AIR POLLUTION
FROM
CHLORINATION PROCESSES
TASK ORDER NO. 23
CONTRACT NO. CPA 70-1
MARCH 31, 1972
PREPARED FOR
OFFICE OF AIR PROGRAMS
ENVIRONMENTAL PROTECTION AGENCY
SUBMITTED BY
PROCESSES RESEARCH, INC.
INDUSTRIAL PLANNING AND RESEARCH
CINCINNATI, OHIO
-------
AIR POLLUTION
FROM
CHLORINATION PROCESSES
Task Order No. 23
Contract No. CPA 70-1
March 31, 1972
Prepared for
Office of Air Programs
Environmental Protection Agency
Submitted by
PROCESSES RESEARCH, INC.
Industrial Planning and Research
Cincinnati, Ohio
-------
AIR POLLUTION
FROM
CHLORINATION PROCESSES
INDEX
Section Title Page
I Introduction 1
II Manufacturing Technology
A. Classes of Processes 4
B. Discussion of Industries, Products, Processes,
and Sources of Pollution from Chlorination
Processes 7
C. Catalog of Sources from Chlorination Processes 11
III Conclusions
A. General 63
B. Pollution by Processes 65
IV Recommendations 66
V Bibliography 67
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SECTION I - INTRODUCTION
Industrial use of chlorine is growing at a rapid rate. In 1960, 9.3 billion
pounds were used. In 1970, the amount used increased to 19.5 billion pounds and
it is estimated that by 1980 we will be producing 45.5 billion pounds for use.
About 3.0 percent of the total is used for water sanitation and 16.0 percent is
consumed in the pulp and paper industry. The balance of 81.0 percent is used in
the production of chlorinated hydrocarbon products. Because of the apparent
potential for atmospheric pollution with chlorine, hydrochloric acid and various
hydrocarbon compounds, a survey of the processes employed for the production of
the sixteen most important chlorinated hydrocarbon products was undertaken.
Past, present and projected production figures for these materials are shown in
Table I. This list includes all products to which consumption of 1 percent or
more of the chlorine used in 1970 could be attributed. Processes producing these
sixteen selected products consume 68 percent of the 1970 chlorine production.
Table II shows most of the remaining products of commercial importance. The
analysis of processes was performed only for those products shown in Table I.
It was felt that the twenty processes in this group would be representative of
all processes involving chlorine.
Processes and production data were accumulated using forms and techniques
developed under Environmental Protection Agency, Office of Air Programs,
Contract 70-1, Task Order No. 4. An explanation of the system is shown in
Section II of this report.
-------
All of the processes involved in the production of the sixteen major prod-
ucts studied are classifiable as one of five basic process types. A discussion
of the process classes is included in Section II.
TABLE 1
MAJOR PRODUCTS FROM CHLORINE
Product
Carbon tetrachloride, CC14
Chloroform, HCC13
Epichlorohydrin, C3H50C1
Ethyl chloride,
Allyl chloride,
Hydrogen chloride, HC1
Methyl chloride, H3CC1
Methylene chloride, CH2C12
Monochloro benzene, C6H5C1
Phosgene, COC12
Propylene oxide,
Tetrachloroethylene, C2C14
Vinyl chloride, C2H3C1
Total
Total chlorine production
Required
1960
Production of
1970
Chlorine
1980
(Estimated)
Millions of Pounds /Year
CC14
iCl
C2H4C12
•2C12
5C1
I
:2Cl4
ane, C2H3C13
ylene, C2HC13
ion
620
140
300
220
290
540
380
130
230
420
Nil
200
360
Nil
470
450
4,750
9,280
1,500
450
500
300
2,140
900
260
550
610
490
400
820
1,340
680
830
1,410
13,180
19,500
3,420
1,460
850
350
7,070
1,550
440
2,000
1,550
570
1,650
2,630
3,580
2,700
1,820
4,340
35,980
45,500
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TABLE 2
MINOR PRODUCTS FROM CHLORINE
Product
Ethylene oxide,
Chloral, C2C13HO
Dichlorobenzene, Cglty
Benzene hexachloride,
Calcium hypochlorice,
Chloroparaffins (C10-C3Q)C1
1, 2 - dichloropropane, C3
Monochloroacetic acid, C2H
Pentachlorophenol, C5C150H
Phosphorus trichloride, PC13
Sulfuryl chloride, SOC12
Vinylidene chl
Minor total
Required
1960
Production of
1970
Chlorine
1980
(Estimated)
Millions of Pounds/Year
1,845
270
12 180
CgClg 70
Ca(OCl)2 30
:30)C1 10
, C3H6C12 15
C2H302C1 40
15OH 50
;, PC13
12
:H2 = CC19
-
140
170
-
100
20
70
80
60
100
120
80
-
80
240
-
280
60
210
130
80
200
160
_
2,510
940
1,440
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SECTION II - MANUFACTURING TECHNOLOGY
A. CLASSES OF PROCESSES
The chemical industrial processes involving chlorine can be classified
into five groups or types. Starting with the processes which react under the
mildest conditions, the classification is as follows:
1. Liquid phase chlorinations at less than 100C and at near atmospheric
pressure. In general, these are addition reactions; a typical example being:
C12 + C2HA *°° C2H4C12
2. Hydrochlorinations at less than 200C and 40 psig. These are addi-
tion reactions; a typical example being:
HC1 + C2H4 - AOC ) C7HSC1
2 A 40 psig' Z 5
3. Vapor phase chlorinations at over 500C and at 2 to 15 psig
pressure. In general, these are thermal substitution reactions; a typical
example being:
2C1, + CH/. 500C \ CHoClo + 2HC1
2 * 15 psig / Z Z
4. Vapor phase dehydrochlorinations at over 600C and at less than
60 psig. These are thermal cracking reactions driving off HC1; a typical ex-
ample being:
C7H/C1, -2P°C s CH, = CHC1 + HC1
242 50 psig/* 2
5. Vapor phase oxychlorination at 300C and 75 psig, namely:
C2H4 + 2HC1 *L/202 _C> C2H4C12 + H20
-------
Certain dual step processes have been included in only one classifica-
tion because the products of this reaction are the only ones on which there are
production data. For example, trichloroethylene is made by these two reactions:
2C12 + C2H2 *- C2H2Cl4
C2H2Cl4 ^ C2HC13 + HC1
The first reaction is a mild addition reaction at 50C and atmospheric
pressure, and the second reaction is a thermal dehydrochlorination, carried out
at about 600C. There are no production figures for tetrachloroethane, C2H2Cl4
(which is very toxic). Therefore, trichloroethylene is discussed under
Class 4, Dehydrochlorination.
Other aspects of the classification are the multiple reactions which
can be carried out using one raw material. Ethylene can be chlorinated, chloro-
hydrinated, and hydrochlorinated. Methane has four levels of chlorination:
methyl chloride, methylene chloride, chloroform, and carbon tetrachloride.
Table 3 lists the classified processes. The trends in designing plants
which use chlorine are to carry out the reactions in the vapor phase under more
severe conditions, and to use atmospheric oxygen as a hydrogen stripper. The
purpose behind these trends is to provide low capital cost plants with high
production capacities. The disadvantages of the trend are higher feed stock
consumption due to more side reactions, and more pollutants due to the products
of the side reactions.
-------
PAGE NOT
AVAILABLE
DIGITALLY
-------
PAGE NOT
AVAILABLE
DIGITALLY
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B. DISCUSSION OF INDUSTRIES, PRODUCTS. PROCESSES. AND SOURCES OF
POLLUTION FROM CHLORINATION PROCESSES
Production of the sixteen chlorinated products which have been studied
involves the use of twenty different processes. These processes are used in
four industries as defined by the Standard Industrial Classification system
established by the Department of Commerce. These Department of Commerce in-
dustry classifications were used in a recent EPA-OAP funded study aimed at
development of a method for cataloging information on all air pollution sources
associated with any process used to generate products for which the Department
of Commerce routinely collects statistical information. The methodology pro-
duced by this earlier study was used to assemble information for the present
project. In the earlier study, a system of nomenclature involving the basic
categories of "industry," "product," "process," and "source" was developed,
using definitions for each category which are believed applicable to all indus-
tries. These categories are defined below:
Industry. An industry, as defined for cataloging purposes, will
correspond with headings in the SIC Manual. This manual is subdivided into
"Major Group," each with a unique two-digit numerical code, and subcategories
within each Major Group called "Group Number," each of which has a number of
designated subgroups called "Industry Number." For example, Major Group 28
"Chemicals and Allied Products" includes the Group Number 281 "Industrial Inor-
ganic and Organic Chemicals," which is further subdivided into Industry Number
groups such as 2818 - "Industrial Organic Chemicals Not Elsewhere Classified" and
2819 - "Industrial Inorganic Chemicals Not Elsewhere Classified." Under each
-------
four-digit industry number, a listing of included products is shown. Two-digit
major group titles, three-digit group number titles, or four-digit industry
number titles were selected for use with this system, depending on anticipated
importance of the category as far as air pollution is concerned. Where initial
selection of two-digit or three-digit categories leads to an excessive number of
processes in a given category, the original group can be divided subsequently
into the smaller three-digit or four-digit subgroups.
Process. As the term is used here, it includes both processes in which
a single product is prepared by a specific procedure involving chemical change
or change in state, and unit operations where a class of products is manufactured
by use of essentially identical equipment and operations, e.g., the product sul-
furic acid is produced both by the chamber process and by the contact process,
and both would be included as processes. Also included in the classification of
process would be the unit operations such as galvanizing, degreasing, and other
unit operations used in the manufacture of many different fabricated metal prod-
ucts. All such processes fall within some industry category as previously
defined. Where there is doubt as to which industry category is appropriate, the
classification is determined by locating the category in which the product of
the process is listed in the index for the SIC Manual.
Product. As the term is used for this study, it includes all products
listed in the SIC Manual. This category is useful for relating process to in-
dustry as described in the SIC codes. Also, it is useful as a subdivision for
certain industries such as 2818 - Industrial Organic Chemicals, where a large
-------
number of processes are included, despite the fact that the smallest subdivision
in the SIC Manual is used for definition of the industry. For complex indus-
tries, the product category would be used. For less complex industries, only
the basic terms industry, process, and source would be used.
Source. As defined for the study, a source is a piece of equipment,
essential to the economic operation of a process, from which air pollution
emissions occur unless the emissions are prevented by application of pollution
control technology. By contrast, a piece of equipment installed for the primary
purpose of minimizing air pollution emissions is considered control equipment
for a source. Thus a specific type of equipment, such as a scrubber,may be clas-
sifiable as a source or as control equipment, depending on its role in the
process.
The general format developed for cataloging information on all
industries, products, processes and sources, is illustrated by the following
description of chlorination processes. Abbreviations and mechanics of this
system are also defined below:
1. Product. For each product, a general discussion on how the
product is made from various processes is included, along with production and
capacity data from 1960. Also included is a 1980 production forecast and the
principal uses of the product.
2. Process. For each specific process, a detailed description
has been included, along with a process flow sheet, covering these items: feed
preparation, reaction conditions, product purification, recycle systems, raw
materials, by-products and sources of air pollution.
-------
3. Process Data Tabulation. This sheet tabulates the producers,
the location of their plants along with the Air Quality Control Regions (AQCR),
the capacity of the plants in millions of pounds per year and rates the quality
of the data. See attached form.
4. Source Data Tabulation. This sheet tabulates the sources or
origins of air pollution. It defines the composition of the pollutant and the
quantity of emissions in pounds per ton of product. It shows the effect of
control devices and the extent that control devices are used.
5. Data Limitations. Complete and valid data were not always
available. Therefore, it became necessary in some Instances to estimate emission
factors, source control factors, processes, or production levels. To qualify
the validity of the data, the following code was used:
A = Valid data. The result of census or experiment. «*"
B = Estimated data. Estimate based on limited census
or experimental data.
C = Estimated data. Estimate based on little or no
census or experimental data.
Emission factors which were used were an average factor for
all sources, and the source factor (estimated percent of existing sources which
are controlled) is a national average. Application of such numbers to individual
plants or to a small number of plants in a given geographical area could yield
erroneous results.
10
-------
SIC. NO.
T5A7E7
INDUSTRY
PROCESS DATA TABULATIO
PRODUCT
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bIC. NO. • 1.4
PRODUCT :
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COMPUTER CODE NOS.
AQCR
19 22
STATE
23 24
26
CITY
36
37
COMPANY
48
60 51
CAPACITY
52 66
YEAR
57 68
MISCELLANEOUS
RELATED SIC. NOS:
-------
SOURCE DATA TABULATION
INDUSTRY
NO.
DATE
PREPARED
INDUSTRY
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PRODUCT
SOURCE
COMPUTER CODE NOS.
SIC. NO.
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POLLUTANT
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DESCRIPTION
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TYPE
EFF.
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FACTOR
COMPUTER CODE NOS.
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18 20
21
CNO
23
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30
31
32
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36
36
37
SCF
40
41
YR
42
DATE ISS.
REV. NO.
REV.DATE
FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
-------
C. CATALOG OF SOURCES FROM CHLORINATION PROCESSES
1. Cyclic Intermediates - SIC Industry No. 2815
Establishments primarily engaged in manufacturing cyclic organic
intermediates. Important products of this industry include:
Derivatives of benzene, toluene, naphthalene, anthracene, pyridine,
carbazole, and other cyclic chemical products
Synthetic dyes
Synthetic organic pigments
Cyclic (coal tar) crudes
Some of the chlorinated products of this industry include:
Benzene hexachloride
Monochlorobenzene
Chloronaphthalene
Chlorophenol
Chlorotoluene
Fentachlorophenol
Only monochlorobenzene has enough production to be included in this
study. In general, this industry (No. 2815) is not a big consumer of chlorine or
chlorinated products.
11
-------
Product : Monochlorobenzene
Where the end product is monochlorobenzene, benzene is chlorinated in
the liquid phase reaction:
- ^ C6H5C1 + HC1
As an intermediate for phenol, these oxychlorination reactions are used:
C6H6 + HC1 + 1/2 02 - ^ C6H5C1 + H20
C6H5C1 + H20 - ». C6H5OH + HC1
without the separation of the monochlorobenzene. The volume of the oxychlorina-
tion reaction is about twice that of the direct chlorination process. However,
phenol production is outside the scope of this study.
The production and capacities of monochlorobenzene, from 1960 through
1970, have been plotted on Chart 4. A projection indicates that, in 1980, the
production will be approximately 700 million pounds. With the decline of DDT
production, it is expected that the growth rate of monochlorobenzene will be
small.
The raw materials are benzene, chlorine, iron turnings, and sodium
hydroxide. The by-products are hydrogen chloride, dichlorobenzenes, heavies and
spent caustic sludge.
The main use of monochlorobenzene is as an intermediate, for example,
DDT or nitrochlorobenzene.
12
-------
-------
Process; Chlorination of Benzene
Benzene and chlorine are fed to a liquid phase reactor containing iron
turnings as a catalyst. The liquid phase is a boiling mixture of chlorobenzenes
and benzene. The pressure is atmospheric and the temperature range is 80 to 100C.
The HC1 from the reaction is scrubbed with recycled benzene for hydrocarbon re-
moval and then absorbed in water forming 20°Be hydrochloric acid.
The bottoms from the reactor are washed with sodium hydroxide to remove
the last of the HC1 and most of the dichlorobenzenes. After decanting from the
sodium hydroxide solution, the product is fed to a stripping column, where the
benzene is stripped off overhead and the benzene is recycled to the HC1 scrubber.
The bottoms from the stripper are fed to a fractionating column where the pure
monochlorobenzene is taken off overhead and where the bottoms are mostly dichloro-
benzenes. Yields of monochlorobenzene are about 75 percent, while dichlorobenzene
yields are 10 to 20 percent.
There are two sources of air pollution, the vent on the tail gas absorber
and the vent on the stripper. The vents are continuous. Benzene is the major
air pollutant.
13
-------
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RELATED INDUSTRIES
BIBLIOGRAPHY
-------
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DATE ISS.
REV. NO.
REV.DATE
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RELATED INDUSTRIES
BIBLIOGRAPHY
-------
2. Industrial Organic Chemicals Not Elsewhere Classified - SIC Industry
No. 2818
Establishments primarily engaged in manufacturing industrial organic
chemicals, not elsewhere classified. Important products of this industry include:
Non-cyclic organic chemicals
Solvents such as alcohols, acetates, ethers, ketones, and chlorinated
hydrocarbons
Polyhydric alcohols
Synthetic perfume and flavoring materials
Rubber processing chemicals
Plasticizers
Synthetic tanning agents
Chemical warfare gases
Esters and amines of polyhydric alcohols
Some of the chlorinated products of this industry include:
Bromochloromethane
Carbon tetrachloride
Chloral
Chlorinated solvents
Chloroacetic acid
Chloroform
Chloropicrin
Dichlorodlfluoromethane
Ethyl chloride
Methyl chloride
Methylene chloride
Monochlorodifluorormethane
Perchloroethylene
Phosgene
Tetrachloroethylene
Trichloroethylene
Thirteen products from this industry have been included in the
study. This industry (No. 2818) is a major consumer of chlorine and chlorinated
products and is the principal source of air pollutants from the chlorination
processes.
14
-------
Product; 1,2-Dichloroethane
In 1970 approximately 85 percent of the 1,2-dichloroethane (DCE) was
made by chlorinating ethylene in the liquid phase, namely:
C12 + C2H4 ^ C2H4C12
The remaining portion of DCE is made by a newer process, the oxychlorina-
tion of ethylene, namely:
2 HC1 + 1/2 02 (Air) + C2H4 ^ C2H4C12 + H20
Because of cheaper raw materials and good yields (95 percent), most
new facilities are using the oxychlorination process.
DCE is the largest product of the chlorohydrocarbon compounds. It is
used as an intermedia for vinyl chloride, chlorinated solvents and antiknock
compounds. It is expected that 1,2-dichloroethane will have a 10 to 12 percent
annual growth rate.
Chart 3 shows a plot of total 1,2-dichloroethane production from 1960
to 1970 along with capacity data.
15
-------
-------
Process; Ethylene Chlorination
Chlorine gas and ethylene gas are fed into the bottom of a tower-type
reactor filled with liquid DCE, containing some ferric chloride catalyst. The
temperature is about 90C and the pressure about 7 pounds per square inch gage.
The reaction at these conditions is fast, complete, and exothermic, with some
formation of 1,1,2-trichloroethane. The top of the reactor vessel is a fraction-
ator, complete with reflux condenser. Liquid 1,2-dichloroethane, which is
99 percent pure, is withdrawn from near the top of the fractionator. Yields are
about 95 percent.
The raw materials are ethylene, acetylene-free chlorine, and ferric
chloride catalyst. The by-products are 1,1,2-trichloroethane and hydrogen
chloride.
The vent on the reflux condenser, which runs continuously, is the only
source of air pollutants.
16
-------
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DATE ISS.
REV.NQ
REV. DATE
FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
-------
Process; Oxychlorination of Ethylene
Pure ethylene, hydrogen chloride, and air are reacted in the vapor phase
over a fixed bed catalyst of cupric chloride on alumina. Conditions are 250 to
315C and 50-100 pounds per square inch gage. The reaction is fast and exothermic.
The resulting reaction products are passed through a caustic scrubbing tower
where the DCE is condensed, the excess hydrogen chloride is absorbed and neutral-
ized, and the inerts and noncondensable gases are vented. The bottoms from the
caustic scrubbing tower are passed to a decanter tank, where the bottom layer is
the crude product, DCE. The decanter bottoms are fractionated to yield a 99 per-
cent pure .product. The yields are over 95 percent.
The raw materials are ethylene, hydrogen chloride, air, caustic soda,
and cupric chloride catalyst. The by-products are carbon dioxide, 1,1,2-
trichloroethane, 1,2-dichloroethylene, water, and spent caustic soda.
There is one source of air pollution, the vent from the caustic scrubbing
tower.
17
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REV. DATE
FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
-------
Product; Epichlorohydrin
Epichlorohydrin was initially developed as an intermediate for synthetic
glycerol, but more recently has become an epoxy resin component. Using a two-
step process, it is made by chlorohydrinating allyl chloride:
C1CH2-CH = CH2 + HOC1 *• C1CH2-CHC1-CH2OH
followed by hydrolysis to epichlorohydrin:
C1CH2-CHC1-CH2OH +1/2 Ca(OH)2 »- 1/2 CaCl + H-O +
C1CH2 - CH - CH2
0
Chart 2 shows an estimate of total epichlorohydrin production.
Epichlorohydrin is a new compound but is expected to have good growth
due to the needs for epoxy resins and glycerol.
Although the hydrolysis reaction second step is not a chlorination
process, in general the hydrolysis step immediately follows the chlorohydrination,
and production figures are not available on the intermediate.
18
-------
-------
Process; Chlorohydrination of Allyl Chloride
The first reaction, the Chlorohydrination of allyl chloride, can be
carried out in a stirred tank at atmospheric pressure in the liquid phase, using
water as the solvent. The temperature range is 30 to 80C, with some heat evolu-
tion. Yields are over 90 percent. The reaction is complete when no more
chlorine can be added.
The raw materials of the first step are allyl chloride, chlorine, and
water. The by-products are trichloropropane, tetrachloropropyl ether and hydro-
gen chloride.
Most of the air pollutants, such as HC1, are absorbed in the tail gas
absorber.
Reactor products from the Chlorohydrination of allyl chloride are treated
with a lime slurry in a column-type reactor, using trichloropropane as a solvent.
The temperature range is 70 to 100C with some heat evolution. Atmospheric pres-
sure is used. In a crude stripping column most of the water and trichloropropane
are distilled off and recycled to the liming column. The bottoms from the crude
column are fed to the product distillation column, where the epichlorohydrin is
withdrawn overhead. The bottoms of the product column are extracted with water,
the water extraction being fed back to the reactor. The solids are settled out
of the washed bottoms, and the liquor is returned to the solvent tank.
The raw materials of the second step are dichlorohydrin and calcium
hydroxide, while the by-products are calcium chloride and water. The reactor
column is vented.
19
-------
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FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTIN6
RELATED INDUSTRIES
BIBLIOGRAPHY
-------
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REV. NO.
REV. DATE
FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
-------
Product; Carbon Tetrachloride
Carbon tetrachloride is made by three industrial processes.
In 1970, approximately 40 percent of the carbon tetrachloride was made
by the thermal chlorination of methane, namely:
4C12 + CH4 500C^_ CC14 + 4HC1
When methane is chlorinated, co-products such as chloroform are produced.
These co-products show good growth rates. Chloroform, for example, has a 10 per-
cent per year growth rate. Although methane chlorination does not have the best
economics, continued growth of the process is forecast, because of the versatility
of the process equipment and product distribution.
About 35 percent of the carbon tetrachloride was made by the thermal
chlorination of propane, namely:
(C3Hs) + 8C12 *• CC14 + C2C14 + 8HC1
Recent developments in this process have been the use of partially
chlorinated by-products, such as dichloropropane, as feed stocks. If the trend
continues, this process may become dominant due to cheaper feed stocks and lower
chlorine consumption.
The co-product, perchloroethylene, is a valuable product having a 1960-
1970 annual growth of over 12 percent. Perchloroethylene is discussed in
Section II.
Approximately 25 percent of the carbon tetrachloride, or 225 million
pounds, was made by chlorinating carbon disulfide, either directly or indirectly.
This is an old and declining process. Most of the disulfide plants are located
20
-------
in the northeast near the markets, but are being replaced by plants in the Gulf
Coast area, which use cheaper feed stocks.
Carbon tetrachloride is toxic, and is used mainly as an intermediate
for freons. Chart 1 shows a plot of total carbon tetrachloride production and
capacity from 1960 to 1971, along with a production projection to 1980.
21
-------
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-------
Process; Chlorination of Methane
The process sequence requires four main steps: (1) reaction, (2) HC1
recovery, (3) chlorides recovery, and (4) chlorides refining. High-purity
methane, chlorine, and recycle methane are premixed and fed to the reactor. The
reactor effluent, containing organic chlorides, HC1, excess methane, and only
traces of chlorine, is cooled and fed to the HC1 recovery system. The first
column in this system is an absorber designed for efficient HC1 removal. The
bulk of the absorbing liquor is HC1 azeotrope (about 20 percent by weight HC1).
The rich acid is thus above the azeotrope and allows stripping of anhydrous HC1.
The second column distills off anhydrous HC1 and produces the required azeotrope
in the bottoms.
The HCl-free gases from the absorber are washed with caustic soda to
remove final traces of HC1 and are then ready for chlorides recovery. For the
intermediate product distribution under discussion, compression, cooling, and
drying with sulfuric acid are an economical combination.
The reactor is operated at 15 pounds per square inch gage and 400 to
500C. The yields are over 95 percent. There is one source of air pollution.
It is a purge on the recycled methane to remove inerts. The vents from the
product purification system are returned to the suction side of the recycle
compressor.
The raw materials are chlorine (dry gas), methane (99 percent plus),
sulfuric acid, and caustic soda. The by-products are other chloromethanes,
perchloroethylene, hydrogen chloride, heavy ends, and spent caustic sludge.
22
-------
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REV.NQ
REV. DATE
FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
-------
Process: Thermal Chlorination of Propane
Fresh chlorine feed, together with recycled chlorine, and the propane
feed are introduced into a vaporizer where they are mixed with recycled chlorides
in the vapor space. The chlorine is in 10 to 25 percent excess, based on the
propane. The recycle chloride diluent rate (controlled by heat input to the
vaporizer) is designed to control adiabatic reactor temperature at 550 to 700C
and is usually about 75 mole percent of the total stream; its composition also
serves to control CC1^-C2C1^ ratio. The mixed gases, at atmospheric pressure,
are fed to a refractory-lined reactor where they are rapidly mixed with the con-
tents, thereby heated to ignition, and reacted adiabatically. The reaction is
self-sustaining and supported by the considerable heat of reaction (after start-
up), but is tempered and controlled by the diluent action of the recycle chlorides.
The reactor effluent is essentially free of unreacted hydrocarbon and
consists mainly of carbon tetrachlorlde, perchloroethylene, HC1 and excess
chlorine. It is rapidly quenched by intimate contact with a liquid which is
largely perchloroethylene. The rapid quench serves to preserve the equilibrium
ratio attained in the reactor and prevents formation of undesirable by-products.
It also serves to dissolve any quantities of hexachlorobenzene which may be
present (these are small if reaction temperature is maintained below 650C) and
which might introduce difficulties due to deposition of solids on heat transfer
surfaces and in vessels. Some heat economy is obtained from the hot reactor
effluent, which serves to boil the contents of the quench tank and thus provide
boil-up for the CCl^ column. Hexachlorobenzene is purged from the quench tank
by allowing liquid to overflow to the recycle surge tank.
23
-------
The CC1, column, operating on boil-up from the quench tank, returns
quench liquid rich in perchloroethylene as a bottoms stream. Fractionation re-
sults in an overhead which is largely free of perchloroethylene. The condenser
yields carbon tetrachloride, the desired quantity of which is withdrawn as
product, the remainder being used as reflux. Chlorides-free gases (HC1 and
chlorine) are also disengaged at the overhead. These gases are scrubbed with
water to remove HC1, the effluent liquor forming the aqueous HC1 by-product.
They are subsequently dried with concentrated sulfuric acid and purged to main-
tain the balance of inert gases; the remaining chlorine (with some uncondensed
chlorides) is recycled to feed.
A perchloroethylene-rich stream is removed as a side stream from the
CCl^ column and processed to produce perchloroethylene product. Heavy ends are
first removed by distillation and returned to the recycle surge tank. The over-
head from the heavy ends column is fractionated in the C2C1^ column where the
desired quantity of perchloroethylene product is removed as the bottoms and the
overhead (largely carbon tetrachloride) is sent to recycle.
The recycle surge tank serves as a reservoir for three recycle streams:
(1) the quench tank overflow (largely perchloroethylene with some hexachloro-
benzene), (2) heavy ends from the heavy ends column, and (3) the C2C1/ column
overhead (largely carbon tetrachloride). Proper control results in a recycle
mixture of the desired composition, and this is fed to the vaporizer where the
vapors are mixed with the feed materials.
To prevent buildup of hexachlorobenzene in the system, liquid is with-
drawn from the vaporizer and sent to the heavies still. Here the more volatile
24
-------
components are stripped off and returned to the vaporizer, while heavy liquid
consisting of hexachlorobenzene and some hexachloroethane is purged from the
still pot.
The raw materials are propane, chlorine, catalyst (CuCl^ and BaC^) ,
water and sulfuric acid. The by-products are tetrachloroethylene (perchloro-
ethylene), hexachlorobenzene, hydrogen chloride, hexachloroethane, and spent
sulfuric acid.
There is one source of air pollution, the purge on the dry chlorine
recycle, which removes inerts. This purge is continuous,with chlorine being
the pollutant. The major cause of the pollution is impurities in the raw
materials.
25
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TYPE
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SOURCE
FACTOR
2.0
FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
-------
Process; Carbon Disulfide Chlorination
Industrially, both direct and indirect chlorination of carbon disulfide
are employed. In a direct chlorination process, a mixture of carbon tetra-
chloride, carbon disulfide and sulfur chlorides, recycled from a subsequent
process step, is directly contacted with excess chlorine at about 30C over a
divided iron catalyst, converting over 99 percent of the carbon disulfide to
carbon tetrachloride. Some fresh carbon disulfide feed may also be diverted to
the primary chlorinator for purposes of controlling downstream loads. It is
essential that the reaction be complete but that over-chlorination of sulfur to
sulfur monochloride be avoided to prevent appearance of carbon disulfide and
sulfur monochloride in the distilled crude product. Distillation of the reactor
effluent yields a bottoms product and an overhead product of relatively pure
carbon tetrachloride. This material may be treated with a base to destroy sulfur
chlorides, and dried.
An indirect chlorination process is similar. Fresh carbon disulfide
feed reacts with sulfur monochloride under conditions such that the carbon disul-
fide is all but completely reacted. However, the reactor product contains a
fraction of a percent of carbon disulfide,as well as carbon tetrachloride and
sulfur. A direct-chlorination polishing reactor is used to convert this re-
maining carbon disulfide and to facilitate the subsequent distillation, where
crude carbon tetrachloride is removed overhead and molten sulfur containing some
sulfur monochloride is the bottoms product. The crude carbon tetrachloride may
be purified as in the direct chlorination process, an alcoholic caustic treatment
26
-------
with redistillation is shown on the flow sheet. Sulfur equivalent to the fresh
carbon disulfide feed is separated from the bottoms product and may be returned
to the C&2 plant for processing. The residual sulfur stream is directly chlor-
inated to provide the sulfur chlorides chlorinating agent for the first reaction
stage. The flow sheet shows the indirect process.
The raw materials are carbon disulfide, chlorine, iron catalyst, and
caustic soda. The by-products are heavy ends, sulfur chlorides, sulfur, and
spent caustic sludge.
The quantities of air pollutants from the chlorination of carbon disul-
fide are very small. The neutralizer-dryer, using caustic soda, absorbs most
of the noncondensables such as carbon dioxide or excess chlorine. The vacuum
jets on the product still are vented back into the neutralizer-dryer.
27
-------
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DATE ISS. REV. NO.
IREV.I
REV. DATE
FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
-------
Product ; Propylene Oxide
Starting in the early sixties, there was a rapid growth in the capacity
for propylene oxide (FO) as the chlorohydrin plants for ethylene oxide were
modified for PO production. The production growth rate exceeds 10 percent per
year. Shown on Chart 5 are the production and capacities for PO, from 1960 to
1970. A projection indicates a 1980 production of over 3000 million pounds.
The two industrial reaction steps for making PO are as follows:
Chlorohydrination :
C3H6 + HOC1 - ^ C3H6(OH)C1
Hydrolysis:
C3H6(OH)C1 + 1/2 CaOH - »» 1/2 CaCl2 + H20 + CHgO
Though a direct oxidation plant (known as the Oxirane process) has been
built in Texas for the production of 170 million pounds of PO per year, great
expansion of this process in the seventies is not expected. However, after
1980, the Oxirane process will probably dominate. The reaction is:
C3H6 + 1/2 02 - *
The main use of PO is an intermediate for making polyols.
28
-------
-------
Process: Chlorohydrination of Propylene, then Hydrolysis
Propylene, chlorine, and water are introduced into the bottom of a
packed tower where they react under controlled conditions to form propylene
chlorohydrin. The chlorine/propylene/water ratio of the feed to the tower is
so chosen that the liquid effluent leaving the tower contains about 5 percent
propylene chlorohydrin. The temperature of the effluent from the tower is about
50C, and the pressure is atmospheric. Yields of chlorohydrin are about 90 per-
cent. Unreacted propylene, which is in excess in the tower feed, leaves the top
of the tower and is scrubbed with a dilute caustic solution to remove hydro-
chloric acid and any residual chlorine, and then is recycled. A portion of the
recycled propylene is vented to control inert gases.
The liquid stream leaving the chlorohydrin tower is pumped to the flash
hydrolyzer, where the chlorohydrin solution is mixed with an excess (10 to 20 per-
cent) of 10 percent solution of milk of lime. By heating the mixture with live
steam at about 100C and in a vacuum of 1.5 pounds per square inch absolute, the
PO is removed from the hydrolysis zone as it forms. The vapors are partially
cooled to remove part of the water, and then sent to dual distillation columns
to separate the PO out overhead. The bottoms are mostly water and dichloropro-
pane.
Yields of PO, based on the entering propylene, are about 80 percent with
dichloropropane the main by-product. The other by-products are sodium chloride,
calcium chloride, chloropropenes, and heavies. The raw materials are propylene,
chlorine, water, lime, and caustic soda.
The hydrolyzer is vented back into the lime feed system.
29
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TYPE
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DATEISS.
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REV.DATE
FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
-------
•••
INDUSTRY
NO.
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DATE
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INDUSTRY
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TYPE
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DATE ISS. REV.NQ
JREVI
REV.DATE
FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
-------
Product; Ethyl Chloride
In 1970, over 80 percent of the ethyl chloride was made by hydrochlor-
inating ethylene in this liquid phase reaction:
HC1 + C2H4 *-C2H5Cl
The remaining ethyl chloride was made by these two reactions:
Thermal chlorination of ethane:
C12 + C2H6 »» C2H5C1 + HC1
Hydrochlorination of ethanol:
HC1 + C2H5OH ^ C2H5C1 + H20
The first of these reactions is handicapped by high-cost chlorine and
lower yields. The second is almost completely obsolete, due to the high-cost
ethanol, although the yields are very good.
The capacity and production of ethyl chloride is declining very slowly.
The decline is probably due to the reduction in the use of tetraethyl lead.
However, the decline is offset by the increasing use of gasoline. It is esti-
mated that the production will stay at 640 million pounds per year through 1980.
See Chart 6 for production and capacities from 1960 to 1970.
The main use of ethyl chloride is as an intermediate for making tetra-
ethyl lead. This use is in decline due to tetramethyl lead growth and the
environmentalists fight against "leaded" gasolines.
30
-------
C14 KLT
-------
Process; Hydrochlorination of Ethylene
Ethyl chloride is produced by addition of hydrogen chloride to ethylene
under anhydrous conditions in the presence of a catalyst such as aluminum
chloride.
Ethylene gas and substantially anhydrous hydrogen chloride are mixed
in approximately equimolecular proportions and passed into a reactor partially
filled with ethylene dichloride or a mixture of ethyl chloride and ethylene
dichloride. In the presence of 0.2 to 0.3 percent aluminum chloride, at a
temperature of 35 to 40C, and a pressure of 40 pounds per square inch gage, the
exothermic hydrochlorination takes place. The vaporized products are fed into
a column or "flash drum," where the lower boiling ethyl chloride is separated
from the heavier polymers. The crude ethyl chloride is refined by fractiona-
tion. Catalyst is continually withdrawn, and new makeup catalyst is added.
The overall yield based on ethylene is about 90 percent.
The raw materials are ethylene, hydrogen chloride, and aluminum chloride
catalyst. The main by-product is ethylene polymer oil.
The only vent on the process is a purge on the recycled ethylene system,
which keeps inerts (such as CO^ and CH,) from building up.
31
-------
Job
ETHYL
i»o$$iiui
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CINCINNATI
NEW
Q3363
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INDUSTRY
NO.
8818
DATE
PREPARED
INDUSTRY
PROCESS
PRODUCT
SOURCE
COMPUTER CODE NOS.
SIC. NO. :c?.f
PRODUCT:
PROCESS : °9?i3
SOURCE
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CONTROL
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DESCRIPTION
EMISSION FACTOR
TYPE
EFF.
FACTOR
SOURCE
FACTOR
IS"
C8MPUTER CflK NOS.
PNO
18
21
CNO
23
24
UNCONEMI8S
30
CEF
3637
8CF
48
JA
DATE ISS.
REV.
NQ
REV. DATE
FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
-------
Process; Chlorination of Ethane
Ethyl chloride is produced by the thermal chlorination of ethane:
Cl + C2H6 »- C2H5C1 + HC1
After preheating the ethane, equimolecular mixtures of ethane and
chlorine are reacted in the vapor phase in a tank reactor at 375 to 475C and
15 to 50 pounds per square inch gage to yield about 75 percent ethyl chloride.
The reacted mixture is quenched, scrubbed for HC1 removal, dried, the excess
ethane stripped off and the crude ethyl chloride fractionated. The excess
ethane is recycled.
The raw materials are ethane and chlorine. The main by-product is
dichloroethane. The purge on the recycled ethane is the only source of air
pollutants.
32
-------
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r
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38
COMPANY
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INDUSTRY
NO.
2818
DATE
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PROCESS
OF
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PRODUCT
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SOURCE
COMPUTER CODE NOS.
SIC. NO.
PRODUCT
PROCESS
SOURCE
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8
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POLURMT
CONTROL DEVICE
DESCRIPTION
EMISSION FACTOR
TYPE
EFF.
FACTOR
SOURCE
FACTOR
/>» WE
COMPUTER CHE MS.
PNO
IS 2C
CNO
21 23
24
UNCONEMISS
DATE ISS. REV.NQ
;. IREV.I
REV. DATE
FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
-------
Process: Hydrochlorination of Ethanol
The reaction of ethyl alcohol and hydrogen chloride in the presence of
a catalyst yields ethyl chloride.
Warm 95 percent ethyl alcohol is fed into the bottom of a jacketed
glass-lined reactor containing a 45 percent aqueous zinc chloride solution.
Countercurrent to the alcohol, substantially anhydrous hydrogen chloride is fed
into the aqueous zinc chloride solution, which is maintained at about 145C.
The rates of feed are approximately 0.17 and 0.13 parts per hour per part of
zinc chloride solution for the alcohol and hydrogen chloride, respectively.
The reactor pressure is maintained at 30 pounds per square inch. The catalyst
concentration remains about constant, while vapors of ethyl chloride, water, and
some hydrogen chloride are withdrawn from the reactor and passed countercurrent
to a stream of water at 80C in a glass-lined scrubber. The scrubber, operating
at about 30 pounds per square inch, removes the free acid from the incoming
vapors. The scrubbed vapors are cooled to about 20C; at the condenser pressure
(30 pounds per square inch) substantially complete condensation takes place.
%
The liquid is passed into a decanter where ethyl chloride is separated from
water. The process operates continuously to produce 99 percent ethyl chloride
in a yield of 95 to 98 percent based on ethyl alcohol.
The raw materials are ethanol, zinc chloride catalyst, and HC1. The
by-products are small and unimportant. The vent on the condenser is the only
source of air pollutants.
33
-------
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-------
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20 18
DATE:
II-
INDUSTRY
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PRODUCT.
PROCESS
SH OF
COMPUTER CODE NOS.
SIC. NO. :
PRODUCT :
PROCESS :™'
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AQCR
COMPANY
LOCATION
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CAPACITY O VIA*
MISCELLANEOUS
RELATED SIC. NOS:
-------
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INDUSTRY
NO.
ee/8
DATE
PREPARED
INDUSTRY
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PROCESS
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SOURCE
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PROCESS : ?S '
SOURCE
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CONTROL DEVICE
DESCRIPTION
EMISSION FACTOR
TYPE
EFF.
FACTOR
SOURCE
FACTOR
HsCJl
Ha
COMPUTER CUE NOS.
PNO
18 20
CNO
21 23
UNCONEMISS
24 30
CBF
32 35
37 ** 40
3
41
R
DATE ISS. REV.NQ
TREV.I
REV. DATE
FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
-------
Product; 1,1,1-Trichloroethane
The fine solvent properties of 1,1,1-trichloroethane (TCE) have long
been known, but in the past TCE has been difficult to make. With cheap vinyl
chloride (about 5 cents per pound), the growth of TCE has been about 23 percent
per year. See Chart 7 for production data.
TCE is made in two steps. First, vinyl chloride is hydrochlorinated
in the liquid phase:
HC1 + C2H3C1 »- C2H4C12
This reaction will be studied in this part of the report. In the
second step, 1,1-dichloroethane is thermally chlorinated:
C12 + C2H4C12 ^ C2H3C13 4- HC1
which will also be studied here.
As indicated above, the main use of TCE is as a solvent.
-------
HOC.AJ^ rfii--;"i
-------
Process; Hydrochlorination, Then Chlorination of Vinyl Chloride
Recycled 1,1-dichloroethane (DCE) vapor and chlorine gas are fed to
a tower-type reactor, at about AOOC and atmospheric pressure, producing ICE and
hydrogen chloride. Yields are over 95 percent. After cooling the reactor
products to about AOC, they are mixed with fresh vinyl chloride (VC) and fed
to a tower-type hydrochlorinator in which a liquid mixture of DCE and TCE, con-
taining some ferric chloride catalyst, is recirculated. The hydrogen chloride
reacts with the VC producing DCE. The hydrochlorinator is maintained at about
40C by cooling the recycled DCE/TCE mixture and at atmospheric pressure by
venting the inerts. The hydrochlorinator products are decanted from the cata-
lyst and fed to the purification-separation system. Yields are over 95 percent.
The purification-separation system consists of the following steps:
Adjustment of chlorination
Steam distillation
Decanting
Drying
DCE stripping
TCE fractionation
The chloride contents of the products from the hydrochlorinator are
adjusted by a light chlorination. The products are then stripped from the
heavies by steam distillation, decanted from the condensed steam, and dried.
From the drier the products are fed to the first distillation column, where the
DCE is stripped off and recycled. The first column bottoms are fed to the
second distillation column, where the TCE is taken off overhead.
The raw materials are vinyl chloride, chlorine, ferric chloride, and
dessicant. The by-products are chloroethanes and heavies.
35
-------
There are two sources of air pollution. First, to keep inerts from
building up in the hydrochlorinator, it is vented to the atmosphere. Second,
there is a purge on the recycled DCE line, for inerts control.
36
-------
J.T-o C H
-------
SIC. NO.
DATE:
INDUSTRY
PROCESS
MTA TftMUTIN
PRODUCT
PT
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SH ' OF
COMPUTER CODE NOS.
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SIC. NO. • 1.4
PRODUCT :
PROCESS :
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AQCR
COMPANY
LOCATION
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38
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-------
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INDUSTRY
NO.
29 8
DATE
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INDUSTRY
PROCESS
\/C.
PRODUCT
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SOURCE
COMPUTER CODE NOS.
SIC. NO. :C
-------
SOURCE DATA TMUtTION
INDUSTRY
NO.
28 (B
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INDUSTRY
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PROCESS : C£lf
.COLS.
X
X
X
POLLUTAMT
CONTROL DEVICE
DESCRIPTION
EMISSION FACTOR
TYPE
EFF.
FACTOR
SOURCE
FACTOR
C,
PNO
18 20
CNO
21 23
24
UNCON EMI8S
31
32
CEF
_Q 8CF
41
VR
42
DATE ISS. REV.NO.
REV. DATE
FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
-------
Product; Allyl Chloride
Allyl chloride is made by chlorinating propylene at high temperatures
(400 to 500C). If lower temperatures (less than, say, 300C) are used, the
reaction becomes an addition reaction, yielding dichloropropane. For allyl
chloride, the equation is:
C12 + C3H6 500C ^ C3H5C1 + HC1
The yields are about 85 percent.
Allyl chloride is an important intermediate. Glycerol, allyl alcohol,
and epichlorohydrin are made from allyl chloride. Chart 9 shows an estimate of
the production of allyl chloride from 1960 to 1970, with a projection to 1980.
These data are based on synthetic glycerol, epoxy resins, epichlorohydrin pro-
duction, and miscellaneous uses.
37
-------
1012
9...
8...
7...
6..
1*
6..
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3 y
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-------
Process; Chlorination of Propylene
Industrial scale allyl chloride facilities perform three major pro-
cessing operations: feed preparation, reaction, and product recovery.
Feed Preparation. The propylene is purified by fractionation and
drying. The chlorine is also dried.
Reaction. The reaction is carried out in an adiabatic reactor designed
to provide rapid and intimate mixing. Reaction temperature is controlled by
balancing the mole ratio of the feed (usually A moles of propylene to one of
chlorine) and propylene preheat temperature. The usual reaction temperature
range is 500 to 510C; pressures of 15 pounds per square inch gage are used.
Chlorine utilization is in excess of 99 percent. Reactor products are then
cooled to about 50C.
Product Recovery. After initial removal of hydrogen chloride and
propylene, the allyl chloride fraction is separated in a conventional two-step
distillation. Yields of allyl chloride are about 85 percent.
The raw materials are chlorine (dry gas) and propylene (dry gas). The
by-products are coke, dichloropropane, hydrogen chloride, and chloropropenol
(mostly 2-chloropropene).
There is one air pollution source from the allyl chloride process,
the purge on the propylene recycle circuit to remove inerts, mainly impurities
in the raw materials. The noncondensables from the stripping column are vented
into the suction of the recycle compressor.
38
-------
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-------
SOURCE DATA TABUATI
INDUSTRY
NO.
2918
DATE
PREPARED
INDUSTRY
UTOC
PROCESS
OF
PRODUCT
ALL-I
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SOURCE
COMPUTER CODE NOS.
SIC. NO. : C0.4S
PRODUCT:
PROCESS : ^n
COLS
SOURCE : 14-17
X
8
S
POLLUTANT
CONTROL DEVICE
DESCRIPTION
EMISSION FACTOR
TYPE
EFF.
FACTOR
SOURCE
FACTOR
COMPUTER CODE NK.
PNO
18 201
CNO
23
24
UNCON EMISS
GEF
5837
8CF
40
41
VR
42
DATE ISS.
REV. NO.
REV. DATE
FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
-------
Product; Chloroform
Chloroform is a co-product from the chlorination of methane, along with
methyl chloride, methylene chloride, and carbon tetrachloride. The reaction is:
CH4 + 3C12 *- CHC13 + 3HC1
Chart 10 shows the production and capacity figures for chloroform.
The production growth rate for the past ten years has been 12 percent per year.
A production rate of 800 million pounds per year is expected in 1980.
The main use (52 percent) of chloroform is as an intermediate for making
Freon-22, monochlorodifluoromethane.
39
-------
n »
-------
Process; Chlorination of Methane
The process sequence requires four main steps: (1) reaction, (2) HC1
recovery, (3) chlorides recovery, and (4) chlorides refining. High-purity
methane, chlorine, and recycle methane are premixed and fed to the reactor.
The reactor effluent, containing organic chlorides, HC1, excess methane, and
only traces of chlorine, is cooled and fed to the HC1 recovery system. The first
column in this system is an absorber designed for efficient HC1 removal. The
bulk of the absorbing liquor is HC1 azeotrope (about 20 percent by weight HC1).
The rich acid is thus above the azeotrope and allows stripping of anhydrous HC1.
The second column distills off anhydrous HC1 and produces the required azeotrope
in the bottoms. For high yields of chloroform, the amount of recirculating
methane is reduced. Temperature and pressures have little effect. Equipment
design does have effect and is important.
The HCl-free gases from the absorber are washed with caustic soda to
remove final traces of HC1 and are then ready for chlorides recovery. For the
intermediate product distribution under discussion, compression, cooling, and
drying with sulfuric acid are an economical combination.
The reactor is operated at 15 pounds per square inch gage and 400 to
500C. The yields are over 95 percent. There is one source of air pollution.
It is a purge on the recycled methane to remove inerts. The vents from the
product purification system are returned to the suction side of the recycle
compressor.
The raw materials are chlorine (dry gas), methane (99 percent plus),
sulfuric acid, and caustic soda. The by-products are other chloromethanes,
perchloroethylene, hydrogen chloride, heavy ends, and spent caustic sludge.
40
-------
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PROCESS :
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POLLUTANT
CONTROL
BEVRE
DESCRIPTION
EMISSION FACTOR
TYPE
EFF.
FACTOR
SOURCE
FACTOR
CJUOI
CONPHtt&KHS.
FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
-------
Product; Methyl Chloride
In 1970, over 70 percent of the methyl chloride was made by chlori-
nating methane:
Cl + CH4 *• CH3C1 + HC1
An older process, using methanol and hydrogen chloride, produced about
22 percent of the methyl chloride in 1970. The reaction is:
CH3OH + HC1 ^ CH3C1 + H20
In 1960 this reaction produced about 77 percent of the methyl chloride.
Chart 12 shows the production and capacity data of methyl chloride.
For the past ten years the annual growth rate has been 19 percent. For the
future, the growth is expected to be at about half this rate.
The main uses of methyl chloride are as an intermediate for producing
silicones and tetramethyl lead.
-------
-------
Process; Chlorination of Methane
The process sequence requires four main steps: (1) reaction, (2) HC1
recovery, (3) chlorides recovery, and (A) chlorides refining. High-purity
methane, chlorine, and recycle methane are premixed and fed to the reactor.
The reactor effluent, containing organic chlorides, HC1, excess methane, and
only traces of chlorine, is cooled and fed to the HC1 recovery system. The
first column in this system is an absorber designed for efficient HC1 removal.
The bulk of the absorbing liquor is HC1 azeotrope (about 20 percent by weight
HC1). The rich acid is thus above the azeotrope and allows stripping of anhy-
drous HC1. The second column distills off anhydrous HC1 and produces the
required azeotrope in the bottoms. For high yields of methyl chloride, the
amount of recirculating methane is increased.
The HCl-free gases from the absorber are washed with caustic soda to
remove final traces of HC1 and are then ready for chlorides recovery. For the
intermediate product distribution under discussion, compression, cooling, and
drying with sulfuric acid are an economical combination.
The reactor is operated at 15 pounds per square inch gage and 400 to
500C. The yields are over 95 percent. There is one source of air pollution.
It is a purge on the recycled methane to remove inerts. The vents from the
product purification system are returned to the suction side of the recycle
compressor.
The raw materials are chlorine (dry gas), methane (99 percent plus),
sulfuric acid, and caustic soda. The by-products are other chloromethanes,
perchloroethylene, hydrogen chloride, heavy ends, and spent caustic sludge.
42
-------
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SIC MO.
2818
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-------
INDUSTRY
NO.
2818
DATE
PREPARED
INDUSTRY
PROCESS
PRODUCT
SOURCE
COMPUTER CODE NOS.
SIC. NO. •COLS
1-4
PRODUCT:
PROCESS : ^if
SOURCE :*i°i7
X
CONTROL
DESCRIPTION
EMISSION FACTOR
TYPE
EFF.
FACTOR
SOURCE
FACTOR
CfUCJ!
.
ia an
CNO
91 93
UNCONEMISS
CtP
DATE MS. WEV.NQ
REV. DATE
FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
-------
Process: Hydrochlorination of Methanol
Methyl chloride is produced by the action of hydrogen chloride on
methanol, with the aid of a catalyst, in the vapor phase.
Vapors of methanol and hydrogen chloride are continuously mixed in
approximately equimolecular ratios and passed through a preheater maintained
at about 180C. The gas mixture is then passed at substantially atmospheric
pressure through a converter at a temperature of 340 to 350C. The converter
is packed with previously ignited alumina gel of 8- to 12-mesh size or a similar
acting catalyst, such as zinc chloride on pumice, cuprous chloride, or activated
carbon. The converter is externally heated by electric coils or some other
suitable means. Space velocities of about 275 cubic feet per hour per cubic
foot of gross catalyst volume are generally used (based on gas volumes at STP).
The effluent gases from the reactor are scrubbed with water to remove
excess HC1, and alkali wash, and a strong sulfuric acid wash (to dry the product).
Crude methyl chloride is distilled under pressure and at minus 24C to yield pure
methyl chloride. The raw materials are 95 percent methanol, hydrogen chloride,
and catalyst along with caustic and sulfuric acid. The by-products are heavies
and excess HC1 absorbed in water. There are no air pollution sources.
43
-------
t*
i ^=«TP
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2B(g
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INDUSTRY
moss NT* TftNumN
PRODUCT
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PROCESS
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SH OF
COMPUTER CODE NOS.
SIC. NO. :
PRODUCT . : '
PROCESS :
26
8
PIHICTLH MTA
AQCR
COMPANY
LOCATION
Qi
PRODUCTION
Q2
11 S
53
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MISCaiANEOUS
RELATED SIC. NOS:
-------
Product; Methylene Chloride
Methylene chloride is made by chlorinating methane:
2C12 + CH4 ^ CH2C12 + 2HC1
Its annual growth rate in the sixties was 14 percent. For the seven-
ties, the growth rate is expected to decline to'about half this rate, or about
7 percent. Chart 13 shows the production and capacity data.
The main use of methylene chloride, about 40 percent, is as a paint
remover.
44
-------
c
T- 13
9..
8...
7___
6._
4...
2__
£i
8__
7.
5..
: = r±=
p
3..
s
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^:
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i^'-
-------
Process; Chlorination of Methane
The process sequence requires four main steps: (1) reaction, (2) HC1
recovery, (3) chlorides recovery, and (4) chlorides refining. High-purity
methane, chlorine, and recycled methane are premixed and fed to the reactor.
The reactor effluent, containing organic chlorides, HC1, excess methane, and
only traces of chlorine, is cooled and fed to the HC1 recovery system. The
first column in this system is an absorber designed for efficient HC1 removal.
The bulk of the absorbing liquor is HC1 azeotrope (about 20 percent by weight
HC1). The rich acid is thus above the azeotrope and allows stripping of anhy-
drous HC1. The second column distills off anhydrous HC1 and produces the
required azeotrope in the bottoms.
The HCl-free gases from the absorber are washed with caustic soda to
remove final traces of HC1 and are then ready for chlorides recovery. For the
intermediate product distribution under discussion, compression, cooling, and
drying with sulfuric acid are an economical combination.
The reactor is operated at 15 pounds per square inch gage and AGO to
500C. The yields are over 95 percent. There is one source of air pollution.
It is a purge on the recycled methane to remove inerts. The vents from the
product purification system are returned to the suction side of the recycle
compressor.
The raw materials are chlorine (dry gas), methane (99 percent plus),
sulfuric acid, and caustic soda. The by-products are other chloromethanes,
perchloroethylene, hydrogen chloride, heavy ends, and spent caustic sludge.
45
-------
-------
t&m.
£918
SH I ' OF
MeTrtA/->e
sie.«o. :
a
8
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PRODUCTION
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-------
INDUSTRY
NO.
2918
DATE
PREPARED
INDUSTRY
OToc
PROCESS
C l-V c oJL (
PRODUCT
(_t f~\
i»~. v..
SOURCE
COMPUTER CODE NOS.
PRODUCT:
_______ COLS.
PROCESS : 9-13
SOURCE : 14-17
X
3
e
CONTROL
DESCRIPTION
EMISSION FACTOR
TYPE
FACTOR
SOURCE
FACTOR
Cfr-
CH.
ii
PNO
1
R
DATE as. REV.NQ
REV. DATE
FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
-------
Product; Phosgene
Phosgene is made by reacting chlorine and carbon monoxide:
C12 + CO ^ COC12
Phosgene is very toxic, and was used as a poisonous gas in World War I.
However, it is an excellent intermediate, especially for Isocyanate production.
Chart 14 shows the production and capacity data. In the sixties it had annual
growth rate of 26 percent. For the seventies, an annual growth rate of 15 per-
cent is forecast.
Its main use (62 percent) is as an intermediate for making tolylene
di-isocyanate.
46
-------
CHAR
-------
Process; Chlorination of Carbon Monoxide
Carbon monoxide and chlorine gases are dried, filtered, metered, and
mixed, and then fed to a reactor with a very slight excess of CO. The reactor
consists of water-cooled iron tubes filled with activated charcoal. Reactor
conditions are 200C and 2 to 4 pounds per square inch gage. The reaction is
highly exothermic. The hot gases from the reactor are cooled to about 0-C, and
liquid phosgene condenses out. The noncondensables are scrubbed with benzene
or toluene to remove the last traces of phosgene, and are vented. Yields are
99 percent.
The raw materials are carbon monoxide (dry), chlorine (dry), and acti-
vated charcoal. There are no by-products.
There is only one source of air pollutants, the noncondensables from
the solvent absorber.
-------
- J
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MI
m
N
i 2
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Z JS
- 52 8
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0
uo
00
00
-------
SIC. NO.
2913
TOTE
INDUSTRY
QC
RUCKS
A-Tr
cF-
SH I OF
COMPUTER CODE NOS.
SIC. NO.
PRODUCT.
PROCESS
26
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AQCR
COMPANY
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Q.
PRODUCTION
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53
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HfUHD SIC. NOS:
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SIC. NO.
DATE:
INDUSTRY
PROCESS
MTI TftMUflMI
PRODUCT
SH_2 OF 2
COMPUTER CODE NOS.
cir uo • COLS.
SIC. NO. . 1.4
PRODUCT :
PROCESS :
PMIWTHM DIM
AOCR
COMPANY
LOCATION
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PRODUCTION
0-2
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CAPACITY
MISCELLANEOUS
RELATED SIC. NOS:
-------
SNME MTA TMKATIM
INDUSTRY
NO.
28 8
DATE
PREPARED
INDUSTRY
PROCESS
C
PRODUCT
SOURCE
5
COMPUTER CODE NOS.
SIC. NO. :
PRODUCT
PROCESS
SOURCE
X
8
8
GONTINH. DEVICE
DESCRIPTION
EMISSION FACTOR
TYPE
EFF.
FACTOR
SOURCE
FACTOR
CO
Uvu
Cc
2.5
is"10*,
24
UNOON EM«
»
DATE ISS. REV.NQ
m
REV. DATE
FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
-------
Product; Perchloroethylene (Tetrachloroethylene)
In 1970, 80 percent of the tetrachloroethylene production was made by
the thermal chlorination of propane:
(C3Hg) + 8C12 *- CC14 + C2C14 + 8HC1
The remaining 20 percent was made from acetylene, which is being phased out of
DuPont's Niagara Falls Plant (60 millions of pounds per year) in 1972 and
Detrex's Ashtabula Plant (25 millions of pounds per year) in 1971:
C2HC13 + C12 »- C2HC15
C2HC15 *- C2C14 + HC1
For the future, all tetrachloroethylene is expected to come from propane;
Chart 15 shows the production and capacity data. In the sixties, the annual
growth rate was over 12 percent. For the seventies, a 7 percent growth rate is
expected.
73 percent of the tetrachloroethylene is used as a dry cleaning
solvent. The second use is as a chemical intermediate.
48
-------
15
-------
Process; Thermal Chlorination of Propane
Fresh chlorine feed, together with recycled chlorine, and the propane
feed are introduced into a vaporizer where they are mixed with recycled
chlorides in the vapor space. The chlorine is in 10 to 25 percent excess,
based on the propane. The recycle chloride diluent rate (controlled by heat
input to the vaporizer) is designed to control adiabatic reactor temperature
at 550 to 700C and is usually about 75 mole percent of the total stream; its
composition also serves to control CC1^-C2C1^ ratio. The mixed gases, at
atmospheric pressure, are fed to a refractory-lined reactor where they are
rapidly mixed with the contents, thereby heated to ignition, and reacted adia-
batically. The reaction is self-sustaining and supported by the considerable
heat of reaction (after start-up), but is tempered and controlled by the diluent
action of the recycle chlorides.
The reactor effluent is essentially free of unreacted hydrocarbon and
consists mainly of carbon tetrachloride, perchloroethylene, HC1 and excess
chlorine. It is rapidly quenched by intimate contact with a liquid which is
largely perchloroethylene. The rapid quench serves to preserve the equilibrium
ratio attained in the reactor and prevents formation of undesirable by-products.
It also serves to dissolve any quantities of hexachlorobenzene which may be
present (these are small if reaction temperature is maintained below 650C) and
which might introduce difficulties due to deposition of solids on heat transfer
surfaces and in vessels. Some heat economy is obtained from the hot reactor
effluent, which serves to boil the contents of the quench tank and thus provide
-------
boil-up for the CCl^ column. Hexachlorobenzene is purged from the quench tank
by allowing liquid to overflow to the recycle surge tank.
The CCl^ column, operating on boil-up from the quench tank, returns
quench liquid rich in perchloroethylene as a bottoms stream. Fractionation
results in an overhead which is largely free of perchloroethylene. The conden-
ser yields carbon tetrachloride, the desired quantity of which is withdrawn as
product, the remainder being used as reflux. Chlorides-free gases (HC1 and
chlorine) are also disengaged at the overhead. These gases are scrubbed with
water to remove HC1, the effluent liquor forming the aqueous HC1 by-product.
They are subsequently dried with concentrated sulfuric acid and purged to main-
tain the balance of inert gases; the remaining chlorine (with some uncondensed
chlorides) is recycled to feed.
A perchloroethylene-rich stream is removed as a side stream from the
CCl^ column and processed to produce perchloroethylene product. Heavy ends are
first removed by distillation and returned to the recycle surge tank. The
overhead from the heavy ends column is fractionated in the ^2^^ column where
the desired quantity of perchloroethylene product is removed as the bottoms
and the overhead (largely carbon tetrachloride) is sent to recycle.
The recycle surge tank serves as a reservoir for three recycle streams:
(1) the quench tank overflow (largely perchloroethylene with some hexachloro-
benzene), (2) heavy ends from the heavy ends column, and (3) the C~Ci, column
overhead (largely carbon tetrachloride). Proper control results in a recycle
mixture of the desired composition, and this is fed to the vaporizer where the
vapors are mixed with the feed materials.
50
-------
To prevent buildup of hexachlorobenzene in the system, liquid is with-
drawn from the vaporizer and sent to the heavies still. Here the more volatile
components are stripped off and returned to the vaporizer, while heavy liquid
consisting of hexachlorobenzene and some hexachloroethane is purged from the
still pot.
The raw materials are propane, chlorine, catalyst (CuCl2 and BaC^),
water and sulfuric acid. The by-products are tetrachloroethylene (perchloro-
ethylene), hexachlorobenzene, hydrogen chloride, hexachloroethane, and spent
sulfuric acid.
There is one source of air pollution, the purge on the dry chlorine
recycle, which removes inerts.
51
-------
-------
SIC. NO.
SH
/ <* I
PR008CT
COMRUTEIICOOENOS.
SIC. NO. :
PRODUCT.
__-__.. COLS.
PROCESS ; »i3
ae
AQCR
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PRODUCTION
0.2
3e
3-3
53
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-------
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INDUSTRY
NO.
391 8
DATE
PREPARED
INDUSTRY
PROCESS
PRODUCT
C H LoRo
SOURCE
Oi" (4-l
COMPUTER CODE NOS.
SIC. NO. : uY-4
PRODUCT
PROCESS :
SOURCE :
X
8
CONTROL DEVICE
DESCRIPTION
EMISSION FACTOR
EFF.
FACTOR
SOURCE
FACTOR
CJL.
2.0
COMPUfER OK NOS.
PNO
18 26
CNO
21 23
UNttWEMISS
24 301
OF
aa 36
J8CF
37 4OJ41
YR
42
DATEISg.JREV.Na
REV.DATE
FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
-------
Process: Chlorination, Then Dehydrochlorination of Trichloroethylene
In a two-step process, trichloroethylene, made from acetylene, is
reacted with chlorine in the liquid phase using pentachloroethane as the sol-
vent and SbCl3 as the catalyst. The conditions are 80C and about 2 pounds per
square inch gage:
C2HC13 + C12 -
The pentachloroethane is then hydrolyzed at 80C in a column-type reactor using
calcium hydroxide.
2C2HC15 + Ca(OH)2 - »- 2C2Cl4 + CaCl2 + 2H20
The products from the hydrolyzer are fed to a stripper where the lights are
removed. The bottoms from the stripper are fed to a fractionator where the
product, C2C1^, is taken off overhead and where the bottoms are heavies. Yields
are about 90 percent.
The raw materials are chlorine, trichloroethylene and calcium hydroxide.
The by-products are heavies and calcium chloride.
The only source of air pollutants is the inerts purge on the reflux
condenser atop the reactor.
52
-------
Mt MSIMC*
•ew ton
i ^T P'-'-S
C -.
-------
SIC. NO.
29 8
DATE:
INDUSTRY
HTcc
MIA TANUTNN
PRODUCT 77?7M Cf-Uc.-j>c
PROCESS
(6/J
SH \ OF I
COMPUTER CODE NOS.
SIC. NO. :
PRODUCT . : '
PROCESS i
£
HOBICmi BATA
AQCR
COMPANY
LOCATION
Qi
PRODUCTION
32.
22.
A/i/V^APA FA IAS,
WA
H
A
A
A
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CIIPITEI CMf MS.
ITATE
23 24
CITY
MISCaiANEOUS
RELATED SIC. NOS:
-------
SOURCE DATA TIHUTWI
INDUSTRY
NO.
DATE
PREPARED
M-aa-'U
INDUSTRY
Toe,
PROCESS CHL
,OAJ
PRODUCT 'fa 7
SOURCE
COMPUTER CODE NOS.
SIC. NO. :
PRODUCT :
PROCESS :
COLS
SOURCE : 14-17
X
9
g
POLLUTANT
CONTROL DEVICE
DESCRIPTION
EMISSION FACTOR
TYPE
EF.
FACTOR
SOURC
FACTO
c,,
5.
c.
C.
c,
COMPUTER CBDE DOS.
PNO
18 20
CNO
21 23
24
UNCONEMISS
30
32
CEF
3
37** 40
YR
DATE ISS.
REV.NQ
REV. DATE
FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
-------
Product: Trichloroethylene
Trichloroethylene is an old compound produced by a well-established
process based on acetylene. Over 90 percent of the trichloroethylene is made
by this dual step process:
Chlorination of acetylene:
2C12 + C2H2 ^C2H2Cl4
followed by dehydrochlorination:
C2H2Cl4 ^C2HCl3 -I- HC1
The remaining 10 percent of the trichloroethylene is made by the oxychlorination
of 1,2-dichloroethane:
02 (air) + HC1 + C2H4C12 *- C2HC13 + 2H20
This process will probably increase in capacity, phasing out the acetylene-based
plants.
Chart 16 shows the production and capacity data. In the past, the
annual growth rate was about 5 percent, but this rate is expected to decline to
about 3-1/2 percent per year in the seventies. Over 90 percent of the trichlo-
roethylene is used in metal degreasing. The rest is used in solvent extractions
such as making decaffeinated coffee.
53
-------
10.0?
1O.O
8_-
Z_.
6..
sin
5 „
I &
-1 -
2..
* I
- -1 f - -
zr
f'ttfo
-------
Process; Chlorination, then Dehydrochlorination of Acetylene
High purity chlorine gas, containing no oxygen, is fed with acetylene
into a packed tower in which tetrachloroethane is refluxing. The pressure is
atmospheric and the temperature is about 50C. The tower is equipped with a
reflux condenser. The chlorine and acetylene react to form tetrachloroethane.
The tetrachloroethane is withdrawn from the reactor, vaporized, superheated to
300C, and fed to the dehydrochlorinator (which is a tower filled with activated
carbon), yielding trichloroethylene. The temperature is 300C, and the pressure
is atmospheric. The hydrogen chloride, trichloroethylene, and unconverted
tetrachloroethane from the dehydrochlorinator, are fed to a stripping column
where the HC1 is stripped off overhead and absorbed in water as hydrochloric
acid. The conversion of the tetrachloroethane is about 90 percent. The bottoms
are fed to a second stripper where the product, trichloroethylene, is taken off
overhead. These bottoms are fed to a third stripper, where the by-product
perchloroethylene is taken off overhead. These last bottoms are fed to a
fractionator where the tetrachloroethane is taken off overhead and recycled.
The bottoms from the fractionator are discarded.
The raw materials are chlorine (high purity, oxygen-free), acetylene,
and water. The by-products are perchloroethylene, hydrogen chloride, and
heavies.
In the process for producing trichloroethylene, there are two sources
of air pollution, the vent on the reflux condenser connected to the reactor,
and the vent on the tail gas absorber.
54
-------
Hex
-------
SIC. NO.
8
INDUSTRY
raooiCT
77?i c H L
SH ' OF
G^BVTfflCODEfMK.
AQCR
94
ff o. K
53
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INDUSTRY
NO.
28(8
DATE
PREPARED
INDUSTRY
Toe
PROCESSc Hto*iMK-Ti« jo
PRODUCT
SOURCE
COMPUTER CODE NOS.
SIC. NO. i00"^
PRODUCT:
PROCESS : C£}f'
SOURCE
'
X
DESCRIPTION
EMISSION FACTOR
TYPE
EFF.
FACTOR
SOURCE
FACTOR
7-5
1.0
PNO
CNO
UNOONEMI8S
DATE ISS. IREV.NQ
REV. DATE
FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
-------
INDUSTRY
NO.
28/8
DATE
PREPARED
II- t- •pl\
INDUSTRY
Xoc
PRODUCT
T/^lC 1-ArL o JU E 1 K^ 6 £ jus.
SOURCE
TA\L GAS
A B 5 ok BJ5-5*-
COMPUTER CODE NOS.
SIC. NO. :°?!f-
PRODUCT :
_______ COLS.
PROCESS : 9-13
SOURCE
9
4
CONTROL DEVICE
DESCRIPTION
EMISSION FACTOR
TYPE
EFF.
FACTOR
SOURCE
FACTOR
HcJi
0. Z_
AJftMJE
o.
CflftPOTEJt CODE NOS.
PNO
18 20
UNCON-MISS
C6F
R
DATE iss.
c
NQ
REV. DATE
FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
-------
Process; Oxyhydrochlorination of Dichloroethane
Dichloroethane is oxychlorinated by air and hydrogen chloride to
produce trichloroethylene. With the hydrogen chloride in excess, air, hydrogen
chloride, and dichloroethane are mixed and reacted in the vapor phase in a
tubular reactor at 300 to 400C and about 100 pounds per square inch gage. The
reaction is exothermic, requiring cooling of the reactor. The reaction products
are scrubbed with caustic, condensing the product and absorbing the excess HC1.
The unreacted air is vented.
The crude product is decanted from the scrubber fluid and fed to a
stripper. In the stripper, the product is stripped from the heavies and is fed
to a fractionator. In the fractionator, pure product, trichloroethylene, is
taken as bottoms.
The raw materials are dichloroethane, hydrogen chloride, caustic, and
air. The by-products are spent caustic, heavies, and a small amount of lights.
The yields are estimated at 90 percent.
There is a single source of air pollutants, the spent air vent on the
absorber.
55
-------
PR 109
Job
PROCESSES KSCAtCI, INC.
INOUSTIIAl PLANNING
NfW YOU
FJI. MO
3 3 ^ 3
u,,,
CINCINNATI
Checked br .
Computed by .
f= 7 HA
-------
SIC. NO.
28 18
DATE:
INDUSTRY
BAT* UWUTIM
PRODUCT
1= 7
PROCESS
DlC
\ (f
e T H A ME
SH OF
COMPUTER CODE NOS.
cir un •
SIC. NO. •
. COLS.
PRODUCT . :
PROCESS :
as
8
PRODICTI6N BiTA
AQCR
COMPANY
LOCATION
Qi
PRODUCTION
Q2
/C/E
A
A
A
35
A
CNPUTEI CUE 10$.
AQCft Bra
W 22 TM 24
CITV
COMPANY
CAPACITY
YIAH
MISCELLANEOUS
RELATED SIC. NQS:
-------
INDUSTRY
NO.
2818
DATE
PREPARED
INDUSTRY
SINCE UTA TAWUTIM
PRODUCT 77?/c H
B T K -Y <-
-------
2. Industrial Inorganic Chemicals Not Elsewhere Classified - SIC
Industry No. 2819
Establishments primarily engaged in manufacturing industrial inor-
ganic chemicals not elsewhere classified. Important products of this industry
include inorganic salts, inorganic compounds such as alums, peroxides, carbides,
and ammonia, rare earth metal salts, and elements.
Some of the chlorine products of this industry include:
Aluminum chloride
Ammonium chloride
Ammonium perchlorate
Bleaching powder
Brine
Calcium chloride
Calcium hypochlorite
Calomel
Chlorosulfonic acid
Cobalt chloride
Ferric chloride
Hydrochloric acid
Indium chloride
Lime bleaching compounds
Magnesium chloride
Mercury chlorides
Potassium chloride
Perchloric acid
Potassium chlorate
Potassium hypochlorate
Radium chloride
Sodium chlorate
Sodium hypochlorite
Sulfur chloride
Tin chloride
Zinc chloride
This industry is not a big consumer of chlorine or its compounds.
Only hydrogen chloride has been included in this study.
56
-------
Product; Hydrogen Chloride
In 1970, about 7 percent of the nearly 4 billion pounds of total hydro-
gen chloride production came from chlorinating hydrogen, or 265 million pounds
of 100 percent HC1:
H2 + C12 ^.2HC1
About an equal amount of hydrogen chloride is produced as a by-product
from salt cake production. The chlorination of organic chemicals produces the
remaining 85 percent of the hydrogen chloride, as a by-product. Chart 11 shows
the synthetic hydrogen chloride production. Little or no growth is expected in
synthetic hydrogen chloride production.
Hydrogen chloride has many uses. The metal industries use vast quan-
tities. As an acid, it is replacing sulfuric acid as a pH adjusting reagent.
Because of its nontoxicity, the food industry uses hydrogen chloride extensively,
57
-------
ii
-------
Process; Chlorination of Hydrogen
Dry chlorine and hydrogen gases, with the H2 in 2 to 5 percent excess,
are fed to a burner and burned in a hydrogen-chlorine flame. The hot gases are
passed to a water-cooled chamber which operates at near atmospheric pressure
and then cooled to 300F. The HC1 gas is then passed to a cooler-absorber where
20°Be hydrochloric acid is produced. The inerts and excess hydrogen, which are
vented through the tail gas absorber, are the only air pollutants.
The raw materials are hydrogen, chlorine, and water. There are no by-
products.
58
-------
MIOT
Job
EPA
IHOOSTIU1
AM IISUICN
CMKMMUfl
MW TOIK
Cbttkfd by
0«lt.
. • 1
y
1
1
i
Chlorine L
Hydrogen |
Flame.
arrester
Ming
M
j i '
•Dl
Bums
•y Witer sprays
it it n n « n Hg ^
Lbu3«on
ehamter Outtet-* —
' Cooling/
J overflow i
Inlet >
fl
Fo sever -
Product
acid
Fen inter r * •
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— Weak gas
|:v,.;;'
f,
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•gas M8 5 «V2-7b r~Jl—
'
H
• ;:-:' _*.•-,.
- .. -.s-^r-
. :' ' ."'<•
-------
SIC. NO.
28IR
INDUSTRY
urn nminM
PRODUCT
Hex
SH OF
COMPUTER CODE NOS.
SIC. NO.
PRODUCT :
PROCESS :
a
MM
AQCR
COMMWV
IflCATION
Qi
PRODUCTION
A/Y
53
E*
32-
A/f/VOV FA ex
11
31
32-
VUNA
C ir-f f
r^ / MI
, \A/A
C
C.
d
c
-------
sic. on.
TRIE
iNOusrav
piKtss tin
PRODUCT
SH 2 OF 2
TROCRT
COMPUTER CODE NOS.
cir un •
SIC. NO. •
PRODUCT.:^?7
PROCESS :
UOCWION
Q.
PRODUCTION
0
TX
It
PITTS
CA
145
d
c
c
\/
.A
mscaumtous
(BUNCO SIC. NOS:
-------
INDUSTftY
NO.
BATE
PREPARED
I o -1* -*
PRODUCT
C
COMPUTER CODE NOS.
SIC. MO.
PRODUCT
PROCESS
SOURCE
X
OfSCBtfTtON
EMI8SHMI FACTOR
TYPE
WF.
FACTOR
SOURCE
FACTOR
; /
FOR PROOUCTIOM CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBilOQRAfHY
-------
3. Plastic Materials - SIC Industry No. 2819
Establishments primarily engaged in manufacturing synthetic resins.
Important products of this industry include the following resins: phenolic urea,
vinyl, styrene, acrylic polethylene, polypropylene, and silicones.
Some of the chlorinated compounds of this industry include:
Epoxy resins
Polyvinyl chloride resins
Of this industry (No. 2819), only polyvinyl chloride resins are big
consumers of chlorine or chlorinated compounds.
59
-------
Product: Vinyl Chloride
In 1970, less than 20 percent of the vinyl chloride production was made
by this acetylene-based process:
HC1 + C2H2 »• C2H3C1
This older reaction is being replaced by an ethylene dichloride based
process, which will also be studied:
C2H4C12 ^ C2H3C1 + HC1
This is a thermal cracking reaction carried out at 900C and low pressures.
Less than A percent of the vinyl chloride is made by a combination of
the two processes.
Chart 8 shows the production and capacity for vinyl chloride. The
future growth rate is estimated at 13 percent per year, or a production of
10 billion pounds per year by 1980. Vinyl chloride is used to make polyvinyl
chloride and its copolymers.
60
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Process; Dehydrochlorination of Ethylene Bichloride
EDC is dehydrochlorinated in a furnace over a mercuric chloride
catalyst supported on charcoal. The temperature is 900C and the pressure is
50 pounds per square inch gage. After cooling with liquid EDC in a quenching
tower, the HC1 is separated from the products of the furnace. In a stripping
column, the light ends are stripped from the vinyl chloride. The vinyl chloride
is then fractionated, coming off overhead. The heavies are recycled.
The raw materials are EDC and mercuric chloride catalyst. The by-
product is hydrogen chloride. The yields are over 95 percent.
There is one source of air pollution, the tail gas scrubber on the hydro-
gen chloride recovery system.
61
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RELATED INDUSTRIES
BIBLIOGRAPHY
-------
Process: Hydrochlorination of Acetylene
The vapor-phase reaction between acetylene and hydrogen chloride in
the presence of a mercuric chloride catalyst yields vinyl chloride. Anhydrous
hydrogen chloride (slight excess) and dry, purified acetylene gas (free from
ammonia, hydrogen sulfide, phosphine, and arsine) are mixed and fed to a reactor
containing carbon pellets impregnated with mercuric chloride. The reaction is
exothermic, so a coolant is circulated around the tubes to hold the reaction
temperature at about 200C and 10 pounds per square inch gage.
Effluent gases from the reactor are cooled by heat exchange and finally
condensed and fractionated in a refrigerated column from which unreacted acety-
lene and hydrogen chloride go overhead. The acid-free monomer or "crude" is
further fractionated in a second column in which vinyl chloride goes overhead,
and by-product ethylidene chloride and aldehydes are removed as bottoms. The
condensed vinyl chloride is stabilized with a small amount of phenol before
going to storage. Yields are about 80 to 85 percent.
The raw materials are hydrogen chloride (dry), acetylene, dry (high
purity) and mercuric chloride catalyst. The by-products are ethylidene
dichloride and aldehydes.
There is a purge on the recycled acetylene to prevent the buildup of
inerts, which are mainly impurities in the raw materials.
62
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-------
SECTION III - CONCLUSIONS
A. GENERAL
In general, chlorination processes are designed to give high efficiency
containment of potentially hazardous emissions of Cl2, HC1, and chlorinated
hydrocarbons within the process. They do not always have control equipment
installed exclusively for the purpose of preventing emissions, but typically
they will have one or more gas cleaning devices installed to collect unreacted
gases and vapors so that they can be recycled to the process. The cost and the
obnoxious character of the materials both provide incentives for high efficiency
cleaning,over 95 percent,of exit gases.
The collection methods used are condensation, adsorption, and absorp-
tion. Condensers and solid adsorbents are generally used to collect materials
for recycle to the process. The data available on adsorption are limited, but
metal oxides, molecular sieves, silica gel, activated carbon, and alumina have
been used. The adsorbent is used to collect and concentrate dilute components
in exit gases. Absorption systems are most commonly used, for final gas cleaning.
Scrubbing liquids used include water, caustic solutions, lime or limestone
slurry, carbon tetrachloride, sulfur monochloride, benzene, and toluene. Where
high efficiency scrubbing is practiced with organics, absorbent losses will be
the main atmospheric pollutant, e.g., where toluene or benzene is used to clean
emissions from equipment handling phosgene. Generally, such systems are used,
because of the cost,only for very hazardous materials.
63
-------
It was not possible in the present study to determine whether systems
are in practice designed to meet prevailing air pollution control requirements.
Calculated emission factors for processes relying exclusively on condensation
control suggest that they may not meet the requirements of some agencies, but
high levels of control can be effected using sorbent systems so that prevention
of air pollution from routine operations does not appear to be dependent upon
availability of improved technology.
Consideration was given to the potential for production of hazardous
emissions when processes are out of control. All of the processes studied are
exothermic, but most seem unlikely to be prone to run out of control so that it
will become necessary to open the reactor to the atmosphere to prevent a disaster.
Many are liquid phase reactions and consequently are not subject to violent up-
sets. For the gas phase reactions, large excesses of one reactant will generally
be used. While this approach gives potential for loss of control if a massive
increase in minor reactant feed were to occur, control system designs make this
unlikely in practice for most processes studied. The reaction of H2 and Cl£ to
produce HC1 is one exception which was noted, and others could exist. It does
not appear, however, that this problem is of sufficient magnitude to warrant
special consideration in a Federal R&D program, but further investigation of
industry practice may be desirable to confirm conclusion which is based on
limited data.
At present, no feedback control system can be designed to respond to
Cl2 and/or HC1 in exit gas streams because of the unavailability of methods
64
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of analysis for C12 and HC1. It is conceivable that the availability of a feed-
back system would permit economies in emissions control and might be useful in
preventing some process upsets and attendant emissions to the atmosphere.
Definitive estimates of potential impact of successful work to develop a feed-
back system could not be made but incentives for such work appear to be weak.
Lastly, calculated emission factors suggest the need for further study.
B. POLLUTION BY PROCESSES
Totaling the emission factors as shown on the source data tabulation
sheets for each process and using the production data of Table 3, the total
quantity of air pollutants for each process was calculated for 1970. The results
are shown in Table 4.
65
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PAGE NOT
AVAILABLE
DIGITALLY
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SECTION IV - RECOMMENDATIONS
It is recommended chat consideration be given to field investigation of
current practice to define the economic limitations for the best available
control technology. This would provide information useful both in setting
standards and in the refinement of R&D objectives.
While R&D work, targeted specifically at prevention of emissions from chlori-
nation processes, does not seem to be needed, present and contemplated studies of
control devices should consider the possible applicability of development work
to produce increased efficiency and lower costs for control.
66
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SECTION V - BIBLIOGRAPHY
1. Kirk and Othmer, Encyclopedia of Chemical Technology, 2nd Ed., 1963-1970
2. Sconce, J. S., Chlorine, 1962, Reinhold
3. Chemical Week, Oct. 28, 1970, Part Two
4. Standard Industrial Classification Manual, 1967, Office of Statistical
Standards
5. Air Pollutant Emission Factors, NAPCA, August, 1970, McGraw, M. J.
6. Du Prey, R. L., Compilation of Air Pollutant Emission Factors, NAPCA,
1968, AP-42
7. The Chlorine Institute, Pamphlet Mo. 10, July 1971
8. Preliminary Air Pollution Survey of Hydrochloric Acid, Oct. 1969,
APTD 69-23
9. Chemical Profiles, Schnell Publishing Company
10. Chemical Economics Handbook, Stanford Research Institute
11. Faith, Keyes, Clark, Industrial Chemicals, 3rd Ed., 1965, Wiley
12. Sittig, Organic Chemical Process Encyclopedia, 1967, Noyes
13. Synthetic Organic Chemicals, TC Publication, U. S. Production and Sales;
I960 TC Publication 34 TC 1.33:960
1961 TC Publication 72 TC 1.33:961
1962 TC Publication 114 TC 1.33:962
1963 TC Publication 143 TC 1.33:963
1964 TC Publication 167 TC 1.33:964
1965 TC Publication 206 TC 1.33:965
1966 TC Publication 248 TC 1.33:966
1967 TC Publication 295 TC 1.33:967
1968 TC Publication 327 TC 1.33:968
1969 TC Publication 412 TC 1.33:969
14. Hahn, The Petrochemical Industry, 1970, McGraw-Hill
15. Processes Research, Inc., Catalog of Atmospheric Pollutant Sources and
Pilot Computer Program, 1971, Prepared for EPA
67
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