United States Office of Air Quality EPA-450/3-80-023
Environmental Protection Planning and Standards December 1980
Agency Research Triangle Park NC 27711
Organic Chemical
Manufacturing
Volume 1: Program
Report
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EPA-450/3-80-023
Organic Chemical Manufacturing
Volume 1: Program Report
Emissison Standards and Engineering Division
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Air, Noise, and Radiation
Office of Air Quality Planning and Standards
Research Triangle Park, North Carolina 27711
December 1980
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This report was furnished to the Environmental Protection Agency by IT Enviro-
science, 9041 Executive Park Drive, Knoxville, Tennessee 37923, in fulfillment
of Contract No. 68-02-2577. The contents of this report are reproduced herein
as received from IT Enviroscience. The opinions, findings, and conclusions
expressed are those of the authors and not necessarily those of the Environmen-
tal Protection Agency. Mention of trade names or commercial products is not
intended to constitute endorsement or recommendation for use. Copies of this
report are available, as supplies permit, through the Library Services Office
(MD-35), U.S. Environmental Protection Agency, Research Triangle Park, North
Carolina 27711, or from National. Technical Information Services, 5285 Port
Royal Road, Springfield, Virginia 22161.
D124R
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PROGRAM REPORT
R. E. White
IT Enviroscience
9041 Executive Park Drive
Knoxville, Tennessee 37923
Prepared for
Emission Standards and Engineering Division
Office of Air Quality Planning and Standards
Environmental Protection Agency
Research Triangel Park, North Carolona
March 1981
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PREFACE
Concern over widespread violation of the national ambient air quality standard
for ozone (formerly photochemical oxidants) and over the presence of a number
of toxic and potentially toxic chemicals in the atmosphere led the Environmen-
tal Protection Agency to initiate standards development programs for the con-
trol of volatile organic compound (VOC) emissions. The Synthetic Organic Chem-
icals Manufacturing Industry (SOCMI) standards development program was ini-
tiated in 1976. Its purpose was to gather technical and cost data on the
control of air pollution in organic chemical manufacture and then to prepare
(1) New Source Performance Standards (NSPS) for total volatile organic compound
(VOC) emissions, (2) Control Technique Guidelines (CTG) for VOC emissions, and
(3) National Emission Standards for Hazardous Air Pollutants (NESHAP) for
specific volatile organic chemical emissions. This program is part of the on-
going technical activities of the Emissions Standards and Engineering Division,
Office of Air Quality Planning and Standards, EPA.
IT Enviroscience (ITE) contracted with the EPA to perform the task of gather-
ing, assembling, and analyzing data and to evaluate the VOC emission control
options available to SOCMI, assess their practicality, and develop preliminary
design and cost-effectiveness conclusions for the most appropriate control op-
tions. Four years of work were needed to accomplish the program objectives.
The efforts of many ITE and ESED engineers were required. The program organi-
zation chart is shown in Appendix A.
The project was initiated by David R. Patrick, who continued to lead the pro-
gram as the EPA project officer for the first two and one-half years of the ITE
contract. Jack R. Farmer served as project officer from September 1979 to
January 1980, when the present EPA project officer, Robert E. Rosensteel, was
given responsibility for the program. Ralph E. White served as full-time proj-
ect manager for ITE.
During the first year of the ITE contract, ITE and ESED engineers worked to-
gether as teams for process site visits and data gathering. During this period
Paul Clifford and Alan Goldfarb of Mitre Corporation contributed constructively
as third-party advisors. Victor Kalcevic (ITE) and Leslie Evans (ESED) served
as lead engineers throughout the program. Leslie Evans and David Beck (ESED)
have made major contributions to data evaluation and report organization. The
ITE task leaders are shown on the organization chart in Appendix A and are
listed as report authors for the 54 reports comprising this 10-volume report,
which is the final product of the complex four-year program.
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V
CONTENTS
Page
I. INTRODUCTION 1-1
A. Background 1-1
B. Industry Description 1-3
C. VOC Emissions from the SOCMI 1-4
D. Technical Program 1-5
E. Summary 1-7
II. HISTORY OF THE PROGRAM II-l
A. Program Evolution II-l
B. Survey and Ranking II-4
C. Data Gathering II-5
D. Confidentiality II-8
III. GENERIC REGULATIONS OF SOCMI EMISSIONS III-l
A. Storage Vents III-l
B. Fugitive Leaks III-l
C. Waste Disposal III-2
D. Process Vents III-2
IV. PROGRAM REPORTS IV-1
A. Generic Process-Vent Standards IV-1
B. Nonprocess Emissions IV-4
C. Control Device Evaluations IV-5
D. Product/Process Reports IV-5
V. TOTAL-VOC-EMISSION SUMMARY V-l
A. Estimated Emissions V-l
B. Conclusions V-3
*
APPENDICES
A. PROGRAM ORGANIZATION A-l
B. SURVEY AND RANKING B-l
C. ESTIMATES OF TOTAL SOCMI VOC EMISSIONS FOR 1982 C-l
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TABLES
Number Page
II-l VOC Emission Estimates for 1982 II-6
IV-1 Emissions Associated with Unit Processes IV-2
IV-2 Emissions Associated with Unit Operations IV-3
IV-3 Cost-Effectiveness Summary of Control Devices IV-6
IV-4 SOCMI VOC Emissions Addressed IV-7
FIGURES
Number Page
II-l Number of Products Ranked 11-2
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1-1
I. INTRODUCTION
The Synthetic Organic Chemicals Manufacturing Industry (SOCMI) program was ini-
tiated to gather the data necessary to develop New Source Performance Standards
(NSPS) and Control Techniques Guidelines (CTG) for volatile organic compound
emissions from organic chemical manufacturing. The data would also support
development of National Emission Standards for Hazardous Air Pollutants (NESHAP)
for benzene and other organic hazardous pollutants to be listed in the future.
The total SOCMI program is complex because the industry is large and complex.
First, there are at least 400 or 500 major, commercially significant, organic
chemicals being manufactured by 600 to 700 processes. Second, the industry is
technologically advanced, growing, and highly competitive; thus new chemi-
cals and processes are being constantly introduced. Finally, a significant
portion of the emissions from this industry are from fugitive leaks, storage
and handling losses, and secondary sources rather than from process vents.
For these same reasons it was also decided to pursue a new approach to regula-
tion. Consequently, the program was designed to result in generic standards
for manufacture of organic chemicals. In other words, instead of writing stan-
dards for each of 600 to 700 different processes, the EPA intends to write a
relatively limited number of standards for the unit operations (physical proc-
esses) and unit processes (chemical processes) in use in the SOCMI. Thus stan-
dards would regulate the emissions without regard to the chemical. Aside from
providing the best hope of quickly and efficiently regulating a highly complex
and constantly changing industry, this approach also provides the added benefit
of controlling toxic chemicals now and potentially toxic organic chemicals before
they are specifically found to be toxic.
A. BACKGROUND
The SOCMI program was initiated in March 1976 with the formation of an EPA
Hydrocarbon Task Force. Their charge was to conceive of and initiate a program
that would lead to regulation of air emissions from the organic chemicals
industry. It was generally understood that a process and equipment standard
approach would be needed, although plans for implementation had not been formu-
lated. Obviously, the first goal was to develop a well-structured, logical
program within reasonable resource and time requirements.
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Several activities preceded initiation of the program. Energy and Environmen-
tal Analysis, Inc., and GCA/Technology Division were asked to outline work
plans for generating the information required to implement an air-pollution
control program for manufacture of organic chemicals. Concurrently, Monsanto
Research Corporation was asked to identify critical organic chemical processes
and operations with respect to their pollution potential. Their reports are
on file at EPAs Emission Standards and Engineering Division. The results of
these studies and internal CMS planning then led to a request of the Mitre Cor-
poration to develop a Request for Proposals (RFP) for a program, to be competi-
tively bid (Mitre is not eligible to bid competitively against profit-making
concerns), for gathering the information necessary to develop regulations for
organic chemical manufacture. After extensive collaboration, Mitre provided a
draft RFP. This draft was further refined by EPA and then submitted to EPA
Contracts for bid and award.
During the period preceding award of the ITE contract several other projects
were undertaken. First, Mitre was asked to identify and rank potential organic
air toxicants. This resulted in the 5-volume report Preliminary Scoring of
Selected Organic Air Pollutants, EPA 450/3-77-008. In that report 643 organics
were identified that are produced in quantities of about 1 MM (million) lb/yr
or more. Pertinent physical, chemical, toxicological, and production data were
summarized and the chemicals rank-ordered on the basis of emission potential
toxicity.
ORD/IERL, Cincinnati, also completed at that time a study by Radian entitled
Organic Chemical Producers Data Base, which was useful in establishing the flow
of basic organic chemicals and in initially pinpointing important chemicals,
manufacturers, and locations. Other ORD and ESED work available or in progress
at that time was also useful.
As a supplement to locating the preliminary chemical industry data, Mitre was
asked to identify and survey all pertinent organic chemical information
sources, to evaluate those sources, and to provide an annotated bibliography on
organic emissions from the SOCMI. This resulted in Mitre report MTR-7377.
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A decision document and a public participation plan were prepared. Final pro-
gram approval by the EPA Administrator was received on September 29, 1976 (copy
in CMS files). Following a Federal Register notice on October 22, 1976,
announcing the program, additional notification was given to approximately
100 major chemical companies, state and local agencies, public interest groups,
and interested federal agencies.
The program planning phase officially ended with the contract award to IT
Enviroscience in March 1977.
B. INDUSTRY DESCRIPTION
Organic chemicals are manufactured in an industrial chain that begins with
about ten feedstock materials produced principally in petroleum refineries.
These feedstocks then proceed through one or more processing tiers that result
in literally thousands of final products. Generally speaking, each tier con-
tains more chemicals than the preceding tier, the plants manufacturing the
products are smaller than the plants supplying the feedstock, and the volatil-
ities of the product are lower than those of the feedstocks. For these reasons
in its early stages the SOCMI program was narrowed to the basic and intermedi-
ate organic chemical manufacturing industry, which encompasses about 350 to 400
of the higher volume, higher volatility products. These chemicals are also
predominately manufactured in large-scale, continuous processes.
For various reasons about 65% of the SOCMI volume is produced in Texas and
Louisiana, although other plants are located in most industrialized areas of
the country. Each plant site may manufacture from one to several organic
chemicals, using one or more processes. Most processes result in one basic
product, although some produce a family of chemicals. Conversely, many chemi-
cals are produced by more than one process. Yearly production quantities at
each plant can range from a few million to several billion pounds.
Each SOCMI chemical is generally manufactured by a small number of companies
(this averages less than 10, with a range of 1 to more than 20). The SOCMI
chemicals are also generally manufactured at a small number of separate plant
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sites (this, too, averages less than 10, but ranges from 1 to more than 50).
Many companies operate more than one plant to manufacture the same chemical.
When these variations are combined with differences in plant age, location, and
operation, it is not surprising that few chemical plants are alike. This is
true even within a single company manufacturing the same chemical, at different
sites. An added complication is that many chemical companies license processes
from other chemical companies or third parties, often foreign.
Finally, the SOCMI is a highly competitive industry whose economic lifeblood is
technology and that is characterized by rapid growth and technological change.
Thus the introduction of new and more economical processes is common, as is the
termination of older processes that are no longer economical. Under these con-
ditions it is understandable that the industry is highly protective of its tech-
nology .
The above description of the SOCMI clearly shows why regulation of VOC emis-
sions from this industry in the normal way, i.e., by individual chemical pro-
cess, would have been very difficult. That approach would have necessitated
literally hundreds of individual standards. Furthermore, each standard would
affect only a limited number of plants and would have to be changed frequently
as the industry changed. This would be neither cost effective nor practically
achievable. Obviously, a more generalized approach to regulating VOC emissions
from the SOCMI was necessary.
C. VOC EMISSIONS FROM THE SOCMI
Preliminary analysis showed that, although the SOCMI is complex and diverse,
VOC emissions occur from four main types of sources: vents on storage and
transportation vessels (storage and handling emissions), leaks and spills of
VOC (fugitive emissions), evaporation of VOC from solid, liquid, and aqueous
wastes (secondary emissions), and process vents. Each source is briefly
described below.
Emissions from storage vents occur predominately as working and breathing
losses from fixed- and floating-roof tanks, and those from transportation
vessels result from filling and breathing. Fugitive emissions are principally
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leaks from defective or inadequate seals in such equipment as pumps, valves,
and compressors. They also include losses from open-ended valves, sampling purge
material, and cooling towers. Secondary emissions, so-called because they
frequently occur away from the process site at a wastewater treatment plant or
landfill, result from waste disposal and include evaporation of VOC from solid,
liquid, and aqueous wastes generated within the process. Emissions of VOC from
process vents occur predominately as the result of venting of inert gases or
from the release of volatiles that cannot be economically captured. Upset
releases also fall in this category.
Total SOCMI VOC emissions are projected to be about 1.4 billion lb/yr by 1982.
This estimate is adjusted on the basis of a 5.9% industry growth rate per year.
Of this amount 9% are attributed to storage losses, 32% to fugitive emissions,
4% to secondary emissions, and 55% to process vent emissions. These estimates
are based on Texas and Louisiana emission inventory data supplemented with de-
tailed information obtained through a large number of plant visits and industry
inquiries. Uncontrolled plant emissions range from a few thousand to many millions
of pounds per year. The total VOC emission estimate is less than half of that
presented in the earlier report, Control Techniques for Volatile Organic Emis-
sions from Stationary Sources, EPA-450/2-78-022 (Hay 1978) and likely reflects
recent pollution control efforts by the industry and inaccuracies in the earlier
estimates.
D. TECHNICAL PROGRAM
Development of a broad approach to regulate VOC emissions from the SOCMI was
initiated in 1976 based on the suggestions of B. J. Steigerwald, EPA. The ini-
tial goal was to develop an expeditious method for preparation of NSPS, for the
organic chemical industry, that would broadly control both oxidant precursors
and potentially toxic organics. A number of possible approaches were identi-
fied and assessed. Some of the important problems that were recognized were
(1) how to factor toxicity and reactivity into regulations, (2) the lack of
authority at that time for EPA promulgating equipment standards, and (3) the
uncertainty of methodology for economic analysis.
After three short studies were initiated with contractors to assess some of the
problems. GCA/Technology Division and EEA, Inc., recommended longer range EPA
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activities aimed at efficient regulation of the SOCMI. Monsanto Research
Company evaluated the possible use of unit operations and unit processes in
I
SOCMI regulation. After these studies were completed and reviewed, an RFP was
issued in July 1976, and a contract was awarded to Hydroscience, Inc. (a wholly
owned subsidiary of the Dow Chemical Company) in March 1977. In April 1980 the
Knoxville, Tennessee, operations of Hydroscience, Inc., underwent a name and
ownership change. The Hydroscience Tennessee operation became IT Enviroscience
(ITE), a wholly owned subsidiary of IT Corporation, a California-based environ-
mental management company whose major interests are in hazardous waste treatment,
recycle, and disposal. The contract performance continued uninterruptedly under
the new entity.
Although structured to generate data and report on unit processes and unit opera-
tions, the SOCMI contract laid out only the broad concept of the regulations.
ITE was required only to develop relevant technical and cost data, in a form to
be agreed upon with the EPA; then the EPA would prepare standards. Actual
standards preparation was not planned as part of this contract because the suc-
cessful bidder was required to have detailed chemical industry experience.
Standards development by such a contractor would likely involve conflicts of
interest.
After award of the contract EPA and ITE developed a detailed work plan that was
believed to be capable of providing the necessary documentation for the desired
generic standards. That work plan identified storage and handling, fugitive
leaks, and waste disposal as separate emission sources and as sources that could
more quickly lead to a generic regulatory package than could the unit processes/
unit operations. The work plan also called for the preparation of detailed
technical reports on the manufacture of the 350 or 400 SOCMI chemicals. These
reports would be prepared by a small number of very detailed early studies being
conducted first and then the level of details progressively reduced and extra-
polated to a larger number of later studies. Each chemical report would thus
require less effort than the one preceding it.
The first work plan was predicated on several assumptions: (1) It was believed
that the SOCMI was easily separable into 350 or 400 chemicals and that there
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were significant emissions from most of these. (2) It was assumed that data
existed in public and/or open industry files on a majority of the emission
sources. (3) It was assumed that there were sufficient similarities between
the many chemical manufacturing processes to allow extrapolation across chemi-
cal and process lines. (4) It was assumed that some well-controlled examples
existed for a majority of emission sources as the result of state or local
regulation. These assumptions had to be changed as discussed in the next
section.
At the beginning of this program the problem of developing the proper data base
for standards and guidelines to cover the manufacture of literally thousands of
organic chemicals in hundreds of different processes seemed almost insurmount-
able. However, after careful analysis of the industry and its sources and an
extensive review of basic chemical engineering literature, a solution began to
emerge. First, it was found that the bulk of emissions come from the manufac-
ture of a limited number of chemicals. Next, it was found that, although the
manufacture of organic chemicals is complex and diverse, VOC emissions occur in
only four ways: (1) emissions from storage tanks and transportation vessels,
(2) fugitive leaks and spills, (3) losses of VOC from liquid, aqueous, and
solid wastes, and (4) emissions from process vents. The solution to the stand-
ards problem, then, was to develop a data-base program suitable for standards
and guidelines specific to the four sources. These were designated generic be-
cause they represented a limited number of standards capable of encompassing a
large number of different emission sources independent of the specific chemical
and process.
E. SUMMARY
This 10-volume report is the final product of the ITE contract for assessment
of SOCMI VOC emissions and evaluation of emission control options. This
program report constitutes Volume I. Following is a brief description of the
contents of the remaining volumes of this final report:
1. Volume II: Analysis of Emissions from Carrier Gas Producing Reactions, Air
Oxidation Process Emissions, Vacuum System Emissions, and Upset Releases
This volume contains a detailed discussion of the carrier-gas generic standard
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approach and explains its use for projecting VOC emissions. Through four sepa-
rate reports the generic approach is used to demonstrate the projection of VOC
emissions from chemical reactions in general, air-oxidation processes specifi-
cally, vacuum operations, and potential emissions from upset releases. The VOC
emissions discussed in these four reports cover essentially all VOC process
emissions from SOCMI. Each report also discusses the control options appli-
cable for the VOC emissions projected.
2. Volume III: Analysis of Fugitive Emission Sources, Storage and Handling, and
Secondary Emission Sources
This volume contains three reports covering the VOC emission estimates from
nonprocess sources. The available control options are discussed, and a cost
analysis is presented for each appropriate control device. The EPA plans to
develop generic NSPS for the control of VOC emissions covered by Volumes II
and III.
3. Volume IV: Control Device Evaluations of Thermal Oxidation, Catalytic Oxidation,
and Flares
Volume V: Control Device Evaluations of Carbon Adsorption, Absorption, and
Condensation
The combustion control devices covered by Volume IV plus the three control
device reports of Volume V cover all of the significant add-on VOC emission
control devices used by SOCMI. The reports include descriptions of the control
devices, their capabilities and limitations in controlling VOC emissions, con-
trol efficiencies, cost of control, and environmental impact considerations.
This work is intended to be the most comprehensive and up-to-date assessment of
VOC emission controls developed by the Office of Air Quality Planning and Stan-
dards (OAQPS). These volumes should be valuable not only for selecting and
evaluating control options for emission sources within SOCMI but also for other
VOC emission sources.
4. Volumes VI—X: Chemical Process Reports
The last five volumes of the report are a consolidation of 39 ITE product
reports. Each product report is an in-depth technical analysis presenting
information on the plants producing a particular chemical product or products,
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typical production routes, associated VOC emissions, feasible emission con-
trols, control costs (from a new-plant perspective), and other impacts from
application of the controls. These studies substantially constitute the data
base for the generic source analyses of Volumes II and III.
All of the data presented in the 39 product reports of Volumes VI-X and the
non-process emission reports of Volume III are given in the metric system.
This is in keeping with the EPA overall plan to convert to the metric system.
By the time these reports were completed, it became apparent that the effort
required for this conversion was much more time consuming and costly than had
been anticipated. Industry had also expressed strong opposition to the conver-
sion. Furthermore, the concepts covered by the control device evaluations and
generic process emission studies are quite complex and comprehension of these
concepts would be considerably more difficult if presented in the metric sys-
tem. Therefore, all of the data in the remaining reports were retained in con-
ventional English units.
5. Product Report Grouping
The chemicals covered in each product report volume are listed in each table of
contents. Basically the chemicals are grouped according to the type of feedstock
used in their production. The chemicals in Volume VI and VII are produced from
cyclic chemical feedstock (mainly benzene and cyclohexane). The chemicals in
Volume IX are produced from Cj and C2 feedstocks, and those in Volume X are
produced from C3 and C4 feedstocks. Volume VIII was formed from the decision
to include all the major halogenated chemical products in one volume.
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II. HISTORY OF THE PROGRAM
A. PROGRAM EVOLUTION
As the study progressed through its first two years the original perception of
the SOCMI study underwent drastic changes as the result of data that were
gathered from over 75 plant visits, several hundred detailed inquiries of SOCMI
companies, and detailed surveys of the Texas and Louisiana air pollution files.
Some of the conclusions that were reached, particularly as they relate to the
assumptions existing at the time that the program was initiated, are as
follows:
First, perhaps as many as two-thirds of the 350 or 400 chemical processes
appear to result in negligible nationwide emissions, with the exception of
storage and fugitive emissions, with the bulk of industry emissions appearing
to be concentrated in the highest volume processes. Figure II-l shows the
cumulative percent of SOCMI estimated emissions for the top 140 ranked prod-
ucts. (The top 140 ranked products are shown in Appendix B.) The 140 ranked
products result in almost 90% of the total estimated SOCMI emissions. It can
be concluded from this that detailed work on 140 chemicals would be much more
cost effective than work on 350 or 400 chemicals.
Second, it became apparent that information on emissions was scarce, particular-
ly for smaller sources. Even the manufacturers themselves do not have data in
many emission areas. Furthermore, the emission inventory information in state
files was often estimated, as well as frequently confidential and therefore not
easily accessible. Also, technical literature was general and was rarely
directed toward air emissions. These facts further argued against preparation
of 350 or 400 documents and argued for the broader generic approach.
Next, although unit operations and unit processes appeared to be sufficiently
similar across chemical processes to allow generic process emission standards
to be developed at completion of the program, each complete chemical process
was so different that extrapolation across processes for efficiency in report
preparation appeared to be virtually impossible. This raised further questions
concerning the feasibility of preparing 350 to 400 specific chemical reports.
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II-2
100
Number of Products Versus Percent of Total 1982 Emissions Addressed
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Fia. II-l Number of Products Ranked
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II-3
Finally, although there are many well-controlled plants, many are still signi-
ficant emitters. State regulations have been responsible for some control, but
only a few states have vigorously pursued regulation of the SOCMI. A factor
very important to emission reduction has been the controls applied for other
than air pollution reasons, for example, odor, flammability, and high chemical
costs.
As a result of these findings the program plan was revised to focus on fewer
individual chemicals and processes. The revised approach required focus by ITE
on the top 140 chemicals and preparation of detailed technical reports for only
the more significant ones. Storage, fugitive, and secondary emissions remained
as major subject categories, and unit process/unit operation data continued to
be gathered for generic process emission standards. Analysis continued to indi-
cate that the ability to develop the necessary industry-wide regulations would
not be adversely affected. In other words, the data necessary to support the
desired generic standards still appeared to be available, even though fewer
individual processes were to be studied.
The only major program casualty was the loss of a large number of individual
chemical process CTGs. It had been originally planned that up to 350 or
400 chemical process CTGs would be written as described above. This number had
to be dramatically reduced. However, this loss does not appear.to be serious,
for the following reasons. CTGs are most effective when they apply to a large
number of separate sources in several states, when the sources are in nonattain-
ment areas, and when little control is currently present. Since the majority
of the emission sources are located in Texas and Louisiana, a large number of
CTGs could prove burdensome to those state agencies. Furthermore, many sources
are in attainment areas, which would reduce the effectiveness of the CTGs.
Finally, many sources are already controlled, and so the CTG benefit would be
further reduced. All these facts indicate that the incremental benefits of a
large number of CTGs would be marginal at best.
The more reasonable approach appeared to be to prepare individual chemical proc-
ess CTGs on only the larger, more widely dispersed, and less well-controlled
processes and to supplement them with the planned CTGs for storage, fugitive,
waste disposal, and unit processes/unit operations, along with technical
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reports on other chemicals for information. Not only would this approach be
most likely to best interface with the NSPS program, but it would also probably
help state and local agencies to best utilize their resources in meeting their
needs to attain the oxidant standard as expeditiously as possible and to con-
trol problem chemical processes.
B. SURVEY AND RANKING
At the program inception it was apparent that an important factor in the suc-
cess of the overall program was going to be the ranking of processes in order
of importance. It was considered necessary for the generic concept that unit
operations and unit processes be evaluated in proportion to their importance.
If the generic concept turned out not to work, it would be important to have
studied the most important emission sources for regulation. It was also con-
sidered important that the processes with the more toxic emissions take some
measure of precedence over those with less toxic emissions. Therefore an exten-
sive survey and ranking operation was established. The goal of this operation
was to compile all pertinent data related to VOC emissions, growth, process
design, and toxicity. Preliminary survey and ranking studies had previously
been performed by Radian and Mitre, but those studies had incorporated simplify-
ing assumptions that were not adequate for the depth and degree of effort
expended by this program. By using the Radian and Mitre studies as starting
points and incorporating Monsanto Research Corporation studies, Houdry studies,
and data from the Texas and Louisiana Air Control Agencies (covering 65% of
SOCMI), the resulting survey and ranking tables of Appendix B were believed to
be the most up-to-date, complete, and accurate VOC emission projections from
SOCMI available. However, several changes have occurred during the programs
that necessitated major adjustments.
Prior to this program previous studies had indicated that, in general, storage
and handling emissions constituted approximately 8% of SOCMI VOC emissions,
fugitive emissions ~20%, and secondary emissions up to 5%. As the result of
more recent studies the estimate for storage and handling emissions is now 9%,
fugitive emissions 32%, and secondary emissions up to 4%. These estimates are
discussed in detail in their respective reports in Volume III. The initial
estimates were with reference to a total 1982 SOCMI VOC emission projection of
approximately 1779 MM lb. The current estimate is based on a revised total
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1982 VOC emission projection of 1434 MM lb. As a result of the detailed
studies covered by the 39 product reports presented in Volumes VI—X, there is
every indication that the VOC emissions from the SOCMI have been dramatically
reduced.
Table II-l is a comparison of the initial emission estimates and current esti-
mates for nearly all the individual processes studied and reported in
Volumes VI—X. Since the initial estimates were made, the fugitive-emission
factors have essentially doubled, the storage-emission factors have decreased,
and the secondary emission estimate has remained unchanged. The updated fac-
tors have been applied to all components of the current estimate. As with any
such table, inconsistencies persist. With both estimates care was taken to
include all emissions but avoid double counting. During preparation of the
initial program estimates it was often necessary to prorate combined emission
data from several different processes. In some cases this proration was very
inaccurate and may distort the comparison of emissions for specific products,
but does not diminish the accuracy for larger groups of products.
The results clearly indicate that the VOC emissions from the processes studied
are only half the emissions estimated at program initiation. Since both emis-
sion estimates were created from data reported by industry, it appears that the
SOCHI has accomplished a dramatic reduction of VOC emissions. Indications are
that, if studies are continued for all products listed in Appendix B, a similar
reduction of VOC process emissions would be observed.
C. DATA GATHERING
At the program inception it was reasoned that the air quality control agencies
for many states would be visited, requiring a large number of trips to be made
to several states. It was soon determined that approximately 65% of SOCMI was
concentrated in Louisiana and Texas, especially the first- and second-tier
chemicals of major interest for this program. Therefore early efforts were
concentrated on obtaining industry emission data from the Louisiana and Texas
Air Control Agencies. Both agencies extended excellent cooperation, and after
careful attention to prevent the release of confidential information approx-
imately 7000 pages of emissions data were copied that contributed greatly to
the survey and ranking information included in this report.
21
-------
II-6
Table
II-l. VOC
Emission Estimates for 1982
Product
Production
(MM lb)
VOC Emissions (MM lb)
Growth
(%) Current Estimate Initial Estimate
Acrylonitrile
2,440
8
145.50
254.00
DMT/TPA
8,243
8
99.38
141.41
Ethylene dichloride
14,005
5
90.92
116.48
Ethylene
33,138
4.5
73.31
81.97
Propylene oxide
2,420
5
29.54a
49.98
Formaldehyde
7,539
4.5
27.42
40.91
Cyclohexanol/eyelohexanone
2,448
1.5
26.52
43.35
Acetic acid
3,315
5
23.4a
26.80
Acrylic acid
788
8
22.48
25.38
Ethylene oxide
6,105
5
21.39
137.87
Maleic anhydride
451
8
16.46
36.18
Butadiene
3,956
3
15.83®
12.50
Ethylbenzene/styrene
6,831
6
15.75
57.84
Ethylene glycols
5,447
4
15.59
15.24
Fluorocarbons
1,009
5.5
11.449
5.00
Phenol/acetone
3,287
4.5
9.68
32.23
Methanol
9,423
7
8.31
38.49
Cyclohexane
2,779
5
4.40
1.80
Chloromethane/MeOH
1,929
8
4.17
2.85
Perchloroethylene
834
0
3.9a
4.40
Acetic anhydride
1,555
1
3.18a
18.45
Alkylbenzene
607
2
3.17
0.08
Caprolactam
1,071
5.5
2.86a
4.88
Toluene diisocyanate
684
3.5
2.8ia
6.52
Chlorobenzene
405
0
2.70
2.25
Chloromethane/methane
440
0
2.37
11.19
Nitrobenzene
752
7
1.67
3.70
Vinyl acetate
2,055
6
1.37a
19.73
Carbon tetrachloride
519
(-10.0)
1.21
9.54
Cumene
3,282
4.4
0.98
3.99
Epichlorohydrin
378
5.5
0.68a
1.88
22
-------
II- 7
Table II-l. (Continued)
Production
Growth
VOC Emissions (MM lb)
Product
(MM lbs)
(%)
Current Estimate
Initial Estimate
Glycerin
125
0
0.59a
21.48
1,1,1-Trichloroethane
710
6
0.48
14.89
Chloroprene
396
3
0.4ia
13.69
Acrolein
50
2
0.24a
6.13
Adipic acid
2,020
4.5
0.18
0.41
Aniline
833
8
0.16a
2.66
Glycol ethers
833
5
0.143
0.47
Methyl ethyl ketone
653
5
o.na
0.43
Ethyl acetate
183
3
0.04a
1.21
Acetaldehyde
988
3.5
o.oia
7.27
136,013
726
1373.78
Waste sulfuric acid recovery*3
7.26
733
aEstimates were doubled because the study estimate for these products did not include
storage, fugitive, or secondary emissions.
bWas not a part of the initial emissions estimate.
23
-------
II-8
Technical data collection from industry was initiated through the Chemical
Manufacturers Association (CMA) and the Texas Chemical Council. Three meetings
were held during the first year, including a detailed presentation of the data
ITE had assembled on the first ten processes. CMA technical work groups were
set up to assist with data collection and to review the ITE draft reports.
Draft report reviews by industry and the CMA task groups have been very helpful
in improving the quality and accuracy of reports throughout the program.
To obtain the industry data required, it was necessary to have direct contact
with the production managers for the products involved. This necessitated more
than 60 process discussions involving more than 30 separate companies. On some
occasions brief plant tours were included, and on other occasions central meet-
ings were held with a group of production managers during which several proc-
esses were covered. In all cases the ITE engineers studied previous EPA
reports concerning the process and available technical literature. The ITE
engineers always prepared moderately detailed process flow sheets before making
the site visit so that discussions of process emissions and factors related to
VOC emissions would be as efficient and rewarding as possible. The process
information prepared before site visits also established the data as being in
the public domain and therefore nonconfidential.
D. CONFIDENTIALITY
After the program was initiated, an additional problem surfaced that neces-
sitated some program redirection. Although it had been anticipated that some
resistance would be encountered when data were being gathered that might be
considered as proprietary, the determined resistance from some industries was
found to be greater than the EPA had expected. It became apparent that the
SOCMI, perhaps more than any other industry studied by the ESED, considers
their process technology, know-how, and other information to be absolutely
vital to their competitive positions. Therefore both ESED and ITE had to spend
an inordinate amount of time (weeks) on problems dealing with trade secrets,
confidentiality agreements (in excess of 50 agreements between ITE and over
30 separate companies), and in general working out mechanisms by which industry
would release information needed for the program and still retain their propri-
etary protection.
i
^4
-------
II-9
The standard procedure employed by ITE to protect industry's confidential data
was to allow the company to thoroughly review all notes. In many instances all
plant visit notes were left with the companies. Any data considered confiden-
tial was so indicated or removed. Trip reports were always submitted to the
company before release to ensure that they contained no confidential data. No
company data were ever reproduced in a product report that did not already
appear in the released nonconfidential trip report. At the conclusion of this
program confidential data will not be retained by ITE but will be forwarded to
ESED, returned to the company, or destroyed.
Although some of the confidential data obtained during the program were useful
for verifying design concepts and emission factors, the quality of the reports
has not suffered by their exclusion. The most common problem was the desire of
industry to keep specific plant capacities and production rates confidential;
however, industry always agreed to reveal the emission factors (lb of VOC emis-
sion/lb of product), which were the most important data required for this pro-
gram. To project total emissions from a chemical process, ITE used the
model-plant approach as explained in the product reports (Volumes VI—X),
combined with production and capacity data from published literature.
When industry was given the opportunity to review draft product reports, they
realized that none of their confidential information was revealed and the fear
of releasing proprietary information to the public was abated. Once the problem
of confidentiality was cleared, industry was quick to realize that it was in
their best interest to aid in the development of reports that were as practical
and accurate as possible, with an absence of large data gaps that would have
required further effort. The cooperation by industry in general has been
excellent.
25
-------
III-l
III. GENERIC REGULATIONS OF SOCMI EMISSIONS
As was discussed earlier, are only four major sources of emissions: storage
vents, fugitive leaks, waste disposal, and process vents. Although the methods
of control differ for these four sources, in each case the emissions result from
the volatility of the organic chemicals involved, the conditions (e.g., tempera-
ture, pressure, and inert-gas flow) that affect volatility, and the potential
for emission (e.g., vent release, high inert-gas flow, etc.). Thus it was
assumed from the beginning of the program that all these sources could be re-
gulated and that regulations could be independent of specific chemical or process;
that is, that they could be generic in nature. A second assumption was that
generic regulation of SOCMI could result in the same degree and extent of control
that would be obtained by the more normal process specific regulations but with
far fewer total regulations. Finally, analysis indicated that storage, fugi-
tive, and secondary controls should be relatively straightforward but that
process vent control would be much more complicated.
A. STORAGE VENTS
Storage emissions are easily characterized and identified. In fact, equations
were generally available at program inception both for predicting emissions and
pinpointing factors affecting them. The major difficulty in the SOCMI program
was characterization of storage in the chemical industry, since this effort
spans hundred of chemicals, thousands of tanks and vessels, and a wide range of
volatility. Computer assistance was applied to adequately deal with these vari-
ables. The regulatory approach, nevertheless, was straightforward. Control
equipment (pressure tanks, floating-roof tanks, and add-on control devices)will
be required, depending on the volatility of the stored material, the size of
the tank or vessel, and analysis of the impacts of the control.
B. FUGITIVE LEAKS
Fugitive emissions were also expected to be easily characterized and identi-
fied. Potential leak sources were well known, with predominant emissions coming
from defective valve, pump, and compressor seals. The regulatory approach was
again seen as straightforward, centering on better housekeeping through a directed
leak detection and maintenance program. Certain equipment requirements were
also envisioned, all of which were to be based on the potential for leakage,
26
-------
III-2
which includes consideration of the physical state of the leaking material and
the frequency of seal failure. The major difficulties would be in defining the
leak potential in the SOCMI and in establishing the best approach for leak detec-
tion. Because of the occupational exposure that results from most fugitive leaks,
coordination with the Occupational Safety and Health Administration (OSHA) was
also expected to be necessary.
C. WASTE DISPOSAL
Secondary emissions were expected to be significant but difficult to define
since little relevant literature appeared to be available. The SOCMI program
was thus designed specifically to gather information relating to solid, liquid,
and aqueous waste streams and the VOC content of those streams. Control of
emissions at the waste disposal or treatment sites was beyond the scope of this
program,- however, focus on control of VOC entry into the waste streams was
believed to hold great promise as a general and environmentally sound method of
emission reduction. Thus standards were planned to improve plant operation and
maintenance. The major difficulty expected to be encountered was lack of data,
and thus quantification, on the part of industry. Coordination with pending
regulations under the Resource Recovery and Conversation Act (RRCA) was ex-
pected to be necessary.
D. PROCESS VENTS
Process vents in the SOCMI create several unique problems that make regulation
of air emissions difficult. Normally a regulation is developed to cover a
source that is common to a sizable industry segment. In this case, however,
there are literally thousands of different process vents associated with the
many processes involved in the manufacture of SOCMI chemicals. Waste gases
also span a wide range of chemical and physical properties. For these and
other reasons, process vents required a more general approach to regulation
than had been used in the past.
Chemical engineering principles suggested a way to handle this problem. First,
all chemical manufacturing is made up of unit processes and unit operations.
Chemical reactions, such as oxidation and chlorination, take place in unit
processes. Physical changes, such as separation and drying, take place in unit
operations. Although a large number of different unit processes and unit opera-
27
-------
Ill- 3
tions are known, only a small number are both widely used in the SOCMI and capa-
ble of emitting significant quantities of VOC.
Next, although there is a wide range of emissions from process vents, only a
few different reasons exist for their release. These reasons include pressure
relief, removal of inert gases or other undesired volatiles, and evacuation of
equipment for vacuum processing. Analysis further indicated that the major
causes of SOCMI emissions are release of inert gases or reaction gases and vent-
ing of VOCs when their capture is not economical.
The approach to regulation of process vents, then, was to focus on only the
significant unit processes and unit operations and to develop regulations
around common gas-stream properties.
Several problems were anticipated: (1) Many separate chemical processes would
have to be examined in order for sufficient data to be obtained to support
standards. (2) It would have to be determined whether the unit processes and
unit operations were similar enough across different manufacturing processes to
permit common regulations, which, in fact, might not be determined until late
in the data-gathering effort. (3) A method of performing the impact analyses
for process vent standards, as with the other generic standards, would have to
be developed. Nevertheless, it was believed that these hurdles could be over-
come. Add-on controls would likely form the basis for process vent control,
although improved operation and maintenance should also find use. Size and
volatility cutoffs would probably be necessary, depending on the results of the
impact analyses.
28
-------
IV-1
IV. PROGRAM REPORTS
This final report contains all the specific study reports developed throughout
the program. It is intended to serve as the formal compilation of technical
and cost data to support the standards to be developed covering process-vent
emissions, storage emissions, fugitive emissions, secondary sources, and any
other standards developed as a result of this program.
A. GENERIC PROCESS-VENT STANDARDS
The generic process-vent-emission reports comprise Volume II. The approach to
development of generic process-vent standards is conceptually straightforward.
First, a theoretical prediction of maximum VOC concentration in the emission
was developed and the major influencing variables were identified. These
variables were checked against the data gathered for the 39 product reports
contained in Volumes VI—X. A similar procedure was developed to project flow
rate ranges, primarily based on an inert-gas flow relationship. These concepts
are explained in detail in Volume II.
A range or regime of potential waste-gas concentrations and flows was estab-
lished. With reference to the control device evaluations of Volumes IV—V, the
control device options applicable to each flow regime are discussed. The next
step planned in the subsequent program to develop standards for these process-
vent emissions will be to determine cost effectiveness based on the costs pre-
sented in the control device evaluation reports and to determine the cost
impacts on industry. These economic analysis steps are not part of the SOCMI
program covered by this report. However, specific cost-effectiveness determin-
ations are presented for the products reported on in Volumes VI—X.
*
Preliminary estimates indicated the relative emission contributions of the
various unit processes and unit operations shown in Tables IV-1 and IV-2.
Through analyses of this type of data, including the distribution of reaction
modules, process modules, and control modules (Survey and Ranking, Appendix B),
it was determined that the process-vent emissions could be essentially covered
by the process-emission reports presented in Volume II. The principal emission
mechanism and the most important variable is inert-carrier-gas flow. Attempts
to characterize this variable have been reasonably successful, with stoichiome-
29
-------
IV-2
Table IV-1. Emissions Associated with Unit Processes
Estimated
No. of Products
Produced Using
Unit Process Unit Process
No. of Ranked
Products Containing
Unit Process
Contribution to
Total Unit Process
Emissions (%)
Cumulative
Contribution
(%)
Oxidation
63
43
48. 3
48.3
Halogenation
67
43
14.5
62.3
Hydrogenation
26
13
10. 8
73.1
Esterification
24
8
6.9
80.0
Alkylation
15
5
4.0
84.0
Sulfonation
11
6
3.4
87.4
Dehydrogenation
15
4
2.7
90.1
Hydrolysis
27
8
2.4
92.5
Reforming
1
1
2.2
94.7
Carbonylation
10
8
1.2
95.9
Cxyacetylation
1
2
1.0
96.9
Nitration
12
1
0.8
97.7
Dehydration
18
4
0.7
98.4
Ammonolysis
11
6
0.6
99.0
Condensation
51
4
0.5
99.5
Dealkylation
4
1
0
99.5*
*I.ess than 100 because of rounding errors.
30
-------
IV-3
Table IV-2. Emissions Associated with Unit Operations
Unit Operation
No. of Times
Unit Operation
Used in the SOCMI
Estimated
Contribution to
Total Unit Process
Emissions (%)
Cumulative
Contribution
(%)
Absorption
Scrubbing/washing
Distillation
Drying
Filtration
Extraction
Settling
Crystallization
Separation
Quenching
Evaporation
Ion exchange
Dilution
Mixing/blending
475
543
3651
251
120
110
24
144
384
146
127
120
71
56
58.1
27.9
10.4
3.3
0.1
0
0
0
58.1
86.0
96. 4
99.7
99.8
99.8
99.8
99.8*
*Less than 100 because of rounding errors.
31
-------
IV-4
try, vapor pressure, and explosive limits being the major factors influencing
waste-gas VOC concentrations. The methodology of projecting waste-gas flow and
VOC concentrations is described in detail in Volume II.
The conclusion from the above estimates was that a limited number of process-
vent standards may very well successfully result in a high degree of coverage
of the SOCMI process vents. To be significant and not economically prohibi-
tive, VOC emissions must have either low concentration/high volume or high
concentration/low volume. Furthermore, highly efficient, widely applicable
control mechanisms for these two types of exit gas streams are limited in num-
ber. Therefore present analysis indicates that only very few generic standards
will be necessary to deal adequately with SOCMI process vents. The principal
difficulty will be in developing appropriate techniques for economic analysis.
NONPROCESS EMISSIONS
Volume III presents the nonprocess-emission studies for storage, fugitive, and
secondary sources. Based on test results reported by the EPA the estimate
of emissions from storage-tank vents has been reduced. This is because the
AP-42 emission equations used to estimate storage losses have been found to
overstate the breathing losses by a factor of 4.
Fugitive emissions consist primarily of leaks from equipment handling the flow
of VOC, i.e., pumps, flanges, and valves. The fugitive emissions estimates
reported by this study are based on equipment count estimates for the processes
studied and fugitive emission factors provided by other EPA contract studies.
These fugitive emission factors are much greater than the emissions factors
used at the start of the program and the estimates for fugitive emissions
have been increased accordingly.
Even though a serious attempt was made during site visits to obtain data for
estimating emissions resulting from VOC wa^te disposal, very little useful
information was obtained. Industry apparently had done very little to assess
this situation. Based on the information obtained and with heavy reliance on
theoretical calculations, the secondary VOC emissions are estimated to be
approximately 90 MM lb/yr. The EPA plans to conduct a sampling program to
improve this estimate and to establish a better basis for regulation.
-------
IV-5
C. CONTROL DEVICE EVALUATIONS
Volumes IV and V discuss in detail the VOC emission control devices used through-
out the SOCMI. For comparison purposes Table IV-3 lists the resulting rela-
tive cost-effectiveness estimates for the ranges of VOC concentrations and flow
rates for each applicable control device. Table IV-3 does not include the very-
high-temperature thermal oxidation required for VOC containing halogens or
sulfur, nor does it include flares since they are primarily dedicated to inter-
mittent flows at very high flow rates.
D. PRODUCT/PROCESS REPORTS
Table IV-4 lists all the individual products and processes studied during the
program. These studies are covered by the 39 reports that constitute
Volumes VI—X of this final report. The primary consideration for selecting
the product to be studied was the amount of VOC emissions estimated for 1982.
Toxicity was also an important selection factor, as is discussed in Appendix B.
For study and site visit efficiency, products and processes were studied in
groups. Therefore some products were covered that appear far down the survey
and ranking list of Appendix B. Even though the studies were initiated on a
priority basis, the final completion dates are out of sequence. The product
studies shown in Table IV-4 are listed in the essentially random order of
completion.
As shown by Table IV-4, the 39 product reports have addressed 64 products manu-
factured by 97 processes. These reports account for approximately 80% of the
SOCMI VOC emissions initially projected for 1982. Since approximately 30% of
the SOCMI VOC initial emission estimate is covered by the reports for fugi-
tive, storage and handling, and secondary emissions, this total program has
*
addressed approximately 85% of the total SOCMI VOC emissions. Not counted are
the VOC emissions addressed by the generic process-emission reports.
33
-------
Table IV-3. Cost-Effectiveness Summary of Control Devices3
Co
j -
voc
Concentration
(PPnv,)
Flow
Rate
(scfm)
Cost
Effectiveness (per
lb of VOC Removed)
Thermal
Oxidation
Catalytic^
Oxidation
Carbon
Adsorption
Gas
Q
Absorption
Q
Condensation
1,000
100
1,000
$2.30
$1.80
$0.63
$1.28
5,000
0.90
0.73
0.27
0.83
50,000
0.60
0.41
0.12
0.55
100,000
0.56
0.39
0.11
5,000
100
0.62
1,000
0.43
0.32
0.15
0.33
0.14
5,000
0.17
0.12
0.08
0.14
50,000
0.10
0.05
0.05
0.11
100,000
0.10
0.05
0.05
10,000
100
0.32
1,000
0.19
0.17
0.17
0.08
5,000
0.06
0.05
0.07
50,000
0.03
0.02
0.05
100,000
0.03
0.02
25,000
110
0.14
1,000
0.08
0.07
0.03
5,000
0.03
0.04
50,000
0.02
0.02
100,000
0.02
0.02
Values in some cases interpolated from cost effectiveness given in individual control device reports.
^Based on recuperative heat recovery.
-------
IV-7
Table IV-4. SOCMI VOC Emissions Addressed
Product
Process
1982 Emissions
(%)a
Maleic anhydride
Cyclohexane
Ethylbenzene
Styrene
Methylene chloride
Chloroform
Methyl chloride
Nitrobenzene
Ethylene
Propylene
Acrylic acid
Methyl acrylate
Ethyl acrylate
Butyl acrylate
2-Ethylhexyl acrylate
Chlorobenzene
o-Dichlorobenzene
p-Dichlorobenzene
Acrylonitrile
Hydrogen cyanide
Cyclohexanol/
cyclohex anone
Linear alkylbenzene
Adipic acid
Benzene oxidation
Butane oxidation
Benzene
Petroleum extraction
Benzene alkylation
Benzene alkylation
Methanol
Methanol
Methanol
Benzene nitration
E/P cracking
N/G cracking
E/P cracking
N/G cracking
Propylene oxidation
HP modified Reppe
Direct esterification
LP modified Reppe
Direct esterification
Trans-esterification
Benzene chlorination
Benzene chlorination
Benzene chlorination
Propylene ammoxidation
Propylene ammoxidation
Cyclohexanone oxidation
Phenol hydrogenation
Paraffin chlorination
Paraffin dehydrogenation
Nitric acid oxidation
2.2
0.1
2.9
0.4
0.1
0.0
0.1
0.2
4.6
1.9
1.4
0.2
o.'o
0.1
14.3
2.5
2.4
0.0
0.0
-------
38
IV-8
Table IV-4. (Continued)
Product
Process
1982 Emissions
(%)a
Formaldehyde
Ethylene dichloride
Ethylene oxide
Butadiene
Vinyl acetate
Methyl chloride
Methylene chloride
Chloroform
Carbon tetrachloride
Acetaldehyde
Acetic anhydride
Glycol ethers
Fluorocarbons
Methyl methacrylate
Acetic acid
Acetic acid
Acetic acid
Formic acid
Methyl ethyl ketone
Ethyl acetate
Carbon tetrachloride
Perchloroethylene
Epichlorohydrin
Allyl chloride
Acrolein
Dehydrogenation/oxidation -
silver catalyst
Oxidation - metal oxide catalyst
Direct chlorination
Oxychlorination
Air-oxidation
Oxygen-oxidation
n-Butane dehydrogenation
n-Butene oxidative dehydrogenation
Ethylene by-product
Ethylene vapor phase
Methane chlorination
Methane chlorination
Methane chlorination
Methane chlorination
Ethylene air-oxidation
Ethylene oxygen-oxidation
Acetic acid pyrolysis
Ethylene oxide
Fluorination
Acetone cyanohydrin
Methanol carbonylation
Butane oxidation
Acetaldehyde oxidation
Butane oxidation
Butanol dehydrogenation
Esterificatio.i
Hydrocarbon chlorinolysis
Hydrocarbon chlorinolysis
Allyl chloride
Propylene chlorination
Propylene oxidation
2.3
6.5
7.7
0.7
1.1
0.0
0.3
0.3
0.0
0.4
1.0
0.0
0.2
2.9
0.3
0.6
0.6
0.0
0.0
0.1
0.3
0.1
0.7
0.3
-------
Table IV-4. (Continued)
Product
Process
1982 Emissions
(%)a
Allyl alcohol
Allyl chloride hydrolysis
0.0
Propylene oxide
Glycerin
Epichlorohydrin
0.5
Glycerin
Acrolein
0.0
Allyl alcohol
Methanol
Methane
2.2
Caprolactam
Conventional
0.2
Caprolactam
BASF
0.1
Caprolactam
DSM/HOP (Stamicarbon)
0.0
Toluene diisocyanate
Diaminotoluene
0.4
Ethanolamines
Ethylene oxide
0.1
Dimethyl terephthalate
Via TPA
1.0
Dimethyl terephthalate
Hereofina
5.6
Terephthalic acid
Oxidation and purification
1.8
1,1,1-Trichloroethane
Vinyl chloride
0.8
Ethane chlorination
Perchloroethylene
EDC chlorination
0.2
EDC oxychlorination
Trichloroethylene
EDC chlorination
EDC oxychlorination
Vinylidene chloride
Trichloroethane
0.1
Cumene
Phosphoric catalyst
0.2
Aiumium chloride catalyst
Ethylene glycol
Ethylene oxide
0.9
Sulfuric acid
Direct evaporation
0.2
Indirect evaporation
i
Regeneration
Propylene oxide
Chlorohydrination
2.6
Propylene oxide
Isobutane hydroperoxidation
0.1
Ethylbenzene hydroperoxidation
0.1
Chloroprene
Butadiene
0.8
Aniline
Nitrobenzene hydrogenation
0.1
Phenol
Cumene
1.1
Acetone
Cumene
0.5
79.4
aPercent of initial 1982 SOCMI emission projections addressed.
^Emissions from waste sulfuric acid recovery not initially considered.
-------
V-l
V. TOTAL-VOC-EHISSION SUMMARY
A. ESTIMATED EMISSIONS
The generic reports of Volume III present independent estimates of the total
SOCMI VOC emissions. These estimates are based primarily on study data of
1978 and have not been projected to 1982.
VOC Emissions
(MM lb)
Storage and handling 80
Secondary 90
Fugitive 460-700
The estimate of total SOCMI emissions presented in the Storage and Handling
report in Volume III is 35% lower than the estimate for 1982 projected from the
product study reports. This is because the average vapor pressures estimated
in the Storage and Handling report are lower than those observed during the
product studies and the fact that the Storage and Handling report is based on
1978 data.
For the estimate of total SOCMI emissions presented in the Secondary Emissions
report in Volume III it is assumed that the VOC in wastewater has the average
vapor pressure of the products. The actual average vapor pressure may be
somewhat lower and therefore result in fewer secondary emissions. The secondary
emissions projected from product studies are based on a very limited amount
of actual data. Both estimates are only order-of-magnitude estimates and the
difference between the two estimates presented for secondary emissions is
considered to be within the accuracy expected.
The above emissions estimate for fugitive emissions is based on data collected
in 1978. The fact that new plants come on stream every year indicates that
fugitive emissions would be expected to increase. However, this is largely
offset by the fact that many older obsolete plants are shut down and replaced
with modern high volume facilities with reduced fugitive emissions because
fewer valves and pumps are used for handling a greater volume of VOC liquids.
38
-------
V-2
- 33
The above range of 460 to 700 MM lb of VOC fugitive emissions per year repre-
sents the difference between an estimate that the SOCMI has the same degree
of fugitive emissions control as observed by a petroleum industry study
(defined by this program as uncontrolled emissions) and an estimate that the
SOCMI averages 50% of the maintenance and monitoring prescribed to control
fugitive emissions. Based on the observations made during the performance of
this program and the SOCMI incentives concerning economics, odor, toxicity,
and regulatory pressures, it is estimated that the SOCMI fugitive VOC emissions
in 1982 will be approximately 460 MM lb.
Based on the SOCMI product studies in Volume VI-X, the emission estimates in
Tables II-1 and C-l, and the futitive emissions estimate explained above,
the total VOC emissions projected for 1982 are estimated to be 1434 MM lb.
The initial projection for 1982 was 1779 MM lb. The methods for determining
these projections are explained in Appendix C. The breakdown of this 1982
emission projection by source is as follows:
VOC Emissions
(MM lb)
Amount
1%1
Process
792
55
Fugitive
460
32
Storage and handling
124
9
Secondary
58
4
1434
100
As shown in Table IV-1 and discussed in the Air Oxidation Emission Projection
report in Volume II, oxidation process reactions contribute close to 50% of all
process-source emissions. From the standpoint of unit operations the greatest
volume of VOC emissions is contributed by vacuum systems. As is discussed in
the Vacuum System Emission Projections report of Volume II, the number of
vacuum systems incorporated by the SOCMI is difficult to estimate, but these
systems are believed to contribute at least 158 MM lb of VOC per year.
While the studies described in Volumes VI—X were being conducted, particular
attention was given to the potential for benzene emissions. Following is a
summary of the SOCMI benzene emissions projected for 1982. Over 90% of the
benzene emissions result from the manufacture of four products.
-------
V-3
Estimated Benzene Emissions
Product
(MM lb/yr)
Maleic anhydride
Ethylbenzene/styrene
Ethylene
Alkylbenzene
Nitrobenzene
Chlorobenzene
Caprolactam
Acetic anhydride
Aniline
12.78
0.92
0.02
0.01
0.04
2.62
2.81
6.83
1.17
Total
27.20
B. CONCLUSIONS
As shown in Table II-l and discussed in Appendix C, the estimated emissions
from the manufacture of the products studied are only about half the initial
estimate made early in the program. The initial estimate was based largely on
Louisiana and Texas Air Control Agency data supplied to them by industry sur-
veys for 1975 and 1976. The current estimate is based on site visits to many
of these same industry sources. The evidence clearly shows that a dramatic
improvement in emissions from the SOCMI has occurred during the last few years.
The greatest improvement has been in the control of emissions from process
vents. The motivation for these improvements obviously includes the economic
advantage of VOC loss prevention, industry's genuine concern for the environ-
ment, plus current and anticipated regulatory pressures.
i*0
-------
APPENDIX A
PROGRAM ORGANIZATION
hi
-------
APPENDIX A
A *3
| IT ENVIROSCIEUCE
PRESIDENT
K. Honeycutt
ITE MGR-IN-CHARCE
T. Dehnke
ITE PROJECT MANAGES!
R. White
PROCESS SPECIALIST I
v. Kalcevic
SAMPLING SPECIALIST
W. OConne11
GENERIC PROCESS
EMISSIONS
J. Blackburn
TECHNICAL EDITOR
v. Hamrlck
MITRE/METREX
PROGRAM CONSULTANT
P. Clifford
A. Goldfarb
ESED ENGS.
L. Evans
D. Beck
J . ShunaXer
D. Mascone
R. weber
EMISSION
TESTING
CD ^TRACTORS
manufacturers
OF
SYNTHETIC
ORGANIC
CHEMICALS
EPA/ESED
PROJECT OFFICER
D. Patrick
R. Ro9ensteel
TECH. R£V. BOARD
C. Parmele
R. Fox
T. Dehnke
R. NcvaX
K.. Honeycut'
H. Basdekis
J. Cudahy
C. EriXson
TASK ENGINEERS
COST ESTIMATING
SECONDARY EMISSIONS
V. Kalcevic
J. Fordyce
R. Stand iter
J. Cudahy
PROCESS TASK LEADERS
J. Blackburn
S. Oylewski
J . Key
R. Love 11
C. Peterson
R. Standifer
C. Stueve
F. Hobbs
CONTROL DEVICE EVAL.
SURVEY AND RANKING
STORAGE AND HANDLING
FUGITIVE EMISSIONS
V. Kalcevie
D. Erikson
J. Hal)
W. OConnell
SAMPLING
EVALUATION
PROGRAM ORGANIZATION
-------
APPENDIX B
SURVEY AND RANKING
M 3
-------
B- 3
APPENDIX B
SURVEY AND RANKING
The primary objective of the survey and ranking task was to provide the
necessary data to rank order the processes to assure that the most
significant processes were studied in the most detail early in the project.
This report describes the methods used and gives the results for ranking
140 products.
Four areas were identified and considered to rank order the processes:
1. Gross Emissions - The total quantity of non-methane hydrocarbons
emitted from the manufacture of a specific com-
pound by each one or more processes annually.
2. Growth Factor - The projected rate of annual growth expected
through 1982. Very low or negative growth com-
pounds were given lower priority than potentially
high growth compounds.
3. Modular Contribution - A breakdown of the various manufacturing
processes into the specific types of reaction
processes and emission control modules associated
with each process. Primary emphasis was given
to processes which would yield information that
could be utilized to help study similar aspects
of other processes.
4. Toxicity Score - A means of differentiating the potential health
hazards between processes that emit varying amounts
of less toxic and more toxic chemicals.
Gross Emissions Determination
Total annual production multiplied by an emission factor (lbs. material
lost per lb. of product) yields the annual gross non-methane hydrocarbons
(NMHC) emissions. 1976 was used as the base year since it was the most
recent year for which complete actual production data could be obtained.
Production data was supplied by the annual chemicals manufacturing report
in Chemical and Engineering News and Chemicals Economics Handbook published
by Stanford Research Institute.
Information used to determine emission factors was gathered from the
Texas and Louisiana State Air Control Boards. Non-confidential emissions
inventories, some selected construction permit files in Louisiana, and
most of the pertinent non-confidential construction permit files in
Texas were also used when available.
-------
B-4
Considerable judgment was used in calculating emission factors from the
data in the inventory questionnaires and permits. Many files did not
contain adequate production breakdowns for individual plant sites. In
these cases, plant production was estimated by taking the capacities
listed in The Chemical Marketing Reporter Chemical Profiles or the
1976 Directory of Chemical Producers and multiplying by the average
industry percentage of production in relation to capacity. Several
questionnaires did not contain sufficient information to enable the
designation of which emission point originated with which process. When
apparently good analytical data was available and the vented emissions
were broken down into components, the processes could be separated with
some degree of certainty.
In some cases, where multiple processes used common vents, the emissions
had to be allocated, usually on a weight percentage basis of production.
Judgments were also required even when all information was available
and emission factors could be readily calculated. The factors for
two similar facilities were often quite dissimilar. If a factor for
one facility agreed well with published data, then that factor was
selected as being more accurate. In some cases, where no comparable
data was available, an average was taken. In a number of cases, the
calculated emission factors were rejected as being unreasonably below
expected levels.
In those cases where an emission factor could not be obtained because
of the reasons stated above or because there were no producing sites
in Texas and/or Louisiana, the Radian, Monsanto, or Houdry data were
used when available.
When a compound was produced by two or more distinctly different
processes, emission factors were determined for each significant
method of manufacture. Radian's production percentage breakdown for
each process was used where revised data were not available. The VOC
emissions estimated for the top 140 chemicals are shown by Table I.
Growth Factor Determination
Rank ordering is based on 1982 projected gross NMHC emissions. Since
most pre-1975 growth projections are invalid due to the economic recession
of 1975, revised figures were needed. The source of these revised
projections were the Chemical Economics Handbook and Chemical Marketing
Reporter. Using the new growth rates, the 1982 gross emission data
was obtained by compounding the 1976 data over six years. The average
annual growth was approximately 6%.
Modular Contribution
The various units which comprise the anatomy of a synthetic organic
chemical production plant had to be broken down and identified. Although
-------
B-5
kS
each plant has an individual character of its own, there are still common
operations or sections which can be related to other processes. These
sections or modules were assigned to three categories: reaction, process,
and emission control. Reaction modules describe the initial portion
of the process where the compound is made, i.e., alkylation, oxidation,
chlorination, etc. Process modules conprise the various unit operations
that the compound or product must go through during its manufacture and
which can result in the release of emissions, i.e., distillation,
absorbtion, extraction, etc. Emission control modules define the device
or devices used to prevent or control emissions, i.e., flare, condensor,
thermal oxidizer, etc.
Modular contribution was a judgment assessment of the value of studying a
particular process with regard to the transfer of emission related technology
to other process studies where similar process modules can be identified.
Three (3) grids depicting the various reaction, process, and emission
control modules are shown in Tables II, III, and IV.
Toxicity Score Determination
Toxicity score was obtained by multiplying the annual gross emissions
(broken down by MM lbs. of each major component) by a toxicity factor
assigned to each component. These quantities are then totaled, resulting
in a toxicity score for the compound under consideration. (See Figure 1
as an example).
Two methods were used to determine the toxicity factor and resulting
toxicity score.
Exponential toxicity scores were computed from the EPA's formula which
uses the MITRE toxicity ratios. The MITRE scoring (EPA-450/3-77-008a)
has been "expanded" to show more accurately the "real" difference in
toxicity between less toxic and more toxic chemicals. In the MITRE
system a very toxic chemical, vinyl chloride, has a score of 0.7 while .
a typical chemical, with few toxic properties, methylal, has a score
of 0.04. The ratio between these two MITRE scores is only 17.5. A
judgment was made that the ratio of 1000 better shows the real
difference in toxicity of these two chemicals, then the MITRE scoring
was used as as exponent to calculate an "expanded score". The
formula for the expansion is ES - g57 g 10.5 (MS)
1,000
IOO
I.C ~MITRE SCORE (MS-)
O .04
-------
B-6
11
The expanded score was used in the same way as the MITRE score would
be used. The toxicity score is obtained by multiplying the expanded
score by the MM lbs. of VOC emissions. The exponential toxicity
scores are shown in Table I.
Linear toxicity scores were computed by multiplying the component gross
emissions (MM lbs.) times two different toxicity numbers. The first
number, ranging from 1 to a maximum of 6, represents the MITRE score
plus _1 for acute toxicity. This is consistent with other toxicity
scoring such as the one sited in "Clinical Toxicity of Commercial
Products". The second number represents the carcinogenic, mutagenic,
and teratogenic potential. If a compound was given a 4 or 5 per the
MITRE score in any or all of the three categories, it was assigned a 5;
if under test, a 3, and if it had not been tested or had scored a negative
result, it was given a 1. (See Figure 1 for example). The maximum toxicity
factor for this method was 6 x 5 = 30. The minimum was 1x1=1. The
linear toxicity scores are also shown in Table I.
Rank Ordering
The processes, as rank ordered for this study, are listed in Table I. All
four of the areas previously described were considered in rank ordering
the compounds for selection. The 1982 total projected NMHC emissions were
given the most weight in a selection decision; however, modular contri-
bution and toxicity scores were used to choose between compounds having
relatively equal amounts of gross emissions.
The study ranking table is ranked according to the most significant process
for each compound. The secondary processes are grouped under each com-
pound, and the decision regarding their study priority is made on an
individual process comparison basis. Process studies were grouped
for practical study convenience.
Other factors also entered into the selection process. Vinyl chloride,
for instance, was omitted for study, even though it ranked first because
a considerable amount of effort and resulting reports have already been
compiled on this compound. Processes which use benzene as a raw material
such as nitrobenzene, chlorobenzene, and linear alkyl benzene were
assigned early in the project as a result of increased governmental
interest and investigation into benzene's toxological effects. Some
compounds have arbitrarily been put on hold due to their negative growth
forecast.
In some cases, compounds were grouped with other compounds for practical
study efficiency and were selected for study earlier than they would
have been if they were studied "on their own merits".
-------
B-7
This method of survey and ranking is considered to be a significant
improvement over previous methods because of the following incorporations
1. Actual plant data, regarding the quantity and composition of
emissions, was used to calculate emission factors in the majority
of cases.
2. Toxicity scores are based on the relative toxicity and amount of
each individual component in the emission, not just the compound
or product being manufactured.
3. The chemical manufactures in the states of Texas and Louisiana,
which were used as the data source, accounting for approximately
65% of the total U.S. synthetic organic chemical production.
-------
FORMALDEHYDE
FIGURE I
Production
M Pounds
5621.0
Emission Factor
lb/lb of Product
.00077
.00036
.00400
.00513
Component
Formaldehyde
Methanol
Ethanol
Annual Gross
Emissions M Pounds
4. 330
2.020
22.480
28.830
EPA Exponential
Toxicity Factor
152.10
4.59
2.75
Toxicity
Score
659.0
9.3
61.8
730.1
Linear Toxicity Score
Component
Formaldehyde
Methanol
Ethanol
Gross Emissions
4.330
2.020
22.480
x
x
X
Acute Toxicity
Factor
4
4
3
Teratogen
Carcinogen
Mutagen
x 5
x 1
X 1
Toxicity
Score
86.6
8.1
67.4
28.830
162.1
Growth Rate = 6%/Year (Over next 6 years, i.e. 1982)
Gross Emissions 28.83 x 1.419 = 40.92-
Exponential Toxicity 730.1 x 1.419 = 1036
Linear Toxicity 162.1 x 1.419 = 230
1982 Projected
See (->•) on Tables II, III, and IV
-------
9/10/78
table; i
page 1
SEL.
RANK CHEMICAL
NO. NAME
VINYL CHLORIDE
ACRYLONITRILE
10
11
12
ETHYLENE
OICHLORIOE
5 ETHYLENE OXIDE
dimethyl
terephthalate (
OMTI
7 ETHYLENE
8 ETHYLBENZENE
HYDROGEN CYANIDE
(HCN)
STYRENE
I.I.I.
TRICHLOROETHANE
CARBON
TETRACHLORIDE
SURVEY AND RANKING PROC
ESS STUDIES
190?
1976 GROSS
1982 GROSS
ASSIGNED
* OF
MM'tC
NMHC
1982 TOXICITY
EMISSION
EMISSION
T ASK
TOTAL
PROCESS
EMISSIONS
percent
EMISSIONS
SCORE
RANK
factor
factor
LEADED
PROD.
USEO
M L3S
growth
M LBS RANK
EXPON.
linear
LB/LB
SOURCE
1*
ACETYLENE
.395
6.99x
.593
105
27
110
.00689
3
99*
ethylene
4 0.034
6.99%
60.080
5
1
6
.00704
B
DICHLORIDE
KEY
100*
PROPYLENE
151.1496
B.99X
254.0#
1
5
3
.09979
A/3
OXIDATION
KEY
OX
ACETYLENE
KEY
50*
DIRECT
29.494
7.36X
45.165
10
4
1
.00759
A
CHLORINAT ion
KEY
50*
OXYCHLOKINATIOM
¦46. 569
7.36*
71.314
4
3
2
.01199
3
LAWSON
85*
3ENZENE
23.165
9.15X
39.190
13
2
4
.09334
A/B
oxidatiom
LAWSON
15*
BUT ANE
oxidatiom
LOVELL
66*
air oxidation/
51.955
5.99X
130.4*
2
9
7
.03329
C
ethylene
lovell
31*
02 oxidation/
5.263
5.99X
7.466
40
96
84
.00369
r;
ETHYLENE
DYLEWSKI
23*
AMOCO VIA TPA
5.551
7.99X
8.809
34
80
55
.00861
C
dylews
5.209
¦4.00X <4.077 59
10
29
.01599
-------
9/10/78
TA3LE
I
PAGE 2
SURVEY AND RANKINS PROCESS STUDIES
SEL,
RftMK
NO.
CHEHICaL
NAME
ASSIGNED
Task
leader
1982
X OF
TOTftL
PROO.
PROCESS
USED
1976 SROSS
MMHC
EMISSIONS
M L3S
1982 GROSS
NMHC
PERCENT EMISSIONS
growth m lds rank
1982 TOXICITY
score rank
EXPON. LINEAR
emission emission
factor factor
LB/L3 SOURCE
c.n
12
CARBON
STUEWE
¦42*
chloroparaffin
6.117
-4.00*
4.786
56
43
51
.01699
3
TETRACHLORIDE
CHLOROLrSIS
STUEWE
20X
METHANE
. 956
- 4. 0 0 X
.670
101
39
80
.00499
A
13
FORMALDEHYDE
lovell
23*
metal oxide/
6.632
5.99X
9.407
32
48
32
.00512
A
methanol
lovell
77*
SILVER
22.203
5.99X
31.496
16
26
10
.00512
A
CATALYST/
methanol
14
methyl
9LACKBJRN
100*
ACETONE
32.972
7.49*
50.886
7
58
14
.06049
A/3
METHACRYLATE «
cyanohydrin
MMA )
15
PROPYLENE OXIDE
STUEWE
60 *
chlorohydrin
35.067
5.BOX
49.199
9
46
12
.02959
3
STUEWE
MO*
PEROXIDATION
.4 3 3
1U.45X
. 786
100
125
104
.00070
A
16
propylene
54 *
NAPTHA/GAS OIL
12.730
14.4 9*
28.673
17
19
26
.00342
0
PYROLYSIS
16*
NATURAL GAS
3.049
7.49*
4.706
58
49
76
.00189
0
LI3UIDS PYROL
30*
REFINERY BY
PRODUCT
17
NITROBENZENE
STUEWE
100*
BENZENE
2.268
0.49*
3.701
61
12
27
.00299
0
NITRATION
IS
ethylene glycol
lovell
100*
ethylene oxide
10.742
5.99*
15.238
22
13
21
.00319
A
19
cyclohexanol/
BLACKBURN
75*
cyclohexane
35.020
3.49*
43.048
12
63
15
.04446
A
cyclohex-anone
BLACKQJRN
25*
PHENOL
. 241
3.49*
.296
123
127
128
.00091
A
20
CUMENE
STUEWE
100*
BENZENE
2. 661
6.99X
3.994
60
14
37
.00097
A
21
METHANOL (METHYL
KEY
100*
METHANE
25.650
6.99X
38.494
14
62
18
.00410
A
ALCOHOL)
22
PHENOL
STUEWE
3*
BENZENE
CHLORINA TI ON
STUEWE
2K
3ENZENE
SULFONAT ION
STUEWE
93X
CUMENE
12.627
6.99X
18.950
19
21
13
.00621
A
STUEWE
2*
TOLUENE
oxidation
23
ANILINC
STUEWE
100*
NITROBENZENE
1.631
B.49X
2.661
67
15
35
.00299
D
hydrogenatiom
24
FLUOROCARBONS
standifer
100*
CCI4/C2CI6
5.001
.00*
5.001
52
18
4 3
.00499
3
FLUOR INA TI ON
25
PERCHLOROETHYLENE
standifer/*
0*
ACETYLENE
standifer/*
66*
ethylene
1. ?53
15.59*
2.991
66
34
44
.00544
B
dichloride
STANDIFER/*
34*
METHANE
1.314
1.22X
1.413
89
23
64
.00499
A
26
terephthalic acid
DYLEWS-U
39*
AMOCO
4. 334
7 • 9 9 X
6. 878
42
83
63
.00854
C
« TPA)
DYLEWSKI
47*
EASTMAN
6.201
7.99*
9.841
30
64
28
.01014
C
DYLEWSKI
14*
MOBIL
10.033
7.99*
15.922
21
81
34
.05512
c
to
I
-------
9/10/78
T A 3LE: I
PAGE 3
SURVEY AND NANKINS PROCESS STUDIES
191?
1976 GROSS
19B2 gross
SEL.
ASSIGNED
* OF
WMHC
NMHC
198? TOXICITY
EMISSION
EMISS
rank
CHEMICAL
Task
TOTAL
PROCESS
EMISSIONS
PERCENT
EMISSIONS
SCORE
RANK
factor
FACTl
NO.
name
leader
PROD.
U3ED
M L9S
GROWTH
M LBS R
ANK
EXPON.
LINEAR
L3/L3
SOJRl
27
CHLOROBENZENE
DYLEWSKI
100*
3ENZENT
1. 996
1.99*
2.240
74
20
53
.00434
3
CHLORONATION
28
acrylic acid
BLACKBURN
25*
MODIFIED repp
• 21 B
.169
132
149
134
.00195
A
BLACKBURN
77*
PROPYLENE
10.933
1 '4 . 9 3 X
25.205
18
32
20
.08703
B
OXIDATION
29
ACETIC ACID
KEJt
33 X
ACETALOEHYDE
10.012
1.B2*
11.158
27
56
16
.00980
9
KEY
44*
BUTANE
.342
77. 43*
10.692
28
71
39
.00704
3
OXIDATION
KEY
19*
METHANOL
2.915
9.07X
"4.911
53
77
69
.00749
3
KEY
4*
others
30
CHLOROPRENE
DYLEWSKI
100*
VIA butadiene
11.975
2.39*
13.691
24
29
11
.03149
A
31
alkyl leads
5X
eletrolysis
95*
ETHYL CHLORIDC
4.827
-11.0*
2.399
71
22
71
.0081?
A
32
ACETONE
STUEWE
69*
CUMENE
5.658
7.05*
8.517
35
30
24
.00521
A
STUEWE
31*
isopropanol
5.102
-1.13*
4.765
57
B 7
52
.00649
9
33
ETHYL CHLORIDE
4*
ET'IANOL/ETHANE
96*
ETHYLENE
8.672
"7.00*
5.611
49
25
30
.01349
B
CHLORINATION
34
ETHANOLAMINES
lovell
100*
ETHYLENE OXIDE
1 - <+ 31
2.99*
1 .709
84
24
45
.00499
9
35
VINYL ACETATE <
DYLEWSKI
13*
acetylene vapor
1 .630
6.99X
2.447
70
92
73
. 00846
;
VA)
PHASE
DYLEWSKI
72*
ETHYLENE VAPOR
6.515
6.99x
9.777
31
65
25
.00610
C
PHASE
OYLEWSKI
15*
ETHYLENE LIQUID
5.002
6.99*
7.507
39
61
38
.02251
c
PHASE
36
METHYLENE
STUEWE
35*
METHANE
3.561
9 . 0 IX
5.978
47
38
42
.01699
3
CHLORIDE
CHLORINATION
STUEWE
65*
methanol/methyl
. 538
12.16*
1.273
90
51
58
.00194
A
chloride
-
37
1.3 BUTADIENE
STANDI PER
BOX
ETHYLENE
1.011
14.04*
8.827
33
36
61
.00267
D
COPROOUCT
stanoifer
13*
N-3UT ANE
7.157
-12.?~
3.270
65
108
83
.00610
3
stanoifer
7*
N-3UTENE
.979
-11.1.
.<~81
108
150
140
.00166
3
3B
VINYLIDENE
stanoifer
50*
1.1.1
1.772
6.99X
2.660
68
31
49
.01899
B
CHLORIDE
TRICHLOROETH*
STANDIFER
50*
1.1.2
TRICHLOROETH*
39
TOLUENE
stanoifer
100*
DIaMINOTOLUENE
3.9B4
0.99*
6.515
45
35
40
.00699
A/3
DIISOCYANATE I
TDI1
<~0
CHLOROFORM
STUEWE
61*
methane
3.017
B.99X
5.060
51
41
49
.01699
B
chloronation
STUEWE
39*
methanol
.221
B.99X
.371
119
73
86
.00194
A
CHLORONATION
HI
PHTHALATE
30*
NAPTHALENE
anhydride
70*
O-XYLENE
1.338
6.49*
1.953
76
37
47
.00211
A
-------
9/10/78
T A 3L E I
SURVEY AND RANKING PROCESS STUDIES
1982
;el.
ASSIGNED
* OF
VMK
CHEMICAL
Task
TOTaI
JO.
name
leader
PROD,
42
ISOPROPANOL (
100*
ISOPROPYL
ALCOHOL)
43
ACETIC ANHYDRIDE
KEY
loot
44
GLYCEROL (
PETERSON
14 )t
SYNTHETIC ONLY)
PETERSON
15*
PETERSON
71*
45
NITROPHENOL
100*
46
CYCLOHEXANE
BLACKBURN
84*
BLACKBURN
16*
47
BISPHENOL A
100*
48
CELLULOSE ACETATE
100*
49
CA PROLACTAH
BLACKBURN
100*
50
PENTAERYTHRlTOL
100*
51
nonyl PHENOL
100*
52
acrylamide
100*
53
diethylene,
LAwsON
100*
TRIEThYLENE
glycols
94
fumaric acid
100*
55
PROPYLENE GLYCOLS
100*
(MONO, nit TRI)
56
EPICHLOROHYDRIN
PETERSON
100*
57
ALLYL CHLORIDE
PETERSON
100*
58
adiponitrile/hmda
OYLEWSKI
11*
OYLEWSKI
24*
dylewski
65*
59
trichloroethylene
STAnOIFER
9*
stanoifer
91*
60
METHYL isobutyl
100*
keytone i«ibk)
61
PYRIDINE
100*
62
BENZENE
no*
20k
PROCESS
USED
100* PR0PYLENE/H2S04
1976 330SS
MMH;
EMISSIONS
M L3S
4.566
15.452
.<+21
1982 GROSS
NMHC
PERCENT EMISSIONS
GROWTH M lbs RANK
1.99* 5.142 50
ALLYL ALCOHOL .756
EPICHLOROHYD^IN 7.233
PHENOL 1.337
NITRATION
3ENZENE 1.228
HYDROGENATION
petroleum
DISTILLATION
PHENOL/ACETONE .841
CELLULOSE 7.997
ESTERIFICATI*
CYCLOHEXANONE 3.541
FORMALDEHYDE/ 1.309
ACE T ALDEHYOE
PHENOL .511
ALKYLATION
ACRYLONITRILE .122
COPRODUCTS W/ 1.157
ETHYLENE
GLYCOL
MALEIC ACID/ .398
SO.MERIZATION
PROPYLENE OXIDE 6.507
HYDRATION
ALLYL CHLORIDE/ 1.621
HCI
PROPYLENE B.963
CHLORINftTI ON
ACRYLONITRILE
ADIPIC ACIO
3UTADIENE 8.336
ACETYLENE
ETHYLENE 1.486
MESITYL ALCOHOL 8.354
FORMALDEHYDE:/ .727
ACETALDEHYDE
NOT IN PROJECT
SCOPE
TOLUENE .326
HYOROnrALKYI *
99X
99X
18.451
.474
20
109
99X
99*
49*
.852
6.145
2.25B
9fl
36
73
53*
1.796
78
99X
49*
1.574
8.137
87
37
49*
99*
4.882
?. 160
55
75
49X
.628
104
49x
99*
.199
1.641
126
B5
99*
.437
113
49*
10.043
29
49*
1.880
77
99*
12.012
25
99*
11.171
26
o o
O Q
.901
5.763
96
48
99*
.869
97
21*
.331
122
PAGE 4
cr1
1982 TOXICITY
EMISSION
EMISSION
SCORE
rank
factor
Factor
EXPON.
linear
L3/LB
source
40
60
.00235
A
74
62
.01009
t)
122
130
.01909
c
86
102
.03199
c
47
65
.0&459
c
42
46
. 05249
B
44
70
.00072
D
45
54
.00199
A
59
56
.01099
B
53
66
.00453
A
57
36
.01719
A
50
75
.00655
A
52
92
.00239
A
55
81
.00319
A
54
95
.01149
B
75
50
.01258
A
60
88
.00286
A
95
74
.02699
A
101
78
.01499
B
67
82
.00538
A
82
41
.04229
A
w
(-•
KJ
69 67 .01499
68 105
.00010
A
-------
9/10/78
TA 3UE I
SURVEY AND NANKINS PROCESS STUDIES
SEL.
rank
NO.
chemical
NAME
ASSIGNED
task
leaded
standifer
lovell
lovell
63 ETHA\JOL CETHyL
ALCOHOL)
64 UREA
63 ACETaLDEHYDE
66 ISOPRENE
67 FURFURAL
6B GLYCOL ETHERS
69 DINITROTOLUENE
70 SEC-3UT ANOL
71 LINEAR alkyl
BENZENE
7? ACROLEIN
73 OIPHENYLAMINE
74 METHYL styrene
75 ETHYLENE DIAMINE/
TRIETHYLENE
tetramine
76 ETHYL ACRYLATE BLACKBURN
LOVELL
LOVELL
PETERSON
PETERSON
77 METHYL CHLORIDE
BLACKBURN
STUEWE
STUEWE
78 METHYLENE
DIPHENOL
DIISOCYANATE «•
79 N-BUTYRALOEHyDE
60 NITROANILINE
91 ACETOPHONE
1982
X Or
TOTAL process
PROO. USED
100* ETHYLENE
100* NH3/C02
OX CTHANOL
OXIDATION
100* ETHYLENE
67* C4 HYDROCARBONS
33* SIOAMYLENT
extraction
100* POLY
saccharides
HYDROLYSIS
97* ETHYLENE OXITE
3* PROPYLENE OXIDE
100* TOLUENE
DINITRATION
100* 3UTYLENES
100* BENZENE
alkylation
100* PROPYLENE
OXIDATION
ioo* aniline
AMINATION
15* CUMENE
DEHYOROGENAT»
05* CUMENE PROCESS
BY-PRODUCTE
100* EOC ammonolysis
61* ACETYLENE <
REPPE)
39* direct
ESTER1FICATI»
2* methane
CHLORINA TI ON
98* METHANOL
HYOROCHLORIN*
100* OPMDA/PHOSGENE
100* Oxo PROCESS
100* NITRO CHLOR
benzene
60* CUMENE
PEROXIDATION
UOX ETHYL BENZENE
OXIDATION
1976 3R0SS
EMISSIONS
1982 GROSS
NMHC
PERCENT EMISSIONS
PAGE 5
1982 TOXICITY EMISSION EMISSION
SCORE RANK FACTOR FACTOR
.as
GROWTH
M LBS 1
RANK
EXPON.
LINEAR
LB/L9
SO'JRCE
.759
2.49*
6.679
44
91
57
.00384
A
, 386
5.69*
7.512
38
99
59
.00065
A
,649
.00999
3
,488
4.30*
7.271
41
93
77
.00586
A
. 246
11.99x
.486
107
70
85
.00210
A
, 341
1.99*
2.636
69
7b
79
.01499
3
3?1
5.99*
.455
11?
72
99
.00058
A
,009
5.99*
.014
163
166
165
.00050
A
, 920
10.99*
1.721
83
79
B 7
.00175
A
,426
6.79*
3.601
62
84
72
.00699
3
,068
1 .99*
.077
143
70
126
.00009
A
,942
3.99*
6.127
46
107
90
.07449
3
,039
4.99*
.053
151
85
127
.00099
tJ
272
5.99*
.386
117
89
103
.00521
A
131
4.99*
.176
130
80
112
.00099
3
098
7.99*
1.742
81
136
114
.00609
3
093
7.99*
1.734
82
104
91
.00949
a
189
-3.26X
.155
135
102
131
.01699
a
975
3.67*
1.210
93
106
100
.00269
A
089
10.99*
.168
134
94
118
.00023
A
1.B27 4.24X 2.346 72 109 09 .00243
.071 .00* .071 144 97 122 .00599
.134 5.99* .191 128 98 116 .00521
W
I—•
LJ
cn
-c-
-------
9/10/78 PAGE! 6
TA3LE I
SURVEY ANO RANKING PROCESS
STUD IE
r
1 98?
1976 GROSS
1992 GROSS
SEL.
ASSIGNED
* OF
MMHC
NMHC
1932 TOXICITY
EMISSION
EM I SS I 0'
Rank
chemical
task
TOT jyL PROCESS
EMISSIONS P
ERCENT
EMISSIONS
SCORE
rank
FACTOR
FftC TOR
no.
name
leaded
PROq.
USED
M L3S
GROWTH
M LBS 1
rank
EXPON.
LINEAR
L3/L3
SOURCE
82
ISOPHTHALATE ACID
100*
M-XYLENE
• 235
11.99*
.465
110
100
9B
.00199
H
OXIDATION
83
BENZOIC ACID
100*
TOLUENE AIP
.279
<~.99*
.375
llfl
105
96
.00199
3
OXIOATION
84
diisooctyl
100*
PHTHALATE
.593
6 . 1 9*
.851
99
103
109
.00199
3
PHTHALATE (012-
anhydride/
ETHYLHEXYL)
ALCOHOL
85
2-ETrlYL l-HEXANOL
100*
ALDO CONO./OXO
1.130
7.99*
1.794
79
117
94
.00252
A
86
N-BUT ANOL (BUTYL
20*
acetaldehyde
ALCOHOL)
80*
3X0 PROCESS
1.265
3.99*
1.601
86
120
97
.00252
A
8 7
PROPIONIC ACID
7*
OTHERS
93*
3X0 PROCESS
. 424
6.99*
.637
103
115
93
.00599
3
B8
ETHYL ACETATE
KEY
100*
ACETIC ACID
1.077
1.99*
1.213
92
121
101
.00499
3
89
ETHYLENE
100*
ETHYLENE
1.508
-3.00*
1.256
91
119
107
.00 749
3
DI3R0MI0E
BROMINATION
9D
ACETONE
BLACKBURN
100*
ACETONE
.283
8. 49*
.462
111
110
117
.00051
A
CYANOHYDRIM
CYANATION
91
BENZYL CHLORIDE
100*
toluene
.131
3.99*
.170
131
116
108
.00149
3
CHlORINATION
92
DICHLOROPHENOL
45x
phenol
.009
2.99*
.011
165
118
152
.00099
3
CHLORINATION
55*
TRICHL0RO3ENZE*
.219
2.99*
.261
124
134
135
.01896
A
93
ISOBUTYRALDEHYDE
100*
0X0 PROCESS
. 911
2.99X
1.123
94
128
106
.00252
A
94
cresylic acios <
¦4*
CYMENE
SYM)
OXIDATION
80*
NATURAL COAL
TAR
B*
PHENOL/METHANOL
.013
¦~.99*
.018
161
123
149
.00099
B
8*
TOLUENE
.013
'*.99*
.018
162
130
143
.00099
3
SULFONATION
95
N-N DIMETHYL
100*
analine
.039
4.99*
.053
150
111
132
.00199
3
ANILINE
AMIN0LYS1S
96
ACETYLENE
30*
CALCIUM CARBIDE
8*
ETHYLENF BY-
PRODUCT
6?*
HYDROCARBON
1.779
.00*
1.779
80
133
113
• 00 5B 0
A
OXIDATION
97
PHOSGENE
100*
C0/CI2
,1U
9.99*
.259
125
114
129
.00017
A
9B
T-BUTANOL
21*
isobutylene
.167
.0 7*
.168
133
160
156
.00049
3
79*
PROPYLENE OXIDE
.556
8.36*
.901
95
126
119
.00070
A
CO-PRODUCT
99
SALICYLIC ACID
100*
SOOlUM PHENATE
.023
1.99*
.027
160
112
137
.00049
3
100
DIMETHYL
100X
NITROSODIMETHTL
.001
"~.99*
.00268
173
113
164
.00049
3
HYDRAZINE
amine
101
DODECENE
100*
MONENE
1.1H
.99*
1.533
88
135
120
.00499
3
COPRODUCT
CD
I
-------
9/10/70
T ft 3LE I
PAGE 7
SURETY AND RANKING PROCESS STUDIES
1982
1976 GROSS
1902 GROSS
SEL.
ASSIGNED
* OF
NMHC
NMHC
1982 TOXICITY
EMISSION
EMISSION
«ank
chemical
Task
TOTaL
PROCCSS
EMISSIONS
PERCENT
EMISSIONS
SCORE
RANK
FACTOR
factor
NO.
NAmE
leader
PROD.
IISFD
M L3S
GROWTH
M LBS RANK
EXPON.
LINEAR
LB/LB
SOURCE
102
01ISOLDCTL
loox
PHTHALA rE
• ?B6
3.19*
.351
121
121
133
.00199
(3
PHTHaLATE
anhydride/
1 SODECAN3L
105
buttl acrylate
blackbjrn
100*
ACRYLIC ACID
.mo
7.99*
.651
102
132
111
.00199
9
ESTERIFICAIQVJ
101
CHLOROSULFONIC
100*
SOS
.311
1.99*
.308
116
1?9
125
.00219
3
ACID
HYDROCHLORIN*
103
METHYL ETHYL
KEY
25*
3UTANE
KEYTONE
-------
9/10/78
TA3LE I
PAGE 8
SURVEY AND RANKING PROCESS STUDIES
19B?
1976 GROSS
1982 GROSS
SEL.
assigned
* OF
\JMIC
NMHC
1902 TOXICITY
EMISSION
E"!SSI Dl
~.99*
.00093
.00099
9
30*
BENZYL ALCOHOL/
.000
4 . 99*
.00093
.00099
3
acid
140
BENZOYL CHLORIDE
100*
BENZOIC ACID
.000
*4.99*
.00010
.00004
3
Source Codes: A - State EIQ's; B - Monsanto Research Corp./Radian; C - Houdry; D - HI Site Visits;
E - Product Report
-------
TABLE II
SURVEY AND RANKING PROCESS STUDIES
ot» Ivct iori
K niKi nq
Ho.
1
2
Chemical
10
11
Aerylonitrile
Ethylene Dichloride
Ethylene Oxide
EthyIbenzcne
Ethylene
Vinyl Chloride
Dimethyl Terephthalate
Maleic Anhydride
Propylene Oxide
Methyl Methacrylate
Formaldehyde
1982
% of Total
Production
* 100%
* 50*
» 50%
* 66%
* 34%
* 90%
2%
* 100%
99%
1%
* 25%
35%
23%
17%
85%
15%
60%
40%
100%
77%
Process
Amoxidation
Direct- chlorinat ion
Oxychlorination
Acetylene
Air Oxidation ethylene
O^ Oxidat.Ion ethylene
Benzene alkylation
Mixed xylene extraction (not in
scope)
Crackinq
Ethylene dichloride
Acetylene
Hcrculnn
DuPont
Amoco via TPA
Eastman via TPA
Benzene oxidation
Butane oxidation
Chlorohydrin
Peroxidation
Ace tone cyanohydrin
Silver catalyst high methanol
•Processes assigned for study
REACTION MODULES **
63
"¦8
** Letter indicates the order of occurance.
CT7
-------
3
WO
Oct
0
•OH-
>>> > > E>> > 1 Oxidation
> > > | Chlorination
o n n) i Hvdrocenation
Pvrolvsis
Estenf ication
>
Hydration
Dehvdroch ion nation
Arcnor.olvs is
>
Sultonation
Alkyiation
Hydrorornulation
©
Neutralization
Jenydration
Dehydroqenation
Condensation
Hvdrolvsis
Arjnoxication
Oxvcnlorination
>
Kydrochlorination
Peroxidation
> >
Carbor.olation
>
Reduction
CO
Cleavinq
O ("1
Acidification
Oxvacetvlation
Phosqenation
Alcoholysis
Saponification
Hydrocvanation
Mitration
o
Fusion
CD
Refonr.ina
Hvdrod ir.er ization
Addition Ester
Fluoronaticn
Bromination
Hvdrodealkvlation
Hvdrctromr.a tion
LL/1/W
-------
TABLE II
(Continued)
SURVEY AND RANKING PROCESS STUOTES
So 1 cct ion
Rankinq
No. Chemical
21 Styrene
22 Chloroprene
?3 Acetic Anhydride
24 Cyclohcxanol/Cyclohexanone
25 AUyl Chloride
26 Adiponitrile/HMDA
27 Carbon Tetrachloride
20 Vinyl Acetate
29 Methylene Chloride
JO Acetone
31 Methyl Chloride
*Piocesse9 assigned Cor study
19R2
% of Total
Production Procenn
•
100%
Ft.hylbon7.one
100%
Butadiene
*
100%
Acetic acid
•
75%
Cyc]ohexane
25%
Phenol
100%
Propylene Chlorination
65%
Butadiene
24%
Adipic acid
11%
AcrylonLtrile
•
3fl%
CS2
*
42%
HC Chlorination
ft
20%
Mo thane
*
72%
Ethylene vapor phafie
15%
Ethylene liquid phase
13%
Acetylene vapor phase
ft
61%
Me thane1
*
39%
Methane
*
60%
Cumcne
40%
Tsopropanol (two cepara
•
97%
Methanol
«
3%
Methane
REACTION MODULES
pro'jesso3)
O
-------
TABLE II
(Continued)
SURVEY AND RANKING PROCESS STUDIKS
1902
% of Total
Chemical Production Process
32
Glycerol
71*
Fpi rh 1 orchyclrin
151*
Allyl alcohol
14%
Acrolein
33
Urea
100%
Nnyco
j i
34
Acetaldehyde
*
100%
Ethylene
Elhanol oxidation
J*
Toluene Diisocyanate
100*
Dinmi notoluene
16
Ethyl Chloride
, 96*
Ethy Lene
4%
Ethanol/ethane
37
Cumene
*
100*
Benzene
3fl
Chlorobenzene
*
100*
Benzene
39
Hydrogen Cyanide
50«
Andrurn'?w process
50*
Aerylonitrile by-pr<
<10
Fluorocarbons
100*
CC1./C.C1. Fluorina'
4 2 6
41
Perchloroethylene
*
66*
Ethylene dichloridc
•
34*
HC Chlorination
Acetylene
42
Butadiene
*
80*
Ethylene co-product
*
131
n-butane
*
7*
n-butenes
43
Acrolein
•
100*
Propylene
Processes assigned for study
CD
1—
I Oxidation _J
\ Chlorination |
c
o
V
•T>
c
u
o
0
Vi
V
>
X
| Pyrolvsis [
i Esterification I
I Hydration |
c
o
u
TJ
c
H
U
0
c
u
0
u
z)
>,
c
rO
C,
0
¦H
f\
C
o
H
u
fO
H
>.
2
c:
0
H
4J
H
J
6
0
0
U
o
>1
X
I Neutralization 1
A
A
C
B
C
n
A
A
A
A
A
A
A
B
A
A
A
A
B
A
REACTION MODULES
C
o
rH
4J
(TJ
u
o
>
c
Q)
~
| Dehvdroqer.ation I
1 Condensation 1
I Hydrolysis 1
c
o
H
P
a
X
o
s
1 Oxvcruor ination !
1 Hvdrochlorination 1
1 Peroxidation 1
1 Carbonolation 1
c
0
H
*J
•a
o
i*:
I Cleavino I
I Acidification 1
I Oxvacetylation 1
I Phosqenation 1
I Alcoholysis I
I Saponification 1
1 Hydrocyanation I
c
o
*->
(0
u
tJ
7.
1 Fusion 1
1 Reforming 1
c
o
*J
10
N
>4
u
4J
E
TJ
O
u
T>
>
X
u
0>
•u
in
W
c
0
iJ
H
'O
TJ
<
C
0
TJ
c
0
u
0
n
u.
c
o
o
n
c
E
o
u
£U
Hvdrodealkylation 1
c
o
4J
<0
l:
e
o
Vi
n
o
u
u
r
A
D
B
A
A
A
A
A
A
-------
TABLE II
(Continued)
SURVEY AND RANKING PROCESS STUDIES
Selection 1982
R.mking % of Total
No. Chemical Production
44
Ethanol
100%
Ethylene
•IS
Chloroforn
•
61%
Methane
•
39%
Methanol
46
Ethanolamlnes
100%
Ethylene oxide
47
2-Ethyl Hexanol
100%
0*<*•»
48
Vlnylldene Chlorldo
•
50%
l«lfl Trlchloroethane
*
50%
1,1,2 Trlchloroethane
49
Alkyl Leads
95%
Ethyl chloride
5%
Electrolysis
50
Isopropanol
100%
H^SO^ hydration of propylene
51
Phthallc Anhydride
70%
o-xylene
30%
Napthalene
52
Hethyl Isobutyl ketone
100%
Mcsityl alcohol
53
Pentaerythrltol
100%
HCHO/Acetaldehyde
54
Sec butanol
100%
Butylcncs
55
Blsphenol A
100%
Phenol acetone
56
Trlchloroethyene
•
91%
Ethylene
9%
Acetylene
57
n-butyraldchydo
100%
OXO process
58
dl/trl ethylene glycol
100%
Ethylene glycol co-products
'Processes assigned for study
REACTION MODULES
x c
il
W
I
N>
CD
ho
-------
TABLE II
(Continued)
SURVEY AND RANKING PROCESS STUDIES
Solcction
linking
No.
59
60
61
62
63
65
67
68
69
70
Epichlorohydrin
Nonyl Phenol
Ethyl aerylate
Ethylene dlbronlde
Acetylene
n-butanol
t-butyl alcohol
Isoprene
Glycol ethers
Isophthallc acid
Ethyl acotato
Methyl ethyl ketone
1982
• ot Total
Production
• 100*
100%
39*
61*
100*
62*
30*
8*
80*
20*
70*
30*
n*
67*
• 97*
3*
100*
100*
75*
25*
Process
Allyl chloride chlorohydrinatlon
Phenol alkylation
Direct esterificatlon
Acetylene
Bromination of ethylene
Natural ga6
Calcium carbide (not In soope)
Ethylene co-product
OXO process
Acetaldehydc
Propylene oxide by-product
Isobutylenes
Isoamylene extraction
Ethylene oxide
Propylene oxide
n>-xylene oxidation
Acet.lc acid
Sec butanol
Butane oxidation
'Processes assigned for study
CD
I
fsj
K)
-------
oct.
nk i
No.
71
72
73
74
75
76
77
78
79
110
01
U2
03
04
85
R6
07
08
reaction
MODULES
TABLE II
(Continued)
SURVEY AND RANKING PROCESS STUDIES
Chemical
1902
% of Total
Production
Process
Benzoic acid
Adipic acid
Benzene
Ethylene diamine
Methyl amines
Isobutyl alcohol
Phosgene
Diisodecyl phthalate
Isobutyraldehyde
Methylene diphenyl
Benzyl Chloride
Diethyl ether
Linear alKyl benzene
Ethyl amine®
Chloroacetic acid
Linear alkyl sulfonates
Formic acid
Methyl bromide
100% Toluene oxidation A
100% Cyclohexane p*
26% Hyrirodealkylation of toluene
72% Not in project scope
100% EDC ammonolysis
100% Methanol anvnonolysis
100% OXO process
100% Carbon monoxide chlorinatlon
100% Phthalic anhydride, lsodecanol
100% 0X0 process
100% Diphenyl methane diamine/phosgene
100% Toluene chlorination
100% Ethanol based
100% Benzene
100% Ethanol ammonolysis
100% Acetic acid chlorinatlon A
100% LAB sulfonation A
98.5% Butane oxidation
1.5% Others
100% Hydrobromlnation of methanol
I
\
t-
\
CD
-c-
-------
^ *
TABLE II
(Continued)
nrACTion modulp.s
r
o
r)
r:
C)
c
c:
c
c>
c
0
r
n
<:
c.
0
n
0
0
o
-~
«->
c
c
r.
C
c
C
c
0
u
O
Ll
4'
L
r>
u
o
V)
c
¦'
M
c
*0
0
o
rj
-
0
0
in
»'
-
trt
t
r
r:
0
U
C
r)
C
1l
•ft
I/)
o
¦ 4
C
0
c.
u
0
•n
T)
o
CI
u
0
H
a
01
0
o
ti
't,
Vt
kJ
n
H
U
o
0
r.
u
n
X,
n
o
c
o
c
c
n
u
u
4J
<¦;
C
V)
0
c
r.
0
o
c
o
E
r
r,
•j
r.
o
u
O
o
rj
n
Rank
•ti
U
0
0
t<
u
0
la
v<
QJ
U
n
u
0
(1
>-
t;
r.
0
i;
0
>
0
I,
u
It
o
o
r
0
jr.
i)
c:
o
u
u
0
i:
11
0
u
p
X
o
Vj
0
u
u
u
o
TJ
a
u
<0
o
v.
0
c:
O
u
c.
0
o
TJ
rj
u
c
c
c
b
u
•n
».
c
L
O
c
u
o
L
O
No.
Chemical
Process
O
u
A.
lil
X
Q
i!
0
t
r
Q
o
X.
'J
X
a.
U
CL
O
<
.1.
<
X
*•
U-
r
t.
o
-
i.
89
Propylene glycols
Propylene oxide hydration
A
90
Caprolactam
Cyclohexanone
A
91
Dinitrotoluene
Toluene dinitration
2
A
92
Fumaric acid
Malelc acid isomerization
A
93
Diisoctyl phthalate
Phthalic anhydride
A
94
Propionic acid
Oxo process
A
LPG oxidation
A
95
Acetone cyanohydrin
Acetone/HCN
A
96
Acrylamide
Acrylonitrile
A
97
Methyl styrene
Cumene byproduct
A
Others
98
Chloronitrobenzenes
Chlorobenzene
A
99
Carbon disulfide
Thacker procoss
100
Diphenyl
Toluene/Benzene
A
101
n-butyl acetate
Butanol/acetic acid
A
102
Benzophenone
Benzone/carbon tetrachloride
B
103
Benzyl benzoate
Benzaldehyde
Pl
3
A
Benzyl alcohol
A
.
-------
TABLE II
(Continued)
REACTION MODULI S
Rank
No. Chemical Process
f
O
"j
o
t:
0
u
o
i:
u
c:
•)
c:
0
<*i
c;
c
o
10
o
(X.
r.
D
i j
u
tj
(>i
c:
0
l«
0
o
(1
l/>
0
0
1.
• 1
()
¦n
i:
O
j
n
r.
o
u
t;
r
C)
•T3
L
O
0
<)
6
i)
n
fj
r)
U
"J
r;
O
t:
0
a
r
"j
c
o
•t)
6
o
r:
o
«n
o
CO
l/>
O
'V,
c
o
0
r;
r,
t:
0
c!
o
y.
J
c
(,
<1
0
c:
u
(>
r
0
1 J
C
X
0
01
a.
c
0
o
c:
0
.n
u
c
(J
u
a
u
ri;
c
t:
c,
U
c
c
*J
u
•:1
O
•t
r
%
j.j
o
c
X
O
(.
L
U
r;
y
"'j
o
r
'j
c
0
-•
n
r:
O
;;
c
n
c.
r
D
_f-.
t:
o
¦n
c.
r.
m
L.
•J
.i:
c:
tj
t_
0 .
I.
0 '
.
"I
|
c
M
»:
0
104 Aminoethylethanolamine Ethylene oxide
-
105 Chlorosulfuric acid (Chlorobenz.ene)
A
-
A
1.06 Dimethylhydrazine Dimethy l amine
107 n-dimethyl aniline Aniline/methanol
A
108 Hexachlorobenzenc Hexach.lorocyclohexane
A
109 Methyl acetate Acet.ic acid
A
110 n-propyl alcohol Propion aldehyde
-
A
B
111 Salicylic acid Sodium phenate
A
A
-
A
F
112 Diphenylamine Aniline
A,
113 Acetophenone Cumene
n
Ethylbenzene
B
114 Acetyl chloride Sodium acetate
A
-
115 Propylene Naptha/qas oil
J\
-
-
Natural gas/liquids
A
Refinery byproduct
A
116 Aniline Nitrobenzene hydrogenation
117 Furfural Polysaccharides hydrolysis
A
118 Butyl amines Butyraldehyde hydrogenation
ft
h
-
A
\
(S"
-------
TABLE II
(Continued)
nnACTJOti nonut.K.r.
Rank
No. Chemical Process
c:
0
•u
it
0
i>
"J
0
i:
t j
r.
0
r\
0
0
1
•ft
I'l
0
ru
r.
u
u
r.
o
u
c
o
0
I)
0
p
1?
•fl
1ft
0
t:
0
:)
• P.
O
u
t;
c
0
O
<;
O
i<
•tJ
it
n
rt
0
»;
0
1 J
<:
0
0
r;
f,
o
'J
t)
X
c
o
s
c
0
r.
u
0
r.
0
n
G
>:
o
1>
a.
c
f)
G
c
0
n
w.
n
c:
o
i'
u
V.
fj
¦f.
r
c.
a
c:
c
-)
r
r
o
>
1
f.
U".
'J
o
•J
c
L.
0
0
;;
f.
')
I
ii
L>
n
L
V.
'J
c:
»;
"J
It
c
o
r.
c
G
o
-1
n
¦j
c
i.
0
SI
::i
C'
i.
o
vi
119 Allyl alcohol Allyl chloride hydrolysis
A
Propylene glycol dehydration
A
PronvJene oxide isomerization
A
120 Pyridine/pico]ine Formal de'nyde/acetaldehyde
A
121 Cyclohexyl amine Aniline
A
Cyclohexanone
A
122 Cresylic acids Phenol methanol
A
Toluene sulfonation
A
p
Cymene oxidation
--
Natural coal tar
12 3 Crotonaldehyde Aldo process
f
A
124 Hydroquinone Acetone coproduct
Pi
r*
-
125 Isodecanol Oxo process
p
n-paraffin oxidation
A
-
126 Isooctyl alcohol Oxo process
B
f
127 Cellulose acetate Cellulose esterificat.ion
A
P
128 Isopropyl acetate Isopropanol
0|
129 Cyclooctadiene Butadiene
A
-------
TABLE II
(Continued)
REACTION MOnUl.KS
Rank
No. Chemical Process
C .
I*
O
"J
v<
0
.i:
c:
0
o
o
o
CI
()
"1
(.}
0
n
A
¦n
0
'6
j;
r:
0
o
r.
0
i>
1
u*
0
¦j
i>
c.
a
4J
n
i
L
0
¦V
r'j
0
(;
O
(. ¦
i/l
o
o
0
1 ,
i:
O
d
'/
"j
c
0
<-5
r
¦)
i¦
u
o
c:
o
o
n.
c
c
c:
c
n
u
L"
o
u
a:
c.
r.
a.
(.'
0
n
o
r.
L
.j
i:
C
C.
1
•j
t;
h
-
r>
<:
o
c:
c.
;1
r
i:
§
r|
c|
V
c;
t:
o
i;
r,
o
c
0
»J
('
o
130 Dinitrophenol DNC benzene
A
131 Dichlorophenol Phenol chlorinntion
A
132 Butyl acrylate Acrylic acid
A
133 Propyl amines n-propanol
A
A
n-propyl chloride
ft
134 Dodecene Nonenc coproduct
7\
135 Nitro aniline Nitrochlorobenzene
136 Nitrophenol Phenol nitration
B
137 Ethylene glycol MEE Acetate Ethoxy ethanol
-
138 Butyric acid Butyraldehyde
\
Butane oxidation
139 Toluene sulfonic acid Toluene
A
140 Benzoyl chloride Benzoic acid
-------
o
0
a
H
2
>
r.
>
h-«
•*3
2
<
-a
2
c/>
n
F5
<
0
O
<
O
r»
Q
O
rr
r-
rr
0
3
n
rr
0
•<
3"
3
O
„
3*
rr
•<
3
3"
<
3
-<
•<
•<
3*
O
0
g"
fr
•<
K-
C
h*
3
r
3"
O
*—
n
3
O
O
rr
O
O
O
rr
~
a.
&
0
c
3
O
rt
i-l
X
a»
0
3
O
3
c.
0)
Q
3*
0
C:
O
Q>
3"
O
0
ft
3
3
O
O
3
O
rr
rr
N
O
0
r»
3"
a
Q
0
U
y
&
0
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X
l-<
3"
3
O
Qi
rr
X
c.
3
<
\
ft
0
ft •
n
O
Ci«
CL
H
0
O
(A
0
a
0
O
3
O
rr
3*
a>
3
0
a>
i/i
&
r-
3
rr
3"
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O
*
rr 25
3* C
0 I-
>0 0)
h n
o
O H-
(D 3
u a
05 H-
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OJ
ft
(D
W
ft
3*
(D
a>
o
i-h
C
3
H-
ft
W
Di
W
w
o
o
H-
o
ft
o
a
ft
3*
2
CT
<
•35
T
T5
~
0"
>
71
T3
n
T3
n
re
*3
X
O
c
n
¦<
0
n-
rt
O
rr
£j
rr
~
~~
.
r-
10
ir
3
3*
3*
X
T
y
3*
<
3"
rs
n
P!
<
-r
•<
N
¦<
N
-<
*<
•-<
•<
&
><
a
(
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O
0
0
—
O
r—•
O
3
0
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O
3
n
r
3
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0
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T)
c
3-
a
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0
2j
1.
O
3
5
3
z
2
3
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C
3
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0
0
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0
3*
ji
X
3"
0
s
5
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3*
ro
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n
0
X.
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rr
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N
1
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a
0
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0
a
0
3
&
p.
X
c
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X
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0
0
-1
0
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X
h-'
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a
3
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w-
n
— •
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H
1
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3"
O
r»
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c •
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a
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&
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0
0
0
0
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fT
<
C.
rr
c
0
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T
rT
0
c
• j
K
l-v
rr
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3
3"
3
0
P--
J
3
'0
3
a
3*
rr
0
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ii
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3
J
D
i,
3
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c:
O
rr
Cl.
0
3
O
3
c
i-»
0
M-
3"
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ri
j
O
t—.
O
5
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0
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c
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T
O
q
3
3
3
0
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cn
i_-
j:
3
3"
0
w
-<
rr
2
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3
-s
3
3*
o>
a
rt
r%
3
3
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3
3
in
0
0
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G
.1
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03
r
w
i 1
- -r
r —
i j l
: J
-
r-
-
X
U,
-
O
0
-
-
0
Dis ci 112ti 0:1
!
U
~
"
H
1
NJ
-
_
-
.^iscrrnon
-
1
i ! ¦ ^
» 1 ;
1 i 1-
1 1
Ni
-
1 i
NJ
Scrubbina/Vfashing
! ;
-
NJ
Extraction
, 1
i
-
SJ
Evaporation
i
i 1
1 i
t—
Crystallization
-
H-
-
NJ
Drying
1
!
1
1
1
Screening/Settling
Mi xir.c/B lending
w
I—
Separating
I
1
I
Filtration
NJ
1
1
1
I
h-
Quenching
NJ
I
1
1
Ion Exchange
f
1
|
-
1
! 1
1 !
j
Dilution
o ;j
93-9
-------
TABLE III
(Continued)
No. Product
25. Chloroform
2ft. Methyl chloride
27. Nitrobenzene/aniline
28. Ethylene glycol
. Glycerol
10. Adiponitrile/HMDA
1). chloroprene
32. Cyclohexanol/cyclohexanone
33. Acetaldehyde
34. 2 ethyl 1 hexanol
35. Toluene diisocyanate
36. Chlorobenzene
37. Ethyl acrylate
Linear alkyl benzenes/sulfonates
39. Acrolein
40. Ethyl chloride
41. Mol.hyl i^obutyl Ketone
4?.. Acetylene
43. Lead alkyls
P rocess
Methane chlorination
Methanol rhlorination
Benzene nitration
Ethylene oxide hydration
AlLyl chloride - edichlotohydrin
fin t. ad i one chlor ination
fiutadene chlorination
Cyclohexane ox idation
Ethylene oxidation
•\-bntryaldohyde a Idol condensation
Amine phonqenation
Benzene chlorination
Acrylic acid es r.er if icat ion
Alkyl benzene s»ilfonation
Propylene oxidation
Ethylcne/HCl
Acetor.e dehydt anion
Methane paitial oxidation
Sodium/lead alloyinq with ethyl chlor'
Process Modules
IZ
H. c
2
1
1
2
2
3
1
1
2
3
3
1
7
2
1
1
3
I
3
5
2
2
1
1
1
2
1
4
4
I
1
4
i
1
2
1
1
1
2
1
3
|
3
i
I
i.
3
B
4
3
2
&
c
•H
f—4
0^
*J
r.
4J
-H
0)
•o
o
l/l
r
a-
\
oj
CT>
c
c
c
0
rr>
d
c
cn
-H
c
c.
r.
•r(
\
u
4->
o
o
c
tr
rtj
m
JZ
X
•-*
a>
r.
i-i
u
u
iJ
-------
\
-J
TABLE III
Proces
Modules
Rank
No.
Chemical
Process
| Distillation
Absorption
Scrubbing/Washing
Extraction
Evaporation
Crystallization
Drying
Screening/Settling
Mixing/Blending
Separating
Filtration
Quenching
Ion Exchange
Dilution
44
Terephthalic acid
Eastman
2
1
2
2
3
1
Mobil
Amoco
1
1
4
3
4 5
Acetic anhydride
Acetic acid
4
1
46
Allyl chloride
Propylene;
3
2
1
1
47
Vinyl acetate
Ethylene vapor
8
2
3
1
Ethylene liquid
Acetylene
3
48
UREA
Ammonia/carbondioxide
2
1
1
1
49
Cumenc
Benzene; alkylation
2
50
Caprolactam
Cyclohexanone
2
1
1
51
Hydrogen cyanide
Andrussow process
2
3
Acrylonitrile byproduct
52
Fluorocarbons
CCL4/CH3CL3 Fluor i nation
3
1
1
3
1
53
Ethano1
Ethylene
4
1
3
2
54
Ethanolamines
Ethylene oxide
4
1
55
Vinylidene chloride
1,1,1 Trichloroethane
1,1,2 Trichloroethane
56
Isopropanol
Propylene/H?SC>4
2
1
1
1
57
Perchloroethylene
Ethylene dichloride
4
1
2
3
Me tha.no. chlorination
3
-------
Rank
No.
58
Chemical
Sec-butanol
TABLE III
(Continued)
Process Modules
Process
Butylenes
c
o
-H
-P
(d
u
o
aj
nT
>
w
C
TJ
c:
0)
rH
CQ
\
c
c
o
•H
•p
4J
cn
c
•H
.C
o
c
-------
oo
TABLE III Process Modules
iLonunuea)
Rank
No. Chemical Process
Distillation
Absorption
1
Scrubbing/Washing
Extraction
Evaporation
Crystallization
Drying
Screening/Settling
Mixing/Blending
Separating
Filtration
Quenching
Ion Exchange
Dilution
75 Isophthalic acid m-xyleno oxidation
1
1
1
1
76 Ethyl acetate Acetic acid
3
2
1
77 Propionic acid Oxo process
LPG oxidation
78 Acetone cyanohydrin Acetone/HCN
2
2
1
79 Benzoic acid Toluene oxidation
5
1
3
1
1
1
80 Methyl ethyl ketone Sec-butanol
2
1
2
But.inol oxidation
3
2
81 Adipic acid CycLohexane
]
1
1
1
1
Phenol
1
1
1
1
1
82 Benzene Toluene hydrodealkylation
3
1
1
Not in Scope
83 Acrylamide Acrylonitrile
1
1
1
—
84 Methyl styrene Cum?ne byproduct
2
Others
85 Ethylene diamine EDC ammonolysis
3
86 Diphenyl methane diisocyanate Diamide/phosgene
2
1
87 Phosgene C0/C19
2
88 Methylamines Methanol ammonolysis
6
1
1
89 Isobutanol Oxo process
6
1
-------
TABLE III
(Continued)
Process Modules
Rank
No.
Chemical
Process
Distillation j
Absorption
Scrubbing/Washing
Extraction
Evaporation
Crystallization
Drying
Screening/Settling
Mixing/Blending
Separating
Filtration
Quenching
Ion Exchange
Dilution
90
Diisodecyl phthalate
Toluene
2
1
1
91
Isobutyraldehyde
Oxo process
6
1
92
Benzyl chloride
ToLuene chJ.orination
2
1
9:5
Chloron i. trobenzenes
Chlorobenzene
1
2
94
Diethyl ether
Ethanol
2
1
Qi
Ethylamines
F.thanolamnopo lysis
4
9b
Carbon disulfide
Methane/sulCur
3
2
97
Ch.loroacotic acid
Acetic acid
1
1
1
98
Formic acid
Butane oxidation
2
1
Others
2
1
99
Biphenyl
Toluene/benzene
3
1
1
LOO
n-butyl acetate
Butanol/acetic acid
2
1
1
101
Methyl bromide
Methanol hydrobromination
1
1
1
102
Benzo phenone
Benzene/CCl4
2
1
1
1
10 3
Beyzyl benzoate
Benzaldehyde
Benzyl alcohoL
104
Amino ethyl ethanolamine
Ethylene oxide
5
1
1
105
Chloronulfonic acid
Chlorobenzene
106
Dimethyl hydrazine
Dimethyl amine
107
n-n dimethyl aniline
Aniline/methanol
03
I
u>
OJ
—4
-------
TABLE III
(Continued)
Process Modules
Rank
No. Chemical Process
1
Distillation |
Absorption
Scrubbing/Washing
Extraction
Evaporation
| Crystallization
Drying
Screening/Settling
Mixing/Blending
Separating
Filtration
Quenching
Ion Exchance
Dilution
108 Hexachlorobenzene Hexachlorocyclohexane
109 Methyl acetate Acetic acid/methanol
2
1
1
110 n-propyl alcohol Propionaldehyde
4
3
1LI Salicylic acid Sodium phenate
2
1
1
1
1
112 Diphenylamine Aniline
1
1
113 Acetophenone Cumeme
4
1
1
Ethyl benzene
2
1
114 Acetyl chloride Sodium acetate
115 Propylene Naptha/gas oil
8
1
1
1
Natural gas/liquids
8
1
1
1
Refinery byproduct
116 Aniline Nitrobenzene hydrogenation
2
1
1
117 Furfural Polysacchrides hydrolysis
3
1
1
1
118 Butylamines Butyraldehyde
4
119 Allyl alcohol Allyl chloride hydrolysis
Propylene glycol dehydration
Propylene oxide
120 Pyridine/picoline HCHO/Acetaldehyde
121 Cyclohexylamine Aniline
Cyclohexanone
-------
u>
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ft
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c
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n
a
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3
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M
c
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C
13
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(D
3
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3
o
rr
3"
6)
3
0
/O
Z CD
0 3
• X
O i-3
§ s
rr p
H- S
3
C M
O H
CL H
Distillation
AbsorDtion
Scrubbing/Mashing
Extraction
Evaporation
13
o
0
-------
U)
O
O
o
o
o
sr
O
o
X
o
o
o
o
in
cn
u> OJ
o x
CO
ro
3
N
O
a
3
rt
0)
l—•
a
a>
a
ro
z ju
C 3
• **
o
o
D
rt
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3
C
(D
CL
Distillation
Absorotion
Scrubbing/Washing
Extraction
Evaporation
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o
o
ct>
w
cn
3
0
a
c
h-1
01
u
Drying
Screening/Settling
Mixing/Blending
Separating
Filtration
Quenching
Ion Exchange
11
Dilution
a
-------
1 Vent Restriction
X
X
X
X
i Drcclet Separation
X
X
X
X
X
X
X
X
X
X
X
| Surface Condensation
X
X
X
X
Contact Condensation
Cor.oression Condensation
r
j
X
X
X
X
X
Solvent Absorption
Solvent Absorption/Stripping
X
Cherr.ical Absorption
X
X
X
X
Carbon Adsorption
x x i Molecular Sieve
X X
X
X
X
X X
X
X
X
X
X x
Combustion
X X
X
X
X
X X
X
X
X
X
X X
Vaoor Thermal Oxidizer
Liquid Thermal Oxidizer
X
X
X
X
X
Particulate Removal
91
lz- a
-------
TABLE IV
(continued)
FMISSIOM CONTROL MODUI.KS
Selection
Ranking
No.
10.
11.
12.
13.
14.
15.
16.
Chemical
Propylene Oxide
Methyl Methacrylate
Formaldohyde
Nitrobenzene/Ani1ine
Acrylic Acid
Phenol
Cyclohexanol/Cyclohexanone
Methyl Alcohol (Methanol)
Process
Chlorohydrin
Peroxidation
Acetone Cyanohydri n
Silver Catalyst
Metal Oxide
Hcnzeno
Propy 1ene OxidaL ion
Acetyl one (Foppo)
Cumene
Hen2ene Ch1orination
Ti-* lucne Oxi dat i on
Henzone Su 1 fonation
Cyclohcx.mone
Phenol
Methane
—4
C.jj
c
o
c
a
o
u
u
at
4J
at
N
c
c
<0
in
N
H
0
c
0
w
\
c
H
*0
1-^
c
0
C
C
c
0
T1
TJ
o
4-J
4J
QJ
0
o
¦'<
c
X
>
c
fi
•U
o
X
o
o
o
1/1
rfl
V)
C
a
H
a>
O
E
•rl
<0
c
w
c.
o
0,
a
«J
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u
<
jr
(->
o
f
in
4J
m
4J
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n
Cf,
o
u
3
Vl
a
c:
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0,
>
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f=
13
at
.Q
0
o
u
c
0
V-
a)
c
G
>—i
rH
at
U
d
o,
cr
u
n
J
ft.
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
>
X
X
X
X
X
X
X
X
-------
TABLE IV
(Continued)
EMISSION CONTROL MODULES
Selection
Ranking
No.
17.
19.
Chemical
Proc(»sr»
20.
21.
22.
23.
24.
25.
26.
1,1,1 Trichloroethan
-1
C
d
u
v<
u
0
a
0)
.—i
«TJ
tr.
L)
0)
tj
o
o
v)
u
•TJ
f;
o
c
TJ
c
r.
(/I
in
jq
o
i/»
fl
U
0)
U
(1)
o
C
0
0
XI
n
<
(/I
c
0)
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tn
u
o
u
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<
2
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V-t
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TJ
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TJ
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01
o
P
4 i
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c
1":
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o>
u
u
co
u
a
X
o
>
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a.
X
X
X
X
X
X
>
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
CD
o
-------
Vent Restriction
X
Droolet Separation
X
X
X
X
X
X
X
X
Surface Condensation
Quench Ccr.densation
X
X
X
X
Contact Condensation
Compression Condensation
Solvent Absorption
Solvent Absorption/Stripping
X
X
X
X
X
X
X
Chenical Absorption
Carbon Adsorption
I Molecular Sieve
X
X
X
X
X
Corbustion
X
X
X
X
Vapor Thermal Oxidizer
X
X
X
X
X
Liquid Thermal Oxidizer
*
X
Particulate Removal
TO
ofr-a
-------
W
W
j Vent Restriction
X
i Droolet Separation
X
X
X
X
X
w
I Surface Condensation
Cuer.ch Ccncer.sat ion
X
*
*
w
Cent a ct Condensation
Comoression Condensation
i Solvent Absorption
' Solvent Absorption/Stripomq
X
X
Cher.ical Absorption
Carbon Adsorption
Molecular Sieve
X
X
X
X X
XXX
X
Combustion
* *
Vapor Thermal Cxidizer
X
X
Liquid T'nerr-.al Oxidizer
X
X
Particulate Removal
Z9
Tf-a
-------
X
X
X
Vent Restriction
Droplet Separation
X
X
X X
X
!<
Surface Condensation
Quench Condensation
l Contact Condensation
i Corr.oression Condensation
X X
Solvent Absorption
Solvent Absorption/Stripping
X
X
X
X
X
X
X
X
X
Chemical Absorption
Carbon Adsorption
Molecular Sieve
X X
X
X
Combustion
X
X
X
Vacor Themal Oxidizer
X
X
Liauid Themal Oxidizer
X
w w
Particulate Removal
£3
Zt-B
-------
TABLE IV
(Continued)
EMISSION CONTROL MODI 11 £5
Selection
Ranking
No.
66.
67.
08.
69.
70.
71.
72.
73.
74.
75.
76.
77.
Chemical
Process
Diisooctyl Phthalate
Ethylene Dibromide
Acetylene
ri -Butanol
t-ButanoJ
Glycol Ethers
Isoprene
Isopthalic Acid
Ethyl Acetate
Propionic Acid
Acetone Cyanohydrin
Benzoic Acid
1'hthalu; Anhydride
Ethylene Hrominat i on
H.C. Oxidation
Calcium Carbide
Ethylene
Oxo Process
Acetaldehyde
Propylene Oxide
Isobut.y lencs
Ethylene Oxide
Propylene Oxide
I.soamy lene Extraction
C^ Hydrocarbons
m-Xy 1 one Ox i da t. ion
Acetic Acid
Oxo Process
LPG Oxidation
Acetone/MCN
Toluene Oxidation
o
c
0
c
a,
0
Vi
Vi
a>
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c
m
u
<0
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4J
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o
o
O
in
T)
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c
i)
a
0)
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t":
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c
to
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a
a
u
+J
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a>
r.
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n.
w
x>
o
to
f:
L
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0)
0
c
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0
n
h
<
in
c
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jJ
to
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rj
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3
a:
u
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C
tj
r.
o
tfi
'd
U
u
u
(1)
0)
o
u
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u*
c
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0
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f=
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a
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0
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C.
n
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01
u
V.
a.
CT
u,
o
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3
0
0
o
0
JZ
0
0
ifl
•'
Q
(O
o
f.J
u
cn
I/)
u
u
s
u
>
J
o.
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
-------
TABLE IV
(Continued)
EMISSION CONTROL MODULES
Selection
Ranking
No. Chemical ¦ rroccss
79. Methyl Ethyl Ketone Sec-butanol
Butane Oxidation
79 Adipic Acid Cyclohnxane
Phenol
00. Benzene Toluene Hydrodo Alkylation
Not in Project Scope
91. Acrylamide Acrylonitrilo
92. a-Methyl Styrene Cumens Product
Others
93. Ethylene Diamine EDC Ammonolysis
94. Methylene Diisocyanate Diamido/Phosgcm?
85. Phosgene CO/Cl^
05. Methyl Amines Methanol Anunonolyn is
97. Isobutanol Oxo Process
99. Diisodecyl Phthalate P.A./]sodccanol
g9. Isobutyraldehyde Oxo Process
90. Benzyl Chloride Toluene Chlorination
91. Chloronitro Benzenes Chlorobcnzciu;
92. Diethyl (Ethyl) Ether Kthanol
u
J
c:
0
(I.
0
u
•H
u
u
0)
U
IJ
QJ
N
c
c.
o
1/5
N
0
r:
o
in
\
c
rH
1)
cH
c
o
c
c
c:
o
Tj
H
0
o
4-»
r~*
p
q;
o
O
H
c
• \
X
>
c
u
7)
r-i
..-i
CJ
X
0
0
0
1'
o't
TJ
in
C
4->
Q.
a>
O
e
C
W
c
0
n.
u
4->
4)
v.
U
C
QJ
(J
Vt
O
ai
o
«-H
«
u
TJ
T1
o
i:
0
0
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w
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4J
en
u
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u
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r.
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a;
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a
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0
a
r.
n1
a>
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1!
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cr
u
V
V(
n
D
o
o
0
0
r.
TJ
o
0
O
>
n
in
O
u
u
CO
co
cj
u
X
U
>
J J
a
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
-------
TABLE IV
(Continued)
EMISSION CONTROI. MODULES
Sc1ecrion
Rank i ng
No. Chemical Process
93. Linear Alkyl Honr.cno Benzene Alkylation
94. Ethyl Amines Kth.inol Ammonolyui
95. Carbon Disulfide Motliane/r>ul f ur
9f>. Chloro Acetic Acid Acetic Acid
97. Linear Alkyl Sulfonates I>AB Su\Conation
9B. Formic Acid Butane Oxidation
Othern
99. Methyl Bromide Mot.hauoi/HBr
100. Biphenyl Toluene/Benzene
101. n-Uutyl Acetate Butanol/HOAC
o
c.
i)
r'j
. i
v
t>
J
-i
r;
c
n
o
c
o
u>
\
c
. <
a
t:
r
c
o
7;
u
r-t
i>
CJ
o
0
H
c
1
•<
rt)
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T5
o
l>
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x
0
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t/>
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a
u
c
L
C.
t/)
n
o
0.
n.
O
0)
c
(U
u
V.
o
a
a:
T)
o
T)
0
0
w
r.
r.
•t)
C
>
C:
Si
,-l
.0
c
t-J
Va
10
U
u
•-
~ 3
it
—
X
X
X
X
X
X
X
X
X
X
X
DO
I
Ul
Rev i sod:
l?/0/7-
DGU
m
-------
Control Modules
TABLE IV
(Continued)
Rank
No. Chemical Process
Vent Restriction |
Droplet Separation |
Surface Condensation
Quench Condensation |
Contact Condensation I
Ccmcression Condensation |
Solvent Absorption
Solvent Absorption/Stripping 1
C'nerr.ical Absorption |
r—
t:
0
¦-«
4 J
0,
U
o
ir»
<
c
0
V.
Vi
n
u
Molecular Sieve I
c
0
JJ
I/)
J
•o
0
o
v,
c>
N
XJ
r-i
6
*-<
l:
^1
o
sz
H
u
0
t:.
0
s
c
j
¦ H
T3
H
y
6
*
r4,
V.
Vi
C
s:
*¦-1
c:'
- H
~ ]
r-1
>
0
(':
0
Cf.
i)
--4
U
u
Vi
rl
a,
102 Benzo phenone Benzene/carbon tetrachloride
—
103 Benzyl benzoate Benznldehydc
Benzyl alcohol
104 Aminoethylethanolamine Ethylene oxide
X
X
105 Chlorosulfuric acid (Chlorobenzene)
—
106 Dimethyl hydrazine
—
107 n-dimethyl aniline Ani1ine/methanol
—
108 Hexachlorobenzene Hexachloro cyclohexane
X
X
109 Methyl acetate Acetic acid
110 n-propyl alcohol Propionaldehyde
X
111 Salicylic acid Sodium phenatc
X
112 Dinhenylamine Aniline
113 Acetophenone Cumene
X
X
Ethylbenzene
114 Acetychloride Sodium acetate
115 Propylene Naptha/gas oil
X
X
X
X
X
Natural gas/liquid
X
X
X
X
X
Refinery byproduct
-------
Cont.rol. Modules
TAB1.E IV
(Continued)
Rank
No. Chemical Process
Vent Restriction j
Droolet Separation
Surface Condensation ]
Quench Condensation 1
Contact Condensation j
r
0
1 J
rrJ
tn
c:
V
•o
c
0
u
c
0
¦
in
01
GJ
a,
C:
0
U
a
0
i)
ih
0
U)
3
4J
c
CD
>
0
0'
c:
—<
>-{
\>
4J
U)
\
c:
o
•r \
u
r* (
U
O
n
2
c
9
r—4
0
CO
Chemical Absorption
C
0
1 j
v/
0
0".
<
a
c
si
Vv
r}
U
| Molecular Sieve ]
c
o
- »H
U
V)
ZJ
•n
o
u
u
*1
fi
• *
-J
-i
o
n
r;
Vi
o
r.
6-
v.
0
i:.
n
¦'J
i
n
y.
O
•—i
c
1;
0
s:
E-
'C
•h
¦j
~'
r-4
-J
n
>
0
l:
O
o:
o
'¦}
;)
O
H
|J
Vl
Tj
fU
116 Aniline Nitrobenzene hydrogonation
X
11^ Furfural Polysaccalirides hydrolysis
118 Butylamines Butvraldehyde
X
X
X
X
X
119 Allyl alcohol Allyl chloride hydrolysis
X
X
X
Propylene glycol
Propylene oxide
X
120 Pyridine/pi coline HCHO/acet,"aldehyde
X
—
X
121 Cyclohexylamine Aniline
X
X
Cyclohexanone
X
X
—
—
122 Cresylic acids Phenol/methanol
--
X
X
—
Toluene sulfonation
X
X
Cuinene oxidation
Natural coal t.ar
—
X
12 3 Crotonaldehyde Aldo process
—
124 Hydroquinone Acetone coproduct
X
X
125 Isodecanol Oxo process
X
n-paraffin oxidation
X
126 Isooctyl alcohol Oxo process
X
-------
Control Modules
TABLE IV
(Continued)
r
V
c
c,
0.
1
Rank
No.
Chemical
Process
Vent Restriction
Droolet Secaration
Surface Condensation
c
0
D
n
in
i:
C.)
'0
c
0
u
J-
u
c
0)
;)
O'
Contact Condensation
Compression Cor.densatio;
c
0
•H
A J
0.
Vi
O
(0
3
u
c
0)
>
r—1
0
V)
Solvent Absorotion/Stri
c
0
•
4J
o.
v.
0
§
»—1
r}
(J
•
G
O
sz
o
c
0
1 >
V4
o
(.0
'0
<
0
.n
U
O
b
-1—4
in
u
rj
:i
u
o
.-I
0
c:
0
H
JJ
10
ZJ
t:
0
(J
Vapor Therr.ai Oxidizer
Vi
o
n
"4
y.
o
a
.c
H
T)
H
p
0'
k-J
Particulate Removal
127
Cellulose acetate
Cellulose es tor i f icat.ion
X
128
Isopropyl acetate
Lsopropnnol
129
Cyclooctadiene
Butadiene
130
Dinitrophenol
Oini trochlorobenzeno
131
Dichlorophenol
Phenol chlorination
X
132
Butyl acrylate
Acrylic acid
133
Propylamines
n-propanol
X
X
X
X
n-propylchlorido
X
X
X
X
134
Dodecene
Nonene coproduct
X
135
Nitroaniline
Nitrochlorobenzene
136
Nitrophenol
Phenol nitration
137
Ethylene glycol MF.E acetate
F.thoxy ethanol
138
Butyric acid
Dutyraldehyde
Butane oxidation
139
Toluene sulfonic acid
Toluene
X
X
140
Benzoyl chloride
Benzoid acid
-------
APPENDIX C
ESTIMATES OF TOTAL SOCMI VOC EMISSIONS FOR 1982
-------
ESTIMATES OF TOTAL SOCNI VOC EMISSIONS FOR 1982
31
A. INITIAL EMISSIONS ESTIMATE
Basis: Survey and Ranking Studies
SOCHI production = 200,000 MM lb (1976)
6% growth = 283,700 MM lb (1982)
140 products address 205,438 MM lb of production (1982) 72.6%
1,584 MM lb of emissions (1982)
283,700—205,438 = 78,262 MM lb of production not covered by survey and
ranking studies.
An estimated emission factor for the unranked chemicals was obtained by using
the weighted average for the last 25 chemicals ranked on Fig. II-l (0.0025 lb
of VOC emissions/lb of production):
78,262 X 0.0025 = 195 MM lb of VOC emissions from unranked chemicals
1,584 + 195 = 1779 MM lb of VOC emissions for SOCMI in 1982,
based on the initial survey and ranking studies.
B. REVISED EMISSIONS ESTIMATE
From Table II-l the estimated emissions for the products studied are reduced
from 1374 MM lb to 733 MM lb, a reduction of 47%. From all indications it ap-
pears to be a logical assumption that process emissions would be reduced by a
similar amount for the remainder of the industry. However, as discussed in the
Fugitive Emissions report of Volume III, fugitive emissions are more a function
of equipment count than of production volume. This indicates that the initial
VOC emission estimate shown above underestimated fugitive emissions for the
large number of plants not studied.
By analysis of Tables II-l and C-l it can be seen that the first four products
account for more than half of the VOC production addressed by all full-report
studies. They are considered to be atypical of the great majority of produc-
tion sites and were not used to determine emission factors for the remainder of
the industry. The VOC emission-to-production-volume ratios for all the remain-
ing full-study reports were used as the basis for projecting the VOC emission
-------
Table C-l. VOC Emission Estimates by Point Source for 1982
VOC Emissions (MM lb)
Product
Process
Fugitive
Storage and
Handling
Secondary
Total
Acrylonitrile
130.9
1.5
1.5
11.6
145.50
DMT/TPA
93.3
4.0
2.0
Neg
99.38
Ethylene dichloride
87.7 '•
0.5
0.9
1.8
90. 92
Ethylene
32.3
33.0
7.3
0.7
73. 31
Formaldehyde
19.7
6.9
0.8
Neg
27.42
Cyclohexanol/cyclohexonone
24.7
1.3
0.3
0.3
26.52
Acrylic acid
4. 6
7.3
2.5
8.1
22.48
Ethylene oxide
19.9
1.3
0.2
Neg
21.39
Maleic anhydride
9.1
4.4
2.6
0.3
16.46
Ethylbenzene/styrene
7.6
0.9
6.5
0.8
15.75
Ethylene glycol
14.0
0.8
0.1
0.6
15.59
Phenol/acetone
3.1
5.1
1.4
0.1
9.68
Methanol
0.6
3.2
4.4 ,
0.1
8.31
Cyclohexane
Neg
0.9
3.4
0.1
4.40
Chloromethane-methanol
0.8
1.0
2.3
0.1
4.17
Alkylbenzene
1.3
0.6
1.0
0.3
3.17
Chlorobenzene
1.6
0.8
0.2
0.1
2.70
Chloromethane-methane
1.0
0.8
0.5
0.1
2.37
Nitrobenzene
0.4
0.8
0.2
0.2
1.67
Carbon tetrachloride
0.1
0.8
0.3
Neg
1.21
Cumene
Neg
0.4
0.5
0.1
0.98
1,1,1-Trichloroethane
Neg
0.3
0.2
Neg
0.48
Adipic acid
0.1
0.1
Neg
Neg
0.18
Full-study3
' 453
75.7
40.1
25.4
594
(76.2%)
(14.0%)
(6.7%)
(4.3%)
Starting with formal-
108.6
37.7
27.4
11.3
185
dehyde*3
(58.7%)
(20.4%)
(14.8%)
(6.1%)
aFull-study reports addressed a total annual production of 113,588 MM lb.
^All full-study reports (except the first four) starting with formaldehyde address a
total annual production of 55,762 MM lb.
-------
C-5
93
estimate for all SOCMI products not covered by a full-study report. Since the
ratio of equipment components to production volume increases so dramatically in
the many smaller volume plants not studied and since fugitive emissions are
more a function of equipment count than of production volume, no fugitive
emission factor was developed for processes not covered by study reports.
The emission projection factors derived from Table C-l are as follows:
109
Process Emissions = 0.002 lb of VOC/lb of production
JJ,/0£
27 4
Storage and handling 5_ = 0.0005 lb of VOC/lb of production
Secondary 55^752 = 0.0002 lb of VOC/lb of production
The abbreviated product studies represent 22,425 MM lb of production projected
to 1982. Based on the above factors to project the 1982 emission estimates for
the abbreviated studies and the 147,627 MM lb of production not covered by full-
study reports, the total estimated VOC emissions for 1982 are as follows:
Amount (MM lb)
Process Fugitive
Full report studies
Abbreviated-report studies
Not studied
453
45
294
792
(55%)
76
29
355
460
(32%)
Storage and
Handling
Secondary Total
40
11
73
124
(9%)
25
4
29
58
(4%)
594
89
751
1434
-------
TECHNICAL REPORT DATA
fPleasc read Instructions on the reverse before completing/
1 REPORT NO.
EPA-450/3-80-023
3. RECIPIENT'S ACCESSION NO.
nn 22050 1
i. TIT^E AND SUBTITLE
Organic Chemical Manufacturing
Volume 1: Study Summary
5. REPORT DATE
December 1980
6. PERFORMING ORGANIZATION CODE
7. AUTHORiS!
8. PERFORMING ORGANIZATION REPORT NO.
R. E. White
9. PERFORMING ORGANIZATION NAME AND ADDRESS
IT Enviroscience, Inc.
9041 Executive Park Drive
Suite 226
Knoxville, Tennessee 37923
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-02-2577
12.SPQNSORING.AGENCYNAME AND ADDRESS , _j ,
DAa for Air Quality Planning and Standards
Office of Air, Noise, and Radiation
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
13. TXPE Of REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
EPA/200/04
IE. SUPPLEMENTARY NOTES
16. ABSTRACT
EPA is developing new source performance standards under Section 111 of
the Clean Air Act and national emission standards for hazardous air pollutants
under Section 112 for volatile organic compound emissions (V0C) from organic
chemical manufacturing facilities. In support of this effort, data were gathered
on chemical processing routes, V0C emissions, control techniques, cortrol costs,
and environmental impacts resulting from control. These data have been analyzed
and assimilated into the ten volumes comprising this report.
This volume contains a brief history of the four year project ar.d includes
emission ranking information for 140 manufactured organic chemicals.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b. IDENTIFIERS/OPEN ENDED TERMS
COSATi Field/Group
13B
b distribution statement
Unlimited Distribution
19 SECURITY CLASS /This Report)
Unclassified
20 SECURITY CLASS (This page/
¦ Unclassified
. . NO. OF PAGES
92
2 PRICE
EPA Form 2220-1 (Rev. 4-77)
PREVIOUS EC'TiON 'S OBSOLETE
01
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