EPA-450/3-73-005-C
APRIL 1974
SURVEY REPORTS
ON ATMOSPHERIC EMISSIONS
FROM THE PETROCHEMICAL
INDUSTRY
VOLUME III
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-C
SURVEY REPORTS
ON ATMOSPHERIC EMISSIONS
FROM THE PETROCHEMICAL
INDUSTRY
VOLUME III
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-C
11
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PETROCHEMICAL AIR POLLUTION STUDY
INTRODUCTION TO SERIES
This document is one of a series of four volumes prepared for the
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 v?ork 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)
Maleic Anhydride
Nylon 6
Nylon 6,6
Oxo Process
Phenol
High Density Polyethylene
Low Density Polyethylene
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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II. Discussion
A. Petrochemicals to be Studied
There are more than 200 different petrochemicals in current
production in the United States. Many of these are produced by 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 (I)
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 vas submitted by Air Products to the Environmental
Protection Agency. It had been decided that completion of this
questionnaire by industry would provide much of the information
necessary to the performance of the study. The nature and format of
each question was reviewed by EPA engineers and discussed vith Air
Products engineers to arrive at a modified version of the originally
proposed questionnaire.
The modified questionnaire was then submitted to and discussed
with an Industry Advisory Committee (IAC) to obtain a final version for
submission to the Office of Management and Budget ''OMB) for final
approval, as reauired prior to any U. S. Government survey of national
industries. The following listed organizations, in addition to the
EPA and Air Products, were 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
New Jersey
Texas
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- 4 -
The questionnaire, along with a detailed instruction sheet and
an example questionnaire (which had been completed by Air Products
for a fictitious process that was "invented" for this purpose) were
submitted to the OMB for approval. In due course, approval was
received and OMB Approval Number 158-S-72019 was assigned to the
questionnaire. Copies of the approved instruction sheet, example
questionnaire are included as Appendix II of this report.
The questionnaires were mailed in accordance with the mailing
list already discussed and with a cover letter that had been prepared
and signed by the EPA Project Officer. The cover letter was typed in
a manner that permitted the insertion of the name and address of the
receipient at the top of the first page and the name of the process,
the plant location and an expected return date at the bottom of the
first page. A copy of this letter of transmittal is also included in
Appendix II.
Understandably, because of the dynamic nature of the petrochemical
industry, about 10 percent of the questionnaires were directed to plants
which were no longer in operation, were still under construction, were
out-of-date processes or were too small to be considered as typical.
This did not present a serious problem in most cases because (a) 100
percent of the plants were not surveyed and (b) the project timing per-
mitted a second mailing when necessary. Appendix III tabulates the
number of questionnaires incorporated into each study.
One questionnaire problem that has not been resolved is confiden-
tiality. Some respondents omitted information that they consider to
be proprietary. Others followed instructions by giving the data but
then marked the sheet (or questionnaire) "Confidential". The EPA is
presently trying to resolve this problem, but until they do the data
will be unavailable for inclusion in any Air Products' reports.
D. Screening Studies
Completed questionnaires were returned by the various respondents
to the EPA's Project Officer, Mr. L. B. Evans. After reviewing them
for confidentiality, he forwarded the non-confidential data to Air
Products. These data form the basis for what has been named a "Survey
Report". The purpose of the survey reports being to screen the various
petrochemical processes into the "more" and "less - significantly
polluting processes". These reports are included as appendicies to
this report.
Obviously, significance of pollution is a term which is difficult
if not impossible to define because value judgements are involved.
Recognizing this difficulty, a quantitative method for calculating a
Significant Emission Index (SEI) was developed. This procedure is
discussed and illustrated in Appendix IV of this report. Each survey
report includes the calculation of an SEI for the petrochemical that
is the subject of the report. These SEl's have been incorporated into
the Emissions Summary Table that constitutes part of this report. This
table can be used as an aid when establishing priorities in the work
required to set standards for emission controls on new stationary
sources of air pollution in accordance with the terms of the Clean Air
Amendments of 1970„
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The completed survey reports constitute a preliminary data bank on
each of the processes being studied. In addition to the SEI calculation,
each report includes a general introductory discussion of the process,
a process description (including chemical reactions), a simplified
process (Block) flow diagram, as well as heat and material balances.
More pertinent to the air pollution study, each report lists and
discusses the sources of air emissions (including odors and fugitive
emissions) and the types of air pollution control equipment employed.
In tabular form, each reports summarizes the emission data (amount,
composition, temperature, and frequency); the sampling and analytical
techniques; stack numbers and dimensions; and emission control device
data (types, sizes, capital and operating costs and efficiencies).
Calculation of efficiency on a pollution control device is not
necessarily a simple and straight-forward procedure. Consequently,
two rating techniques were established for each type of device, as
follows:
1. For flares, incinerators, and boilers a Completeness of Combustion
Rating (CCR) and Significance of Emission Reduction Rating (SERR)
are proposed.
2. For scrubbers and dust removal equipment, a Specific Pollutant
Efficiency (SE) and a SERR are proposed.
The bases for these ratings and example calculations are included
in Appendix V of this report.
E. In-Depth Studies
The original performance concept was to select a number of petro-
chemical processes as "significant polluters", on the basis of data
contained in completed questionnaires. These processes were then to
be studied "in-depth". However, the overall time schedule was such
that the EPA requested an initial selection of three processes on the
basis that they would probably turn out to be "significant polluters".
The processes selected in this manner were:
lo The Furance Process for producing Carbon Black-
2. The Sohio Process for producing Acrylonitrile.
3. The Oxychlorination Process for producing 1,2 Dichloroethane
(Ethylene Bichloride) from Ethylene.
In order to obtain data on these processes, the operators and/or
licensors of each were approached directly by Air Products' personnel.
This, of course, was a slow and tedious method of data collection because
mass mailing techniques could not be used, nor could the request for
data be identified as an "Official EPA Requirement". Yet, by the time
that OMB approval was given for use of the Industry Questionnaire, a
substantial volume of data pertaining to each process had already been
received. The value of this procedure is indicated by the fact that
first drafts of these three reports had already been submitted to the
EPA, and reviewed by the Industry Advisory Committee, prior to the
completion of many of the survey reports.
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In addition, because of timing requirements, the EPA decided that
three additional processes be "nominated" for in-depth study. The
chemicals involved are phthalic anhydride, formaldehyde and ethylene
oxide. Work on these indicated a need for four additional in-depth
studies as follows:
1. Air Oxidation of Ortho-Xylene to produce Phthalic Anhydride.
2. Air Oxidation of Methanol in a Methanol Rich Process to
produce Formaldehyde over a Silver Catalyst.
3. Air Oxidation of Methanol in a Methanol-Lean Process to
produce Formaldehyde over an Iron Oxide Catalyst.
4o Direct Oxidation of Ethylene to produce Ethylene Oxide.
Drafts of these have been submitted to the EPA and reviewed by the
Industry Advisory Committee. The phthalic anhydride report also includes
a section on production from naphthalene by air oxidation, a process
which is considered to be a significant polluter in today's environment
but without significant growth potential.
These seven in-depth studies will be separately issued in final
report form, under Report Number EPA-450/3-73-006 a, b, c, etc.
An in-depth study, besides containing all the elements of the
screening studies, delves into questions such as "What are the best
demonstrated systems for emission reduction?", "What is the economic
impact of emission control on the industry involved?", "What deficiencies
exist in sampling, analytical and control technology for the industry
involved?".
In striving to obtain answers to these questions, the reports
include data on the cost effectiveness of the various pollution control
techniques source testing recommendations, industry growth projections,
inspection procedures and checklists, model plant studies of the
processes and descriptions of research and development programs that
could lead to emission reductions.
Much of the information required to answer these questions came
from the completed Industry Questionnaires and the Process Portfolios.
However, the depth of understanding that is required in the preparation
of such a document can only be obtained through direct contact with the
companies that are involved in the operation of the processes being
studied. Three methods for making this contact were available to Air
Products. The first two are self-evident, as follows: Each
questionnaire contains the name, address and telephone number of an
individual who can provide additional information. By speaking with
him, further insight was obtained into the pollution control problems
that are specific to the process being studied; or through him, a
visit to an operating plant was sometimes arranged, thus achieving a
degree of first hand knowledge.
However, it was felt that these two techniques might fall short of
the level of knowledge desired. Thus, a third, and unique procedure was
arranged. The Manufacturing Chemists Association (MCA) set up, through
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its Air Quality Committee (AQC), a Coordinating Technical Group
(CTG) for each in-depth process. The role of each CTG was to:
1. Assist in the obtaining of answers to specific questions.
2. Provide a review and commentary (without veto power) on
drafts of reports.
The AQC named one committee member to provide liaison. In
several cases, he is also one of the industry's specialists for the
process in question. If not, one other individual was named to
provide CTG leadership. Coordination of CTG activities was provided
by Mr. Howard Guest of Union Carbide Corporation who is also on the
EPA's Industry Advisory Committee as the MCA Representative. CTG
leadership is as follows:
Chemical AQC Member Other
Carbon Black C. B. Beck None
Cabot Corporation
Acrylonitrile W. R. Chalker R. E. Farrell
Du Pont Sohio
Formaldehyde W. B. Barton None
Borden
Ethylene Bichloride W. F. Bixby None
B. F. Goodrich
Phthalic Anhydride E. P. Wheeler Paul Hodges
Monsanto Monsanto
Ethylene Oxide H. R. Guest H. D. Coombs
Union Carbide Union Carbide
F. Current Status
Survey Reports on each of the 33 processes that were selected for
this type of study have been completed, following review of the drafts
by both the EPA and the Petrochemical Industry. These reports constitute
the subject matter of this report.
In-depth studies of the seven processes mentioned above have been
completed in draft form, submitted to the EPA for initial review,
discussed in a public meeting with the Industry Advisory Committee and
re-submitted to the EPA in revised form. They are currently receiving
final EPA review and will be issued as final reports, following that
review.
The EPA has now selected two additional processes for in-depth study
and work on these is currently in progress. They are:
1= High Density Polyethylene via the Low and Intermediate Pressure
Polymerization of Ethylene.
2. Low Density Polyethylene via the High Pressure Polymerization
of Ethylene.
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III. Results
The nature of this project is such that it is not possible to report
any "results" in accordance with the usual meaning of the word. Obviously,
the results are the Survey Reports and In-Depth Studies that have been
prepared. However, a tabulation of the emission data collected in the
study and summarized in each of these reports will be useful to the EPA
in the selection of those processes which will be either studied in-depth
at some future date, or selected for the preparation of new source standards,
Such a tabulation, entitled "Emissions Summary Table", is attached.
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IV. Conclusions
As was stated above under "Results", the conclusions reached are
specific to each study and, hence, are given in the individual reports.
Ultimately, some conclusions are reachable relative to decisions on
processes which require future in-depth studies or processes which warrant
the promulgation of new source standards.
A firm basis for selecting these processes is difficult to achieve,
but the data contained in the Emissions Summary Table can be of value in
setting a basis, or selecting processes.
It is imperative, when using the table, to be aware of the following
facts.
1. The data for some processes are based on 100 percent survey of
the industry, while others are based on less than 100 percent
with some as few as a single questionnaire.
2. Some of the reported data are based on stack sampling, others on
continuous monitoring and still others on the "best estimate" by
the person responsible for the questionnaire.
3. Air Products attempted to use sound engineering judgement in
obtaining emission factors, industry capacities and growth
projections. However, other engineering firms, using the same
degree of diligence would undoubtedly arrive at somewhat different
final values.
Thus, the tabulation should be used as a guide but not as a rigorous
comparison of process emissions.
Furthermore, data on toxicity of emissions, odors and persistence of
emitted compounds are not included in the tabulation. In addition, great
care must be used when evaluating the weighted emission rates because of
the wide range in noxiousness of the materials lumped together in the two
most heavily weighted categories. For example, "hydrocarbons" includes
both ethane and formaldehyde and "particulates" includes both phthalic
anhydride and the permanent hardness of incinerated water.
Bearing all of these qualifications in mind, several "top 15" rankings
of processes can be made, as in Tables II through V. Obviously, one of
these tables could be used to select the more significant polluters directly.
Of course, other rankings could be made, such as leading emitters of NOX or
particulates, etc. Using these four tables, however, one analysis might be
that the number of times a process appears in these tables is a measure of
its pollution significance, or in summary:
Appear in 4 Tables
Carbon Black
Low Density Polyethylene
High Density Polyethylene
Cyclohexanone
Polypropylene
Polyvinyl Chloride
Ethylene Oxide
Appear in 3 Tables
Acrylonitrile
Adiponitrile (Butadiene)
Ethylene Dichloride (Oxychlorination)
Dimethyl Terephthalate
Ethylene Dichloride (Direct)
Ethylene
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Appear in 2 Tables Appear in 1 Table
Maleic Anhydride Phthalic Anhydride
Isocyanates Formaldehyde (Iron Oxide)
Phenol Polystyrene
Formaldehyde (Silver) Nylon 6
Nylon 6,6
Vinyl Chloride
Thus, on this basis and in retrospect, it could be concluded that four
of the selected in-depth studies (carbon black, ethylene oxide, and both
low and high density polyethylene) were justified but that three of them
(phthalic anhydride and both formaldehyde processes) were of lesser importance.
On the same basis, seven processes should be considered for future
in-depth studies, namely:
Cyclohexanone
Polypropylene
Polyvinyl Chloride
Adiponitrile (Butadiene Process)
Dimethyl Terephthalate (and TPA)
Ethylene Bichloride (Direct)
Ethylene
Obviously, many alternative bases could be established. It is not
the function of this report to select a basis for initiating future studies
because the priorities of the EPA are unknown. The most apparent of these
bases are the ones suggested by Tables II through V, namely the worst total
polluters, the worst polluters on a weighted basis, the greatest increase
in pollution (total or weighted) or the largest numbers of new plants. In
addition, noxiousness of the emissions (photo-chemical reactivity, toxicity,
odor, persistence) could be considered in making a selection.
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TABLE I
Acetaldehyde via Ethylene
via Ethanol
Acetic Acid via Methanol
via Butane
via Acetaldehyde
Acetic Anhydride via Acetic Acid
Acrylonitrile (9)
Adipic Acid
Adiponitrile via Butadiene
via Adipic Acid
Carbon Black
Carbon Disulfide
Cyclohexanone
Dimethyl Terephthalate (+TPA)
Ethylene
Ethylene Dichloride via Oxychlorination
via Direct Chlorination
Ethylene Oxide
Formaldehyde via Silver Catalyst
via Iron Oxide Catalyst
Glycerol via Epichlorohydrin
Hydrogen Cyanide Direct Process
Isocyanates
Maleic Anhydride
Nylon 6
Nylon 6,6
Oxo Process
Phenol
Phthalic Anhydride via 0-Xylene
via Naphthalene
High Density Polyethylene
Low Density Polyethylene
Polypropylene
Polystyrene
Polyvinyl Chloride
Styrene
Styrene-Butadiene Rubber
Vinyl Acetate via Acetylene
via Ethylene
Vinyl Chloride
Totals
EMISSIONS SUMMARY
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
1
1
2
15
1
8
8
7
5
3
25
3
1
5
3
4
3
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.
2
7
5
1
3
4
2
4
8
5
5
01
1
9
3
4
1
4
07
6
ESTIMATED
Oxides of
0
0
0
0
0
0
5
29
50
0
6
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
t1) CURRENT AIR EMISSIONS,
Nitrogen
.01
.04
.5
.6
.5
.04
.9
.1
.1
.2
.3
.41
.07
.3
.14
TR
6
0
Sulfur Oxides
0
0
0
0
0
0
0
0
0
0
21.6
4.5
0
1.0
2.0
0
0
0.1
0
0
0
0
0.02
0
0
0
0
0
2.6
0
0
0
0
1.2
0
0
0.9
0
0
0
Page
1 of 3
MM LBS./YEAR
Carbon Monoxide Total
0
27
0
14
1.
5.
196
0.
0
0
3,870
0
77.
53
0.
21.
0
0
107.
24.
0
0
86
260
0
0
19.
0
43.
45
0
0
0
0
0
0
0
0
0
0
3
5
14
5
2
8
2
9
5
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
TR
18
.2
Total Weighted ^
86
27
1
3,215
490
253
15,000
1,190
3,200
30
17,544
120
5,700
7,460
1,240
7,650
2,300
6.880
1,955
2,070
1,280
56
231
2,950
90
330
440
1,940
422
160
6,400
6,100
2,950
1,650
5,700
355
870
425
TR
1,460
1,227.6
49.1
94.2
33.9
4,852.6
6,225.9
(7)
110,220 <7>
(1) '-in most instances numbers are based on less than 100% survey. All based on engineering judgement of best current control. Probably has up to 107. lov bias.
(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-450/3-73-006 b for up-to-date information.
-------
TABLE I
EMISSION SUMMARY
ESTIMATED ADDITIONAL *2^
Hydrocarbons ( '
I.
0
0
0
12.
0.
284
0
10.
0
64
0.
77.
73.
14.
110
34.
32.
14.
17.
8.
0
1.
31
0
0
3.
21.
0.
0
210
262
152
20
53
3.
1.
4.
0
26.
1,547.
2
2
73
5
04
2
8
8
2
8
8
6
9
2
86
3
3
1
85
5
3
2
Particulates (*'
0
0
0
0
0
0
0
0
4
0
3
0
0
1
0
0
0
0
0
0
0
0
0
0
3
5
0
0
13
0
6
5
0
0
10
0
0
0
0
0
55
.14
.4
.5
.3
.07
.1
.2
.5
.7
.2
.3
.01
.2
.2
.5
.34
.05
.31
.9
.9
Oxides of
0
0
0.
0
0
0
8.
19.
47.
0.
2.
0.
0
0.
0.
0
0
0.
0
0
0
0
0
0
0
0
0.
0
0.
0
0
0
0
0
0
0.
0
0
TR
0
79.
Ni trogen
04
5
3
5
04
8
03
07
2
15
05
8
1
5
AIR EMISSIONS IN
Sulfur Oxides
0
0
0
0
0
0
0
0
0
0
8.9
1.1
0
0.84
61.5
0
0
0.05
0
0
0
0
0.02
0
0
0
0
0
6.8
0
0
0
0
1.13
0
0
0.18
0
0
0
80.5
1980, MM I.BS./YE
Page 2
AR
of 3
Carbon Monoxide Total
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
1.
0
0.
0
14.
2.
596
19.
62.
0.
1,670
1.
162
118.
77
136
34.
33
81.
34.
8.
0
87
272
3.
5.
18.
21.
134
0
216
267
152.
21.
63
3.
2.
4.
TR
27.
4,351.
2
04
7
15
5
4
54
24
7
2
5
6
9
2
3
2
3
5
47
25
34
5
2
9
Total Weighted (5.6)
-
23
3
7
6
6
2
8
2
2
1
1
2
1
1
17
21
12
1
4
2
134
96
0
2
0
980
60
,000
779
,010
30
,200
30
,260
,040
,430
,800
,740
,650
,250
,445
700
0
225
,720
194
318
325
,704
,100
0
,200
,300
,190
,640
,840
225
170
360
TR
,170
,213 (?)
Acetaldehyde via Ethylene
via Ethanol
Acetic Acid via Methanol
via Butane
via Acetaldehyde
Acetic Anhydride via Acetic Acid
Acrylonltrile (9)
Adipic Acid
Adiponitrile via Butadiene
via Adipic Acid
Carbon Black
Carbon Disulfide
Cyclohexanone
Dimethyl Terephthalate (+TPA)
Ethylene
Ethylene Bichloride 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
Lov Density Polyethylene
Polypropylene
Polystyrene
Polyvinyl Chloride
Styrene
Styrene-Butadiene Rubber
Vinyl Acetate via Acetylene
via Ethylene
Vinyl Chloride
Totals
(1) In most instances numbers are based on less than 100% survey. All based on engineering judgement of best current control. Probably has up to 107 lov bias.
(2) Assumes future plants will employ best current control techniques.
(3) Excludes methane, includes H2S and all volatile organics.
(4) Includes non-volatile organics and inorganics.
(5) Weighting factors used are: hydrocarbons - 80, particulates - 60, NOX - 40, SOX - 40, and CO - 1.
(6) Referred to elsevhere in this study as "Significant Emission Index" or "SEI".
(7) Totals are not equal across and dovn duw to rounding.
(9) See sheet 1 of 3.
-------
TABLE I
Acetaldehyde via Ethylene
via Ethanol
Acetic Acid via Methanoi
via Butane
via Acetaldehyde
Acetic Anhydride via Acetic Acid
Acrylonitrile (9)
Adipic Acid
Adiponitrile via Butadiene
via Adipic Acid
Carbon Black
Carbon Dlsulflde
Cyclohexanone
Dimethyl Terephthalate (-KTPA)
Ethylene
Ethylene Bichloride via Oxychlorination
via Direct Chlorination
Ethylene Oxide
Formaldehyde via Silver Catalyst
via Iron Oxide Catalyst
Glycerol via Kpichlorohydrin
Hydrogen Cyanide Direct Process
Igocyanates
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
Styrine-Butadiene Rubber
Vinyl Acetate via Acetylene
via Ethylene
Vinyl Chloride
Emissions
Total hy 1980
2.3
27
0.05
54
22
10.8
980
50
128.8
1.1
5,730
6.3
310
265
94
253
63
120
212.5
85
25
0.5 (10)
175
566
4.7
10.8
43
46
186
47
297
343
190
43
137
7.4
14
9.8
TR
45
EMISSION'S SUMMARY
("9, MM I.bs./Yenr
Total Weighted (s) by 1980
182
27
3
3,215
1,470
313
38,000
1,970
6,210
bO
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,(>30
Page 5 ol
Totals
10,605
(7)
244,420
(7)
Ksl i m;lt i'il Number of New Plants
__ _ ( 1973 - 1980) _
0
4
0
3
3
5
7
4
3
13
2
10
8
21
8
10
15
40
12
1
0
10
6
10
10
6
11
6
0
31
41
32
23
25
9
4
1
4
10
Esl im.il rd Cnp.ici ty
MM l.bs./YP.'lr
1 , 1 60
91)6
400
1 .020
875
1 .705
1 ,165
1 ,430
435
280
3,000
871
1 ,800
2,865
22,295
4,450
5,593
4,191
5,914
1 ,729
245
412
1 ,088
359
486
1 ,523
1 ,727
2,3»3
720
603
2,315
5,269
1 , 1 60
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
1 1
6
9
3
2
1
3
3
4
1
8
21
5
h
8
10
r)
2
13
,41)0
9h(.
,800
500
,015
,100
,700 (8)
,200
845
550
,000 (8)
,100
,600
,900
,000
,250 (8)
,540
,800 (8)
,000
,520 (8)
380
202
,120
720
,500
,000
,000
,200
,800 (8)
528
,500
,100
,800
,700
,000
,000
,230
356
,200
,000
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
In most instances numbers are based on less than 1007. survey. All based on engi neer i nj; judgement ol" best eurrenl control. Probably has up in 107 low bias.
Assumes future plants will employ best current control techniques.
Excludes methane, includes H2S and all volatile organics.
Includes non-volatile organics and inorganics.
Weighting factors used are: hydrocarbons - 80, particulars - 60, NOX - 40, SOX - 20,
Referred to elsewhere in this study as "Significant Emission Index" or "SEI".
Totals are not equal across and down due to rounding.
By 1985.
See sheet 1 of 3
Due to anticipated future shut clown of marginal plants.
-------
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.
-------
Maleic Anhydride
-------
Table of Contents
Section Page Number
I. Introduction MA-1
II. Process Description MA-2
III. Plant Emissions MA-3
IV. Emission Control MA-5
V. Significance of Pollution MA-7
VI. Maleic Anhydride Producers MA-8
List of Illustrations and Tables
Flov Diagram Figure MA-I
Net Material Balance Table MA-I
Gross Heat Balance Table MA-II
National Emissions Inventory Table MA-HI
Catalog of Emission Control Devices Table MA-IV
Number of New Plants by 1980 Table MA-V
Emission Source Summary Table MA-VI
Weighted Emission Rates Table MA-VII
-------
MA-1
I. Introduction
Maleic Anhydride is a white crystalline solid that is normally marketed
in tablet form although some producers have a substantial bulk market in tank
cars or wagons. Its major use, accounting for about 50% of total production,
is in the formulation of polyester resins. Additionally, it is an inter-
mediate in the production of fumaric acid and agricultural pesticides.
Alkyd resins and other miscellaneous uses account for the remaining 25% of
production.
With one exception, all U. S. maleic anhydride (direct) production is
based on the vapor phase oxidation of benzene, as licensed by Scientific
Design. Petro-tex, however, utilizes a feedstock of mixed butylene at
their Houston plant. Lower yields and higher investment costs apparently
tend to off-set the economic advantage offered by the cheaper C^ charge
material. Also, minor quantities of maleic anhydride are produced as a
by-product with phthalic anhydride when the naphthalene based process is
used.
-------
MA-2
II. Process Description
Benzene in the presence of a suitable catalyst may be oxidized to
raaleic anhydride. The primary overall, reaction is:
CH CH H.C — C
|i I + 9/2 02 - >• |1 ^0+2 H20 + 2 C02
CH CH HC—C
Benzene Maleic Anhydride
78.11 98.06
Standard commercial practice is to conduct the reaction in the vapor
phase, utilizing a V205 based catalyst.
Benzene is either carbureted with air and preheated or vaporized and
then mixed with an excess of preheated air prior to being admitted to a
multi-tubular catalytic reactor. The vapors pass downward (or upward in
some cases) through the tubes, which contain a pelleted V20c catalyst, and
exit the reactor at a temperature in the range of 750 to 850° F. The very
large heat of reaction (up to 2,600 BTU/lb. of MAN) is removed by the heat
of transfer fluid - molten salt or boiling mercuy - that circulates around
the outside of the tubes, and by air preheat.
The effluent vapors, consisting of maleic anhydride, maleic acid, carbon
oxides, water and benzene, are cooled and then passed through a partial
condenser and separator, where the bulk of the maleic anhydride is separated
from the non-condensibles . The overhead material from the separator still
contains some maleic anhydride, this material is recovered thru absoprtion in
aqueous (or non-aqueous) solvents and recovered as maleic acid.
The crude maleic acid is converted to the anhydride by dehydration,
usually by azeotropic distillation. This material is combined with the
maleic anhydride recovered from the partial condenser and purified by vacuum
and/or azeotropic distillation. The product is then either tableted or flaked
and packaged or marketed in bulk.
The above described processing scheme is consistent with the presented
flow diagram, Figure I (which see), and typical of the methods used by domestic
producers. However, the reader should be cognizant of the fact that a wide
variety of product recovery and purification techniques exist within the
industry today.
-------
MA-3
III. Plant Emissions
A. Continuous Air Emissions
1. Product Recovery Condenser Vent (Scrubber Exhaust)
This stream is the only source of emissions reported by four
of the seven respondents. Thus, it seems reasonable to categorize
it as the single most important emission source for the subject
process. The two main components, of a polluting nature, are
carbon monoxide and benzene. The concentration of carbon monoxide
varies from .87 Ibs. CO/lb. of MAN to .44 Ibs./lb, vhile the
concentration of benzene varies from .20 Ibs. benzene/lb. of MAN
to .06 Ibs./lb. As mentioned in the process description section
of this report, the vapors from the condenser are vented to a
scrubber for recovery of uncondensed maleic anhydride, prior to
venting the effluent gases to the atmosphere. Many plants route
streams from other sections of the unit to this same scrubber in
order to minimize emissions and affect economy of operation through
the utilization of a single large scrubber rather than several
smaller ones. Unfortunately, lack of data preclude calculation of
scrubber efficiency. A summary of emissions from this source are
listed in Table III.
2. Product Flaking, Pelleting, Packaging and Storage
Three respondents report emissions from this type of operation.
Respondent 18-2 reports emitting .0002 Ibs./lb. of maleic anhydride
from his pelleting and packaging operation. Respondent 18-6 reports
'losing1 0,6 Ibs./hr. of maleic anhydride from his product storage
area, however, a scrubbing device removes all of that material from
the vent stream before atmospheric discharge. Respondent 18-7 also
reports emissions from the subject area, again he states vater
scrubbing results in the complete removal of pollutants from the
vent.
3. Aqueous Waste Incinerator Flue Gas
Only respondent 18-2 has reported an emission from this source.
It results from the incineration of various plant generated aoueous
waste streams. The respondent indicates that the only pollutants
discharged as a result of this operation are .0001 Ibs. of
particulates (Na2C03)/lb. of product.
4. Distillation and Dehydration Section Vent
Only respondent 18-2 reports emissions from this source. This
is so because most other operators direct the light ends resulting
from these operations to the main scrubber (see Section III-A-1).
Emissions reported consist of .0001 Ibs./lb. of maleic anhydride plus
varying quantities of non-polluting gases. The emission is summarized
in Table III.
B. Intermittent Air Emissions
No intermittent air emissions were reported.
-------
MA-4
C. Continuous Liquid Wastes
The following data relating to waste liquid production and
disposal were reported by the respondents:
Plant
18-1
18-2
18-3
18-4
18-5
18-6
18-7
Type of Waste
Liquid
Still washing
Process vater
Cooling tower water
Total water outfall
Purification system
wash water
Amount
MM Gal./Yr.
0.9
6.3
32.8
34.0
15.
17.
110.
5
.3
,5
3.6
Treatment and/or
Disposal Method
Outside contractor
Biological treatment
Lime neutralization
To municipal sewer
To municipal sewer
D. Solid Wastes
Only three of the seven respondents reported the generation of
solid waste materials. The only type of solid waste reported by the
three was spent catalyst. The amounts and disposal method are
reported below:
Plant
18-3
18-5
18-6
E. Fugitive Emissions
Tons of Catalyst/Yr.
18
30
53
Disposal Method
Landfill
Reprocessed
Landfill
None of the respondents have offered a quantitative estimate of
fugitive emissions. Aside from the normal sources, such as leaking
pump seals, packing gland, etc., there are two (probable) principal
sources for emissions of this type in most maleic anhydride plants.
They are;
(1) Storage tank vents - very fev of the respondents indicate
the use of conservation vents on storage tanks. Since
benzene is relatively volatile, it is reasonable to assume
that moderate amounts of that material at least is 'lost'
to the atmosphere.
(2) Packaging, pelleting and flaking - most plants employing
this type of solids handling eouipment suffer at least
some losses. It seems reasonable to assume, therefore,
that these areas would represent emission sources.
F. Odors
In general, the respondents indicate that maleic anhydride is
not the cause of a significant odor problem. Only one respondent
reported receiving a community odor complaint in the past 12 months.
Maleic anhydride was identified as the source of odor in that
instance. No other respondents reported the detection of odors off
the plant site.
-------
MA-5
IV. Emission Control
The various emission control devices that have been reported as being
utilized by operators of maleic anhydride plants are summarized in Table IV
of this report, vhich 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
devices are assigned efficiency ratings (when data permits). Efficiencies
are defined in terms of:
(1) "CCR" - Completeness of Combustion Rating
CCR = Ibs. of 0? reacting (with 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 x
(3) "SERR" - Significance of Emission Reduction Rating
SERR = (pollutant x weighting factor)in - (pollutant x weighting
factor)out
(pollutant x weighting factor)in
A more detailed discussion of these ratings may be found in Appendix V
of this report.
Combustion devices are normally assigned a CCR and a SERR rating whereas
non-combustion devices are assigned SE and SERR ratings, Unfortunately none of
the respondents provided sufficient data to calculate the above indicated
efficiencies. Therefore, only a few general observations about the expected
device performance can be made.
Scrubbers
Most plants scrub the uncondensed portion of the reactor effluent after
it passes through the partial condenser. This is done principally to
recover maleic anhydride. Many plants utilize this same device to scrub
vent gases from various areas of the plant. However, CO and hydrocarbon
emissions from this device are quite high. Appreciably better control
would be achieved by coupling the product scrubber vith a combustion
type device. One plant (18-4) plans such an installation They state
total costs will be $1,000,000.
Plant 18-2 and 18-7 utilize separate scrubbers to control the emissions of
MAN particles from their flaking, tableting packaging operations, One
would expect scrubbing efficiencies to be quite high for this service —
98%+.
Incinerators
Only one plant employs an incineration device - plant 18-2» It is used
to dispose of aqueous wastes. The respondent shows no hydrocarbons, CO
or other pollutants in the incinerator flue gas. However, this does not
x 100
-------
MA-6
the device performs with 100 efficiency because incinerator effluents are
difficult to sample or monitor„ Considering that there are no sulfur,
nitrogen or halogen bearing compounds used in the process, a high SERR
rating is to be expected.
Developmental work directed toward reduction in emissions for the
subject process falls into the following general areas, as has been suggested
by questionnaire respondents and general literature.
(1) Substitution of oxygen for air; as the oxidizing agent.
(2) Development of fluid bed process to permit reduction of air/
benzene feed ratio.
(3) Development of more selective catalyst.
(4) More efficient design and better utilization of pollution control
devices currently being used.
(5) Investigate use of recycle air to improve yield and reduce
emissions.
This list is by no means intended to be exhaustive, nor is knowledge
available as to whether or not some of these types of work are in progress.
-------
MA-7
V. Significance of Pollution
It is recommended that no in-depth study of this process be undertaken
at this time. The predicted grovth and emission rates are both moderate.
Therefore, the resultant SET is less than for other processes that are
currently being survyed.
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 nev plants.
This work is summarized in Tables V and VI.
Published support for the annual growth rate upon which the Table V
forecast of new plants is based may be found in the April 3, 1973 issue
of Chemical Marketing, Chemical Profiles section.
On a weighted emission basis a Significant Emission Index of 2,721 has
been calculated in Table VI. Thus, this number, in part, is the basis for
recommending the exclusion of this process from the in-depth portion of the
overall petrochemical industry study that is scheduled for the near future.
-------
MA-8
VI. Maleic Anhydride Producers
The following list shows the production capacity of the maleic anhydride
producers and their location by plant.
Name
Allied. Chemical Corp.
Koppers Company
Monsanto Company
Location
Moundsvilie, W. Va.
Bridgeville Pa.
St. Louis, Mo.
Petro-tex Chemical Corp. Houston, Texas
Reichhold Chemical
Tenneco Chemical
USS Chemical Division
Elizabeth, N. J.
Morris, 111.
Fords, N. J.
Pittsburgh, Pa.
Capacity - MM Lbs./Year
20
34
105
50
30
60
20
40
Total - 359*
*1973 capacity is estimated to be 9% higher than 1972 capacity, i.e.,
1.09 x 359 - 391 MM Ibs./year.
-------
PAGE NOT
AVAILABLE
DIGITALLY
-------
TABLE MA-I
Stream I. D. No.
Component
CO
co2
02
N2
Benzene
Maleic Anhydride
H20
Misc. HC's
MALEIC ANHYDRIDE UNIT
NET MATERIAL BALANCE - T/T
12 3 4
Scrubber Vacuum
Fresh Feed Air Vent Gas Light Ends '1'
0.303
1.189
9.152 7.082
30.124 30.124
1.331 0.067
1 . 644
0.133 n)
1.331 39.276 40.409 0.133
Cl) In some units this stream is recycled to reactor.
Product
Maleic Anhydride
1.000
1.000
Refiner
Heavy Ends
0.066
0.066
(2} Includes 1.001 T/T of vater lost from vater scrubber. If other scrubbing medium such as dibutyl phthalate
is employed, vater in vent is reduced to 0.553 T/T.
(3) Arbitrary split, contains oxygenated compounds rejected in vaste vater streams.
-------
TABLE MA-II
MALEIC ANHYDRIDE
EX
BENZENE
GROSS REACTOR HEAT BALANCE
HEAT IN BTU/LB. OF MAN
Benzene vaporizer and superheater 250
Exothermic heat of reaction 18,000
Total - 18,250
HEAT OUT
Reactor heat loss
Reactor temperature control
Differential enthalpy*
Total - 18,250
''--Enthalpy Effluent - Enthalpy Feed
-------
TABLE MA-III
NATIONAL EMISSIONS INVENTORY
MALEIC ANHYDRIDE PRODUCTION
EPA Code Number
Date on stream
Capacity - Tons Maleic Anhydride (MAN)/Yr.
Average Production - Tons MAN/Yr.
Range in Production - % of Max.
Emissions to Atmosphere
Stream
Flov - SCFM
Flov Characteristic - Continuous or Intermittent
if Intermittent - Hrs./Yr. of Flov
Composition - Tons/Ton of MAN
Particulate
°2
N2
C02
CO
H20
MAN (a)
Maleic Acid
Benzene
Formaldehyde
Formic Acid
Xylene
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problems
Vent Stacks
Flov - SCFM per stack
Number
Height - Feet
Diameter - Inches
Exit Gas Temperature - °F
Emission Control Device
Type
Catalog I. D. Number
Total Hydrocarbon Emissions - Ton/Ton of MAN
Total Particulate/Aerosol Emissions - Ton/Ton of MAN
Total NOX Emissions
Total SOX Emissions
Total CO Emissions
18-1
20,000
0
Scrubber
Vent'
42,000
Continuous
6.1280
26.3280
1.8416
0.8674
2.2354
0.0040
0.0624
0.0154
0 0012
Top of Stack
Benzene - 3/veek Others I/week
MS, GLC, FT. Wet Chemical
Yes - In plant - No - Off Plant
21,000
2
79 and 99
24
109
Water Scrubber
0.0830
0
0.8674
Benzene and Product
Recovery Vent
43,100
Continuous
5.6727
26.7818
1.2800
0.6109
0.8727
0.0027
0.0033
Stack
Design Calc.
No
43,100
1
90
42
100
Not Specified
Page 1 of 3
18-2
1972
22,000
0
Vacuum System
Vent
16
Continuous
Top of Stack
Design Calc.
No
16
1
85
2
80
Not Specified
Scrubber
Vent
2890
Continuous
0 0030
0.0100
0.0009
0 0001
0.5598
1 8348
0 0449
0 0002
Top of Stack
Design Calc.
No
2 890
1
20
14
86
Water Scrubber
0.0062
0.0001
0.6109
Incinerator
Vent
7400
Continuous
0.0001 (Na? COj)
0.1091
1.8000
0.3727
2 4764
Top of Stack
Design Calc
No
7.400
1
36
14
200
Water Scrubber
NOTES: (See also sheets 2 and 3 of 3)
(a) Often emitted as maleic acid, but common practice is to report it as the anhydride.
-------
TABLE MA-III
NATIONAL EMISSIONS INVENTORY
MALEIC ANHYDRIDE PRODUCTION
Page 2 of 3
EPA Code Number
Date on stream
Capacity - Tons Maleic Anhydride (MAN)/Yr.
Average Production - Tons MAN/Yr.
Range in Production - 7. of Max.
Emissions to Atmosphere
Stream
Flow - SCFM
Flow Characteristic - Continuous or Intermittent
if Intermittent - Hrs./Yr. of Flow
Composition - Tons/Ton of MAN
Particulate
02
N?
co2
CO
H-0
MSN (a)
Maleic Acid
Benzene
Formaldehyde
Formic Acid
Xylene
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problems
Vent Stacks
Flow - SCFM per stack
Number
Height - Feet
Diameter - Inches
Exit Gas Temperature - °F
Emission Control Device
Type
Catalog I. D. Number
Total Hydrocarbon Emissions - Ton/Ton of MAN
Total Particulate/Aerosol Emissions - Ton/Ton MAN
Total NOX Emissions
Total SOX Emissions
Total CO Emissions
18-3
1961
10.000
Scrubber
Vent
17,000
Continuous
6.9296
22.8232
0.8480
0.6844
0.3928
0.0020
0.1008
0.0116
Scrubber
Four since 1968
Gravimetric - Wet Chemical
No
17,000
1
72
24
65
Vater Scrubber
0.1144
0
0.6844
18-4
17.000
0
Scrubber
Vent
30,000
Continuous
)32.1810
)
0.6706
1.5139
0.0059
' 0.0616
Not Sampled
Not Sampled
Mat. Balance
No
30,000
1
74
24
100
Water Scrubber
0.0675
0
0.6706
18-5
25.000
0
Scrubber
Vent
42,000
Continuous
4.9550
24.2656
1.3126
0.4434
1.3642
0.0115
0.0627
)Incl. vith
)Maleic Acid
Not Specified
Infreauent
Not Specified
Yes
42.000
1
65
36
100
Water Scrubber
0.0742
0
0.4434
-------
EPA Code Number
Date on stream
Capacity - Tons Maleic Anhydride (MAN)/Yr.
Average Production - Tons MAN/Yr.
Range in Production - "L of Max.
Emissions to Atmosphere
Stream
Flov - SCFM
Flow Characteristic - Continuous or Intermittent
if Intermittent - Hrs./Yr. of Flow
Composition - Tons/Ton of MAN
Particulate
°2
N2
C02
CO
H?0
MSN (a)
Maleic Acid
Benzene
Formaldehyde
Formic Acid
Xylene
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problems
Vent Stacks
Flow - SCFM per stack
Number
Height - Feet
Diameter - Inches
Exit Gas Temperature - °F
Emission Control Device
Type
Catalog I. D. Number
Total Hydrocarbon Emissions - Ton/Ton of MAN
Total Particulate/Aerosol Emissions - Ton/Ton MAN
Total NOy Emissions
Scrubber
Vent
78,000
Continuous
3.9896
19.7250
1.0363
0.4703
1.2219
) 0.0047
)
0.0879
)Incl. with
)MAN
Not Sampled
Not Sampled
Mat. Balance
No
Not Specified
Not Specified
Not Specified
Not Specified
140
Water Scrubber
TABLE MA-III
NATIONAL EMISSIONS INVENTORY
MALEIC ANHYDRIDE PRODUCTION
18-6
52.500
Fume Scrubber
Vent
45
Continuous
0.0015
Not Sampled
Not Sampled
Mat. Balance
No
45
1
9.5
3
100
Venturi Scrubber
Page 3 of 3
18-7
15.000
0
Product Recovery
Vent
20,000
Continuous
2.4587
19.0421
1.0776
0.6859
0.6541
0.1976
Not Speci-fied
Bz. - 2-3/week. CO - 1/2 month
GLC and Mat. Balance
No
20,000
1
56.8
24
104
Not Specified
Scrubber
Vent
7.000
Continuous
1.8912
6.6232
0.2315
Not Sampled
Not Sampled
Design Calc.
No
7.000
1
30
24
77
Water Scrubber
0.0926
0
0.1976
0
Total CO Emissions
0.4703
0.6859
-------
TABLE MA-IV
CATALOG OF EMISSION CONTROL DEVICES
MALEIC ANHYDRIDE V[A
THE OXIDATION OF BENZENE
Page 1 of 3
WATER SCRUBBERS
Flov Diagram Stream I. D.
Device 1. D. No.
EPA Code Number of plant
Purpose - Control Emission of
Type - Spray
Packed Column
Trays - Type
Number
Plenum Chamber
Other
Water Rate
Design or Operating Temp. - F°
Gas Rate - SCFM (Ib./hr.)
Height (T-T), Ft.
Diameter - Ft.
Washed Gases to Stack
Stack Height - Ft.
Stack Diameter - Inches
Installed Cost - Mat'l. & Labor - $
Installed Cost - Mat'l. & Labor - c/lb. MAN/Yr.
Operating Cost - Annual - $
Operating Cost - c/lb. MAN/Yr.
Efficiency - 7.
MAN-1
18-1
Maleic Anhydride
Not Specified
Not Specified
109
42,000
Not Specified
Not Specified
79 and 99
24
Not Specified
MAN-2
18-2
Benzene and Maleic Anhydride
Not Specified
Not Specified
100
43,100
Not Specified
Not Specified
90
42
Not Specified (a)
MAN-3
18-2
Maleic Anhydride
45 GPM
86
3,600
16.5
42
20
14
Not Specified (a)
MAN-3
18-2
Particulate
X
X
Venturi
110 GPM
1600
4 600
Not Specified
Not Specified
36
14
Not Specified <"»)
MAN-4
18-3
Maleic Anhydride
Not Specified
Not Specified
65
17.000
Not Specified
Not Specified
72
24
Not Specified
i
(a) Total cost of all pollution control devices plus incinerator is $610,000.
-------
TABLE MA-IV
WATER SCRUBBERS
Flov Diagram Stream I. D.
Device I. D. No.
EPA Code Number of plant
Purpose - Control Emission of
Type - Spray
Packed Column
Trays - Type
Number
Plenum Chamber
Other
Water Rate
Design or Operating Temp. - F°
Gas Rate - SCFM (Ib./hr.)
Height (T-T), Ft.
Diameter - Ft.
Vashed Gases to Stack
Stack Height - Ft.
Stack Diameter - Inches
Installed Cost - Mat'l. 6. Labor -
Installed Cost
Operating Cost
Operating Cost
Efficiency - %
Mat'l. & Labor - c/lb. MAN/Yr.
Annual - $
C/lb. MAN/Yr.
CATALOG OF EMISSION CONTROL DEVICES
MALEIC ANHYDRIDE VIA
MAN-5
18-4
Maleic Anhydride
X
Bubble Cap
Not Specified
17 - 37 GPM
100
30,000
22.5
11
74
24
80,000
0.24
12,500
0.04
Unknown
THE OXIDATION OF
MAN- 6
18-5
Maleic Anhydride
Not Specified
Not Specified
100
42,000
Not Specified
Not Specified
65
36
Not Specified
i
V
BENZENE
MAN- 7
18-6
Maleic Anhydride
Not Specified
Not Specified
140
78,000
Not Specified
Not Specified
Not Specified
Not Specified
Not Specified
i
V
Page
MAN-8
18-6
Maleic Anhydride
Venturi
Not Specified
50
45
Not Specified
Not Specified
9.5
3
11,000
0.01
230
I'nkhovn
2 of 3
MAN -9
18-7
Maleic Anhydride
Not Specified
Not Specified
104
20,000
Not Specified
Not Specified
Not Specified
t
i
V
MAN-10
18-7
Maletc Anhydride
X
20 - 30 GPM
70 - 100
7,000
15
4
30
24
50,000
0 .17
7.800
0.03
Ufikr.ot-'i:
-------
INCINERATION DEVICES
Flov Diagram Stream I. D.
Device I. D. No.
EPA Code Number of plant
Types of Compounds Incinerated
Type Device
Materials Incinerated, SCFM (Ib./hr.)
Auxiliary Fuel Required (excl. pilot)
Auxiliary Fuel Type
Auxiliary Fuel Rate - MM BTU/Hr.
Device Elevation - Ft. above grade
Installed Cost - Mat'1 & Labor - $
Installed Cost - Mat'l. & Labor - c/lb.
Operating Cost - Annual - $
Operating Cost - r/lb. of MAN
Efficiency - CCR - %
Efficltncy - SERR - %
of MAN
TABLE MA-IV
CATALOG OF EMISSION CONTROL DEVICES
MALEIC ANHYDRIDE VIA
THE OXIDATION OF BENZENE
MAN-11
18-2
Aaueous Vastes
Incinerator
(3400) Includes Water
Yes
Natural Gas
12 (Max.)
Not Specified
Not Specified (a>
99+ (Expected)
Near 100 (c)
Page 3 of 3
Proposed
18-4
Organic Vapors. CO (k
Boiler & Incinerator
30.000 Includes Air
Yes
Natural Gas/Oil
Not Specified
Not Specified
1.000.000 Total
Not Applicable
Not Available
Not Available
99+ (Expected)
Near 100 (c)
(a) Total Installed cost for all pollution control devices including scrubbers is $610,000.
(b) Scrubber vent will supply combustion air to new gas/oil fired boiler-incinerator, which will eliminate odors, hydrocarbon emissions and carbon monoxide
from this source. New boiler-incinerator will replace existing coal-fired boiler for steam generation.
(c) Depends upon time/temperature relationship for NOx formation.
-------
TABLE MA-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 Nev
Plants
390
30
360
720
720
360
60
NOTE: All capacities in MM Ibs./year.
-------
Emission
TABLE MA-VI
EMISSION SOURCE SUMMARY*
TON/TON MALEIC ANHYDRIDE
Source
Scrubber Vent
Storage Losses
and Fugitive Emissions
Hydrocarbons
Particulates
.086
Note (1)
Note C2)
so.
CO
.670
NOTES:
(1) There vill be small amounts of hydrocarbon emissions from storage tanks but the amount
is not available.
f2) Fugitive dust emissions vill mostly be composed of maleic anhydride povder from the
pelletizing, handling and storage operations of maleic anhydride. The amount is not
indicated and vill vary from plant to plant depending on operations.
-------
TABLE MA-VII
WEIGHTED EMISSION RATES
Chemical Maleic Anhydride
Process Oxidation of Benzene
Increased Capacity by 1980 360 MM Lbs,/Year
Increased Emissions Weighting Weighted Emissions
Pollutant Emi ssions , Lb. /Lb. MM Lbs. /Year Factor MM Lbs . /Year
Hydrocarbons .086 31 80 2,480
Participates 60
NOX 40
SOX 20
CO .670 2.41 1 241
Significant Emission Index = 2,721
-------
Nylon 6
-------
Table of Contents
Section Page Number
I. Introduction NYL-1
II. Process Description NYL-2
III. Plant Emissions NYL-3
IV. Emission Control NYL-5
V. Significance of Pollution NYL-6
VI. Nylon 6 Producers NYL-7
List of Illustrations and Tables
Flow Diagram Figure NYL-I
Net Material Balance Table NYL-I
Gross Heat Balance Table NYL-II
Emission Inventory Table NYL-III
Catalog of Emission Control Devices Table NYL-IV
Number of Nev Plants by 1980 Table NYL-V
Emission Source Summary Table NYL-VI
Weighted Emission Rates Table NYL-VII
-------
NYL-1
I . Introduction
f — — I
Nylon 6, HIHN(CH2)5CO nOH, is a linear aliphatic polyamide. It can
be either spun into a fiTjer or made into a molding resin. The fiber is used
for apparel, home furnishings, tire cord and industrial applications, while
the resin is used for films, coatings for vires and cables, automotive parts
and numerous other industrial and consumer applications.
Nylon 6 is produced commercially by the continuous polymerization of
caprolactam,
In the old process the polymer was produced by batch polymerization, but
because the reaction produces no water it was relatively easy to put the
process on a continuous basis. Small quantities of the polymer are still
produced by the old method.
Today, nylon 6 capacity stands at around 500 MM Ibs./year. It is
expected that by 1980 the capacity will reach 1.5 billion Ibs./year,
requiring about ten new nylon 6 plants each having a capacity of 100 MM
Ibs . /year.
Air emissions associated with nylon 6 polymerization are caused by small
vents from numerous process operations. In general, the process could be
characterized as a moderately low polluter.
-------
NYL-2
II. Process Description
Nylon 6 is produced by the continuous polymerization of caprolactam.
+ H20
n HN(CH?)5CO - > H |HN(CH2)5CO |n
The mechanism of the reaction is considered to involve an addition
reaction of an open lactam ring into the growth chain initiated by the
combined catalytic effect of water and acid groups. Contrary to amino acid
polymerization, the reaction does not involve any significant removal of
water since only small amounts are used as catalyst. The overall reaction
is an equilibrium reaction with conversions of monomer of 85 to 90%. A
substantial amount of oligomers (57«) are formed and they must be removed
in part (1-2% of product") if high quality polymer is desired.
The following is a description of a typical process to produce nylon 6
(see Figure NY! 1).
Molten caprolactam is mixed with water, catalysts, stabilizer and
delusterant (if fibers .are to be made) and is fed into a reactor which is
operated at about 500° F. The mass slowly proceeds down the reactor which
is usually divided into several zones. The overall reaction is slightly
exothermic and heat exchange is provided by dowtherm. The reactor effluent
consists of molten polymer, monomer, oligomers and water. Monomer and
oligomer constitute 10-1570 of the reactor effluent.
There are two methods being used to purify the crude polymer and
recover unreacted polymer. In the first, the polymer is cast into ribbon
form, quenched and cut into chips. Unreacted monomer and some oligomer are
removed from the chips by extraction with hot water. The water is sent to
monomer recovery where the oligomers are depolymerized and the monomer is
dehydrated and returned to the system. The chips are dryed and are then
ready for melting and spinning or bagging.
In the second method, the molten polymer exiting from the reactor is
sent to a vacuum distillation column where monomer, water and oligomers are
removed overhead. The molten polymer can then be spun directly into fibers
or cut into chips for bagging.
-------
NYL-3
III. Plant Emissions
A. Continuous Air Emissions
A majority of the air pollution associated vith nylon 6 polymerization
is caused by small vents from a number of process units. Although plant
19-3 was the only respondent to report any emission control devices from
these sources, it is believed that other producers use vent condensers
to recover some caprolactam The following is a description of the
sources of air emissions from the nylon 6 process.
1. Mix and Spin Tank Vents
Only respondent 19-4 reports losses due to the mixing of molten
caprolactam with water and catalysts prior to reaction. Since the
system is nitrogen padded, the main constituent of this vent is
nitrogen. The only noxious emission is .00012 Ibs./lb. nylon 6
of caprolactam.
2. Polymerization Vent
Nitrogen present as an inert in the reaction chamber along with
some water is purged from the system by venting from the polymerization
reactor. Some caprolactam is carried with the gases to the
atmosphere. Emission rates vary from plant to plant but on the
average, about .00034 Ibs./lb. nylon 6 of caprolactam enters the
atmosphere from this source,
3. Chip Formation Vent
When the molten polymer ribbon is ouenched with either cold
water or an inert gas, some caprolactam vapor is lost to the
atmosphere before the polymer solidifies. Plant 19-3 reports
significant emissions of .00337 Ibs./lb. of nylon 6 of caprolactam.
4. Nylon Chip Slurry Tank
Plant 19-4 reports small losses of caprolactam from the slurry
tank prior to the extraction system.
7. Depolymerizer Vent
Oligomers extracted from the product are in many plants
depolymerized to caprolactam. Some caorolactam is usually vented
to the atmosphere from the depolymerizing reactor. The ouantity
released varies from insignificant to significant quantities.
6. Pellet Drying
Small amounts of caprolactam are lost when the extracted pellets
are dried with an inert gas or air. The quantity released to the
atmosphere is small.
8. Caprolactam Recovery Vent
Plant 19-3 reports that trace amounts of caprolactam are lost
during the caprolactam recovery distillation process.
-------
NYL-4
B. Intermittent Air Emissions
1. Equipment Cleaning Furnaces
Equipment such as filters, etc., vhich become fouled with
polymer and oligomers are cleaned, in some operations, in a furnace.
The two respondents vhich report such operations claim that only
carbon dioxide and water are emitted. One of the plants reports an
afterburner, without which, smoking will probably occur.
C. Continuous Liquid Waste
1. Waste Water
Waste water discharges and methods of treatment used by nylon 6
producers are summarized below.
Plant Code No. Waste Water - GPM Treatment Used
19-1 .12 Not Specified
19-3 20-50 (cooling water) Chlorine Treated
Evaporative Ponds
(Reclaimed)
19-4 .5 (process) Untreated
1.8 (cooling) Untreated
D. Solid Wastes
Solid waste in the form of oligomers and waste polymer is
produced at many installations. The vaste can be disposed of in
a land fill.
E. Odor
There are no community odor problems associated with the
nylon 6 polymerization process.
F. Fugitive Emissions
No sources of air emissions due to leaks, spills, etc.,
were reported. It is assumed that such losses exist but are
not significant.
G. Noise
Although not reported, or requested in the questionnaire, it has
been reported by industry that noise from cutters may be an environ-
mental problem.
-------
NYL-5
IV. Emission Control
Details on emission control devices reported by the respondent can be
found in Table IV, Catalog of Emission Control Devices. A brief description
of the devices follows:
Condensers
Plant 19-3 employs vent condensers to lover emissions and increase
recovery of caprolactam from the polymerization reactor vent and the
caprolactam recovery column vent.
Scrubbers
Spray type scrubbers are employed in plant 19-3 to reduce emissions from
the pelletizer vent and the depolymerizer vent.
Afterburner
Plant 19-3 employs an afterburner to insure that only carbon dioxide
and water exit from the equipment cleaning furnace. The operator
reports that the exhaust is smokeless and odorless so complete com-
bustion is assumed.
-------
NYL-6
V. Significance of Pollution
It is recommended that no in-depth study be made of the subject process.
The quantity of air emissions released as air pollutants is less for this
process than for processes currently under in-depth study.
The methods outlined in Appendix IV of this report have been used to
forecast the number of nev plants that vill be built by 1980 and to estimate
the total weighted annual emission of pollutants from these nev plants.
This work is summarized in Tables V, VI and VII.
On a weighted emission basis, a Significant Emission Index of 194 has
been calculated in Table VII. Hence, the recommendation to exclude an
in-depth study of Nylon 6 Polymerization from the overall scope of work
for this project.
-------
NYL-7
VI. Nylon 6 Producers
Company
Allied Chemical Co.
American Enka Corp.
Dow Badische Co.
Firestone Tire & Rubber Co.
Foster Grant Co.
Gulf Oil Corp.
Rohm & Haas Co.
Location
Chesterfield, Va.
Enka, N. C.
Lowland, Tenn.
Freeport, Texas
Hopewe11, va.
Pottstown, Pa.
Leominster, Mass.
Henderson, Ky.
Fayetteville, N. C.
Capacity - MM Lbs./Year
238
79
20*
80
47
2*
5*
5*
Total - 486
^Capacities are approximate.
-------
PAGE NOT
AVAILABLE
DIGITALLY
-------
TABLE NYL-I
MATERIAL BALANCE
NYLON 6 (1)
T/T NYLON 6
V7aste
Fresh Recycle Polymer (Oligomers &
Caprolactam Caprolactam (2) Nylon 6 Oligomers Waste Polymer)
1.147 .146 .985 .015 .001
(1) Based on information found in literature and respondents comments.
(2) Unreacted caprolactam and caprolactam recovered from oligomer
depolymerization.
-------
TABLE NYL-II
HEAT BALANCE
NYLON 6
There is insufficient information available on vhich to base an
overall energy balance for Nylon 6 polymerization.
-------
TABLE NYL-III
NATIONAL EMISSinNSTNVENTORV
NYLON 6
Page 1 of
Plant EPA Code Number
Capacity - Tons/Yr. of Nylon 6
Production - Tons/Yr. of Nylon 6
Emissions to Atmosphere
Stream I. D. No. (Figure NYL-I)
Stream Hot Melt
Filter Vent
Flow - Lbs./Hr. 6200 SCFM
Flov Characteristic - Continuous or Intermittent Continuous
if Intermittent - Hrs./Yr.
Composition - Ton/Ton of Nylon 6
Caprolactam .000001
Benzene
Nitrogen
Air (1)
Water (1)
Carbon Dioxide
Oligomer
Phosphoric Acid
Hydrogen .
Vent Stacks Yes
Number 1
Height - Feet 36
Diameter - Inches 19.5 by 14.5
Exit Gas Temp. - F° 100
Flov - SCFM 6200
Emission Control Devices No
Type
Analysis Yes
Sample Tap Location None
Date or Frequency of Sampling March, 1972
Type of Analysis Chromatograph
Odor Problem No
Summary of Air Pollutants
Hydrocarbons - Ton/Ton of Nylon 6
*Particulates & Aerosols - Ton/Ton of Nylon 6
NOX - Ton/Ton of Nylon 6
S0x - Ton/Ton of Nylon 6
CO - Ton/Ton of Nylon 6
Vash Vater Recovery
Vacuum Jet Exhaust
Never Measured
Continuous
(2)
Yes
1
46
2
90
No
None
None
No
19-1
40,000
40.000
D
Pellet
Drying
1363
Continuous
.143169
.005618
.000153
Vaporized Benzene
from Waste Water
Continuous
.003852
Equipment Cleaning
Furnace Afterburner Exhaust
^318 SCFM
Intermittent
416
(3)
(3)
003852
.000001
0
0
0
*Caprolactam vapors are considered as aerosols.
(1) Mostly vater and air.
(2) Mostly air.
(3) Complete combustion to CO- and H20 reported.
-------
TABLE NYL-III
NATIONAL EMISSIONS INVENTORY
NYLON 6
Page 2 of 4
Plant EPA Code Number
Capacity - Tcms/Yr. of Nylon 6
Production - Tons/Yr. of Nylon 6
Emissions to Atmosphere
Stream I. D. No. (Figure NYL-I)
Stream
Flow - Lbs./Hr.
Flow Characteristic - Continuous or Intermittent
if Intermittent - Hrs./Yr.
Composition - Ton/Ton of Nylon 6
Caprolactam
Benzene
Nitrogen
Air
Water
Carbon Dioxide
Oligomer
Phosphoric Acid
Hydrogen
Vent Stacks
Number
Height - Feet
Diameter - Inches
Exit Gas Temp. - F°
Flow - SCFM
Emission Control Devices
Type
Analysis
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problem
Summary of Air Pollutants
Hydrocarbons - Ton/Ton of Nylon 6
*Particulates & Aerosols - Ton/Ton of Nylon 6
NOX - Ton/Ton of Nylon 6
SOX - Ton/Ton of Nylon 6
CO - Ton/Ton of Nylon 6
B
Melt
Polymerizer
260
Continuous
Nearly 100%
Yes
1
70
1.44
260
Yes
Vent Condenser
None
Material Balance
No
19-2
Confidential (1)
Confidential
Chip
Polymerizer
22
Continuous
Nearly 100%
Yes
1
70
1 44
250
Yes
Vent Condenser
None
Material Balance
No
Depolymerizer
Vent
477
Continuous
Nearly 100%
Yes
1
70
.33
212
Yes
Vent Condenser
None
Material Balance
No
(1) Published capacity is 45 MM Ibs./year.
-------
TABLE NYL-III
Plant EPA Code Number
Capacity - Tons/Yr. of Nylon 6
Production - Tons/Yr. of Nylon 6
Emission to Atmosphere
Stream I. D. No. (Figure NYL-I)
Stream
Flow - Lbs./Hr.
Flow Characteristic - Continuous or Intermittent
if Intermittent - Hrs./Yr.
Composition - Ton/Ton of Nylon 6
Caprolactam
Benzene
Nitrogen
Air
Vater
Carbon Dioxide
Oligomer
Phosphoric Acid
Hydrogen
Vent Stacks
Number
Height - Feet
Diameter - Inches
Exit Gas Temp. - F°
Flow - SCFM
Emission Control Devices
Type
Analysis
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problem
Summary of Air Pollutants
Hydrocarbons - Ton/Ton of Nylon 6
*Particulates & Aerosols - Ton/Ton of Nylon 6
NOx - Ton/Ton of Nylon 6
SOX - Ton/Ton of Nylon 6
CO - Ton/Ton of Nylon 6
NATIONAL EMISSIONS INVENTORY
B
Reactor
Vent
Continuous
.000960
.064991
.041780
Yes
1
90
Unknown
80
685
Yes
Condenser
No
Estimated
No
NYLON 6
C
Pelletizer
Vent
Continuous
.003374
.472925
Yes
1
95
12
80
2400
Ye 8
Water Spray
No
Estimated
No
19-3
119.000
119.000
Nylon Chip
Slurry Tank Vent
Continuous
.000062
.001797
Yes
1
Unknown
Unknown
78
20
No
No
Estimated
No
0
.004396
0
0
0
Page 3 of 4
F
Caprolactam Recovery
Distillation Column Vent
Continuous
+
.008605
Yes
1
90
Unknown
^,200° F
235 Ibs /hr
Yes
Condenser. Steam Ejector
No
Estimated
No
E
Depolymerization
Reactor Vent
Intermittent
1800
Unknown (Small)
Unknown
Yes
1
65
12 by 12
Ambient to 12QO F
1800
Yes
Water Spray
No
None
No
-------
TABLE NYL-III
NATIONAL EMISSIONS INVENTORY
NYLON 6
Page 4 of 4
Plant EPA Code Number
Capacity - Tons/Yr. of Nylon 6
Production - Tons/Yr. of Nylon 6
Emissions to Atmosphere
Stream I. D. No. (Figure NYL-I) A
Stream Mix Tank
Vents
Flow - Lbs./Hr.
Flow Characteristic - Continuous or Intermittent Continuous
if Intermittent - Hrs./Yr.
Composition - Ton/Ton of Nylon 6
Caprolactam .000005
Benzene
Nitrogen .000195
Air
Water
Carbon Dioxide .000001
Oligomer
Phosphoric Acid
Hydrogen
Vent Stacks Not Specified
Number
Height - Feet
Diameter - Inches
Exit Gas Temp. - F°
Flow - SCFM
Emission Control Devices No
Type
Analysis None
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis Estimate
Odor Problem
Summary of Air Pollutants
Hydrocarbons - Ton/Ton of Nylon 6
*Partitulates & Aerosols - Ton/Ton of Nylon 6
NOy - Ton/Ton of Nylon 6
SOX - Ton/Ton of Nylon 6
CO - Ton/Ton of Nylon 6
Spin Tank
Vents
Continuous
.000118
.001433
Not Specified
No
None
Estimate
19-4
39,275
39,275
B
Polymerization
Reactor Vent
Continuous
.000100
.003233
.000016
Not Specified
No
None
Estimate
0
.0262
0
0
0
Part Cleaning
Furnace Off-Gas
Intermittent
Not Specified
(D
(D
+
Not Specified
No
No
None
Depolymerization
Reactor Vent
Continuous
254220
(2)
(2)
Not Specified
No
No
None
(1) Composition unknown.
(2) A total of 3 vol. %, approximately .026 Ibs./lb. nylon 6 (not considered typical).
-------
INCINERATION DEVICES
EPA Code No. for plant using
Device I. D. No.
Type of Compound Incinerated
Type of Device
Material Incinerated - SCFM
Auxiliary Fuel - Excluding 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 Nylon 6/year
Operating Cost - Annual - $ (1972)
Net Value of Recovered Heat
Net Operating Cost - $/year
Net Operating Cost - c/lb. of Nylon 6
Efficiency - CCR (1)
TABLE NYL-IV
CATALOG OF EMISSION CONTROL DEVICES
NYLON 6
19-1
IN-1
Hydrocarbon and CO (1)
After Burner
800
Yes
Methane
9.6
7.700
1971
.0096
1900
1900
.0024
1007.
Page 1 of 2
(1) For explanation and definition see Appendix V.
-------
SCRUBBERS
EPA Code No. for plant using
Flov Diagram (Fig. Nylon 1) Stream No.
Device I. D. No.
Control Emission of
Scrubber Type
Scrubbing Liquid
Scrubbing Liquid Rate - GPM
Operating Temp. - F°
Gas Rate - SCFM
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 Nylon 6/year
Operating Cost - Annual - $
Value of Recovered Product - $
Net "Operating Cost - c/lb. Nylon 6
Efficiency - 7. - SE (1)
Efficiency - 7. - SERR (1)
TABLE NYL-IV
CATALOG OF EMISSION CONTROL DEVICES
NYLON 6~
19-3
C
SC-I
Caprolactam
Spray Eductor
Water
Yes
95
12
45,000
1973
.018
2200
.009
Page 2 of 2
19-3
E
SC-II
Caprolactam
Duct Spray
Vater
Yes
65
12 by 1?
40,200
1961
.017
CONDENSERS
Type
EPA Code No. for plant using
Flov Diagram (Fig. Nylon 1) Stream No.
Device I. D. No.
Control Emission of
Cooling Liquid
Cooling Liquid Rate
Gas Rate - SCFM
Temperature to Condenser - F°
Temperature out of Condenser - F°
Quantity Condensed - Ibs./hr.
Non-Condensibles - SCFM
Installed Cost - Mat'l. & Labor - $
Installed Cost based on "year" - dollars
Installed Cost - c/lb. of Nylon 6/year
Operating Cost - Annual - Annual - $ '1972)
Value of Recovered Product - S
Net Operating Cost - Annual - $
Net Operating Cost - c/lb. of Nylon 6
Efficiency - % - SE (1)
Efficiency - "I. - SERR (1)
Heat Exchanger
19-3
B
CON-1
Caprolact«m
Water
r-700
60,000
1961 - 1970
.025
11,000
340,000
329,000
(.138)
Stream Ejector and Condenser
19-3
F
CON-II
Caprolactsm
Steam
Trace
1.500
1968
.006
1400
1400
(.006)
Near 1007,
Near 1007.
-------
486
TABLE NYL-V
Current
Capacity C1)
Marginal
Capacity
NUMBER OF NEW PLANTS
NYLON 6
Current
Capacity
on-stream
in 1980
BY 1980
Demand
1980
Capacity
to be
Added
Economic
Plant
Size
Number
of Nev
Units
486
1500 (2)
1014
100
10
(1) MM Ibs./year.
(2) Process Research, Inc., report for the EPA.
-------
TABLE NYL-VI
EMISSION SOURCE SUMMARY
Pollutant
Hydrocarbon
Aerosols & Particulates ( )
NOX
S°x
CO
NYLON 6
T/T NYLON 6
Source
Mixing
Tank Vents ' Reactor Vent
0 0
.00012 .00034
0 0
0 0
0 0
Pellet Formation Furnace
Washing & Drying Vents Cleaning
0
.00172
0
0
0
0
0
Trace
0
0
Total
Caprolactam
Recovery
0 0
0.001 0.00318
0 Trace
0 0
0 0
(1) Caprolactam is considered an aerosol.
-------
TABLE NYL-1II
WEIGHTED EMISSION RATES
Chemical Nylon 6
Process Continuous Polymerization of Caprolactam
New Added Capacity 1,014 MM Lbs./Year
Pollutant Emissions, Lb./Lb.
Hydrocarbons 0
Aerosols & Particulates (*) .00318
NOX Trace
sox o
CO 0
Increased Emissions Weighting
MM Lbs./Year Factor
0 80
3.2 60
0 40
0 20
0 1
Significant Emission
Weighted Emissions
MM Lbs. /Year
0
194
0
0
0
Index = 194
-------
Nylon 6,6
-------
Table of Contents
Section Page Number
I. Introduction N6,6-l
II. Process Description N6,6-2
III. Plant Emissions N6,6-4
IV. Emission Control N6,6-6
V. Significance of Pollution N6,6-7
VI. Nylon 6,6 Producers N6.6-8
List of Illustrations and Tables
Flow Diagram Figure N-I
Net Material Balance Table N6,6-I
Gross Heat Balance Table N6,6-II
Emission Inventory Table N6,6-II!
Catalog of Emission Control Devices Table N6,6-IV
Number of Nev Plants by 1980 Table N6,6-V
Emission Source Summary Table N6,6-V1
Weighted Emission Rates Table N6,6-VII
-------
Nylon 6,6-1
I. Introduction
Nylon 6,6 is synthesized from its monomer, hexamethyl diammonium adipate
or nylon salt, by polymerizing the monomer to a molecular weight of 12,000
to 20,000 under temperature and pressure. Nylon salt is made by neutralization
of aqueous solutions of its components, hexamethylene diamine and adipic acid.
There are two processes used to make nylon 6,6. The older process is
batch polymerization, which usually ends with the nylon 6,6 as a flake or
pellet, which may then be remelted and spun to yarn. The second process,
the newer of the two, is a continuous polymerization and spinning process,
which produces a nylon yarn or filament directly.
Although there is a large installed capacity for nylon 6,6 production,
some 1.5 billion pounds annually, the amount of air pollution associated with
these plants is comparatively small on a mass emission basis. Hovever,
depending on plant size, the emissions which can produce a "blue haze" may
become sufficiently significant to make their abatement desirable. In such
circumstances the most conventional abatement approach is scrubbing. This
produces a biodegradable liquid waste. One plant estimates a $4 million
investment in its combined air-liquid abatement facilities. A modest amount
of solid waste is generated which has no commercial value .
-------
Nylon 6,6-2
II. Process Description
Nylon 6,6 is made by polymerization of nylon salt (hexamethylene diammo-
nium adipate) from an aqueous suspension at elevated temperature and pressure.
Two processes are in general use, batch and continuous. Nylon salt is
usually stored as a 10 - 20% aqueous solution and can easily be made from
aqueous solutions of adipic acid and hexamethylene diamine.
Batch Process - the reaction is:
(a) Neutralization
HOOC-(CH2)4- COOH
Adipic Acid
Mol. Wt. 146.1
(b) Polymerization
Nylon Salt
-> OOC-(CH2)4 • COO
Hexamethylene
Diamine
116.2
Hexamethylene Diammonium Adipate
(Nylon Salt)
262.3
fs
ic
Q H
- C — N
(CH2)6- N-j- n + 2n
Nylon 6,6
Mol. Wt. (repeat unit) 226.8
Nylon monomer (nylon salt) is usually fed as a water suspension or
homogeneous mixture to an evaporator where it is concentrated to a 50 - 60%
aqueous slurry by removal of water. This aqueous slurry together with
additives such as 0.5% by weight acetic acid as a chain terminator (viscosity,
m. wt. control), Ti02 as a delusterant, are pumped to an autoclave reactor.
Here temperature is increased to 260° - 280° C (
-------
Nylon 6,6-3
step at 540° F to be sure polymerization is complete or it may by-pass this
step. In any event the hot molten polymer goes directly to spinning, drawing
and beaming operations rather than cooling and casting into resin as in the
batch process.
-------
Nylon 6,6-4
III. Plant Emissions
A. Continuous Air Emissions - Batch & Continuous Processes
1. Evaporator Off-Gas - Code Letter (A) on drawing
Both respondents report essentially all steam from this
source with very small traces of hexamethylene diamine present.
No scrubbing or incinerator devices are used. No odors were
reported.
2. Reactor or Polymerizer Off-Gas - Code Letter (B) on drawing
Again the main constituent of this vent stream is steam with
small amounts of hexamethylene diamine. The presence of monomer
and polymer is noted as detectable and has the potential for
causing off-plant odors. One plant is installing scrubbers to
control this potential odor source and the attendant "blue haze"
which periodically forms.
3. Flasher or Separator Off-Gas - Continuous Process - Vent (C)
This stream is reported to be similar in composition to the
reactor off-gas (code letter C) but much less in terms of Ib.
gas per Ib. finished product. No odors were reported.
4. Finisher Exhaust - Code Letter (D) - Continuous Process
Not all continuous processes employ a finishing step after the
high pressure reaction - atmospheric pressure flashing step. Those
that do, report very small emissions compared to the other stages.
This stream is normally not scrubbed although one respondent scrubs
this stream with a water spray in some of his units. No odor
problems were reported.
5. Miscellaneous Streams
(a) When the flaked nylon resin is pneumatically conveyed, the
conveying gas can be a source of emissions to the atmosphere. The
one piece of data on this stream, a cyclone exhaust shows only
minimal traces of water vapor, hexamethylene diamine and nylon.
(b) One respondent showed an emission from the spinning
operation. Presumably this is cooling air contaminated with
infinitesimal quantities of particulates, hydrocarbons and nylon
6,6. The stream was not scrubbed and no estimate of quantity was
available.
(c) Nylon scraps (see also D-Solid Wastes). One respondent
reports incineration of about 0.003 Ib. nylon scraps per Ib.
nylon 6,6. Complete incineration of the scraps would give roughly
0.00123 Ib. NOX per Ib. nylon 6,6. No data on this incineration
are available.
B. Intermittent Air Emissions
No intermittent air emissions were reported.
-------
Nylon 6,6-5
C. Continuous Liquid Wastes
Only one respondent reported waste water quantities from the
processes as follows:
Process Type Waste Water from GPM Treatment
Batch Casting 36 in-plant
Continuous Not Specified 135 in-plant
D. Solid Wastes
Operator of plant EPA code 20-1 reports production of 1,160 Ibs.
per day of casting scraps (nylon polymer), which are incinerated.
Plant code EPA 20-3, a continuous process reports "no solid wastes
associated with this process". No comment was available from
another respondent.
E. Odors
The polymerization of nylon salt to nylon 6,6 is a process for
which no odor problems or complaints were reported. The odor of
hexamethylene diamine is detectable at times on site and under some
atmospheric conditions it may also be detected beyond the plant
borders.
F. Fugitive Emissions
Neither respondent reports any fugitive losses. The only
comment was that there are "no other known emissions although
minor leakages probably occur".
G. Other Emissions
Fuel oil for heating was reported by only one respondent.
About 56 million Ibs. of fuel oil are consumed at amaximum of
3% sulfur (estimated average is 2.57»). At the maximum level,
this is 1.7 million Ibs. of S per year or 3.4 million Ibs. S02
per year, the largest single reported source of pollution in
the process (0..0093 Ibs. S02/lb. nylon 6,6).
Dowtherm is used for a heat transfer medium. Losses here are
75 gal./year (one source of data), which is insignificant.
-------
Nylon 6,6-6
IV. Emission Control
Two plants report using emission control devices. One instance is a
vater scrubber used on the exhaust from the finishing operations. Water
is the scrubbing medium and the effluent is treated in-plant before discharge
to the sewer. The following efficiencies were calculated on the basis of
reported data.
SE* - Specific Efficiency - 99.7%.
SERR* - Significance of Emission Reduction Rating - 99.7%.
The other plant is in the process of adding scrubbers to their polymerizer
equipment which they consider to be the major source of air pollution from the
process ("blue haze" and hexamethylene diamine odor).
*See Appendix V for explanation of these terms.
-------
Nylon 6,6 -7
V. Significance of Pollution
It is recommended that no in-depth study of this process be made. Emissions
are low and roughly equal to the combustion product emissions from the fuels
used in some of the plants.
A modest 10% per year growth is projected for the period up to 1980. Even
if this growth were off by 50 to 100%, the Significance of Emission Index* would
still be low. An SEI of 318 has been calculated for this process. Doubling
this figure would still leave the process in the low pollution category.
Emissions consist mostly of particulates (hexamethylene diamine is the major
component), which could easily be removed by water scrubbing (as one respondent
is doing) should this ever be necessary.
*See Appendix IV for an explanation of this term.
-------
Nylon 6,6-8
VI. Producers of Nylon 6,6 Resins and Fibres from Monomer
The capacities and plant locations listed belov are based on information.
provided in the Questionnaire and in the literature.
Company
Fibre Producers
Allied Chem. Fibres Div.
E. I. duPont
Beaunit Corporation
Fibre Industries, Inc.
Monsanto
Rohm & Haas, Sauquoit Fibres Div.
Resin Producers
Celanese Corporation
DuPont Plastics Department
Beaunit Corporation
Monsanto Corporation
Location
V. Conshohocken, Pa.
Camden, S. C.
Chattanooga, Tenn.
Martinsville Va.
Richmond, Va.
Seaford, Del.
Etovah, Tenn.
Odessa, Texas
Greenville S. C.
Guazama, P. R.
Greenvood, S. C.
Pensacola, Florida
Scranton, Pa.
La Porte, Texas
Parkersburg, W. Va.
Etovah, Tenn.
Pensacola, Florida
MM Lbs.
1971 Capacity
N. A.
40
140
100
200
365
100
80
60
100
240
4
Sub - 1,429
12
70
2
10
Total - 1,523
-------
PAGE NOT
AVAILABLE
DIGITALLY
-------
TABLE N6..6-I
MATERIAL BALANCE
The conversion of nylon 6,6 salt (hexamethylene diammonium adipate) to
nylon 6,6 polymer is almost 100% of theoretical according to the literature
and data surveyed. A comparison of actual reported yields vs theoretical
is shown below:
Lb. Adipic Acid
per
Source Lb. Nylon 6,6
Theory 0.646
Actual 0.653
Lb. Hexamethylene
Diamine per
Lb._Ny_lon_6i6
0.513
0.521
Lb. Nylon 6,6
Polymer
1.000
1.000
Lb. Water
per
Lb. Nylon 6,6
0.159
0.174*
*includes vaste products which are reported minimal.
-------
TABLE N6.6-II
GROSS REACTOR HEAT BALANCE
There are not sufficient published data available to permit the construction
of a detailed heat balance for this proces.
-------
TABLE N6.6-III
Plant Code No.
Capacity - Tons Nylon 6,6/Year
Range in Production - 7, of Max.
Emissions to Atmosphere
Stream
Flov - Lbs./Hr.
Flow Characteristic
Composition, Ton/Ton Nylon 6,6
Nylon Salt
Water
Hexamethylene Diamine
Adipic Acid
Nylon 6,6 Polymer
Cyclopentanone
Halides
Tot. Organic Carbon
Sulfonamide
Vent Stacks
Number
Height - Feet
Diameter - Inches
Exit Gas Temp., °F
SCFM/Stack
Emission Control Devices
Type
Analyses
Date or Frequency of Sampling
Sample Location
Type of Analysis
Odor Problem
Summary of Air Pollutants
Hydrocarbons, Ton/Ton Nylon 6,6
Particulates & Aerosols - Ton/Ton Nylon 6,6
NOX - Ton/Ton Nylon 6,6
SOX - Ton/Ton Nylon 6,6
CO - Ton/Ton Nylon 6,6
NATIONAL EMISSIONS TNVE1TOP.V
V - - -
None
(A) - Evaporator
Off-Gas
4700
Continuous
0.274700
0.000175
1
10
8
155°
1665
None
Never
Calc'd.
No
NYLON 6,6 FROM >IYLON SALT
20-1 - - I
75,000
None None
(B) Autoclave (C) Conveyor
Off-Gas Air Exhaust
540 7500
Continuous Continuous
0.031480 +
0.000090 +
-t-
1 1
26 Cyclone
4
400° 129°
178 5400
None None
Never Never
Calc'd. Calc'd,
No No
0
0.000265
0
0
0
page 1 u f 4
93.500
Mone
(IA) - Evaporator
Off -dap
4708
Continuous
1. 10500
0.00090
5
86
8
360°
1650
None
Occasional
TIT, GC, GRAV, TOC
No
i
20-2
None
(IB) - Autoclave
Off-Gap
610
Continuous
0.61000
0 00200
-1-
21
88
4
300°
216
None
Occasional
TIT. GC, GRAV, TOC
No
0
0.002900
0
0
0
-------
TABLE N6.6-III
NATIONAL EM I fK I ONE
.
NYLON 6 , 6 FROM NYLON SALT
Page 2 of 4
Plant Code No.
Capacity - Tons Nylon 6,6/Year
Range in Production - 7, of Max.
Emissions to Atmosphere
Stream
Flow - Lbs./Hr.
Flow Characteristic
Composition, Ton/Ton Nylon 6,6
Nylon Salt
Water
Hexamethylene Diamine
Adipic Acid
Nylon 6,6 Polymer
Cyclopentanone
Halides
Tot. Organic Carbon
Sulfonamide
None
(IIA) - Evaporator
Off-Gas
1422
Continuous
0.34100
0.00009
20-2 --
36,500
None
(IIB) - Reactor
Off-Gas
4554
Continuous
1.09300
0.00350
None
C'' - Separator
Off-Gas
980
Continuous
0.23500
0.00350
None
(IID) Finisher Exhaust
730
Continuous
0.17500
0.00013
Vent Stacks
Number
Height - Feet
Diameter - Inches
Exit Gas Temp. , °F
SCFM/Stack
Emission Control Devices
Type
Analyses
Date or Frequency of Sampling
Sample Location
Type of Analysis
Odor Problem
Summary of Air Pollutants
Hydrocarbons - Ton/Ton Nylon 6,6
Particulates & Aerosols - Ton/Ton Nylon 6,6
NOX - Ton/Ton Nylon 6,6
SO
CO
- Ton/Ton Nylon 6,6
- Ton/Ton Nylon 6,6
2
.88
4
265°
450
None
Occasional
TIT, GRAV, TOC
No
2
95
12
330°
1490
None
Occasional
TIT, GRAV, TOC
No
0
0.007200
0
0
0
2
83
2%
600°
325
None
Occasiona 1
TIT, GRAV, TOC
No
2
88
4
300°
240
None
Occasiona I
?
No
-------
TABLE N6.6-III
NATIONAL EMISSIONS INVENTORY
NYLON 6,6 FROM NYLON SALT
Page 3 of 4
Plant Code No.
Capacity - Tons Nylon 6,6/Year
Range in Production - 7. of Max.
Emissions to Atmosphere
Stream
Flow - Lbs./Hr.
Flow Characteristic
Composition - Ton/Ton Nylon 6,6
Nylon Salt
Water
Hexamethylene Diamine
Aidpic Acid
Nylon 6,6 Polymer
Cyclopentanone
Halides
Tot. Organic Carbon
Sulfonamide
None
(IIIA) Evaporator
Off-Gas
6080
Continuous
0.70200
0.00016
20-2
38,000
None
(IIIB) Reactor
Off-Gas
6080
Continuous
0.70200
0.00180
None
(IIIC) Separator
Off-Gas
1130
Continuous
0.13050
0.00066
(HID) Finisher Exhaust
560
Cont inuous
0.064700
0.000003
Vent Stacks
Number
Height - Feet
Diameter - Inches
Exit Gas Temp., °F
SCFM/Stack
Emission Control Devices
Type
Analyses
Date or Frequency of Sampling
Sample Location
Type of Analysis
Odor Problem
Summary of Air Pollutants
Hydrocarbons - Ton/Ton Nylon 6,6
Particulates & Aerosols - Ton/Ton Nylon 6.6
NOX - Ton/Ton Nylon 6,6
SOX - Ton/Ton Nylon 6,6
CO - Ton/Ton Nylon 6,6
1
101
6
300°
2000
None
Occasional
TIT, GRAV, TOC
No
1
112
12
570°
2000
None
Occasional
TIT, GRAV, TOC
No
0
0.00262
0
0
0
1
101
2
590°
370
None
Occasional
TIT, GRAV, TOC
No
1
101
2
300°
185
None
Never
No
-------
TABLE N6.6-III
Plant Code No.
Capacity - Tons Nylon 6,6/Year
Range in Production - 7. of Max.
Emissions to Atmosphere
Stream
Flow - Lbs./Hr.
Flow Characteristic
Composition - Ton/Ton Nylon 66,
Nylon Salt
Water
Hexamethylene Diamine
Adipic Acid
Nylon 6,6 Polymer
Cyclopentanone
Halides
Tot. Organic Carbon
Sulfonamide
Vent Stacks
Number
Height - Feet
Diameter - Inches
Exit Gas Temp., °F
SCFM/Stack
Emission Control Devices
Type
Analyses
Date or Frequency of Sampling
Sample Location
Type of Analysis
Odor Problem
Summary of Air Pollutants
Hydrocarbons - Ton/Ton Nylon 6,6
Particulate & Aerosols - Ton/Ton Nylon 6,6
NOX - Ton/Ton Nylon 6,6
SOX - Ton/Ton Nylon 6,6
CO - Ton/Ton Nylon 6,6
NATIONAL EMISSIONS INVENTORY
^
None
(IVA) Evaporator
Off-Gas
1780
Continuous
0.78070
0.00048
1
98
4
230°
580
None
Occasional
TIT, GRAV, TOC
No
NYLON 6,6
- 20-2
10,000
None
(IVB) Reactor
Off-Gas
3100
Continuous
1.36000
0.00250
+
,
1
110
12
400°
560
None
Occasional
TIT, GRAV, TOC
No
0
0.00339
0
0
0
FROM NYLON SALT
^ ' ._
'
None None
(IVC) Separator (A) Evaporator
Off-Gas Off-Gas
273 11.500
Continuous | Continuous
0.1197
0.00041
+
1
95
4
610°
0. 781800
0.000180
0.000008
0.000002
0.000510
9
90 1
None ! None
Never , Occasional
TIT, GC, TOC
No
No
i
|
Paee 4 of i
20-3
62.500
None
(B) Reactor
Off-Gas
8800
Continuous
0.626700
0.002500
0.000063
0.00002
0.001800
9
None
Occasional
TIT, GC, TOC
No
. . ..
None None
(C) Separator (E) Finisher
Off-Gas Off-Gas
410 40
Continuous Continuous
0.029135 0.002857
0 000070 +
0.000001 +
0.000002 +
Nil 4-
0.000033 +
0.000045 +
? 1
None Scrubber
Occasional Once
TIT, GC. TOC TIT, GC, TOC
No No
0
0.002891
0
0
0
-------
TABLE N6.6-III (CONTINUED)
NATIONAL EMISSIONS INVENTORY '
NYLON 6,6 FROM NYLON SALT""
NOTES
1. Composition + symbol means presence of compound as a trace.
2. Type of Analysis, symbols mean:
TIT - Titration
GC - Gas Chromatography
TOC - Total Organic Carbon
GRAV - Gravimetric Analysis
3. Particulates/Aerosols
Counts the following compounds: Hexamethylene Diamine, Adipic Acid,
Nylon Salt, Nylon 6,6 Polymer, Cyclopentanone, Halide, Sulfonamide.
-------
Absorber/Scrubber
EPA Code
Flov Diagram Stream I. D.
Device I. D. No.
Control Emission of
Scrubbing/Absorbing Liquid
Type
Scrubbing/Absorbing Liauld Rate GPM
Design Temp. (Operating Temp.)°F
Gas Rate SCFM (Ib./hr.)
T-T Height - Feet
Diameter - Feet
Washed Gases to Stack
Stack Height - Feet
Stack Diameter- Feet
Installed Cost, Mat'l. 6, Labor - $
Installed Cost Based on - "year" - dollars
Installed Cost - c/lb. Nylon 6,6/Yr.
Operating Cost - Annual - $
Value of Recovered Product, $/Yr.
Net Operating Cost, c/lb. Nylon 6,6
Efficiency - 7. - SE
Efficiency - 7. - SERR
TABLE N6.6-IV
CATALOG OF EMISSION CONTROL DEVICES
NYLON 6.6
20-3
(E)
Hexamethylene Diamine and others
Water
Spray Column
15
(100° F)
(40)
89,000
1968
0.071
19,850
0
0.016
99.7
99.7
20-2
(B)
Hexamethylene Diamine
Water
*
^Details not available - equipment in process of being designed for addition in near future.
-------
TABLE N6,6-V
Current
Installed
Capacity
1,523
Marginal
Capacity
0
NUMBER
Current
Capacity
on- stream
in 1980
1,523
OF NEW PIANTS BY 1980
Demand*
1980
2,400
Capacity
1980
3,000
Capacity
to be
Added
1,477
Economic
Plant
Size
150
Number
of New
Units
10
Notes:
1. All capacities in MM Ibs./year (million Ibs./year).
2. Demand estimated at 80% of installed capacity.
3. Growth rate of 10%/year assumed.
-------
TABLE .-N6.6-VI
EMISSION SOURCE SUMMARY
Emission
Hydrocarbons
Particulates & Aerosols
NOX
SOX
CO
Evaporation Section
0
0.000333
0
0
0
TON /TON NYLON 6,6
Source
Reactor Section
0
0.002100
0
0
0
Flasher Section Finishing
0 0
0.001100 0.000044
0 0
0 0
0 0
Fugitive
0
0
0
0
0
Total
0
0.003577
0
0
0
-------
TABLE N6,6-VII
Chemical Nylon 6,6
Process Batch and
Increased Capacity by 1980
Pollutant
Hydrocarbons
Particulates & Aerosols
NOX
SOx
CO
WEIGHTED EMISSION RATES
Continuous Polymerization
1,480 MM Lbs. /Year
Emissions, lb,/lb. Increased Emissions
Nylon 6,6 MM Ibs./year
0 0
0.003577 5.294
0 0
0 0
0 0
Weighting
Factor
80
60
40
20
1
Weighted Emissions
MM Ibs. /year
0
317.6
0
0
0
Significant Emission Index =318
-------
Oxo Process
-------
Table of Contents
Section Page Number
I. Introduction OA-1
II. Process Description OA-2
III. Plant Emissions QA-4
IV. Emission Control QA-6
V. Significance of Pollution OA-7
VI. Oxo Alcohol Producers OA-8
List of Illustrations and Tables
Flov Diagram Drawing R-229
Net Material Balance Table QA-I
Gross Heat Balance Table OA-II
Emission Inventory Table OA-III
Catalog of Emission Control Devices Table OA-IV
Number of New Plants by 1980 . Table QA-V
Emission Source Summary Table OA-VI
Weighted Emission Rates Table OA-VII
-------
OA-1
I . Introduction
One of the processes which gained world wide importance during recent
years is the so called Oxo synthesis for the production of aldehydes and
alcohols from olefins and synthesis gas (CO + t^). Although the oxo
synthesis or hydroformylation was discovered in 1938, the big industrial
success has been only recently - within the last 15 to 20 years.
In terms of production capacity the oxo process (combined with an aldol
condensation to double molecular weight) is the largest process for producing
alcohols from the butanols (04) up through the hexadecanols (C]^) and higher.
Hydrocarbons and particulates are the main air pollutants associated with
these plants. To a lesser degree, CO is a problem but a very minor one.
The main odor problem appears to be trace quantities of aldehydes and
alcohols in vents from distillation columns and tanks. Unfortunately, even
trace quantities of these compounds are enought to create a local odor problem
in the plant. Particulates arise from loss of catalyst (metallic oxides)
from the system in vent gases but these losses are very small and constitute
no apparent problem. Off-gases from the process consist of CO, H£ and
hydrocarbons, chiefly C± to C^ paraffins. These gases are either flared or
sent to refinery fuel gas. In either event, proper combustion should give
C02 and water. (1) Combustion efficiencies are estimated at 98 to 100 percent
and CO and hydrocarbon release to the air is under control almost all of the
time.
Current oxo alcohol production is about 1727 million Ibs./year. Assming
a growth of 8 - 9 percent per year, an installed capacity of 3000 million Ibs .
is predicted by 1980 which will be equal to the demand by then. This is
based on current use of plasticizers in PVC plastics and as bases for
surfactants. Both these uses should increase up through 1980.
(1) Although the flaring will produce small quantities of NOX.
-------
OA-2
II. Process Description
The oxo process is the commercial application of a chemical reaction
called oxonation or, more properly, hydroformylation. In this reaction,
hydrogen and carbon monoxide are added across an olefinic bond (C=C) to
produce aldehydes containing one more carbon atom than the olefin. Several
reactions are involved but for simplicity, we shall mention only the three
basic reactions taking place.
(1) Hydroformylation of an olefin to an aldehyde (Oxo Process).
R-CH = CH2 + H2 + CO >R CH2 CH2 CHO + R CH - CH3
C HO
n - aldehyde iso - aldehyde
The straight chain n - aldehyde is the preferred product.
(2) Aldol Condensation - Doubling of the molecular veight of an aldehyde.
Example - n - butyraldehyde.
caustic
2 CH3 CH2 CH2 CHO » CH3 • CH2-CH2« CHOH-CH-CHO
CH2
CH3
n - butyraldehyde n - butyraldol
The n - butyraldol may be dehydrated and hydrogenated to an alcohol,
2 ethyl hexanol.
(3) Hydrogenation of the aldehydes to the corresponding alcohol.
/ 0 OH
sy r»f HO i
R-CH2 CH2 C - H - ' * > R-CH2-CH2 CH2
an- aldehyde an- alcohol
In commercial practice all three of these reactions are used individually
or in common as follows:
Oxo Process
The reaction of an olefin (propylene, octenes, etc.) with carbon
monoxide and hydrogen (syn gas made by steam reforming of methane, ethane,
etc.) at 200 - 400° F and 500 - 5000 PSI pressure, in the presence of a
cobalt catalyst produces a mixture of aldehydes and alcohols with one
more carbon atom than the starting olefin. This reaction is properly
known as oxonation (hence "oxo") or more accurately, hydroformylation.
Following removal of the catalyst (decobalting) the reaction mixture is
catalytically hydrogenated. The resulting product is then fractionated
to yield the finished "oxo" alcohol. Except when ethylene is used as
the starting olefin, a mixture of straight chain and branched chain
alcohols are produced. With propylene and higher molecular weight linear
olefins, the percentage of normal alcohol product can be significantly
increased by modifying the cobalt catalyst system, e.g. with phosphine
ligands. All alcohols produced by this technioue are primary, regardless
of the feedstock usd.
-------
OA-3
Aldol Process
N - butyraldehyde in the presence of caustic condenses to form
2 - ethyl hexeneal which on hydrogenation and distillation yields pure
2 - ethyl - 1 - hexanol (2 EH). This alcohol was the first large
volume synthetically produced higher aliphatic primary alcohol and is
still today the most important member of the group. N - butyraldehyde
may be made by subjecting propylene to the oxo reaction. The aldol
condensation doubles the number of carbon atoms in the alcohol precursor
made in the oxo reaction.
Oxo Aldol (Combined) Process
In the combined process, with propylene as the feedstock and a
special catalyst system, 2 - ethyl hexanol is produced via the oxo -
aldol route in one operation. One of the special catalyst systems is
a tributyl phosphine cobalt carbonyl complex (plus KOH) which
promotes a high degree of linearity of the intermediate butyraldehyde and
hence high yields of 2 - ethyl hexanol. Branched chain hexadecyl
alcohol is also made by a combined oxo - aldol process. In this case
branched chain heptenes are the feedstock and the cobalt catalyst is
modified by the addition of metal organic compounds such as zinc,
cadmium or lead stearates.
Plants covered by this report include plain oxo plants with subsequent
hydrogenation to alcohols and plants with oxo - aldol routes to higher
molecular weight alcohols.
-------
OA-4
III. Plant Emissions
No two oxo alcohol plants are exactly alike or even closely alike.
The comments belov refer to the generalized flov diagram OA-1 in this report
which gives all the basic steps which most of these plants possess.
A. Continuous Air Emissions
1. Reforming Furnaces Vent Gas ' '
Some respondents gave data on operation of their steam reforming
furnaces (to CO + H2 "syn gas") and hydrogen production facilities.
Emissions from this source represent emergency flarings of gases
due to upsets. The figures given are probably low since all plants
have these furnaces but data was not given for all plants.
2. Oxo Reactor System Off-Gas
All plants have a reactor system off-gas which is normally flared.
Usual composition is steam, N2, CO, H2 and light hydrocarbons. Gases
are burned to C02 and 1^0 with better than 987,, efficiency. Some
hydrocarbons and CO may escape unburned and these are shown on
Table III. One respondent had a measure of the small Quantity of
NOX found in the flare gas from ^ present in the combustion air.
Very small quantities of particulates fcatalyst - metallic oxides)
were reported in several streams and this has been noted also on
Table III.
3. Catalyst System Vent Gas (D)> (E)
Chief emission here is water as steam but small quantities of
hydrocarbons are reported (aldehydes, alcohols) and these represent
a minor in-plant odor problem. Also trace quantities of particulates
(catalyst - metal oxide) are present in this stream.
4. Compressor Engine Exhaust
One respondent uses methane fueled engines to drive his compressors
which are used to feed syn gas and hydrogen to the process. Since
all the plants using the oxo process are pressure plants (1500 -
6500 PSIG) in the reaction section, they all must have compressors.
Others may be methane or gas fueled also but were not reported.
Since engine exhaust is a pollutant, we reported this source.
Even though it is small, it is an inherent part of the process.
The figure shown is probably low since other plants may well have
gas fueled engines on their compressors also.
5. Distillation Purification System Vents
Gases here are chiefly steam and hydrocarbon (aldehyde and
alcohol in this case) and represent a local odor problem.
6. Heavy Liquids Incinerator Stack Gas
Some plants burn the heavy by-products made in an incinerator,
others send them to disposal in refinery fuel oil where we have no
-------
OA-5
data. Those incinerating this stream report practically complete
combustion but in every case trace amounts of aldehydes and alcohols
can be detected in the stack gas. This stream also represents a
local odor problem.
Many of the respondents have only one or two emissions listed. Other
vent streams go into the refinery fuel system and are not counted as emissions
in this report. One respondent (21-3) reports no emissions at all - everything
being sent to the refinery fuel system. One cannot help but wonder that there
must be some emergency venting to a flare or the atmosphere in this plant too -
every other plant reports some of this but no emission data were forthcoming
from 21-3. Nevertheless, this plant was averaged in with all the others and
in effect diluted the emissions shown in Table III because of the claimed
1007o purity.
B. Intermittent Air Emissions (see A-l)
Some plants vent the reforming furnaces continuously and some report
only intermittent emissions due to upsets or start-up.
C. Continuous Liquid Wastes
All plants have liquid waste consisting of heavy organics which
are-incinerated, burned in refinery fuel, or reprocessed. (See
Section A-6.)
Waste Water (J^
Every plant has a V7aste vater stream which varies from 0.06 gal/lb.
product to 1.7 gal/lb. product. Five of seven respondents treat this
vater at least thru primary treatment. The remaining tvo have no
treatment other than oil skimming.
D. Solid Wastes ^°
Five of seven respondents report periodic removal of solid vastes
from the process in the form of spent catalyst. They are disposed of
by landfill in the plant or sold to an outside firm for reclamation.
Amounts vary from 0.000053 Ib./lb. product to 0.001680 Ib./lb. product
but the data is sketchy.
E. Odors
Some respondents reported the odor of heavy aldehydes and alcohols
in plant but no one reported any outside odor complaints. As stated
earlier, these compounds have odors enduring enough that they could
probably be detected off-site if the wind and atmospheric conditions
were right.
F. Fugitive Emissions
None of the respondents report any fugitive emissions or even offer
an estimate.
G. Other Emissions
None reported.
-------
OA-6
IV. Emission Control
Emission control devices used in this process are summarized in Table IV.
All plants have flares which are used to burn excess gas or gases emitted due
to process upset or start-up. In all cases, using the data reported,
combustion efficiency is better than 9870 and all components could burn
completely to CC>2 and F^O. No nitrogen compounds are present although traces
of NOX have.been reported in the flared gas, presumably from N2 present in
small quantities in the syn gas and from the air required for complete
combustion in the flare. No sulfur compounds are used in these plants.
Emissions to the air, when they occur, are hydrocarbons (chiefly GI - C^
aliphatics), particulate and CO and take place generally during an upset or
start-up with the resultant surge of feed to the flare.
Heavy residual liquids are incinerated and the only source of emissions
here are trace quantities of heavy aldehydes and alcohols which are detectable
by their odor in the stack gas. This source represents a minor local odor
problem at the plants.
One respondent has a water scrubber on his aldehyde and alcohol column vents
to attempt to reduce the odor of gases emitted. The scrubbed gases still present
an odor problem although the aldehyde and alcohol content can only be reported
as "trace". The major constituent is air. Since actual quantitative data
are not available for the flared and incinerated gases, a Completeness of
Combustion Rating ("CCR") and Significance of Emission Reduction Rating ("SERR")
cannot be calculated. From the sparse and incomplete data available, however,
we estimate a 98+% for both these ratings and generally rather close to 100%.
The one water scrubber used removes trace quantities of aldehydes and
alcohols from distillation column vent gases. Since the odor of aldehydes
and alcohols is still detectable in the scrubbed off-gas, one must conclude
that the efficiency of this device is not 100% but a lesser figure. Lack of
quantitative data precludes calculation of an exact efficiency.
-------
OA-7
V. Significance of Pollution
It is recommended that no in-depth study of this process be made. Reported
emissions on a weighted basis (Table VII, SEI = 325) put the plants on the
lower end of the emission spectrum,, It should be mentioned that several
plants reported a local in-plant odor problem with heavy alcohols and
aldehydes in storage tank breathers and distillation column vents. Although
no odor complaints were reported, these odors are tenacious enough that they
probably could be detected off-site if the wind were in the proper direction.
Methods outlined in Appendix IV of this report have been used to estimate
the total weighted annual emissions from new plants. This work is summarized
in Tables V, VI and VII.
The projected increase in oxo alcohol production has been estimated from
literature comments on possible future uses. Published support for this
forecast has not been found. Assumptions made were:
1. A major use of C^ - C^2 alcohols will continue to be as bases for
plasticizers for polyvinyl chloride plastics. PVC plastics are
projected to grow 9-12 percent per year through 1980.
2. A major use of C^2 " ^18 alcohols will be as bases for surfactants
and this market is projected to grow also.
3. No more natural fatty alcohol plants will be built.
4. The recent oversupply of oxo alcohols has now been alleviated by
increased demand. Supply and demand will be about equal in 1980.
Using the above assumptions, it was projected that the oxo alcohol market
will increase from 1,727 million Ibs./year to about 3,000 million Ibs by 1980.
One marginal oxo unit has already been shut down. All the others apparently
will keep on running until at least 1980. New plants (six required) will
have a capacity averaging 200 million Ibs./year. On a weighted emission
basis, an SEI of 325 was calculated for this project and as such it is
recommended that no in-depth study be made.
-------
OA-8
VI. Producers of Oxo Alcohols
The capacities and plant locations listed belov are based on information
provided in the questionnaires and in the literature.
Company
Dov Badische.
Location
Freeport, Texas
Eastman Kodak, Longviev, Texas
Eastman Chem. Prod.
Getty Oil
Gulf Oil
Monsanto
Shell
Exxon Corp.
Del. City, Del.
Phi la. Pa.
Texas City, Texas
Deer Park, Texas
Geismar, La.
Baton Rouge, La.
Capacity MM Lbs./Yr.
180
435
42
40
200
150
150
160
Type*
i & n C^, i & n
butal, 2 EH
i & h C^, i & n
butal, 2 EH,
prop. aid.
i r -i r
R ' I \\ ^
i c13
i C13
n - Cj, Cg, Cn
i & n C^; i & n
butal, 2 EH
n - C12, C13,
C14* C15
1* • c* r* f^
V-/Q 5 V^Q > ^»1 rt
C13' C16
Union Carbide Corp. Seadrift, Texas
Texas City, Texas
U. S. Steel Haverhill, Ohio
100
200
i & n C^, n - butal
i C6, C8, C10,
prop. aid.
Same as Seadrift
plant & n C3 & G
70 i - C8 - C10
Total = 1,727 million Ibs/year
*Key to type of alcohol
i & n C^
i Cg etc.
= iso & normal butyl alcohol
= iso hexyl alcohol
= iso octyl alcohol
i & n butal • iso & normal butyraldehyde
2 EH =2 ethyl - 1-hexanol
n Cg - Cn = normal C6 to Cj_j_ alcohols (linear)
prop - aid. = normal propionaldehyde
-------
PAG E N OT
AVAILABLE
DIGITALLY
-------
TABLE OA-I
ALCOHOLS FROM THE 0X0 PROCESS
MATERIAL BALANCE - T/T ALCOHOL
There are insufficient data for a good material balance on this complex
process. A partial balance can be made on olefins charged to the process vs
alcohol made. Data given belov do not account for either syn. gas (CO + l^)
charged or gaseous products leaving the process.
1.578 Ib. olefin C1) 1.000 Ib. alcohol (2)
0.264 light oxo "gasoline"
0.133 heavy liquid ends
0.181 light ends (gas) (3)
It should be noted that this is an "average" balance and does not
apply to any individual product or grade of products.
(1) C3 to C12.
(2) C4 to C16.
(3) By difference.
-------
TABLE OA-II
ALCOHOLS VIA THE 0X0 PROCESS
REACTOR HEAT BALANCE
There are not sufficient data available to permit the construction of
a detailed heat balance for this complex series of reactions. The literature
lists the folloving;
(1) The reaction is highly exothermic once initiated.
(2) The reaction is first order relative to the olefin charge.
(3) Heat release.
(a) 50,000 BTU/lb. mol olefin converted to alcohol.
(b) 62,500 BTU/lb. mol ethylene converted to alcohol.
(c) Ethylene > propionaldehyde + 34.8 kcal./mol released.
-------
TABLE OA-III
NATIONAL EMISSIONS INVENTORY
ALCOHOLS BY THE 0X0 PROCESS
Page 1 of
Plant EPA Code No.
Capacity - Tons Alcohols/Year
Range of Production - 7. of Max.
Emissions to Atmosphere
Stream
Flov - Lbs./Hr. (SCFM)
Flov Characteristic
If IntermittMt
Composition - Ton/Ton Ale.
Hydrogen
Nitrogen (Air)
CO
C02
Steam
NO*
Ct - C$ & Higher Hydrocarbons
Aldehydes & Alcohols
Particulates
Vent Stacks
Number
Height - Feet
Diameter, Inches
Exit Gas Temp. °F
SCFM/Stack
Emission Control Devices
Analysis
Date or Frequency of Sampling
Tap Location
Type Analysis
Odor Problem
Summary of Air Pollutants
Hydrocarbons - Ton/Ton Ale.
Aerosols - Ton/Ton Ale.
NOX - Ton/Ton Ale.
SOX - Ton/Ton Ale.
CO - Ton/Ton Ale.
21-1
90,000
0
Aid., Ale., Heavy Liquids
to Incinerator
9879
Continuous
0.01113
0.28483
0.13356
Trace
1
18
60
9
Incinerator
Never
At times
21-2
75,000
0
Compressor
Engine Exhausts
9000
Continuous
(c)
0.07609
0.11956
O.U565
4
14' & 10.5"
24" & 16"
850° F
750
None
Oxo Reactor
Vent Gas
3112
Continuous
0.00006
0.00044
0.15268
0.01092
0.00006
1
20
4
100°
470
None
Ale. Dlstn.
Section Vent
?808
Continuous
0.00003
0.00118
0.14054
0.02002
0.00076
6
20 - 200
2-4
90° - 200°
4 - 200
None
Aid.. Ale., Heavy Liquids
to Incinerator
(50,000)
Continuous
(«)
0.32959
0.08789
0.02199
Trace
Trace
Incinerator
Up-set r.as to
Emergency Flare
(228 Avg.)
Variable
(b)
0.00012
0.00009
0.00006
0.00132
0.00035
0.00006
1
100
14
1000°
228
Flare
Never
Estimate
No
Trace
0.07609
Never Once
Vent
Mat'l. Balance M.S.
No No
Never
Estimate
Yes
Never
Estimate
No
0.02090
0.00050
-------
Plant EPA Code No.
Capacity - Tons Alcohols/Year
Range of Production - 7. of Max.
Emissions to Atmosphere
Stream
Flow - Lbs./Hr. (SCFM)
Flow Characteristic
if Intermittent, Hrs./Yr.
Composition - Ton/Ton Ale.
Hydrogen
Nitrogen (Air)
CO
C02
Steam
NOX
GI - C4 & Higher Hydrocarbons
Aldehydes & Alcohols
Particulates
Vent Stacks
Number
Height - Feet
Diameter - Inches
Exit Gas Temp. °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 Ale.
Aerosols - Ton/Ton Ale.
NCj - Ton/Ton Ale.
SOX - Ton/Ton Ale.
CO - Ton/Ton Ale.
21-4
48,000
0
Oxo Reactor
Vent Gas
119,026
Continuous
(b)
6.9287
3.8915
0.00027
0.00002
1
120
Flare
Never
Est. from Feed
No
0.00002
0.00027
TABLE OA-III
NATIONAL EMISSIONS INVENTORY
ALCOHOLS BY THE 0X0 PROCESS
21-5
217,500
0
Oxo Reactor
Vent Gas
2072
Continuous
(b)
0.00002
0.00026
0.00030
0.02827
0.01287
1
100
20
Flare
12/Day
in-line
G. C.
No
Page 2 of 4
Cat. Regenerator
Vent Gas
(1800)
Continuous
0.08102
0.00012
0 00012
Trace
1
60
14
212°
1800
None
I/Month
in-line
Mat. Bal., TOC.TIT
Yes
0.00024
Trace
0.00030
21-6
35,000
0
Oxo Reactor
Vent Gas
18,240
Continuous
(b)
0.02589
1.7295
0.95710
1
125
16
213°
360,000
Flare
Once
in-line
G. C.
. No
-------
Plant EPA Code No.
Capacity - Tons Alcohols/Year
Range of Production - % of Max.
Emissions to Atmosphere
Stream
Flov - Lbs./Hr. (SCFM)
Flov Characteristic
if Intermittent, Hrs./Yr.
Composition - Ton/Ton Ale.
Hydrogen
Nitrogen (Air)
CO
C02
Steam
NOX
Ci - C4 & Higher Hydrocarbons
Aldehydes & Alcohols
Particulates
Vent Stacks
Number
Height - Feet
Diameter - Inches
Exit Gas Temp. °F
SCFM/Stack
Emission Control Devices
Analysis
Date or Frequency of Sampling
Tap Location
Type of Analysis
Odor Problem
Sunmary of Air Pollutants
Hydrocarbons - Ton/Ton Ale.
Aerosols - Ton/Ton Ale.
NOX - Ton/Ton Ale.
SOX - Ton/Ton Ale.
CO - Ton/Ton Ale.
Hyd. Reformer
Vent
(7 Avg.)
Intermittent
8
0.000032
0.000002
0.000178
0.000577
0.000006
TABLE OA-III
NATIONAt KMSti Hms~TKVENTORY
ALCOHOLS BY THE 0X0 PROCESS
21-7
80,000
0
CC^ Removal
Vent
302
Continuous
0.000063
0.009404
Page 3 of 4
None
Never
Estimate
No
Cat. Recovery
System Vent
730
Continuous
0.022260
Trace
Cat. Regenerator
System Vent
19
Continuous
0.00058
Trace
42
None
Once
in-line
G.C.
No
151
None
Never
Calculated
Yes
4
None
Never
Calculated
Yes
-------
Plant EPA Code No.
Capacity - Tons Alcohols/Year
Range of Production - % of Max.
Emission* to Atmosphere
Stream
Flov - Lbs./Hr. (SCFM)
Flov Characteristic
If Intermittent, Hrs./Yr.
Composition - Ton/Ton Ale.
Hydrogen
Nitrogen (Air)
CO
C02
Steam
N°x
GI - CA 6. Higher Hydrocarbons
Aldehydes & Alcohols
particulates
Vent Stacks
Number
Height - Feet
Diameter - Inches
Exit Gas Temp. °F
SCFM/Stack
Emission Control Devices
Compressor
Flush Lines
(0.01 Avg.)
Intermittent
1
Trace
Trace
Trace
Trace
Trace
Trace
TABLE PA-ill
NATIONAL EMISSIONS INVENTORY
ALCOHOLS BY THE 0X0 PROCESS
21-7
80,000
0
Distn. Column
Vent
110
Continuous
Page A of 4
0.00338
0.00006
Storage Tank
Vents
96
Continuous
0.00301
Trace
None
35
None
None
Oxo Reactor
Vent Gas, Etc.
3544
Continuous
(b)
0.000113
0.017857
0.000940
0.53571
0.038496
1
200
24
7
606
Flare
Analysis
Date or Frequency of Sampling
Tap Location
Type of Analysis
Odor Problem
Summary of Air Pollutants
Hydrocarbons - Ton/Ton Ale.
Aerosols - Ton/Ton Ale.
NOx - Ton/Ton Ale.
SOjf - Ton/Ton Ale.
CO - Ton/Ton Ale.
Never
No
Never
Calculated
No
Never
Calculated
No
3 times/year
line to flare
M.S.
No
0.000066
0.000942
-------
EXPLANATION OF NOTES
TABLE OA-III
NATIONAL EMISSIONS INVENTORY
ALCOHOLS VIA THE 0X0 PROCESS
(a) Respondents furnished composition of liquid to incinerator. Figures
shown are calculated combustion products assuming complete combustion to
C02 and water unless other data were available. Usually trace
Quantities of alcohols, aldehydes or particulates were noted in the
incinerator stack gases and usually there is a minor odor problem
associated with these incinerators.
(b) Respondents furnished composition of gas streams to the flare. Figures
shown are calculated on 9870 complete combustion to C02 and H20 unless
other data were available. In most cases, some pollutants appear to be
in the flared gas but they were so low that no odor problem was reported.
Small quantities of NOX are present in the flared gas from N2 in the
combustion air.
Type of Analysis
M.S. = Mass Spectrograph
G.C. = Gas Chromatograph
TOC = Total Organic Carbon
TIT = Titration
(c) Plant 21-1 gives large volume of methane as fuel to gas compressors.
Compressor exhaust estimated by an arbitrary choice of 507 CH^ going
to C02 and 507« to CO in the engines.
Many plants vent gas streams to refinery fuel systems and use the flare only
in cases of upset or emergency. Hence, some plants listed show no flared gas
at all or low flow to the flare. One respondent shoved all gas streams going
to plant fuel line and no atmospheric emissions at all. This appears overly
optimistic and this data was taken with a grain of salt.
-------
TABLE Oft-IV
CATALOG OF EMISSION CONTROL DEVICES
ALCOHOLS VIA THE 0X0 PROCESS
Page 1 of 3
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
Material Incinerated, Lb./Hr. (SCFM)
Auxilliary Fuel Req'd. (axel, pilot)
Type-
Rate - BTU/Hr.
Device or Stack Height - Feet
Installed Cost - Mat'l. & Labor - $
Installed Cost Based on "year" - $
Installed Cost - c/lb. Alcohol - Yr.
Operating Cost - Annual (1972) - $/Yr.
Operating Cost - c/lb. Alcohol
Efficiency - % - CCR
Efficiency - % - SERR
21-1
(L) (M)
101
Heavy Alcohols & Aldehydes & Misc. Waste Liquid
Incinerator
2350
18
$12,700
1967 - 1972
0.0071
$5,800
0.0032
Approximately 99%
Approximately 997.
21-1
(C)
102
Syn. Gas & Hydrocarbons
Flare
1019
75
$10,365
ca. 1967
0.0058
$5,600
0.0031
100 (1)
100 (1)
21-2
(A) (C)
101
Syn. Gas & Hydrocarbons
Flare
38
Natural Gas
5.5 x Ifl6
100
$145,000
1941 to 1972
0.0967
$40.000
0.0267
66 - 100 (i>
15 - 100 (2)
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
Material Incinerated, Lb./Hr. (SCFM)
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" - $
. Installed Cost - c/lb. Alcohol - Yr.
Operating Cost - Annual (1972) - $/Yr.
Operating Cost - c/lb. Alcohol
Efficiency - % - CCR
Efficiency - % - SERR
21-2
(L) (M)
102
Butanol, Butyl Ether, Heavy Ends. Cat. Salts
Incinerator
1920
Natural Gas
10 x 106
7
$155,000
1959 - 1970
0.1033
$51,200
0.034
Approximately 99%
Approximately 99%
21-4
(A) (C)
101
Syn. Gas & Hydrocarbons
Flare
35281
120 m
$9,077 (J'
1971 - 1972
0.00946
$20,284
0.02113
100 (1)
100 (!)
21-5
(A) (C)
101
Syn. Gas & Hydrocarbons
Flare
754
100
$97,000
1968 - 1969
0.0223
$16,000
0.00368
98 (D
98 (D
(1) So reported by respondent.
(2) Worst case based on no burning of hydrocarbons during up-sets. Best case assumes all go to COj & HjO actual performance lies between these extremes, not enough
data to pin dovn any closer.
(3) Tip only and steam line on existing flare tower.
-------
INCINERATIOH 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
Material Indlncerated, Lb./Hr. (SCFM)
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" - $
Installed Cost - c/lb. Alcohol - Yr.
Operating Cost - Annual (1972) - $/Yr.
Operating Cost - c/lb. Alcohol
Efficiency - % - CCR
Efficiency - "I. - SERR
TABLE OA-IV
CATALOG OF EMISSION CONTROL DEVICES
ALCOHOLS VIA THE 0X0 PROCESS
21-6
(A) (C)
101
Syn. Gas
Flare
(6000)
125
$50,000
1962
0.0714
$4,220
0.00603
100 (D
100 (D
Page 2 of 3
21-7
(A) (C)
101
Syn. Gas & Hydrocarbons
Flare
631
200
$245,000
1966
0.1531
$61,500
0.0384
Approximately 98
Approximately 98
(1) So reported by respondent.
(2) Worst case based on no burning of hydrocarbons during up-sets.
data to pin down any closer.
(3) Tip only and steam line on existing flare tower.
Best case assumes all go to C02 & H20 actual performance lies betveen these extremes, not enough
-------
ABS ORBERS/S GRUBBERS
EPA Code No. for plant using
Flov Diagram (Fig. I) Stream I. D.
Device I. D. No.
Controls Emission of
Scrubbing/Absorbing Liquid
Type
Scrubbing/Absorbing Liquid Rate GPM
Gas Rate - SCFM (Ib./hr.)
T-T Height, Feet
Diameter, Feet
Washed Gases to Stack
Stack Height - Feet
Stack Diameter - Inches
Installed Cost•••-.Blt'l. & Labor - $
Installed Cost - Based on "year" - $
Installed Cost - c/lb. Alcohol/Yr.
Operating Cost - Annual - $ (1972)
Value of Recovered Product, $/Yr.
Net Operating Cost - c/lb. Alcohol
Efficiency - % - SE
Efficiency - % - SERR
TABLE OA-IV
CATALOG OF EMISSION CONTROL DEVICES
ALCOHOLS VIA THE 0X0 PROCESS
21-1
(F) (I)
103
Alcohol & Aldehyde Vapors
Water
Scrubber
2
7.5
1.5
15
3
$1,680
1967 - 1972
0.00093
$3,600
0
0.0020
.£100
£. 100
Page 3 of 3
-------
TABLE OA-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 Nev
Units
1727 0 1727 3000 3000 1273 200 6
NOTE: All capacities in million Ibs./year.
*Based on use of alcohols as plasticizers in PVC and detergents and assuming that no nev natural fatty alcohol
plants will be built. Current over capacity of oxo alcohols should be over veil before 1980 and new plants or
expansion of existing facilities necessary to meet a growth rate of 8.970/year.
-------
TABLE OA-VI
EMISSION SOURCE SUMMARY
Emission
Hydrocarbons
Par ticu la tes /Aerosols
NOV
TON /TON
ALCOHOL
Source
Reforming
Furnaces
Vent Cas
0.000009
Oxo Reactor System
Off-Cas
0.000010
0.000003
0.000040
Catalyst Compressor
System Engine
Vent Gas Exhausts
0.000040
TR
Distillation
Purification
System Vents
0.002970
Heavy Liquid
Incinerator
Stack Gas
TR
TR
Total
0.003029
0.000003
0.000040
SO,
CO
0.000009
0.000240
0.011000
0.011249
-------
TABLE OA-VII
Chemical Alcohols
Process
Increased Capacity
Pollutant
Hydrocarbons
Particulates
NOX
sox
CO
Oxo
by 1980 1273
Emissions Lb
0.003029
0.000003
0.000040
0.011249
WEIGHTED EMISSION RATES
MM Ibs. /year
Increased Emissions
. /Lb. MM Lbs./Year
3.856
0.0038
0.0509
14.320
Weighting
Factor
80
60
40
20
1
Weighted Emissions
MM Lbs. /Year
308.5
0.3
2.0
0
14.3
Significant Emission Index - 325.1
-------
Phenol
-------
Table of Contents
Section Page Numbers
I. Introduction PH-1
II. Process Description PH-2
III. Plant Emissions PH-3
IV. Emission Control PH-7
V. Significance of Pollution PH-10
VI. Phenol Producers PH-11
List of Illustrations and Tables
Block Flov Diagram, Phenol from Cumene Figure PH-1
Simplified Flov Diagram Phenol from Cumene Figure PH-2
Basic Chemical Reactions Table PH-I
Net Material Balance Table PH-II
Gross Heat Balance Table PH-II-A
Emission Inventory Table PH-III
Catalog of Emission Control Devices Table PH-IV
Number of New Plants by 1980 Table PH-V
Emission Source Summary Table PH-VI
Weighted Emission Rates Table PH-VII
References Table PH-VIII
-------
PH-1
I. Introduction
Half the phenol produced goes into phenolic resins, vhile a substantial
proportion is used to make the nylon-6 intermediate caprolactam. Natural
phenol capacity accounts for only 2% of present day production, and the cumene
process has replaced other synthetic phenol processes to such an extent that
over 907» of U. S. capacity involves the use of cumene charge stock today.
In common vith other air oxidation processes, venting of "spent air" accounts
for a major portion of the emissions from the cumene derivation phenol process.
In addition, since acetone is a major by-product, there is a roughly equivalent
quantity of primarily low molecular weight hydrocarbon emissions associated
with the product recovery and purification sections of the plant. Emissions of
phenolic material is lov, in keeping vith the recognized toxicity of these
materials, though respondents have noted phenolic odors are detectable at
times, usually only vithin the plant. In general, air pollutant emissions
from these phenol plants can be characterized as lov to moderate.
This air pollution study report includes information provided by eight
of the ten cumene process producers in the United States. According to Chemical
Marketing Reporters' June 19, 1972 Chemical Profile, only three plants vith
a total capacity of 310 million pounds annually continue to produce phenol
using other than the cumene process. Current cumene process capacity is
approximately 2.5 billion pounds of phenol per year and is expected to increase
to some 4.2 billion pounds per year by 1980.
No change in emission rate (i.e., tons emission/ton phenol") is forseen
except that, based on indications from respondents utilizing activated carbon
for recovery of cumene from vented "spent air", other producers may find such
pollution control equipment economically justified, and average hydrocarbon
rate of emissions vill actually be less in the future.
-------
PH-2
II. Process Description
The cumene process was developed by Hercules, and Distillers, Ltd. of
England and concurrently, independently by Allied Chemical Corporation. First
commercial production began in the early 1950's, with the cumene route taking
over 507, of the market by 1968 and roughly 90% at the present time.
There are essentially two steps in the liquid phase production of phenol
from cumene (see Table I and Figures PH-1 and PH-2). (i, ii, iii, iv, v ref.).
1. Air is introduced to a vigorously stirred, slightly alkaline aqueous
sodium carbonate emulsion with purified cumene to produce cumene
hydroperoxide (CHP).
2. Dilute sulfuric acid is added to a second agitated reactor to effect
cleavage of the cumene hydroperoxide directly into phenol and acetone.
In the oxidation step, oil-soluble heavy metal catalyst and promoters may
be present, and an emulsifying agent such as sodium stearate may be used. With
a sodium carbonate solution pH in the range 8.5 to 10.5, and water-to-oil ratio
between 2 and 5, reaction is carried out using about 0.5 pounds of oxygen per
pound of phenol, and cumene recycle ratio of «->2:l, at temperatures up to
260° F and atmospheric or moderate superatmospheric pressure. Cooling is
required (see Table II-A) to avoid thermal decomposition of the cumene
hydroperoxide, and with conversion maintained in the range of 30 to 507., "spent
air" is vented through an effective refrigerated condensing system and other
equipment for recovery and recycle of unconverted cumene. During this oxidation
step, some formaldehyde is produced (along with some lesser Quantities of other
reaction products), indicating that the minor by-product acetophenone is also
being formed.
Some producers elect to use a vacuum concentrator on the oxidation reactor
effluent at this point, and to recycle separated overhead cumene to the
oxidizer. In any case, precautions must be taken to avoid explosive con-
centrations of peroxides.
The cleavage step, which follows, involves intimate contact with dilute
sulfuric acid (X/5 - 257.) at temperatures in the range of 130 to 150° F and
pressure slightly above atmospheric. Considerable heat is generated, and again
it is important to provide adequate cooling to avoid thermal decomposition.
There are undoubtedly a number of minor side reactions which occur in the cleavage
reactor; it appears likely that the small amount of alpha methyl styrene produced
results from loss of oxygen from CHP to form cumyl alcohol, followed by
dehydration of the alcohol in the presence of sulfuric acid (see reactions III .(A)
and III (B) in Table I).
An aqueous acid phase from the cleavage reaction effluent separation is
recycled back to the cleavage reactors with makeup acid, and the oil phase is
water washed with appropriate means for selective extraction where required.
The oil layer is sent on through a distillation train for recovery and
purification of product acetone, recycle cumene, alpha methyl styrene (part
or all of which may be hydrogenated and recycled), product phenol, and
acetophenone, which may be purified for marketing or simply left with the
residual oil for use as fuel, or for incineration.
-------
PH-3
III. Plant Emissions
A. Continuous Air Emissions
1. Feed Purification Vent
Literature references indicate the necessity for "clean" cumene
feed and certainly those who find alpha methyl styrene unmarketable
must hydrogenate this material for recycle. Hovever, only respondent
22-1 mentions feed purification, and his information suggests that
emissions here are negligible.
2. Oxidizer Vent
"Spent air" exhausted from the oxidizer is the largest single
source of emissions from cumene process phenol plants. Although not
all respondents provided details, it appears that multiple stage
condensing systems involving refrigeration under moderate pressures
up to 70 or 80 psig are virtually integral to the oxidation section.
Variations in emissions are found because individual producers operate
at a different pressure , cool to a different temperature , use a
scrubber , rely on an activated carbon adsorber , or send the vent stream
to an incinerator. Reported emissions, running from "trace" through
.0015 up to .0067 tons/ton phenol normally (with occasional 1 to 4
hour eauipment failure breaks, in one case up to .049 tons/ton phenol"),
are summarized in Table III.
3. Concentrator Vent
Where respondents reported emission for a post oxidizer cumene
hydroperoxide concentrator vent (22-1, 22-6 and 22-6), emission levels
were low, in the range .0003 tons/ton of phenol and less. Reported
emissions summarized in Table III.
4. Cleavage Section Vent
Respondent information on cleavage section vent emissions is very
mea'gre, with only one actual figure of .0002 tons/ton phenol reported.
However, the fact that acetone is produced here, together with one
respondent's design calculation figure of .0024 tons of acetone plus
.0013 tons of aldehydes per ton of phenol indicates that low to
moderate light hydrocarbon emissions from cleavage may be "normal".
Reported emissions are summarized in Table III.
5. Distillation Train Vents
Acetone is the prominent emission component from this .section of
the plant, with some formaldehyde. Respondent 22-6 has calculated
on the basis of vapor pressure over the analysed condensed liauid,
and finds emissions at .0043 tons of acetone and .0003 tons of
formaldehyde per ton of phenol from an acetone topping tower, and
22-4 uses design calculations to show acetone .0012 and formaldehyde
.0009 tons/ton of phenol similarly. No other emissions of any
consequence are reported, though trace amounts of cumene, mesityl oxide,
and phenol are mentioned. See Table III for details.
6. Plant Flares and Boiler Operations
In some cases, waste "light oil", "heavy oil", or "heavy ends"
-------
PH-4
are sold or transferred to refinery sections of the overall plant
for use as fuel. Respondent 22-3 reports continuous delivery of
light and heavy oil waste to boilers for fuel, vhere excess air is
reported to result (design basis) in complete combustion so that no
significant air pollution occurs. Respondent 22-8 accumulates
phenolic heavy ends and about once a month sends this liquid to a
fuel gas fired flare, again vith reported (design basis) complete
combustion.
B. Intermittent Air Emissions
Aside from the intermittent flaring of liauid vaste (see 6 above)
the only intermittent air emissions involved are those associated
vith atmosphere venting during start-ups and plant emergencies, or
in those cases vhere equipment changeover or refill is required, as
vith spent activated carbon sorbent. An example of the latter is
mentioned by respondent 22-6 vith regard to the infrequent direct
venting of the oxidizer off-gas ("averaging /••». 04 and up to .049 tons
of hydrocarbon emission/ton of phenol) vhen spent activated carbon
sorber is taken off the line. Another example is given by respondent
22-8, again vith regard to venting of the oxidizer off-gas (hydro-
carbon emissions up to as high as .004 tons/ton of phenol for 1 to 4
hour periods possibly ten times per year vhen "recovery equipment
(may) fail"). Emissions in this category may be expected to vary
greatly, and no valid "normal" figure can be inferred from the
information at hand.
C. Continuous Liquid Wastes
1. Heavy Ends
"Phenolic heavy ends" or light 'and "a heavy oil" or "residual
fuel" bottoms from the distillation train most certainly have to be
disposed of one vay or another. Literature information indicates
that the amount of heavy oil vaste isroughly 0.1000 tons per ton of
phenol product. The six respondents providing information on this
point gave figures running from .05 to .26, vith a comparable average
of 0.11 tons per ton of phenol, though accompanying charge stock
or product components considered not vorth recovering vould raise
the actual amount of "vaste" perhaps 50%, or even more, in some
cases.
Only three respondents actually indicated hov their residual
oil vas handled, and in each case incineration or flaring vith fuel
gas vas reported. Complete combustion, vith no significant air
pollution emissions is the design basis, although some NOX probably forms.
2. Aqueous Waste
Acidic vaste vash water from the cleavage reactor separator has
been combined together vith aqueous phenolic vaste streams and other
waste water in figures supplied by the respondents, though presumably
some selective handling is practiced in disposal. The total amounts
handled and method of disposal was reported as follows:
Respondent Code Tons vaste vater Disposal Method
per ton phenol
22-1 15.9 Refinery treating
system
-------
PH-5
Respondent Code Tons waste water Disposal Method
per ton phenol
22-3 1.6 Injection well
22-4 2.2
22-5 ? Injection well
22-6 1.6 In-plant waste
treatment
22-7 4.3
22-8 0.33 In-plant waste
treatment
22-9 0.13 Refinery waste
treatment
D. Solid Wastes
Only respondents reporting solid wastes were 22-7, with an
undefined 81,000 Ib./month, 22-8, with 50,000 Ib./year of diatomaceous
earth for water filtration sent to in-plant land fill, and 22-9,
with 100 Ib. waste solid disposed of on company property.
E. Odors
There was no mention of odor complaints during the past year by
any of the eight respondents. Six of the respondents reported in-plant
odor problems associated with the oxidation section (mainly cumene),
with no complaints mentioned, and only infrequent off-plant odors
noted from this source by two of those reporting. Respondents
22-4 and 22-6 mentioned in-plant odor from the acetone topping unit,
with the latter referring to infrequent off-plant odor being observed
from this source, though again, no complaints. The 22-6 alpha
methyl styrene tower had in-plant odor problems, again infrequently
off-plant. Only respondent 22-8 mentioned odor from the cleavage
section, and this was in-plant. Only respondent 22-1 mentioned
phenolic type odors, and these were said to be associated with a
phenolic water sump and a process bottoms transfer pump, detectable
only on plant property. Respondent 22-8 reported that on occasions
when the fuel gas fired incinerator was used to burn liquid phenol
waste, there was an odor (not identified) on the plant property,
and infrequently off-plant, though no complaints had been noted.
F. Fugitive Emissions
Most producers made no attempt to estimate fugitive emissions.
Respondents who did make estimates provided figures which compare as
shown here in the right hand column.
Fugitive or
Identified Emissions "other emissions"
Respondent Code No. total tons/ton phenol total tons/ton phenol
22-1 .0028 .0005
22-4 .0091 .0003
22-6 .0046 .0010
In some cases, mention was made of fugitive emissions involving
leaks from pump seals, valve stems, packing glands, waste oil end
water sumps, etc., with no attempt at an estimate. One respondent
lumped all emissions and leakage together without distinguishing air
-------
PH-6
or water pollutants, by suggesting approximately 2% losses according
to weight balance on cumene charge, a figure equivalent to .0285
tons per ton of phenol. This figure is high, but perhaps has meaning
in terms of potential for air and water pollution together.
Calculations based on vapor pressure and tank volume and turnovers
per year provide an upper limit estimate for losses to atmosphere
from storage tanks. The total hydrocarbon figures obtained in this
way vary greatly, from less than .00001 tons/ton of phenol to as
much as .0018 tons/ton, in most cases the major portion being acetone.
In many cases, producers have floating roof tanks or have installed
N£ blanket or other type conservation vents, or else the tanks are
normally kept filled. The one respondent from California had
apparently provided floating roof or vapor seal devices so that
tankage vapor losses were virtually eliminated.
None of the respondents gave any figures for appreciable
actual phenol emissions, and with its low vapor pressure, one would
not expect much loss to the atmosphere. However, phenol is highly
toxic, and does have an extremely low TLV or threshold limit value
in air, set by the American Conference of Governmental Industrial
Hygienists, as recorded by N. Irving Sax in "Dangerous Properties
of Industrial Materials", 3rd Edition, (1968). Sax gives
a recommended 5 ppm TLV for phenol, compared to a recommended
25 ppm for benzene or a tentative 50 ppm for cumene. Sax points
out (page 3) that literal application of XL values is dangerous
for a number of reasons.* Nevertheless, one can calculate that
considerable quantities of air would be "contaminated" to the TLV
level when, for example, a large phenol tank held at 130° F is
filled with liquid phenol with vapor escaping through an unprotected
vent to the atmosphere. For one respondent's tank conditions,
assuming complete purging of the vapor space for each reported tank
fill, the average daily phenol emission would be sufficient to
bring a 400 x 400 foot square, 1000 foot depth layer of air to the
5 ppm TLV level. For another respondent, the volume of air brought
to the 5 ppm phenol TLV level each day would correspond to 570 x 570
feet square and 1000 foot depth. Thus, on general principles, for
a toxic material such as phenol, one might well recommend the
installation of protected vent systems for storage tanks and other
vessels whereever feasible.
*0ne of these being, of course, that material which is picked up by skin contact
is included and thus makes establishment of air limits difficult.
-------
PH-7
IV. Emission Control
Table IV of this report, "Catalog of Emission Control Devices", provides
a summary of the devices reported by operators of cumene process phenol plants.
The control devices may be divided into tvo broad categories: (1) Combustion
Devices - those vhich depend on thermal or catalytic oxidation of combustibles
for emission control, and (2) Non-Combustion Devices - Those that do not
depend on combustion. In Table IV, all combustion devices vill be assigned tvo
efficiency ratings (vhen data are available):
(1) CCR - Completeness of Combustion Rating
CCR = Ibs. of 02 that react vith pollutants in feed to device x 100
Ibs. of 02 that theoretically could react vith these pollutants
(2) SERR - Significance of Emission Reduction Rating
SERR = veighted pollutants in - veighted pollutants out ,„„
veighted pollutants in
A more detailed discussion of these ratings may be found in Appendix V
of this report.
Most non-combustion devices vill be assigned a Specific Efficiency, SE,
based on percent reduction of a specific compound vith that compound defined.
A few non-combustion devices vill receive SERR ratings.
In some cases, respondents included helpful information on a venting
device which, vhen carefully maintained, provided effective emission control,
but they were quick to point out that the device was really an economically
necessary integral part of the plant eauipment, therefore, not legitimately
an emission control cost item. In other cases, the large amount of hydrocarbon
recovery attributable to the device made it obvious that it vas an economic
necessity, but the difficult-to-assess incremental cost of further reducing
condensate temperature, or maintaining a slightly higher pressure in a knock-
out drum, or more frequent change over to a freshly reactivated carbon sorbent
tower, or the like, might veil be considered part of the expense of emission
control.
Undoubtedly due, at least in part, to the strict attention being paid to
environmental considerations in California, the one cumene process phenol
producer responding to the questionnaire from that state has installed devices
on virtually every vent, outlet, or tank to keep air emissions lov. It
appears that emissions are indeed lov for this plant, vhich is a small one,
but unfortunately the respondent does not have Quantitative data to orovide a
means for comparison vith other plants.
The folloving is a brief summation of the various emission control devices
identified by respondents in this survey. Details are to be found in Table IV
vith accompanying footnotes for that table.
Sorbers/Scrubbers
Activated carbon sorber beds are identified as effective emission
control devices for recovering cumene from spent air from the oxidizer,
by both 22-6 and 22-7 respondents; respondent 22-3 likevise mentions
that activated carbon is used to advantage in the same location, but
-------
PH-8
ordinarily relies on a gas fired incinerator for further clean-up
of this high volume effluent stream (see belov).
Pressure and temperature conditions for the stream entering the
PH-VII carbon bed are such that a relatively high cumene content is
present, and the device, with a specific efficiency of 91%, is shovn to
recover sufficient cumene in one year's time to pay off the installed
cost. Carbon sorber PH-VIII is also effective, though its Specific
Efficiency is only 82% and the respondent had no operating cost figures.
"Scrubber" device PH-I listed by 22-1 is merely a vater seal leg
trap on the feed purification system, and vater "scrubber" tank PH-XIV
is a "catch-all" emergency relief provision vhich also serves to scrub
normal wash section vents from several plant locations.
The "Scrubber-Cooler" device, vhich is part of the PH-II combination
emission control used by 22-1 to recover cumene from the oxidizer
off-gas, must really be considered an integral part of the plant, an
economic necessity. It involves circulation of cooled cumene condensate
down a 15 tray column to recover cumene in the vent stream and return
to the oxidizer.
Condensers and K. 0. Drums
Respondents 22-1, 22-4 and 22-5 all rely on refrigerated condensing
equipment with knock-out drums under moderate pressure to achieve sub-
stantial removal of cumene from the oxidizer off-gas, vith PH-II, PH-V
and PH-VI respectively. In all three cases, the eauipment is primarily
needed for returning cumene to the oxidizer and only secondarily is an
emission control device. Respondent 22-1 used a three stage vater condenser,
PH-III to control emission from the post oxidation concentrators, obtaining
65% Specific Efficiency, incurring a net cost in the operations.
Respondent 22-4, with water condenser PH-IX above a post-oxidation vash
unit, really considers this an economic necessity, hence, provided no
recovery or operating cost data.
Respondent 22-1 shovs single cold vater condensers vith knock-out
drums PH-X and PH-XI for the cleavage reactor and an acetone tower,
respectively; two-stage cold water condensers with steam jet ejectors and
knock-out drums (PH-XII and PH-XIII) for acetone purification and phenol
recovery, respectively. In each case the eauipment is a legitimate
emission control cost item, but there is insufficient data provided to
allow an estimate of efficiency.
Incineration Devices
Producer 22-3 identifies a gas-fired incinerator PH-IV normally* serving
to virtually eliminate hydrocarbon emissions from the oxidizer off-gas that
has already passed through vhat appears to be fairly efficient activated
carbon beds. Analytical data given indicate no unburned hydrocarbon or
pollutant other than a trace of NOX in the effluent, hence, virtually
100% Specific Efficiency.
Respondent 22-8 lists PH XV gas fired flare for periodic burning of
heavy ends waste, and reports that on equipment design basis, combustion
is complete, so 100% efficiency is indicated (though an infrequent off-plant
*0ut of service for extensive repairs at the time of responding to the
questionnaire, August, 1972.
-------
PH-9
odor problem is mentioned). Respondent 22-3 reports that both light
and heavy oil waste is sent to plant boilers as fuel, but no information
is provided to indicate efficiencies. Both of these incinerators
probably cause the formation of at least traces of NOX.
Future Possibilities
Among items mentioned by respondents for improvement in emission
control were these:
1. Installation of vapor recovery or vapor conservation equipment
on tanks.
2. Improvement in pump seals for phenolic stocks.
3. General process improvements. Areas for investigation in this
regard include the following:
(a) Reexamination of proposals to use oxygen in place of air,
with due emphasis on safety and economic considerations.
(b) Further use of refrigerated condenser equipment.
(c) Further use of hydrocarbon recovery systems like activated
carbon.
-------
PP-10
V. Significance of Pollution
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
total weighted annual emissions of pollutants from these new plants. The
results are summarized in Tables V, VI and VII.
On a weighted emission basis, a Significant Emission Index of 1,704 has
been calculated in Table VII. This is well below the SEI's anticipated for
other processes in the study.
Because of the relatively low SEI, it is recommended that no in-depth
study of the Cumene Oxidation Process for the production of Phenol be
undertaken in the current study. Although, a review of this recommendation
may be justified at a future date. The reasons for review are somewhat
subjective in nature, and no one of them would be justification on its own
for an in-depth study. However, taken together they might be sufficiently
important to warrant the collection of data that are pertinent to the setting
of emission standards on new stationary sources. Briefly, these reasons are;
1) The reported oxidizer emissions factors range from a trace to nearly
0.01 with an emergency factor of nearly .05 reported in one instance.
This is understandable since pollution control devices range from
simple condenser systems through scrubbers to carbon absorbers and
incinerators.
2) The reported oxidizer emissions include pollutants such as formaldehyde,
acetophenone and cumene. If traces of cumene hydroperoxide are also
present in this stream, it could be acid cleaved in the surroundings
to form phenol.
3) Cleavage vents also contain noxious substances such as aldehydes.
4) Emission factors alone do not tell the story since some plants report
emissions in terms of hundreds of pounds per hour of hydrocarbons or
aldehydes.
5) An amount of liquid waste which is equivalent to about 10% of the
production capacity is typically incinerated, which if uncontrolled
could produce significant air pollution, expecially NOX or products
of incomplete combustion.
6) Occasional off-plant odors are reported.
7) Phenol is highly toxic.
8) The process is clearly a growth one. Thus, economics of scale and new
design might force shut downs of more marginal plants than were assumed
in the prediction of the numbers of new plants. Hence, a greater
number of candidates for new source standards would exist.
9) Phenol storage techniques are such that significant quantities of the
substance could be emitted.
-------
PH-H
VI. Phenol Producers
vii, viii)
Natural phenol hardware capacity was about 60 MM pounds of phenol per
year in 1972, but actual capacity was somewhat lower because of a scarcity
of feedstocks for coal-tar derived material. Producers in this natural
product category include Kaiser Steel, Fontana, California, Koppers Co., Inc.,
Follansbee, W. Va., Merichem Co., Houston, Texas, Productol Chemical, Santa
Fe Springs, California, Stinson Lumber Co., Anascortes, Washington and
U. S. Steel Corporation, Clairton, Pa.
Synthetic phenol, as mentioned previously, isderived from cumene for
the most part, other processes being found unable to compete except for
certain special circumstances. For example, as noted by Stanford Research
Institute in "Chemical Economics Handbook", Dow Chemical maintains a benzene
chlorination plant, Kalama Chemical, Inc. a toluene oxidation plant and
Reichhold Chemicals, Inc. a benzene sulfonation plant because of special by-
products obtained. Following is a list of companies and locations vhere
synthetic phenol is now being produced (see CEH, July, 1972). In many
cases, a large proportion of the capacity is committed for captive use.
Published Synthetic Phenol Capacity '*-'.
Company
Location
Allied Chemical Corp. Frankford, Pa.
Manufacturing
Process
Cumene
Clark Oil &
Refining Corp.
Dow Chemical Co.
Georgia-Pacific Corp.
Kalama Chemical, Inc.
Monsanto Co.
Reichhold Chemicals
Shell Chemical Co.
Skelly Oil Co.
Std. Oil Co. of
California
Union Carbide Corp.
United States
Steel Corp.
Blue Island, 111.
Oyster Creek, Texas
Midland, Mich.
Palquemine, La.
Kalama, Wash.
Chocolate Bayou,
Texas
Tuscaloosa, Ala.
Houston, Texas
El Dorado, Kansas
Richmond, Cal.
Bound Brook, N. J.
Penuelas, P. R.
Haverhill, Ohio
Cumene
Cumene
Chlorina. Benzene
Cumene
Toluene
Cumene
Sulfonation
Cumene
Cumene
Cumene
Cumene
Cumene
1972 Capacity
MM Lb./Yr.
500
75
400
100
200
48
375
135
60
50
55
150
(2)
Cumene
Total
-------
PH-12
(1) As given by J. L. Blackford, July, 1972, Chemical Economics Handbook,
Stanford Research Institute.
(2) Union Carbide Penuelas, Puerto Rico, 200 MM Lb./Yr. nev capacity,
scheduled by January, 1973.
C3) U. S. Steel, Haverhill plant capacity expansion up to 305 MM Lbs./Yr.
in progress, see CW 1/31/73, page 19.
-------
PAGE NOT
AVAILABLE
DIGITALLY
-------
PAGE NOT
AVAILABLE
DIGITALLY
-------
MAIN REACTION
I. Step A. Oxidation
TABLE PH-I
BASIC CHEMISTRY
OF
PHENOL PRODUCTION FROM CUMENE (ix, x, xl, xil)
H
CH,
C I "
// \ ' I '
HC C—C—H
I II I
HC CH CH3
H
Cumene
120.2
°2
+ Oxygen
32
CH,
/A I 3
HC C— C 0 OH
I II I
HC ^CH CH3
H
Cumene Hydroperoxide
152.2
I. Step B. Cleavage
H
C CH3
//\ I
HC C C 0 OH
I ." I .
HC CH CH,
V 3
H
Cumene Hydroperoxlde
152.2
SECONDARY REACTION'S
II. Production of Acetophenone
CH
C
/A
HC C - C - 0 - OH + % 0
I II I
HC CH CH,
,
2
H
Cumene Hydroperoxide + Oxygen
152.2 16
H
C
// \
HC C—OH
I II
HC ,CH
V
H
Phenol
94.1
CH3
0=C
+ \
CH3
+ Acetone
58.1
H
,C 0
// \ // .
•-> HC C C
I 'I \
HC CH CH,
*(/ ^
H
--> Acetophenone
120.2
+ 0 +
CHj
•f Formaldehyde +
30
H-0
Water
18
III. Production ofocMethylstyrene
A f
HC C - C - 0 - OH
I II
HC CH
-^^™^
CH3
H
H
C
//\
HC C
CH,
C—OH-
HC CH
H
1
(B)
CH,
//\ H
HC C - C
I I I
HC
\/
CH CH,
H
Cumene Hydroperoxide
152.2
Cumyl Alcohol
136.2
Oxygen
16
-i>- ocMethyl Styrene + Water
118.2 9
-------
TABLE PH-II
Stream No. (Fig. II)
Stream Name
Cumene
Cumene Hydroperoxide
Phenol
Acetone
otMe-Styrene
AcCtophenone
Formaldehyde
Oxygen
Nitrogen
Water
Total
Stream No. (Fig. II)
Stream Name
Cumene
Cumene Hydroperoxide
Phenol
Acetone
oiMe-Styrene
Acetophenone
Formaldehyde
Oxygen
Nitrogen
Water
PHENOL PRODUCTION EX CUMENE
MATERIAL BALANCE* TONS /TON OF PRODUCT
(D (2) (3) (1, 2 & 3) (5)
Oxidizing Gross Oxidizer Oxidizer
Air Feed Recycle Feed Effluent
1.4450 3.2611 4.7061 3.2611
1.7621
<
: .0505
.5007 .5007
1.7319 1.7319
.0052
2.2326 1.4450 3.2611 6.9387 5.0789
(9) (10) (11) (12) (13) (14)
Acetone Cumene
n
o
Total
.0026
3.2611
.1009
.0596
1.000
Notes: "A" Oxidation is facilitated thru the use of an alkaline - aqeous emulsion - PH of 8.5 - 10.0 - a Na2C03 solution is normally used Vith emulsifying agents,
H20/oir ratio 1* thought to be In the'range'of 2/1'to 5'/l '(vol.).
"B" Dilute (<*107.) sulfuric acid is recycled for cleavage - make-up rate is unknown.
"C" Wash water to remove residual acid, rate unspecified.
"D" Consists of wash water and resludal
*See notes "A" & "B" and Phenol Table II Material Balance Limitations.
-------
PHENOL TABLE II MATERIAL BALANCE LIMITATIONS
1. Cumene conversion is set (a 30.7%; conversion usually reported between
25 and 45%.
2. Selectivity (moles phenol formed/moles cumene converted expressed as %)
is set (3 88.47o. If methyl styrene is hydrogenated and recycled so that
\ goes to phenol, selectivity would be 92%. Since demand f or cxMS is less
than \ rated capacity, recycle is often preferred.
3. A review of respondents data reveals that heavy residual material amounting
to •"•-< .1000 tons/ton of phenol is produced. This is not included in the
material balance shown here because definitive composition information
is lacking. If it be assumed that a like amount of cumene (0.1000 tons/ton
of phenol) be consumed producing this heavy material, along with recycle
of methyl styrene (see 2 above) a selectivity of 86 mole % would be
realized, in line with the average figure reported by the eight respondents
in the present study.
4. Oxidizing air fixed at 50 Ib./lOO Ib. product phenol, which is '--1407,,
of theoretical for conversion and selectivity shown.
5. Hydrocarbons are shown only for the two vent streams (6) and (9) where
emissions are appreciable, though other vent streams do contain measurable
emissions, as indicated in Table III.
6. All cumene recycle here is shown in cleavage section effluent, though,
as indicated in Figure II, some proportion is usually taken out for
recycle following oxidation and/or concentration.
7. V7ater amounts shown here represent only reaction product as indicated
in Table I where formaldehyde and methyl styrene are produced. Sub-
stantial quantities of water are required for the alkaline acmeous emulsion
in the oxidation section (2 to 5 times hydrocarbons present), for the
dilute sulfuric acid (--lOT, concentration) in the cleavage section, and
in the subsequent wash tower.
-------
TABLE PH-IIA
PRODUCTION OF PHENOL FROM CUMENE
GROSS HEAT BALANCE (xiii, xiv, xv)
BASIS MATERIAL BALANCE TABLE II
AND REACTIONS IN TABLE I
BTU/Lb. Phenol Product
OXIDATION REACTOR Exothermic Endothermic
(Cooling Rea'd.) (Heating Req'd.)
Reaction I (A) producing cumene hydroperoxide 483
" II " acetophenone 58
Heating cumene charge from 90 to 250° F 346
Heating N2 & 02 from 90 to 250° F 87
Totals 541 433
Net heat exchange requirement (difference) 108
CLEAVAGE REACTOR
Reaction I (B) producing phenol & acetone 991
Reactions III (A) producing cumyl alcohol
and III (B) producing methyl styrene 31
Cooling cumene from 250° F to 140° F 165
Cooling cumene hydroperoxide & acetophenone
to 140° F 120
Totals 1,307 0
Net heat exchange requirement (difference) 1,307
-------
TABLE PH-III
NATIONAL EMISSIONS INVENTORY
PHENOL PRODUCTION FROM CUMENE
Plant - EPA Code Number
Capacity - Tons of Phenol/Yr.
Average Production - Tons of Phenol/Yr.
Quarterly Production Variation - % of Max.
Emissions to Atmosphere
Stream
Flov - Lb./Hr.
Flov Characteristics - Continuous or Intermittent
if Intermittent - Hrs/Yr. Flov
Composition - Tons/Ton of Phenol (5)
Cumene
Cumene Hydroperoxide
Phenol
Acetone
— Methyl Styrene
Acetophenone
Acetaldehyde
Formaldehyde
Mesityl Oxide
Dimethyl Benzyl Alcohol
Benzene
Toluene
Ethyl Benzene
Misc. Hydrocarbons
Cumyl Phenol & Phenolic Tars
Water
Carbon Dioxide
Nitrogen
Oxygen
Sample Tap Location
Date or Freouency of Sampling
Type of Analysis
Odor Problems
Vent Stacks
Flov - SCFM/stsck
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 Phenol
Total Particulate 6. Aerosol Emissions - Ton/Ton of Phenol
Total NOX Emissions - Ton/Ton of Phenol
Total SOX Emissions - Ton/Ton of Phenol
Total CO Emissions - Ton/Ton of Phenol
22-1
26,500
26,500
0
Feed
Purification
Section
Vent
Unknovn (1)
Continuous
12' up
Never
No
1
112
2
Ambient
Yes
Liquid Trap
PH-I
Oxidation
Section
Vent
21,800 <2>
Continuous
.0025
(2)
Elevated (7)
Twice
G.C. +57.
Yes Ctn olant)
4350 (2)
1
125
10
Ambient
Yes
Scrubber-Cooler
PH-II
.0025 (2>
0
Page 1 of 13
Concentration
Section Vapor
Condenser
Vent
51.3 (2>
Continuous
.00001
.00025 (2)
Elevated (7)
Tvice (1970 & 1972)
G.C. +107.
No
10.2 (2)
1
40
2
Ambient
Yes
Vapor Condenser
PH-III
.0003 (2)
0
Cleavage
Section Vapor
Condenser
Vent
Unknovn
Continuous
+ (5%)
Elevated
(7)
Once (1972)
G.C. +107.
No
1
20
2
Ambient
Yes
Vapor Condenser
PH-X
-------
TABLE PH-III
NATIONAL EMISSIONS INVENTORY
PHENOL PRODUCTION FROM CUMENE
Page 2 of 13
Plant - EPA Code Number
Capacity - Tons of Phenol/Yr.
Average Production - Ton* of Phenol/Yr.
Quarterly Production Variation - % of Max.
Emissions to Atmosphere
Stream
Flov - Lb./Hr.
Flov Characteristics - Continuous or Intermittent
If Intermittent - Hrs./Yr. Flov
Composition - Tons/Ton of Phenol (5)
Ciimene
Cumene Hydroperoxlde
Phenol
Acetone
.< Methyl Styrene
Acetophcnone
Acetaldahyde
Formaldehyde
Mesityl Oxide
Dimethyl Benzyl Alcohol
Benzene
Toluene
Ethyl Benzene
Misc. Hydrocarbons
Cumyl Phenol & Phenolic Tars
Water
Carbon Dioxide
Nitrogen
Oxygen
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 Emission - Ton/Ton of Phenol
Total Participate 6, Aerosol Emissions - Ton/Ton of Phenol
Total NOx Emissions - Ton/Ton of Phenol
Total SOjj Emissions - Ton/Ton of Phenol
Total CO Emissions - Ton/Ton of Phenol
Phenol & Acetone
Sep'nv/FuTlfteatIon
Section
Vapor Cond, Vents
Unknovn
Continuous
Elevated
Never
No
1
120
3
Ambient
res
Vapor Condenser
PH-XI, XII
(+) <*>
0
22-1
26,500
26,500
0
Phenol Recovery.&
Sep'n. Section
Vapor Cond.
Vent
Unknovn
Continuous
(-0
Elevated (7)
Never
No
1
125
3
Ambient
Yes
Vapor Condenser
PH-XIIT
Residual
Oil
Sump
Vent
Unknovn
Continuous
Phenolic
Water
Simp
Vent
Unknovn
Continuous
No port
Never
(7)
No
(6)
1
30
2
Ambient
Yes
Yes
(6)
PH-XIV
(+)
0
No port
Never
Yes (8)
1
24
6
Ambient
None
(7)
-------
Flint - EPA Code Npaber
Capacity - Tons of Phenol/Yr.
Average Production - Tons of Phenol/Yr.
Quarterly Production Variation - % of Max.
Emissions to Atmosphere
Stream
Flov - Lb./Hr.
Flov Characteristics - Continuous or Intermittent
If Intermittent - Hrs./Yr. Flov
Composition - Tons/Ton of Phenol (5)
Cunene
Cumene Hydroperoxlde
Phenol
Acetone
^.Methyl Styrene
Acetophenone
Acetaldahyde
Formaldehyde
Mesityl Oxide
Dimethyl Benzyl Alaohol
Benzene
Toluene
Ethyl Benzene
Misc. Hydrocarbons
Cumyl Phenol & Phenolic Tars
Water
Carbon Dioxide
Nitrogen
Oxygen
Simple 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 Phenol
Total partlculate & Aerosol Emissions - Ton/Ton of Phenol
Total NOX Emissions - Ton/Ton of Phenol
Total SOx Emission! - Ton/Ton of Phenol
Total CO Emissions - Ton/Ton of Pkemol
TABLE PH-III
NATIONAL EMISSIONS INVENTORY
PHENOL PRODUCTION FROM CUMENE
OtHation
Concentration
Cleavage Section Pump
Drain Sampling Vent
1.455
Continuous
.0000009
(9)
At grade (7)
Once (1972)
G.C. +57.
No
.29
1
70
2
Ambient
None
.0000009
0
(9)
Page 3 of 13
22-1
26,500
26,500
0
Mlsc Vent
Water Scrubber
Stack "0)
Unknovn
Continuous
Procepf Bottom?
Transfer
Pump
Unknovn
Occasional
Need platform
Never
No
1
87
14
Ambient
Yes
PH-XIV
(+)
0
(7)
Hot Ftack l'
Not Sampled
Occasional
(8)
-------
Plant - EPA Code Number
Capacity - Tons of Phenol/Yr.
Average Production - Tons of Phenol/Yr.
Quarterly Production Variation - % of Max.
Stream
Flow - Lb./Hr.
Flov Characteristics - Continuous or Intermittent
if Intermittent - Hrs./Yr. Flow
Composition - Tons/Ton of Phenol (5)
Curoene
Cumene Hydroperoxide
Phenol
Acetone
o
Continuous
0 to .005
"trace" forgs.)
0 to .0024
2.2625
.1190
Stairway access
at original- start-up
Org. G.C. +207.
Yea (in plant)
25,700
50°
Actlva. Carbon
0 to .005
(12)
22-3
200,000
200,000
0
Oxidation
Section
Incinerator
Stack
128,600 <13>-
Continuous
Gases CCalc.) ex
Incineration of
Light Oil Waste
Gases fCalc.) ex
Incineration of
Heavy Oi 1 Waste
47,100
Continuous
142,000
Continuous
Trace
Difficult
Never
.052?
.1521
.6679
.1093
None
.0833
.3583
2.1813
.3354
None (18)
No
(15)
20,250
1
55
72
450°
Yes (15)
PH-IV
"trace"
0
Boiler (Fuel)
Boiler #1
Boiler (Fuel)
Boiler #2
-------
TABLE PH-III
NATIONAL EMISSIONS INVENTORY
'PHENOL PRODUCTION FROM CUMENE
Page 5 of 13
Plant - EPA Code Number
Capacity - Tons of Phenol/Yr.
Average Production - Tons of Phenol/Yr.
Quarterly Production Variation - % of Max.
Stream
Flov - Lb./Hr.
Flov Characteristics - Continuous or Intermittent
if Intermittent - Hrs./Yr. Flov
Composition - Tons/Ton of Phenol (5)
Cutnene
Cumene Hydroperoxide
Phenol
Acetone
»< Methyl Styrene
Acetophenone
Acetaldehyde
Formaldehyde
Mesityl Oxide
Dimethyl Benzyl Alcohol
Benzene
Toluene
Ethyl Benzene
Misc. Hydrocarbons
Cumyl Phenol & Phenolic Tars
Water
Carbon Dioxide
Nitrogen
Oxygen
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 Temp. °F
Emission Control Devices
Type - Incinerator
Flare
Scrubber
Other
Catalog I. D. Number
Total Hydrocarbon Emissions - Ton/Ton of Phenol
Total Particulate & Aerosol Emissions - Ton/Ton of Phenol
Total NO,, Emissions - Ton/Ton of Phenol
Total SOX Emissions - Ton/Ton of Phenol
Total CO Emissions - Ton/Ton of Phenol
Oxidizer
Section
Vent
53,500
Continuous
.0020
.0032
.0015
.0017
1.6550
.1000
Easily arranged
Never (lf)
No
12,000
1
70
14
45°
Refrig. 73 psig Cond. (2°)
PH-V
.0067
22-4
125,000
125,000
0
Post Oxidizer
Washer, Surge Tank
Combination
Vent
790 d9)
Continuous
.0003
(21)
Never(19)
Yes (in plant)
180
1
30
4
85°
18 psig Chiller (2°)
PH-IX
.0003
Cumene Stripper
Jet Condenser
Vent
Unknovn
Continuous
Could arrange
Never
No
Unknown
1
40
6
130°
C. W Condenser
Acetone Topping
Column Overhead
Accumulator
64 (19)
Continuous
.0012
.0009
'
Could arrange
Never (19)
Yes (in plant)
7.8
1
80
10
110"
C. W. Condenser
.0021
-------
TABLE PH-III
NATIONAL EMISSIONS~INVKirrORY
PHENOL PRODUCTION FROM CUMENE Page 6 of 13
Plant - EPA Code Number 22-4
Capacity - Tons of Phenol/Yr. 125,000
Average Production - Tons of Phenol/Yr. 125,000
Quarterly Production Variation - % Of Max. 0
Stream Post Cleavage Post Cleavage Phenol-Acetone Acetone rolumn Phenol Recovery
Reactor Vapor Washer Still Vapor Vapor Condenser Overhead Accumulator
Condenser Vent Condenser Vent Section Vent
Vent Vent
Flov - Lb./Hr. Unknovn Unknovn Unknovn Unknovn Unknovn
Flov Characteristics - Continuous or Intermittent Continuous Continuous Continuous Continuous Continuous
if Intermittent - Hra./Yr. Flov
Composition - Tons/Ton of Phenol "'
Cumene
Cussne Hydroperoxlde
Phenol (+>
Acetone (+) (+) (+)
„< Methyl Styrene
Acetophenone
Acetaldehyde (+)
Formaldehyde (+)
Mesityl Oxide
Dimethyl Benzyl Alcohol
Benzene
Toluene
Ethyl Benzene
Misc. Hydrocarbons (+) (+) (+) (+) (+)
Cttnjrl Phenol & Phenolic Tars
Water (+)
Carbon Dioxide
Nitrogen (+)
Oxygen (+)
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problem
Vent Stacks
Flov - SCFM/stack
Number . 1
Height - Feet ?
Diameter - Inches
Exit Gas Temp. °F
Emission Control Devices
Type - Incinerator
Flare
Scrubber
Other C. W. Condenser C. W. Condenser Condenser
Catalog I. D. Number
Total Hydrocarbon Emissions - Ton/Ton of Phenol (+) (+) (+) (+) +
Total Particulate & Aerosol Emissions - Ton/Ton of Phenol
Total NOX Emissions - Ton/Ton of Phenol
Total SOX Emissions - Ton/Ton of Phenol
Total CO Emissions - Ton/Ton of Phenol
-------
TABLE PH-III
NATIONAL EMISSIONS INVEHTORY
PHENOL PRODUCTION FROM CUMENE
Page 7 of 13
Plant - EPA Code Number
Capacity - Tons of Phenol/Yr.
Average Production - Tons of Phenol/Yr.
Quarterly Production Variation - 7. of Max.
Emissions to Atmosphere
Stream
Flov - Lb./Hr.
Flov Characteristics - Continuous or Intermittent
if Intermittent - Hrs./Yr. Flow
Composition - Tons/Ton of Phenol (5)
Curaene
Cumane Hydroperoxide
Phenol
Acetone
„< Methyl Styrene
Acetophenone
Acetaldehyde
Formaldehyde
Mesityl Oxide
Dimethyl Benzyl Alcohol
Benzene
Toluene
Ethyl Benzene
Misc. Hydrocarbons
Cumyl Phenol & Phenolic Tars
Water
Carbon Dioxide
Nitrogen
Oxygen
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problems
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 Phenol
Total Particulate & Aerosol Emissions - Ton/Ton of Phenol
Total NOX Emissions - Ton/Ton of Phenol
Total SOX Emissions - Ton/Ton of Phenol
Total CO Emissions - Ton/Ton of Phenol
22-5
107,500
107,500
0
Spent
Oxidation
Air
Vent
48,080
Continuous
.0015 (22)
Oxidizer
Off-gas
Vent (23)
36,995
(See note)
.0383
.0015
1.6642
.1309
Could install
Never
None
No
10,190
1
86
10
40°
Refrig. 70 pslg Condenser
PH-VI
.0015 (22)
.0015
.0295
1.3022
.1032
Easy access
/^Monthly from 9/71
Acetone Scrub. GLC
Yes (in plant)
7576
100° @ 28 psig
.0398 (23)
22-6
100,000
100,000
0
Post Oxidizer
Cumene Recovery
Spent Air
Vent
33,973
Continuous
.0020
.0014
Carbon Absorber
PH-VII
.0034 (24)
Post Oxidizer
Concentration
Condenser
Vent
6.0
Continuous
.00002
.000007
(+)
.0408
1.2203
.0951
Easy access
3 x/month from 9/71
Acetone Scrub. GLC
No
7576
1
86
12
140°
. 000002
.000001
. 0000002
.00001
.00013
.00007
Easy, 10' up
9/18 6, 9/20/72
G.C. + 20%
No
1.1
1
76
2
105°
.00003
Cleavage
Condenser
Vent
6.5
Continuous
.0002
up
.00003
.00003
.00002
Easy. 5
Never
Design Calc
No
0.83
1
76
2
95°
+ 207.
.0002
-------
- TABLE PH-III
NATIONAL EMISSIONS INVENTORY
PHENOL PRODUCTION FROM CUMENE
Plant - EPA Code Number
Capacity - Tons of Phenol/Yr.
Average Production - Tons of Phenol/Yr.
Quarterly Production Variation - % of Max.
Emissions to Atmosphere
Stream
Flow - Lb./Hr.
Flow Characteristics - Continuous or Intermittent
If Intermittent - Hrs./Yr. Flow
Composition - Tons/Ton of Phenol (5)
Cumene
Cumene Hydroperoxlde
Phenol
Acetone
»*J*thyl Styrene
Acetophenone
Acetaldehyde
Formaldehyde
Mesityl Oxide
Dimethyl Benzyl Alcohol
Benzene
Toluene
Ethyl Benzene
Misc. Hydrocarbons
Cunyl Phenol & Phenolic Tars
Water
Carbon Dioxide
Nitrogen
Oxygen
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problems
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 Phenol
Total Particulate & Aerosol Emissions - Ton/Ton of Phenol
Total NOX Emissions - Ton/Ton of Phenol
Total SC^ Emissions - Ton/Ton of Phenol
Total CO Emissions - Ton/Ton of Phenol
22-6
100,000
100,000
0
Acetone
Topping Column
Vent
115
(25)
Continuous
.0043
.0003
Easy access
Dally (liquid)
Calc. •> G'.C. ofl equll. liquid
Yes, Infrequently off plant
12.8
1
86
6
130°
.0046
(25)
Acetone
Tower
Vent
Unknown
Intermittent
~1600 (26)
Remove drain bell
Never
Calc.
No
1
86
18
95°
(26)
Page 8 of 13
ex Methyl
Styrene Tower
Vent
11
Continuous
.0001
Natural Gas
Fired Rebeller
Stack
.00005
.00004
.0002
Difficult
Daily for >1 year
Calc. ex G.C. on eauil. liquid
Yes, Infrequently off plant
0.70
1
70
4
289°
.0004
(27)
.00000004
-------
TABLE PH-III
NATIONAL EMISSIONS INVENTORY
PHENOL PRODUCTION FROM CUMENE Page 9 of 13
Plant - EPA Code Number 22-7
Capacity - Tons of Phenol/Yr. 40,000
Average Production - Tons of Phenol/Yr. ' 40,000
Quarterly Production Variation - 7. of Max. 0
Emissions to Atmosphere
Stream Post Oxidizer Post Oxidizer Phenol Recovery Product Acetone
Carbon Sorber Steam Jet Purification Recovery Section Recovery Section
Vent Vent Vent Steam Jet Vent
Vent
Flow - Lb./Hr. 23,800 (28> No data No data No data No data
Flow Characteristics - Continuous or Intermittent Continuous Continuous
if Intermittent - Hrs./Yr. Flov
Composition - Tons/Ton of Phenol (5)
Cumene .0029 (+)
Cumene Hydroperoxide
Phenol (+)
Acetone (+)
o< Methyl Styrene
Acetophenone
Acetaldehyde
Formaldehyde (+)
Mesityl Oxide
Dimethyl Benzyl Alcohol
Benzene
Toluene
Ethyl Benzene
Misc. Hydrocarbons (+) (+) (-f) (+)
Cumyl Phenol & Phenolic Tars
Mater (+)
Carbon Dioxide
Nitrogen (+)
Oxygen (+)
Sample Tap Location Difficult
Date or Frequency of Sampling 4 times per year
Type of Analysis GLC on cond. liq.
Odor Problems Undetermined
Vent Stacks
Flow - SCFM/stack 5330
Number Not given 111 1
Height - Feet 50 70 75 75
Diameter - Inches 444 4
Exit Gas Tenp. °F 41° 70° 70° 70° 70°
Emission Control Devices
Type - Incinerator
Flare
Scrubber
Other Carbon Adsorber
Catalog I. D. Number PH-VIII
Total Hydrocarbon Emissions - Ton/Ton of Phenol .0029 (+) (+) (+) (+)
Total Partlculate & Aerosol Emissions - Ton/Ton of Phenol
Total NOX Emissions - Ton/Ton of Phenol
Total SOy Emissions - Ton/Ton of Phenol
Total CO Emissions - Ton/Ton of Phenol
-------
TABLE PH-III
NATIONAL EMISSIONS INVENTORY
PHENOL PRODUCTION FROM CUMENE
Plant - EPA Code Number
Capacity - Tons of Phenol/Yr.
Average Production - Tons of Phenol/Yr.
Quarterly Production Variation - % of Max.
Emissions to Atmosphere
Stream
Flov - Lb./Hr.
Flov Characteristics - Continuous or Intermittent
If Intermittent - Hrs./Yr. Flov
Composition - Tons/Ton of Phenol (5)
Cumene
Cumene Hydroperoxide
Phenol
Acetone
o< Methyl Styrene
Acetophenone
Acetaldehyde
Formaldehyde
Mesityl Oxide
Dimethyl Benzyl Alcohol
Benzene
Toluene
Ethyl Benzene
Misc. Hydrocarbons
Cumyl Phenol & Phenolic Tars
Water
Carbon Dioxide
Nitrogen
Oxygen
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problems
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 Phenol
Total Particulate & Aerosol Emissions - Ton/Ton of Phenol
Total NOX Emissions - Ton/Ton of Phenol
Total SOX Emissions - Ton/Ton of Phenol
Total CO Emissions - Ton/Ton of Phenol
Product
Recovery Section
Vent
No data
22-7
40,000
40,000
0
oCMethyl Styrene
Recovery Section
Steam Jet Vent
No data
Page 10 of 13
iXMethyl Styrene
Recovery Section
Vent
No data
Residual Fuel
Recovery Section
Vent
No data
00
oo
(•O
00
oo
1
75
4
70°
1
50
4
70°
1
50
4
70°
1
75
4
70°
00
(•O
-------
TABLE PH-III
NATIONAL EMISSIONS INVENTORY
PHENOL PRODUCTION FROM CUMENE
Page 11 of 13
Plant - EPA Code Number
Capacity - Tons of Phenol/Yr.
Average Production - Tons of Phenol/Yr.
Quarterly Production Variation - 7. of Max.
Emissions to Atmosphere
Stream
Flow - Lb./Hr.
Flov Characteristics - Continuous or Intermittent
if Intermittent - Hrs./Yr.
Composition - Tons/Ton of Phenol
Cumene
Cumene Hydroperoxlde
Phenol
Acetone
eX Methyl Styrene
Acetophenone
Acetaldehyde
Formaldehyde
Mesityl Oxide
Dimethyl Benzyl Alcohol
Benzene
Toluene
Ethyl Benzene
Misc. Hydrocarbons
Cumyl Phenol & Phenolic Tars
Water
Carbon Dioxide
Nitrogen
Oxygen
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 Phenol
Total Partlculate & Aerosol Emissions - Ton/Ton of Phenol
Total NOX Emissions - Ton/Ton of Phenol
Total SOX Emissions - Ton/Ton of Phenol
Total CO Emissions - Ton/Ton of Phenol
Oxldizer
Section
Vent
14,220
Continuous
.0040
(29)
.0040
1.7711
.0959
None (difficult)
Never
Design Calc. (+207.)
Yes, In plant
3200
1
50
6
65°
.0040 (29)
Concentration
Section
Combined
Vents
18
Continuous
.00005
.00003
.0019
i.,0005
None (difficult)
Never
Design Calc. (+30%)
No
.89
1
67
20
4.85 .06
1 1
15 50
2 3
^1250(30)7150 100o
.0001
22-8
30,000
30,000
7. 5%
Cleavage
Section
Combined
Vents
48
Continuous
.0024
.0013
.0026
None (difficult)
Never
Design Calc. (+507.)
Yes, in plant
.2
1
60
1
3.8
1
93
16
6.6
1
15
3
150°~i25 (30)215°
.0037
Product
Recovery Section
Combined
Vents
47.5
Continuous
.0000007
.0062
. 00003
None (difficult)
Never
Design (4407.)
No
0.5
1
2
1
16.63
1
15
4
140° (30) 215°
.0000007
Phenolic
Heavy Ends
Flare
72,800 (31)
Intermittent
168
.0217
.0241
.1371
.0210
Very difficult
Never
Design Calc.r+207.)
Yes, In plant
16,500
1
4
15
1000°
Yes
Yes
PH-XV
-------
TABLE PH-III
NATIONAL EMSSIOMS INVENTORY
PHENOL PRODUCTION FROM CUMENE
Page 12 of 13
Plant - EM Code Number
Capacity - Tons of Phenol/Yr.
Average Production - Tons of Phenol/Yr.
Quarterly Production Variation - % of Max.
Emission* to Atmosphere
Stream
Flow - Lb./Hr.
Flov Characteristics - Continuous or Intermittent
if Intermittent - Hrs./Yr.
Composition - Tons/Ton of Phonal
Cumene
Cumene Rydroperoxlde
Phenol
Acetone
•< Methyl Styrene
Acetophenone
Acetaldehyde
Formaldehyde
Mesltyl Oxide
Dimethyl Benzyl Alcohol
Benzene
Toluene
Ethyl Benzene
Misc. Hydrocarbons
Cumyl Phenol & Phenolic Tars
Water
Carbon Dioxide
Nitrogen
Oxygen
Sample Tap Location
Date or Frequency of Sampling
Type of Analysis
Odor Problems
Vent Stacks
Flov - SCFM/stack
Number
Height - Feet
Diameter - Inches
Exit Gaa Temp. °F
Emission Control Devices
Type - Incinerator
Flare
Scrubber
Other
Catalog I. D. Number
Total Hydrocarbon Emissions - Ton/Ton of Phenol
Total Particulate & Aerosol Emissions - Ton/Ton of Phenol
Total NOjj Emissions - Ton/Ton of Phenol
Total SOX Emissions - Ton/Ton of Phenol
Total CO Emissions - Ton/Ton of Phenol
22-9
28,500
28,500
29%
Post Oxidizer
Cuattne
Recovery Section
Vent
11,270 (32)
Continuous
CHP Conc'n. &
Decomp. Section
Steam Eductor Vent
Unknovn
Continuous
Rav Acetone
Column
Vent
Unknown
Continuous
Cumene
Column Steam
Eductor
Vent
Unknown
Continuous
.XMethyl
Styrene Column Steam
Eductor
Vent
Unknown
Continuous
1.6744
None, difficult
Never
None
Yes, off plant infreq.
2500
1
45
14
70°
Very difficult
Never
None
No
2
57
1.5
200°
Very difficult
Never
None
"Not applicable"
1
80
3
70°
Very difficult
Never
None
No
1
105
1.5
200°
Very difficult
Never
None
No
1
95
1.5
200°
-------
TABLE PH-III
NATIONAL EMISSIONS INVENTORY
PHENOL PRODUCTION FROM CUMENE Page 13 of 13
Plant - EPA Code Number 22-9
Capacity - Tons of Phenol/Yr. 28,500
Average Production - Tons of Phenol/Yr. 28,500
Quarterly Production Variation - 7. of Max. 29%
Bmiisloni to Atmosphere
Stream Phenol!* f ' Residue ' Acetone Dilution Acetone Acetophenone
Coloam Steam Stripper Steam Column Concentration Purification Batch
Muctor Vent Eductor Vent Vent Column Vent Still Steam Eductor
Flow - Lb./Hr. Unknown Unknown Unknown Unknown Unknown
Flow Characteristics - Continuous or Intermittent Continuous Continuous Continuous Continuous Intermittent
if Intermittent - Hrs./Yr. Flow
Composition - Tons/Ton of Phenol '"
Cumene
Cumene Hydroperoxide : ~
Phenol (+) (+)
Acetone + +
•< Methyl Styrene
Acetophenone (+)
Acetaldehyde (+)
Formaldehyde
Mesityl Oxide
Dimethyl Benzyl Alcohol
Benzene
Toluene
Ethyl Benzene
Misc. Hydrocarbons + + +
Cumyl Phenol & Phenolic Tars
Water + + +
Carbon Dioxide
Nitrogen 4- + (+) (+) +
Oxygen + / + (+) (+) +
Sample Tap Location Very difficult Very difficult Very difficult None, Very difficult None, Very difficult
Date or Frequency of Sampling Never Never Never Never Never
Type of Analysis None None None None None
Odor Problems No No "Not applicable" "Not applicable" No
Vent Stacks
Flow - SCFM/stack
Number 1111 1
Height - Feet 65 65 80 93 95
Diameter - Inches 1.5 1.5 3 3 2
Exit Gas Temp. °F 200° 200° 70° 70° 200°
Emission Control Devices
Type - Incinerator ,'
Flare
Scrubber
Other
Catalog I. D. Number
Total Hydrocarbon Emissions - Ton/Ton of Phenol + + + + + (33)
Total Partlculate & Aerosol Emissions - Ton/Ton of Phenol
Total NOX Emissions - Ton/Ton of Phenol
Total SOX Emissions - Ton/Ton of Phenol
Total CO Emissions - Ton/Ton of Phenol
-------
EXPLANATION OF NOTES
TABLE PH-III
NATIONAL EMISSIONS INVENTORY
PHENOL PRODUCTION FROM CUMENE
(1) No information given for estimating emissions, device presumably
releases some small quantities of hydrocarbons.
(2) Since sampling involved plant operation (3 857 of capacity, stream flov
has been adjusted in simple proportion to correspond to 1007 capacity
rate,
(3) Toluene , ethyl benzene and cumene here accounted for as cumene.
(4) Vents from PH-XI and PH-XII are combined and presumably carry acetone
vapor, but the amount is unknown, and no odor problem is indicated.
(5) The (+) notations shown here were not reported by the particular
respondent, but indicate probable presence of at least a trace emission
as judged from specific process step, in line with other respondents
information on a like stream.
(6) Sump seal and vent improved in 1970 to eliminate a previous occasional
in-plant odor emission.
(7) Hazardous area, protective clothing and gear required.
(8) Phenolic odor occasionally detectable on plant property.
(9) Sampled during capacity operation.
(10) Vents from acetone purification, post-cleavage neutralizing and wash
section and phenolic water stripper, together with occasional emergency
relief, delivered to scrubber PH-XIV.
(11) Total for other emissions, including occasional pump seal and other
minor leakages estimated by respondent at 30,000 Ibs. total hydrocarbons
per year, equivalent to 0.0006 tons/ton phenol.
(12) Freshly regenerated active carbon beds (not specifically identified by
respondent) prevent organics in effluent to incinerator? spent carbon
permits up to 0.27, organics in gas and stream to incinerator.
(13) Sampled at /v707, production rate; stream flow proportionately adjusted
to level corresponding to normal production rate of 48,000 Ibs. phenol/hr.;
stream for incinerator stack similarly adjusted.
(14) Odor off property only one time when equipment malfunctioned.
(15) Incinerator damaged by fire, undergoing repairs, but not in operation as
of August 4, 1972.
(16) Light oil liquid waste stream of 2,500 Ibs./hr. from cleavage and distillation
section (tons/ton of phenol amounts: .0260 cumene, .0078 AMS, .0078 acetone
and .0104 other oils) pumped to boiler, and for present purpose assumed
to undergo complete combustion with 1007, excess air.
-------
EXPLANATION OF NOTES
TABLE PR-Ill CONTINUED
(17) Heavy oil liquid waste stream of 6,000 Ib./hour from cleavage and
distillation section (tons/ton of pehnol amounts: .00625 cumene,
.0375 phenol, .01875 acetophenone and .0625 liquid "heavies") pumped
to second boiler, and for present purpose assumed to undergo complete
combustion with 100% excess air.
(18) Liauid streams analysed before pumping to boilers.
C19) Data calculated from engineering design using known vapor pressures of
components, with exception of 62 which is continuously metered and
analysed.
(20) System primarily designed for material recovery, hence, not listed as an
air pollution control cost.
(21) Vent streams believed to be carrying less than 10 Ibs. of organic flow
per hour were not surveyed in answer to the Questionnaire• only two of
these streams involved have measurable organic flow, and these together
were estimated at 11 Ibs./hour, equivalent to about 0.0003 tons/ton of
phenol.
(22) Figures given calculated from design material balances supplied by
original contractor.
(23) This vent stream, which can have as high as .049 tons organic emissions/ton
of phenol, is sent to PH-VII activated charcoal adsorption recovery system,
which normally is in service and removes about 90% of organics present.
(24) Depending on time since last regeneration, PH-VII effluent can go to
.0109 tons organic emissions/ton phenol.
(25) Higher in warm weather, + 40% over year.
(26) Flow (rate unknown) has been observed /^6 times/month over 4 months, or 207
the time, while operating @ 100 - 110% of design capacity, the stream
consists primarily of acetone.
(27) Other emissions believed to be insignificant relative to thru-put (-;.0.1%,
or <-0.0010 tons/ton phenol).
(28) Sampled at -93.8% of capacity, figures adjusted.
(29) Hydrocarbons can reach 0.0240 tons/ton phenol ;Len times per year for
'"I - 4 hours each time, when recovery system failure occurs.
(30) Combined concentration section vents '-'125° F exit gas temperature,
cleavage section •*J125° F, recovery section ^150° F.
(31) Flare operated to burn an annual total of 500,000 Ibs. phenolic heavy ends
(? 3,000 Ib./hour, 12 times per year for •--14 hours each occurrence at
(intermittent) flow rate shown. Desipn burner feed operation with 1007
excess 62 assumed together with steam injection ratio of 2 Ib. steam
per 1 Ib. hydrocarbon fuel, assuming complete combustion.
-------
EXPLANATION OF NOTES
TABLE PH-III CONTINUED
^32) Design calculation.
(33) Other emissions not knovri, total loss for unit may be approximately
2 vt. % of cumene charged as determined by material balance. (Equiva-
lent to 0.0200 tons/ton phenol).
-------
TABLE PH-IV
CATALOG OF EMISSION CONTROL DEVICES
PRODUCTION OF PHENOL FROM CUMENE
Plant Section
Device Class
EPA Code No. for plant using
Flov Diagram (Fig. II) Stream I, D.
Device I. D. No.
Purpose - Control Emission of
SCRUBBING/SORBING MEDIUM
Type - Spray
Packed Column(s)
Trays - Type
Number
Plenum Chamber
Other
Scrubbing/Sorbing Medium Usage - GPM (Ibs./lb. phenol)
.Design Temp, (operating temp.) °F
Gas Rate - SCFM (Ib./hr.)
T-T Height - Ft.
Diameter - Ft.
Wash/Vent Gases to stack
Stack Height - Ft.
Stack Diameter - Ft.
K. 0. TYPE - CONDENSER 6. K. 0. DRUM
Demister
Degasser
Other
Design Pressure (operating pressure) PSIG
Flov Rate of Treated Stream
Liquid - Ib./hr. (GPM)
Gas - Ib./hr. (SCFM)
SCFM/Stack
Primary Condenser Refrigeration Liquid
Capacity of Refrigeration Unit - Tons
Temperature to Condenser - 'Sorber) - °F
Temperature out of Condenser - CSorber) - °F
Compound- Types Incinerated
Combustion Device - Flare
Incinerator
Other
Materials to Incinerator - SCFM (Ib./hr.)
Auxilliary Fuel Req'd. (Excl. pilot)
Type
Rate BTU/Hr.
Installed Cost - Mat'l. & Labor $
Installed Cost Based on "year" - dollars
Installed Cost - Mat'l. 6, Labor - c/lb. of Phenol/Yr.
Operating Cost - Annual - $ (1972, excl. depreciation)
Value of Recovered - $/Yr.
Net Operating Cost - Annual - $ (excl. depreciation)
Net Operating Cost - c/lb. of Phenol
Efficiency - 7. SE (7. CCR)
Efficiency - % SERR
Feed Purification
Scrubber
22-1
A
PH-I
Hydrocarbons
:r (D
Wate
Seal Leg Trap
-vlOOO GP Yr.
Ambient
Unknown
?
.167
Yes
112
.167
800
1953
.0015
150
0
150
.0003
Virtual 100
Virtual 100
Scrubber Condenser
22-1
A
PH-II
Hydrocarbons
Cumene
15
100 (3> 40 (
3700
43
3.5
40
6
3
Vent
125
.84
Yes
80
Unknown (recy.)
(3700)
3700
Fre-12
.75
100
40
100,000
1953
.1887
15,800
3,000
12,800
87
87
(5)
Oxidation
Condenser (
22-1
H-III
Hydrocarbons
5.7
1.4
(8.7)
8.7
Water
(6)
130
Ambient
20,000
1953
.0377
7,500
1,000
6,500
.0123
65
65
Page 1 of 3
Incinerator
22-3
Condenser
22.-4
PH-IV
Hydrocarbons
PH-V
Hydrocarbons
(80,000)
Stack
55
6
(73,300)
Vent
70
1.17
Yes
— 73
Water
Yes
NH.
(8)
Hydrocarbons
Yes
(80,000)
Yes
Nat. Gas
Not given
75,000
1971
.0188
66,000 l ;
0
^56,000 (7)
.0140 (7>
100
100
300,000
1970
.1200
(8)
(8)
-------
TABLE PH-IV
CATALOG OF EMISSION CONTROL DEVICES
PRODUCTION OF PHENOL FROM CUMENE
Plant Section
Device Class
EPA Code No. for plant using
Flov Diagram (Fig. II) Stream I. D.
Device I. D. No.
Purpose - Control Emission of
SCRUBBING/SORBING MEDIUM
Type - Spray
Packed Column (s)
Trays - Type
Number
Plenum Chamber
Other
Scrubbing/Sorbing Medium Usage - GPM (Ibs./lb. phenol)
Design Temp, (operating temp.) °F
Gas Rate - SCFM (Ib./hr.)
T-T Height - Ft.
Diameter - Ft.
Wash/Vent Gases to stack
Stack Height - Ft.
Stack Diameter - Ft.
K. 0. TYPE - CONDENSER & K. 0. DRUM
Demister
Degasser
Other
Design Pressure (operating pressure) PSIG
Flov Rate of Treated Stream
Liquid - Ib./hr. (GPM)
Gas - Ib./hr. (SCFM)
SCFM/Stack
Primary Condenser Refrigeration Liquid
Capacity of Refrigeration Unit - Tons
Temperature to Condenser - (Sorber) - °F
Temperature out of Condenser <• (Sorber) - °F
Compound Types Incinerated
Combustion Device - Flare
Incinerator
Other
Materials to Incinerator - SCFM (Ib./hr.)
Auxilliary Fuel Req'd. (Excl. pilot)
Type
Rate BTU/Hr.
Installed Cost - M»t'l. & Labor - $
Installed Cost Based on "year" - dollars
Installed Cost - Mat'l. & Labor - c/lb. of Phenol/Yr.
Operating Cost - Annual - $ (1972, excl. depreciation)
Value of Recovered - $/Yr.
Net Operating Cost - Annual - $ (excl. depreciation)
Net Operating Cost - c/lb. of Phenol
Efficiency - % SE (% CCR)
Efficiency - 7. SERR
Condenser (8)
Hydrocarbons
(66,670)
Vent
86
.855
Yes Yes
73
Water
226
110
70
(8)
110
140
179.000 (est.)
1969
. 0833
24,600
(8)
Carbon Sorber
22-6
PH-VII
Hydrocarbons
Actlva. Carbon
2 (alternate)
Oxidation
(9)
(36,995)
9
8
Vent
86
1.0
908 recycle
(7576)
7576
100
140
220,000
1970
.1100
120,000
340,000
-220,00
-.1100
91
91
Carbon Sorber
PH-VIII
Hydrocarbons
Activa. Carbon
2 (alternate)
41
5,000
Not given
it M
Vent
Page 2 of 3
Condenser
PH-IX
Hydrocarbons
172
129 recycle
(5000)
5000
41
41
33
Unknown
(172)
172
Water
Not given
85
18,000 <10>
1969
.0225
Unknown
48,310
-.0604 <12>
82
82
30,000
1970
(13)
Unknown
Cleavage Reaction
Condenser
22-1
&
PH-X
Hydrocarbons
Unknovn
Vent
20
.167
Yes
2
Unknovn
ii
Water
170
Ambient
18,000
1953
.0340
2,600
1,000
1,600
.0030
-------
TABLE PH-IV
CATALOG OF EMISSION CONTROL DEVICES
PRODUCTION OF PHENOL FROM CUMENE
Page 3 of 3
Plant Section
Device Class
EPA Code No. for plant using
Flov Diagram (Fig. II) Stream I. D.
Device I. D. No.
Purpose - Control Emission of
SCRUBBING/SORBING MEDIUM
Type - Spray
Packed Colunm(s)
Trays - Type
Number
Plenum Chamber
Other
Scrubbing/Sorting Medium Usage - GPM (Ibs./lb. phenol)
Design Temp, (operating temp.) °F
Gas Rate - SCFM (Ib./hr.)
T-T Height - Ft.
Diameter - Ft.
Wash/Vent Gases to stack
Stack Height -Ft.
Stack Diameter -Ft.
K. 0. TYPE - CONDENSER & K. 0. DRUM
Demister
Degasser
Other
Design Pressure (operating pressure) PSIG
Flov Rate of Treated Stream
Lifuid - Ib./hr. (GPM)
Gas - Ib./hr. (SCFM)
SCFM/Stack
Primary Condenser Refrigeration Liquid
Capacity of Refrigeration Unit - Tons
Temperature to Condenser - (Sorber) - °F
Temperature out of Condenser - (Sorber) - °F
Compound Types Incinerated
Combustion Device - Flare
Incinerator
Other
Materials to Incinerator - SCFM (Ib./hr.)
Auxllliary Fuel Req'd. (Excl. pilot)
Type
Rate BTU/Hr.
Installed Cost - Mat'l. 6. Labor - $
Installed Cost Based on "year" - dollars
Installed Cost - Mat'l. & Labor - c/lb. of Phenol/Yr.
Operating Cost - Annual - $ (1972, excl. depreciation)
Value of Recovered - $/Yr.
Net Operating Cost - Annual - $ (excl. depreciation)
Net Operating Cost - c/lb. of Phenol
Efficiency - % SE (7. CCR)
Efficiency - % SERR
Acetone
Tower
Condenser
22-1
PH-XI
Hydrocarbons
Unknovn
(15)
Vent
120
.25
Yes
Unknovn
Water
135
5,000
1953
.0094
1,150
100
1,050
.0020
Acetone
Purification
Condenser (^
22-1
4
PH-XII
Hydrocarbons
Phenol
Recovery
Condenser
Unknovn
Vent <15>
120
.25
(14)
10 psla
Unknovn
Water
105
Ambient
15,000
1953
.0283
2,900
500
2,400
.0045
PH-XIII
Hydrocarbons
Unknovn
Vent
125
.25
Yes
1 psia
Unknovn
Water
85
Ambient
10.000
1953
.0189
3.500
500
3.000
.0057
Wash S. Kmergency
Relief (.Mlsc )
Scrubber
22-1
PH-XIV
Phenolic? (, HC's
Water
Tank
.03
Ambient
Unknovn
12
18
Wash/Stack
86.5
1.17
Unknovn
18,000
1953
.0340
2,000
100
1,900
.0036
Product
Recovery
Tnci nerator
22-8
piTxv
Heaw Ends
(17)
(3,000 llouid)
Stack
4
1.25
(17)
Heavy phenols, tars
Yes
16,500
Fu-1 Gas
155,000
1959 - 1970
.2583
51,200
0
51,200
.0853
100
100
-------
EXPLANATION OF NOTES
TABLE PH-IV
CATALOG OF EMISSION CONTROL DEVICES
PRODUCTION OF PHENOL FROM CUMENE
(1) Effluent water is sent to phenolic water stripper, vhich is vented
through PH-XIV.
(2) Device PH-II involves a combination of a water-cooled vent gas scrubber-
cooler and a knock-out drum operating at 80 PSIG.
(3) Outlet temperatures for scrubber-cooler and subsequent refrigerated
condenser respectively (PH-II).
(4) Vapor pressure calculation for temperatures indicated around this PH-II
device show very good agreement with the amount of cumene reported
leaving the oxidizer, but consistent vapor pressure calculations for
cumene leaving the scrubber and then escaping the post refrigeration
knock-out drum suggest a cumene recovered value ((3 $.032/lb.) for the
latter (refrigerated condenser) of v$39,000, it may be that recovery costs
do not allow full credit.
(5) Specific efficiency (SE) calculated using vapor pressure data around
the refrigerated condenser and knock-out drum. SE for the entire
scrubber-condenser unit is 99.47», but at least the scrubber section must
be considered an economically necessary integral part of the process
equipment.
(6) Three-stage water condenser with steam jet ejectors.
(7) Incinerator PH-IV, normally operating @ 1400° F with 400° F exit gas,
was out of service for repairs when the questionnaire was filled out
in August, 1972, due to damage by fire. Operating costs for 1972
include $20,000 maintenance, high due to repairs needed* net operating
cost given here assumes $10,000 maintenance for normal year. Respondent
22-3 reports that the oxidizer section effluent stream normally sent
to PH-IV incinerator actually comes from activated carbon beds, which
can allow as much as 0.2% organics (=_ up to .0033 tons cumene/ton phenol)
emissions when activated carbon bed recovery equipment is near exhaustion.
(8) Two-stage cooling system, with a water-cooled and a refrigerated
condenser, each followed, by 73 PSIG knock-out drums, vith final release
of uncondensable gas to atmosphere? this PH-VI unit is an economic
necessity (respondent 22-4 reports recovery of 99% of the 20,000 Ib./hour
hydrocarbon content) and only secondarily an emission control device,
hence, no assignable operating costs for emission control as such.
(9) Two beds down-flow operation (AP ~28 PSI for PH-VII 22-6) alternately,
with upflow low-pressure steam regeneration, recondensation and recyle
of recovered cumene.
(10) Figure given is double the installed cost of a new adsorber installed by
22-7 in 1969; cost of original PH-VIII adsorbers unknown.
(11) Negative numbers here indicate credit.
(12) Credit shown does not take 22-7 PH-VIII operating costs (unknown) into
account.
-------
EXPLANATION OF NOTES
TABLE PH-IV CONTINUED
(13) This PH-IX condenser, according to 22-4 respondent, is primarily
designed for material recovery, thus considered inappropriate as an
air pollution control cost.
(14) Two-stage vapor condenser with steam jet ejectors (PH-XII).
(15) Common vent for acetone tower and purification section of PH-XI and
PH-XII of 22-1.
(16) Up to once per year, PH-XIV of 22-1 serves as an emergency relief tank
for oxidation, concentration and other sections, as well as providing
normal venting from wash section; normal water level is 6 foot depth.
(17) Cumyl phenol and phenolic" tar ("60 wt. %) , acetophenone (30 wt. 7»)
and phenol (8 wt. 70) liquid stream burned at rate shown about 12 times
a year for«~14 hours each time, for a total of 500,000 Ibs./year.
(18) Flow of 16,500 SCFM for PH-XV of 22-8 assumes design operation of tvo
identical burners in parallel with 10070 excess 62. together with steam
injection rate of 2 Ibs. steam/lb. of hydrocarbon fuel, using 10,000
SCFH fuel gas and 10,000 Ib./hr. steam while flare is being operated
to burn liquid waste.
-------
TABLE PH-V
NUMBER OF NEV
Current
Capacity
Marginal
Capacity
Current
Capacity
On-stream
in 1980
CAPACITIES
Demand
1980
PLANTS FY 1980
MM LBS./YR.
Capacity
1980
Capacity to
be added Plant
by 1980 . Size
Number of
Nev Units
2,363 233 (b) 2,130 3,800 4,200 2,070 Cc) 200 10 - 11
Notes:
(a) See Section VI, Phenol Producers, for source.
(b) Arbitrary 50% of 1972 non-cumene and smaller plants.
(c) Including replacement for marginal capacity.
-------
TABLE PH-VI
EMISSION SOURCE SUMMARY
TON/TON OF PHENOL PRODUCT
Emissions
Location in Plant
Hydrocarbons
Participates & Aerosols
NOX
S°x
CO
Oxidation Section
.0038
None
None
None
None
Source
Concentration
Cleavage Section
.0021
None
None
None
None
Distillation Section
.0038
None
None
None
None
Fugitive Emissions
.0006
None
None
None
None
Total
.0103
None
None
None
None
-------
TABLE PH-VII
WEIGHTED EMISSION RATES
Chemical Phenol
Process Air
Increased Capacity
Pollutant
Hydrocarbons
Particulates
NOX
S0x
CO
Oxidation of Cumene
by 1980 2.070 MMLbs./Yr.
Projected New Capacity . Projected New Capacity
Current Capacity Increased Emissions Weighting Weighted Emissions
Emissions, Lb./Lb. MMLbs./Yr. Factor MMLbs./Yr.
.0103 21.3 80 1,704
0 . 60
0 40
0 20
0 1
Significant Emission Index = 1.704 MM Lbs./Yr.
-------
TABLE PH-VIII - REFERENCES
i P. VI. Shervood, Pet. Proc. 8_, p 1348 (September, 1953).
ii J. Gordon, Hydr. Proc. & Pet. Ref. 40, p 193 (June, 1961).
iii M. Sittig, " " " " 41, p 129 (August, 1962).
iv R. B. Stobaugh, Hydr. Proc. 45, p 143 ("January, 1966).
v I'irk-Othmer, 2nd Ed. Vol. 15, p 147 (1968) .
vi Processes Research, Inc. Task Order No. 14, Final Report Air Pollution
Control in Phenol Industry (8/13/71).
vii Chemical Profile, Chemical Marketing Reporter "Phenol", (6/19/72).
viii J. L. Blackford "Chemical. Economics Handbook", Stanford Research Institute,
(July, 1972).
ix G. P. Armstrong, et al J. Chem. Soc. p 666 (1950).
x A. G. Davies, et al " " " p 2204 '1954).
xi M. Bassey, et al " " " p 2471 '1955).
xii Alwyn G. Davies, "Organic Peroxides" Buttervorths, London ('1961).
xiii P. Gray & A. Williams. Chem. Revievs .59, P 239 (1959).
xiv Perry, "Chemical Engineers Handbook, 4th Ed., Me Grav Hill ''1969).
xv S. W. Benson, et al, "Additivity Rules for the Estimation of Thermo-
chemical Properties", Chem. Revievs 69, p. 279 - 324 (1969).
-------
High Density Polyethylene
-------
Table of Contents
Section Page Number
I. Introduction HP-1
II. Process Description HP-2
III. Plant Emissions HP-3
IV. Emission Control HP-6
V. Significance of Pollution HP-7
VI. HOPE Producers HP-8
List of Illustrations & Tables
Flow Diagram Figure HD-I
Net Material Balance Table HP-I
Gross Heat Balance Table HP-II
Emission Inventory Table HP-Ill
Catalog of Emission Control Devices Table HP-IV
Number of New Plants by 1980 Table HP-V
Emission Source Summary . Table HP-VI
Weighted Emission Rates Table HP-VII
-------
HP-1
I. Introduction
More polyethylene is produced in the United States than any other plastic.
Several types of polyethylene are produced. The two most important basic
types are High Density Polyethylene (HDPE) - the subject of this survey
report - Low Density Polyethylene (LDPE). HDPE currently holds roughly one-
third of the total polyethylene market; however, due to a higher predicted
growth rate, it is expected to significantly increase its share of the
market by 1980. The major portion of the noxious emissions resulting
from the production of HDPE is related to the separation and repurification
of solvents and unreacted monomers from the virgin polymer, Significant
emissions may also emmanate from the pneumatic conveyor vent system - the
pneumatic conveyors being used to transport the HDPE granules to various
blending and storage facilities. In addition the the vapor emissions,
waste water, spent catalysts and off-spec HDPE are 'produced' and must be
disposed of by the operator. Also some plants produce a relatively low
molecular weight 'wax' which, if incinerated, would add to the volume of
air emissions,,
There are three basic types of process, namely solution, slurry and
vapor phase. The slurry process, as licensed by Phillips, accounts for
most of today's capacity and as such is the primary subject of this
report. Union Carbide is now offering licenses on a vapor phase process
but none is yet in operation in the U.S. Total U.S. capacity for HDPE
is expected to reach 8.5 billion pounds by 1980.
-------
HP-2
II. Process Description
Any description of current commercial ethylene polymerization techniques/
processes will necessarily be quite sketchy since the details of these
processes are closely guarded trade secrets. Hence, the following section
is more abbreviated than in most of the survey reports.
There is great variety in the various HOPE processes utilized today.
Processes of similar design may be grouped together if classification is
determined by the types of phases present in the polymerization reactor.
Accordingly, there are three major categories: (1) solution, (2) slurry,
and (3) vapor phase. These categories may be further subdivided according
to the physcial state of the catalyst, but that detail will not be discussed
here. The solution process is thought by many to be on the way out. Union
Carbide has recently shut down the solution line at its Seadrift, Texas
plant. The vapor phase process, may be of more importance in the future.
The slurry process, as exemplified by Phillips Particle Form (PF) process,
accounts for the bulk of the HDPE produced in the U.S. Indeed, Phillips
claim (1) that their process accounts for more HDPE capacity in the U.S.
than all other processes combined. Consequently, this process description
will confine itself to that variation.
The mechanism of ethylene polymerization on a metal oxide surface -
Phillips uses a chromic oxide catalyst - is quite complex (2). The simplified
net reaction is:
c
H'
H
— c ,.__.
XH
"H H 1
* -^C-j
LH H J n
The ethylene feed plus any co-monomer are treated to remove catalyst
poisons; primarily C02, 02, and ^0; prior to their dissolution in an
appropriate solvent - such as pentane. The solution of monomers and pentane
is then heated and pumped to a bank of stirred or loop-type reactors, where
it is mixed with a previously activated, powdered catalyst that has been
slurried in the C5 solvent. The monomers polymerize around the fine catalyst
particles, which are kept in suspension by agitation. The heat of poly-
merization is absorbed by the water-cooled reactor jacketing. Polymer
molecular weight or chain length is controlled by the addition of small
amounts of hydrogen or other telogens.
After a suitable residence time in the reactor, the effluent slurry is
pumped (continuously or batch-wise) to the 'flash1 section where part of the
solvent, unreacted monomers, oligomers-'waxes', and light gases are flashed
overhead. The flash gases are separated and purified, with the solvent and
monomers being recycled. The "waxes' are rejected and incinerated or disposed
of in some other manner.
The HDPE 'granules' may be dissolved in hot solvent and the catalyst
particles filtered out, however, it is believed that current practice is to
allow the small amount of catalyst now required for polymerization to remain
in the HDPE. Then the polymer is stripped of the remaining solvent, dried
and conveyed to a blending or storage area.
(1) C.W. 5/10/72, PP 42.
(2) See "Crystalline Olefin Polymers" - Part I by Raff & Doak for discussion.
-------
HP-3
III. Plant Emissions
A. Continuous Air Emissions
1. Flue Gas
Two operators (EPA Code No 24-10 and 24-9") report using natural
gas as fuel. Operator 24-9 specifies that the fuel is used in a
catalyst activation heater. The amounts of fuel; 6 and 40 mm
scf/year, respectively; and the quantity of sulfur, 1 to 3 ppm,
are such that S02 emissions are negligible.
2. Monomer and Solvent Recovery Vents
All producers recycle solvent and most recycle unreacted
monomer. These recycled streams require purification. The light
and heavy ends from the purifaction process are either vented,
flared, or sent to another process or a pollution control device.
This operation is one of the main sources of air pollution in
the production of HDPE. The reported vent streams in this cat-
egory, along with their pollution control devices, are summarized
in Tables III and IV.
3. Conveyor Losses
Semi-finished and finished HDPE granules are transported
in-plant via pneumatic conveyors, by at least one operator (EPA
Code No. 24-9). The various atmospheric vents that are associated
with such a system are a source of hydrocarbon and particulate
emissions. These emissions represent a significant portion of
the total emissions dispite employment of various pollution
control devices. The emission and device data are summarized
in Tables III and IV.
B. Intermittent Air Emissions
1. Catalyst Activation
The Phillips type catalysts require activation prior to use.
Activation is accomplished by blowing hot air over/through the
catalyst. Operator EPA Code No. 24-9 states that this is a
batch-type operation. The emissions resulting from this operation
are listed in Table III.
2. Feed Treatment
Polar substances poison Phillips type catalysts; consequently,
water must be removed from the feed. This is accomplished through
the use of mole seive absorbers. The absorbers are periodically
regenerated and eventually dumped. During these operations the
vessels are purged with the vent stream blowing to the atmosphere.
These relatively small emissions are summarized in Table III.
3. Reactor Catalyst Charging/Dumping
One operator (EPA Code No. 24-1) who uses a supported Zeigler
type catalyst reports weekly emissions of a nitrogen-alumina stream.
This apparently occurs during catalyst dumping operations, but it is
not perfectly clear. The emissions resulting from this operation
are summarized in Table IV.
-------
HP-4
4. Start-Up and Emergency Vents
This type of discharge is universally encountered in the
petrochemical industry and will vary from process-to-process,
from operator-to-operator, and from year-to-year. According to
the responses received to the HDPE questionnaires, all of these
vents are flared. This need not necessarily be the case for the
entire industry but since they are primarily hydrocarbon streams,
it is probable that they are flared.
Flaring is a very effective method of reducing air pollution,
especially in situations such as this where the only products of
complete combustion are carbon dioxide and water. The only problem
with flares is that they must have a finite design limitation,
beyond which they will not achieve complete combustion and thus
are no longer "smokeless". In extreme emergencies they are apt to
receive entrained liquids or excessive gas flows, resulting in
smoky effluents.
One respondent (EPA Code 24-9) reported the smokeless design
rate at 122,900 Ibs./hour. This is nearly five times their hourly
production rate of polyethylene so it is probably an adequate safety
margin for most situations. However, the solvent circulation rate
is probably six or more times the production rate and vessel
capacities are even a greater multiple of capacity, therefore, it
is possible that some smoky flare conditions could be encountered.
One additional point, about which all respondents were silent is
NOX. The reaction between atmospheric nitrogen and oxygen is known
to produce these pollutants at high temperatures. Hence, it is
probable that some small concentration of NOX is produced in the
flame.
Co Liquid Wastes
The only liquid waste reported was water. Operator EPA Code No.
24-10 reported discharging 330 gpm of waste water. Operator EPA
Code No. 24-9 reported discharging 100 to 150 gpm of water after
primary treatment. It was stated that this water was used for cooling
and as a HDPE pellet transfer medium. Operator EPA Code No. 24-1
reported a waste water stream of 1000 gph containing 15 ppm
cyclohexane. This concentration of cyclohexane represents <.000001
ton/ton of HDPE.
D. Solid Wastes
1. Spent Catalysts
Depending on the process used, catalyst may or may not be
removed from the polymer. One operator who obviously does remove
it (EPA Code No. 24-1) reports the disposal of 1 x 106 Ibs./yr.
of this material. It is hauled away by a waste disposal contractor.
2. Polyethylene Waste
The amount of non-specification HDPE produced is a function of
the process used, the stringency of product molecular weight
-------
HP-5
range specifications, and many other factors* The actual amount
reported varied from 2 x 105 to 2 x 10^ Ibs./yr. Some of this
material may be applied in lower specification uses, but the
remainder is either incinerated or removed by contract haulage.
3. Waxes
Varying amounts of relatively low molecular weight 'waxes'
are produced by most HDPE processes. One operator (EPA Code No,
24-1) reported that 2 x 105 Ibs./yr. are produced and disposed of
by a contractor. Another operator (Code 24-10) reports "con-
siderably less" than this amount.
Eo Odors
No odors are reported by any of the questionnaire respondents.
However, many of the reported vent streams contain materials that
have odors.
F. Fugitive Emissions
Two of the four respondents reported fugitive emissions, both
of fairly significant proportions, as follows:
Code 24-10 "Assuming 507» of unaccounted for non-methane
hydrocarbons to flare and 50% to atmosphere - 5,900 tons/
year fugitive loss".
Code 24-4 "Fugitive losses amounting to 7 MM Ibs./year occur.
These include ethylene, butene, cyclohexane, pentane and
iso-butane and are equivalent to 0,5% of throughput."
These are each of the order of 0.03 Ibs./lb, of product and
thus are significant, being about equal to the total of all other
reported hydrocarbon emissions. Yet, the other respondent reports
no fugitive emissions, "other than small leaks".
Two rather obvious questions occur as a result of these reports,
namely:
Are these estimates of losses real or can they be attributed
to metering inaccuracies or material balance non-closure caused
by small differences between very large members?
If these losses are real, are they air emissions or do most of
them enter the flare header because of leaking relief valves?
It is assumed that the losses are in fact atmospheric emissions
resulting and are of the order of 200 SCFM per plant.
-------
HP-6
IV. Emission Control
The various emission control devices that have been reported as being
employed by operators of high density polyethylene plants are summarized
in the Catalog of Emission Control Devices - Table IV. In general, no
quantitative information on the device performance has been made available.
(In some instances, approximate numerical efficiencies have been assigned
to these devices, see Table IV - on the basis of the operator's estimate
of effluent composition). Never-the-less, certain generalizations about
the performance of the devices utilized can be made:
Water Scrubbers
Only one water scrubber was reported as being used. That is, operator
EPA Code No. 24-1's device HP-2, which is used to remove "small quantities
of alumina dust" from the exhaust gates of a reactor vent cyclone during
weekly catalyst transferrals. The effluent from the device is described as
being "essentially dust free". Since the device in question is a multi-tray
scrubber working on what may be assumed to be a stream only lightly laden
with particulate matter; its efficiency should be reasonably high. However,
it would be imprudent to attempt to characterize the performance of all the
scrubbers used by the industry on the basis of that single report.
Cyclones
In high density polyethylene production these devices are used to remove
or reduce the amount of HDPE dust emitted from the pneumatic conveyor vent
system. The size of the particles being removed is reported as varying from
10 to 150 microns. The device efficiencies cannot be calculated from the data
reported; but one may infer, from the variations in the description of cyclone
exhaust gases, that there are significant differences in the performances of
existing equipment. For example the operator of device HP-1 reports that
the effluent from that device is "essentially dust free", whereas the operator
of device HP-7a states that there are visible particulate emissions exhausting
from it. The operator of device HP-7a (Plant EPA Code No. 24-9) further states
that the currently existing cyclones will be replaced in the future - with
higher efficiency cyclones and bag filters.
Bag Filters
In general, bag filters are utilized for the same type of service as
cyclones. The single exception is device HP-5 which is used by the operator
of plant EPA Code No. 24-9 to remove catalyst fines from the atmospheric vent
stream resulting from catalyst activation operations. The device is reported
to remove all of the 10 to 200 micron particles which comprise its (particulate)
feed.
Bag filters, when used to service pneumatic conveyor vent streams,
apparently exhibit the same variation in performance that was reported for
cyclones. Descriptions of filter exhaust Ftreams range from "no particulates"
to "visible (particulate) emissions". Unfortunately more quantitative data
are lacking. Operator EPA Code No. 24-9 states that single compartment bag
filters used in this service will be replaced with more efficient multi-
compartment bag filters.
Incinerators & Flares
All HDPE plant operators report the employment of a flare system. Again,
the data necessary to calculate efficiencies have not been reported. Where
-------
HP-7
specified, all flares are associated with the reactor section. Only one
plant operator, (EPA Code. No» 24-1) reports incinerating off-spec HDPE.
No details are given as to the type of incineration used or the amount
of HDPE incinerated, except that the total amount of off-spec HDPE
produced is 2 x 1C)5 IbSo/yr, with a part being incinerated and part
removed by a solid waste disposal contractor.
Possible Methods for Emission Reduction
It seems unlikely that any change in operating conditions could be
made within a given process, that would reduce air emissions without .
affecting various product qualities. However, it is conceivable that
the choice of solvents could have a significant effect in overall
emissions. Additionally, catalysts (or processes) that produce less 'wax'
and off-spec HDPE will lessen pollution resulting from the production of
HDPE.
Development work directed toward reductions in emissions from this
process falls into the following general categories:
(1) Design and utilization of closed-loop pneumatic tionveying systems,
i.e., no atmospheric vents.
(2) Development of catalysts that produce no wax and minimize off-spec
HDPE.
(3) Determination of solvent system that reduces emissions without
adversely affecting the HDPE quality.
(4) Controlled combustion of hydrocarbon vent streams to minimize
formation of NOX and to recover heat, where justified.
-------
HP-8
V. Significance of Pollution
It is recommended that an in-depth study of this process be undertaken.
Both the grovth rate and quantity of pollutants emitted to the atmosphere
are significant,,
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.
The Table V forecast of new plants is based on the assumption that the
HDPE growth experienced from 1965 to 1972 will extend to 1980, This is
supported in part by the forecast in the final report, task order No. 15,
page B-12, prepared for the EPA by Process Research, Incorporated. On the
other hand Chemical Marketing of January 18, 1971, predicts a growth rate
of 10% per year until 1975. If this rate were extrapolated to 1980, HDPE
capacity at that time would be only 60% of the rate that Table V is based
on. Obviously, there are serious differences of opinion on the future of
HDPE.
A Significant Emissions Index (SEI) of 17,196 has been calculated in
Table VII. However, as explained above, the basis for the SEI calculation,
i.e., the 1980 capacity is subject to question,, Furthermore, more than
half of the total SEI is attributable to "fugitive emissions", yet some
respondents have reported only minimal losses in this category. It is
only by means of an in-depth study that these uncertainties can be clarified
and the need for new source standards evaluated. Hence, the recommendation
for such a study has been made.
-------
HP-9
VI. High Density Polyethylene Producers
The following tabulation of producers of high density polyethylene
indicates published capacity:
Company
Allied Chemical Corp.
Amoco Chemicals Corp.
Celanese Corporation
Chemplex Co.
Dow Chemical Co.
E. I. DuPont deNemours &
Company
Gulf Oil Corporation
Hercules, Inc.
Monsanto Company
National Petro Chemicals
Corporation
Phillips Petroleum Co.
Sinclair-Koppers Co.
Union Carbide
Location
Baton Rouge, La.
Chocolate Bayou, Texas
Deer Park, Texas
Clinton, Iowa
Freeport, Texas
Plaquemine, La.
Orange, Texas
Orange, Texas
Lake Charles, La.
Texas City, Texas
La Porte, Texas
Pasadena, Texas
Port Arthur, Texas
Seadrift, Texas
Capacity MM Lbs./Yr.
225
100
225
125
100
100
180
100
90
180
220
300
200
140
Total - 2,315
-------
PAGE NOT
AVAILABLE
DIGITALLY
-------
TABLE HP-I
TYPICAL* HIGH DENSITY POLYETHYLENE UNIT
Stream No.
Ethylene
Butene-1
Polyethylene
Solvent
Lov M. Wt. 'wax'
Catalyst
MATERIAL BALANCE, T/T OF HOPE
1 2 3-4 5
Fresh Feed Make-up Catalyst Recycle Gross Reactor***
Solvent Feed
1.0156 0.1144 1.1300
0.0086 0.0258 0.0344
.0340 5.6999 5.7339
. 000002
67 8
Reactor Solvent Recovery Heavy
Effluent Vent & Losses Reject
0.1147 0.0003
0.0258
1.0010
5.7339 .0340
0.0229 0229
9 10
HOPE Handling Product
Losses
.0010 . 1.0000
1.0242
.0340
.000002
5.8401
6.8983
6.8983
.0543
.0229
.0010
1.0000
*No single material balance can be truly typical of the various processes used to produce HDPE.
The above balance Is an approximation (from sparse published data) of the Phillips Suspension
Process which has been represented** as the process accounting for the major portion of HDPE
capacity in the U. S. today.
**C.W. 5-10-72, pp 41
***There is considerable variation in the solv«nt/ethylene ratio reported in the literature. It
is possible that it is considerably higher than shown in the material balance.
-------
TABLE HP- II
HIGH DENSITY POLYETHYLENE
VIA
ETHYLENE POLYMERIZATION
GROSS HEAT BALANCE
The exothermic heat of ethylene homopolymerization is 1450 BTU/LB. • (of
ethylene) .
There are not sufficient published data available to permit the construction
of a typical commercial reactor section gross heat balance for this process.
(1) Chem. Eng. 73 (16) 68 - August 1st, 1966.
-------
Company
Location
EPA Code No.
Capacity - Tons of H.D. Polyethylene/Yr.
Average Production - Tons of H.D. P. E./Yr.
Range in Production - % of Max.
Emissions to Atmosphere
Stream
Flow - Lb./Hr.
Flow Characteristic - Continuous or Intermittent
if Intermittent - Hrs./Yr. Flow
Composition - Ton/Ton of H.D. P.E.
Hydrogen
Ethylene
Butene
Isobutane
Isopentane
Hexene
Polyethylene
Cyclohexane
Air
Alumina
Co-Monomers
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
Bag House
Cyclone
Water Scrubber
Other
Catalog I. D. Number
Total Hydrocarbon Emissions - ton/ton H.D. P. E.
Total Particulate - ton/ton
Total NOX - ton/ton
TABLE HP-Ill
NATIONAL EMISSIONS INVENTORY
HIGH DENSITY POLYETHYLENE PRODUCTION Page 1 of 5
P.E. Stripping & React
Blending Vent ' Vent
200,400 3,540
!
24-1 i
90,000
90,500
0
1_ ! ,
I ,
or Emergency Vent ! Equipt. Purge & Eguipt. Purge t Eauipt. Pur^e &
ex. Distillation ! Emergency Vent Emergency Vent Emergency Vent
i ' ex. Compress Sect. ex. Reactor Feet i ex. Polymer Recovery Section
Not Specified Not Specified Not Specified Not Specified
Continuous Intermittent • Intermittent Intermittent Intermittent Intermittent
i 1,250
.01768
8.83978 j +
I +
Up-stream of HP-1 None
Continuous Not S
"Flammability" anal.
No No
Not Specified Not S
Yes Yes
X
"Dust Precipitator"
HP-1 HP- 2
(3 min/incident) Not Specified Not Sepci f ied Not Specified
;
+ .4- , + +
None None . None None
ampled Not Sampled • Not Sampled Not Sampled Not Sampled
No No L No _[ No
pecified Yes
1
235
i 30
Not Specified
Yes
X
HP-3
Cannot be determined but ~>".'0l768"
Cannot be determined
Total SO
Total CO
- ton/ton
- ton/ton
-------
TABLE HP-Ill
NATIONAL EMISSIONS INVENTORY
HIGH DENSITY POLYETHYLENE PRODUCTION
Page 2 of 5
Company
Location
EPA Code Number
Capacity - Tons of H.D. Polyethylene/Yr.
Average Production - Tons of H.D. P.E./Yr.
Range in Production - °l. of Max.
Emissions to Atmosphere
Stream
Flow - Ib./hr.
Flow Characteristic - Continuous or Intermittent
if Intermittent - hrs./yr. flow
Composition - ton/ton of H.D. P.E.
Hydrogen
Ethylene
Butene
Isobutane
Isopentane
Hexene
Polyethylene
Cyclohexane
Air
Alumina
Co-Monomer
Nitrogen
Fuel Gas
Silica Gel
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
Bag House
Cyclone
Water Scrubber
Other
Catalog I. D. Number
Total Hydrocarbon Emissions - ton/ton HOPE
Total Particulate - ton/ton HOPE
Total NOX Emissions ton/ton HOPE
Total SOX Emissions ton/ton HOPE
Total CO Emissions ton/ton HOPE
Feed Prep
Section Purge
Not Specified
Intermittent
Not Specified
Not Sampled
Mat'l Bal.
No
24-9
110,000
103,500
0
Solvent Recov.
Section Purge
Not Specified
Intermittent
Not Specified
Not Sampled
Emergency Vent
ex. Reactor
80,000
Intermittent
(15 min/incident)
Emergency Vent
ex Solvent Process!
200-1500
Intermi ttent
Not Speci fied
Mat'l Bal.
No
Yes
Not Specified
1
150
Yes
+
HP-4
Not Sampled
j Mat'l Bal.
i No
Not Sampled
Mat'l Bal.
No
See Continuation of This Table
-------
TABLE HP-III
NATIONAL EMISSIONS INVENTORY
HIGH DENSITY POLYETHYLENE PRODUCTION
Page 3 of 5
Company
Location
EPA Code Number
Capacity - Tons of H.D. Polyethylene/Yr.
Average Production - Tons of H.D. P.E./Yr.
Range in Production - "L of Max.
Emissions to Atmosphere
Stream
Flow - Ib./hr.
Flow Characteristic - Continuous or Intermittent
if Intermittent - hrs./yr. flow
Composition - ton/ton of H.D. P.E.
Hydrogen
Ethylene
Butene
Isobutane
Isopentane
Hexene
Polyethylene
Cyclohexane
Air
Alumina
Co-Monomer
Nitrogen
Fuel Gas
Silica Gel
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 Temperature - F°
Emission Control Devices
Type - Flare
Bag House
Cyclone
Water Scrubber
Other
Catalog I. D. Number
Total Hydrocarbon Emissions - ton/ton HOPE
Total Particulate - ton/ton HOPE
Total NOX Emissions ton/ton HDPE
Total SOX Emissions ton/ton HDPE
Total CO Emissions ton/ton HDPE
24-9
110,000
103,500
0
Catalyst Activation
Section Vent
200
Continuous
Dovnstream of HP-5
.00850
Not Sampled
Mat'l Bal.
No
Not Specified
Yes
HP-5
HDPE Conveying
ex. Blending Vent
42,172 (A)
Continuous
Dovnstream of HP-6
Intermed. Stg.
Conveying Vent
6800 (C)
Continuous
Dovnstream of HP-7
(Total) 1.79280
Not Sampled
Mat'l Bal.
No
Not Specified
Yes
HP-6 (B)
(Total) .27200
Not Sampled
Mat'l Bal.
No
Not Specified
Yes
HP-7 (D)
.035564
Packaging
Conveyor
96,400 (E)
Continuous
Dovnstream of HP-8
(Total) 3.85600
Not Sampled
Mat'I Bal.
No
Not Specified
Yes
HP-8 (F)
-------
TABLE HP-III
NATIONAL EMISSIONS INVENTORY
High Density Polyethylene
Page 4 of 5
Company
Location
EPA Code No.
Capacity - Tons of H.D. Polyethylene/Yr.
Average Production - Tons of H.D. P.E./Yr.
Range in Production - 7. of Max.
Emissions to Atmosphere
Stream
Flow - Lb./Hr.
Flow Characteristic - Continuous or Intermittent
if Intermittent - Hrs./Yr. Flow
Composition - Ton/Ton of H.D. P.E.
Hydrogen
Ethylene
Butene
Isobutane
Isopentane
Hexene
Polyethylene
Cyclohexane
Air
Alumina
CO-monomers
Methane
Carbon Monoxide
Carbon Dioxide
Unspecified Hydrocarbons
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
Bag House
Cyclone
Water Scrubber
Other
Catalog I. D. No.
Total Hydrocarbon Emissions - Ton/Ton H.D. P.E.
Total Particulate - ton/ton
Total NOX - Ton/Ton
Total SOX - Ton/Ton
Total CO - Ton/Ton
Pit. II Stripper
System Vent
1040
Continuous
.00185
. 00044
.02188
.00107
.00198
1966
GLC
No
Yes
218
1
86
2
90
No
Pit. Ill Conveyer
Purge Vent
25
Continuous
.00065
1963
GLC
No
Yes
1
36
2
Ambient
No
24-10
151,000
151,000
0
Pit. Ill Conveyor
Purge Vent
110
Continuous
.00290
1963
GLC
No
Yes
1
95
2
Ambient
No
.04894
0
0
0
0
Pit. IV Purge
Column Vent
210
Continuous
. 00008
.00007
(N2) .00249
,
.00089
.00190
1972
GLC
No
Yes
35
1
160
2
Ambient
No
Plant
Flare
Not Speci£i
Continuous
Yes
1
100
16
Yes
X
HP- 9
led
Fugit ive
Emissions
Intermi ttent
24-4
275!
Not Specified
.03907
Estimate
No
No
Yes
X
HP-10
Not Specified
but 0.0206 if
calculated on
basis of publi-
shed capacity
-------
TABLE HP-Ill
EXPLANATION OF NOTES
NATIONAL EMISSIONS INVENTORY
HIGH DENSITY POLYETHYLENE PRODUCTION Page 5 of 5
Note Comment
A Total maximum flow for four separate streams.
B Device HP-6 consists of 14 separate bag filters with
an average of four compartments per filter and 15
bags per compartment.
C Reported data interpreted as meaning stated flow is
total for eight separate streams.
D Device HP-7 consists of 34 cyclones and 11 bag
filters. Table IV lists the cyclones under HP-7a
and the bag filters under HP-7bo
E Reported data interpreted as meaning stated flow is
total for four separate streams.
F Device HP-8 consists of four cyclones.
G Respondent has verbally reported that his conveyor
emission factors are camparable to those reported by
respondent 24-10.
-------
TABLE HP-IV
CATALOG OF EMISSION CONTROL DEVICES
HIGH DENSITY POLYETHYLENE
Page 1 of 3
FLARE SYSTEM
Flow Diagram Stream I. D. Letter
Device I. D. Number
EPA Code No. for plant using
Types of compounds incinerated
Amount incinerated - Ib./hr. (SCFM)
Device or stack height - ft.
Stack diameter (? tip - inches
Installed Cost - Mat'l & Labor
Installed Cost - Mat'l & Labor
Operating Cost - Annual - $
Operating Cost - Annual - c/lb
Efficiency (v) CCR - 7.
Efficiency (V> SERR - 7.
- $
- c/lb. of HOPE - Yr.
of HDPE - Yr.
WATER SCRUBBERS - Device I. D. Number
Flow Diagram Stream I. D. Letter
EPA Code No. for plant using
Purpose - Control emission of
Type - Spray
Packed column
Trays - Type
Number
Plenum chamber
Other
Water rate - GPM
Design (operating) Temp. - F°
Gas Rate - SCFM
TT - Height - ft.
Diameter - ft.
Installed Cost - Mat'l & Labor, $
Installed Cost - Mat'l 6, Labor,
Operating Cost - Annual - $
Operating Cost - c/lb. of HDPE/Yr.
Efficiency
C/lb. of HDPE/Yr.
(B)
HP-3
24-1
Various Lt. H.C.
235
30
76,000
.04199
5,000
.00276
HP- 2
(B)
24-1
Alumina Dust
X
X
10
800
12.75
2
20 , 000
.01105
4,000
.00221
Reactor
(B)
HP-4
24-9
Various Lt. H.C.
150
22,600
.01092
12.250
.00592
Section
fRI
HP-9
24-0
Various I r . '!. C.
100
Ib
9.500
.00315
26,500
.00878
L
*
HP-10
24-4
Not Specified 1
i
149
24
55,000
11,300
-------
TABLE HP-IV
CATALOG OF EMISSION CONTROL DEVICES
HIGH DENSITY POLYETHYLENE
Page 2 of 3
BAG FILTERS
Flow Diagram Stream I. D. Letter
Device I. D. Number
EPA Code No. for plant using
Purpose - control emission of
Number of compartments
Bags per compartment
Type cloth used for bags
Total bag area - ft.2
Design (operating) temp - F°
Design (operating) pressure - PSIG
Installed Cost - Mat'l & Labor - $
Installed Cost - c/lb."of HOPE - Yr.
Operating Cost - Annual - $ .
Operating Cost - Annual - c/lb. of HOPE - Yr.
Efficiency - %
CYCLONES
Flow Diagram Stream I. D. Letter
Device I. D. Number
EPA Code No. for plant using
Purpose - control emission of
TT - Height - Ft.
Diameter - Ft.
No of Stages
Installed Cost - Mat'l 6. Labor - $
Installed Cost - c/lb. of HOPE - Yr.
Operating Cost - Annual - $
Operating Cost - c/lb. of HOPE - Yr.
Efficiency
Catalyst
Activation
Section
(A)
HP-5
24-9
Catalyst Dust
1
Orion
200
250
3640
.00176
250
.00012
100
Reactor Section
HOPE
Stripping &
Product
Conveying
Blending Sect. Vent
(C)
HP-6 (I)
24-9
HOPE Dust
4
15
(Total) 101,000
(Total) .04879
(Total) 3,500
(Total) .00169
100
(C)
HP-1
24-1
HOPE Dust
Not Specified
30,000
.01658
6,000
.00332
(D)
HP-7b (II)
24-9
HOPE Dust
Not Specil
(Total) :
(
(
(D)
HP-7a (II
24-9
HOPE Dust
5
1.8
1
(Total) i
0
0
~ 100 (on particulates)
1
31 800
.01536
0
0
43,200
.02087
Product
Packaging
Vent
(E)
HP-8 CIV)
24-9
HOPE Dust
Not Specified
CTotal)
(Total)
(Total)
(Total)
~ '100'
9,700 I
.00469 i
1.500 j
.00073 j
-------
TABLE HP-IV
EXPLANATION OF NOTES
CATALOG OF EMISSION CONTROL DEVICES
HIGH DENSITY POLYETHYLENE PRODUCTION Page 3 of 3
Note Comment
I Device HP-6 consists of 14 separate bag filters
with an average of four compartments/filter and
15 bags/compartment.
II Device HP-7b consists of 11 individual bag filters.
Ill Device HP-7b consists of 34 individual cyclones.
IV Device HP-8 consists of four separate cyclones.
V See Appendix V of this report for explanation of
CCR and SERR efficiencies.
-------
2,315
TABLE HP-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
New
Units
of
2,315
8,500
8,500
6,186
200
30 - 31
NOTE: All capacities in MM Ibs./yr.
*1980 demand based on Stanford Research Institute's 'Chemical Economics Handbook1, Section 580.1330.
See also discussion on page HP-8o
-------
TABLE HP-VI
Emissions
Hydrocarbons
Particulates
NOX
SOX
CO
EMISSION SOURCE SUMMARY*
TON/TON HDPE
Source
Catalyst Solvent Polymer Product
Prep. Reactor Recovery Stripping Conveying Fugitive
.0020 .0090 .0030 .0200
.0010
Negligible Negligible
Total
Flare
.0340
.0010
.0001 0
0
0
*A11 quantities used in this table are based on data reported in questionnaires from plants with EPA Code Nos.
20-0, 20-1, 20-4, and 20-9. Most numbers have been subject to some adjustment - as dictated by the demands of
engineering judgement.
-------
TABLE HP-VII
Chemical High Density
Process Intermediate
Increased Capacity by 1980
Pollutant
Hydrocarbons
Particulates
NOX
sox
CO
WEIGHTED EMISSIONS RATES
Polyethylene
and Low Pressure Polymerization
6,185 MM Lbs./Year
Increased Emissions
Emissions, Lbs./Lb. MM Lbs./Year
o034 210o3
oOOl 602
TR TR
0 0
0 0
Weighting
Factors
80
60
40
20
1
Weighted Emissions
MM Lbs./Year
16,824
372
TR
0
0
Significant Emission Index = 17,196 (MM Ibs./yr.)
-------
Low Density Polyethylene
-------
Table of Contents
Section
I. Introduction
II. Process Description
III. Plant Emissions
IV. Emission Control
V. Significance of Pollution
VI. LDPE Producers
List of Illustrations & Tables
Net Material Balance
Gross Heat Balance
National Emissions Inventory
Catalog of Emission Control Devices
Number of New Plants by 1980
Emissions Source Summary
Weighted Emission Rates
Flow Diagram
Page Number
LP-1
LP-2
LP-3
LP-5
LP-6
LP-7
Table LP-I
Table LP-II
Table LP-III
Table LP-IV
Table LP-V
Table LP-VI
Table LP-VII
Figure LD-1
-------
LP-1
I. Introduction
More polyethylene is produced in the United States than any other plastic.
Several types of polyethylene are produced. The two most important types are
High Density Polyethylene (HOPE) and Low Density Polyethylene (LDPE). The
screening effort in this report is based on questionnaires returned by seven
LDPE manufacturers.
As of January, 1971, approximately 5,300,000,000 Ibs./year of LDPE capacity
existed in domestic facilities. Emissions arising from these facilities come
primarily from materials handling; purges and venting of equipment and lines;
gas separation and other recovery operations; and fugitive emissions. The
pollutants are predominantly hydrocarbon vapors and fine polymer particulates.
Relative to pollution significance, LDPE projections to the year 1980 indicate
an SEI* of about 21,300. This index rating places LDPE in the ranks of
petrochemicals which qualify for in-depth studies.
Note: Questionnaire response Code No. 24-8 came to review status just
prior to issuance of this screening report„ Therefore, the
information in response 24-8 does not participate in the detailed
structuring of this report. It can be stated, however, that -
except for minor nuances such as in emission stream component
concentrations - the 24-8 report content in general, fits the
pattern of previous reports on LDPE.
*See Appendix IV for explanation.
-------
LP-2
II. Process Description
This is a simplified description of a modern high pressure ethylene
polymerization process for the production of low density polyethylene (LDPE).
A detailed technological description is 1) not necessary to fulfill the ob-
jectives of this screening report, and 2) not possible from information
currently available in published form.
A simplified composite flow diagram is attached. Please see fold-out
Drawing No. R-209. (Figure LD-I)
The characterizing variable in the LDPE reaction is pressure, which
normally ranges from 10,000 to 30,000 PSIG, and can reach levels as high as
45,000 PSIG. The mechanism of ethylene polymerization on the catalyst surface
is quite complex. The simplified net reaction:
r
H H
i i
C=C
i i
H H
High H H H H
Pressure;
i i i
-*•
O (C2H4Xn-2j-C-C-R2
Catalyst
(free-radical H H H H
sources)
R], and R2 represent chain-terminations resulting from the introduction
of "telogens" specifically chosen to accomplish this end. (Although not shown
above, LDPE polymer structures are usually characterized by branched chains.)
The ethylene monomer polymerizes in a stirred autoclave or a tubular reactor.
During the reaction sequence, temperature is controlled at predetermined
levels by a heat transfer system which can add or remove heat in exact
accord with processing requirements. (Copolymers and other variations are
commercially important; e.g., the vinyl acetate copolymer, "EVA".)
After a suitable residence time in the reactor, the monomer-polymer mix
continues to the flash section where unreacted monomers and some "waxy"
material are flashed overhead. The flash vapor components are separated and
purified. Recovered monomers are recycled, and the waxy materials are buried,
incinerated or handled by some other suitable means of disposal.
The crude LDPE is extruded and pelletized (or otherwise mechanically
prepared) so that it can be fed to the materials handling and finishing sytem
which follows.
The most common form of materials handling system for the pellets is
airveying. This type of system permits intermediate and pre-shipment storage
in an effectively deployed network of silos.
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LP-3
III. Plant Emissions
Ao Continuous Air Emissions
1. Flue Gas
No process fuel usage is reported.
2. Purification and Recovery Vents
All producers recycle unreacted monomer„ The recovery streams
require purification. The light and heavy ends from the purification
process are either vented, flared, sent to another process, or to a
pollution control device. These operations can be one of the
sources of air pollution in the production of LDPE. The reported
vent streams in this category, along with their pollution control
devices, are summarized in Tables III and IV.
3. Materials Handling Losses
Semi-finished and finished LDPE granules are most often transported
in-plant via pneumatic conveying systems. The various atmospheric
vents that are associated with these systems are a source of
hydrocarbon and particulate emissions. The hydrocarbon content of
these emissions arises from a significant monomeric ethylene
residual in the pellets,, The ethylene diffuses from the pellets
into the conveying air and silo purge air. Continuous particulate
emissions are presumed not significant with suitable retention means
such as cyclones and bag filters. Emission and control device data
are summarized in Tables III and IV.
Be Intermittent Air Emissions
1. Catalyst Activation, Feed Treatment and Reactor Charging and
Dumping
These operations, are accompanied by significant intermittent
emissions in the case of high density polyethylene production,,
These categories of operations are, therefore, mentioned here and
are excluded as significant intermittent emissions sources in the
case of LDPE production.
2. Start-Up and Emergency Vents
According to the responses received to the LDPE questionnaires,
these vents are normally tied into flare systems. The products of
combustion are carbon dioxide and water, except in certain
emergencies when the flares receive entrained liquids or excessive
gas flows, and may briefly show smoky effluents.
The LDPE respondents' reports indicate that smokeless flare
designs contain adequate safety margin for most situations. However,
extreme swings in design parameters occasionally lead to upset
conditions; e.g,,, pilot flame-out; excessive turndown demands; low
or zero steam pressure.
NOX formation resulting from the above start-up and emergency vent
-------
LP-4
flaring is not considered appreciable, relative to the national
emissions inventory,
C. Waste Water
Water is used in the extrusion steps for cooling; as a pellet
transfer medium; and as a means of "floating: oily liquids.
However, no waste water was reported by any respondent.
D. Solid Wastes
1. Spent Catalysts
In contrast to HDPE operations, LDPE catalyst does not pose a
solid waste problem.
2. Polyethylene Waste
The amount of non-specification and scrap LDPE produced is a
function of the process used, the stringency of product molecular
weight range specifications, and many other factors. The material
is disposed of via incineration, landfill or contract haulage.
3. Waxes
Varying amounts of relatively low molecular weight solid waxes
are produced by LDPE processes. Disposal is by methods similar to
those employed for waste polyethylene.
E. Odors
No significant odors are reported by the questionnaire respondents.
However, many of the reported vent streams contain materials that
have odorso
F. Fugitive Emissions
The respondents indicate fugitive emissions (= "other emissions")
of significant proportions, as shown quantitatively in the tabular
portions of this report. It is assumed for the purposes of this
screening study that all LDPE operations have significant fugitive
emissions.
Liquid storage is 1) padded, 2) pressurized, 3) refrigerated,
4) or low volatility atmospheric tankage. The respondents are
presumed to allot any liquid storage losses to "other emissions",
Section VIII of the questionnaires, which they, in general, have
calculated from their overall material balance.
-------
LP-5
IV. Emission Control
The various emission control devices that have been reported as being
employed by operators of low density polyethylene plants are summarized in
the Catalog of Emission Control Devices - Table IV. In general, no
quantitative information on the device performance has been made available.
Never-the-less, certain generalizations about the performance of the devices
utilized can be made.
Water Scrubbers
No water scrubber or similar device was reported.
Cyclones
In low density polyethylene production, these devices are used to remove
or reduce the amount of LDPE dust emitted from the pneumatic conveyor
and silo vent systems. The device efficiencies cannot be calculated from
the data reported. But the conclusion may be tentatively drawn that
future installations may be teamed up with bag filters.
Bag Filters
Although none were reported, bag filters appear to be the ultimate
final-step device for the LDPE plant of the future. A properly chosen
device, according to data collected in this study and reported in Report
No. EPA-450/3-006a, should remove substantially all LDPE particulate dust
escaping the cyclones.
Flares & Incinerators
All LDPE plant operators are presumed to make use of a flare system.
Data necessary to calculate combustion efficiencies of existing flares
have not been reported. Where specified, flares are mainly associated
with the purification and recovery sections. It is likely that some NOX
is formed in these flares.
Most operators are presumed to employ incinerators for the (relative small)
combustible liquid waste effluents. Existing incinerators, where reported,
appear to make no contribution to the national emissions inventory.
-------
LP-6
V. Significance of Pollution
It is recommended that LDPE be placed in the ranks of petrochemicals
which qualify for in-depth studies. The projected LDPE capacity and the
corresponding quantity of pollutants emitted to the atmosphere are
significant. The significance lies principally in the large cumulative
production capcity, rather than in the emissions from any single installation.
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 Tablve V, VI, and VII.
The Table V forecast of new plants is based on the assumption that the
LDPE growth rate experienced from 1960 to 1969 will extend to 1980. A
Significant Emissions Index (SEI) of 21,300 has been calculated. See Table
VII, although the bulk of this is in the category of "fugitive emissions".
This fact, along with uncertainties in the growth forecast are reasons why
an in-depth study is required to determine the applicability of new source
standards to the LDPE process.
-------
LP-7
VI. Low Density Polyethylene Producers
The following tabulation of producers of low density polyethylene indicates
published production capacity:
Company
Allied Chemical Corp.
Location
Orange, Texas
As of 1970, Installed
Capacity, MM Lb s./Yr.
25
Chemplex Co.
Cities Service Co.
Columbian Carbon Co.
Cosden Oil & Chemical Co.
Dart Industries, Inc.
Dow Chemical Co.
E. I. DuPont deNemours & Co.
Eastman Kodak Co.
Exxon Chemical Co. - U.S.A.
Gulf Oil Corp.
Monsanto Co.
National Distillers
& Chemical Corp.
Phillips Petroleum Co.
Sinclair-Koppers Co.
Union Carbide
Clinton, Iowa
Lake Charles, La.
Lake Charles, La.
Calumet City, 111.
Odessa, Texas
Freeport, Texas
Plaquemine, La.
Orange, Texas
Victoria, Texas
Longview, Texas
Baton Rouge, La.
Cedar Bayou, Texas
Orange, Texas
Texas City, Texas
Tuscola, 111.
Deer Park, Texas
Houston, Texas
J?ort Arthur, Texas
Seadrift, Texas
South Charleston, W. Va.
Texas City, Texas
Torrence, Calif.
Whiting, Indiana
300
220
220
20
365
300
200
425
200
250
330
200
300
140
150
300
39
220
360
120
225
120
240
Total
5,269
-------
PAGE NOT
AVAILABLE
DIGITALLY
-------
TABLE LP-I
COMPOSITE LOW DENSITY POLYETHYLENE
NET MATERIAL BALANCE
(TONS/TON OF LDPE CAPACITY)
INPUT
Stream No,,
on
Simplified
Flow
Diagram Tons/Ton LD
Ethylene 1 1.0105
Catalysts 2 0.0004
Modifiers & Co-monomers* 3 0.0179
Misc. Other Additives 4 0»0071
Mineral Spirits 5 0.0046
Total Input 1.0405
OUTPUT
Polyethylene Resin Product 6 1.0000
Waste Solids 7 0.0196
Fugitive Emissions 8 0.0100
Compressor Pot Liquids 9 0.0046
Misco Atmospheric Vents - Q.QQ63
Total Output 1.0405
^Including telogens (chain terminators).
**InCludes vinyl acetate, propylene, iso-butane and organic peroxides.
-------
TABLE LP-II
LOW DENSITY POLYETHYLENE
GROSS HEAT BALANCE
The exothermic heat of ethylene homopolymerization is 1450 BTU/LB. ^ ' of
monomer.
A commercial reactor section gross heat balance for this process cannot be
suitably estimated from the available published data.
(1) Chem. Eng. 73 (16) 68 - August 1st, 1966
-------
TABLE LP-III
NATIONAL EMISSIONS INVENTORY
LOW DENSITY POLYETHYLENE PRODUCTION
Page 1 of 3
Company
Location
EPA Code No.
Capacity - Tons of LD Polyethylene/Tr.
Average Production - Tons of LDPE/Yr.
Seasonal Range In Production - 7. of Max.
Emissions to Atmosphere
Stream - Letter on Flow Diagram
24-2
150,000
112,750
0
24-3
110,000
110,000
0
24-5
180,000
180,000
0
24-6
110.000
110,000
0
Description .
Flow - Lb./Hr. of Pollutants
Flov Characteristic - Continuous or Intermittent
if Intermittent - Hrs./Yr. Flow
Composition - Ton/Ton of LDPE
Ethylene
Polyethylene
Air
Hydrocarbons
Sample 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 Device
Type - Flare
Bag House
Cyclone
Water Scrubber
Other
Catalog I. D. Number
Total Hydrocarbon Emissions - ton/ton LDPE
Total Particulate - ton/ton LDPE
Total NOX - ton/ton LDPE
Total SOX - ton/ton LDPE
Total CO - ton/ton LDPE
Other Emissions
514*
Continuous
0.0143
None
None indicated except
for emergency
reactor overpressure
No
0.0143
None Listed
None
None
None
Other Emissions
3**
Continuous
0.0001
None
None Indicated
Iso-Col. Emission
28
Continuous
0.0006
Open Vent
Not Routinely
Mass Spectrograph '
No
Not Specified
Storage Vent
92
Continuous
0.002
****
Not Sampled
***
Not Analyzed
Not Applicable
None Indicated
Other
360*
Cont in
0.008
None
None I
No
0.0001
None
None
None
None
No
0.0006
None
None
None
None
Not Indicated
0.002
****
None
None
None
Other Emissions Storage Vert Other Emissions
< 1 6
: Continuous Continuous
0.00003
0.03
None
Not Sampled
Indirect
Not Applicable
None Indicated Yes
160 Total
Not Indicated
75
10
Ambient
No No
0.005
None
None Indicated
0.008
None Listed
None
None
None
0.00003
None Listed
None
None
None
0 0005
None Listed
None
None
None
*From material balance.
**Assumption
***'Tests have been conducted at several (other) locations vith good agreement".
****"Polyethylene fines may also be entrained in the air stream."
Note: For non-polluting streams, please see Simplified Flov Diagram Figure LD-1, (Draving R-209) and Table IV.
-------
TABLE LP-III
NATIONAL EMISSIONS INVENTORY
LOW DENSITY POLYETHYLENE PRODUCTION
Page 2 of 3
Company
Location
EPA Code Number
Capacity - Tons of LD Polyethylene/Yr.
Average Production - Tons of LDPE/Yr.
Seasonal Range in Production - ?„ of Max.
Emissions to Atmosphere
Stream Letter on Flov Diagram
24-7
182,500
182,500
0
B
Description
Flov - Ib./hr. of Pollutants
Flow Characteristic - Continuous or Intermittent
if Intermittent - hrs./yr. flov
Composition - Ton/Ton of LDPE
Ethylene
Polyethylene
Air
Hydrocarbons
Sample Location
Date or Frequency of Sampling
Type of Analysis
Odor Problem
Vent Stacks
Flov SCFM per stack
Number
Height - Feet
Diameter - Inches
Exit Gas Temperature - F°
Emission Control Devices
Type - Flare
Bag House
Cyclone
Water Scrubber
Other
Catalog I. D. Number
Total Hydrocarbon Emissions - Ton/Ton LDPE
Total Particulate - ton/ton LDPE
Total NOX Emissions Ton/Ton LDPE
Total SOX Emissions Ton/Ton LDPE
Total CO Emissions Ton/Ton LDPE
Compressor Purge
23
Continuous
0.0005
Not Sampled
None*
None
Yes
0.243 Ave.
21
50
4
100
None
0.0005
None
None
None
None
Storage Vent
180
Continuous
0.0039
0.54
Top of pellet bins
**
**
No
Yes
186
29
25
8
90
None
0.0039
None
None
None
None
*"Equipment volume plus purge procedure" used to determine composition and flov.
**Samples taken during the last revisions to the purge air system, about 1968.
***Flow determined from purge air system capacity.
****In addition, there are "compounding" :and "fines removal" vents vhich total less than 2 Ibs./hr. LDPE fines
Intermediate Storage vent****
48
Continuous
0.001
1.08
Not Sampled
Composition Estimated
No
Yes
345***
31
50
20
90
None
0.001
None
None
None
None
Note: For non-polluting streams, please see Simplified Flov Diagram Figure LD-1, (Draving R-209) and Table IV.
-------
TABLE IP-Ill
NATIONAL EMISSIONS INVENTORY
LOW DENSITY POLYETHYLENE
page 3 of 3
Company
Location
EPA Code No.
Capacity - Tons of LD Polyethylene/Yr.
Average Production - Tons of LDPE/Yr.
Seasonal Range in Production - 7, of Max.
Emissions to Atmosphere
Stream Letter on Flov Diagram F
Purification &
Description Recovery Flare
Flow - Lb./Hr. of Pollutants 2 .
Flov Characteristic - Continuous or Intermittent Continuous
if Intermittent - Hrs./Yr. Flov
Composition - Ton/Ton LDPE
Ethylene
Polyethylene
NOX 0.00006
Water Vapor 0.042
Carbon Dioxide 0.095
Hydrocarbons
Sample Tap Location None
Date or Frequency of Sampling
Type of Analysis *
Odor Problem None Indicated
Vent Stacks Yes
Flov SCFM per Stack 1,500
Number 1
Height - Feet 100
Diameter - Inches 20
Exit Gas Temperature - F° 3500
Emission Control Devices Yes
Type - Flare +
Bag House
Cyclone
Water Scrubber
Other
Catalog I. D. No. 24-11 101
Total Hydrocarbon Emissions - Ton/Ton LDPE None
Total Particulate - ton/ton LDPE None
Total NOX - Ton/Ton LDPE 0.00006
Total SOX - Ton/Ton LDPE None
Total CO - Ton/Ton LDPE None
24-11***
150,000
150,000
0
Other Emissions
211
Continuous
0.006
None
**
None Indicated
Not Indicated
None Indicated
0.006
None
None
None
None
24-12
150,000
150,000
0
Materials!
Handling Vent****
44
Continuous
0.0008
0.0003
None
No
Ye?
725 Ave
69
60
24
100
No
0.0008
0.0003
None
None
None
D
Depressuring
Vents*****
8
Intermittent
54
0.0002
None
Odor, but no problem
Yes
?50
50
35
1 to 3
50 - 200
None Indicated
0.000?
None
None
None
None
*Composition calculated.
**Estimate based on plant-vide material balance.
***Combustion products from a liquids incinerator also exist, in addition to "other emissions". These combustion products
present no emissions inventory contribution (the NOX and CO are so lov that they have no sigr.ificance as pollutants).
****Composition & flov estimated from material balance and estimated pneumatic conveyor blover capacity.
*****"Composition based on process composition - flov estimated".
Note: For non-polluting streams, please see Simplified Flov Diagram Figure LD-1 (Draving R-209) and Table IV.
-------
TABLE LP-IV
CATALOG OF EMISSION CONTROL DEVICES
LOW DENSITY POLYETHYLENE
FLARE SYSTEM
Device I. D. Number*
Types of Compounds Flared
Amount Flared - Ib./hr.
Device or Stack Height - Ft.
Stack Diameter @ tip - inches
Installed Cost - Mat'l. 6. Labor
Installed Cost - Mat'l
Operating Cost - Annual
Operating Cost - Annual
Efficiency - CCR - 7.
Efficiency - SERR - 7.
Years Installed
Source
MISCELLANEOUS
Device I, D. Number *
Purpose - Control Emission of
Type
- $
& Labor - c/lb. of LDPE Production
$ (1972)
C/lb. of LDPE Production
24-12 102
Various Lt. H.C.
Normally zero (5*)
120
36
530,000
16,000
*****
near 100%
over 99.57.
Rate
Installed Cost -
Installed Cost -
Operating Cost -
Operating Cost -
Efficiency
Years Installed
Source
Mat'l. & Labor, $
Mat'l. & Labor, C/lb. of LDPE Production
Annual - $ (1972)
<}/lb. of LDPE Production
Presumed
Presumed
1961-1969
John Zink tip
Minneapolis Tank Stack
24-2 100
LDPE Dust
Cyclone,
tangential, central pipe
w/top outlet » ptvot, no apportionment was made relative to LDPE plant emergencies.
Note: Respondents 24-6 and 24-7 indicate that there is no emission control device.
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5,269
564
TABLE LP-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 by 1980
Economic
Plant
Size**
Number
Nev
Units
of
4,705
19,000
21,100
16,395
400
41
Note: All capacities in MM LBS./YR.
*1980 demand based on Stanford Research Institute's
'Chemical Economics Handbook', Section 580.1330.
**Estimated.
-------
TABLE LP-VI
EMISSION SOURCE SUMMARY*
TON/TON OF LDPE
Emissions
Hydrocarbons
Particulates
NOX
SOX
CO
Source
Compressor
Purge Reactor
o.ooi A
I
Negligible
j
V
Materials
Handling
0.005
0.0003
None
None
None
Gas-Separation
Recovery Operation,
Fugitive Emissions**
0.010
None
None
None
None
Total
Flare***
TR 0.016
None 0.0003
<,.0001 <0.0001
None 0
None 0
*At the time that this report was written, there were seven questionnaires on hand, with EPA Code No's. 24-2, 24-3,
24-5, 24-6, 24-7, 24-11, 24=13. The entries in the above table are adjudged to represent a modern plant with
adequate capture and non=release of emissions candidates, and efficient particulate (polyethylene fines)
removal means.
**The expressions "fugitive emissions" and "other emissions" are currently used interchangeably. "Other emissions"
is the label used in the questionnaire form, Section VIII.
***Flares, where used are either intermittent, or also served other plant processes.
-------
TABLE LP-VII
WEIGHTED EMISSION RATES
Chemical Low Density Polyethylene
Process High Pressure Polymerization
New Added Capacity by
Pollutant
Hydrocarbons
Particulates
NOX
SOX
CO
1980 16,395 MM Lbs./Yr.
Increased Emissions
Emissions, Lbs./Lb. MM Lbs./Year
0.016 262
0.0003 5
Negligible Negligible
None 0
None 0
Weighting
Factors
80
60
40
20
1
Weighted Emissions
MM Lbs. /Year
21.000
300
Significant Emission Index = 21,300 fMM Lbs./Year)
-------
Appendix I, II, & 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 Chemical's 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
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ENVIRONMENTAL PROTECTION AGENCY
Office of Air Programs
Research Triangle Park, North Carolina 27711
Dear Sir:
The Environmental Protection Agency, Office of Air Programs is
engaged in a study of atmospheric emissions from the Petrochemical
Industry. The primary purpose of this study is to gather information
that will be used to develop New Stationary Source Performance Standards
which are defined in Section 111 of the Clean Air Act as amended
December 31, 1970 (Public Law 91604). These new source standards will
not be set as part of this study but will be based (to a large extent)
on the data collected during this study.
A substantial part of the work required for this study will be per-
formed under contract by the Houdry Division of Air Products and Chemicals.
Several other companies not yet chosen will assist in the source sampling
phase of the work.
Very little has been published on atmospheric emissions from the
petrochemical industry. The first part of this study will therefore
rank the most important petrochemical processes in their order of importance
in regard to atmospheric emissions. The Petrochemical Emissions Survey
Questionnaire will be the primary source of data during the first phase.
This ranking will be based on the amount and type of emissions from the
process, the number of similar processes and the expected growth of the
process. A second in-depth phase of the study to document emissions more
completely will be based on information obtained through actual stack
sampling.
Attached you will find a copy of the petrochemical questionnaire
which you are requested to complete and return to the Enviromental
Protection Agency within forty-two (42) calender days.
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-2-
You are required by Section 114 of the Clean Air Act to complete
each applicable part of this questionnaire except for question II.A. 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 17BA1,
5600 Fishers Lane, Rockville, Maryland 20852. Emission data cannot be
considered confidential.
Final authority for determining the status of the information resides
with the Enviromental Protection Agency. A reply describing the decision
reached will be made as soon as possible after receipt of the claim and
supporting information. During the period before the final determination
this office will honor any request to treat the questionnaire information
as confidential.
Information declared to be a trade secret is subject to protection
from being published, divulged, disclosed or made known in any manner
or to any extent by Section 1905 of Title 18 of the United States Code.
The disclosure of such information, except as authorized by law, shall
result in a fine of not more than $1,000 or imprisonment of not more
than one year, or both; and shall result in removal of the individual
from his office or employment.
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-3-
f
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".
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-2-
(iv) Emissions from fueled heaters such as "heat
transfer medium" heaters, steam generators,
or cracking furnaces need not be shown if
they are fueled completely by fuels listed in
Question VII and are not used to incinerate by-
products or off gases.
(v) Emissions from 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.
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-3-
5. Waste solids. Is there a waste solids discharge from this
process? How is it disposed of? Give the approximate
daily total of waste solids and indicate if this is mea-
sured or estimated.
III. Emissions (composition and flow) ; For each stream requested in
II. 2. a. and shown on the block diagram by letter provide the
following: (Use separate sheets for each identified location - 6
copies are provided). All of the questions will not be appli-
cable for each stream.
As an example, question 10, odor problem, applies only to streams
which are emitted to the atmosphere.
1. Chemical composition and flow. Give composition as completely
as possible from information you have available. Do not omit
trace constituents if they are known. If anything (e.g. fuel)
is added upstream of any emission control devices, give the
chemical composition and flow prior to the addition, and give
the quantity and composition of the added material. If liquids
or solids are present (in gas stream) provide the composition
and amount of these also. Give flow volume (SCFM) , temperature
(F°) and pressure (psig or inches
2. Variation in chemical composition and flow. If average stream
composition or flow varies significantly over some period of
time during normal or abnormal operation, discuss this varia-
tion and its frequency. Relate this to the average and range
of composition given in III.l.
As examples :
"During start-up (once a month) the benzene is about 12% by
volume for one hour" or "the benzene can be expected to go
from 5% to 9% by volume during life of catalyst, the 'average'
figure given is about average over the catalyst life" or
"power failures occur about once each winter causing stream
A to increase from 0 to (initially) 50,000 lbs/hr., and about
8,000 Ibs is vented over a 15 minute period."
3. Production rate during sampling. If stream composition and
volume flow rates given in answer to questions III.l. and
III. 2. were measured at a plant production rate different
than the capacity of the plant given in I.I. give the rate
at which the measurements were made.
As example :
Figures given for this stream (A) were made when plant was
operating at 90% of capacity given in I.I.
-------
-4-
4. Methods used to determine composition and flow. Is information
from material balance, from sample and analysis, or other?
Describe briefly.
5. Sampling procedure. If samples have been taken, give summary
description of sampling procedure or give reference if
described in open literature.
6. Analytical procedure. If samples have been taken, give sum-
mary description of analytical procedure or give reference if
described in open literature.
7. Sampling frequency. How often is the stream sampled?
As Examples:
"continuous monitor" or "twice a shift for last 18 months"
or "once in the fall of 1943".
8. Confidence level. Give some idea how confident you are in
regard to compositions in III.l.
As examples:
"probably correct + 20%" or "slightly better than wild guess".
9. Ease of sampling. How difficult is it to sample this stream?
As examples:
"sample line runs into control room" or "sample port provided
but accessible only with 20-ft. ladder."
10. Odor problem. Is the odor of this emission detectable at
ground level on the plant property or off the plant property?
If odors carry beyond the plant property are they detectable
frequently or infrequently? Have you received a community
odor complaint traceable to this source in the past year?
Has the odorous material been chemically identified? What
is it?
-------
—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 1.1. 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
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
PYRROLIDONE
STORAGE
HEAT EXCHANGERS
&
FLUID BED CATALYTIC
REACTORS
fc
RECYCLE
PRODUCT
RECOVERY
&
PURIFICATION
HEAVY
ENDS
0
PRODUCT
FILTER
WATER RECYCLE
EMERGENCY VENT TO
INCINERATOR 102
0
STACK
^—
C
SCRUBBER
101
If
t*~~^
*
DISCHARGED
WATER - WASHED
SOLIDS
STACK
O
o
D-
H-
£B
9Q
H
§
WATER
DISCHARGE
INCINERATOR
102
ff
•o
i
O
O
IB
IB
IB
O
X
»
O.
O
00
IB
o
o
i-h
•O
3
IB
O
O
a
3
0!
13
H
O
o
a
a>
0
-------
-4-
II. Process. (Continued)
3. Raw materials and products
Raw materials
Name Quantity
Pyrrolidine 130.000.000 Ibs/vr.
Product and by-products
Name
Pyrrole
Quantity
80.000.000 Ibs/yr.
Composition
pyrrolidlne
other amines
98%
2%
Composition
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. 1.Emissions (composition and flow).
Six copies provided
this section
Stream flow shown on block diagram by letter A.
1. Flow ? Temperature ? Pressure
Component
Name
Particulate
Formula
State
Solid
Average amount
or composition
Composition
Range
Depending upon cause of emergency, emissions could range from contaminated feed to contaminated product.
Upset durations seldom exceed 15 minutes during which time incinerator operation would be modified. For
initial 1-2 minutes after upset pollutants might leave incinerator stack. Following that, stack gases will
be nearly 100% C02, H20 & N2. On average, such upsets occur two or three times per year. Particulates are
possible, depending upon cause of upset. One such upset occurred in 1969.
* Particulate matter should be described as fully as possible.
-------
-7-
(a)
III. Continued For stream flow shown on block diagram by letter A
2. Composition variation.
See III-l
3. Production rate during sampling.
Never Sampled
4. Method used to determine composition and flow.
Not applicable
-------
III. Continued For stream flow shown on block diagram by letter A
5. Sampling procedure.
Not Applicable
6. Analytical procedure.
Not Applicable
7. Sampling frequency.
Never
-------
—9™
(a)
III. Continued For stream flow shown on block diagram by letterA
8. Confidence level.
Not Applicable
9. Ease of sampling.
Impossible
10. Odor problem. (Circle yes or no or mark "not applicable")
Is the odor of this emission ever detectable at ground level
on the plant property? Yes/no Off the plant property? Yes/no
If odors carry beyond the plant property are they detectable
infrequently? Yes/no Frequently? Yes/no Have you received a
community odor complaint traceable to this source in the past
year? Yes/no Has the odorous material been chemically identified?
Yes/no What is it?
Not Applicable
-------
I. l.Erdssions (composition
and flow) .
Stream flow shown on block diagram by
1. Flow 10*000 SCBHTemperature 110°F
Component
Name
Particulate
Nitrogen
Oxygen
Carbon Monoxide
Carbon Dioxide
Hydrogen
Water
Various Amines
Nitrogen Oxides
Formula
*
N2
°2
CO
co2
H2
H20
**
N0x
"(b)
letter B
Pressure 25 PSIG
State
Solid
Gas
Gas
Gas
Gas
Gas
Vapor
Vapor
Gas
* Particulate matter should be described as fully as possible.
contains cobalt and chromium on alut
less than 5 microns;
5Z less than 1
nlna base 1002 lees fhan
micron.
Six copies provided
this section
Average amount Composition
or composition Range
150 Ibs./hour 100-200 Ibs./hour
83.8 Vol. % 80-85Z
1.4 " 1-2%
4.1 " 3-5Z
1.4 " 1-2Z
2.1 " 2-2. 5Z
7.1 " 6.5-7.5Z
0.1 " 0.05-0.2Z
300 VPPM 200-500 VPPM
Catalyst Dust (composition is proprietary^
** Composition unknown - mixture of feed, products and other 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.
-------
(I)
III. Continued For stream flow shown on block diagram by letter B
8. Confidence level.
9. Ease of sampling.
No sample taps are available, but one could be easily installed
in readily accessible location. However, it would not be 8 pipe
diameters from a disturbance.
10. Odor problem. (Circle yes or no or mark "not applicable")
Is the odor of this emission ever detectable at ground level
on the plant property? Yes/no Off the plant property? Yes/no
If odors carry beyond the plant property are they detectable
infrequently? Yes/no Frequently? Yes/no Have you received a
community odor complaint traceable to this source in the past
year? Yes/no Has the odorous material been chemically identified?
Yes/no What is it?
No applicable - this stream is no longer
emitted to the atmosphere.
-------
I. 1. Emissions (composition and flow).
Stream flow shown on block diagram by letter
1. Flow 10.000SCFM
Component
Name
Particulate
Nitrogen
Oxygen
Carbon Monoxide
Carbon Dioxide
Hydrogen
Water
Various Amine
Nitrogen Oxides
-6-
(c)
C
;
Six copies provided
this section
Temperature 100°F Pressure 0 PSIG
Formula
*
N2
°2
CO
co2
H2
H20
**
NOV
A
* 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 Composition
or composition Range
10 Ibs./hour 5-20 Ibs./hour
83.9 Vol. % 80-85%
1.4 " 1-2%
4.1 " 3-5%
1.4 " 1-2%
2.1 " 2-2.5%
7.1 " 6.5-7.5%
50 YPPMV 30-100 PPMV
300 YPPMV 200-500 PPMV
See "B". Size distribution 100% less than
** See "B".
-------
III. Continued For stream flow shown on block diagram by letter 9
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.
Amine, CO and C02 determined by infra-red analysis.
7. Sampling frequency.
Once, - one month after scrubber was put on stream.
-------
-9-
(c)
III. Continued For stream flow shown on block diagram by letter
8. Confidence level.
Oxygen, CC^, CO and H may be jh 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.
-------
(fr
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
NH,
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 letter
2. Composition variation.
Not applicable. - unknown - never analyzed.
3. Production rate during sampling.
See "B"
4. Method used to determine composition and flow.
Rotameter in liquid line for flow. Composition unknown,
-------
-o-
U)
III. Continued For stream flow shown on block diagram by letter D
5. Sampling procedure.
Not applicable.
6. Analytical procedure.
Not applicable.
7. Sampling frequency.
Not applicable.
-------
-9-
(d)
III. Continued For stream flow shown on block diagram by letter D
8. Confidence level.
Not applicable.
9. Ease of sampling.
Liquid drain line is available at ground level. Could be used
for sample tap.
10. Odor problem. (Circle yes or no or mark "not applicable")
Is the odor of this emission ever detectable at ground level
on the plant property? Yes/no Off the plant property? Yes/no
If odors carry beyond the plant property are they detectable
infrequently? Yes/no Frequently? Yes/no Have you received a
community odor complaint traceable to this source in the past
year? Yes/no Has the odorous material been chemically identified?
Yes/no What is it?
Not applicable - not an emitted stream.
-------
III. 1 .Emissions (composition and flow).
Six copies provided
this section
Stream flow shown on block diagram by letter
1. Flow 10,OOOSCFM Temperature 450°F Pressure 0 PSIG
Component
Name
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 VPPI
* Particulate matter should be described as fully as possible.
See "D1
-------
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.
-------
—o—
(e)
III. Continued For stream flow shown on block diagram by letter g_
5. Sampling procedure.
Never sampled.
6. Analytical procedure.
Never analyzed
7. Sampling frequency.
See (5) above
-------
-9-
(e)
III. Continued For stream flow shown on block diagram by letter E
8. Confidence level.
+ 10%
9. Ease of sampling.
No sample tap, very hot stream, no access ladders, minimal insulation.
10. Odor problem. (Circle yes or no or mark "not applicable")
Is the odor of this emission ever detectable at ground level
on the plant property? Yes/no Off the plant property? Yes/no
If odors carry beyond the plant property are they detectable
infrequently?* Yes/no Frequently? Yes/no Have you received a
community odor complaint traceable to this source in the past
year? Yes/jjo Has the odorous material been chemically identified?
Yes/no What is it? Amines
* 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.
f
GAS TO
STACK
GAS
DISTRIBUTOR
MIST
.--"WEIR
Multi-nozzle spray tower manu-
factured by Rebburcs Corp.
Model No. 10,000-W
Water rate: 100 GPM
Gas rate: 10,000 SCFM
Temperature: 100°F.
Pressure: Atmospheric
Gas AP: 8 in, H20
Water Pump Head: 150 Ft.
Discharge Pump Head: 100 Ft.
Diameter of Tower: 6 Ft.
T-T Length: 60 Ft.
WATER PUMP
\ DOWNCOMER
DISCHARGE
PUMP
PAN
Utilities:
35 HP for Pumps
10,000,000 BTU/Hr. Additional steam in product recovery section.
1500 GPM Additional cooling water circulation in product recovery section,
-------
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, fue] ,
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
PUMP
HEAVY ENDS
1. Engineering description.
TO STACK
CONVECTIVE
CTION
RADIANT
SECTION
PR!
1AKT
STEAM
SECONDARY
-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
-------
IV. Continued For device shown on block diagram by number 1Q2
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
(b) Check list. Mark whether items listed are included in total
cost included in IV.2.a. Do not give dollar value -
Yes 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
No
Yes
X
Was outside engineering contractor used?
X | 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
ii
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 (Lov 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.
2. Prediction of emissions from the new plants on a weighted
(significance) basis.
The subject covered in the Appendix V discussion is:
Calculation of pollution control device efficiency on a variety of
bases, including a weighted (significance) basis.
It should be noted that the weighting factors used are arbitrary.
Hence, if any reader of this report wishes to determine the effect of
different weighing factors, the calculation technique permits changes in
these, at the reader's discretion.
-------
APPENDIX IV
Number of New Plants by 1980
Attached Table 1 illustrates the format for this calculation.
Briefly, the procedure is as follows:
1. For each petrochemical that is to be evaluated, estimate what
amount of today's production capacity is likely to be on-stream
in 1980. This will be done by subtracting plants having marginal
economics due either to their size or to the employment of an
out-of-date process.
2. Estimate the 1980 demand for the chemical and assume a 1980
installed capacity that will be required in order to satisfy
this demand.
3. Estimate the portion of the excess of the 1980 required capacity
over today's remaining capacity that will be made up by
installation of each process that is being evaluated.
4. Estimate an economic plant or unit size on the basis of today's
technology.
5« Divide the total required new capacity for each process by the
economic plant size to obtain the number of new units.
In order to illustrate the procedure, data have been incorporated
into Table I, for the three processes for producing carbon black, namely
the furnace process, the relatively non-polluting thermal process, and
the non-growth channel process.
-------
Table 1. Number of New Plants by 1980
Current
Chemical
Carbon Black
Process
Furnace
Channel
Thermal
Current
Capacity
4,000
100
200
Marginal
Capacity
0
0
0
Capacity
on-stream
in 1980
4,000
100
200
Demand
1980
4,500
100
400
Capacity
1980
5,000
100
500
Capacity
to be
Added
1,000
0
300
Economic
Plant
Size
90
30
150
Number
New
Units
11 -
0
2
of
12
to
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
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
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.
2. Multiply these emission rates by the estimate of increased production
capacity to be installed by 1980 (as calculated while determining
the number of new plants), to determine the estimated pounds of
new emissions of each pollutant.
3. Multiply the pounds of new emissions of each pollutant by its
weighting factor to determine a weighted pounds of new emissions
for each pollutant„
4o 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:
!„ 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 fr 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 y 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:
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V-3
Efficiency of Pollution Control Devices
2o Significance of Emission
Pollutant
Hydrocarbons
Particulates
NOX
SOX
CO
Total
SERR = 8000 -
Weighting
Factor
80
60
40
20
1
958.5
Reduction
Rating (SERR)
Pounds in
Actual
100
0
0
0
0
(continued)
Pounds out
Weighted Actual Weighted
8000 0
14
1
0
66
8000
.2 852
40
,5 66.5
958.5
8000 x iuu 00/°
Example 2 - The same as Example 1, except the hydrocarbons are
burned to completion. Then,
CCR = 342
342
and
SERR = 8000 - 40
8000
x 100 = 100%
= 99.5%
Example 3 - One hundred pounds per unit time of methyl chloride is
incinerated, in accordance with the following reaction.
2 CHjCl + 3 02
2 C02 +2 H20 + 2 HC1
This is complete combustion, by definition, therefore, the CCR is
10070o However, (assuming no oxides of nitrogen are formed), the SERR
is less than 100% because 72.5 Ibs. of HC1 are formed. Hence,
considering HCl as an aerosol or particulate;
SERR = 100 x 80 - 72.5 x 60
100 x 80
x 100 = 45.5%
The conclusion from this final example, of course, is that it is
an excellent combustion device but a very poor pollution control device,
unless it is followed by an efficient scrubber for HCl removal.
Example 4 - The stacks of two hydrogen cyanide incinerators, each
burning 100 pounds per unit time of HCN are sampled. Neither has any
carbon monoxide or particulate in the effluent. However, the first is
producing one pound of NOX and the second is producing ten pounds of
NOX in the same unit time. The assumed reactions are:
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V-4
Efficiency of Pollution Control Devices
2. Significance of Emission Redaction Rating (SERB.) (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, SERR, = 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
9970 efficient relative to particulates, but will remove little
or none of the SOX and NOX which are usually present.
2. A bag filter on a carbon black plant will remove 99 + °L of the
particulate but will remove none of the CO and only relatively
small amounts of the compounds of sulfur that are present.
3. A water scrubber on a vinyl chloride monomer plant will remove
all of the hydrogen chloride but only relatively small amounts
of the chlorinated hydrocarbons present.
40 An organic liquid scrubber on an ethylene dichloride plant will
remove nearly all of the EDC but will introduce another pollutant
into the air due to its own vapor pressure.
For these reasons, it is suggested again that two efficiency ratings be
applied. However, in this case, the first is merely a specific efficiency as
is typically reported, i.e., "specific to the pollutant (or pollutants) for
which it was designed", thus:
SE = specific pollutant in - specific pollutant out
specific pollutant in x
The second rating proposed is an SERR, defined exactly as in the case
of incinerators.
Two examples will illustrate these ratings.
-------
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 Ibs0 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
= 987°
and SERR = (50 x 20) - (1 x 20 + 2 x 80)
(50 x 20) x 10°
= 1000 - 180
1000
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-450/3-73-005-C
2.
3. RECIPIENT'S ACCESSION'NO.
4. TITLE AND SUBTITLE
5. REPORT DATE
Survey Reports on Atmospheric Emissions from the
Petrochemical Industry, Volume III
9. ncrwn i u»« i c , »
April 1974 (date of issue)
6. PERFORMING ORGANIZATION CODE
J*UWH. 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: Maleic Anhydride, Nylon 6,
Nylon 66, Oxo Processes, Phenol, High-Density Polyethylene, and Low-Density
Polyethylene. 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.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b. IDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Air Pollution
Carbon Monoxide
Hydrocarbons
Nitrogen Dioxide
Sulfur Dioxide
Phenol
Polyethylene
Maleic Anhydride
Petrochemical Industry
Particulates
Nylon 6
Nylon 66
Oxo Processes
High-Density Polyethylene
Low-Density Polyethylene
7A
7B
7C
13B
13H
3. DISTRIBUTION STATEMENT
Release Unlimited
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
259
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
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