U.S. Environmental Protection Agency Industrial Environmental Research EPA-600/7'77-11 0
Office of Research and Development Laboratory ~ ^ 0-7-7
Research Triangle Park, North Carolina 27711 September 1977
HYDROCARBON POLLUTANTS
FROM STATIONARY SOURCES
Interagency
Energy-Environment
Research and Development
Program Report
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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 seven series.
These seven broad categories were established to facilitate further
development and application of environmental technology. Elimination
of traditional grouping was consciously planned to foster technology
transfer and a maximum interface in related fields. The seven 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
This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series. Reports in this series result from
the effort funded under the 17-agehcy Federal Energy/Environment
Research and Development Program. These studies relate to EPA's
mission to protect the public health and welfare from adverse effects
of pollutants associated with energy systems. The goal of the Program
is to assure the rapid development of domestic energy supplies in an
environmentally—compatible manner by providing the necessary
environmental data and control technology. Investigations include
analyses of the transport of energy-related pollutants and their health
and ecological effects; assessments of, and development of, control
technologies for energy systems; and integrated assessments of a wide
range of energy-related environmental issues.
REVIEW NOTICE
This report has been reviewed by the participating Federal
Agencies, and approved for publication. Approval does not
signify that the contents necessarily reflect the views and
policies of the Government, nor does mention of trade names
or commercial products constitute endorsement or recommen-
dation for use.
This document is available to the public through the National Technical
Information Service, Springfield, Virginia 22161.
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by
E.G. Cavanaugh, Ml. Owen, T.P. Nelson,
J.R. Carroll, and J.D. Colley
Radian Corporation
8500 Shoal Creek Boulevard
Austin, Texas 78757
Contract No. 68-02-1319
Task Order No. 48
Program Element No. EHE623A
EPA Task Officer: Lewis D. Tamny
Industrial Environmental Research Laboratory
Office of Energy, Minerals, and Industry
Research Triangle Park, N.C. 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, D.C. 20460
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TABLE OF CONTENTS
PAGE
1.0 INTRODUCTION 1
1.1 Obj ectives 1
1.2 Approach 2
1.3 Methodology 4
1.4 Definitions 5
1. 5 Summary of Results 10
1.6 Conclusions and Recommendations 12
2.0 RESULTS 17
2.1 Overall Organic Emissions and Effluents 17
2.1.1 Atmospheric Emissions 17
2.1.1.1 Volatile Organic Emissions 30
2.1.1.2 Organic Particulate Emissions .. 30
2.1.2 Water Effluents 35
2.2 Process Organic Emissions and Effluents 35
2.2.1 Process Atmospheric Emissions 40
2.2.1.1 Volatile Organic Emissions 40
2.2.1.2 Particulate Organic Emissions .. 42
2.2.2 Process Water Effluents 47
3.0 REDUCTION POTENTIALS OF ORGANIC EMISSIONS AND
EFFLUENTS FROM THIRTEEN MAJOR CATEGORIES 51
3.1 Fossil Fuel Extraction 51
3.1.1 Crude Oil Production 54
3.1.2 Natural Gas Extraction 61
3.1.3 Coal Production 63
3.2 Fossil Fuel Processing 66
3.2.1 Natural Gas Processing 67
3.2.2 Coal Processing 69
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PAGE
3.3 Fossil Fuel Transportation, Storage, and
Distribution 72
3.3.1 Gasoline Marketing 74
3.3.1.1 Bulk Terminals 74
3.3.1.2 Bulk Stations 78
3.3.1.3 Service Stations 31
3.3.2 Jet Fuel Marketing 85
3.3.3 Distillate and Diesel Fuel Marketing .... 87
3.3.4 Residual Fuels Marketing 91
3.3.5 Crude Oil Transport 93
3.4 Fossil Fuel Refining 99
. 3.4.1 Petroleum Refining 103
3.4.1.1 Process Description 103
3.4.1.2 Atmospheric Emissions and
Control 108
3.4.1.2.1 Combustion Sources .. 108
3.4.1.2.2 Storage and Loading
Sources 108
3.4.1.2.3 Process Sources 109
3.4.1.2.4 Fugitive Sources ... 117
3.4.1.3 Water-borne Effluents and
Control 118
3.4.2 Coke Manufacturing 125
3.4.2.1 By-Product Coking 126
3.4.2.1.1 Process Description . 126
3.4.2.1.2 Atmospheric Emissions 127
3.4.2.1.3 Water-Borne Effluents
and Control 128
3.4.2.2 Beehive Coking 133
3. 5 Fossil Fuel Combustion 134
3.5.1 External Combustion Stationary Sources .. 134
3.5.1.1 Coal Combustion 137
3.5.1.2 Fuel Oil Combustion 139
111
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PAGE
3.5.1.3 Natural Gas Combustion 140
3.5.1.4 Wood Combustion 141
3.5.2 Internal Combustion Stationary Sources .. 142
3.6 Organic Chemical Processing 144
3.6.1 Atmospheric Emissions 144
3.6.1.1 Ammonia Production 150
3.6.1.2 Carbon Black Production 152
3.6.1.3 Acrylonitrile Production 156
3.6.1.4 Ethylene Dichloride Production . 159
3.6.1.4.1 Process Description . 159
3.6.1.4.2 Atmospheric Emissions 160
3.6.1.4.3 Control of Emissions. 161
3.6.1.5 Toluene Production 162
3.6.1.6 Carbon Tetrachloride Production. 163
3.6.1.6.1 Process Description . 163
3.6.1.6.2 Atmospheric Emissions
and Control 165
3.6.1.7 Soap and Detergent Manufacture . 167
3.6.2 Water Effluents 168
3.6.2.1 Dyes and Pigment Production .... 179
3.6.2.2 Polyvinyl Chloride Production .. 181
3.6.2.3 Methyl Methacrylate Production . 182
3.7 Noncumbustion Organic Chemical Utilization 186
3.7.1 Surface Coating 186
3.7.1.1 Process Description 186
3.7.1.2 Atmospheric Emissions and
Control 192
3.7.2 Graphic Arts 194
3.7.2.1 Process Description 194
3.7.2.2 Atmospheric Emissions and
Control 196
3.7.3 Dry Cleaning 197
IV
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PAGE
3.7.4 Rubber and Plastic Processing 199
3.7.4.1 Process Description 200
3.7.4.2 Atmospheric Emissions and
Control 202
3.7.4.3 Water Effluents and Control .... 202
3.7.5 Fabric Treatment 204
3.8 Agricultural and Forest Products 205
3.8.1 Pulp and Paper Industry 210
3.8.1.1 Process Description 210
3.8.1.2 Atmospheric Emissions and
Control 215
3.8.1.3 Water Effluents and Control .... 219
3.8.2 Wood Waste Combustion 226
3.8.3 Beer Brewing 227
3.8.4 Fruit and Vegetable Processing 230
3.8.5 Tobacco Manufacture 236
3.8.6 Grain and Feed Mills and Elevators ...... 237
3.9 Open Sources 240
3.9.1 Agricultural Field Burning and Land
Clearance 240
3.9.2 Prescribed Forest Burning 242
3.10 Natural Sources 245
3.10.1 Process Description 247
3.10.2 Control of Emissions 250
3.11 Solid Waste Disposal 251
3.11.1 Process Description 253
3.11.2 Control of Emissions and Effluents 263
3.11.3 Potential Reduction of Emissions and
Effluents 264
3.12 Municipal Wastewater Treatment 267
3.12.1 Effluent Sources 267
3.12.2 Application of Control Technology 271
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PAGE
3 .13 Other Sources 276
3.13.1 Forest Wildfires 276
3.13.2 Structural Fires 278
3.13.3 Coal Refuse Fires 279
BIBLIOGRAPHY 282
APPENDIX
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LIST OF TABLES
NUMBER TITLE PAGE
2.0.1 ORGANIC EMISSIONS AND EFFLUENTS FROM MAJOR
CATEGORIES 18
2.0-2 POTENTIAL REDUCTIONS OF ORGANIC EMISSIONS
AND EFFLUENTS FROM MAJOR CATEGORIES 24
2.0-3 SUMMARY OF EMISSIONS AND EFFLUENTS FROM
CATEGORIES , MT/YR 29
2.1-1 AIR - VOLATILE ORGANIC EMISSIONS 31
2.1-2 AIR - PARTICIPATE ORGANICS 33
2.1-3 WATER EFFLUENTS 36
2.2-1 VOLATILE NON-METHANE ORGANIC EMISSIONS FROM
CONTROLLABLE PROCESSES 41
2.2-2 AIR - PARTICULATE ORGANIC EMISSIONS FROM
CONTROLLABLE PROCESSES 44
2.2-3 WATER - ORGANIC EFFLUENTS FROM CONTROLLABLE
PROCESSES 48
3.1-1 FOSSIL FUEL EXTRACTION - VOLATILE EMISSIONS 52
3.1-2 FOSSIL FUEL EXTRACTION - ORGANIC EFFLUENTS 53
3.2-1 FOSSIL FUEL PROCESSING - ATMOSPHERIC EMISSIONS.. 66
3-3-1 FOSSIL FUEL TRANSPORTATION, STORAGE, AND
DISTRIBUTION ATMOSPHERIC EMISSIONS 73
3.3-2 U.S. BULK STORAGE CAPACITY BY TANK SIZE 77
3.3-3 U.S. GASOLINE SERVICE STATION SALES VOLUME
DISTRIBUTION 83
3. 3-4 PROPERTIES OF DISTILLATE FUELS 89
3.3-5 U.S. DISTILLATE FUEL OIL DOMESTIC DEMAND BY
USES 90
3.3-6 TANKER AND BARGE MOVEMENTS OF CRUDE OIL 94
3.3-7 CRUDE OIL IMPORTS 95
vii
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LIST OF TABLES (Continued)
NUMBER TITLE PAGE
3.4-1 FOSSIL FUEL REFINING EMISSIONS. 100
3.4-2 REFINERY SIZE DISTRIBUTION - 1971 106
3.4-3 QUALITATIVE EVALUATION OF WASTEWATER FLOW
AND CHARACTERISTICS BY FUNDAMENTAL REFINERY
PROCESSES 119
3.4-4 PETROLEUM REFINERY ORGANIC EFFLUENTS 120
3.4-5 COKE MANUFACTURE ORGANIC EFFLUENTS 130
3.5-1 FOSSIL FUEL COMBUSTION - ATMOSPHERIC
EMISSIONS , 135
3.5-2 ATMOSPHERIC ORGANIC EMISSIONS FROM COAL
COMBUSTION 138
3.5-3 ATMOSPHERIC ORGANIC EMISSIONS FROM FUEL OIL
COMBUSTION 139
3.5-4 ATMOSPHERIC ORGANIC EMISSIONS FROM NATURAL
GAS COMBUSTION . 141
3.5-5 ATMOSPHERIC ORGANIC EMISSIONS FROM WOOD
COMBUSTION 142
3.5-6 ATMOSPHERIC ORGANIC EMISSIONS FROM STATIONARY
INTERNAL COMBUSTION SOURCES 143
3.6-1 CONTROL OF ATMOSPHERIC EMISSIONS IN THE
FOSSIL FUEL CHEMICAL PROCESSING INDUSTRY 151
3.6-2 MAJOR RWL'S OF POLLUTANTS BASED ON PROCESS
WASTEWATER USE 172
3.6-3 WASTE REDUCTION FACTORS ACHIEVABLE THROUGH
USE OF BPCTCA LEVEL OF WATER TREATMENT 175
3.6-4 MAJOR WATER EFFLUENTS FROM THE ORGANIC
CHEMICAL PROCESSING INDUSTRY 178
3.6-5 CHARACTERISTICS OF WATER EFFLUENT FROM SPENT
ACID RECOVERY UNIT 184
Vlll
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LIST OF TABLES (Continued)
NUMBER TITLE PAGE
3.7-1 NONCOM3USTION ORGANIC CHEMICAL UTILIZATION -
ATMOSPHERIC EMISSIONS 187
3.7-2 NONCOMBUSTION ORGANIC CHEMICAL UTILIZATION -
ORGANIC EFFLUENTS 189
3.7-3 ATMOSPHERIC ORGANIC EMISSIONS FROM SURFACE
COATING OPERATIONS 193
3.7-4 ATMOSPHERIC ORGANIC EMISSIONS FROM GRAPHIC
ARTS PROCESSES 197
3.8-1 ATMOSPHERIC EMISSIONS FROM THE AGRICULTURAL
AND FOREST PRODUCTS INDUSTRY 206
3.8-2 CONTROL OF ATMOSPHERIC EMISSIONS IN THE
AGRICULTURAL AND FOREST PRODUCTS INDUSTRY 207
3.8-3 WATER EFFLUENTS FROM THE AGRICULTURAL AND
FOREST PRODUCTS INDUSTRY 209
3.8-4 CONTROL OF WATER EFFLUENTS IN THE AGRICULTURAL
AND FOREST PRODUCTS INDUSTRY 211
3.8-5 UNCONTROLLED EMISSION FACTORS FOR SULFATE
PULPING 216
3.8-6 EMISSIONS FROM NSSC PULPING 218
3.8-7 WATER USAGE AND WASTE CHARACTERIZATION IN
APPLE PROCESSING 232
3.8-8 WATER USAGE AND WASTE CHARACTERIZATION IN
CITRUS PROCESSING .' 233
3.8-9 WATER USAGE AND WASTE CHARACTERIZATION IN
POTATO PROCESSING 234
3.9-1 ATMOSPHERIC EMISSIONS FROM OPEN SOURCES 241
3.10-1 ATMOSPHERIC EMISSIONS FROM NATURAL SOURCES 246
3. 10 . 2 GLOBAL TERPENE EMISSION ESTIMATES 249
3.11-1 SOLID WASTES IN THE AGRICULTURAL AND
FOREST PRODUCTS INDUSTRY 252
IX
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LIST OF TABLES (Continued)
NUMBER TITLE PAGE
3.11-2 SOLID WASTE DISPOSAL METHODS 254
3.11-3 ATMOSPHERIC EMISSIONS FROM SOLID WASTE DIS-
POSAL OPERATIONS IN METRIC TONS PER YEAR 255
3.11-4 WASTEWATER EFFLUENTS FROM SOLID WASTE
DISPOSAL IN METRIC TONS PER YEAR 256
3.11-5 ORGANIC SOLIDS FROM SOLID WASTE DISPOSAL
OPERATIONS 257
3.11-6 ESTIMATED QUALITIES OF DUMP AND LANDFILL
LEACHATES 259
3.11-7 POTENTIAL REDUCTION OF ORGANIC EMISSIONS
AND EFFLUENTS 261
3 . 12- 1 WASTEWATER EFFLUENTS (MT/YR) 269
3.12-2 POTENTIAL REDUCTION OF ORGANIC WATER
EFFLUENTS FROM MUNICIPAL WASTEWATER
TREATMENT FACILITIES 272
3.13-1 ATMOSPHERIC EMISSIONS FROM OTHER SOURCES 277
A-l AIR EMISSIONS FROM ORGANIC CHEMICAL
PROCESSING IN METRIC TONS/YR 304
A-2 WATER EFFLUENTS FROM ORGANIC CHEMICAL
PROCESSING IN METRIC TONS/YR 310
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LIST OF FIGURES
NUMBER TITLE PAGE
2.1-1 DISTRIBUTION OF TOTAL VOLATILE NON-METHANE
EMISSIONS 32
2.1-2 DISTRIBUTION OF CONTROLLABLE VOLATILE NON-
METHANE EMISSIONS 32
2.1-3 DISTRIBUTION OF TOTAL ORGANIC PARTICULATE
EMISSIONS 34
2.1-4 DISTRIBUTION OF CONTROLLABLE ORGANIC
PARTICULATE EMISSIONS 34
2.1-5 DISTRIBUTION OF TOTAL ORGANIC WATER EFFLUENTS... 37
2.1-6 DISTRIBUTION OF CONTROLLABLE ORGANIC WATER
EFFLUENTS 37
2.2-1 DISTRIBUTION OF VOLATILE NON-METHANE EMISSIONS
FROM CONTROLLABLE PROCESSES 43
2.2-2 DISTRIBUTION OF CONTROLLABLE VOLATILE NON-
METHANE EMISSIONS FROM CONTROLLABLE PROCESSES... 43
2.2-3 DISTRIBUTION OF TOTAL PARTICULATE ORGANIC
EMISSIONS FROM CONTROLLABLE PROCESSES 46
2.2-4 DISTRIBUTION OF CONTROLLABLE PARTICULATE
ORGANIC EMISSIONS FROM CONTROLLABLE PROCESSES... 46
2.2-5 DISTRIBUTION OF TOTAL ORGANIC EFFLUENTS FROM
CONTROLLABLE PROCESSES 50
2.2-6 DISTRIBUTION OF CONTROLLABLE ORGANIC EFFLUENTS
FROM CONTROLLABLE PROCESSES 50
3.3-1 THE GASOLINE MARKETING DISTRIBUTION SYSTEM
IN THE UNITED STATES 75
3.3-2 VAPOR AND LIQUID FLOW IN A TYPICAL BULK
STATION WITH RECOVERY OF DISPLACED VAPORS 80
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LIST OF FIGURES (Continued)
NUMBER TITLE PAGE
3.3-3 VAPOR AND LIQUID FLOW IN A TYPICAL SERVICE
STATION 84
3.3-4 TRANSPORTATION OF CRUDE OIL, 1973 97
3.4-1 TYPICAL MOVING-BED CATALYTIC CRACKING UNIT 110
3.4-2 TYPICAL FLUIDIZED BED CATALYTIC CRACKING UNIT... 110
3.4-3 TYPICAL STEAM EJECTOR-BAROMETERIC CONDENSER 112
3.4-4 FLOW DIAGRAM OF ASPHALT BLOWING PROCESS 115
3.6-1 ORGANIC CHEMICAL PROCESSING INDUSTRIES 145
3. 12-1 WASTEWATER TREATMENT ALTERNATIVES 268
XI1
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1.0 INTRODUCTION
The purpose of this report is to provide the Environ-
mental Protection Agency with an identification and quantifica-
tion of the important multi-media organic emissions, effluents,
and wastes from stationary sources on a nationwide basis.
This report divides the major pollutant sources into
thirteen categories. The organic emissions and effluents from
these categories are quantified and the major sources are iden-
tified within the categories. The sources with the largest po-
tential for reduction of organic emissions and effluents are
identified and the controls required to achieve the reductions
are discussed. Because all but a few of the numbers in this re-
port are estimates of indeterminate accuracy, errors of 1070 and,
in some cases, 15% are to be expected.
1. 1 Obj ectives
The objective of this program is to describe the rela-
tive importance of existing multi-media organic emissions and
effluents from domestic stationary sources. The quantity and
control potential of the discharges are addressed. The station-
ary sources considered are grouped in thirteen major categories.
These categories are as follows:
Category Description
I Fossil fuel extraction (gas wells, oil wells, oil/
gas wells, coal mines, etc.)
II Fossil fuel processing (natural gasoline plants,
sulfur recovery, coal preparation, etc.'
Ill Fossil fuel transportation, storage, and distri-
bution (pipelines, gasoline transfer, etc.)
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Category
IV
Description
Fossil fuel refining (petroleum refineries, coke
ovens, etc.)
V
VI
VII
VIII
IX
X
XI
XII
XIII
Fossil fuel combustion (commercial, industrial,
utility, etc.)
Fossil fuel feedstock chemical processing (all
processes which start with feedstock derived from
fossil fuels and produce intermediate or end
products)
Non-combustion organic chemical utilization (in-
dustrial/commercial, printing, dry cleaning, etc.)
Agricultural and forest products (corn oil, turpen-
tine, food processing, etc.)
Open sources (agricultural burning, etc.)
Natural sources (pine forests, etc.)
Solid waste disposal (solid waste incineration,
landfilling, etc.)
Municipal wastewater treatment
Other sources (forest fires, etc.)
1.2
Approach
In the initial phase of the program, readily available
information on stationary sources of organic emissions and efflu-
ents was assembled. Information concerning process descriptions,
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operating parameters, current organic chemical controls, and
control problems were also obtained. The information sources
include previous and current EPA studies, new source performance
standard studies, known emission factors, Radian files, and
other published or unpublished information.
As the data base was assembled, the data was divided
into the major categories for subsequent evaluation. Pollutants
resulting from process streams were evaluated along with "fugi-
tive" type emissions associated with equipment leaks such as
those from pumps, valves, and flanges. Emissions resulting from
"open" sources such as forest fires and from natural sources
such as pine forests are also included.
The information collected for each category was di-
vided into logical classes and grouped for further assessment
of emissions and effluents from processes and operations. A
complete list of the emission and effluent rates from the pro-
cesses and operations studied is presented in Section 2. An
attempt was made to identify the major sources of emissions and
effluents from each category.
The controllability of the source was assessed. Then,
specific processes and operations that represented the greatest
potential for the reduction of organic emissions and effluents
by the application of control technology were selected for
further study.
The selected processes and operations are described
in detail in Section 3. The descriptions give considerable at-
tention to the specific nature and source of the organic emis-
sions and effluents. Also discussed in detail are the control
technologies required for reduction of the emission and effluent
rate, and the potential reduction in organic pollutants result-
ing from the application of that control technology.
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1.3 Methodology
Procedures were established for assessing the emission
and effluent rates for the various sources and for determining
the control of these sources. The procedures apply to all the
categories studied.
-o
The quantification of the organic pollutants was ac-
complished by assembling readily available information. Occa-
sionally, sources gave conflicting information on pollutant
quantities. In these instances, several approaches were used to
select the source which provided the most accurate information.
These approaches are discussed below.
1) Frequently, information sources provide an evalua-
tion of the quality of the data used to estimate
the pollutant rates. This evaluation was particu-
larly valuable in the fossil fuel feed stock chemi-
cal processing (FFFCP) category. The definitions
of the data quality and an example of the distribu-
tion of the quality in the FFFCP category is sum-
marized as follows:
Percent of
Quality Meaning Total Data
A Adequate data of reasonable
accuracy. 1%
B Partially estimated data of 55%
indeterminate accuracy.
C Totally estimated data of 36%
indeterminate accuracy.
D No data; estimates based on 8%
generalized loss factor.
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When conflicting data were encountered and the
data quality was rated, the best quality data
were used.
2) Occasionally, data of the same estimated quality
gave conflicting pollutant rates or conflicting
data had no estimated quality. In these instances,
the reports were assessed and references were
checked when necessary to evaluate the data and
procedures used. Then, the best data were selected
on that basis.
3) Finally, if none of the above information was pro-
vided, engineering judgement was used to select
the best data. The engineering judgement was
based on a knowledge of the process operation and
pollutant rates from similar processes.
Specific examples of poor quality data or a lack of
data are discussed in Section 3.
1.4 Definitions
Three terms are used throughout this report. The term
emissions is used to describe pollutants emitted to the atmo-
sphere. Effluents refers to pollutants emitted to bodies of
water. Wastes refers to solid waste emissions. These terms
and some other terms are defined further in the following para-
graphs .
Atmospheric Pollutants
The atmospheric pollutants are separated into volatile
organics and organic particulates. Each emission type is analyzed
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and discussed separately since the two types have different ef-
fects on the ambient air quality. Also, the control technologies
for the two types are significantly different and the potentials
for emission reduction must be assessed separately.
Special emphasis was given to the quantification and
control of the volatile organics. The organic particulate emis-
sions were determined by estimating the fraction of organics
present in the total particulate emissions. Where possible, the
emissions were quantified by assuming the current degree of con-
trol practiced today. Reduction potentials were determined by
estimating emissions to be fully controlled by currently avail-
able technology.
Water Effluents
In general, current estimates of organic water ef-
fluents are lacking. However, EPA publications of development
documents for effluent limitations guidelines are available for
a large segment of industry. The guidelines provide information
sources relating to effluent limitations for 1977 (Best Practica-
ble Control Technology Currently Available, BPCTCA) and 1983
(Best Available Technology Economically Achievable, BATEA).
Consequently, this report assumes 1977 effluent limits as "cur-
rent" control levels and the 1983 effluent limits as the control
technology providing potential effluent reductions. This assump-
tion may provide higher rates and reductions than actually antic-
ipated since the 30-day limitations were used and these are
usually higher than the average yearly effluent. However, the
assumption is generally consistent within the report and con-
sequently, the effluent and reduction comparisons should be
realistic.
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The organic content of water effluents was selected
as the parameter to assess the organic effluent quantity from
the processes and operations studied. Organic content refers to
the actual quantity of organics present in effluent water streams.
This parameter was selected in the study as the best measure of
organics actually introduced into the environment. Biochemical
oxygen demand (BOD), chemical oxygen demand (COD), and total
organic carbon (TOG) are more commonly used parameters associated
with water quality studies; however, these parameters do not esti-
mate the actual mass rate of organic effluents. For example, BOD
is the most commonly reported parameter in the literature, but
many organic compounds are not biologically degradable and their
presence is not indicated by BOD measurements.
The organic content of water effluents is estimated
from information on biochemical oxygen demand (BOD), chemical
oxygen demand (COD), and total organic carbon (TOC) . The organic
content of effluents was estimated by several methods which are
listed in decreasing order of preference:
1) from the literature, determine correlations
between BOD, COD, or TOC and organic content,
2) from TOC information, calculate the organic
content by assuming the composition and
average molecular weight of the organic,
3) from BOD:TOC correlations in literature for
similar processes, calculate the organic
content as in 2), or
4) from COD information, estimate the carbon
present assuming complete oxidation of the
organic and calculate the organic content
as in 2).
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There are inaccuracies associated with the above
methods for estimating organic content of water effluents. The
first method should be reasonably accurate. The basic assump-
tion associated with the other methods is that, since TOG is
directly related to the organic content, the organic composi-
tion of the effluent can be represented by one typical compound.
The typical compound is selected as the major product from a
process or operation. For special cases, such as polymeriza-
tion, the monomer is selected, or for refineries, a typical or
average hydrocarbon is selected. This selection is based on the
assumption that feed material to processes and by-products from
processes which can contribute to effluent rates are similar to
the products of the process. The accuracy of this assumption
decreases for processes having organic effluents that are not
similar to the product, such as diluent streams, lubricants,
solvent refining, and inhibitors.
Other organic water effluent parameters examined are
oil and grease (0/G) effluents and suspended solids (S3). Sus-
pended solids from the processes studied here usually contain
some organic matter. However, information on the organic con-
tent of SS is very limited. Consequently, the total SS rate is
reported with no breakdown of organic content. For this report,
greatest emphasis in assessing importance of waste water ef-
fluents is placed on organic content of the water calculated
from BOD, COD, and TOG.
Solid Wastes
The solid wastes produced are not listed by category
since adequate information was not available. Most operations
and processes dispose of solid waste on site by incineration,
landfill, or other means, or they retain contractors to properly
dispose of solid wastes off site. The solid waste that is
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properly disposed of is not considered a pollutant. However,
the solid waste category does examine the environmental impact
of disposal techniques for municipal facilities handling solid
wastes. In this manner, the environmental impacts of solid
wastes are assessed and compared with atmospheric emissions and
water effluents from other categories, since solid wastes ulti-
mately result in atmospheric emissions by decomposition or in-
cineration and water effluents by leaching.
Stationary Sources
Most organic pollutant sources involve fossil fuels.
These fossil fuel operations involve extraction, various process-
ing and handling steps, and utilization. Other sources not re-
lated to fossil fuels include agricultural and forest products,
open and natural sources, solid waste disposal and municipal
sewage.
Some sources not related to fossil fuels are also not
point sources. An example of this is the natural source category.
This category examines organic emissions from such natural sources
as living plants, decomposition of organic material and enteric
fermentation in animals. Evaluation of emissions from natural
sources allows comparisons between them and the fossil fuels
categories. These comparisons are made so that the results of
pollution controls can be determined realistically on a mass
basis.
Hydrocarbons
In general, organic compounds are composed primarily
of carbon and other elements such as hydrogen, oxygen, nitrogen
and halogens. Hydrocarbons refer to a specific class of organics
composed solely of carbon and hydrogen. For the purposes of this
report, the term "hydrocarbons" sometimes refers to other organic
materials also.
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Organic Chemical Control Technology
The reduction in organic emissions and effluents from
the major categories and individual processes and operations is
determined from current control technology. Where possible,
the controls for pollutants from specific sources are those
commonly used. In some cases, commonly used specific control
information was not available. Engineering judgement was then
used to determine a specific control or typical control efficiency
for the class or type of emission to determine a reduction po-
tential. As an example: it is beyond the scope of this report
to determine the most desirable control for a process vent stream
if controls are not used in the industry. However, most process
vents can be controlled by adsorption, absorption, condensation
or incineration. These controls have typical operating effi-
ciencies and control potentials can be estimated. The selection
of a specific control as the most desirable in actual applica-
tions will require an indepth study and may differ for the same
process from one location to the next.
1.5 Summary of Results
1. Total volatile organic emissions are about an
order of magnitude higher than the organic particu-
late emissions and the organic water effluents.
Total non-methane volatile organic emissions are
two-to-three times as high as either the or-
ganic particulate emissions or the organic water
effluents.
2. Forty-eight percent of the non-methane vola-
tile organic emissions and 7570 of the organic
particulate emissions are controllable. About
half of these controllable volatile emissions
-10-
-------
and one-third of the controllable particulate
emissions are from open burning sources which
usually occur in remote areas and contribute
little to photochemical smog. These open sources
account for over 20% of the total non-methane
organic emissions.
3. Thirty-five percent of the particulate emis-
sions are from the plywood and veneer indus-
try and grain and feed processors, all of which
are controllable.
4. Effluents from natural sources were not considered
because a natural BOD is inherent in the aquatic
ecosystem. Thirty-five percent of the remaining
effluents are considered controllable. Twenty-
nine percent could be controlled with tertiary
control of municipal waste water treatment facili-
ties .
5. Process emissions should be considered foremost
because they tend to be in populated areas and
are amenable to control technology. Also, most
toxic emissions are from these sources.
6. Fifty percent of the process volatile non-methane
emissions are from non-combustion organic chemical
utilization and chemical processing. Another 4570
are from fossil fuel refining and transportation.
There is no single large controllable emission
source.
7. Agricultural and forest products account for 9070
of the process organic particulate emissions.
-11-
-------
Seventy-five percent of these emissions are from
the plywood and veneer industry and from grain
and feed processors.
8) Fifty percent of the process organic effluents
are from agricultural and forest products; 4770
.are from chemical processing. These is no single
large controllable effluent source.
1.6 Conclusions and Recommendations
This report incorporates several unique features that
distinguish it from previous studies concerning organic chemical
pollutants from stationary sources. These features are as fol-
low:
It is the first report to assess multi-
media impacts together for comparison.
While it does not generate new data, it
pulls previous studies together into one
package to compare the impacts of impor-
tant processes and operations on a mass
emission basis.
It is the first report to break atmo-
spheric emissions of organics down into
volatiles and particulates for comparison.
It is the first in depth look at major
emission and effluent sources from or-
ganic chemical processing.
-12-
-------
It is the first attempt to address the
quantities of controllable emissions
and effluents from a broad cross section
of sources and to assess and compare the
data.
Conclusions
These unique features and the methodology of the re-
port allow the data to be processed to make the following con-
clusions :
1) The organic emissions and effluents are a
reasonably complete assessment of the major
organic pollutants from the respective in-
dustries .
2) As a result of the time allocated to assess
the major categories, the data for process
type categories are reasonably firm while
the data for the other categories (espe-
cially natural sources, open sources and
"other" sources) are not as firm.
3) Other factors, such as geographical location
of sites, reactivity, toxicity of pollutants,
cost of controls, and meteorological char-
acteristics, must be considered in addition
to mass pollutant rates to develop a control
strategy in the U.S. Pollutant sources
should be considered on an area-wide basis.
These factors and the contribution of all
significant point sources within these areas
should also be considered.
-13-
-------
4) The quantities of organic atmospheric emis-
sions are greater than organics in water
effluents; however, the air emissions are
dispersed in a larger medium.
5) Open sources, which usually occur in remote
areas, are the largest source of non-methane
organic emissions. Other sources of volatile
organic emissions are varied; none is sig-
nificantly large.
6) About half of the non-methane volatile
emissions, most from fossil fuel-related
industries, are controllable.
7) Control of grain and feed processors and
the plywood and veneer industry could re-
duce particulate organic emissions by one
third.
8) Natural sources of organic effluents were not
considered. Tertiary control of municipal
waste water treatment facilities would greatly
. reduce organic effluents. The pulp and paper
industry is the only other contributor of any
consequence.
Recommendations
The evaluation of organic pollutants from stationary
sources and their control potential leads to the identification
of several areas for further consideration. There are;
-14-
-------
1) Specific problem areas relating to organic
pollutants should be identified and assessed
on a source-by-source basis.
2) Additional field work and sampling should
be conducted to verify emission and effluent
rates and identify components.
3) The processes in particular problem areas
with the greatest degree of control should
receive special attention.
4) The chemical processing industry is so com-
plex and diverse that it requires special
attention. The mass emission and effluent
rates should be verified and expanded to
improve the quality of available data. The
pollutants should be characterized by moni-
toring. Specific geographical sites and
complexes should be considered.
5) Additional work is needed to identify BOD/
COD/TOC/Total Organic relationships.
6) Information should be generated on the quantity,
composition and ultimate fate of solid wastes.
7) Additional data is needed regarding the fate
of pollutants in the environment and their
long-term effects.
8) More work is needed to assess the toxicity
and health effects of the pollutants with
-15-
-------
proper consideration for composition changes
and their ultimate fate.
9) The cost effectiveness of various control
strategies should be considered so that relation-
ships between control potentials and control
costs can be optimized to reduce pollutants to
required levels.
-16-
-------
2.0 RESULTS
The organic emissions and effluents from the major
categories are examined in this section so that the impact of
emission controls may be assessed. A listing of the emissions.
and effluents from the selected processes is presented in Table
2.0-1. Reduction potentials are presented in Table 2.0-2. A
summary of these two is presented in Table 2.0-3. A more com-
plete listing of all the emissions and effluents considered in
the fossil fuel feedstock chemical processing category is pre-
sented in the Appendix.
The areas representing the greatest potential for reduc-
tion are discussed in the following sections.
2. 1 Overall Organic Emissions and Effluents
The emissions and effluents and their control potentials
from all the categories are discussed in this section. The effect
of controls for the various categories and processes are assessed.
The total volatile organic emissions are about an order
of magnitude higher than the organic particulate emissions and
the water effluents. Non-methane volatile organics alone are only
three times the organic particulates and twice the organic water
effluents. The controllable volatile emissions are also only 2-3
times the controllable organic particulates and controllable or-
ganic water effluents.
2.1.1 Atmospheric Emissions
The atmospheric emissions are divided into volatiles
and particulates. Both types of emissions are discussed.
-17-
-------
TABLE 2.0-1
ORGANIC EMISSIONS AND EFFLUENTS FROM MAJOR CATEGORIES
Atmospheric Emissions
Category
Volatile Organics Organic Particulates
(MT/yr) (MT/yr)
I. Fossil Fuel Extraction *2,510,000
Major Sources:
Coal Production *1,610,000
Crude Oil and Asso-
ciated Gas Production * 630,000
Natural Gas Extraction * 270,000
Water Effluents
(MT/yr)
Major Sources:
Crude Oil and Asso-
ciated Gas Production
29,000
CO
i
II. Fossil Fuel Processing *1,716,400
Major Sources:
Natural Gasoline Plants *1,714,000
Coal Preparation Plants 2,400
7,300
7,300
III. Fossil Fuel Transportation,
Storage, and Distribution 2,071,000
Major Sources:
Crude Oil Storage 526,000
Gasoline Service Station
Automobile Filling 467,000
Gasoline Service Station
Underground Tank Filling 399,000
Gasoline Bulk Station
Storage 109,000
77,300
-------
TABLE 2.0-1 (Continued)
ORGANIC EMISSIONS AND EFFLUENTS FROM MAJOR CATEGORIES
Atmospheric Emissions
IV.
Category
Fossil Fuel Refining
Major Sources:
Volatile Organics
(MT/yr)
2,173,500
Organic Particulates
(MT/yr)
269,000
Storage, Petroleum
Refineries 965,000
Slowdown, Petroleum
Refining 328,000
Process Drains and Waste
Water Separators,
Petroleum Refineries 216,000
Fluid Catalytic Cracker
Unit, Petroleum
Refineries 147,000
Vacuum Jets, Petroleum
Refineries 117,000
Water Effluents
(MT/yr)
34,700
Major Sources:
Petroleum Refineries 23,600
Coke Manufacturing 11,100
V. Fossil Fuel Combustion 724,000
Major Sources:
Industrial Internal
Combustion Gas . *237,000
Utilities - coal fired 105,000
Industrial - natural gas * 76,400
Industrial Internal
Combustion-Oil
Industrial/Commercial
Fuel Oil
68,200
56,400
-------
TABLE 2.0-1 (Continued)
ORGANIC EMISSIONS AND EFFLUENTS FROM MAJOR CATEGORIES
Atmospheric Emissions
Category
VI. Fossil Fuel Feedstock
Chemical Processing
Major Sources:
i
Ni
O
I
Volatile Organics
(MT/yr)
1,400,000
Organic Particulates
(MT/yr)
45,800
VII. Noncombustion Organic
Chemical Utilization 3,529,000
Major Sources:
Rubber and Plastics
Processing 1,280,000
Paper and Paperboard
Coating 475,000
Sheet, Strip and Coil
Coating 469,000
Miscellaneous Surface
Coating 385,000
Dry Cleaning 367,000
Fabric Treatment 210,000
Graphic Arts-Gravure 107,000
Water Effluents
(MT/yr)
460,000
Major Sources:
Ammonia
Carbon Black
Acrylonitrile
Ethylene Dichloride
Toluene
Carbon Tetrachloride
* 323,000
96,700
83,000
56,300
51,000
43,400
Dyes and Pigments
3,674 Polyvinyl Chloride
Methyl Methacrylate
—
—
60,800
32,300
30,900
Major Sources:
100
100
-------
TABLE 2.0-1 (Continued)
ORGANIC EMISSIONS AND EFFLUENTS FROM MAJOR CATEGORIES
Category
Atmospheric Emissions
Volatile Organics
(MT/yr)
VII. Noncombustion Organic
Chemical Utilization
Major Sources: cont.
Cast Iron Foundry
Core Ovens
Auto and Truck Coating
102,000
100,000
Organic Particulates
(MT/yr)
Water Effluents
(MT/yr)
VIII. Agricultural and Forest
Products 508,000
Major Sources:
Pulp and Paper 143,000
Wood Waste Combustion 137,000
Beer Brewing 67,800
Fruit and Vegetables
Processing 47,700
Tobacco 39,710
3,324,000
108,000
Major Sources:
Pulp & Paper
Processed Fruits
& vegetables
Beer Brewing
488,000
208,000
92,200
73,800
IX. Open Sources
Major Sources:
Agricultural Field
Burning of Land
Clearance
Prescribed Forest
Burning
3,010,000
2,540,000
472,000
973,000
821,000
152,000
Major Sources:
-------
TABLE 2.0-1 (Continued)
ORGANIC EMISSIONS AND EFFLUENTS FROM MAJOR CATEGORIES
Atmospheric
Category Volatile Organics
X. Natural Sources *85
Major Sources:
Decomposition of
Organic Material *71
Living Plants 9
Enteric Ferraenation
in Animals * 4
XI. Solid Waste Disposal 2
Major Sources:
Open Burning of Refuse 1
Open Burning of Uncol-
lected Urban Refuse
Open Burning of Rural
Refuse
Methane from Decomposition
in Dumps and Landfills
Municipal Incineration
(MT/yr)
,300,000
,700,000
,100,000
,500,000
,690,000
,660,000
345,000
322,000
*247,000
51,500
Emissions
Organic Particulates
(MT/yr)
1,500,000
—
1,500,000
—
640,000
378,000
80,000
74,000
0
65,400
Water Effluents
Major Sources:
Major Sources:
Leachate From
Open Dumps
Leachate From
Burning Dumps
Leachate From
Landfills
Leachate From
Sanitary Landfills
(MT/yr)
N/A
N/A
N/A
736,000
293,000
245,000
171,000
25,350
Municipal Sewage Disposal
Major Sources:
N/A - Not applicable natural sources of organics
in surface waters are not considered.
9,980,000
Major Sources:
Septic Tanks 5,700,000
Primary Treatment 1,370,000
None or Minor
Treatment
1,020,000
-------
TABLE 2.0-1 (Continued)
ORGANIC EMISSIONS AND EFFLUENTS FROM MAJOR CATEGORIES
Atmospheric Emissions
Category
XIII. Other Sources
Major Sources:
Forest Wildfires
Structural Fires
Coal Refuse Fires
Volatile Organics
(MT/yr)
917,000
791,000
64,800
61,200
Organic Particulates
(MT/yr)
234,000
Water Effluents
(MT/yr)
Major Sources;
213,000
20,900
CO
*Indicates emissions consisting mostly of methane.
N/A - not available.
-------
TABLE 2.0-2
POTENTIAL REDUCTIONS OF ORGANIC EMISSIONS AND EFFLUENTS FROM MAJOR CATEGORIES
Category
I. Fossil Fuel Extraction
Major Sources:
Coal Extraction
_Atmospheric Emission Reductions
Volatile Organics Organic Particulates
(MT/yr)
*1,830,000
*1,290,000
Crude Oil & Associated
Gas Production * 380,000
Natural Gas Extraction * 162,000
(MT/yr)
Water Effluents
(MT/yr)
29,000
Major Sources:
Crude Oil & Associated
Gas Production 29,000
i
N>
-fi-
Fossil Fuel Processing 1,030,000
Major Sources:
Natural Gasoline Plants 1,030,000
Coal Preparation Plants
3,650
3,650
Major Sources;
III. Fossil Fuel Transportation,
Storage, and Distribution 1,363,000
Major Sources:
Service Station Auto
Filling 420,000
Service Station Under-
ground Tank Filling 383,000
Crude Transportation -
Storage 246,000
Gasoline Bulk Station -
Storage 104,000
Gasoline Bulk Station -
Loading 91,600
69,600
Major Sources:
-------
TABLE 2.0-2 (Continued)
POTENTIAL REDUCTIONS OF ORGANIC EMISSIONS AND EFFLUENTS FROM MAJOR CATEGORIES
Atmospheric Emission Reductions
i
ro
01
IV.
Category
Fossil Fuel Refining
Major Sources:
Petroleum Refining -
Storage
Petroleum Refining -
Slowdown
Volatile Organics
(MT/yr)
1,400,000
452,000
318,000
Organic Particulates
(MT/yr)
243,600
Petroleum
Process Drains and Waste
Water Separators 195,000
Petroleum Refineries-FCCU 147,000
Petroleum Vacuum Jets 117,000
Water Effluents
(MT/yr)
Major Sources:
Petroleum Refining
Coke Manufacturing
26,360
16,700
9,680
V. Fossil Fuel Combustion
Major Sources:
Industrial Internal
Combustion - Gas
Utility Internal
Combustion - Oil
*314,000
234,600
67,500
Major Sources;
VI. Fossil Feedstock Chemical
Processing 1,270,000
Major Sources:
Ammonia 319,500
Carbon Black 96,700
40,900
Major Sources:
Dyes and Pigments
Polyvinyl Chloride
and Copolymers
400,000
52,900
28,100
-------
TABLE 2.0-2 (Continued)
POTENTIAL REDUCTIONS OF ORGANIC EMISSIONS AND EFFLUENTS FROM MAJOR CATEGORIES
Atmospheric Emission Reductions
Category
Volatile Organics
(MT/yr)
Organic Particulates
(MT/yr)
Water Effluents
(MT/yr)
VI. Fossil Feedstock Chemical
Processing, (Cont'd)
Major Sources: (Cont'd)
Acrylonitrile 82,000
Ethylene Dichloride 55,000
Toluene 43,800
Carbon Tetrachloride 41,700
VII. Noncombustion Organic
Chemical Utilization
Major Sources:
Rubber and Plastic
Processing
Surface Coating
Graphic Arts
Dry Cleaning
2,868,000
1,150,000
989,100
337,500
202,000
Major Sources:
Methyl Methacrylate
26,900
1
N>
CT>
Soap and Detergent
Manufacture —
17,900
Major Sources:
-------
TABLE 2.0-2 (Continued)
POTENTIAL REDUCTIONS OF ORGANIC EMISSIONS AND EFFLUENTS FROM MAJOR CATEGORIES
i
ho
Category
Atmospheric Emission Reductions
Volatile Organics Organic Particulates
(MT/yr)
(MT/yr)
VIII. Agricultural and Forest
Products 504,000
Major Sources:
Pulp and Paper 142,000
Wood Waste Combustion 137,000
Beer Brewing 67,100
Processed Fruits and
Vegetables 47,200
Tobacco 39,300
Grain and Feed Milling
and Storage
3,300,000
47,400
103,000
Water Effluents
(MT/yr)
317,000
Major Sources:
Pulp and Paper 104,000
Processed Fruits and
Vegetables 69,900
Beer Brewing 55,530
1,300,000
IX. Open Sources
Major Sources:
Agriculture Field
Burning
Prescribed Forest
Burning
3,010,000
2,540,000
472,000
973,000
820,000
152,000
Major Sources;
X.
Natural Sources
XI. Solid Waste Disposal 2,210,000
Major Sources:
Open Burning Dumps and
Open Dumps Replaced
by Landfills 1,656,000
607,000
378,000
Major Sources:
70,900
Open Burning Dumps and
Open Dumps Replaced
by Landfills 48,900
-------
TABLE 2.0-2 (Continued)
POTENTIAL REDUCTIONS OF ORGANIC EMISSIONS AND EFFLUENTS FROM MAJOR CATEGORIES
Atmospheric Emission Reductions
Category
Volatile Organics
(MT/yr)
Organic Particulates
(MT/yr)
XI. Solid Waste Disposal,
(Cont'd)
Major Sources: (Cont'd)
Replace Open Burning of
Uncollected Refuse with
Landfills
604,000
154,000
Water Effluents
(MT/yr)
Major Sources:
ho
oo
i
XII. Municipal Wastewater
Major Sources:
Major Sources:
Upgrade all Municipal
Water Treatment to
Secondary Biological
Facilities
2,080,000
Upgrade all Municipal
Water Treatment Facil-
ities to Tertiary
Control (Include
Secondary Control) 1,050,000
XIII. Other Sources
*Indicates emissions consisting mostly of methane.
-------
TABLE 2.0-3
SUMMARY OF EMISSIONS AND EFFLUENTS FROM CATEGORIES. MT/yr
VOLATILE OBCAMICS
PAOT1CUIATE OKCAII1CS
K)
VO
I
UATEH EFFLUENTS
11.
111.
IV.
V.
VI.
VII.
VIII.
IX.
X.
XI.
XII.
XIII.
Fossil Fuel Eitructlon
Foaall Fuel Proccaglng
Storage & Distribution
Foeall Fuel luiflnlng
Fossil Fuel Combustion
Chemical Processing
Noncoabuatlan Organic
Chemical Utilization
Agricultural and Forest
Products
Open Sources
Natural Sources
Solid Waste Disposal
feinlclpal Sewagu Disposal
Other Sources
Total
EmluBlona
2,510.000
1,716,400
2,071,000
2.173.SOO
724,000
1,400,000
3,529,000
508,000
1,010,000
85.300.000
2,690,000
917,000
Total Total
Controllable Nonmathane
Emlaslons Emission
1, 810 ,000
1,030,000
1,363,000 2,071,000
1,400,000 2.173,500
314,000 383,900
1,270,000 1,0)7,000
2.868,000 3,529,000
504,000 508,000
3,010.000 3,010.000
9,100,000
2,210,000 2,443,000
917,000
Total Controllable
Honmethanc Nonmethanc
Emlaalons Emissions
Controllable from from
Nonaothane Controllable Controllable
Emissions Sources Sources
1,363,000 2,071,000 1,363,000
1,400,000 2,173,500 1.400.000
67,500
953,000 1,077,000 953,000
2,868,000 3,529,000 2,868,000
504,000 508,000 504,000
3,010,000
2,219,000
Total Controllable
Emissions Emissions
Total from from
Total Controllable Controllable Controllable
Emlaslons Emissions Sources Sources
7,300 3,650
77,300 69,600 77,300 69,600
269,000 243,600 269.OOO 243,600
45,800 40,900 45,800 40,900
3.324.000 3.300,000 3,324,000 3,300,000
973,000 973,000
1,500.000
640,000 607,000
234,000
Total Contrulljible
Effluents Effluent,.
Total from from
Total Controllable Controllable Cuntrul luble
29,000 29,000
34.700 26,400 34,700 26,400
460,000 400,000 460,000 400,000
488,000 317,000 488,000 317,000
716,000 70,900
9,980,000 3,420,000
-------
2.1.1.1 Volatile Organic Emissions
The volatile organic emissions are presented in Table
2.1-1. Non-methane emissions are also identified and the con-
trollable non-methane emissions are presented by category. The
processes and operations representing the greatest potential for
emission reduction are presented. Processes which can poten-
tially reduce the total non-methane emissions by less than 1
percent are considered too small for the purpose of reduction of
emissions on a mass basis. These relationships are shown
graphically in Figures 2.1-1 and 2.1-2.
Approximately 49% of the total non-methane volatile
organic emissions are controllable. This total may be subdivided
as follows: agricultural and prescribed forest burning, 1270;
open burning of refuse, 9%; petroleum refining and plastics
processing industries, 1070; gasoline marketing and surface
coating, 870; graphic arts and dry cleaning, 270; all other pollu-
tant sources, 870.
2.1.1.2 Organic Particulate Emissions
The organic particulate emissions are presented in
Table 2.1-2. The controllable particulate emissions are also
presented along with operations and processes representing the
largest emission reduction potential. These relationships are
presented graphically in Figures 2.1-3 and 2.1-4.
Approximately 7470 of the total organic particulate
emissions are controllable. This total is distributed as follows
grain and feed milling and storage, 1870; plywood and veneer, 1770;
agricultural and forest prescribed burning, 1470; open refuse
burning, 9%; coal rail transportation and beehive coke ovens, 370;
all other sources, 1370.
-30-
-------
TABLE 2.1-1
i
LO
Category
I Fossil Fuel Extraction
II Fossil Fuel Processing
III Fossil Fuel Transportation
IV Fossil Fuel Refining
V
VI
VII
Fossil Fuel Combustion
Fossil Fuel Feedstock
Chemical Processing
Fossil Fuel Product
Utilization
VIII
IX
X
XI
Agriculture and Forest
Products
Open Sources
Natural Sources
Solid Waste ^Disposal
AIR - VOLATILE ORGANIC EMISSIONS
Largest Non-Methane
Total Organic Non-Methane ' Controllable Non-Methane Reductions From Operations
MT/yr MT/yr; Percent* Emissions (MT/yr); Percent* MT/yr; Percent*; Operation
2,510,000
1,716,400
L 2,071,000 2,071,000 8%
2,173,500 2,173,500 9%
724,000 383,900 1%
1,400,000 1,077,000 4%
3,529,000 3,529,000 14%
508,000 508,000 2%
3,010,000 3,010,000 12%
85,300,000 9,100,000 36%
2,690,000 2,443,000 10%
917,000 917,000 4%
106,548,900 25,212,400 100%
1,363,000 5% 1,013,000
67,900
1,400,000 6% 1,229,000
67,500 <1%
953,000 4% 96,700
2,868,000 11% 1,150,000
989,100
338,000
202,000
189,000
504,000 . 27, 142,000
3,010,000 12% 3,010,000
2,219,000 9% 2,210,000
_
12,384,500 49% 10,636,700
4% Gasoline
Marketing
<1% Diesel &
Distillate
5% Petroleum
Refining
<1% Carbon Black
5% Rubber&Plastic
Processing
4% Surface
Coating
1% Graphic Arts
1% Dry Cleaning
<1% Fabric Treatment
<1% Pulp and Paper
12% Agricultural
and Prescribed
Forest Burning
9% Open Burning
of Refuse
_
41%
XII Municipal Waste Water
XIII Other Sources
TOTAL
*Percent of Total Non-Methane Emissions, which are 25,212 ,400 MT/yr.)
-------
FOSSIL FUEL
COMBUSTION
1%
FOSSIL
FUEL
PRODUCT
UTILIZATION
14%
AGRICULTURAL &
FOREST PRODUCTS
2%
FIGURE 2.1-1 DISTRIBUTION OF TOTAL VOLATILE NON-METHANE EMISSIONS
DRY CLEANING &
GRAPHICS ARTS
2%
PETROLEUM
REFINING &
PLASTICS \ BURNING/& SURFACE
PROCES-1 9% /COATING
, 8%
AGRICULTURAL \ SING
PRESCRIBED \ 10%
FOREST BURNING
UNCONTROLLABLE
SOURCES
51%
ALL OTHER
CONTROLLABLE
SOURCES
8%
FIGURE 2.1-2 DISTRIBUTION OF CONTROLLABLE VOLATILE NON-METHANE EMISSIONS
-32-
-------
TABLE 2.1-2
AIR - PARTICULATE ORGANICS
Category
Total
Part iculates
MT/yr
I Fossil Fuel Extraction
II Fossil Fuel Processing 7,300
III Fossil Fuel Transporta- 77,300
tion
IV Fossil Fuel Refilling 269,000
V Fossil Fuel Combustion
VI Fossil Fuel Feedstock 45,800
Chemical Processing
VII Fossil Fuel Product
Utilization
VIII Agricultural & Forest 3,324,000
Products
IX Open Sources
973,000
X Natural Sources 1,500,000
XI Solid Waste Disposal 640,000
XII Municipal Wastewater
XIII Other Sources 234,000
Total 7,040,400
Percent
Total
1%
4%
1%
14%
21%
9%
3%
100%
Largest Reductions
Controllable Percent From Operations Percent
il MT/yr
3,650
69,600
243,600
40,900
Total
J%
3%
47% 3,300,000 47%
973,000 14%
606,500 9%
MT/yr
3,650
69,600
126,000
17,900
1,300,000
1,196,000
973,000
606,500
5,237,250 74%
4,292,650
Total Operation
<1% Coal Processing
1% Coal Rail
Transportation
2% Beehive Coke
Ovens
<1% Soap and
Detergent
18% Grain & Feed
Mill ing and
Storage
17% Plywood and
Veneer
14% Agriculture and
Forest Pres-
cribed Burning
9% Open Burning
of Refuse
61%
-------
CHEMICAL
PROCESSING
1%
FOSSIL FUEL
TRANSPORTATION
1%
OTHER SOURCES
3%
AGRICULTURAL &
FOREST PRODUCTS
FOSSIL FUEL
REFINING
4%
FIGURE 2.1-3 DISTRIBUTION OF TOTAL ORGANIC PARTICULATE EMISSIONS
GRAIN &FEED
MLUNG & STORAGE
18%
AGRICULTURAL
FOREST
PRESCRIBED BURNING
14%
OPEN REFUSE
BURNING
9%
UNCONTROLLABLE
SOURCES
26%
ALL
OTHER
CONTROLLABLE
SOURCES
13%
BEEHIVE COKE OVENS
2%
FOSSIL FUEL
TRA IMPORTATION
1%
FIGURE 2.1-4 DISTRIBUTION OF CONTROLLABLE ORGANIC PARTICULATE EMISSIONS
-34-
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2.1.2 Water Effluents
The organic water effluents from the major categories
are presented in Table 2.1-3 along with the controllable organic
effluents and the processes and operations representing the
greatest potential for organic effluent reduction. Processes
which reduce the total organic effluents by less than 1 percent
were not included as potential methods for pollutant reduction.
Effluents from natural sources were not quantified. A natural
BOD is inherent in the aquatic ecosystem. Figure 2.1-5 repre-
sents the distribution of the total organic water effluent.
Upgrading of municipal wastewater systems to tertiary
control accounts for a reduction of 29 percent out of the total
35 percent potentially controllable effluents. The pulp and
paper industry is the only other process or operation that rep-
resents a reduction potential of 1 percent or more. This dis-
tribution is presented graphically in Figure 2.1-6.
2.2 Process Organic Emissions and Effluents
The data from the thirteen major categories presented
in Section 2.1 indicate that a few large emission and effluent
sources dominate the organic emission and effluent picture in
the U.S. This is especially true for the volatile atmospheric
emissions and water effluents. Therefore, other considerations
are important when assessing reduction potentials for organic
emissions and effluents. These other considerations include
site-specific problems relating to geographical areas, pollutant
toxicities, meteorological and dispersion characteristics, cost
effectiveness of controls, photochemical reactivity, health
effects, and other effects such as odor and plant ecology.
-35-
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TABLE 2.1-3
WATER EFFLUENTS
i
11
in
IV
V
VI
VII
VIII
IX
X
XI
XII
XIII
Total Organic
Category MT/Vr; Percent Total
Fossil Fuel Extraction 29,000 <1%
Fossil Fuel Processing
Fossil Fuel Transportation
Fossil Fuel Refining 34,700 < 1%
Fossil Fuel Combustion
Fossil Fuel Feedstock 160,000 4%
Chemical Processing
Fossil Fuel Product 100 <1Z
Utilization
Agricultural and
Forest Products 488,000 5%
Open Sources
Natural Sources*
Solid Waste Disposal 736,000 6%
Municipal Wastewater 9,980,000 85% 3
Other Sources
TOTAL 11,727,800 100% 4
Controllable Organic Largest Reduction from Operations
MT/Yr; Percent Total MT/Yr; Percent Total; Operation
29,030 <1% 29,000 <1% On Shore Crude
Production
_
--
26,400 <1% 16,700 < 1% Petroleum Refining
_
384,000 3% 52,900
-------
CHEMICAL PROCESSING
4%
AGRICULTURAL &
FOREST PRODUCTS
5%
FIGURE 2.1-5 DISTRIBUTION OF TOTAL ORGANIC WATER EFFLUENTS
PULP & PAPER
1%
TERTIARY
CONTROL OF
MUNICIPAL WASTE
FACILITIES
29%
ALL OTHER
CONTROLLABLE SOURCES
5%
FIGURE 2.1-6 DISTRIBUTION OF CONTROLLABLE ORGANIC WATER EFFLUENTS
-37-
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A detailed assessment of these considerations is
beyond the scope of this report. However, certain general
assumptions can be made to provide insight into the impact of
some of these considerations:
1) Methane emissions are of secondary importance
because of their negligible health effects
and photochemical reactivity. Therefore,
the methane emitters are not considered as
important as the others in this report.
2) Natural emissions are of secondary importance
since they occur over a large geographical
area and are, therefore, relatively dilute.
Natural emissions also occur in remote
locations with minimal effect on large
population centers. Since MOX emissions
are concentrated in heavily populated
areas, the photochemical smog effects from
natural organic emissions are not as impor-
tant. Finally, natural sources are
essentially uncontrollable.
3) Other categories excluded from consideration
for similar reasons are "open" sources and
"other" sources. "Other" sources are usually
uncontrollable and occur most often in remote
areas. "Open" sources, though mostly con-
trollable, also tend to occur in remote areas.
Therefore,, consideration of the process emission cate-
gories is logical when benefits from organic emission reductions
are assessed. These categories include fossil fuel transporta-
tion, refining, combustion, feedstock chemical processing,
-38-
-------
organic chemical utilization and agricultural and forest
products. In general, these process operations are located
mostly in populated areas where health effects are very impor-
tant and where high NOX concentrations combine with the emissions
to create photochemical smog problems. Also, process emissions
usually are amenable to existing control technology (although
the economics still remain a question for many specific pro-
cesses). Finally, most of the toxic emissions result from
these categories.
Consequently, these assumptions allow the process
emission categories to be assessed separately by the impact of
their reduction potentials as a class.
Similarly, process water effluents are completely
dominated by the municipal wastewater category. Overall, the
effluents from septic tanks are the most serious problem but
septic tanks are considered uncontrollable effluents from rural
or remote sources. Municipal sewage is considered to be a
minor problem after controls are implemented. Therefore, the
impact of the process effluents can be considered.
The non-methane volatile organic emissions from the
process categories are over twice as large as the organic par-
ticulate emissions and an order of magnitude higher than the
organic water effluents. Similarly, controllable non-methane
volatile organic emissions from the process categories are more
than twice as large as controllable organic particulate emis-
sions and an order of magnitude higher than the controllable
water effluents.
-39-
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2.2.1 Process Atmospheric Emissions
Atmospheric emissions from fossil fuel transportation,
refining, feedstock chemical processing, non-combustion organic
chemical utilization, and agricultural and forest products cate-
gories are considered in this section.
2.2.1.1 Volatile Organic Emissions
The volatile organic emissions from the process cate-
gories are presented in Table 2.2-1. The processes selected for
study in this project are also presented. These processes are
generally the largest emitters in their category and have the
largest reduction potential.-
The non-combustion organic chemical utilization cate-
gory accounts for 38% of the total volatile organics from pro-
cess categories. Next are fossil fuel refining and transpor-
tation with 23.2% and 22.1% of the total, respectively. Fossil
fuel chemical feedstock processing is next with 11.5% of the
total followed by agricultural and forest products which account
for 5.4% of the total process type emissions.
Table 2.2-1 also presents the estimated total controll-
able emissions for each category. The organic chemical utili-
zation category has the highest reduction potential with 30.6%
of the total emissions estimated to be controllable from this
category. Next are the refining, transportation and chemical
processing categories with reduction potentials of 15%, 14.6%
and 10.2%, respectively. The smallest reduction potential is
from the agricultural and forest products category with 5.4%.
Therefore, a reduction potential of approximately 75.8% exists
for all the process type categories.
-40-
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TABLE 2.2-1
VOLATILE NON-METHANE ORGANIC EMISSIONS FROM CONTROLLABLE PROCESSES
246
2i
Subtotal 1,244
313
195
L47
117
Subtotal 1.229
VI Fosill Fuel Feedstock 1,077.000 LI. 51 953,000 IQ.il 96
Ch«l«L Processing 3Q
55
43
Subtotal 317
Cham leal Utilization
422
338
202
131
Subtotal 2,368
VIEl Agricultural and Focest 508,000 5.4Z 504.000 5. .'.I 142
Products jjj
67
47
39
Subtotal 432
•Total 9.358,500 100. Ot 7.033 .000 75.3? 6.091
,000
.600
,000
.000
,000
.000
,000
,900
,000
,800
.100
.000
,000
.000
.000
,000
.000
,000
,100
.200
,300
.600
.300
2.61
13.3:
3.4X
2.1Z
1.61
L.2X
13. LI
0.91
0.6Z
0.5Z
3.4Z
4.3X
3.6Z
2.2 =
1.51
30. 61
1.5Z
1.5S
0.73
0.5Z
O.iZ
i-6;
65.01
QobUe Filling
groutid Tank Pilling
Crude Transportation -
Storage
Storage
Load ing
Storage
Petroleum Refining -
Slowdown
Pecroleuo Refining -
Petroleua RaflnLng
Units
Petroleua Refining -
Vacuua Jecs
Acrylonitrlle
Ethylen* Dlchloclde
Toluene
Procesalng
Cutting
Sheet, Strip, and Coll
Coating
Graphic Arts
Dry Cleaning
Miscellaneous Surface
Coating
Pulp and Paper
'-'aate Wood Combustion
Bear Brewing
Processed FrultJ and
Vegetables
Tobacco
-41-
-------
The processes studied in this report account for 65.0%
of the total estimated reduction potential of 74.2%. The pro-
cesses studied account for all but 1% of the estimated reduction
potential in each category except chemical processing and fossil
fuel transportation. The chemical processing and hydrocarbon
utilization categories in particular have many more emission
sources than do the other categories. The chemical processing
category emissions result from many smaller operations grouped
into chemical complexes which can have a significant emission
rate at processing sites.
The above relationships are presented graphically in
Figure 2.2-1 and Figure 2.2-2.
2.2.1.2 Particulate Organic Emissions
Emphasis is placed on the quantification and control
of volatile organic air emissions rather than particulate organic
emission. Consequently, the processes selected for further study
are usually chosen on the basis of the control potential for the
volatile organics. The control potential for the organic par-
ticulates is usually assessed only when a large volatile organic
reduction is also achievable. However, large particulate organic
emitters are occasionally selected when they have a large impact
on a category such as soap and detergent production in the fossil
fuel feedstock chemical processing category and grain and feed
mills and elevators in the agricultural and forest products
category.
The particulate organic emissions from the process
categories are presented in Table 2.2-2. The processes selected
for further study in this project are also presented. These
processes are generally the largest emitters in their category
-42-
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NONCOMBUST1ON
. ORGANIC CHEMICAL
UTILIZATION
38%
AGRICULTURAL & 5%
FOREST
PRODUCJJ
CHEMICAL
FOSSIL
PROCESSING / FUEL
12% / TRANSPORTATION
22%
FIGURE 2.2-1 DISTRIBUTION OF VOLATILE NON-METHANE EMISSIONS FROM CONTROL
LABLE PROCESSES
SPECIFIC
NONCOMBUSTION
ORGANIC CHEMICAL
UTILIZATION
OPERATIONS
31%
UNCONTROLLABLE
SOURCES
24%
SPECIFIC
FOSSIL FUEL
TRANSPORTATION
OPERATIONS
13%
"'SPECIFIC
FOSSIL FUEL REFINING
ALL
OTHER
CON-
TROLLABLE
SOURCES
11%
SPECIFIC AGRICULTURAL
& FOREST
PRODUCTS OPERATIONS
5%
SPECIRC CHEMICAL
PROCESSING OPERATIONS
3%
FIGURE 2.2-2 DISTRIBUTION OF CONTROLLABLE VOLATILE NON-METHANE EMISSIONS
FROM CONTROLLABLE PROCESSES
-43-
-------
TABLE 2.2-2
AIR - PARTICULATE ORGANIC EMISSIONS FROM CONTROLLABLE PROCESSES
Total Emissions
*Conttollable Emissions
Largest Reductions From Operations
MT/yr ; Percent Total
111. Fossil Fuel Transportation 77,300 ; 2%
Storage and Distribution
IV. Fossil Fuel KefJning 269.000 ; 7%
VI. Fossil Fuel Feedstock 45,800 ; J%
Chemical Processing
VIII. Agricultural and Forest 3,324,000 ; 90%
Products
Subtotal
Total 3.7J6, 100 100%
MT/yr ; Percent Total MT/yr ; Percent Total ; Operation
69,600 ; 2% 69,600 ;
243,600 ; 7% 126,000 ;
40,900 ; U 17,900 ;
3,300,000 ; 89% 1,580.000 ;
*1, 200, 000 ;
2,780,000
3,654,100 98% 2,993,500
2%
3%
< 1%
43%
32%
75%
80%
Coal. Rail
Transportation
Beehive Ovens,
Coke Production
Soap and
Detergent
Grain and Feed
Mills & Elevators
Plywood & Veneer
* Estimated
-------
and have the largest reduction potential. Some organic
particulate emitters are not listed in this table but were
assessed for reduction potentials that are too small for
further consideration.
The agricultural and forest products category is by
far the largest emitter of organic particulates from the pro-
cess type categories with 90% of the total emissions. Next is
fossil fuel refining with 7% of the total followed by fossil
fuel transportation, storage, and distribution and by feedstock
chemical processing with 2% and 1%, respectively.
Table 2.2-2 also presents the estimated total con-
trollable emissions for each category. The agricultural and
forest products category has the highest potential for reduc-
tion with 89% of the total estimated controllable emissions.
Next are the refining, transportation, and chemical processing
categories with 7%, 2%, and 1%, respectively. Therefore,
approximately 98% of the total emissions from the process type
categories are controllable.
The fossil fuel, grain and feed mills, and elevators
categories account for a reduction potential of 48%. When an
estimated reduction potential of 32% for plywood and veneer is
added (this process was not selected for study) the reduction
potential for 5 processes is 8070 of the emission total. There-
fore, the difference between the reduction potentials for the
listed processes and the total reduction potentials of the pro-
cess categories is 18%. Most of this difference is in the agri-
cultural and forest categories. Several other large sources of
particulates (see the Appendix) have reduction potentials.
These relationships are shown graphically in Figures 2.2-3 and
2.2-4.
-45-
-------
CHEMICAL
PROCESSING
1%
FOSSIL FUEL
TRANSPORTATION
2%
FIGURE 2.2-3 DISTRIBUTION OF TOTAL PARTICULATE ORGANIC EMISSIONS FROM CQW
TROLLABLE PROCESSES
UNCONTROLLABLE
SOURCES
2%
COAL RAIL
TRANSPORTATION
2%
GRAIN & FEED
MILLS & ELEVATORS
43%
ALL OTHER
CONTROLLABLE
SOURCES
18%
BEEHIVE OVENS.
COKE PRODUCTION
3%
FIGURE 2.2-4 DISTRIBUTION OF CONTROLLABLE PARTICULATE ORGANIC EMISSIONS
FROM CONTROLLABLE PROCESSES
-46-
-------
Although this analysis does not account for secondary
particulate generation, it does illustrate the impact that geo-
graphical considerations can have on emission reduction poten-
tials of organic particulates in the U.S.
2.2.2 Process Water Effluents
Water effluents from fossil fuel refining, feedstock
chemical processing, and agricultural and forest products cate-
gories are considered in this section. Water effluents from
organic chemical utilization and fossil fuel transportation are
considered to be too small for this discussion.
The organics present in water effluents from the pro-
cess categories are presented in Table 2.2-3. The processes
selected for study in this project are generally the largest
sources of organic effluents in their category and have the
largest reduction potential.
The fossil fuel chemical processing and agricultural
and forest products categories are the largest sources of organic
water effluents with 46.8% and 49.7% of the total, respectively.
The fossil fuel refining category accounts for 3.5% of the total
organic water effluents.
Table 2.2-3 also presents the estimated total controll-
able organic water effluents for the categories. The chemical
processing category has the largest potential for reduction with
40.7% of the total effluents estimated to be controllable from
this category. The agricultural and forest products category
follows with 32.3% and last is the refining category with 2.7%.
Therefore, a reduction potential of about 75.7% exists for all
the process type categories.
-47-
-------
TABLE 2.2-3
WATER - ORGANIC EFFLUENTS FROM CONTROLLABLE PROCESS
Total I'.I I liianls
(.:i'_l HISl'lY
IV. I'M:;:, II I'lie I KrfInIng
*r/*C _! PC'"cunt Tola I
3'., 700 ; 1. 57,
MT/yi ; Percent Total
26.400 ; 2.7Z
_ eut Kuiluct Ions From O|MJI.H IOOH
M'fyr ; Percent futiil ; Ojiurnl IIIM
|l>,/00 ; l./Z rclnilL-iim Hi-riiilii|;
_ 9,700 ; _JL'01 • lly-rrojm:ln Cuke Ovi;ii!i
2f>.'.00 2.7Z
I
-P-
oo
i
VI. l-ossll I'l
(il 10 in I (:;i I
VMI. AK> i' uiu.i.i i .IM.I
I'ln.lucl S
Suliloliil
Tot.I I
4f,0,000 ;
don, ooo -.
9H2,700
10(17.
IiOO.OOO ;
M>. 71
J17.000 ;
7'i 3. 400 ;
12. JZ
75. 7Z
211.100 ;
2f. ,901) [
107,9011 j
104.000 ;
69,900 ;
51,500 ;
229.400 ;
163.700 ;
i.
-------
The processes studied in this report have a combined
reduction potential of only 37.0% of the total 75.7% controll-
able organic water effluents. In the refining category, the
two operations studied account for all the emissions from this
category. However, for the agricultural and forest products
category a 9% difference exists between the reduction potential
of the processes studied and that of the category total. For
the chemical processing category the difference between the re-
duction potential of selected processes and that of the category
total is 29.7%. Many processes in the agricultural and forest
products category are water effluent sources; the chemical pro-
cessing category has even more water effluent sources, none of
which are extremely large. However, chemical processes tend to
be grouped together in chemical complexes, causing a significant
organic water effluent rate at processing sites. These relation-
ships are shown graphically in Figures 2.2-5 and 2.2-6.
The analysis of the organic water effluents again
illustrates the impact that geographical considerations can
have on organic water effluent reduction potentials overall in
the U.S.
-49-
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FOSSIL FUEL
REFINING
3%
AGRICULTURAL & FOREST PRODUCTS
50%
CHEMICAL PROCESSING
FIGURE 2.2-5 DISTRIBUTION OF TOTAL ORGANIC EFFLUENTS FROM CONTROLLABLf
PROCESSES
SPECIFIC
CHEMICAL
PROCESSING
OPERA -
UNCONTROLLABLE
SOURCES
24%
SPECIRC FOSSIL FUEL
REFINING OPERATIONS
3%
FIGURE 2.2-6 DISTRIBUTION OF CONTROLLABLE ORGANIC EFFLUENTS FROM CON
TROLLABLE PROCESSES
-50-
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3.0 REDUCTION POTENTIALS OF ORGANIC EMISSIONS AND
EFFLUENTS FROM THIRTEEN MAJOR CATEGORIES
This section of the report describes the industrial
processes employed in each category and discusses in detail the
emissions and effluents from the processes selected for further
study, the control methods available for effluent and emission
reduction from each process, and an estimate of the potential
reduction of organics in metric tons (MT) per year.
3 .1 Fossil Fuel Extraction
The fossil fuel extraction category encompasses the
crude oil, natural gas, and coal production industries. Almost
all of the organic emissions associated with extraction of
fossil fuels result from fugitive sources.
A summary of the atmospheric emissions from the in-
dustries in this cateogry is presented in Table 3.1-1.
Organic water effluents from fossil fuel extraction
are also considered in ths section. Enough data was available
that the organic effluents could be estimated from crude oil
production. Table 3.1-2 contains these estimates. However,
organic emissions due to oil spills from crude production into
surface waters are not quantified in this report. The impact
on the environment is difficult to assess, since limited informa-
tion is available on the parameters involved. Data such as
amount of organic recovered after the spill, amount of organic
reaching the atmosphere by evaporation, amount of organic reaching
surface waters, and amount of organic soluble in surface waters
are generally unavailable. Waterborne effluents are produced
only from crude production. The generation of solid wastes from
fossil fuel extraction is assumed to be negligible.
-51-
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TABLE 3.1-1. FOSSIL FUEL EXTRACTION - VOLATILE EMISSIONS
Emissions of
Year Volatile Organics Ref,
Fossil Fuel Extraction
Crude Oil 1975 630,000 1
Natural Gas 1975 270,000 1
Coal 1973 1,610,000 2
Total: 2,510,000
Source: 1. MO-201
2. IR-011
-52-
-------
TABLE 3.1-2. FOSSIL FUEL EXTRACTION - ORGANIC EFFLUENTS
Effluents (MT/year)
Total Organics BOD COD SS 0/G
Fossil Fuel Extraction
Crude Oil
Onshore 29,000 41,000 56,000 8,000 12,000
Offshore 30 N/A N/A N/A 12
Total: 29,030
Sources: EN-154
-53-
-------
3.1.1 Crude Oil Production
Process Description
In an onshore producing oil well, three methods are
used for bringing the oil to the surface: natural flow, gas
lifting (injection of gas into the flowing column), and pumping.
Most producing wells are operated by mechanical lifting methods
using either plunger or centrifugal type subsurface pumps.
The production from each well is then sent to a complex
gathering system which consists of pipes, valves, and fittings
necessary for combining all of the production or for separating
the individual well'productions in the case of varying qualities.
There are, in addition, test separators and tanks for testing
the oil quality.
Because the crude oil is produced in association with
gases and water (usually brine), the crude must be separated.
The water can be removed by one of several means: (1) heat,
(2) chemical destabilization, (3) electrical coalescence, and
(4) gravitational settling. The associated hydrocarbon gases
are separated by one of two methods. The two-phase method is
used for separating oil and gas while the three-phase method is
used when gas, oil, and water are being separated.
Following water and gas separation, the crude oil is
usually sorted in tanks prior to shipment to the refinery. The
recovered liquids produced with the crude are handled in hori-
zontal cylinders or spheres. The associated gas separated from
the crude is usually sent to processing plants for upgrading.
Occasionally, the recovered gases are vented or flared if their
quantity does not warrant the expense of shipment for processing
and sales and/or the well is located in a remote area.
-54-
-------
Offshore production operations are very similar to
onshore operations with the added complications of space limita-
tions and the generally hostile environment. As with onshore
wells, offshore oil is brought to the surface by natural flow,
gas life, or pumping with subsurface pumps.
The crude is commonly sent to a central production
platform via pipeline for processing. Delivery to shore for
processing is also a possibility, but the usual practice is the
separation of gas and water from the oil on offshore platforms.
Offshore production is generally transported to land
via pipelines to minimize the storage of crude on the offshore
structures. However, as development proceeds farther from shore,
more offshore storage will be utilized. The oily water that has
been separated from the crude may be delivered onshore for treat-
ment at a conventional cleaning and dehydrating plant before
release to the ocean. Alternatively, it may be reinjected to
the reservoir to help maintain pressure. Reinjection is wide-
spread in offshore California operations. The separated gases
are either collected and processed for market or they are vented
and flared.
Atmospheric Emissions and Control
The atmospheric emissions from domestic offshore and
onshore crude production result primarily from fugitive sources:
wastewater separators, pump seals, compressor seals, relief
valves, pipeline valves, and flanges. Other sources include the
storage tanks which emit light hydrocarbons not removed in the
gas separation units and the gases which are vented from remote
production facilities. Monsanto Research Corporation estimates
that 630,000 metric tons per year of volatile organics are
-55-
-------
emitted to the atmosphere from petroleum extraction (MO-201) ..
These losses are almost entirely low molecular weight saturated
gases such as methane and ethane. These types of hydrocarbons
are among the least photochemically reactive volatile organics.
In brief, the existing control technology for petroleum
production of hydrocarbon emissions consists of the following:
Storage Facilities:
Floating roof tanks or internal
floating covers
Vapor recovery units
Wastewater Separators:
Seal from atmosphere
Vent to vapor recovery
Floating covers
Pump and Compressor Seals:
Convert packed seals to mechanical
seals
Install double seals
Relief Valves:
Upstream rupture discs
Vent to vapor recovery or flare
-56-
-------
Pipeline Valves:
• Regular maintenance of stuffing
boxes
Heaters and Compressor Engines:
Carburetion adjustments
Remote Location Vents:
Incineration
Miscellaneous Losses:
Regular maintenance
Good housekeeping
The potential for reduction of the organic emissions
from petroleum production is difficult to assess due to the
scarcity of data on the degree of organic emission control cur-
rently practiced by the industry. Assuming the use of the above
controls on petroleum production facilities, the organic emissions
could be reduced 60 percent. This results in a reduction of
378,000 MT/year.
Water Effluents and Control
Waterborne organic effluents from the crude oil
production industry result from one of two sources: the disposed
oily brine produced along with the crude, and the accidental
spills resulting from the production activities and equipment.
-57-
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On the average, two to three cubic meters of water are
produced per cubic meter of oil produced onshore. Thus, approxi-
mately 4,0 million cubic meters (1.05 x 109 gallons) of oily salt-
water are produced daily in the United States. Approximately
four percent of this total is discharged to rivers. The bulk of
the remaining water is injected in underground formations, used
for secondary recovery, or disposed of in such a way that the
oily water does not reach United States waterways.
Based on average pollutant concentration figures
reported for produced formation water in the EPA's Effluent Guide-
lines Document for the Offshore Segment of the Oil and Gas Extra-
ction Point Source Category, estimates for the amount of BOD,
COD, TOC, suspended solids, and oil and grease emitted can be
calculated (EN-376). These calculations reveal that roughly
41,000 MT/year of BOD; 24,000 MT/year of TOC; 56,000 MT/year of
COD; 8,000 MT/year of suspended solids; and 12,000 MT/year of
oil and grease are discharged to water from onshore petroleum
production. Assuming an organic compound to carbon molecular
weight ratio of 1.2 for the discharged organic compounds, the
total organic emission level is calculated to be 29,000 MT/year
for onshore production.
Crude oil spills from production activities represent
another potential for water pollution. Estimates for the yearly
quantity of oil spilled from production systems have been cal-
culated from data presented by EPA in its Petroleum Systems
Reliability Analysis document (RI-107). Calculations show that
approximately 260,000 MT/year of oil is lost from onshore pro-
duction systems primarily from leaking pipes and valves. All
of this oil does not reach the waterways; much is recovered,
some volatilizes, and some biodegrades on the land. However,
data on the disposition of spilled oil is not available, so for
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the purpose of this report, spilled oil is not quantified for
air and water pollution. An estimate of 40,000 MT/year for off-
shore petroleum spills was obtained from data on offshore pro-
duction systems. Again, much of this oil is recovered, but some
volatilizes so that the disposition of the spilled oil is unknown
The major sources are leaking pipes, valves, pumps, malfunction-
ing level sensors causing system overloads, relief valves, and
rupture discs.
The offshore production of petroleum produces roughly
one barrel of brine water per barrel of oil (EN-376). In 1973,
0.253 hm3/day (1.59 x 106 barrels/day) of oil was produced from
offshore wells. Therefore, approximately the same amount of
brine water was also produced. Assuming the offshore segment of
the oil and gas extraction industry will meet the EPA regulations
established for its water effluents for 1977, the discharge of
organics from offshore production of oil can be estimated. That
regulation states that 48 mg of oil and grease per liter of water
discharged is the maximum allowable rate. This amounts to a
total organic discharge of 30 metric tons per year from offshore
crude production, based on the same assumptions made concerning
onshore production effluent wastes.
A wide range of control and treatment technologies
have been developed to deal with petroleum production wastes.
Local factors, discharge criteria, availability of space, waste
characteristics, and other factors influence the method of treat-
ment. Techniques used to separate oil from the produced forma-
tion water include: (1) gas flotation, (2) parallel plate
coalescers, (3) filters, (4) gravity separation, and (5) chemical
treatment. Two "zero discharge" techniques commonly used to
dispose of oily wastewater are: (1) discharge of the water to
pits, ponds, or reservoirs for evaporation, and (2) reinjection
to acceptable underground formations.
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The control techniques involved in reducing crude oil
production spills include the application of regular inspection
and maintenance practices especially for spill-prone equipment
such as level sensors, relief valves, pump gaskets, seals, pack-
ing, saltwater dump valves, and rupture discs. Another control
measure includes the piping of relief valve and rupture disc
overflow to a sump or secondary containment. The use of cor-
rosion preventing techniques such as chemical inhibitors,
sacrificial cathodes, galvanizing, or increased use of plastic,
glass reinforced or similar pipe materials in limited low pressure
areas of the gathering subsystem are several other methods which
help prevent the spillage of crude oil or oily water from pro-
duction systems.
The reduction potential for the oil spillage from
crude production systems appears rather high since many field
operations have eliminated spill problems with preventive pro-
grams. Data is lacking for the calculation of an organic emission
reduction percentage, but proven spill control measures are avail-
able. The reduction potential is difficult to determine for oil
spills to waterways.
The best available control technology achievable for
treating produced formation water has been identified by the EPA
as evaporation ponds or holding pits and reinjection (EN-376).
Thus, the potential for reduction of this source of organic ef-
fluent is assumed to be 100 percent. This amounts to a reduction
of 29,030 MT/year of organic effluents from offshore and onshore
oil production.
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3.1.2 Natural Gas Extraction
Process Description
Natural gas produced in facilities separate from crude
oil production comprises 80 percent of the total amount of gas
marketed in the United States. Gas produced from underground
reservoirs not containing crude oil varies considerably in
composition. The basic production equipment for onshore and
offshore wells is practically the same. However, the gas-
conditioning equipment located at the well site or at some nearby
central location usually varies depending upon the gas composition,
The basic equipment at the wellhead includes various
valves and fittings commonly referred to as a Christmas tree.
The wellhead equipment regulates the high pressure natural flow
of the gas from the reservoir. After the wellhead, the gas is
treated according to its composition. The conditioning equip-
ment may include separators which remove liquid hydrocarbons and
condensed water from the gas stream, heaters, dehydrators, and
compressors. Should the natural gas contain corrosive elements
such as H2S, the gas may be treated by chemical injection for
inhibition of corrosive attach on the flow system equipment. In
some cases removal of the corrosive compound or compounds is
economical.
Offshore gas wells are similar in many respects to
their onshore counterparts. However, space limitations usually
prohibit processing of the produced gas. Therefore, this gas
is usually sent to shore for conditioning. Safety precautions
and regulations ordinarily necessitate better maintenance .
practices offshore than for onshore operations.
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Atmospheric Emissions and Control
Volatile organic emissions from natural gas extraction
result primarily from fugitive sources. The valves, pipe flanges,
corroded pipelines, compressor seals, separators, and dehydrators
are all potential sources of fugitive emissions. Monsanto
Research Corporation (MO-201) estimates that 270,000 metric tons
of volatile organics are emitted from natural gas extraction to
the atmosphere yearly. These volatile organics are composed
primarily of the light saturated hydrocarbons commonly found in
natural gas with methane being the primary component of the
emissions.
The control of organic emissions from natural gas
production relies heavily upon regular maintenance of equipment
and good housekeeping at the well site. Equipment 'changes can
offer some help in reducing the organic emissions. For example,
the substitution of mechanical seals for packed seals on centrif-
ugal compressors and the installation of dual packed seals on
reciprocating compressors are control methods used to reduce
emissions from compressors.
Pressure relief valves are occasional sources of
organic emissions, especially during system upsets. Their
emissions may be controlled by manifolding to a vapor control
device or a blowdown system. For relief valves where dis-
charge into a 'closed system is not desirable because of con-
venience or safety, fragile blanks called rupture discs can
be installed before the valve. Rupture discs prevent the
pressure relief valve from leaking and protect the valve seat
from corrosive environments (WA-086). The organic emissions
from relief valves controlled by rupture discs or blowdown
systems are negligible.
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Organic emissions originating from product leaks at
valves and flanges can only be controlled by regular inspection
and prompt maintenance of valve packing boxes and flange gaskets.
The emissions reduction from control of valves and flanges is
undefinable because of its dependence on the corrosiveness of
the gas handled, the degree of maintenance, and the characteristics
of the equipment.
As with crude oil production, insufficient data exists
for a reliable estimate of the reduction potential for the mass
emissions of atmospheric hydrocarbons from natural gas extraction.
Because the primary source of atmospheric emissions of organics
from gas production is fugitive emission sources, as is that for
oil production, the reduction potential is assumed to be the
same--60 percent. This amounts to a mass emission reduction
potential of 162,000 MT/year of volatile organics from natural
gas production.
3.1.3 Coal Production
Process Description
Coal mines are classified by the methods used to
extract the coal. The actual method selected, whether sur-
face mining or underground mining, is based upon a number of
physical and economic factors. However, only underground coal
mines have reported organic chemical emissions to the atmosphere
(IR-011). For this reason only underground mining will be
discussed.
Underground mines are developed by driving entryways
into a coal seam and are classified according to the manner in
which the seam is entered. The three common methods of entry
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to the coal seam are: (1) drift mines, (2) slope mines, and
(3) shaft mines.
The mining techniques used in the mines are not depen-
dent on the type of entryway in use. The majority of the coal
mines in the United States use the room and pillar extraction
technique. Room and pillar extraction begins with the driving
of main tunnels, or headings, from the points of entry to the
seam. From these main headings, perpendicular secondary headings
are driven. Blocks of coal are then extracted in a systematic
pattern, forming rooms along both sides of the headings. Pillars
of intact coal are left between the mined areas to support the
roof and prevent surface subsidence above the mine. Initial
development in an underground mine may leave as much as 60 per-
cent of the coal in pillars. Following development, some of
those pillars may be safely mined and removed as the machinery
retreats from an area of the mine. This may significantly in-
crease the coal recovery.
Atmospheric Emissions and Control
All coal beds contain hydrocarbon gases. These gases
(98 percent methane) are contained in the fine pore structure
in the beds and migrate into active mine workings when the bed's
equilibrium conditions are upset. However, the deeper coal beds,
accessible only by underground mining techniques, are the only
ones which contain significant amounts of methane.
The Bureau of Mines estimated for 1973 that over
6.5 hm3 of methane are emitted daily (229.7 x 105 ft3/day) from
underground coal mines (IR-011). This amounts to approximately
1,608,000 metric tons of methane emitted yearly from coal extrac-
tion. This estimation is a conservative one. The Bureau of
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Mines included in their study only those mines which produced
methane in excess of 2,830 m3/day (100,000 ft3/day),
A promising control method for reducing th.e emissions
of methane from underground coal mines is the drilling of verti-
cal boreholes from the surface into the coal seam at selected
spots and recovering the methane as natural gas. This control
technique offers the advantage of recovering a marketable product
which could be sold if produced in enough quantity, The Bureau
of Mines reports several mines which emit around 280,000 m3/day
(10 x 106 ft3/day) of methane. Other promising control methods
available include (ZA-044): the use of horizontal holes in a
coal seam to infuse an active face area with water, thus divert-
ing the flow of methane away from the mining area; the use of
long horizontal holes to degasify a section prior to mining; and
hydraulic fracturing of the bed to increase its permeability,
thus aiding methane flows through the coal to a vertical or
horizontal degasification hole.
The procedures mentioned above have been found effective
for removing 20 to 50 percent of the methane that would ordinarily
be ventilated to the atmosphere (ZA-044). Based on these effi-
ciencies , a reasonable estimate is that the reduction potential
for hydrocarbon emissions from coal extraction is rather high
and the percent reduction could be up to 80 percent. This results
in a reduction potential of 1,290,000 MT/year.
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3.2
Fossil Fuel Processing
Organic emissions from the natural gas processing and
coal processing industries, and their control, are examined here
The primary source of atmospheric emissions from gas processing
is fugitive leaks in equipment. Most volatile organic emissions
from coal processing are from process vents and stacks such as
thermal driers.
A summary of the atmospheric emissions from the indus-
tries in this category is presented in Table 3.2-1.
TABLE 3.2-1
FOSSIL FUEL PROCESSING - ATMOSPHERIC EMISSIONS
Emissions (MT/yr)
Fossil Fuel Processing
Natural Gas
Coal
Total
Year
1975
1975
Volatile
Organics
1,714,000
2,400
1,716,400
Particulate
Organics
7,300
7,300
Reference: MO-201
No information was found concerning the water or solid
wastes from natural gas and coal processing. For the purposes of
this study, solid wastes processed on site by landfill, spoil
pile, or other means were not assumed to be an environmental
problem. Organic solid waste emissions and organic water efflu-
ents are assumed to be negligible for this category.
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3.2.1 Natural Gas Processing
Process Description
The gas treatment facilities normally encountered in
the field are designed to condition the natural gas to make it
marketable. The operations may include the removal of impurities
such as H2S and C02, dehydration, product recovery, and the con-
trol of delivery pressure through the use of pressure reducing
regulators or compressors.
Gas-processing plants, on the other hand, are usually
operated to recover valuable products which may be left in the
gas following field processing. These products may include nat-
ural gasoline, butane, propane, ethane, and even pure methane at
some plants. To accomplish this, the processing plant includes
many of the functions performed by gas-conditioning equipment
such as dehydration and acid gas removal. For this reason a gas
plant may be considered as another gas-conditioning facility.
These facilities, often referred to as natural gasoline plants,
usually provide fractionating equipment for separating the re-
covered liquid hydrocarbons into pure products or predetermined
mixtures. Where HzS is removed from the gas, a plant may include
facilities to recover elemental sulfur.
The units found in gas-plant operations are similar to
those found in the field; the primary difference is the size and
perhaps the mechanical design of the units. The typical types
of equipment found in natural gasoline plants are absorbers,
strippers, fractionators, heat exchangers, and air coolers or
cooling towers.
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Atmospheric Emissions and Control
The primary sources of atmospheric organic emissions
from natural gas processing operations are fugitive losses and
natural gas venting. The fugitive losses occur from sources such
as pipeline valves, flanges, gaskets, and compressor seals.
Venting losses occur primarily during processing system upsets
or from the faulty operation of pressure relief valves. An esti-
mated 1.714 x 105 metric tons per year of hydrocarbons are emitted
from natural gas processing (MO-201). These emissions are com-
posed primarily of methane with lesser quantities of ethane, pro-
pane, butane, and other low-molecular weight saturated hydro-
carbons .
The control of these emissions from natural gas process-
ing relies heavily upon regular maintenance of equipment and good
housekeeping at the processing site. Equipment changes can offer
some help in reducing the emissions of hydrocarbons. For example,
substituting mechanical seals for packed seals on centrifugal com-
pressors and installing dual packed seals on reciprocating com-
pressors are control measures which reduce the quantity of hydro-
carbons emitted.
The controls used to reduce the loss of hydrocarbons
from relief valves include the installation of manifolding to a
vapor control device or a blowdown system. For relief valves
where discharge into a closed system is not desirable, fragile
rupture discs prevent the relief valve from leaking and protect
the valve seat from corrosive environments (WA-086). These con-
trols effectively reduce the emissions from relief valves to
negligible quantities.
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The emissions from product leaks at valves and flanges
can only be controlled by regular inspection and prompt mainten-
ance of valve packing boxes and flange gaskets. The emissions
reduction from proper maintenance of valves and flanges is diffi-
cult to determine because it is dependent on the corrosiveness of
the gas handled, the degree of maintenance, and the character-
istics of the environment. However, because the primary source
of atmospheric hydrocarbon emissions from gas processing is fugi-
tive leaks, the reduction potential is assumed to be the same as
that for crude oil and natural gas processing, 60 percent. This
means a mass emission reduction potential of 1,030,000 MT/yr of
hydrocarbons to the atmosphere.
3.2.2 Coal Processing
Process Description
Coal processing consists of the operations used by the
industry to upgrade the quality of raw coal prior to its sale.
The physical character and chemical composition of the raw coal
and the customer specifications on the product determine the
extent and type of processing.
Three types of processing plants are used to prepare
the various types of product coal demanded by the market: 1)
"complete processing", 2) "partial processing", in which only
coarse coal is cleaned; and 3) "coal crushing", in which the
coal is merely crushed to a specified maximum size. Because the
complete preparation plant includes all processing operations,
it is the only one described.
At the preparation plant, coal from the mine is broken
and screened to remove oversized material, then stored until the
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batch processing in the plant begins. From storage the coal is
classified according to size by screening and then routed to
various cleaning process equipment. In general, this cleaning
process may be wet, dry, or a combination of both.
Wet cleaning systems utilize centrifugal or gravity
separation of heavier impurities from the coal. The wet cleaning
itself does not emit organics; however, the auxiliary processes
of handling and drying can be major sources. After the cleaning,
the coal is mechanically dried by dewatering screens and centrif-
ugal driers. Should the customer desire low surface moisture
coal, secondary drying is required. Low moisture levels are best
accomplished by thermal drying. A survey of the industry indi-
cates that new coal preparation plants installing thermal driers
will use a fluidized-bed type. In this drying technique, hot
flue gases from a coal-fired furnace pass up through a moving
bed of fine wet coal. The coal is dried as the coal particles
come into intimate contact with the hot gases during fluidization
Particulate organic emissions occur in the form of ultrafine coal
particles entrained and carried from the drier by the combustion
gases. The dried coal is stored prior to shipment.
All coal cleaning systems installed since 1966 have
used pulsating air columns to separate coal from its impurities
(EN-220). The particulate organic chemical emissions from these
operations are negligible.
Atmospheric Emissions and Control
Potential particulate organic emissions for fluidized-
bed driers upstream of control equipment are in the range of 115
to 460 grams per normal cubic meter. The emissions measured
downstream of cyclones, which are an integral part of the coal
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cleaning process, range from 1.6 to 32 grams per normal cubic
meter (EN-220).
The products of combustion from the coal burned in the
drier to generate the hot gases contain measurable quantities of
gaseous organics. Particulate emissions from thermal driers
amount to about 7.3 x 103 metric tons per year while the gaseous
organic emissions are 2.4 x 103 metric tons per year (MO-201).
Single cyclone collectors and multiple cyclones for
product recovery have efficiencies of 70 and 85%, respectively.
Water sprays following cyclones have an efficiency of 95% (EN-071),
and wet scrubbers following cyclones have efficiencies of from
99 to 99.9%.
The reduction potential for particulate organic emis-
sions from coal processing is fairly high because of the limited
number of processing plants and the extent of the development of
applicable control technology. However, the reduction potential
for gaseous hydrocarbon emissions from thermal drying is very
low. Only combustion modifications could reduce the gaseous
emissions, and only limited control is available from this method.
The percent reduction estimated for particulate emissions from
thermal driers is a little less than 50 percent (EN-071, EN-220).
This results in a reduction potential of 3650 MT/yr of organic
particulates.
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3.3 Fossil Fuel Transportation, Storage, and Distribution
This category includes emissions from the distribution
network for the transportation of fossil fuels and their products.
The emissions associated with the distribution network result
from storage at distribution facilities and loading and unloading
at distribution points.
The category is divided into subgroups by the type of
material transported. The major subgroups are gasoline market-
ing, jet fuel marketing, distillate and diesel fuel marketing,
residual fuels marketing and crude transport. These major sub-
groups are characterized by emissions from storage facilities,
pipelines, and loading operations. Loading operations include
both marine loading and rail and truck loading.
A summary of the atmospheric emissions from the pro-
cesses in this category is presented in Table 3.3-1.
The total emissions from the transportation category
are over 2.0 x 106 MT/yr. The potential reduction in emissions
from storage operations is nearly 0.5 x 10s MT/yr and from load-
ing operations is almost 0.9 x 106 MT/yr. These potential re-
ductions are estimated by assuming that current use of controls
is extended to complete application of controls. These controls
are generally assumed to be floating-roof tanks for the storage
facilities and bottom loading or submerged fill along with vapor
recovery and vapor balance for loading operations.
Water effluents and solid wastes are negligible in this
category. Contamination of surface waters from spills during
distribution is a source of water pollution. However, the impact
on the environment depends on a knowledge of the amount of organic
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TABLE 3.3-1
FOSSIL FUEL TRANSPORTATION, STORAGE, AND DISTRIBUTION ATMOSPHERIC EMISSIONS
Emissions (MT/yr)
Crude Oil Storttge
Gasoline Service Station Automobile Filling
Gasoline Service Station Underground Tank Filling
Gasoline Hulk Terminal Loading
Gasoline Bulk Station Storage
Gasoline Bulk Station Loading
Diesel •& Distillate Storage
Refinery Loading, Products
Petroleum Gathering and Distribution, 1'ipellne
Gasoline Bulk Station Pump Seals
Gasoline Service Station Storage
Gasoline lluLk Terminal Storage
Crude Oi.l Transportation, Marine Loading
Gasoline- UnJ k Terminal Pump Seals
Gasoline Marketing, Marine Loading
Jet Kcrosine Marketing, Storage
Jet Naphtha Marketing, Storage
Crude Oil Transportation, Rail, i, Truck Loading
Diesel. £, Distillate Marketing, Kail & Truck Loading
Aviation Gasoline Marketing, Storage
Aviation Caso.llne Marketing, Loading
Jet Naphtha Marketing, Rail & Truck Loading
Gasoline Bulk Station Valves
Jet Ke cosine Marketing, Rail &
Diesel & Distillate Marketing,
Gasoline Bulk Station Valves
Jet Keroslne Marketing, Marine
Truck Loading
Marine Loading
Loading
Coal Kail Transportation, Unloading
SUBTOTAL, LOADING
STORAGE
FUGITIVE
TOTAL
REFERENCES: 1. BU-185
2. Kl-107
3. CA-246
Year
1973
1973
1973
1973
1973
1973
.1973
1973
1970/71
1973
1973
1973
1973
1973
1973
1973
1973
1973
1973
1973
1973
1973
1973
1973
1973
J973
1973
1973
Volatile
Oirgan1.cs
526,000
i>t,l ,000
399,000
189,000
109,000
9/..700
79,100
65,600
63,200
52,300
42,400
33,400
17 ,600
10,700
9,030
8,940
6,950
6,620
4,970
4,640
3,870
.1,990
1,960
662
662
410
331
-
1,195,435
810,430
65,370
2,071,235
Part leu late
Ref. Organic Kef.
1 - -
1
1 - -
1 - -
1 - -
1 - -
1 - -
1
2 -
1
1 - -
1 - -
1 _ _
1 - -
1 -
1 - -
1 - -
1 - -
1 - -
1 - -
1 - . ~
1 -
1 - -
"1 _ —
1
1
1
77,300 3
77,300
-------
recovered after the spill, the amount of organic reaching the
atmosphere by evaporation, the amount of organic reaching sur-
face waters, and the amount of organic soluble in surface waters.
Little information is available on these factors. In addition,
the overall quantity of organics spilled is small when compared
to total emissions from the transportation category. The poten-
tial for reduction of these spills is not as large as for many
other emission sources. For these reasons, spills during trans-
portation operations will not be quantified in this report.
The important processes which emit organic chemicals
in the fossil fuel transportation, storage, and distribution
category are identified in this section. These processes are
examined to determine the point of organic emissions from the
processes. Emissions from process effluent streams and from
fugitive sources are considered. The current level of control
of' organic emissions from the processes or operations is assessed
when possible.
3.3.1 Gasoline Marketing
The gasoline marketing industry includes all transfer
and storage operations that occur when gasoline products are
transported from petroleum refineries to the consumer. Figure
3.3-1 .shows flow patterns for motor gasoline from refinery stor-
age to the vehicle refueling stations in the U.S. marketing net-
work. Gasoline is transported from refinery storage to terminals
by pipelines, tankers and barges, or rail tank cars.
3.3.1.1 Bulk Terminals
The primary distribution facility in the gasoline mar-
keting network is the bulk terminal. Gasoline products arrive
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SHIP, RAIL, BARGE
SERVICE STATION
REFINERY STORAGE
BULK TERMINALS
TANK TRUCK
AUTOMOBILES, TRUCKS
PIPELINE
AIRPORT DISTRIBUTION
BULK PLANTS
COMMERCIAL,
RURAL USERS
FIGURE 3.3-1
The Gasoline Marketing Distribution System
In The United States
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at the bulk terminal by pipeline and are stored in large above-
ground tanks. From these storage tanks the gasoline is loaded
into tank trucks and transported to smaller bulk loading sta-
tions and to service stations.
Statistics from the 1967 Census of Business show 2701
terminals in that year. Total national liquid storage capacity
of motor gasoline at terminals was 23 hm3 (6.2 billion gallons)
with an average capacity of 8700 m3 (2.3 million gallons) per
terminal (US-031). Table 3.3-2 contains a compilation of the
nation's bulk storage capacities as a function of tank size.
By 1973, gasoline consumption had increased to 401 hm3 (106
billion gallons). Sales volume at bulk terminals had presumably
increased at a rate commensurate with the increase in gasoline
consumption while the number of bulk terminals remained unchanged,
Generally, the gasoline storage tanks are subject to
regulations requiring that they be equipped with floating roofs.
Organic chemical emissions from tanks of this design are limited
to vapors escaping past the wall seals and to gasoline evapora-
ting from the wetted walls as the liquid level is lowered. These
minor organic chemical emissions are generally less than 0.3
gallons/1000 gallons handled (DU-001).
Organic chemical emissions from the tank truck loading
racks are potentially much greater than those from the storage
tanks at bulk terminals. As the empty tank trucks are filled,
the organic chemicals in the vapor space are displaced to the
atmosphere unless vapor collection facilities have been provided.
The quantity of organic chemicals contained in the displaced
vapors is dependent on the Reid Vapor Pressure, temperature,
method of tank filling, and the conditions under which the truck
was previously loaded.
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TABLE 3.3-2
U. S. BULK STORAGE CAPACITY BY TANK SIZE
Tank Size Storage Capacity
hm3 (103 gal)
Less Chan 42,000 gallons 0.36 (95,975)
42,000 - 62,000 gallons 0.92 (242,837)
63,000 - 83,000 gallons 0.94 (249,542)
84,000 - 104,000 gallons 0.52 (137,078)
105,000 - 209,000 gallons 0.81 (214,148)
210,000 - 1,049,000 gallons 0.71 (186,960)
1,050,000-- 2,099,000 gallons 0.84 (221,792)
2,100,000 - 6,299,000 gallons 5.25 (1,386,821)
6,300,000 - 20,999,000 gallons 8.92 (2,357,165)
Greater than 21,000,000 gallons 8.03 (2,120,770)
Source: US-031
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3.3.1.2 Bulk Stations
Bulk loading stations are secondary distribution
facilities which receive gasoline from bulk terminals by large
tank trucks, store the gasoline in somewhat smaller aboveground
storage tanks, and subsequently dispense the gasoline via smaller
tank trucks to local farms, businesses, and service stations.
In 1967 there were 26,338 bulk stations. Liquid storage capacity
of gasoline at bulk stations was 4 hm3 (1.0 billion gallons) with
an average capacity of 151 m3 (40,000 gallons) per bulk station
(US-031).
There were fewer bulk stations and terminals in 1972
than in 1967. Oil company officials and industry representatives
confirm this assessment. They indicate that this reduction, pri-
marily in the number of bulk stations, is for economic reasons.
More gasoline deliveries will be made directly from terminals
with large tank trucks. Storage volumes at terminals will be
increased. The decrease in number of bulk stations will not
necessarily have a major impact on overall marketing operations.
The combined sales volume at bulk stations and terminals
is presumed to have increased at a rate commensurate with the
steady increase in gasoline consumption.
Atmospheric Emissions and Control
Significant organic emissions from storage tanks are
generated at bulk stations. Because the storage tanks are often
horizontal and cannot be fitted with floating roofs, or because
roof regulations do not apply to such small tanks, the storage
tanks at bulk loading stations are generally uncontrolled and
are thus a significant source of organic emissions.
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Organic emissions from bulk stations can be controlled
with the installation of a vapor recovery system, since control
with floating roof tanks may not be feasible. A vapor recovery
system designed for a bulk station may be designed to recover
emissions from both storage and tank truck loading operations.
Figure 3.3-2 is a schematic drawing of the vapor and liquid flow
at a typical bulk station with controls.
The organic emission reduction potential for bulk
station storage operations is 95%. This will amount to a re-
duction in emissions of 104,000 MT/yr of hydrocarbons from the
present emission rate of 109,000 MT/yr.
The other significant emission source from gasoline
bulk stations results from tank truck loading operations. During
the loading operation, vapor in the transport truck is displaced
to the atmosphere as it is being filled from bulk station storage.
The amount of emissions generated is dependent primarily on the
type of loading operation.
Top loading and bottom loading are the two basic methods
of filling transport tanks. The top loading procedure can be
done with splash fill or submerged fill. With splash loading,
gasoline is discharged into the upper part of the tank compart-
ment through a short spout which never dips below the surface
of the space liquid. The free fall of the gasoline droplets
promotes evaporation and may even result in liquid entrainment
of some gasoline droplets in the expelled vapors.
With subsurface or submerged loading, gasoline is dis-
charged into the tank compartment below the surface of liquid in
the tank. This is accomplished for top loading operations by
the use of a long spout or fixed pipe extending internally from
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oo
O
I
Vent Gas
t
Vapor to Recovery Unit* Vapor
Vapor Displa
to Transpo
r
i
pJ Terminal
Transport
0 O O
to
ced*
rt
t
Gasoli
Stora
ne
ge
Storage
Tank(s)
f Recovery
Unit
Recovered Gasoline
4 ~ | •<- Vapor Return
to Storage
Tank 1
Truck 1
1
Gasoline^ ^
to Truck
*Vapor emissions from bulk plants may potentially be controlled
by vapor displacement, in which case the recovery unit would
be eliminated.
FIGURE 3.3-2
Vapor and Liquid Flow in a Typical Bulk Station
With Recovery of Displaced Vapors
-------
the top tank entry to the bottom of the compartment. With direct
bottom loading, transfer piping is connected directly to the tank
bottom. This method achieves the same effect as submerged top
loading while providing other advantages such as ease of loading
operations and safety. Consequently, many bulk stations have
already been converted to bottom loading.
Organic emission levels from loading operations are
partly influenced by the transport's previous operation. If
low volatility products were transported previously or the
transport was purged of organic vapor prior to loading, the
organic emissions from gasoline loading may be significantly
lower. The potential reduction in emissions from loading oper-
ations using vapor recovery systems is estimated to be 95%.
This would result in a reduction of organic emissions of 91,500
MT/yr from a present level of 94,700 MT/yr.
3.3.1.3 Service Stations
In 1973 there were 218,000 service stations (NA-168).
A gasoline service station is defined by the U.S. Department of
Commerce as a retail outlet with more than 50% of its dollar
volume coming from the sale and service of petroleum products.
The total number of gasoline service stations is undergoing
rapid change. A survey conducted in May and June 1974 by Audits
and Surveys, Inc., a New York firm, reveals that in 1974 there
were 196,000 U.S. service stations, 9.1% less than their 1973
survey figure of 216,000 (AU-020).
Detailed breakdowns of service station sizes as func-
tions of sales volumes are difficult to obtain due to the reluc-
tance of oil companies to make this information public. In
1973, average monthly service station throughput was 117 m3
-81-
-------
(30,800 gallons) per month according to an estimate by Lundberg
Survey, Inc. (LU-044).
An EPA analysis of service station sales statistics
from the 1967 Census of Business reveals the totals shown in
Table 3.3-3 for the number of stations in various size categor-
ies (MA-314).
Service stations are the final facility in the gasoline
marketing network. At the stations, gasoline is received by tank
truck, stored in underground tanks, and dispensed to automobile
fuel tanks.
Figure 3.3-3 is a schematic drawing of vapor and liquid
flow through a typical service station.
Atmospheric Emissions and Control
Volatile organics in the storage tank vapor space are
displaced as the tank is filled with gasoline from the tank truck,
The quantity of these emissions is dependent on filling rate,
filling method, Reid Vapor Pressure, and the system temperature.
An analogous situation occurs when a partially empty vehicle tank
is filled.
Breathing losses from the underground gasoline storage
tanks are another source of organic emissions. Because the
tanks are underground, breathing losses due to diurnal temper-
ature effects are minimized.
Emissions resulting from underground tank filling
vary with the method of tank loading, i.e., splash or submerged
loading. Use of splash loads results in large emissions of
-82-
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TABLE 3.3-3
U.S. GASOLINE SERVICE STATION
SALES VOLUME DISTRIBUTION
Service Station Sales Volume Number of Stations
(Gallons/Year) in 1967
Less than 150,000 54,100
150,000-200,000 17,100
200,000-250,000 21,200
250,000-300,000 25,500
Larger than 300,000 98,100
216,000
-83-
-------
oo
-f>
i
T Underground Tank
•*- Vent Line
Displaced Vapors
to Tank Truck I
Terminal
Transport or
Tank Truck
f
o o o
Gasoline Co
Storage ->-
Gasoline
Dispenser
Underground
Storage
Tank
Dispensed Gasoline
to Vehicle ->
"IT
O
FIGURE 3.3-3
Vapor and Liquid Flow in a Typical Service Station
-------
organics. Submerged loading reduces the vapors generated. In
addition, test data indicate that 9570 of the displaced vapor
can be recovered by returning the displaced vapors to the tank
truck. This data indicates that a well-designed vapor balance
or displacement system will provide efficient control of under-
ground tank refilling vapors with the use of emission control
technology and equipment commercially available today.
The estimated potential reduction of volatile organics
emitted from service station underground tank filling is 95%.
This provides a reduction in volatile organic emissions of
383,000 MT/yr from 399,000 MT/yr.
There are two basic types of emission control systems
for vehicle refueling: vapor displacement and vacuum assist.
There is some disagreement on the relative effectiveness of these
two systems. The vapor displacement, or vapor balance, system
operates by simply transferring vapors from the vehicle fuel tank
to the underground tank where they are stored until final trans-
fer to a tank truck. Vacuum assist systems employ a blower or a
vacuum pump and a secondary recovery device. The vacuum pump
creates a negative pressure in the vehicle fillneck which "pulls"
hydrocarbon vapor to a secondary recovery unit.
The estimated potential reduction in organic emissions
from refueling operations by using vapor balance or vacuum assist
systems is 90%. This reduces the current emission rate of
467,000 MT/yr by 420,000 MT/yr.
3.3.2 Jet Fuel Marketing;
Jet fuel is essentially kerosene-boiling-range material
with critical freeze point, flash point, and smoke point specifi-
cations. The flash point is controlled by the amount of naphtha
-85-
-------
blended into the jet fuel. Naphtha tends to lower the pour
point and in most instances maximum naphtha (up to flash point
restrictions) is used. Hydrocrackers can be used to produce
high-quality kerosene blend stocks by isomerizing the paraffins.
This isomerization lowers the freeze point and raises the smoke
point by saturating the aromatics (DO-070).
Data for 1973 shows that approximately 95% of all jet
fuel consumed in the U.S. was for airline or military use. The
demand for kerosene-type jet fuel for 1973 was 48 hm3 (303 mil-
lion barrels), while the demand for naphtha-type jet fuel was
13 hm3 (80 million barrels). These figures show an increase in
the demand for kerosene-type fuel and a decrease in the demand
for naphtha-type fuel when compared to 1972 figures, 46.6 hm3
(293 million barrels) and 14 hm3 (88 million barrels), respec-
tively.
Of the 60.5 hm3 (381 million barrels) of jet fuel con-
sumed in the U.S. in 1972, 7.6 hm3 (48 million barrels) were
transported by barge and tanker (AM-099), while 36.4 hm3 (229
million barrels) were transported by pipeline (US-144). Accord-
ing to this data, 15 hm3 (95 million barrels) of jet fuel were
transported by some other means, such as railroad tank car or
tank truck, with some 1.4 hm3 (9 million barrels) left un-
accounted (AM-099).
Nonrefinery storage capacities for jet fuels in 1968
with a refinery throughput of 55.5 hm3 (349 million barrels)
was 2.76 hm3 (17.4 million barrels) (MS-001). Since the 1973
throughput exceeds the 1968 figure by 10"o, storage capacities
are assumed to have also increased, although 1973 capacities
are unavailable. Within the marketing system, jet fuels are
stored at bulk stations and bulk terminals. Petroleum bulk
-86-
-------
stations are defined generally as those having capacities less
than 8 dam3 (2 million gallons) and receiving their supply by
truck or rail transport. Bulk terminals generally handle large
throughputs and are supplied primarily by pipeline, tanker, or
barge.
Storage capacities for naphtha-type jet fuels amounted
to 1 hm3 (6.1 million barrels) in 1968, while those for kerosene-
type jet fuels amounted to 1.79 hm3 (11.3 million barrels)
(MS-001).
Organic emission sources in the jet fuels marketing
industry are very similar to the emission sources in the gasoline
marketing industry. In brief, storage losses can be controlled
by converting to floating-roof tanks or by venting excess vapor
from fixed-roof tanks to a vapor recovery system. Loading and
unloading emissions can be controlled by venting the displaced
vapors to a vapor recovery unit.
3.3.3 Distillate and Diesel Fuel Marketing
Distillate fuel oil refers to petroleum products which
boil in the 176 to 343°C (350 to 650°F) range. This includes
Numbers 1, 2, and 4 fuel oils. Diesel fuels are also included
in this fraction. Grade No. 2 fuel oil is the designation given
to the heating or furnace oil most commonly used for domestic
and small commercial space heating and is the fuel oil generally
referred to as distillate fuel. Domestic heating oil is gener-
ally a clean product with a low sulfur and ash content and no
asphaltic matter. As a result, distillate fuels form no sediment
in storage and have less tendency to form ash or carbon deposits
when burned. These properties, combined with viscosities much
lower than residual fuels, make clean and trouble-free combustion
easier to achieve.
-87-
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Diesel fuel is similar to distillate fuel. Diesel
fuel is often referred to by ASTM grade numbers 1-D and 2-D,
since it is marketed as burner fuel and grades 1 and 2. Some
typical specifications for fuel oil and diesel fuels are listed
in Table 3.3-4 (DO-070).
Diesel fuel is burned in the compression ignition
engine rather than in a fuel burner. As a result, ignition
quality becomes an important characteristic. This ignition
quality is expressed as a cetane number which may be improved
(raised) by the removal of aromatics or by the inclusion of
additives to initiate the combustion processes. Paraffinic
fuels are better suited for diesel use because of lower self-
ignition temperatures.
Forty-eight percent of the 174 hm3 (1.1 billion barrels)
of distillate fuel oil consumed in the U.S. in 1973 was used as
heating oil. Twenty-four percent of the total was used as diesel
fuel. Table 3.3-5 shows a breakdown of distillate fuel oil de-
mand by uses in 1973.
Transportation data for 1972 show that of the 168 hm3
(1.06 billion barrels) of distillate fuel oil used in the U.S.,
21.9 hm3 (138 million barrels) were moved by tanker and barge
(AM-099) and 104 hm3 (657 million barrels) were moved by pipeline
(US-144). The remaining 42.5 hm3 (268 million barrels) were
transported by means of railroad tank car and tank truck. Pipe-
line movement figures are not available for 1973, but of the
174 hm3 (1.1 billion barrels) consumed, 17.2 hm3 (108 million
barrels) were moved by tanker and barge (AM-099).
Storage capacities for distillate fuel oil in the
marketing system in 1968 (with a throughput of 138 hm3 (872 mil-
lion barrels) amounted to 26.8 hm3 (169 million barrels) (MS-001).
-88-
-------
TABLE 3.3-4
PROPERTIES OF DISTILLATE FUELS
Property
No. 2. Fuel Oil
Diesel Fuel
Flash, min., °C(°F)
60(140)
62.7to68.3(145tol55)
Pour Point, max., °C(°F) -20(- 5)
-23 to-12 (-10to+10)
Sulfur, max. wt%
0.5
0.5
Cetane Number, min.
40.0
52.0
-89-
-------
TABLE 3.3-5
U.S. DISTILLATE FUEL OIL DOMESTIC DEMAND BY USES
(Daily averages in dam3 (103 42 gallon barrels)
1973
Heating Oils:
No. 1
Automatic Burners 14 ( 91)
Other Heating 6 ( 40)
No. 2 194 (1,222)
No. 4 18 ( 115)
Total 233 (1,468)
Industrial 29 ( 184)
Oil Company Fuel 7 ( 41)
Electric Utility Company 34 ( 214) l
Railroads . 45 ( 282)
Vessel Bunkering 12 ( 73)
Military Use 9 ( 54)
Diesel Type
On Highway 94 ( 594)
Off Highway 25 ( 155)
Total 119 ( 749)
All Other 2 ( 15)
TOTAL 489 (3.08Q)1
1 Includes 11 dam3/day (68,000 barrels per day) of distillate
fuel used by steam electric plants. Also included are 3
dam3/day (17,000 barrels per day) of kerosene-type jet fuel
used by electric-utility companies.
-90-
-------
In 1973 throughput exceeded the 1968 figure by 29 percent.
Storage capacities have also been increased accordingly.
Organic emissions from the marketing of distillate
and diesel fuels primarily originate from storage tank evapora-
tion and from tank truck and railcar loading.
Emission controls have not been applied to diesel and
distillate fuels marketing because of their relatively low
volatility and organic emission rate.
3.3.4 Residual Fuels Marketing
Residual fuel oils are generally defined as crude oil
distillation residues having a boiling point of 343°C(650°F) or
greater. In addition to these "straight-run" oils, fuels of
the residual type are produced from the various refinery
cracking processes. Residual oil is not considered a choice
energy source among the fossil fuels. It is composed of the
heaviest parts of the crude and contains asphaltic matter,
asphaltenes, sulfur, and small amounts of metals. Typically,
residual fuels are used to provide steam and heat for industry
and large buildings, generate electricity, and power ships.
Residual fuel oils can be defined as Number 5 and
Number 6 heating (burner) oils, heavy diesel, heavy industrial,
and heavy marine (Bunker "C") fuel oils. Fuel oil terminology
is not sharply defined. For example, Bunker C fuel is a heavy
fuel oil that generally corresponds to Grade 6 fuel oil. The
terms heating oils and burner fuel oils are often used
synonymously.
The steady increase in the use of catalytic cracking
refineries following World War II had the effect of decreasing
-91-
-------
the percentage yield of residual fuels as well as changing their
makeup. As more high-boiling materials were charged to catalytic
cracking, the remaining oil sold as residual fuel became heavier
and heavier. Previous common industry practice was to blend these
heavy stocks with lighter distillates to reduce their viscosities
to a salable fuel level. After the war, refining processes in
.the United States began to produce the more profitable products
more efficiently. Residual fuel oils account for 7.6 percent
of average national petroleum production and refining yields
(EN-043). In 1973, 0.15 hm3/day (971 thousand barrels per day)
of residual oils were produced in domestic refineries while
another 0.29 hm3/day (1827 thousand barrels per day) were
imported (AM-099). U.S. refineries have continued to reduce
the yield of residual fuels; however, if the current residual
shortages and higher prices prevail, this trend could be slowed
or even reversed.
Fixed-roof tanks operated at atmospheric pressure are
predominantly used in the storage of residual fuel oils. These
fuels have low volatilities; and evaporation, breathing, and
working losses are minimal. Residual fuels are heated throughout
storage and transportation operations to maintain manageable
viscosities.
Residual fuel oil can be transported by tanker, barge,
pipeline, tank truck, or railroad tank car. Of the 0.4 hm3/day
(2.8 million barrels per day) of residual oil consumed in the
U.S. in 1973, 0.25 hm3/day (1.8 million) were imported; thus, the
majority of residual fuels are handled by tanker and barge.
Furthermore, in 1973, 7 dam3/day (44,000 barrels per day) of
residual oils were transported by tanker and barge from the
Gulf Coast to the East Coast and 4 dam3(24,000 barrels per day)
were transported from the Gulf Coast to the Midwest via the
Mississippi River (AM-099).
-92-
-------
The possibility of substantial atmospheric hydrocarbon
emissions from residual fuel oils during storage or transportation
is minimal. Number 6 residual fuel oil has a negligible vapor
pressure, i.e., less than 690 Pa(0.1 psia) , and as a result, hydro-
carbon emissions from marketing this fuel are negligible.
3.3.5 Crude Oil Transport
The most important mode of transporting petroleum over-
land is the pipeline. The basic function of trunk pipelines in
domestic oil fields is that of transporting crude oil from field
storage to refinery storage. In 1973 a daily average of 1.3 hm3
(8.0 million barrels) of domestic crude was moved to refineries
through pipelines. This figure represented 87 percent of domestic
production for that year (AM-099).
Before the pipelines are buried, they are wrapped with
a protective coating to prevent corrosion of the pipe exterior.
The pipe may also be equipped with cathode protection. Internal
corrosion is a problem only in those lines carrying crudes
containing sulfides.
Nearly all of the existing pipelines are laid below
grade. Subsurface installation protects them from weather and
from accidental damage by earth-moving equipment. Offshore pipe-
lines are laid in trenches on the floor of the sea to guard
against damage by wave action, storms, and shipping accidents.
Although the U.S. pipeline system is extensive, it is
sometimes necessary and economical to transport crude by barge
or tanker to refineries in certain parts of the country. Many
refineries are located on navigable waters and operate docks for
receiving or shipping oil by tanker or barge. Tankers of many
-93-
-------
sizes transport crude oil and products in coastal traffic and
over inland waterways. The United States has 20,000 km(12,000
miles) (EN-045) of coastline and 40,000 km(25,000 miles) (AM-155)
of navigable inland waterways and therefore offers a large
potential for domestic traffic by water.
Tanker and barge movements of crude oil for several
recent years are shown in Table 3.3-6 in daily averages of dam3
(thousands of barrels). Crude transported by water is usually
moved by pipeline from the point of production to the point of
water shipment. The barges used for transport of crude oil are
called tank barges. They are designed to carry liquid products
in bulk and are powered by towboats or tugboats. Other forms of
crude transport are railway tank cars and tank trucks. These are
less commonly used methods, but they are necessities in some
areas. The daily average of crude transported to the refineries
by tank car and tank truck in 1973 was 2.42 dam3(159,000 barrels),
or about 2 percent of the domestic production.
Imports of crude oil for 1973 averaged 0.5 hm3(3.2
million barrels per day). This figure constituted a 46 percent
increase of crude imports over 1972 figures. Table 3.3-7
provides an illustration of the rate of growth of crude imports
over the past years.
TABLE 3.3-6
TANKER AND BARGE MOVEMENTS OF CRUDE OIL
dam3/day (103 barrels/day)
1971
Gulf Coast to East Coast
Gulf Coast to Mid-West
Gulf Coast to West Coast
89.7 (565)
7.9 ( 50)
--
1972
46.4 (292)
7.9 ( 50)
0.3 ( 2)
1973
24.6 (155)
4.4 ( 28)
--
Source: AM-099
-94-
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TABLE 3.3-7
CRUDE OIL IMPORTS
in dam3 (103 barrels/day)
1968
205
(1290)
1969
224
(1409)
1970
210
(1324)
1971
267
(1680)
1972
352
(2216)
1973
515
(3244)
1974*
556
(3500)
1975**
609
(3830)
* Preliminary
** January
Source: AM-099
A large percentage of the imports must be transported
over the ocean in marine tankers. Since more and more oil has
been transported from the lesser developed countries to the
highly industrialized nations, the world tanker fleet has grown
in numbers and in capacity. In 1950 tankers totaled 25.7 Gg
(25.3 million deadweight tons (DWT)). By 1972 tanker tonnage
was 186.1 Gg(183.2 million DOT). The average size tanker
increased in the same time period from 12 Mg(12,000 DWT) to
60 Mg(58,000 DWT). The largest tanker in use in 1950 was under
25 Mg(25,000 DWT), but in 1972 the largest tanker in use was in
excess of 305 Mg(300,000 DWT), and vessels of 548 Mg(540,000 DWT)
were under construction (PR-074). The increasing emphasis on
large carriers results from the favorable economics of carrying
large loads on long trips.
The existing United States ports are unable to accomo-
date the large "supertankers". This fact has necessitated loading
and unloading at offshore anchorages. The oil may be loaded and
unloaded via submarine pipeline to the shore. It may also be
handled in an offshore storage facility and later transported to
shore by smaller tankers and barges.
-95-
-------
Crude oil is handled in a system closed except for
points of transfer. Crude is supplied to refineries through a
transportation system which includes tank farms, bulk terminals,
and other storage points connected by overland and water trans-
portation systems. Figure 3.3-4 illustrates the relative sizes
of systems involved in transporting crude oil to refineries.
Atmospheric Emissions and Control
The organic chemicals emitted in transferring crude to
the refinery are mostly low molecular weight saturated hydro-
carbons. If the oil transportation system is open to the
atmosphere at any point, dissolved light gases will be lost. As
in every other phase of production, storage tanks are potential
sources of emission.
Pipelines are subject to losses caused by corrosion
damage or accidents. Spills account for only a small percentage
of the quantity of products carried, but the volume of products
carried is very large. Other emissions sources in pipeline
systems are valves, pumps, flanges, and other fittings. Even
small leaks in the many fittings and pumping equipment may result
in sizable emissions because of the large volumes transported
through the pipeline network.
Most emissions from tank cars, tank trucks and marine
facilities occur during loading operations. Most tank cars and
trucks are filled from the top by subsurface loading and marine
tankers are filled from the bottom through fill pipes which are
integral parts of the carriers. These methods of loading create
the least amount of turbulence and result in the least amount of
vaporization when compared to splash loading methods.
-96-
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DOMESTIC PRODUCTION
1.5 (9.2)
FIELD
STORAGE
VD
~-J
I
Pipeline 1.26 (7.95)
Rail and Tank Car 0.03 (0.16)
Barge and Tanker 0.17 (1.09)
IMPORTS
0.51 (3.2)
Pipeline 0. 17 (1. 1) _
Marine Tanker ___
0.33 (2.1)
ONSHORE
STORAGE
Pipeline
Tanker or _
Barge
REFINERY
STORAGE
FIGURE 3.3-4
Transportation of Crude Oil, 1973
Rates in hm3/day (106barrels/day
-------
Storage tanks are another significant source of organic
emissions. Light hydrocarbon gases which have remained with the
crude may be discharged to the atmosphere from a storage tank or
during filling operations as a result of ambient temperature
changes. In 1968, approximately 75% of the storage tanks at re-
fineries were equipped with floating-roof tanks. It is assumed
that storage facilities in the crude transportation system are
similarly equipped. The reduction in organic emissions result-
ing from the application of floating-roof tanks to the remaining
storage tanks is 246,000 MT/yr from the total emission rate of
526,000 MT/yr. The actual emission rate and, thus, the reduction
potential for organic emissions from storage tanks in the crude
transportation system may be considerably less, since it is
likely that floating roofs have been employed in many of the
tanks that were uncontrolled in 1968.
-98-
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3.4 Fossil Fuel Refining
Organics produced by the fossil fuel refining category
include air emissions and water effluents resulting from the
refining of petroleum and coal. Emissions resulting from natural
gas processing and natural gasoline plant operation are discussed
in Section 3.2, Fossil Fuel Processing.
The emissions and effluents associated with petroleum
refining result from the processing steps that make up today's
complex petroleum refinery. Coal coking operations are the major
source of organic emission and effluents from coal refining in
the U.S. Other coal processing and refining operations such as
coal gasification and liquefaction are not yet conducted on a large
enough scale to impact overall U.S. organic emission rates.
The petroleum refining and coal coking operations are
further divided into subgroups relating to processing steps or
operations contributing to atmospheric emissions. A summary of
the atmospheric emissions from the processes and operations in
this category is presented in Table 3.4-1. Water effluents
resulting from petroleum refining and coal coking are also
examined. For this study organics from solid waste processed by
industry on site by incineration, landfill, or other means were
_not quantified. However, the environmental impact of any
industrial solid waste disposed of by municipalities is considered
in Section 3.12. Section 3.12 also contains an evaluation of the
impact of organic emissions resulting from solid waste disposal.
The important organic emission sources in the fossil
fuel refining category are identified in this section and are
examined to determine the point of organic emission. Emission
from process effluent streams and from fugitive sources are
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TABLE 3.4-1
o
o
i
Fossil Fuel Refining
Storage, Petroleum Refining
Blowdown, Petroleum Refining
Process Drains & Waste Water
Separators, Petroleum Refining
FCC Unit, Petroleum Refining
Vacuum Jets, Petroleum Refining
Charging, By-Product Coke Oven
Coking Cycle, By-Product Coke
Oven
Pipeline Valves and Flanges,
Petroleum Refining
Pump Seals, Petroleum Refining
Compressor Engines, Petroleum
Refining
Pressure Relief Valves,
Petroleum Refining
Boilers & Heaters, Petroleum
Refining
Cooling Tower, Petroleum Refining
Compressor Seals, Petroleum
Refining
Discharging, By-Product Coke
Oven
FOSSIL
Year
1973
1973
1973
1973
1973
1974
1974
1973
1973
1973
1973
1973
1973
FUEL REFINING EMISSIONS
Volatile
Organ ics (MT/yr.)
965,000
328,000
216,000
147,000
117,000
102,000
61,200
57,600
34,800
32,800
22,500
20,500
20,500
Ref
1
1
1
1
1
2
2
1
1
1
I
1
1
1973
1974
10,300
8,170
Particulate
Qrganics (MT/yr.)
Ref
61,200
4,080
2
2
24,500
-------
TABLE 3.A-1 (Continued)
FOSSIL FUEL REFINING EMISSIONS
i
i—•
o
h-1
i
Year
TCC Unit, Petroleum Refining 1973
Beehive Ovens, Coke Products 1974
Sampling, Petroleum Refining 1973
Blind Changing, Petroleum
Refining 1973
Misc. Fugitive, Petroleum Refining J973
Quenching, By-Product Coke Oven 1973
Unloading, By-Product Coke Oven 1974
Subtotal, Petroleum Refineries,
Coke Manufacture
Volatile
Organics (MT/yr.)
5,470
5,040
4,830
610
14,200
1,997,110
176,410
Ref
1
2
1
1
1
Participate
Organics (MT/yr.)
126,000
kef
36,700
16,300
TOTAL
2,173,520
268,780
Sources: 1 BL1-185
2 EN-071
-------
considered. The process vent and storage losses are the largest
volatile emissions and also have "the greatest potential for
reduction.
The specific operations which represent the largest
potential for reduction of volatile organic emissions result
mainly from the petroleum refining industry. The coke manu-
facturing industry has potential for organic emission reduction
but these reductions are smaller and less defined than those in
the petroleum industry (BA-283).
The total volatile organic emission rate from the
refining category is nearly 2.2 x 106 MT/yr. The potential
reduction in emissions is about 0.9 x 106 MT/yr from process vents
and is nearly 0.5 x 106 MT/yr from storage operations. The
potential reduction for fugitive emissions in only 0.02 x 105
MT/yr. Where possible, the potential reductions are estimated
by assuming the degree of application of current controls and
extending the use of the controls across the industry.
Development documents for proposed effluent limitations
guidelines and new source performance standards in fossil fuel
refining industries provided the most recent and comprehensive
assessment of organic effluents and their control. For this
reason, the anticipated petroleum refining and coking effluent
rates reflect the BPCTCA for industries to achieve by July 1, 1977.
Many facilities have already converted to meet BPCTCA effluent
rates and many more are in the process^of converting.
The potential for reduction of organic water effluents
is assumed from effluent guideline documents to be the July 1,
1983 effluent limitation or Best Available Technology Economically
-102-
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Achievable (BATEA). The reduction of organic effluents from the
BPCTCA level to the BATEA level is the potential organic water
effluent reduction.
A significant reduction is achievable in both the
petroleum refining and by-product coking industries. No poten-
tial reduction for beehive ovens is achievable from BPCTCA to
BATEA since BPCTCA results in no effluents from this operation.
3.4.1 Petroleum Refining
3.4.1.1 Process Description
Petroleum refining is the third largest industry in the
United States and represents a potential organic emission problem
because of the large quantities of petroleum liquids refined and
the intricacy of the refining process.
Generally, each petroleum refinery is a unique hybrid
whose design is determined by the local market demands and the
characteristics of the crude being processed. However, refineries
normally can be classified into one of the following five basic
refinery types.
The diverse range of products and manufacturing pro-
cesses in petroleum refineries suggests that subcategories for
different segments of the industry be developed. A process
oriented subcategorization of the industry has been developed.
Subcategories are based on raw waste load characterisitcs and
are related to the complexity of refinery operations.
The American Petroleum Institute (API) has developed
a cl'assification system which uses this technology breakdown.
The U.S. refineries have been divided into five classifications
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with varying degrees of processing complexity and a characteris-
tic distribution of products. The API classification system is
presented below (EN-407):
Topping - Primary operation is separation of
crude into its major fractions but may
include some hydrotreating.
Topping and Cracking - Operations include
separation, conversion, and cracking processes
for maximization of gasoline product.
Topping, Cracking and Petrochemical - Some
petrochemical processing is performed in
addition to cracking, conversion, and
topping operations.
Integrated - Lube oil, wax, and asphalt
processing are integrated into topping,
cracking and conversion processing.
Integrated and Petrochemical - Petrochemical
manufacturing is combined with the refining
operations of an integrated refinery.
Approximately 28 percent of the refineries in the U.S.
are topping and cracking refineries; 20 percent are topping,
cracking, and petrochemical refineries; and 20 percent are
integrated refineries.
As of January 1, 1974, were 247 petroleum refineries
were operating in the U.S. with a total crude capacity of 2.26 hm3
(14,200,000 barrels per day) (AN-089). Individual refinery
-104-
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capacities range from 159 m3 (1,000 barrels per day) to 70 dam3
(445,000 barrels per day). The ten largest refineries comprise
over 25 percent of the nation's capacity (EN-043). Table 3.4-2
presents a distribution of the refinery sizes for 1971 (EN-043)
There is a trend toward larger and fewer refineries.
Characterization of the refining processes applied to
a so-called "typical" refinery is difficult because of the wide
variety of refining schemes and processes available to the refiner
Because of the emphasis today on gasoline, a fully integrated
gasoline refinery will be used in the example of a typical
refinery.
The commonly used refinery process units are:
atmospheric and vacuum distillation;
gas treating and light ends recovery;
conversion processes - alkylation, reforming,
isomerization;
hydrodesulfurization;
cracking;
alternative vacuum residual processing, such as
solvent deasphalting, coking, and asphalt
distillation; and
lube processing.
-105-
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TABLE 3.4-2
REFINERY SIZE DISTRIBUTION - 1971
Refinery Capacity
% of Total
Refineries
% of Total
Refining Capacity
1 dam3 (<70,000 b/cd)
75.9
1-3.2 dam (70,000-200,000 b/cd)
19.0
41.6
>3.2 dam (>200,000 b/cd)
5.1
30.0
-106-
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In addition, there are several important auxiliary
processes, such as:
crude desalting,
sulfur recovery and tail gas treatment,
hydrogen production,
blending and storage,
sour water stripping,
wastewater stripping,
wastewater treatment, and
utility steam boilers.
Organic emissions vary greatly from one petroleum
refinery to another depending on such factors as capacity, age,
crude type, processing complexity, application of control measures,
and degree of maintenance (EN-043).
Because refineries are a complex collection of integrated
processing units, the pinpointing of individual organic emission
sources would be an extensive task. This section attempts to
characterize and, where possible, to quantify the organic
emissions from major sources within a typical refinery.
-107-
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3.4.1.2 Atmospheric Emissions and Control
These emission sources are grouped into combustion
sources, tankage and loading sources, process sources, and
fugitive sources.
3.4.1.2.1 Combustion Sources
A typical petroleum refinery has several major com-
bustion sources which include process heaters, boilers and
compressor engines. Organics are emitted from these sources
because of incomplete fuel combustion.
3.4.1.2.2 Storage and Loading Sources
The high volatility of feedstocks, intermediates, and
products stored and loaded in refinery tank farms makes storage
and loading losses one of the largest potential volatile organic
emission sources in the refining industry. Because most products
and feedstocks are transported by pipeline, storage losses are
greater than loading losses.
Fixed-roof, floating-roof, and internal floating cover
tanks are the most common tanks in refinery service. These tanks
range in size from 3 to 25 dam3 (20,000 to 160,000 barrels) and
average 11 dam3 (70,000 barrels) (MS-001). The major sources of
organic emissions from fixed-roof tanks are breathing and filling
losses, while the major source of emissions from floating roofs
and internal floating covers is standing storage losses.
In 1968 approximately 75 percent of the storage tanks
at refineries were equipped with floating roofs. The reduction
in organic emissions resulting from the application of floating
roofs to the remaining storage tanks is 452,000 MT/yr. The
actual emission rate and, thus, the reduction potential for
-108-
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organic emissions from storage tanks in refineries may be con-
siderably less today since floating roofs have probably been
employed in many of the tanks that were uncontrolled in 1968.
The greatest determinant in the total emissions gen-
erated in product loading is the method of dispensing. In
splash loading the liquid is discharged by a short spout into
the upper part of the tank. The resultant free fall not only
increases evaporation but may result in a fine mist of liquid
droplets. In submerged surface and bottom loading, the product
is discharged within a few inches of the tank bottom. Turbulence
decreases markedly, therefore, losses by evaporation and en-
trained droplets are correspondingly reduced.
3.4.1.2.3 Process Sources
A substantial portion of the volatile organic emissions
from petroleum refineries can be attributed to individual refining
processes or to individual auxiliary processes. These sources
include catalyst regenerators, barometric condensers, blowdown
systems, wastewater separators, air blowing, and cooling towers.
Because process emission sources are identifiable, their emissions
are more accurately quantified and more easily controlled.
Catalytic Cracker Catalyst Regenerators
An integral part of a catalytic cracking unit is the
catalyst regenerator (Figures 3.4-1 and 3.4-2) where coke that
is formed on the catalyst surface during cracking is burned off.
Catalytic cracker regenerators operate continuously. Because
the combustion rate is controlled by limiting the air to the
regenerator, there is only partial oxidation, leaving many
unburned hydrocarbons in the regenerator flue gas.
-109-
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REGENERATED
CATALYST
AIRLIFT OR
ELEVATOR
WET GAS TO POLY. OR
ALKYLATION UNITS
CPACXEO GASOLINE
LIGHT FUEL OIL
»- GAS OIL RECYCLE
HEAVY FUEL OIL
FIGURE 3.4-1 TYPICAL MOVING-BED CATALYTIC CRACKING UNIT
PRODUCTS
REGENERATOR
REGENERATED^
CATALYST
WET GAS TO POLY. OR
ALKYLATION UNITS
-CRACKED GASOLINE
-»- LIGHT FUEL OIL
•RECYCLE GAS OIL
-•-HEAVY FUEL OIL
GAS OIL CHARGE
FIGURE 3.4-2 TYPICAL FLUIDIZED BED CATALYTIC CRACKING UNIT
-110-
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The main control method for the reduction of volatile
organic emissions in this flue gas is incineration in a carbon
monoxide waste heat boiler. The emissions can be almost completely
eliminated and valuable thermal energy can be recovered from the
flue gas.
Although CO boilers are not extensively used today,
they are becoming standard equipment in new refineries and expan-
sions of existing units. This is a result of both energy con-
servation and increased concern for air quality.
The reduction potential for volatile organic emissions
from catalytic cracking units, assuming fuel addition for complete
combustion of hydrocarbons, is 147,000 MT/yr (BU-185). This is
the result of controlling essentially 100 percent of the volatile
organics from catalytic cracking units.
Vacuum Jet-Barometric Condensers
Most refineries operate some processing equipment
below atmospheric pressure. The vacuum distillation column is
the most common of the processes operating at a vacuum. Steam
driven vacuum jets or ejectors coupled with a barometric con-
denser are frequently used in refineries to produce and maintain
vacuums (Figure 3.4-3). Light hydrocarbons which do not condense
in the barometric condenser are discharged to the atmosphere.
Volatile organic hydrocarbon emissions from barometric
condensers on vacuum jets are attributable to both the venting of
non-condensable hydrocarbons as well as to the evaporation of
hydrocarbons from the oily barometric condensates.
Three measures for minimizing oily condensate generation
are mechanical vacuum pumps, lean oil absorption, and surface
-111-
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STEAM INLETS
SUCTION
A
WATER
INLET-
-STEAM INLET
i 1
(
— c
r**"^
I
1
\
-« — BAROM
-DISCHARGE
\_ WATER AND CONDENSED
HYDROCARBONS OUTLET
FIGURE 3.4-3 TYPICAL STEAM EJECTOR-BAROMETRIC CONDENSER
-112-
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condensers. While mechanical vacuum pumps have little effect on
the quantity of non-condensable hydrocarbons generated, they do
eliminate the generation of oily steam condensate. The insertion
of a lean oil absorption unit between the vacuum tower and the
first stage vacuum jet helps to minimize the quantities of both
non-condensables and oily condensate (AM-055). The rich oil
effluent is reused as charge stock and not regenerated. Surface
condensers in place of barometric condensers minimize oily con-
densates but have little effect on the quantity of non-condensables
(AT-040).
Because generation of non-condensable vapors cannot
be completely eliminated from vacuum pumps or steam ej.ectors,
these emissions must be controlled by either vapor incinerators
or vapor recovery units. Vapor incinerators combust the vapors
by catalytic or direct flame methods. Vapor recovery units on
the other hand recover the hydrocarbon vapors and return them to
processing streams.
The reduction potential for organic chemical emissions
from vacuum jets in the petroleum refining industry is 117,000
MT/yr.
Slowdown Systems
Periodic maintenance and repair of equipment are
essential to refinery operation.
Slowdown emissions resulting from the purging of
organics from equipment can be effectively controlled by venting
into an integrated vapor-liquid recovery system. All units and
equipment subject to shutdowns, upsets, emergency venting, and
purging are manifolded into a multi-pressure collection system.
-113-
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Discharges into the collection system are segregated according
to their operating pressures. A series of flash drums and con-
densers arranged in descending pressures separates the blowdown
into vapor pressure cuts. These recovered gaseous and liquid
cuts can be flared and/or re-refined.
Fully integrated recovery systems can reduce refinery
blowdown emissions and have a reduction potential of 318,000
MT/yr of organics (BU-185). This reduction potential assumes
that most refineries are currently applying some degree of blow-
down system control.
Air Blowing
Air blowing of petroleum products is today confined
largely to the manufacture of asphalt, although air is occasion-
ally blown through heavier petroleum products to remove moisture.
Figure 3.4-4 depicts a typical asphalt air-blowing process. The
use of air blowing for agitation, formerly quite common, is today
practically non-existent.
Prosess Drains and Waste Water Separators
Some equipment and a number of operations in oil re-
fineries including blind changing, sampling, turnarounds, leaks,
and spills, allow organic chemicals'to reach drains and eventually
the wastewater separators. In addition, much of the water routed
to the drains, including water from processing, pump seal cooling,
and flushing, is already contaminated with hydrocarbons. Drains
generally flow to an API separator for gravity separation of the
oil and water prior to treatment in the wastewater treatment
plant. If the drains and wastewater separator are uncovered,
organics can evaporate to the atmosphere.
-114-
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STEAM
l
I-1
M
Ui
OFF GAS TO
INCINERATOR
EFFLUENT TO
COVERED OIL-WATER
SEPARATOR
HEATER
BLOWING STILL
SCRUBBER
KNOCKOUT DRUM
FIGURE 3.4-4 FLOW DIAGRAM OF ASPHALT BLOWING PROCESS
-------
Control measures for reducing the evaporative emissions
from process drains and wastewater separators center around (1)
reducing the quantity of organics evaporated and (2) enclosing
the wastewater systems.
The quantity of organic chemicals evaporated can first
be reduced by minimizing through good housekeeping the volume of
oil leaked to the wastewater systems. Lowering the temperature
of the wastewater will also reduce organic chemical evaporation
(AM-055).
Measures for enclosing the wastewater systems include
manhole covers, catch basin liquid seals, and fixed or floating
roofs for API separators. The potential also exists for some
form of vapor disposal or vapor recovery device in conjunction
with fixed roofs on API separators (EL-033).
The potential for reduction of volatile organic emis-
sions, accounting for the existing degree of control, is 195,000
MT/yr (BU-185).
Cooling Tower
Petroleum refineries use large quantities of water for
cooling. Before the water can be reused, the heat absorbed in
passing through process heat exchangers must be removed. This
cooling is usually accomplished by allowing the water to cascade
through a cooling tower where evaporation removes the sensible
heat from the water. Organic chemicals are leaked into the cool-
ing water system by heat exchangers. Organic emissions are gen-
erated at the cooling towers when these organics evaporate to
the surface.
-116-
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3.4.1.2.4 Fugitive Sources
One of the largest, yet hardest to control, categories
of volatile organic emissions from petroleum refineries is fugi-
tive sources. Fugitive emissions are not solely attributed to a
particular type of refining processes or auxiliary processes but
occur throughout the refinery. Fugitive losses from individual
sources are generally small, but they become significant because
of their prevalence. Fugitive sources include pump seals, relief
valves, pipeline valves, sampling, and blind changing.
Pump and Compressor Seals
Pumps and compressors can leak at the point of contact
between the moving shaft and the stationary casing. If volatile,
the leaked product will evaporate to the atmosphere. The two
types of seals commonly used in the petroleum industry are packed
seals and mechanical seals.
Pressure Relief Valves
For safety and equipment protection, high pressure
vessels are commonly equipped with relief valves to vent excessive
pressures. Corrosion may cause pressure relief valves to reseat
improperly after blowoff, creating a potential source for volatile
organic leaks and emissions.
• o
Pipeline Blind Changing
Refinery operations frequently require that a pipeline
be used for more than one product. To prevent leakage and con-
tamination of a particular product, other product-connecting or
product-feeding lines are customarily "blinded off". "Blinding"
a line involves inserting a flat solid plate between two flanges
-117-
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of a pipe connection. In inserting or withdrawing a blind,
spillage of the product in the pipeline can occur. The magnitude
of volatile organic emissions from the spillage is a function of
the spilled liquid's vapor pressure, type of ground surface,
distance to nearest drain, and amount of liquid spilled.
Purging Sampling Lines
The operation of process units is constantly checked
throughout the refinery by routine analysis of feedstocks and
products. To obtain representative samples for these analysis,
sampling lines must be purged, resulting in possible organic
vapor emissions.
Others
Every refinery has several unaccountable volatile
organic emission sources plus sources not common to all refineries,
such as asphalt blowing, coke processing, and lube processing.
This category of emissions amounts to about 20 kg of organics/
dam3 (7. Ibs of organics/103 barrels) of refinery feed (AT-040) .
3.4.1.3 Water Effluents and Control
Considerable information is available for making
meaningful qualitative interpretations of organic effluent loadings
from refinery processes. A summary of this information is
presented in Table 3.4-3. The pollutant parameters describing
organic effluents are BOD, COD, TOG, oil and grease, and sus-
pended solids. Phenol is another common parameter, but phenol
values are much smaller than on a mass emission rate basis. The
organic effluent parameters and associated rates are listed in
Table 3.4-4. The potential reductions are estimated as the
difference between BPCTCA levels and BATEA levels.
-118-
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TAI5LE 3.4-3
Production Processes
Crude Oil. and
Product Storage
Crude Desalting
Crude 1)1 s u il la L Lo n
Th (_• r ma 1 C ra c k i n g
Catalytic Cracking
llyd rocracking
i Po.l ymer:[ za t ion
i — i
i — i
vo A.I kyJ.a Lion
i
Isomeriza t ion
Re to ruling
Solvent Kel'inJng
Asphalt lilowing
Dewaxing
Hydro t real ing
Drying and Sweetening
QUALITATIVE
Flow
XX
XX
XXX
X
XXX
X
X
XX
X
X
X
XXX
X
X
XXX
EVALUATION
liY FUN DAME
HOD
X
XX
X
X
XX
X
X
0
XXX
XXX
X
XXX
OF WAST
NTAL REF
COD
XXX
XX
X
X
XX
X
X
0
X
XXX
XXX
X
X
E WATER
INERY
Phenol
X
X
XX
X
XXX
XX
O
0
X
X
X
X
XX
FLOW AND CHARACTERISTICS
PROCESSES
Oil Emulsified Oil
XXX XX
X XXX
XX XXX
X
X X
X 0
X 0
X 0
X
XXX
X 0
0
0 X
Process
Susp. Solids Complexity
XX A,B,C,D,E
XXX A,B,C,D,E
X A,B,C,D,E
X B,C,D E
X B.C.D.E
B.C.D.E
X B.C.D.E
XX B.C.D.E
B.C.D.E
0 B.C.D.E
D,E
D,E
D,E
0 B , C , D , E
XX A,B,C,D,E
XXX - Major Contribution, XX - Moderate Contribution, X - Minor Contribution, 0 - No Problem - No Data
Source: EN-407
-------
TABLE 3.4-4. PETROLEUM REFINERY ORGANIC EFFLUENTS
Effluent Parameter by Class
300
COD
Oil
-A
-B
-C
-D
-E
-A
-3
-C
-D
- r)
and
Totals
Potential Reduction (MT/yr) '
Totals
Potential Reduction (MT/yr) '
Grease -A
-B
-C
-D
-E
Totals
Potential Reduction (MT/yr)1
RWL2
(MT/yr)
23,
27,
. 32,
18,
102,
2,
69,
73,
81,
31,
256,
9,
8,
18,
7,
43,
Suspended Solids -A
TOC
-A
-3
-C
-D
-E
-3
-C
-D
-E
Totals
Potential Reduction (MT/yr) '
Totals
Potential Reduction (MT/yr) L
5,
7,
10,
5,
30,
_
.
-
-
-
-
772
200
500
500
600
572
140
000
200
300
100
740
476
910
370
000
070
826
673
690
590
700
450
103
BPCTCA
(MT/yr)
2
' 1
2
1
3
2
21
10
17
11
64
1
1
4
3
2
3
2
12
. 6
3
5
3
19
412
,810
,720
,390
,620
,952
,180
,700
,800
,500
,900
,080
191
,250
812
,130
803
,186
557
,770
,260
,330
,100
,017
906
,190
,780
,250
,570
,696
BATEA
(MT/yr)
1
7,061
3
1
3
2
10
53,710
3,802
1
10,126
1
]_
1
1
5
13,931
70
511
350
559
401
,391
290
,070
,720
,020
,270
,370
15
109
72
107
81
38^
70
511
350
559
401
,891
215
,600
,080
,630
,240
,765
Source: EM-407
! Potential reduction of organic from 3PCTCA controls to BATEA controls
2 RWL - Raw Waste Load
-120-
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The potential reduction in organic effluents from
petroleum refineries is estimated to be 16,700 MT/yr of organics.
This reduction is estimated from the difference between BPCTCA
levels and BATEA levels for TOC. The TOG reduction is increased
by a factor of 1.2 to calculate the organic effluent reduction.
The 1.2 factor is the ratio of organic carbon molecular weights
obtained by assuming most of the organics are C5 hydrocarbons
with an average molecular weight of 72.
The actual potential organic reduction may be less than
that estimated from BPCTCA and BATEA since these values represent
30-day maximums rather than yearly averages. However, the poten-
tial reduction for the refining industry should be consistent
with the other categories since the method of calculation is
similar.
The BPCTCA is based on both in-plant and end-of-pipe
controls. The in-plant technology includes the following (EN-407)
installation of sour water strippers to
reduce sulfide and ammonia loads entering
the wastewater treatment plant,
elimination of once-through barometric
condenser water by using surface condensers
or recycle systems with oily water cooling
towers,
segregation of unpolluted storm runoff and
once-through cooling waters from normally
treated process waters, and
better monitoring and maintenance of surface
condensers or use of wet and dry recycle
-121-
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systems to eliminate pollution of once-through
cooling water.
The BPCTCA end-of-pipe treatment consists of (EN-407)
equalization and storm diversion,
initial oil and solids removal (API separators
or baffle plate separators),
further oil and solids removal (clarifiers,
dissolved air flotation, or filters),
carbonaceous waste removal (activated sludge,
aerated lagoons, oxidation ponds, trickling
filter, activated carbon, or combinations
of these), and
filters (sand, dual media, or multi-media)
following biological treatment methods.
The BATEA results from further reduction of water
flows in-plant and the addition of activated carbon treatment
to the end-of-pipe controls.
Required treatment to achieve BPCTCA and BATEA is
dependent upon the needs and operations of the individual
refinery and requires specific studies.
Crude Oil and Product Storage
During storage, water and suspended solids in crude
oil separate; the water layer accumulates below the oil and
is drawn off. Finished product storage is also a source of
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separated water layers. Tank cleaning can contribute large
amounts of water streams high in organic content.
Ballast waters from tankers are often discharged into
ballast water tanks or holding ponds at refineries.
Crude Desalting
Two common methods are used for crude oil desalting:
chemical desalting and electrostatic desalting. Both methods
employ process water to remove impurities, resulting in a waste-
water stream.
Crude Distillation
Several processes can be used to fractionate crude.
These are atmospheric distillation, vacuum distillation, vacuum
flashing, and three-stage crude distillation. There are two
sources of wastewater from crude oil fractionation:
wastewater from overhead accumulators, and
wastewater from barometric condensers.
Organic wastewater loading can also be increased during
sampling when oil sampling lines are discharged to the sewer.
Cracking
The major source of wastewater in cracking is from the
steam strippers and overhead accumulators on the fractionators.
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Polymerization
Most of the wastewater comes from the pretreatment of
feedstock to the reactor by caustic washing.
Alkylation
The major discharge from sulfuric acid alkylation is
the spent caustic wash from the neutralization of hydrocarbon
streams leaving the sulfuric acid alkylation reactor. Water also
is drawn off the overhead accumulators.
Hydrofluoric acid alkylation does not have spent acid
or caustic waste streams. The major sources of wastewater are
the overhead accumulators on the fractionator.
losmerization
Isomerization wastewaters present no major pollutant
discharge problems (EN-407).
Reforming
A small volume of wastewater containing a low concentra-
tion of oil is produced by the reformer overhead accumulator (EN-407)
Solvent Refining
The major solvent refining processes are solvent de-
asphalting, dewaxing, lube oil solvent refining, aromatic ex-
traction, and butadiene extraction. The major potential pollutants
from the various solvent refining processes are the solvents them-
selves. The main source of wastewater is from the bottom of
fractionation towers. Some solvent enters the sewer from pump
seals, flange leaks and other sources.
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Hydrotreating
The principle hydrotreating processes are pretreatment
of catalytic reformer feedstock, naphtha desulfurization, lube
oil polishing, pretreatment of catalytic cracking feedstock,
heavy gas-oil and residual desulfurization, and naphtha satura-
tion. The organic loading and quantity of wastewater generated
by hydrotreating depends on the process used and the feedstock.
Asphalt Blowing
Wastewaters from asphalt blowing contain high concen-
trations of oils and have a high oxygen demand (EN-407).
Drying and Sweetening
The most common waste stream from drying and sweetening
operations is spent caustic which has high BOD5 and COD. Other
waste streams from the process result from water washing of the
treated product and regeneration of the treating solution.
3.4.2 Coke Manufacturing
The majority of coke manufacturing in the United
States is performed to supply coke to the steel industry. In
an integrated steel mill, coke is a basic raw material for the
blast furnace. This section describes the coking industry and
sources of organic emissions associated with coking processes.
The beehive and the by-product processes are used for
coke manufacture in the United States today. Beehive ovens are
not widely used because of economic and environmental disadvant-
ages. Volatile organic emissions in the beehive process are high
because they are not recovered, but organic effluents are low.
-125-
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Today the by-product process, which recovers the volatile organics,
produces about 99 percent of the metallurgical coke (EN-395).
Coke production in 1974 decreased from previous years
because of a strike. In 1973, probably a more representative
year, 61.7 x 106 MT of coke was produced from by-product pro-
cesses and 0.8 x 10s MT of coke was produced from the beehive
process.
3.4.2.1 By-Product Coking
3.4.2.1.1 Process Description
Coke manufacturing by the by-product process is
accomplished in ovens in which bituminous coal is heated to drive
off the volatile components. Air is excluded from the ovens.
The residue remaining in the ovens is coke, and the volatiles
are recovered in the by-product plant to produce tar, light oils,
coke oven gas, and other potentially valuable materials. The
coking is done in narrow, rectangular, silica brick ovens arranged
side by side in groups called batteries. Each oven is typically
45 centimeters wide, 4.5 meters high, and 12 meters long. Heat
is supplied by burning gas in flues between the walls of the
adjacent ovens. Typically forty percent of the coke oven gas
produced is used to heat the ovens. Usually, the remaining gas
is used as fuel in other steel mill operations (EN-395).
Coal is charged through ports located on the top of
an oven and then heated. At the end of the coking period, the
coke is pushed out of the oven with a ram into an open railway
car. The coke is transported to a tower for water quenching and
then transferred to a sizing plant.
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3.4.2.1.2 Atmospheric Emissions
Volatile organic emissions can occur during the following
coking steps: charging, coking cycle, and discharging. In
addition, organic particulate emissions can occur during the
following coking steps: unloading, charging, coking cycle, dis-
charging, and quenching.
Unloading
Organic particulates in the form of coal are emitted
as the coal is unloaded at the coking site and stockpiled for
future use.
Charging
The coal is charged into the coke ovens by a mobile
machine called a larry car, traveling on rails on top of the
coke ovens. A leveler bar is inserted into the oven to level
the coal. Lids which seal the charging holes in the oven roof
are then set in place. The emissions during charging result from
the displacement of about 90 percent of the free space in the oven
by the coal charge. Heating of the coal during charging produces
volatiles. As a result, steam, gas, and displaced air blow out
of the oven ports carrying volatile organics and organic parti-
culates .
Coking Cycle
After charging, coal is heated in the ovens. During
the heating cycle, the oven is sealed and usually maintained at
a slight positive pressure to prevent air infiltration. Gases
can evolve from the coke ovens around seals at the charging
ports and doors.
-127-
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Discharging
After the coking cycle, a pushing machine removes the
oven door on the pushing end of the oven and aligns a ram inside
the door jams. On the coke side, a machine removes the door
and positions a coke guide against the door jams. The pushing
machine then pushes the slab of hot coke out of the oven and
into a quench car positioned below the coke guide.
The emissions during the discharging cycle are smoke
from imcompletely coked coals and dust from thermal drafting of
particles of abraded coke.
Quenching
The quench car containing the discharged coke is moved
to a semi-enclosed tower where water is sprayed on the hot coke.
After the coke has been quenched and cooled, the quench car moves
to a coke wharf where the coke is dumped onto a conveyor belt
moving to the coke handling area.
Fine coke breeze formed during the push and settling
in the quench car is raised into the plume of quenching steam
by the draft from the steam formation.
3.4.2.1.3 Water Effluents and Control
A variety of methods, usually by-product recovery
techniques, has been used through the years. These methods have
changed due to changing economic factors, effluent quality
restrictions and treatment technology capabilities.
As in petroleum refineries, the significant pollution
parameters relating to organic effluents are BOD, TOG, oil and
-128-
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grease, and suspended solids. Estimates of COD levels are not
available. The organic effluent parameters and associated rates
for coke manufacture are presented in Table 3.4-5. The potential
reductions are estimated as the difference between BPCTCA levels
and BATEA levels (EN-395).
The potential reduction in organic effluents from coke
manufacture is estimated to be 9680 MT/yr of organics. This
reduction is estimated as the difference between BPCTCA levels
and BATEA levels. The TOC for BPCTCA is estimated to be similar
to petroleum refineries and, therefore, a factor of 2.2 higher
than BOD5. The TOC for BATEA is estimated by assuming an 87%
reduction in TOC from BPCTCA levels. Experimental data in the
organic chemicals industry indicates 87% removal from a cross-
section of processes with similar wastewater treatment (EN-384).
To obtain the potential organic reduction, the TOC
reduction is increased by a factor of 1.2 which assumes that
most of the organics present are hydrocarbons with an average
molecular weight of 72.
As mentioned earlier, the actual potential organic
reduction may be less than that estimated from BPCTCA and BATEA
since these values represent 30-day maximums rather than yearly
averages. However, the potential reduction for the coke manu-
facturing industry should be consistent with the other categories
The base level of treatment in Table 3.4-5 is an
estimate of the effluents with a level of treatment in existence
for practically all plants within the industry (EN-395).
The BPCTCA is based on the employment of the following
technologies (EN-395) :
-129.-
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TABLE 3.4-5
COKE MANUFACTURE ORGANIC EFFLUENTS
Effluent Parameters
By- Product Ovens
BOD
Oil and Crease
Suspended Solids
TOG 2
Base Line1
(MT/yr)
12,700
844
2,110
-
BPCTCA
(MT/yr)
4,220
422
2,110
9,280
BATEA
(MT/yr)
482
241
241
1,210
Potential
Reduction
(MT/yr)
3,738
181
1,869
8,070
OO
o
I
Beehive Ovens
No effluents for BPCTCA and BATEA
JBase Line - Minimum level of treatment in existence for practically all plants
within the industry.
2TOC for BPCTCA is estimated to be 2.2 x BOD. The TOC for BATEA is estimated
assuming 871 removal from BPCTCA levels (EN-384).
Source: EN-395
-------
weak ammonia liquor equalization and storage,
free and fixed leg ammonia still operation
with lime addition,
dephenolization,
sedimentation,
final cooler blowdown to dephenolizer,
benzol wastes blowdown to dephenolizer,
once-through crystallizer effluent to
sedimentation, and
pH neutralization.
The BATEA results, from controls established in
addition to BPCTCA, are as follows (EN-395):
recycle crystallizer effluent to final
cooler recycle system,
clarification,
multi-stage biological oxidation with
methanol addition, and
pressure filtration.
The most significant water wastes resulting from the
by-product coke plant are excess ammonia liquor, final cooling
water overflow, light oil recovery wastes, and indirect cooling
-131-
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water (EN-395). In addition, small volumes of water may result
from wharf drainage, quench water overflow and coal pile runoff.
Ammonia Liquor
In the reduction of coal to coke, the coal volatiles
are collected and cooled by spraying with water. This cooling
condenses a large portion of tar in the gas and the mixture
flows to a decanter tank. The partially cooled gas passes through
primary coolers where the temperature is further reduced. The
water and tar resulting from this operation are also pumped to
the decanter tank. Moisture in the coal accounts for the net
production of water from these cooling steps. The excess liquid
is the ammonia liquor and is the major single source of contami-
nated water from coke making.
Final Cooling Water Overflow
Direct contact of the gas in the final cooler with
sprays of water absorbs remaining soluble gas components and
removes condensed or solidified organics. This water is usually
recirculated. When a closed system is not used, this wastewater
may exceed the ammonia liquor as the major source of high con-
tamination loads (EN-395).
Light Oil Recovery Wastes
The light oil recovery system produces contaminated
wastewater from the stripping operations. Cooling water is also
discharged to the sewer.
-132-
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Indirect Cooling Water
Indirect cooling water is not usually considered waste,
but leaks in coils and tubes may contribute significantly to the
organic loading of this stream (EN-395).
Miscellaneous Effluents
Coke xtfharf drainage and stock pile runoff are minor
sources of effluents. These areas are usually trenched and the
wastewaters do not enter a receiving stream.
3.4.2.2 Beehive Coking
In the beehive process, air is admitted to the coking
chamber in controlled amounts to burn the volatile products dis-
tilled from the coal and to generate heat for further distilla-
tion. The beehive oven produces only coke and no successful
attempts have been made to recover the products of distillation.
The oven is charged from above and coking proceeds
from the top of the coal. At the end of the coking cycle the
coke is quenched in the oven with water and then the coke is
drawn from the oven. The process is very dirty and generates
smoke which discharges to the atmosphere when the brickwork
door is removed. Water is used only for coke quenching. The
use of recycle in the beehive process can greatly reduce the
the volume of wastewater. A properly controlled beehive oven
will have very little water discharge.
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3.5 Fossil Fuel Combustion
The fossil fuel combustion category examines the
organic emissions from external combustion stationary sources
as well as internal combustion stationary sources. External
combustion sources include steam-electric generating plants,
industrial boilers and furnaces, commercial and institutional
boilers, and commercial and residential space heating units.
Internal combustion stationary sources include internal com-
bustion engines used to generate electricity and engines used
to pump gas and other fluids.
Volatile organics from fossil fuel combustion are
discharged with the flue gases from the combustion unit. The
organics result from the incomplete combustion of the fuel.
Table 3.5-1 summarizes atmospheric organic emissions from fossil
fuel combustion in stationary sources. The organic water
effluents and solid wastes from fossil fuel combustion are
negligible. The magnitude of an overall reduction potential
for this category could not be determined from the available
literature. Assuming that catalytic converters could be
adapted to industrial internal combustion engines, a reduction
in that subgroup's emissions has been calculated. This is
discussed in Section 3.5.2.
3.5.1 External Combustion Stationary Sources
The external combustion sources are organized according
to the type of fuel burned in the unit. Coal, fuel oil, and
natural gas are the primary fuels used in stationary external
-134-
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TABLE 3.5-1
Fossil Fuel Combustion
Coal Combustion
Utility
Industrial
Residential
Commercial
Fuel Oil Combustion
Industrial/
Residential
Utility
Industrial
Residential
Commercial
Utility
Wood Combustion
Indus trial
Residential
FOSSIL FUEL COMBUSTION - ATMOSPHERIC EMISSIONS
Emissions (MT/yr)
Year
s tion
n
1975
1975
1975
1975
s tion
Commercial 1975
1975
1975
inbus tion
1972
1975
1975
1975
n
1972
1972
Volatile
Organics
105,000
55, AGO
11,700
8,900
56,400
24,300
20,800
76,400
12,400
1,800
1,700
28,000
4,300
Ref
1
1
1
2
1
2
1
3
2
1
1
3
3
-------
TABLE 3.5-1 (Cont'd.)
FOSSIL FUEL COMBUSTION - ATMOSPHERIC EMISSIONS
Emissions (MT/yr)
Internal Combustion
Natural Gas - Industrial
Fuel Oil - Utility
Natural Gas - Industrial
Year
1975
1975
1975
Volatile
Organics
237,000
68,200
11,800
Ref
4
4
4
OJ
cr.
i
TOTAL
724,000
References:
1.
2.
3.
4.
PU-036
MO-201
EN-226
AE-014
-------
combustion units. Wood is used in some instances and is a
significant source of atmospheric organic emissions. The follow-
ing sections discuss coal, oil, natural gas, and wood combustion
in externally fired units.
3.5.1.1 Coal Combustion
Coal is the most abundant fossil fuel in the United
States. It is burned to produce heat and steam in a wide variety
of furnaces ranging in size from small hand-fired units with
capacities of 4.5 to 9 kilograms (10 to 20 pounds) of coal per
hour to large pulverized-coal-fired units which may burn 275 to
360 MT (300 to 400 tons) of coal per hour. Approximately 480 x
10s MT (530 x 10s tons) of coal were consumed in 1972 to supply
thermal energy in the United States (US-205).
Atmospheric Emissions and Control
The combustion of coal in externally fired equipment
results in the emission of hydrocarbons and other organic
material if combustion is not complete. Due to variations in
combustion efficiency, organic emissions depend on the particular
size and type of combustion unit. Also, considerable variation
in organic emissions can occur depending on the operation of an
individual unit. Atmospheric organic emissions from coal
combustion in externally fired units are presented in Table 3.5-2.
Organic emissions from stationary combustion of coal
can be reduced by improved operating practices and improved
equipment design. Good operating practice is the most practical
technique available for controlling atmospheric organic
emissions from coal combustion. The combustion units should
always be operated within their design limits and according to
-137-
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the specifications recommended by the manufacturer to achieve a
high degree of combustion efficiency. Combustion units and
equipment should be kept in good repair to meet design specifi-
cations. Flue gas monitoring equipment is helpful in detecting
changes in the performance of the unit and thus is useful in
keeping organic emissions at a minimum.
The organic emissions from coal combustion may also
be controlled by improved equipment design. Improved design can
reduce emissions by reducing the quantity of fuel required for
a given energy output.
These organic emission controls provide some potential
for a reduction of emissions; however, no information is avail-
able concerning the percent reduction that can be expected. The
reduction potential is not anticipated to be large, however,
especially for the smaller units such as those found in commercial
and residential applications. Smaller units do not have air-fuel
mixing ability comparable to larger units. They operate at some-
what lower temperatures and therefore have lower average combustion
efficiencies.
TABLE 3.5-2
ATMOSPHERIC ORGANIC EMISSIONS
FROM COAL COMBUSTION
Source
Utility
Industrial
Residential
Commercial
Refs
1
1
2
1
Emiss
105
55
11
8
ions
.0
.4
.7
.9
X
X
X
X
(MT/yr)
103
103
103
103
Source: 1. PU-036
2. MO-201
-138-
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3.5.1.2 Fuel Oil Combustion
The two major types of fuel oil are residual and
distillate. Distillate fuel is primarily a domestic fuel, but
it is used in some commercial and industrial applications where
a high-quality oil is required. The primary differences between
residual oil and distillate oil are the higher ash and sulfur
content of residual oil and the fact that residual oil is much
more viscous and therefore harder to burn properly.
Atmospheric Emissions and Control
Organic emissions from fuel oil combustion are
dependent on type and size of equipment, method of firing, and
maintenance practices. Table 3.5-3 presents the estimates for
the yearly atmospheric emission rates of organics from fuel
oil combustion in externally fired units.
TABLE 3.5-3
ATMOSPHERIC ORGANIC EMISSIONS
FROM FUEL OIL COMBUSTION
Source
Refs
Industrial/Commercial 1
Residential 2
Utility
Sources :
1
1. PU-306
2. MO-201
Emissions (MT/yr)
56.4 x 103
24.3 x 103
20.8 x 103
These emissions can be reduced by good operating
practice and improved equipment design. No information was
found concerning the expected percent reduction of emissions
-139-
-------
through the application of these control methods. However, the
potential is not estimated to be very large.
3.5.1.3 Natural Gas Combustion
Natural gas has become one of the major fuels used
in the U.S. It is used primarily in power plants, industrial
heating, and domestic and commercial space heating. Marketed
production of natural gas in the United States in 1974 totaled
almost 600 billion cubic meters (22 trillion ft3) according
to the U.S. Bureau of Mines (US-474). The majority of this
total was used as fuel with most of the remainder going to
feedstock for chemical plants.
Atmospheric Emissions and Control
Natural gas is considered to be a relatively clean
fuel. However, some organic emissions do occur from its
combustion. When insufficient air is supplied to the combustion
unit, large amounts of volatile organic chemicals may be emitted
to the atmosphere. The emission from natural gas combustion
varies according to the type and size of equipment and attention
given to maintenance. Table 3.5-4 presents estimates for the
yearly atmospheric organic emission rates from natural gas
combustion in externally fired units.
The control of these emissions is accomplished in the
same manner as are the organic emissions from coal and oil
combustion. Proper operating practices and improved equipment
design allow for more efficient combustion of the gas/air mixture
and therefore reduce the quantity of hydrocarbons (and carbon
monoxide) emitted. No information was found which discussed the
percent reduction of emissions following application of these
-140-
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control methods. However, assuming most natural gas combustion
units operate in a reasonably efficient manner, the reduction
potential is not expected to be very large.
TABLE
3.5-4
ATMOSPHERIC ORGANIC EMISSIONS
FROM NATURAL
GAS COMBUSTION
Source
Industrial
Residential
Commercial
Utility
Sources: 1. EN-226
2. MO-201
3. PU-036
Wood Combustion
Refs Emissions
1 76.4 x
2 12.4 x
3 1.8 x
3 1.7 x
(MT/yr)
103
103
103
103
Wood is no longer a major energy source for industrial
heat or power generation. However, it is used as a domestic
heat source and to some extent in those industries which
generate considerable quantities of wood wastes. This section
is concerned with the combustion of wood in furnaces and resi-
dential fireplaces for process or space heating purposes. It is
not concerned with the burning of wood wastes as a means of
solid waste disposal.
Atmospheric Emissions and Control
Atmospheric organic emissions resulting from the
burning of wood in furnaces and fireplaces are due mostly to
-141-
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inefficient combustion. As with coal, oil, and gas combustion,
the size of the furnace and degree of maintenance affect the
quantity of hydrocarbons emitted. Another major factor is the
water content of the fuel. Moisture increases the atmospheric
organic emissions. Table 3.5-5 presents the yearly organic
atmospheric emissions from the external combustion of wood
(EN-226).
TABLE 3.5-5
ATMOSPHERIC ORGANIC EMISSIONS
FROM WOOD COMBUSTION
Source Emissions (MT/yr)
Industrial 28.0 x 10
Residential 4.3 x 10
Source: EN-226
The control of organic emissions from wood-fired
furnaces is best accomplished through the proper maintenance of
the combustion equipment. No information was found regarding
the percent reduction of emissions from applying proper mainte-
nance practices. The reduction potential for these emissions
may be moderate assuming that most wood-fueled furnaces are not
subject to regular maintenance. However, the percent reduction
cannot be determined from available literature.
3.5.2 Internal Combustion Stationary Sources
i
In general, sources included in this category are
internal combustion engines used in applications similar to
those associated with external combustion sources. This
category includes gas turbines and large, heavy-duty, general
-142-
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utility reciprocating engines. Most stationary internal com-
bustion engines are used to generate electric power, to pump
gas or other fluids, and to compress air for pneumatic machinery
Atmospheric Emissions and Control
The organic emissions from stationary internal
combustion sources result from incomplete combustion of the fuel
and subsequent discharge of the unburned hydrocarbons in the
exhaust. The organics emitted may contain components present
in the fuel as well as organics formed from the partial combus-
tion and thermal cracking of the fuel (aldehydes and low molecu-
lar weight saturated and unsaturated hydrocarbons).
Table 3.5-6 presents estimates of the quantities of
organics emitted yearly to the atmosphere from fuel oil and gas
combustion in stationary internal combustion engines (AE-014).
TABLE 3.5-6
ATMOSPHERIC ORGANIC EMISSIONS
FROM STATIONARY INTERNAL COMBUSTION SOURCES
Source Emissions (MT/yr)
Industrial - Gas 237.0 x 103
Utility - Oil 68.2 x 103
Utility - Gas 11.8 x 103
Source: AE-014
The quantity of organics emitted from these sources
may be minimized by proper operating practices and good mainte-
nance. The organic emissions could be essentially eliminated
through the application of catalytic converters to the engine
exhaust. For this reason, the percent reduction of these emis-
sions is assumed to be 99 percent. This results in a reduction
potential of nearly 314,000 MT organics/yr.
-143-
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3. 6 Organic_Chemic_al Processing
The organic chemical processing industries (OCPI)
convert hydrocarbons obtained mainly from petroleum, coal and
natural gas into synthetic intermediates and products. The
major products of these industries are synthetic organic chemicals
which include solvents, pesticides, plastics and resins, surface
active agents, elastomers, explosives, fibers, plasticizers, and
dyes and pigments. Processes normally considered as operations
of petroleum refining and natural gas and coal processing are
excluded from the OCPI. Figure 3.6-1 shows the relationships
between the industries and examples of organic chemicals pro-
cessed in the industries (RA-222).
3.6.1 Atmospheric Emissions
Organic pollutants may be emitted to the atmosphere
from organic chemical processing in various ways. Vented gases
from various process operations may contain organic compounds.
Vents are required for pressure control and removal of by-products
or inerts, and venting may be necessitated by upset conditions
in the plant. Other sources of organic pollutants considered
fugitive emissions include evaporation from storage tanks, load-
ing facilities, sampling, spillage, processing equipment leakage,
barometric condensers, cooling towers, and miscellaneous sources.
The quantity of volatile organics and organic' particu-
late emissions from significant processes and groups of processes
included in the OCPI has been estimated. Estimates for 140
operations which produce basic petrochemicals, synthetic organic
chemicals, or industrial organic chemical products are summarized
in Table A-l in the Appendix. The 140 products included in
Table A-l were selected on the basis of production volume data
and descriptions of processing from the literature (RA-222),
-144-
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BASIC PETROCHEMICALS
INDUSTRY
INDUSTRIAL ORGANIC
CHEMICALS INDUSTRY
DOWNSTREAM PROCESSING
INDUSTRIES
Produces Products From
Natural Gas and Petroleum
Refinery Streams:
Benzene
To 1u e n e
Xylenes
Naphthalene
Cresols
Ethylene
Propylene
Butylenes
Butadiene
Paraffins
Produces Some 400
Synthetic Organic
Intermediates From
Basic PetrocKemicals
Maj or Examples:
Acetic Acid
Cumene
Cyclohexane
E thyIbenzene
Ethylene Dichloride
Ethylene Glycol
Ethylene Oxide
Methanol
Phenol
S tyrene
Terephthalic Acid
Toluene
Urea
Vinyl Chloride
Produce Industrial
Organic Chemical Products
From Synthetic Inter-
mediates
Industry Examples;
Pes ticides
Organic Dyes and Pigments
Surfactants
Plastics and Resins
Elastomers
Synthetic Fibers
Explosives
Plast:
FIGURE 3.6-1
ORGANIC CHEMICAL PROCESSING INDUSTRIES
-------
ER-030, MO-201, EN-68). Generally, organic chemical intermediates
were included if their production volume exceeded 23,000 MT
(50 x 10s pounds) (RA-222) or if published emission rates were
greater than 1000 MT/yr. Table A-l gives production volumes
and the products are listed in order of decreasing quantities of
volatile organic emissions. The total estimated atmospheric
emissions from these industries are 1,400,000 MT/yr volatile
organics and 45,800 MT/yr organic particulates.
The best emission data was selected from estimates in
the literature (ER-030, PE-160, MO-201, EI-017, SH-241, HO-244,
PR-115, PR-116). Large discrepancies were found in the emission
estimates obtained from various sources; therefore, the quality
of each estimate was considered. Estimates were ranked by the
following index of uncertainty levels based on the quality of
the data used in making the estimate. Uncertainty levels are
given for each estimate in Table A-l.
Level Meaning
A Adequate data of reasonable accuracy
B Partially estimated data of indeterminate
accuracy
C Totally estimated data of indeterminate
accuracy
D No data; estimates based on generalized loss
factor
-146-
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Quantitative data on fugitive emissions from chemical
processes are extremely scarce. The available information is
generally based totally on estimated data and is not substantiated
by actual field tests. In some cases, fugitive emission estimates
have been based on "unexplained" losses appearing in material
balances around processing units. Estimates based on this type
of data are probably inaccurate, since the "unexplained" losses
represent small differences between large numbers subject to
metering and analytical inaccuracies.
Calculations of fugitive organic emissions from a
227,000 MT (500 x 108 pound) per year ethylene plant were done
in 1967 by Mencher (ME-136) using emission factors found in
Public Health Service Publication No. 763 for a plant practicing
stringent control. Organic losses from valves, pumps, compressors,
cooling water, relief valves, storage tanks, and other miscella-
neous losses were estimated to be equal to 0.21 percent of
throughput for the plant. Mencher stated that most calculations
of this sort show that the total emissions of hydrocarbons from
hydrocarbon processing plants range from 0.1 to 0.6 percent of
total plant throughput. The low value of 0.21 percent determined
for the ethylene plant is applicable to plants where stringent
control is practiced.
Fugitive emissions from petrochemical processing plants
were addressed by Pervier, et al. (PE-160) in a recent survey of
atmospheric emissions from the petrochemical industry. In these
survey reports, operators within the industry estimated that fugi-
tive emissions from their plants ranged from 0.01 to 2.0 percent
of throughput with an average of about 0.5 percent of throughput.
It has been concluded from the above information that
fugitive emissions from fossil fuel chemical processing plants
average about 0.5 percent of throughput and that process emissions
-147-
-------
average about 0.73 percent of throughput. The summation of these
emission factors gives the industry-wide total organics emission
factor of 1.23 percent of throughput.
Several investigations have concluded that emissions
during the production, conversion and handling of organic chemicals
range from about 0.5 to 2.0 percent of total production (ER-030).
The results of this study indicate that emissions from the OCPI
average 1.23 percent of total production, which is approximately
equal to the median value of the previous studies. This type of
emission factor is not necessarily applicable to individual pro-
cesses since emissions vary greatly with plant design, maintenance
and operational procedures, feedstocks, products, and other fac-
tors, but the factor appears to be applicable to the industry as
a whole.
Process emissions normally emanate from vents within a
plant. The volatile organics in these vent streams can be con-
trolled by conventional methods of controlling organic atmospheric
pollutants from stationary sources, i.e., combustion, condensation,
adsorption, absorption, and process changes. These controls can
be used to achieve almost a 100 percent removal efficiency. A
removal efficiency of 99 percent of volatile organics will be
assumed as feasible for vent streams in the OCPI in determining
reduction potentials. In most cases, further study will be
required to determine the economically feasible reduction poten-
tials for the various processes.
Organic particulate emissions in vent streams can be
reduced by conventional methods of particulate removal, i.e.,
mechanical collectors, electrostatic precipitators, scrubbers,
and filters. The removal efficiency of these devices varies
depending on design, operation, and particle size.
-148-
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Fugitive emissions can be minimized by various methods
including (ME-136):
1) Good housekeeping and maintenance practices.
2) Installation of floating roof tanks to control
evaporation of light hydrocarbons.
3) Installation of vapor recovery lines to vents
of vessels that are continually filled and
emptied.
4) Manifolding of purge lines used for startups
and shutdowns to vapor recovery or flare
systems.
5) Venting of vacuum jet exhaust lines to
suitable recovery positions or replacement
of vacuum jets with vacuum pumps.
6) Shipment of products by pipeline rather
than by railcar or trucks.
7) Covering of wastewater separators.
8) Discharging of relief valves to a flare
manifold.
In calculating the reduction potential associated with fugitive
emissions, stringent control practices will be assumed capable
of maintaining fugitive emissions at 0.21 percent of throughput
and that the industry's current, average emissions from fugitive
sources are equal to 0.50 percent of throughput. These values
inducate that a 58 percent reduction of fugitive emissions is
achievable by the application of stringent controls.
-149-
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Industry-wide reduction of volatile organic process
emissions by 99 percent and fugitive emissions by 58 percent
would result in the reduction of an estimated 1,270,000 MT
per year of volatile organic emissions. Descriptions of the
processes, emissions, and control techniques for the seven major
sources of volatile organic emissions and organic particulates
within the OCPI are given in Sections 3.6.1.1 through 3.6.2.3.
The reduction potential for each of the specific processes dis-
cussed is given in Table 3.6-1.
In general, the seven processes discussed, approximately
45 percent of the volatile organics emitted from the volatile
organics emitted from the industry, are large volume processes
which require major purge streams. These types" of process
emissions are amenable to conventional hydrocarbon control
techniques for stationary sources and represent the greatest
potentials for reduction within the industry.
3.6.1.1 Ammonia Production
Process Description
Ammonia is manufactured by the catalytic reaction of
hydrogen and nitrogen at high temperatures and pressures. In a
typical plant a hydrocarbon feed stream is desulfurized, mixed
with steam, and catalytically reformed to carbon monoxide and
hydrogen. Air is supplied to the secondary reformer to provide
oxygen and a nitrogen to hydrogen ratio of 1 to 3. The gases
enter a two-stage shaft converter where the carbon monoxide
reacts with steam to form carbon dioxide and hydrogen. The gas
stream is scrubbed to yield a gas containing less than 1 percent
C02. A methanator may be used to convert unreacted CO to inert
CFU before the gases are compressed and fed to the converter.
-150-
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TABLE 3.6-1
CONTROL OF ATMOSPHERIC EMISSIONS IN THE FOSSIL FUEL
CHEMICAL PROCESSING INDUSTRY
SUBCATEGORY
Ammonia
Carbon Black
Acrylonitrile
Ethylene Bichloride
Toluene
Carbon Tetrachloride
Soap and Detergent
AIR EMISSIONS (MT/YR)
VOLATILE ORGANICS REDUCTION
(ORGANIC PARTICULATES) POTENTIAL (%)
322,700 99
96,700 99
(3,670) nil
83,000
56,300
51,000
43,400
(18,400)
99
96
86
96
97
CONTROL METHODS
Fabric filters commonly
used, represent best control
""Volatile organic emissions can be controlled by conventional methods including incineration
adsorption, absorption, condensation, and various methods for reducing fugitive emissions.
Individual processes must be studied to determine best application of control devices.
IParticulate emissions can be controlled by conventional methods including settling chambers,
cyclones, electrostatic precipitators, scrubbers, and baghouses. Individual study of
processes is required to determine best application.
-------
Alternatively, the gases leaving the C02 scrubber may pass through
a CO scrubber and then to the converter. The synthesis gases are
converted to ammonia in the converter.
Atmospheric Emissions and Controls
The converted ammonia gases are partially recycled, and
the balance is cooled and compressed to liquefy the ammonia. The
noncondensable portion of the gas stream, consisting of unreacted
nitrogen, hydrogen, and traces of inert gases such as methane,
carbon monoxide, and argon, is largely recycled to the converter.
To prevent the accumulation of these inert gases some of the
noncondensable gases must be purged from the system. Atmospheric
emissions of purge gas produce 45 kg organics per MT of ammonia
(EN-071). The purge gas is sometimes scrubbed with water to
reduce atmospheric emissions of ammonia, but other organics are
not reduced by this control method. Fugitive organic emissions
from ammonia processes have not been estimated, but they are
probably negligible when compared to purge gas emissions.
The organic compounds in the purge gas stream can be
almost completely eliminated (approximately 99 percent removal)
by conventional methods of controlling organic emissions from
stationary sources. This reduction potential applied to the total
organic emissions from the ammonia process, 322,700 MT per year
(MO-201) , would result in a-reduction of 319,500 .MT organics
per year. These emissions are considered to be essentially
methane.
3.6.1.2 Carbon Black Production
Process Description
Carbon black is produced by the reaction of oil and/or
gas with a limited supply of air at temperatures of 1,370 to
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1,650°C. Three basic processes for producing carbon black
currently exist in the United States. They are the furnace
process, accounting for about 89 percent of production; the older
channel process, which accounts for less than 2 percent of pro-
duction; and the thermal process (SC-312) .
The channel process has the greatest potential for
atmospheric pollution; however, this process is unlikely to be
incorporated into any future plant designs and the single re-
maining plant in the United States may soon be phased out (RA-
222). Usage of the thermal process is expected to achieve only
limited growth. Effluent gases are recycled in this process;
therefore, there are essentially no atmospheric emissions (SC-
312). For these reasons, the channel and thermal processes do
not warrant further consideration in this report.
The furnace process employs either gas or oil as the
primary source of the carbon black. In either process, the fuel
is injected into a reactor with a limited supply of combustion
air. The processes are similar, but the furnace designs are
different.
The flue gases, largely carbon monoxide, hydrogen,
nitrogen, and water vapor, carry the carbon from the furnace to
a cooling tower where water sprays reduce the temperature to
about 260°C. Agglomeration of the fine black particles occurs
in either an electrostatic precipitator or cyclone collector.
The eletrostatic precipitator, when used, is generally followed
by cyclone collectors and bag filters. The gases are discharged
through the stack of the final collector directly to the atmos-
phere.
The recovered carbon black is transported to the finish-
ing area by screw or pneumatic conveyors where it is passed through
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a pulverizer to break up lumps. The carbon black is then con-
verted to pellets or beads by a x^et procedure. The wet product
is then sent to driers, screened, bagged, and sent to storage.
Atmospheric Emissions and Controls
An extensive engineering and cost study of air pollutior
control for carbon black manufacture by the furnace process has
been published (SC-312) and was the basis for this discussion.
The main process vent gas consists of the gross reactor
effluent plus quench water after recovery of carbon black. This
gas represents the main source of emissions from the carbon black
plant. For a "typical" 40,800 MT/yr (90 million Ib/yr) furnace
oil carbon black process, the vent stream emits about 318 kg of
hydrocarbons (methane and acetylene) and 11 kg of particulate
carbon black per hour (SC-312).
In carbon black plants where pneumatic conveyors are
used for moving products to the finishing area, the carrier gas
may be vented after recovery of entrained carbon black. Data
indicates that this stream can emit from 0.06 to 0.3 kg of carbon
black particulates per MT of production (SC-312). Some plants
use a closed loop system and eliminate this venting.
In most plants much of the hot gas used in the drying
operation does not come in direct contact with the carbon black
but is used as an indirect heat source and, therefore, contains
no entrained carbon black. The remainder of the hot gas, 35 to
70 percent, is charged directly to the drier interior for re-
moval of water vapor. This purge gas entrains carbon particles
and is usually vented after passing through a filter or water
scrubber for particulate removal. This vent stream typically
contains about 2 kg of carbon black particles per MT of product
(SC-312).
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Carbon black content of this baggage and storage area
vent stream varies depending upon the operations being performed
in the storage area. The storage and bagging areas are usually
within a building and a vacuum clean-up system which ejects
filtered air is typically included. No estimates of the quantity
of carbon black emitted from this vent were available.
Some plants vent the furnace reactors directly to the
atmosphere during reactor warm-up. This venting occurs only when
a new reactor is put into service to meet increased production
requirements. Reactor warm-up is accomplished by burning natural
gas before the reactor is put on line feeding only oil. Therefore,
essentially no carbon black or hydrocarbons are emitted during
this venting operation.
Particulate emissions can occur from a number of mis-
cellaneous sources including:
1. inadvertent spillages when drawing samples
from production line,
2. unplugging production line stoppages,
3. cleaning of process equipment and hopper
cars ,
4. leaks in process equipment,
5. bagging operation of hopper cars, and
6. bags torn during stacking in warehouses or
loading and unloading of box cars or trucks.
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Miscellaneous carbon black losses equal about 0.1 kg/MT of product
(SC-312). No fugitive emissions of volatile organics were re-
ported in the literature.
Based upon observations and economics, the best feasible
air pollution control system for existing carbon black plants
would include bag filters for recovery of product from combus-
tion process vent gas, entrained carbon black from driers, and
product finishing vent gas streams. In addition, a plume burner
or flare system, depending upon the off-gas heating value, should
be used to combust burnable material in the effluent of the pro-
cess vent gas filter. The drier vent should also be burned if
it contains combustible material. The best control systems for
new plants would include the above equipment plus a waste heat
boiler and steam driven process equipment. The implementation
of these controls would essentially eliminate the emissions of
volatile organics from the furnace carbon black process and
result in a reduction of approximately 96,700 MT hydrocarbons
per>iyear. Bag filters are commonly us.ed for product recovery
in furnace carbon black plants (SC-132); since this represents
the best control method, the reduction potential for particulates
is considered negligible.
3.6.1.3 Acrylonitrile Production
Process Description
Acrylonitrile is produced in the U.S. by the Sohio
version of the ammoxidation of propylene. In this vapor-phase
catalytic process , approximately stoichiometric proportions of
air, ammonia, and propylene are fed to a fluid bed reactor at
400-510°C. Prior to 1972, an antimony-uranium oxide system
(Catalyst 21) was used as a reaction catalyst. Since that time,
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a new catalyst (Catalyst 41) has been introduced which increases
the yield of acrylonitrile and hydrogen cyanide and produces 35
percent less hydrocarbon emissions. Catalyst 41 is gradually
replacing the older catalyst.
The reaction is exothermic and heat removal is required.
The reaction heat is usually used to generate steam, and the cooled
effluent is then sent to a water quench tower where unconverted
ammonia is neutralized. The stream is then fed to a water absor-
ber-stripper system where reaction products are recovered and
inert gases are rejected. The reaction product stream contains
acetonitrile, acrylonitrile, and hydrogen cyanide. This stream
is usually fractionated to remove HCN and then acetonitrile is
separated from the tower bottoms by extractive distillation
using water as the extraction solvent. The final two steps
involve drying of the acrylonitrile stream and distillation to
remove heavy ends.
Atmospheric Emissions and Controls
An extensive engineering and cost study of air pollution
control for acrylonitrile manufacture has been published and
was the basis for this discussion (SC-287).
The main process gas vent from the absorber is the
chief source of air emissions from the process. The composition
and flow rate of the vent gas vary somewhat depending on the
type of catalyst and reactor conditions. In a 90,700 MT per
year plant, the vent gas flow averages about 9,220 moles per
hour if Catalyst 21 is used and about 7,180 moles per hour if
Catalyst 41 is used. The organic content of the vent gas is
normally 0.4-1.7 mole percent using Catalyst 21 and 0.8 mole per-
cent with Catalyst 41. The volatile organics consist primarily
of propylene, propane, and acetonitrile. All plants use a mist
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eliminator on this stream to remove entrained water. However, no
additional air pollution control devices are currently used on
this stream.
The product fractionation vent is a small vent stream
which varies greatly in composition depending upon the type of
product recovery system used. Normally the vent streams from the
fractionation system are combined and sent to an incinerator
or flare.
The production of acetonitrile and hydrogen cyanide
by-products usually exceeds demand and the excess production is
sent to an incinerator. The composition of this material would
be expected to result in emissions of volatile organics and
other pollutants.
A plant start-up usually occurs every one or two years.
During this operation, the reactor effluent may be directly vented
to the atmosphere. A start-up normally requires less than one
hour. Vent streams resulting from plant upsets or other emer-
gencies are diverted to the flare stack or by-product incinerator.
Therefore, emissions resulting from these occurrences are minimal.
Fugitive emissions result from vents on acrylonitrile
and acetonitrile storage tanks xvhich are directly vented to the
atmosphere. In some cases, conservation type vents are employed
on these tanks. Hydrogen cyanide is stored under a positive
pressure and vapors are normally cooled to recover hydrogen
cyanide and then sent to incinerators. No quantitative estimates
of organic emissions from these or other fugitive emissions
sources were made..
The use of Catalyst 41 instead of Catalyst 21 reduces
hydrocarbon emissions from the process by approximately 35 percent
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The most feasible control method for future reductions of organic
air emissions would be to provide a thermal incinerator on the
absorber vent. Plants using Catalyst 21 and thermal incineration
of the absorber vent stream would emit approximately 0.5 kg of
hydrocarbons per MT of production, or less than 1 percent of the
165 kg per MT of hydrocarbons emitted by a typical plant using
Catalyst 21 without an incinerator. The application of these
control methods to acrylonitrile plants would result in an esti-
mated reduction of 82,000 MT per year of volatile organic emis-
sions .
3.6.1.4 Ethylene Dichloride Production
Ethylene dichloride (EDC) is produced from ethylene
by either a direct or oxychlorination process. Most EDC plants
are based on a balanced combination of these two processes. About
58 percent of the EDC is produced by direct chlorination and the
remaining portion by oxychlorination (SC-316). Both of these
processes have significant environmental impacts and will be
discussed.
3.6.1.4.1 Process Descriptions
Direct Chlorination
Stoichiometric quantities of chlorine and ethylene
are fed to the bottom of a tower-type reactor filled with liquid
EDC and a ferric chloride catalyst. The reactor operates at
about 43°C and 2 kg per cm2 (PE-160). The top of the column is
a fractionator. The vapors exiting the column pass condensers
and then absorbers to remove EDC, hydrogen chloride, and
chlorine. The crude EDC is washed with a dilute caustic solution
and then dried. In some plants the EDC undergoes a final dis-
tillation to remove heavy ends.
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Oxychlorination
Approximately stoichiometric amounts of ethylene,
anhydrous hydrogen chloride, and air (or oxygen) are fed to a
catalytic reactor operating at 200-300°C (SC-316). The reactor
effluent is initially cooled by either a direct water quench or
indirect heat exchange. After further cooling, the partially
condensed effluent is sent to a phase separator. Noncondensable
gases, primarily nitrogen, are vented to the atmosphere. Usually
the gases are contacted with either water or an aromatic solvent
for removal of hydrogen chloride and EDC recovery. The crude
EDC from the separator undergoes the same final processing steps
as in the direct process .
3.6.1.4.2 Atmospheric Emissions
Engineering and cost studies of air pollution control
for EDC manufacture have been published (PE-160, SC-316). These
reports provide the basis for the discussion of emissions and
controls.
Direct_Process
The scrubbing column vent is the major source of air
emissions from the direct chlorination process. The stream
contains small amounts of ethylene, ethylene dichloride, vinyl
chloride, ethyl chloride, and inert impurities in the feed.
About 4.7 kg of organic compounds are emitted from this source
per MT of EDC produced.
Fugitive emissions from leaks, spills, and miscellaneous
causes are estimated to be 0.71 kg per MT of EDC produced. EDC
storage tanks are usually vented directly to the atmosphere.
Emissions are reduced in some cases by nitrogen padding. Storage
losses are equal to about 0.6 kg per MT of EDC produced.
-160-
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Oxychlorination Process
The main process vent gas stream usually is vented
from a scrubber and is the primary air emission source in the
process. The stream consists of the gross reactor effluent after
quenching and trim cooling to recover EDC. The vent stream flow
averages about 36 MT per hour (2740 moles per hour) in a typical
318,000 MT per year (700 million pounds per year) EDC plant.
The organic fraction of the stream normally ranges from 0.27 to
11.2 mole percent consisting primarily of ethylene, ethane, EDC,
ethyl chloride, and methane (if present in the feed). The quantity
and composition of the stream vary depending on factors such as
feed purity, catalyst activity, reactor operating conditions,
and the specific processing scheme employed.
The product fractionation vent is a small stream which
varies greatly in composition, depending upon the type of frac-
tionation system used and the final product purity. Fugitive
emissions are reported to be "minor". EDC storage tanks are
vented directly to the atmosphere and losses are estimated to be
about 0.6 kg per MT of EDC produced.
3.6.1.4.3 Control of Emissions
The organic emissions from vent streams in both pro-
cesses can be eliminated by thermal incineration of the streams.
Emissions from the fractionation area can be controlled by vent
condensers. An incinerator should be followed by an absorber
to remove any hydrogen chloride produced in the incinerator.
Fugitive emissions can be reduced by stringent application of
controls such as good housekeeping and maintenance practices and
installation of floating roof tanks. The reduction potential
which could be achieved by the application of these control
methods is estimated to be 55,400 MT of volatile organics per
year.
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3.6.1.5 Toluene Production
Process Description
Approximately 85 percent of the recovered toluene is
isolated from petroleum refinery catalytic reformate, approxi-
mately 12 percent is obtained from pyrolysis gasoline (a by-
product of olefin manufacture), and the remainder comes from
coke-oven light oil and as a by-product of styrene manufacture
(HE-154).
Several methods are used for extracting aromatics from
reformate. These methods include extractive distillation, liquid/
liquid extraction, and adsorption on silica gel. The favored
method is solvent extraction using sulfonane (CA-303).
In the extraction process, feed is introduced to the
center of a continuous countercurrent-extraction column. The
rich solvent is charged to a stripper. A fraction is removed
overhead and the partially stripped extract is further distilled
to recover the aromatics. The raffinate and extract are water
washed to recover small amounts of entrained solvents.
In obtaining aromatics from pyrolysis gasoline, the
feed must first be stabilized by hydrotreating prior to the
recovery of aromatics by solvent extraction. The feedstock and
recycled hydrogen are preheated and passed through a series of
hydrotreating reactors containing a platinum catalyst. The
reactor effluent is cooled and discharged into a separator. The
gas stream taken overhead is scrubbed with caustic solution and
recycled to the reactor. The liquid phase from the separator
is passed through a coaleser where water is used to trap coke
particles and a stabilizer where light hydrocarbons are removed.
The stabilized liquid is then extracted with a solvent to recover
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aromatics in a process similar to that discussed above for
recovering aromatics from catalytic reformate.
Atmospheric Emissions and Control
No data is available concerning atmospheric emissions
from these processes for producing toluene. The total emissions
from the processes are estimated to be 1.5 percent of the pro-
duct (ER-030). This estimate was based on the normal range of
emissions occurring from the production, conversion, and handling
of organic chemicals (0.5 - 2.0 percent) and was adjusted for
the volatility and solubility of toluene. It is also estimated
that the fugitive emissions from the processes are equal to
one-third of the total emissions (0.5 percent) based on the in-
dustry average (PE-160, ME-136).
Process (vent) emissions can be almost completely
eliminated (approximately 99 percent reduction) by conventional
methods, i.e., condensation, incineration, adsorption, etc. The
fugitive emissions can be reduced to about 0.21 percent (ME-136)
of throughput by stringent maintenance. Based on these reduction
potentials and the emissions estimates, the annual volatile
organic emissions from toluene manufacturing processes could be
reduced by about 43,800 MT per year.
3.6.1.6 Carbon Tetrachloride Production
3.6.1.6.1 Process Descriptions
Carbon tetrachloride is made by the following three
industrial processes:
(1) thermal chlorination of methane,
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(2) thermal chlorination of propane, and
(3) chlorination of carbon disulfide.
In 1970, approximately 40 percent of the carbon tetrachloride
was produced by the first process, about 35 percent by the second
process, and the remainder by the third process (PR-116).
Chlorination of Methane
This process involves four main steps: (1) reaction,
(2) hydrogen chloride recovery, (3) chlorides recovery, and
(4) chlorides refining. High purity methane, recycle methane,
and chlorine are mixed and fed to the reactor operating at 400°
to 500°C. The reactor effluent is cooled and fed to the HC1
recovery system. This system consists of two columns; in the
first, the hydrogen chloride is absorbed in water and the second
column strips anhydrous HC1.
The HCl-free gases from the absorber are scrubbed
with caustic soda to remove final traces of HC1 and are fed to
chlorides recovery. Compression, cooling, and distillation
are used to separate the carbon tetrachloride and by-products.
Unreacted methane is separated, dryed with sulfuric acid in the
dehydrator column, and recycled.
Thermal Chlorination of Propane
Chlorine and propane feeds are introduced to a vaporizor
where they are mixed with recycled chlorides. The gases are fed
to an adiabatic reactor which operates at atmospheric pressure
and 550° to 700°C. The reactor effluent is essentially free of
unreacted hydrocarbon and consists mainly of carbon tetrachloride,
perchloroethylene, HC1 and excess chlorine. The effluent is
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rapidly quenched by contact with a liquid which is largely per-
chloroethylene. The cooled effluent is fed to a column which
separates perchloroethylene as a bottoms stream. Carbon tetra-
chloride is withdrawn from the condenser as a liquid, and hydro-
gen chloride, chlorine, and traces of hydrocarbon gases and
removed overhead. The vapor stream is scrubbed with water to
remove hydrogen chloride, dried with concentrated sulfuric acid,
and recycled to feed. A portion of the dried gas is purged to
remove inerts.
Carbon Bisulfide Chlorination
Both direct and indirect chlorination of carbon di-
sulfide are employed industrially. In the direct process, a
recycled mixture of carbon tetrachloride, carbon disulfide and
sulfur chlorides is contacted with excess chlorine over an iron
catalyst at approximatley 30°C. Distillation of the reactor
effluent yields an overhead product of relatively pure carbon
tetrachloride. This material may be treated with a base, to
remove sulfur chlorides, and then dried.
The indirect process is similar. Fresh carbon disulfide
feed is reacted with sulfur monochloride. A direct-chlorination
polishing reactor is used to convert residual carbon disulfide
and to facilitate the subsequent distillation, where crude carbon
tetrachloride is removed overhead and molten sulfur containing
some sulfur monochloride is the bottoms product. The crude
carbon tetrachloride may be purified as in the direct chlorina-
tion process.
3.6.1.6.2 Atmospheric Emissions and Control
Processes for the thermal chlorination of both methane
and propane require continuous purging of recycled vapor for
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inerts removal. The methane process is vented at the dehydrator
column. The streams contain both raw materials and chlorinated
materials. One estimate of the quantities of the organic com-
pounds emitted from the methane based process is shown below
(PR-116).
Quantity Emitted
Compound (kg/NT Product)
CH3C1 13
CH2C12 2
CH, 1
ecu i
CC13H 1
The dry chlorine recycle in the propane process is purged. Chlo-
rine is the major pollutant in this stream, but trace quantities
of chlorocarbons are expected to be present. No estimates of
the quantities of these organic compounds in the purge stream
were available. Reportedly, no organic control devices are
utilized on these purge streams.
The vent from the neutralizer in the carbon disulfide
process contains an estimated 2 kg CS2 and 14 kg CCU per MT of
product (PR-116).
No estimates of fugitive emissions from the carbon
tetrachloride manufacturing processes were available. However,
unexplained (fugitive) losses were included in the total emissions
estimate, 43,398 MT of organics from the methane and carbon di-
sulfide processes, in 1973 (MO-201)*. These losses were deter-
mined by material balances, conversion, and yield data for the
processes.
"This estimate indicates that the total emissions from the process
are equal to approximately 9.4 percent of the weight of the total
tetrachloride production. This base factor seems abnormally high.
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Approximately 99 percent of the organic compounds in
the process vent streams can be eliminated by conventional control
methods, i.e. condensation, incineration, adsorption, etc. If
incineration is used for vent stream control, the incinerator
or afterburner should be followed by a scrubber to remove HC1
formed by the combustion of the chlorocarbons. Fugitive emissions
and storage losses can be reduced from the estimated industry
average of about 0.5 percent of throughput to about 0.21 percent
of throughput by stringent maintenance (ME-136).
Application of these potential reductions to the esti-
mated total emissions from carbon tetrachloride manufacture
indicates a reduction potential of about 41,700 MT/yr.
3.6.1.7 Soap andJDetergent Manufacture
Process Description
Soap is manufactured by the catalytic hydrolysis of
various fats or oils to produce fatty oils which are then neutra-
lized or "saponified" with sodium or potassium hydroxide to
form the soap. Glycerin may be generated as a by-product of
fatty acid manufacture or as a by-product from saponification
of the fatty acid in the kettle-boil process. The glycerin is
concentrated to 80 percent and refined by distillation.
Detergent manufacture generally begins with sulfuration
by sulfuric acid of a fatty alcohol or linear alkylate. The
sulfurated compound is neutralized, and various dyes, perfumes,
and other compounds are added. The resulting paste or slurry is
then sprayed into a vertical drying tower where it is dried with
a stream of hot air. The dried product is cooled and packaged.
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Atmospheric Emissions and Control
The major air pollutants in the manufacture of soap and
detergent are odor and particulates. Odors may be controlled by
scrubbing all exhaust fumes and, if necessary, incinerating the
remaining compounds. Uncontrolled particulate emissions are
about 45 kg per MT of dried detergent and 7.5 kg per MT of soap
produced (EN-071, HO-244). Application of the best particulate
control system (combinations of cyclones, scrubbers, etc.) can
reduce the particulate emissions to approximately 0.22 kg per
MT of dried detergent and 0.013 kg per MT of soap produced
(HO-244). The reduction of particulate emissions to these levels
would result in the reduction of an estimated 17,900 MT per year
of organic particulates.
3.6.2 Water Effluents
Wastewater sources within the organic chemical pro-
cessing industry can be divided into the following five general
categories (JE-027):
1. wastes containing raw material or product
resulting from the stripping of the product
from solution;
2. by-products;
3. spills, slab washdowns, vessel cleanouts,
sample overflows, etc;
4. cooling tower and boiler blowdown, steam
condensate, water-treatment wastes, and
general washing water; and
5. storm run-off.
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The large variety of compounds produced by the organic
chemical processing industry makes characterization and treat-
ment of wastewaters difficult and complex. Wastewaters from
plants manufacturing similar or even the same products usually
have dissimilar characteristics. These differences can be
ascribed to the use of different manufacturing processes, operat-
ing procedures and by-product disposal practices. The wastes
are, however, related to the method of water usage associated
with the various manufacturing processes. The organic chemicals
industry has been subcategorized (EN-153) by the type of process
water usage in the processes. Process water is defined as all
water coming in contact with chemicals within the process and
includes:
1. water required or produced in the
chemical reaction;
2. water used as a solvent or as an aqueous
reaction medium;
3. water entering the process with a reactant
or which is used as a diluent;
4. water associated with a catalyst system,
either during the reaction or during
catalyst regeneration;
5. water used as an absorbent or as a
scrubbing medium for separation purposes;
6. steam used in steam stripping operations;
7. water used to wash, remove, or separate
chemicals from the reaction mixture;
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8. water associated with mechanical devices such
as steam jet ejectors;
9. water used as a quench or direct contact
coolant;
10. water used to clean or purge equipment; and
11. runoff or wash water associated with the
process area.
Four process-oriented subcategories describing mode
of water usage have been established for the organic chemicals
industry. Subcategories A, B, and C relate to continuous pro-
cesses, while subcategory D relates to batch processes. These
subcategories were further described by waste loads from pro-
cesses within the subcategories. The subcategories are described
as follows (EN-153):
A. Nonaqueous Processes
Minimal contact occurs between water and reactants or
products within the process. Water is not required as a reactant
or diluent and is not a reaction product. The only water usage
stems from periodic washes of working fluids or catalyst hydra-
tion.
B. Processes with Process Water Contact as Steam
Diluent or Absorbent
Process water usage is in the form of diluent steam,
a direct contact quench, or as. an absorbent for reactor effluent
gases. Reactions are all vapor phase and occur over solid cata-
lysts. Most processes have an absorber coupled with steam
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stripping of chemicals for purification and recycle. Steam is
also used for catalyst de-coking.
C. Continuous Liquid-Phase Reaction Systems
Process water usage involves liquid-phase reactions
where the catalyst is in an aqueous medium. Additional water
may be required for final purification or neutralization of
products.
D. Batch and Semicontinuous Processes
Processes are carried out in reaction kettles. Many
reactions are liquid-phase with aqueous catalyst systems. Filter
presses and centrifuges are commonly used to separate solid pro-
ducts from liquid.
Raw waste load (RWL) data were obtained in field surveys
of representative processes for the four subcategories (EN-157).
These data are summarized in Table 3.6-2. The RWL's associated
with the continuous processes are based on contact process water
only. Most continuous processes achieve segregation and do not
include noncontact cooling water or steam. Subcategory D in-
cludes all wastewater associated with the process.
The RWL's for the various processes of the OCPI were
estimated from data generated in the above study and similar
studies made for various segments of organic chemical industry
(EN-385, EN-160, EN-154, EN-162, EN-384). The RWL's were derived
from data on the specific processes xvhenever possible. When data
was unavailable for a process, its RWL was estimated by using the
average RWL of the subcategory to which it was assigned.
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TABLE 3.6-2
Cone .
Cone .
Cone .
Cone .
Category
A
Range
11
Range
C
Range
D
Range
MAJOR
Flow
gal. /I
0.25
50
30
10,000
RWL's OF
RWL
,000 Ib
- 2,000
- 3,000
- 3,000
- 100,000
POLLUTANT
HOD 5
I.'S RASED ON
RWL
kg/MT(mg/£)
0.1 -
(400 -
0.09 -
(50 -
1.3 -
(3,000 -
52 -
(100 -
0..13
1,000)
7.0
500)
125
10,000)
220
3,000)
PROCESS WAS
COD
TEWATER USE
RWL
kg/MT(mg/«.)
0.3 -
(200 -
0.47 -
(200 -
1.9 -
(10,000 -
180 -
(1,000 -
3.7
10,000)
21.5
5,000)
385
50,000)
4., 800
10,000)
TOG RW
kg/MT(mg/£)
0.034 - 0.9
(50 - 2,000)
0.2 - 40
(100 - 2,000)
1.5 - 150
(3,000 - 15,000)
60 - 1,600
(200 - 2,000)
-------
Three different levels of treatment to reduce the dis-
charge of aqueous pollutants have been designated. These levels
of treatment are listed below; the first two are applicable to
existing plants and the third to new plants.
Best Practicable Control Technology Currently Available
(BPCTCA) (by 7-1-77)
Best Available Technology Economically Achievable
(BATEA) (by 7-1-83)
Best Available Demonstrated Control Technology
(BADCT) (new sources)
Effluent limitation guidelines have been defined for
the various processes in the previously mentioned development
documents. Many alternate systems of end-of-pipe wastewater
treatment and in-process modification and pollution control
equipment exist. Individual manufacturers select specific com-
binations of pollution control measures best suited for complying
with the published limitations and standards.
BPCTCA and Current Effluent Estimates
BPCTCA for the organic chemicals industry includes both
in-process controls and end-of-process treatment technologies.
These technologies are exemplary of those for the entire OCPI.
Waste characterization studies indicate which contami-
nated contact process water streams can be segregated from non-
contaminated streams to reduce the waste volume to be treated
in a centralized waste treatment plant. In addition, process
water streams can be characterized by the ease with which certain
constituents can be recovered or difficulty of ultimately treating
the wastes.
-173-
-------
BPCTCA process modifications include the substitution
of nonaqueous media for carrying out the reaction or purifying
the products. Changes in the reactants, reactant purity, or
catalyst systems can sometimes eliminate aqueous waste by-products
Reuse of water within the process also should be investigated.
Equipment for separation of an organic phase from aqueous phase
are provided with backup coalescers or polishing filters for the
aqueous phase. Direct vacuum-jet condensers replace indirect
condensers or vacuum pumps.
In addition to waste reductions through the above
practices , recovery of products and by-products can be combined
with wastewater purification. Chemical recovery from the waste-
waters includes physical separation of the chemicals from the
wastewater as well as subjecting the wastewaters to additional
chemical reactions that will render them more amenable to recovery
and purification.
End-of-process treatment technologies commensurate with
BPCTCA are based on the utilization of biological oxidation
systems including activated sludge, extended aeration, aerated
lagoons, trickling filters, and anaerobic and floculative lagoons.
These systems include additional treatment operations such as
equalization, neutralization, primary clarifications with oil
removal, nutrient addition, and effluent polishing steps such
as coagulation, sedimentation, and filtration. Effluent sus-
pended solids (primarily biological solids) are expected to be
maintained below 60 mg/liter for the maximum 30-day average (EN-
153). The waste reduction factors shown in Table 3.6-3 are con-
sistent with BPCTCA (SI-105):
-174-
-------
A
B-l
B-2
C-l
C-2
D
BOD s
90
90
98
95
99
95
TABLE 3.6-3
WASTE REDUCTION FACTORS ACHIEVABLE
THROUGH USE OF BPCTCA LEVEL OF WATER TREATMENT
Process Water Use BPCTCA Reduction of RWL Median
Subcategory Values (70)
COD1
75
75
75
75
75
75
!COD effluent limitations have not been specified
for BPCTCA.
For quantifying emissions in this report, current
effluents from the various processes are assumed at the levels
achievable by application of BPCTCA required in 1977. The total
quantity of pollutants was estimated using production data from
the most recent available year along with COD, BOD5, SS, and
TOG emissions based on BPCTCA. The quantity of pollutants
emitted after application of BPCTCA was estimated by either
applying reduction factors for BPCTCA to the estimated RWL.'s or
by utilization of the published effluent limitations (maximum
average of daily values for any period of 30 consecutive days).
The first method was normally used to estimate effluent COD,
since BPCTCA effluent limitations for most segments of the
industry do not include COD values. The latter method was
usually used to estimate effluent BOD5 and SS. The 30-day
maximum average limitation allows for normal variations of
exemplary designed and operated waste treatment systems; there-
fore, this method probably gives a somewhat high estimate of
effluent concentrations.
-175-
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The estimated current emissions from the processes
within the organic chemical processing industries are presented
in Table A-2 in the Appendix. The accuracy of these estimates
is questionable due to the assumptions involved in making the
estimates and the differences noted previously between processes
which produce similar or even the same products.
BATEA and Reduction Potential
The BATEA is based upon the most exemplary combination
of in-process and end-of-process treatment and control technologies
The following in-process controls are included:
1. the substitution of noncontact heat exchangers
for direct contact water cooling;
2. the use of nonaqueous quench media where direct
contact quench is required;
3. the recycle and reuse (after treatment) of water,
where possible;
4. the use of process water to produce low pressure
steam by noncontact heat exchangers in reflux
condensers of distillation columns;
5. the recovery of spent acids or caustic solutions
for reuse;
6. the recovery and reuse of spent catalyst solutions;
and
7. the use of nonaqueous solvents for extraction
of products.
-176-
-------
The model end-of-process treatment system-was determined to be
biological treatment followed by filtration and additional
activated carbon treatment.
This model system or equivalent combinations can pro-
vide 90 percent BOD5 and 69 percent COD reductions below BPCTCA
effluents. The SS BATEA effluent limitations average approximately
45 percent of BPCTCA limitations. The TOG BATEA levels average
about 87 percent reduction below BPCTCA.
The reduction potentials for organic water pollutants
in the organic chemical processing industry were calculated from
the difference between effluents with BPCTCA systems and BATEA
systems. These differences were usually estimated by one of
three methods: (1) application of the reduction factors for
BATEA to the estimated effluents with BPCTCA; (2) use of the
difference between the published effluent limitations (maximum
30-day averages) for BPCTCA and BATEA; or (3) reductions below
BPCTCA effluent levels by control methods applicable to a specific
process. The specific processes found to be the largest sources
of organic water pollutants within the industry are discussed
in detail in the following section. The BOD5, COD, TOG, and
total organics in effluents from these processes and their
reduction potentials are shown in Table 3.6-4.
The concentration of total organics in the effluents
was estimated from the TOC values for BPCTCA and BATEA. The
TOG values were assumed to result from the major product of
the process or, for processes such as polymers, the major feed-
stock of the process. This assumes that the by-products are
similar to the feedstock or product. This assumption does not
consider other materials that can add to the waste load such as
organic diluents, inhibiters, or lubricants. To calculate total
organics, the TOC values were multiplied by the ratio of molecular
-177-
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TABLE 3.6-4
CO
MAJOR WATER EFFLUENTS FROM THE
ORGANIC CHEMICAL PROCESSING
Effluent: Parameters
RWL
(MT/yr)
BPCTCA
(MT/yr)
INDUSTRY
BATEA
(MT/yr)
Reduction Potential1
(MT/yr)
Dyes and Pigments
Po
BODS
COD
TOG
Total Organics
lyvinyl Chloride and
63
262
72
144
,300
,000
,300
,600
8,230
73
30
60
,300
,400
,800
905
22,700
3,950
7,900
7
50
26
52
,325
,600
,450
,900
Copolymers
Me
BOD5
COD
TOG
Total Organic
thyl Methacrylate
BODS
COD
TOG
Total Organics
11
51
29
76
13
112
44
73
,800
,700
,700
,600
,000
,000
,100
,600
1
14
12
32
1
31
18
30
,532
,500
,500
,300
,690
,300
,500
,900
168
4,490
1,620
4,180
186
9,720
2,410
4,020
1
10
10
28
1
21
16
26
,364
,010
,880
,120
,504
,580
,090
,880
Reduction Potential calculated from the difference between BPCTCA and BATEA.
-------
weights shown in equation 1, where MW product is the molecular
weight of the process product or feedstock.
(MW )
Product x (TOG) = Total Organics
(MW , )
x carbon'
3.6.2.1 Dyes and Pigment Production
Process Description
The organic dyes and pigments industry converts inter-
mediate organic chemicals into more complex materials and
ultimately into dyes and pigments. The industry is extremely
complex due to the diversity of the products. The organic dyes
and pigments industry in the United States sells more than 1000
different products.
Because of the large number of compounds that are
produced, most dyes and pigments are produced in small batches.
A total of forty-eight processes summarize the operations carried
out in manufacturing dyes and pigments (RA-222). Detailed dis-
cussions of these operations will not be included in this report;
however, the great majority of dyes and pigments are manufactured
by processes similar to a typical azo dye manufacturing process
(EN-153).
Raw materials (including aromatic hydrocarbons, inter-
mediates , various acids and alkalies, and solvents) are fed into
the reactor which normally operates at atmospheric pressure.
The reactions are exothermic and temperature control is accom-
plished primarily by direct addition of ice to the reactor. Jacket
cooling is also commonly practiced.
-179-
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The dye particles precipitate from the reaction mix-
ture. The vent gases from the reactor are scrubbed with water
before being discharged into the atmosphere. The liquid effluent
from the reactor is treated in a plate-and-frame filter press
where the dye particles are separated from the mother liquor.
The mother liquor is either directly discharged into sewers or
treated to recover some of the metal salts. The moist cake is
discharged into shallow trays which are placed in a circulating
air dryer. Vacuum dryers and drum dryers may also be used. The
dried dye is ground and mixed with a diluent, such as salt, to
make it uniform in color strength.
Water Effluents and Control
The major water pollution sources from the azo dye
process are the mother liquor from the filter press, intermittant
reactor clean-up waters, the draw-off from the vent gas scrubber,
and general cleaning waters. Because of the frequent changing of
feed materials and products, large amounts of water and cleaning
aids are required to clean reactors and filter presses.
Plant wastewater surveys have been conducted at dye
and pigment plants (EN-385). The RWL's were found to vary
greatly, due to the batch nature of the processes. The high
organic loading in the wastewater is due primarily to incomplete
crystallization and separation of the products from the mother
liquor. Organic losses and cleaning aids also contribute to
the organic loading.
Noncontact cooling water is discharged into sewers to
dilute the wastewaters to be treated. Reuse or recycle of the
wastewater from this type of process is considered unfeasible
because the wastewater is contaminated with salts, metal ions,
and a high color intensity (EN-153).
-180-
-------
The application of BATEA will reduce effluents of BOD5,
COD, and SS by approximately 90, 69, and 55 percent, respectively,
below effluent with BPCTCA (EN-153). By utilizing these reduction
factors, annual effluents from dye and pigment plants could be
reduced by about 52,900 MT of organic/yr. The BOD5, COD, TOG and
organic loads are presented in Table 3.6-2.
'3.6.2.2 Polyvinyl Chloride Production
Process Description
Polyvinyl chloride (PVC) is produced by a free radical
polymerization of vinyl .chloride. All vinyl chloride polymeriza-
tions are conducted in batch operations at low temperature and
pressure. PVC is primarily made by suspension polymerization,
but it may also be made by bulk polymerization or emulsion
polymerization (HE-154).
In emulsion and suspension polymerization the vinyl
chloride monomer is dispersed in an aqueous phase during the
reaction. Some technical differences between emulsion and sus-
pension systems pertain to the polymerization reaction itself,
but these do not have a bearing on the potential aqueous pollu-
tion problem (EN-160). Therefore, both processes will be dis-
cussed together.
Jacketed, stirred batch reactors for PVC polymerization
vary in size from 8 to 40 m3 (2000 to 10,000 gallons). . The batch
cycle consists of the introduction of a water-monomer emulsion to
the stirred reactor. The heat of reaction is removed by circulat-
ing cooling water through the reactor jacket. The reactor is
vented through a condenser for monomer recovery and the conden-
sate, including any water, is returned directly to the vessel.
-181-
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On completion of the batch a short "soaking" time is
allowed for completion of the reaction. The wastewater load
depends on the final processing steps including coagulation, steam
stripping, washing, and drying.
Water Effluents and Control
The major wastewater stream from PVC production by
emulsion or suspension polymerization processes is the water
separated from the emulsion or suspension after the batch reactor
(EN-160). The major wastewater flow from the bulk polymerization
process is decanted condensate from the condenser at the vacuum
stripper which removes untreated monomer, contaminants and by-
products from the reactor (EN-160).
The potential reduction of organic waste in effluents
from PVC production resulting from application of BATEA to BPCTCA
is 28,100 MT organic/yr. The reduction is estimated by determin-
ing the difference in BPCTCA and BATEA TOG levels (EN-160) and
multiplying by the ratio of the molecular weight of vinyl chloride
to carbon. This assumes that most of the organic load is vinyl
chloride monomer or an organic by-product of similar composition.
The BOD5, TOC, COD and organic loads are presented in Table 3.6-2.
3.6.2.3 Methyl Methacrylate Production
Process Description
Methyl methacrylate is produced commercially in the U.S.
by the acetone cyanohydrin process. First, acetone cyanohydrin
.is made by reacting hydrogen cyanide and acetone in a cooled
reactor with an alkaline catalyst. The excess catalyst is neu-
tralized and crude acetone cyanohydrin is stored in holding tanks.
The salt formed by neutralization is filtered and the crude acetone
-182-
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cyanohydrin is fed to a two-stage distillation unit. Water and
acetone are removed and recycled in the first column, and the
remainder of the water is removed at high vacuum from the second
column.
Acetone cyanohydrin and concentrated sulfuric acid
react in a cooled hydrolysis kettle to make methacrylamide sul-
fate. Methacrylamide sulfate reacts continuously with methanol
in an esterification kettle. Inhibitors are added at various
points to prevent polymerization. The esterified stream is pumped
to the acid stripping column from which the acid residue (1070 wt.
organic substances) can be sent to a spent acid recovery unit
(SAR). The recovered sulfuric acid is recycled to the hydrolysis
reactor.
The acid stripping column overhead stream is distilled
to remove methyl methacrylate and unreacted methanol. The methanol
is recycled. The remaining traces of methanol in the methyl
methacrylate are removed by water extraction, after which the
monomer is purified in a rerun tower.
Water Effluents and Control
The acid residue from the acid stripping column is the
major waste stream generated in the process. This waste stream
is sent either to the SAR unit previously mentioned or it is
discharged into sewers. The waste streams generated as bottoms
from various stills are combined, with the acid residue for spent
acid recovery. Water samples from streams entering and exiting
the SAR unit have been analyzed (EN-153), and the results are
shown in Table 3.6-5.
-183-
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TABLE 3.6-5
HARACTERISTIC
Flow
COD
BOD5
TOG
S OF WATER EFFLUENT FROM SPENT
SAR Influent
4440 1/MT
178,000 mg/1
20,700 mg/1
69,998 rag/1
ACID RECOVERY
SAR Effluent
3550 1/MT
110 mg/1
15 mg/1
18 mg/1
UNIT
The stream entering the SAR has a high concentration
of floating solids. The floating solids removed in the SAR may
be incinerated. High concentrations of metal contaminants such
as copper and iron are also indicated. A large portion of the
metals is removed along with floating solids in the SAR unit;
however, the metal concentration in the streams discharged to
sewers is still higher than general discharge criteria for bio-
logical processes. The sulfuric acid concentration is reduced
from 40 percent by weight in the influent to the SAR to 1 percent
by weight in the effluent, but the sulfate concentration in the
discharge stream is still high enough to inhibit the normal
functioning of a biological treatment process.
Because of the highly exothermic reactions involved,
the process requires a large amount of cooling water. The
survey data (EN-163) show that gross cooling water usage amounts
to 366 kg per kg of methyl methacrylate. Process water, 0.56 kg
per kg of product, is introduced into the system as direct stream
s tripping.
The BATEA for this process is a Spent Acid Recovery
unit. The economics of a 220,000 MT/yr spent acid recovery plant
have been estimated (EN-153) for two different processes: spent
acid recovery by neutralization and by complete combustion. A
possible alternative to SAR, where geology is favorable, is deep
well disposal.
-184-
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The use of SAR throughout the industry would reduce
effluent organic levels by 26,900 MT organic/yr. The BOD3, COD,
TOG and organic effluent loads are presented in Table 3.6-2.
-185-
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3.7 Noncombustion Organic Chemical Utilization
The noncombustion organic chemical utilization category
examines organic emissions from operations which utilize indus-
trial and commercial grade organic chemical products. The bulk
of the emissions from this category results from the evaporation
of solvents used in various processing and coating operations.
The category is divided into subgroups based upon the
industries examined as listed in Table 3.7-1. The major subgroups,
including surface coating, graphic arts, dry cleaning, rubber and
plastic processing, and fabric treatment, are described in
Sections 3.7.1 through 3.7.5. A summary of the air emissions
from the industries in this category is presented on Table 3.7-1.
Water effluents and solid wastes were also examined
for this category. The only source of water effluents from this
category was the tire and inner tube segment of the rubber pro-
cessing industry. No data was found on solid wastes for any
subgroups in this category. Table 3.7-2 contains a summary of
the organic water effluents from the tire and inner tube produc-
tion industry.
3.7.1 Surface Coating
3.7.1.1 Process Description
Surface coating operations consist of one or more of the
following processing steps: degreasing, surface coating applica-
tion, and drying and curing. Each of these steps will be discussed
in the following sections.
-186-
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TABLE 3.7-1
I
M
GO
I
NONCOMBUSTION ORGANIC CHEMICAL UTILIZATION
Dustion Organic Chemical Utilization
Rubber and Plastic Processing
Surface Coating
Paper and Paperboard-
Sheet, Scrip, and Coil
Automobile and Truck
Major Appliance
Wood Furniture
Industrial Machinery
Metal Furniture
Graphic Arts
Gravure
Flexography
Letterpress
Lithography
Metal Decorating
Drycleaning
Fabric Treatment
Year
1975
1975
1975
1975
1975
1975
1975
1975
1975
1975
1975
1975
1975
1975
1975
- ATMOSPHERIC EMISSIONS
Emissions (MT/yr)
Volatile
Organics
1.280,000
475,000 ">
469,000
100,000
30,000
9,000
8,000
8,000
107,000
98,000
66,000
62,000
59,000
367,000
210.000
Ref
1
1
1
1
1
1
1
1
2
2
2
2
2
1
3
-------
TABLE 3.7-1 (Cont'd.)
NONCOMBUSTION ORGANIC CHEMICAL UTILIZATION - ATMOSPHERIC EMISSIONS
Emissions (MT/yr)
Year
Volatile
Qrganics
Ref
oo
oo
Cast Iron Foundry
Asphalt Batching
Paint Manufacturing
Printing Ink Manufacturing
Varnish Manufacturing
Asphalt Roofing
TOTAL
1975
1975
1975
1975
1975
1975
102,000
53,000
19,000
8,000
7,000
6.000
3,540,000
2
2
2
2
2
2
References:
1. MO-201
2. 110-244
3. HU-100
-------
TABLE 3.7-2
NONCOMBUSTION ORGANIC CHEMICAL UTILIZATION - ORGANIC EFFLUENTS
Effluents (MT/yr)
Total Organics BOD
COD
SS
Oil and Grease
Noncombustion Organic Chemical
Uilization
I
h-1
OO
Rubber and Plastic
Processing
Tire and Inner Tube
Indus cry
NA
NA
160
40
Ref: EN-154
-------
Degreasing
The surface of metal products is lubricated with oils,
greases, or stearates during their fabrication to facilitate the
various drawing, forming, and machining operations. These lubri-
cants, as well as dust and dirt, must be removed from the metal
surface prior to surface coating. This cleaning operation is
called degreasing, and it is used to ensure that the surface
coating adheres to the metal surface.
Three chlorinated hydrocarbon compounds are used in units
for degreasing. These are trichloroethylene, 1,1,1-trichloroethane,
and perchloroethylene. Equipment used includes vapor spray de-
greasers, dip tank degreasers, liquid spray degreasers, and diphase
degreasers employing an aqueous solvent along with the organic
solvent.
Surface Coating Application
Manufactured articles often receive coatings for surface
decoration and/or protection before being marketed. A number of
basic coating operations are utilized for this purpose. Included
below is a list of these different operations and a brief
description.
Spraying - Spraying operations are performed
in a booth or enclosure vented by a draft
fan. In the operation, a coating material
is forced through a nozzle which directs
the coating as a spray upon the desired
surface. The organic solvent vapors are
vented through the fume hood system.
-190-
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Dip Coating - In dip coating operations, the
object to be coated is immersed in a tank
containing the surface coating just long
enough to be coated completely. The excess
paint drains back into the tank.
Flow Coating - This technique is used on
items which cannot be dipped due to the
buoyancy. The article is coated by the
liquid release from overhead nozzels
and flowing in a steady stream over
the article. Excess paint drains from
the coated object and is recirculated.
Coil Coating - In this operation, long,
flat strips or coils of metal are coated
by means of rollers. Three rollers are
commonly used, one partially immersed in
the coating material and two others which
apply the paint by transfer from the first
roller.
Drying and Curing
Applied surface coatings are dried and cured by both
natural evaporation and by forced evaporation with heating.
The forced evaporation of solvent is accomplished in bake
ovens. Before entering the oven, the wet, coated object is
allowed to dry by natural evaporation to remove the highly
volatile solvent components. This is done to prevent the forma-
tion of bubbles in the coating during oven drying.
-191-
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The ovens are designed for either batch or continuous
operation. They are equipped with temperature regulation, air-
circulation, and exhaust systems. The heat required by a bake
oven may be supplied by gas, electric, steam, or waste heat from
the other processes.
The evaporated organic vapors from drying and curing are
vented through an exhaust system to prevent their escape into the
plant. The exhaust system collects these vapors and either vents
them to the atmosphere or directs them to a vapor control device
for disposal.
3.7.1.2 Atmospheric Emissions and Control
The two types of emissions from surface coating plant
operations are point source emissions and fugitive emissions.
The point source emissions include the controlled and uncontrolled
emissions from the degreasing, surface coating, and drying and
curing operations. Other point sources include the degreasing
solvent storage tank vent, surface coating solvent vent, and
surface coating blending tank vent (HU-100).
The fugitive emission sources include solvent evaporation
losses from degreased, coated, and dried products. They also
include losses from each piece of processing equipment and from
the transfer of organic liquids within the plant.
Table 3.7-3 presents estimates of the quantities of
organics emitted yearly to the atmosphere from surface coating
operations. Monsanto Research Corporation estimates the quality
of this data to be within 50-100 percent of the true value (HU-100),
-192-
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TABLE 3.7-3
ATMOSPHERIC ORGANIC EMISSIONS FROM
SURFACE COATING OPERATIONS
Source Emissions (MT/yr)
Paper & Paperboard Coating 475,000
Sheet, Strip & Coil Coating 469,000
Automobile & Truck Coating 100,000
Major Appliance Coating 30,000
Wood Furniture Finishing 9,000
Industrial Machinery Coating 8,000
Metal Furniture Coating 8,000
TOTAL 1,099,000
Source: HU-100
The control of organic vapors from surface coating
sources can be accomplished by the application of condensation,
compression, absorption, adsorption, or incineration technology.
The emissions from the degreasing phase are best reduced by carbon
adsorption units. They can potentially recover nearly 100 percent
of the vapors in exhaust gases from a degreaser. For the actual
coating application phase, the evaporated solvents are best con-
trolled by adsorption (should solvent recovery be desired) or
incineration (if the solvent is not to be recovered). The emis-
sions from the drying and curing operation are best controlled
through incinceration of the solvent vapors (DA-069).
Based on the relatively high reduction efficiencies of
these control devices (greater than 90 percent), a high reduction
potential is expected for organic emissions from surface coating
-193-
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operations. An assumed percent reduction for this stationary source
is estimate to be as high as 90 percent. This results in a reduc-
tion potential of 989,000 MT/year of hydrocarbons from the described
surface coating operations.
3.7.2 Graphic Arts
This section reviews the organic emissions from the
various printing processes comprising the graphic arts industry.
The five processes considered are offset lithography, letterpress,
metal decorating, gravure, and flexography. A brief discussion of .
each of these processes is followed by the organic emission esti-
mates for each segment and the controls used to reduce these
emissions.
3.7.2.1 Process Description
Offset Lithography
Lithography involves transferring, by direct contact,
an immage on a plate to a paper surface using ink and water.
Offset lithography usually involves transferring the image from
the plate to a rubber surface on a cylinder in contact with the
paper. The image is therefore transferred first from the image
plate to the cylinder and then to the paper. The water used in
offset lithography may contain as much as 15 to 30 percent
isopropanol (GA-168).
From the image transfer operation, the paper is passed
through a drier, where the ink is dried. The exhaust from the
drier contains organics evaporated from the ink.
-194-
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Letterpress
In this process, the ink is transferred to the paper
from the image surface, which is slightly raised in relation to
the nonprinting surface of the plate. As with the offset litho-
graphy operation, when the paper exits from the letterpress
printing operation it is passed through a drier where most of the
ink is dried. The exhaust from the drier contains the organic
solvent evaporated from the ink (GA-168).
Metal Decorating
Sheet-fed metal decorating is done with lithographic
inks containing mainly alkyd resins and a 'small amount of solvent.
The image is transferred by lithography to a dried lacquer under-
coat rather than to the base metal. After printing, the sheet of
metal may or not be coated and then it is sent to drying. In
the case of metal can decorating, the can receives a coating of
varnish following printing.
Since the ink contains little or no solvent, the organic
emissions from the lithographing process are insignificant. The
points of organic emissions in metal decorating are the roller
coating area and the drier exhaust.
Gravure
In this type of printing, ink is transferred directly
from the image carrier to the paper or film. The ink used in high
speed gravure printing contains a relatively large amount of
volatile solvent.
Following printing, the product is dried by a steam
drum or hot air drier. The majority of the solvent emissions
-195-
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from this process are present -in the drier exhaust with most of
the remainder coming from the press unit.
Flexography
The flexographic process is similar to letterpress in
that the image area is raised above the surface of the plate. Ink
is transferred directly to the image area of the plate and directly
from the plate to the paper or substrate. Flexography includes
processes in which the plate is made of rubber and the inks are
alcohol based. Flexographic processes differ primarily in the
type of ink and solvent used. Following printing, the product
is dried by forced evaporation in a hot air drier or steam drum.
As with the other printing processes, the primary
sources of solvent vapors are the inking area and the drier exhaust.
3.7.2.2 Atmospheric Emissions and Control
The types and amounts of solvents emitted from printing
processes vary widely depending on the printing process being
used. The gravure and flexographic processes account for the
majority of the organic emissions from graphic arts. There are
eight groups making up the solvents commonly used for flexogra-
phic and gravure inks: aromatic hydrocarbons, aliphatic hydro-
carbons , mixed aromatic and aliphatic hydrocarbons, alcohols,
glycol ethers, esters, ketones, and miscellaneous solvents. The
solvents used in the letterpress and lithographic inks are either
aliphatic hydrocarbons or glycols (MS-001).
Table 3.7-4 presents estimates of the quantitites of
organics emitted yearly to the atmosphere from graphic arts
processes (HO-244). TRC of New England did not estimate the
quality of these emissions.
-196-
-------
TABLE 3.7-4
ATMOSPHERIC ORGANIC EMISSIONS FROM
GRAPHIC ARTS PROCESSES
Source Emissions (MT/yr)
Gravure 107,000
Flexography 98,000
Letterpress 66,000
Lithography 62,000
Metal Decorating 59,000
TOTAL 392,000
Source: HO-244
The control of these emissions may be accomplished by
several techniques: modification of process , change of process
material, incineration, and adsorption. The application of
solventless inks, incineration, or adsorption can reduce the organic
emissions from 90 to 100 percent (GA-168). Based on this informa-
tion, the reduction potential for hydrocarbon emissions from graphic
arts is assumed high. The percent reduction achievable is estimated
to be 90 percent. This results in a reduction potential of 353,000
MT of organics per year from graphic arts.
3.7.3 Dry Cleaning
Process Description
Clothing and other textiles may be cleaned by treating
them with organic solvents. This treatment process involves
agitating the clothing in a solvent bath, rinsing with clean
solvent, and drying with warm air.
-197-
-------
There are basically two types of dry-cleaning installa-
tions : 'those using petroleum solvents and those using chlorinated
synthetic solvents (perchloroethylene). The trend in dry-cleaning
operations today is toward smaller package operations. Typically,
they are located in shopping centers and suburban business districts
and handle approximately 675 kg (1,500 Ibs) of clothes per week on
the average. These plants almost exclusively use perchloroethylene,
whereas the older, larger dry-cleaning plants use petroleum solvents
It has been estimated that perchloroethylene is used on 50 percent
by weight of clothes dry-cleaned in the United States and that 70
percent of the dry-cleaning plants use perchloroethylene (EN-071).
Atmospheric Emissions and Control
The amount of solvent vapors emitted to the atmosphere
from a dry-cleaning plant is dependent upon the type of equipment
used, the amount of cleaning performed, and the precautions prac-
ticed by the operating personnel (DA-069).
The primary source of organic emissions from dry cleaning
is the tumbler through which hot air is circulated to dry the
cleaned clothes (EN-071). Other sources of organic emissions
include the vents for the washing and extraction equipment for
synthetic solvent plants which combine these operations and
evaporated solvent which is spilled in transferring wet fabrics
from one machine to another. The estimated yearly rate of atmos-
pheric organic emissions from dry-cleaning operations is 367,000
metric tons (MO-201).
Petroleum solvent dry-cleaning operations do not control
emissions of evaporated solvents since there is no economic incen-
tive for recovery. The principal control, then, is the prevention
of solvent loss and evaporation by proper maintenance and good
operating practices.
-198-
-------
Synthetic solvent dry-cleaning installations on the
other hand lend themselves to easy installation of air pollution
control equipment. Adsorption is the most practical means of
controlling synthetic solvent vapors from dry-cleaning equipment.
Packaged adsorption units employing activated carbon are used most
often. Despite the high efficiency of adsorption and the operating
methods used to prevent solvent emissions, a reduction of more
than 70 percent is seldom achieved, when calculated on the basis
of total solvents purchased with and without adsorption control
(DA-069). Based on this information, the reduction potential for
hydrocarbon emissions from dry-cleaning is expected to be moderate
to high. Assuming adsorption control of petroleum solvent dry-
cleaning operations would reduce their emissions 70 percent and
assuming 25 percent of all synthetic solvent installations are
already controlled by adsorption, the percent reduction of atmos-
pheric hydrocarbon emissions from dry cleaning could be as high
as 55 percent. This results in a reduction-potential of 202,000
MT of organics per year.
3.7.4 Rubber and Plastic Processing
Rubber and plastic processing includes those industries
producing products from raw rubber and plastic. The industries
are similar in that many ingredients other than the raw base material
are added to produce desired properties in the finished product.
The ingredients have several functions, and they include plasticizers,
antioxidants, vulcanization additives, and fire retardants.
The following sections briefly identify each industry.
Because of the similarity in the type and nature of the organic
emissions from rubber and plastic processing, the mass emission
rates for the two industries are combined.
-199-
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3.7.4.1 Process Description
Rubber Processing
Rubber in its raw state is too plastic for most commer-
cial applications, and its use is limited to items such as rubber
shoe soles, rubber cements, and adhesives. Vulcanization, a curing
process, can cause the raw rubber to lose its plasticity and gain
elasticity. The most important rubber processing operations up
to and including vulcanization are: (1) physical treatment of
raw rubber to prepare it for addition of compounding ingredients;
(2) incorporation of various substances, especially fillers: (3)
pretreatment of mix to make it satisfactory for preparing the
final product; (4) forming the final product; and (5) vulcanization
or curing the molded article.
The first step in rubber processing is plasticization
which can be done in several ways: (1) mechanical plasticization;
(2) heat plasticization; and (3) chemical plasticization. Next,
various additives are compounded into the rubber to give its desired
properties. After the rubber is compounded, it is formed into the
desired shape and cured at the required temperature. In the forming
steps, large amounts of organic solvents are often used in the form
of rubber adhesives. These compounds, known as antioxidants, typi-
cally include aromatic amines, aldehyde-amine condensation products,
derivatives of secondary naphthylamines, aromatic diamine derivatives,
and ketoneamine condensation products (NA-032). Finally, the molded
article is vulcanized or cured between 93 and 149°C (200 to 300°F)
for periods from a few seconds to several hours. During this opera-
tion many of the plasticizers, accelerators, antioxidants, and other
organics are volatilized and driven off as air emissions (NA-032).
-200-
-------
Plastic Processing
There are numerous possible classifications for plastics;
however, nearly all fall into one of two major categories: ther-
mosetting (or thermosets) or thermoplastic materials. Basically,
thermosetting plastics are not remeltable, while thermoplastics
are. This difference in properties results from different processing
techniques.
Thermosetting plastics processing starts with a partially
polymerized material that is softened and activated by heating
(either in or out of the mold), forcing it into the desired shape
by pressure. It is held at the curing temperature until poly-
merization reaches the point where the part hardens and stiffens
sufficiently to. keep its impressed shape. Solvents are not used
in this processing sequence, thus thermoset processing does not
represent a significant source of atmospheric organic emissions.
One typical sequence of thermoplastic processing is
to heat the material so that it softens and flows and then to force
it through a die or into a mold to give it final shape. This does
not represent a source of atmospheric organic emissions. However,
the processing of the th.ermoplas tic vinyl chloride polymers and
copolymers into permanently pliable materials by addition of
suitable plasticizers is a significant source of atmospheric
organics. The most common plasticizer used for this purpose
is dioctyl phthalate (DOP), and sometimes diisooctyl phthalate
(DIOP) is used. The products are cured at high temperatures,
causing volatilization of the plasticizers (NA-032).
-201-
-------
3.7.4.2 Atmospheric Emissions and Control
For rubber and plastic processing, the primary source
of atmospheric emissions is the curing process. This operation
drives off volatile organics present in the rubber or plastic at
elevated temperatures. The atmospheric emissions of organic
chemicals from this industry have been reported to be 1.28 x 10^
MT/year (1.41 x 10 short tons per year) (MO-201).
The principal techniques used to control organic air
pollutants from rubber processing are: reformulation, condensa-
tion, adsorption, absorption, and incineration (NA-032). These
methods would be applicable to the control of organics from
plastic processing as well. Direct-flame incineration has proven
to be very successful in controlling both organics and odors
from rubber processing. Recovery efficiencies as high as 97 per-
cent have been achieved in some plants (NA-032). Based on this
information, the percent reduction for rubber and plastic pro-
cessing is estimated to be over 90 percent, assuming limited
emission control application to date. This results in a reduction
potential of 1,150,000 MT of organics per year.
3.7.4.3 Water Effluents and Control
The tire and inner tube segment of the rubber processing
industry discharges organic water effluents. A development docu-
ment for proposed effluent guidelines and new source performance
standards for tire and inner tube processing has been published
(EN-154). This publication provides the most recent and compre-
hensive assessment of the industry's organic effluents and their
control. For this reason, the July 1, 1977 effluent limitations
-202-
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or Best Practicable Control Technology Currently Available (BPCTCA)
were selected to describe the current degree of control and the
associated organic effluent rate.
This document places limitations on the oil and grease
discharge and the suspended solids discharge from tire and inner
tube production facilities. The primary source of oil and grease
is the leakage of lubricating oils from process machinery into
wastewater streams. The suspended solids from normal daily pro-
duction originate primarily from nonprocess blowdowns and the water
treatment wastes. Table 3.7-2 contains estimates of effluents
annually discharged from tire and inner tube production.
The best control and treatment technologies currently
in use emphasize in-house control of solution wastes with end-of-
pipe treatment of combined process and non-process waste waters
(EN-154). Control and treatment of oily waste streams involves
segregation, collection, and treatment of these wastes. The
wastes to be segregated include runoff from oil storage and un-
loading areas and leakage and spills from the mill and press
basins. These waste waters are sent to an API-type gravity
separator where the separable oil and solids fraction is removed
and disposed.
No additional reduction is proposed for the limitations
and standards represented by the BATEA or for new sources coming
on stream after effluent limitation guidelines are put into effect
(EN-154). Therefore, the reduction potential for organic effluents
from the tire and inner tube industry is zero.
-203-
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3.7.5 Fabric Treatment
Fabric treatment consists of two major processes:
finishing and coating. The finishing process is designed to change,
improve, or develop the appearance or desired behavior characteris-
tics of the fabric. Most fabrics receive one or more special
finishes. The types of finishes used include shrinkproofing,
crease resistance, water repellency and waterproofing, flame-
proofing, stainproofing, antistatic finishing, and others.
The application of the various finishes is followed
by a curing step which exposes the fabric to temperatures above
200°C. At these temperatures, the solvents used in the applied
finishes, the softeners and conditioners, and the by-products from
resin curing are volatilized from the fabric. Drying is achieved
using both direct contact driers and by forced air drying.
Atmospheric Emissions and Control
The primary source of atmospheric organic emissions from
fabric treatment is the curing or drying operation. The estimated
yearly quantity of organics emitted from fabric treatment is
210,000 metric tons (HU-100).
The control of these emissions is similar to that
used for paint-baking ovens. The most successful and most often
used control is the afterburner. Both thermal and catalytic
incinerators may be used. The efficiency for this control device
is estimated to be greater than 95 percent. For this reason, the
hydrocarbon reduction potential for this industry is assumed to be
high. The potential percent reduction in emissions is estimated to
be 90 percent. This results in a reduction potential of 189,000 MT
of organic per year.
No information was found concerning organic effluents
from this industry.
-204-
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3.8 Agricultural and Forest Products
The agricultural and forest products industry includes
a variety of processing steps which convert agricultural and
forest products into consumer goods. These processing steps
include refining, preservation, product improvement, storage,
handling, and packaging. The processing operations involved in
this industry produce gaseous, liquid, and solid wastes.
Atmospheric Emissions
Estimates of volatile and particulate organic emissions
from major sources in the agriculture and forest products indus-
try are presented in Table 3.8-1. These values were derived
from emission factors and estimates found in the various litera-
ture sources indicated in the table. The largest emission
sources including pulp and paper production, wood waste combus-
tion, beer brewing, fruit and vegetable processing, tobacco
manufacture, and grain and feed mills are discussed in detail
on the following pages. The reduction potentials shown in
Table 3.8-2 were determined by estimating the reductions which
would be realized by the application of the best available con-
trol methods. In most cases, additional study of specific
processes is required to determine the economic feasibility of
controls and the best application of available control techniques
Water Effluents
Many operations involved in the processing of agri-
cultural and forest products are water-intensive and result in
organic water pollutants. The wastes generally have high oxygen
demands and can make water unsightly, unpalatable and malodorous.
Estimated quantities of water effluents from processes in the
-205-
-------
TABLE 3.8-1
ATMOSPHERIC EMISSIONS FROM THE AGRICULTURAL
AND FOREST PRODUCTS
INDUSTRY
Emissions (MT/Yr)
Volatile
Subcategory
Pulp and Paper
Wood Waste Combustion
Beer
Fruit and Vegetable
Processing
Tobacco
Charcoal
Distilled Spirits
Cottonseed Oil Milling
Plywood and Veneer
Deep Frying
Vegetable Oil Milling
Coffee Roasting
Leather Tanning and
Finishing
Fish and Seafood
Processing
Meat Smokehouses
Sawmills
Grain and Feed
Milling & Storage
Grain Food Processing
Sugar Processing
Wood Preserving
CATEGORY TOTAL
Sources: 1. EN-071 3.
2. EN-197 4.
Year
1974
1968
1973
1973
1973
1973
1973
1973
1974
1975
1975
1974
1973
1973
1975
1971
1971
1975
1971
HO -2 24
MO-201
Organics
143
137
67
47
39
28
10
10
9
6
3
1
1
$
507
5."
6.
,000
,000
,800
,700
,700
,600
,600
,300
,070
,090
,865
,400
,100
745
462
346
-
-
,778
US-303
VA-067
Ref
1,2
1,2,
4
4
4
4
4
4
2
3
/,_
1,5
4
4
3
2
4
Particulate
Organics
6 47
108
100
13
6
1,220
6
23
7
414
1,311
55
8
3,323
,400
,000
945
794
,000
,300
,160
,000
,900
,496
,080
64
397
,000
,000
,520
,800
78
,934
Ref.
1,2,6
i^
4
4
4
3
4
2
3
4
1,5
3
3
2
6
4
2
-206-
-------
i
ro
o
TABLE 3.8-2
CONTROL OF ATMOSPHERIC EMISSIONS IN THE AGRICULTURAL
AND FOREST PRODUCTS INDUSTRY
Subcategory
Pulp & Paper
Wood Waste Combustion
Beer
Processed Fruits &
Vegetables
Tobacco
Grain & Feed Milling
& Storage
Air Emissions (MT/Yr)
Volatile Organics
Reduction
(Organic Particulates) Potential (%)
Control Methods
143,000
137,000
(47,400)
67,800
(108,000)
47,700
(945)
39,700
(794)
(1,311,000)
99
100
100
99
95
99
99
99
Process modifications*
Utilization of other disposal metho
rVolatile organic emissions can be controlled by conventional methods including incineration,
adsorption, absorption, condensation, and various methods for reducing fugitive emissions.
Individual processes must be studied to determine best application of controls.
rParticula te emissions can be controlled by conventional methods including settling chambers,
cyclones, electrostatic precipitators, scrubbers, and baghouses. Individual study of processes
is required to determine best application of controls.
-------
industry are presented in Table 3.8-3. Effluent quantities
were estimated from raw waste loads (RWL) by calculations based
on an assumed level of treatment according to effluent guideline
limitations.
RWL data were obtained from the various literature
sources indicated in Table 3.8-3. These data generally re-
sulted from sampling studies at plants representative of the
industry. Effluent guideline limitations for BOD5 and SS have
been developed for some segments of the industry. The develop-
ment documents for these guidelines provided useful data on
reduction factors for waste treatment systems.
Total organic effluents were estimated by assuming
that mg/2, BOD approximately equals 52 mg/5, TOG (SO-080). This
correlation was developed for biologically treated municipal
wastes. The wastes treated at municipal sewage systems have
similar components to the wastes from agricultural and forest
processes and operations.
Effluent limitations to be achieved by July 1, 1977
(Best Practicable Control Technology Currently Available,
BPCTCA) are generally based upon the average of the best exist-
ing performance by processes within the industry. The averages
are not based upon a broad range of processes, but are based
upon performance levels achieved by exemplary ones. This tech-
nology normally involves in-process changes to reduce waste
loads and end-of-process treatment consisting of any required
primary treatment followed by biological oxidation.
For quantification of effluents in this report, pre-
sent effluents were assumed to be those resulting from the ap-
plication of BPCTCA or equivalent technology to the processes.
Reduction factors for BPCTCA and effluent guideline limitations
(BPCTCA 30-day maximum averages) were used to calculate effluents
-208-
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TABLE 3.8-3
WATER EFFLUENTS FROM THE AGRICULTURAL
AND FOREST PRODUCTS INDUSTRY
Effluents ('MT/
yr)
Total
Sub category
• Pulo & Paoer Indus
• Processed Fruits <5<
Vegetables
• Beer Brewing
• Sugar Processing
• Plywood/Veneer
• Grain Mills
cry
. Red Meat Processing
• Dairy Products
• Poultry Processing
• Fish & Seafood
Processing
• Leather Tanning &
Finishing
• Misc. Food Product
• Rayon
s
• Rendering (Independent)
• Distilled Spirits
• Wood Preserving
• Hardwood
TOTAL 300: 234,
TOTAL OIL: 14,
TOTAL SS: 325,
TOTAL ORGANIC: 488,
Sources: 1. AM- 134
2. CA-281
3. CL-073
4. EC-010
5. EN-152
6. EM- 156
7. EN- 160
691
355
869
044
3.
9.
10.
11.
12.
13.
14.
Year
1972
1975
1974
1974
1974
1974
1972
1974
1974
1972
1974
1975
1974
1968
1974
1971
1972
EM- 175
EM -19 7
EM-294
EN-380
EM-331
EN-332
EM-383
BOD
100,
44,
35,
9,
3,
7,
6 ,
5 ,
3,
2 ,
2,
2,
1,
i_ _
1,
15.
16.
17.
13.
19.
20.
21.
000
800
500
080
600
720
450
810
760
8^0
330
180
880
580
160
329
Or^anic COD
208
93
73
18
17
16
13
12
7
5
5
4
3
3
2
,000
,200
,300
,900
,900
,100
,400
,100 10,200
,820
,910
,890
,530
,910 28,200
,490
,410
675
684
SS Oil
196
42
36
7
8
7
8
5
2
1
3
3
2
,000
,400
,400
,160
,330
,560
,330 3,490
,990
,290
,050 330
,550 534
650
,450
,080 9,910
21
629
Ref
3,9,21
2 ,
10
16
9,
5 ,
15
3,
4,
12
6
2
1,
14
2 _
13
13
13
,20
,17,20
13,20
11
20
19,20
7
19,20
EM- 336
EN-387
EM-
ME-
SI-
US-
VA-
397
126
106
303
067
-209-
-------
Best Available Technology Economically Achievable
(BATEA) effluent limitations have been established for some
segments of the industry. These guidelines were developed by
identifying either the best performance within a given sub-
category or the very best control and treatment technology
employed by a specific point source within a subcategory. This
level of technology emphasizes both in-process improvements and
external treatment of the wastewaters.
The reduction potential for water effluents from the
industry was determined to be the reduction in effluents below
levels with BPCTCA-type controls achieved by the application of
BATEA-type controls. These reduction potentials were found by
using the reduction factors for BATEA or by the difference
between BPCTCA and BATEA effluent guidelines (maximum 30-day
averages). Effluents and reduction potentials of processes for
which effluent limitations have not been written were estimated
by the use of the development documents for effluent limitations
guidelines for similar processes.
The major sources of organic water pollutants within
the agricultural and forest products industry are discussed on
the following pages. These descriptions 'exemplify the types of
effluent sources found within this industry and application of
control technologies to the sources. The estimated reduction
potentials for water emissions from these sources are presented
in Table 3.8-4.
3.8.1 Pulp and Paper Industry
3.8.1.1 Process Description
Most pulp is made by integrated companies and consumed
captively. Wood pulp is prepared wither mechanically or
-210-
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TABLE 3.8-4
CONTROL OF WATER EFFLUENTS IN THE AGRICULTURAL AND
FOREST PRODUCTS INDUSTRY
Pulp & Paper
Water Effluents
(MT/Yr)
BOD5
Reduction Potential
O) _
Total Organic BOD5 Total Organic
100,000 208,000 50 50
Control Methods
Processed Fruits &
Vegetables
44,800
93,200
75
75
Beer
35,500
73,800
75
75
""Organic wastewater effluents are controlled by in-process modifications and
primary treatment of wastewater followed by biological oxidation and filtration.
-------
chemically. In the mechanical processes, groundwood, defibered
and exploded wood are shredded or separated by physical means.
Chemical wood pulping involves the extraction of cellulose from
wood by dissolving the lignin that holds the cellulose fibers
together. The principal chemical pulping processes are kraft,
acid sulfite, neutral sulfite semichemical (NSSC), dissolving
and soda.
The type of pulping process utilized is determined by
the product being made, the type of wood species used, and
economic considerations. The kraft, acid sulfite, and NSSC
processes account for approximately 80 percent of the pulp pro-
duced in the United States (about 65 percent is produced by the
kraft process) and have the greatest potential for gaseous emis-
sions (EN-071). These processes will be discussed in this sec-
tion.
Kraft Pulping
In the kraft process , wood chips are cooked under
pressure in the presence of a cooking liquor in either a batch
or continuous digester. The cooking liquor (white liquor), an
aqueous solution of sodium sulfide and sodium hydroxide, dissolves
the lignin.
When cooking is completed, the contents of the digester
are fed to the blow tank. The major portion of the spent cooking
liquor (black liquor) is drained from the blow tank. The pulp
from the blow tank is charged to the knotter where unreacted
chunks of wood are removed. The pulp is then washed and some-
times bleached before being pressed and dried into the finished
product.
-212-
-------
Recovery or the inorganic cooking chemicals and heat
content of the black liquor is economically necessary. Recovery
is accomplished by concentrating the liquor to a level that will
support combustion and then feeding it to a furnace where burn-
ing and chemical recovery take place.
The black liquor is concentrated initially in a multi-
ple effect evaporator. Further concentration is achieved in a
direct contact evaporator. This is generally a scrubbing device
in which combustion gases from the recovery furnace mix with the
black liquor.
The concentrated black liquor is sprayed into the
recovery furnace. The organic content supports combustion and
the inorganic compounds fall to the bottom of the furnace and
are then dischared to the smelt dissolving tank. The solution
from the smelt dissolving tank (green liquor) is conveyed to a
causticizer where calcium hydroxide is added prior to recycling
the liquor. Lime sludge from the causticizer can be recycled
after being dewatered and calcinated in the hot lime kiln.
Acid Sulfite Pulping
The acid sulfite pulping process is similar to kraft
pulping except that different chemicals are used in the cooking
liquor. In place of the caustic solution used in the kraft
process, a sulfurous acid solution is employed which is buffered
by sodium, magnesium, calcium, or ammonium bisulfite.
Due to the variety of chemicals employed in the cook-
ing liquor, numerous schemes for heat and/or chemical recovery
have evolved. Chemical recovery is not practical in calcium-
base systems, which are used mostly in older mills, and the spent
liquor is normally discarded. In ammonium-base mills, heat can
-213-
-------
be recovered from the spent liquor through combustion, but the
ammonium is consumed. In sodium or magnesium-base mills (the
latter being utilized most frequently in newer mills) heat,
sulfur, and chemical recovery are all feasible.
The recovery process involves a multiple-effect evap-
orator and recovery furnace arrangement similar to that in the
kraft process. The combustion gases from the furnace pass
through absorbing towers where sulfur dioxide is recovered for
use in subsequent cooks. The base can be recovered by feeding
the inorganic residue from the furnace to the absorbing tower
to react with the sulfur dioxide.
Neutral Sulfite Semichemical (NSSC) Pulping
The NSSC pulping process involves the cooking of wood
chips in a neutral solution of sodium sulfite and sodium bi-
carbonate. The major difference between this process and the
kraft and acid sulfite processes is that only a portion of the
lignin is removed during cooking, after which the pulp is fur-
ther reduced by mechanical means.
The NSSC process varies since some mills dispose of
their spent liquor, some mills recover the cooking chemicals,
and some, which are operated in conjunction with kraft mills,
mix their spent liquor with the kraft liquor as a source of
makeup chemicals. The recovery process, when practiced, in-
volves steps parallel to those of the sulfite process.
Paper Production
Paper is made by depositing, from a dilute water sus-
pension of pulp, a layer of fiber on a fine screen which allows
water to drain through but retains the pulp. The fiber layer is
-214-
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removed from the wire and sent through a series of pressing and
drying machines.
Two general types of machines are commonly employed.
One is a cylinder machine in which the wire screen is placed on
cylinders, and the other is the fourdrinier in which the wire
screen is an endless belt. The water draining through the
paper machine is known as white water and contains suspended
fiber, pulp fines, and chemicals used as additives in the paper
or board. White water is commonly used in the paper and board
making operation and the pulping process.
3.8.1.2 Atmospheric Emissions and Control
Kraft Pulping
The characteristic odor of kraft mills is caused in
part by an assortment of organic sulfur compounds; all have ex-
tremely low odor thresholds. Methyl mercaptan and dimethyl
sulfide are formed in reactions with lignin. Dimethyl disulfide
is formed by the oxidation of mercaptan groups derived from
the lignin. Table 3.8-5 shows the quantity of these compounds
(expressed as sulfur) emitted from various points in the mill.
Devices for controlling the organic sulfur compounds
are generally not applied in kraft mills; however, control of
these compounds can be accomplished by process modifications and
by optimizing operating conditions. A three-volume report by
E. R. Henderson, et al. (HE-128) presents a detailed discussion
of control methods for atmospheric emissions from the pulping
industry and is summarized in this section.
Black liquor oxidation systems, which oxidize sulfides
into less reactive thiosulfates, can reduce odorous sulfur emis-
sions from the direct contact evaporator, although the vent gases
-215-
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TABLE 3.8-5
UNCONTROLLED EMISSION FACTORS FOR SULFATE PULPING
Source
Digester Relief and Blow Tank
Emissions of Methyl Mercaptan,
Dimethyl Sulfide^
Dimethyl Disulfide
(kg/MT of Air Dry Pulp)
0.75
Brown Stock Washers
Multiple-Effect Evaporators
Recovery Boiler and Direct Contact
Evaporator
0.1
0.2
0.5
Smelt Dissolving Tank
Lime Kilns
0.2
0.125
Turpentine Condenser
0.25
Miscellaneous Sources
0.25
These reduced sulfur compounds are usually expressed as
sulfur.
Includes knotter vents, brown stock seal tanks, etc. When
black liquor oxidation is included a factor of 0.3 should
be used.
Source: EN-071
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from such systems become minor odor sources themselves, The
sulfur compound emissions from the recovery boiler and direct
contact evaporator are typically reduced by 50 percent when
black liquor oxidation is employed, but can be cut by 90 to 99
percent when oxidation is complete and the recovery furnace is
operated optionally (EN-071). Noncondensable organic sulfur
gases vented from the digestor/blow tank system and multiple-
effect evaporators can be destroyed by thermal oxidation in the
lime kiln or recovery furnace. Using fresh water instead of
contaminated condensates in the scrubbers and pulp washers re-
duces organic sulfur emissions.
Use of these and other control methods could almost
completely eliminate the organic sulfur emissions from kraft
mills. Organic sulfur emissions could be reduced approximately
135,000 MT per year.
Acid Sulfite Pulping
Volatile reduced sulfur compounds are not products of
the lignin-bisulfite reactor involved in acid sulfite pulping;
therefore, these organic sulfur compounds are not emitted from
acid sulfite pulping mills. No mention of atmospheric emissions
of other organic compounds from this pulping process was found
in the literature.
NSSC Pulping
The NSSC process differs greatly from mill to mill and
there is a scarcity of adequate data. The data in Table 3.8-6
were extracted and compiled from the literature (EM-197). The
data for new technology represents improvements made in the past
seven to eight years. Combination of NSSC spent liquor with kraft
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TABLE 3.8-6
EMISSIONS FROM NSSC PULPING
Source
Recovery Furnace
Blow Tank
Evaporator
Fluidized Bed
Emissions (kg/MT Air Dry
Pollutant
CH3SH
CH3SH
Other Organic
Total Organic S
Total Organic S
Copeland Process Total Organic S
Source: EiN-197
Old
Technology
0.15
0. 78
1.56
0.045
Newer
Technology
0.05-0.025
0.39
0.75
0.045
0.002-0.004
0.09-0.16
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black liquor prior to evaporation and combustion results in in-
creased emissions from the kraft recovery system. No quantita-
tive data on this increase in emissions are available.
The emissions from the NSSC processes could be almost
completely eliminated by control methods similar to those for
the kraft process resulting in a reduction of approximately
6850 MT of organic atmospheric emissions per year.
3.8.1.3 Water Effluents and Control
Information presented in the following section was
obtained primarily from the results of plant surveys (EM-147)
Wood is received at the mills in various forms and, consequently,
must be handled in a number of different ways. In mills re-
ceiving chips from saw mills or barked logs which can be chipped
directly, little or no water is employed in preparation of the
wood and no effluent is produced. Most mills receive logs with
bark which must be removed. Logs are frequently washed before
dry or wet barking. The water from this operation is very low
in BOD5 and its suspended solids content is largely salt.
Most pulpwood used in the United States is small in
diameter and is barked in dry drums. When large diameter or
long wood is used, wet barking is commonly employed. Wet bark-
ing is accomplished in drums, pocket barkers, or hydraulic
barkers.
The wet drum consists of a slotted drum equipped with
internal staves rotating in a pool of water. The bark falls
through the slots and is removed with an overflow of water.
Barkers of this type contribute from 7.5 to 10 kg BOD 5 per MT
of wood barked, and from 15 to 20 kg of suspended solids per
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MT of wood barked. The water supplied to them is frequently
spent process water, and recycling within the barking unit
itself is often practiced.
Wet pocket barkers remove bark from timber by jostling
and gradually rotating the logs against an endless chain belt
equipped with projections. Hydraulic barkers use high pressure
water jets to blow bark from the timber.
Water discharged from all three types of wet barking
is generally combined with log washwater. This stream first
passes through coarse screens to remove the pieces of bark and
wood slivers and then through fine screens. Screenings are re-
moved and conveyed away continuously and dewatered in a press.
Press water is combined with the fine screen effluent. The
total waste flow, about 19,000 to 26,600 liters per cord,
generally contains from 0.5 kg of BOD5 and 3 to 22 kg of sus-
pended solids per ton of product.
Wastewater from unbleached kraft pulping comes pri-
marily from three areas of the process. The effluent from pulp
washing accounts for the highest percentage of the total effluent.
Currently, the use of hot stock washing has considerably reduced
the waste load generated in the washing operation. Another waste-
water source is condensate streams. Relief condensate from the
digesters is condensed and the terpentine is recovered from it
by decantation. The residual water is sewered. Blow and evapora-
tion condensates are contaminated with methanol, ethanol, and
acetone to various degrees depending on the wood species pulped.
When using surface condensers, the volume of this stream is low
and its BOD5 can be reduced by air or steam stripping. These
condensates are frequently reused for pulp washing. Chemical
recovery operations and other minor losses also constitute a
BOD5 source. The total raw waste load from unbleached kraft
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mills, including both pulping and paper making operations, is
typically 15 to 20 kg BOD5 and 10 to 15 kg of suspended solids
per MT of product.
In sodium base NSSC mills, liquor digester relief and
blow gases are condensed, and in some mills the condensate is
used for pulp washing. Other than spent liquor, the pulping
and washing operations discharge little wastewater. Without
recovery of the liquor, effluents would range from 1500 to
5000 rug BOD5/& with a suspended solids content of from 400 to
600 mg/£.
The ammonia base NSSC process is similar to the sodium
base process. The four significant sources of wastewater in the
ammonia base NSSC pulp manufacturing processes are: the evap-
orators, the powerhouse and maintenance area, the pulp mill,
and the paper machine. The raw waste load from this process
averages about 33.5 kg BOD5 and 17 kg suspended solids per MT
of product (EN-147).
The spent sodium base NSSC liquor can be introduced
into a kraft recovery system. The raw waste load for unbleached
kraft-NSSC (cross recovery) mills averages about 19.4 kg BOD5 and
20.5 kg suspended solids per MT of product.
The raw waste load of paperboard from waste paper
mills comes from the stock preparation area and is a function
of the type of raw materials and additives. The raw waste load
for these mills averages about 11.2 kg BOD5 and 2.8 to 81 kg
suspended solids per MT of production.
BPCTCA effluent limitations (July 1, 1977 standards)
are based upon the average of the best existing performance by
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plants of various sizes, ages, and unit processes within the
industry. BATEA effluent limitations have been established by
identifying the very best control and treatment technology em-
ployed by a specific point source, or by applying technology
from other industry areas where it is transferable. Technol-
ogies have been identified below which will allow mills to meet
the limitations, but mills have the option to use other internal
and external controls which may prove to be more cost effective.
Identification of BPCTCA
Unbleached Kraft and Kraft-NSSC
1) Hot Stock Screening - a process modification
in which the pulp is passed through a fibro-
lizer to fractionate knots and then through
a hot stock screen to remove shives.
2) Spill Evaporator Boil-Out Storage - material
from these sources can be stored in a tank
from which it can be slowly returned to the
process or discharged to the wastewater
treatment system.
3) Efficient Pulp Washing - the use of multi-
stage countercurrent washers for more ef-
ficient recovery of black liquor.
Sodium and Ammonia-Base NSSC
Non-Polluting Spent Liquor Disposal - partial
evaporation followed by incineration.
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Paper Machines
1) Water Showers - use of low-volume and high-
pressure showers in the machines.
2) Segregation of White Water Systems - permits
maximum reuse of white water and allows only
low fiber content white water to enter the
sewer.
3) Press Water Filtering - use of a vibrating
or centrifugal screen to remove felt hairs
prior to press water reuse.
4) Collection System for Vacuum Pump Seal
Water - collection for partial reuse.
5) Save-all and Associated Equipment - recovery
of fibrous and other suspended material which
escapes from the paper machine.
6) Gland Water Reduction - flow control of seal
water to equipment packing glands.
External Treatment
1) Suspended Solids Reduction - This step in-
volves removal of the suspended solids from
the raw waste stream. Screens can be used
to remove coarse solids. The suspended solids
removal can incorporate: a) an earthen 'Still-
ing basin; b) mechanical clarification; and/or
c) dissolving air floatation.
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2) BODS Reduction - BOD5 removal is accom-
lished by biological oxidation with nutrient
addition. The treatment system can consist
of an activated sludge process (AS), aerated
stabilization basins (ASB), and/or storage
oxidation ponds (SO).
3) Biological Solids Removal - Biological solids
may be removed by either mechanical clarifiers,
stilling ponds (or an SO following an ASB),
or a quiescent zone in an ASB beyond the in-
fluence of the aeration equipment.
4) Sludge Disposal - Stilling pond disposal of
biological sludge or sludge thickening and
dewatering with ultimate disposal by incinera-
tion or sanitary landfilling.
Identification of BATEA
BATEA consists of the 3PCTCA defined above plus the
following additional mill improvements and external advanced
wastewater treatment practices.
Internal Controls
Pulping operations of all applicable subcategories
can implement modification and procedures for:
1) Reuse of fresh water filter backwash;
2) Control of spills such that major pollution
loads enter a retention basin and are ulti-
mately either reused, greadually discharged
into the treatment system, or treated separately;
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3) Minimize pulp wash and extraction water
without decreasing washing efficiencies;
4) Extensive internal reuse of process waters;
5) Segregation and reuse of cooling waters; and
6) Extensive reduction of gland water spillage.
All of the above procedures, except (1) and (3), can be imple-
mented by paper machine systems.
External Treatment
BATEA external treatment is defined as BPCTCA with
the addition of the following external processes:
1) BOD5 Reduction - treatment system consisting
of biological oxidation with nutrient addi-
tion for further removal of BOD5.
2) Suspended Solids Reduction - additional sus-
pended solids removal can be achieved by
mixed media filtration with, if necessary,
chemical addition and coagulation.
3) Color Reduction - color reduction can be
achieved by minimum lime treatment and re-
verse osmosis.
The application of the BATEA limitations to pulp and
paper mills would result in an estimated reduction of approxi-
mately 49,600 MT BOD5, 103,000 MT organic, and 132,274 MT of
suspended solids per year below effluents with BPCTCA.
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3.8.2 Wood Waste Combustion
Process Description
A common method of disposing of wood residues from
forestry operations and lumber processing is incineration in
conical burners. Approximately 24.9 million MT of wood waste
is combusted annually in these incinerators according to a
1971 estimate (VA-067).
Conical burners, truncated metal cones with a screened
top vent, are charged by introducing the material to a grate
using either conveyer or bulldozer. No supplemental fuel is
used, but combustion air is often supplemented by air blown into
the chamber below the grate and by air introduced through periph-
eral openings in the shell.
Atmospheric Emissions and Control
The quantity and types of pollutants emitted from
conical burners depend on the composition and moisture content
of the waste, control of combustion air, type of charging system
used, and the condition in which the incinerator is maintained.
The most critical factor seems to be maintenance practices.
The burners sometimes have missing doors and holes in the shell,
resulting in excessive combustion air, or low temperatures, with
resultant high emission rates of organic pollutants.
Emission factors for waste wood incineration in coni-
cal burners without controls are about 5-5 kg of hydrocarbons
per MT burned and from 1 to 20 kg of particulates per MT burned,
depending on the operation and maintenance of the burner (EN-071)
Typically, a conical burner produces 5 kg of particulates per
ton of waste burned (EN-197), estimated to be approximately 38
-226-
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percent organic matter (VA-067). Based on these emission fac-
tors and the 1971 estimate of 24.9 million MT of wood waste
combusted annually, the emissions from conical burners are
137,000 MT hydrocarbons and 47,400 MT organic particulates per
year.
Emissions from conical burners can be reduced by using
conveyors instead of bulldozers for charging, proper control of
combustion air, and good maintenance practices. Particulate
control systems have been adapted to conical burners with some
success. These control systems include water curtains (wet
caps) and water scrubbers (SI-106).
Conical burners have been banned in most states (EN-197)
This measure is the most effective method of eliminating emissions
from the burners. When using this method the waste wood can be
used as a raw material for other processes such as production of
pulp or wood chemicals, or disposed of by some other method.
3.8.3 Beer Brewing
Process Description
The four major production stages of brewing operations
are listed below (EN-071):
1) Brewhouse operation, which include:
a) malting of the barley,
b) addition of adjuncts to barley mash,
c) conversion of starch in barley and adjuncts
to maltose sugar by enzymatic processes ,
d) separation of wort from grain by straining,
and
d) hopping and boiling of the wort.
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2) Fermentation, which includes:
a) cooling of the wort,
b) addition of yeast cultures,
c) fermentation for 7 to 10 days,
d) removal of settled yeast, and
e) filtration and carbonization.
3) Aging for 1 to 2 months under refrigeration, and
4) Packaging, which includes:
a) bottling - pasteurization, and
b) racking draft beer.
Atmospheric Emissions and Control
Gaseous organic chemicals are emitted from the drying
of spent grains and yeast in beer. The results of a study of
gaseous emissions from whiskey fermentation units, which are
similar to those for beer production, showed that at least six
organic compounds were emitted from these units: ethyl acetate,
ethyl alcohol, isopropyl alcohol, n-propyl alcohol, isoamyl
alcohol, and isoamyl acetate (CA-281). Other compounds were
detected by chromatograph but were present in trace amounts
only. Organic particulate emissions occur from the handling of
grain and from the drying operations.
The emissions from malt beverage production in 1973
were estimated to be 67,810 MT of organic chemicals and 108,500
MT of particulates (MO-201). These values are based on totally
estimated emission factors of indeterminate accuracy (EI-017).
-228-
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The application of best available control technology for organic
chemicals and particulates can reduce emissions of these pollu-
tants from beer brewing operations by approximately 99 and 95
percent, respectively (HO-244). The application of these re-
duction factors provides reduction potential of 67,100 MT hydro-
carbons and 103,000 MT particulates per year.
Water Effluents and Control
Wash water from the various brewing vessels, general
plant washdown, and waste beer from breakage and spillage in the
packaging lines contribute large waste loads. Another large
waste source is press liquor from grain drying. Some brewers
partially dry the spent grain with large mechanical presses
prior to selling the grain as feed. The liquor from these
presses has a very high BOD content and may constitute 25 per-
cent or more of the total plant BOD load (EN-294).
Effluent characteristics have been reported for ten
breweries (EN-294). Individual waste parameters fluctuated
considerably over the brewing day because of the batch-type
operation. The BOD concentration in the brewery effluents aver-
aged 2200 mg/2, and suspended solids concentration averaged 900
mg/&. Soluble BOD constituted about 75 percent of the total
BOD. A COD:BOD ratio of about 2:1 was indicated, but this fac-
tor was somewhat variable. Water consumption in the industry
was found to range from 5 to 15 liters per liter of beer.
Most breweries discharge waste to large municipal
sewage systems where it undergoes various types of primary and
secondary treatment. The treatment efficiencies for the wastes
from the ten breweries studied averaged approximately 90 percent
BOD removal and 75 percent suspended solids removal.
-229-
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Additional treatment similar to that required for
BATEA of fruit and vegetable processing wastes could be applied
to brewery wastes, i.e., in-plant waste reduction practices
plus additional secondary treatment or advanced treatment such
as a sand filter and disinfection. Assuming that this addi-
tional treatment would result in the same reductions in BOD and
suspended solids as those estimated for the fruit and vegetable
industry (approximately 75 percent), the effluents from' beer
production could be reduced by about 26,600 MT BOD5, 53,500 MT
organic, and 27,260 MT suspended solids per year.
3.8.4 Fruit and Vegetable Processing
Process Description
Many of the steps used in the proce.ss of canning and
freezing of fruits and vegetables are common to the industry as
a whole. Typically, the fruit or vegetable is received, washed,
and sorted to prepare it for subsequent processing. Commodities
such as apples, citrus and potatoes are then usually peeled when
the end product is a solid (slices, cubes, or powder). If the
final product is a juice or liquid product, the peel is not
removed from either the citrus or the apples. Subsequent process-
ing steps include trimming, slicing, blanching, cooking, cooling,
transport, etc., and the final canning and freezing operations.
In packing operations for fresh fruits and vegetables,
picked fruit is sometimes exposed to heat, moisture, and ethylene
to bleach out the chlorophyll masking the color. Some products
are dyed with an oil-soluble non-toxic dye and waxed to improve
appearance.
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Atmospheric Emissions and Control
Atmospheric emissions of volatile organics are known
to occur from operations involved in the processing of fruits
and vegetables; however, quantitative data for these emissions
are practically nonexistent. The most significant sources are
probably the cooking operations in the canning and freezing
processes and the artificial ripening of fruits and vegetables
with ethylene. The volatile organic emissions from these
processes would occur in vent streams. Control methods such as
incineration and adsorption could be applied to effectively
eliminate these emissions. Monsanto Research Corporation esti-
mated that 1974 emissions from the processing of fruits and
vegetables were 47,700 MT of hydrocarbons and 945 MT of particu-
lates (MO-201). The data used to obtain these estimates is
totally estimated and is of indeterminate accuracy (EI-017).
The reduction potential for volatile organics is 47,200 MT/yr.
Water Effluents and Control
Water is used extensively in many phases of the fruit
and vegetable processing industry. Waste characteristics have
been determined for processing steps for apples, citrus, and
potatoes through in-plant sampling and supplemental data from
processors. Data from 10 apple plants, 20 citrus plants, and
15 potato plants were used to develop the tabulations of the
waste characteristics from these plants presented in Tables
3.8-7, 8, and 9. These tables show the water usage and waste
characteristics associated with various operations in the in-
dustry.
The total raw waste load due to processing fruits and
vegetables has been estimated to be 448,200 MT BOD5 and 2,118,300
MT SS (SI-106). The use of BPCTCA level controls (in-process
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TABLE 3.8-7
WATER USAGE AND
Process Steps
Washing
Peeling
Mechanical
Slicing
Deaeration
Cooking
Cooling (1)
Transport
Clean-up
(1) 95% recircu
WASTE CHARACTERIZAT
Water
Usage
I /MT
.142
104
638
71
267
58
58
1,558
lated
ION
k
0
0
2
2
0
0
0
1
IN APPLE
BOD5
g/MT
.09
. 16
.49
.21
. 14
.02
.02
.90
PROCESSING
Suspended
Solids
Kg/MT
0 .03
0.015
0. 182
0.12
0.05
0.005
0 .005
0. 30
Source: EN-408
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TABLE 3.8-8
WATER USAGE AND WASTE CHARACTERIZATION
Procenr. Stcor,
Fruit Cleaning
Extracting
Pasteurizing /Homogenizing
Cooling (1)
Juice Products
Segments
Juice Condensing
Barometric Condensing (2)
Juice Products
Waste Heat Evaporator
Peeled Fruit Washing
Caustic Treatment
Centrif uging
Container Washing
Waste Heat Evaporator
Condensate
Waste Heat Evaporator
Scrubber Effl.
Oil Lean Residue From
Separator
Boiler Blowdown
Regeneration Brine
Cleanup
Juice Products
Segments
Peel Products
(1) 90% recirculated
(2) 2% cooling tower blowdown
Water
Usage
K,/MT
303
389
62
221
400
50
71
129
1
144
75
334
351
126
60
13
705
371
484
IN CITRUS
BOD5
kg/MT
0.08
0.40
0
0.03
0.01
0.06
0.07
0.15
0.04
0.01
3.07
0
0.33
0.22
0.16
0.01
0
0.16
0.36
0.07
PROCESSING
Suspended
Solids
kg/MT
0.04
0.27
0
0.02
0.01
0.02
0.09
0.09
0.01
0.01
0.51
0
0.11
0.08
0.25
0.01
0
0.16
0.07
0.11
Source: EN-408
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TABLE 3.8-9
i
N3
LO
-!>
I
WATER
Process Steps
Washing
Peeling
Dry Caustic
Wet Caustic
Steam
Trimming
Slicing
Dehydrated
Frozen
Blanching
Dehydrated
Frozen
Cooling
Cooking
Dewatering
Fryer Scrubber
Fryer Belt Spray
Refrigeration
Transport Water
Cleanup
USAGE AND WASTE CHARACTERIZATION IN POTATO PROCESSING
Water Usage
», /MT
1,102
1,448
3,000
2,391
793
764
1,519
175
1,043
668
448
513
417
417
1,602
292
951
kg AIT
0.676
7.325
20.245
15.215
0.777
0.296
2.630
0.701
5.461
1.172
1.192
0.471
-
-
-
0.261
2.725
BOD5
Ib/T
1.35
14.62
40.41
30.37
1.55
0.59
5.25
1.40
10.9
2.34
2.38
0.94
-
-
-
0.52
5.44
Suspended
kR/MT
1.383
9.569
28.662
13.427
0.26
0.701
1.303
0.601
2.104
-
-
0.351
-
-
-
-
Solids
Ib/T
2.76
19.1
57.2
26.8
0.52
1.4
2.6
1.2
4.2
-
-
0.70
-
-
-
-
Source: EN-408
-------
and end-or-pipe treatment assumed to be currently utilized) re-
sults in estimated reductions of 90 percent BOD5 and 80 percent
suspended solids (EN-408). Therefore, the effluents from fruit
and vegetable processing are estimated to be 44,820 MT BOD5,
92,200 MT organics, and 42,370 MT SS per year.
The BATEA control treatment for wastes from apple,
citrus, and potato processing includes housekeeping and water
use practices to reduce the raw waste, preliminary screening,
primary settling, and secondary biological treatment (BPCTCA)
plus additional secondary treatment or advanced treatment such
as a sand filter and disinfection (EN-408). Several in-plant
controls and modifications that provide alternatives and trade-
offs between controls and additional treatment facilities re-
quired to meet the BATEA effluent guidelines are:
1) recycle of raw material wash water following
solids removal and chlorination;
2) utilization of low water usage peel removal
equipment;
3) removal of solids from transport and slicing
waters;
4) reduction of belt wash water by improved mechan-
ical cleaning of belts;
5) reuse of cooling water; and
6) extensive dry cleanup to replace washing.
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The effluent guideline limitations for BATEA average
approximately 75 percent less than the limitations for BPCTCA
(EN-408). Application of BATEA would therefore result in the
reduction of about 34,072 MT of BOD5, 69,900 MT organic, and
31,780 MT of SS per year from fruit and vegetable processing
operations.
3.8.5 Tobacco Manufacture
Process Description
Tobacco manufacturers usually maintain a pack house
operation near each major tobacco market for preparing the
tobacco for shipment. This preparation consists of pressing
leaf into cylindrical wooden containers called hogsheads or
bundling in large burlap sheets.
Leaf tobacco is transported to a steaming and/or
redrying plant where it is reclassified and rehumidified. The
larger leaf stems are removed prior to redrying and pressing
into hogsheads. These hogsheads are stored in warehouse-type
sheds.
The cigarette manufacturing process begins with re-
moval of tabacco from storage. It is rehumidified and removed
from the hogsheads. Leaf strip next passes through various
cleaning, tumbling, blending, and treating operations to pre-
pare it for the shredding operation. After shedding, the tobacco
is bulk aged and conveyed to cigarette making machines inhere it
is metered, formed, and wrapped with paper into continuous rods.
The cigarettes then undergo the final processing and packing
operations.
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Atmospheric Emissions and Control of Organic
Emissions from Tobacco Manufacture
Organic atmospheric emissions from tobacco manufactur-
ing consist of tobacco volatiles and particles. Measured data
for these emissions are practically nonexistent, but they have
been estimated to be 39,710 MT volatile organics and 794 MT
particulates in 1973 (MO-201). The emissions exit in vent
streams from the various manufacturing processes and could be
elimianted by control devices such as incinerators, adsorbers,
scrubbers, and filters. The reduction potential for voaltile
organics is 39,300 MT/yr.
3.8.6 Grain and Feed Mills and Elevators
process Description
Grain elevators are primarily transfer and storage
units. In addition, many elevator locations also contain feed
manufacturing facilities. A variety of grain handling configura-
tions are used at elevators depending on the number and quantity
of grains handled and the amount of processing required. The
following operations can occur at grain elevators: receiving,
transfer and storage, cleaning, drying, and milling or grinding.
Grain processing may include wet and dry milling (cereals),
flour milling, oil-seed crushing, and distilling. Feed manu-
facturing involves receiving, conditioning (drying, sizing,
cleaning), blending, packaging, and loading.
Atmospheric Emissions and Control
Particulate emissions occur in grain and feed opera-
tions because of the dry, light nature of most grains and the
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methods of handling in pneumatic and mechanical conveyors.
Emissions from grain operations may be separated into transfer
losses and those occurring at processing operations. Loading
and unloading areas have the greatest emissions. Conveying
equipment and storage bins are also sources of dust emissions.
Belt conveyors have less friction than either screw or drag
conveyors and generate less dust. Emissions occur at belt trans-
fer points as material moves on or off a belt. The discharge
points of pneumatic conveying equipment are potential sources of
dust emissions. Storage bins vent dust-laden air during loading
operations.
Factors affecting the emissions from grain elevators
include the type of grain, the moisture content of the grain,
the amount of foreign material in the grain, and the degree of
enclosure at loading and unloading areas. Approximately 89 per-
cent of the dust' in grain loading areas is organic (VA-067) .
Wet milling operations are not conducive to major
dust formation, although particulates may escape from drier
cyclones. Dry milling is somewhat dusty in its operation.
Most handling and transfer in these operations is pneumatic,
allowing good dust control. Losses can occur from extracting
and drying operations and from cyclone collectors used in oil-
seed crushing operations.
Heated air in rotary, column, or shelf driers is
•normally used to dry the grain. The particulate material emanat-
ing from the driers is generally classified as chaff or, in the
case of corn, "beeswing." Particle size is large, but the par-
ticles are extremely light and can be carried miles on a windy
day.
-238-
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operations include the type of processing (wee or dry), quantity
of grain processed, che amount of cleaning, the degree of drying
and heating, the type of drier, the amount of grinding, and the
type of grain processed.
The dust from grain and feed mills and elevators may
be collected by inertial devices, fabric filters, and electro-
scatic precipitators. Enclosures or hoods with proper ventila-
tion and recovery should be installed for control of loading
and unloading operations. The use of particulate concrol equip-
ment can reduce the emissions from grain and feed mills and
elevators by approximately 99 percenc (HO-244). The application
of these controls would result in a reduction of about 1,300,000 MT
per year of parciculaces (VA-067).
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3 . 9 Open Sources
This category includes open burning of agricultural,
land clearance, and forest wastes. The quantities of organic
air pollutants resulting from these practices are shown in
Table 3.9-1. It was determined that the reduction potentials
in this category are 100 percent based on the elimination of
open burning of these wastes. No estimates were made for water
effluents or solid waste.
3.9.1 Agricultural Field Burning and Land Clearance
A common method of controlling pests and disposing of
agricultural and land clearance wastes such as cut grass, weeds,
and field residues is open burning. Agricultural operations
contributing heavily to the waste burning problem include grass
seed production and maintaining grain 'fields, rangelands, and
sugar cane fields.
Atmospheric emissions from burning straw and stubble
are generally characteristic of vegetable plant sources. Cel-
lulose and lignin are the major constituents of the plants.
Emissions consist of volatile organic compounds and smoke plus
the combustion products. Approximately 10 kg of volatile or-
ganics and 8.5 kg of particulates are emitted per ton of waste
burned (EN-071).
About 254 million MT of crop residues, brush, weeds,
and other vegetation are burned annually (US-336). This open
burning produces approximately 2,540,000 MT volatile organics
and 820,000 MT organic particulates per year. Regulations
against open burning have probably reduced current emissions
below these levels. Open burning emissions are affected by
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TABLE 3.9-1
ATMOSPHERIC EMISSIONS FROM OPEN SOURCES
Subcategory
Emissions (MT'/yr)
Volatile
Particulate
Year Organics Ref Organics Ref
Open Sources
Agricultural Field
Burning & Land Clearance 1968 2,540,000 1,5
820,000
Prescribed Forest
Burning
1968
471.700 1,3 152,300 1,3,4
TOTAL
3,011,700
972,800
Sources: 1. US-336
2. WA-252
3. EN-071
4. VA-067
5. MS-001
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many factors including wind; ambient temperatures; moisture
content, size and shape of the fuel; and compactness of fuel
bed (VA-067). The emissions and their effects can be reduced
by choosing periods with optimum conditions for burning of the
refuse. Collection and incineration of the wastes in properly
controlled incinerators could significantly reduce emissions.
The most effective method of controlling the emissions
is to use other disposal methods for the wastes and eliminate
open burning of agricultural and land clearance waste. Alter-
natives include abandonment or burying at the site, transport
and disposal in remote areas, and waste utilization. Potential
harmful aspects of abandoned or buried vegetation such as odor,
water pollution, fire hazards, insects and organisms should be
considered before employing these methods. Composting and ani-
mal feeding are potential alterantives to burning (NA-032).
3.9.2 Prescribed Forest Burning
Prescribed burning of forest wastes has been practiced
since the turn of the century. This practice is used in the fol-
lowing instances (EN-186):
1) to reduce the fuel accumulation and there-
fore the hazard of uncontrollable wildfires;
2) to control undesirable species of trees;
3) to improve the habitat for wildlife;
4) to prepare a seedbed for natural reseeding
and for planting of pines;
5) to enhance grazing;
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6) to control the brown spot fungus disease
of longleaf pine; and
7) to increase volume growth of trees.
The United States Forest Service estimates that 1.42
million hectares (representing 69.3 million MT of combustible
material) were burned in controlled forest fires in 1966 (US-336).
Open burning of landscape and pruning refuse, representative of
forest wastes, produces about 10 kg of organics and 8.5 kg of
particulates per MT burned (EN-071). Twenty-four gaseous or-
ganic emissions have been identified in slash burning experiments
(SA-223). The gas chromatographic analysis of the organic gases
showed that 15 to 40 percent of the gas was composed of methane
and ethylene and that ethane and acetylene were the next most
abundant materials. The smoke from rye-grass burns contained
about 38 percent organic 'matter (VA-067). This value is probably
representative of the organic content of particulates from slash
burning.
The annual emissions from controlled forest burning
are estimated to be 693,000 MT of volatile organics and 224,000
MT of organic particulates. The obvious method of eliminating
these organic emissions is to use disposal methods other than
combustion for the forest wastes. Forest scraps can be processed
by chipping or crushing and used as raw materials for kraft pulp
mills or processes producing fiberboard, charcoal, or synthetic
firewood: At present, the economic feasibility of alternative
methods including collection and transport for landfilling or
chipping appears to be low. The cost of eliminating the waste
by burning is about $0.91 per MT, whereas disposal by chipping
costs about $11 per MT (WA-252). Despite the costs of alternative
disposal methods, the reduction potential for prescribed forest
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burning is determined to be 100 percent, resulting from com-
plete elimination of open burning of the wastes.
In lieu of complete elimination of open burning, the
air pollution aspects of slash burning can be minimized by
various practices. Tests have shown that the smoldering phase
of combustion is of greatest significance in air pollutant pro-
duction during slash burning. The initial 80 percent of the
fuel burned accounts for only 20 to 30 percent of the organic
emissions (SA-223). This suggests that the air pollution from
slash burns could be substantially reduced by choosing condi-
tions that promote a high energy fire and by rapid mop-up of
the burns.
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3.10 Natural Sources
The major natural sources of organic air pollutants
that have been identified and for which quantitative estimates
of emissions are available include decomposition of organic
matter, plant functions, and enteric fermentation in animals.
These are discussed in this section.
Natural organic materials contribute to the organic
load of waterways in many ways. Sources include dead organic
material originating in the water such as fish or aquatic plants
and natural organic material in the runoff from watersheds such
as leaves, wood, carcasses, and animal waste. This organic
material is normally removed in nature by either aerobic or
anaerobic processes. No quantitative data on natural water pol-
lutants were available.
Natural processes also produce solid wastes such as
plant residues, animal waste, and carcasses. These solid wastes
are normally decomposed in situ unless they are washed or blown
into a body of water. Occasionally, these wastes are burned or
otherwide disposed of for safety reasons or to allow utilization
of the land.
Quantitative estimates of water quality impact and
solid waste contributions from natural processes are not avail-
able; therefore, these types of emissions will not be discussed
in detail. Estimates of the quantities of atmospheric emissions
from major natural sources are shown in Table 3.10-1. The values
given in this table are only estimates based on the best data
available on natural emissions.
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TABLE 3.10-1. ATMOSPHERIC EMISSIONS FROM NATURAL SOURCES
SUBCATEGORY
Decomposition of
Organic Material
Plants
Enteric Fermentation
in Animals
CATEGORY TOTAL
Emissions (MT/yr)
VOLATILE PARTICULATE
YEAR ORGANICS REF ORGANICS REF
1968 71,700,000 3
1972 9,100,000 4,5,6 1,500,000
1963 4,500,000 1 --
85,300,000 1,500,000
Sources: 1. KO-172
2. WA-252
3. RO-228
4. RA-156
5. AB-044
6. RA-209
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3.10.1 Process Description
Decomposition of Organic Material
Methane is produced by the anaerobic bacterial decora-
position of organic matter. This process occurs in such places
as lakes, marshes, and paddy fields. Trace quantities of ethane,
acetylene, ethylene, propane, and propylene are also products of
methane fermentation. Robinson and Robbins (RO-228) estimated
that, on a worldwide basis, 13.7 x 108 MT of methane per year
are emitted to the atmosphere from swamps, tropical areas, lake
sediment, and various soils. They also estimated that carotene
decomposition of organic material releases an estimated 63.5
million MT per year of terpene-type hydrocarbons to the atmosphere
From these global estimates, the annual production
rate of organics due to the decomposition of organic material
in the United States is estimated to be 71.7 million MT. This
estimate was obtained by assuming that the United States' pro-
duction rate per unit area is one-half that of the average for
the vegetated earth surface. This assumption is based on the
fact that emission rates are higher in tropical than nontropical
areas, and that a significant portion of the global emissions
are from paddy fields (KO-172).
There is no feasible method of controlling organic
atmospheric emissions from this source. However, when reduction
of the area covered by rice paddies and marshes is attractive,
this will result in a reduction of atmospheric emissions.
Plant Functions
Plants release a variety of volatile organics. The
major organic substances emitted to the atmosphere from plants
-247-
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are monoterpentenes (Ci0) such as a-pinene, B-pinene and limonene
and the hemiterpene (C5) isoprene (RA-156). Rasmussen and Went
(RA-209) conducted in situ gas chromatographic studies at tem-
perate forests and fields. They reported that the emission rates
of organic volatiles from plants show diurnal and temperature
variations and are related to the mass and activity of the
foliage.
The biological and atmospheric fates of organic foliar
emissions are poorly understood. It is believed that significant
amounts of the naturally occurring organic compounds are disposed
of in a biological sink, i.e., populations of fungi, microbial
life growing on vegetation surfaces, and absorption by components
in the soil (AB-044). Terpenes which have been studied show the
high reactivity predicted by their olefinic structures (RA-156).
It has been suggested that these photochemically reactive com-
pounds undergo the photochemical reaction for smog formation in
which olefins, nitric oxides, and sunlight react to form ozone,
peroxyacyl nitrate-like compounds, and aerosol material (RA-209).
The aerosols (Aitken nuclei) produced by this photochemical
polymerization process are believed to be responsible for the
blue haze associated with vegetation.
Estimates of worldwide volatile organic emissions vary
greatly. Table 3.10-2 summarizes global terpene emission estimates
determined by various investigators. Went's estimate of 154
million MT of terpenes emitted per year is approximately the
median value and corresponds to Rasmussen's estimate at a canopy
depth of 75 cm. A United States' emission estimate of 15.4
million MT per year was derived from this global estimate of
154 million MT per year by assuming that the terpene emission
rate per unit area for the total United States area (1017 cm2)
is equal to that of the total vegetated earth surface (1018 cm2)
(RA-156). Abeles, et al., (AB-044) estimated that the natural
-248- •
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TABLE 3.10-2. GLOBAL TERPENE EMISSION ESTIMATES
Inves tigator
Rasmussen (1972)
Went (1960)
Rasmussen and Went (1964)
Ripperton, White and
Jeffries (1967)
Method
Intact plants in leaf
assimilation chambers
Sum of sagebrush emission
and terpenes as per-
centage of plant tissues
1. Bagging foliage
2. Enclosure forbs
3. In-situ ambient con-
centration
Rx rate 03/pinene
Estimate
(10s MT/vr)
23.4 - 464
154
23.4
13.5
432
. 2tolO times
previous
estimates
Emissions vary with canopy depth (10-200 cm canopy depths in study)
Source: RA-156
-249-
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production of ethylene from plants in the United States is ap-
proximately 18,000 MT per year.
Ragweed, goldenrod, bermuda grass, walnut trees, and
numerous other weeds, economic plants, and trees produce pollens.
There is evidence that 1.5 million MT of pollen move into the
atmosphere over the United States every year (WA-252). The
major detrimental effect of pollen is, of course, its allergenic
nature.
Enteric Fermentation in Animals
Methane is produced as the result of enteric fermenta-
tion in animals. The global production of methane from this
source is estimated to be approximately 45 million MT (KO-172).
The United States' methane emissions from this source are about
4.5 million MT per year assuming that the animal population is
uniformly distributed over all vegetated land areas.
3.10.2 Control of Emissions
The only method of controlling emissions from natural
processes is to reduce the quantity of plants and animals causing
the emissions. This control method is not practical in most
cases; therefore, the reduction potential for emissions from
natural process is negligible.
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3.11 Solid Waste Disposal
This section describes techniques and processes for
the disposal of the following solid wastes:
1) Wastes generated by urban, rural, commercial,
municipal, institutional and industrial
sources, collected and disposed of by
municipal agencies.
2) Municipal sewage solids.
3) Solid waste disposed of by non-industrial
intermediate size incinerators, such as
apartment house incinerators. This cate-
gory does not cover, however, industrial
wastes handled on-site or off-site by the
industries themselves or by private con-
tractors who do not use municipal facilities.
4) Non-collected urban and rural solid wastes
which are disposed of by various unidentified
and/or unquantified methods.
Subcategories within the agricultural and forest pro-
ducts industry also produce organic solid wastes. Table 3.11-1
shows the composition of solid wastes generated by various
processes within the industry. These wastes are normally either
allowed to decompose in situ or are disposed of by methods in-
cluding incineration, open burning, landfills and spreading,
open dumping, or utilization within another process.
Eventually all solid waste is disposed of by some type
of open dumping or landfilling. Incineration merely produces
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TABLE 3.11-1. SOLID WASTES IN THE AGRICULTURAL
AND FOREST PRODUCTS INDUSTRY
Subcategory
Lives Cock/Poultry
Grains
Logging Operations
Fruits & Vegetables
Sawmills
Pulp & Paper
Secondary Wood Mfg.
Processed Foods
Meat Products
Paper Products
Leather
Fats, Oil, Misc
Foods
Bakery
Coffee Roasting
Tobacco
Solid Waste Composition Ref
Manure, carcasses 2
Field residue 2
Logging residue 4
Field residue 2
Residual from canning & freezing 2
Unused sawdust 2
Pulp residue & unusable
paper residue 2
Chips, shavings, sawdust 2
Processing residuals 2
Paunch manure 2
Contaminated or unusable paper
and wood 2
Flesh scrapings, hair & nonleather
residuals 2
Various processing residuals 2
Residuals & unusable materials
& products 2
Chaff 1, 3
Fines, lints, unacceptable
material 2
Sources :
1.
2.
3.
4.
DA-069
EN-067
US-303
WA-234
-252-
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a less voluminous, more stable product for landftiling. Today,
other reasons such as recovering heating value and recycling of
valuable metals have made incineration even more attractive.
Table 3.11-2 lists the types of solid waste disposal techniques
examined in this category.
The organic atmospheric emissions, liquid effluents,
and solid wastes from the disposal methods are described in
this section. The organics were quantified and are listed in
Tables 3.11-3, 3.11-4, and 3.11-5. The values are based on a
collected municipal refuse rate of 240 x 106 MT/year and a con-
version factor of 25 mg/£ BOD approximately equals 52 mg/2. total
organics (SO-080).
3.11.1 Process Description
Open Dumping
Burning at open dumps is the largest single atmospheric
emitter of organics of all the solid waste disposal methods. The
total emission rate in 1970 was approximately two million metric
tons per year of both volatile organics and organic particulates.
Since that time there has been a major effort to shut down all
burning dumps in the United States. The success of this effort
has not been documented, but it is believed to be only partially
completed.
If waste at the dumps is not burned, decomposition of
the organic matter will produce organic gases consisting mainly
of methane. The methane produced in open dumps is estimated
at 67,000 metric tons per year. This emission rate is, at best,
an order-of-magnitude estimate due to the complicated and
variable processes involved in the decomposition of the organic
material.
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TABLE 3,11-2. SOLID WASTE DISPOSAL METHODS
1) Open Dumps
a) Open burning - collect and uncollected refuse
b) Open dumping
c) Sewage sludge lagooning and dumping
2) Landfills
a) Landfill
b) Sanitary Landfill
3) Incineration
a) Municipal incinerators
b) Intermediate non-industrial incinerators
c) Sewage sludge incinerators
d) Incineration of uncollected urban and rural refuse
-254-
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TABLE 3.11-3. ATMOSPHERIC EMISSIONS FROM SOLID WASTE
i
ro
Ui
DISPOSAL OPERATIONS IN METRIC TONS PER YEAR
Year Volatile Organics Ref Organic ParCiculates Ref
Open burning of collected
refuse
Open burning of uncollected
urban refuse
Open burning of uncollected
rural refuse
Methane from decomposition
in dumps and landfills
Municipal incineration
Intermediate size
incinerators
Schools
Commercial
High-rise apartments
Medical
Sewage sludge incinerators
Sources - 1. LA-204
2. MS-001
3. MA- 2 56
4. CH-281
1963 1,656
1972 345
1972 322
1974 246
1974 51
1972 59
1972 35
1972 18
1972 3
1972 2
1974 4
5. BR-279
6. EN-341
7. HE- 159
8. FO-001
,000
,000
,000
,900
,500
,800
,300
,600
,280
,640
,150
1
2
2
3
4
5
5
5
5
5
6
378,000
80,000
74,000
0
65,400
38,450
18,100
16,500
1,800
2,050
4,900
7
2
2
8
4
5
5
5
5
5
6
-------
TABLE 3.11-4. WASTEWATER EFFLUENTS FROM SOLID WASTE
DISPOSAL IN METRIC TONS PER YEAR
Leachate from open dumps
Leachate from burning dumps
Leachate from landfills
Leachate from sanitary
landfills
i
t_n Leachate from lagoons
^ and oxidation ponds
Total Suspended
Year Oruanics ^01) COD Solids
S? „
1974 293,000 141,000 176,000 106,000
1974 245,000 118,000 141,000 70,600
1974 171,000 82,300 103,000 61,700
1974 24,500 11,800 14,700 8,800
1974 850 410 1,500
Uef
1
1
2
3
1
TOTAL 736,000 354,000 436,000 247,000
Sources: 1. SA-103
2. BO-181
3. HO-250
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TABLE 3.11-5. ORGANIC SOLIDS FROM SOLID WASTE DISPOSAL OPERATIONS
Year
Organic Solids
(MT/Yr)
Ref
Bottom ash from non-industrial
intermediate size incinerators
1972
257,000
Bottom ash from municipal
incinerators
1970
154,000
Bottom ash from sewage sludge
incinerators
1974
77,400
Collected fly ash from
municipal incinerators
1970
47,600
Sources: 1. BR-279
2. CH-281
3. EN-341
-------
The majority of the liquid organic effluent from open
dumps is leachates formed by percolation of rainfall and infil-
tration of ground water. The leachate rate is estimated at
1.76 x 1010 liters per year. This value is an order-of-magnitude
estimate. The actual leachate rate will depend on hydrology,
geology, topography, type of refuse, and age of the refuse. The
estimated leachate quality for open dumps and burning dumps is
shown in Table 3.11-6.
Also considered in open dumping is the lagooning of
sewage sludge. Lagooning is the most popular method of handling
sewage solids. Air emissions can result from the lagoons due
to aerobic and anaerobic decomposition of organics within the
sludge liquor. The gaseous products are mainly HaS and methane.
Although the total gas quantity is relatively small, the gas
produced is often offensive in odor and may be a nuisance.
Infiltration of wastewater into the soils making up
the pond may also be considered a source of organic effluents.
The estimated volume for this leachate was the smallest of all
those calculated in this solid waste category. The BOD, COD,
and total organics emitted are estimated to be 410, 1,500, and
850 metric tons per year, respectively. These numbers are
order of magnitude estimates.
Open Burning of Uncollected Refuse
A 1972 report estimated the volume of uncollected
urban and rural residential and municipal refuse to be 58 x 106
MT/year (MS-001). Of this amount approximately 29 x 10s MT/year
was open burned. The emissions from open burning were estimated
from the same emission factors used for the open burning dump.
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TABLE 3.11-6. ESTIMATED QUALITIES OF DUMP AND LANDFILL LEACHATES
Open Dump
Burning Dump
Landfills
Sanitary Landfills
BOD
mg/£
8,000
10,000
8,000
8,000
COD
mg/S,
10,000
12,000
10,000
10,000
Dissolved Solids
mg/£
2,000
6,000
2,000
2,000
Total Solids
mg/i
8,000
12,000
8,000
8,000
Sources: SA-103, RO-211, HU-111, BO-181, HO-250, EM-007,
FU-021, EM-003.
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The remaining 29 x 106 MT/year was disposed of by
intermediate size incinerators to be discussed later and by open
dumping. Approximately 90 percent of the remaining refuse was
open dumped in unidentified locations. There were no calculated
emissions for the open dumped uncollected solid waste.
Landfills
Regular landfills covered with soil periodically and
those classified as the sanitary-type covered on a daily basis
are similar in design and, therefore, have similar emissions
and effluents. The effluent source from landfills is leachates
from the landfill sites. The emissions result from gases
produced by decomposition of the organic matter.
The leachate from landfills results from percolation
of -rainfall infiltration of ground waters into the fill site.
In the United States, the volume of such leachates has been
estimated as 1.03 x 1010 liters per year for regular landfills
and 1.47 x 109 liters per year for sanitary landfills. The
estimated quality of leachates is shown in Table 3.11-7. The
actual composition depends on hydrology, geology, topography,
type of refuse, and age of the refuse.
The main organic constituent of the gases formed
during the decomposition of organic materials is methane. The
atmospheric emissions from regular landfills are estimated to
be 157,000 metric tons per year, and for sanitary landfills
22,400 metric tons per year.
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TABLE 3.11-7. POTENTIAL REDUCTION OF ORGANIC EMISSIONS AND EFFLUENTS
REDUCTION METHOD
1. Replacement of open burning dumps and
open dumps wLl.li sanitary landfills
2. Replacement of open burning of
uncoLLccted refuse with collection and
sanitary landfill ing.
3. Containment of Leachatcs and flaring
decomposition gases from existing
sanitary landfills.
4. Application of afterburners or
auxiliary burners to:
municipal incinerators
intermediate incinerators
sewage sludge inc i ne ra tors
TOTAL
ATMOSPHERIC
EMISSIONS REDUCTIONS (MT/YR)
Vo1 at i1e Organic
Organics Part Leu Lares
1. , 520.000
607,000
21,000
48,900
12,000
3^900
2,210 ,000
378.000
154,000
62,100
7.740
4, 660_
607,000
WATER EFFLUENTS REDUCTIONS (MT/YR)
Total Organj.cs liOD COD
48,900 23,500 23.500
22,000
10.600
13.200 8.380
70,900
34,100
66,700 8,380
-------
Incineration
As mentioned previously, incineration produces a more
stable and less voluminous material which is suitable for land-
filling. Variations in emissions from municipal, non-industrial,
and sewage sludge incineration processes result from the type of
incinerator, the size of the incinerator, the kind of refuse
incinerated, and the controls used. Wastes from incinerators
include combustion products emitted in stack gases, bottom ash
and collected fly ash, and wastewater from the ash handling
systems and flue gas scrubbing systems.
About six percent of the ash material is organic
(HO-122). The organic content of ash generated by municipal
incinerators, intermediate non-industrial incinerators, and
sewage sludge incinerators is 201,000 MT/year, 257,000 MT/year,
and 77,400 MT/year, respectively.
Ten percent of all generated and collected residential,
municipal, commercial, institutional, and industrial solid
wastes are combusted in municipal incinerators. The estimated
volatile organic and organic particulate emissions from these
units are 51,500 and 65,400 metric tons per year, respectively.
Intermediate size incinerators are employed in schools,
stores, office buildings, high-rise apartments, and hospitals.
There is much less wastewater effluent from" ash handling
systems and particulate scrubbers than other wastewater streams
in the solid waste cateogry. Since ash sluice water and scrubber
water are generally treated and recycled, the final effluent
streams are easily handled by municipal sewage systems or on-
site evaporation ponds.
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3.11.2 Control of Emissions and Effluents
Both open dumping and open dump burning are inadequate
methods for waste disposal. A major effort has been undertaken
in the United States in recent years to replace all open and
burning dumps with landfills.
The major pollutants from sanitary landfills are
leachates and gases formed during decomposition of organic matter
within the landfill. To control leachates, the solid materials
should be contained and water flow through it minimized. Control
systems for gases such as methane, which is an environmental
and a safety hazard, include containment, venting, and flaring.
Control of volatile organics from incineration is
accomplished by three methods. Close control of incinerator
operating parameters may be employed. Design of multiple chamber
incinerators reduces emissions. The use of auxiliary fuel-fired
burners in the mixing chamber increases the combustion temperature
which results in more complete combustion.
The add-on controls presently used on municipal in-
cinerators are designed for removal of particulates but not for
the control of volatile organics. These controls include expan-
sion chambers, spray chambers, wet and dry scrubbers, electro-
static precipitators, and fabric filters. Organics are, however,
controlled by design of the incinerator with multiple chambers
or afterburners.
Intermediate size non-industrial incinerators are
smaller and have irregular loading rates. Regulation of excels
air, firebox temperature, and residence time for these incinera-
tors is more difficult than for larger ones. Approximately 70
to 90 percent of these incinerators are equipped with afterburners
-263-
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which eliminate approximately 95 percent of the organic emissions
(BR-279). Some intermediate size incinerators have particulate
control systems which further reduce the organic particulates
in the stack.
Sewage sludge incinerator controls are similar to the
municipal and intermediate incinerator control systems. The
control systems are usually designed to control particulates and
not volatile organics. Before 1960, most sewage sludge incin-
erators had no air pollution controls. Between 1961 and 1967,
most new installations were equipped with low energy venturi
scrubbers to meet the 1960 ASME particulate standards. After
1967, stricter standards required the installation of impinge-
ment plate scrubbers or high energy venturi type scrubbers on
all new installations.
To eliminate air pollution problems associated with
incineration, sanitary landfills could be employed as an al-
ternative disposal method. However, landfill requires six to
ten times the land area necessary for incineration and water
effluents are a potential problem.
3.11.3 Potential Reduction of Emissions and Effluents
Table 3.11-7 summarizes the potential reductions in
organic emissions and effluents from solid waste disposal
operations. Reductions can be achieved by:
1) replacement of open burning and dumping
of collected and uncollected refuse with
sanitary landfills ,
2) containment of leachates from existing
landfills.
-264-
-------
3) flaring decomposition gases from existing
landfills, or
4) application of afterburners or auxiliary
burners to incinerators.
The total potential reduction in volatile organics is 2,210,000
MT/year. The potential for reduction of organic particulates
is 607,000 MT/year. Organic water effluents can be reduced by
70,900 MT/year.
There are some alternative control methods to sanitary
landfilling and incineration. These methods are composting,
pyrolysis, and salvage-recycle operations. These methods have
yet to be proven on a large-scale nationwide basis.
Composting has been proven in Europe as a viable
solid waste control method, although it has yet to be accepted
on a large-scale in the United States. Composting is generally
more expensive than landfilling and incinerating and also has
problems with odors and vermin. Both of these problems can be
reduced by use of covering material, insecticides, and pesticides
Composting has the advantages of requiring less land than the
landfill and of recycling the decomposed material as a useful
product.
Pyrolysis is still in the pilot-plant stage of develop-
ment. If it is perfected, pyrolysis could effect a reduction •
in organic emissions from solid waste handling due to the fact
that waste streams are collected and treated. Added incentive
to develop the process is the potential for production of valu-
able fuels such as light oils and fuel gas.
-265-
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A method of reducing the volume of refuse is to remove
and recycle all valuable, reusable constituents. These constit-
uents include ferrous metals, non-ferrous metals (especially
aluminum), glass, and plastics. Ash material from incinerators
can also be classified and recycled. Major recycle operations
are also carried out in the area of bulky metal wastes (such as
junk automobiles and heavy household appliances), paper products,
aluminum cans, and used tires. Recycle operations eliminate
the need for disposal of a fraction of the original solid waste
by eliminating organic wastes from the solid waste disposal
process. However, some wastes will still be generated from
the recycle process.
-266-
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3.12 Municipal Wastewater Treatment
Processes for treatment of all sewered and unsewered
residential wastewaters and for all sewered commercial, industrial,
and institutional wastewaters treated in municipal facilities
are included in this cateogry. All unsewered wastewaters are
assumed to be handled by septic tanks.
Figure 3.12-1 shows the available wastewater treatment
alternatives discussed in this section. Modern designs of large
treatment facilities include some type of secondary organic
removal process along with lagoons or drying beds for handling
the sludge.
The BOD, COD, suspended solids, and total organic
from each of the different types of waste treatment facilities
were quantified. EPA estimates were used to estimate the extent
of use of each type of facility. These estimates included only
the sewered United States wastewater. The quality of the waste-
waters from the wastewater treatment facilities was based on an
average of effluents given in literature (BA-416, RE-176). The
quantity and quality of the wastewaters from each type of facility
were combined to give the total effluents contained in Table
3.12-1. The values for total organics were calculated by the
conversion factor of 25 mg/£ BOD approximately equals 52 mg/£
total organics (SO-080). The handling and disposal of sludge
solids generated by the wastewater processes are discussed in
Section 3.11.
3.12.1 Effluent Sources
Unsewered septic tanks are calculated to be the largest
sources of BOD, COD and suspended solids. The BOD and COD con-
centrations of septic tank effluents are comparable to those of
-267-
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Large Wastewater Treatment Facilities
None or Minor
Treatment
Primary
Treatment
J
Secondary
Treatment
Tertiary
Treatment
^ Final
* Effluent
Trickling Filters
2. Activated Sludge
3. Oxidation Ponds
4. Intermediate Treatment
I
K)
CO
Single Family Wastewater Facilities
None or Minor
Treatment
Septic Tanks
Final Effluent
FIGURE 3.12-1. WASTEWATER TREATMENT ALTERNATIVES
-------
TABLE 3.12-1. WASTEWATER EFFLUENTS (MT/YR)
lethod of Wastewater Treatment
None or minor
Septic tank
Septic tank (unsewered)
Primary
intermediate
Trickling filters
Activated sludge
Oxidation ponds
Secondary unknown
Tertiary
Year
1974
1974
1974
1974
1974
1974
1974
.1.974
1974
1974
To t a 1
Organics
]
0
5
1
0
0
0
0
0
0
.02x10°
.603xl06
.70xiOG
.37xl06
.27xlOc
.20ixl.OG
.395xl06
.2()8xlOG
. 201x10 6
.OlOxlO6
0.
0.
2.
0.
0.
0.
0.
1.
0.
0.
HOI)
49x.lOG
29xlOG
74xlOG
66xi06
13xl.06
097xlOG
19xlOG
10xlOG
097xlOG
005xlOG
1
0
4
1
0
0
1
0
0
0
con
.23x10
.46x10
.33x10
.52x10
.39x10
.77x10
.55x10
.36x10
.48x10
Suspended
So. lids
G
6
6
6
6
6
G
6
G
.037x.l06
0
0
0
0
0
0
0
0
0
0
. 369x1.0°
.057xlOb
. 526xl06
.436xl06
.OlBxlO6
.OSOxlO6
. 136xl06
.020xl06
.039xl06
.003xl06
REF
1,3
2,3
2,3
1,3
1,3
1,3
1,3
1,3
1,3
1,3
9.98xlOL
4.8lxlO(
U. .1x10
Iv68xl0
Sources: 1. RE-176
2. BA-416
3. MI-208
-------
medium to strong raw municipal wastewater. The septic effluents
are usually evaporated to the surrounding environment from an
absorption field.
Primary wastewater treatment facilities are the second
largest source of pollutant effluents. These facilities provide
pretreatment (i.e., grit removal, flocculation, etc.) and sus-
pended solids removal, but not biological treatment. The ef-
fluent from primary treatment processes is characterized by BOD,
COD, and suspended solids concentrations of approximately 150
mg/fc, 350 mg/£, and 100 mg/fc, respectively (RE-176, CE-014).
Most new designs for large wastewater treatment
facilities employ secondary 'biological treatment of the waste-
water. These processes include trickling filters, activated
sludge, and aerated lagoons or oxidation ponds. Biological
treatment provides BOD and COD reduction of 65 to 95 percent
and suspended solids reduction of 65 to 92 percent. Any desired
degree of reduction can usually be attained through proper design
of the facility. Secondary biological treatment generally
provides enough pollutant reduction to meet all existing waste-
water effluent guidelines. In 1974, approximately 49 percent
of the United States population was serviced by some type of
secondary biological treatment facility (MI-028).
Tertiary treatment of municipal wastewater removes
particularly hard to treat pollutants or meets very stringent
wastewater effluent standards. Tertiary processes include ion
exchange, membrane separation processes (i.e., reverse osmosis),
activated carbon, microfiltration, and chemical treatment such
as chlorination. All of the above listed processes have been
proven on full-scale municipal wastewater operations. Only
slightly over one percent of the United States population is
served by a tertiary treatment facility.
-270-
-------
Organic gases from a municipal treatment facility are
difficult to quantify but are expected to be relatively small.
These vapors are emitted from screening areas, aeration tanks,
trickling filters, and clarifiers. The emission rates are low,
but the constituents generally cause odor problems. The activated
sludge treatment plant emits more volatile organics than does
the screening area or the settling ponds. The emissions from
activated sludge treatment result from the partial stripping
from the liquor of various volatile oils, fats, and other organic
compounds present in the sewage (NA-032).
3.12.2 Application of Control Technology
Although the single-family septic tanks have been
designated as the greatest impactor in the wastewater category,
there is currently no viable substitute for septic tanks. In
areas where septic tanks have been used and the population has
now grown reasonably close together, one possible alternative
is to gather all the wastewater to a common treatment facility.
Generally, this is not feasible in rural areas, and the septic
tank is the only alternative.
Of the wastewater which is currently gathered and
treated at one site, a reduction in the total BOD, COD, and
suspended solids can occur with upgrading of the existing
facilities. One step in upgrading would be the addition of
secondary biological treatment to plants which have no treat-
ment or only primary treatment. The estimated reduction achieved
by upgrading to secondary treatment is shown in Table 3.12-2.
If more stringent wastewater effluent guidelines are
adopted, addition of tertiary processes to all wastewater
treatment facilities may be required. The expected reduction
-271-
-------
TABLE 3.12-2. POTENTIAL REDUCTION OF ORGANIC WATER EFFLUENTS
FROM MUNICIPAL WASTEWATER TREATMENT FACILITIES
Water Effluent: Reductions MT/yr
Total Organics
BOD
COD
Suspended Solids
Upgrading of nonexistant
treatment and primary treatment
to secondary biological
treatment facilities
2.08x10°
l.OOxlO6 l.llxlO6
0.728xl06
2. Converting all the upgraded
facilities listed in 1. to
tertiary treatment facilities
3. Reuse of the treated wastewater
from the tertiary facilities
listed in 2. with 5070 used
for irritation and 5070 used
for industrial process
cooling water
1.05x10°
0.293xlOG
0.503xl06 2.37xlOG
0.141xl06 1.13xl06
0.189x10'
0.105x10°
Total
3.42x10'
1.64x10° 4.61x10°
1.02x10°
-------
resulting from addition of tertiary control is also shown in
Table 3.12-2. The cost of the tertiary controls is expected to
be relatively expensive for the amount of reduction.
As water resources become scarce and wastewater quality
requirements more stringent, wastewater reclamation and reuse
will become increasingly popular. Areas where wastewater reuse
is currently being practiced are:
1) irrigation and other agricultural
uses ,
2) cooling water,
3) industrial process water,
4) boiler feed water,
5) recreational lakes,
6) fish propagation, and
7) nonpotable domestic use.
In 1971, the greatest amount of reuse was for irrigation and
industrial process water. With proper crop selection and irriga-
tion management, even very poor quality effluents were used
successfully. The total water reuse that same year amounted to
less than the annual water use of New York City.
Wastewater reuse is economically feasible under the
following conditions (SC-310):
-273-
-------
1) Existing freshwater supplies are limited,
and substantial future expenditures are
contemplated, making it essential to
develop additional supplies.
2) Existing freshwater supplies are relatively
expensive.
3) Private or public developments with need
for large volumes of water exist in the
area.
4) The treatment provided the wastewater pro-
duces an effluent of very high quality that
is not wasted into receiving waters.
5) Regulatory agencies are planning to require
a higher degree of treatment for discharge
to receiving waters, such as nutrient
removal.
Increased reuse of treated municipal wastewater could
provide a reduction in organic water from municipal water treat-
ment. An estimation of the reduction was made based on the
following assumptions:
1) Approximately 50 percent of the wastewater
is reused as irrigation water and thus has
an environmental impact.
2) The other 50 percent of the wastewater is
reused in industrial process and cooling
waters and will not impact the environment.
3) Wastewater from septic tanks is not recycled.
-274-
-------
If these three assumptions are included with the upgrading of
all the existing wastewater treatment facilities to tertiary
type controls, the expected organic reduction in total organic
effluents would be 3.42 x 10G MT/year.
-275-
-------
3.13 Other Sources
Known sources of organic pollutants not previously
discussed are included in this cateogry. Included here are
forest wildfires, coal refuse fires and structural fires. The
quantities of volatile organics and organic particulates emitted
from these sources are shown in Table 3.13-1. These emission
estimates are based on numerous assumptions and are "ball park"
values. The emissions from these fires can be reduced by more
extensive application of control and prevention methods, but
it was not possible to determine reduction potentials associated
with the methods.
3". 13.1 Forest Wildfires
The size, intensity, and occurrence of wildfires are
dependent on such variables as local meteorological conditions,
the species of trees and their moisture content, and the weight
of combustible fuel per unit area (fuel loading). After ignition,
small dry matter burns first, then larger living plants.
The United States Forest Service is developing a nation-
wide fuel identification model to provide estimates of fuel load-
ing by tree size class. A National Fire Danger Rating System
(NFDR) is produced when wind, slope, and expected moisture
changes are superimposed on this fuel model.
Hypothetically, the nature and quantity of pollutant
emissions are related to the intensity of the wildfire, its
direction relative to the wind, and the rate at which it spreads
(EN-071). Laboratory tests have shown that the smouldering phase
of combustion is a major source of pollution. The initial 80
percent of the fuel burned accounts for only about 20-30 percent
of the organic emissions (SA-223).
-276-
-------
TABLE 3.13-1. ATMOSPHERIC EMISSIONS FROM OTHER SOURCES
Sub-Category
Year
Emissions (MT/yr)
Volatile
Organic
Ref
Particulate
Organic
Ref
Forest Wildfires 1971 791,000 1
213,000 1,2
Structural Fires
1973
64,800 4,6
20,900 2,6
Coal Refuse Fires 1972
Category Total
61,200 3,5,6
917,000
N/A
233,900
Sources: 1. EN-071 4. NA-032
2. VA-067 5. EN-226
3. MS-001 6. MO-201
-277-
-------
Gas chrotnatographic analysis of emissions from the
burning of ponderosa pine showed that 15-40 percent of this gas
was methane and ethane (SA-223). Ethane and acetylene were the
next most abundant compounds of the 24 organic compounds identi-
fied by the analysis. The smoke from rye grass burns contains
about 38 percent organic matter (VA-067) and is thought to be
representative of particulate matter from forest wildfires.
Forest wildfires produce about 791,000 MT of organics
(as methane) and 560,000 MT of particulate matter (213,000 MT
organic particulates assuming 38 percent organic content) annually
(EN-071). These rough estimates were obtained by using data on
areas consumed by wildfires in 1971, the fuel loading in the
areas consumed, and emission factors.
The most effective control method for forest wildfires
is fire prevention. Considerable activity has been, and is
being, directed toward reducing the number and severity of wild-
fires. These activities include publishing information on fire
prevention and control, surveillance of forest areas where fires
are likely to occur, prevention of recreational usage of these
areas, prescribed controls for burning of litter and underbrush,
and various firefighting and control activities, The tests
mentioned previously indicate that emissions could be substantially
reduced by rapid mop-up operations to minimize smoldering. The
reduction potential associated with these techniques cannot be
quantitatively estimated.
3.13.2 Structural Fires
Approximately one million buildings are damaged an-
nually by fires in the United States (US-336). Emissions from
these fires can be roughly approximated by using various
-278-
-------
assumptions for the quantity of combustibles and emission factors
Monsanto Research Corporation estimated that in 1973 structural
fires emitted 64,800 MT of volatile organics and 55,100 MT of
particulates. The emission of organic particulates equals about
20,900 MT per year, assuming that the smoke from these fires
is represented by that from rye grass burns which contain about
38 percent organic matter (VA-067).
Prevention and control techniques can reduce these
emissions. Fire prevention techniques include the use of fire-
proof construction materials; information programs on fire
prevention; and proper handling, storage, and packaging of flam-
mable materials. Fire control techniques include methods for
rapidly extinguishing fires such as the use of sprinklers, foam,
and inert gas systems, and provision of adequate alarm systems,
firefighting facilities, and personnel.
3.13.3 Coal Refuse Fires
Large amounts of refuse are generated during the clean-
ing of coal. About 80 percent of the total bituminous coal
production in 1968 was cleaned, generating 88 million MT of
refuse, or about 18 percent of the total production (MS-001).
These wastes are normally disposed of in hillside dumps, valley
fills, and earthen dumps. The wastes cover many thousands of
hectares of land. For example, in Pennsylvania and West Virginia
alone, the disposal of deep mine wastes has covered 16,000
hectares of land (CO-168).
Fires have been burning for many years in accumulations
of coal refuse. The most important causes of these fires are
(CO-168):
-279-
-------
1) spontaneous combustion,
2) intentional ignition to obtain "red dog"
for use as a road base material,
3) camp fires left burning near disposal
sites,
4) forest fires, and
5) careless burning of trash on or near
the refuse piles.
It was estimated that 538 million cubic meters of
burning coal refuse piles existed in the United States in 1964.
A more recent study cited reports which estimated that in 1969
there were 292 burning refuse piles, with a total volume of 206
million cubic meters and containing an estimated equivalent of
16 million MT of coal (MS-001). These figures indicate signif-
icant progress has been made in efforts to extinguish and prevent
fires in coal refuse piles.
By using assumed densities, average lives for coal
piles, and emission factors, a rough estimate of emissions can
be obtained. Burning coal refuse piles emitted about 61,200 MT
of volatile organics in 1973 (MO-201). The composition of the
gaseous organics is not known. The emission rate for organic
particulates is unknown. Total particulates are emitted at a
rate of 123,000 MT/yr. (CO-168, US-144).
There are numerous approaches for control and pre-
vention of fires in coal refuse piles. Control methods include
various ways of applying water and slurries of non-combustibles
-280-
-------
to the fires and the use of bulldozers to isolate and extinguish
the fires. Prevention methods include proper choice and prepara-
tion of the dump sites, minimizing the quantity of combustibles
in the refuse, systematic dumping techniques, compaction, and
sealing of the piles. The Office of Coal Research has prepared
a report concerning the stabilization, reclamation, and utiliza-
tion of coal refuse piles which examines these control and pre-
vention techniques and their application (CO-168). The reduction
potential associated with more stringent application of the con-
trol and prevention methods is unknown.
-281-
-------
BIBLIOGRAPHY
AB-044 Abeles, F. B., et al., "Fate of Air Pollutants:
Removal of Ethylene, Sulfur Dioxide, and Nitrogen
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AE-014 Aerospace Corp., Private Communication, Los Angeles,
Feb-. , 1976.
AM-055 American Petroleum Inst., Committee on Refinery
Environmental Control, Hydrocarbon Emissions from
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D.C., 1973.
AM-099 American Petroleum Institute, Annual Statistical
Review. Petroleum Industry Statistics 1964-1973,
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AM-155 American National Standard Institute, National
Electrical Safety Code, 1973 edition, N.Y.,
IEEE., 1973.
AN-089 '"Annual Refining Survey", Oil & Gas J., 1 April 1974.
AN-134 Anderson, Earl V., "Recession Stifles Output of Top
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Washington, D.C., Public Health Service, 1960.
-282-
-------
BIBLIOGRAPHY (Continued)
AU-020 Audits and Surveys Inc., "1974 Nationwide Retail
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-283-
-------
BIBLIOGRAPHY (Continued)
CA-R-246 Cavanaugh, E. C., et al., Atmospheric Environmental
Problem Difinition o_f Facilities for Extraction, On-Site
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CE-014- Cecil, Lawrence K., ed., Complete Water Reuse--
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CH-281 Chansky, Steven H., et al., Systems Study ojf Air
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-284-
-------
BIBLIOGRAPHY (Continued)
CO-168 Coalgate, Jerry L., David J. Akers, and Russell W. Frum,
Gob Pile Stabilization, Reclamation, Utilization,
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Morgantown, W. Va., Coal Research Bureau, School of
Mines, W. Va. Univ., 1973.
CO-388 Considine, Douglas M., ed., Chemical and Process Tech-
nology Encyclopedia, N.Y. McGraw-Hill, 1974.
DA-052 Davis, John C., "S02 Removal Still Prototype", Chem.
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DA-069 Danielson, John A., comp. and ed., Air Pollution
Engineering Manual, 2nd ed., AP-40, Research Triangle
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Chem. Eng. 7_7 (17), 96 (1970).
DU-001 Duprey, R. L. , Compilation of_ Air Pollutant Emission
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EC-010 Eckenfelder, W. Wesley, Jr., Effluenc Quality and
Treatment Economics for Indus trial Was tewater,
Austin, Texas, October 1967.
EI-017 Eimutis, Edward C., Source Assessment: Prioritization
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-285-
-------
BIBLIOGRAPHY (Continued)
EL-033 Elkin, H. F. and R. A. Constable, "Source/Control of
Air Emissions", Hydrocarbon Proc. 5_L(10) , 113 (1972).
EM-003 Emrich, Grover K., "Guidelines for Sanitary Landfills-
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EM-007 Emrich, Grover H., "Management of Hazardous Geologic
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Advancement of Science, Symposium on Geologic Implica-
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EN-043 Environmental Conservation, Washington, D. C., National
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EN-045 Environmental Research Catalog, 2 parts, Smithsonian
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GPO, 1972.
EN-067 Smoke Plume Opacity Related to the Properties cxf
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-286-
-------
BIBLIOGRAPHY (Continued)
EN-147 Environmental Protection Agency, (Office of Air and
Water Programs, Effluent Guidelines Div., Development
Document for Proposed Effluent Limitations Guidelines
and New Source Performance Standards for the Unbleached
• Kraft and Semichemical Pulp Segment p_f the Pulp, Paper,
and Paperboard Mills Point Source Category, EPA 44071-
74/025, Washington, D.C., 1974.
EN-152 Environmental Procection Agency, (Office of Air and
Water Programs, Effluent Guidelines Div.), Development
Document for Effluent Limitations Guidelines and New
Source Performance Standards for the Grain Processing
Segment of_ the Grain Mills Point Source Category,
EPA 400/1-74-028-a, Washington, D.C., 1974.
EN-153 Environmental Procection Agency, (Office of Water and
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Development Document for Effluent Limitations Guidelines
and New Source Performance Standards for the Mai or
Organic Products Segment of che Organic Chemicals
Manufacturing Point Source Category, EPA 440/1-74-009-a,
Washington, D.C., 1974.
EN-154 Environmental Protection Agency, (Office of Air and
Water Programs, Effluent Guidelines Div., Development
Document for Effluent Limitations Guidelines and New
Source Performance Standards for the Tire and Synthetic
Segment o_£_ the Rubber Processing Poinc Source Category,
EPA 440/1-74-013-a, Washington, D.C., 1974.
-287-
-------
BIBLIOGRAPHY (Continued)
EN-156 Environmental Protection Agency, (Office of Air and
Water Programs, Effluent Guidelines Div.) Development
Document for Effluent Limitations Guidelines and New
Source Performance Standards for the Leather Tanning
and Finishing Point Source Category, EPA 400/1-74-016-a,
Washington, D.C., 1974.
EN-157 Environmental Protection Agency, (Office of Air and
Water Programs, Effluent Guidelines Div.), Development
Document for Effluent Limitations Guidelines and New
Source Performance Standards for the Primary Aluminum
Smelting Subcategory of the Aluminum Segment ojf the
Nonferrous Metals Manufacturing Point Source Category,
EPA 440/1-74-019-d, Washington, D.C., EPA, 1974.
EN-160 Environmental Protection Agency, (Office of Air and
Water Programs, Effluent Guidelines Div.), Development
Document for Effluent Limitations Guidelines and New
Source Performance Standards for the Synthetic Res ins
Segment cxf the Plastics and Synthetic Materials Manu-
facturing Point Source Category, EPA 440/1-74-010-a, •
Washington, D.C., 1974.
EN-162 Environmental Protection Agency, (Office of Air and
Water Programs, Effluent Guidelines Div.), Development
Document for Proposed Effluent Limitations Guidelines
and New Source Performance Standards for the Soap and
Detergent Manufacturing Point Source Category, EPA
440/1-74-18, Washington, D.C., 1973.
-288-
-------
BIBLIOGRAPHY (Continued)•
EN-163 Environmental Protection Agency, "Iron and Steel
Manufacturing Point Source Category. Effluent Guidelines
and Standards", Fed. Reg. 39_(126) , 24114-24133(1974).
EN-175 Environmental Protection Agency, (Office of Air and
Water Programs, Effluent Guidelines Div.), Development
Document for Proposed Effluent Limitations Guidelines
and New Source Performance Standards for the Dairy
Product Processing Point Source, EPA 440/1-73-021,
Washington D.C., 1974.
EN-186 Environmental Protection Agency, (Office of Air and
Water Programs), Methods for Identifying and Evaluating
the Nature and Extent o£_ Nonpoint Sources of Pollutants,
EPA 430/9-73-014, Washington, D.C., 1973.
EN-197 Environmental Science and Engineering, Inc., Trace
Pollutants from Forest Materials, Preliminary Draft,
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EN-220 Environmental Protection Agency, (Office of Air Quality
Planning and Standards), Background Information for
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2 vols., Vol. 1, Proposed Standards; Vol 2, Summary
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Park, N.C., 1974.
-289-
-------
BIBLIOGRAPHY (Continued)
EN-226 Environmental Protection Agency, National Air Data
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Emissions Reporting Systems (AEROS), EPA 450/2-74-012,
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EN-268 Environmental Protection Agency, (Office of Toxic
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EN-294 Environmental Protection Agency, Pacific Northwest
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EPA-R2-72-018, 12060/08/72, November 1972.
EN-340 Environmental Protection Agency, (Office of Air and
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EN-341 Environmental Protection Agency, Background Information
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and Mercury, EPA-450/2-74-009a, Research Triangle Park,
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-290-
-------
BIBLIOGRAPHY (Continued)
EN-376 Environmental Protection Agency, Effluent Guidelines
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Limitations Guidelines and New Source Performance
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Extraction Point Source Category, EPA 440/1-75-055,
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EN-380 Environmental Protection Agency, (Effluent Guidelines
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Animal Feed, Breakfast Cereal, and Wheat S tarch Segments
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EN-381 Environmental Protection Agency, (Effluent Guidelines
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-291-
-------
BIBLIOGRAPHY (Continued)
EN-383 Environmental Protection Agency, (Effluent Guidelines
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Washington, D.C., 1975.
EN-384 Environmental Protection Agency, (Effluent Guidelines
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Organic Chemicals Manufacturing Point Source Category,
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EN-385 Environmental Protection Agency, (Effluent Guidelines
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-292-
-------
BIBLIOGRAPHY (Continued)
EN-387 Environmental Protection Agency, (Effluent Guidelines
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Washington, D.C., April 1974.
-293-
-------
BIBLIOGRAPHY (Continued)
EN-408 Environmental Protection Agency, (Effluent Guidelines
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Canned and Preserved Fruits and Vegetables Point Source
Category, EPA 440/l-74-027a, Washington, D.C., March 1974
ER-030 Ervin, Warren, Private Communication, EPA, Stationary
Source Analysis Staff, Nov. 1975.
FA-098 "Facts and Figures, the U.S. Chemical Industry",
C & E News 2 June 1975.
FO-001 Fogel, M. E., et al., Comprehensive Economic Cost
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Technical Foundation, Aug. 1970.
-294-
-------
BIBLIOGRAPHY (Continued)
HE-128 Hendrickson, E. R., J. E. Roberson, and J. B. Koogler,
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Petrochemical Processes, Final Report, Contract
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A Proposed Program and Preliminary Analysis for the
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Source Performances Standards on 1985 National Emissions
from Stationary Sources , Volume I_, Final Report, Main
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Task No. 3, Wethersfeld, Conn., TRC, The Research
Corporation of New England, Oct. 1975.
-295-
-------
BIBLIOGRAPHY (Continued)
HO-250 Ho, S., W. C. Boyle, and R. K. Ham, "Chemical Treatment
of Leachates from Sanitary Landfills", J. WPCF 46_ (7),
1777 (1974) .
HU-100 . Hughes, T. W. , et al. , Prioritization p_f Sources o_f Air
Pollution from Industrial Surface Coating Operacions,
Contract No. 68-02-1320, Dayton, Ohio, Monsanto Research
Corp., 1975.
HU-111 Hughes, G. M., R. A. Landon, and R. N. Farvolden,
Hydrogeology of_ Solid Wa. ste Disposal Sites in North-
eastern Illinois, final report, SW-12d, EPA, 1971.
IR-011 Irani, M. C., P. W. Jeran, and Maurice Deul, Methane
Emission from U. S_. Coal Mines in 1973, A Survey,
I.C. 8659, Supplement to I.C. 8558, Pittsburgh,
Pittsburgh Mining and Safety Research Cntr., BuMines, 1974.
JE-027 Jewell, Wm. and Davis L. Ford, Preliminary Investiga-
tional Requirements -- Petrochemical and Refinery
Waste Treatment Facilities, Project 12020 EID, '-
Engineering-Science, Inc.
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and Paddy Soils and the Production of Atmospheric Methane
and Hydrogen", J. Geophys, Res. 68_ (13), 3971 (1963).
LA-204 Larson, Gordon P., George I. Fischer, and Walcer J.
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(5), 1970 (1953) .
-296-
-------
BIBLIOGRAPHY (Continued)
LU-044 Lundberg Survey, Inc., "Service Station Throughpuc.
Average Monthly Sales of Gasoline Per Station, 1973-74
United States", Lundberg Letter Issue 046, Sept. 1974.
MA-314 Maxwell, Robert, Private Communication, EPA, Mobile
Source Enforcement Div., Sept. 10, 1974.
MA-502 Makela, Robert G. and Joseph F. Malina, Jr., Solid
Wastes in the Petrochemical Industry, EHE-72-14,
CRWR-92, Austin, Tx. , Center for Research in Water
Resources, University of Texas at Austin, Aug. 1972.
MA-256 MacFarlane, I. C., "Gas Explosion Hazards in Sanitary
Landfills", Public Works 101 (5), 76-8 (1970).
ME-126 Mercer, Walter A., Walter W. Rose, and Kenneth G.
Weckel, Liquid Wastes From Canning and Freezing Fruits
and Vegetables, Berkeley, California, National Canners
Association, August 1971.
ME-136 Mencher, S. K., "Minimizing Waste in the Petrochemical
Industry", CE^ 6^ (10), 80 (1967).
MI-208 Michel, Robert, Private Communication, Municipal
Construction Division, EPA, Washington, D. C.
MO-201 Monsanto Research Corp, Dayton Lab., Overview Matrix
f or Air Pollution Sources, Special Project Report,
EPA Contract No. 68-02-1874, Dayton, Oh, July 1975.
-297-
-------
BIBLIOGRAPHY (Continued)
MS-001 MSA Research Corp., Hydrocarbon Pollutant Systems Study,
Vol. 1. Stationary Sources, Effects and Control,
PB-219-073, APTD 1499, Evans City, Pa., 1972.
NA-032 National Air Pollution Control Admin., Control Techniques
for Hydrocarbon and Organic Solvent Emissions from
Stationary Sources, AP-68, Washington, D.C., 1970.
NA-168 National Petroleum News, Fact Book, Mid-May 1974,
N.Y., McGraw-Hill, 1974.
PE-160 Pervier, J. W., et al., Survey Reports on Atmospheric
Emissions from the Petrochemical Industry, Final Report,
4 Vols., EPA 450/3-73-005 a-d, Contract No. 63-02-0255,
Marcus Hook, Pa., Air Products & Chemicals, Houdry
Div., March 1974.
PR-074 Pross, T. W., "Marine Transportation—state-of-the-art",
Presented at the Intersociety Conf. on Transportation,
Denver, Colo., Sept. 1973, N.Y., ASME, 1973.
PR-115 Processes Research, Inc., Air Pollution from Nitration
Processes, Contract No. CPA 70-1, Task Order 22,
Cincinnati, Ohio, March 1972.
t
PR-116 Processes Research, Inc., Air Pollution from Chlorination
Processes, Contract No. CPA 70-1, Task 23, Cincinnati,
March 1972.
-298-
-------
BIBLIOGRAPHY (Continued)
PU-036 Putnam, A. A., E. L. Kropp, and R. E. Barrett,
Evaluation p_f National Boiler Inventory, Final Report,
Contract No. 68-02-1223, Task 31, Columbus, Ohio,
Battelle Columbus Labs., Oct. 1975.
RA-156 Rasmussen, Reinhold A., "Waht Do the Hydrocarbond from
Trees Contribute to Air Pollution?" J . APCA 2_2_ (7) ,
537 (1972) .
f
RA-209 Rasmussen, Reinhold A. and F. W. Wenc, "Volatile
Organic Material of Plant Origin in the Atmosphere",
Proc. Nat. Acad, Sci. 53_, 215 (1965) .
RA-222 Radian Corp., ed., Industrial Process Profiles for
Environmental Use, 1st ed., 7 vols., EPA Contract No.
68-02-1319, Task S2, Austin, Tx. , in progress, 1976.
RE-,176 Recycling Municipal Sludges and Effluents on Land,
'Proceedings or the Joint Conference, Champaign, 111. ,
July 1973.
RI-107 Ritchie, J. E., Jr., et al., Petroleum Systems
Reliability Analysis, A Program for Prevention o_f
Oil Spills Us ing an Engineering Approach t_p_ A Study of_
Offshore and Onshore Crude Oil Petroleum Systems, Vol.
Appendices, EPA-R2-73-280b, Contract No. 68-01-0121,
Computer Sciences Corp., Aug. 1973.
RO-211 Robertson, J., C. R. Toussaint, and M. Jerque,
Organic Compounds Entering Ground Water from a
Landfill, EPA-660/2-74-077, Norman, Oklahoma, Uni-
versity of Oklahoma, School of Civi Engineering and
Environmental Science, Sept. 1974.
-299-
-------
BIBLIOGRAPHY (Continued)
RO-228 Robinson, E. and R. C. Robbins, Sources, Abundance,
and Fate of Gaseous Atmospheric Pollutants, Final
Report, N71-25147, Stanford Research Inst., Feb. 1968.
SA-103 Salvato, Joseph A., Win. G. Wilkie, & Berton E. Mead,
"Sanitary Landfill-Leaching Prevention and Control",
J. WPCF 43 (10), 2084-2100 (1971).
SA-223 Sandberg, D. V., S. G. Pickford, and E. F. Darley,
"Emissions from Slash Burning and the Influence of
Flame Retardant Chemicals", J. APCA 25 (3), 273 (1975).
SC-310 Schmidt, Curtis J., Irwin Kugelman, and Ernest V.
Clements III, "Municipal Wastewater Reuse in the U.S.",
J. WPCF 47 (9), 2229 (1975):
SC-312 Schwartz, W. A., et al., Engineering and Cost Study
of Air Pollution Control for the Petrochemical Indus cry,
Vol. 1: Carbon Black Manufacture by_ the Furnace
Process, Final Report, EPA-450/3-73-006-a, PB 238-324,
Contract No. 68-02-0255, Marcus Hook, Pennsylvania,
Houdry Division/Air Products and Chemicals, Inc.,
June 1974.
SC-287 Schwartz, W. A., et al., Engineering and Cost Study of
Air Pollution Control for the Petrochemical Industry,
Volume 2_: Acrylonitrile Manufacture, Final Report,
EPA-450/3-73-006-b, PB 240 986, Contract No. 68-02-0255,
Marcus Hook, Pennsylvania, Houdry Division/Air Products
and Chemicals, Inc., Feb. 1975.
-300-
-------
BIBLIOGRAPHY (Continued)
SC-316 Schwartz, W. A. , et al. , Engineering and Cost S tudy of
Air Pollution Control for the Petrochemical Industry,
Volume 3_: Ethylene Dichloride Manufacture by_ Oxychlori-
nation, Final Report, EPA-450/3-73-006-C, PB 240-492,
Contract No: 68-02-0255, Marcus Hook, Pennsylvania,
Air Products and Chemicals, Inc., Houdry Div. , N7ov. 1974
SH-241 Shamel, R. E., et al., Preliminary Econimic Impact
Assessment o_r_ Possible Regulatory Action to Control
Atmospheric Emissions p_f Selected Halocarbons , Final
Report, EPA 450/3-75-073, PB 247 115, Contract Mo.
68-02-1349, Task 8, Cambridge, Massachusetts, Arthur
D. Little, Inc., Sept. 1975.
SI-105 Simmons, Henry, The Economics or_ America ' s Energy
Future, Washington, D. C., ERDA, 1975.
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Handbook, Park Ridge, N. J., Noyes Daca, 1975.
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ST-203 Stanford Research Inst., Chemical Information Services,
Chemical Origins and Markets; Produce Flow Charts;
Tables p_f_ Ma j or Organics and Inorganics , Menlo Park,
Ca., 1967.
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Census of_ Bus iness , Vol. Ill. Wholesale Trade Subj ect
Reports, Washington, GPO, 1971
-301-
-------
BIBLIOGRAPHY (Continued)
US-144 U. S. Bureau of Mines, Minerals Yearbook 1972, Vol. 1,
Metals, Minerals, and Fuels, Washington, D. C., 1974.
US-205 U. S. Dept. of Commerce, Social & Economic Statistics
Admin. , Statistical Abstract o_£ the U. S_. 1974,
95th Annual Edition, Washington, D. C., 1974.
US-303 U. S. Dept. of Commerce, Bureau of the Census,
Statistical Abstract of the United States: 1975,
96th Ed., Washington, D. C., 1975.
US-336 U. S. Dept. of Health, Education, and Welfare, Public
Health Service, Nationwide Inventory o_f_ Air Pollution
Emissions, Raleigh, N. C., Aug. 1970.
US-356 U. S. Bureau of Mines, Div. of Fuels Data, Natural Gas
Production and Consumption: 1974, Mineral Industry Sur-
veys, Natural Gas, Annual, Washington, D. C., Aug. 1975.
VA-067 Vandergrift, A. E., et al., Particulate Pollutant System
Study, Vol. 3_, Handbook of_ Emission Properties , Contract
No. CPA-22-69-104, Kansas City, Mo., Midwest Research
Inst., 1971.
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Pollution Requirements", CEP_ 6_8 (11), 85 (1972).
WA-252 Wadleigh, C. H. , Wastes i.n Relation t£ Agriculture and
Forestry, Misc. Pub. No. 1065, USDA, March 1968.
ZA-044 Zabetakis, M. G., Methane Control in U. S_. Coal Mines -
An Overview, Pittsburgh, Pa., Bureau of Mines, Pittsburgh
Mining and Safety Research Center.
-302-
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APPENDIX
-303-
-------
TABLE A-l
Product
A.iraionia
Carbon Black
Acrylonitrile
Echylene Dichloride
Toluene
Carbon Tetrachloride
2-Echylhexanol
Dimethyl Terephthalate
I
ELhylene Oxide
O
y Ethyl Benzene
High Density Polyethylene
Low Density Polyethylene
Cyclohexanone and
Cyclohexanol
p-Xy lene
Polyvinyl Chloride and
Copolymers
E thy lene-Propy lene
Polymers
Propylene Oxide
Methyl Methacrylate
Forraaldehyde (37%)
Butylenes
AIR EMISSIONS
"Best
Organic
Production
(10JMT/yr)
13,694 (1974)
1,520 (1974)
635 (1974)
3,493 (1974)
3,398 (1974)
460 (1974)
182 (1974)
1,243 (1974)
1,763 (1974)
2,586 (1974)
1,283 (1974)
2,703 (1974)
574 (1972)
1,214 (1974)
2,250 (1974)
1,690 (1972)
789 (1974)
290 (1973)
2,654 (1974)
1,074 (1971)
Volatil.es
(MT/yr)
322,700
96,700
83,000
56,300
51,000
43,400
41,400
41,300
38,900
38,800
35,800
34,000
31,700
28,800
28,100
24,500
23,900
23,400
22,400
21,500
Ref
1
2
2
4
1
1
2
2
4
2
2
2
1
2
1
1
1
2
4
FROM ORGANIC CHEMICAL PROCESSING IN METRIC TONS/YR
Estimate" of
Air Emissions
Particulates Additional Estimates of Volatile Organic Emissions
(J (MT/yr) Ref Q (MT/yr) Ref Q (MT/yr) Ref Q (MT/yr) Ref
A 616,256 9 B 753,000 3 C
3,700 2 B 83,250 1 B 39,540 3 C
B 0 2 B 134,600 1 B 1,714 8 C 30,838 3
B 0 2 B 135,788 1 B 18,146 3 C 54,795 5
D
B 7,122 5 D
B
B 600 2 B 49,440 1 C
B 0 2 B - 84,850 1 B 239,000 3 C
D
B 1,000 2 B
B 600 2 B 31,900 1 B 8,163 3 C
B 0 2 B 31,240 1 B
B
B 5,400 2 B 76,110 1 B 9,977 3 C
C
B
B
B 0 2 B 22,440 1 C 30,838 3 C
D
-------
TABLE A-l (Continued)
AIR EMISSIONS FROM ORGANIC CHEMICAL PROCESSING IN METRIC TONS/YR
"best Estimate" of
Organic Air Emissions'
Production
Product
Br.taiiiene
Acetic Acid
Acrylic Acid
Methanol
Polypropylene and
Copolyraers
MaleLc Anhydride
j Phenol
CO
O Trichloroetliylene
1
Polystyrene Copolymers
Glycerol
Acrylics
Acetal dehyde
Cyclohtixane
Printing Ink
Pesticides
Ethylene from Chemical
Conversion
1, 1, 1-Trichloroethane
Polychloroprcne Rubber
(Neoprene)
o-Xylenc
Methylisobutyl Ketone
Adiponi trile
Kthyl Chloride
(10JM'i
1,663
1,030
430
3,112
1,048
128
1,044
197
2,431
165
236
635
1,061
301
571
10,699
267
177
475
73
324
299
L/yO
(1974)
(1974)
(1974)
(1974)
(1974)
(1974)
(1974)
(1974)
(1974)
(1972)
(1974)
(1974)
(1974)
(1975)
(1972)
(1974)
(1974)
(1972)
(1974)
(1974)
(.1974)
(1974)
Volacilcs
(i-lf/yr)
21,000
20,900
18,500
17,100
17,000
15,400
11,000
10,200
9,100
9,000
8,300
8,200
7,800
7,700
7,000
6,800
6,100
5,700
5,400
5,200
5,000
4,900
ReC
1
2
1
1
2
2
2
1
2
2/1
3
2
1
3
2
1
1
1
1
2
1
Participates Additional Estimates of Volatile Organic Emissions
Q (MT/yr) Uef Q (MT/yr) Ref Q (MT/yr) Ref Q (MT/yr) Ref Q
B
B 8,000 1 B
B
C
B 50 2 B 9,768 1 B 362 3 C
B 0 2 B 16,630 1 B 15,328 3 C
B 0 2 B 2,026 1 B 3,221 5
B 1,693 6 C 2,041 5
B 200 2 B 16,740 1 C 3,900 3 C
B/C 02 B 21,798 1 C/B
• C
B 0 2 B
C
C 17,010 1 D
D
B 100 2 B 10,060 1 B
B 5,085 6 C 2,495 5
C
C
C
B 0 2 B 4,715 1 C
B 5,005 B 30 5
-------
TABLE A-l (Continued)
Product
Chloroprene (2 chloro-
1, 3-butadiene)
Acetone
Vinyl Chloride
Scyrene-Butadiene Rubber
Methyl Chloride
Methylene Chloride
nitrobenzene
Glycol
O
O^ Acetylene
Ethyl Acrylate
Vinyl Acetate
Chloroform
Phenolic 6. Other Tar
Resins
Dyes & Pigments
(Organic)
S tyrene
Cellulose Acetate
Acrolein
Curaene
Dodecylbenzene Sulfonic
Acid-Sodium Salt
Echanolamines
AIR EMISSIONS FROM ORGANIC PROCESSING IN METRIC TONS/YR
"Best Estimate" of
Organic Air Emissions1
Production .
(10JMT/yr)
2
1
1
2
1
80
934
,541
,465
208
268
297
,411
181
75
635
136
599
160
,694
172
28
,302
181
138
(1972)
(1974)
(1974)
(1974)
(1974)
(1974)
(1974)
(1974)
(1974)
(1968)
(1974)
(1974)
(1974)
(1973)
(1974)
(1974)
(1974)
(1974)
(1974)
(1974)
Volatiles Participates Additional Estimates of Volatile Organic Emissions
(MT/yr)
4,
4,
4,
4,
3,
3,
3,
3,
2,
2,
2,
2,
2,
2,
2,
1,
1,
1,
1,
1,
800
700
500
300
700
700
400
000
800
400
400
300
300
000
000
900
900
700
700
500
Ref
1
1
1
2
6
1
1
1
1
1
2
1
3
2
1
1
1
1
1
Q (MT/yr) Kef Q (MT/yr) Ref Q (MT/yr) Ref Q (MT/yr) Ref Q
B
C
B 22,455 6 C 6,577 5
B 700 2 B 0 1 B 3,265 2 B
C 4,953 1 C 1,724 5
B 4,817 6 C 2,359 5
B 0 8 C 2,466 8 C
B
C
D
• B 0 2 B 13,278 1 B
B 2,450 6 B 1,724 5
C
D
B 30 2 B 2,203 1 B
C
B
C
C
C
-------
TABLE A-l (Continued)
AIR EMISSIONS FROM ORGANIC CHEMICAL PROCESSING IN METRIC TONS/YR
Produce
s-Butyl Alcohol
Euhanol (synthetic)
Acetic Anhydride
Polyainid Resins
Urea- Formaldehyde Resins
Dichlorobenzene
Chlorobenzene
Rayon
' Naphthalene
O
•-J Tetraethyl ?, Tetraraethyl
1 Lead
Pulybucadiene Rubber
Polyester Resins
Cresol (Synthetic)
Cresyllc Aci.d
Toluene Diisocyauates
Pentaerythritol
Fluorocarbon 12
Acetonitrile
Diethylcne Clycol
Dodecyl Benzene
Sulfonic Acid
Isodecanol
Production
(102MT/yr)
525 (1974)
816 (1974)
775 (1974)
47 (1970)
454 (1970)
63 (1972)
183 (1973)
372 (1974)
254 (1970)
272 (1970)
326 (1974)
1,334 (1974)
41 (J970)
31 (1971)
290 (1974)
47 (1973)
231 (1974)
63 (1973)
152 (1973)
63 (1970)
82 (1973)
(MT/y
1 , 500
1,500
1,400
1,300
1,300
1,300
1,300
1,200
1,200
1,200
1,200
1,100
1,100
1,100
1,000
1,000
800
800
800
700
700
"Best
Organic
Volatiles
r) Hei:
1
1
2
1
3
1
1
1
1
1
1
1
1
1
1
1
1
4
4
1
4
Estimate" of
Air EmJssi.ons1
Partic.ulntes Additional Estimates of Volatile Organic Emissions
(J (MT/yr) Rcf Q (MT/yr) Kef Q (MT/vr) Rcf Q (KT/yr) Re£ 0
C
B
BO 2 B 12,361 1 B
C
C
B
B
B
C
C
B-
C 1,207 3 C
B
B
C
C
C 2,223 5
D
D
C
D
-------
TABLE A-l (Continued)
Product
Fluorocarbon 22
Melamine Resins
Acetone Cyanohydrin
Perchloroethylene
Hydrogen Cyanide
Benzoic Acid
Isopircne
Epoxy Resins
Methyl Ethyl Ketone
LJ Diisodecyl Phthalate
O
00 Heptenes
Polyisoprerie Rubber
Isophthalic Acid
Aniline
Benzyl Chloride
Nonyl Phenol
Benzene from Chemical
Conversion
Ethyl Ether
Chloroacetic Acid
Carbon Disulfide
2-Methoxyethanol
Phthalic Annydride
Isooctyl Alcoliols
AIR EMISSIONS FROM ORGANIC CHEMICAL PROCESSING IN METRIC TONS/YR
"Best
Organic
Production
(103MT/yr)
64 (1974)
77 (1974)
244 (1969)
332 (1974)
138 (1973)
36 (1974)
181 (1974)
82 (1972)
229 (1974)
70 (1970)
54 (1971)
91 (1974)
54 (1974)
242 (1974)
41 (1971)
81 (1970)
5,021 (1972)
80 (1974)
29 (1969)
348 (1972)
77 (1972)
467 (1974)
45 (1970)
Vo la tiles
(MT/yr)
600
300
300
300
200
200
200
200
200
200
100
100
100
100
100
100
80
80
70
70
50
50
40
Ref
5
3
1
1
2
1
1
1
1
1
1
1
1
1
1
1
1
1
1
2
1
2
1
Estimate" of
Air Emissions1
Particulates Additional Estimates of Volatile Organic Emissions
Q (MT/yr) Ref Q (MT/yr) Ref Q (MT/yr) Ref Q (MT/yr) Ref q
C
C
B 272 6 C
B 0 2 B 0 1 B
C
C
C
B
C
C
C
B
C
C
C
C
C
C
B 0 2 B
C
B 3,200 2 B 1,450 1 B 12,700 3 C 2,568 7 D
C
-------
TABLE A-l (Continued)
AIR EMISSIONS FROM ORGANIC CHEMICAL PROCESSING IN METRIC TONS/YR
"Best E
Organic
Production
Product'
Polyisobutylene - Isoprene
(Butyl) Rubber
n-BuLyl Acetate
2-Bu Loxyethanol
2-Ethoxyethanol
n-Octyl-n-Decyl Fhthalate
Pluorocarbon 113
Din i t ro toluene
Fluorocarbon 114
Hexamethylene Diaraine
1
tjO Isopropyl Alcohol
O
Ally! Chloride
Aery] on it rile-Butadiene
Styrune Resins
Fluo roca rbon 11
Aery Ionic rile-Butadiene
Rubber (Mitrile)
Cellopane
Nylon 6
Nylon 66
Phosgene
Soap & Detergent
Urea
(10JMT/yr)
163
43
52
71
91
64
131
.12
322
866
395
238
157
86
141
445
921
330
5,840
3,348
(1974)
(1972)
(1971)
(197.1)
(1970)
(1974)
(1970)
(1970)
(1971)
(1974)
(1970)
(1970)
(1974)
(1974)
(1972)
(1970)
(1970)
(1973)
(1973)
(1974)
Vola tiles
(MT/yc)
40
40
40
30
30
30
20
20
10
10
10
10
3
0
0
0
Ref
1
1
1
1
1
1
1
1
1
1
1
1
5
2
2
].
1
1
stimate" of
Air Eniiss j ons
Par ciciil aces Additional Estimates of Volatile Organic Emissions
Q (MT/yr) Ref
C
C
C
C
C
D
C
C
C
B
B
C
B 1,400 2
B 2,400 2
B
C 18,400 3
C
q (MT/yr) Ref Q (MT/yr) Ref Q (MT/yr) Re£ Q
272 5
136 5
10,655 6 C
687 3 C
B 1,364 1 B
B 2,858 1 B
413 6 C
C
'Estimates rounded to nearest 100 metric tons.
SOURCES: HO-201, PE-160, HO-244, ER-030, SH-241, PR-116, EN-071, PR-115, GL-011
-------
TABLE A-2
i
LO
o
I
Product
AceLaldehyde
Acetic Acid
Acetic Anhydride
Acetone
Acetone Cyanohydrin
( 2-ine t liyl lac tonit ride)
Acetonitrile (vinyl cyanide,
propane nitrile)
Acetylene
Ac rolein
Acrylic Acid
Acrylics
Acrylon i.t r i le
Acrylon Ltrile-Butadiene-
Styrene Resins (ABS)
Acrylonit rile-Butadiene
Rubbers (Nitrile)
Adipic Acid
Adiponitri 1 e
Alkyd Resins
Ally! Chloride
Ammonia (Synthetic,
anhydrous)
Aniline (Aminobenzene)
WATER EFFLUENTS FROM
Current
Total
Organ ics
4,584
484
2,122
4,780
de) 3,628
-anide,
149
147
553
3,960
4,508
ie-
i) 2,390
ie
1,080
7,048 2
8,990
10,] 00
1,870
3,775
ORGANIC
CHEMICAL
PROCESSING
Emissions (MT/yr)
(BPCTCA)1
BOD 5
162
46.9
84.6
926 5
723 4
7.42
45.2
41.2
838 3
974 5
642 2
52.9
,042 11
809 12
680 5
210 1
0.62 1
COD
777 2,
225
861
,240 2,
,106 2,
TOC
505
194
996
970
050
75.6 87.4
302
197
,125 2,
,690 3,
,240 1,
874
,594 5,
,258 5,
,400 ft,
,090
,435 1,
136
no dcitci
276
690
067
930
752
788
993
640
n c\ f\ fi t~ i
— 1 1 U ( J O. L Ct
937
950
IN METRIC
TONS/YR
Potential Level of
Control (MT/yr) (BATEA)
Total
Organics
597
62.8
275
621
471
19.5
19.1
71.8
522
587
311
141
917
1,]70
1,310
244
438
BOD 5
17.8
5.16
9.31
102
79.6
0.82
4.97
4.53
92.2
107
70.6
5.82
225
89.0
74.8
23.2
0.07
COD
241
69.7
267
1,630
1,273
23.4
93.5
61.2
969
1,764
694
271
3,594
3,800
1,674
337
445
2
TOC
326
25.1
129
386
266
11.4
17.7
35.9
350
399
251
97.8
752
779
603
122
253
-------
TABLE A-2 (Continued)
i
LO
Product
benzene
Benzole Acid
Benzyl Chloride
Bisphenol A
Bud ad lent:
n-Butyl Acetate
n-Uutyl Alcohol (n-Butanol)
s-Butyl Alcohol
Hutylenes ( L-, 2-, iso-)
Ca |>ro.l ae tain
Carbon black
Carbon d Lsu I. f ide
Ca rbon Tet rach.l or jde
Cellopane
Cellulose Acetate
(Resins and Fibers)
Chloroacetic Acid
Ch l.orobenzene
Chl.oroform (Tricli I oroine-
thane)
Chlorop rene
Cre.so I (Synthetic)
WATER EFFLUENTS
FROM ORC
AN 1C CHEM
Current Emissions (MT
(Bl'CTCA) '
Total
Organ ics
34.3
438
79.0
480
651
536
nol) 3,168
3,681
1,495
218
2,840
996
12,200
963
28.6
211.0
1,240
761
BOD 5
9.79
122
4.46
-
388
129
726
440
1.1.7
1,120
38.0
14.3
2,780
86.7
0.36
3.90
238
253
COD
74.5
522
45.4
843
1,227
730
4,121
2,587
1,194
537
387
132
6,050
442
19 . 7
35.9
1,351
1,154
ICAL PROCE
/yr)
TOC
31.6
302
52.5
379
562
364
2,057
2,390
1,380
146
no
448
77.7
no
5,200
246
18.3
21.2
674
595
SSING IN METRIC
TONS/YR
Potential Level of
Control (MT/yr) (BATEA)
Total
Qrganics
4.43
57.0
10 . 3
62.6
84.7
69.7
411
479
193
28.4
d ti t f\
369
129
da ta
1,590
125
3.71
27.5
161
98.9
BODf,
1 . 08
13.4
0.49
-
42.7
14 . 2
79.8
48.4
12.9
123
4 . 18
1.57
306
9.54
0.04
0.43
26.2
27.8
COD
23.1
162.0
14.1
261
380
226
1,278
802
370
166
120
40.8
1,870
137
6 . .1 1
11. 1.
419
358
2
TOC
4.1
39.3
6.82
49.3
73.0
47.4
267
311
179
18.9
58.2
10 . 1
676
32.0
2.38
2.76
87.7
77.3
-------
TABLE A-2 (Continued)
i
OJ
Product
Cresylic Acid
Cumene
Cyclohexane
Cyciohexanone and Cyclo-
hexanol (coproducts)
Dichlorobenzene (m-,o-,p-)
DLetliylene glycol
Di(2-ethylhexyl) phLhalate
IKisodecyl phthalate
Dimethyl terephthaJate
Din it rotoluene
Dodccyl benzene sulfonic
acid
Dodecyl benzene suJ fonic
acid, sodium salt
Dyes and pigments
Epich. l.orohydr in
Epoxies
EthanoL (Synthetic)
Ethanolamines
(mono-,d i-,tri-)
Ethyl acetate
Ethyl acrylate
WATER EFFLUENTS
FROM ORGANIC CHEMICAL PROCESSING IN METRIC TONS/YR
Current Emissions (MT/yr)
(BPCTCA) '
Total
Organics
532
0.06
1 —
58.5
p-) 164
2,830
Late '^2
104
8,530
2,400
c
c
60,800
4,830
2,980
7,990
21.6
2.01
4,126
liOD5
94.0
0.02
7.46
6.92
450
21.5
7.59
3,942
390
8,230
665
746
1,320
1.80
0.49
458
COD
534
0.1.1
35.3
70.4
2,560
219
77.3
13,300
2,210
73,300
3,780
1,814
7,720
8.52
2.20
2,464
TOC
266
0.06
40.9
81.4
1,280
254
89.4
4,700
1 , 1 00
30,400
1,880
1,562
4,160
9.88
1.10
2,500
Potential Level of
Control (MT/yr) (UATEA)2
Total
Organics
69.2
0.01
7 . 34
21.3
367
40.6
13.6
1,110
312
7,890
627
388
1,040
2.80
0.26
536
BOD5
10.3
neg
0.82
0.76
50
2.37
0.84
434
42.9
905
73.2
82.1
145
0.20
0.05
50.4
COD
165
0.03
11.0
21.8
793
68.0
24.0
4,120
686
22,700
1,170
562
1,290
2.64
0.68
764
TOC
34.6
0.01
5.32
10.6
166
33.0
11.6
611
144
3,946
245
203
541
1.28
0.14
325
-------
TABLE A-2 (Conuinued)
I'roduc t
Ethy l.benx.ene (pheny lethane)
Ethyl chloride
2-Ethoxyethanol
Etliylene (clium)
Ethylene dibromide
Ethylene d i c 111 o r i d e
Ethylene gJ.yco.l.
2-Ethyl hexanol.
Ethylene oxide
Ethyl ene-propylene polym
Ethyl ether
Fl uoroea rbon .1.1
FLuorocarbon 1.2
FLuorocarbon 22
Fl no coca rbon 1.13
l? I. i.i o i: oc a c b o n 1 I. 4
Formaldehyde (37%)
Glyeuro'l.
Glycol nionobuLyl ether
Heptenes (mixed)
llexanio Lhy I ene d i a mine
1 ene tet ram:; ne
JATliK Kl-'FLUE
Tota
Org£in i
me) 788
57.5
9.51
5,520
1,508
5,270
6,925
2,060
3,940
ierb 430
593
2,290
2,970
590
289
1.1 .1.
8,530
2,050
6. L/i
4.49
832
365
NTS FROM ORGANIC CHEMICAL PROCESSING IN METRIC TONS/YR
Current Einiss
(liPCT
1
cs llODs
45.7
3.89
0.92
1,168
16 . 5
-
62.4
539
162
24.8
122
17.2
25.2
6.98
3 . 1 7
1.34
290
254
0.68
0.70
1.66
54.6
i.ons (M'l'/y
CA)1
COD
1,361
18.4
4.37
8,960 4
168
4,732 1
3,464 2
3,070 1
3,800 2
427
7.15
.1.75
257
71.1
32.2
13.6
2,950 3
1,480
3.21
3.32
1,480
376
r)
TOC
71.7
21.4
5.06
,718
1.95
,305
,680
,528
,150
368
385
202
297
82.2
37.3
1.5.7
,410
800
3.72
3.85
517
188
Potential Level o£
Control (MT/yr) (UA'J'EA)
Total
Organlcs
103
7.48
1.21
717
196
687
900
269
512
55.9
77
297
386
76.7
37.5
1.4 . 5
1,1.10
266
0.79
0.58
.108
47.3
1JOI)5
5.03
0.42
0.10
128.5 2
1.82
1
6.86 1
59.3
1.7.9 1
2.73
• 13.5
1.89
2.77
0.77
0.34
0.14
31.9
27.9
0.07
0.77
18.2
6.01
COD
422
5.72
1.35
,780
52.2
,470
,074
951.
,180
132
222
54.2
79.6
22.0
10.0
4.22
914
460
1 .00
1.03
458
11.6
2
TOC
93.2
2.78
0 . 66
613
25.3
170
349
199
280
47.8
50
26.3
38.6
10.7
4 . 84
2.05
443
.104
0.48
0.50
67.2
24 .4
-------
TABLE A-2 (Continued)
•P-
Product.
Hydrogen Cyanide
Isodecyanol
Isooctyl alcohols
Isophthalic acid
Isoprene
Isopropyl alcohol
Maleic anhydride
Melamine resins
Metlianol
Methyl chloride
2-Methoxyethanol
Methylene chloride
Metliyl. ethyl ketone
Methyl isobutyl ketone
Methyl methacrylate
Naphthalene
Nitrobenzene
NonyJ phenol
Nylon 6 (resins and fibers)
Nylon 66 (resins and fibers)
n-Octy]-n-decylphthala te
WATER EFFLUENTS
FROM ORGANIC CHEMICAL PROCESSING
Current Emissions (MT/yr)
(BPCTCA) '
Total
Organ! cs
2,608
86.2
48.9
119
264
802
13,500
1,850
2,410
10.4
294
98.5
1,153
30,900
19.4
3,190
6.97
sers) 1,410
Lbers) 3,530
:e 152
BO 1) 5
20.9
34.0
18.8
5.84
19.9
112
1,803
372
242
1.00
7.65
117
216
1,690
3.30
881
1.05
685
830
9.91
COD
2,320
96.7
53.8
59.5
202
725
10,300
1,516
1,851
4.75
70.4
137
1,230
31,300
15.6
5,000
4.97
1 ,047
2,620
101
TOG
1,160
65.8
36.5
68.8
234
480
647
unknown
693
547
5.51
41.6
65.7
613
18,500
18.1
2,490
5.76
900
2,250
116
IN METRIC TONS/YR
Potential Level of
Control (MT/yr) (BATEA)2
Total
Organics
808
11.2
6.35
15.5
34.4
104
17,500
240
314
1 .35
38.3
12.8
150
4,020
2.52
415
0.90
184
460
19.9
BODS
2.30
3.74
2.07
0.64
2 . .18
12.3
198
40.9
26.6
0.11
0.84
12.9
23.8
186
0.36
96.9
0.12
75.4
91.3
1.09
COD
720
30.0
16.7
18.4
62.7
225
3,190
470
573
1.47
21.8
42.5
381
9,720
4.85
1,550
1.54
324
811
31.2
TOC
359
8.56
4.74
8.94
30.4
62.4
841
90.0
74.7
0.72
5.41
8.54
79.7
2,407
2.36
324
0.74
117
293
15.2
-------
TABLE A-2 (Continued)
P r o d u c t'
Paint Manufacture
Pentaerythriol
PercliJ oroethy lene
P11 e n o 1
Phenolic resins (and
ot h e r tar resins)
Phosgene
Phthalic anhydride
Polyamid resins
PolyhuLadi.ene resins
Po I.ycli loroprene rubber
Pol.yester (resins and
H hers)
Pol ye thy Lene
1ow dens i ty
11 i g 11 density
PoLy Lsobuty Lene-i soprene
(Butyl) rubbers
Po I y i soprene rul.)ber
'"'(i 1 y p ropy J.ene and copolymers
PoLystrene and ropo.l.ymers
Po I y v i ny I ace ta tu
WATER EFFLUENTS
FROM ORGANIC CM EMI
Current Einiss
(BPCT
Total
Organics
23,800
158
258
15,600
1.92
6.04
929
1,830
7,060
8,900
405
e
390
341
ymers 2 , 760
rs 1,620
1 30
HOD 5
2,370
18.9
760
2,570
4.29
7.77
54.0
58.9
682
1,504
156
23.9
20.4
63. 7
27.1
36 . 5
CAL PROCESS fNC
ions (MT/yr)
CA)1
COD
20,700 1
262
3,240
1.2,900 1
20.3
83.9
930
1,060
4,550
8,840
402
412
35.1
2,740
L.750
84.3
TOC
6,300
23.1
197
1,100
23.6
3 . 90
801
908
3,920
7,607
346
355
302
2,360
1 ,500
72.5
IN METRI
C TONS/YR
Potential
Control (M'l'/y
Total
Organics
3,100
20.5
33.5
2,020
25.0
0.78
121
237
91 8
1 ,160
52.7
50.7
44.4
359
2.12
1.6.9
BOD 5
261
2.08
83.6
283
0.47
0.85
5.93
6.48
75.0
165
17. 1
2.63
2.24
70.0
29.8
4 .02
Level of
r) (1SATEA)
COD
6,418 2
81.1
1,000
4 , 000 L
6.30
26.0
288
327
1,410
2,740
125
128
109
850
542
26. 1
2
TOC
,120
3.00
25.6
,440
3.06
0.51
104
1.18
510
989
45.0
46. 1
39.3
307
I.9C)
9 . 4 3
-------
TABLE A-2 (Continued)
LO
H-1
cr>
Produce
Po'Jyvinyl chloride and
copoIymers
Printing inks
I'ropy ] ene
Propylene gl.ycol
Pr:opylc>ne oxide
Kay on
Soap and Detergent
S L y r e n e
Styrene-butadiene rubber
Tereph tluil ic acid
Tetraethyl and tetra-
nif.tliyl lead
Toluene
Toluene diisocyanates
ill. Trichloroethane
Trich1oroethylene
Urea
Urea-formaldehyde resins
Vinyl acetate monomer
Vinyl chloride monomer
Vinylidene chloride
WATER EFFLUENTS
FROM ORGANIC CHEMICAL PROCESSING IN METRIC TONS/YR
Current Emissions (MT/yr)
(BPCTCA) '
Total
Organics
32
2
11
-r 9
18
2
3
1
1
2.1.
IIS
,100
,290
1.29
,400
147
,230
,200
,149
23.5
,290
,860
,370
,500
115
916
396
BOD 5
1,530
486
4.74
3,015
133
579
3,700
141
6.59
86L
29.3
2 I. 5
266
3.03
155
8.42
COD
14,500
3 , 7 30
37.4
31,600
1,760
9,570
14,100
8,380
50 . 4
4,880
298
219
3,720
23.1
5,450
79.9
TOC
12,500
1,960
0.61
7,061
136
8,241
9,200
640
21.4
2,440
344
253
4,302
66.7
352
99.1
Potential Level of
Control (MT/yr) (BATEA)2
Total
Organics
4,180
298
0.17
1,480
19.0
1 , 200
2,380
280
3.06
428
242
178
2,800
,
15.0
119
51.6
BOD 5
168
53.5
0.52
332
1.47
63.7
406
15.6
0.72
94.8
3.22
2.37
40.2
0.36
17. i
0.92
con
4,490
1,160
11.6
9,790
547
2,970
5,930
2 , 600
15.6
1,510
92.4
67.9
1,153
7.16
1,690
24.8
TOC
1,620
255
0.08
917
1.7.6
1,070
1,200
83.2
2.78
317
44.8
32.9
559
8.67
45.8
L2.9
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TABLE A-2 (Continued)
WATER EFFLUENTS FROM ORGANIC CHEMECAL PROCESSING IN METRIC TONS/YR
Product
ni-Xylene and mixed xylenes
o-Xylene
p-Xylene
Current Emissions (MT/yr)
(BFCTGA) '
To t a I
Orgaivi.cs BOD5 . COD TOG
1.52 0.42 3.26 1.39
3.29 0.92 7.05 2.99
3.93 .1.58 8.50 3.57
Potential Level of
Control (MT/yr) (BATEA):
Total
Organics BOD5 COD
0.20 0.05
0.43 0.10
0.51 0.17
TOG
1.01 0.18
2.1.8 0.39
2.63 0.46
'Best practicable control technology currently available.
Best availabJe technology economically achievable
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TECHNICAL REPORT DATA
(Please read liiiLructiuns on ihe reverse before completing)
1. REPORT NO.
EPA-600/7-77-110
2.
4. TITLE AND SUBTITLE
Hydrocarbon Pollutants from Stationary Soi
7.AUTHOR(s> E. (j. CJavanaugh, M. L.Owen, T. P
J.R.Carroll, and J. D. Colley
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Radian Corporation
8500 Shoal Creek Boulevard
Austin, Texas 78757
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Labora
Research Triangle Park. NC 27711
is. SUPPLEMENTARY NOTES ERL-RTP task officer
Drop 61, 919/541-2709.
3. RECIPIENT'S ACCESSION NO.
5. REPORT DATE
irces September 1977
6. PERFORMING ORGANIZATION CODE
. Nelson 8- PERFORMING ORGANIZATION REPORT NO.
10. PROGRAM ELEMENT NO.
EHE623A
1 1. CONTRACT/GRANT NO.
68-02-1319, Task 48
13. TYPE OF REPORT AND PERIOD COVERED
Task Final; 12/75-6/76
14. SPONSORING AGENCY CODE
tory
EPA/600/13
for this report is Lewis D
. Tamny, Mail
10. ABSTRACT rpke rep0rt gjyes results of a. study of hydrocarbon pollutants from station-
ary sources. Early in the study, readily available information was assembled on
stationary sources of hydrocarbon emissions and effluents. Information was also
obtained on process descriptions, operating parameters, current controls, and
control problems. As the database was assembled, the data was divided into major
categories for subsequent evaluation. Pollutants from process streams were eval-
uated along with fugitive emissions associated with equipment leaks (e.g. , from
pumps, valves, and flanges). Emissions were also included from open sources
(e.g. , forest fires) and from natural sources (e.g. , pine forests). Information in each
category was divided into logical classes and grouped for further assessment of
emissions and effluents from processes and operations. A list of the emission and
effluent rates from the processes and operations studied is in the Appendix. Major
emission and effluent sources in each category were identified and assessed as to
source controllability. Specific processes and operations representing the greatest
potential for the reduction of hydrocarbon emissions and effluents by the application
of central technology were selected for further study.
17.
KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS
Pollution
Hydrocarbons
Emission
Effluents
Industrial Processes
13. DISTRIBUTION STATEMENT
Unlimited
b. IDENTIFIERS/OPEN ENDED TERMS
Pollution Control
Stationary Sources
Fugitive Emissions
Open Sources
19. SECUHI TV CLASS (This Report)
Unclassified
20. SECURITY CLASS (Tin's page/
Unclassified
c. COSATI ricld/C.ruup
13B
07C
13 H
21. NO. OF PA.iES
330
22. PRICE;
EPA Form 2220-1 (9-73)
-318-
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