
-------
TABLE FS-III
NATIONAL EMISSIONS INVENTORY
FORMALDEHYDE VIA SILVER CATALYST PROCESS
EPA Code No.
Date on-stream
Capacity - Tons of 377. HCHO/Yr.
Average Production - Tons of 377. HCHO/Yr.
Range in Production - 7, of Max.
Emissions to Atmosphere
Stream
Flov - Ibs./hr.
Flov Characteristic - Continuous or Intermittent
if Intermittent - hrs./yr.
Composition - Tons/Ton of 377. HCHO
Formaldehyde
Methanol
Methyl Formate
Di-methyl Ether
Methylal
Oxygen
Nitrogen
Carbon Monoxide
Carbon Dioxide
Methane
Water
Hydrogen
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problem
Vent Stacks
Flow - SCFM per stack
Number
Height - Feet (elev. @ tip)
Diameter - Inches
Exit Gas Temperature - F°
Emission Control Devices
Type - Water Scrubber
Incinerator
Catalog I. D. No.
Total Hydrocarbon Emissions - Ton/Ton HCHO (377,)
Total Particulflte & Aerosol Emissions - Ton/Ton HCHO (377.)
Total NOX - Ton/Ton HCHO (377.)
Total SOX - Ton/Ton HCHO (377.)
Total CO - Ton/Ton HCHO (377.)
Absorber #1
Vent
4040
Continuous
.00035
.00111
.00269
.25569
.00238
.03354
.00946
.00523
None
Never
Calc.
No
Yes
1090 to 1152
1
60
.9
104° to 140°
No
14-4
52,500
52,500
0
Absorber #2
Vent
1350
Continuous
.00012
.00037
. 00090
.08523
. 00080
.01115
.00315
.00174
Never
Calc.
No
Yes
,363 to 384
1
50
.6
104° to 140°
No
. 00348
0
0
0
.00556
Absorber 03
Vent
4040
Continuous
.00035
.00111
.00269
.25569
.00238
.03354
. 00946
.00523
None
Never
Calc.
No
Yes
1090 to 1152
1
65
9
104° to 140°
No
Stripper
Overhead Vent
54
Continuous
.00002
. 00005
+ .0037?
+
*t
.00038
None
Never
Estimate
No
Yes
5 to 20
1
65
4
78° to 110°
No
-------
TABLE FS-III
NATIONAL EMISSIONS INVENTORY
FORMALDEHYDE VIA SILVER CATALYST PROCESS
Page 3 of 6
EPA Code Number
Date on-stream
.Capacity - Tons of 377. HCHO
Average Production - Tons of 377. HCHO
Range in Production - 7. of Max.
Emissions to Atmosphere
Stream .
Flov - Ibs./hr.
Flov Characteristic - Continuous or Intermittent
if Intermittent - hrs./yr.
Composition - Tons/Ton of 377. HCHO
Formaldehyde
f Methanol
Methyl Formate
Di-methyl Ether
Methylal
Oxygen
Nitrogen
Carbon Monoxide
Carbon Dioxide
Methane
Water
Hydrogen
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problem
Vent Stacks
Flow - SCFM per stack
Number
Height - Feet (elev. @ tip)
Diameter - Inches
Exit Gas Temperature - F°
Emission Control Devices
Type - Water Scrubber
Incinerator
Demister
Other
Catalog I. D. No.
Total Hydrocarbon Emissions - Ton/Ton of 377, HCHO
Total Particulate & Aerosol Emissions - Ton/Ton of 377, HCHO
Total NO Emissions - Ton/Ton of 377, HCHO
Total
Total CO
Emissions - Ton/Ton of 37%
HCHO
HCHO
14-7
50,000
0
Absorber Vent
7369
Continuous
.00035
. 00340
.00230
. 53000
.00100
.03850
.02750 ,,
.01100 .'
None
Never
Calc'd. ex Design
No
Yes
2000
1
98
8
95
Yes
+
FS-3
.00605
0
0
0
.00100
14-8
75,000
75,000
0
Absorber Vent
11,600
Continuous
,00067
.56129
.00529
.05920
.00634
.01263
Stack
1972
GLC + Titration
No
Yes
3200
1
100
16
54
Yes
+
FS-5
.00100
0
0
0
.00529
Jet Exhaust
6
Continuous
. 00033
None
Never
Calc'd.
No
Yes
1
43
1.5
200
Yes
+ (condenser)
FS-6
14-9
30,919
30,919
0
Absorber Eraerg. Vents Absorber Vent
Manual/Auto
Not Specified
Intermittent
+
+
+
+
Process
Random
Orsat + ?
No
Yes
1/1
30/20
8/8
50°/50°
No Yes
FS-2
Not Specified
-------
TABLE FS-III
NATIONAL EMISSION INVENTORY
FORMALDEHYDE VIA SILVER 'CATALYST PROCESS
page 4 of 6
EPA Code Number
Capacity - Tons of 377. HCHO/Yr.
Average Production - Tons of 377. HCHO/Yr.
Range in Production - % of Max.
Emissions to Atmosphere
Stream
Flov - Ibs./hr.
Flov Characteristic - Continuous or Intermittent
if Intermittent- - hrs./yr.
Composition - Ton»/ton of 377. HCHO
Formaldehyde
Methanol
Methyl Formate
Di-methyl Ether
Methylal
Oxygen
Nitrogen
Carbon Monoxide
Carbon Dioxide
Methane
Water
Hydrogen
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problem
Vent Stacks
Flov - SCFM per stack
Number
Height - Feet (elev. @ tip)
Diameter - Inches
Exit Gas Temperature - F°
Emission Control Devices
Type - Water Scrubber
Incinerator
Catalog I. D. Number
Total Hydrocarbon Emissions - Ton/Ton HCHO (377.)
Total Particulate & Aerosol Emissions - Ton/Ton HCHO (377.)
Total NOX - Ton/Ton HCHO (377.)
Total S0?
Total CO
- Ton/Ton HCHO (377.)
- Ton/Ton HCHO (377.)
14-10
240,000
0
Absorber Vent Incinerator
Flue gas
39,727
Continuous
TR
TR
.01005
.47940
.04269
.18491
TR
Never
GLC
No
Yes
10,050
1
85
60
900
Yes
+
FS-7
0
0
0
0
0
14-6
200,000
0
Not Specified
i
Yes
+ Boiler
FS-6
Cannot Be Determined
-------
TABLE FS-III
NATIONAL EKISSIONS~INVENTORY
FORMALDEHYDE VIA SILVER CATALYST PROCESS
Page 5 of 6
EPA Code No.
Date on-stream
Capacity - Tons of 37% HCHO
Average Production - Tons of 37% HCHO
Range in Production - 7, of Max.
Emissions to Atmosphere
Stream
Flow - Ibs./hr.
Flow Characteristic - Continuous or Intermittent
If Intermittent - hrs./yr.
Composition - Tons/Ton of 377. HCHO
Formaldehyde
Methanol
Methyl Formate
Di-methyl Ether
Methylal
Oxygen
Nitrogen
Carbon Monoxide
Carbon Dioxide
Methane
Water
Hydrogen
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problem
Vent Stacks
Flow - SCFM per stack
Number
Height - Feet (elev. @ tip)
Diameter - Inches
Exit Gas Temperature - F°
Emission Control Devices
Type - Water Scrubber
Incinerator
Demister
Other
Catalog I. D. No.
Total Hydrocarbon Emissions - Ton/Ton of 377. HCHO
Total Particulate & Aerosol Emissions - Ton/Ton of 377= HCHO
Total NOX Emissions - Ton/Ton of 37% HCHO
Total SOX Emissions - Ton/Ton of 37% HCHO
Total CO Emissions - Ton/Ton of 37% HCHO
14-12
35,000
35,000
0
Absorber Vent
5,855
Continuous
.00041
. 00082
.00276
.00191
.01390
Daily
Calc'd.
Yes
.460
1
73
18
80
Yes
FS-4
.00123
0
0
0
.00276
14-18
20,000
20,000
0
Jet Exhaust Absorber Vent
1000 3360
Continuous Continuous
.00250
.54828
. 00292
.05856
.00167
.18519
.00989
None Top of Tover
Never Bi-annual
Great + ?
No No
Yes Yes
891
1 1
22 44
1 6
200 50
No No
0 ,
0
0
0
.00292
14-20
50.000
50,000
0
Absorber Vent Distillation Tover
Overhead Vent
7386 30
Continuous Continuous
.00035 .00120
.00326 .00120
.00224
.51016
.00104
.03688
.02656
. 01040
Random Never
Calc'd. Not Specified
No No
Yes
1 1
95 95
132 132
95 95
No No
.00825
0
0
0
.00104
-------
TABLE FS-III I
NATIONAL EMISSIONS INVENTORY '
FORMALDEHYDE VIA SILVER CATALYST QOCESS
Page 6 of 6
EPA Code No.
Date on-stream
Capacity - Tons of 37% HCHO/Yr.
Average Production - Tons of 37% HCHO/Yr.
Range in Production - "I, of Max.
Emissions to Atmosphere
Stream
Flov - Lbs./Hr.
Flov Characteristic - Continuous or Intermittent
if Intermittent - Hrs./Yr.
Composition - Tons/Ton of 377. HCHO
Formaldehyde
Methanol
Methyl Formate
Di-methyl Ether
Methylal
Oxygen
Nitrogen
Carbon Monoxide
Carbon Dioxide
Methane
Water
Hydrogen
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problem
Vent Stacks
Flow - SCFM per stack
Number
Height - Feet (elev. @ tip)
Diameter - Inches
Exit Gas Temperature - F°
Emission Control Devices
Type - Water Scrubber
Incinerator
Catalog I. D. No.
Total Hydrocarbon Emissions - Ton/Ton HCHO (37%)
Total Particulate & Aerosol Emissions - Ton/Ton HCHO (37%)
Total NOX - Ton/Ton HCHO (37%)
Total SOX - Ton/Ton HCHO (37%)
Total CO - Ton/Ton HCHO (37%)
14-11
427,500
0
Absorber Vent
54,640
Continuous
<. 00001
.00076
.00829
.00120
.396975
.021010
.092096
.000126
.016271
Ground Level
Daily
Chromatograph
No
'.. Yes
4200 3600 10,000
1 1 1
90 93 95
10 12 14
50 50 50
No
.01025
.02101
14-20
50,000
50,000
0
Absorber Vent Distillation
Tover Overhead Vent
7386 30
Continuous Continuous
.00035 -001?0
.0326 .00120
.00224
.51016
.00104
.03688
.02656
.01040
Random Never
Calc'd. Not Specified
No No
Yes
1 1
.95 95
132 132
95 95
No No
.00825
0
0
0
.00104
-------
TABLE FS-IV
CATALOG OF EMISSION CONTROL DEVICES
FORMALDEHYDE VIA THE SILVER CATALYST PROCESS
Page 1 of 2
ABSORBER/SCRUBBERS
EPA Code No. for plant using
Flow diagram (Fig. I) stream I. 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 - Inches
Installed Cost - Mat'l. & Labor - $
Installed Cost based on - "year" - dollars
Installed Cost - c/lb. of 37% HCHO - Yr.
Operating Cost - Annual - $ - 1972
Value of Recovered product, $/Yr.
Net Operating Cost - Annual, $
Net Operating Cost r c/lb. of 377. HCHO
Efficiency - % - SE
Efficiency - 7. - SERR
INCINERATION DEVICES
EPA Code No. for plant using
Flow Diagram (Fig. I) stream I. D.
Device I. D. No.
Type of Compound Incinerated
Type of Device - Flare
Incinerator
Other
Material Incinerated. SCFM (Lb./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 - r/lb. of 37% HCHO
Operating Cost - Annual - $ (1972)
Operating Cost - c/lb. of 37% HCHO
Efficiency - % - CCR
Efficiency - % - SERR
14-4
B
FS-8
Formaldehyde & Methanol
Water
1
2
12 & 14
Bubble Cap
8 to 15
12 to 16
Yes
Not Available
14-7
A
FS-3
Formaldehyde & Methanol
N/A
+ Dcnliter
None
2,000
Yes
98
8
1,440
14-12
A
FS-4
Formaldehyde & Methanol
N/A
+ Demister
None
(80)
1,460
Yes
73
18
5,000
1972
.00714
14-1 14-6
& A
FS-1 FS-6
Formaldehyde & Methanol Formaldehyde 6. Methanol
14-8
A
FS-5
Formaldehyde & Methanol
N/A
+ Demister
None
3,200
Yes
100
16
700
1971
.00047
400
0
400
.00027
14-9
A
FS-2
Formaldehyde & Methanol
Not Specified
43.75
100
100
+ Boiler
3028
Yes
Not Disclosed
+ Boiler
Yes
Not Disclosed
14-10
A
FS-7
Formaldehyde & Methanol
10,050
No
85
200,000
1972
.04111
60,000
.01233
100
100
-------
TABLE FS-IV
CATALOG OF EMISSION CONTROL DEVICES
FORMALDEHYDE VIA THE SILVER CATALYST PROCESS
page 2 of 2
CONDENSERS
EPA Code No. for plant using
Flov Diagram Stream I. D.
Device I, D. No.
Controls Emission of
Primary Refrigeration Liquid
Capacity of Refrigeration Unit - Tons
Gas Rate - SCFM
Temperature to Condenser - F°
Temperature out of Condenser - F°
Liquid Recovered - GPM
Non-Condensibles - SCFM
Installed Cost - Mat'l. & Labor - $
Installed Cost based on - "year" - dollars
Installed Cost - c/lb. of 37% HCHO/Yr.
Operating Cost - Annual - $ (1972)
Value of Recovered Products - $/Yr.
Net Operating Coat - Annual - $
Net Operating Cost - c/lb. of 377. HCHO
Efficiency - 7. - SE
Efficiency - % - SERR
14-8
A
FS-6
Methanol
Unknown
131 Lb./hr.
3,300
1971
.00220
2,000
Unknown
-------
TABLE FS-V
NUMBER OF NEW PLANTS BY 1980
Current
Capacity
5,914
Marginal
Capacity
614
Current
Capacity
on-stream
in 1980
5,300
Demand
1980 (2)
8,000
Capacity
1980 (2)
9,000
Capacity
to be
Added
3,700
Economic
Plant
Size
200
Number
of New
Units
18-19
Note:
(1) All capacities in MM Ibs./year.
(2) All capacity estimates based on assumptions that silver catalyzed process does and will account for 77 percent
of total U. S. capacity.
-------
TABLE FS-VI
EMISSION SOURCE SUMMARY
TON/TON OF 377. FORMALDEHYDE
Emission
Absorber Vent
Hydrocarbons .00385
Participates 0
NOX 0
SOX 0
CO .0180
Source
Fractionator Vent
.00015
0
0
0
0
Fugitive Emissions
S3
to
00
I-1
H-
OQ
H-
cr
i—1
n>
Total
.0040
0
0
0
.0180
-------
TABLE FS-VII
Chemical
Process
Increased Capacity
Pollutant
Hydrocarbons
Participates
NOX
SOX
CO
Formaldehyde
Silver Catalyst
3,700 MM Lbs./Year
Emissions, Lb./Lb.
.0040
0
0
0
.0180
WEIGHTED EMISSION RATES
Increased Emissions
MM Lbs./Year
14.8
0
0
0
66.7
Weighting
Factors
80
60
40
20
1
Weighted Emissions
MM Lbs./Year
1,184
0
0
0
67
Significant Emission Index = 1,251
-------
Glycerol (Ally! Chloride)
-------
Table of Contents
Section Page Number
I. Introduction G-l
II. Process Description G-2
HI. Plant Emissions G-5
IV. Emission Control G-ll
V. Significance of Pollution G-12
VI. Glycerol Producers G-13
List of Illustrations & Tables
Flow Diagram Figures G-l & G-2
Material Balance, Detailed Table G-I
Gross Heat Balance Table G-II
Emission Inventory Table G-III
Catalog of Emission Control Devices Table G-IV
Number of New Plants by 1980 Table G-V
Weighted Emission Rates Table G-VI
Component Emission Ratios Table G-VII
-------
G-l
I. Introduction
As of January, 1971, approximately 300 million pounds per year of synthetic
glycerol capacity existed in domestic facilities; in addition, there were
approximately 160 million pounds per year of "natural" glycerol capacity. By
1980, installation of approximately 140 mm Ibs./yr. of new capacity is
envisioned.
The screening effort in this report is limited to the synthetic glycerol
category. The specific process studied is the allyl chloride-epichlorohydrin
process, and the two questionnaires received are both for this process. Re-
latively large amounts of chlorine and caustic soda are used, and there is
formation of appreciable quantities of chlorinated hydrocarbons - such as
propyl chlorides - when this process is employed, but there is basis for its
continued use and expansion. The emphasis on this process stems from the
fact that epichlorohydrin is formed as an intermediate. Epichlorohydrin is
in a favored product position because of its increasing use in materials such
as epoxy elastomers.
Other full-scale process routes for glycerol exist. Among these are
acrolein-allyl alcohol; and allyl alcohol-peracetic acid-glycidol.
Relative to pollution significance, glycerol capacity projections to the
year 1980 indicate a weighted SEI (Significant Emissions Index)* of about 700.
On this basis, glycerol does not qualify as a petrochemical for in-depth studies.
*See Appendix IV for a definition of this term.
-------
G-2
II. Process Descriptions
Simplified flow diagrams of the two processes reported are attached.
Please see fold-out Drawing No. R-202 and R-203.
Allyl chloride is transformed into glycerol by means of three
successive reaction steps. The first reaction step is from allyl
chloride to glycerol dichlorohydrin. The second is from glycerol
dichlorohydrin to epichlorohydrin. And the final step is from
epichlorohydrin to glycerol.
First reaction step. Glycerol dichlorohydrin is formed by the
reaction between chlorine, water and allyl chloride:
70.91
C12 +
Chlorine
76.53
2II
H C
I
H2C - Cl
Allyl chloride
18.02
HOH —
Water
(excess)
36.46
HCl
Hydrochloric
Acid
52.46
HOCl
Hypochlorous
Acid
52.46
HOCl
Hypochlorous
Acid
128.99
H2C - OH
H C - Cl
I
HP - ri
n\J — Ijl
beta-glycerol
dichlorohydrin
(2,3 dichloro, 1-propanol)
The overall reaction of allyl chloride to glycerol dichlorohydrin,
called the "hypochlorination" reaction, may be expressed as:
70.91 18.02
HOH
76.53
CH2 = CHCH2C1
chlorine water Allyl chloride
(excess)
36.46
HCl
hydro-
chloric
acid
128.99
CH2OHCHC1 CH2C1
beta-glycerol
dichlorohydrin
(2,3 dichloro,
1-Propanol)
Second reaction step. Epichlorohydrin is formed by the reaction
between dilute sodium hydroxide and glycerol dichlorohydrin. The
products of the first reaction step (see above) participate as follows
in epichlorohydrin formation:
-------
G-3
36.46 128.99 80.00 92.53 116.88 36.04
HC1 + H9C - OH + 2 NaOH —>- H0C -0+2 NaCl + 2 H90
I I/
H C - Cl H C
I I
H2C - Cl H2C - Cl
hydro- beta-glycerol sodium epichloro- sodium water
chloric dichlorohydrin hydroxide hydrin chloride
acid aqueous
From the above descriptions, it is seen that an overall materials
balance can be written for the formation of epichlorohydrin:
70.91 18.02 76.53 80.00 116.88 92.53 36.04
Clo + HOH + CH9 = CHCHoCl + 2 NaOH-^2 NaCl + H9C -0 + 2 H90
I/
H C
I
HP _ PI
«L< " L.1
Notes:
1) The net water increase in the above balance does not represent
the source of water for the hypochlorination reaction because there
is an overbalancing loss of water from this part of the system.
This loss occurs through rejection of inorganic salt solutions as
waste water.
2) The hypochlorination of allyl chloride also forms 1,3 dichloro,
2-propanol; this material, when reacted with dilute sodium hydroxide,
also forms epichlorohydrin:
HC1 + H2C - Cl +2 NaOH —> H9C - 0 +2 NaCl + 2 H20
I \/
H C - OH H C
I I
H2C - Cl H2C - Cl
hydro- alpha-glycerol sodium epichloro- sodium water
chloric dichlorohydrin hydroxide, hydrin chloride
acid (153 dichloro, aqueous
2 propanol)
Third reaction step. Glycerol is formed from the epichlorohydrin
obtained in the second reaction step in accordance with the following
balance:
92.53 18.02 40.00 92.10 58.44
H2C - 0 + HOH + NaOH > H,C - OH + NaCl
I/ I
H C H C - OH
I I
H2C - Cl H2C - OH
-------
G-4
Note that in one of the respondent processes, crude epichlorohydrin
is a process feed material. See Drawing No. R-202.
For the entire allyl chloride-to-glycerol process, neglecting side
reactions, a simplified balance may be- written:
70.91 76.53 120.00 92.10 175.32
C12 + H2C + 3 NaOH >• H2C - OH +3 NaCl
H C (I) H C - OH
I I
H2C Cl H2C - OH
(I) In the process referenced on Drawing No. R-202, a portion of the
total alkali requirement is supplied by CaC03.
Material balance figures for the two processes reported in the
questionnaires are presented in Table I,
The two glycerol questionnaire responses show allyl chloride as a
starting material for the glycerol plant operations. It is apparent
that this allyl chloride reflects the output of installed plant capacity
for reacting propylene with chlorine to make the allyl chloride.
Since the resultant glycerol is the reason for making the equivalent
quantities of allyl chloride, consideration should be given to the
inclusion of allyl chloride process emissions, if glycerol processes
should qualify later for in-depth studies.
Further, note should be made of the rapid upswing occurring in
epichlorohydrin production, arising from its use in relatively new
materials such as epoxy elastomers. This development might result
in a future need for review of epichlorohydrin capacity per se, and a
subsequent "screening" study for emissions.
An estimated heat balance for the glycerol formation step is shown
in Table II.
-------
G-5
III. Plant Emissions
A. Continuous Air Emissions
1. Process Vent Streams (see Table III)
Vent streams such as non-condensibles from vacuum process
condensing equipment can contain lachrymaters and other potentially
undesirable constituents. Principal among this type of constituent,
as listed by the questionnaire respondents, are
propyl chlorides
trichloropropane
epichlorohydrin
chlorine
acrolein
dichloropropenes
dichlorohydrins
acetone
Hydrogen is listed in streams B, F and G reported in the 15-1
questionnaire reply. The respondent submitted the following
statement as a follow-up to the questionnaire reply:
"The source of hydrogen in the vent samples taken from streams
B, F and G is unknown. The quantity of hydrogen reported
would not be expected from process considerations. Before the
data could be accepted as typical, additional analyses would
be required".
The letter containing the statement quoted above is included in
the project file.
Note 1. See Table III heading. Emission figures shown in
Table III are for "average amount or composition" as
reported in the questionnaire reply submitted by a
respondent. The respondent's reply in full is con-
tained in his completed questionnaire under "III,
Emissions (composition and flow)".
Note 2. See "Total, Pounds per Stream Hour", stream flow rate.
For these two plants, 15-1 and 15-2, flow rates are
not characterized as other than continuous by ques-
tionnaire respondents.
Note 3. See stream "A", Drawing R-202. Stream "A" is not an
emission stream, except when it is vented directly
about 107o of the time through vent "B". During
direct venting, propyl chlorides are present; however,
they are shown flowing at the same rate as that listed
in Table III for stream "B", Drawing R-202. Apparently,
propyl chlorides are essentially unaffected in passing
through Device No. 101, Drawing, R-202. During upsets,
chlorine can be vented; such upsets occur 5 to 6 times
a year for less than 15 minutes each.
Note 4. See stream "B", Drawing, R-202. In addition to the
pollutant factors listed, this stream contains COo
-------
G-6
Note 5.
1.2 mol. %; air 25.1 mol. %; hydrogen 2.5 mol. %;
and water vapor 61.7 mol. 7°. The water vapor includes
the motive steam used for the ejector. Propyl chloride
content can double when impure allyl chloride is fed
(allyl chloride raw material is listed by the respondent
at 97.5 wt. 7« allyl chloride). During upsets, chlorine
can be present, and allyl chloride content can increase
up to five times; such upsets occur 5 to 6 times a year
for less than 15 minutes each. Production rate during
sampling: 50 to 80% of capacity.
Method used to determine (1) composition: mass
spectroscopy; (2) flow: vane anemometer. Sampling
procedure: evacuated container. Sampling frequency:
one spot sample. Confidence level (1) composition:
some components may not be accurately identified;
(2) flow: "low level of accuracy". Ease of sampling:
very difficult. Odor problem: odorous material,
chemically identified as propyl and allyl chlorides;
detectable at ground level on plant property.
See stream "C", Drawing, R-202. Stream "C" is not an
emission stream. There is no statement by the respondent
similar in principle to the entry on page 6(a) of his
questionnaire reply, where he says that stream "A"
can vent directly through vent "B". Also, for stream "C",
the respondent's entry for item III, 10, Odor Problem,
is "not applicable".
Note 6. See stream "D", Drawing, R-202. In addition to the
pollutant factors listed, this stream contains misc.
non-pollutants 0.24 mol. 7, and water vapor 99.48 mol. %.
"Inerts and organics may vary + 1007o of listed value."
Production rate during sampling: approximately 507»
of capacity. Method used to determine (1) composition:
mass spectroscopy; (2) flow: vapor feed meter. Sampling
procedure: evacuated cylinder. Two spot samples were
obtained; required "climbing column and handling steam
sample". Confidence level: "+ 507o". Odor problem:
odors detectable beyond plant property; chemical
identification trichloropropane and epichlorohydrin.
Note that the listings of non-substituted hydrocarbons
(less than 0.04 vol. 7») are discounted here as unreal
and/or inconsequential.
Note 7. See stream "E", Drawing, R-202. Stream "E" is not an
emissions stream.
Note 8. See stream "F", Drawing, R-202. In addition to the
pollutant factors listed, this stream contains COo
64.9 mol. 7.,, misc. non-pollutants 8.1 mol. °L\ and water
vapor 18.2 mol. 7«. The "organic components are subject
to an error of +2007<> of listed values." Production
rate during sampling: approximately 507o of capacity.
Method used to determine (1) composition: mass
spectroscopy and equilibrium relationships; (2) flow;
-------
Note 9.
G-7
based on design C02 absorption efficiency. Recir-
culating water sample analyzed "and the data used to
calculate the vent analysis." One spot sample was
obtained. No reasonable means to obtain vent vapor
sample. Odor problem: odors detectable beyond plant
property and affirmative answer relative to community
complaint; chemical identification isopropyl chloride
and trichloropropane.
See stream "G", Drawing R-202. This stream is stated
to contain hydrogen 18.6 mol. % and water vapor 79.0
mol. %. Confidence level + 50%. Production rate during
sampling: approximately 50% of capacity.
The stream "includes 5 vacuum jets and 4 accumulator
vents". The largest jet was sampled via evacuated
cylinder and its flow measured by vane anemometer. The
smaller jets are estimated to total 5 to 10% of the
large jet emissions. One spot sample was taken and
analyzed by mass spectroscopy. Odor was detectable
at ground level on plant property. If the stream
analysis is qualitatively correct, this odor is presumably
one or more components from the group propylene, butylene,
acetone, and ethane. It will be observed that the
average molecular weight of the stream is a little over
one-half that of air.
Subsequent to the questionnaire's return, the respondent
submitted a letter (on file) indicating that the
analytical data are possibly atypical with respect to
hydrogen.
Note 10. See stream "A" Drawing, R-203. Chlorine average
composition is 0.7 mol. %; range is 0 - 3 mol. %.
Epichlorohydrin average composition is 0.02 mol. %;
range is 0 - 0.04 mol. %,. Production rate corresponding
to estimated stream "A" flow rate is not reported.
Stream "A" flow rate estimated from chlorine feed rate
(no sampling). Composition estimated from inerts
composition in chlorine. (For sampling) would use
vacuum sample bottle. (For analytical procedure)
would use flame VPC for organic constituents.
Confidence level for composition is "fair"; for (flow)
rate is "high". Ease of sampling: (Sampling would be)
difficult. Odor is detectable at ground level on plant
property; odorous material chemically identified as
chlorine.
Note 11. See stream "B" - Propyl chlorides average composition
is 0.25 mol. %; range is 0.15 - 0.75 mol. %. Epichloro-
hydrin average composition is 0.025 mol. °L; range is
0.015 - 0.050 mol. %. Production rate during sampling
"14,000 Ibs./hr. crude EPI". Method used to determine
(1) composition: flame VPC; (2) flow: air anemometer.
Sampling procedure: "Vacuum bottle". Analvtical pro-
cedure: flame VPC. Sampling frequency: "Infrequently".
Confidence level (1) composition: high; (2) flow:
moderate. Ease of sampling: moderate. Odor problem:
No problems.
-------
G-8
Note 12.
Note 13.
Note 14.
Note 15,
Note 16.
Note 17,
Note 18,
Note 19.
Note 20.
See stream "C". (This stream vas) never sampled.
Composition variation, composition and flov are
estimated. There is no sampling or analytical
procedure. Confidence level fl) Composition:
relatively high; (2) flow: rather questionable.
Ease of sampling, rather difficult. Odor problem:
No problems.
See stream "D". Same notes as under Note 12, except
ease of sampling relatively simple.
See stream "E". Production rate during sampling
380,000 Ibs./day glycerol. Composition by VPC; flov
estimated. Sampling by vacuum bottle; analytical
procedure, VPC. Sampling frequency, "Once". Ease
of sampling, "Very difficult; poor access to sampling
point". Odor problem: No problems.
See stream "F". Stream F never sampled. Composition
and flow estimated. Ease of sampling, "Possible".
Odor problem: No problems.
See stream "G". Same notes as under Note 15, except
ease of sampling, difficult.
See stream "H". Same notes as under Note 15, except
ease of sampling, no entry.
See stream "I". Same notes as under Note 15, except
ease of sampling, no entry.
See stream "J". Same notes as under Note 15, except
ease of sampling, no entry.
See stream "K". Same notes as under Note 15, except
ease of sampling, "relatively simple".
-------
G-9
III. Plant Emissions
A. Continuous Air Emissions (Cont'd.)
2. Storage Losses
The following materials are stored without vapor conservation:
Epichlorohydrin
Toluene
Glycerol & related
Materials stored with a "pad" are reported as follows:
Acetone
Various mixtures containing items such as glycerol, acetone and
p-dioxane dimethanols.
The contributions to emissions relative to the above storage
categories have no significant effect on the SEI.
B. Intermittent Air Emissions
One respondent reports nothing of consequence. The other provides
no comment. There is not any indication that intermittent emissions
associated with start-ups or emergencies would have a significant effect
on the SEI. If allyl chloride production (from chlorine and propylene)
were included (at a future time) within the scope of the glycerol
production category, then chlorine could be an emergency vent.
C. Continuous Liquid Wastes
One respondent indicates 1,200 GPM of waste water, with 100%
treatment by primary and secondary in-plant treatment. The other says
"1,500 GPM aqueous waste, most of this to disposal well".
Neutralization reactions occur in the process. These (net) reactions
are between caustic soda and hydrochloric acid, or calcium carbonate
and hydrochloric acid. Please see under Process Description for specific
reactions. The sodium chloride solutions and calcium chloride solutions
leaving the process as a result of these neutralization reactions are
considered part of the waste water stream.
D. Intermittent Liquid Wastes
There is no indication of significant contribution from such sources.
And, barring double jeopardy, the influence of intermittent liquid waste
factors would presumably be damped out by the realtively large flow of
continuous liquid wastes.
E. Solid Wastes
There are no discreet solid wastes.
F. Odors
Odors reported by the two questionnaire respondents are chemically
identified by them according to the following list of constituents:
-------
G-10
Propyl chlorides, normal and iso-
Allyl chloride
Trichloropropane
Epichlorohydrin
Chlorine
There are other odorous materials in some of the vent streams;
for example,
Acrolein
Dichloropropenes
Dichlorohydrins
Acetone
Hydrocarbons, non-substituted
Some of the entries in the above lists are lachrymators. And the
maximum allowable concentration in air can range as low as 0.5 parts
per million for an item such as acrolein.
G. Fugitive Emissions
One respondent leaves this category blank (Section VIII, Other
Emissions); the other indicates that there are the usual contributions
from leaks, sampling, gauge glass blowdowns, and equipment purging for
maintenance. The magnitude of these losses is not known.
Emergency release from pressure saftey valves, rupture discs, etc.,
is excluded from consideration here. Further, it is assumed that the
contents of storage tanks listed as "padded" do not contribute to
"Fugitive Emissions". On this basis, there remains for review the
category of storage tanks without pads.
Atmospheric storage tanks listed by the respondents as being unpadded
or not requiring a method of vapor conservation are stated to contain one
or more of the following materials:
Glycerol
Polyglycerols
Nad
Water
Toluene
Epichlorohydrin
The maximum storage temperature is at the high end of the ambient
range, say 130 °F (54 °C). The materials in the list above have
relatively low vapor pressures, except for toluene and epichlorohydrin
which exhibit vapor pressures of approximately 2 PSIA at 130 °F.
For atmospheric storage of these items, vapor pressure = partial pressure.
Thus, a fugitive emission could arise during toluene or epichlorohydrin tank
filling. For epichlorohydrin, the order-of-magnitude of such emission
could be as high as 50 Ibs./hr. at a vent concentration of about 14
volume per cent in air.
-------
G-ll
IV. Emission Control
Emission control devices indicated by the questionnaire respondents are
listed in Table IV.
Since the SEI for glycerol is low and not within the in-depth study bounds,
the devices indicated are presumed adequate.
It should be noted that there are lachrymator components in some of the
emission streams.
The efficiencies of the control devices as determined by the definition
included in Table IV show extreme values running from "zero" to over 99%
efficiency. The explanation of this variation from one stream component to
another is found by examining the objective of each emission control device.
The objective of emission control device 15-1-101 is to scrub out the CC>2
in the entering vapor stream. The use of a relatively mild alkaline solution
achieves this objective. Components such as propyl chloride which encounter
this same alkaline scrubbing solution (along with the C02) are essentially
unaffected, however. Thus, with the component flow leaving the device equal
to the component flow entering (expressed in consistent units such as
pounds per hour), the efficiency calculated equates to zero.
Referring to Table IV, it will be noted that Emission Control Device
15-1-102 shows a behavior akin to that of device 15-1-101, except that the
efficiency of the control means for the epichlorohydrin is 5270. In this
instance, the epichlorohydrin exhibits significant reactivity with the alkaline
scrubbing medium. This behavior reflects the relative ease with which the
(strained) oxygen-carbon bonds are broken under the condition existing in the
scrubber.
-------
G-12
V, Significance of Pollution
It is recommended that no in=depth study of this process be undertaken
at this time. Although the projected growth rate of glycerol capacity is
significant, the emission data indicate that the quantity of pollutants
emitted to the atmosphere is less, on a weighted basis, than from many of
the other processes that are currently being surveyed.
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 of pollutants,, See Tables
V, VI and VII.
On a weighted emission basis, a Significant Emission Index (SEI) of
700 has been calculated (Table VI). This is substantially less than SEl's
that are anticipated for other processes in the study.
-------
G-13
VI. Glycerol Producers (Domestic)
Company
Alba Manufacturing
Armour - Dial
Ashland Chemical
Colgate-Palmolive
Dow Chemical
Emery Industries
FMC Corporation
Kewanee Oil,
Harshaw Chem. Div.
Kraftco Corporation
Humko Products Div.
Lever Brothers
Murro Chemical
Pacific Soap
Procter & Gamble
Purex Corporation
Shell Oil Co,
Shell Chem. Co.
Swift & Co.
Swift Chem. Co.
Union Camp. Corp.
Harchem Div.
Location
Aurora, 111.
Montgomery, 111.
Peoria, 111.
Berkeley, Calif.
Jeffersonville, Ind.
Jersey City, N. J.
Kansas City, Kansas
Freeport, Texas
Cincinnati, Ohio
Los Angeles, Calif.
Bayport, Texas
Gloucester City, N. J,
Memphis, Tenn.
Baltimore, Md.
Hammond, Ind.
Los Angeles, Calif.
Portsmouth, Va.
Los Angeles, Calif.
Baltimore, Md.
Chicago, 111.
Dallas, Texas
Ivorydale, Ohio
Long Beach, Calif.
Port Ivory,
Staten Island, N. Y.
Bristol, Pa.
Houston, Texas
Norco, La.
Hammond, Ind.
Dover, Ohio
Capacity
MM Lbs./Year
*
*
*
*
*
*
*
120
*
*
40
*
*
*
*
*
*
*
*
*
*
*
*
*
*
125
50
*
*
*"Natural" glycerine sources, capacities not listed,
-------
PAG E N OT
AVAILABLE
DIGITALLY
-------
PAG E N OT
AVAILABLE
DIGITALLY
-------
TABLE G-I
MATERIAL BALANCE FOR GLYCEROL PLANTS USING EPICHLOROHYDRIN
AND/OR ALLYL"CHLORIDE AS RAW MATERIALS
Page 1 of 3
Company
Location and/or EPA Coded Number
Nameplate capacity in short tons of glycerol product per year
Simplified flow diagram stream designation
Description
of
Stream
Component
Allyl chloride
Other organic chlorides (presumed other monochloroprenes)
Chlorine
Chlorine inerts
Sodium hydroxide
Sodium chloride
Water
Sodium hydroxide in aqueous solution
Calcium carbonate
Calcium carbonate inerts
Hydrogen chloride
Epichlorohydrin
Epichlorohydrin heavy ends
Epichlorohydrin light ends
Glycerol
ISO-propyl and N-propyl chlorides
Acrolein
2, 3 dichloropropene
1, 2, 3 trichloropropane
Bis-dichloropropyl ether
Glycerol dichlorohydrin
Polyglycerol mixture
P-dioxane dimethanols
2-2 dimethyl, 1,3 dioxolane, 4-methyol
Acetone
Sodium carbonate
Calcium chloride
Waste water
1
Allyl
Chloride
Feed
1.2316
0.03158
15-1
47,500
2
Chlorine
Feed
1.1567
0.00116
Process
Water
Feed
Not given
Crude epi-
chlorohydrin
Feed
5
Hydro-
chloric
Acid
6
Sodium
Hydroxide
Aaueous
Ca 1c i um
Carbonate
0.01158
0.5095
0.04632
0.01158
0.05158
0.02211
1.421]
0.7658
0.0237
Total, tons per ton of glycerol capacity
1.2632
1.1579
Not given
0.5790
0.07369
1.4211
0.7895
-------
TABLE G-I
MATERIAL BALANCE FOR GLYCEROL PLANTS USING EPICHLOROHYDRIN
AND/OR ALLY1. CHLORIDE AS RAW MATERIALS Page 2 of 3
Company
Location and/or EPA Coded Number 15-1
Nameplate capacity in short tons of glycerol product per year 47,500 x
Simplified flow diagram stream designation 89 JO 11 12 13
Description Clycerol Epichloro- Sodium Fodiuro Calcium Aqueous
of Product hydrin Carbonate Chloride. Chloride. Waste
Stream - Product 20% Aqueous Aqueous Aqueous
Component
Allyl chloride
Other organic chlorides (presumed other monochloroprenes)
Chlorine
Chlorine inerts
Sodium hydroxide
Sodium chloride 2.053
Water 0.003 0.04211 Present Present
Sodium hydroxide in aqueous solution
Calcium carbonate
Calcium carbonate inerts
Hydrogen chloride
Epichlorohydrin 0.7309
Epichlorohydrin heavy ends
Epichlorohydrin light ends 0.00589
Glycerol 0.997
ISO-propyl and N-propyl chlorides
Acrolein
2, 3 dichloropropene
1, 2, 3 trichloropropane
Bis-dichloropropyl ether
Glycerol dichlorohydrin
Polyglycerol mixture
P-dioxane dimethanols
2-2 dimethyl, 1,3 dioxolane, 4-methyol
Acetone
Sodium carbonate 0.01053
Calcium chloride 0.8737
Waste water
Total, tons per ton of glycerol capacity 1.000 0.7368 0.05264 2.053+ 0.8737+ (1.200 CPM)
Water Water
-------
TABLE G-I
MATERIAL BALANCE FOR GLYCEROL PLANTS USING EPICHLOROHYDRIN
AND/OR ALLY! CHLORIDE AS RAW MATERIALS
Page 3 of 3
Company
Location and/or EPA Coded Number
Nameplate capacity in short tons of glycerol product per year
Simplified flow diagram stream designation
Description
of
Stream
Component
Allyl chloride
Other organic chlorides (presumed other tnonochloroprenes)
Chlorine
Chlorine inerts
Sodium hydroxide
Sodium chloride
Water
Sodium hydroxide in aqueous solution
Calcium carbonate
Calcium carbonate inerts
Hydrogen chloride
Epichlorohydrin
Epichlorohydrin heavy ends
Epichlorohydrin light ends
Glycerol
ISO-propyl and N-propyl chlorides
Acrolein
2, 3 dichloropropene
1,2,3 trichloropropane
Bis-dichloropropyl ether
Glycerol dichlroohydrin
Polyglycerol mixture
P-dioxane dimethanols
2-2 dimethyl, 1, 3 dioxolane, 4-methyol
Acetone
Sodium carbonate
Calcium chloride
Waste water
101
Allyl
Chlorine
Feed
1.0925
0.01664
102
Chlorine
Feed
0.98023
0.05160
15-2
55,000
103 104
Process Caustic
Water
Feed*
0.2355
Feed,
10 wt.
1.309
1.964
9.818
105
EPI.
Lights
0.005236
106 107 108
1. 2, 3 Tri- Caustic Aqueous
Chloro- Feed, Waste
propane 50 wt. %
0.5818
0.5818
109 110
Poly- Polyol
glycerol 80
111
Glycerol
Product
0 002
0.0007273 0.001455
0.007127
0.0007273
0.0007273
0.1164
0.01745
0.01018
0 02727 0.998
0.08182
0.006909
0.001455
0 0007273
Total, tons per tone of glycerol capacity
1.109
1.0318
0.2355
*Amount
Required
for
Reaction
Only
13.091
0,01455
0.1455
1.1636 (1.500 CPM) 0.08182 0.03636 1000
-------
TABLE 6-II
GLYCEROL PLANTS
USING EPICHLOROHYDRIN AND/OR ALLYL CHLORIDE
GROSS HEAT BALANCE (EST'D.)
GLYCEROL REACTION STEP
Heat Out
Heat of vaporization of vater,
vacuum evaporation
Losses, sensible heat effects,
heats of solution, etc.
Heat In
Exothermic heat of reaction
Total
Total
250 BTU/LB. Glycerol Formed
18
268
268 BTU/LB. Glycerol Formed
268
-------
TABLE C-III
NATIONAL ATMOSPHERIC EMISSIONS INVENTORY
FOR .
GLYCEROl PLANTS USING EPICHLOROHYDRIN AND/OR ALLYL CHLORIDE (NOTE 1)
Company
Location and/or EPA Coded Number
Date on-stream
"Nameplate" capacity in short tons
of glycerol product per year
Approximate average production rate,
tons glycerol per year
Seasonal variation in production rate,
percent of nameplate capacity
Simplified flow
Description diagram stream designation
Allyl chloride
chlorine
Iso-propyl alcohol
Iso-and n-propyl chlorides
1, 2,3 trichloropropane
Acrolein
2, 3 dichloropropene
Epichlorohydrin
Acetone
Water
Air
Hydrocarbon, non-substituted
(for example, ethane, propene, butene)
C02
2, 3 dichlorohydrin
Total, Tons per ton of glycerol capacity
(330 operating days/Cy assumed)
Total, pounds per stream hour (note 2)
Total, SCFM at 60° F and 14.7 PSIA
Temperature, op
Temperature, °C
Pressure, PSIG
Sampling location
Date or frequency of sampling
Type of Analysis
Odor presence
Vent stacks
Number
Height, Feet
Diameter, Inches
Temperature, Stack exit, °F
°C
Emission Control Devices
Type
Catalog Identification No.; see Table IV
Total emissions expressed as tons/ton glycerol capacity
Hydrocarbon
Participate, Aerosol
Note 3
15-1
47,500
None
B
Incl'd in propyl chlorides
0.02631
0.008238
Note 4
0.03455
414
300
250
121
Atm.
Scrubber Vent
One spot sample
Mass spectro.
1
60
250
121
Scrubber
15-1-101
0.03455
None
None
None
None
Note 5
D
0.001665
0.003269
0.001539
0.005151
Note 6
0.01162
140
2,100
220 - 240
104 - 116
3-7
Note 7
1
100
8
230
110
Scrubber
15-1-102
0.01162
None
None
None
None
Page 1 of 4
Incl'd in propyl chlorides
0.0004283
0.001791
0.001681
0.003622
Note 8
Oi007522
91
54
150
66
Atm.
1
100
10
150
66
Scrubber
15-1-103
0.007522
None
None
None
None
0.001840
0-01026
Note 9
0.0121
146
400
250
12]
Atm
5 vaeftn Jets/
4 Bciuuwlator went*
50/30
4/2
250/200
121/93
0.0121
None
None
None
None
See pages G-5 through G-8 for explanation of notes.
-------
Company
Location and/or EPA Coded Number
Date on-stream
"Nameplate" capacity in short tons
of glycerol product per year
Approximate average production rate,
tons glycerol per year
Seasonal variation in production rate,
percent of nameplate capacity
Simplified flow
Description diagram stream designation
Allyl chloride
chlorine
Iso-propyl alcohol
Iso-and n-propyl chlorides
1, 2, 3 trichloropropane
Acrolein
2, 3 dichloropropene
Epichlorohydrin
Acetone
Water
Air
Hydrocarbon, non-substituted
(for example, ethane, propene , butene)
co2
2, 3 dichlorohydrin
Total, tons per ton of glycerol capacity
(330 operating days/cy assumed)
Total, pounds per stream hour (note 2)
Total, SCFM at 60° F and 14.7 PSIA
Temperature, °F
Temperature, °C
Pressure, PSIG
Sampling location
Date or frequency of sampling
Type of analysis
Odor presence
Vent stacks
Number
Height, Feet
Diameter, Inches
Temperature, Stack exit, °F
°C
TABLE G-III
NATIONAL ATMOSPHERIC EMISSIONS INVENTORY
FOR
GLYCEROL PLANTS USING EPICHLOROHYDRIN AND/OR ALLYL CHLORIDE (NOTE 1)
15-2
55.000
Page 2 of 4
Hypochlorination vent
0.0009467
0.00001527
0.00003627
0.003165
0.04982
Note 10
0.0540
750
167.4
86 - 122
30 - 50
0-3
None
None
None
Chlorine
1
70
8
113
45
None
B
Hydrolizer vent
0.0001717
0.00002015
0.001425
0.02286
Note 11
EPI. Lights dist'n. vent
0.0001056
0.0001894
0.00004284
0.000009720
0.00001332
Note 12
0.02448
340
76.4
69 - 104
20 - 40
0-1
Not Given
Infrequent
Flame VPC
None
1
42
4
104
40
0.00036
5
Arab.
Arab.
0-1
None
None
None
None
1
55
2
Arab.
Arab.
D
EPI. finishing dist'n vent
0.000002882
0.0001355
0.0001499
Note 13
0.000288
4
86 - 104
30 - 40
0-1
None
None
None
None
1
58
2
104
40
Glycerol reactor vent
Trace
Trace
Majority
Trace
Note 14
0.000205
2 85
1
104
40
Atm
Not Given
Once
VPC
None
1
30
10
104
40
Emission Control Devices
Type
Catalog Identification No. , see Table IV
Total emissions expressed as tons/ton glycerol capacity
Hydrocarbon
Particulate, Aerosol
SO
Jet Fume Scrubber
Glycerol 15-2.101
0.001015, incl. chlorine 0.000195
None None
None None
None None
None
See pages •;-? through G-3 for explanation of notes.
None
0.00036
None
None
None
None
0.000138
None
None
None
None
None
None
None
None
None
-------
TABLE G-III
NATIONAL ATMOSPHERIC EMISSIONS INVENTORY
FOR
GLYCEROL PLANTS USING EPICHLOROHYDRIN AND/OR ALLYL CHLORIDE (NOTE 1)
Page 3 of
Company
Location and/or EPA Coded Number
Date on-stream
"Nameplate" capacity in short tons
of glycerol product per year
Approximate average production rate,
tons glycerol per year
Seasonal variation in production rate,
percent of nameplate capacity
Simplified flow
Description diagram stream designation
Allyl chloride
chlorine
Iso-propyl alcohol
Tso-and n-propyl chlorides
1, 2,13, trichloropropane
Acrolein
2, 3 dichloropropene
Epichlorohydrin
Acetone
Water
Air
Hydrocarbon, non-substituted
(for example, ethane, propene, butene)
CO
2,3 dichlorohydrin
Total, tons per ton of glycerol capacity
(330 operating days/cy assumed)
Total, pounds per stream hour (note 2)
Total, SCFM at 60°F and 14.7 PSIA
Temperature, °F
Temperature, °C
Pressure, PSIG
Sampling Location
Date or frequency of sampling
Type of analysis
Odor presence
Vent stacks
Number
Height, Feet
Diameter, Inches
Temperature, Stack exit, °F
15-2
55,000
None
Glycerol Evap. Vent
100%
Note 15
0.0216
300
105.3
212
100
0-3
None
None
None
None
1
49
1
104
40
Glycerol Dist'n. Vent
H
Glycerol Light Dist'n Vent
100%
Note 16
Unknown
"Very Small1
95 - 100
35 - 38
Atm.
None
None
None
None
1007.
Note 17
0.03600
500
175.5
212
100
5
None
None
None
None
No information supplied
Emission Control Devices
Type
Catalog Identification No., See Table IV
Total emissions expressed as tons/ton glycerol capacity
Hydrocarbon
Particulate, aerosol
NOX
S0x
CO
See pages G-5 through G-8 for explanation of notes.
None
None
None
None
None
None
None
None
None
None
None
None
None
None
None
-------
Company
Location and/or EPA Coded Number
Date on-stream
"Nameplate" capacity in short tons
of glycerol product per year
Approximate average production rate,
tons glycerol per year
Seasonal variation in production rate,
percent of nameplate capacity
Simplified flow
Description diagram stream designation
Allyl chloride
chlorine
Iso-propyl alcohol
Iso-and n-propyl chlorides
1,2,3 trichloropropane
Acrolein
2, 3 dichloropropene
Epichlorohydrin
Acetone
Water
Air
Hydrocarbon, non-substituted
(for example, ethane, propene, butene)
C02
2, 3 dichlorohydrin
Total, tons per ton of glycerol capacity
(330 operating days/cy assumed)
Total, pounds per stream hour (note 2)
Total, SCFM at 60° F and 14.7 PSIA
Temperature, °F
Temperature, °c
Pressure, PSIG
Sampling Location
Date or frequency of sampling
Type of analysis
Odor presence
Vent stacks
Number
Height, Feet
Diameter, Inches
Temperature, Stack exit, °F
°C
Emission Control Devices
Type
Catalog Identification No., See Table IV
Total emissions expressed as tons/ton glycerol capacity
Hydrocarbon
Particulate, aerosol
NOX
SO,,
TABLE G-III
NATIONAL ATMOSPHERIC EMISSIONS INVENTORY
FOR
GLYCEROL PLANTS USING EPICHLOROHYDRIN AND/OR ALLYL CHLORIDE (NOTE 1)
15-2
55,000
Page 4 of 4
Acetone Removal Vent
Final Dist'n. Vent
Trace
* 100%
Note 18
0.07200
1,000
350.9
212
100
0-5
None
None
None
None
Trace
None
None
None
None
100%
Note 19
0.0288
400
140.4
212
100
0-5
None
None
None
None
No Information Supplied
None
None
None
None
None
Solvent Recovery Vent
100%
Note 20
0.00144
20
2.2
95 - 104
35 - 40
Arm.
None
None
None
None
None
None
None
None
None
See
W G-5_ through r.-H
-------
TABLE G-IV
EMISSION CONTROL MEANS (1972)
GLYCEROL VIA ALLYL CHLORIDE-EPICHLOROHYDRIN
Company
Location of Plant and/or EPA Coded Number
Type of Emission Control Means &
Manufacturer
Emission Device Identification No.
Device to Control Emission of
Jets
Type
Number
Packing
Type
Material
Size, Inches
Nominal Height, Feet of Packed Section
Trays
Type
Material
Number
Temperature, °C. (°F)
Pressure
Liquid Contacting Medium
Rate, USGPM, through Contacting Medium
Composition, Nominal (when fresh)
Make-up rate
f.et flow leaving, USGPM
Vapor Rate, SCFM (Lbs./Hr.) into device
leaving device
Column Height, T/T, Feet
Column Diameter, Inches
Efficiency of Control Means
Pump ii. P.
Steam Rate, Lbs./Hr.
Cost Data
Installed Cost, Material 61 Labor, Direct
Installed Cost, Dollars per Ton Glycerol Capacity/Yr.
Year of Installed Cost Accounting
Operating Cost, Annual (1972)
Operating Cost, Dollars per ton Glycerol Capacity/Yr.
Accounting Credits
Packed Scrubber
Pioneer Industrial
15-1 - 101
C02 & Chlorinated Organics
Steam
One ?
Shaped Bodies
Polypropylene
3
15
66 (150)
SI. Vacuum
40
NaOH Solution
2,000 Lbs./Hr.
NaOH (lOO?. basis)
500
150 to Jet
30
24
C02 99.2:
Propyl Chloride Eff. = 0
V 1/2
1.200
$20,000
$0.4211
1960
$20,000
$0.4211
NaCOo Recovered offsets
NaOH make-up
(NaOH 2,000 Lbs./Hr.)
15-1
Packed Scrubber
Pioneer Industrial
15-1 - 102
C02 & OrganicB
None
Rings
Steel
3
30
110 (230)
5 PSIG
70
NaOH Solution
40 GPM fresh;
40 GPM from 15-1 - 101
To 15-1 - 103, 80 GPM
2,000
50
48
CO, 99.0; Epi-
chlorohydrin 52
15
No Steam
$50,000
$1.053
1957
$3,000
$0.0632
Na2C03
Recovered offsets
NaOH make-up
(NaOH 7,000 Lbs./Hr.)
Steam Recovery Credit
is $15,000
Scrubber Trays & Packing.
Pioneer Industrial
15-1 - 103
C02 & Organics
None
Units
Polypropylene
3
40
Distribution
66 (150)
SI. Positive
80 each for tr*ys & packing
85 GPM from
15-1 - 102
500
50
65
36
C02 92.6
20
$75.000
$1.58
1957
$71,000
$1.50
("Other Disposal"
entry = $50,000
per year)
15-2
Jet Fume Scrubber
S & K
15-2 - 101
Chlorine & Chlorinated Organic?
Fume Scrubber
One
50 (122)
0-3 PSIG
$15,000
$0.2727
1969
Maint. $1,000, Credit $1,000
Zero
Operating Copts lifted
are balanced by credits
-------
TABLE G-V
NUMBER OF NEW PLANTS BY 1980
Chemical
Glycerol
Process
Allyl chloride-
epichlorohydrin
Acrolein -
allyl alcohol
Allyl alcohol-
peracetic acid-
glycidol
"Natural"
Total
Current
Capacity
MM Lbs./Yr.
245
50
40
160
495
Marginal
Capacity
MM Lbs./Yr.
0
0
40
40
1971 Capacity
Extant as of 1980
MM Lbs./Yr. _
245
50
0
160
455
Consumer
Demand 1980
MM Lbs./Yr.
470
Projected
Capacity 1980
MM Lbs./Yr.
380
50
160
590
Nev Capacity
by 1980
MM Lbs./Yr.
135
New Units
by 1980*
135
*Basis new unit designed for economic rate = 135 MM Lbs./Yr.: 1971 units are about 100 MM Lbs./Yr. capacity each
**Assume marginal drop-outs are balanced off by closer approach to full capacity by surviving plants.
-------
TABLE G-VI
WEIGHTED EMISSION RATES
Chemical: Glycerol
Process: Allyl chloride -
epichlorohydrin**
Est. New Capacity as of 1980: 135 MM LBS./YR.
Emissions
Est. New Emissions
Pollutants
Hydrocarbons*
Particulate
N°x
S°x
CO
Lb. per Lb.
Glycerol Capacity
0.06579 ***
None
None
None
None
as of 1980,
MM LBS./YR.
8.88
None
None
None
None
Grand Total, Weighted
Weighting
Factors
80
60
40
20
1
Pollutant Emission Index
Weighted Emissions
as Index Units
700
0
0
0
0
- 700
*Including organic compounds containing oxygen and/or chlorine, as well as hydrogen and carbon.
**0ther processes are not in questionnaire respondent status (as of November, 1972); see Table V.
***See Table VII for component sources of this cumulative figure.
-------
Pollutants***
Hydrocarbons
Particulate
NOX
CO
Total
TABLE G-VII
COMPONENT EMISSION RATIOS*
Stream from Table
B
0.03455
None
None
None
None
III, Process
D
0.01162
None
None
None
None
15-1**
F
0.007522
None
None
None
None
G
0.0121
None
None
None
None
Total
0.06579
None
None
None
None
0.03455
0.01162
0.007522
0.0121
0.06579
*Used in cumulative total form in Table VI.
**Process 15-1 was selected (rather than Process 15-2) as representing the more conservative approach for
SEI calculation purposes.
***Units are tons of pollutants per ton of glycerol capacity.
-------
Table of Contents
Section Page Number
I. Introduction HCN-1
II. Process Description HCN-2
III. Plant Emissions HCN-3
IV. Emission Control HCN-5
V. Significance of Pollution HCN-7
VI. Hydrogen Cyanide Producers HCN-8
List of Illustrations and Tables
Simplified Block Flov Diagram, Andrussov Process
for Hydrogen Cyanide Figure HN-1
Basic Chemical Reactions Table HCN-I
Net Material Balance Table HCN-II
Gross Heat Balance Table HCN-II-A
Emission Inventory Table HCN-III
Catalog of Emission Control Devices Table HCN-IV
Number of Nev Plants by 1980 Table HCN-V
Emission Source Summary Table HCN-VI
Weighted Emission Rates Table HCN-VII
References Table HCN-VIII
-------
HCN-1
I. Introduction
According to information in SRI's Chemical Economics Handbook, 'viii),
probably considerably less than 107,, of the hydrogen cyanide produced in the
United States today is available in the merchant market. Most producers
have integral facilities for captive use, and ordinarily maintain relatively
small quantities in intermediate storage. Discrepancies in published figures
for both.capacity and consumption apparently stem from this difficult-to-
assess captive use. Although substantial cmantities of hydrogen cyanide vere
going into the production of acetylene derived acrylonitrile, this use has
been eliminated by the propylene process, which actually results in production
of hydrogen cyanide instead. In the early 1960's, over 507- of the HCN
produced vas consumed in the making of acrylonitrile and since this outlet no
longer exists, and anticipated hydrogen cyanide consumption increases for
nitrilotriacetate have not materialized, gains in other areas have been
barely enough to make up for the loss. With the trends predicated in the
January, 1971 CEH report, estimated breakdovn for consumption of hydrogen
cyanide is as shovn here;
Acetone Cyanohydrin (for methacrylate polymers) 457,
Adiponitrile (HCN derivation only) for Nylon 6,6 337,
Chelating agents 117.
Sodium Cyanide 57,
Other 67,
Emissions from the direct production of hydrogen cyanide from methane,
ammonia and air are very lov, in keeping with the fact that the product is
highly toxic. Normal sample pot vents result in low-level hydrogen cyanide
emission, and air dilution and dissipation by release from high stacks ,.
provides the means for safe disposal. Flaring of process off-gas and certain
other process equipment vent streams results in NOX formation which is
negligible except at times of start-up or emergency.
The advent of an acrylonitrile process that actually produces by-product
hydrogen cyanide instead of using it as rav material has resulted in excess
capacity and leveling off of consumption. Some direct process hydrogen
cyanide vill undoubtedly remain on-stream due to captive market predominance
but nev capacity will be provided via the by-product route in an expanding
market for acrylonitrile. No new direct process capacity is anticipated and
for that reason, emissions from this process will likely decrease as plants
become obsolete.
-------
HCN-2
II. Process Description
The direct route used in this country for producing hydrogen cyanide
from methane, ammonia and air is based on the Andrussow process with certain
modifications initiated by Degussa, Montecatini, B. F. Goodrich and others.
Figure I presents a simplified block flow diagram. (i, ii, iii, iv, v, vi,
ix) With the air preheated, purified reactants are passed over a precious
metal gauze or impregnated catalyst at one atmosphere and 1000 to 1200° C
(1830 to 2200° F). The catalyst promotes the complex oxidation reaction,
which is carried out beyond the flammable limits on the fuel-rich side
(see Table I for the significant reactions involved). Although the production
of hydrogen cyanide directly from methane and ammonia would be endothermic,
the overall reaction involving oxidation is highly exothermic, and to
minimize non-selective decomposition products, the reactor effluent must
quickly be cooled in a vaste heat boiler. The catalyst, feed gas purity
and ratios, contact time, materials of construction, reactor and ouench
zone geometry and other factors all have an influence on conversion, yield
and productivity. Table II attached provides typical weight balance data,
here based on an air:methane:ammonia mol. ratio of 6:1:0.9. Conditions are
chosen so that reactions III and IV ("Table I) , giving rise to carbon dioxide
formation, and ammonia decomposition, respectively are kept at a minimum.
In the example given, approximately 1070 decomposition takes place and about
19% of the ammonia passes through unreacted. The ammonia can be handled
either by reaction with sulfuric acid for by-product ammonium sulfate, or by
ammonia recycle. In one operation, mono-ammonium phosphate solution is
used to sorb ammonia, and the resulting ditmmonium phosphate is partially
decomposed to recover ammonia for recycle.
The ammonia absorber overhead is sent to a hydrogen cyanide absorber
and the aaueous hydrogen cyanide solution therefrom is sent to a stripper
and fractionator for recovery of the hydrogen cyanide. In most cases,
relatively little product is maintained in storage, and the hydrogen cyanide
is taken directly to integrated process equipment for conversion to the
ultimate commerical product.
-------
HCN-3
III. Plant Emissions
A. Continuous Air Emissions
1. Process Off-Gas CAir Preheater Fuel)
A substantial quantity of hydrogen-rich hydrogen cyanide
stripper off-gas from respondent 16-1 is delivered to the
boiler house for use as fuel in process air preheaters. Hydrogen
cyanide content of the off-gas runs 100 to 1000 PPM, though
additional fuel (natural gas) is mixed with the relatively low
heating value off-gas ( 7470 inert), and complete combustion is
presumed in the air heater burner. The only emissions under the
stated conditions is a lov level of nitrogen oxide CNOX),
calculated on the basis that 307C of the nitrogen in hydrogen
cyanide can be expected to convert to NOX. (See Table III with
associated notes and summary Table VI.)
2. Process Sample Pot Vents
Streams from normal sample pot vents and other process
equipment openings in respondent 16-1 plant are diluted vith large
quantities of air so that effluent stack concentrations average
about 50 PPM (by vol) hydrogen cyanide. Variations from 25 to
as high as 200 PPM can occur, at times, depending on leaking
rupture discs or the like. Once-a*week sampling allows detection
so that high levels do not persist. Dissipation from 120 to 150
foot stacks is designed to bring the concentration to safe levels.
Sax (xiii) gives for hydrogen cyanide an ACGIH Threshold Limit
Value (TLV) of 10 PPM in air. As an ordinary pollutant, the
amount is small, but on TLV basis, one can calculate that
sufficient HCN is emitted in one day to bring a 1000 cubic foot
volume of air to the TLV level of 10 PPM (see Table III and
associated notes, together with summary Table VI for details.)
'l
3. Process Tank and Off-Gas Vents to Flares
These 16-1 plant streams are flared and include continuous
small quantities (estimated 150 SCFM) of 0 up to 3% HCN by volume
in nitrogen with concentration depending on tank fill timing, tank
nitrogen purging, etc. Also included are continuous streams
totalling 37,000 SCFM of the same composition, 100 to 1000 PPM
hydrogen cyanide, as those in A-l above. Flaring of these streams
is assumed to effect complete combustion and on the assumption
that 307o of hydrogen cyanide nitrogen converts to NOX, NOX after
flaring is estimated to total 0.0016 tons per ton of hydrogen
cyanide product. Table III and associated notes provide details,
B. Intermittent Air Emissions
Process Start-Up and Emergency Venting to Flares
Process start-up and emergency vents of feed gas and reactor
effluent streams are sent to flares, normally for about 20 minutes
at any one time and although several of these intermittent stream
vents are tied into one flare stack in some cases, it is considered
unlikely that more than one of these streams vould "load up" a
stack at any given time. Thus, combustion is assumed to be complete
and the short term (' 20 minutes at a time) emissions could raise a
-------
HCN-4
given stack NOX content from the normal continuous levels below
0.0010 tons/ton hydrogen cyanide product to as high as 0.08 tons/ton
when feed gas is being vented (assuming 60% of ammonia nitrogen
converts to NOX in a flare). When hydrogen cyanide, containing
reactor effluent gas is being vented, the short term flare emissions
can go to .026 tons of NOX per ton of hydrogen cyanide product
(assuming 30% of HCN nitrogen converts to NOX in a flare). Since
the intermittent start-up and emergency vent situations do not
occur for long, calculations on an annual basis for all these
intermittent streams together result in an estimate of a low
overall flared stream total of 0.0016 tons of NOX per ton of
hydrogen cyanide product. (See summary Table VI and details in
Table III with associated notes.)
C. Continuous Liquid Wastes
Liquid wastes are produced but the amount is unreported.
D. Solid Wastes
None reported.
E. Odors
Respondent 16-1, of course, is cognizant of the need to keep
hydrogen cyanide emissions nil for safety of personnel and reports
that odors from the plant are not a probelm.
E. Fugitive Emissions
None are reported. Only tvo small tanks are listed by respondent
16-1, and although they contain 5 - 10 wt. % hydrogen cyanide in
water, they are maintained at 10° C, and back pressure controller
vents connect to flares.
System leaks, if any, are such that they are "undetectable by
material balances". Fugitive losses have never been determined,
but due to hazard, any leaks discovered are quickly repaired.
-------
HCN-5
IV. Emission Control
Combustion devices are the only type of emission control equipment
reported by respondent 16-1 for the direct production of hydrogen cyanide
from methane, ammonia and air. The details are to be found in Table IV,
"Catalog of Emission Control Devices", with associated notes. In Table IV,
all combustion devices are assigned two efficiency ratings:
(1) CCR - Completeness of Combustion Rating
CCR = Ibs. of 02 that react with pollutants to feed device x ]_QQ
Ibs. of C>2 that theoretically could react with these pollutants
(2) SERR - Significance of Emission Reduction Rating
SERR = weighted pollutants in - weighted pollutants out 1_n
weighted pollutants out
A more detailed discussion of these ratings may be found in Appendix V
of this report.
Combustion Devices
Respondent 16-1 reports that 625 SCFM, a small proportion of the
process off-gas from No. 1 train, is used as fuel for the HN-1 process
air preheater. He indicates that a much larger flow, 16,000 SCFM, of
No. 2 train process off-gas is similarly used, though no "device"
information is provided for the latter. (All No. 3 train "off-gas"
goes to HN-5 flare.)
Except for vents identified as sample pot vents, etc., which are
simply diluted with large quantities of air (see previous Section III),
the remaining vent streams are flared. In all cases, the "emission
control" device, whether it be the gas-fired preheater HN-1 or the four
indicated flares, is assumed to bring about complete combustion.
Where hydrogen cyanide is present, the level is low in the overall
stream being subjected to combustion, and no odor problem has been
noted. Thus, the only pollutant that may be of any significance is NOX.
There are conflicting statements in the literature concerning the extent
to which chemically-bound nitrogen is converted to NOX in combustion
devices. In large scale commercial boilers, heaters and steam generation
equipment, high temperatures and significant residence time situations
result in appreciably nitrogen fixations from the air; the contribution
made under such circumstances, by fuel nitrogen is "relatively inconsequen-
tial" according to Robert T. Walsh in Chapter 9 of the HEW "Air Pollution
Manual", Public Health Service Publication 999-AP-40.
On the other hand, R. W. Rolke, et al, in "Afterburner Systems Study",
EPA Publication S-14121, page 204, suggests that under the lower temperature
conditions found in afterburner operations, very little NOX is formed
from nitrogen in the air and "most of the chemically-bound nitrogen in
the waste can be expected to form NOX along with that formed by nitrogen
fixation in the burner flame".
Another conclusion may be reached by calculation based on S. Gordon and
B. J. McBride, "Computer Program for Calculation of Complex Chemical
Equilibrium Composition, Rocket Performance, etc.", (NASA-SP-173). From
-------
HCN-6
this source, it may be calculated that at 2000° F, less than one
percent of the ammonia and about zero percent of the hydrogen cyanide
will convert to NOX at equilibrium.
For the combustion of waste, as practiced in the present operation,
no definitive data appear to be available. Industry sources have
indicated that in an incinerator, from 60 to perhaps as high as 80
percent of the nitrogen in ammonia can convert to NOx when burned,
whereas the conversion is lower, on the order half as much for the
nitrogen in hydrogen cyanide. Hence, for the fuel stream, 60 percent
of the ammonia and 30 percent of the HCN are assumed to go to NOx.
From general knowledge of flare operation, one might expect effective
temperatures around 2000° F. If residence time at 2000O F were
appreciable, higher conversion to NOX might be expected, but under the
short duration flare conditions, an assumption has been made here that
about 10 percent of the chemically bound nitrogen goes to NOx. Details
are to be found in Table IV.
-------
HCN-7
V. Significance of Pollution
It is recommended that no in-depth study of this process be undertaken.
No new direct (Andrussow) process capacity is anticipated. In fact, as
discussed earlier in this report, direct process capacity likely will be
phased out, and any new demand for hydrogen cyanide will be supplied from
excess by-product capacity in conjunction with acrylonitrile plants now on
stream or to be built.
Since no new capacity is anticipated, the Significant Emission Index*
for the direct route hydrogen cyanide process is zero.
*For a discussion of Significant Emission Index concepts, see Appendix IV.
-------
HCN-8
VI. Hydrogen Cyanide Producers
Since over 907, of the hydrogen cyanide produced in the United States
today is destined for captive use, and often is immediately converted in
integral production facilities, accurate tabulation of capacities and con-
sumption figures is difficult. The relatively nev propylene acrylonitrile
production process vhich provides approximately 0.175 pounds of hydrogen
cyanide by-product per pound of acrylonitrile (xiv), (instead of a requirement
of over 0.5 pounds per pound for the old ethylene oxide or acetylene
processes) has completely changed the picture for hydrogen cyanide. Following
is a listing of direct and by-product hydrogen cyanide producers vith plant
locations and capacities; (x, xi, xii)
Company
American Cyanamid Co.
Dow Chemical Co.
E. I. duPont
M
II
II
II
B. F. Goodrich Co.
Hercules, Inc.
Monsanto Co.
Rohm & Haas Co.
Vistron CStd. Ohio)
Location
Fortier, La.
Freeport, Texas
Beaumont, Texas
Memphis, Tenn.
ii ii
Victoria, Texas
La Place, La.
Calvert City, Ky.
Glens Falls, N. Y
Alvin
(Choc. Bayou), Tx
Texas City, Texas
Deer Park, Texas
Lima, Ohio
Annual
Capacity
4/1/71
MM Lbs.
27
5
30
115
27
'20/^
'2/»
Process
By-product
Direct
By-product
Direct
By-product
Direct
Direct
By-product
Direct
56
75
155
30
By-product
Direct
Direct
By-product
Remarks
Captive
Captive
Captive
Partly captive
Captive
Captive
Captive
Merchant
Captive
Captive
Captive
Captive
Merchant
Based on January, 1971 CEH estimate including certain captive use approx-
imations noted.
-------
PAGE NOT
AVAILABLE
DIGITALLY
-------
TABLE HCN-I
BASIC CHEMISTRY
OF
ANDRUSSOW HYDROGEN CYANIDE PROCESS
MAIN REACTION
Reaction I. Controlled Catalytic Oxidation of Methane and Ammonia
2 CH4 + 3 02 + 2 NH3 - -^ 2 HCN + 6 H20
Precious
Metal
Catalyst
SECONDARY REACTIONS
Reaction II. Partial Oxidation of Methane
CH4 + 02 - > CO + H20 + H2
Reaction III. Complete Oxidation of Methane
CH4 + 2 02 • - > C02 + 2 H20
Reaction IV. Dissociation of Ammonia
N2 + 3
-------
TABLE HCN-II
HYDROGEN CYANIDE BY THE ANDRUSSOV' PROCESS
MATERIAL BALANCE
TONS /TON OF HYDROGEN CYANIDE PRODUCT
Stream No, 1 2
(Fig. HN-1)
Stream Name Fresh Recycle
Feed Ammonia (2)
Methane .9626
Ammonia .8679 .1991 (2)
Oxygen 2.5553
Nitrogen 8.0352
Hydrogen
Hydrogen Cyanide
Carbon Dioxide
Carbon Monoxide
Water
Sulfuric Acid (.5739) (2^
Ammonium Sulfate
(3)
Total 12.4210 .1991
3 4
Total Reactor
Feed Effluent
.9626 .0085
1.0670 .1991
2.5553 0
8.0352 8.2282
.0829
1.0062
.0703
.5813
2.4436
12.6201 12.6201
5
Ammonia Absorber
Overhead
.0085
0
0
8.2282
0829
1.0062
.0703
.5813
9.9774
6
HCN Absorber
Overhead (Vent)
.0085
0
0
8.2282
.0829
.0062
.0703
.5813
8.9774
7
HCN Absorber
Bottoms to Fractionator
0
0
0
0
0
1 0000
0
0
+ X (1)
1.0000 + X (1)
8 9
Acid Inlet Ammonia
Absorber Bottoms
0 0
0 0
0 0
0 0
0 0
0 0
0 0
0 0
.5739 (2)
.7730 <2>
.5739 .7730
(1) Conversion and selectivity are based on information provided in Kirk-Othmer. 2nd Edition (1964), Vol. 6, pages 577-578: mol. 70 methane conversion to HCN is 627.,
ammonia conversion is taken at 59? . 19"? of the ammonia passed thru unreacted, 1070 decomposes and ultimate hydrogen cyanide yield is 7370 on ammonia; polymer or
carbon formation is assumed negligible and the ammonia absorber is assumed 1007 efficient.
'21 Onanti ty of wai er i r. stream dependent on tover operating condit ions .
(3^ Tot a 1 fresh 1 fed f i pir*> exc l:ides sul fnri c acid, unreacted ammoni a may be recycled or recovered as ammonium sulfate.
-------
TABLE HCN-II-A
PRODUCTION OF HYDROGEN CYANIDE BY THE ANDRUSSOW PROCESS
GROSS HEAT BALANCE
Basis: Material Balance, Table II and reactions (vii, viii)
shown in Table I, producing 1.0000 Ib. hydrogen cyanide.
Catalytic Reactor Section, including waste heat boiler.
Heat Out
Heat exchange to cool products to 80° F 10,984 BTU/lb. hydrogen cyanide
Losses and heat required for steam
generation in waste heat boiler 7,926 BTU/lb. hydrogen cyanide
Total 18,910 BTU/lb. hydrogen cyanide
Heat In
Reaction I - Exotherm producing 1.0000 Ib. HCN - 7,570
Reaction II " " 0.5813 Ib. CO - 2,481
Reaction III " " 0.070 Ib. C02 - 552
Reaction IV Endotherm " .1930 Ib. N2 - (272)
Overall Exotherm ex Reaction I - IV 10,331 BTU/lb. hydrogen cyanide
Sensible heat of incoming charge 8,579 BTU/lb. hydrogen cyanide
Total 18,910 BTU/lb. hydrogen cyanide
-------
TABLE HCN-III
NATIONAL EMISSIONS INVENTORY
HYDROGEN CYANIDE (ANDRUSSOW PROCESS)
Page 1 of 4
Plant EPA Code No.
Capacity - Tons of HCN/Yr.
Average Production - Tons HCN/Yr.
Quarterly Production Variation, % of Max.
Emissions to Atmosphere
Stream
Plant Train No.
Flow - Lb./Hr.
Flow Characteristics - Continuous or Intermittent
if Intermittent - Hrs./Yr. Flow
Composition - Tons/Ton of Hydrogen Cyanide
Methane
Ammonia
Nitrogen
Oxygen
Hydrogen
Hydrogen Cyanide
Carbon Dioxide
Carbon Monoxide
Water
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problem
Vent Stacks
Flow - SCFM/Stack
Number
Height - Feet
Diameter - Inches
Exit Gas Temperature, °F
Emission Control Devices
Type - Incinerator
Flare
Scrubber
Other
Catalog I. D. Number
Total Hydrocarbon Emissions - Ton/Ton Hydrogen Cyanide
Total Particulates & Aerosol - Ton/Ton Hydrogen Cyanide
Total NOX (8) - Ton/Ton Hydrogen Cyanide
Total SOX - Ton/Ton Hydrogen Cyanide
Total CO Emissions Ton/Ton Hydrogen Cyanide
Product Recovery & Purification
Section Off-Gas
(Air Heater Fuel)
1
5,350
Continuous
.1408
.0505
.0477
None
Never
Calc'd.
1250
1
85
54
Air Heater
HN-1
0
0
.00002 (8)
0
0
16-1
83,000
Start-Up and
Emergency Feed
Gas Venting
1
21,600
Intermittent
16
.5396
.1794
.2468
None
Never
Calc'd.
5250
1
76.5
24
Yes
HN-2
0
°009 (3) (8)
0
0
Start-Up & Emergency Reactor Effluent
& Continuous Process Tank &
Off-Gas Vents
1
112,900
Intermittent
48
(3)
None
Never
Calc'd.
Not Applicable
27,400
1
76.5
24
Yes
HN-3
0
0
.006
0
0
(8)
Process Tank &
Process Off-Gas
Vents
1
95.200
Continuous
3.2022
.4193
.6290
None
Never
Calc'd.
22,550
1
76.5
24
Yes
HN-3
0
0
.0001 (8)
0
0
-------
TABLE HCN-III
NATIONAL EMISSIONS INVENTORY
HYDROGEN CYANIDE (ANDRUSSCM PROCESS)
Page 2 of A
Plant EPA Code No.
Capacity - Tons of HCN/Yr.
Average Production - Tons HCN/Yr.
Quarterly Production Variation, 7, of Max.
Emissions to Atmosphere
Stream
Plant Train No.
Flow - Lb./Hr.
Flow Characteristics - Continuous or Intermittent
if Intermittent - Hrs./Yr. Flow
Composition - Tons/Ton of Hydrogen Cyanide
Methane
Ammonia
Nitrogen
Oxygen
Hydrogen
Hydrogen Cyanide
Carbon Dioxide
Carbon Monoxide
Water
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problem
Vent Stacks
Flow - SCFM/Stack
Number
Height - Feet
Diameter - Inches
Exit Gas Temperature, °F
Emission Control Devices
Type - Incinerator
Flare
Scrubber
Other
Catalog I. D. Number
Total Hydrocarbon Emissions - Ton/Ton Hydrogen Cyanide
Total particulates & Aerosol - Ton/Ton Hydrogen Cyanide
Total NOX (8) - Ton/Ton Hydrogen Cyanide
Total SOX - Ton/Ton Hydrogen Cyanide
Total CO Emissions - Ton/Ton Hydrogen Cyanide
Process
Sample Pot
Vents
1
296,000
Continuous
10.1493
3.0660
.0006
Accessible
Weekly
GLC
No
65,000
1
150
60
Ambient
None
.0006
0
0
0
0
16-1
83,000
Product Recovery & Purification
Section Off-Gas
(Air Heater Fuel)
2
137,000
Continuous
3.6042
1.2927
1.2210
None
Never
Calc'd.
16,000
2
Air Heater
0
0
.0006
0
0
Process
Off-Gas
Vent
2
17.800
Continuous
.5977
Yes
HN-4
0 (6)
0
.00004
0
0
Process Tank &
Process Off-Gas
Vents
2 & 3
48,700
Continuous
1.6367
.0783
. 1174
None
Never
Calc'd.
Not Applicable
4.200
1
74
24
.2143
.3215
None
Never
Calc'd.
Not Applicable
11,500
1
110
48
Yes
HN-5
0
0
.00005
0
0
-------
TABLE HCH-III
NATIONAL EMISSIONS INVENTORY
HYDROGEN CYANIDE (ANDRUSSOW PROCESS)
Page 3 of 4
Plant EPA Code No.
Capacity - Tons of HCN/Yr.
Average Production - Tons HCN/Yr.
Quarterly Production Variation, 7. of Max.
Emissions to Atmosphere
Stream
Plant Train No.
Flov - Lb./Hr.
Flov Characteristics - Continuous or Intermittent
if Intermittent - Hrs./Yr. Flow
Composition - Tons/Ton of Hydrogen Cyanide
Methane
Ammonia
Nitrogen
Oxygen
Hydrogen
Hydrogen Cyanide
Carbon Dioxide
Carbon Monoxide
Water
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problem
Vent Stacks
Flow - SCFM/Stack
Number
Height - Feet
Diameter - Inches
Exit Gas Temperature - °F
Emission Control Devices
Type - Incinerator
Flare
Scrubber
Other
Catalog T. D. Number
Total Hydrocarbon Emissions - Ton/Ton Hydrogen Cyanide
Total Particulates & Aerosol - Ton/Ton Hydrogen Cyanide
Total NOX (8) - Ton/Ton Hydrogen Cyanide
Total SOX - Ton/Ton Hydrogen Cyanide
Total CO Emissions - Ton/Ton Hydrogen Cyanide
Start-Up or Emergency Feed-Gas Relief
& Continuous Process Tank &
Process Off-Gas Vents
2
66,300
Intermittent
12
None
Never
Calc'd. <6>
Not Applicable
15,900
1
110
48
Yes
HN-5
0 (6)
0
.02
0
0
16-1
83,000
Start-Up or Emergency Feed Gas Relief
& Continuous Process Tank &
Process Off-Gas
3
66.300
Intermittent
None
Never
Calc'd. (6>
Not Applicable
15,900
1
110
48
i
Yes
HN-5
0 (6)
.02
0
0
Start-Up or Emergency Reactor Effluent
Relief & Continuous Process Tank &
Process Off-Gas Vents
2
66.400
Intermittent
40
None
Never
Calc'd. <6>
Not Applicable
16,400
1
110
48
i
Yes
HN-5
0
0
.006 (3) (8)
0
0
-------
TABLE HCN-III
NATIONAL EMISSIONS INVENTORY
HYDROGEN CYANIDE (ANDRUSSCTJ PROCESS)
Page 4 of 4
Plant EPA Code No.
Capacity - Tons of HCN/Yr.
Average Production - Tons HCN/Yr.
Quarterly Production Variation, 7. of Max.
Emissions to Atmosphere
Stream
Plant Train No.
Flow - Lb./Hr.
Flov Characteristics - Continuous or Intermittent
if Intermittent - Hrs./Yr. Flov
Composition - Tons/Ton of Hydrogen Cyanide
Methane
Ammonia
Nitrogen
Oxygen
Hydrogen
Hydrogen Cyanide
Carbon Dioxide
Carbon Monoxide
Water
16-1
83,000
0
Start-Up or
Emergency Reactor Effluent Relief
& Continuous Process Tank &
Process Off-Gas Vents
3
66,400
Intermittent
24
Process
Sample Pot
Vents
2
296,000
Continuous
10.1493
3.0660
.0006
Process
Sample Pot
Vents
3
18.200
Continuous
.6246
.1887
. 00004
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problem
Vent Stacks
Flov - SCFM/Stack
Number
Height - Feet
Diameter - Inches
Exit Gas Temperature - °F
Emission Control Devices
Type - Incinerator
Flare
Scrubber
Other
Catalog I. D. Number
Total Hydrocarbon Emissions - Ton/Ton Hydrogen Cyanide
Total Particulates & Aerosol - Ton/Ton Hydrogen Cyanide
Total NOX (8) - Ton/Ton Hydrogen Cyanide
Total SOX - Ton/Ton Hydrogen Cyanide
Total CO Emissions - Ton/Ton Hydrogen Cyanide
None
Never
Calc'd.
(6)
Not Applicable
16,400
1
110
48
Yes
HN-5
0
?006
0
0
Accessible
Weekly
GLC
No
65,000
1
150
60
Ambient
None
.0006
0
0
0
0
None
Never
Calc'd
No
4,000
2 (alternating)
120
16
Ambient
None
.00004
0
0
0
0
-------
EXPLANATION OF NOTES
TABLE HCN-III
NATIONAL EMISSIONS INVENTORY
HYDROGEN CYANIDE (ANDRUSSOW PROCESS)
(1) Only a small proportion of the hydrogen containing off-gas stream from
No. 1 train is sent to the air heater, remainder is flared.
(2) Intermittent stream flow and instantaneous ton/ton concentrations
indicated in this column apply only during the hours/year shown.
(3) Total vent flows when flaring start-up or emergency reactor effluent
for perhaps a 20 minute period at any one time along with continuous
vents indicated, total weight and volume flows as well as the instan-
taneous emission rate are shown for this relatively short time situation,
though weights of individual gases are not indicated, since air input
is assumed to remain unchanged. Complete combustion is assumed.*
(4) Pollutant in this stack effluent is solely the very toxic HCN, which,
according to N. Irving Sax (xiii), has an American Conference of
Governmental Industrial Hygienists (ACGIH) Threshold Limit Value (TLV)
of 10 PPM or 11 milligrams per cubic meter of air. The air dilution
in the stack brings the level to 50 PPM and safe dissipation is presumed,
due to the 150 foot stack height.
(5) A large proportion of the hydrogen containing off-gas stream from No. 2
train is sent "to boilerhouse", therefore, not necessarily utilized in
one particular heater, though two stacks for the process air heater
were indicated. Complete combustion is assumed. All off-gas from No. 3
train is sent to flare.
(6) Complete combustion is assumed.
(7) Start-up and emergency relief streams are intermittent as indicated and
for brief periods of perhaps 20 minutes in each instance, are combined
with the continuous stream for flare (HN-5), the respondent reports
that flow from more than one of these intermittent streams at one time
is unlikely, hence, only one at a time is shown in combination in Table III.
(8) The questionnaire respondent 16-1, provided no information on NOX- The
figures given for NOX in Table III (and the SERR figures in Table IV)
are Houdry estimates based on the assumption that (a) NOX conversion from
ammonia is 60% of the stoichiometric amount, and (b) NOX conversion from
hydrogen cyanide is 30% of stoichiometric. Contribution to NOX by
fixation of nitrogen from the air is negligible (see Section VI discussion).
*Except for NOx procution, see Section VI discussion.
-------
TABLE HCN-IV
CATALOG OF EMISSION CONTROL DEVICES
HYDROGEN CYANIDE FY THE ANDURSSOV PROCESS
Plant Section
(6)
Feed Gas
(No. 1)
rvl6 hrs. /yr.
16-1
B
HN-2
Methane & Ammonia
Yes
4440
None
76.5
2
47,100
1968
.02P4
1800
.0011
100 (2)
78 (3) (4)
Page 1 of 2
Process Tanks & Process
Off-Gas (No. 1)
Continuous
16-1
C
HN-3
Methane & Hydrogen Cyanide
Yes
22,550
None
76.5
2
41,750
19f8
.0252
3300
.0020
100 '2)
95 (3) (4)
Same & Reactor Effluent
Start-Up 6. Emergency (No. 1)
/V48 hrs /yr.
16-1
C
HN-3
Hydrogen Cyanide {* Methane
Yes
27,400
None
95 (3) (4)
-------
TABLE HCN-IV
Plant Section
(Process Train No.)
INCINERATION DEVICES
EPA Code No. for plant using
Flow Diagram (Fig. I) Stream I. D.
Device I. D. No.
Purpose - Control Emission of
Combustion Device - Flare
Incinerator
Other
Materials to Incinerator - SCFM (Ib./hr.)
Auxilliary Fuel Req'd. (Excl. Pilot)
Type
Rate - BTU/hr.
Device or Stack Height - Ft.
Device or Stack Diameter - Ft.
Installed Cost - Mat'l. & Labor - $
Installed Cost Based on "year" - dollars
Installed Cost - Mat'l. & Labor - .-/lb. Hydrogen Cyanide/Yr.
Operating Cost - Annual - S (1972)
Operating Cost - .J/lb. of Hydrogen Cyanide
Efficiency - % - CCR
Efficiency - % - SERR
CATALOG OF EMISSION
HYDROGEN CYANIDE BY THE
Process Off-Gas '"
(No. 2)
Continuous
16-1
C
HN-4
Methane &
Hydrogen Cyanide
Yes
4,200
None
74
2
30,600
1958
.0184
3100
.0019
100 (2)
95 (3) (4)
CONTROL DEVICES
ANDURSSOV PROCESS
Process Tanks & Process
Off-Gas (No. 2 & 3)
Continuous
16-1
C
HN-5
Hydrogen Cyanide &
Methane
Yes
11,500
None
100 (21
95 (3) (4)
Page 2 of 2
Feed Gas Vent & HN-5
Continuous Vent (No. 2 & 3)
1 "'12 or 8 hrs. /yr.
16-1 —
C
HN-5
Hydrogen Cyanide &
Ammonia & Methane
Yes
15,900
None
110
4
65,000
1972
.0392
3800
.0023
100 (21
79 (3) (4)
Reactor Effluent 6, HN-5
Continuous Vent (No 2 6. 3)
fUQ or 24 hrs./yr.
16-1—
C
HN-5
Hydrogen Cyanide 6. Methane
Yes
16.400
None
100 '^
95 (3) (4)
-------
EXPLANATION OF NOTES
TABLE HCN-IV
CATALOG OF EMISSION CONTROL DEVICES
HYDROGEN CYANIDE BY THE ANDURSSOW PROCESS
(1) Air heater HN-1 is not primarily a control device, it is fueled with
123 SCFM natural gas and, to recover heating value, 625 SCFM of waste
process (nitrogen-diluted) off-gas containing hydrogen, carbon monoxide,
a small amount of methane, and about 600 PPM hydrogen cyanide, all of
which is presumed to undergo complete combustion.
(2) Complete hydrocarbon combustion is assumed.
(3) The % SERR shown here ignores the presence of methane.
(4) Calculations in this report are based on the assumption that flare
temperature is 2000° F, and about 10 percent of the chemically bound
nitrogen converts to NOx.
(5) yOnly one-fourth of the 16-1 plant off-gas from No. 2 train is flared,
the remainder being sent to the boiler house, presumably to heat process
air as was done in device HN-1 for No. 1 train.
(6) For this fuel stream, calculations are based on 60 percent of ammonia
nitrogen and 30 percent of hydrogen cyanide nitrogen converting to NOx.
(See Section IV.)
-------
TABLE HCN-V
NUMBER OF NEW PLANTS BY 1980
By-product
Processes
Direct
Process
Total
Current
Capacity
177
412
589
Marginal
Capacity
37 (a)
210 (a)
247
MM LBS . /YR .
Current
Capacity
on- stream Demand
in 1980 1980
140
202
342 430
Capacity
1980
510 (b)
202
712
Capacity to
be added
by 1980
360
0
360
Economic Number
Plant of Nev
Size Units
(b) (b)
0
(a) Arbitrary estimates with the assumption that roughly half the direct process producers will maintain operations
for captive use.
(b) Acrylonitrile plant of economic 200 MM Ib./year capacity has capability for /^35 MM Ib./year of hydrogen cyanide
by product (xiv). Not all acrylonitrile producers recover the hydrogen cyanide.
-------
Emission
TABLE HCN-VI
EMISSION SOURCE SUMMARY
TON/TON OF HYDROGEN CYANIDE
Source
Hydrocarbons
Participates & Aerosol
NOX
S°x
CO
Process Off-Gas
to Air Preheaters
0
0
.0007 (a)
0
0
Process Start-up
and Emergency
Reactor Effluent
0
0
.0001 fb)
0
0
Process Sample
Pot Vents
.0012 (c)
0
0
0
0
Process Tank &
Process Off-Gas Vents
0
0
.0002 (d)
0
0
Fugitive
Emissions
0
0
0
0
0
(a) NOX estimate, deriving from burning of hydrogen cyanide in hydrogen-rich process off-gas used for air preheater fuel.
(b) NOX estimate from flaring of hydrogen cyanide and ammonia in streams and calculated on annual tonnage basis from
instantaneous emission figures of Table III, according to hours per year there given.
(c) Actually hydrogen cyanide.
(d) NOX estimate from flaring of hydrogen cyanide content of streams.
-------
TABLE HCN-VII
WEIGHTED EMISSION RATES
Chemical - Hydrogen Cyanide
Process - Direct CAndrussov) ex methane, ammonia and air.
Increased Capacity by 1980 - None using direct process. New and replacement
capacity for hydrogen cyanide is expected to
derive from nev acrylonitrile plant installations.
Direct Process - Significant Emission Index = 0 MM Ibs./year.
-------
TABLE HCN-VIII - REFERENCES
i A. Lee, Chem. Eng., page 134 (February, 1949).
ii M. L. Kastens & R. Barraclough, I. & E.D. 43, page 1882 (September, 1951).
iii N. Updegraff, Pet. Ref. 3£, page 196, (September, 1953).
iv P. W. Sherwood, Pet. Proc., page 384, (March, 1954).
v M. Salkind & E. H. Riddle, I. & E. C. 51_, page 1232 (October, 1959).
vi Kirk-Othmer, 2nd Edition, Volume 6, Hydrogen Cyanide, page 574 (1964).
vii J. H. Perry, Chem. Eng. Handbook, 4th Edition, McGraw-Hill (1969).
viii S. W. Benson, et al, Chem. Rev. 69, page 279 (1969).
ix A. V. Hahn, The Petrochemical Industry: Markets and Economics,
McGraw-Hill (1969).
x B. J. Johnson, Chemical Economics Handbook, "Hydrogen Cyanide",
Stanford Research Institute, (January, 1971).
xi Chemical Profile, Chemical Marketing Reporter "Hydrogen Cyanide",
(April 1, 1971).
xii MSA Research Corporation, Contract No. EHSD 71-12, Mod. I, Task II,
Final Report MSAR 71-123 for EPA Hydrogen Cyanide, page 50 (July 23, 1971)
xiii N. I. Sax, "Dangerous Properties of Industrial Materials", 3rd Edition,
Reinhold, (1967).
xiv Houdry Div. APCI, "In-Depth Study of Acrylonitrile Manufacture1^
prepared for EPA under Contract No. 68-02-0255.
-------
Isocyanates via Amine Phosgenation
-------
Table of Contents
Section Page Number
I. Introduction TDI-1
II. Process Description TDI-2
III. Plant Emissions TDI-4
IV. Emission Control TDI-7
V. Significance of Pollution TDI-9
VI. Isocyanate Producers TDI-10
List of Illustrations and Tables
Flow Diagram Figure TDI-I
Net Material Balance Table TDI-I
Gross Heat Balance Table TDI-II
Emission Inventory Table TDI-III
Catalog of Emission Control Devices Table TDI-IV
Number of New Plants by 1980 Table TDI-V
Emission Source Summary Table TDI-VI
Weighted Emission Rates Table TDI-VII
-------
TDI-1
I. Introduction
This survey report covers the production of aromatic di-and poly-isocyanates.
Although other isocyanates are commercially available (aliphatic, alicyclic di-&
poly-isocyanates and mono-isocyanates) the aromatic based isocyanates account for
almost the entire market. Of the aromatic isocyanates, three particular
compounds comprise over 90% of the production. These are TDI (toluene diisocyanate
2,4 - and 2,6 - isomers), PMPPI (polymethylene polyphenylisocyanate) and MDI
(4,4'-methylenediphenyl isocyanate). Manufacture of these three isocyanates is
covered in this report.
Development by Farhenfabriken Bayer A. G. of a diisocyanate - polyester
system lead to the production of a foam similar to rubber latex foam and lit the
fire of true commercialization for both isocyanates and foams. Toluene diisocyanate
(TDI) was used rather universally; diols and triols vere used for flexible foams,
the more highly functional polyols for rigid foams. Flexible polyurethane foams
are made mostly from 80/20 TDI (80/20 = % of the 2,4 and 2,6 isomers respectively).
PMPPI is used in semi-flexible foams as in automotive safety cushioning and in
rigid foams. MDI and 80/20 TDI are the major isocyanates used in polyurethane
surface coatings, elastomers, fibers and other applications. Di & polyisocyanates
account for the bulk of isocyanates consumed. Mono isocyanates are used as
chemical intermediates, mostly to produce pesticides.
Isocyanates are made almost exclusively by the phosgenation of amines dissolved
in a (chlorinated) aromatic solvent. The main pollutants from this process are
HCl (by-product of the phosgenation reaction), traces of phosgene, vhich hydrolizes
to HCl in moist air, chlorinated hydrocarbons and CO from the phosgene generation
step. Since phosgene and CO are both quite poisonous, it appears that care has
been exercised in pollution control. Continuous emissions have been reported
from these plants, but they are relatively minor air polluters, although
characteristically the emissions are odorous.
-------
TDI-2
II. Process Description
Organic amines are reacted with phosgene in a suitable solvent to form
the corresponding isocyanate and HCl as a by-product. Several side reactions
and associated complications make this a far from simple reaction scheme.
In the case of aromatic isocyanates, the subject of this survey report, all
commercial manufacturing processes have the following approach:
1. Solution of the amine in an aromatic solvent such as xylene,
monochlorobenzene or o-dichloro benzene.
2. This solution is mixed with a solution of phosgene (COC12) in the same
solvent at a temperature below 140° F.
3. The resulting reaction mixture slurry is then digested in one to three
stages for several hours at progressively increasing temperatures up to
390° F with the injection of additional phosgene.
4. The final solution of reaction products is fractionated to recover
hydrogen chloride, unreacted phosgene and solvent for recycling,
isocyanate product and distillation residue for incinerations.
The chemistry involved in the production of TDI, PMPPI and MDI is quite
similar. TDI production from basic rav materials is shovn for simplicity.
1. Di Nitration of Toluene
2 HNO. -H2S°4 * \f + 2 H20
NX>2
Toluene Nitric Acid Dinitrotoluene
92.1 M.W. 63.0 M.W. 182.1 M.Wa
The nitration is done in two stages, mono-and di-. The product of the
second nitration contains about 76% by weight of the 2,4 isomer (shovn),
19% of the 2,6 isomer and the balance 2,3 and 3,4 isomers.
2. Reduction to an Amine
The mixture of dinitrotoluene isomers is fed to hydrogenators and
reduced catalytically to toluene diamine (TDA), also a mixture of isomers.
+ 6 H2 ^ —» V J +4 H20
N02 ^ff
Dinitro- NH2
toluene Hydrogen Toluenediamine
182.1 M.W. 2.0 M.W. 122.1 M.W.
3. Phosgene Generation
(a) CH4 + 02 » CO + H2 <'syn. gas)
Hydrocarbons other than methane may be used in this partial oxidation.
-------
TDI-3
(b) CO + Cl,
Carbon
Cat.
coci2
Phosgene
M.W. 98.9
4. Phosgenation of the Amine
2 COC1,
Toluene
diamine
M.W. 122.1
Phosgene
M.W. 98.9
Toluene
Diisocyanate
M.W. 174.1
4 HC1
Hydrogen
Chloride
Mr.W. 36.5
The TDI product contains about 80% 2,4 isomer and 20% 2,6 isomer.
The manufacture of MDI and PMPPI begins with the acid condensation of
aniline and formaldehyde to yield diphenyl methane amine (MDA).
1. Acid Condensation
N»2
2 V V- + HCHO
HC1
Aniline
M.W. 93.1
Formaldehyde
M.W. 30.0
Diphenylmethane diamine
M.W. 198.3
When PMPPI is the desired product, the amount of aniline and formaldehyde
present and the reaction conditions are modified so that diphenyl methane
diamine further condenses with aniline and formaldehyde to form tri-amine,
tetramine and polyamines. This mixture is usually called polymethylene
polypheny1amine.
2. Phosgenation of the Amines
Diphenylmethane
diamine
M.W. 198.3
2 COC1
Phosgene
M.V. 98.9
OCN
NCO + 4 HC1
4,4 methylene diphenyl Hydrogen
isocyanate MDI Chloride
M.V. 250.1 . M.V. 36.5
NH
Polymethylene Polyphenylamine
NCO / NCO
I /
CH2
Polymethylene Polyphenyllsocyanate
PMPPI
-M*
+ (n -I- 2) COC12
NCO
Phosgene
+ 2 (n + 2) HCL
Hydorgen
Chloride
MDI, like TDI, is purified by distillation. PMPPI need not be distilled.
-------
TDI-4
III. Plant Emissions
A. Continuous Air Emissions
1. Phosgene Decomposer Vent
All plants have some sort of a phosgene decomposer. Usually,
the HCL and COC12 go through a separator where the bulk of the
phosgene is removed and recycled. In most cases, the next step
is absorption of the HC1 in water to give hydrochloric acid,
which may either be sold or disposed of in some other manner.
Residual quantities of phosgene and HCl go to a caustic scrubber
where the HCl is absorbed as NaCl and the phosgene is decomposed
to C02 and HCl and thence to NaCl and Na2C03. Inert gases, CO
(if present) and trace quantities of HCl and COC12 go to either a
stack or an incinerator. In either case, a chloride aerosol
emission is the end result. In plants which do not flare this
stream, there is an emergency NH3 stream which is injected into
the stack if the COC12 content exceeds approximately 100 PPM.
In this case, the phosgene is converted to ammonium chloride
which is emitted as a particulate, albeit a non toxic particulate.
None of the plants which had this emergency protection stated as
to how often, if ever, it had been used.
The phosgene decomposers work very well and their efficiency
is normally 99.9+%. However, in one case, respondent 17-10
reported an off-gas from the decomposer which contained two percent
HCl and COC12. This is directed to the plant flare along with
streams from other processes. HCl passes thru a flare unchanged
and phosgene is probably decomposed to C02 and C12. While the
CCR* rating is nearly 100 percent for this stream, the Specific
Emission Reduction Rating (SERR*) is nine percent reflecting only
the change COC12 ••> C02 and C12. Both COC12 and C12 are
counted as aerosols and the flare does practically nothing to
this stream. Respondent 17-7 takes gas from his decomposers
containing traces of CO and COC12 and runs it up a stack with 5000
CFM dilution air. This stack is also a fugitive emission collector
and the purpose of the air dilution is personnel protection in the
event of equipment failure or up-set.
Off-gas from most of these scrubbers (decomposers) is an
occasional in-plant odor problem. In general, it can be concluded
that emissions from phosgene decomposers are low, but pollution
and hazard resulting from their malfunction is potentially
significant.
2. Isocyanate Scrubber Vent
This vent is shown as coming from the TDI purification column
overhead drum. This may or may not be true for each plant but it
represents the general scheme for the process. This vent stream is
mainly nitrogen (air) with small quantities of isocyanates and
chlorinated hydrocarbons. A caustic scrubber is normally used to
control pollution and both SE* and SERR are over 99.9 percent for
these scrubbers. This stream contributes only a minor amount of
pollution to the overall plant output, but does contribute to
in-plant and out-of-plant odors.
*See page TDI-7 for definitions.
-------
TDI-5
3. Residual Material Gas Scrubber
Scrubbed gas from this source contributes only trace quantities
of pollutants and occasional in-plant odors. For those respondents
who incinerate this residual stream, the incinerator off-gas
contributes CO and hydrocarbon pollutants to the air and an
occasional in-plant odor problem.
4. Miscellaneous Vents
These have been noted but contribute only trace quantities of
pollutants. No numbers were available other than trace.
5. HC1 Absorbers
Where the HCl is to be sold, it is absorbed in a chloride
resistant packed column using water as the absorbing medium. A
35% acid can be recovered. Normally this scrubber would be followed
by a caustic scrubber which would neutralize any HCl left in the
gas plus decompose any phosgene in the stream.
If the HCl is not to be recovered, it may still be absorbed in
water in a packed column but weak caustic is generally used. One
respondent reports a novel scheme. In this case the HCl is not to
be recovered but is fed into a large pit containing ground limestone
and water. The HCl is converted to CaCl2 and C02 is given off. The
vent gas from this operation is reported as almost 100% air and C02
with trace quantities of HCl and ^S from sulfur in the limestone.
The H2S traces cause an in-plant odor problem. One might suspect
some HCl in the area since these are open pits but none was reported.
6. Plant Flares
Only two respondents reported venting streams to a flare. One
stream is an off-gas from the TDA reactors which.feed H2 and dinitro-
toluene. The gas consists mainly of ethanol, H2, nitrogen and
ammonia. Flared gas is reported as 100% C02, ^0 and N2 so any
efficiency rating of this unit is 100%. One would suspect some
NOX formed during the flaring.
The other respondent feeds a stream of inerts and HCl and COC12
to his plant flare. This was covered in Section III-l, Phosgene
Decomposer Vent. It makes little sense to flare HCl and COC12 other
than the dilution provided by other streams and the coversion of
toxic COC12 to somewhat less toxic C^. CCR on the flare is 100%
but the SERR is a lowly nine percent. A stopgap operation. A better
method should be used.
B. Intermittent Emissions
None reported.
C. Continuous Liquid Wastes
The amount of waste water varies considerably from plant to plant.
All plants treat this waste water although the treatment may be
described as minimal in two cases. Waste water runs between 0.5
-------
TDI-6
and 50 gal./lb. TDI, the bulk being 0.5 to 5.0 gal./lb. In the
MDI/PMPPI plants, the figure is much lower at 0.05 to 0.4 gals./
Ib.
D. Solid Wastes
Most TDI plants report a solid waste varying from 0.05 to 0.14
Ibs./lb. TDI which is hauled away for landfill. Two respondents
report no solid waste. For MDI, PMPPI a figure of 0 to 0.01
Ibs./lb,, applies. One respondent (TDIplant) occasionally burns
this residue in the plant furnaces but no data were given on
combustion efficiency or pollutants.
E. Odors
Most plants have an in-plant odor problem. Phosgene emissions
are minimal, less than 100 PPM in the stack gas and many stacks
are monitored to inject NH3 into the vent stream if this figure is
reached due to an upset. However, trace quantities of isocyanates
are emitted and these compounds have rather strong and characteristic
odors. Phenyl isocyanate has best been described as an offensive
lachrymatory liquid, for example.
F. Fugitive Emissions
No respondent offered any estimate of fugitive emissions
although several agreed that there were minor emissions at valves,
joints and pump seals. One respondent keeps a vacuum system
operable which is used to control emissions by sucking them up as
they occur until the leak can be repaired. Many of the isocyanate
storage tanks are nitrogen blanketed, venting to the air. All HC1
storage tnaks vent thru a water scrubber. On the negative side, a
minor number of isocyanate storage tanks have no vapor barrier and
vent directly to the air. This could well be a source of odor.
G. Other Emissions
Only insignificant quantities of sulfur in the natural gas
fuels used.
-------
x 100
TDI-7
IV. Emission Control
The emission control devices that have been reported as being employed
by the operators of the isocyanates by phosgenation plants are 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 Q£ reacting (with pollutants in device feed) ^QQ
Ibs. of 02 theoretically capable of reacting
(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 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 an "SE" and/or an "SERR" rating. A more
complete description of this rating method may be found in Appendix V of this
report.
A. Phosgene Decomposers
These units consist of one or two chloride resistant packed columns
scrubbed with a nominal 10 percent caustic solution or recycle. In
some cases water is the absorbing/decomposing medium. Efficiencies
are usually 994%. One respondent dilutes the off-gas because it is
combined with the effluent from a fugitive "sniff" system. This keeps
the total stream well, under 100 PPM COCl2« Another respondent's data
indicate a 75 percent efficiency but the off-gas from this unit is sent
to a flare where it is diluted with material from other sources. A
more efficient decomposing system would seem to be in order.
Almost every respondent has made provision to kill any phosgene break
thru because of a decomposer malfunction by injecting ammonia in the
stack to form NH/Cl. Assuming the use of some excess ammonia to completely
neutralize the toxic COCl2> this system would lay down a blanket of
NH^Cl particulate and also introduce ammonia vapor into the atmosphere.
No one indicated how often this emergency system was used. Indications
were that it was infrequent.
B. Isocyanate Fume Scrubbers
Without exception, all of these units are packed bed weak caustic
(recycle) scrubbers and efficiencies are 99.9+%. However, there is usually
a persistent in-plant odor problem associated with this source despite
the high efficiency.
-------
TDI-8
C. Residual Vent Scrubbers
These scrubbers are spray towers using water. Apparently the odor
problem here is negligible. Some respondents incinerate the residual
stream. See D.
D. Residual Incinerator
Two types of incinerators were described. The first appears to be a
conventional fire-box combustion chamber and stack,, The respondent gave
no indication of any odor associated with the off-gas. The other
respondent used what was referred to as a "pit" incinerator with
excess combustion air. Although the data supplied gave an efficiency
of 100 percent, an odor problem was reported as being associated with
this incinerator. One can only conjecture that this problem could be
solved if an incinerator with a fire-box and adequate combustion chamber
were used instead of a "pit". Neither reported any NOx formation.
E. Flares
Two plants used flares. One plant flaring H2 and ethanol vapors
from manufacture of dinitrotoluene reported an efficiency of 100
percent, although this unit is strictly outside the scope of this report.
The only potential unreported emission from this flare is NOx from either
the combustion air or small quantities of NH3 in the gas stream.
The other respondents flare was discussed in this section under A,
since it received the phosgene decomposer off-gas. As stated, a flare
is not an appropriate way to dispose of chlorides.
F. Miscellaneous
The unit under plant 17-7, Incineration and Dispersion Device, Table
IV is a dilution stack and was mentioned in Section A. It does not
decompose any HCl or COC12 which enters. It dilutes them and as such
should be considered a personnel protection device rather than a pollution
control device.
-------
TDI-9
V. Significance of Pollution
On a weighted emission basis, a Significance Emission Index of 225 has
been calculated for this process. This is on the lower end of the spectrum
and as a result, no in-depth study of the process is recommended.
Methods outlined in Appendix IV of this report have been used to
estimate the total weighted annual emissions from the new plants forecast
up to 1980. The work is summarized in Tables V, VI and VII.
Isocyanates have had a tremendous growth throughout the 1960's. TDI, MDI
and PMPPI account for over 90% of the total U. S. isocyanate production and
polyurethane foams are the largest market for these materials. Isocyanates
have grown is sales volume by 15-20% per year from 1965 to 1970. The projected
growth rate for the period 1970 - 1975 is 8-12% per year.
Installed capacities of isocyanate plants seems to be generally overstated
and, on the average, sales run about 85%, of the published capacity. At the
end of 1973, published capacity (Table VI) was 1088 million Ibs./year or about
924 million Ibs. production at 85%. If a 10%/year growth is assumed until
1980, installed capacity will then be 2120 million Ibs., a production rate of
about 1800 million Ibs. (demand). This will require about 10 new plants of
100 million Ibs. capacity each.
These numbers were used to calculate the SEI of 225. .The major pollutants
from this process are HC1 and organic chlorides as aerosols and CO. There are
odors associated with the various isocyanates, a rather unpleasant smelling
family of compounds.
It should be noted that the reported data include a vide range in emissions
In fact, one plant (17-6) reports an emission rate for hydrocarbons that is
40 times that used in the SEI calculation. If the large rate had been used,
the SEI value would be greater than 400.
-------
TDI-10
VI. Producers of Cyclic Isocyanates
The capacities and plant locations listed below are based on information
provided by the Questionnaires and literature. All capacities are in million
of pounds per year.
Company Location Capacity, 1973
Allied Chemical Moundsville, W. Va. 65
BASF Geismar, La. 40
Du Pont Deepwater, N. J. 105
Jefferson Chemical Port Neches, Texas 50*
Kaiser Gramercy, La. 20*
Mobay New Martinsville, W. Va. 100
100*
Cedar Bayou, Texas 150
Olin Ashtabula, Ohio 40
Lake Charles, La. 90
Rubicon Geismar, La. 31
67*
Union Carbide South Charleston, W. Va. 60
Upjohn . La Porte, Texas 170*
Total = 1,088
TDI - 681
PMPPI/MDI = 407*
-------
PAGE NOT
AVAILABLE
DIGITALLY
-------
TABLE TDI-I
ISOCYANATES
MATERIAL BALANCE - T/T ISOCYANATE
1. TDI production from TDA. Average of data from four respondents. ^v
IN OUT
Actml Theo.4-
Lb. TDA 0.884 0.702
Lb. COC1 1.448 1.136
Lb. Inserts 0.084 0.0
2.416
1.838
Lb. TDI
Lb. HC1 (1007.)
Lb. Residuals
Lb. Gas, Inert
Lb. Unaccounted for
Actual Theo.+
1.000
1.011
0.067
0.020
0.318
2.416
1.000
0.838
0.0
0.0
0.0
1.838
+Basis TDA
NH2 + 2 COClj
2. MDI and PMPPI - production from MDA. Average of data from three respondents
Lb. MDA
Lb. COC1,
IN
Actual iheo.*
0.831
0.855
1.686
0.800
0.770
1.570
Actual Theo.*
Lb. PMPPI (MDI) 1.000 1.000
Lb. HC1 (1007.) 0.597 0.570
Ib. Residuals 0.001 0.00
Lb. Unaccounted for 0.088 0.00
1.686 1.570
*Basis
NH,
NH
|: .4- CH2 { —ft- i
CH_
x -
NH
/\
•ii-
Polymethvlene - polyphenvlamine
if n=o, then diphenyl methane diamine (MDA)
+ (n + 2) COC1..
NCO
\
NCO
PMPPI
+ 2 (n + 2) HC1
-^- 4,4 methylene diphenyl isocyanate (MDI)
-------
TABLE TDI-II
ISOCYANATES
GROSS REACTOR HEAT BALANCE
There vere no published data readily available to allow any kind of
a heat balance to be calculated for this process.
-------
Plant EPA Code No.
Capacity Tons Isocyanates/Yr.
Range of Production - 7. of Max.
Emissions to Atmosphere
Stream
Flow - Lb./Hr. (SCFM)
Flow Characteristic - Continuous or Intermittent
if Intermittent - Hrs./Yr.
Composition - Ton/Ton Iso.
Hydrocarbons
Nitrogen (Air)
CO
C(>2
Steam
COCl2-Phosgene
Chlorinated Hydrocarbons
HC1
Aniline
Isocyanates
H2S, SOX
Participates
Vent Stacks
Number
Height - Ft.
Diameter - Inches
Exit Gas Temperature - F°
SCFM/Stack
Emission Control Devices
Analysis
Date or Frequency of Sampling
Tap Location
Type of Analysis
Odor Problem
Summary of Air Pollutants
Hydrocarbons - Ton/Ton Iso.
Aerosols - Ton/Ton Iso.
NOX - Ton/Ton Iso.
SOX - Ton/Ton Iso.
CO - Ton/Ton Iso.
TABLE TDI-III
NATIONAL EMISSIONS INVENTORY
ISOCYANATES
Phosgene Decomposer Vent Gas
(9000)
Continuous
0.016212
0.005628
0.008800
0.000296
0.002431
Page 1 of 5
17-1
100,000
0
1
725
12
212
1000
Scrubber
Once per year
In Stack
GC, IR
N. C.
Residue Gas Scrubber Vent
No Data
1
700
6
70
?
Scrubber
N. C.
0.002431
0.000296
0.005628
-------
TABLE TDI-III
NATIONAL EMISSIONS INVENTORY
ISOCYANATES
Plant EPA Code No.
Capacity Tons Isocyanates/Yr.
Range of Production - 7. of Max.
Emissions to Atmosphere
Stream
Flow - Lb./Hr. (SCFM)
Flow Characteristic - Continuous or Intermittent
if Intermittent - Hrs./Yr.
Composition - Ton/Ton Iso.
Hydrocarbons
Nitrogen (Air)
CO
C02
Steam
COC12 - Phosgene
Chlorinated Hydrocarbons
HC1
Aniline
Isocyanates
H2S, SOX
Particulates
Vent Stacks
Number
Height - Ft.
Diameter - Inches
Exit Gas Temperature - F°
SCFM/Stack
Emission Control Devices
Analysis
Date or Frequency of Sampling
Tap Location
Type of Analysis
Odor Problem
Summary of Air Pollutants
Hydrocarbons - Ton/Ton Iso.
Aerosols - Ton/Ton Iso.
NOX - Ton/Ton Iso.
SOX - Ton/Ton Iso.
CO - Ton/Ton Iso.
Phosgene Decomposer
Vent Gas
(8)
Continuous
0.000200
0.011560
1
45
3
125
8
Scrubber
Occasional
In Stack
GC
No
HC1 Absorber
(27)
Continuous
0.006400
0.029800
17-2
20,000
+ 8
TDI Scrubber Vent
(28)
Continuous
0.024234
1
50
4
100
27
Absorber
Never
No
1
70
6
100
28
Scrubber
Occasional
In Stack
GC
No
Page 2 of 5
Residue Gas
Scrubber Vent
(870)
Continuous
0.843343
1
12
8
80
870
Scrubber
Never
Est.
No
CO Furnace
Purge Vent
(180)
Intermittent
TR
0.266760
TR
1
98
8
0
None
Never
Est.
No
CO, Removal
Regenerator Vent
(414)
Continuous
0 236571
TR
1
66
4
250
309
None
Occasional
Wet
No
TR
TR
-------
TABLE TDI-III
Plant EPA Code No.
Capacity Tons Isocyanates/Yr.
Range of Production - °l. of Max.
Emissions to Atmosphere
Stream
Flow - Lb./Hr. (SCFM)
Flow Characteristic - Continuous or Intermittent
if Intermittent - Hrs./Yr.
Composition - Ton/Ton Iso.
Hydrocarbons
Nitrogen (Air)
CO
C02
Steam
COC12 - Phosgene
Chlorinated Hydrocarbons
HC1
Aniline
Isocyanates
H2S, SOX
Particulates
Vent Stacks
Number
Height - Ft.
Diameter - Inches
Exit Gas Temperature - F°
SCFM/Stack
Emission Control Devices
Analysis
Date or Frequency of Sampling
Tap Location
Type of Analysis
Odor Problem
Summary of Air Pollutants
Hydrocarbons - Ton/Ton Iso.
Aerosols - Ton/Ton Iso.
NOX - Ton/Ton Iso.
SOx - Ton/Ton Iso.
CO - Ton/Ton Iso.
Phosgene Decomposer
Vent Gas
1151
Continuous
0.003548
0.011759
0.101368
TR
No Data
Scrubber
No
NATIONAL EMISSIONS INVENTORY
IS OCYANATES
17-3
33,500
0
MDI Fume Distillation
Scrubber Vent Scrubber Vent
2080 223
Continuous Continuous
1.02088 0.011657
0.010846
TR
0.000023
No Data No Data
ii it it ti
II II il n
it M n n
Scrubber Scrubber
No No
0.000023
TR
0.011759
Page
Phosgene De
Vent Gas
(22)
Continuous
0.021292
TR
0.006654
1
55
6
150
9
Scrubber
No
17-8
15,500
0
TDI Scrubber Vent
242
0.058650
1
76
4
125
?
Scrubber
No
Residue
Incinerator Vent
(8300)
8.28672
0.695137
0.338495
TR
No Data
Incinerator
No
0.006654
0.716429
-------
TABLE TDI-III
Plant EPA Code No.
Capacity Tons Isocyanates/Yr.
Range of Production - 7. of Max.
Emissions to Atmosphere
Stream
Flow - Lb./Hr. (SCFM)
Flow Characteristic - Continuous or Intermittent
if Intermittent - Hrs./Yr.
Composition - Ton/Ton I so.
Hydrocarbons
Nitrogen (Air)
CO
C02
Steam
COC12 - Phosgene
Chlorinated Hydrocarbons
HC1
Aniline
Isocyanates
H2S, SO
Particulates
Vent Stacks
Number
Height - Ft.
Diameter - Inches
Exit Gas Temperature - F°
SCFM/Stack
Emission Control Devices
Analysis
Date or Frequency of Sampling
Tap Location
Type of Analysis
Odor Problem
Summary of Air Pollutants
Hydrocarbons - Ton/Ton Iso.
Aerosols - Ton/Ton Iso.
NOX - Ton/Ton Iso.
SOX - Ton/Ton Iso.
CO - Tpn/Ton Iso.
NATIONAL EMISSIONS INVENTORY
ISOCYANATES paee 4 Of ^
17-4
13,000
0
tt)I Recovery
Unit Vent
(50)
Intermittent
675 est.
0.004875
0.000141
0.000044
0.000150
TR
1
50
2
Ambient
50
None
Never
None
Estimate
Yes
0.000291
0.000044
17-9
85,000
0
Reactor Vent Amine Scrubber Vent
100 1200
Continuous Continuous
0.003517 0.406780
0.000085
0.000636 0.144068
TR
TR
1 1
Ground 50
10 6
110° 110°
None Scrubber
Never Never
None None
Estimate Estimate
Yes Yes
0.000291
0 . 000044
Reactor Vent Reactor Cond .
(375) (39.5)
Continuous Continuous
TR
0.021442 0.027875
0.049513
0.185965 0.005263
1 1
175 Ground
18 3' x 5'
2000° 130°
Flare None
Never Never
None In Line
Calculated Calculated
No Yes
17-6
20,000
+ 8, - 16
Phosgene Destruction
Vent Unit Off-Gas
(1833)
Continuous
0 041326
1 614425
0 062183
1
130
12"
102°
Scrubber
Never
None
Calculated
No
Incinerator
Stack Gas
(9000)
Intermittent
7
TR
8.507602
0.115010
0.024951
TR
Ground
8' x 8'
?
Pit Incinerator
Never
None
Calculated
Yes
0 041326
-------
TABLE TDI-III
Plant EPA Code No.
Capacity Tons Isocyanates/vr.
Range of Production - '/,, of Max.
Emissions to Atmosphere
Stream
Flov - Lb./Hr.
Flov Characteristic - Continuous or Intermittent
if Intermittent - Hrs./Yr.
Composition - Ton/Ton Iso.
Hydrocarbons
Nitrogen (Air)
CO
co2
Steam
COC12 - Phosgene
Chlorinated Hydrocarbons
HCl
Aniline
Isocyanates
H2S, SO
Partlculates
Vent Stacks
Number
Height - Ft.
Diameter - Inches
Exit Gas Temperature - F°
SCFM/Stack
Emission Control Devices
Analysis
Date or Frequency of Sampling
Tap Location
Type of Analysis
Odor Problem
Summary of Air Pollutants
Hydrocarbons - Ton/Ton Iso.
Aerosols - Ton/Ton Iso.
NOX - Ton/Ton Iso.
SOX - Ton/Ton Iso.
CO - Ton/Ton Iso.
Plant Scrubber
(10,000)
Continuous
4.103120
0.010429
0.000083
TR
2
160
30"
Ambient
5000
Scrubber
Continuous for
In Line
Calc'd.
Yes
NATIONAL EMISSIONS INVENTORY
ISOCYANATES page
17-7
52,500
0
Stack Residue Vent Gas
(200)
Continuous
0.002419
0.047555
0.000083
4
60
4"
200»
50
None
COC12 Never
None
Est.
Yes
0.000166
0.010429
Plant Flare
1000
Continuous
(Calc'd.)
0.126316
0.003211
0.000921 (C12)
0.001316
1
110
1
1600°
Scrubber 6. Incinerator
Never
None
Calc'd.
No
5 of 5
17-10
30,000
0
TDI Reactor
Emergency Vent
600
Intermittent
8
0.000002
0.000070
0.000006
0.000001
0.000001
1
60
2"
212°
None
Never
None
Calc'd.
No
Residue Gas Vent
250
Continuous
0.006184
0.000493
0.026316
TR
TR
TR
1
80
2"
120°
None
Never
None
Calc'd.
Yes
HCl Neut.
Off-Gas
22.876
Continuou
2.693947
0.258816
0 060132
0 001210
0.000092
3
20
10"
100°
Limestone
Neut.
Never
None
Calc'd.
Yes
0.000002
0 003448
0.000092
-------
EXPLANATION OF NOTES
TABLE TDI-III
NATIONAL EMISSIONS INVENTORY
ISOCYANATES
1. Phosgene has been counted as an aerosol because in moist air,
COC12 > 2 HC1 + C02- HCl has been routinely reported as an
aerosol in other reports.
2. Chlorinated hydrocarbons, aniline and isocyanates have been counted
as hydrocarbons.
3. Under "Type of Analysis", GC means gas chromatograph and IR means infra
red analysis.
-------
TABLE TDI-III
ABSORBER/SCRUBBERS
EPA Code No. for plant using
Flow Diagram (Fig. TDI-1) Stream I. D.
Device I. D. No.
Control Emission of
Scrubbing/Absorbing Liquid
Type - Spray
Packed Column
Tray Column
Scrubbing/Absorbing Liquid Rate - GPM
Design Temperature (Operating Temperature) - 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" - $
Installed Cost - c/lb. Isocyanate
Operating Cost - Annual - $ (1972)
Value of Recovered Product - $/Yr.
Net Operating Cost - c/lb.
Efficiency - % - SE
Efficiency - "I. - SERR
ABS ORBER fSGRUBBERS
EPA Code No. for plant using
Flow Diagram (Fig. TDI-1) Stream I. D.
Device I. D. No.
Control Emission of
Scrubbing/Absorbing Liquid
Type - Spray
Packed Column
Tray Column
Scrubbing/Absorbing Liquid Rate - GPM
Design Temp. (Operating Temperature) - 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" - $
Installed Cost - c/lb. Tsocyanate
Operating Cost - Annual - S (1972)
Value of Recovered Product - S/Yr.
Net Operating Cost - c/lb.
Efficiency -7. - SK
Efficiecnv - 7, - SKRR
CATALOG OF
17-1
E
F-101
Phosgene
Water
X
120 - 150
Ambient
400 - 700
30
4 towers - 6 f t .
Yes
725'
12
750,000
1971
0.375
80,000
0.040
Insufficient Data
Insufficient Data
17-2
F
F-102
TDI Residue Gas
Water
X
80
870
10
2
Yes
12
8
16,000
1972
0.04
560
0
0.0014
100
100
EMISSION CONTROL DEVICES
ISOCYANATES
17-1
F
F-102
TDI Residue Gas
Water
X
15 - 20
Ambient
9
15
each 1
Yes
700
6
10,500
1971
0 0053
4,000
0.002
No Data
No Data
17-2
E
F-101
Phosgene
107. Caustic
X
70
5
46
2i
Yes
66
4
86,000
1964 - 1972
0.215
66,500
0
0. 166
100
100
Page 1 of 3
17-2
E
F-101
Phosgene
Water
80
Ambient
25 - 50
25
3
Yes
45
3
7,500
1970
0.019
1,400
0.0035
100
100
17-8
F
F-102
Reactor Fumes
87. Caustic
100
150
200
55 (ea)
2 in serieSj 6'
Yes
55
72
139.271
1966 - 1972
0.449
130,000
0.419
99.9
99 9
17-2
I
F-105
HCl
Water
17-8
E
F-101
Phosgene
87. Caustic
190
125
2000
76
4
Yes
76
48
44,318
1966 - 1972
0.142
57,700
0
0.186
100
100
17-2
E
F-102
TDI Off-Gas
107. NaOtf
19
<50° F
(4600)
11
1. 3
Yes
50
4
199,000
1968
0.498
10,600
400,000
(0.97)*
100
100
7
100
28
35
5 and 8
Yes
70
6
293,000
1964
0.733
229,250
0.573
100
100
17-3
F
F-102
Reactor Fumes
107. Caustic
190
125
2000
81
4'
Yes
81
48
38,630
1972
0.057
45,000
0
0 067
100
100
*Proflt of 0.970/11). isucyanatc from sale of HCl.
-------
TABLE TDI-IV
ABS ORBER/S GRUBBERS
EPA Code No. for plant using
Flow Diagram (Fig. TDI-1) Stream I. D.
Device 1. D. No.
Control Emission of
Scrubbing/Absorbing Liquid
Type - Spray
Packed Column
Tray Column
Scrubbing/Absorbing Liquid Rate - GPM
Design Temperature (Operating Temperature) - 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" - $
Installed Cost - c/lb. Isocyanate
Operating Cost - Annual - S (1972)
Value of Recovered Product - $/Yr.
Net Operating Cost - c/lb.
Efficiency - 7. - SE
Efficiency - 7. - SERR
ABS ORBER /S GRUBBERS
EPA Code No. for plant using
Flow Diagram (Fig. TDI-1) Stream I. D.
Device I. D. No.
Control Emission of
Scrubbing/Absorbing Liquid
Type - Spray
Packed Column
Tray Column
Scrubbing/Absorbing Liquid Rate - GPM
Design Temperature (Operating Temperature) - 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" - S
Installed Cost - c/lb. Isocyanate
Operating Cost - Annual - S (1972)
Value of Recovered product - S/Yr.
Net Operating Cost - c/lb.
Kfficiency - 7. - SK
Efficiency - '/, - SKRR
CATALOG
17-3
E
F-101
Phosgene
107. Caustic
X
400
150
200
62 (ea)
2 in series 7
Yes
62
84
92 , 905
1972
0.139
99,000
0
0.148
100
100
17-6
E
F-101
Phosgene
87. NaOH
X
50
140
65
24.5
2
No
88,487
1965 - 1970
0.22
6620
0
0.016
100
98.1
OF EMISSION CONTROL DEVICES
ISOCYANATES
17-4
F
F-102
Reactor Gas
107. NaOH
X
100
Ambient
13
30
2
No - to sump
Ground
8 ft.
34 , 700
1969 - 1971
0.13
41,900
0
0.16
100
100
17-6
E
F-101
CO and Phosgene
107. Caustic
(3)
X
25 1800
104 102
109 ?
53.5 57.7
2 7
No Yes
130
12
655,245
1965 - 1971
1.64
239,750
0
0.60
COC12 100, Toluene 0
78.2
17-9
I
F-101
HC1 & Phosgene
107. Caustic
(2)
X
X
3000 1500
Ambient Ambient
(140) ( 140)
22 32
7 7
Yes Yes
Ground
10
1,122,000
1966 - 1970
0.66
218,000
0
0 128
99 9+
99.9+
17-7
E
F-101
Phosgene
187. Caustic
(4)
X
1900 1200
Ambient Ambient
5000 5000
38.3 27.7
7 7
Yes Yes
160 160
30 30
568,000
1971
0.54
241,600
0
0.23
99+
88. 1
Page 2 of 3
17-9
Aniline
Water
X
110
100 - 133
9
2
Yes
50
6
2000
1966 - 1970
0.001
1000
0
0 0006
99.9+
99 9+
17-10
E
F-101
Phosgene
207. Caustic
X
300
113
(700 - 1000)
16, 20
3 , 9
No
240.000
1965
0.40
185,000
0
0.31
HC1 51.4, COC12 73.
66
17-6
F
F-102
Ami ne s
N. A.
Condenser
N. A.
300°
78
N. A.
N. A.
No - to sump
Ground
3' x 5'
9600
1970
0.024
1200
0
0 003
100
100
17-10
I
F-105
HC1
Limestone
Limestone Absorbing Pit
4224 PPH Limestone
Ambient
2945
2'
15' x 15'
Yes
20
10
200,000
1963 - 1965
0.33
211,000
0
0.351
9 99.7
99.7
-------
TABLE TDI-III
INCINERATION AND DISPERSION DEVICES
EPA Code No. for plant using
Flow Diagram (Fig. TDI-1) Stream 1. D.
Device I. D. No.
Type of Compound Incinerated
Type of Device
Material Incinerated, Lb./Hr. (SCFM)
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" - S
Installed Cost - c/lb. Isocyanate/Yr.
Operating Cost - Annual - $/Yr.
Operating Cost - c/lb.
Efficiency - 7. - CCR
Efficiency - 7. - SERR
17-6
G
F-103
Heavy Isocyanate Residuals
Pit Incinerator
433
Ground TM scharge
36,739
1967
0.092
10,560
0.026
100
100
CATALOG OF EMISSION CONTROL
ISOCYANATES
17-6'
A
F-104
.s Ethanol and H2
Flare
120
Gas
1.25 MM est.
175
332,019
1966
0.83
9,340
0.023
100
100
DEVICES
17-7
A
F-104 (3)
CO and Phosgene
Dilution Stack
(5000)
None
160
(D
(D
(D
(D
(D
0 (2)
0 (2)
Page 3 of 3
17-8
G
F-103
Heavy Isocyanate Residuals
Incinerator
8300
Nat. Gas
7
No Data
No Data
No Data
No Data
No Data
No Data
No Data
No Data
17-10
A
F-104
Phosgene Decomp
Flare
1000
None
110'
3500*
1963
0.006
600*
0 001
100
9.3
Off-Gas
*Prorated
-------
EXPLANATION OF NOTES
TABLE TDI-IV
CATALOG OF EMISSION CONTROL DEVICES
ISOCYANATES
1. One column of two different diameters, packed vith pall rings.
2. Two sets of two columns in series. Flow evenly split between the two
sets. Costs are for entire system.
3. Two columns in series. Part of the gas flows thru both columns, the
rest goes to the second column only.
4. Two columns and stacks in parallel. Costs are for both systems.
-------
1088
0
TABLE TDI-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
1088
1800
2120
1032
NOTE;
All capacities in millions of Ibs./year.
100
10
-------
TABLE TDI-VI
EMISSION SOURCE SUMMARY
TON/TON ISOCYANATE
Emission
Hydrocarbons
Participates & Aerosols
NOX
S°x
CO
Source
Phosgene
Decomposer
0.001134
0.000033
0
0
0.004298
Isocyanate
Scrubber
Vent
0.000032
0.000014
0
0
0.001159
Residual Gas
Scrubber Vent
0.000015
TR
0
0.000015
0.077237
Miscellaneous
Vents
TR
0.000383
0
0
0
Total
Plant Flare
0 0.001181
0.000249 0.000679
0 0
0 0.000015
0 0.082694
-------
TABLE TDI-VII
Chemical
Process
Increased Capacity
Pollutant
Hydrocarbons
Aerosols
N°x
S0x
CO
Isocyanates
Phosgenation
by 1980 1032
Emissions Lb
0.001181
0.000679
0
0.000015
0.082694
WEIGHTED EMISSION RATES
MM Lbs./Year
Increased Emissions
./Lb. MM Lbs./Year
1.22
0.700
0
0.015
85.3
Weighting
Factor
80
60
40
20
1
Weighted Emissions
MM Lbs./Year
97.6
42.0
0.0
0.3
85.3
Significant Emission Index • 225.2
-------
Appendix 1,11, & I
-------
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 3986
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 Chemicars 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
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
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
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
-------
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.
-------
-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, diyulged, 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.
-------
-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 durine power failures ;or
other emergencies should be shown, identified
by letter and labeled "emergency".
-------
—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 Glaus units associated with
process need not be shown. Stream to Glaus
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.
-------
-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
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 lbs/hr., and about
8,000 Ibs is vented over a 15 minute period."
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?
-------
-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.4. 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.
-------
OMB Approval Number 158 S 72019
This example questionnaire has been
completed for a fictitious company
•n«4 nirst/* AC o
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 O.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
AIR
COMPRESSION
FUEL
PYRROLIDINE
STORAGE
PYRROLE
STORAGE
HEAT EXCHANGERS
&
FLUID BED CATALYTIC
REACTORS
EMERGENCY VENT TO
'' INCINERATOR 102
STACK
(
L^-*
\_
©
PRODUCT
DRUM
RECYCLE
PRODUCT
RECOVERY
&
PURIFICATION
PYRROLIDONE
STORAGE
FILTER
SCRUBBER
101
DISCHARGED
WATER - WASHED
SOLIDS
WATER RECYCLE
HEAVY
ENDS
©
STACK
a
(-•
o
o
o.
M-
a>
H
WATER
DISCHARGE
INCINERATOR
102
50
A
0
•O
O
O
0
(B
IB
O
X
H-
O.
P)
n
a.
0
f
n
o
OQ
i
o
•o
VJ
9
0
if
O
O
a
IB
ID
o
o
a>
I
u>
-------
-4-
II.
Process. (Continued)
3. Raw materials and products
Raw materials
Name Quantity
130.000.000 Ibs/vr.
Pyrrolidine
Composition
pyrrolidine
other amines
98%
2%
Product and by-products
Name Quantity Composition
Pyrrole 80.000.000 Ibs/yr. 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.
-------
-6-
(a)
III. l.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 letter
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
-------
III.1.Emissions (composition and flow).
Six copies provided
this section
Stream flow shown on block diagram by letter
Flow 10*000 SCMTemperature 110°F Pressure 25 PSIG
Component
Name
Particulate
Nitrogen
Oxygen
Carbon Monoxide
Carbon Dioxide
Hydrogen
Water
Various Amines
Nitrogen Oxides
Formula
*
N2
°2
CO
co2
H2
H20
**
NO,
* Particulate matter should be
contains cobalt and chromium
less than 5 microns
; 5% less
State
Solid
Gas
Gas
Gas
Gas
Gas
Vapor
Vapor
Gas
described as fully as possible.
on al'iulfla base. 100Z IP^B »-han
than 1 micron.
Average amount
or composition
150 Ibs./hour
83.8 Vol. %
1.4 "
4.1 "
1.4 "
2.1 "
7.1 "
0.1 "
300 VPPM
Catalyst Dust (compos!
Composition
Range
100-200 Ibs./hour
80-85%
1-2%
3-5%
1-2%
2-2.5%
6.5-7.5%
0.05-0.2%
200-500 VPPM
tion is nroori^t'Ofv^
15 mirrnna- 60X IPRB than 10 nHfi-nna- 9OT
**-£pmposition unknown - mixture of feed, products and^ther amines.
-------
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.
4. 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.
-------
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.
-------
1. 1. Emissions (composition and flow).
Stream flow shown
on block diagram by letter
-6-
(c)
C
i
Six copies provided
this section
1. Flow 10.000SCFM 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
co2
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 "B1
-------
III. Continued For stream flow shown on block diagram by letter
2. Composition variation.
See "BV
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—
(c)
III. Continued For stream flow shown on block diagram by letter_
5. Sampling procedure.
a. Participates 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.
Amlne, 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/np_ Has the odorous material been chemically identified?
Yes/no What is it? Amine compounds.
-------
(fc
III. 1 .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.
-------
III. Continued For stream flow shown on block diagram by letterD
2. Composition variation.
Not applicable - unknown - never analyzed,
3. Production rate during sampling.
See "B"
Method used to determine composition and flow.
Rotameter in liquid line for flow. Composition unknown.
-------
-e-
(d)
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 A50°F Pressure 0 PSIG
Component
Name
Particulate
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 "D1
-------
f*-
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"
4. Method used to determine composition and flow.
Calculation based on incinerator vendor's specifications, guarantees
and laboratory tests.
-------
(e)
III. Continued For stream flow shown on block diagram by letter
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.
+ 10X
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/ji2 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.
r
GAS TO
STACK
GAS
DISTRIBUTOR
MIST
ILIMINATOR
Multi-nozzle spray tower manu-
factured by Rebburcs Corp.
Model No. 10,000-W
Water rate: 100 GPM
Gas rate: 10.00Q SCFM
Temperature: 100°F.
Pressure: Atmospheric
Gas AP: 8 in, H2
-------
-11-
(a)
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
Yes
(b) Check list. Mark whether items listed are included in total
cost included in IV.2.a. Do not give dollar value -
No
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
Yea
X
X
X
No
X
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 *
(c) Labor (No Additional Operators)
(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)
(g) Other disposal
(h) By-product or product recovery
Total operating costs
CREDIT
$ 68.000
10,000
14,000
20,000
$89,000 )
$ 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.
TO STACK
CONVECTIVE
CTION
RADIANT
SECTION
PR!
STEAM
SECONDARY
ORKT
PUMP
HEAVY ENDS
-O
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-
0.)
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-
(a)
IV. Continued For device shown.on block diagram by number 101
Yes
(b) Check list. Mark whether items listed are included in total
cost included in IV.2.a. Do not give dollar value -
No
Cost
Facilities outside
battery limits*
Explanation
X
X
X
X
X
X
X
X
X
X
Site development Additional foundation reauired 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-
(b)
IV. Continued For device shown on block diagram by number 102
Yes
No
Was outside engineering contractor used?
Was cost included in capital cost?
X 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 $ 5,000
(b) Chemicals
(c) Labor (\ man per shift - excludes supervision & 7,000
overhead)
(d) Maintenance (labor & materials) 40,000
(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)
(g) Other disposal
(h) By-product or product recovery CREDIT- STEAM ($100,000;
Total operating credit $ 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 2 ft
3. Gas temperature stack exit 100 °_F
4. Stack flow * SCFM(70°F & 1 Atm.)
For stack or vent shown on block diagram by letter E .
1. Stack height 60 Ft.
2. Stack diameter 3 Ft.
3. Gas temperature stack exit 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.
-15-
No. of
tanks
3
4
composition
Pyrrolidine
(CH2)4NH
Pyrrole
(CH>4NH
capacity
temp. (each)
Ambient 100,000
gal. (ea)
Ambient 100,000
gal. (ea)
approximate
turnovers
per year
50
25
method of vapor conservation
None, vents to air
ti
Pyrrolidone Ambient 100,000
(CH)2CH2CONH gal.(ea)
25
-------
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
8
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 of
New
Units
11 - 12
0
2
M
ro
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
77.9
28.1
1
Primary
125
21.5
22.4
15.3
1
Secondary
125
37.3
22.4
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
55.3
40.9
21.6
1
Rounded
80
60
40
20
1
-------
Chemical_
Process
Increased Capacity_
Table 2. Weighted Emission Rates
Pollutant
Hydrocarbons
Particulates
NOX
sox
CO
Increased Emissions Weighting
Emissions, Lbs./Lb. Lbs./Year Factors
80
60
40
20
1
Weighted Emissions
Lbs./Year
-p-
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,
2» 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.
20 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
completely 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:
lo 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.
20 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:
C2H4 + 3 02 ^ 2 C02 +2 H20
Thus, this device would have a CCR of 265/342 or 77.5%
Assuming that one pound of nitric oxide is formed in the 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
2« 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 QOI
Pounds out
Actual Weighted
0
14.2 852
1 40
0
66.5 66.5
958.5
8000
x
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
= 99.57,
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 HCl
This is complete combustion, by definition, therefore, the CCR is
1007oo However, (assuming no oxides of nitrogen are formed), the SERR
is less than 1007» because 72.5 Ibs. of HCl are formed. Hence,
considering HCl as an aerosol or particulate;
SERR = 100 x 80 - 72.5 x 60
100 x 80
x 100 = 45.57,
The conclusion from this final example, of course, is that it is
an excellent combustion device but a very poor pollution control device,
unless it is followed by an efficient scrubber for HCl removal.
Example 4 - The stacks of two hydrogen cyanide incinerators, each
burning 100 pounds per unit time of HCN are sampled. Neither has any
carbon monoxide or particulate in the effluent. However, the first is
producing one pound of NOX and the second is producing ten pounds of
NOX in the same unit time. The assumed reactions are:
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V-4
Efficiency of Pollution Control Devices
Significance of Emission Reduction Rating (SERR) (continued)
4 HCN + 5 02 " > 2 H20 + 4 C02 + 2 N2
N2 (atmospheric) + X02 V 2 NOX
Thus, CCRi = 1007» and CCR2 = 100% both by definition.
However, SERRi = 100 x 80 - 1 x 40
1 100 x 80
and SERRo = 100 x 80 - 10 x 40
2 - 100 x 80 - x 10° = 95/°
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.
20 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 ln_
specific pollutant in x UU
The second rating proposed is an SERR, defined exactly as in the case
of incinerators.
Two examples will illustrate these ratings.
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V-5
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
and SERR = (50 x 20) - (1 x 20 + 2 x 80)
(50 x 20)
x 10°
= 1000 - 180
1000
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TECHNICAL REPORT DATA
(Please read Inunctions on the reverse before completing)
1. REPORT NO.
EPA-450/3-73-Q05-b
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
Survey Reports on Atmospheric Emissions from the
Petrochemical Industry, Volume II
5. REPORT DATE
April 1974 (date of issue)
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
J. W. Pervier, R. C. Barley, D. E. Field, B. M. Friedmar
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: Carbon Disulfide, Cyclohexanone,
Dimethyl Terephthalate and Terephthalic Acid, Ethylene, Ethylene Dichloride via
Direct Chlorination, Formaldehyde Manufacture with Silver Catalyst, Glycerol,
Hydrogen Cyanide, and Isocyanates. 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
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI r'icld/Group
Air Pollution
Carbon Monoxide
Hydrocarbons
Nitrogen Dioxide
Sulfur Dioxide
Carbon Disulfide
Cyclohexanones
Ethylene
Formaldehyde
Glycerol
Hydrogen Cyanide
Isocyanates
Petrochemical Industry
Particulates
Dimethyl Terephthalate
Terephthalic Acid
Ethylene Dichloride
1-2 Dichloroethane
Toluene Diisocyanate
7A
7B
7C
13B
13H
13. DISTRIBUTION STATEMENT
Release Unlimited
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
329
20. SECURITY CLASS (Tins page)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
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