AEPA
United States
Environmental Protection
Agency
Industrial Environmental Research
Laboratory
Research Triangle Park NC 27711
EPA-600/2-79-019g
August 1979
Research and Development
Source Assessment:
Chlorinated Hydrocarbons
Manufacture
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved technology required for the control and treatment
of pollution sources to meet environmental quality standards.
EPA REVIEW NOTICE
This report has been reviewed by the U.S. Environmental Protection Agency, and
approved for publication. Approval does not signify that the contents necessarily
reflect the views and policy of the Agency, nor does mention of trade names or
commercial products constitute endorsement or recommendation for use.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/2-79-019g
August 1979
Source Assessment: Chlorinated
Hydrocarbons Manufacture
by
Z.S. Khan and T.W. Hughes
Monsanto Research Corporation
P O. Box 8. Station B
Dayton, Ohio 45407
Contract No. 68-02-1874
ROAP 21AXM-071
Program Element No. 1AB015
EPA Project Officer Bruce A. Tichenor
Industrial Environmental Research Laboratory
Office of Energy. Minerals, and Industry
Research Triangle Park, NC 27711
Prepared for
U.S ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
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PREFACE
The Industrial Environmental Research Laboratory (IERL) of EPA
has the responsibility for insuring that pollution control tech-
nology is available for stationary sources to meet the require-
ments of the Clean Air Act, the Federal Water Pollution Control
Act, and solid waste legislation. If control technology is
unavailable, inadequate, or uneconomical, then financial support
is provided for the development of the needed control techniques
for industrial and extractive process industries. Approaches
considered include: process modifications, feedstock modifica-
tions, add-on control devices, and complete process substitution.
The scale of the control technology programs ranges from bench-
to full-scale demonstration plants.
The Chemical Processes Branch of the Industrial Processes Division
of IERL has the responsibility for investing tax dollars in pro-
grams to develop control technology for a large number (more than
500) of operations in the chemical industries. As in any tech-
nical program, the first question to answer is, "Where are the
unsolved problems?" This is a determination which should not be
made on superficial information; consequently, each of the
industries is being evaluated in detail to determine if there is,
in EPA's judgment, sufficient environmental risk associated with
the process to invest in the development of control technology.
This report contains the data necessary to decide whether air
emissions reduction is necessary for emissions from chlorinated
hydrocarbons manufacture.
Monsanto Research Corporation has contracted with EPA to investi-
gate the environmental impact of various industries which repre-
sent sources of pollution in accordance with EPA's responsibility
as outlined above. Dr. Robert C. Binning serves as Program
Manager in this overall program entitled "Source Assessment,"
which includes the investigation of sources in each of four
categories: combustion, organic materials, inorganic materials,
and open sources. Dr. D. A. Denny of IERL-RTP serves as EPA
Project Officer. In this study of chlorinated hydrocarbons
manufacture, Mr. Edward J. Wooldridge, Dr. I. Atly Jefcoat, and
Mr. Bruce A. Tichenor served as EPA Task Officers.
111
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ABSTRACT
This report describes a study of air pollutants released during
the manufacture of chlorinated hydrocarbons. The potential envi-
ronmental effect of the source was evaluated using source severity,
S, defined as the ratio of the maximum ground level concentration
of an emission to the ambient air quality standard for criteria
pollutants or to a modified TLV for noncriteria pollutants.
Chlorinated hydrocarbons are manufactured in the U.S. by one of
four processes: 1) direct chlorination (a hydrocarbon is reacted
with chlorine); 2) hydrochlorination (hydrogen chloride is reacted
with a hydrocarbon); 3) oxyhydrochlorination (hydrogen chloride is
reacted with a hydrocarbon in the presence of oxygen or air); and
4) chlorohydrination (the reaction between a hydrocarbon and hydro-
chlorous acid is followed by a reaction of the products with lime
slurry to obtain the final product). In the U.S. during 1975, 32
companies with a total capacity of 11.5 x 106 metric tons/yr pro-
duced 8.52 x 106 metric tons of chlorinated hydrocarbons at 58
locations.
A representative plant was defined for each manufacturing process
type, and the environmental effects were determined on the basis
of capacity instead of production. Source severities for direct
chlorination, hydrochlorination, oxychlorination, and chloro-
hydrination are 1.69, 1.94, 31.3, and 2.75, respectively.
Pollution control technology within the chlorinated hydrocarbon
industry consists primarily of control of hydrocarbons emitted
from the main process vent, product fractionating vent, storage
tanks, fugitive sources, and waste disposal. Assuming that the
same level of control will exist in 1980 as existed in 1975, air
emissions from the industry are expected to increase by 20% over
that period.
This report was submitted in partial fulfillment of Contract No.
68-02-1874 by Monsanto Research Corporation under the sponsorship
of the U.S. Environmental Protection Agency. The study described
in this report covers the period January 1976 to August 1978.
IV
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CONTENTS
Preface iii
Abstract iv
Figures viii.
Tables xi
Abbreviations and Symbols xvi
I Introduction 1
II Summary 2
III Source Description 5
A. Process Description 7
1. Direct Chlorination 7
2. Hydrochlorination 24
3. Oxyhydrochlorination 31
4. Chlorohydrination 35
B. Geographical Distribution 42
IV Emissions 48
A. Selected Pollutants 48
B. Locations and Descriptions 48
1. Emissions from Main Process Vent 48
2. Emissions from Product Fractionation Vent 50
3. Emissions from Storage Tanks 50
4. Fugitive Emissions 51
5. Emissions from Waste Disposal 51
C. Emission Factors 52
D. Definition of a Representative Source 57
E. Environmental Effects 57
1. Determination of Severity 57
2. Industry Contribution to Total Atmospheric
Emissions 63
3. Affected Population and Affected Area 63
4. Growth Factor 66
V Control Technology 67
A. Absorption 67
B. Condensation 70
C. Incineration 71
1. Thermal Incineration 71
2. Catalytic Incineration 75
3. Flares 76
D. Adsorption 77
E. Control of Emissions from Storage Tanks 79
F. Control of Fugitive Emissions 82
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CONTENTS (continued)
G. Waste Disposal Techniques 83
1. Incinerator Section (Sub-X
Incinerator-Scrubber) 84
2. HC1 Recovery System (UCAR System) 86
VI Growth and Nature of the Industry 88
A. Methyl Chloride 88
1. Present Technology 88
2. Industry Production Trends 88
3. Outlook 91
B. Methylene Chloride 91
1. Present Technology 91
2. Industry Production Trends 92
3. Outlook 94
C. Chloroform 94
1. Present Technology 94
2. Industry Production Trends 95
3. Outlook 95
D. Carbon Tetrachloride 97
1. Present Technology 97
2. Industry Production Trends 98
3. Outlook 99
E. Perchloroethylene 100
1. Present Technology 100
2. Industry Production Trends 100
3. Outlook 102
F. Ethylene Dichloride 102
1. Present Technology 102
2. Industry Production Trends 102
3. Outlook 104
G. Phosgene 105
1. Present Technology 105
2. Industry Production Trends 106
3. Outlook 106
H. Monochlorobenzene 108
1. Present Technology 108
2. Industry Production Trends 108
3. Outlook 110
I. Dichlorobenzenes 110
1. Present Technology 110
2. Industry Production Trends 111
3. Outlook 111
J. Ethyl Chloride 113
1. Present Technology 113
2. Industry Production Trends 114
3. Outlook 114
K. 1,1,1-Trichloroethane 115
1. Present Technology 115
2. Industry Production Trends 116
3. Outlook 117
VI
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CONTENTS (continued)
L. Trichloroethylene 117
1. Present Technology 117
2. Industry Production Trends 118
3. Outlook 119
M. Epichlorohydrin 120
1. Present Technology 120
2. Industry Production Trends 120
3. Outlook 121
N. Propylene Oxide 122
1. Present Technology 122
2. Industry Production Trends 123
3. Outlook 124
References 125
Appendices
A. Derivation of Maximum Severity Equations 132
B. Field Sampling Results 144
C. Field Sampling Methods 154
D. Analytical Procedures 159
E. Sample Calculations 163
Conversion Factors and Metric Prefixes 171
vn
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FIGURES
Number Page
1 Methyl chloride, methylene chloride, chloroform
and carbon tetrachloride by the direct
chlorination of methane. 10
2 Carbon tetrachloride by the direct chlorination
of carbon disulfide. 13
3 Carbon tetrachloride and perchloroethylene by
the direct chlorination of propane. 15
4 Ethylene dichloride by the direct chlorination
of ethylene. 18
5 Phosgene by the direct chlorination of carbon
monoxide. 21
6 Monochlorobenzene and dichlorobenzene by the
direct chlorination of benzene. 23
7 Methyl chloride by the hydrochlorination
of methanol 26
8 Ethyl chloride by the hydrochlorination
of ethylene. 29
9 1,1,1-Trichloroethane by the hydrochlorination and
direct chlorination of vinyl chloride. 30
10 Ethylene dichloride by the oxyhydrochlorination
of ethylene. 34
11 Trichloroethylene by the oxyhydrochlorination
of ethylene dichloride. 36
12 Epichlorohydrin by the chlorohydrination of
allyl chloride. 39
13 Propylene oxide by the chlorohydrination of
propylene. 41
Vlll
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FIGURES (continued)
Number Page
14 Geographical distribution of chlorinated
hydrocarbon plants. 43
15 Schematic diagram of a bubble-cap tray tower. 69
16 Packed tower. 69
17 Venturi scrubber. 69
18 Spray tower. 69
19 Surface condenser: shell and tube. 72
20 Surface condenser: fin fan. 72
21 Surface condenser: finned hairpin section. 72
22 Surface condenser: integral finned section. 72
23 Surface condenser: tubular. 73
24 Contact condenser: spray. 73
25 Contact condenser: jet. 73
26 Contact condenser: barometric. 73
27 Schematic diagram of a catalytic afterburner 75
28 Carbon adsorption system. 79
29 Baffle construction. 81
30 Air baffle. 81
31 Schematic flow diagram for the disposal of
chlorinated hydrocarbon wastes. 85
32 Schematic diagram of the Sub-X Incinerator-
Scrubber. 86
33 Methyl chloride production, 1960 to 1980. 90
34 Methylene chloride production, 1960 to 1980. 93
35 Chloroform production, 1960 to 1980. 96
36 Carbon tetrachloride production, 1960 to 1980. 99
ix
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FIGURES (continued)
Number Page
37 Perchloroethylene production, 1960 to 1980. 101
38 Ethylene dichloride production, 1960 to 1980. 104
39 Phosgene production, 1965 to 1980. 107
40 Monochlorobenzene production, 1965 to 1980. 109
41 p-Dichlorobenzene and o-dichlorobenzene production,
1965 to 1980. 112
42 Dichlorobenzene production, 1965 to 1980. 112
43 Ethyl chloride production, 1965 to 1980. 115
44 1,1,1-Trichloroethane production, 1966 to 1979. 116
45 Trichloroethylene production, 1945 to 1979. 119
46 Epichlorohydrin production, 1962 to 1978. 121
47 Propylene oxide production, 1965 to 1980. 123
A-l AAQS as a function of distance. 142
C-l Gas sampling train. 154
C-2 High volume organic sampling system. 156
C-3 XAD-2 sorbent trap module. 156
C-4 Sample handling and transfer—XAD-2 module. 157
C-5 Porous polymer vapor sampling method. 157
C-6 Chlorine/chloride sampling train. 158
D-l Analysis flow scheme for organic compounds Cg
and above. 161
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TABLES
Number Page
1 Chlorinated Hydrocarbons with 1975 Production
Capacities Greater Than 105 Metric Tons/Yr 6
2 Direct Chlorination Processes 7
3 Material Balance for Ethylene Dichloride by Direct
Chlorination of Ethylene 19
4 Hydrochlorination Processes 24
5 Oxyhydrochlorination Processes 31
6 Chlorohydrination Processes 37
7 Chlorinated Hydrocarbon Manufacturing Facilities
Including Company, Plant Locations, Product Types,
Population Density, and Capacity 44
8 Unit Operations Involved in the Manufacture of
Chlorinated Hydrocarbons with Emission Sources
Identified 49
9 Material Emitted from Chlorinated Hydrocarbon
Manufacturing Plants 50
10 Emission Factors by Unit Operations for Processes
Using Direct Chlorination 53
11 Emission Factors by Unit Operations for Processes
Using Hydrochlorination 54
12 Emission Factors by Unit Operations for Processes
Using Oxyhydrochlorination 55
13 Emission Factors by Unit Operation for Processes
Using Chlorohydrination 56
14 Summary of Criteria Used to Define Representative
Chlorinated Hydrocarbon Plants 58
XI
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TABLES (continued)
Number Page
15 Source Severity: Direct Chlorination Process 60
16 Source Severity: Hydrochlorination Process 61
17 Source Severity: Oxyhydrochlorination Process 61
18 Source Severity: Chlorohydrination Process 62
19 Source Severity: Representative Direct Chlorination,
Hydrochlorination, Oxyhydrochlorination, and
Chlorohydrination Processes 62
20 Chlorinated Hydrocarbon Industry Contribution to
National Sationary Source Emissions of
Criteria Pollutants 63
21 Chlorinated Hydrocarbon Industry Contributions to
State Emissions of Hydrocarbons 64
22 Affected Population and Affected Area 66
23 Manufacturer, Plant Location, and Capacity for
Methyl Chloride Production by the Chlorination
of Methane 89
24 Manufacturer, Plant Location, and Capacity for Methyl
Chloride Production by the Hydrochlorination of
Methanol 89
25 Methyl Chloride Consumption in 1975 91
26 Manufacturer, Plant Location, and Capacity for
Methylene Chloride Production by the Chlorination
of Methane 92
27 Manufacturer, Plant Location, and Capacity for
Methylene Chloride Production by the Hydrochlorina-
tion of Methanol 92
28 Methylene Chloride Consumption in 1975 93
29 Manufacturer, Plant Location, and Capacity for
Chloroform Production by the Chlorination of
Methane 94
30 Manufacturer, Plant Location, and Capacity for
Chloroform Production by the Hydrochlorination
of Methanol 95
xii
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TABLES (continued)
Number page
31 Chloroform Consumption in 1975 96
32 Manufacturer, Plant Location, and Capacity for
Carbon Tetrachloride Production by the
Chlorination of Methane 97
33 Manufacturer, Plant Location, and Capacity for
Carbon Tetrachloride Production by the
Chlorination of Carbon Disulfide 98
34 Manufacturer, Plant Location, and Capacity for
Carbon Tetrachloride Production by the
Chlorination of Propane 98
35 Carbon Tetrachloride Consumption in 1975 98
36 Manufacturers, Plant Locations, and Capacities for
Perchloroethylene Production by the Chlorination
of Propane 101
37 Perchloroethylene Consumption in 1975 102
38 Manufacturers, Plant Locations, and Capacities for
Ethylene Dichloride Production by the Chlorination
of Ethylene " 103
39 Manufacturers, Plant Locations, and Capacities for
Ethylene Dichloride Production by the Oxyhydro-
chlorination of Ethylene 103
40 Ethylene Dichloride Consumption in 1975 105
41 Manufacturers, Plant Locations, and Capacities for
Phosgene Production by the Chlorination of Carbon
Monoxide 106
42 Phosgene Consumption in 1975 107
43 Manufacturers, Plant Locations, and Capacities for
Monochlorobenzene Production by the Chlorination
of Benzene 108
44 Monochlorobenzene Consumption in 1975 109
45 Manufacturers, Plant Locations, and Capacities for
p-Dichlorobenzene Production by the Chlorination
of Benzene 110
Xlll
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TABLES (continued)
Number Page
46 Manufacturers, Plant Locations, and Capacities for
o-Dichlorobenzene Production by the Chlorination
of Benzene 111
47 p-Dichlorobenzene Consumption in 1975 113
48 o-Dichlorobenzene Consumption in 1975 113
49 Manufacturers, Plant Locations, and Capacities for
Ethyl Chloride Production by the Hydrochlorination
of Ethylene 114
50 Ethyl Chloride Consumption in 1975 115
51 Manufacturers, Plant Locations, and Capacities for
1,1,1-Trichloroethane Production by the Hydro-
chlorination and Chlorination of Vinyl Chloride 116
52 1,1,1-Trichloroethane Consumption in 1975 117
53 Manufacturers, Plant Locations, and Capacities for
Trichloroethylene Production by the Oxyhydro-
chlorination of Ethylene Dichloride 118
54 Trichloroethylene Consumption in 1975 119
55 Manufacturers, Plant Locations, and Capacities for
Epichlorohydrin Production by the Chlorohydrination
of Allyl Chloride 120
56 Epichlorohydrin Consumption in 1975 121
57 Manufacturers, Plant Locations, and Capacities for
Propylene Oxide Production by the Chlorohydrina-
tion of Propylene 122
58 Propylene Oxide Consumption in 1975 124
A-l Pollutant Severity Equations for Elevated Sources 132
A-2 Values of a for the Computation of a 134
A-3 Values of the Constants Used to Estimate Vertical
Dispersion 134
A-4 Summary of National Ambient Air Quality Standards 138
B-l Atmospheric Emissions from Scrubber Inlet 145
xiv
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TABLES (continued)
Number Page
B-2 Atmospheric Emissions from Scrubber Outlet 145
B-3 Atmospheric Emissions from Waste System 146
B-4 Atmospheric Emissions from Chlorocarbon System 146
B-5 Atmospheric Emissions from Boilerhouse Outlet 148
B-6 Atmospheric Emissions from Boilerhouse Inlet 149
B-7 Atmospheric Emissions from Process Stack 150
B-8 Atmospheric Emissions from Intermediate Storage 151
B-9 Atmospheric Emissions from Monochlorobenzene
Storage 151
B-10 Atmospheric Emissions from Benzene Storage 151
B-ll Atmospheric Emissions from Oxy-vent 152
B-12 Atmospheric Emissions from Heads Column 153
B-13 Atmospheric Emissions from High Boils Vent 153
xv
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ABBREVIATIONS AND SYMBOLS
A — affected area
A — factor defined as Q/aciru
AAQS — ambient air quality standard
a r . . e ,
v..z — constants
BR — factor defined as -H2/2c2
C. — production capacity of plant i
D — (capacity weighted) mean population density
Dp — county population density for plant i
e — constant; 2.72
exp --natural log base, e
F — hazard factor; for criteria pollutants, F is the
primary ambient air quality standard; for noncri-
teria pollutants, F is a reduced TLV value, i.e.,
F = TLV • 8/24 • 1/100
H — effective emission height
KI,..KS — coefficients in overall stoichiometric equations
P — total affected population
Q — mass emission rate
S — source severity
SCQ — source severity for carbon monoxide emissions
S c — source severity for hydrocarbon emissions
S o — source severity for nitrogen oxide emissions
a
Sp — source severity for particulate emissions
— source severity for sulfur oxide emissions
t — averaging time
t — short-term averaging time
TLV — threshold limit value
u — wind speed
xvi
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u —average wind speed
x —downwind distance from source of emission
xi* X2 —roots of equation for affected area calculation
y —horizontal distance from centerline of dispersion
z —vertical distance from centerline of dispersion
TT —constant; 3.14
a —standard deviation of horizontal dispersion
o —standard deviation of vertical dispersion
Z
X —downwind ground level concentration of a pollutant
X —average downwind ground level concentration of a
pollutant
X—-,, —maximum ground level concentration of a pollutant
ITlclX
X^ —time-averaged maximum ground level concentration
of a pollutant
X (x) —annual mean ground level concentration of a pollu-
tant at a specific distance (x) from the source
XVII
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SECTION I
INTRODUCTION
Fourteen major chlorinated hydrocarbons are included in this
study, excluding pesticides and vinyl chloride, that have U.S.
production capacities equal to or greater than 105 metric tons
per year. Chlorinated hydrocarbons are principally used as sol-
vents and chemical intermediates, in the manufactures of gasoline
additives and chlorofluorocarbons for metal degreasing and
cleaning, and in miscellaneous applications.
Four processes are currently used in the United States to manu-
facture chlorinated hydrocarbons: direct chlorination, hydro-
chlorination, oxyhydrochlorination, and chlorohydrination.
This document presents a detailed study of the chlorinated hydro-
carbon industry from the standpoint of atmospheric emissions and
their potential environmental impact. Major results of this
study are summarized in Section II. Section III includes a brief
description of the four chlorinated hydrocarbon manufacturing
processes and the various compounds produced by each process.
Included in the section are process chemistry, major processing
steps, and block flow diagrams. Section IV discusses the types
of material emitted from the unit operations of each manufac-
turing process, emission points, and the mass of material emitted.
Several factors designed to measure the environmental hazard
potential of chlorinated hydrocarbon manufacture are also
determined. These consist of the source severity, the industry
contribution to total atmospheric emissions of criteria pollu-
tants, and the number of persons exposed to high contaminant
levels from representative plants.
Section V reviews the current pollution control technology
applicable to the control of atmospheric emissions from the manu-
facture of chlorinated hydrocarbons. The growth and nature of
the industry are analyzed in Section VI.
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SECTION II
SUMMARY
Chlorinated hydrocarbons are manufactured in the U.S. by one of
four types of processes: direct chlorination, hydrochlorination,
oxyhydrochlorination, and chlorohydrination. Direct chlorination
represents 50% of the total chlorinated hydrocarbon capacity;
hydrochlorination represents 11%; oxyhydrochlorination, 30%; and
chlorohydrination, 9%. Chlorinated hydrocarbons considered for
this study are those with annual production capacities more than
100,000 metric tons. During 1975 in the U.S., there were 32
companies with a total chlorinated hydrocarbon capacity of
11.5 x 106 metric tons/yr producing 8.52 x 106 metric tons of
chlorinated hydrocarbons at 58 locations.
In the direct chlorination process, a hydrocarbon is reacted with
chlorine. Hydrogen chloride is reacted with a hydrocarbon in the
hydrochlorination process. In the oxyhydrochlorination process,
hydrogen chloride is reacted with a hydrocarbon in the presence
of oxygen (air). Chlorohydrination involves a reaction between a
hydrocarbon and hydrochlorous acid and a further reaction of the
products with lime slurry to obtain the final product. The
products contained in the effluents from the reactor in all four
processes are separated from byproducts and unreacted raw
materials. This separation step is followed by distillation to
obtain the pure product.
Major uses of chlorinated hydrocarbons are as solvents and chem-
ical intermediates. They are also used in the manufacture of
gasoline additives, chlorofluorocarbons, pesticides, and herbi-
cides, and as solvents in drycleaning, cold cleaning, and vapor
degreasing.
Sources of atmospheric emissions within a chlorinated hydrocarbon
plant include the main process vent, product fractionation vent,
storage tanks, fugitive sources, and waste disposal operations.
The potential hazard from the manufacture of chlorinated hydro-
carbons was quantified by generating a number of factors,
including: source severity, national and state burdens for
criteria pollutants, affected population, and growth factor.
The source severity was defined as the ratio of the maximum time-
averaged ground level concentration, determined by using Gaussian
-------
plume methodology, of a pollutant from a representative source to
the hazard potential of the pollutant. The hazard potential for
criteria pollutants is defined as the primary ambient air quality
standard; for noncriteria pollutants, it is defined as a reduced
threshold limit value (TLV®).
A representative plant was defined for each manufacturing process
type. The parameters used to define the four representative
plants include process type, population density, plant production
rate, unit operations used, average emissions from specific unit
operations, and emission rates for hydrocarbons. To depict a
worst case analysis, capacities instead of production figures
were used in all calculations.
For representative chlorinated hydrocarbon plants, emission rate
and source severities for hydrocarbon emissions were determined
to be:
Hydrocarbon Hydrocarbon
emission emission
factor, rate,
Process g/kg g/s Severity
Chlorination 2.78 6.88 1.69
Hydrochlorination 8.62 11.4 1.94
Oxyhydrochlorination 1.87 15.0 2.06
Chlorohydrination 123 480 46.8
The total mass of hydrocarbons emitted nationwide by the
chlorinated hydrocarbon industry has been estimated to be 14,600
metric tons for the direct chlorination process, 9,950 metric
tons for the hydrochlorination process, 62,000 metric tons for
the Oxyhydrochlorination process, and 120,000 metric tons for the
Chlorohydrination process. The percent contributions to national
emissions are 0.06%, 0.04%, 0.024%, and 0.48% for the direct
chlorination, hydrochlorination, Oxyhydrochlorination, and Chloro-
hydrination processes, respectively.
Statewide hydrocarbon emissions to the atmosphere from chlorin-
ated hydrocarbon plants using the direct chlorination process
are below 1.0% for Alabama, California, Delaware, Illinois,
Indiana, Kansas, Kentucky, Louisiana, Maryland, Michigan, Nevada,
New Jersey, New York, Ohio, Texas, and West Virginia. For the
hydrochlorination process, statewide contributions range between
0.00% and 1.08% for California, Kansas, Kentucky, Louisiana,
Michigan, New Jersey, New York, Texas, and West Virginia. For
the Oxyhydrochlorination process, state contributions to hydro-
carbon emissions range between 0.014% and 0.26% for California,
Texas, Kentucky and Louisiana.
-------
For the chlorhydrination process, conbribtuions to state hydro-
carbon emissions are 2.2% for Kentucky, 1.2% for Louisiana, 1.4%
for Michigan, and 3.7% for Texas.
The average number of persons exposed to high contaminant levels
from chlorinated hydrocarbons production was estimated and des-
ignated as the affected population. The calculation was made
for total hydrocarbons emitted from all points within a represen-
tative plant for which the source severity exceeds 0.1. The af-
fected populations were 2,820, 2,772, 4,580 and 297,600 for the
direct chlorination, hydrochlorination, oxyhydrochlorination, and
chlorohydrination processes, respectively.
The growth factor was determined from the ratio of known chlo-
rinated hydrocarbon production in 1975 to projected production
in 1980. Since 1975 production data and projected data for 1980
were unavailable for each process type, the growth factor was
determined for the entire chlorinated hydrocarbon industry.
Assuming that the same level of control will exist in 1980 as
existed in 1975, emissions from the chlorinated hydrocarbon in-
dustry are expected to increase by 20% over that period; i.e.,
Emissions in 1980 _ Production in 1980 _ 10.4 x 10s , 2
Emissions in 1975 Production in 1975 8.52 x 106
Pollution control technology within the chlorinated hydrocarbon
industry consists primarily of control of hydrocarbons emitted
from the main process vent and product fractionating vent. Con-
trol techniques include absorption, condensation, incineration,
and adsorption; and measures to control storage tank emissions,
fugitive emissions, and emissions from waste disposal.
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SECTION III
SOURCE DESCRIPTION
The chlorinated hydrocarbons source type is defined as those
plants which currently produce the 14 chlorinated hydrocarbons
listed in Table 1. All of those compounds listed have U.S. pro-
duction capacities of 100,000 metric tons per year or more. One
of the 14 compounds, propylene oxide, is not a chlorinated hydro-
carbon, but it is included in this study because most of its U.S.
production is accomplished by the chlorohydrination process using
a chlorinated hydrocarbon as a chemical intermediate. Specifi-
cally excluded from the list are those chlorinated hydrocarbons
which are classified as pesticides since these materials are the ,
subject of an independent study. Vinyl chloride will also be
separately studied and is not included in this document.
In 1975 there were 32 companies with a total capacity of
11.5 x 106 metric tons/yr producing 8.52 x 106 metric tons/yr
of the 14 chlorinated hydrocarbons at 58 locations in the United
States.1"12
Chemical Profile,
Reporter, 209(13)
2Chemical Profile,
Reporter, 210(12)
3Chemical Profile,
210(13):9, 1976.
^Chemical Profile,
Reporter, 207(22)
5Chemical Profile,
Reporter, 210 (6) :
6Chemical Profile,
206(1):9, 1974.
7Chemical Profile,
Reporter, 206(20)
8Chemical Profile,
Reporter, 209(11)
Methyl Chloride. Chemical Marketing
:9, 1976.
Methylene Chloride. Chemical Marketing
:9, 1976.
Chloroform. Chemical Marketing Reporter,
Carbon Tetrachloride. Chemical Marketing
:9, 1975.
Perchloroethylene. Chemical Marketing
9, 1976.
Phosgene. Chemical Marketing Reporter,
Monochlorobenzene.
:9, 1974.
p-Dichlorobenzene.
:9, 1976.
Chemical Marketing
Chemical Marketing
(continued)
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TABLE 1. CHLORINATED HYDROCARBONS WITH 1975 PRODUCTION CAPACITIES
GREATER THAN 10s METRIC TONS/YR1-12
Product type
Ethylene dichlonde
Propylene oxide9
Carbon tetrachloride
Phosgene
Perchloroethylene
Ethyl chloride
1,1, 1-Trichloroethane
Methylene Chloride
Honochlorobenzene
Methyl chloride
Trichloroethylene
Epichlorohydrin
Chloroform
Dichlorobenzeneb
Totalc-d
1975
Production
capacity,
10s metric
tons/yr
58.90
11.93
7.63
7.22
5.01
3.86
3.36
3.18
3.13
2.81
2.18
2.04
1.95
1.34
114.54
Percent
of total
chlorinated
hydrocarbon
capacity
51.42
10.42
6.66
6.30
4.37
3.37
2.93
2.78
2.73
2.45
1.90
1.78
1.70
1.17
99.98
1975
Production ,
10s metric
tons/yr
49.98
6.80
4.76
4.41
3.16
2.61
2.79
2.22
1.76
1.42
1.61
1.71
1.27
0.66
85.16
Percent
of
production
58.69
7.98
5.59
5.18
3.71
3.06
3.28
2.61
2.07
1.67
1.89
2.01
1.49
0.72
99.95
Percent
of available
capacity
utilized
84.9
57.0
62.4
61.1
63.1
67.6
83.0
69.8
56.2
50.5
73.9
83.8
65.1
49.3
74.3
Estimated
annual
growth
during
1975-1980, %
+4.0
+10.5
-10.0
+12.0
+3.5
-40.0
+4.0
+11.0
+2.0
+6.0
-8.0
+5.3
+9.0
+3.5
Estimated
1980
production,
10s metric
tons/yr
60.81
11.20
2.81
7.77
3.75
0.20
3.39
3.74
1.94
1.90
1.06
2.22
1.95
0.78
103.52
Percent of
estimated
chlorinated
hydrocarbon
production
in 1980
58.7
10.8
2.7
7.5
3.6
0.2
3.3
3.6
1.9
1.8
1.0
2.2
1.9
0.8
100.00
"propylene oxide is produced using two processes: 70% of the U.S. propylene oxide is produced from chlorohydrination of
propylene while 30% is produced from peroxidation of propylene.
bDichlorobenzene includes both para- and ortfco-dichlorobenzenes.
°Total includes those product types having production capacities of 100,000 metric tons/year or more. Chlorinated
hydrocarbons having production capacities less than 100,000 metric tons/year have not been included.
Totals include rounding errors.
-------
A. PROCESS DESCRIPTION
The production of chlorinated hydrocarbons can be categorized
into four groups based on the four unit processes used during
manufacture: (1) direct chlorination, (2) hydrochlorination,
(3) oxyhydrochlorination, and (4) chlorohydrination. Direct
chlorination represents 50% of the total chlorinated hydrocarbon
capacity; hydrochlorination represents 11%; oxyhydrochlorination
30% and chlorohydrination 9%. A description of the four proc-
esses follows.
1. Direct Chlorination
Direct chlorination involves the reaction of a hydrocarbon with
chlorine gas. The products and processes used to manufacture
chlorinated hydrocarbons pertinent to this study are summarized
in Table 2 together with the chemical equation representing each
reaction.
TABLE 2. DIRECT CHLORINATION PROCESSES
Product
Methyl chloride
Methylene chloride
Chloroform
Carbon tetrachloride
Carbon tetrachloride
Carbon tetrachloride
Perchloroethylene
Ethylene dichloride
Phosgene
Monoch lorobenzene
Dichlorobenzene
Manufacturing process
Direct chlorination of methane
Direct chlorination of methane
Direct chlorination of methane
Direct chlorination of methane
Direct chlorination of carbon disulfide
Direct chlorination of propane
Direct chlorination of propane
Direct chlorination of ethylene
Direct chlorination of carbon monoxide
Direct chlorination of benzene
Direct chlorination of benzene
Chemical reactions
CHi, + C12 * CH3C1 + HC1
CHu + 2C12 * CH2C12 + 2HC1
CHi, + 3C1 2 •» CHCla + 3HC1
ail, + 4C12 •» CCli, -I- 4HC1
CS2 + 3C12 * CCli, + S2C12
C3H8 + 8C12 •* CCli, + C2Cli, + 8HC1
C3HB + 8C12 •* CCli, + C2Cli, + 8HC1
CH2=CH2 * C12 * C1CH2CH2C1
CO + C12 * COC12
C6H6 + C12 •* C6H5C1 + HC1
CeHe + 2C12 •» C6Hi,Cl2 + 2HC1
Equation
No.
1
2
3
4
5
6
7
8
9
10
11
Table 2 indicates that a typical direct chlorination reaction can
be represented by a general chemical reaction such as:
Hydrocarbon + chlorine
chlorinated hydrocarbon
+ hydrogen chloride + (byproduct)
(12)
Chemical Marketing
9Chemical Profile, o-Dichlorobenzene.
Reporter, 210(10):9, 1976.
10Chemical Profile, Trichloroethylene. Chemical Marketing
Reporter, 208(12):9, 1975.
11Chemical Profile, Ethyl Chloride. Chemical Marketing Reporter,
210(13):9, 1976.
12Chemical Profile, Propylene Oxide.
Reporter, 209(18):9, 1976.
Chemical Marketing
-------
The overall stoichiometric equation describing direct chlorina-
tion processes is:
C H Cl O S + (Ki)Cl2 •* Ctt Cl O + (K2)HC1 + (K3)S2Cl2 + (Ki»)H2O + (K5)C2Cli,
vwxyz cl JJ U 6
(13)
where K! =j(2v+w-x-2y+z-2a-b+d+ 2e)
K2 = w - 2y - b + 2e
K3 = |z
K4 = y - e
K5 = |(v - a)
The direct chlorination process used in the manufacture of the
above mentioned nine chlorinated hydrocarbons consists of three
basic steps: (1) chlorination, (2) absorption, and (3) separa-
tion. Chlorination is carried out in a reactor, also called a
chlorinator, where the hydrocarbon reacts with chlorine to pro-
duce the chlorinated hydrocarbon. The reaction is dependent on
factors such as hydrocarbon used, catalyst used, reaction tem-
perature, reactor space velocity, pressure, and the ratio of
hydrocarbon to chlorine.
Effluents from the chlorinator include crude product, byproducts,
unreacted raw materials, and catalyst. Effluents from the
chlorinator are passed through an absorber, the second important
section of the process, where they are condensed and where unre-
acted raw material is recovered. Hydrogen chloride formed during
chlorination is now recovered from the system. Any remaining
hydrogen chloride is neutralized in a neutralizer by scrubbing
with caustic.
The crude product so obtained is then purified by separation,
which can be carried out in one operation or a series of opera-
tions including fractional distillation, stripping, or phase
separation. From the separator, the pure final chlorinated
hydrocarbon, which has been separated from byproducts of the
chlorination process, is withdrawn and sent to storage for sale
or use.
a. Direct Chlorination of Methane—
Methyl chloride, methylene chloride, chloroform, and carbon
tetrachloride are commercially produced by direct chlorination of
methane.
-------
(1) Chemistry—The basic chemical equations representing the
chlorination of methane to methyl chloride, methylene chloride,
chloroform, and carbon tetrachloride are:13'1*4
CH4 + C12 + CH3C1 + HC1 (14)
(methyl chloride) (hydrogen chloride)
CH3C1 + C12 -»• CH2C12 + HC1 (15)
(methylene chloride) (hydrogen chloride)
CH2C12 + C12 -»• CHC13 + HC1 (16)
(chloroform) (hydrogen chloride)
CHC13 + C12 ->• CCli, + HC1 (17)
(carbon tetrachloride) (hydrogen chloride)
Raw materials used for the chlorination of methane are methane
(99+%), chlorine (dry gas), caustic soda, sulfuric acid, and
water. Products of the reaction are methyl chloride, methylene
chloride, chloroform, and carbon tetrachloride. Byproducts
include hydrogen chloride, caustic sludge, and chlorinated heavy
ends.15 Copper and barium chlorides are used as catalysts.
Yields for these reactions are between 85% to 90% based on
methane.13
(2) Process—Figure 1 is a simple flow diagram for the chlorina-
tion of methane to produce methyl chloride, methylene chloride,
chloroform, and carbon tetrachloride.l3-16•a The reaction
between chlorine and methane may be controlled so as to yield pre-
dominantly methyl chloride, with the formation of smaller amounts
of methylene chloride, chloroform, and carbon tetrachloride. If
methylene chloride is desired in largest amount, the methyl
13Lowenheim, F. A., and M. K. Moran. Faith, Keyes, and Clark's
Industrial Chemicals, Fourth Edition. John Wiley & Sons, Inc.,
New York, New York, 1975. 904 pp.
ll*Gruber, G. I. Assessment of Industrial Hazardous Waste
Practices, Organic Chemicals, Pesticides, and Explosives
Industries. EPA/530/SW-118C (PB 251 307), U.S. Environmental
Protection Agency, Washington, D.C., April 1975. 377 pp.
15Air Pollution from Chlorination Processes. EPA Contract
EPA 70-1, Task Order No. 23, U.S. Environmental Protection
Agency, Office of Air Programs, March 31, 1972. 67 pp.
16Chloromethanes - Vulcan Materials Co. Hydrocarbon Processing,
54(11):127, 1975.
Some information provided by personal communication from
T. H. Capps, Allied Chemical Company, Industrial Chemicals
Division, Moundsville, West Virginia, July 28, 1976.
-------
PURGE ON RECYCLED METHANE (GAS)
METHANE CHLOROFORM
i METHYL CHLORIDE CARBON TETRACHLORIDE
TMETHYLENE CHLORIDE
METHANE
CHLORINE
CARBON
TETRACHLORIDE
COLUMN
HEAVY ENDS
METHYL CHLORIDE
Figure 1.
METHYLENE CHLORIDE
CHLOROFORM
CARBON TETRACHLORIDE
Methyl chloride, methylene chloride, chloroform and carbon
tetrachloride by the direct chlorination of methane.
-------
chloride may be recycled to the chlorinator. Usually carbon
tetrachloride is the most desired chloromethane, in which case
most of the other chloromethanes are recycled.13
Methane is mixed with chlorine, preheated and fed to a reactor
fitted with mercury arc lamps to promote the reaction at 350°C
to 370°C and only slightly above atmospheric pressure and with
residence times controlled so that the temperature desired may
be held, chlorine is completely used up, and about 65% of the
methane is reacted.13 A typical range of products leaving the
reactor is: methyl chloride - 58.5%; methylene chloride - 29.3%;
chloroform - 9.7%; and carbon tetrachloride - 2.3%. The effluent
gases from the reactor also contain unreacted methane and hydro-
gen chloride. These are separated from the chloromethanes by
scrubbing the reacted gases with a mixture of liquid chloro-
methanes, usually a refrigerated mixture of chloroform and carbon
tetrachloride. Methane and hydrogen chloride are not absorbed
and go overhead. They are subsequently separated in a water
absorber, and the methane recycled. The chloromethane absorbent,
enriched with the chlorinated products removed from the reaction
gases, is fed to a stripping column. Methyl chloride and some
methylene dichloride go overhead. They are condensed and then
purified by a hot water wash (to remove residual hydrogen chlo-
ride) , an alkali wash, and a strong sulfuric acid wash (to dry
the solvent mixture). The methyl chloride, methylene chloride,
and any heavy ends are separated by fractional distillation.13
Not all the bottoms from the stripping column are recirculated
to the reaction effluent absorber. A considerable portion of the
liquid is fed to a secondary reactor, where more chlorine is
added and a chlorination reaction is again carried out photo-
chemically, but this time in the liquid phase. Hydrogen chloride
is vented from the reactor. The reaction products are purified
and separated by a sequence similar to that used for methyl
chloride and methylene chloride, except that any product less
chlorinated than chloroform is recycled. Desired quantities of
chloroform are removed by distillation, and the remaining
material is chlorinated in a third reactor to produce carbon
tetrachloride.13
There is one source of air pollution. It is a purge on the
recycled methane to remove inerts.15
b. Direct Chlorination of Carbon Disulfide—
Carbon tetrachloride is produced commercially by direct chlorina-
tion of carbon disulfide.
11
-------
(1) Chemistry—The chemical reaction for the chlorination of car-
bon disulfide to produce carbon tetrachloride can be represented
as:13,17,18,a
CS2 + 3C12 •*• S2C12 + CC11+
(carbon disulfide) (chlorine) (sulfur monochloride) (carbon tetrachloride)
(18)
(sul
2S2C12 + CS2 ->• 6S + CGI.*
(sulfur monochloride) (carbon disulfide) (sulfur) (carbon tetrachloride)
(19)
6S + 3C •»• 3CS2 (20)
(sulfur) (carbon) (carbon disulfide)
Iron is used as the catalyst for the reaction. Yields are approx-
imately 90% based on carbon disulfide.
(2) Process—In the direct chlorination process, carbon tetra-
chloride, carbon disulfide, and sulfur chlorides are contacted
directly with excess chlorine at 30°C in the presence of divided
iron catalyst.15 Figure 2 is a simple block flow diagram for the
direct chlorination of carbon disulfide to produce carbon
tetrachloride.l5•a
A slight excess of carbon disulfide feed is treated with sulfur
monochloride in the primary reactor. Unconverted carbon disul-
fide is chlorinated in the chlorinator in the presence of divided
iron catalyst. Effluents from the chlorinator reactor are dis-
tilled to separate crude product as overhead. Molten sulfur con-
taining some sulfur monochloride is removed as bottoms. Sulfur
equivalent to the fresh carbon disulfide feed is separated from
the bottoms and returned to the carbon disulfide plant for
processing. The residual sulfur stream is directly chlorinated
in the sulfur chlorinator to form sulfur monochloride for the
primary reactor.l5
17Austin, G. T. Industrially Significant Organic Chemicals,
Part 3. Chemical Engineering, 81(6):87-92, 1974.
18Kirk-Othmer Encyclopedia of Chemical Technology, Second Edition,
Vol. 5. John Wiley & Sons, Inc., New York, New York, 1967.
pp. 85-281.
Information also provided by personal communication from
J. R. Hofts, FMC Corporation, South Charleston, West Virginia,
November 10, 1076.
12
-------
IRON CAT*
VEN
ATMOS
i
VENT TO
ATMOSPHERE
. CCL
M 4 j ,
i i
(\ f\ (
^^_
1 Y1T X^^^X. ^~"
— 1 UKUUt wtui
CHLORINE
CARBON
DISULFIDE
PHI OPIMATHP UlillLLMMUN
rH^RFArZ COLUMN
^s^KtALlUK i I
-J I 1
X^^^^- X* -^ ^ x^"^ ^ _p
Clll Clip' ^rl
i CAU
PRIMARY SULFUR SEPARATOR
*v REACTOR ^^ — ^CHLORINATOR V^V.^
CHLORINE } 1
Tl
Pf
>.
\Ri
ro
tfRE
cs2 ]
cci4
s2ci2
cci4 J
p«| ICTI/"
LAUbl 11
MIZER
CARBON
TETRACHLORIDE
k
/
PRODUCT
DISTILLATION
COLUMN
f7 Y
ENT HEAVY ENDS
STIC
SULFUR
Figure 2. Carbon tetrachloride by the direct chlorination
of carbon disulfide.
-------
Overhead from the crude distillation column, consisting mainly
of crude carbon tetrachloride, is purified by caustic treatment
and product distillation.15
c. Direct Chlorination of Propane —
Carbon tetrachloride and perchloroethylene are produced commer-
cially by direct chlorination of propane.
(1) Chemistry — The basic chemical equation representing the
direct chlorination of propane to produce carbon tetrachloride
and perchloroethylene is:13'15'19'20
C3H8 + 8C12 •* CClit + C2Clit + 8HC1 (21)
(propane) (chlorine) (carbon (perchloroethylene) (hydrogen
tetrachloride) chloride)
Raw materials used for this process are propane, chlorine, sul-
fur ic acid, copper chloride, barium chloride catalyst, and water.
Products of the reaction are carbon tetrachloride and per-
chloroethylene. Yields for this reaction exceed 90%, based on
propane.1* The byproducts formed during the reaction include
hexachlorobenzene, hexachloroethane, chlorinated waste, hydrogen
chloride, and spent sulfuric acid.13
(2) Process — Figure 3 is a simple block flow diagram for the
production of carbon tetrachloride and perchloroethylene by
direct chlorination of propane.
Fresh chlorine, together with recycled chlorine, and propane are
introduced into a vaporizer where they are mixed with recycled
chlorides. Chlorine is used in 10% to 25% excess.15 The mixed
gases, at atmospheric pressure, are fed to a refractory-lined
reactor. The gases are first heated to ignition point, and the
reaction then takes place adiabatically . The temperature within
the reactor ranges between 550°C and 700°C. After startup, the
reaction is self-sustaining. The reaction temperature is con-
trolled by the diluent action of recycled chlorides which serve
to control the carbon tetrachloride/perchloroethylene ratio.13'15
Effluent from the reactor consists mainly of carbon tetrachloride,
perchloroethylene, hydrogen chloride, and excess chlorine as well
19Elkin, L. M. Chlorinated Solvents. Report No. 48 (a private
report by the Process Economics Program), Stanford Research
Institute, Menlo Park, California, February 1969. 377 pp.
20Hedley, W. H., S. M. Mehta, C. M. Moscowitz, R. B. Reznik,
G. A. Richardson, and D. L. Zanders. Potential Pollutants
from Petrochemical Processes. EPA Contract 68-02-0226, Task 9,
U.S. Environmental Protection Agency, Research Triangle Park,
North Carolina, December 1973. 362 pp.
14
-------
PURGE ON RECYCLED CHLORINE (GAS)
CARBON
TETRACHLORIDE
CARBON
TETRACHLORIDE
COLUMN
CHLORINE
QUENCH
TOWER
PROPANE
VAPORIZER
HEAVIES
DISTILLATION
COLUMN
HEAVY ENDS
J71 I
R*ATERR.
-I^Lr^ DRYER
HCI
ABSORBER
L
T T
HCI SPENT
ACID ACID
HEAVY ENDS
COLUMN
V
PERCHLOROETHYLENE
COLUMN
•^-PERCHLOROETHYLENE
Figure 3. Carbon tetrachloride and perchloroethylene by the
direct chlorination of propane.13'15
-------
as unreacted hydrocarbon. It is quenched by intimate contact
with perchloroethylene to preserve the equilibrium ratio attained
in the reactor, thereby preventing formation of undesirable
byproducts. The hot effluent also serves to heat the contents of
the quench tank, providing boilup for the carbon tetrachloride
column.}5
The carbon tetrachloride column, operating on boilup from the
quench tank, returns bottom liquid that is rich in perchloro-
ethylene to the heavy ends column. Carbon tetrachloride separated
by fractionation is condensed and withdrawn. Hydrogen chloride
and chlorine are separated and scrubbed with water in an hydrogen
chloride absorber to remove HCl as hydrochloric acid byproduct.
The noncondensables are subsequently dried with concentrated
sulfuric acid. Chlorine and some uncondensed chlorides are
recycled to feed.15
In the heavy ends column, the perchloroethylene-rich stream is
distilled to remove the heavy ends that are returned to the
recycle surge tank. Overhead from the heavy ends column is
fractionated in the perchloroethylene column where the desired
quantity of perchloroethylene is removed as bottoms and the
overhead, containing largely carbon tetrachloride, is sent to
recycle.15
The recycle surge tank serves as a reservoir for three recycle
streams:15 (1) the quench tank overflow (largely perchloro-
ethylene and some hexachlorobenzene), (2) heavy ends from the
heavy ends column, and (3) the perchloroethylene overhead
(largely carbon tetrachloride). Proper control results in a
recycle mixture of the desired composition, and this is fed to
the vaporizer to be mixed with the fresh feed.15
d. Direct Chlorination of Ethylene—
Ethylene dichloride is produced commercially by direct chlorina-
tion of ethylene.
(1) Chemistry—The chemical reaction for the direct chlorination
of ethylene to produce ethylene dichloride can be represented as
follows:13. 15, 2°-2"
2 Austin, G. T. Industrially Significant Organic Chemicals,
Part 5. Chemical Engineering, 81 (9) :143-150, 1974.
22Reilly, J. H. Chlorination of Ethylene Chloride. U.S. Patent
2,140,548 (to Dow Chemical Company), December 20, 1938. 1 p.
23Risbud, H. Description of Manufacturing Processes and
Significant Air Emission Points at Ethyl Corporation Houston
Plant. Region VI, Texas Air Control Board, Austin, Texas,
August 1975. 18 pp.
(continued)
16
-------
CH2=CH2 + C12 * C1CH2CH2C1 (22)
(ethylene) (chlorine) (ethylene dichloride)
Ethylene is chlorinated catalytically in a vapor- or liquid-phase
reaction in the presence of ethylene dibromide as an anticatalyst
against polychlorination at temperatures ranging between 50°C and
150°C and at 69 to 138 kPa gage (10 to 20 psig) pressure.15'21
The catalysts used are metallic chlorides; e.g., ferric, aluminum,
copper, or antimony.13'15'22 Commercially, ferric chloride is
employed as a catalyst in a liquid phase system. Yields are re-
ported at approximately 90% based on ethylene theoretical.13'15
(2) Process—Figure 4 is a simple block flow diagram for the
chlorination of ethylene to produce ethylene dichloride.13'15'211
The composition of each process stream is shown in Table 3.21*
Chlorine is mixed with ethylene and fed to a reactor containing
ethylene dibromide and ferric chloride catalyst. The reaction
takes place in the liquid phase with an excess of reaction
products. The reaction is exothermic (217.6 MJ/mole or 52 kcal/
mole), and heat is removed by jacketed walls, internal cooling
coils, or external heat exchange. A liquid and a vapor stream
are obtained from the reactor.*3'21*
The overhead vapor effluent from the reactor is condensed in a
water-cooled condenser or a refrigerated heat exchanger to con-
dense any ethylene dichloride present in the vapor stream.1 3 • 1 5/ 2I*
Noncondensables are sent through a scrubber to remove small
amounts of hydrogen chloride and chlorine before venting to
the atmosphere. Water or dilute caustic is used in the
scrubber.13»1 5'2t*
Liquid effluent from the reactor consisting mainly of crude
ethylene dichloride is cooled, then washed with a 6% to 8% caus-
tic solution. Water is removed either by coalescing and phase
separation or by phase separation and light ends distillation.
Ethylene dichloride is obtained as overhead in a heavy ends
distillation column. The bottoms comprised mainly of heavy ends
is further separated into useful chlorinated hydrocarbons and
tar.13,15,"
e. Direct Chlorination of Carbon Monoxide—
Phosgene is manufactured by direct chlorination of carbon
monoxide.
(continued)
2l*Pervier, J. W. , R. C. Barley, D. E. Field, B. M. Friedman,
R. B. Morris, and W. A. Schwartz. Survey Reports on Atmospheric
Emissions from the Petrochemical Industry, Volume II. EPA-450/
3-73-005-b (PB 244 958), U.S. Environmental Protection Agency,
Research Triangle Park, North Carolina, April 1974. 332 pp.
17
-------
00
VENT TO
ATMOSPHERE
SCRUBBER
WATER OR
DILUTE CAUSTIC
WASTEWATER
6% CAUSTIC
WASH
TOWER
SEPARATOR
IUVVCK I
u »
>^-^ PAIIC
CAUSTIC
WASTE
r
?) ETHYLENE
DlCHLORIDE
TO STORAGE
HEAVY ENDS
COLUMN
HEAVY ENDS
I
TAR'
USEFUL
-CHLORINATED
HYDROCARBONS
Figure 4. Ethylene dichloride by the direct chlorination
Etnyiene aicnloriae by
of ethylene.3'13'15'24
Composition of each stream is shown in Table 3.
-------
TABLE 3. MATERIAL BALANCE FOR ETHYLENE DICHLORIDE BY DIRECT CHLORINATION OF ETHYLENE2''
(kg/kg of product)
Component
Ethylene
Chlorine
Inerts
C02
02
N2
H2
Ethylene dichloride
Ethylene trichloride
Hydrogen chloride
Tar
TOTAL
1 2
Ethylene Chlorine
feed feed
0.2916
.0.7258
0.0040
0.0087
0.0076
0.0002
0.2916 0.7463
3
Total
feed
0.2916
0.7258
0.0040
0.0087
0.0076
0.0002
1.0379
4 and 5
Reactor
effluent
0.0031
0.0001
0.0040
0.0087
0.0076
0.0002
1.0030
0.0101
0.0004
0.0007
1.0379
a
Stream number
6 7
Scrubber
Product vent
0.0031
0.0040
0.0087
0.0076
0.0002
0.9990 0.0022
0.0010
1.0000 0.0258
8
Acid, chlorine,
and ethylene
dichloride in
scrubber waste
0.0001
0.0018
0.0004
0.0023
9 10
Useful
heavy
ends Tar
0.0091
0.0007
0.0091 0.0007
Stream numbers are indicated in Figure 4.
NOTE: Blanks indicate component not present in stream.
-------
(1) Chemistry—The chemical reaction for the chlorination of
carbon monoxide to produce phosgene can be represented as
follows:25-27
activated
charcoal
CO + C12 + COC12 (23)
(carbon monoxide) (chlorine) (phosgene)
There are no byproducts formed during this reaction, and yields
are approximately 99% based on carbon monoxide.15'25
(2) Process—Figure 5 is a simple block flow diagram for the
chlorination of carbon monoxide to produce phosgene.13•l5'a
Carbon monoxide and chlorine are separately dried, filtered, and
fed into the chlorinator reactor. Temperature within the reactor
is approximately 200°C, and pressure is 14 to 28 kPa gage (2 to
4 psig).l 3'15'2^ The reactor is equipped with water-cooled tubes
and is filled with activated charcoal. The reaction is very
rapid and exothermic. Efficient heat removal is important to
avoid reversion of phosgene into its raw materials.
Reactor effluents flow into a condenser where liquid phosgene is
separated from the system. Noncondensables are sent to an
absorber where toluene or benzene serves as a solvent for the
removal of final traces of phosgene. Phosgene is separated from
the solvent in the solvent still and is recycled back to the
condenser.13
f. Direct Chlorination of Benzene—
Monochlorobenzene and para- and ortfco-dichlorobenzenes are produced
commercially by direct chlorination of benzene.
25Austin, G. T. Industrially Significant Organic Chemicals,
Part 8. Chemical Engineering, 81(15):107-116, 1974.
26Lord, A., and H. 0. Pritchard. Thermodynamics of phosgene
formation from carbon monoxide and chlorine. Journal of
Chemical Thermodynamics, 2 (2):187-191, 1970.
27Shreve, R. N. The Chemical Process Industries. 3rd Edition.
McGraw Hill Book Company, Inc., New York, New York, 1967. 905 pp.
Information also provided by personal communication with
R. A. Coates, Mobay Chemical Company, New Martinsville, West
Virginia, April 1, 1976.
20
-------
VENT
COLD WATER
CHLORINE
BRINE-
c
CARBON MONOXIDE
REACTOR CONDENSER
ABSORBER
;w
SOLVENT
DISTILLATION
STILL
BENZENE OR TOLUENE
PHOSGENE
Figure 5. Phosgene by the direct chlorination of
carbon monoxide.
(1) Chemistry — The basic chemical equations representing the
chlorination of benzene to produce monochlorobenzene and dichloro
benzene are: l 3~l si l 8 i 28» 29
C6H6
(benzene)
C12
(chlorine)
20°C to 60°C
C6H5C1
(monochlorobenzene)
HC1
(hydrogen chloride)
(24)
C6H5C1 + C12 -> C6Hi,Cl2 + HC1
(monochlorobenzene) (chlorine) (dichlorobenzene) (hydrogen chloride)
(25)
28Sittig, M. Pollution Control in the Organic Chemical Industry,
Noyes Data Corporation, Park Ridge, New Jersey, 1974. 304 pp.
29Austin, G. T. Industrially Significant Organic Chemicals,
Part 7. Chemical Engineering, 81(13) :149-156 , 1974.
21
-------
Raw materials used for the process are benzene, chlorine, iron
turnings as catalyst, and sodium hydroxide. Products of the
reaction are monochlorobenzene and dichlorobenzene. Byproducts
formed during the process include hydrogen chloride, spent caus-
tic sludge and chlorinated waste. Yields of monochlorobenzene
are approximately 75%, while dichlorobenzene yields are 10% to
20% based on benzene.15
(2) Process—Figure 6 is a simple block flow diagram for the
chlorination of benzene to produce monochlorobenzene and dichloro-
benzene .13-15,29
Iron turnings are used to catalyze the reaction between liquid
phase dry benzene and gaseous chlorine. The chlorine is bubbled
into the charge at a rate sufficient to maintain a temperature
at 40°C to 60°C. The product distribution varies with the quan-
tity of chlorine added to the reactors; for monochlorobenzene
only, the chlorination temperature is maintained at about 40°C
and about 60% of the theoretical chlorine used.13'15 When all
the benzene is chlorinated, the reaction is run at the higher
temperature (55°C to 60°C) and a density of 1.280 (15°C) is
reached in about 6 hours.
The hydrogen chloride produced is scrubbed with benzene or chlo-
robenzene to remove entrained organics and is absorbed in water
to produce commercial-grade hydrochloric acid. Vent gas from the
absorber/scrubber contains a small amount of residual HC1.13'15
Product crude chlorobenzene from the reactor kettle is agitated
in a steam-jacketed neutralizer with warm dilute (10%) sodium
hydroxide solution to remove residual acidity. After neutra-
lization, the bulk of the dichlorobenzene is retained in the
sludge which is sent for recovery by distillation. Supernatant
liquor from the separator is sent to fractionating towers for
recovery of benzene, monochlorobenzene, and dichlorobenzene.13'14
If the chlorination is carried out so that the theoretical quan-
tity of chlorine is consumed (100% chlorination), the following
fractions are obtained in approximately the indicated percentages:
Percent
Benzene and water 3
Benzene and chlorobenzene 10
Chlorobenzene 75
Chlorobenzene and dichlorobenzenes 10
Resinous materials and loss 2
The first two fractions are returned to the system for further
processing, and the third (chlorobenzene) is run to storage. The
fourth fraction is allowed to accumulate and is then distilled.
The para isomer is collected in the distillate; the residue con-
tains the ortho isomer contaminated with some para isomer and
polychlorobenzenes, principally 1,2,4-trichlorobenzene. Of the
22
-------
BENZENE OR
CHLOROBENZENE'
HCI
ABSORBER
M
OJ
HCISCRUBBER
"VENT TO ATMOSPHERE
-WATER
TAIL GAS
SCRUBBER
T
i
CATALYSJj
I RON TURN INGS
HYDROCHLORIC ACID
(CAUSTIC
NEUTRALIZER I SETTLER
| _ SETTLER
-&
SPENT DICHLOROBENZENE
CAUSTIC SLUDGE TO RECOVERY
N
Sf
CD S
-ORTHO AND PARA
DICHLOROBENZENE
MONOCHLOROBENZENE
TRICHLOROBENZENE AND
POLYCHLORINATED
AROMATIC RESINOUS
MATERIAL
Figure 6. Monochlorobenzene and dichlorobenzene by the direct
chlorination of benzene.13'15'29
-------
two isomeric dichlorobenzenes, (practically no meta isomer
formed), the para compound is formed in the larger quantity; the
ratio of para to ortho is approximately 3:1. The composition of
the chlorinated products varies according to the chlorination
temperature, rate, degree, and catalyst. However, a 100% chlo-
rination will yield approximately the following composition:
chlorobenzene - 80%; p-dichlorobenzene - 15%; and o-dichloroben-
zene including polychlorobenzenes - 5%. Distillation residues
discharged from the fractionating columns contain about 0.04 kg
of polychlorinated aromatic resinous material per kilogram of
monochlorobenzene product, and these are discharged to solid
waste disposal.1**
2. Hydrochlorination
Hydrochlorination involves the reaction of a hydrocarbon with
hydrogen chloride. The products and processes used to manufac-
ture chlorinated hydrocarbons pertinent to this study are
summarized in Table 4 together with the chemical equation repre-
senting each reaction.
TABLE 4. HYDROCHLORINATION PROCESSES
Equation
Product Manufacturing process Chemical reactions No.
catalyst
Methyl chloride Hydrochlorination of methanol CHjOH + HC1 •• CHsCl + H2<> 26
liquid phase
catalyst
Ethyl chloride Hydrochlorination of ethylene CjHi, + HC1 » C2HsCl 27
catalyst
1,1,1-Trichloroethane Hydrochlorination of vinyl chloride CHj'-CHCl + HC1 »• CjH^Cl; 28
(by hydrochlorination, then chlorination) C2H^C12 * Cli •» CH3CC13 + HC1 29
As shown in Table 4, a typical hydrochlorination reaction can be
represented by a general chemical equation such as:
catalyst
Hydrocarbon + hydrogen chloride >• chlorinated hydrocarbon + (byproducts)
(30)
The overall stoichiometric equation describing hydrochlorination
processes is:
C H ClzOw + (K^HCl + CaHbCld + (K2)H20 (31)
where Kj = d - z
_ d + y-z -b
K2
24
-------
The hydrochlorination process used in the manufacture of the
above-mentioned three chlorinated hydrocarbons consists of three
basic steps: (1) hydrochlorination, (2) absorption, and (3) sep-
aration.
Chlorinated hydrocarbons are formed by the reaction of the hydro-
carbon and hydrogen chloride in the presence of a catalyst. The
reaction depends on various factors including hydrocarbon used,
catalyst used, reaction temperature and pressure, and the ratio
of hydrocarbon to hydrogen chloride. Effluents from the hydro-
chlorinator reactor include crude product, byproducts, unreacted
raw materials, and catalyst.
The second step of the hydrochlorination process is absorption.
Reactor effluents are passed through an absorber to condense and
recover unreacted raw materials. Hydrogen chloride not removed
in the absorber is neutralized by scrubbing with caustic.
The third step of the process is fractional distillation where
the product is separated from the byproducts and waste. Separa-
tion can be one operation or a series of operations, including
stripping, decanting, or distillation. The final product is
withdrawn and sent to storage.
a. Hydrochlorination of Methanol—
Chloromethanes are manufactured by hydrochlorination of methanol.
(1) Chemistry—The chemical reaction for the hydrochlorination
of methanol to produce methyl chloride can be represented as
follows:13-15/1?*28
catalyst
CH3OH + HC1 •* CH3C1 + H20 (32)
(methanol) (hydrochloric liquid phase (340°C) (methyl (water)
acid) chloride)
Zinc chloride on pumice, cuprous chloride, or activated charcoal
is used as catalyst. Yield for the reaction is 90% to 95%, based
on methanol.l7
(2) Process—Figure 7 is a simple block flow diagram for the
hydrochlorination of methanol to produce methyl chloride.13"15
During startup operation, the plant uses an external supply of
HC1 to react with methanol to produce methyl chloride. Subse-
quently, the plant generates the hydrogen chloride needed via
the reaction of chlorine with methyl chloride and with methyl
chloride chlorination products recycled from the various puri-
fication towers. Reactions occurring in the thermal chlorinator
are: l1*, 15, 17,28
CH3C1 + C12 -»• CH2C12 + HC1 (33)
(methyl (chlorine) (methylene (hydrochloric
chloride) chloride) acid)
25
-------
METHANOL
REACTOR
—WATER
QUENCH
TOWER
WEAK ACID
TO RECOVERY
HYDROGEN CHLORIDE
A
NJ
CTi
INITIAL
PRODUCT
RECOVERY
CAUSTIC
SODA
SCRUBBER
METHYL
CHLORIDE
TOWER
DRYING
TOWER
T T
SPENT
CAUSTIC
SPENT
ACID
A
QUENCH
TOWER
y^
THERMAL
CHLORINATOR
A" *
METHYLENE
CHLORIDE
TOWER
METHYL CHLORIDE
-CHLORINE
CHLOROFORM
TOWER
Y
CARBON
TETRACHLORIDE
TOWER
Y
CARBON TETRACHLORIDE
-»~ METHYLENE CHLORIDE
"*" CHLOROFORM
Figure 7.
HEAVY ENDS
Methyl chloride by the hydrochlorination of methanol.14'15
-------
CH2C12 + C12 •* CHC13 + HC1 (34)
(methylene (chlorine) (chloroform) (hydrochloric
chloride) acid)
CHC13 + C12 -»• CC14 + HC1 (35)
(chloroform) (chlorine) (carbon (hydrochloric
tetrachloride) acid)
The excess hydrogen chloride produced in the reaction is separ-
ated, dried, compressed, and sold as anhydrous HC1.
Hydrogen chloride and methanol react in the liquid phase in the
presence of a catalyst to produce methyl chloride. The methyl
chloride vapor phase is quenched, washed with caustic soda solu-
tion to remove traces of hydrogen chloride, and dried with sul-
furic acid prior to transfer as a liquid to product storage . * 3 i l 4
The weak acid produced in the quench tower is fortified with
hydrogen chloride gas and sold as commercial hydrochloric acid.
Spent caustic solution and spent sulfuric acid "bleeds" are
neutralized and discharged to the water treatment facilities.1**
Mixed chloromethanes formed in the thermal chlorinator reactor
after separation of hydrogen chloride are fractionated to recover
the chlorinated hydrocarbon solvents. A portion of the methyl
chloride, methylene chloride, and chloroform from the fractiona-
tion towers is recycled to produce hydrogen chloride. The remain-
der is sent to storage as product. Carbon tetrachloride after
rectification goes to storage as product. Heavy ends composed of
higher chlorinated hydrocarbons (predominantly crude hexachloro-
benzene and hexachlorobutadiene) are sent to the waste disposal
system. 1 **
b. Hydrochlorination of Ethylene —
Ethyl chloride is manufactured by hydrochlorination of ethylene.
(1) Chemistry — The chemical reaction for the hydrochlorination
of ethylene to produce ethyl chloride can be represented as
follows:13-15'21'28
A1C1 3
C2Hi, + HC1 -»• C2H5C1 (36)
(ethylene) (hydrochloric 35°C to 40°C (ethyl
acid) chloride)
Anhydrous hydrogen chloride, in the presence of aluminum chloride,
reacts with ethylene in both liquid and vapor phases to give 90%
to 95% yields of ethyl chloride based on ethylene13'11*'21 Yields
of polychloro compounds are reduced by the addition of ethylene
dichloride to the reaction mixture.11*
27
-------
(2) Process — Figure 8 is a simple block flow diagram for the
hydrochlorination of ethylene to produce ethyl chloride. This
continuous hydrochlorination process accounts for 88% of ethyl
chloride production.13"15'21
Ethylene gas and hydrogen chloride from storage tanks are fed to
a mixer where equimolar quantities are combined. The gaseous
mixture is fed to a reactor partially filled with ethylene
dichloride. Temperature within the reactor ranges between 40°C
and 45°C, and the pressure is 277 kPa gage (40 psig) . Under
these conditions and in the presence of aluminum chloride
catalyst, the exothermic hydrochlorination of ethylene to produce
ethyl chloride takes place.13"15
Vaporized products from the reactor include ethyl chloride, hydro-
polymer oil, and miscellaneous chlorinated hydrocarbons. Effluents
from the reactor are sent to a separator where the hydropolymer
oil (0.02 kg per kg of ethyl chloride) is separated to be sold as
byproducts. Crude ethyl chloride is refined by fractionation .
Chlorinated hydrocarbon tails, obtained as bottoms (0.093 kg per
kg of ethyl chloride) , are sent to chlorinated solvent manufac-
turers. Ethylene dichloride detained in the fractionation column
is recycled back to the reactor. Pure ethyl chloride obtained as
overhead in the fractionator is sent to storage.11*
c. Hydrochlorination of Vinyl Chloride —
Hydrochlorination of vinyl chloride followed by direct chlorina-
tion is commercially used for the manufacture of
1,1, 1-trichloroethane .
(1) Chemistry — The chemical reactions for the hydrochlorination
and chlorination of vinyl chloride to produce
1,1, 1-trichloroethane can be represented as follows:13"15
Fed 3
CH2=CHC1 + HC1 -* (37)
(vinyl (hydrogen 35°C to 40°C CZE^C'\.2
chloride) chloride) (dichloroethane)
+ C12 •* CH3CCl3 + HC1 (38)
(dichloroethane) (chlorine) 400°C (1,1, 1-trichloroethane) (hydrogen
chloride)
The yield is 95% based on vinyl chloride in the presence of
ferric chloride catalyst.13
(2) Process — Figure 9 is a simple block flow diagram for the
hydrochlorination and chlorination of vinyl chloride to produce
1 , 1 , 1-trichloroethane . 1 3~ 1 5 , i 9
28
-------
ETHYLENE
HYDROGEN
CHLORIDE
M
VO
PURGE ON RECYCLED
ETHYLENE (GAS)
ETHYLENE RECYCLE
ETHYL CHLORIDE
FRACTIONATING
-9
•^
SP
1^ ALUMINUM •>"-'
REACTOR CHLORIDE
V M
ENT CATALYST
rtKttl
UR COLUMN
L
T Y
(TO REGENERATION) POLYMER HEAVY ENDS
BOTTOMS
(HYDROPOLYMEROIL)
i
ETHYLENEDICHLORIDE
Figure 8. Ethyl chloride by the hydrochlorination of ethylene.l3•15~2l
-------
HYDROGEN CHLORIDE +TRICHLOROETHANE +DICHLOROETHANE
U)
o
HYDROCHLORINATOR VENT
TO ATMOSPHERE
DICHLOROETHANE
TRICHLOROETHANE
HYDROGEN CHLORIDE
DICHLOROETHANE
HYDROGEN
CHLORIDE
VINYL CHLORIDE
DECANTER^
J
PURIFICATION
STEAM STRIPPER
GAS EFFLUENTS
DICHLOROETHANE
TRICHLOROETHANE
VINYL CHLORIDE
HYDROCHLORINATOR
REACTOR
)R
JLUITII
CHLORINE „„..
«— STEAM
CHLORINATOR STRIPPER
REACTOR _^
STEAM
t
T
1.1.1 TRICHLOROETHANE
Figure 9.
STEAM STRIP PER
EFFLUENT CONTAINING
CHLORINATED ORGAN ICS
1,1,1-Trichloroethane by the hydrochlorination and direct
chlorination of vinyl chloride.13'15
-------
Vinyl chloride, makeup and recycled hydrogen chloride, recycled
dichloroethane, and recycled trichloroethane are fed to a tower
reactor for the catalyzed hydrochlorination reaction, which
produces the dichloroethane intermediate. The hydrochlorination
reaction takes place at 35°C to 40°C in the presence of ferric
chloride catalyst.13"15
Dichloroethane, obtained as overhead from the purification column,
is chlorinated in the chlorinator reactor at a temperature of
400°C to form 1,1,1-trichloroethane and hydrogen chloride. Crude
trichloroethane, the hydrogen chloride produced, and excess
dichloroethane are recycled to the hydrochlorinator reactor.
Crude trichloroethane, obtained as the high boiling fraction from
the purification column, is steam stripped and distilled to pro-
duce 1,1,1-trichloroethane for storage and sales.13"15
3. Oxyhydrochlorination
Oxyhydrochlorination entails the chlorination of a hydrocarbon
with hydrogen chloride and oxygen (air). The products and proc-
esses used to manufacture chlorinated hydrocarbons pertinent to
this study are summarized in Table 5 together with the chemical
equation representing each reaction.
TABLE 5 OXYHYDROCHLORINATION PROCESSES
Equation
Product Manufacturing process Chemical reactions No.
Ethylcne dichloride Oxyhydrochlorination of ethylene 2CH2=012 * O2 + 4HC1 * 2C1CH2CH2C1 + 2H2O 39
Tnchloroethylene Oxyhydrochlorination of ethylene dichloride C1CH2-CH2C1 + O2 + HC1 - C2HC13 + 2H2O 40
As indicated in Table 5, a typical Oxyhydrochlorination reaction
can be represented by a general chemical equation, such as:
, , , . . . hydrogen chlorinated . ., , . . / „ n N
hydrocarbon + oxygen (air) +:,.,-»•., . + water + (byproducts) (41)
3 '^ chloride hydrocarbon
The overall stoichiometric equation for Oxyhydrochlorination
processes is:
C H ClzOw + (K^HCl + (K2)O2 ^ CaHbCld + (K3)H2O (42)
where Kj = d - z
_ d + y - z - b w
K2 4 2
d + y - z - b
J\ Q — A
£,
31
-------
The oxyhydrochlorination process used in the manufacture of the
above two chlorinated hydrocarbons consists of three basic steps:
(1) oxyhydrochlorination, (2) absorption, and (3) separation.
Oxyhydrochlorination reactions are usually exothermic. In the
reactor, which must be designed for efficient heat removel,
hydrocarbon, hydrogen chloride, and oxygen react to form the
chlorinated hydrocarbon. The reaction is dependent on various
factors, including hydrocarbon and catalyst used, reaction tem-
perature and pressure, and the ratio of hydrogen chloride to
hydrocarbon. The effluents from the reactor include crude pro-
duct, byproducts, unreacted raw materials, and catalyst (when
used).
Resulting reaction products are sent to an absorber where
unreacted hydrogen chloride is removed and the reaction products
are condensed. Remaining hydrogen chloride is removed by scrub-
bing with caustic. Crude product is then purified by separation.
Separation can be carried out in a single unit or a series of
multiple units and includes distillation, stripping, or phase
separation. Pure product is separated from byproducts and is
withdrawn and sent to storage.
a. Oxyhydrochlorination of Ethylene—
Ethylene dichloride is manufactured by oxyhydrochlorination of
ethylene.
(1) Chemistry—The chemical reaction for the oxyhydrochlorina-
tion of ethylene to produce ethylene dichloride can be represented
as follows:13'15'21'30-32
2CH2=CH2 + 02 + 4HC1 -> 2C1CH2CH2C1 + 2H2O (43)
(ethylene) (oxygen) (hydrogen (ethylene (water)
chloride) dichloride)
Air and hydrogen chloride react with ethylene in a fluidized-
or fixed-bed catalytic process to produce ethylene dichloride.
The catalyst used is a mixture of copper chloride and other
chlorides. Reactor temperature varies between 180°C and 280°C,
30DeForest, E. M., and S. E. Penner. Fired-Bed Oxychlorination
yields 1,2-Dichloroethane. Chemical Engineering, 79 (17) :54-55,
1972.
3 Schwartz, W. A., F. B. Higgins, Jr., J. A. Lee, R. Newirth, and
J. W. Pervier. Engineering and Cost Study of Air Pollution
Control for the Petrochemical Industry, Volume 3: Ethylene
Dichloride Manufacture by Oxychlorination. EPA-450/3-73-006-C
(PB 240 492), U.S. Environmental Protection Agency, Research
Triangle Park, North Carolina, November 1974. 104 pp.
32Hahn, A. V. The Petrochemical Industry, Market and Economics.
McGraw-Hill Book Company, New York, New York, 1970. 620 pp.
32
-------
and pressure ranges from 340 to 680 kPa gage (50 to 100 psig).
Yields are over 90% based on ethylene, depending on the presence
of excess ethylene or hydrogen chloride. Excess hydrogen
chloride favors the reaction.13'15
(2) Process—Figure 10 is a simple block flow diagram for the
oxyhydrochlorination of ethylene to produce ethylene dichlo-
ride.13'15'30'31 Stoichiometric amounts of ethylene, anhydrous
hydrogen chloride, and air are fed to a catalytic reactor. The
air is compressed and preheated prior to entering the reactor as
a means of initiating the reaction. Conversion of ethylene is
virtually complete in one flow through the reactor. The reaction
is highly exothermic,, and heat is recovered, as steam, with
internal cooling coils or fixed-bed multitube reactors, which
resemble a heat exchanger, with the catalyst contained inside the
tubes, while coolant flows through the shell.31
Effluent from the reactor is cooled by either direct water quench
or indirect heat exchange. Condensed effluent is sent to a phase
separator. Noncondensable gases consisting mainly of nitrogen
are contacted in an absorber with either water or aromatic solvent
for removal of HC1 and recovery of ethylene dichloride before
venting to the atmosphere.15'3*
The organic liquid product obtained in the phase separator and
from the ethylene dichloride stripper is contacted with aqueous
caustic soda to neutralize any remaining hydrogen chloride.
Effluent from the neutralizer is distilled for removal of water
and chlorinated hydrocarbon impurities, which are recovered as
overhead and sent to waste disposal.15'31 Bottoms from the heads
column, which consist mainly (96% to 98%) of ethylene dichloride,
are sent to the final products finishing column. Pure ethylene
dichloride is obtained as overhead and sent to storage. Bottoms
consisting of heavy ends are sent to waste disposal.31
b. Oxyhydrochlorination of Ethylene Dichloride—
Trichloroethylene is manufactured by oxyhydrochlorination of
ethylene dichloride.
(1) Chemistry—The chemical reaction for the oxyhydrochlorina-
tion of ethylene dichloride to produce trichloroethylene can be
represented as follows:13'15'19
O2 + HCl + C1CH2CH2C1 -»• C2HC13 + 2H2O (44)
(oxygen) (hydrogen (ethylene (trichloroethylene) (water)
(air) chloride) dichloride)
Copper chloride is used as catalyst in a vapor phase reaction at
300°C to 400°C under 690 kPa gage (100 psig) pressure.28
33
-------
VENT TO
ATMOSPHERE
OJ
ABSORBER
CHLORIDE
T
VENT TO
ATMOSPHERE
VENT TO
ATMOSPHERE
ETHYLENE
DlCHLORIDE
STRIPPER
Y
HEADS
COLUMN
SPENT
CAUSTIC
ETHYLENE
DICHLORIDE
I — ^
ETHYLENE
BICHLORIDE
FINISHING
COLUMN
HEAVY ENDS
Figure 10.
Ethylene dichloride b
of ethylene.13,15,30,
the oxyhydrochlorination
-------
(2) Process—Figure 11 is a simple block flow diagram for the
oxyhydrochlorination of ethylene dichloride to produce
trichloroethylene.13»15,33-37
Air, ethylene dichloride, and an excess of hydrogen chloride (or
chlorine) are mixed in a tubular reactor at 300°C to 400°C and
^690 kPa gage. The reaction is highly exothermic and requires
cooling of the reactor.l 3 '1 5 • 3I*~37
Effluents from the reactor pass through an absorber where excess
hydrogen chloride is absorbed. Absorbed products are condensed
after caustic scrubbing. The noncondensables are recycled to the
absorber and, if still not condensed, vented to the atmosphere.
Crude product from the phase separator is fed to the stripper,
where the heavy ends are separated from the crude trichloro-
ethylene. Effluent from the stripper is fed to a product
purification column where light ends are fractionated from the
pure product. Trichloroethylene is obtained as bottoms and fed
to product storage.13,15,19,33,34,38
4. Chlorohydrination
Chlorohydrination reactions consist of chlorination of a hydro-
carbon with hypochlorous acid. The products and processes used
to manufacture chlorinated hydrocarbons pertinent to this study
are summarized in Table 6 together with the chemical equation
representing each reaction.
33Improvements in or relating to Perchloroethylene and Hydrogen
Chloride Manufacture. British Patent 856,664 (to Diamond
Alkali Company), December 21, 1960. 7 pp.
34PPG Industries: Chlorinated Solvents from Ethylene. Chemical
Engineering, 76(26):90-91, 1969.
35Perchlor and trichlor (per/tri) - PPG Industries. Hydrocarbon
Processing, 52(11):157, 1973.
36Kroop, J. F., and G. R. Neikirk. Oxychlorinate for per/tri.
Hydrocarbon Processing, 51(11):109-110, 1972.
37Perchloroethylene-trichloroethylene - PPG Industries, Inc.
Hydrocarbon Processing, 54(11):169, 1975.
3Production of Chlorinated Hydrocarbons. British Patent 913,040
(to Pittsburgh Plate Glass Company), December 12, 1962. 9 pp.
35
-------
U)
CTl
VENT TO
ATMOSPHERE
1 1
tm
/*S
ETHYLENE . ABSORBER £=
tiniLciMC x^^S. WATER IN
DICHLORIDE— ». ^J/v«itK IIM ^_j
AIR*- REACTOR _^
^ } ». L-^- i^
111,1 y^1"^/ WATtR OUT I
VY^
S~
PHAS
1 »~SEPARA
AND SCRUB
CONDENSER
ff— *~ COOLANT IN
It*— COOLANT OUT
LcONDENSER H
If-— *• WATER OUT
|^ — WATER IN p
L
E CAUSTIC j
TOR
T
SPENT
CAUSTIC
^
EAVY ENDS
STRIPPER
to»
p*- LIGHT ENDS
o
§
-^ o:
7 7
1 L^
1EAVYENDS TRICHLOROETHYLENE
Figure 11.
Trichloroethylene by the oxyhydrochlorination of
ethylene dichloride.13»15• 3^-37
-------
TABU 6. CHLOROHYDRINATION PROCESSES
Equation
Product Manufacturing process Chemical reactions _ No.
Epichlorohydrin Chlorohydrination of allyl chloride Cli + H2O^±HC1 + HOC1 15
C1CH2-CH-CH2 + HOC1 •» C1CH2-CHC1-CH2OH 46
2C1CR2-OBC1-CI<2OH + C«(OH)2 * 2C1CH2-CH-CII2 + CaClj + 2H2O 47
O
Propylene oxide Chlorohydrination of propylene C12 + R2O)^HC1 + HOC1 48
CH3-CH-CH2 + HOC1 * CH3-CHC1-CH2OH 49
2CH3-CHC1-CH2OH + Ca(OH>2 » 2CH3-CH-CH2 * CaCl2 * 2H2O SO
0
A typical Chlorohydrination reaction can be represented by a
general chemical equation such as:
Hydrocarbon + chlorine + water + calcium hydroxide ->•
hydrogen chloride + water + calcium chloride + chlorinated hydrocarbon (51)
The overall stoichiometric equation describing Chlorohydrination
processes is:
C H Cl + (KOHOCl + (K2)Ca(OH) -»• C H.C1,O + (K3)H2O + (Ki,)CaCl2 (52)
w x y SL D u 6
where K: = |(2e + x-b + |
K2 = K4 = (2e + x-b-d + y)
K3 = e + x - b
The Chlorohydrination process used in the manufacture of the
above two chlorinated hydrocarbons consists of five basic steps:
(1) acid generation, (2) Chlorohydrination, (3) separation,
(4) conversion, and (5) separation.
Hypochlorous acid is generated by dissolving chlorine in water in
a packed tower. The hydrocarbon is chlorohydrinated with hypo-
chlorous acid in a stirred tank reactor. Reactor effluents are
separated by phase separation into unreacted hypochlorous acid,
which is recycled back to the packed tower, and chlorohydrin .
Chlorohydrin is fed to the second reactor where it is converted
by reaction with lime slurry to the required product. Effluent
from the converter (second reactor) is separated into crude
product and byproducts. The crude product is further fraction-
ated to recover pure product and byproducts.
a. Chlorohydrination of Allyl Chloride —
Epichlorohydrin is produced by Chlorohydrination of allyl chloride,
37
-------
(1) Chemistry—The chemical reactions for the chlorohydrination
of allyl chloride to produce epichlorohydrin can be represented
as follows:13
30°c to 40°c
C1CH2CH=CH2 + HOC1 >• C1CH2-CHC1-CH2OH
(allyl chloride) (hypochlorous acid) (dichlorohydrin)
(53)
60°C to 70°C
2C1CH2-CHC1-CH2OH + Ca(OH)2 »• 2C1CH2-CH-CH2 + CaCl2 + 2H2O
(dichlorohydrin) (slaked \/ (calcium (water)
lime) O chloride)
(epichlorohydrin)
(54)
(2) Process—Figure 12 is a simple block flow diagram for the
production of epichlorohydrin by chlorohydrination of allyl
chloride.l3
Allyl chloride is fed continuously to a stirred tank where it
reacts at atmospheric pressure and at 30°C to 40°C in the liquid
phase with a solution of hypochlorous acid.11* Hypochlorous acid
is produced in a packed tower by dissolving chlorine in water.
Reaction tank effluent is fed to a separator, and the upper layer
(aqueous phase) is recycled to the hypochlorous acid tower.1**
The bottoms, chiefly dichlorohydrins, are fed to the second
agitated reactor, where virtually quantitative conversion to
epichlorohydrin occurs by reaction with lime slurry. Trichloro-
propane is used as a solvent for the epichlorohydrin. 1 "* Effluent
from the second reactor is steam stripped, removing epichloro-
hydrin as the water azeotrope. The bottoms, calcium chloride
solution, and excess lime in suspension are sent to byproduct
recovery or discharged to the water treatment facility. The
water and organic phases in the distillate are separated, and the
bottoms are fed to a fractionating tower for recovery of
epichlorohydrin and solvent. Purified epichlorohydrin is sent to
storage. Recovered solvent is recycled.13'11*
b. Chlorohydrination of Propylene—
Propylene oxide is manufactured by chlorohydrination of propylene.
(1) Chemistry—The chemical reactions for the chlorohydrination
of propylene to produce propylene oxide can be represented as
follows:13'15'25'39"*2
39Fyvie, A. C. Propylene Oxide and Its Derivatives. Chemistry
and Industry, 83(10):384-388, 1964.
**°Stobaugh, R. B., V. A. Calarco, R. A. Morris, and L. W. Stroud.
Propylene Oxide: How, Where, Who - Future. Hydrocarbon Proc-
essing, 52(1):99-108, 1973.
* (continued)
38
-------
VENT TO
ATMOSPHERE
KALLYL CHLORIDE)
VENT TO
ATMOSPHERE
U)
\D
ALLYL CHLORIDE
CHLORINE
TRICHLOROPROPANE
HYDROGEN CHLORIDE
EPICHLOROHYDRIN
ALLYL
CHLORIDE
LIME SLURRY
TRICHLOROPROPANE
SOLVENT
STRIPPER
CaCL
SEPARATOR
EPICHLOROHYDRIN
PRODUCT
FRACTIONATOR SOLVENT
^TRICHLOROPROPANE
TO RECYCLE
T
WATER HEAVY
CONTAINING ENDS
DICHLOROHYDRIN
Figure 12.
Epichlorohydrin by the chlorohydrination
of allyl chloride.13, I1*
-------
CH3CH=CH2 + HOC1 •* CH3-CH-CH2 (55)
(propylene) (hypochlorous acid) | |
OH Cl
(propylene chlorohydrin)
2CH3-CH-CH2 + Ca(OH)2 •»• 2CH3-CH-CH2 + CaCl2 + 2H2O (56)
| | (slaked \/ (calcium (water)
OH Cl lime) 0 chloride)
(propylene (propylene
chlorohydrin) oxide)
In aqueous solution, several reactions occur in addition to the
chlorohydrination reaction. Byproducts include isomers of pro-
pylene chlorohydrin, propylene dichloride, dichlorodiisopropyl
ether, and chloroacetone.*9
The saponification reaction must be completed rapidly since pro-
pylene chlorohydrin is volatile and, if unconverted, may be lost
in the aqueous effluent. Propylene oxide formed in the above
manner is rapidly hydrated to monopropylene glycol by the alka-
line conditions in the reactor. Therefore, it is important that
the oxide be recovered from the solution as quickly as possible
after it is formed.39
(2) Process—Figure 13 is a simple block flow diagram for the
production of propylene oxide by the chlorohydrination of
propylene. l 3 • 1 = / 39, "»0 ,43 Propylene, chlorine, and water are
introduced into a reactor where they react under controlled con-
ditions to form propylene chlorohydrin. Actually, the chlorine
and water react to form hypochlorous acid (HOC1) and hydrochloric
acid (HC1) which, under the conditions in the tower, react much
more rapidly with the propylene present than the chlorine does.
The chlorine/propylene ratio of the gaseous feed to the tower is
so chosen that the liquid ef-fluent leaving the tower contains
3% to 4% propylene chlorohydrin.13 It is necessary to operate in
dilute solution to avoid a separate propylene chloride oil phase
which would preferentially dissolve chlorine and propylene with
increased conversion to the undesirable byproduct propylene
(continued)
14 ^irk-Othmer Encyclopedia of Chemical Technology, Second Edition,
Vol. 16. John Wiley & Sons, Inc., New York, New York, 1968.
pp. 595-609.
**2Lunde, K. E. Propylene Oxide and Ethylene Oxide. Report No. 2
(a private report by the Process Economics Program), Stanford
Research Institute, Menlo Park, California, January 1965.
311 pp.
43Propylene Oxide - Caicel Ltd. Hydrocarbon Processing,
54(11) :202, 1975.
40
-------
PURGE ON RECYCLED
PROPYLENE (GAS)
•CAUSTIC
SCRUBBER
RECYCLED
PROPY
ENE
Y
SPENT
CAUSTIC
/CHLORINE-
NPROPYLENE
WATER
REACTOR
I CALCIUM
J HYDROXIDE
SEPARATOR
HYDROLYZER
STEAM
i-»-LIGHT ENDS
PROPYLENE
- OXIDE
PRODUCT
DISTILLATION
COLUMN
DISTILLA
FION
COLUMN
TO THICKENER
Figure 13. Propylene oxide by the chlorohydrination
of propylene.13'1*'39'"0'43
TO PROPYLENE
DI CHLORIDE
SEPARATION
-------
dichloride.l3 Unreacted propylene and propane contained in the
propylene feed, on leaving the top of the tower, are scrubbed
with caustic soda solution to remove hydrochloric acid and any
residual chlorine, and may then be recycled or used elsewhere in
the plant as fuel.13 A portion of the gas may be vented to fuel
or incinceration to control the concentration of inert gases in
a recycle process.
The dilute propylene chlorohydrin solution mixed with a 10%
slurry of slaked lime is pumped to the hydrolyser. Here the
chlorohydrin is converted to propylene oxide. To prevent further
hydrolysis to propylene glycol, the oxide is rapidly flashed out
of the reaction zone. The excess lime may be recovered for
recycle in thickeners which remove the spent calcium chloride
brine by decantation. The lime used should contain less than 1%
magnesium oxide, since the latter catalyses the isomerization of
propylene oxide to aldehydes. If economics warrant, caustic soda
may be used instead of lime or as a supplement to lime.13
The overhead from the hydrolyser, predominantly propylene oxide
and water, is contaminated with propylene dichloride, chloro-
propenes from dehydrohalogenation of propylene chloride and pro-
pionaldehyde from isomerization of propylene oxide. The oxide
is purified by fractionation in multiple distillation columns to
produce a specification grade product.13
B. GEOGRAPHICAL DISTRIBUTION
In 1975 there were 32 companies with a total capacity of
11.5 x 106 metric tons/yr at 58 locations in the United States
producing 8.52 x 106 metric tons of the 14 chlorinated hydro-
carbons included in this study.
Most of the chlorinated hydrocarbon industry, as shown in
Figure 14, is concentrated in three regions: Northeastern,
South Central, and the West. Table 71-12 lists manufacturing
company, plant location, capacity, product type, and population
density of each region.
42
-------
UJ
KEY
12 PLANTS JU| 4 PLANTS
6 PLANTS iH 2 PLANTS
5 PLANTS ^ 1 PLANT
0 PLANTS
Figure 14. Geographical distribution of chlorinated hydrocarbon plants
-------
TABLE 7. CHLORINATED HYDROCARBON MANUFACTURING FACILITIES INCLUDING COMPANY, PLANT LOCATIONS,
PRODUCT TYPES, POPULATION DENSITY, AND CAPACITY.1"12
Manufacturing company
Allied Chemical Corporation
BASF, Wyandotte Corporation
Continental Oil Company
Chemetron Corporation
Diamond Shamrock Corporation
Dow Chemical, U.S.A.
Plant location
Syracuse, NY
Moundsville, WV
Wyandotte, MI
Geismar, LA
Lake Charles LA
LaPorte, TX
Belle, WV
Deer Park, TX
Freeport, TX
Population
density,
Product type persons/km2
Monochlorobenzene 222
Dichloroben zene
Carbon tetrachloride 47
Chloroform
Methyl chloride
Methylene chloride
Phosgene
Propylene oxide 1,686
Phosgene 47
Methyl chloride 50
Ethylene dichloride
Phosgene 386
Chloroform 95
Methyl chloride
Methylene chloride
Perchloroethylene 386
Trichloroethylene
Ethylene dichloride
Carbon tetrachloride 29
Chloroform
Epichlorohydrin
Ethyl chloride
Ethylene dichloride
Methyl chloride
Methylene chloride
Perchloroethylene
Propylene oxide
1,1, 1-Tr ichloroethane
Trichloroethylene
Capacity,
metric tons/yr
11,300
7,300
3,600
13,600
11,300
22,700
44,500
79,400
24,900
45,400
535,900
9,100
18,100
11,300
45,400
74,800
22,700
199,600
61,200
45,400
113,400
34,000
725,700
31,800
90,700
54,400
415,000
204,100
68,000
(continued)
-------
TABLE 7 (continued)
Manufacturing company
Dow Chemical, U.S.A. (continued)
Dow Corning Corporation
E.I. duPont De Nemours & Co., Inc.
Ethyl Corporation
F.N.C. Corporation
General Electric
Plant location
Midland, MI
Oyster Creek, TX
Pittsburg, CA
Plaquemine, LA
Carrollton, KY
Midland, MI
Corpus Christi, TX
Deepwater Point, NJ
Baton Rouge, LA
Houston, TX
S. Charleston, WV
Baltimore, MD
Mount Vernon, IN
Waterford, NY
Population
density,
Product type persons/km2
Monochlorobenzene
Dichlorobenzene
Ethylene dichloride
Perchloroethylene
Carbon tetrachloride
Carbon tetrachloride
Chloroform
Ethylene dichloride
Methyl chloride
Methylene chloride
Perchloroethylene
Propylene oxide
Methyl chloride
Methyl chloride
Carbon tetrachloride
Ethyl chloride
Phosgene
Ethyl chloride
Ethylene dichloride
Methyl chloride
Perchloroethylene
1,1, 1-Trichloroethane
Trichloroethylene
Ethylene dichloride
Ethyl chloride
Carbon tetrachloride
Phosgene
Phosgene
Methyl chloride
47
386
290
19
25
47
27
64
233
386
95
493
20
57
Capacity,
metric tons/yr
136,100
27,200
499,000
9,100
36,300
56,700
45,300
601,000
68,000
81,600
68,000
154,200
9,100
6,800
136,100
49,900
61,200
95,300
317,500
45,400
45,400
22,700
18,100
118,000
68,000
136,100
2,700
27,200
22,700
(continued)
-------
TABLE 7 (continued)
Manufacturing company
The B. F. Goodrich Company
Hooker Chemical Corporation
Jefferson Chemical Company
Hobay Chemical Corporation
Monsanto Company
Montrose Chemical Corporation
Olin Corporation
Oxirane Corporation
PPG Industries, Inc.
Rubicon Corporation
Shell Chemical Company
Plant location
Calvert City, KY
Taft, LA
Port Neches, TX
New Martinsville,
Cedar Bayou, TX
Sauget, IL
Henderson, NV
Ashtabula, OH
Lake Charles, LA
Brandenburg, KY
Bayport, TX
Barberton, OH
Lake Charles, LA
Natrium, WV
Geismar, LA
Deer Park, TX
Nor co, LA
Population
density,
Product type persons/km2
Ethylene dichloride
Perchloroethylene
Trichloroethylene
Phosgene
Propylene oxide
WV Phosgene
Phosgene
Monoch loroben zene
Dichlorobenzene
Monochlorobenzene
Phosgene
Phosgene
Propylene oxide
Propylene oxide
Phosgene
Ethyl chloride
Ethylene dichloride
Perchloroethylene
1,1, 1-Trichloroethane
Trichloroethylene
Dichlorobenzene
Monochlorobenzene
Phosgene
Ethylene dichloride
Ethyl chloride
Epichlorohydrin
Epichlorohydrin
Ethylene dichloride
25
37
98
21
98
161
13
53
50
23
386
514
50
88
47
386
37
Capacity,
metric tons/yr
453,600
27,200
18,100
13,600
68,000
111,100
59,000
52,200
12,700
31,800
22,700
54,400
59,000
417,300
2,300
54,400
544,300
108,900
79,400
90,700
18,600
31,800
56,700
544,300
38,600
63,500
27,200
528,400
(continued)
-------
TABLE 7 (continued)
Manufacturing company
Solvent Chemical Company
Specialty Organics, Inc.
Standard Chlorine Chem. Co., Inc.
Stauffer Chemical Company
Story Chemical Corporation
Union Carbide Corporation
The Upjohn Company
Van De Mark Chemical Compant, Inc.
Vulcan Materials Company
Plant location
Niagara Falls, NY
Irwindale, CA
Delaware City, DE
Carson, CA
Cold Creek, AL
Le Moyne, AL
Carson, CA
Louisville, KY
Niagara Falls, NY
Muskegon , MI
Institute, WV
Taft, LA
Texas City, TX
LaPort, TX
Lockport, NY
Geismar, LA
Wichita, KS
Population
density,
Product type persons/km2
Dichlorobenzene
Dichlorobenzene
Dichlorobenzene
Monochlorobenzene
Ethyl chloride
Phosgene
Carbon tetrachloride
Ethylene dichloride
Carbon tetrachloride
Chloroform
Methyl chloride
Methylene chloride
Carbon tetrachloride
Phosgene
Phosgene
Methyl chloride
Ethylene dichloride
Ethylene dichloride
Phosgene
Phosgene
Carbon tetrachloride
Chloroform
Ethylene dichloride
Methylene chloride
Perchloroethylene
1,1, 1-Tr ichloroe thane
Carbon tetrachloride
Chloroform
Methylene chloride
Perchloroethylene
169
662
341
662
6
6
662
709
169
120
95
37
160
386
169
47
134
Capacity,
metric tons/yr
9,100
1,800
56,700
34,000
45,400
11,300
90,700
154,200
15,900
34,000
6,800
27,200
68,000
4,500
49,900
22,700
68,000
68,000
90,700
3,600
40,800
80,900
149,700
36,300
68,000
29,500
27,200
18,100
13,600
22,700
-------
SECTION IV
EMISSIONS
A. SELECTED POLLUTANTS
Process emissions from the chlorinated hydrocarbon industry are
usually hydrocarbons. These may be raw materials, impurities in
the raw materials, products, and byproducts. Major sources of
hydrocarbon emissions to the atmosphere within the chlorinated
hydrocarbon industry include emissions from the main process vent
and from the product fractionation vent, storage tank emissions,
fugitive emissions, and emissions from waste disposal. Due to
the complexity of this industry in terms of the wide range of
products and byproducts, plant sizes, and operating rates, and a
lack of data on the entire industry, storage tank emissions,
fugitive emissions, and emissions from waste disposal will be
discussed but not evaluated. Table 8 summarizes the unit opera-
tions involved in the manufacture of each chlorinated hydrocarbon
and identifies emission points.
On the basis of data available in the literature, the materials
listed in Table 9 were identified as being emitted during the
manufacture of chlorinated hydrocarbons and were selected for
detailed analysis in this study. Also listed in Table 9 are the
threshold limit values (TLV's) for each compound. ** **
B. LOCATIONS AND DESCRIPTIONS
1. Emissions from Main Process Vent
Atmospheric emissions from the main process vent, usually vented
from an absorber or a scrubber, generally consist of chlorine,
hydrogen chloride, and process raw materials, products, and by-
products. They represent a small percentage of the gross reactor
effluents that are not recovered in the absorber or scrubber
system. This source of emission is usually the primary one
within a chlorinated hydrocarbon manufacturing facility. The
composition of these emissions varies within the industry, based
on the chlorinated hydrocarbon being manufactured. Within a
s®. Threshold Limit Values for Chemical Substances and
Physical Agents in the Workroom Environment with Intended
Changes for 1975. American Conference of Governmental Indus
trial Hygienists, Cincinnati, Ohio, 1975. 97 pp.
48
-------
TABLE 8. UNIT OPERATIONS INVOLVED IN THE MANUFACTURE OF CHLORINATED
HYDROCARBONS WITH EMISSION SOURCES IDENTIFIED
vo
Product
Methyl chloride
Nethylene chloride
Chloroform
Carbon tetrachloride
Carbon tetrachloride
Carbon tetrachloride
Perchloroethylene
Bthylene dichlonde
Phosgene
Monochlorobenzene
Dichlorobenzene
Methyl chloride
Ethyl chloride
1,1, 1-Trichloroe thane
Ethylene dichloride
Trichloroethylene
Epichlorohydrin
Propylene oxide
Manufacturing Absorp-
process tion Drying
Direct chlorination
of methane
Direct chlorination
of methane
Direct chlorination
of methane
Direct chlorination
of methane
Direct chlorination
of carbon disulfide
Direct chlorination
of propane
Direct chlorination
of propane
Direct chlorination
of ethylene
Direct chlorination
of carbon monoxide
Direct chlorination
of benzene
Direct chlorination
of benzene
Hydrochlorination of
methanol
Hydrochlorination of
ethylene
Hydrochlorination of
vinyl chloride
Oxyhydrochlorination
of ethylene
Oxyhydrochlorination of
ethylene dichloride
Chlorohydrination of
allyl chloride
Chlorohydrination of
propylene
A W
A W
A W
A W
A
D AH
D AW
A
A
A
A
W W
-
-
A
A
A
AW
a
Unit operation
Fluid Heat Material Separa-
flow transfer handling Mixing tion Storage
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
-
D
D
D
D
D
D
D
~
A
D
D
-
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D W A
D W A
D W A
D W A
D A W S A
D W S A
D W S A
D W S A
A
W S A
V S A
W S A
D AW A
AW A
A W S A
D W S A
A W S A
W S A
Waste
disposal
W
W
W
W
W S
W S
W S
N S
A
W S
W S
W S
W
W
W S
W S
W S
W S
3A = Atmospheric emission, w - Wastewater discharge, S = Solid waste, D = Unit operation performed but no process emissions are
anticipated, - = Unit operation not performed.
-------
TABLE 9. MATERIAL EMITTED FROM CHLORINATED
HYDROCARBON MANUFACTURING PLANTS
Material emitted
Allyl chloride
Epichlorohydrin
Vinyl chloride
Propylene oxide
Methane
Butane
Methyl chloride
Propylene
Methylene chloride
Chloroform
Carbon tetrachloride
Carbon disulfide
Chlorine
Sulfur monochloride
Ethylene
D i ch loroprop iona 1
Bis ( B-chloroisopropyl)
ether
TLV,
g/m3
0.003
0.019
0.0026
0.240
0.710
2.59
0.210
1.88
0.720
0.120
0.065
0.060
0.003
0.006
1.25
0.001
Material emitted
Ethylene dichloride
Hydrogen chloride
Vinylideue chloride
Phosgene
Carbon monoxide
Toluene
Monochlorobenzene
Dichlorobenzene
Ethane
Ethyl chloride
Dichloroethane
Trichloroethylene
Perchloroethylene
Trichloroethane
Trichloropropane
Benzene
Dichloropropane
Naphthalene
Dichloroethylene
TLV,
g/m3
0.20
0.007
0.004
0.0002
0.055
0.375
0.35
0.30
1.34
2.60
0.82
0.535
0.670
1.90
0.30
0.0035
0.35
0.050
0.790
specific plant, these emissions depend on catalyst activity,
reactor operating conditions, and the specific processing scheme
employed.
2. Emissions from Product Fractionation Vent
The product fractionation vent represents a second major source
of atmospheric emissions within the chlorinated hydrocarbon manu-
facturing industry. Stream composition varies greatly with the
chlorinated hydrocarbon being manufactured, with the type of
fractionation system used for product recovery, and with the de-
sired product purity.
3. Emissions from Storage Tanks
Hydrocarbon vapors are emitted from storage tanks due to the
volatility of the stored material. Heat or pressure changes
within the tank affect the rate of evaporation of the stored
material. Heat from direct solar radiation or from contact with
warm ambient air, or heat introduced during processing can all be
prime factors causing vaporization of the volatile stored mate-
rial. The evaporation rate depends upon the atmospheric tempera-
ture, weather conditions, tank shell temperature, vapor space
temperature, and liquid body and surface temperatures.1*5
**5Air Pollution Engineering Manual, Second Edition,
J. A. Danielson, ed. Publication No. AP-40, U.S. Environmental
Protection Agency, Research Triangle Park, North Carolina, May
1973. 987 pp.
50
-------
To a degree that depends upon the total vapor pressure exerted
by the liquid at storage temperatures, the air in the vapor space
of a storage tank will be saturated with vapor. As temperature
and, correspondingly, pressure increase, some of this air vapor
mixture will be emitted to the atmosphere.45
With temperature decrease occurring at night or resulting from
cloudiness or rain, the vapor contracts, and fresh air is sucked
into the storage tank, upsetting the existing equilibrium of
saturation. More volatile hydrocarbons evaporate from the stored
liquid in the tank to restore equilibrium. When the atmospheric
temperature increases, as occurs with daylight, expansion occurs
again and hydrocarbons are emitted. This cycle is repeated
continually.45
Emissions from storage tanks also occur due to filling, with the
rate of emission being proportional to the tank filling rate.
Withdrawing liquid from storage tanks creates empty space, caus-
ing fresh air to enter the tank and allowing more evaporation to
occur.45
Wind blowing through a free-vented tank also causes an emission
problem, termed windage emissions. The quantity of emission from
this source is not as large as that from breathing or filling
cycles.45
Emission problems associated with floating roof tanks are differ-
ent and are known as wicking and wetting. Wicking emissions are
caused by the capillary flow of the liquid between the outer side
of the sealing ring and the inner side of the tank wall. Wetting
emissions occur when the floating roof moves toward the bottom of
the tank during emptying and leaves the inner tank shell covered
with a film of liquid, which evaporates when exposed to the
atmosphere.4 5
4. Fugitive Emissions
Emissions occurring from pressure relief valves, pumps, compres-
sors, agitator seals, valve stems, and flanges; from process
upsets; and from loading and unloading of raw materials, products,
and byproducts; purging of equipment before reports; and sampling
for laboratory analysis are defined as fugitive emissions.
Due to the complexity of the chlorinated hydrocarbon manufactur-
ing industry in terms of the different products manufactured,
the large range of plant sizes, and the lack of data on fugitive
emissions, the emissions from this source will not be determined.
5. Emissions from Waste Disposal
Liquid and solid wastes are generated during the manufacture of
chlorinated hydrocarbons. When hydrogen chloride or chlorine
reacts with hydrocarbons under various conditions, chlorinated
51
-------
hydrocarbons are formed. Along with the major product several
byproducts are produced due to side reactions occuring with
chlorine, hydrogen chloride, raw material, and contaminants
present in the raw material. These byproducts will be present in
liquid and solid waste streams.
Other sources of liquid waste include water condensed from the
reactor effluent, plus spent caustic from the neutralizer and
spent sulfuric acid from the dryer. The combined flow of streams
varies considerably from plant to plant. The wastewater is usu-
ally sent for treatment or used for pH control in other process-
ing areas. Other solid waste, consisting primarily of catalyst
particles removed from the reactor effluent, may be removed from
the reject water settling ponds. Since this report deals with
atmospheric pollution, the quantities of liquid and solid waste
generated will not be studied in this report.
C. EMISSION FACTORS
Tables 10 through 13 list products, manufacturing processes, unit
operations, materials emitted, and emission factors for all chlo-
rinated hydrocarbons being studied for this project and manufac-
tured by the four process types (direct chlorination, hydrochlo-
rination, oxyhydrochlorination, and chlorohydrination).
The emission factors were derived from field sampling, and emis-
sion data and material balances reported in References 14, 15,
20, 31, and 42, and the following personal communications:
• T. H. Capps, Allied Chemical Company, Moundsville, West
Virginia, July 28, 1976.
• J. R. Hofts, FMC Corporation, South Charleston, West
Virginia, November 10, 1976.
• R. A. Coates, Mobay Chemical Company, New Martinsville, West
Virginia, April 1, 1976.
Total hydrocarbon values reported in Tables 10 - 13 include all
compounds containing a hydrogen-carbon bond. The value is
reported in methane equivalents and cannot therefore be obtained
as a direct sum of the individual components.
52
-------
TABLE 10. EMISSION FACTORS BY UNIT OPERATIONS FOR
PROCESSES INVOLVING DIRECT CHLORINATION
Product
Manufacturing
process
Unit
operation
Material emitted
Emission
factor ,
Methyl chloride,
methylene chlo-
ride, chloroform,
and carbon tetra-
chloride
Carbon tetrachloride
Direct chlorination
of methane
Direct chlorination
of carbon di-
sulfide
Absorption Total hydrocarbons
(CHu equivalent) 0.012°
Absorption Carbon tetrachloride 2.57D
Carbon tetrachloride
and perchloro-
ethylene
Ethylene dichloride
Phosgene
Monochlorobenzene and
dichlorobenzene
MRC sampling report -
b
Correspondence, J. R.
November 10, 1976.
CNot reported.
d
Reference 15.
Reference 3.
Total hydrocarbons
(CHu equivalent)
Separation Carbon disulfide
Carbon tetrachloride
Chlorine
Sulfur monochloride
Total hydrocarbons
(CHu equivalent)
Direct chlorination Drying chlorine
of propane
Total hydrocarbons
(CHu equivalent)
Direct chlorination Absorption Ethylene
of ethylene Ethylene dichloride
Hydrogen chloride
Ethylene trichloride
Other hydrocarbons
Total hydrocarbons
(CHu equivalent)
Direct chlorination Absorption Phosgene
of carbon monoxide carbon monoxide
Toluene
Total hydrocarbons
(CHu equivalent)
Waste disposal Phosgene
Hydrogen chloride
Total hydrocarbons
(CHu equivalent)
Direct chlorination Absorption Hydrogen chloride/
of benzene chlorine
Monochlorobenzene
Dichlorobenzene
Benzene
Other hydrocarbons
Total hydrocarbons
(CHu equivalent)
carbon tetrachloride by direct chlorination of methane.
Hofts, FMC Corporation, South Charleston, West Virginia,
_C
2.00d
0.25b
0.00013d
1.00d
_c
10.00d
_c
3.10e
2.206
0.01e
0.01e
0.01
4.22
0.01f
0.01f
1.25d
1.52
0.01f
0.01f
_c
0.069
0.039
<0.00l9
0.0029
-------
TABLE 11. EMISSION FACTORS BY UNIT OPERATION FOR PROCESSES
USING HYDROCHLORINATION
Manufacturing Unit
Product process operation Material emitted
Methyl chloride, Hydrochlorination - No reported atmos-
methylene chlo- of methanol pheric emission
ride, chloro-
form, carbon
tetrachloride
Ethyl chloride Hydrochlorination Separation Ethane
of ethylene Ethyl chloride
Dichloroethane
Chlorine
Hydrogen chloride
Methane
Ethylene
Total hydrocarbons
(CH<» equivalent)
1,1,1-Trichloroethane Hydrochlorination Heat transfer Dichloroethane
of vinyl chloride Trichloroethane
Hydrogen chloride
Other hydrocarbons
Total hydrocarbons
(CHit equivalent)
Separation Dichloroethane
Trichloroethane
Hydrogen chloride
Vinyl chloride
Other hydrocarbons
Total hydrocarbons
(CHit equivalent)
Emission
factor ,
gAg
_a
b
2'5b
2'5b
6.0 b
0.0005?
0.0005
2.5b
2.5t>
11.2
8-50c
9.005
o.oid
0.01
4.9
0.50^
0.505
O.Ol"
0.50d
0.01
0.54
Not applicable.
Reference 15.
Reference 20.
d
Engineering estimate.
-------
TABLE 12. EMISSION FACTORS BY UNIT OPERATIONS FOR
PROCESSES USING OXYHYDROCHLORINATION
LH
U1
Manufacturing Unit
Product process operation
Ethylene dichloride Oxyhydrochlorination Absorption
of ethylene
Separation
Trichloroethylene Oxyhydrochlorination Absorption
of ethylene
dichloride
Material emitted
Chlorine/hydrogen
chloride
Carbon tetrachloride
Methane
Ethylene
Chloroform
Ethylene dichloride
Methylene chloride
Vinyl chloride
Trichloroethane
Total hydrocarbons
(CHi« equivalent)
Ethylene
Chlorine/hydrogen
chloride
Ethylene dichloride
Methylene chloride
Vinyl chloride
Chloroform
Carbon tetrachloride
Ethyl chloride
1 , 1-Dichloroethane
Methane
Vinylidene chloride
Dichloroethylene
Total hydrocarbons
(CHi, equivalent)
Ethylene dichloride
Trichloroethylene
Carbon tetrachloride
Total hydrocarbons
(CHit equivalent)
Emission
factor ,
q/kq
a
0.0019
<0.003
0.988
0.332
<0.005
0.46
<0.003
0.01
<0.005
1.52
0.000013
a
0.005
0.085
0.0015
°'012a
0.042
0.094*
°-047a
0.004
0.000004
0.00009
0.0008
0.064
b
13. Ob
8-5b
13.0
6.3
8MRC sampling report - ethylene dichloride by Oxyhydrochlorination of ethylene.
Reference 15.
-------
TABLE 13. EMISSION FACTORS BY UNIT OPERATIONS FOR
PROCESSES USING CHLOROHYDRINATION
Ul
CTi
Manufacturing Unit
Product process operation Material emitted
Epichlorohydrin Chlorohydrination of Absorption Allyl chloride
allyl chloride Chlorine
Hydrogen chloride
Total hydrocarbons
(CHi» equivalent)
Separation Allyl chloride
Chlorine
Trichloropropane
Hydrogen chloride
Epichlorohydrin
Total hydrocarbons
(CHi» equivalent)
Propylene oxide Chlorohydrination of Absorption Hydrogen chloride/
propylene chlorine
Methane
Dichloropropane
Ethene
Epichlorohydrin
Trichloropropane
Bis (8-chloroisopropyl)
ether
Naphthalene
Other hydrocarbon
Total hydrocarbons
(CHi» equivalent)
Emission
factor ,
gAg
2.003
0.0005*
0.0005
1.2
a
2.00
0.0005
0.50a
0.0005
1.50a
2.13
b
3-T
26.7bb
8.42
iosb
1.54 b
0.405
b
2.03b
0.08
0.10
155
Reference 20.
MRC sampling report - Chlorohydrination of propylene.
-------
D. DEFINITION OF A REPRESENTATIVE SOURCE
For the purpose of assessing the environmental impact of the
chlorinated hydrocarbon industry, four representative plants were
defined based on the four basic processes used by the industry.
The parameters used to define a representative plant include
process type, population density around the plant site, plant
capacity, unit operations used, and average emission rate for
total hydrocarbons. Table I420,2«t,3l,«*2,a summarizes the para-
meters used for determining a representative plant. For each
manufacturing process type, the population density for a represen-
tative plant is a capacity weighted average of the population
densities of the counties where the plants are located. The
representative plant capacity is the average capacity of the
existing plants under each process type. The hydrocarbon emission
factors are derived from those presented in Tables 10 through 13
by using a capacity weighted average.
E. ENVIRONMENTAL EFFECTS
1. Determination of Severity
a. Maximum Ground Level Concentration—
The maximum ground level concentration, Xmax, for each material
emitted from each unit operation for each manufacturing process
was estimated by Gaussian plume dispersion theory. The maximum
ground level concentration, Xmax (in g/m3), was calculated
using the equation:
X = -&— (57)
max .K'eu
where Q = mass emission rate, g/s
H = effective emission height, m
e = 2.72
TT = 3.14
u = average wind speed (= 4.47 m/s)
b. Time-Averaged Maximum Ground Level Concentration—
Xmax, the time-averaged maximum ground level concentration cal-
culated from Xmax. The averaging time is 24 hr for noncriteria
pollutants (chemical substances). For criteria pollutants, aver-
aging times are the same as those used in the primary ambient air
quality standards; e.g., 3 hr for hydrocarbons_and 24 hr for par-
ticulates. The relationship between Xmax and Xmax is expressed
as:
3 Information also obtained by personal communication from
J. R. Hofts, FMC Corporation, South Charleston, West Virginia,
November 10, 1976; and from R. A. Coales, Mobay Chemical
Corporation, New Martinsville, West Virginia, April 1, 1976.
57
-------
TABLE 14. SUMMARY OF CRITERIA USED TO DEFINE REPRESENTATIVE
CHLORINATED HYDROCARBON PLANTS
Process
Criterion
Direct
chlorination Hydrochlorination Oxyhydrochlorination Chlorohydrination
en
CD
Population density, persons/km2 277 160
Capacity, metric tons/yr 77,284 41,465
Unit operations used, %
Absorption
Drying
Extraction
Fluid flow
Heat transfer
Material handling
Mixing
Separation
Storage
Waste disposal
Hydrocarbon emission factor, g/kg
100
55
9
100
91
100
73
91
100
100
33
33
a
100
67
100
33
100
100
100
198
250,706
100
a
"a
loo
100
100
50
100
100
100
2.78
8.62
1.87
333
122,470
100
a
~50
100
a
100
a
loo
100
100
123
Unit operation not used.
-------
"max * xmax\t> (58)
where t0 = short-term averaging time (= 3 min)
t = averaging time, min
c. Source Severity —
To obtain a quantitative measure of the hazard potential of the
emission source, the source severity, S, is defined as:
S = -. (59)
where Xmax *-s tne maximum time-averaged ground level concentration
of each pollutant and F is defined as the primary ambient air qual-
ity standard for criteria pollutants; i.e., particulates, SOX, NOX,
CO, and hydrocarbons.3 For noncriteria pollutants:
F - TLV ' IT ' iw (60)
where TLV (threshold limit value) represents the airborne concen-
tration of a substance under which it is believed that nearly all
workers may be repeatedly exposed day after day without adverse
effect. The factor 8/24 adjusts the TLV to a continuous rather
than work day exposure, and the factor 1/100 accounts for the fact
that the general^ population is a higher risk group than healthy
workers. Thus Xmax/F represents the ratio of the maximum mean
ground level concentration to the concentration constituting an
incipient hazard potential.
Because actual production data by plant are unavailable, and to
illustrate the worst case hypothetical situation, total capacities
were used to calculate emission rate, maximum ground level concen-
tration, time-averaged maximum ground level concentration, source
severity, industry contribution to state and national emissions,
affected population, and affected area. As shown in Table 1, an
average of 74% of the total capacity was utilized in 1975; hence,
actual emissions could be as much as 26% lower.
Tables 15, 16, 17, and 18 contain emission rates, maximum ground
level concentrations, time-averaged maximum ground level concen-
trations, and source severities of materials emitted from the unit
3There is no primary ambient air quality standard for hydrocarbons.
The value of 160 pg/m3 used for hydrocarbons in this report is a
recommended guideline for meeting the primary ambient air quality
standard for oxidants.
59
-------
TABLE 15. SOURCE SEVERITY: DIRECT CHLORINATION PROCESS
Source type
methylene chloride.
chloroform, and
carbon tetrachloride
Carbon tetrachloride
Carbon tetrachloride
and perehloroethylene
Ethylene dichloride
Phosgene
nonoch Lorobenzcne
and dichlorobenzcne
'Not reported
bTLV not available
Manufacturing
process
of methane
Direct chlorination
of carbon dlsulflde
Direct chlorination
of propane
Direct chlorination
of ethylene
Direct chlorination
of carbon monoxide
Direct chlonnation
of benzene
Unit
operation
Absorption
Absorption
Separation
Drying
Absorption
Absorption
Haste dispos
Absorption
Material emitted
Total hydrocarbons
(CH. equivalent)
Carbon tetrachloride
Total hydrocarbons
(CHi* equivalent)
Carbon disulfide
Carbon tetrachloride
Chlorine
Sulfur monochloride
Total hydrocarbons
(CR. equivalent)
Chlorine
"otal hydrocarbons
(CP. equivalent)
Ethylene
Ethylene dichloride
Hydrogen chloride
Ethylene trichloride
Total hydrocarbons
(CH. equivalent)
Phosgene
Carbon monoxide
Toluene
Total hydrocarbons
(CR. equivalent)
al Phosgene
Hydrogen chloride
Total hydrocarbons
(CH. equivalent)
Hydrogen chloride/
chlorine
Honoehlorobencene
Dichlorobenzene
Benzene
Total hydrocarbons
(CH. equivalent)
Emission
factor,
3/kq
0. 012
2.57
_a
2.00
0.25
0.00015
1.00
_a
10.00
_a
3.10
2.20
0.01
0.01
4 22
0.01
0.01
1.25
1.52
0.01
0.01
_a
0.06
0.03
0.001
0.002
0.03
Average plant
capacity, metric
tons/yr
52,475
75,598
75,598
23,360
352,670
40,118
40,118
52.000
Emission
height,
m
25.00
21.49
21 43
21.43
21.43
21.43
30 48
28.55
28.55
28.55
26.55
26.55
30.46
30.48
30.48
30.46
30.48
30.48
20 00
20.00
20.00
20.00
20.00
Emission
rate,
q/s
0.020
6.16
4 79
0.60
0.00036
2.4
7.40
34.67
24.60
0.11
0.11
47.6
0.013
0.013
1.S9
1.95
0.013
0.013
0.10
0.05
0.002
0.003
0.05
Xmax,
q/m>
1.67 x 10~*
6.99 x 10-*
5.47 x 10-"
6 85 x 10-*
4.10 x 10-'
2.74 X 10-*
4.17 x 10-"
2.23 X 10-'
1.S8 X 10->
6.75 x 10-«
6.75 x 10-«
2.92 x 10-*
7.16 x 10-'
7.16 x 10-'
8.97 X 10-*
1.05 x 10-«
7.16 x 10-'
7.16 x 10-'
1.3 x 10-»
6.5 x 10-*
2.6 X 10-'
3.9 x 10-'
6.25 x 10-«
W,
a/a'
5. 85 x 10" '
2.45 X 10-«
1.91 x 10-«
2.40 X 10-*
1.43 x 10-«
9.58 x 10-*
1.46 x 10-*
7.60 x 10-*
5.54 x 10-«
2.36 x 10-«
2.36 x 10-«
1.46 x 10-»
2.51 x 10-'
2.51 X 10-'
3.14 x 10-*
S.25 X 10-*
2.51 x 10-'
2.51 X 10-'
4.6 x 10-*
2.3 x 10-«
9.2 X 10-"
1.37 X 10-'
3.13 x 10-«
Source
severity
0 0037
1.13
0.96
0.32
0.0014
_D
14.60
0.19
0.83
0.00132
0.02
9.11
0.376
0.001
0.0251
0.128
0.176
0.011
0.46
0.002
0.00009
0.012
0.021
-------
TABLE 16. SOURCE SEVERITY: HYDROCHLORINATION PROCESS
Source tvoo
Methyl chloride.
•ethyl en* chloride.
chloroform, and
carbon tetrachloride
Btbyl chloride
1.1, l-Trichloroethane
bTLV not available.
Manufacturing Unit
proceea operation Material emitted
Hydroehlorinatlon of -* -'
aethanol
Hydroehlorinatlon of Separation Ethane
ethylene Ethylehloride
Dichloroe thane
Chlorine
Hydrogen chloride
Methane
Ethylene
Total hydrocarbona
(CH. equivalent)
vinyl chloride Trlchloroethane
Hydrogen chloride
Total hydrocarbona
(CH. equivalent)
Separation Didlloroatbaiw
Trlehloroethane
Hydrogen chloride
Vinyl chloride
Total hydrocarbona
(CB. equivalent)
factor, capacity, metric rate.
q/kg tona/yr q/e
2
2
6
0
0
2
2
11
fl
9
0
4
0
0
0
0
0
-•
5
5
.0
.0009
0005
5
.5
.2
.50
00
01
9
.SO
.50
01
.50
54
-*
55.000 4
-•
36
4.36
10.46
8.7
8 7
4
4
19
104.000 28
29
0
16
104,000 1
1
0
1
1
x 10—
x 10"
.36
.36
7
.10
75
033
.3
65
65
.033
.65
.80
height.
m
-*
30.48
30.48
30.48
30 48
30 48
30 48
30 48
30 48
30.48
30 48
30.48
30.48
30.48
30.48
30.48
30 48
30.48
'max.
g/m»
46
.46
.90
.90
.90
46
46
1 11
1.6
1 7
1 9
9 3
9 3
9 3
1.9
9 3
1 00
-'
x
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
10—
10—
1Q-.
10—
10-a
10 —
10 —
10-"
io-t
10—
10—
10—
10—
*max,
q/m»
-•
8 6 x 10->
a 6 x 10-*
2.06 x 10-
1.72 x 10—
1 72 x 10-*
8 6 x 10-*
8.6 X 10-*
5.55 x 10—
5.5 x 10-*
5 9 x 10—
6 5 x 10-'
4 5 x 10-*
3.3 x 10—
3 3 x 10-*
6 5 x 10-'
3 3 x 10—
5.0 x 10-*
Source
ae verity
_a
1 93 x 10—
9 92 x 10-'
0.31
1.72 x 10-'
7 36 x 10—
0 04
0 02
3.47
0 B3
9 3 x 10-"
2 8 x 10—
2.81
4.9 x 10—
Six 10-*
0.03
3 81
0.31
TABLE 17. SOURCE SEVERITY: OXYHYDROCHLORINATION PROCESS
Unit
Source type Manufacturing proceaa operation Material emitted
Ethylene diehloride Oxyhydrochlorination Abaorption Chlorine/hydrogen
of othylcno chloride
Carbon tetrachloride
ethylene
Chloroform
Ethylene diehloride
Methyl one chloride
vinyl chloride
Trlchloroethane
Total hydrocarbona
(CHb equivalent)
Separation Chlorine/hydrogen
chloride
Ethylene
Ethylene diehloride
Meth>lene chloride
vinyl chloride
Chloroform
Carbon tetrachloride
Ethyl chloride
1.1-Dlchloroethane
Methane
vlnylidene chloride
Dichloroethylene
Total hydrocarbona
(CHb equivalent)
factor, capacity oetnc
g/kg tone/yr
0
• 0
0
0
<0.
0
0
i
0
0
0.
0
0
0
0
0
0.
0
0
0.
0
0019 340.000
03
988
332
005
46
003
01
005
52
005
0001
085
0015
012
042
094
047
004
000004
0009
008
064
rate,
g/a
0
0
3
A
5
0
0
0
16
0
0.
0.
0
0
0
1.
0
0
0
0
0.
0.
021
032
6
oos
0
032
11
05
4
054
0001
92
016
13
45
02
51
043
00004
0010
0086
70
height, Amax,
m g/m'
55
55
CE
55
EC
55
55
55
55
55
16
16
16
16
16
16
16
16
It
16
16
16
16
.00
.00
00
00
00
00
00
.00
00
.00
00
.00
00
00
00
00
00
00
00
.00
00
.00
00
3 6 x 10-'
5 4 x 10-'
6 1 x 10—
8 5 x 10—
5.4 x 10-'
1 9 x 10—
8 5 x 10-'
2 7 x 10-"
1 1 x 10-*
2 0 x 10-*
1 8 x 10—
3 2 x 10—
2 6 x 10-*
9 0 x 10 —
2 04 x 10—
1 02 x 10-*
a e > 10-*
8 0 x 10-*
2 0 x 10-*
1 7 x 10—
1.4 x 10-*
1
1
2
3
1
6
3
1
3
7
6
1
9
3
7
3
3
2
7
6
7
g/nV
3 x
.9 x
1 x
0 x
9 x
7 x
0 x
.4 X
.9 x
0 X
3 x
1 x
1 x
2 x
1 x
6 x
0 x
a x
0 x
0 x
0 x
10-'
10-'
10—
10—
10-'
10-'
10-'
10 —
10 —
10 —
10—
10—
10-.
10—
10—
10—
10-*
10—
10—
10-'
10-"
Source
aeverity
0.013
8.6 x 10-*
0 027
0 005
0 04
7.9 x 10-»
0 077
4.7 x 10-"
0 88
0 39
1 7 x 10-'
0 094
4 6 x 10—
1 0
0.08
0 32
4 1 x 10-'
1 1 x 10-'
1 2 x 10—
1 3 x 10—
2 3 x 10—
0 44
Triehloroetnylene
oiyhydrocolorln.it ion
of ethylene dlehloride
Absorption
Etnylone diehloride
Tr ichloroethy lane
Carbon tetrachlorlda
Total hydrocerboni
(CH. equivalent)
13 0
28.5
13 0
20 60
45.16
20 60
30 48
30.48
30.48
1 2 x 10-'
2.5 x 10-'
1.2 x 10-'
4 1 x 10—
8.9 x 10—
4.1 x 10—
0 61
0 50
1.88
5 6 x 10-* 2 9 x 10—
-------
TABLE 18. SOURCE SEVERITY: CHLOROHYDRINATION PROCESS
CTi
to
Unit
Epichlorohydnn Chlorohydrination of allyl Absorption Allyl chloride
chloride Chlorine
Hydrogen chloride
Total hydrocarbons
(CHU equivalent)
Separation Allyl chloride
Chlorine
Tr ichloropropane
Hydrogen chloride
EpichlorohydrLn
Total hydrocarbons
(CHk equivalent)
Propylenc oxide Chlorohydrination of Absorption Hydrogen chloride/
propylene chlorine
Methane
Dichloropropane
Ethene
Epichlorohydrin
Tr ich loropropane
Bis (B-chloro-
isopropyl) ether
Naphthalene
Other hydrocarbons
Total hydrocarbons
(CIU equivalent)
factor. capacity metric rate*
g/kq tona/yr q/s
2
0
0
1
2
0
0
0
1
2
3
26
8
106
1
0
2
0
0
155
.00 68,000
.0005
0005
2
.00 68.000
.0005
.50
.0005
.50
.13
73 155.128
7
.42
.54
405
.03
.08
10
4.11
0.0011
0 0011
2.S9
4.31
0.0011
1.08
0.0011
3.24
4.S7
18 3
130
41 2
530
7.5
1 9B
9 9
0.39
0 49
760
Emission
height,
m
30.48
30 48
30.48
30.48
30 48
30.48
30 48
30.48
30.48
30.48
50 00
50.00
50.00
50.00
50.00
SO. 00
50.00
50.00
50.00
50 00
'max.
q/m»
2.43
6.20
6 20
1.46
2 43
4.20
6.01
6.20
1.83
2.S8
3 &
2 6
8.2
1 1
1.5
4 0
1 9
7 8
9 B
1 S
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
io-«
io-«
10-"
10--
10"
JO-"
io-»
io-«
10--
10"
10 -
10-'
10 •
10-"
10--
10-«
10"
io-«
10-«
10 >
'max,
q/m>
8. 51
2 17
2 17
7 32
51
17
.11
.17
.40
1 29
1 3
9 1
2.9
3.9
5.3
1 4
6.7
2.7
3 4
7 5
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
io-«
10-"
10 •
io-«
10-'
10 •
10-*
io-«
io-«
10"
10-.
10--
10 •
10"
10-t
10-"
io-»
io-«
10 •
10-1
Source
severity
8 51
0 00217
0.00093
0 46
8 5)
0 00217
0.0213
0.00093
1.01
0.81
13
0.40
0 24
0.9]
0.84
0.014
20.3
0 016
0 02
47
TLV not available.
TABLE 19. SOURCE SEVERITY: REPRESENTATIVE DIRECT CHLORINATION, HYDROCHLORINATION,
OXYHYDROCHLORINATION, AND CHLOROHYDRINATION PROCESSES
Manufacturing
process
Chlonnation
Hydrochlorination
Oxydrochlori nation
Chlorohydrination
Material
emitted
Hydrocarbons
Hydrocarbons
Hydrocarbons
Hydrocarbons
Emission
factor ,
g/kg
2.78
8.62
1.87
123
Emission
rate,
g/s
6.88
11.4
15.0
480
Emission
height,
m
25.1
30.5
33.8
40.2
xmax,
g/m3
5.4 x 10-*
6.1 x 10-*
6.6 x 10-*
1.5 x 10-2
xmax,
g/m3
2.7 x 10-*
3.1 x 10-*
3.3 x 10-*
7.5 x 10-3
Source
severity
1.69
1.94
2.06
46.8
-------
processes of direct chlorination, hydrochlorination, oxyhydro-
chlorination, and chlorohydrination, respectively. Table 19
presents the source severity of representative processes. For
each unit process, the source severities are calculated by source
types, manufacturing process, materials emitted, and unit opera-
tions involved. The appendix contains the derivations of source
severity equations.
2. Industry Contribution to Total Atmospheric Emissions
The mass emissions of criteria pollutants resulting from the manu-
facture of chlorinated hydrocarbons were calculated for each of
the four processes used to produce chlorinated hydrocarbons.
Emission factors used in the calculations were obtained from
Table 14. The appropriate emission factors were multiplied by
the chlorinated hydrocarbon capacity nationwide to obtain the
industry contribution to national emissions as shown in Table 20.
Similarly, emission factors were multiplied by the statewide
capacity of chlorinated hydrocarbons to obtain the industry con-
tribution to statewide emissions as shown in Table 21. The total
annual mass emissions of criteria pollutants from all sources
nationwide and from sources within appropriate states were
obtained from Reference 46. The percentages of the total emis-
sions resulting from chlorinated hydrocarbon manufacture were
computed using these values and are also presented in Tables 20
and 21.
TABLE 20. CHLORINATED HYDROCARBON INDUSTRY CONTRIBUTION TO
NATIONAL STATIONARY SOURCE EMISSIONS OF
CRITERIA POLLUTANTS1*6
Emissions from
Material
emitted
Total
national
emissions,
10* metric
tons/yr
Direct
chlorination
Percent
of
10 3 metric national
tons/yr emissions
the chlorinated hydrocarbon industry
Hydrochlorination
103 metric
tons/yr
Percent
of
national
emissions
Oxyhydrochlori nation
103 metric
tons/yr
Percent
of
national
emissions
Chlorohydrination
103 metric
tons/yr
Percent
of
national
emissions
Hydrocarbons
25
14.6
0.06
9.95
0.04
6.10
0.024
120
0.48
3. Affected Population and Affected Area
A measure of the population which is exposed to a high contami-
nant concentration (S 0.05, 0.1, and >1.0) due to a representa-
tive chlorinated hydrocarbon plant can be obtained as follows.
The values of x, the distance from the source, for which
(61)
63
-------
TABLE 21. CHLORINATED HYDROCARBON INDUSTRY CONTRIBUTIONS TO
STATE EMISSIONS OF HYDROCARBONS **6
State
Alabama
California
Delaware
Illinois
Indiana
Kansas
Kentucky
CM
>C» Louisiana
Maryland
Michigan
Nevada
New Jersey
New York
Ohio
Texas
West Virginia
Total
State
hydrocarbon
emissions,
103 metric
tons
643.4
2,161.0
63.9
1,826.0
600.5
309.6
326.3
1,920.0
295.9
717.9
53.7
819.5
1,262.0
1,153.0
2,219.0
116.2
Direct chlorination
State
capacity,
10* metric
tons
102.1
47.2
90.7
64.9
27.2
65.8
83.9
2,506.0
2.72
167.8
31.8
61.2
111.6
25.0
1,471.9
395.5
Emissions,
metric
tons
283.8
131.2
252.1
180.4
75.62
182.9
233.2
6,970
7.56
466.5
88.40
170.1
310.2
69.5
4,090
1,099
14,610
Percent
0.044
0.006
0.395
0.010
0.0126
0.059
0.071
0.36
0.0026
0.065
0.16
0.021
0.025
0.006
0.18
0.95
Hydrochlorination
State
capacity. Emissions,
103 metric metric
tons tons Percent
45.4 391.3 0.018
15.9 -3 -3
9.1 -8 -a
569.7 4,910 0.26
6.8 -3 -a
49.9 430.1 0.052
22.7 -3 -3
344.7 2,971 0.13
145.2 1,251 1.08
9,953
Oxyhydrochlorination Chlorohydrination
State State
capacity, Emissions, capacity. Emissions,
10J metric metric 10* metric metric
tons tons Percent tons tons Percent
156.2 292.8 0.014
459.4 861.3 0.26 59.0 7,260 2.2
1,032.3 1,935 0.10 181.4 22,300 1.2
79.4 9,780 1.4
1,611.3 3,020 0.14 660.0 81,300 3.7
6,109 120,600
Note.—Blanks indicate that process not used in state.
No reported emissions.
-------
are determined by iteration. The value of x(x)» the annual mean
ground level concentration, is computed from the equation:
? te) = ioiji exp i y_ 2 (62)
a ux z
z
where Q = emission rate, g/s
H = effective emission height, m
x = downwind distance from source, m
u = average wind speed (= 4.5 m/s)
o = vertical dispersion coefficient, m
Z
For atmospheric stability class C (neutral conditions) , o is
given by:^7
a = 0.113X0-911 (63)
z
The affected area is then computed as
A = n(x22 X!2) , km2 (64)
where xx and x2 are the two roots of Equation 62.
The (capacity weighted) mean population density, 6p, is
calculated as follows:
.
Dp = ±j£ — -' persons/km2 (65)
where C . = production capacity of plant i
Dp = county population density for plant i
i
The product A • 5 is designated the "affected population."
The affected areas and affected populations were calculated for
the hydrocarbon emission from representative plants using direct
chlorination, hydrochlorination, oxyhydrochlorination , and are
reported in Table 22 for S >0.05, 0.1 and 1.0.
**7Eimutis, E. C., and M. G. Konicek. Derivations of Continuous
Functions for the Lateral and Vertical Atmospheric Dispersion
Coefficients. Atmospheric Environment, 6 (11) :859-863, 1972.
65
-------
TABLE 22. AFFECTED POPULATION AND AFFECTED AREA
Manufacturing
process
Direct chlorination
Hydrochlorination
Oxy hydrochlor i nat ion
Chlorohydrination
Affected area
S20.05
21.4
36
48.5
1,850
20.1
10.2
17.3
23.1
894
, tan*
21.0
0.57
1.0
1.45
79.4
Affected population,
persons
20.05
5,923
5,812
9,600
615,000
>0.1
2,820
2,772
4,580
297,600
21.0
158
167
286
26,400
4. Growth Factor
In 1975, 8.52 x 106 metric tons of the 14 chlorinated hydrocar-
bons listed previously in Table 1 were produced in the United
States. Production in 1980 is expected to total 10.4 x 106
metric tons. Assuming that the same level of control technology
exists in 1980 as existed in 1975, the emissions from the
chlorinated hydrocarbon industry will increase by 20% over that
period; i.e.,
Emissions in 1980 _ 10.4 _ , ~
Emissions in 1975 8.52
For individual chemicals emission increases or decreases should
follow production trends projected in Section VI.
66
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SECTION V
CONTROL TECHNOLOGY
Emissions from the manufacture of chlorinated hydrocarbons consist
primarily of hydrocarbons. Control techniques applicable to hydro-
carbon emission sources include:
• Absorption • Incineration
• Condensation • Adsorption
Other areas warranting controls include:
• Control of storage tank emissions • Waste disposal
• Control of fugitive emissions
A. ABSORPTION
Absorption is the process by which one or more soluble components
are removed from a gas mixture by dissolution in a relatively
nonvolatile liquid. The absorption process may consist of dis-
solving the component in the nonvolatile liquid followed by reac-
tion with the liquid or simply dissolving without reaction.48
This control technology is common within the chlorinated hydro-
carbon manufacturing industry. Absorption is used primarily to
control hydrogen chloride and chlorine vapors rather than hydro-
carbons, because low concentrations of hydrocarbon vapors require
long contact time and large quantities of absorbent.1** When
absorption is used to control hydrocarbon vapors, the solution
must be used as a process makeup stream or the absorbent must be
regenerated. Otherwise, the absorbent stream presents an addi-
tional waste disposal problem. Absorption is also used in conjunc-
tion with other control techniques such as incineration or adsorp-
tion to achieve a greater degree of emission control than these
techniques alone provide.1*9
**8Hughes, T. W. , D. A. Horn, C. W. Sandy, and R. W. Serth. Source
Assessment: Prioritization of Air Pollution for Industrial Sur-
face Coating Operations. EPA-650/2-75-019-a, U.S. Environmental
Protection Agency, Research Triangle Park, North Carolina,
February 1975. 303 pp.
**9Control Techniques for Hydrocarbon and Organic Solvent Emissions
from Stationary Sources. Publication No. AP-68, U.S. Department
of Health, Education, and Welfare, Washington, D.C., March 1970.
pp. 3-1 through 3-26.
67
-------
Absorption is an important processing step in the chlorinated
hydrocarbon industry. Products absorbed in a product recovery
step in industrial processes include hydrocarbons, chlorine, and
hydrogen chloride. Absorption has also been employed in scrubbing
to remove unreacted raw materials from the main process vent.1*9
The ideal absorption system should meet the following requirements:
• The gas should be readily soluble to increase absorption
rate and decrease the quantity of absorbent required.
Solvents chemically similar to the solute generally pro-
vide good solubility.
• The solvent should be nonvolatile, noncorrosive (to
reduce equipment costs), readily available, and
inexpensive.
• The solvent should have low viscosity to increase absorp-
tion and reduce flooding.
• The solvent should be low in toxicity, nonflammable,
chemically stable, and have a low freezing point.
The common absorbents for chlorine and hydrogen chloride are
water, sodium carbonate and sodium hydroxide, and for hydrocar-
bons, nonvolatile hydrocarbon oils.*4*
Absorption equipment provides good contact between the gas and
liquid solvent to permit interphase diffusion of the materials.
Types of equipment providing contact include bubble elate columns,
packed towers, spray towers, and venturi scrubbers."4** Figures 15,
16, 17, and 18 show diagrams of a bubble-cap tray tower, packed
tower, venturi scrubber, and spray tower, respectively.49
In the bubble plate column, a number of plates or trays are
arranged so that the gas is dispersed through a layer of solvent
on each plate. Each plate acts as a separate stage, and the num-
ber of plates used depends upon the difficulty of the mass trans-
fer operation and the degree of separation required. A packed
tower is filled with a packing material having a large surface-to-
volume ratio. The packing material is wetted by the solvent to
provide a large surface area of liquid film for continuous contact-
ing of the gases. In a spray tower, the liquid is sprayed and the
gas mixture is passed through the spray. In a venturi scrubber,
gas and solvent come into contact in the throat of the venturi noz-
zle. The gas-liquid mixture then enters an entrainment separator
tangentially, and centrifugal force separates the liquid droplets
from the gas.49
Absorption of a gaseous component by a liquid occurs when the
liquid contains less than the equilibrium concentration of the com-
ponent. This departure of the liquid stream from equilibrium
68
-------
SHELL-
TRAY
DOWNSPOUT
TRAY
SUPPORT,,,
RING
TRAY —if
STIFFENER
VAPOR
RISER
FROTH
INTERMEDIATE
FEED
LIQUID OUT
Figure 15.
Schematic diagram
of a bubble-cap
tray tower.49
GAS OUT
I
LIQUID
IN
LIQUID
DISTRIBUTOR
PACKING
RESTRAINER
SHELL
RANDOM
PACKING
LIQUID
RE-DISTRIBUTOR
PACKING
SUPPORT
— GAS IN
-LIQUID
OUT
Figure 16. Packed tower.
CLEAN GAS
OUTLET
LIQUID
ABSORBENT INLET
EXHAUST
GAS •
INLET
ENTRAPMENT
SEPARATOR
ABSORBENT.
CONTAMINANT
SOLUTION
OUTLET
EXHAUST
GAS
INLET
CLEAN
GAS
OUTLET
LIQUID
SPRAY
MOISTURE
ELIMINATORS
=1 LIQUID
ABSORBENT
INLET
ABSORBENT.
CONTAMINANT
SOLUTION
OUTLET
Figure 17. Venturi scrubber.49 Figure 18. Spray tower
69
-------
provides the driving force for absorption. The absorption rate
depends upon the temperature, diffusivity, viscosity, and density
of the substance, the tower conditions—particularly the gas and
liquid mass flow rates—and the type of packing material.
The design of absorbers has been discussed by Treybal50 and Perry
and Chilton.51 The problems which arise in designing absorbers
can be attributed to variation of solubilities because of non-
isothermal operating conditions, semi-ideal liquid solutions, and
the change in the gas and liquid flow rates caused by transfer of
the solute from the gas phase to the liquid phase.
B. CONDENSATION
Hydrocarbons can be removed from a gas stream by condensation.
Because of their relatively high boiling points, many hydrocarbons
readily condense even though they are not highly concentrated. A
hydrocarbon vapor will condense when, at a given temperature, the
partial pressure of the compound is equal to or greater than its
vapor pressure. Alternatively, if the temperature of a gaseous
mixture is reduced to the saturation temperature (the temperature
at which the vapor pressure equals the partial pressure of one of
the constituents), condensation will also occur. Thus either
increasing the system pressure or decreasing the temperature can
cause condensation. In most air pollution control applications,
decreased temperature is used to condense hydrocarbons, since
increased pressure is usually impractical.1**
Condensers have found a wide range of application in the chlorina-
ted hydrocarbon industry where their purpose has been to condense
concentrated vapors in the process rather than to reduce atmos-
pheric emissions, although they are used for the latter purpose.
When applied in the process, condensers recover valuable products
and reduce the volume of effluent gas.1*9
The equilibrium partial pressure limits the control of organic
emissions by condensation. As condensation occurs, the partial
pressure of material remaining in the gas decreases rapidly, pre-
venting complete condensation. For example, even at 0°C, toluene
has a vapor pressure of approximately 800 Pa (6 mm Hg). At atmos-
pheric pressure of 101.3 kPa (760 mm Hg), a gas stream saturated
with toluene would still contain about 8,000 ppm of that gas.
Thus, to achieve a high degree of overall efficiency, a condenser
must usually be followed by a secondary air pollution control
device such as an afterburner.1*9
50Treybal, R. E. Mass Transfer Operations. McGraw-Hill Book
Company, New York, New York, 1968. 666 pp.
5Chemical Engineers Handbook, Fifth Edition, J. H. Perry and
C. H. Chilton, eds. McGraw-Hill Book Company, New York,
New York, 1973.
70
-------
Condensation is usually achieved by lowering the vapor tempera-
ture. Thus condensation is induced by deploying a cold surface
or a cooling liquid.1*9 There are basically two types of
condensers—surface and contact—used for condensation. In a
surface condenser, the vapor to be condensed and the cooling
medium are separated by a metal wall; in a contact condenser, the
vapor and the cooling medium are brought into direct contact.1*9
Surface condensers include the common shell and tube-type heat
exchangers, where the cooling medium, usually water, flows through
the tubes, and the vapor condenses on the outside surface of the
tubes; i.e., in the shell. The condensed vapor forms a film on
the cold tubes and can be drained for storage or disposal. Air-
cooled condensers are usually constructed with finned tubes, and
the vapor condenses inside the tubes.1*9
In contact condensers, the vapor is cooled by direct spraying of
the gas stream with a cold liquid, usually water. The mixture of
water and condensed vapor obtained may be discarded or recovered.
Contact condensers generally are less expensive, more flexible,
and more efficient in removing hydrocarbons than surface condens-
ers. Types of contact condensers include spray tower, steam or
water ejector, and barometric condensers. Figures 19 through 26
show different types of surface and contact condensers.
When hydrocarbons are being condensed, important design consider-
ations of condensers include the type(s) of compounds to be
condensed and their temperature, volume, concentration, vapor
pressure, and specific heat. For surface condensers, it is
important to know the heat transfer coefficients on both the
vapor and the liquid sides, the temperature, and the amount of
coolant available. For contact condensers, the amount of cooling
water required is a critical design factor.**9
C. INCINERATION
Because of the formation of noxious compounds (e.g., HC1),
incineration alone is seldom used for the control of chlorinated
hydrocarbons. An adsorber may be used in conjunction with the
incinerator to achieve greater emission control.52
1. Thermal Incineration
Direct-flame afterburners depend upon flame contact and high tem-
peratures to burn the combustible material in gaseous effluents to
52Rolke, R. W., R. D. Hawthorne, C. R. Garbett, E. R. Slater,
T. T. Phillips, and G. D. Towell. Afterburner Systems Study.
EPA-R2-72-062 (PB 212 560), U.S. Environmental Protection Agency,
Research Triangle Park, North Carolina, August 1972. 336 pp.
71
-------
INLET OUTLET
INLET
OUTLET
Figure 19.
Surface condenser:
shell and tube.
Figure 20.
Surface condenser:
fin fan.
Figure 21. Surface condenser:
finned hairpin section.
Figure 22. Surface condenser:
integral finned section.
72
-------
VAPOR
WATER
SPRAY
Figure 23. Surface condenser:
tubular.
Figure 24. Contact condenser:
spray.
DISCHARGE
Figure 25. Contact condenser:
jet
Figure 26. Contact condenser;
barometric.
73
-------
form carbon dioxide and water.52 The combustible materials may
be gases, vapors, or entrained particulate matter which contri-
butes opacity, odor, irritants, photochemical reactivity, and
toxicity to the effluent. Direct-flame afterburners consist of a
refractory-lined chamber, one or more burner temperature indicator-
controllers, safety equipment, and, sometimes, heat recovery
equipment.52
The afterburner chamber consists of a mixing section and a com-
bustion section. The mixing section provides contact between the
contaminated gases and the burner flame. Good mixing is provided
by high velocity flow which creates turbulence. The combustion
section is designed to provide a retention time of 0.3 to 0.5 sec-
onds for completion of the combustion process. Afterburner
discharge temperatures range from 540°C to 800°C, depending on
the air pollution problem. Higher temperatures result in higher
afterburner efficiencies.52
The gas burners used in afterburners are of the nozzle-mixing,
premixing, multiport, or mixing plate type. Burner placement
varies depending on burner type and on the design objective of
providing intimate contact of the contaminated air with the
burner flames.52
Nozzle-mixing and premixing burners are arranged to fire tangen-
tially into a cylindrical afterburner. Several burners or noz-
zle's are required to ensure complete flame coverage, and addition-
al burners or nozzles may be arranged to fire along the length of
the burner. Air for fuel combustion is taken from the outside
air or from the contaminated air stream, which is introduced
tangentially or along the major axis of the cylinders.52
Multiport burners are installed across a section of the after-
burner separate from the main chamber. Although all air for com-
bustion is taken from the contaminated airstream, multiport
burners are not capable of handling all of the contaminated
airstream. Contaminated air in excess of that used for fuel
combustion must be passed around the burner and mixed with the
burner flames in a restricted and baffled area.52
Mixing plate burners, developed for afterburner applications, are
placed across the inlet section of the afterburner. The contami-
nated air and the burner flames are mixed by profile plates
installed around the burner between the burner and afterburner
walls. The high velocities (1 m/s) provided by the burner and
profile plate design ensure mixing of the burner flames and the
contaminated air not flowing through the burner. The contamin-
ated airstream provides air for fuel combustion.52
The efficiency of an afterburner is a function of retention time,
operating temperature, flame contact, and gas velocity. No quanti-
tative mathematical relationship exists between these variables
74
-------
because the kinetics of the combustion process are complex, and
flow inside afterburners is not defined. However, for good design,
the following observations can be made with respect to afterburner
efficiency:5*
• Efficiency increases with increasing afterburner operat-
ing temperature.
• Efficiency decreases if the contaminated gases entering
the afterburner are excessively preheated.
• Efficiency increases with increasing contact between the
contaminated gases and the burner flame.
• Efficiency increases with increasing retention time for
retention times less than 1 second.
• Efficiency is a function of the afterburner design and
the inlet concentration of organic materials.
• Ninety percent afterburner efficiency is difficult to
reach below a 700°C operating temperature if the genera-
tion of carbon monoxide in the afterburner is included
in the calculation of efficiency.
2. Catalytic Incineration
A catalytic afterburner contains a preheat burner section, a cham-
ber containing a catalyst, temperature indicators and controllers,
safety equipment, and heat recovery equipment. The catalyst in
such an afterburner promotes combustion by increasing the rate of
the oxidation reactions without itself appearing to change chemi-
cally.1*8 (See Figure 27.)
PR
Bl
FUME STREAM
20°C - 200°C
EHEAT CATALYST
IRNER ELEMENT
:3^JSF 300°C - 500°C
£122.
400°C - 600°C
CLEAN GAS
TO STACK
COMBUSTION/MIXING
CHAMBER
OIMIONAI
IIIA1 RICOVIHY
1RF.GENERATIVF OR
RECYCLE SYSTEM)
Figure 27. Schematic diagram of a catalytic afterburner.1*8
The contaminated air entering a catalytic afterburner is heated to
the temperature necessary for carrying out the catalytic
75
-------
combustion. The preheat zone temperature, in the range of 300°C
to 500°C, varies with the combustion and type of contaminants.
Because of thermal incineration in the preheat zone, the preheat
burner can contribute to the efficiency of a catalytic afterburner
Catalysts used for catalytic afterburners may be platinum-family
metals supported on metal or matrix elements made of ceramic honey
combs. Catalyst supports should have high geometric surface area,
low pressure drop, structural integrity and durability, and should
permit uniform distribution of the flow of the waste stream
through the catalyst. Catalysts can be poisoned by phosphorus,
bismuth, arsenic, antimony, mercury, lead, zinc, and tin, which
are thought to form alloys with the metal catalyst. Catalysts are
deactivated by materials which form coatings on them, such as the
particulate material, resins, and carbon formed during organic
material breakdown. High temperatures will also deactivate cata-
lysts. Because the combustion reaction is exothermic, the cata-
lyst bed temperature is above the inlet temperature. The tempera-
ture increase depends on the concentration of organic material
burned and the heat of combustion of that material. Compensation
for decreased catalyst activity can be made by: (1) initial over-
design in specifying the quantity of catalyst required to attain
required performance, (2) increasing preheat temperature as chemi-
cal activity decreases, (3) regenerating the catalyst, and
(4) replacing the catalyst.48
The quantity of catalyst required for 85% to 95% conversion of
hydrocarbons ranges from 0.5 m3 to 2 m3 of catalyst per
1,000 m3/min of waste stream. Although the catalyst temperature
depends on the hydrocarbon burned and the condition of the cata-
lyst, the operating temperatures of catalytic afterburners range
from 400°C to 600°C.52
3. Flares
Flares are used for the combustion of low concentration chlorin-
ated hydrocarbon streams and intermittent emissions caused by
plant upset. Flares are not considered an ideal form of control.
Their usefulness is limited because:1*5
• Oxidation of chlorinated hydrocarbons produces hydrogen
chloride which itself is a pollutant.
• Dilute gas streams cannot support combustion, and small
changes in vent gas composition can extinguish the burner
unless supplemental fuel and adequate instrumentation are
provided.
• Heat produced is wasted.
• Improper firing of the burner can result in operating
temperatures which favor NO formation.
X
76
-------
• Efficiency for removing contaminants is less than that
of other combustion devices.
D. ADSORPTION
Adsorption is a mechanism for removing molecules from a liquid or
gas by contacting them with a solid. Gases, liquids, or solids
can be selectively removed from airstreams with materials known
as adsorbents. The material which adheres to the adsorbent is
called the adsorbate.48
The mechanism by which components are adsorbed is complex, and
although adsorption occurs at all solid interfaces, it is minimal
unless the adsorbent has a large surface area, is porous, and pos-
sesses capillaries. The important characteristic of solid adsorb-
ents are their large surface-to-volume ratio and preferential
affinity for individual components.1*8
The adsorption process includes three steps. The adsorbent is
first contacted with the fluid, and adsorption results. Second,
the unadsorbed portion of the fluid is separated from the adsorb-
ent. For gases, this operation is completed when the gases leave
the adsorbent bed. Third, the adsorbent is regenerated by removal
of the adsorbate. Low pressure steam is used to regenerate the
adsorbent, and the condensed vapors are separated from the water
by decantation, distillation, or both.1*8
Activated carbon is capable of adsorbing 95% to 98% of the organic
vapor from air at ambient temperature in the presence of water in
the gas stream.53 When an organic vapor in air mixture starts to
pass over activated carbon, complete adsorption of the organic
vapor takes place. As the adsorptive capacity of the activated
carbon is approached, traces of vapor appear in the exit air,
indicating that the breakpoint of the activated carbon has been
reached. As the air flow is continued and although additional
amounts of organic materials are adsorbed, the concentration of
organic vapor in the exit air continues to increase until it
equals that in the inlet air. The adsorbent is saturated under
these operating conditions.1*8
The adsorption of a mixture of adsorbable organic vapors in air is
not uniform, and the more easily adsorbed components are those
with the higher boiling points. When air containing a mixture of
organic vapors is passed over activated carbon, the vapors are
equally adsorbed at the start. However, as the amount of the
higher boiling component in the adsorbent increases, the more
53Cooper, W. J., et al. Hydrocarbon Pollutant Systems Study;
Volume I - Stationary Sources, Effects, and Control. APTD-1499
(PB 219 073), U.S. Environmental Protection Agency, Research
Triangle Park, North Carolina, October 20, 1972. 379 pp.
77
-------
volatile component revaporizes. The exit vapor consists primarily
of the more volatile component after the breakpoint has been
reached. This process continues for each organic mixture compo-
nent until the highest boiling component is present in the exit
gas. In the control of organic vapor mixtures, the adsorption
cycle should be stopped when the first breakpoint occurs as deter-
mined by detection of vapors in the exit gas. Many theories have
been advanced to explain the selective adsorption of certain
vapors or gases. These theories are presented in Perry and
Chilton51 and will not be discussed here.
The quantities of organic vapors adsorbed by activated carbon are
a function of the particular vapor in question, the adsorbent, the
adsorbent temperature, and the vapor concentration. Removal of
gaseous vapors by physical adsorption is practical for gases with
molecular weights over 45.51 Each type of activated carbon has
its own adsorbent properties for a given vapor, and the quantity
of vapor adsorbed for a particular vapor concentration in the gas
and at a particular temperature is best determined experimentally.
The quantity of vapor adsorbed increases when the vapor concentra-
tion increases and the adsorbent temperature decreases.48
After breakthrough has occurred, the adsorbent is regenerated by
heating the solids until the adsorbate has been removed. A car-
rier gas must also be used to remove the vapors released. Low
pressure saturated steam is used as the heat source for activated
carbon and also acts as the carrier gas. Superheated steam at
350°C may be necessary to remove high boiling compounds and return
the carbon to its original condition when high boiling compounds
have reduced the carbon capacity to the point where complete regen-
eration is necessary.52
Steam requirements for regeneration are a function of external
heat losses and the nature of the organic material. The amount of
steam adsorbed per kilogram of adsorbate, as a function of elapsed
time, passes through a minimum. The carbon should be regenerated
for this length of time to permit the minimum use of steam.51
After regeneration, the carbon is hot and saturated with water.
Cooling and drying are done by blowing organic-free air through
the carbon bed. Evaporation of the water aids cooling of the car-
bon. If high temperature steam has been used, other means of cool-
ing the carbon are required.
Fixed-bed adsorbers arrayed in two or more parallel bed arrange-
ments are used to remove organic vapors from air. (See Figure 28.)
These are batch-type arrangements where a bed is used until break-
through occurs and is then regenerated. The simplest adsorber
design of this type is a two-bed system where one carbon bed is
being regenerated as the other is adsorbing organic vapors. In a
three-bed arrangement, a greater quantity of material can be
adsorbed per unit of carbon because the effluent passes through
two beds in series while the third bed is being regenerated. This
78
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EXHAUST
,3800
ADSORBER II
COOLING
WATER
CONTAMINATED
STREAM
ORGANIC WASTE
STREAM WATER
Figure 28. Carbon adsorption system.53
permits the activated carbon to be used after breakthrough since
the second bed in the series removes organic vapors in the exit
gas from the first bed. When the first bed is saturated, it is
removed from the stream for regeneration; the bed which was used
to remove the final traces of organic vapors from the effluent
then becomes the new first bed; and the bed which has been regen-
erated becomes the new second bed.48
Heat is released in the adsorption process, which causes the tem-
perature of the adsorbent to increase. If the concentration of
organic vapors is not high, as in the case of room ventilators,
the temperature rise is typically 10°C.1*5'1*8
The pressure drop through a carbon bed is a function of the gas
velocity, bed depth, and carbon particle size. Activated carbon
manufacturers supply empirical correlations for pressure drop in
terms of these quantities. These correlations usually include
pressure drop resulting from directional change of the gas stream
at inlet and outlet.^
E. CONTROL OF EMISSIONS FROM STORAGE TANKS
Emissions from storage tanks are controlled to reduce or eliminate
atmospheric emissions, reduce or eliminate fire hazards, and
79
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prevent loss of valuable products. Techniques used to control
storage tank emissions include the use of floating roofs, plastic
blankets, variable vapor space systems, various recovery systems,
and modified pumping and storage operations.1*5
Floating roofs control emissions from a volatile liquid by elimi-
nating the vapor space so that the liquid cannot evaporate and
later be vented. A well-designed floating roof must completely
seal off the liquid surface from the atmosphere. The seal for the
floating roof is therefore very important.45
A floating plastic blanket operates much like a floating roof.
The blanket is usually made of polyvinyl chloride but can be made
of other plastics. Its underside is constructed of a large number
of floats of the same plastic material.45 The blanket is custom
designed to fit within an inch around the periphery. A vertically
raised skirt at the edge of the blanket serves as a vapor seal
over the annular area. Once this area is saturated with vapor, no
further evaporation occurs, and atmospheric loss occurs only
through gaseous diffusion.45
Variable vapor space systems, designed to contain the vapors pro-
duced in storage, can include storage of similar or related prod-
ucts. They use the advantage of inbalance pumping situations
where only the tank vapor spaces are manifolded together. The
manifold system maintains a balanced pressure drop in all the
branches while not exceeding allowable pressure drops. Each tank
has an isolating valve so that it can be removed from the vapor
balance system during gauging or sampling operations. When vapors
exceed the capacity of the balance system, they are incinerated.4*5
The vapor recovery system is very similar yet superior to the
vapor balance system. It is more flexible as to the number of
tanks and products being stored and can handle vapors from filling
operations as well as from tank breathing. Vapors are recovered,
compressed, and charged to an absorption unit for recovery of con-
densable hydrocarbons. Noncondensable vapors are used as fuel or
flared.45
Fixed-roof tank breathing emissions can be reduced by increasing
storage pressure. An increase of 431 Pa (0.063 Ibs/sq in.) was
found to result in an 8% decrease in emissions due to breathing.
Tanks operated at 119 kPa (2 1/2 psig) or higher were found to
have little or no breathing emissions. However, the pressure
setting must not exceed the weight of the roof. Another method
of reducing storage tank emissions is based upon the degree of
saturation in the vapor space. A baffle located horizontally
below the tank vent, as shown in Figures 29 and 30, directs
entering atmospheric air into a stratified layer next to the top
of the tank. Being lighter, air remains in the tank top area,
minimizing mixing with the vapor phase above the liquid surface.
This air is also the first expelled during the outbreathing cycle.
This system can reduce surface evaporation as much as 25% to 50%.45
80
-------
INTERKEDIATE
LOCATING FLANGE
s
POSITIONING ROD
BAFFLE PLATE-
Figure 29. Baffle construction.45
Figure 30. Air baffle.1*5
A protective coating of paint applied to the outside shell and
roof of a tank can influence vapor space and liquid temperatures.
Reflectivity and glossiness of a paint can determine the amount of
heat a tank receives via radiation. Breathing emission reductions
of 25% for aluminum over black paint and 25% for white over alumi-
num paint have been reported.45
Insulation, spraying water on the roof surface, refrigeration, and
autorefrigeration all can reduce heat energy normally conducted to
the liquid in the tanks.1*5
Routine operations such as the reading of gauges or sampling can
be properly scheduled to minimize emissions from storage tanks.
Use of remote level-reading gauges and sampling devices can also
reduce emissions.1*5
81
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F. CONTROL OF FUGITIVE EMISSIONS
Rapid detection and quick repair of leaks are necessary to reduce
fugitive emissions. Leaks may be detected by several methods,
the descriptions of which follow.
A fixed multipoint gas chromatograph, including analyzer and
recorder, may be used to sample for chlorinated hydrocarbons peri-
odically at points within the plant.5*4 The exact location of the
leak in a section where a high concentration has been detected
can be determined by a portable flame ionization-type hydrocarbon
sensing device.51* Another method of detecting fugitive leaks is
to periodically check each possible leak point with a portable
detector.51* A third method is to hydrostatically test piping,
flanges, vessels, manholes, and other process equipment after con-
struction, maintenance, or inspection. **
Control of pump, compressor, and agitator seals is provided by the
use of double mechanical seals between which a liquid is main-
tained at a pressure greater than that which exists in the pump,
compressor, or agitator. Any leakage that occurs will thus leak
into the pump, not out of it.51* All flanged pipe joints are poten-
tial leak sources for which welded connections can be used.
Emissions resulting from sampling for laboratory analysis can be
eliminated by letting the gas to be sampled flow through the sam-
ple flask to a lower pressure point in the process. The sample
flask is then blocked off, and any material that remains in the
sample lines can be purged with inert gas to a recovery system or
a control device.51*
During loading and unloading of raw material, byproducts, and prod-
ucts, two hoses are connected to a railroad car or barge. The bot-
tom hose transfers the material while the other, located at the
top, maintains pressure. Material left in the hoses may be lost
to the atmosphere on disconnection. This can be controlled by
purging the lines to a control device with inert gas.5M
Emissions from pressure relief valves located on all pressure ves-
sels are controlled by a rupture disc installed between the vessel
and the safety valve and a pressure gauge installed between the
valve and rupture disc.54 Pressure buildup between the disc and
the valve indicates rupture disc failure.
Emissions resulting from excessive pressure are controlled by con-
necting the relief valve discharge to a flare or another control
5**Evans, L. , et al. Standard Support Environmental Impact Docu-
ment, Volume II. Draft copy of report. U.S. Environmental Pro-
tection Agency, Office of Air Quality Planning and Standards,
Emission Standards and Engineering Division, Research Triangle
Park, North Carolina, March 1975.
82
-------
device. Material present in equipment that is opened for mainte-
nance or inspection can be controlled by purging the equipment
with inert gas or displacing the contents with water before
opening. 5I*
G. WASTE DISPOSAL TECHNIQUES
Major sources of pollution are the liquid and solid waste materi-
als that are formed during the manufacture of chlorinated hydro-
carbons. This waste is generated along with useful products by
the side reactions that take place when chlorine or hydrogen chlo-
ride is reacted with hydrocarbons.
Until fairly recently, such waste was disposed of by ocean dumping,
landfilling, deep welling, open pit burning, lagooning, and conven-
tional incineration. But with increasing quantities of waste
being produced and increasing concern over the environment, these
relatively cheap disposal options can no longer be regarded as ade-
quate.55'*7 Incineration still remains the best option
available.58'59
Chlorinated hydrocarbons are very stable compounds, and high tem-
peratures (approximately 1900°C) are required to destroy them.
Moreover, at these high temperatures, chlorine and hydrogen chlo-
ride are produced,60'**1 and this poses a serious corrosion problem.
Conventional incinerators are lined with refractory linings that
cannot stand these high temperatures or tolerate the corrosion
55Solving waste problems profitably. Chemical Week, 104(24):38-39,
1969.
56Ross, R. D., and C. E. Hulswitt. Safe Disposal of Chlorinated
and Fluorinated Waste Materials. For presentation at the 62nd
Annual Meeting of the Air Pollution Control Association,
New York, New York, June 22-26, 1969. 19 pp.
57Hot option for disposal of hydrocarbon wastes. Chemical Week,
110(16):37-38, 1972.
58Lewis, C. R., R. E. Edwards, and M. A. Santoro. Incineration of
Industrial Wastes at a Large Multi-Product Chemical Plant. For
presentation at the National Waste Processing Conference,
New York, New York, June 1976. 9 pp.
59Dunn, K. S. Incineration's role in ultimate disposal of process
wastes. Chemical Engineering, Deskbook Issue, 82(21):141-150,
1975.
60Hulswitt, C. E., and J. A. Mraz. HC1 Recovered from Chlorinated
Organic Waste. Chemical Engineering, 79(10):80-81, 1972.
6Monroe, E. S. Combustion, Air Pollution, and Common Sense. In:
Proceedings of the First Mid-Atlantic Industrial Waste Confer-
ence, University of Delaware, Newark, Delaware, November 13-15,
1967. pp. 215-222.
83
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condition. Combustion at lower temperatures in conventional incin-
erators is incomplete, which causes a pollution problem. Moreover,
highly chlorinated waste will not support combustion in conven-
tional incinerators; it requires high performance burners.55'62
Specialized disposal units are required. They must have high per-
formance burners and be lined with corrosion-resistant refractory
material capable of withstanding high temperatures. They must
also be able to recover chlorine as usable hydrochloric acid or as
anhydrous hydrogen chloride.60. One such unit has been developed
jointly by Thermal Research and Engineering Corporation and Union
Carbide. The system utilizes the Sub-X Incinerator-Scrubber and
the UCAR HC1 Recovery System to destroy chlorinated waste produced
during the manufacture of chlorinated hydrocarbons.55'57'6'''62'63
The waste disposal system is designed to handle chlorinated hydro-
carbon wastes which contain from 20% to 90% chlorine.
A schematic flow diagram for the disposal of chlorinated hydro-
carbon wastes is presented in Figure 31. The disposal system is
comprised of two sections: incinerator and HC1 recovery.
Figure 31 shows the processing scheme used to produce either 27%
HC1 or anhydrous HC1.60
1. Incinerator Section (Sub-X Incinerator-Scrubber)
The incinerator section of the disposal system consists of a
burner and a quencher. The burner is an air-atomized vortex
burner which is capable of atomizing the chlorinated hydrocarbon
waste to about 0.04pm. Chlorinated hydrocarbon wastes containing
less than 70% chlorine will burn without auxiliary fuel.60 Wastes
containing 20% to 30% chlorine have heating values of 23,300 to
28,000 kJ/kg and are capable of producing 1930°C flame tempera-
tures without auxiliary fuel. From 30% to 70% chlorine, heating
values decline to 10,500 to 12,600 kJ/kg, and flame temperatures
decline to 1370°C.62 Auxiliary fuel is required to maintain flame
temperatures in the range of 1370°C to 1930°C. Wastes containing
more than 70% chlorine will not support combustion alone. In this
case, the auxiliary fuel provides:62
• Heat required for waste decomposition
• Flame temperature in the 1,370°C to 1,930°C range
• Hydrogen to prevent formation of chlorine
62Santoleri, J. J. Chlorinated Hydrocarbon Waste Disposal and
Recovery Systems, Chemical Engineering Progress, 69(l):68-74,
1973.
63Finding profits in chlorinated hydrocarbon wastes. Chemical
Week, 111(23):39, 1972.
84
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INCINERATOR SECTION
HCIRECOVERY
oo
CHLORINATED WASTE
FRESH WATER
OR WEAK AC ID
FROM VENT
SCRUBBER
CLEAN GAS
•*- TO ATMOSPHERE
<3-50ppmHCI>
_ WATER OR
CAUSTIC SOLUTION
VENT
SCRUBBER
TO SEWER OR
—ABSORTION TRAIN
PRIMARYSsSJDAR>
CONDENSER koNOENSER
PACKED COLUMN
— STRIPPER
BOTTOMS
ACID COOKER
BRINE
.BRINE (-15°CI
/•
ANHYDROUS HCI
<10°C,20psig.
<50ppm H20)
HC. '??
OPTIONAL ANHYDROUS HCI RECOVERY
Figure 31. Schematic flow diagram for the disposal of chlorinated hydrocarbon wastes.
60
-------
The quencher used in the incinerator section is unique in design
since it must protect the processing equipment from damage from
the 1,930°C flame temperatures.55 Flames from the burner are sub-
merged in a 27% HC1 solution to achieve quenching. Gases leave
the quencher at 150°C to 370°C. The quencher is constructed of
impervious graphite (Karbate®) to prevent corrosion.55
A schematic diagram of the incinerator section is shown in
Figure 32.
AUXILIARY FUEL GAS
I IF REQUIRED I
CHLORINATED
HYDROCARBON •j"^
COMBUSTION AIR 4JT
WATER —>TJ=O Uk
POLYPROPYLENE
DEMISTER-
SPRAYS
DOWNCOMER
-IMPERVIOUS
GRAPHITE
LINING
27* HCl SOLUTION
Figure 32.
Schematic diagram of the Sub-X
Incinerator-Scrubber.56
2. HC1 Recovery System (UCAR System)
Quenched gas from the incinerator section is passed through pri-
mary, secondary, and tertiary falling film absorbers.60 Of the
HCl formed in the incinerator, 99% is recovered as 27% hydro-
chloric acid.60 Gases from the tertiary absorber enter a vent
scrubber designed to reduce HCl emissions to 50 ppm or 3 ppm when
using water or dilute caustic, respectively, as the scrubbing
liquid.60 The overall HCl collection efficiency of the absorbers
and the vent scrubber is 99.96% when using dilute caustic in the
vent scrubber.60
86
-------
The 27% hydrochloric acid can be upgraded to anhydrous HC1 contain-
ing less than 50 ppm H2O.60 A conventional packed column stripper
is used to convert the 27% hydrochloric acid to 75% to 80% vapors.
These vapors are cooled to about 16°C to yield 99% HC1 vapors,
which are further cooled to -12°C in a brine condenser to reduce
water content to 50 ppm.60
87
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SECTION VI
GROWTH AND NATURE OF THE INDUSTRY
A. METHYL CHLORIDE
1. Present Technology
In 1975 total U.S. capacity for methyl chloride was estimated to
be 2.81 x 105 metric tons per year.1 This represents 2.45% of all
major chlorinated hydrocarbon capacity. Production in 1975 was
1.42 x 105 metric tons.1 The major producers in the United States
are Allied Chemical Corporation, Continental Oil Company, Diamond
Shamrock Corporation, Dow Chemical U.S.A., Dow Corning Corporation,
Ethyl Corporation, General Electric Company, Stauffer Chemical
Company, and Union Carbide. The 9 companies manufacture methyl
chloride at 11 locations.1 Tables 231 and 241 list the manufactur-
ing companies with their locations and capacities for the chlorina-
tion and hydrochlorination processes.
Methyl chloride is domestically produced by two industrial proc-
esses: (1) direct chlorination of methane and (2) hydrochlorina-
tion of methanol. In 1975 approximately 86% of the industrial
capacity was based on hydrochlorination of methanol, while 14% was
based on direct chlorination of methane.
2. Industry Production Trends
Historically, growth averaged 5.3% per year between 1965 and 1975
and is expected to be 6% per year through 1980.l Figure 33 shows
production from 1960 through 1980. l • 6t*~72
6l*Synthetic Organic Chemicals - United States Production and Sales,
1974. ITC Publication 776, United States International Trade
Commission, Washington, D.C., 1976. 256 pp.
65Synthetic Organic Chemicals - United States Production and Sales,
1973. ITC Publication 728, United States International Trade
Commission, Washington, D.C., 1975. 258 pp.
66Synthetic Organic Chemicals - United States Production and Sales,
1972. TC Publication 681, United States Tariff Commission,
Washington, D.C., 1974. 260 pp.
88
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TABLE 23. MANUFACTURER, PLANT LOCATION, AND CAPACITY FOR METHYL
CHLORIDE PRODUCTION BY THE CHLORINATION OF METHANE1
Company
Location
Capacity,
metric tons/yr
Dow Chemical U.S.A.
Stauffer Chemical Co.
Total capacity
Average capacity
Percent of total methyl chloride capacity
Freeport, TX
Louisville, KY
31,751
6,804
38,555
19,278
14
TABLE 24. MANUFACTURER, PLANT LOCATION, AND CAPACITY FOT METHYL
CHLORIDE PRODUCTION BY THE HYDROCHLORINATION OF METHANOL
1
Company
Location
Capacity,
metric tons/yr
Allied Chemical Corp.
Continental Oil Co.
Diamond Shamrock Corp.
Dow Chemical U.S.A.
Dow Corning
Dow Corning
Ethyl Corp.
General Electric
Union Carbide
Total capacity
Average capacity
Percent of total methyl chloride capacity
Moundsville, WV
Lake Charles, LA
Belle, WV
Plaquemine, LA
Carrolton, KY
Midland, MI
Baton Rouge, LA
Waterford, NY
Institute, WV
11,340
45,359
11,340
68,039
9,072
6,804
45,359
22,680
22,680
242,673
26,964
86
89
-------
250,000
200.000 -
150.000 •
100.000 -
50.000 •
30.000
1980
Figure 33. Methyl chloride production, 1960 to 1980. l • 61*~7 *
67Synthetic Organic Chemicals - United States Production and Sales,
1971. TC Publication 614, United States Tariff Commission,
Washington, D.C., 1973. 258 pp.
68Synthetic Organic Chemicals - United States Production and Sales,
1969. TC Publication 412, United States Tariff Commission,
Washington, D.C., 1971. 251 pp.
69Synthetic Organic Chemicals - United States Production and Sales,
1968. TC Publication 327, United States Tariff Commission,
Washington, D.C., 1970. 266 pp.
70Synthetic Organic Chemicals - United States Production and Sales,
1967. TC Publication 295, United States Tariff Commission,
Washington, D.C., 1969. 212 pp.
7 Synthetic Organic Chemicals - United States Production and Sales,
1966. TC Publication 248, United States Tariff Commission,
Washington, D.C., 1968. 214 pp.
72Synthetic Organic Chemicals - United States Production and Sales,
1965. TC Publication 206, United States Tariff Commission,
Washington, D.C., 1967. 212 pp.
90
-------
Table 25 gives the uses for methyl chloride.1
TABLE 25. METHYL CHLORIDE CONSUMPTION IN 1975l
Uses Percent
Silicones 40
Tetramethyl lead 35
Butyl rubber 4
Methyl cellulose 4
Herbicides 4
Quaternary amines 4
Miscellaneous uses 9
TOTAL 100
Demand for methyl chloride in the silicone industry is likely to
increase as new silicone capacity comes onstream in 1977,l although
recycling of methyl chloride is increasing in that industry. With
new cars using unleaded gas, demand for methyl chloride in the
manufacture of tetramethyl lead is likely to decrease. Methyl
chloride use in herbicides was disappointing as farmers economized
by using less or no herbicides.1
3. Outlook
Methyl chloride capacity appears to be adequate to supply growing
demands for a long time. No new methyl chloride facilities are
scheduled, but a small increase in production capacity is possible
as one company diverts a portion of its methylene chloride produc-
tion to methyl chloride.1
B. METHYLENE CHLORIDE
1. Present Technology
In 1975 total U.S. capacity for methylene chloride was estimated
to be 3.18 x 10s metric tons/yr.2 This represents 2.8% of all
major chlorinated hydrocarbon capacity. Production in 1975 was
2.22 x 105 metric tons (490 million pounds). The major producers
in the United States are Allied Chemical Corp., Diamond Shamrock
Corp., Dow Chemical U.S.A., Stauffer Chemical Co., and Vulcan
Materials Co.2 The five companies produce methylene chloride at
seven locations. Tables 26 and 27 list the manufacturing com-
panies with their locations and capacities for the chlorination
and hydrochlorination processes.2
Methylene chloride is produced commercially by two processes:
(1) direct chlorination of methane and (2) hydrochlorination of
methanol. Direct chlorination of methane accounts for 39% of
91
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TABLE 26. MANUFACTURER, PLANT LOCATION, AND CAPACITY FOR METHYLENE
CHLORIDE PRODUCTION BY THE CHLORINATION OF METHANE2
Company
Location
Capacity,
metric tons/yr
Dow Chemical U.S.A.
Stauffer Chemical Co.
Vulcan Materials Co.
Total capacity
Average capacity
Percent of total methylene chloride capacity
Freeport, TX
Louisville, KY
Wichita, KS
90,718
27,215
6,804
124,737
41,579
39
TABLE 27. MANUFACTURER, PLANT LOCATION, AND CAPACITY FOR METHYLENE
CHLORIDE PRODUCTION BY THE HYDROCHLORINATION OF METHANOL2
Company
Location
Capacity,
metric tons/yr
Allied Chemical Corp.
Diamond Shamrock Corp.
Dow Chemical U.S.A.
Vulcan Materials Co.
Vulcan Materials Co.
Total capacity
Average capacity
Percent of total methylene chloride capacity
Moundsville, WV
Belle, WV
Plaquemine, LA
Geismar, LA
Wichita, KS
22,680
45,359
81,646
36,287
6,804
192,776
38,555
61
industrial capacity, while the hydrochlorination process accounts
for 61%. Methylene chloride capacities are flexible since methyl-
ene chloride, methyl chloride, and chloroform are made in the same
unit.
2. Industry Production Trends
Historically, growth averaged 13% per year between 1965 and 1975
and is expected to be between 10% and 12% per year through I960.2
Figure 34 shows production from 1960 through 1980.
Table 28 summarizes major uses for methylene chloride.2
Due to the demise of fluorocarbon propellants and trichloro-
ethylene and since methylene chloride can be easily substituted
for fluorocarbons in aerosol applications/ growth for methylene
92
-------
374.000
250.000 •
~ 200.000
I
5
190.000 •
100.000
50,000
1960
1975
1980
YEAR
Figure 34. Methylene chloride production, 1960 to 1980 . 2 ' 6l*~7 2
TABLE 28. METHYLENE CHLORIDE CONSUMPTION IN 19752
Uses
Percent
Paint remover
Aerosols
Export
Chemical processes, mainly solvent degreasing
Plastics
Miscellaneous
TOTAL
30
20
20
10
5
15
100
93
-------
chloride is strong in all major end-use areas. Paint removal,
vapor degreasing, and adhesive applications all show good, steady
growth.2
Exports are likely to decrease since Dow Chemical recently has put
a chloromethane unit onstream in Germany.2
3. Outlook
Methylene chloride is cheap and nonflammable and has a clean
health record and other desirable qualities. It is very likely
to maintain a better than 10% growth. Capacity is being increased
to meet demands expected in 1980. New application, such as use
as a blowing agent for urethane foams, and a single operation
phosphatizing process based on methylene chloride offer even
greater potential.2
C. CHLOROFORM
1. Present Technology
In 1975 total U.S. capacity for chloroform was estimated to be
1.95 x 105 metric tons/yr.* This represents 1.7% of all major chlo-
rinated hydrocarbon capacity. Production in 1975 was 1.27 x 105
metric tons.3 The major producers in the United States are Allied
Chemical Corp., Diamond Shamrock Corp., Dow Chemical U.S.A.,
Stauffer Chemical Co., and Vulcan Materials Co. The five com-
panies produce chloroform at seven locations. Tables 29 and 30
list the manufacturing companies with their locations and capac-
ities for the chlorination and hydrochlorination processes,
respectively.3
TABLE 29. MANUFACTURER, PLANT LOCATION, AND CAPACITY FOR CHLOROFORM
PRODUCTION BY THE CHLORINATION OF METHANE3
Capacity,
Company Location metric tons/yr
Dow Chemical U.S.A. Freeport, TX 77,110
Stauffer Chemical Co. . Louisville, KY 34,019
Vulcan Materials Co. Wichita, KS 9,072
Total capacity 120,201
Average capacity 40,067
Percent of total chloroform capacity 61
94
-------
TABLE 30. MANUFACTURER, PLANT LOCATION, AND CAPACITY FOR CHLOROFORM
PRODUCTION BY THE HYDROCHLORINATION OF METHANOL.3
Company
Location
Capacity,
metric tons/yr
Allied Chemical Corp.
Diamond Shamrock Corp.
Dow Chemical U.S.A.
Vulcan Materials Co.
Vulcan Materials co.
Total capacity
Average capacity
Percent of total chloroform capacity
Moundsville, WV
Belle, WV
Plaquemine , LA
Geismar , LA
Wichita, KS
13,608
18,144
13,608
20,865
9,072
75,297
15,059
39
Chloroform is made commercially by two processes: (1) direct chlo-
rination of methane and (2) hydrochlorination of methanol. Direct
chlorination of methane accounts for approximately 61% of indus-
trial capacity, while hydrochlorination accounts for 39%.
Chloroform, methyl chloride, and methylene chloride are usually
produced in the same unit; hence, most capacities are flexible.
2. Industry Production Trends
Historically, growth averaged 9.2% per year between 1965 and 1975
and is expected to range between 8% and 10% per year through 1980.3
Figure 35 shows production from 1960 through 1980.
Table 31 gives the major uses for chloroform.3
Currently, demand has been exceptionally strong, running close to
capacity for some producers. Barring complications from the
fluorocarbon controversy, growth in the two major end-used areas
should continue. The ozone depletion effect of fluorocarbons has
considerable effect on the future growth of chloroform. An across-
the-board ban on fluorocarbons would significantly affect chloro-
form production.3
3. Outlook
Currently the National Academy of Science is completing a study on
fluorocarbons and their effect on the ozone layer, with the report
due within 2 years. Chloroform growth will depend on the results
of this study. Newer fluorocarbons (fluoropolymers) have proven
to be viable for various end uses and should show good growth
through 1980. New capacity which will soon come onstream will
ease some of the recent pressure felt (1975).3
95
-------
195.000
40.000
30.000
1960
1965
1970
1975
1980
YEAR
Figure 35. Chloroform production, 1960 to 1980.3»64~72
TABLE 31. CHLOROFORM CONSUMPTION IN 19753
Use
Percent
Fluorocarbon refrigerants and propellants 60
Fluorocarbon plastics 30
Export and miscellaneous 10
TOTAL 100
96
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D. CARBON TETRACHLORIDE
1. Present Technology
In 1975 total U.S. capacity for carbon tetrachloride was esti-
mated to be 7.63 x 105 metric tons/yr. This represents 6.7% of
all major chlorinated hydrocarbon capacity. Production in 1975
was 4.8 x 105 metric tons.4 The major producers in the United
States are Allied Chemical Corp., Dow Chemical U.S.A.,
E. I. duPont de Nemours and Co., Inc., FMC Corp., Stauffer Chemi-
cal Co., and Vulcan Materials Co. The 6 companies produce carbon
tetrachloride at 11 locations. Carbon tetrachloride is made by
three industrial processes: (1) direct chlorination of methane,
(2) direct chlorination of carbon disulfide, and (3) direct chlo-
rination of propane. Direct chlorination of methane accounts for
55% of the carbon tetrachloride manufactured. Direct chlorination
of carbon disulfide is the oldest of the three methods and
accounts for 30% of industrial capacity. Direct chlorination of
propane accounts for the remaining 15% of carbon tetrachloride
industrial capacity. Tables 32, 33, and 34 list the manufacturing
companies with their locations and capacities for the three
industrial processes currently used.4
TABLE 32. MANUFACTURER, PLANT LOCATION, AND CAPACITY FOR CARBON
TETRACHLORIDE PRODUCTION BY THE CHLORINATION OF METHANE4
TCapacity,
metric
Company Location tons/yr
Allied Chemical Corp. Moundsville, WV 3,629
Dow Chemical U.S.A. Freeport, TX 61,235
Dow Chemical U.S.A. Pittsburg, CA 18,144
E. I. du Pont de Nemours Corpus Christi, TX 226,795
FMC Corporation South Charleston, WV 68,039
Stauffer Chemical Co. Louisville, KY 7,938
Vulcan Materials Co. Geismar, LA 20,412
Vulcan Materials Co. Wichita, KS 13,608
Total capacity 419,800
Average capacity 52,475
Percent of total carbon tetrachloride capacity 55
97
-------
TABLE 33. MANUFACTURER, PLANT LOCATION, AND CAPACITY FOR CARBON TETRACHLORIDE
PRODUCTION BY THE CHLORINATION OF CARBON DISULFIDE**
Capacity,
metric
Company Location tons/yr
FMC Corporation South Charleston, WV 68,039
Stauffer Chemical Co. Le Moyne, AL 90,718
Stauffer Chemical Co. Niagara Falls, NY 68,039
Total capacity 226,796
Average capacity 75,598
Percent of total carbon tetrachloride capacity 30
TABLE 34. MANUFACTURER, PLANT LOCATION, AND CAPACITY FOR CARBON
TETRACHLORIDE PRODUCTION BY THE CHLORINATION OF PROPANE1'
Company
Dow Chemical U.S.A.
Dow Chemical U.S.A.
Stauffer Chemical Co.
Vulcan Materials Co.
Vulcan Materials Co.
Total capacity
Average capacity
Percent of total carbon tetrachloride capacity
Location
Pittsburg, CA
Plaquemine , LA
Louisville, KY
Geismar, LA
Wichita, KS
Capacity,
metric
tons/yr
18,144
56,699
7,938
20,412
13,608
116,801
23 , 360
15
2. Industry Production Trends
Historically, growth averaged 6.8% per year between 1964 and 1974
and is expected to decline at an average rate of approximately 10%
per year through 1979.u Figure 36 shows production from 1960
through 1980.
Table 35 gives the uses for carbon tetrachloride.4
TABLE 35. CARBON TETRACHLORIDE CONSUMPTION IN 1975*4
Use Percent
Fluorocarbons 11 and 12
(trichlorofluoromethane and dichlorodifluoromethane 95
Other 5
TOTAL 100
98
-------
600.000
140.000
YEAR
Figure 36. Carbon tetrachloride production, 1960 to 1980. M'64~72
Fluorocarbons 11 and 12 are used primarily to manufacture aerosols,
Total fillings of aerosol and pressurized products dropped 5% in
1974. The causes were economic plus the issue of ozone depletion
by fluorocarbons. Health controversies surrounding fluorocarbon
propellants will permanently decrease demand for aerosols even if
fluorocarbons do not cause ozone depletion. This has a very nega-
tive effect on the production of carbon tetrachloride, which is
expected to decrease. **
3. Outlook
If the National Academy of Science report on fluorocarbons con-
firms that these materials destroy the stratospheric ozone layer,
close to one-half of the carbon tetrachloride market will be
closed. **
99
-------
E. PERCHLOROETHYLENE
1. Present Technology
In 1975 total U.S. capacity for perchloroethylene was estimated to
be 5.01 x 105 metric tons/yr.5 This represents 4.4% of all major
chlorinated hydrocarbon capacity. Production in 1975 was
3.16 x 105 metric tons.5 The major producers in the United States
are Diamond Shamrock Corp., Dow Chemical U.S.A., Ethyl Corp., Occi-
dental Petroleum Corp., PPG Industries, Inc., and Vulcan Mater-
ials Co. The six companies manufacture perchloroethylene at nine
locations.5
Perchloroethylene is produced commercially by five processes:
(1) direct chlorination of propane, (2) direct chlorination of
ethylene dichloride, (3) direct chlorination of acetylene, (4) as
a byproduct of propylene oxide manufacture from propylene, and
(5) as a byproduct of vinyl chloride manufacture from ethylene
dichloride.
It is difficult to determine the distribution of production of per-
chloroethylene from feedstocks other than acetylene since many com-
panies use a variety of feedstocks. The original method for
producing perchloroethylene was from acetylene, but because of
expensive raw materials and expensive chlorine recovery from hydro-
chloric acid, this route is being slowly phased out. Currently 3%
of perchloroethylene is made from acetylene.
Chlorination of ethylene dichloride represents 35% of industrial
capacity. The major process for making perchloroethylene is by
chlorination of propane, and it is estimated that this utilizes
44% of industrial capacity.
Table 36 lists the three manufacturing companies, with their
locations and capacities, that manufacture perchloroethylene by
the chlorination of propane process.5
2. Industry Production Trends
Historically, growth averaged 6% per year between 1965 and 1975
and is expected to range between 3% and 4% per year through 1980.5
Figure 37 shows production from 1960 through 1980.
Table 37 gives the major uses for perchloroethylene.5
Perchloroethylene growth has been improving in degreasing and chem-
ical intermediate uses. Being an exempt solvent, perchloroethyl-
ene is in demand.5 However, the domestic drycleaning market is
declining, and the psychological fallout from the fluorocarbon
controversy has hurt intermediate use.5
100
-------
TABLE 36. MANUFACTURERS, PLANT LOCATIONS, AND CAPACITIES FOR PERCHLOROETHYLENE
PRODUCTION BY THE CHLORINATION OF PROPANE5
Company
Dow Chemical U.S.A.
Dow Chemical U.S.A.
Dow Chemical U.S.A.
Vulcan Materials Co.
Vulcan Materials Co.
Total capacity
Average capacity
Percent of total perchloroethylene capacity
Location
Freeport, TX
Pittsburg, CA
Plaquemine, LA
Geismar , LA
Wichita, KS
Capacity,
metric tons/yr
54,431
9,072
68,039
68,039
22,680
222,261
44,452
44
400,000
300,000 -
s
u
1 200.000 •
o
s
a.
100,000 •
50.000
1960
1965
1970
1975
YEAR
Figure 37. Perchloroethylene production, 1960 to 1980.5'64~7:
101
-------
TABLE 37. PERCHLOROETHYLENE CONSUMPTION IN 19755
Use Percent
Drycleaning solvent 63
Industrial metal cleaning 14
Chemical intermediate (mostly fluorocarbons) 13
Export and miscellaneous 10
TOTAL 100
3. Outlook
EPA's regulatory pressure on other solvents will continue to
increase perchloroethylene1s market share somewhat. However, bar-
ring new uses, growth cannot be expected to exceed 4% annually.5
F. ETHYLENE DICHLORIDE
1. Present Technology
In 1975 total U.S. capacity for ethylene dichloride was estimated
to be 5.89 x 106 metric tons/yr. 2I* '*1 This represents 51.4% of
all major chlorinated hydrocarbon capacity. Production in 1975
was 5.0 x 106 metric tons.2*1'31 In 1975, 12 chemical companies
produced ethylene dichloride at 17 locations in the United States.
Major producers are Allied Chemical Corp., Continental Oil Co.,
Diamond Shamrock Corp., Dow Chemical U.S.A., Ethyl Corp., The
B. F. Goodrich Co., PPG Industries, Inc., Shell Chemical Co.,
Stauffer Chemical Co., Texaco, Inc., Union Carbide Corp., and
Vulcan Materials Co. 2 **' 3 l
Prior to 1970, ethylene dichloride was produced as a byproduct in
the chlorohydrin process for the manufacture of ethylene oxide.
Currently, all ethylene oxide is made by the direct oxidation of
ethylene; hence, ethylene dichloride is made either by the oxy-
hydrochlorination or the chlorination of ethylene. It has been
estimated that the oxyhydrochlorination route represents 52% of
current ethylene dichloride capacity and is increasing because of
its cheaper raw materials and higher yields . 21* • 3 l
Tables 38 and 39 list manufacturing companies, plant locations,
and capacities for the manufacture of ethylene dichloride by the
chlorination and oxyhydrochlorination processes.24• 31
102
-------
2. Industry Production Trends
Historically, growth averaged 9% per year from 1969 through 1974
and is expected to be 4% per year through 1979. Figure 38 shows
production capacity of ethylene dichloride from 1960 through
TABLE 38. MANUFACTURERS, PLANT LOCATIONS, AND CAPACITIES
FOR ETHYLENE DICHLORIDE PRODUCTION BY THE
CHLORINATION OF ETHYLENE2 * • 3 l
Company
Location
Capacity,
metric tons/yr
Continental Oil Co.
Dow Chemical Co.
Dow Chemical Co.
Ethyl Corp.
Ethyl Corp.
PPG Industries
Vulcan Materials Co.
Union Carbide Corp.
Total capacity
Average capacity
Percent of total ethylene dichloride capacity
Westlake, LA
Oyster Creek, TX
Plaquemine, LA
Baton Rouge, LA
Pasadena, TX
Lake Charles, LA
Geismer, LA
Texas City, TX
523,900
498,950
601,010
317,510
117,930
544,310
149,680
68,040
2,821,330
352,670
48
TABLE 39. MANUFACTURERS, PLANT LOCATIONS, AND CAPACITIES
FOR ETHYLENE DICHLORIDE PRODUCTION BY THE
OXYHYDROCHLORINATION OF ETHYLENE24•31
Company
Location
Capacity,
metric tons/yr
Allied Chemical Corp.
Diamond Shamrock Corp.
Dow Chemical U.S.A.
B. F. Goodrich
Shell Chemical Co.
Shell Chemical Co.
Stauffer Chemical Co.
Texaco, Inc.
Union Carbide Corp.
Total capacity
Average capacity
Percent of total ethylene dichloride capacity
Baton Rouge, LA
Deer Park, TX
Freeport, TX
Calvert City, KY
Deer Park, TX
Norco, LA
Carson, CA
Port Neches, TX
Taft, LA
319,300
202,100
735,000'
459,400
551,300
535,200*
156,200
32,200
68,900
3,059,600
339,956
52
a
a
Estimated figures.
103
-------
o
6.081.000
5,000,000 -
4,000.000 -
3.000.000 -
2.000.000 -
1.000.000 -
400.000
1960
Figure 38.
1965
1970
1975
1980
YEAR
Ethylene dichloride production,
1960 to 1980.2l4'31'6tl-72
Table 40 summarizes the data for ethylene dichloride uses.24'31
Demand for ethylene dichloride to produce vinyl chloride, its
major end use, has been increasing steadily at 10% per year.
Ethylene dichloride end use to make 1,1,1-trichloroethane,
perchloroethylene, vinylidene chloride, and ethylenediamine has
grown steadily. Due to EPA regulations, production of trichlo-
roethylene and lead scavengers has declined.2'1'31
3. Outlook
No capacity increases for ethylene dichloride have been announced,
With only 76% capacity utilized, there is sufficient capacity
onstream to meet the projected 4% increase in demand.
104
-------
TABLE 40. ETHYLENE DICHLORIDE CONSUMPTION IN 197521*'31
Uses Percent
Vinyl chloride 81
1,1,1-Trichloroethane 3
Trichloroethylene 3
Perchloroethylene 3
Vinylidene chloride 3
Ethyleneamines 3
Lead scavenger 2
Exports 2
Miscellaneous Negligible
TOTAL 100
Vinyl chloride will continue to be the largest end use for ethyl-
ene dichloride. Air pollution control regulations have limited
trichloroethylene production. However, its substitutes,
1,1,1-trichloroethane and perchloroethylene, are also ethylene
dichloride derivatives so essentially the ban on trichloro-
ethylene use will not affect ethylene dichloride total consumption,
Vinylidene chloride and ethyleneamine consumption and, conse-
quently, ethylene dichloride consumption are expected to increase
7% and 5% per year, respectively, through 1979.
Conversion from leaded to unleaded gas could make ethylene dichlo-
ride available for other uses.
G. PHOSGENE
1. Present Technology
In 1975 total U.S. capacity for phosgene was estimated to be
7.22 x 105 metric tons/yr.° This represents 6.3% of all major
chlorinated hydrocarbon capacity. The production in 1975 was
4.41 x 105 metric tons.6 The major producers in the United States
are Allied Chemical Corp., BASF Wyandotte Corp., Chemetron Corp.,
E. I. du Pont de Nemours and Co., FMC Corp., General Electric,
Jefferson Chemical Co., Mobay Chemical Co., Olin Corp., PPG Indus-
tries, Inc., Rubicon Corp., Stauffer Chemical Co., Story Chemi-
cal Corp., Union Carbide Corp., The Upjohn Co., and Van De Mark
Chemical Co., Inc. These 16 companies produce phosgene at 18 loca-
tions.6 Phosgene is manufactured by the chlorination of carbon
monoxide, and its major use (approximately 85%) is in the manufac-
ture of isocyanates.
Table 41 lists manufacturing companies, plant locations, and capac-
ities for the manufacture of phosgene.6
105
-------
TABLE 41. MANUFACTURERS, PLANT LOCATIONS, AND CAPACITIES FOR PHOSGENE
PRODUCTION BY THE CHLORINATION OF CARBON MONOXIDE6
Company
Location
Capacity,
metric tons/yr
Allied Chemical Corp.
BASF Wyandotte Corp.
Chemetron Corp.
E. I. du Pont de Nemours Co., Inc.
FMC Corp.
General Electric Co.
Mobay Chemical Co.
Mobay Chemical Co.
Olin Corp.
Olin Corp.
PPG Industries
Rubicon Chemicals
Stauffer Chemical Co.
Story Chemical Corp.
Tenaco, Inc.
Union Carbide Corp.
The Upjohn Co.
Van De Mark Chemical Co.
Total capacity
Average capacity
Percent of total phosgene capacity
Moundsville, WV
Geismar, LA
LaPorte, TX
Deepwater Point, NJ
Baltimore, MD
Mount Vernon, IN
Baytown, TX
New Martinsville, WV
Lake Charles, LA
Ashtabula, OH
Barberton, OH
Geismar, LA
Cold Creek, AL
Muskegon, MI
Port Neches, TX
South Charleston, WV
LaPorte, TX
Lockport, NY
44,452
24,947
36,287
61,235
2,722
27,215
58,967
111,130
54,431
22,680
2,268
56,699
11,340
4,536
13,608
49,895
136,077
3,629
722,118
40,118
100
2. Industry Production Trends
Historically, growth averaged 15.9% per year between 1963 and 1973
and is expected to be 12% per year through I960.6 Figure 39 shows
actual and estimated production from 1965 through 1980. 6 ' 6l4~7 2
Table 42 gives the major uses of phosgene.6
The growth rate of phosgene closely parallels that of the iso-
cyanates used in urethanes. A strong demand for phosgene-based
pesticides has initiated an expansion of nonisocyanate phosgene
production.6 Shortages of chlorine and its high prices when avail-
able have created problems in phosgene production.6
3. Outlook
Strong growth potential for polycarbonates, pesticides, and iso-
cyanates indicates a continued strong growth for phosgene.6
106
-------
777,000
ion. ooo
1965
1980
Figure 39. Phosgene production,
1965 to 1980.6'64~72
TABLE 42. PHOSGENE CONSUMPTION IN 19756
Use
Percent
Toluene diisocyanate 62
Other (polymeric) isocyanates 23
Polycarbonates 6
Pesticides, carbonates, and specialties 9
TOTAL 100
107
-------
H. MONOCHLOROBENZENE
1. Present Technology
In 1975 total U.S. capacity for monochlorobenzene was estimated to
be 3.13 x 105 metric tons.* This represents 2.7% of all major
chlorinated hydrocarbons capacity. The production in 1975 was
1.76 x 105 metric tons.7 The major producers in the United States
are Allied Chemical Corp., Dow Chemical U.S.A., Monsanto Co.,
Montrose Chemical Corp. of California, PPG Industries, Inc., and
Standard Chlorine Chemical Co., Inc. The six companies produce
monochlorobenzene at six locations.7 Commercially, monochloro-
benzene is manufactured along with ortho- and pam-dichlorobenzene
by the chlorination of benzene. Table 43 lists manufacturing com-
panies, plant locations, and capacities for the manufacture of
monochlorobenzene by the chlorination of benzene.7
TABLE 43. MANUFACTURERS, PLANT LOCATIONS, AND CAPACITIES FOR MONOCHLOROBENZENE
PRODUCTION BY THE CHLORINATION OF BENZENE7
Company
Location
Capacity,
metric tons/yr
Allied Chemical Corp.
Dow Chemical U.S.A.
Monsanto Co.
Montrose Co.
PPG Corp.
Standard Chlorine Co.
Total capacity
Average capacity
Percent of total monochlorobenzene capacity
Syracuse, NY
Midland, MI
Sauget, IL
Henderson, NV
New Martinsville, WV
Delaware City, DE
23,587
136,077
52,163
31,751
31,751
34,019
309,348
51,558
100
2. Industry Production Trends
Historically, the production declined at an average rate of 2%
per year between 1963 and 1973 and is expected to grow at 2% per
year through 1978.7 Figure 40 shows actual and estimated pro-
duction of monochlorobenzene between 1965 and 1980.
Table 44 gives the major uses for monochlorobenzene.7
ortho- and parvz-Nitrochlorobenzene use has been increasing modestly,
The demand for DDT to control malaria in foreign countries is
expected also to increase dramatically, to nearly double current
annual use, by 1982.7 Use of monochlorobenzene to make phenol is
decreasing.
108
-------
150.000
1965
1970 1975
YEAR
1980
Figure 40. Monochlorobenzene production,
1965 to 1980.7,64-^2
TABLE 44. MONOCHLOROBENZENE CONSUMPTION IN 19757
Use
Percent
ortho- and para-Nitrochlorobenzene
Solvent
Phenol
Miscellaneous
TOTAL
50
20
10
20
100
109
-------
3. Outlook
Actual production of monochlorobenzene is not expected to increase
much over the next several years.7 Dichlorobenzene manufacture is
being stressed by manufacturers at the expense of monochloro-
benzene, and newer facilities will favor high ratios of dichloro-
benzene to monochlorobenzene.7
I. DICHLOROBENZENES
1. Present Technology
In 1975 total U.S. capacity for dichlorobenzene was estimated to
be 1.34 x 105 metric tons."'9 This represents 1.17% of all chlo-
rinated hydrocarbon capacity. Production in 1975 was 6.58 x 101*
metric tons.8'9 The major producers in the United States are:
Allied Chemical Corp., Chemical Products Corp., Dow Chemical U.S.A.,
ICC Industries, Inc., Monsanto Co., PPG Industries, Inc., Solvent
Chemical Co., Inc., Specialty Organics, Inc., and Standard Chlo-
rine Chemical Co., Inc. These 9 companies produce dichlorobenzene
at 11 locations.8'9
Commercially, dichlorobenzene is manufactured along with mono-
chlorobenzene by the chlorination of benzene. ortfco-Dichloro-
benzene represents 46% of the dichlorobenzene industrial capacity
while para-dichlorobenzene represents 54%.
Tables 45 and 46 list the manufacturing companies, plant locations,
and capacities for the manufacture of para- and ortfeo-dichloro-
benzenes by the chlorination of benzene, respectively.8'9
TABLE 45. MANUFACTURERS, PLANT LOCATIONS, AND CAPACITIES FOR
p-DICHLOROBENZENE PRODUCTION BY THE CHLORINATION OF BENZENE
8
Company
Location
Capacity,
metric tons/yr
Allied Chemical Co.
Dow Chemical U.S.A.
Monsanto Co.
PPG Corp.
Solvent Chemical Co.
Standard Chlorine Co.
Specialty Organics
Total capacity
Average capacity
Percent of total p-dichlorobenzene capacity
Syracuse, NY
Midland, MI
Sauget, IL
New Martinsville, WV
Niagara Falls, NY
Delaware City, DE
Irwindale, CA
3,629
13,608
5,443
9,525
4,536
34,019
907
71,667
10,238
100
110
-------
TABLE 46. MANUFACTURERS, PLANT LOCATIONS, AND CAPACITIES FOR
0-DICHLOROBENZENE PRODUCTION BY THE CHLORINATION OF BENZENE9
Capacity,
Company Location metric tons/yr
Allied Chemical Co. Syracuse, NY 3,629
Dow Chemical U.S.A. Midland, MI 13,608
Monsanto Co. Sauget, IL 7,257
PPG Corp. New Martinsville, WV 9,072
Solvent Chemical Co. Niagara Falls, NY 4,536
Standard Chlorine Co. Delaware City, DE 22,680
Specialty Organics Irwindale, CA 907
Total capacity 61,689
Average capacity 8,813
Percent of total o-dichlorobenzene capacity 100
2. Industry Production Trends
a. para-Dichlorobenzene—
Historically, growth averaged 0.4% per year between 1965 and 1975
and is expected to decline at a rate of 1% per year through
1980.8 Figure 41 shows actual and predicted production for
p-dichlorobenzene between 1965 and 1980. 8 • 9» 6tf~72 Figure 42
shows production for total dichlorobenzenes. 8 > 9 • 6"+-72 Table 47
gives the major uses of p-dichlorobenzene.8
b. ortfeo-Dichlorobenzene—
Historically, growth averaged 9% per year between 1965 and 1975
and is expected to be 8% per year through 198O.9 Figure 41 shows
actual and predicted production for o-dichlorobenzene. Table 48
gives the major uses for o-dichlorobenzene.9
High-purity ortTzo-dichlorobenzene occupies a strong position in the
synthesis of organic pesticides.9 In the chlorination of benzene,
considerable progress has been made in reducing the ratio of
para- to ortfeo-dichlorobenzene. 9 ortfco-Dichlorobenzene is the more
desirable product, and para-dichlorobenzene can be regarded as an
occasionally troublesome byproduct.9
Higher prices for both benzene and chlorine have resulted in
higher prices for the dichlorobenzenes.8'9
3. Outlook
There are no new outlets in sight for para-dichlorobenzene. Cur-
rent markets are expected to survive but not to grow over the next
five years.8'9 Government regulations for chlorinated benzenes
111
-------
«.oo •
15.000
Figure 41. p-Dichlorobenzene and o-dichlorobenzene
production, 1965 to 1980.9'9'64~72
7*000
Figure 42. Dichlorobenzene production,
1965 to 1980.8'9'6"-71'
112
-------
TABLE 47. p-DICHLOROBENZENE CONSUMPTION IN 19758
Use Percent
Space odorant 50
Moth control 40
Other 10
TOTAL 100
TABLE 48. o-DICHLOROBENZENE CONSUMPTION IN 19759
Use Percent
Organic synthesis (chiefly as pesticide intermediate) 65
Toluene diisocyanate process solvent 15
Miscellaneous solvent uses 10
Dyestuff manufacture 5
Other 5
TOTAL 100
will continue to have an impact on solvent use of
benzene. Growth will follow the long-term agricultural chemical
outlook and capacity should be adequate.8'9 As demand for ortho-
dichlorobenzene and its production increases, so will the para-
dichloro-benzene output. »9
J. ETHYL CHLORIDE
1. Present Technology
In 1975 total U.S. capacity for ethyl chloride was 4.65 x 105
metric tons/yr.11 This represents 3.4% of all major chlorinated
hydrocarbon capacity. The production in 1975 was 2.61 x 105
metric tons.11 The major producers in the United States are Dow
Chemical U.S.A., E. I. du Pont de Nemours and Co., Inc., Ethyl
Corp., PPG Industries, Inc., Shell Chemical Co., and Stauffer
Chemical Co.11 These six companies produce ethyl chloride at
seven locations.
Ethyl chloride is manufactured industrially by two chemical proc-
esses: (1) chlorination of ethane and (2) hydrochlorination of
ethylene. Currently, chlorination of ethane accounts for approxi-
mately 17% of the ethyl chloride industrial capacity, and hydro-
chlorination of ethylene accounts for the remaining 83%. The
plant capacity directed toward the production of ethyl chloride
by the chlorination of ethane is not distinguished from the total
113
-------
industry capacity. For the purposes of this report, all the
ethyl chloride was assumed to be produced by hydrochlorination.
Table 49 lists the manufacturing companies, plant locations, and
capacities for the manufacture of ethyl chloride by the hydro-
chlorination of ethylene.11
TABLE 49. MANUFACTURERS, PLANT LOCATIONS, AND CAPACITIES FOR
ETHYL CHLORIDE PRODUCTION BY THE HYDROCHLORINATION
OF ETHYLENE *l
Company
Location
Capacity,
metric tons/yr
Dow Chemical U.S.A.
E. I. du Pont de Nemours Co., Inc.
Ethyl Corp.
Ethyl Corp.
PPG Industries
Shell Chemical Co.
Stauffer Chemical Co.
Total capacity
Average capacity
Percent of total ethyl chloride capacity
Freeport, TX
Deepwater, NJ
Baton Rouge, LA
Houston, TX
Lake Charles, LA
Houston, TX
Long Beach, CA
34,019
49,895
95,254
68,039
54,431
38,555
45,359
385,552
55,079
83
2. Industry Production Trends
Historically, growth averaged 0.5% per year between 1965 and 1975
and is expected to decline between 30% and 50% per year through
1980.M
Table 50 gives the major uses for ethyl chloride.11
Tetraethyl lead, which is cheaper than tetramethyl lead, is by
far the primary antiknock compound used in gasoline. EPA regul-
ations require refiners to reduce the average lead content of
gasoline to 0.5 gram per gallon, a reduction of from 75% to 80%
from current levels, within 2 years.11 The number of new cars
burning unleaded fuel exclusively may cause the disappearance
of antiknock lead compounds from the market.11
3. Outlook
Producers and petroleum refiners expect lead alkyl antiknock
compounds to totally disappear from the market by the mid-1980's.
Ethyl chloride plants can be converted to manufacture other,
fast-growing hydrocarbons such as methylene chloride.11
114
-------
400.000
1970
1978
1980
YEAR
Figure 43. Ethyl chloride production,
1965 to 19801 > '6t*~72
TABLE 50. ETHYL CHLORIDE CONSUMPTION IN 1975ll
Use Percent
Tetraethyl lead antiknock compounds 90
Export and miscellaneous 10
TOTAL 100
K. 1,1,1-TRICHLOROETHANE
1. Present Technology
In 1975 total U.S. capacity for 1,1,1-trichloroethane was
estimated to be 3.36 x 105 metric tons/yr. 1,1,1-Trichloroethane
represents 2.9% of all major chlorinated hydrocarbon capacity.
The production in 1975 was 2.79 x 105 metric tons. Major prod-
ucers in the United States are Dow Chemical Co., PPG Industries,
Inc., and Vulcan Materials Co. The three companies produce
1,1,1-trichloroethane at three locations. About 7% of the total
115
-------
domestic capacity for 1,1,1-trichloroethane manufacture is based
on ethylene dichloride-derived intermediates.28 Table 51 lists
manufacturing companies, plant locations, and capacities for the
manufacture of 1,1,1-trichloroethane.28
TABLE 51. MANUFACTURERS, PLANT LOCATIONS, AND CAPACITIES FOR
1,1,1-TRICHLOROETHANE PRODUCTION BY THE HYDRO-
CHLORINATION AND CHLORINATION OF VINYL CHLORIDE28
Company
Location
Capacity,
metric tons/yr
Dow Chemical U.S.A.
PPG Industries
Vulcan Materials Co.
Total capacity
Average capacity
Percent of total 1,1.1-trichloroethane capacity
Freeport, TX
Lake Charles, LA
Geismar, LA
204,116
79,378
29,483
312,977
104,326
93
2. Industry Production Trends
Historically, growth averaged over 11.7% per year from 1966
through 1974 and is expected to be 4% per year through 1979.
Figure 44 shows production for 1,1,1-trichloroethane between 1966
and 1979.6U-72
40X000
mono
71 ao.no
i
Figure 44.
1,1,1-Trichloroethane production,
1966 to 1979.&4~72
116
-------
Table 52 summarizes the data for 1,1,1-trichloroethane uses.
TABLE 52. 1,1,1-TRICHLOROETHANE CONSUMPTION IN 197528
Use Percent
Cleaning solvent cold cleaning 33.0
Cleaning solvent vapor degreasing 29.6
Vinylidene chloride 20.5
Exports 11.8
Miscellaneous 5.1
TOTAL 100.0
1,1,1-Trichloroethane is well suited for use as a solvent in hot
and cold cleaning of metals and other materials because of its
nonflammability, excellent solvent properties, and low toxicity.
With a restriction on the use of trichloroethylene, many vapor
degreasing operations have switched to 1,1,1-trichloroethane.
Consumption of 1,1,1-trichloroethane for vapor degreasing in-
creased at an average annual rate of 21% from 1971 through 1974.
1,1,1-Trichloroethane is used as a vapor pressure depressant in
aerosols, as a coolant in metal cutting oils, as a solvent, as
a carrier for lubricants, and in the manufacture of vinylidene
chloride which is consumed chiefly in the production of poly-
vinylidene copolymers.
3. Outlook
To meet the projected growth rate of 4% per year, additional capac-
ity will be required by 1977-78. This is expected since Dow is
expanding its 1,1,1-trichloroethane facilities at Freeport, Texas
and Plaquemine, Louisiana.
1,1,1-Trichloroethane's growth in cleaning operations is expected
to continue, but at a lower rate, unless trichloroethylene is con-
firmed to be carcinogenic.
Consumption of 1,1,1-trichloroethane for vinylidene chloride pro-
duction and air aerosols is expected to remain static.
L. TRICHLOROETHYLENE
1. Present Technology
In 1975 total U.S. capacity for trichloroethylene was estimated
to be 2.18 x 105 metric tons/yr.10 This represents 1.9% of all
chlorinated hydrocarbon capacity. The production in 1975 was
1.61 x 105 metric tons.10 The major producers in the
117
-------
United States are Diamond Shamrock Corp., Dow Chemical U.S.A.,
Ethyl Corp., Occidental Petroleum Corp., and PPG Industries, Inc.
These five companies manufacture trichloroethylene at five
locations.1°
Trichloroethylene is produced commercially by two processes:
(1) oxyhydrochlorination of ethylene dichloride and (2) chlorina-
tion then dehydrochlorination of acetylene. Oxyhydrochlorination
of ethylene dichloride is the major process and accounts for
92% of the industrial capacity.
Chlorination then dehydrochlorination of acetylene currently
accounts for 8% of industrial capacity. It was the original
method of production, although Occidental Petroleum Corp. is the
only company producing trichloroethylene by this process. Its
main drawbacks are its relatively expensive starting raw material
and the expense involved in recovering the chlorine value from
the byproduct hydrochloric acid produced. Table 53 lists manu-
facturing companies, plant locations, and capacities for the
manufacture of trichloroethylene by the oxyhydrochlorination of
ethylene dichloride.l°
TABLE 53. MANUFACTURERS, PLANT LOCATIONS, AND CAPACITIES FOR TRICHLOROETHYLENE
PRODUCTION BY THE OXYHYDROCHLORINATION OF ETHYLENE DICHLORIDE.10
Capacity,
Company Location metric tons/yr
Dow Chemical U.S.A. Freeport, TX 68,039
Diamond Shamrock Deer Park, TX 22,680
Ethyl Corp. Baton Rouge, LA 18,144
PPG Industries Lake Charles, LA 90,718
Total capacity 199,580
Average capacity 49,895
Percent of total trichloroethylene capacity 92
2. Industry Production Trends
Historically, growth averaged 1.25% per year between 1964 and
1974 and is expected to decline 8% per year through 1979.10
Figure 45 shows production capacity from 1945 through 1979. 10'6I*~72
Table 54 gives the major uses for trichloroethylene
10
Trichloroethylene has been widely acclaimed to be the best solvent
for use in vapor degreasing, but it is very photoreactive. Cur-
rent air pollution regulations severely restrict use and emissions
of trichloroethylene in vapor-degreasing plants. Emission reduc-
tion requires removal of trichloroethylene vapors and recycling.
This also reduces overall demand at degreasing plants.10 Evidence
118
-------
1945 1950 1955 1960 1965 1970 1975 1980
YEAR
Figure 45. Trichloroethylene production,
1945 to 1979.l0/64-72
TABLE 54. TRICHLOROETHYLENE CONSUMPTION IN 197510
Use
Percent
Vapor degreasing of fabricated metal parts 87
Exports 11
Miscellaneous 2
TOTAL 100
that trichloroethylene is a potential carcinogen has also affected
its market, causing significant decreases in production.10
3. Outlook
A steady decline in the use of trichloroethylene as a deqreasinq
solvent is currently taking place.10 Alternative solvents such as
perchloroethylene and 1,1,1-trichloroethane are being substituted
for trichloroethylene. It is likely in the future that trichloro-
ethylene will be totally phased out in favor of alternative chlo-
rinated solvents.10
119
-------
M. EPICHLOROHYDRIN
1. Present Technology
In 1975 total U.S. capacity for epichlorohydrin was estimated to
be 2.04 x 105 metric tons/yr. This represents 1.78% of all chlo-
rinated hydrocarbon production capacity. In 1975 the production
was 1.71 x 105 metric tons. The major producers in the United
States are Dow Chemical U.S.A. and Shell Chemical Co. The two com-
panies produce epichlorohydrin at three locations.
Commercially, all epichlorohydrin is manufactured by the chloro-
hydrination of allyl chloride derived by the chlorination of
propylene.28 Table 55 lists manufacturing companies, plant loca-
tions, and capacities for the manufacture of epichlorohydrin.28
TABLE 55. MANUFACTURERS, PLANT LOCATIONS, AND CAPACITIES FOR EPICHLOROHYDRIN
PRODUCTION BY THE CHLOROHYDRINATION OF ALLYL CHLORIDE28
Capacity,
Company Location metric tons/yr
Dow Chemical U.S.A. Freeport, TX 113,398
Shell Oil Company Houston, TX 63,503
Shell Oil Company Norco, LA 27,215
Total capacity 204,116
Average capacity 68,039
Percent of total epichlorohydrin capacity 100
2. Industry Production Trends
Historically, growth for refined epichlorohydrin averaged 8.5% per
year between 1969 and 1973. Growth of crude epichlorohydrin has
averaged a decline of 4% per year from 1967 through 1973.28 Fig-
ure 46 shows actual and predicted production from 1962 through
1978 for refined epichlorohydrin and from 1967 through 1978 for
crude epichlorohydrin. 28 ' 6"*~72
Table 56 gives the major uses for epichlorohydrin.28
Consumption of crude epichlorohydrin to make synthetic glycerin
has declined since 1967 mainly because alternate raw materials,
acrolein and propylene oxide, are now being used. The remaining
crude product is being used to make refined epichlorohydrin to
meet demands for increasing epoxy resins manufacture.28
120
-------
30.000
1962
1979
Figure 46. Epichlorohydrin production,
1962 to 1978. 28,U-72
TABLE 56. EPICHLOROHYDRIN CONSUMPTION IN 197528
Percent
Use
Synthetic glycerin
Epoxy resins
Epichlorohydrin elastomers
Other products
Exports
TOTAL
Crude
epichlorohydrin
46.4
38.8
1.7
9.3
3.8
100.0
Refined
epichlorohydrin
n
72.2
3.3
17.3
7.2
]00.0
121
-------
3. Outlook
Consumption of crude epichlorohydrin for making synthetic glycerin
will remain fairly constant. Use of refined epichlorohydrin is
expected to grow at an average rate of 6% to 7% per year. Epoxy
resins are the primary end use of refined epichlorohydrin, and
these are expected to increase at 10% per year. It is possible
that U.S. capacity will be expanded in the future to meet the grow-
ing U.S. need, expecially for use in the manufacture of epoxy
resins.28
N. PROPYLENE OXIDE
1. Present Technology
In 1975 total U.S. capacity for propylene oxide was estimated to
be 11.93 x 105 metric tons.12 This represents 10.42% of all major
chlorinated hydrocarbon manufacturing capacity. The production in
1975 was 6.80 x 105 metric tons.12 The major producers in the
United States are BASF Wyandotte Corp., Dow Chemical U.S.A., Olin
Corp., Oxirane Corp., and Texaco, Inc. These five companies pro-
duce propylene oxide at six locations.12
Propylene oxide is made by two industrial processes: chloro-
hydrination of propylene and peroxidation of propylene. Although
it is not a chlorinated hydrocarbon, propylene oxide is being con-
sidered in this study because approximately 65% of the material is
produced by the chlorohydrination process using a chlorinated
hydrocarbon (propylene chlorohydrin) as a chemical intermediate.
The remaining 35% of propylene oxide is made by Oxirane's peroxida-
tion of propylene. Table 57 lists the four manufacturing com-
panies, with their plant locations and capacities, that manufac-
ture propylene oxide by chlorohydrination of propylene.12
TABLE 57. MANUFACTURERS, PLANT LOCATIONS, AND CAPACITIES FOR PROPYLENE
OXIDE PRODUCTION BY THE CHLOROHYDRINATION OF PROPYLENE12
Capacity,
Company Location metric tons/yr
BASF Wyandotte Corp.
Dow Chemical U.S.A.
Dow Chemical U.S.A.
Jefferson Chemical Co.
Olin Corp.
Total capacity
Average capacity
Percent of total propylene oxide capacity
Wyandotte, MI
Freeport, TX
Plaquemine, LA
Port Neches, TX
Brandenburg , KY
79,378
415,035
154,221
68,039
58 , 967
775,640
155,128
65
122
-------
2. Industry Production Trends
Historically, growth averaged 12% per year between 1965 and 1975
and is expected to be 13% in 1976 and 10% per year between 1977
and 1980.12 Figure 47 shows actual and predicted production of
propylene oxide between 1965 and 1980. ! 2 » 6**-72
Table 58 gives the major uses for propylene oxide.12
1.120. ooo
800.000
700,000
•S 600.000
&
u
I
z"
o
5 500.000
400.000
300.000
250.000
1965
1970 1975
YFAR
1980
Figure 47. Propylene oxide production,
1965 to 1980. i2,fc4-72
123
-------
TABLE 58. PROPYLENE OXIDE CONSUMPTION IN 197512
Use Percent
Polypropylene glycol and polyether polyols for urethanes 58
Propylene glycol 24
Dipropylene glycol 5
Surfactants 6
Glycol ethers and miscellaneous 7
TOTAL 100
Demand for propylene oxide will continue as the urethane sector
increases its market share. Flexible foams should continue to
grow at 8% to 9% per year or better if exterior auto parts develop
as predicted.12 Energy conservation efforts should promote both
rigid (construction insulation) and flexible (light-weight autos)
urethane growth.12 Growths of unsaturated polyester is expected
to continue at 10% per year.
Long-term growth of propylene oxide depends on construction trends
and the flammability issue. Little or no growth is expected in
the nonurethane polyester sectors, and no significant new uses are
forecast.l2
3. Outlook
Until 1980, based on expansions currently taking place, no supply
difficulty is expected. A new plant, with capacity ranging
between 1.81 x 105 and 2.27 x 105 metric tons, will be required in
the early 1980's.12
124
-------
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APPENDIX A
DERIVATION OF SOURCE SEVERITY EQUATIONS3
1. SUMMARY OF MAXIMUM SEVERITY EQUATIONS
The maximum severity of pollutants may be calculated using the
mass emission rate, Q, the height of the emissions, H, and the
ambient air quality standard, AAQS. The equations summarized in
Table A-l are developed in detail in this appendix.
TABLE A-l. POLLUTANT SEVERITY EQUATIONS FOR ELEVATED SOURCES
Pollutant
Particulate
S0x
N0x
Hydrocarbons
CO
Severity equation
S =
S =
s -
S =
S =
70 Q
H2
50 Q
H2
315 Q
HZ- i
162 Q
H2
0.78 Q
H2
2. DERIVATION OF x FOR USE WITH U.S. AVERAGE CONDITIONS
in 3.x
The most widely accepted formula for predicting downwind ground
level concentrations from a point source is:73
This appendix was prepared by T. R. Blackwood and E. C. Eimutis,
Monsanto Research Corporation, Dayton Laboratory, Dayton, Ohio.
73Turner, D. B. Workbook of Atmospheric Dispersion Estimates.
Public Health Service Publication Mo. 999-AP-26, U.S. Department
of Health, Education, and Welfare, Cincinnati, Ohio, May 1970.
84 pp.
132
-------
y z
where x = downwind ground level concentration at reference
coordinate x and y with emission height of H, g/m3
Q = mass emission rate, g/s
o = standard deviation of horizontal dispersion, m
o = standard deviation of vertical dispersion, m
Z
u = wind speed, m/s
y = horizontal distance from centerline of dispersion, m
H = height of emission release, m
x = downwind emission dispersion distance from source of
emission release, m
TT = 3.1416
We assume that Xmax occurs when x»0 and y = 0. For a given sta-
bility class, standard deviations of horizontal and vertical dis-
persion have often been expressed as a function of downwind distance
by power law relationships as follows:71*
o = axb (A-2)
o = cxd + f (A-3)
Z
Values for a, b, c, d, and f are given in Tables A-2 and A-3.
Substituting these general equations into Equation A-l yields:
x = K+^ H exp|- !r 1 (A~4)
acTruxb d + a*ufxb |_ 2 (cxd + f) 2J
Assuming that Xmax occurs at x<100 m and the stability class is
C, then f = 0 and Equation A-4 becomes:
X = ^-wTT exp[" 7°IJ (A-5)
acTrux
For convenience, let:
_ _ Q -H2
AR " Ic^u" and BR ~ 2c~2~
7l*Martin, D. O., and J. A. Tikvart. A General Atmospheric Diffu-
sion Model for Estimating the Effects on Air Quality of One or
More Sources. Presented at the 61st Annual Meeting of the Air
Pollution Control Association, St. Paul, Minnesota, June 23-27,
1968. 18 pp.
133
-------
TABLE A-2.
VALUES OF a FOR THE
COMPUTATION OF o .a » 3 3
Stability class
A
B
C
D
E
F
a
0.3658
0.2751
0.2089
0.1471
0.1046
0.0722
For Equation A-2:
= ax
where x = downwind distance
b = 0.9031
TABLE A-3.
VALUES OF THE CONSTANTS USED TO
ESTIMATE VERTICAL DISPERSION9 • 7l*
Stability
Usable range
>1, 000 m
100 to 1,000 m
<100 m
class Coefficient
A
B
C
D
E
F
A
B
C
D
E
F
A
B
C
D
E
F
0.00024
0.055
0.113
1.26
6.73
18.05
C2
0.0015
0.028
0.113
0.222
0.211
0.086
0.192
0.156
0.116
0.079
0.063
0.053
2.094
1.098
0.911
0.516
0.305
0.18
d2
1.941
1.149
0.911
0.725
0.678
0.74
0.936
0.922
0.905
0.881
0.871
0.814
-9.6
2.0
0.0
-13
-34
-48.6
f2
9.27
3.3
0.0
-1.7
-1.3
-0.35
0
0
0
0
0
0
aFor Equation A-3:
0
= cxd + f
134
-------
so that Equation A-5 reduces to:
—- (A-6)
Taking the first derivative of Equation A-6
(A-7)
and setting this equal to zero (to determine the roots which give
the minimum and maximum conditions of x with respect to x) yields:
= 0 = ARx-b-d-i^exprBRX-2dlV_2dBRx-2d -b-d) (A-8)
Since we define that x ^ 0 or » at Xmax' tne following expression
must be equal to 0:
-2dBRx-2d -d-b = 0 (A-9)
Therefore
(b+d)x2d = -2dBD (A
K
or
b+d 2c2(b+d) c2(b+d)
Hence
d H2
at *
Thus Equations A-2 and A-3 (at f = 0) become:
b/2d
r u 11 i
a =
/ H «2 \
= a( 1
\c2(d+b)/
= cf d H:
Z \c2(b+<
d/2d 2 l/2
o_ = c( " "" ) 2 =(^-\ 2 (A-14)
(b+d)/ \b+d
135
-------
The maximum will be determined for U.S. average conditions of
stability. According to Gifford,76 this is when oy = oz. Since
b = 0.9031, and upon inspection of Table A-2 under U.S. average
conditions, oy = oz, it can be seen that 0.881 < d < 0.905 (class
C stability3). Thus, it can be assumed that b is nearly equal to
d in Equations A-13 and A-14 or:
cj = — (A-15)
and
(A-16)
y c /2
Under U.S. average conditions, oy = oz and a = c if b = d and
f = 0 (between class C and D, but closer to belonging in class C) .
Then
cj = — (A-17)
y /2
Substituting for oy from Equation A-17 and for oz from Equa-
tion A-15 into Equation A-l and letting y = 0:
or
X
max
3The values given in Table A-3 are mean values for stability class,
Class C stability describes these coefficients and exponents,
only within about a factor of two.
76Gifford, F. A., Jr. An Outline of Theories of Diffusion in the
Lower Layers of the Atmosphere. In: Meteorology and Atomic
Energy 1968, Chapter 3, D. A. Slade, ed. Publication
No. TID-24190, U.S. Atomic Energy Commission Technical Informa-
tion Center, Oak Ridge, Tennessee, July 1968. p. 113.
136
-------
3. DEVELOPMENT OF SOURCE SEVERITY EQUATIONS
Source severity, S, has been defined as follows:
where x = time-averaged maximum ground level concentration
max
AAQS = ambient air quality standard
Values of X-,=v are found from the following equation:
max
(t0\°. 17
r-1 (A-21)
t /
where to is the "instantaneous" (i.e., 3-minute) averaging time
and t is the averaging time used for the ambient air quality
standard as shown in Table A-4.
a. CO Severity
The primary standard for CO is reported for a 1-hr averaging time.
Therefore, t = 60 minutes. Hence, from Equation A-21:
.0.17
Xmax= Xmax(^)
-------
TABLE A-4. SUMMARY OF NATIONAL AMBIENT AIR QUALITY STANDARDS77
Pollutant
Particulate
Sulfur oxides
Averaging
time
Annual
(geometric mean)
24 hrb
Annual
Primary
standards
75 pg/m3
260 pg/m3
80 pg/m3
Secondary
standards
60a yg/m3
150 yg/m3
60 yg/m3
Carbon
monoxide
Nitrogen
dioxide
Photochemical
oxidants
Hydrocarbons
(nonmethane)
(arithmetic mean)
24 hrb
3hrb
8 hrb
Ihr"
Annual
(arithmetic mean)
lhrb
3 hr
(6 to 9 a.m.)
(0.03 ppm)
365 pg/m3
(0.14 ppm)
none
10,000 pg/m3
(9 ppm)
40,000 pg/m3
(35 ppm)
100 pg/m3
(0.05 ppm)
160 pg/m3
(0.08 ppm)
160 pg/m3
(0.24 ppm)
(0.02 ppm)
260C yg/m3
(0.1 ppm)
,300 yg/m3
(0.5 ppm)
none
(Same as
primary)
(Same as
primary)
(Same as
primary)
(Same as
primary
The secondary annual standard (60 yg/m3) is a guide for assess-
ing implementation plans to achieve the 24-hr secondary standard,
Not to be exceeded more than once per year.
The secondary annual standard (260 yg/m3) is a guide for assess-
ing implementation plans to achieve the annual standard.
S =
Amax
AAQS
or
3.12 x 10
-2
CO
0.04 H2
(A-26)
0.78 Q
H2
(A-27)
77Code of Federal Regulations, Title 42 - Public Health,
Chapter IV - Environmental Protection Agency, Part 410 -
National Primary and Secondary Ambient Air Quality Standards,
April 28, 1971. 16 pp.
138
-------
b. Hydrocarbon Severity
The primary standard for hydrocarbon is reported for a 3-hr
averaging time. Therefore, t = 180 minutes. Hence, from
Equation A-21:
xmax = xmax io = °-5xmax (A'28)
Substituting for xma from Equation A-19 yields:
xmax
= (0.5) (0.052) Q = 0.026 Q (A-29)
For hydrocarbons, AAQS = 1.6 x 10"1* g/m3. Therefore
S = ^H* 0-026 Q (A-30)
AAQS 1.6 x 1Q-1* H2
or
_ 162.5 Q ,A_31)
SHC ~2 *A JJJ
c. Particulate Severity
The primary standard for particulate is reported for a 24-hr
averaging time. Therefore, t - 1,440 minutes. Hence, for
Equation A-21:
xmax = xmax (r7T4o)°"17 (A"32)
Substituting for x..,-., from Equation A-19 yields:
IllaX
max
(Q>35) = 0.0182 Q (A_33)
For particulates, AAQS = 2.6 x 10"1* g/m3. Therefore
0.0182 Q
;
2.6 x 10-4 H2
_ xmax _ 0.0182 Q fA-14)
~ < ~ * '
or
Sp = 22-fi (A-35)
P H2
139
-------
d. SCD Severity
The primary standard for SOX is reported for a 24-hr averaging
time. Therefore, t = 1,440 minutes. Hence, proceeding as before:
- 0.0182 Q ,_ ....
xmax = -2 (A'36)
n
For SOx, AAQS = 3.65 x lO'1* g/m3. Therefore
Q _ xmax _ 0.0182 Q
o ^~ ^^^^^j^nr ^ ™ ^™^^™^^^^^^^^^—
3.65 x lO"1* H2
or
e. NO Severity
Since NOX has a primary standard with a 1-yr averaging time, the
Xmax correction equation (Equation A-21) cannot be used. Alterna-
tively, the following equation is used:
- ) (A-39)
z/J
A difficulty arises, however, because a distance, x, from emis-
sion point to receptor, is included in Equation A-39. Hence, the
following rationale is used: Equation A-19 is valid for neutral
conditions or when o = o . This maximum occurs when
H = /Jo,
z
and since, under these conditions,
°z = axb
then the distance x where the maximum concentration occurs is:
/ H \i /
x,= = I-?-} 'b (A-40)
max V/2a/
For Class C conditions, a = 0.113 and b = 0.911. Substituting
these values into Equation A-40 yields:
mflv o
max 0.16
= 7.5
140
-------
Since
"z - °-"3
and
u = 4 . 5 m/s
and letting x = xmo , Equation A-39 becomes:
luclX
-
max
In Equation A-42, the factor
4 Q = 4 Q (A_43)
x 1.911 /T K Hl•°98\1.911
max l/.s H J
Therefore,
. 0.085 Q l_ i/-S\ I (A-43)
xmax
[-
As noted above,
o = 0.113 x°-911
z
Substitution for x from Equation A-41 into the above equation
yields:
o, = 0.113 (7.5 H1-1)0'911 = 0.71 H (A-44)
Z
Substituting for o_ from Equation A-44 into Equation A-42 yields:
Z
[- ^fir
xmax - ,,2.1 exp'- TlR-fT-B J I (A-45)
= 0.085 Q (Q 3?1) = 3.15 x IP"2 Q
H2.1 ' H2.1
Since the NOX standard is 1.0 x 10"1* g/m3, the NOX severity
equation is:
c = xmax _ 3.15 x 10"2 Q
x AAQS 1 x 10~2 H2-1
141
-------
or
NO
= 315 Q
H2.1
(A-48)
4. AFFECTED POPULATION CALCULATION
Another form of the plume dispersion equation is needed to calcu-
late the affected population since the population is assumed to
be distributed uniformly around the source. If the wind direc-
tions are taken to 16 points and it is assumed that the wind
directions within each sector are distributed randomly over a
period of a month or a season, it can be assumed that the efflu-
ent is uniformly distributed in the horizontal withiri the sector.
The appropriate equation for average concentration, x» in g/m3
is then:7^
(A-49)
To find the distances at which x/AAQs = 1-0, roots are determined
for the following equation:
2.03 Q f 1/_H\21
(AAQS) a ux SXP ~ 2' a J
Z I \ Z / I
= 1.0
(A-50)
keeping in mind that:
a = ax + c
z
where a, b, and c are functions of atmospheric stability and are
assumed to be selected for stability Class C. Since Equation A-50
is a transcendental equation, the roots are found by an iterative
technique using the computer.
For a specified emission from a typical source, )(/AAQS as a
function of distance might look as follows:
DISTANCE FROM SOURCE
Figure A-l. AAQS as a function of distance
142
-------
The affected population is contained in the area
A = ir(x22 - X!2) (A-51)
If the affected population density is Dp, the total affected popu-
lation, P, is
P = DpA (persons) (A-52)
143
-------
APPENDIX B
FIELD SAMPLING RESULTS
1. DIRECT CHLORINATION - CARBON TETRACHLORIDE PRODUCTION
Field sampling was performed at a plant producing carbon tetra-
chloride by the direct chlorination process.
The sites sampled included the following:
• Inlet to scrubber
• Outlet from scrubber
• Waste system sniffer
• Chlorocarbon sniffer
At each of the four sites, tests were performed to measure con-
centrations of hydrocarbons, chlorine and chlorides in the stack.
Tests performed included the following:
• Determination of chlorine/chloride
• Determination of the concentration of low molecular weight
hydrocarbons using Tedlar® gas bags.
• Determination of the concentration of high molecular weight
hydrocarbons using HVOSS sampling train.
Results of the tests performed are presented in Tables B-l
through B-4. The stack gas concentrations are summarized in
units of grams per cubic meter and emission factors in grams per
kilogram of carbon tetrachloride produced.
2. CHLOROHYDRINATION - PROPYLENE OXIDE PRODUCTION
Field sampling was performed at a plant producing propylene oxide
by the chlorohydrination of propylene. The sites sampled by MRC
include the following:
• Feed line to flare and/or boilerhouse
• Combusted gases from boilerhouse
144
-------
TABLE B-l. ATMOSPHERIC EMISSIONS FROM SCRUBBER INLET
Concentration
Material emitted by of emission,
tests performed g/m3
Chlorine/chloride:
Chlorine/chloride 66.2 1 791
GC/FID bag samples:
CHt equivalents 2.5
GC/MS HVOSS:
Dichloromethoxy phenol
Trichloromethoxy phenol
GC - C? - Cii Hydrocarbons:
C7
C,
Cio
Cu
Cu
Cu
Cu
C,s
C,t
>Ci,
8.7 x 10-s
4.5 x 10-*
4.1 x 10-'
1.7 x 10~2
1.9 x 10~2
1.7 x 10~2
6.1 x ID"1
9.3 x 10~2
9.0 x ID"3
2.4 x ID"2
1.3 x ID'3
4.0 x 10-2
TABLE B-2. ATMOSPHERIC EMISSIONS FROM SCRUBBER OUTLET
(Stack height: 25 meters)
Material emitted Concentration Emission
by of emission, factor,
tests performed g/m' q/kq
Chlorine/chloride:
Chlorine/chloride ND
GC/FID bag samples.
CHi, equivalent 0.14 1.1 x 10-J
GC/MS HVOSS:
GC - C? - Cn hydrocarbon
Cj] 8.7 x 10-* 6.6 x 10~s
Cu 1.3 x 10-' 9.8 x 10-s
CM 2.6 x 10-* 2.0 x 10"*
Cu 1.1 x 10-2 8.3 x 10-*
C1S 1.1 * 10-' 8.3 x 10-s
Cu 4-7 x 10-s 3.6 x 10-'
>C|» 6.5 x 10-* 4.9 x 10-*
145
-------
TABLE B-3. ATMOSPHERIC EMISSIONS FROM WASTE SYSTEM
(Stack height: 7.6 meters)
Material emitted Concentration Emission
by of emission. factor,
tests performed g/m* g/kg
Chlorine/chloride:
Chlorine/chloride ND "
GC/FID bag samples:
CHi. equivalent 4.3 x 10"2 2.0 x 10~2
GC/MS HVOSS:
GC - C? - Cis hydrocarbon:
Ci
Cl2
CM
Cu
Cis
Cl6
>Cis
6.0 x 10-*
2.6 x 10-*
2.9 x ID"2
7.1 x 10-'
5.3 x 10-'
3.3 x 10~*
2.5 x 10-2
2.8 x 10-*
1.2 x 10-2
1.3 x 10-2
3.3 x 10-'
2.5 x 10-'
1.5 x 10-*
1.2 x ID"2
TABLE B-4. ATMOSPHERIC EMISSIONS FROM CHLOROCARBON SYSTEM
(Stack height: 6.1 meters)
Material emitted Concentration Emission
by of emission, factor,
tests performed g/m' g/kg
Chlorine/chloride:
Chlorine/chloride ND -
GC/FID bag samples:
CJU equivalent
CCli, equivalent 1B.O 6.7
GC/MS HVOSS:
Trichlorobenzene B.2 x 10-' 3.1 x 10-'
Tnchloromethoxy phenol
GC C? - Cu hydrocarbon:
C7 1.2 x 10-' 4.5 x 10~*
C9 9.3 x lO"11 3.5 x 10-11
Cio -4-4 x 10-* 1.6 x 10-'
Cu 5.5 x 10~s 2.0 x 10-5
C>2 5.5 x 10~S 2.0 x 10-5
2.0 x 10-*
€.0 x 10-*
Ci» 2.2 x 10-* B.2 x ID"*
>Ci» 3.3 x 10-* 1.2 x 10-*
146
-------
At each of the two sites tests were performed to measure concen-
trations of hydrocarbons and chlorine/chlorides present in the
lines. Tests performed included the following:
• Determination of chlorine/chloride concentration
• Determination of low molecular weight hydrocarbon concen-
tration using Tedlar® gas bags for sample collection
• Determination of high molecular weight hydrocarbon concen-
tration using HVOSS sampling train
Results of the tests performed are presented in Tables B-5 and
B-6. The stack gas concentrations are summerized in units of
grams per cubic meter and emissions factors in grams per kilogram
of propylene oxide produced.
3. DIRECT CHLORINATION - MONOCHLOROBENZENE PRODUCTION
Field sampling was performed at a plant producting monochloro-
benzene by the direct chlorination of benzene. The sites sampled
included the following:
• Process vent
• Benzene storage tank
• Intermediate storage tank
• Monochlorobenzene storage tank
At each of the four sites tests were performed to measure concen-
tration of material present. The tests performed included the
following:
• Determination of chlorine/chloride concentration
• Determination of low molecular weight hydrocarbons
using Tedlar® gas bags for sample collection
In addition, concentration of high molecular weight hydrocarbons
at the process vent were measured using the HVOSS sampling train.
The results of the tests performed are presented in Tables B-7,
B-8, B-9, and B-10. The gas concentrations are summarized in
units of grams per cubic meter and emission factors in grams per
kilogram of monochlorobenzene produced.
4. OXYHYDROCHLORINATION - ETHYLENE DICHLORIDE PRODUCTION
Field sampling was performed at a plant producing ethylene
dichloride by the oxyhydrochlorination of ethylene. The sites
sampled included the following:
147
-------
TABLE B-5.
ATMOSPHERIC EMISSIONS FROM BOILERHOUSE OUTLET
(Stack height: 60 meters)
Material emitted
by
tests performed
Concentration
of emission,
q/m3
Emission
factor,
q/kg
00
Chlorine/chloride:
Chlorine/chloride
GC/FID bag samples:
Methane
GC/MS HVOSS:
Dichloropropane
Trichloropropane
Dichloropropanol
Epichlorohydrin
Toluene
Ethyl benzene
Benzaldehyde
Bis(6chloro-
iso propylether)
Naphlalene
C^-alkyl biphenyl
C7-C16 hydrocarbons HVOSS:
-------
TABLE B-6.
ATMOSPHERIC EMISSIONS FROM BOILERHOUSE INLET
(Stack height: 60 meters)
Material emitted by
tests performed
Concentration
of emission,
Chlorine/chloride :
Chlorine/chloride
GC/FID bag samples:
Methane
Ethene
GC/MS — bag samples:
Propane
Propylene
Propylene oxide
Pentane
Propion aldelyde
Methyl propane
Butane
Chloropropene
1 , 2-Dichloropropane
GC/MS HVOSS:
Dichloropropane
Epichlorohydrin
Trichloropropane
Bis(8chloro iso-propylether)
Naphthalene
Biphenyl
Aliphatics
C7
C8
C9
hydrocarbons HVOSS:
0.46 ± 129%
3.3
13.3
Detected
Detected
Detected
Detected
Detected
Detected
Detected
Detected
Detected
1.04
0.19
0.05
0.25
0.01
0.002
0.01
12.1
1.8 x 10~2
1.3 x 10~2
3.2 x 10-2
2.5 x 10-"
1.6 x 10-3
1.2 x 10~3
149
-------
TABLE B-7.
ATMOSPHERIC EMISSIONS FROM PROCESS STACK
(Stack height: 10 meters)
Material emitted
by
tests performed
Chlorine/chloride :
Chlorine/chloride
GC/FID bag samples:
Benzene
Monochlorobenzene
GC/MS bag samples:
Benzene
Monochlorobenzene
GC/MS HVOSS:
Benzene
Toluene
Monochlorobenzene
Dichlorobenzene
Trichlorobenzene
Tetrachlorobenzene
Pentachlorobenzene
Bromo benzene
Ethyl styrene
Benzoic acid
Napthalene
C7~C16 hydrocarbons HVOSS:
c?
Co
3
10
c
C13
>ClR
Concentration
of emission,
g/m3
2.2 ± 174%
8.2 x 10~2 ± 174%
1.3 ± 221%
7.3 x ID'2
2.5 x ID-2
1.4 x 10-1*
5.9 x 10~6
4.5 x 10-3
1.3 x 10-u
5.4 x 10-6
4.1 x 10-6
4.5 x 10-7
4.5 x 10-7
5.2 x 10~5
6.6 x 10-1*
8.3 x 10-5
1.4 x 10-3
2.4 x ID"2
3.4 x 10'1*
- 9.8 x lOT1*.
1.6 x ID'14
7.0 x 10-"
5.5 x 10-1*
9.4 x 10-1*
2.1 x 10-3
Emission
factor ,
g/kg
5.6 x ID'2
2.1 x 10~3
3.3 x ID"2
1.9 x 10-3
6.4 x 10-1*
3.5 x 10-6
1.5 x 10-7
1.1 x 10-1*
3.3 x 10-6
1.4 x 10-7
1.1 x 10-7
1.1 x 10-8
1.1 x 10-8
1.3 x 10-6
1.8 x 10-5
2.1 x 10-6
c
3.5 x 10-5
6.1 x 10-**
876 x 10~6
2.6 x 10-5
4.1 x 10-6
1.8 x 10-5
1.4 x 10-3
2.4 x 10-5
5.4 x 10~5
150
-------
TABLE B-8. ATMOSPHERIC EMISSIONS FROM INTERMEDIATE STORAGE
(Stack height: 10 meters)
Concentration
Material emitted by of emission,
tests performed g/m3
Chlorine/chloride:
Chlorine/chloride 424 ± 82%
GC/FID bag sample:
Benzene 44.4 ± 47%
Monochlorobenzene 3.0 x 10"l ± 179%
TABLE B-9. ATMOSPHERIC EMISSIONS FROM
MONOCHLOROBENZENE STORAGE
Concentration
Material emitted by of emission,
tests performed g/m3
Chlorine/chloride:
Chlorine/chloride 3.1 x 10"l ± 312%
GC/FID bag samples:
Monochlorobenzene 6.2 ± 47%
Benzene 1.02 ± 171%
TABLE B-10. ATMOSPHERIC EMISSIONS FROM BENZENE STORAGE
Concentration
Material emitted by of emission,
tests performed g/m3
Chlorine/chloride:
Chlorine/chloride 2.8 ± 42%
GC/FID bag sample:
Benzene 71.2 ± 89%
Monochlorobenzene 6.2 x 10-1 ± 186%
151
-------
• Oxy-vent
• Heads column
• High boils vent
At each of the three sites, tests were performed to measure con-
centrations of hydrocarbons, chlorine, chlorides, moisture, and
flow rates of gases in the stacks. Tests performed included the
following:
• Chlorine/chloride concentration determination
• Low molecular weight hydrocarbon concentration determination
using Tedlar® gas samples
• High molecular weight hydrocarbon concentration determina-
tion using Porapak tubes
• Moisture contents of stack gases
• Flow rates of stack gases
Results of the tests performed are presented in Tables B-ll
through B-13. The stack gas concentrations are summarized in
units of grams per cubic meter.
TABLE B-ll. ATMOSPHERIC EMISSIONS FROM OXY-VENT
(Stack height: 55 meters)
Material emitted by
tests performed
Concentration
of emission,
g/m3
Chlorine/chloride test:
Chlorine/chloride
Bag sample field analysis
Methane
Ethylene
Ethylene dichloride
Vinyl chloride
Porapak tube analysis:
Methylene chloride
Chloroform
Carbon tetrachloride
Ethylene dichloride
Trichloroethane
5.5 x 10~2 ± 34%
28.6 ± 0%
9.6 ± 67%
13.3 ± 50%
0.3 ± 246%
<9.1 x 10~2 ± 140%
<1.4 x ID"1 ± 242%
<9.1 x ID-2 ± 140%
27.7 ± 145%
<1.4 x 10-1 ± 242%
152
-------
TABLE B-12. ATMOSPHERIC EMISSIONS FROM HEADS COLUMN
(Stack height: 20 meters)
Material emitted by
tests performed
Concentration
of emission,
Chlorine/chloride test:
Chlorine/chloride
Bag sample field analysis:
Vinyl chloride
Ethylene dichloride
Methylene chloride
Chloroform
Carbon tetrachloride
Ethyl chloride
Porapak tube analysis:
Ethylene dichloride
1,1-Dichloroethane
Ethyl chloride
Vinylidene chloride
Dichloroethylene
Chloroform
Carbon tetrachloride
Methylene chloride
6.2 x 10-1 ± 180%
27.9
92.8 i 43%
3.5 + 55%
97.1 ± 67%
218.2 i 84%
108.0
17.2 ± 236%
9.2 ± 308%
0.9 ± 142%
0.2 ± 229%
1.8 ± 225%
73.5 ± 266%
39.9 ± 258%
0.6 ± 293%
TABLE B-13. ATMOSPHERIC EMISSIONS FROM HIGH BOILS VENT
(Stack height: 12 meters)
Material emitted by
tests performed
Chlorine/chloride test:
Chlorine/chloride
Bag sample field analysis:
Ethylene dichloride
Methane
Ethylene
Porapak tube analysis:
Ethylene dichloride
Methylene chloride
Chloroform
Concentration
of emission,
g/m3
47.9 ± 132%
442.0 ± 0%
0.04 ± 218%
0.11 ± 75%
321 ± 126%
0.13
0.13
153
-------
APPENDIX C
FIELD SAMPLING METHODS
The field sampling methods presented here, and the analytical
methods described in Appendix D were used to provide data on the
major components of the gaseous compositions as well as informa-
tion on the concentration and identification of organic compounds
present at low levels. Data collected from the plants were in
terms of concentration (ppm) in sample collected; this informa-
tion was converted to concentration (g/m3) in stack gas and
emission factors (g/kg) using the amount of sample collected,
flow rates, and production data.
1. HYDROCARBON
Engineering estimates of the composition of gas streams selected
for field sampling indicated the presence of both low and high
molecular weight hydrocarbons. Sampling techniques used are
described in the following subsections.
a. Low Molecular Weight Hydrocarbons (
-------
The gaseous samples collected in Tedlar bags were analyzed both
on site for C^ to C6 hydrocarbons as well as in the laboratory
for a wide range of organic compounds. On-site analytical proce-
dures, although carried out by sampling personnel in the field,
are described in the section under Analytical Procedures.
b. High Molecular Weight Hydrocarbons (>Ce) - SASS Module
High molecular weight hydrocarbons were collected using a porous
polymer collection technique to trap and concentrate the mate-
rials for gas chromatography/mass spectrometry (GC/MS) analysis
in the laboratory.
The sampling method included a high volume organic sampling sys-
tem (HVOSS), which was a modification of the Source Assessment
Sampling System (SASS) described in the EPA's Level I Environmen-
tal Assessment Procedures. The cydones and filter portions of the
SASS train, normally employed to collect particulate from source
streams, were removed and the remaining portion of the system was
used to collect the organic materials. Thus, the sampling train
was made up of a suitable probe maintained at stack temperature,
the gas cooler module, the thermostated XAD-2 resin cartridge
condensate condenser, cooling and silica gel impingers, and the
control module. This system permitted the collection of a large
quantity of organic components in a relatively short time.
Figure C-2 shows a schematic diagram of the sampling train, and
Figure C-3 shows the XAD-2 sorbent trap module.
The SASS train included four impingers. The first two impingers
contain 1-normal NaOH for coding the gas and neutralizing most of
the chlorine/chlorides present in the gas streams. The third
impinger was empty and served as a spray trap. The fourth
impinger contained silica gel to remove traces of water prior to
the dry test meter. Since no trace metals were expected to be
present in the gas streams, no analyses were carried out on the
impinger contents.
The HVOSS sampling train was cleaned after each sample by follow-
ing a modified Level I procedure. The probe and probe tip were
rinsed with 1:1 CH2Cl2:CH3OH into an amber glass bottle. The
XAD-2 resin sorbent trap was cleaned as shown in Figure C-4.
c. High Molecular Weight Hydrocarbons (>Cg) - Porus Polymer Type
The high molecular weight hydrocarbons were collected using a
porous polymer collection technique to trap and concentrate the
materials for GC/MS analysis in the laboratory.
The organic vapors and hydrocarbons were trapped on Porapak Q and
Porapak N resins. The sampling equipment used for collecting
Porapak tube samples is shown in Figure C-5. The metal cylinder
was evacuated to a low pressure using a good vacuum pump. The
155
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VAC* T C
CAS coatR
OR* CAS WTFR ORI'ICI MTITR
CFNTIIAIIZID TIMPf RAIURE
AND PRESSURE READOUI
CONTROL MODULI
Figure C-2.
• 07J «J/mln VACUUM PUMP
High volume organic sampling
system.1
HOI GAS FROM PROBE
LIQUID PASSAGE
GAS PASSAGE 1
«AS COOLER
XAD-2 CARTRIDGE
CONDFNSATI
•RESERVOIR
3-WAY SOLENOID VALVE
ID COOLING BATH
FROM COOLING BATH
COOLING FLUID
RESERVOIR
i 1
Figure C-3. XAD-2 sorbent trap module.1
156
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NO. 1
COMPUTE XAD-3 MODULE
AFTER SAMH.INO *UN
RELEASE CLAMP JOINING XAD-2
CAirmDGE SECTION TO TMf um«
CAS CONDITIONING StCTON
ttMOVE XAD-? CARTRIDGE PROM
CAtTRIDOE HOLDER. REMOVE FINE
MESH SCREEN FROM TOf OF CART-
RIDGE. EMPTY RESIN RMTO WIDE
MOUTH CLASS AMM M*
[ CLOSE CONDENSATE MSaVOIt VALVE |
"IT
L
ttUASt l»ttt CLAMP AND
tlFI OUT INNB WtLL
JL
WITH OUTH UN1TIZED WASH tonu
(CHjClj^CH-jOHl IINSf INNEI WELL
SUtFAC! INTO AND ALONG CON-
MNSR WALL SO THAT IINSE «UNS
DOWN THROUGH THE MODULE AND
INTC CONOiNSATE COLLtOOt
WM8N INNB WtU. B a€AN,
PLACE TO ONE SIDE
IEPLACE SCIEEN ON CACTIIDCE, tE-
INSEIT CAtTIIOGE INTO MODULE.
XJIN MODULE MCK TOGETMtl.
IEPLACE CLAArV.
OPEN CONDENSATf «£SE«VOI«
VALVE AND MAIN AQUEOUS
CONDENSATE INTO A 1 LITtt
SCPAHATOIY FUNNEL EXTIACT
WITH
IINSE ENTIANCC TUt! INTO MODULE
INTOIOt. HINSE DOWN THE CONOEN-
SEI WA'.l AND ALLOW SOLVENT TO
FLOW DOWN THROUGH TH[ SYSTEM
AND COLLECT IN CONDENSATE CUP
IEL1ASE CENTtAL CLAMP AND
SEPA«ATE THE LOWEI SfCTON
(XAD-2 AND CONDENSATI CUP)
MOM THE UPPEI SECTION (CON-
DENSE! j
THE ENTIIi UPPEt SECTON IS NOW
CLEAN.
•INSt THf NOW EMPTY XAD-J SEC-
TON INTO THE CONDENSATE CUP
•ELEASE LOWEt CLAMP AND
KMOVE CAITtlDGE SECTION
F»OM CONDENSATE CUP
THE CONDENSATE HSEtVOW NOW
CONTAINS ALL RINSES FROM THE
ENTIRE SYSTEM. MAIN INTO AN
AMUR tOTTLE VIA MAIN VALVE.
Figure C-4.
Sample handling and transfer—XAD-2
module.1
STAINLESS STEa PROBE
SOURCE
Figure C-5. Porous polymer vapor sampling method,
157
-------
evacuated cylinder was connected to a sample probe and the Pora-
pak tube. The temperature and pressure of the cylinder were
noted, and the stopcock in the cylinder was opened to admit a
sample for a known period of time. The stopcock was then shut
off, and the final temperature and final pressure of the cylinder
were noted.
The ends of the Porapak tubes were then sealed off, and the tubes
were stored at ice temperatures during shipment back to MRC for
GC/MS analysis.
2. CHLORINE AND HYDROGEN CHLORIDE
Chlorine and hydrogen chloride were sampled as chloride using an
impinger train system shown schematically in Figure C-6. The
system consisted of a Teflon line serving as a sampling probe,
three midget impingers containing 10 ml of 0.1N NaHSOs, an empty
impinger, a plug of glass wool and silica gel, a pump, a flow-
meter, and a dry test meter. The impingers were immersed in an
ice-water bath during sampling, and samples were collected at
known flow rates for known variable periods of time.
GLASS PROBE
\
EMPTY
EXITGAS
DRY TEST
METER
FLOWMETER
NaHS03 ICE BATH
Figure C-6. Chlorine/chloride sampling train,
After sample collection, the first two impinger contents were
transferred to a 100 ml sample bottle. The contents of the third
and fourth impingers were transferred into another bottle. All
glassware, including the empty impinger, were rinsed with three
portions of 0.IN NaHSOs and the rinsings were added to the sample
bottle containing its sample. These bottles were then sealed and
stored at ice-temperature during shipment to the Dayton Laboratory
for subsequent analysis.
158
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APPENDIX D
ANALYTICAL PROCEDURES
The analysis program was carried out both in the field and at the
MRC Dayton Laboratory. Field analysis included Ci to C6 hydro-
carbons by portable gas chromatography with flame ionization
detectors (FID). Higher molecular weight organics (C-? and higher),
chlorine, and hydrogen chloride were analyzed in the laboratory.
In addition to the GI to C& field analysis, bag samples were also
brought back to the MRC laboratories for GC/MS analysis.
1. LOW MOLECULAR WEIGHT HYDROCARBONS
Low molecular weight hydrocarbons and chlorinated hydrocarbons
were analyzed at the plant site employing an Analytical Instrument
Development Inc., (AID) Model 511 portable gas chromatograph with
a flame ionization detector. For the Ci to C3 hydrocarbons, a
1.8 m by 3.2 mm stainless steel column packed with Chromosorb 102
was operated isothermally at an oven temperature of 135°C. For
the G! and C2 chlorinated hydrocarbons, a 1.8 m by 3.2 mm stain-
less steel column packed with 10% FFAP on 80/100 mesh Chromosorb
W HP column (suggested by the National Institute of Occupational
Safety and Health [NIOSH]) was employed.
The flame ionization detector (FID) rather than electron capture
detector (EC) was used for the analysis of the chlorinated spe-
cies on the basis that the FID detection limit was below the
1 ppm sensitivity required for all species.
Prior to field analysis of samples, optimization and verification
of the chromatographic conditions were conducted. Standard gas
mixtures were employed to optimize chromatographic conditions
(temperature, flow rates of carrier, hydrogen, and air), and to
generate calibration curves for the major species expected in
the vent emissions.
2. HIGHER MOLECULAR WEIGHT ORGANIC COMPOUNDS - SASS MODULE
Organic compounds with six and more carbon atoms were collected
by the organic module of the SASS train. The analytical scheme
for this study involved the analysis of the probe washing, XAD-2
resin, and the XAD-2 organic wash and aqueous condensates. In
159
-------
contrast to the normal SASS train analysis scheme, the entire
resin sample was analyzed rather than removing 2-gram portions
for inorganic analysis.
At the completion of the field cleanup, the samples included the
following:
• Bottles containing the CH2Cl2-CH3OH washings of the probe
and probe tip
• XAD-2 resin
• Aqueous condensate from the condensate trap
• Methylene chloride rinse of the resin module
The overall analysis scheme is shown in Figure D-l. The XAD-2
resin was Soxhlet entracted for 24 hours with pentane. The
volume was measured, and a portion was removed for GC analysis of
the Cy to Cie hydrocarbons. The remaining solution was stored
for later combination with the other samples from the run.
The aqueous condensate from the run was extracted with methylane
chloride, and this extract was combined with the probe washings
and methlene chloride rinse of the module. The volume of these
solutions was measured, and a portion, equal to the percentage of
the portion removed from the pentane extract of the XAD-2 resin
extraction, was removed for C? to Cie analysis. The remaining
solution, representing the source percentage of the total as the
remaining pentane solution of the extraction total, was combined
with the pentane extraction solution. The resulting solution was
reduced in volume in a rotovap and then further reduced in volume
in the Kuderna-Danish apparatus. Ten milliliters of hexane were
added to the apparatus and the volume was reduced to 2 ml. The
hexane addition and volume reduction were repeated two more times
in order to effect a solvent exchange (methylene chloride replaced
with hexane). The resulting hexane solution was diluted to 10
ml. Five milliliters of this solution were evaporated to dryness
in order to obtain a weight of the residue. The remaining 5 ml
of the solution was analyzed by GC/MS to identify and quantify
the components.
3. HIGH MOLECULAR WEIGHT HYDROCARBONS - POROUS POLYiMER TUBE
Samples collected by the porous polymer tubes were analyzed at
MRC's Dayton Laboratory using combined gas chromatography/mass
spectrometry. The porous polymer tubes were thermally desorbed
prior to GC/MS analysis. The porous polymer tubes are designed
to be directly interfaceable with a gas chromatograph. Desorp-
tion of the collected species was initiated using carrier flow
and elevated temperature directly onto the analytical column of
the gas chromatograph. Assuming air flow rates of 2 Jl/min and a
160
-------
AQUEOUS
CONDENSATI
FROM MODULE
REMOVES A
FORC7-C16
CC ANALYSIS
Figure D-l.
Analysis flow scheme for organic
compounds Ce and above.
10-minute sampling time, components present at 0.5 yg/m3 in the
ambient air were measured using a flame ionization detector
capable of detecting 10 yg.
The porous polymer tube was connected to the inlet system of the
GC/MS so that the carrier gas passed through the tube in a direc-
tion reverse to that of the original sampling flow. The collected
tube was heated over its entire length, and the desorbed gases
were swept into the instrument. As in any GC-related method, the
choice of the analytical column and conditions determined the
separation possible for the individual compounds collected in the
tubes. Mass spectra were recorded for each peak when it was sus-
pected that several components occurred at the same retention
161
-------
times, additional mass data were obtained. Mass data provided an
identification of the compounds present, and the GC data quanti-
fied these compounds.
4. CHLORINE AND HYDROGEN CHLORIDE
Chloride ion analysis of the impinger solution was executed
employing the Dionex Model 10 analytical ion chromatograph. A
calibration curve was generated using a potassium chloride stand-
ard solution from 1 ppm to 500 ppm. A 0.1 ml aliquot of the
sample was injected into the ion chromatograph and read according
to peak height, and a linear regression equation was used to
interpolate the concentration values.
162
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APPENDIX E
SAMPLE CALCULATIONS
In this appendix, sample calculations are shown in the following
subsections for: 1) volume of gas sampled, 2) percent moisture,
3) calculation of percent error bound, 4) concentrations of
chlorine/chloride in stack gases, 5) concentrations of hydro-
carbons determined by collector tube method, 6) concentrations
of GC/FID determined components in Tedlar bag samples, and 7)
calculation of stack gas flow rates.
1. VOLUME OF GAS SAMPLED
The gas volume sampled was determined by adjusting the volume of
gas metered with respect to the pump leak rate and the standard
conditions of 20°C and 760 mm Hg. Thus,
WMC - 17.71[VM-LR(MIN)]PB _, ,„ , .
VMS -- (TM + 460) - Kl (E"1}
where VMS = volume of dry gas sampled at standard condition, m3
VM = volume of dry gas sampled at meter conditions, ft3
LR = leak rate of pump at meter conditions, ft3/min
MIN = number of minutes sampled
PB = absolute barometric pressure, in. Hg
TM = average meter temperature, °F
K! = 2.8317 x 10~2 m3/ft3
and 460 and 17.71 are constants to adjust degrees Fahrenheit to
absolute temperature and to adjust to standard conditions.
Example; Run 1 Scrubber Outlet
VM = 630.511
LR = 0. 08
MIN = 145
PB = 29.84
TM = 84 °F
163
-------
- 17.711630.511 - 0.08 x 145]29.84 2
VMS (84 + 460) 2.8317 x 10
= 601.24 x 2.8317 x 10~2 ft3 = 17.03 m3
2. PERCENT MOISTURE
Percent moisture was determined by calculating the volume of water
vapor, at standard conditions that the total water volume collected
would comprise, calculated as the mole fraction of water vapor in
the gas stream and changed to percent. Thus,
VL = VL + V2 + V3 + Vi, + V5 (E-2)
VW = (0.0474)VL (E-3)
MW = — (E-4)
VWSF + VW
%M = 100MW (E-5)
where VL = total volume of water collected, ml
Vi = volume of water collected in impinger 1 (final minus
initial volume), ml
V2 = volume of water collected in impinger 2 (final minus
initial volume), ml.
V3 = volume of water collected in impinger 3 (final minus
initial volume), ml.
V4 = weight of water collected in silica gel (final minus
initial weight), ga
V5 = volume of aqueous condensate in condenser, ml
0.0474 = constant to adjust to volume of water vapor at
standard condition
VMSF = volume of dry gas sampled at standard conditions, ft3
VW = volume of water vapor at standard conditions, ft3
MW = mole fraction of water vapor
%M = percent moisture
a
1 gram of water equals approximately 1 millileter of water.
164
-------
Example; Run 1 Scrubber Outlet
Vi + V2 = 30 mi
V3 + VU = 143.5 g
VL = 173.5
VW = 0.0474 x 173.5 = 8.22
VMSF = 601.24
MW = 8.22 = 1.33 x 10~2
601.24 + 8.22
%M = 1.33%
3. CALCULATION OF PERCENT ERROR BOUND
Percent error bounds, ±% are calculated as:
±% = \S^L £ 100 (E-6)
where s = standard deviation
t = value from statistical tables for student "t"
distribution using the 95% confidence level, and
the degrees of freedom, "f"
f = N-l
N = number of measurements
x~ = average of measurements
Example; Run 1 Scrubber Outlet
s = 20.9
x = 66.2
N = 3
t = 4.303
303
-„ _/20.9 x 4.
~\ a
100 = 78.6%
165
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4. CONCENTRATIONS OF CHLORINE/CHLORIDE IN STACK GASES
Analytical results for the chlorine/chloride analysis were re-
ported as grams of chloride collected in the impingers.
Determining concentrations of chlorine/chlorides in gas streams
involves the following:
• Volume of gas sampled at standard conditions.
• Grams per milliliter of chlorine/chloride in blank.
• Grams per milliliter of chlorine/chloride in sample.
• Grams per milliliter of chlorine/chloride in stack gas.
• Grams of chlorine/chloride in stack gas.
• Grams per cubic meter of chlorine/chloride in stack gas.
a. Volume of Gas Sampled/ VMS
WMc _ 17.71 PB(VM) ,„ 7.
VMS TM + 460 (E~7)
where TM = average meter temperature, °F
PB = absolute barometric pressure, in. Hg
VM = volume of gas sampled at meter conditions, ft3
VM = FR x M
FR = flow rate, ft3/min
M = sampling time, min
b. Chlorine/chloride in Stack Gas, grams/m3
Chlorine/chloride
f grams chloride in sample grams chloride in blank"] , _ . ..
= a : ; r-*-: 3 ; 7—rr —;—TT— x volume of sample (mi)
L volume of sample (mi) volume of blank (ml) J _
VMS -m3
Example; Run 1 Scrubber Inlet
Grams of chloride in sample = 1.66 gm
Volume of sample =
Grams of chloride in blank = 6.0 x 10~3 gm
Volume of blank :
VMS
Chlorine/chloride ••
1.25 x 0.0283
46.7 g/m3
166
-------
5. CONCENTRATIONS OF GC/FID DETERMINED COMPONENTS IN TEDLAR
BAG SAMPLES
Low molecular weight hydrocarbons (
-------
Example; Run 1 Scrubber Outlet - Ci5 - Css Aliphatics
Amount of Cie ~ £36 aliphatics detected = 20.146 mg
Amount of CIB - C^z aliphatics in blank = 13.222 mg
Therefore, amount of GIS - C36 aliphatics
in sample = 6.924 mg
Correction for 0.5% removed for €7 - Gig
analysis = 0.035
Total amount of Gig - €35 aliphatics
collected = 6.959 mg
Volume of gas sampled at STP = 17.02 m3
Therefore concentration of Cjg - €35
aliphatics in stack = 0.41 mg/m3
7. CONCENTRATION OF C7 THROUGH Ci6 (ALKENES) DETERMINED BY GC
FROM HVOSS SAMPLE
The concentration of the C7 - Ci6 hydrocarbons detected in the
sample were reported as milligrams of material present in the
sample in a given volume submitted for GC analysis. This sample
represented only 0.5% of the total sample collected, because 99.5%
was sent for GC/MS analysis. Therefore to obtain the total
weight of sample collected the required steps include the
following:
• Subtract the amount of material present in the blank from
the amount present in the sample
• Add 99% to the total to adjust for the removal of a sample
for GC/MS analysis
• Perform the above steps for both XAD-2 resin extract and
for combined organic phases
• Add the results for both XAD-2 resin extract and for com-
bined organic phases
• Divide the amounts of material collected by the volume of
gas sampled to obtain the concentration in g/ft3
• Correct the concentration units to grams per cubic meter
8. STACK GAS FLOW RATE
Stack gas data were obtained by taking a preliminary velocity
traverse across the duct carrying the stack gases. At each
traverse point, the velocity had (A PS) and stack temperature
were determined.
168
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The velocity of the stack gas was determined using the following
equation.
VS . 85.48 x Cp|/|f^f° (/Sp)
average (E-8)
where VS = stack gas velocity, ft/s
CP = pitot tube coefficient
TS = average temperature of stack, °F
PS = absolute pressure of stack gas, in. Hg
MS = molecular weight of stack gas, Ibs/lb mole
(/Aj>) = average of square root of velocity head,
The volumetric flow rate (SCFM) was then determined using the
equation:
Qs =60 [1 - (Mx 10-2)] VS x A x (TS5+°460 ) x(29P|2[(E"9)
where M = percent moisture
A = area of stack, ft2
Example; Run 1 Stack Gas Velocity Calculation - Scrubber Outlet
M = 1.35
CP = 0.75
A = 0.35
TS = 75°F
PS = 29.88
average = (°'98)
VS= 85.48X '—average
/.VS = 85.48 x 0.75V,n'Z0V™ 0 (0.98)
= 49.54 ft/s
169
-------
530 PS
Also Qs = 60 [1 - (M x ID'2)! VS x A x TS + 46Q x ^-5
= 60 [1 - (1.35 x lO-2)! 49.54 x 0.35 x
29.88
28.92
= 1015.32 ft3/min
= 60919 ft?/hr
= 60919 |j- x -
= 1724 'm3/hr
170
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CONVERSION FACTORS AND METRIC PREFIXES78
CONVERSION FACTORS
To convert from
degree Celsius (°C)
gram/second (g/s)
joule (J)
kilogram (kg)
kilogram/meter3 (kg/m3)
kilometer2 (km2)
meter (m)
meter3 (m3)
metric ton
metric ton
pascal (Pa)
pascal (Pa)
pascal (Pa)
to
degree Fahrenheit
pounds/hour
calorie
pound-mass (Ib mass
avoirdupois)
pound/foot3
mile2
foot
feet3
pound-mass
ton (short, 2,000 Ib-mass)
atmosphere
torr (mm Hg, 0°C)
pound-force/inch2 (psi)
Multiply by
t« = 1.8 t» + 32
7.936
2.388 x ID"1
2.204
6.243 x 10~2
3.860 x ID'1
3.281
3.531 x 101
2.205 x 103
1.102
9.869 x 10-6
7.501 x 10~3
1.450 x 10'1*
METRIC PREFIXES
Prefix Symbol
mega
kilo
micro
M
k
u
Multiplication
factor
106
103
io-6
Example
1 MJ = 1 x IO6 joules
1 kPa = 1 x IO3 pascals
1 ug = 1 x 10~" gram
78Standard for Metric Practice. ANSI/ASTM Designation: E 380-76E,
IEEE Std 268-1976, American Society for Testing and Materials,
Philadelphia, Pennsylvania, February 1976. 37 pp.
171
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1 REPORT NO
EPA-600/2-79-019g
2.
3 RECIPIENT'S ACCESSION NO.
4 TITLE AND SUBTITLE
Source Assessment: Chlorinated Hydrocarbons
Manufacture
5 REPORT DATE
August 1979
6. PERFORMING ORGANIZATION CODE
7 AUTHOR(S)
Z.S.Khan and T.W.Hughes
8 PERFORMING ORGANIZATION REPORT NO
MRC-DA-913
9 PERFORMING ORGANIZATION NAME AND ADDRESS
Monsanto Research Corporation
P.O. Box 8, Station B
Dayton, Ohio 45407
10. PROGRAM ELEMENT NO.
1AB015; ROAP 21AXM-071
11. CONTRACT/GRANT NO
68-02-1874
12 SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Task Final; 1/76 - 8/78
14. SPONSORING AGENCY CODE
EPA/600/13
15. SUPPLEMENTARY NOTES JERL-RTP project officer is Bruce A. Tichenor. Mail Drop 62,
919/541-2547. Other source assessment documents are in the EPA-600/2-78-004,
-77-107, and -76-032 series.
16. ABSTRACT Tne repOrt describes a study of air pollutants released during the manufac-
ture of chlorinated hydrocarbons, manufactured in the U.S. by: (1) direct chlorina-
tion (a hydrocarbon is reacted with chlorine); (2) hydrochlorination (hydrogen chloride
is reacted with a hydrocarbon); (3) oxyhydrochlorination(hydrogen chloride is reacted
with a hydrocarbon in the presence of oxygen or air); or (4) chlorohydrination (the
reaction between a hydrocarbon and hydrochlorous acid is followed by a reaction of
the products with lime slurry to obtain the final product). A representative plant was
defined for each manufacturing process type, and environmental effects were deter-
mined on the basis of plant capacity. The potential environmental effect was evaluated
using source severity, S, defined as the ratio of the maximum ground level concen-
tration of an emission to the ambient air quality standard for criteria pollutants.
Source severities for the four processes listed above are 1.69, 1.94, 31.3, and 2.75,
respectively.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b IDENTIFIERS/OPEN ENDED TERMS
c COSATi Field/Group
Pollution
Assessments
Chlorohydrocarbons
Manufacturing
Chlorination
Hydrochlorination
Pollution Control
Stationary Sources
Oxyhydrochlorination
Chlorohydrination
Source Severity
13 B
14 B
07C
05C
07C,07B
18 DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (This Report)
Unclassified
21 NO OF PAGES
188
2O SECURITY CLASS (This page)
Unclassified
22 PRICE
EPA Form 2220-1 (9-73)
172
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