Prepublication issu^ for EPA libraries
and State Solid Waste Management Agencies
AGENCY
OAUAS,
(•Mr
ASSESSMENT OF INDUSTRIAL HAZARDOUS WASTE PRACTICES:
ORGANIC CHEMICALS, PESTICIDES AND EXPLOSIVES INDUSTRIES
This final report (SW~118c) describes work performed
for the Federal solid waste management program
under contract no. 68-01-2919
and is reproduced as received from the contractor
Copies will be available from the
National Technical Information Service
U.S. Department of Commerce
Springfield, Virginia 22161
U.S. ENVIRONMENTAL PROTECTION AGENCY
1976
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This report has been reviewed by the U.S. Environmental Protection Agency
and approved for publication. Approval does not signify that the contents
necessarily reflect the views and policies of the U.S. Environmental
Protection Agency, nor does mention of commercial products constitute
endorsement by the U.S. Government.
An environmental protection publication (SW-118c) in the solid waste
management series.
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PREFACE
This report summarizes the results of a study of land-destined
hazardous wastes and the assessment of treatment and disposal practices
of the organic chemicals, pesticides, and explosives industries con-
ducted for the Environmental Protection Agency. The project is deeply
indebted to the EPA Project Officers, Messrs. Sam Morekas and Timothy
Fields, Jr., of the Hazardous Waste Management Division, for their
continuing advice and guidance during the entire term of the study.
Thanks are also due to the management and other staff members of the
Office of Solid Waste Management Programs, Hazardous Waste Management
Division, who reviewed program progress, assisted with constructive
suggestions, and coordinated this study with the related projects in
other industry categories for which they were responsible.
This project would not have been accomplished without the key
information furnished by the participating private companies, by the
Armed Services, and by other Federal and State Agencies. Our thanks
are conveyed, hereby, to the management and staffs of all of the
cooperating companies listed in Table A-l* for the vital assistance
they furnished. The Armed Services and Federal Agencies made especially
noteworthy contributions to the accomplishment of this study, and we
wish to express our gratitude for this help to the officers and staff,
Headquarters, Edgewood Arsenal, and Picatinny Arsenal, U.S. Army
Armament Command; the U.S. Army Materiel Command Installations and
Services Agency; the U.S. Army Environmental Hygiene Agency; the
Alcohol, Tobacco and Firearms Division, Internal Revenue Service,
Department of the Treasury; the Social and Economic Statistics Admin-
istration, Bureau of the Census, Department of Commerce; the U.S.
International Trade Commission, Department of the Treasury; and the U.S.
Navy Naval Sea Systems Command. The cooperation of the National
Agricultural Chemicals Association is gratefully acknowledged.
''See Appendix A
iii
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CONTRIBUTORS
Gerald I. Gruber, Project Manager
Charles G. Bacon
Clarence D. Bertino
Howard N. Cassey
John F. Clausen
Dennis F. Dal Porto
Robert L. Derham
Masood Ghassemi
Howard E. Green
Clarence Gustavson
J. Warren Hamersma
Marilyn S. Jennings
Mary A. McKay
William H. Moorman
Ethelyn Motley
Charles F. Murray
Gilbert J. Ogle
Sandra C, Quinlivan
Myrrl J. Santy
Christopher C. Shih
Charles T. Weekley
Carol A. Zee
PROPRIETARY RIGHTS/TRADE SECRETS PROTECTION
Alan D. Akers
Benjamin De Witt
MANAGEMENT REVIEW AND COORDINATION
Jack L. Blumenthal
Bernard Dubrow
Robert J. Jones
.John L. Myers
Robert S. Ottinger
iv
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CONTENTS
Page
1. INTRODUCTION ..... 1-1
2. EXECUTIVE SUMMARY 2-1
2.1 INDUSTRY CHARACTERIZATION 2-3
2.2 WASTE CHARACTERIZATION 2-7
2.3 TREATMENT AND DISPOSAL TECHNOLOGY 2-18
2.4 TREATMENT AND DISPOSAL COSTS 2-22
3. METHODOLOGY 3-1
4. INDUSTRY CHARACTERIZATION 4-1
4.1 GENERAL 4-1
4.2 ORGANIC CHEMICALS INDUSTRY 4-3
4.3 PESTICIDES INDUSTRIES 4-24
4.4 EXPLOSIVES INDUSTRIES 4-27
4.4.1 Commercial Explosives Industry 4-27
4.4.2 Military Explosives 4-31
5. WASTE CHARACTERIZATION 5-1
5.1 GENERAL 5-1
5.2 ORGANIC CHEMICALS INDUSTRY 5-2
5.2.1 Typical Plant Process and Waste
Stream Descriptions 5-2
Perch!oroethylene 5-2
Nitrobenzene 5-6
l-Chloro-4-Nitrobenzene 5-7
Chlorinated Solvents (Chloromethanes) 5-11
Chlorobenzene 5-13
Ethyl Chloride 5-14
Epichlorohydrin 5-18
Ethanolamines 5-20
Furfural 5-22
Benzoyl Peroxide 5-24
Pyridines (2-Methyl, 5-Ethyl Pyridine
and a-Picoline) 5-26
Fluorocarbons 5-28
Toluene Diisocyanate 5-31
Vinyl Chloride Monomer 5-34
Methyl Methacrylate Monomer 5-37
Acrylonitrile 5-41
Maleic Anhydride 5-44
Lead Alkyls 5-46
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CONTENTS (CONTINUED)
Page
tf-Chlorotoluene 5-49
Methylene Chloride 5-49
1,1,1-Trichloroethane 5-53
5.2.2 Annual Process Stream Discharge
to Land Disposal 5-55
5.3 PESTICIDES INDUSTRIES 5-78
5.3.1 Typical Plant Process and Waste
Stream Descriptions 5-82
Aldrin 5-88
Atrazine 5-89
Trifluralin 5-92
Parathion and Methyl Parathion 5-96
Malathion 5-98
5.3.2 Annual Process Stream Discharge
to Land Disposal 5-102
Pesticide Formulation 5-107
5.4 EXPLOSIVES INDUSTRY 5-109
5.4.1 Typical Plant Process and Waste
Stream Descriptions 5-111
5.4.1.1 Manufacture of Basic Explosives • • . 5-111
TNT Production 5-111
Nitrocellulose (NC) Production .... 5-114
Nitroglycerine (NG) Production .... 5-118
HMX and RDX Production 5-122
5.4.1.2 Explosives Formulation 5-124
Propellents 5-124
Explosive Compositions 5-125
Dynamites 5-126
Ammonium Nitrate - Fuel Oil
Mixture (ANFO) 5-126
5.4.1.3 LAP Operations 5-128
5.4.2 Annual Process Stream Discharge
to Land Disposal 5-130
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CONTENTS (CONTINUED)
Page
6. TREATMENT AND DISPOSAL TECHNOLOGY 6-1
6.1 GENERAL 6-1
6.2 ORGANIC CHEMICALS AND PESTICIDES INDUSTRIES 6-2
6.2.1 Waste Stream Treatment/Disposal Technologies- • 6-16
Waste Stream No. 1, Perchloroethylene Manufacture 6-16
Waste Stream No. 2, Nitrobenzene Manufacture • 6-18
Waste Stream No. 3, Chlorinated Solvents
Manufacture 6-19
Waste Stream No. 4, Epichlorohydrin Manufacture 6-20
Waste Stream No. 5, Toluene Diisocyanate
Manufacture 6-21
Waste Stream No. 6, Vinyl Chloride
Monomer Production 6-22
Waste Stream No. 7, Methyl Methacrylate • • • - 6-23
Waste Stream No. 8, Acrylonitrile Manufacture • 6-24
Waste Stream No. 9, Maleic Anhydride 6-25
Waste Stream No. 10, Lead Alkyls Manufacture- • 6-26
Waste Stream No. 11, Aldrin Manufacture .... 6-27
Waste Stream No. 12, Atrazine Production- • > • 6-28
Waste Stream No. 13> Trifluralin Manufacture • 6-29
Waste Stream No. 14, Parathion Manufacture • • 6-31
Waste Stream No. 15, Malathion Manufacture • • 6-32
6.2.2 "Off-Site" Contract Disposal in the Organic
Chemicals and Pesticides Industries 6-33
6.2.3 Prevalent Treatment/Disposal Technologies • • • 6-39
Landfill Disposal 6-39
Incineration 6-40
Deep Well Injection 6-45
Evaporation Ponds 6'47
Activated Carbon Adsorption 6-51
6.3 EXPLOSIVES INDUSTRY 6-54
6.3.1 Military Explosives Industry 6-54
6.3.2 Commercial Explosives Industry 6-64
7. COST ANALYSIS 7-1
7.1 ORGANIC CHEMICALS AND PESTICIDES INDUSTRIES 7-1
7.2 EXPLOSIVES INDUSTRY • 7-16
8. REFERENCES AND BIBLIOGRAPHY 8-1
APPENDIX A A-1
APPENDIX B B-"1
vii
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TABLES
Table Title Page
2-1 Production, Thousand Metric Tons, by Standard
Industrial Classification, for CY 1973 for the
Organic Chemicals, Pesticides and Explosives
Industries 2-4
2-2 Total Process Discharge to Land Disposal, Hazardous
Waste Streams, Metric Tons for CY 1973, for the Organic
Chemicals, Pesticides and Explosives Industries 2-14
2-3 Total Process Discharge to Land Disposal, Hazardous
Waste Streams, Metric Tons for CY 1977 for the Organic
Chemicals, Pesticides and Explosives Industries 2-16
2-4 Total Process Discharge to Land Disposal, Hazardous
Waste Streams, Metric Tons for CY 1983, for the Organic
Chemicals, Pesticides and Explosives Industries 2-17
3-1 Hazard Categories and Classes — Rating Table 3-4
4-1 Chemical Products of the Organic Chemicals and
Technical Pesticides Industries Included in this
Study by Standard Industrial Classification 4-5
4-2 Number of Plant Sites by Standard Industrial
Classification, Organic Chemicals and Technical
Pesticides Industries 4-15
4-3 Plant Size by Daily Capacity, Metric Tons
Organic Chemicals and Technical Pesticides
Industries 4-16
4-4 Production Rate, thousand Metric Tons Per Year, By
Standard Industrial Classification, Organic Chemicals and
Technical Pesticides Industries 4-17
4-5 Process Types Used for Manufacture, by Standard
Industrial Classification -Organic Chemicals
and Technical Pesticides Industries 4-18
4-6 Number of Plant Sites by Standard Industrial
Classification - Pesticides Industries 4-26
4-7 Production Rate, Thousand Metric Tons Per Year, CY 1972
by Standard Industrial Classification — Pesticides
Industries 4-28
4-8 Major Commercial Explosives 4-29
viii
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TABLES (CONTINUED)
Table Title Page
4-9 Industrial Explosives and Blasting Agents Sold for
Consumption in the United States, 1973 4-31
4-10 Estimated Production Rate, Metric Tons for CY 1973,
By Explosive Class - Private Explosives
Industry SIC 28921 4-32
4-11 Number of Plant Sites by Standard Industrial
Classification - Explosives Industry 4-33
4-12 Production Rate, Metric Tons for CY 1973, GOCO Plants,
Explosives Industry (SIC 28922) 4-35
5-1 Total Process Waste Stream Discharge to Land Disposal,
Metric Tons for CY 1973 by Standard Industrial
Classification, Organic Chemicals and Technical
Pesticides Industries 5-56
5-2 Total Process Waste Stream Discharge to Land Disposal,
Metric Tons for CY 1977 by Standard Industrial
Classification,Organic Chemicals and Technical
Pesticides Industries 5-59
5-3 Total Process Waste Stream Discharge to Land Disposal,
Metric Tons for CY 1983 by Standard Industrial
Classification,Organic Chemicals and Technical
Pesticides Industries . , 5-60
5-4 Total Process Discharge to Land Disposal, Hazardous
Waste Streams, Metric Tons for CY 1973 by Standard
Industrial Classification, Organic Chemicals and
Technical Pesticides Industries 5-62
5-5 Total Process Discharge to Land Disposal, Hazardous
Waste Streams, Metric Tons for CY 1977 by Standard
Industrial Classification,Organic Chemicals and
Technical Pesticides Industries 5-63
5-6 Total Process Discharge to Land Disposal, Hazardous
Waste Streams, Metric Tons for CY 1983 by Standard
Industrial Classification,Organic Chemicals and
Technical Pesticides Industries 5-64
5-7 Hazardous Component Content, Process Waste Stream
Discharge to Land Disposal, Metric Tons for CY 1973
by Standard Industrial Classification -Organic
Chemicals and Technical Pesticides Industries 5-65
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TABLES'"(CONTINUED)
Table Title Page
5-8 Hazardous Component Content, Process Waste Stream
Discharge to Land Disposal, Metric Tons for CY 1977
by Standard Industrial Classification -Organic
Chemicals and Technical Pesticides Industries 5-66
5-9 Hazardous Component Content,Process Waste Stream
Discharge to Land Disposal, Metric Tons for CY 1973
by Standard Classification - Organic Chemicals and
Technical Pesticides Industries 5-67
5-10 Highly Dangerous Waste Stream Components by Standard
Industrial Classification,Organic Chemicals and
Technical Pesticides Industries 5-69
5-11 Highly Dangerous Component Content, Process Waste Stream
Discharge to Land Disposal, Metric Tons for CY 1973 by
Standard Industrial Classification - Organic Chemicals
and Technical Pesticides Industries 5-75
5-12 Highly Dangerous Component Content,Process Waste Stream
Discharge to Land Disposal, Metric Tons for CY 1977 by
Standard Industrial Classification - Organic Chemicals
and Technical Pesticides Industries 5-76
5-13 Highly Dangerous Component Content,Process Waste Stream
Discharge to Land Disposal, Metric Tons for CY 1983 by
Standard Industrial Classification - Organic Chemicals
and Technical Pesticides Industries 5-77
5-14 Companies Providing Information on Pesticide Manufacturing
Formulation and Waste Disposal Methods 5-80
5-15 Pesticides Considered in SIC 28694 and Their Grouping
into Chemical Classes 5-83
5-16a Trifluralin Production - Process Exhaust
Before Scrubbing 5-96
5-16b Analysis of Typical Aqueous Brine from
Trifluralin Manufacture Before and
After Treatment with Activated Carbon ..... 5-96
5-17 Some General Characteristics of Parathion and
Methyl Parathion 5-99
5-18 Process Waste Discharge to Land Disposal, Metric Tons for
CY 1973, by Type and Standard Industrial Classification,
Pesticides Industries 5-103
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TABLES (CONTINUED)
Table Title Page
5-19 Process Waste Discharge to Land Disposal, Metric Tons for
CY 1977, by Type and Standard Industrial Classification,
Pesticides Industries 5-104
5-20 Process Waste Discharge to Land Disposal, Metric Tons for
CY 1983, by Type and Standard Industrial Classification,
Pesticides Industries 5-105
5-21 Material Balance for TNT Production (Batch Process) and
Associated Satellite Operations 5-l15
5-22 Mass Balance Data for TNT Production by the Continuous
Process (Radford AAP, Radford, Virginia) 5-116
5-23 Mass Balance Data for Modernized Nitrocellulose
Production (kg per kg of NC Produced) 5-119
5-24 Mass Balance Data for Nitroglycerin (NG) Production
(kg per kg NG Produced) 5-121
5-25 Typical Composition of Propel!ants (Percent) 5-125
5-26 Makeup of Major Explosive Compositions 5-127
5-27 Common Ingredients of Dynamites 5-127
5-28 Typical Composition of "Straight" Dynamite with
"Active" Base 5-128
5-29 Material Balance for Two LAP Operations at
Joliet AAP 5-131
5-30 Explosive Wastes Discharged to Land Disposal, Metric
Tons for CY 1973 for the Private Explosives Industry
(SIC 28921) (With Comparative Totals for CY 1977
and CY 1983) 5-132
5-31 Explosive and Explosive Contaminated Wastes Discharged
to Land Disposal, Metric Tons for CY 1973 - GOCO
Plants, Explosive Industry (SIC 28922) 5-134
6-1 Hazardous Waste Treatment/Disposal Methods at
Selected Organic Chemical Plant Sites 6-3
6-2 Hazardous Waste Treatment/Disposal Technology
Distribution - Selected Organic Chemical
Plant Sites ....... 6-9
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TABLES (CONTINUED)
Table Title Page
6-3 Hazardous Waste Treatment/Disposal Methods at Selected
Pesticides Industries Plant Sites 6-10
6-4 Characteristics and Treatment and Disposal Technologies -
Selected Land-Destined Waste Streams from Typical Plants. . 6-15
6-5 Off-Site Contract Disposal Sites and Types of
Wastes Accepted 6-34
6-6 Treatment/Disposal Methods at "Off-Site"
Disposal Sites 6-35
6-7 Incinerators for the Disposal of Chemical
Plant Wastes 6-42
6-8 Data on Selected Deep Well Disposal Systems 6-48
6-9 Analysis of Wastewater 6-54
6-10 Treatment Disposal Technologies for Major Land-Destined
Explosives Wastes in the Military Explosives Industry . . . 6-55
6-11 Use of Spray Irrigation and Evaporation Lagoons for
Waste Disposal in the Commercial Explosives Industry .... 6-67
7-1 Bases and Criteria for Cost Estimation 7-2
7-2 Treatment and Disposal Technology Costs 7-7
7-3 Comparative Data - Current Costs of Chemical Waste
Treatment and Disposal for a Typical Organic
Chemical Plant 7-11
7-4 Major Factors Affecting Treatment and Disposal
Costs at Typical Plants 7-13
7-5 Cost of Waste Disposal by Open Burning at
Selected Army Ammunition Plants 7-17
7-6 Explosive Contaminated Inert Waste Incineration 7-18
7-7 Estimated Construction Cost for an Explosive Contaminated
Inert Waste Incineration Facility (Capacity-5900 kg
(13,000 lbs)/Day) .... 7-19
A-l Companies and Agencies Supplying Information on
Production and/or Disposal A-3
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FIGURES
Figure Title Page
2-1 Total Process Discharge to Land Disposal,
Hazardous Waste Streams, Metric Tons for
CY 1973 for the Organic Chemicals, Pesticides
and Explosives Industries 2-13
4-1 Monthly TNT Production at Joliet Army
Ammunition Plant 4-37
4-2 Monthly Tetryl Production at Joliet Army
Ammunition Plant 4-38
5-1 Perchloroethylene Manufacture 5-4
5-2 Nitrobenzene Manufacture 5-8
5-3 l-Chloro-4-nitrobenzene Manufacture 5-10
5-4 Chlorinated Solvents Manufacture 5-12
5-5 Chlorobenzenes Manufacture 5-15
5-6 Ethyl Chloride Manufacture 5-17
5-7 Epichlorohydrin Manufacture 5-19
5-8 Ethanolamines Manufacture 5-21
5-9 Furfural Manufacture 5-23
5-10 Benzoyl Peroxide Manufacture .... 5-25
5-11 Pyridines (2-Methyl, 5-Ethyl Pyridine and a-Picoline)
Manufacture „ „ 5-27
5-12 Fluorocarbons Manufacture „ 5-30
5-13 Toluene Diisocyanate Manufacture „ 0 ....«, 5-32
5-14 Vinyl Chloride Monomer Manufacture 5-35
5-15 Methyl Methacrylate Manufacture 5-39
5-16 Acrylonitrile (Sohio Process) Manufacture 5-43
xiii
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FIGURES (CONTINUED)
Figure Title Page
5-17 Maleic Anhydride 5-45
5-18 Lead Alkyls Manufacture 5-48
5-19 Chlorotoluene Manufacture 5-50
5-20 Methylene Chloride Manufacture 5-52
5-21 1,1,1-Trichloroethane Manufacture 5-54
5-22 Synthesis of Triazine Pesticides 5-81
5-23 Aldrin Manufacture 5-90
5-24 Atrazine Manufacture 5-93
5-25 Trifluralin Manufacture 5-95
5-26 Parathion Manufacture 5-98
5-27 Malathion Manufacture 5-101
5-28 Liquid Formulation Unit 5-110
5-29 Batch Process TNT Manufacturing and
Satellite Operations 5-112
5-30 Nitrocellulose Production at Radford AAP 5-117
5-31 Schematic Flow Diagram for NG Production 5-120
5-32 Schematic Flow Diagram for RDX Production 5-123
5-33 Operational Flow Chart for a Projectile Loading Line . . . 5-129
6-1 Cross Section of the New Tar Burner at Dow Chemical
Midland Facility 6-43
6-2 Rotary Kiln Incinerator and Control Equipment at an
"Off-Site" Disposal Facility 6-44
6-3 Injection Well Completion „ 6-46
6-4 Portland Waste Treatment Plant,Chipman 6-53
Division/Rhodia .
6-5 Disposal of Explosive Wastes by Incineration 6-57
xiv
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FIGURES (CONTINUED)
Figure Title Page
6-6 Joliet Army Ammunition Plant Contaminated Inert Waste
Incinerator 6-59
6-7 Red Water Waste Disposal Process (Joliet AAP) 6-62
6-8 Fluidized Bed Concept for Utilization and Recycling
of Red Water Ash 6-63
7-1 The Cost of Solid Waste Disposal in Sanitary Landfills . . 7-3
7-2 Cost of Small Scrubber-Equipped Incineration Systems
in 1971 7-4
A-l Plant Characterization Matrix Form A-10
A-2 Hazard Evaluation System A-13
A-3 Calculations - Total Annual Quantities Generated and
Sent to Land Disposal Waste Streams, Hazardous
Components, and Highly Dangerous Components A-l7
xv
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1. INTRODUCTION
This report is the result of a study commissioned by the U.S.
Environmental Protection Agency for the "Assessment of Industrial Hazardous
Waste Practices —Organic Chemicals, Pesticides and Explosives Industries."
Concurrently, the U.S. Environmental Protection Agency is pursuing similar
studies of other industry categories. These programs are intended to pro-
vide the U.S. EPA with detailed and pertinent information on the generation,
management, treatment, disposal and costs related to wastes considered to
be "potentially hazardous."
Throughout this report, wherever the terms "hazardous wastes" or
"potentially hazardous wastes" are used, or where classification of waste
components into "moderately dangerous" or "highly dangerous" has been
performed, it should be kept in mind that no final judgments are intended
as to such classification. It is recognized and understood that additional
information will be required as to the actual fate of such materials in
a given "disposal" or "management" environment, before a final definition
of "hazardous waste" evolves and is used. As an example, for certain of
the waste streams identified in this report, the U.S. EPA is currently
supporting other studies designed to investigate leaching characteristics
in various soil and moisture conditions.
The objectives of this study were to determine, for the manufacturers
of organic chemicals (covered by Standard Industrial Classification (SIC)
286), pesticide preparations and formulations (SIC 2879) and explosives
(SIC 2892):
0 The quantities and geographic distributions of those land-destined
hazardous wastes generated in 1973, and projected for 1977 and 1983.
• Present practices for treatment and disposal of land-destined
hazardous wastes.
• Commercial control technology which could be applied to reduce
the hazards presented by disposal of selected examples of such
wastes.
• The costs of present practices and the applicable commercial
technology as implemented upon the selected examples.
1-1
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To meet these objectives, it was necessary that the contractor perform five
major tasks: Characterize the industries, characterize the land-destined
hazardous waste streams; identify treatment and disposal technologies;
perform cost analyses on implementation of the treatment and disposal tech-
nologies; and document the findings of the study in a final report.
This final report documents the findings of the study performed by TRW
under Contract 68-01-2919, and is presented in the following seven sections
and two appendices:
• Section 2 - EXECUTIVE SUMMARY
Figures, tables, and a brief narrative interpretation, highlighting
the key data and estimates developed.
t Section 3 - METHODOLOGY
A summary of the techniques employed for deriving the quantitative
figures presented on the industries, their hazardous waste streams,
treatment and disposal technology, and costs.
t Section 4 - INDUSTRY CHARACTERIZATION
Statistical summaries by state, U.S. EPA region, and the nation of
the products, numbers of plant sites, production capacities, pro-
cesses and quantities manufactured annually for each product group/
industry.
t Section 5 -WASTE CHARACTERIZATION
Selected typical process flow diagrams, mass balances, and plant
and hazardous waste stream descriptions; estimates for 1973, and
projections for 1977 and 1983, summarized statistically by geograph-
ic area, of land-destined process waste discharge, hazardous pro-
cess waste discharge, and hazardous component content; and listings
of the highly dangerous waste components for each product group.
• Section 6 - TREATMENT AND DISPOSAL TECHNOLOGY
Summaries and analyses of participant company/agency data on treat-
ment and disposal practices; Level I, Level II, and Level III tech-
nology identification for land-destined hazardous waste streams
from the selected typical plants; discussions of prevalent land-
based technology, including off-site contractor processing.
• Section 7 - COST ANALYSIS
Costs per ton of product and costs per ton of waste for treatment
and disposal of hazardous wastes at the selected typical plants
using Level I, II and III technology.
t Section 8 - REFERENCES AND BIBLIOGRAPHY
1-2
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t APPENDIX A
Details of the methodology used in deriving the data contained
in this report.
• APPENDIX B
Injection Well Act, State of Texas; Waste Disposal to Land
Regulations, State of California; Hazardous Waste Law and
Hazardous Waste Regulations, State of California.
1-3
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2. EXECUTIVE SUMMARY
This industry study is one of a series by the Office of Solid Waste
Management Programs, Hazardous Waste Management Division. The studies were
conducted for information purposes only and not in response to a Congres-
sional regulatory mandate. As such, the studies serve to provide EPA with:
(1) an initial data base concerning current and projected types and quanti-
ties of industrial wastes and applicable disposal methods and costs; (2) a
data base for technical assistance activities; and (3) a background for
guidelines development work pursuant to Section 209, Solid Waste Disposal
Act, as amended.
The definition of "potentially hazardous waste" in this study was de-
veloped based upon contractor investigations and professional judgment.
This definition does not necessarily reflect EPA thinking since such a defi-
nition, especially in a regulatory context, must be broadly applicable to
widely differing types of waste streams. Obviously, the presence of a toxic
substance should not be a major determinant of hazardousness if there were
mechanisms to represent or illustrate actual effects of wastes in speci-
fied environments. Thus, the reader is cautioned that the data presented
in this report constitute only the contractor's assessment of the hazardous
waste management problem in these industries. EPA reserves its judgments pend-
ing a specific legislative mandate.
There are approximately 2,200 plant sites (operated by hundreds of pri-
vate companies) spread over the United States, engaged in the manufacture
of organic chemicals, pesticides and explosives. Each of these plant sites
produces at least one, and usually more commodities, classified under SIC's
286, 2879 and 2892, and discharges process wastes from its production lines.
This study reports on the process wastes in 1973 that went (or will go in
1977 and 1983) to land disposal: How much, what, and where; what was done
in industry sample plants for treatment and disposal; what's the best that
was done or the best that can be done commercially; and how much the treat-
ment and disposal methods cost. "Disposal to the land" as employed in this
study includes deep sea disposal* deep well disposal, lagooning, landfill,
burial, and incineration.
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A methodology emphasizing mixtures of hard facts and estimates at the
individual production line and commodity level was developed to produce the
reported results. The exact figures for production at each plant, reported
to the various Federal Agencies, are privileged information protected by
Congressional legislation and company proprietary information rules. The
exact quantities of process wastes discharged to land at each plant for each
process — how much of what — were in the majority of cases, unknown because
the streams were not monitored adequately or with sufficient frequency.
Therefore, we estimated waste quantities based on our assessment of produc-
tion distribution, process technology, literature data, and industry and
Government agency furnished data. The bulk of the estimates (for the organ-
ic chemicals, technical pesticides and Government Owned Contractor Operated
(GOCO) explosives industries) were for each product at each plant in the
study. The remaining estimates (for the pesticides preparations and private
explosives industries) were the total for all plants 1n each Industry 1n
each state. The results were integrated to yield the data presented.
Criteria based on 1973 production rates were imposed to limit the num-
ber of organic chemicals and technical organic pest control chemicals for
which estimates were made. In summary, the study examined:
t Individual organic chemicals whose production in the United States
was 10 million pounds per year or more.
t Technical organic pest control chemicals for which United States
production was 1 million pounds per year or more.
The production in 1973 for chemicals which met the above criteria constitut-
ed approximately 90 percent of the tonnage of organic chemicals and techni-
cal organic pest control chemicals manufactured in the United States.
The Standard Industrial Classification (SIC) systen, splits the pesti-
cides industry into two parts — one under SIC 28694 (pesticides and other
synthetic organic chemicals) and the other, pesticides preparations and for-
mulations, under SIC 2879. For clarity they have been treated as a single
heading, "The Pesticides Industries," in this summary. To avoid redundancy
the data reported for the organic chemicals industry in this summary ex-
cludes SIC 28694.
2-2
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2.1 INDUSTRY CHARACTERIZATION
The five major industries examined were:
SIC 2861 Gum and Wood Chemicals Industry
SIC 2865 Cyclic Crudes and Intermediates Industry
SIC 2869 Industrial Organic Chemicals NEC* Industry
SIC 2879 Pesticides Industries (Including SIC 28694)
SIC 2892 Explosives Industry
The estimated 87 million metric tons of product manufactured by these
five major industries were subdivided into 20 product groups and several
thousand individual commodity products. This summary reports by major
industry.
The industrial organic chemicals (64 million metric tons) and the
cyclic crudes and intermediates (just under 19 million metric tons) industries
manufactured the greatest volume of product during 1973. Texas, with 35
million metric tons, and Louisiana, with 14 million metric tons, led the
states in production. Table 2-1 presents production data for calendar year
(CY) 1973.
This study provides estimates and data for 1,908 plant site?** in the
United States engaged in the manufacture of organic chemicals, pesticides
and explosives. The term plant site has been used to identify each facility
where one or more of the commodities (organic chemicals, pesticides or
explosives) covered in this study are manufactured. A given plant site,
by this definition, may contain any number of processes (in some cases, 30
or more) each producing a different commodity.
Texas had the greatest total number of plant sites (172) for the five
major industries covered in this study. New Jersey had the second largest
number of plant sites (152), and California with 142 plant sites was third
nationally.
There were 765 organic chemical plant sites*** which met the criteria
for inclusion in this study given on page 2-2. New Jersey, Texas and Ohio
ranked first, second and third in number of organic chemical plant sites***,
*NEC-Not elsewhere classified
**This number includes only those plants meeting the production criteria
stated on p. 2-2, and hence is less than the 2,200 plant sites referred
to on p. 2-1.
***Excluding technical organic pest control chemical manufacturing sites
(SIC 28694). 2 3
-------
Table 2-1.
Production, Thousand Metric Tons, by Standard Industrial
Classification, for CY 1973 for the Organic Chemicals1,
Pesticides2 and Explosives Industries
tp»
Rftalon
4
10
_J
6
9
6
1
3
3
4
4
9
10
5
5
7
7
4
6
1
3
1
5
5
4
7
8
7
9
1
2
6
2
4
8
5
6
10
3
2
1
4
8
4
6
8
1
3
10
3
5
8
sutt
AUbMu
Alisk.
Arlzoru
Arkansas
Callfornl.
Colorado
Connecticut
Delaware
District of Columbia
Florida
Georgia
Hawaii
Idaho
Illinois
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maine
Maryland
Massachusetts
Michigan
Minnesota
Mississippi
Missouri
Montana
Nebraska
Nevada
New Hampshire
New Jersey
New Mexico
New York
North Carolina
North Dakota
Ohio
Oklahoma
Oreqon
Pennsylvania
Puerto Rico
Rhode Island
South Carolina
South Dakota
Tennessee
Texas
Utah
Vermont
Virgi n1a
Washington
West Virginia
Hlsconsi n
Wyomi ng
NATIONAL TOTALS
SIC 2861
97
282
49
88
14
29
71
41
670
Irgink Chmlcals
SIC 286b
660
425
2
0.5
333
292
118
547
173
59
75
2.279
374
4
871
23
107
62
32
1.320
96
359
299
23
1,099
645
1
210
350
6,718
57
222
113
697
40
18,682
j
SIC 2869 3
294
290
128
1.985
2
110
433
617
279
. . 1.619
457
298
114
1.876
11.956
131
150
337
70
139
36
18
11
1.435
277
376
997
37
dll
827
7,471
15
246
879
28,350
234
03
l,?97
54
64,368
SIC 28694/2879
90
3
34
215
39
12
3
82
53
3
3
80
17
57
14
3
84
22
20
46
15
fin
QQ
7
in
7
.1
10R
67
40
60
10
20
51
30
53
173
3
13
33
33
23
1,791
SIC 2892
67
2
85
8
30*
10
9
0.06
21
15
1
5
.... 161
55
14
155
?
?
7
T
Pfi H
57
1
.17
3
1
IP
,
,
?q
12
12
n 4
72
16
6
130
0.4
2
ToUl7
1.200
_290
SB
170
2.700
53
130
770
1.300
510
i- A-
2,400
100.
-iZO
iqn
?,mn
i4,nnn
iin
inn
i.inn
on
pan
Tin
if,
- 20
51
? Qnn
29
4sn
nnn
0 4
1.400
_J51-
500
. .2iLOtt.._.
8.100
16
s?n
1 ' ,
1S7 1.500
21 ^ 35,000
18f 73
0.8 ! 08
167
7
70
39
5
1,657
640
260
2,100
160
5
87,000
Production figures based on those organic chemicals whose national production in 1973 was > 10 million pounds
Production figures based on those technical organic pest control chemicals (SIC 28694) whose national production
in 1973 was > 1 million pounds, pijs estimates based on the "1972 Census of Manufacturers" for SIC 2879
txcluding SIC 28694, terhmcM organic pest control chemicals. •
Including SIC 28634, technical organic pest control chemicals
Based on data for CY 1973 consumption by state from "Mineral Industry Survey," U. S. Bureau of Mines and data
froir i HP U S Army Armament Command.
Exc'uaing certain propellant compositions.
A11 production estimates in this column are rounded off to the nearest two significant figures and therefore
may not agree with the State and National totals 1n the body of the text.
2-4
-------
with 121, 89 and 55 sites, respectively. Total organic chemical production
(excluding technical organic pest control chemicals) was just under 84
million metric tons. Texas and Louisiana had the highest levels of organic
chemical production.
The three major industries comprising the organic chemicals industry
were divided into 12 major product groups, for the purpose of estimating
plant size for each product group at each site. Roughly 65 percent of the
product group-plant site combinations had an aggregate production capacity
of less than 100 metric tons per day. Only one combination in 16 had an
aggregate production capacity of 1,000 or more metric tons per day.
The processes employed in the organic chemical industry were divided
into 34 process types, on the basis of the process chemistries involved in
the manufacture of the individual commodities. There were approximately
2,400 chemical product-plant site combinations for the organic chemical
industry* (each representing a production line which manufactured an organic
chemical commodity) classified by process type. The most numerous process
type was "Multi-step synthesis," used at 324 plants.
The pesticides industries (SIC 28694 and SIC 2879) had 522 plant sites.
The national total number of production sites for the technical pesticide
manufacturing industry (SIC 28694) was 134. The pesticide formulating
industry (SIC 2879) had 388 sites. California and Texas had the greatest
number of plants producing pesticides and formulations, 62 and 44 respectively.
Total pesticide and pesticide formulation production was slightly under 1.8
million metric tons. Of this total, just over 0.5 million metric tons were
technical organic pest control chemicals (SIC 28694) and approximately 1.3
minion metric tons were pesticide preparations and formulations (SIC 2879).
California and Texas led the nation in overall pesticide production.
None of the technical organic pest control chemical plants had produc-
tion capacity in excess of 100 metric tons per day. Approximately 60 percent
of the technical organic pest control plants had production capacities less
than 10 metric tons per day. Data on the production capacities of individual
pesticide formulation plants was not available.
Excluding technical organic pest control chemicals.
2-5
-------
There were 11 process types used by the pesticides industries-, 8 by
the technical organic pest control industry, and three by the pesticide
formulation plants. The most numerous process type for the technical
pesticide plants was "Multi-step synthesis," used at 92 per cent of the
plant sites.
The explosives industries (SIC 2892) had 621 plant sites; of this total,
586 were private explosives industry (SIC 28921) sites, and 35 were Govern-
ment Owned Contractor Operated (GOCO) plants (SIC 28922). Pennsylvania,
California and Texas had the greatest numbers of explosives industries (SIC
2892) plants, with 75, 45, and 39, respectively. Total explosives produc-
tion was slightly less than 1.7 million metric tons. GOCO plants produced
just over 0.4 million metric tons of explosives; the private explosives
industry produced the remainder (1.25 million metric tons). Tennessee and
Virginia produced the greatest quantities of explosives, with totals of
187,000 metric tons and 167,000 metric tons, respectively.
The majority of the basic information used for the characterization of
the organic chemicals industry was obtained from three sources: The pre-
liminary reports for 1973 by the United States International Trade Commission
(formerly Tariff Commission) on United States production and sales of synthetic
organic chemicals, ' the Stanford Research Institute "1974 Directory of
Chemical Producers — United States of America,"^ ' and the organic chemical
companies listed in Table A-l, Appendix A. The article by 0. Johnson,
(42}
"Pesticides "72", in Chemical Week was the fourth major information
source used for characterizing the technical organic pest control chemicals
industry, in addition to the three sources just cited. For the characteriza-
tion of the pesticides preparations and formulations industry, the major
information sources were the preliminary report for 1972 on agricultural
chemicals (SIC 2879) of the Bureau of the Census; ' a communication on the
geographical distribution of pesticide manufacturing establishments from
the Bureau of the Census, ' and the pesticides manufacturing companies
listed in Table A-l, Appendix A. The U.S. Army Armament Command furnished
all the information used for characterizing the GOCO plants. The major
information sources for the characterization of the private exolosives
industry were the Bureau of Mines report on apparent consumption of industrial
/ "i CI ^
explosives and blasting agents in 1973,^ i and a private communication
from the Alcohol. Tobacco and Firearms Division of the Internal Revenue
Service on explosive manufacturers. ( '°>
2-6
-------
2.2 WASTE CHARACTERIZATION
Twenty-one hypothetical plants, each using a single process, were
selected as "typical" for this study in order to characterize the waste
streams discharged to land by the plants of the organic chemicals industry.
The processes examined are used for the production of the following organic chemv
cals: Perchloroethylene, nitrobenzene, l-chloro-4-nitrobenzene, chlorinated
solvents (chloromethanes), chlorobenzene, ethyl chloride, epichlorohydrin,
ethanolamines, furfural, benzoyl peroxide, pyridines (2-methyl, 5-ethyl
pyridine and a-picoline), fluorocarbons, toluene diisocyanate, vinyl
chloride monomer, methyl methacrylate monomer, acrylonitrile, maleic anhydride,
lead alkyls, a-chlorotoluene, methylene chloride, and 1,1,1-trichloroethane.
The bases for the selection of the processes were the significance of
their products and process waste streams, the national production volume
for the products of the processes, and the industrial importance of the
chemical product groups represented. The individual national production
volumes for nineteen of the organic chemicals produced by the hypothetical
plants was greater than 23,000 metric tons (50 million pounds) per year.
The twenty-one products selected constituted 9 percent by weight of the total
production of the organic chemicals industry. Because the processes selected
generated far more waste per unit of product than the average for the organic
chemicals industry, the total process wastes (dry basis) discharged to land
by plants producing the twenty-one products represent about 52 percent by
weight of the total land-destined process wastes (dry basis) of all United
States organic chemicals plants. Eighteen of the processes discharge
hazardous process wastes (as described later in this section) tc land
disposal. Two of the three processes which currently discharge no hazardous
wastes to land will probably be required by the Federal Water Pollution
Control Act Amendments to provide land-based treatment and disposal
methods for hazardous wastes currently present in their industrial out-
falls.
Emphasis has been placed in the characterization of wastes from the
pesticides industries on the discharges and technologies of the technical
pesticides manufacturing industry (SIC 28694). The reasons are twofold:
First, and most important, are the much higher quantities of hazardous
wastes anticipated from technical pesticides plants, as opposed to the
2-7
-------
relatively low quantities estimated for pesticides formulations and prep-
arations production. Second is this study's lack of access to quantita-
tive data other than gross national statistics on pesticides formulations
and preparations production. Detailed information on the annual production
of each formulation at each plant site was treated as proprietary by the
companies involved and was not available from trade publications.
Because of the very sensitive nature of the pesticide manufacturing
and formulation industries, very little information is available on specific
details of production and formulation operations for a large number of
individual pesticides and pesticide preparations. Most manufacturers and
formulators are extremely reluctant to reveal technical process data.
Five typical technical pesticide processes were selected for presenta-
tion of process flow diagrams, mass balances, and waste stream descriptions,
to characterize the industry waste streams sent to land. Combined total
production for the five technical pesticides selected was estimated to
constitute approximately 26 percent of the national total for production
of all technical organic pest control chemicals. Combined total process
wastes discharged to land (dry weight basis) for the five technical pesticides
was estimated to constitute 19 percent of the national total dry weight of
process wastes discharged to land by all technical organic pesticides plants.
The five technical pesticides selected were, therefore, considered as
adequately representative of product group SIC 28694. The five technical
pesticides selected were: Aldrin, atrazine, trifluralin, parathion and
methyl parathion, and malathion. Each of the five technical pesticide
production processes discharged hazardous wastes (as defined later in this
section) to land disposal.
Explosives-containing wastes originate from the manufacture of basic
explosives, from explosives formulation, and from loading, assembly, and
packing (LAP) operations. The processes selected to characterize the wastes
of the explosives industry were selected as typical of each of the three
sources. The process and waste stream descriptions were: For basic explo-
sives, trinitrotoluene, nitrocellulose, nitroglycerin, RDX, and HMX; for
explosives formulation, Composition B, dynamites and a double-base pro-
pellent; and for LAP operations, flow diagrams and mass balances for a
typical LAP plant.
2-8
-------
The estimated total quantity (dry weight basis) of process waste
streams discharged to land-based disposal 1n CY 1973 by the three Industries
examined in this study was 2.2 million metric tons. Process waste stream
discharge to land was highest on a dry weight basis in 1973 in Texas and
Louisiana with 916,000 and 268,000 metric tons, respectively. The organic
chemicals industry total process wastes discharged to land (dry weight basis)
in 1973 are estimated as 2.01 million metric tons. The pesticides industries
and the explosives industries sent (estimated, dry weight basis) 175,000
and 21,000 metric tons, respectively, of total wastes to land disposal in
1973.
The dry weight basis has been used throughout this study as the baseline
for all estimates. The majority of the process waste streams sent to land
disposal by the organic chemicals, pesticides, and explosives industries
are relatively low in water content or are nonaqueous. Based on the survey
data for the waste streams of the organic chemicals industry developed
during this study (described in Sections 2.3 and 6.2), 87 percent of the
total number of process waste streams in 1973 were nonaqueous. Thirteen
percent of the total number of process waste streams were treated by deep
well, evaporation pond, and lagooning disposal techniques, which are "wet"
methods. Because of the large quantity of water used by these wet methods,
the wet-basis figures for the total process wastes of the organic chemicals
industry for 1973 are estimated on the basis of the sample cited as 6.4
million metric tons.
The survey ratio of 3.17 between actual tons (wet basis) and dry basis
tons was used above as a conversion factor for estimating wet-basis ("actual")
process waste quantities from the data for dry-basis process wastes sent to
land disposal by the organic chemicals industry. As discharged from the
process, the wastes produced by the organic chemicals industry generally
contain little or no water. To facilitate hydraulic transport for disposal
by deep well injection, lagooning and evaporation pond, and in cases where
the method of ultimate disposal is deep well injection, water is added to
the wastes. The ratio of 3.17 between the wet basis and dry basis thus
reflects the addition of water for hydraulic transport and/or pre-disposal
treatment at some plant sites. Because the waste hydraulic transport and
2-9
-------
pre-disposal treatment characteristics 1n the pesticides and private ex-
plosives industries are generally similar to those for the organic chemicals
industry, the ratio of 3.17 was also assumed to be applicable to the pest-
icides and private explosives Industries. Wastes from GOCO explosives
industry contain little or no water, and are disposed of by incineration
(open burning). For these plants, the actual tons (wet basis) and dry
basis tons were therefore assumed to be equal. For 1973, total wet-basis
process wastes discharged to land are estimated as 554,000 metric tons for
the pesticides industries, and 25,000 metric tons for the explosives
industries. Total "actual" (wet-basis) process wastes discharged to land
disposal in 1973 by the industries covered in this study are estimated
as 7.0 million metric tons.
The total quantity of process waste streams which will be sent to land
disposal by the organic chemicals Industry is estimated for 1977, dn a
dry weight basis, as 3.43 million metric tons. On the basis used above
for 1973 data, the wet-basis figures estimated for 1977 for the land-
destined process wastes of the organic chemicals industry are 10.9 million
metric tons. Analogous estimates for the organic chemical industry wastes
for 1983 are 3.66 million metric tons on a dry weight basis, and 11.6
million metric tons on a wet basis.
Estimates of the land-destined process waste streams for the pesticides
Industries for 1977 and 1983 are 216,000 and 238,000 metric tons, respec-
tively, on a dry weight basis. The wet basis figures for 1977 and 1983 are
684,000 and 753,000 metric tons, respectively.
Currently there is no valid basis for estimating the process waste
discharge to land disposal for 1977 and 1983 for the GOCO explosives plants
because of the extreme unpredictability of munition production. Assuming
that the production of explosives at the GOCO plants in 1977 and 1983
will remain at the 1973 level, and that there will not be significant
changes in the waste generation factors for the production of explosives,
the estimates of total process wastes which will be discharged to land in
2-10
-------
1977 and 1983 by the organic chemicals, pesticides and explosives
Industries, are, therefore, as follows:
1977 (dry basis) - 3.67 million metric tons
(wet basis) - 11.6 million metric tons
1983 (dry basis) - 3.92 million metric tons
(wet basis) - 12,4 million metric tons
The process waste streams have been divided into two major categories-
"hazardous wastes" and "other wastes" -on the basis of the characteristics
of their components and the following waste stream criteria:
• Potential to cause human death, injury, illness or harm to
wildlife/beneficial biota.*
• Possible paths for harmful entry into the environment, through
the entire cycle of waste management.**
Waste streams which meet these criteria, and contain components classified
as "moderately dangerous" or "highly dangerous" are categorized for this
study as "hazardous wastes." Components are classified in accordance with
their health hazard (mammalian toxldty), fire and explosive hazard (flash
point and explosiveness), aquatic toxicity, and reactivity. Examples of the
methodology employed in this study to define "moderately dangerous" and
"highly dangerous" components are mammalian toxicity (expressed as LDgQ,
oral) between 50 and 500 mg/kg for "moderately dangerous," and less than
50 mg/kg for "highly dangerous." A detailed description of the classifica-
tion system 1s given in Appendix A.
The total dry basis tonnage estimated for hazardous waste streams
discharged to land disposal in 1973 — 2.15 million metric tons — is approx-
imately 98 percent of the "dry tons" for all process discharges to land
disposal by the organic chemicals, pesticides and explosives industries.
Virtually all land-destined waste streams from the three industries contain
one or more components classified as "hazardous."
*See Table 3-1 for the quantitative basis used to rate components of
the waste streams.
**Based on consideration of the solubility, dispersibility, physical
form and concentration of all components rated as hazardous by the
methods shown in Figure A-2.
2-11
-------
Texas and Louisiana, the leaders in production, also led the states in
the dry basis tonnage of estimated total process discharge to land disposal
of hazardous waste streams in 1973 with 904,000 and 267,000 metric tons,
respectively. Figure 2-1 presents a graphical interpretation of the distri-
bution by state of the dry weight of hazardous process waste streams to land
disposal.
The estimated total quantity of hazardous components contained in the
process waste streams discharged to land disposal in the United States
during 1973 was 840,000 metric tons - approximately 38 percent of the dry
weight of the three industries' land-destined waste streams. Texas and
Louisiana, with their high concentrations of organic chemical industry
plant sites, are the national leaders.
Components classified as "highly dangerous" in this study constituted
about 30 percent by weight of the hazardous components sent to land disposal
in 1973. Texas and Louisiana accounted for slightly over half of this
national total; other states with between 10,000 and 100,000 metric tons
of "highly dangerous" components, were New Jersey, Pennsylvania, West
Virginia, Tennessee, and Alabama.
The industrial organic chemicals industry (SIC 2869) hazardous process
waste streams, with just under 1.5 million metric tons discharged to land,
constitute approximately two-thirds of the national total from the five
4-digit SIC categories covered in this study (Table 2-2). For each kg
of product, 0.023 kg of hazardous process waste streams were sent to land
disposal by this major industry in 1973. The cyclic crudes and intermediates
industry, at 500,000 metric tons, had a slightly higher hazardous waste
generation factor — 0.027 kg per kg of product. Because of the high ecolog-
ical hazard associated with discharge to water of their process wastes, the
pesticides industries use land-based disposal processes for a high propor-
tion of their hazardous wastes (158,000 metric tons in 1973), and the
hazardous waste stream discharge to land factor is high — 0.088 kg per kg
of product. Waste explosives for which land-based treatment and disposal
practices are used totaled 21,000 metric tons in 1973; the waste discharge
factor was low - 0.013 kg per kg of product. The gum and wood chemicals
2-12
-------
t/1
c: co
o o>
I— -r-
o +.*
•r- CO
s- n
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ai c
ro •!-
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(/) Q.
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s- ^H
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CM
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S-
3
CD
2-13
-------
Table 2-2.
Total Process Discharge to Land Disposal , Hazardous Waste
Streams2, Metric Tons for CY 1973, for the Organic
Chemicals, Pesticides and Explosives Industries
III'" ; ill1
4
1 1
A
if
-1
1
I
-£
=)
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1'
r
-r
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\
i
5
r
-•
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f
i ,
a
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f
i
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i.titi'
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< < T 1,1,1
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in. nor,
1". 1
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.
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Uhnj_
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••rji .to Ci o
!-h,dP I'.l.lrir!
' I'ut r> [ ,)rol i n,a
' l.jtf [1 rot,l
^'firie'.'^i'e
ll.,0
Voiinont
.' 1 1 j i n i i
Wd\h i ngton
Nfs! k' 1 I Jl rila
Wl si orisi n
W_yoi \ ntj
-------
industry, with under 16,000 metric tons of hazardous process waste to land,
is the lowest major industry in both production volume and hazardous waste
discharge.
The impact projected for the Federal Water Pollution Control Act
Ammendments is shown by the sharp increase in the estimate for discharge to
land disposal in 1977 for hazardous waste streams - a jump to 3.5 million
metric tons. The projection includes an increase of 10 percent in produc-
tion from the 1973 level, with the exception of the GOCO portion of the
explosives industry, which actually decreases slightly, and the assumption
that industry plans called for the implmentation by 1977 of land-based
procedures to handle pollutants whose discharge to water and air would no
longer be permitted in 1983. Based on this assumption, 950,000 metric tons
of hazardous waste streams formerly discharged to water and air will be
handled by land-based treatment and disposal techniques in 1977. Table 2-3
shows the projections by state and major industry for 1977. The proportion
of the total national hazardous waste stream discharge due to the industrial
organic chemicals industry (SIC 2869) increases to 72 percent; that due to
the cyclic crudes and intermediates industry drops slightly to 21 percent.
The respective hazardous waste generation factors are both approximately
0.036 kg per kg of product. The hazardous waste generation factor for
the pesticides industries increases to about 0.1 kg per kg of product.
The total quantity of hazardous waste discharged by the explosives industry
is projected to remain relatively constant. The increase in hazardous
waste tonnage projected for the gum and wood chemicals industry in 1977
is due solely to the projected increase in production.
The data presented in Table 2-4 are based upon an increase in production
for 1983 versus 1977 of slightly over 10 percent for all industries other
than the GOCO portion of the explosives industry. The projected total
quantity of hazardous wastes to land for the United States in 1983 is
3.8 million metric tons; waste generation factors and relative proportions
remain the same, except for the explosives industry's fraction, which
decreases.
2-15
-------
Table 2-3.
Total Process Discharge to Land Disposal , Hazardous Waste
Streams^, Metric Tons for CY 1977 for the Organic
Chemicals, Pesticides and Explosives Industries
fPA
Rt
UNION
State
MaMM .
JUisJia. .
Arizona
Arkansas
CaHfornia
Colorado
iopnecticjjt
.Delaware
District of Columbia
f Iprida
Georgia
fawa.i i
Jdjjhu
1 1 1 ) n£ i s
Indiana
Jowa
Kansas
Kentucky
Lou ' i i ana
Ma ' ne
Maryland
Massachusetts H
Michigan
Minnesota
Mi ssissippi
Mi ssouri
Montana ,
Nebraska
Nevada
New Hampshire
New Jersey
New Mexico
New York
North Carol i na
North Dakota
OMp
Ok 1 3honM
Or ecjf'l
Pennsylvania
Puerto RiLn
Phode Island
Srutf' Carol i na
South Dakota
Tpnnf ssee
Texas
Utah
Vermont
Vi r^i nia
Wash i nj^ton
W»st Virginia
Wl sco^sl n
'ftj oini 119
HI TOTALS
0
Ml ,'Hbl
IK9/
y>\e,
^967
68?
1(^707
Sum and Wood
Chemi ca 1 s
lunii l.hpmn^l', •'
SU ,'S(>!i
?7K7!
6,515
J?
?10
25278
110
i%n
51f>
?864
677
97532
2370
11R
22174
M
2751
3046
335
64691
1,970
34498
309!
M
4 y04
^nf,12
32
24585
32803
222,767
341
5£3_3
4904
18137
825
741494
Cyclic Crudes &
ntermedi ates
SU 2B69 3
1595
77
1454
41367
925
1888
21484
99S8
?8S39
6278
!49'j
R36
126412
34 30?6 ]
7
1690
4521
1355
1866 j
447
1?9
20194
9206
49 i',
340 7 j
189
5560
105550
925S9
598
1414
218159
1,236,372
353
993
209021
671
2.521751
Industrial Orrj
Chems NFC
PBS! 11 n|f^
SIC ,'U79/f'H6l)4
4/765
i853
13688
1616
1344
12
423
668
12
12
6169
,'72
6370
JJ12
12
?62 1 7
434
73
8684
?39
10439
"M10
24
36
24
12
15462
1623
il\3
. ;-'.'!27
X>
- VH
709
330
9608
21023
12
1 74
2941
12
717
196979
Prepns ,Formulns ,
& Tech .Pesticides
SIC /II9/
109
7
liin
11
142
19
16
0 3
48
,v
7
9
1211
767
,'99
902
198
1150
3
12
7
32
sn
3
?B1
6
105>>
14
3
5
129
21
20
0.4
. 90
a.
. . _.12
j;j. -
Q^.
. i
j_
8533 .
535
52_3
3514
13
94
659
6
2^950 .
Private "-b !'
GOCO Plants
lotdl
76000
84
ion
yoo
67,000
1/00
2^00
27000
illOO
140HO
14
21
Sin inn
'900
8200
6,300
127000
469000
3
720
1900
35000
350
l',000 '
1 5W
480
1100
370
140
100000
130
1 1000
400QD
0,4.
^JOQD
... 250 ..
7,410 ..
isijuaa
.. JJjflUfl . .
630
2£jOQQ
L
__^tgaoj.
1431000
....__8§0
9.800
ES900_.
22fflQO
2900
6
3500000
a ted, dry |,d' i:
I'd as process waste streams containing one or more components classified as "moderately danqerous" or
'y damjerous tn this study
')""( SII 28694, technical organic pest control chemicals (covered under "Pesticides Industries")
'-!<•< IMS IP Px[j!o5i*es only for the privately owned and operated explosives industry plants
fiuiprninent Owned, Contractor Operated
2-16
-------
Table 2-4.
Total Process Discharge to Land Disposal , Hazardous Waste
Streams2, Metric Tons for CY 1983, for the Organic
Chemicals, Pesticides and Explosives Industries
EPA
"M1fln
4
10
9
6
9
8
1
3
3
4
4
9
10
_5
5
7
7
4
6
1
3
1
5
5
4
7
8
7
9
1
2
6
Z
4
8
5
6
10
3
2
1
4
8
4
6
8
1
3
10
3
5
8
SUtc
Alabana
Alaska
Arizona
Arkansas
California
Colorado
Connecticut
Delaware
District of Columbia
Florida
Georafa
^jlflwal i
Idaho
Illinois
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maine
Mirvland
Massachusetts
Michiaan
Minnesota
M1ss1sslDo1
Missouri
Montana
Nebraska
Nevada
New Hampshire
New Jersey
New Mexico
New York
North Carolina
North Dakota
Ohio
Oklahoma
Oreqon
Pennsylvania
Puerto R1co
Rhode Island
South Carolina
South Dakota
Tennessee
Texas
Utah
Vermont
Virginia
Washington
West Virginia
Wisconsin
Wyominq
NATIONAL TOTALS
l ...
Organic Chen1cals3
SIC 2861
4308
10521
3279
755
18864
Gum and Mood
Chemicals
SIC 2865
3QH16
7201
36
232
27943
121
21570
603
3.166
747
107,817
2620
125
24571
56
3p41
3367
370
71383
2J66
38.1 1 7
3415
56
47862
22786
34
27.172
36^60
246/59
387
6,448
5,241
20p46
912
762^40
Cyclic Crudes 4
Intermediates
SIC 2869 3
1763
R5
1608
45729
1023
2087
23749
11088
31.549
6940
1653
924
1 39.742
379200
8
1868
5406
1497
2063
494
142
22.345
10183
5456
37659
209
6^47
116680
102364
661
1563
241,165
1.366,752
4
390
1097
231,063
741
2)303035
Industrial Org. ,
Chemicals, NbC
Pesticides
SIC 2879/28694
d7?KQ
4,259
29658
1,786
1486
13
468
739
13
13
4820
300
7042
1,893
11
28983
479
80
9r59R
265
11540
104?5
27
40
27
13
17094
\793
335
3,125
40
1920
784
364
10,620
, 23241
13
83
3.251
13
793
2ir,713
"rep'r.s.Formul 'ns
11 Teen Pesticides
Explosives
SIC 2892
i?n
%
110
12
330
22
18
0.2
53
24
Z
10
1218
773
302
903
219
1151
4
13
8
36
66
3
387
7
1058
15
3
5
133
23
22
0.5
99
22
13
189
0.7
4 ..
1
8539
558
166
3
3521
' 14
105
661
7
21,026
Private 4.5 5
UOCU Plants
Total
RdiTnn
93
110
5900
74000
1800
2800
30000
35000
15000
15
23
61.000
R600
9000
6,900
141000
51 ROOD
4
3100
2100
40000
400
16100
16000
530
'100
410
160
111000
110
14000
44,000
0.5
44000
270
8100
166,000
125000
700
2?OOQ ....
1
297,000
1,637,000
430
3
10,400
9,600
251,000
Jl 00
7
3800,000
- Estimated, dry basis.
Defined as process waste streams containing one or rrore components classified as ' rroderately dangerous" or
_ "highly dangerous" in this study.
f Excluding SIC 28694, technical organic pest control chemicals (covered under "Pesticides Industries").
c Includes waste explosives only for the privately owned and operated explosives 'ndustry plants.
GOCO = Government Owned, Contractor Operated.
2-17
-------
2.3 TREATMENT AND DISPOSAL TECHNOLOGY
Three treatment and disposal technology levels are identified in this
study. Level I technology represents the practice currently employed by
typical facilities — broad, average, present treatment and disposal prac-
tice. Level II is the best technology currently in commercial use in at
least one location for the same or a similar application - "best" here
referring to the adequacy of the process from an environmental and health
standpoint. Level III is the technology necessary to provide adequate
environmental protection, and may include pilot or bench scale processes.
Level I, II, and III technology may be identical in those cases where the
broad, average, present treatment is both the best technology currently in
use and is environmentally adequate.
Company and Government agency supplied information, covering treat-
ment and disposal technology employed at 52 major plant sites, was obtained
by plant visits or through other direct contact, for use in this study. For
the organic chemicals and pesticides industries, the data embraced the tech-
nology for disposal of just under 200 waste streams. Data were received
from the U.S. Army Armament Command on waste management activities at
all of the Army ammunition plants. In addition site visits were conducted
at three of the four active basic high explosives manufacturing plant
sites and information was furnished on treatment and disposal development
projects.
The sample of the organic chemicals industry, for which information
on treatment and disposal technology was obtained by direct contact, was
selected on the basis of the types and quantities of products manufactured,
the hazards estimated for the process wastes generated, the geographical
locations of the plants, and the willingness of the plant managements to
cooperate in this study. The data for this sample of the organic chemicals
industry (organic chemical plants produced the bulk of the hazardous waste
discharges included in this study) indicate that uncontrolled on-site
incineration was the Level I technology used on almost one-half (48 percent,
or 67,000 metric tons) of the dry weight of the sample's wastes. Controlled
on-site incineration (considered to be Level II and II technology) was used
2-18
-------
on just under 22 percent, on-site landfill 15 percent, recovery on about
8 percent, contract disposal on slightly over 5 percent, and deep well
Injection on approximately 2 percent of the dry weight of the sample's wastes.
In numerical frequency of use, on-s1te landfill and incineration were
used on approximately 32 and 33 percent, respectively, of the sample's
hazardous waste streams. Contractor disposal was used on 9 percent,
resource recovery on 12 percent, biological treatment/1agooning on 7.5
percent, deep well injection on under 6 percent, and landfarming on 1
percent of the sample's hazardous waste streams.
"Uncontrolled incineration" is defined for this study as the disposal
of wastes by combustion in facilities which lack treatment processes ade-
quate for the protection of the environment from the combustion products.
"Controlled incineration" is defined as the disposal of wastes by combustion
using the technology necessary to provide adequate environmental protection.
The treatment processes and technology currently used in controlled incinera-
tion for protection of the environment from the combustion wastes include
(but are not limited to):
Properly designed and operated afterburners and secondary combusion
systems to abate NOx emissions; settling chambers, impingement and
cyclone separators, bag filters, electrostatic precipitators, packed
towers, and spray chamber, venturi and cyclone scrubbers for the
removal of particulate and gaseous contaminants from the incinerator
vent gases; and evaporators, ponds, lagoons, land farms and chemical
landfill for ash, collected particulate material, and scrubber liquid
wastes not suitable for recovery or reuse.
To place this sample of the organic chemicals industry in perspective,
the number of waste streams injected into deep wells in the sample was ten,
versus a national total of 280 deep wells used for disposal of chemical
process wastes in 1973.^ ' The sample also has a relatively high percentage
of major companies. The 7 percent by weight of the estimated organic chemicals
industry total hazardous waste discharge covered in the sample makes the survey
of treatment and disposal technology statistically significant. The geographic
dispersion is considered sufficient to avoid bias. The proportion of the
wastes handled by contract disposal for the industry as a whole is believed
to be higher than that reported for the sample.
2-19
-------
The data for the treatment and disposal methods used for the 25 waste
streams in the pesticides industries sample indicate that landfill (on-site
and contractor) has the highest usage rate, 40 percent, divided into 28
percent on-site and 12 percent contract disposal. The next three prevalent
practices are incineration (16 percent), storage in drums or open piles*
(13 percent) and resource recovery (8 percent).
For the safety-oriented military explosives industry, the single pre-
valent method of disposal of waste explosives is open burning. Controlled
incineration of waste explosives has been tested successfully in pilot plant
and prototype operations. The other major land-destined waste from the GOCO
explosives industry — red water from TNT manufacture — is incinerated in
rotary kilns; the ash from incineration is stored uncovered on-site.
The majority of the privately owned and operated sector of the explosives
industry uses open burning. Chemical detoxification, contract disposal,
sale of scrap for reclamation, deep-well injection and spray irrigation are
other techniques employed to a lesser extent.
It is believed that many of the applications of treatment and disposal
techniques described above represent real or potential hazards to the
environment. The following waste management technologies, as applied to the
hazardous waste streams of the sample, are considered either inadequate or
of dubious adequacy for environmental protection:
1. Uncontrolled incineration. This technique was used in 1973
on almost one-half of the hazardous wastes of the organic
chemicals and pesticides industries plants in the sample, and on
all of the waste explosives of the GOCO plants. It thus re-
presents Level I technology for the three industries. It afforded
no protection against discharge to the atmosphere of such noxious
pollutants as nitrogen oxides, sulfur oxides, carbon monoxide,
hydrogen halides, residual chlorinated organics, and polynu-
clear aromatic hydrocarbons.
2. Landfill on sites insufficiently characterized and therefore
potentially unsuitable for the disposal of hazardous wastes.
Two-thirds of the hazardous wastes disposed of by landfill at the
organic chemicals and pesticides plants in the sample were disposed
at sites for which there was inadequate knowledge of subsurface
geology, ground water course locations, leaching characteristics,
and run-off and drainage protection requirements. The protection
afforded the environment against contamination by water-soluble
or dispersible toxic materials was therefore doubtful or insufficent.
*Long-term storage was used in 1973 by some companies as an ultimate disposal
technique.
-------
3. Deep well injection of hazardous process wastes. This method for
disposal was used on 2 percent by weight of the sample plants'
hazardous process wastes, with no effective pretreatment at any
plant prior to dilution and injection. There was Httle or no
knowledge of the capabilities of the injection strata to serve as
adequate permanent liquid storage reservoirs or to protect devel-
oped and undeveloped mineral resources, including ground water.
There was a similar lack of knowledge on the migration and
chemical change characteristics of the hazardous materials injected.
One waste stream from each of fifteen hypothetical "typical" plants
(selected from the twenty-six which were listed in Section 2.2) was chosen
for analysis of waste treatment and disposal technology typical of the organic
chemicals and technical pesticides industries. Selection was on the basis
of product significance and the hazardous character of the wastes. The plants
chosen produce perchloroethylene, nitrobenzene, chloromethane solvents,
epichlorohydrin, toluene diisocyanate, vinyl chloride monomer, methyl
methacrylate monomer, acrylonitrile, maleic anhydride, lead alkyls, aldrin,
atrazine, trifluralin, parathion, and malathion.
Each waste stream was selected to give a composite picture of the treat-
ment and disposal technologies employed on land-destined waste streams.
The Level I treatment and disposal technologies selected for the composite
picture were heavily dependent upon the techniques described above. Uncon-
trolled incineration was the disposal method which represented the broad
average of processes used on the hazardous waste at typical vinyl chloride
monomer, methyl methacrylate monomer, acrylonitrile, lead alkyl and parathion
plants. Landfill on sites which were not necessarily environmentally accept-
able for hazardous waste disposal was the Level I technology for the typical
chloromethane solvents, toluene diisocyanate, and maleic anhydride produc-
tion facilities. Level I disposal technology for the hazardous waste streams
of the typical perchloroethylene plant and of the single atrazine producer
was deep well disposal. The Level I technologies for nitrobenzene,
epichlorohydrin, aldrin, trifluralin and malathion were on-site landfill,
on-site storage, lined pond, storage in rubber-lined drums and detoxifica-
tion with NaOH and burial with NaOH in approved landfill, respectively.
2-21
-------
The Level II and III treatment technology was controlled Incineration
for eight of the fifteen waste streams. "Controlled Incineration, with lead
recovery" was the Level II and Level III technology for one additional waste
stream. The use of landfills suitable for the disposal of hazardous wastes
("Secured landfills") was Level II technology for three waste streams, and
Level III technology for two waste streams.
2.4 TREATMENT AND DISPOSAL COSTS
Treatment and disposal costs estimated for Level I technology for the
selected examples of land-destined hazardous wastes discharged by the organic
chemicals and pesticides industries range from $0.24 to $137.27 per metric
ton* of product in December 1973 dollars. The Level I treatment and disposal
technology costs per metric ton of hazardous waste (wet basis) were estimated
to vary between $0.57 and $323.33. The weighted average** of costs estimated
for Levels I, II and III disposal technology for the selected hazardous
waste streams from the typical organic chemicals and pesticides plants were
as follows:
Level I $13.36 per metric ton of waste (wet basis)
Level II $30.56 per metric ton of waste (wet basis)
Level III $30.69 per metric ton of waste (wet basis)
Expressed in terms of cost per metric ton of waste (dry basis), these weighted
averages are for Level I, $48.32; for Level II, $110.54; and for Level III,
$111.02. It should be noted that the Level II treatment and disposal
technology was the same as Level III for thirteen of the fifteen hazardous
waste streams considered and that this is primarily responsible for the
small difference between the estimated costs for these two levels of
technology. The costs of disposal for the 15 commodities, calculated
as percent of 1973 sales values from the U.S. International Trade
(3)
Commission preliminary reports for 1973 on organic chemicals, ' had a
weighted average of 0.9 percent for Level I disposal technology, and
2.2 percent for Level II and III technologies.
*In other sections of this report, "metric ton" and "tonne" have been
used interchangeable.
**Weighted in accordance with the quantity of wastes estimated as
national total for each of the 15 commodities.
2-22
-------
Current open burning techniques (Level I technology) used for
military explosive waste disposal range in cost from $2.90 per metric
ton of waste to $641.30 per metric ton of waste.* Data from the pre-
liminary economic evaluation of pilot plant studies of controlled
incineration (Level II technology) were not available for this report.
The costs of treatment and disposal for the 2.2 million metric
tons (dry basis) total land-destined wastes generated in 1973 by the
organic chemicals, pesticides and explosives industries is estimated
at approximately $106,000,000. The basis used for calculation of this
figure was the weighted average estimate of $48.32 per metric ton of
waste (dry basis) for the application of Level I disposal technology
to the hazardous waste streams of the 15 typical organic chemical and
pesticide plants. The value of organic chemical, pesticide and
explosive industry sales in 1973 was estimated, based on extrapolation
of the data of the U.S. International Trade Commission preliminary
reports for 1973 on organic chemicals, ' as about $21,740,000,000.
The estimated cost of Level I treatment and disposal technology
($106,000,000) for these three industries thus amounts to approximately
0.5 percent of the estimated total sales.
The costs for the application of Level II and Level III treatment
and disposal technologies to the total land-destined wastes generated
in 1973 by the three industries are estimated at approximately $242,000,000
and $243,000,000,respectively. The bases used for the calculation of these
figures were the weighted average estimates of $110.54 per metric ton
of waste (dry basis) for the application of Level II technology, and
$111.02 per metric ton of waste (dry basis) for the application of Level III
technology for the fifteen commodities considered. It should be noted
that, based on these cost data which are for the fifteen commodities
considered, there is little difference between the estimated costs for
the application of Level II and Level III technologies and that the
estimated cost of $242,000,000 - $243,000,000 amounts to approximately
1.1 percent of the total 1973 sales for the three industries.
*This very high cost for disposal is due to the extremely hazardous
character of some of the explosive wastes, and the special precautions
required in waste handling, transportation, and disposal.
2-23
-------
3. METHODOLOGY
The methodology employed for deriving the quantitative figures
presented in this study may be summarized as follows:
• Obtain data from the open literature and industry, government and
trade association sources to the level of maximum detail available
for this study.
t Make qualified estimates of all necessary statistics at the level
of maximum detail where sufficient "hard" data were obtained to
justify estimation.
• Categorize, classify, and assign hazard ratings to all waste compo-
nents.
• Summarize the estimates statistically for each state, by product
first, if possible, and then by five digit Standard Industrial
Classification product group.
• Evaluate the statistical summaries, and develop the descriptions
to characterize the industries, their hazardous waste streams, and
the land treatment and disposal practices employed or avail-
able, and the costs of these practices.
The level of detail of the data available for this study varied con-
siderably. Restrictions on data accessibility depended upon the industry
to which the request was made, and upon the information requested. The ma-
jority of the organic chemical companies contacted considered plant and
company-wide production rate data on individual products to be proprietary
information. They did, however, furnish lists of the names of the chemi-
cals manufactured at each plant site. The national total production for
(3 4)
each synthetic organic chemical was available from Government sources ' .
In consequence, as discussed more completely in Appendix A under "Data Ac-
quisition," although "hard" individual plant production rate data on organ-
ic chemicals was not accessible for use in this study, enough information
was available to justify estimation. Estimates were made of the 1973 pro-
duction rate of each synthetic organic chemical* produced by each plant by
prorating the national total production. In contrast, for the pesticides
preparations and formulations industry (SIC 2879), the available
Restricted to organic chemicals which met the criteria stipulated in Ap-
pendix A under "Data Collation and Analysis."
3-1
-------
literature^ ' and one other information source^ gave TRW access only to
data on the value of total Industry products shipped, nationally and by
census region, and on the number of "establishments" 1n each state- The
estimates made for this industry (SIC 2879) were at the state level.
Ground rules covering the limits of this study were developed to avoid
interface problems and double accounting for production and hazardous waste
data. These were:
1. Organic chemicals, which were manufactured as intermediates to be
used in other industries (e.g., plastics, drugs, and paints), were
considered as products of the organic chemicals industry if their
use was not wholly captive to the plant site, i.e., if portions of
the production were transported to other plant sites for the fur-
ther processing necessary, or sold on the open market as
intermediates/merchant chemicals.
2. Those hydrocarbons which were direct products of oil company refin-
ery operations (e.g., methane, ethylene, propylene, and benzene)
were not considered to be products of the organic chemicals indus-
try. Those chemicals, which were the products of petrochemical
operations (e.g., isopropanol, acetone, and isophthalic acid),
were considered to be products of the organic chemicals industry.
These categorizations followed the practice employed in oil company
reporting to the United States International Trade Commission (for-
merly the U.S. Tariff Commission).
3. Crude coal tar was considered to be a product of the ferrous metals
industry, and a raw material (rather than a product) of the organic
chemicals industry. Refined coal tar, pitch, and coal tar-derived
chemicals were considered to be products of the organic chemicals
industry.
Companies and agencies which supplied information for use in this study
are listed in Table A-l in Appendix A. The details of the approach to data
acquisition, data collation and analysis, hazardous waste identification and
estimation, treatment and disposal technology evaluation and cost analysis
are presented in Appendix A.
Criteria were developed to enable proper identification and estimation
of hazardous wastes, and to assure consistency between the definitions em-
ployed in the separate multi-industry studies of industrial hazardous waste
practices being conducted for the EPA. The criteria divided waste streams
into two major categories on the basis of the characteristics of their
-------
components - "hazardous wastes" and "other wastes". "Hazardous wastes"
were separated further into two classes — "moderately dangerous" and "high-
ly dangerous".
The major bases used to assess the waste streams were:
1. Potential to cause human death, injury, illness, or harm to
wildlife/beneficial biota.
2. Possible paths for harmful entry to the environment, throughout
the entire cycle of waste management.
Under the considerations noted above, "hazardous wastes" was the desig-
nation for all waste streams which contained one or more components which
were:
!• Classified as "moderately dangerous" or "highly dangerous" based
on the rating table shown in Table 3-1. The rating system shown
in the table was developed by TRW based on published literature
data (in particular, Reference 54) and in conjunction with
discussions with other EPA contractors concurrently involved in
similar assessment studies for other industries.
2. Any of the following specific substances or types of substances:
Asbestos, arsenic, beryllium, cadmium, chromium,1 copper, cya-
nides, 2 lead, mercury, halogenated hydrocarbons, pesticides, sele-
nium and zinc.
o
3. Assessed as explosive , carcinogenic, oncogenic (tumor forming),.
teratogenic, mutagenic, subject to bioaccumulation to toxic level ,
strongly corrosive or a strong sensitizer.
In addition, where the actual physical characteristics of a waste
were such as to endanger, actually or potentially, life or limb, the
waste could be classified as a "hazardous waste," e.g., wastes dis-
charged directly to the environment at high temperature or high pressure
could be classified as "hazardous wastes".
The term "other wastes" was applied to all waste streams not classi-
fied as "hazardous wastes".
Hexavalent chromium compounds only
2
Except ferrocyanide compounds
3
As defined in Appendix A
4
All bioconcentratable materials were raised to the next higher
hazard classification
3-3
-------
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3-4
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4. INDUSTRY CHARACTERIZATION
4.1 GENERAL
The organic chemicals, pesticides and explosives industries have been
characterized statistically, to the maximum extent consistent with the best
sources of non-proprietary data available, in the summaries which follow.
The most complete of the summaries - those for organic chemicals (including
technical organic pest control chemicals) and government-owned-contractor-
operated (GOCO) explosives manufacture - describe the industry product groups
in terms of:
• The number and location of manufacturing plant sites
• The distribution of plant sizes, in terms of production capacity at
each plant site, for the commodities in the individual product
groups
• The distribution of processes used
• The distribution of actual production for each product group.
Where the data were more limited (i.e., the pesticides formulations and non-
defense explosives subcategories of the industries) the summaries were
limited to the number and location of manufacturing plant sites, and the
production total for each state.
The term "plant site" has been used herein to identify each facility
where one or more of the commodities (organic chemicals, pesticides or
explosives) covered in this study are manufactured. A given plant site, by
this definition, may contain any number of processes (in some cases, 30 or
more) each producing a different commodity.
This study covers all sources* for commodities meeting the criteria
cited in Appendix A, in the following major industry classifications:^ '
2861 Gum and wood chemicals (organic chemicals industry)
2865 Cyclic crudes and intermediates (organic chemicals industry)
*
The number of plant sites covered in this study is larger than that based
on Census of Manufactures figures, since the Census is concerned only with
those establishments whose primary products are organic chemicals, pest-
cides and explosives.
4-1
-------
2869 Industrial organic chemicals, NEC* (organic chemicals industry)
2879 Agricultural chemicals, NEC (pesticides preparations and
formulations)
2892 Explosives
The five-digit SIC product groups (each of which may cover as many as
a hundred individual commodities) which more thoroughly categorize the
industries are as follows:
.(3,7)
Major Industry
SIC Number
2861
2865
2869
Product Group
SIC Number
28611
28612
28610
28651
28652
28653
28655
28650
28691
28692
Description
Gum and wood chemicals industry
Softwood distillation products
Other gum and wood chemicals (hardwood
distillation products)
Gum and wood chemicals, not specified
by kind
Cyclic crudes and intermediates industry
Cyclic intermediates
Synthetic organic dyes
Synthetic organic pigments, lakes,
toners
Cyclic (coal tar) crudes
Cyclic crudes and intermediates, not
specified by kind
Industrial organic chemicals, NEC,
industry
Miscellaneous cyclic (coal tar) chemi-
cal products
Miscellaneous acylic chemicals and chemi-
cal products
Not elsewhere classified
4-2
-------
Major Industry
SIC Number
2879
2892
Product Group
SIC Number
28693
28694
28695
28791
28792
28793
28794
28790
28921
28922
4.2 ORGANIC CHEMICALS INDUSTRY
Description
Synthetic organic chemicals, NEC (flavor
and perfume materials, rubber processing
chemicals, plasticizers, etc.)
Pesticides and other synthetic organic
agricultural chemicals (except
preparations)
Ethyl alcohol and other industrial
organic chemicals, not elsewhere
classified
Agricultural chemicals, NECS industry
Insecticidal preparations (formulations)
primarily for agricultural, garden and
health service use
Herbicidal preparations (formulations)
primarily for agricultural, garden and
health service use
Agricultural chemicals, NEC
Household insecticides and repellants,
including industrial exterminants
Agricultural chemicals, not specified
by kind
Explosives industry
Explosives, propellants and blasting
accessories (except GOCO plants)
Explosives, propellants and blasting
accessories (GOCO plants)
The only general characterization of the organic chemicals industry
which may be used safely is one which cites the great number and wide
diversity of commodities produced, the enormous number and complexity of
production processes, the wide variation in capital and labor intensity, the
extreme sophistication and frequency of advances and changes in technology,
and the fiercely competitive character of this industry. There were more
than 700 organic chemicals manufactured in 1973 whose individual annual
4-3
-------
interplant shipments or merchant sales in the United States were in excess
of 453 metric tons (1 million pounds)/ ' ' The total value added by manu-
facture in 1972 was over $6 billion, and the total value of product shipped
was $11.4 billion/ ' ' ' The number of plants (regardless of Bureau of
Census classification as to industry)^ ' which produced and shipped these
organic chemicals was 1204.
The organic chemicals industry (SIC 286) is subdivided into three
major industries: SIC 2861, gum and wood chemicals; SIC 2865, cyclic crudes
and intermediates; and SIC 2869, industrial organic chemicals, NEC.** Of
these, the industrial organic chemicals industry is by far the largest
(product shipped in excess of $9 billion) followed by the cyclic crudes and
intermediates industry (shipments of $2 billion). The gum and wood chemi-
cals industry is the smallest with $330 million in shipments.
The average number of total employees per establishment for the organic
chemicals industry, based on the 1972 Census of Manufactures (Preliminary
Report)^ ' ' ' was 1654. The average number of production employees was
1062. Approximately 55 percent of the establishments reporting had 20 or
more employees. The average number of employees was highest (just under
2,000) in SIC 2869, the industrial organic chemicals NEC product group.
Value added by manufacture per plant was, similarly, highest for this pro-
duct group by a significant factor ($9,900,000 versus $3,500,000 for the
remainder of the organic chemicals industry). In 1972 small manufacturing
firms (those with less than 10 employees) accounted for a weighted average
of about 0.5 percent of the total value added by manufacture for the organic
chemicals industry (SIC 286). The portion of value added by manufacture by
small producers for each of the three major industries was: SIC 2861, gum
and wood chemicals, 10 percent; SIC 2865, cyclic crudes and intermediates,
0.3 percent; and SIC 2869, industrial organic chemicals NEC,
0.2 percent.(8'9'10>
A statistical summary characterizing the organic chemicals industry is
presented in Tables 4-1 through 4-5. The summary contains the following
information:
*
**
See footnote on page 4-1.
Not elsewhere classified.
4-4
-------
Table 4-1. Chemical Products of the Organic Chemicals and
Technical Pesticides Industries Included in
this Study by Standard Industrial Classification*
SIC Chemical Products
28611 Charcoal briquettes
Pine oil
Pine tar compounds
Rosin, wood
Turpentine, wood
28612 Charcoal briquettes
Dyewood extracts
Methanol, natural
Naval stores
Rosin, tall oil
Rosin, gum
Tall oil, crude and distilled
Tanning extracts
28651 Acetophenone
Alkylates, branched
Alkylates, linear
4-Amino-diphenyl
Aniline
Anthraquinones, substituted
Benzidine
Benzoic acid
Bisphenol A (para, para1 --isopropylidenediphenol)
Chlorobenzene, mono
Chlorotoluene, alpha
2-Chlorotoluene
4-Chloro-1-nitrobenzene
Cresols
Cumene
Cyclohexane
Cyclohexanone
Cyclohexylamine and derivatives
o-Dichlorobenzine
p-Dichlorobenzine
3,3-Dichlorobenzidine, base and salts
Dicyclopentadiene
4-Dimethylaminoazobenzene
2,4-(and 2,6-) Dinitrotoluene
The nomenclature employed is taken from References 4, 7 and 13.
4-5
-------
Table 4-1.
SIC
28651
28652
28653
28655
Chemical Products of the Organic Chemicals
and Technical Pesticides Industries
Included in this Study by Standard
Industrial Classification* (Continued)
Chemical Products
Diphenylamine
Ethyl benzene
Hydroquinone
(Mono, Di, and Tri) Toluene isocyanates
Isophthalic acid
Mel amine
Moca (4,4 - Methylenebis (2-chloroaniline))
Alpha-naphthylamine
Beta-naphthylamine
Nitroaniline
Nitrobenzene
4-Nitrodiphenyl
Nonylphenol
Phenol
Phthalic anhydride
2-Cu Phthalocyanate
Pyridines
Resorcinol
Salicylic acid
Styrene
Terephthalic acid
Toluene 2,4-diamine
1,2,4-Trichlorobenzene
Acid dyes
Basic Dyes
Direct dyes
Disperse dyes
Fluorescent brightening agents
Solvent dyes
Vat dyes
Pigment blue toners
Pigment green toners
Pigment red toners
Pigment yellow toners
Benzene
Creosote (oil)
Cresylic acid
Naphthalene
The nomenclature employed is taken from References 4, 7 and 13.
4-6
-------
Table 4-1. Chemical Products of the Organic Chemicals
and Technical Pesticides Industries
Included in this Study by Standard
Industrial Classification* (Continued)
SIC Chemical Products
28655 Chlorodifluoromethane
Pitch (coal tar)
Tar (coal)
Toluene
Xylenes
28691 2-Acetylaminofluorene
Benzoic acid, sodium salt
Benzoyl peroxide
Dimethyl terephthalate
Dioxane (1,4-diethylene oxide)
2,6-Di-tert-butyl-p-cresol
Lithium compounds
Methylstyrene, alpha
Morpholine
Naphthenic acid and salts
Oil-soluble petroleum sulfonates; calcium salt
Oil-soluble petroleum sulfonates; sodium salt
Phenol salts
Phosphorous compounds
Pinene, alpha
Pinene, beta
28692 Acetaldehyde
Acetic acid
Acetic acid salts; copper acetate; potassium; zinc
Acetic anhydride
Acetone
Acetylene
Acrylic acid and acrylates plus 2-ethyl-l-hexyl acrylate
Acrylonitrile
Adipic acid
Alcohols; CIQ or higher
Alcohols; CG or lower
Aluminum compounds
Butadiene; 1-3
Butanol-N
Butanol-sec
Butylamines; mono; di; tri
n-Butyl acetate
Butyl acrylate
Butyraldehyde
*
The nomenclature employed is taken from References 4, 7 and 13.
4-7
-------
Table 4-1. Chemical Products of the Organic Chemicals
and Technical Pesticides Industries
Included in this Study by Standard
Industrial Classification* (Continued)
SIC Chemical Products
28692 Caprolactam
Carbon disulfide
Carbon tetrachloride
Cellulose acetate
Cellulose ethers
Chlorinated paraffins
Chloroacetic acid, mono
Chlorodifluoromethane
Chloroform
Citric acid
Diacetone alcohol (4-hydroxy, 4-methyl, 2-pentanone)
1,2-Dibromoethane, (ethylene dibromide)
Dibutyl maleate
Di chlorodi f1uoromethane
1,2-Dichloropropane
Diethyl amine
Diethylenetri ami ne
Diethylene glycol
Dipropylene glycol
Dodecenylsuccinic anhydride
Epichlorohydrin
Ethanol (28695)
Ethanolamines (mono; di; tri)
Ethylene
Ethylenediamine
Ethyleneimine
Ethylene dichloride
Ethylene glycol
Ethylene glycol diacetate
Ethylene oxide
2-Ethyl 1-hexanol
Ethyl acetate
Ethyl acrylate
Ethyl chloride
Ethyl ether
Ethyl hexanediol
2-Ethyl hexanoic acid and salts
Fluorocarbons
Formaldehyde
Formic acid
Formic acid, sodium salt (sodium formate)
The nomenclature employed is taken from References 4, 7 and 13.
4-8
-------
Table 4-1. Chemical Products of the Organic Chemicals
and Technical Pesticides Industries
Included in this Study by Standard
Industrial Classification* (Continued)
SJ£ Chemical Products
28692 Fumaric acid
Furaldehyde-2
Glutamates
Glycol ethers
Glycerin
Hexamethylenetetrami ne
Hexamethylenediammonium adipate
Hexanediamine (1,6-hexamethylenediamine)
Hexylene glycol (2-methyl-2,4-pentanediol)
Hydrocarbons
Isobutyl acetate
Isobutyl alcohol
Isoprene
Isopropyl acetate
Isopropyl alcohol
Isopropyl ether
Lactic acid
Lead aIkyIs
Lithium compounds, acyclic
Maleic anhydride
Mercaptans; sulfides (from petroleum)
Methanol
Methyl amines
Methylene chloride
Methyl chloromethylether
Methyl acetate
Methyl chloride
Methyl ethyl ketone
Methyl isobutyl ketone
Methyl methacrylate
Nitriloacids and salts
N-Nitrosodimethylamine
Olefins, alpha
Organo-tin compounds
n-Paraffins
Pentaerythritol
Perchloroethylene
Phosgene
Phosphorodithioates (thiophosphates)
Phosphorous acid esters
Phosphorous compounds
_
I he nomenclature employed is taken from References 4, 7 and 13.
4-9
-------
Table 4-1. Chemical Products of the Organic Chemicals
and Technical Pesticides Industries
Included in this Study by Standard
Industrial Classification* (Continued)
SIC Chemical Products
28692 Polyethylene glycols and polypropylene glycols
Beta-propiolactone
Propionic acid
Propionic acid salts
Propylamines
Propylene
Propylene glycol
Propylene oxide
Propyl acetate
Propyl alcohol
Sorbitol
Stearic acid salts
Tetraethylenepentami ne
Tetraethyllead
1,1,1-Trichloroethane
Trichloroethylene
Tri chlorof1uoromethane
Trichloromethane
Tri ethylenetetrami ne
Triethylene Glycol
Vinyl bromide monomer
Vinyl acetate monomer
Vinyl chloride monomer
28693 Adipic acid esters
Benzyl benzoate
Dimethyl-3,7-trans-2;6-octadien-l-01 (geraniol)
Dithiocarbamic acid derivatives
Dodecyl mercaptans
Epoxidized esters
Isopropyl myristate
Oleic acid esters
Phenolic compounds
Phosphite compounds
Phosphoric acid esters
Phthalic anhydride esters
Saccharin
Stearic acid esters
Thiazole derivatives
Thiurams
Trimellitic acid esters
The nomenclature employed is taken from References 4, 7 and 13.
4-10
-------
Table 4-1. Chemical Products of the Organic Chemicals
and Technical Pesticides Industries
Included in this Study by Standard
Industrial Classification* (Continued)
SIC Chemical Products
28694 Acrolein
Aldicarb
Alachlor
Aldrin
Alpha-naphthylthiourea
Amitrole
Atrazine
Bacillus thuringiensis
Barban
Benomyl
Bis chloromethyl ether
Binapacryl
l,l-Bis(chlorophenyl)-2,2,2-trichloro-ethanol
Bromacil
2-(p-tert-butylphenoxy)cyclohexyl 2-propynyl sulfite
N-Butyl-N-ethyl-alpha,alpha,alpha-trifluoro-2,6-
dinitro-p-toluidine
Cacodylic acid
Captan
Carbofuran
2-Carbomethoxy-l-methylvinyl dimethyl phosphate, alpha
i somer
Carbaryl
Carbophenothion
Chloramben
Chlorbromuron
Chlordane
2-chloroallyl diethyldithiocarbamate
2-chloro-4,6-bis(isopropyl amino)-S-triazine
2-chloro-N-i sopropylacetani1ide
Chloroneb
Chloroxuron
Chlorpyrifos
Copper naphthenate
Crufomate (4-tert-butyl-2-chlorophenyl methyl
methylphosphoramidate)
Dalapon
N,N-Diallyl-2-chloroacetamide
1,2-Di bromo-3-chloropropane
2,6-Di-tert-butyl-p-tolyl methylcarbamate
Dicamba
S-(2,3-Di chloroallyl)di i sopropylthi ocarbamate
Dichloro diphenyl trichloroethane
The nomenclature employed is taken from References 4, 7 and 13.
4-11
-------
Table 4-1. Chemical Products of the Organic Chemicals
and Technical Pesticides Industries
Included in this Study by Standard
Industrial Classification* (Continued)
SIC Chemical Products
28694 2,6-Dichloro-4-nitroaniline
2,4-Dichlorophenoxyacetic acid
0-(2,4-Dichlorophenyl)0,0-diethyl phosphorothioate
3',4'-Dichloropropionanilide
2,2-Dichlorovinyl dimethyl phosphate
Dieldrin
0,0-Diethyl 0-(3-chloro-4- Methyl-2-oxo-2H-l-benzopyran-
7-yl)phosphorothioate
0,0-Diethyl S-[2-(ethylthio)ethyl]phosphorodithioate
0,0-Diethyl 0-(2-isopropyl-6-methyl-4-pyrimidinyl)
phosphorothioate
0,0-Diethyl 0-[-p(methylsulfinyl)phenyl]
phosphorothioate
0,0-Diethyl 0-2-pyrazinyl phosphorothioate
N,N-Diethyl-meta-toluami de
l,2-Dihydro-3,6-pyridazinedione
3-(0,0-Diisopropyl phosphorodithioate)ester of
N-(2-mercaptoethyl) benzenesulfonamide
Dimethoate
0,0-Dimethyl 0-p-nitrophenyl phosphorothioate
0,0-Dimethyl S-[(4-oxo-l,2,3-benzothiazin-3(4H)-
yl)methyl] phosphorodithioate
Dimethyl phosphate ester with 3-Hydroxy-N,N-dimethyl-
cis-crotonamide
Dimethyl tetrachloroterephthalate
2,4-Dinitro-6-octyl phenyl crotonate;2,6-Dinitro-4-octyl
phenyl crotonate
Dinoseb
Dioxathion
Diphacinone
Diphenamid
Dipropyl isocinchomeronate
Disodium methanearsonate
Diuron
Dodecachlorooctahydro-l,3,4-metheno-lH-
cyclobuta[cd]pentalene
Dodine
Endosulfan
Endothall
Endrin
Ethyl 4,4-dichlorobenzilate
*
The nomenclature employed is taken from References 4, 7 and 13.
4-12
-------
Table 4-1. Chemical Products of the Organic Chemicals
and Technical Pesticides Industries
Included in this Study by Standard
Industrial Classification* (Continued)
SIC Chemical Products
28694 Ethion
S-ethyl cyclohexylethylthiocarbamate
S-ethyl diisobutylthiocarbamate
0-ethyl S,S-dipropyl phosphorodithioate
S-Ethyl dipropylthiocarbamate
0-Ethyl hexahydro-lH-azepine-1-carbothioate
0-Ethyl S-phenyl ethylphosphorodithioate
M-(l-Ethylpropyl)phenyl methylcarbamate mixture with
M-(1-Methylbutyl)phenyl methylcarbamate
S-[2-Ethylthio)ethyl] 0,0-dimethyl phosphorodithioate
Fenthion
Fluometuron
Fluorodifen
Folpet
Isopropyl N-(3-chlorophenyl)carbamate
Isopropyl 4,4-dichlorobenzilate
Lindane (gamma isomer of benzene hexachloride)
Linuron
Malathion
Methomy1
Methoxychlor
Methyl bromide
4-(Methylsulfonyl)-2,6-dinitro-N,N-dipropyl-aniline
Monosodium acid methanearsonate
Monuron
Naled
N-1-Naphthylphthalamic acid
Nicotine
Norea
N-Octyl bicycloheptenedicarboximide
Paradichlorobenzene
Parathion
Pentachloroni trobenzene
Pentachlorophenol and sodium and potassium salts
Phosphamidon
Picloram
Piperonal,bis[2-butoxyethoxy)ethyl]acetal
Piperonyl butoxide
S-Propyl butyl ethylthiocarbamate
S-Propyl dipropylthiocarbamate
Pyrethrins
Ronnel
Rotenone
*
The nomenclature employed is taken from References 4, 7 and 13.
4-13
-------
Table 4-1. Chemical Products of the Organic Chemicals
and Technical Pesticides Industries
Included in this Study by Standard
Industrial Classification* (Continued)
S_IC Chemical Products
28694 Siduron
Si 1 vex
Simazine
Sodium fluoroacetate
Terbacil
Cis-N-[(1,1,2,2-Tetrachloroethyl)thio]-4-cyclohexene-
1,2-dicarboximide
Tetraethyl pyrophosphate
0,0,0,0-Tetrapropyl dithiopyrophosphate
0,0,0',0'-Tetramethyl 0',0'-thiodi-p-phenylene
phosphorothioate
Toxaphene
S,S,S-Tributyl phosphorotrithioate
Tributyl phosphorotrithioite
S-(2,3,3-Trichloroallyl)diisopropyl thiocarbamate
Trichloroacetic acid
2,3,6-Trichlorobenzoic acid and related polychlorobenzoic
acids, dimethylamine salts
2,4,6-Trichlorophenoxyacetic acid
Trifluralin
Warfarin
Zinc naphthenate
28695 Ethanol
The nomenclature employed is taken from References 4, 7 and 13.
4-14
-------
Table 4-2.
Number of Plant Sites1 by Standard Industrial Classification
Organic Chemicals and Technical Pesticides Industries^
EPA
Ret Ion
4
_lfl_
9
6
5
a. ,
_j
-j
_ _3__
A.
4
.. }....
_LQ
5
. 5_ _
7
7
4
6
1
3
1
5
5
4
7
8
7
9
1
2
6
2
4
8
_5__
6
10
3
2
1
4
8
4
6
8
]
3
10
3
5
8
State
-Alabama
Alaska
Arllona
_Arlansas
_CaJJfornta
JjilQLfldC
.£QnM£ii£lLt__ . __
Delaware
D.ts-trlct of Columbia
_Elflr_Ldi
Georgia
Jiwaj 1
JUllnfiiL
Indiana
Kansas
Kentucky
Louisiana
Maine
Maryland
Massachusetts
Michigan
MlSSlSSlDDl
Missouri
Montana
Nebraska
Nevada
New Hampshire
New Jersey
New Mexico
Hew Vork
North Carolina
North Dakota
.Ohio
Oklahoma
Puerto Rico
Rhode Island
South Carolina
South Dakota
Tennessee
Texas
Utah
Vermont
Virginia
Washington
West Virginia
Wisconsin
W vomi ng
NATIONAL TOTALS
REGION TOTALS
1
2
3
4
5
6
7
8
9
10
28610
1
0
0
0
0
0
0_
0
0
2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
"6
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
3
0
0
0
3
0
0
0
0
0
0
2861
1
0
0
0
0
0_
0_
0
0
7
1
0
0
0
0
0
0
0
2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
ft
0
0
0
11
0
0
0
9
0
2
0
0
0
0
2861
4
0
0
0
0
0_
_0_
0
0
3
4
0
0
0
0
0
0
0
5
0
0
0
1
0
0
0
0
0
0
0
0
0
0
3
0
1
1
0
0
0
0
2
0
1
2
c
0
0
2
0
0
0
29
2865
0
0
0
0
0
__Q._
0_
0
0
0
0
0
0
0
]
0
0
0
_p_
0
0
0
0
0
0
0
0
0
0
0
0
0
r o
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
0
17
2
8
0
0
0
2
0
0
0
0
1
0
0
0
0
0
286S
6
0
0
m.
1_
_L.
3
0
2
2
0
0
12
4
0
2
4
16
1
3
4
8
0
1
1
0
0
2
0
tl
0
13
5
0
17 _
0
0
14
4
1
1
0
7
33
1
0
3
3
8
4
0
47
2865?
1
JL_
0
2
__0.
0_
0
0
0
0
0
0
0
0
0
0
1
0
0
1
4
1
0
0
0
0
0
0_
0
15
0
3
4
0
4
0
0 __
4
0
1
2
0
1
0
0
0
1
0
2
0
0
47
2865
0
8
0
]
__a_
- JL
a
a
0
-.0.
0
0
2
0
0
0
1
0
0
0
2
1
0
0
0
0
0
0
0
10
0
5
2
0
3
0
0
3
0
1
0
0
0
0
0
0
0
0
2
0
0
33
10
59
31
:•!
45
50
3
2
12
3
5
18
jj
9
5
0
0
0
2
0
3
15
5
j
6
0
0_
0
28655
_.JL.
5
_B
0
1
.-.!_
_JL_
1
&
jj
. 1_
0
0
7
0
0
1
1
0
2
0
5
1
1
1
0
0
0
0
2869
I
g
_J3_
.^JL_
jl
Q
Ji
._Z_
-_fi_
0
J.
1
1
5_
i
4
LJL
0
j
2
J
3
2
0
1
_o__
1
4 J 12
0 J 0
.^ .J _.._
_.°T_.r
0
7
0
1
7 1
_Q _ _ .
0
°-
0
2
13
2
0
2
0
3
0
0
81
0
5
0
0
1
1
3
0
0
5
10
0
0
1
1
2
1
0
86
2869
Ji
_2.
Jl
j
..22
Jl
L
4_
a
. A.
_i
Q_
_a
14
10
4
IS
-23_
0
5
_i
U_
i
3
1
Q
0
1
1 6J
0
17
10
0
28
2
8_
IS
5
2
6
0
8
67
0
0
6
3
8
2
0
?4
28693
Ji
Jl
0
i
1_
-.!_
n_
a.
i_
fl...
ji
JL
7
2_
0
i
1
1.
0
J
J
1
p._
3
1.
fi
JJ
_-£L..
P
^1L_
0
7
i .
JJ
..B-.
0
Jl
6
„ L.
_L
J!
_ J>__
.3..
5
0
0
0
0
6
0
0
OR
I
° -1 '
6 1 19
17 J 1
13
n
R._
i
3
_L
21
J4_
IS
__4_.
_o__
i
12
90
42
61
1J_
mi_.
_9
i
-22.-
U
8
38
13
14
21
.3 _
1
1
1
-0
2B694
7
Q
J
i
_. j.
I.
JL
J
1
o_
JL.
i
_3_
_4_.
J_
Q_
8
2
,
J
4_
2
0 j
Q_
a
._.fl_.
16
fl.
Ji
J _
Q
..6. .
a
_2
4
Jl .
L
JL
b
9
0
0
1
*
5
1
0
134
3
21
1J
25
J2
15
JJ .
_i
i_
6
2869
Q
^
D
a
. ,0-
ji
Q
2
I
_. 1 -
a
^
_2_
ji_
.. a
ji
0.
ji
0 .
Q
n.
Q
.. Q ..
J__
0
fl.
a -
fl
.0.
a
ji
i
i
ji
_o
0
jj
2
0
0
0
1
0
0
0
13
0
2
!
0
. J ._
ii
-.1
.0- -
\
1 -
ToU I3
7
44
4
8
8
16
15
0
47
16
8
8
16
52
11
12
26
,,
13
12
1
I
I
1
137
0
43
28
0
61
3
11
44
8
7
18
0
22
96 '
2
0
10
13
23
7
0
899
29
188
96
159
159
160
29
7
46
26
was manufactured
References 11 and 12, and the industry $ou
-------
Table 4-3. Plant Size by Daily Capacity, Metric Tons
Organic Chemicals and Technical Pesticides
Industries(3,4,8,ll,12)*
EPA
4
10
9
3
8
3
3
4
4
10
_ 5—
5
7
_7
4
6
1
3
]
5
5
4
7
a
7
9
_J
Z
6
2
4
8
_5 1
_6
10
3
2
1
4
8
4
6
8
1
3
10
3
5
8
State
Alabama
Alaska
Arizona
California
Delaware
District of Columbia
Florida
Geortna
Idaho
1 1 1 1 noj s
-Kansas
Louisiana
Maryland
Massachusetts
Michigan
Mississippi
Nebraska
Nevada
New Hampshire
New Jersey
New Mexico
Ne« »ork
North Carolina
North Dakota
Ohio
Oklahoma
Oregon
Pennsylvania
Puerto R CO
Rhode Is and
South Ca ollna
South Da ota
Tennesse
Texas
Utah
Vermont
Virginia
Washington
West Virginia
Wisconsin
Wyoml nq
NATIONAL TOTALb
REGION TOTALS
2
3
4
5
6
7
8
9
10
1
-
-
1
1
^f'JBi-iiiH w^.^lMB4v•J-JB^^-^w*w^•^l•MBJ-l•M•Bt'^:^S'llBJ•.ll'^^•'^:'-1'!(••'4•'^':•y
i
—
—
i
i
•
6
—
4
10
HUM
6 2 2
1 1 4
.._ i
2
2
2
2 1
1 1
2 5
434
6
4
7 214 2
2
8
1 1
J 1 1 _L
-ii- i
1 -
- 1- -
1_
5 4
, j
. .11.. _
11 1
. . Z i. i
J i J_
J .1,
1
S 8 6 1 HI
33 3
1 1 3
1 6 i.
2 7 1.
1 3 1
1
2 2 1
1 2 1
2B16 3
1 1 1
1 1
2 2
9 661010
4
2
]
1
1
9
i S
12 9 2 U
57 8
S 310 1 7
13 S 1 4
17 J) S
1 2
4 2 2
1 1
6
2
1
J_
_2_
_L
8
4
2
?
?
1
6
3
12
4
3
3
1
••RBI in
2 2
JL
^.2.
J ' 1
J 3 J ]_
112
J J.
J 1
» _ J
1
1
1
_Z_ J ' . 2J.
1 J 1
2
E 2 j
1
_.22
1
J
J ' J J-
3U 1 ! 3
1 1 1
1 1 2
2 758 1 2121
J J. .
2 : j.i j 4 1
_ 45 i.
1 5 5 Ji.
2811 Jll
1-3JU JA1
JJ--
2J 1
--?! ^ .
lElRRIMH
J J 8 J J.1
1 J.
.
1 J J.
4^ 4. J j 1
_ ja
ji'a i.
a j j. a
J J J _3 J-
J JL 1
J J j i
i
B'UJ 1'i
j j j j^
J_i- J.I. „
4 7 _I J i
J j
J J
^JJS- J.J. .
1 1 4
J_l_2
i j. a j j.
2 92725 3
1 3 2
i
232 121
S 83416 0 2 i
Jj i -1
SKEiPj.
jS*i J-IJL
Tija j 4 4
!1!!ZJ. Hi
i e E 34 J -i
iJJ JL
- J J
3JJ3.1 JJL
5 8
B
-
4
1
1
A
2.
2.
2.
a.
a
i
i
i
j
-
7
1
f
t
1
i
2
1
1
3
56
mi
_L
1_ -
1
?
_L
-i- .
X
.1 . _
_2_
6 1
7
}
-J
. J
1
4
1
1
1
37 1 2
1
9
9
U
S
i
7
4
1
8 1 1
1
5
7
7
3
1
2
2 1
(UL.
__
j_
__
__
2
X
i_
i
See Appendix A "Methodology Details" for the procedures employed to obtain the estimates of individual plant sizes. The
referents nteH as data sources were supplemented by the industry sources listed in Table A 1
NOTL
Production data was not available for 385 SIC-plant site combinations
CODE
A 0-9 metric tons/day
B 10-99 metric tons/day
C 100 - 999 metric tons/day
D 1000 or more metric tons/day
4-16
-------
Table 4-4. Production Rate, Thousand Metric Tons Per Year, By Standard
Industrial Classification Organic Chemicals and Technical
Pesticides Industries(3f4,8fTl,12)*
EM
iULian
..-.«,
.-UL-
_ S_
6_
i_
8
1
3
3
4
4
9
10
5
._5__
7
7
4
6
1
3
1
5
5
4
7
8
7
9
1
2
6
2
4
8
5
_6__
10
3
2
1
4
8
4
6
6
1
3
10
3
5
s
State
_ililuM
Alaskt
Arlwna
Arkansas
California
Colorado
Connecticut
Delaware
District of Columbia
Florida
Georaia
Hawal 1
Idaho
Illinois
Iowa
Kentucky
Louisiana
Milne
Maryland
Massachusetts
Michigan
Minnesota
Mississippi
Missouri
Montana
Nebraska
Nevada
New Hampshire
New Jersey
New Mexico
New York
North Carolina
North Dakota
Ohio
Oklahoma
Oregon
Pennsylvania
Puerto Rfco
Rhode Island
South Carolina
South Dakota
Tennessee
Texas
Utah
Vermont
Virginia
4ash1 ngton
West Virginia
Wisconsin
doming
NATIONAL TOTALS
REGION TOTALS
1
2
3
4
5
e
7
8
9
10
28610
47
33
80
28611
NH
90
7
4
101
78612
50
159
42
_ 84
14
.03
NA
29
NA
71
41
490
ZM50
SL
NA
Z865
_J61
_HS
2Z1
-J.
. i
L-iBB-
_222
_sa_
120
_S1
__5i
5 57Q
NA
.05
_-62i
107
u ,62
32
pjfi.
J5_
_.245_
78
-21Z .
u&
Us
205 I
312
,575
15
222
113
610
40
5,589
20652
2
-,4_
.5
.5
3
.01
44
17_
i.
7
_J.
5_
.2
4
2
100
?8o53
J
—
M
J_
JL.
^L_
13
2
2_
.—J-
.5
_,2
3
23
28B55
— Ut
-151L
JS
4i
-5JL
__1EL_
-J2i^
^L
_«&_
_212__
i4fi__
j21_
M
_25
J8_
215
23
154
38
1.143
42
NA
82
,973
28(91
..Ji_
__4_
JW
_3A_
J
5
Ni
_9_
32
_j(4_
__5L_
,
.. l._
6
a
-17
.25.
u_22-
NA
il__
,2
23
240
NA
NA
33
NA
743
2869 i
-_aa_
2flJX
. .128 _
1 ,9.6fi
433
-_SKL_
_2Z6_
JUfiL
450
?P9
1U
_LJ42_
11, (Lift
131
14i__
_JZ1_.
J*_
J14
3A_
5
1.335
247
345
963
17
451
MU
J8fi_
--SA.
246
841
,859
_234^_
54
,212
54
2,366
28693
2
6
t
9
L
^2_
?4
NA
7
13
?4
ZD.
13
_.fi
IP
.17
-li_
15
6
52
321
2H94
_- 41-
&.
13
^
_2J
g
21_
4
as_
2
_JO_
2
22 ,
23
«
JJ
>,
17
4
2
.5
23
58
1
7
30
7
526
28695
_..M-
437
MA
3
J?S
9
245
15
935
80
97
4
294
.03
155
41
NA
6
1,922
2,217
1,823
,213
7,854
l.'l
16
306
113
4
6:
9
20
5
.4
1
15
4
Z
,7
4
63
494
325
733
1.143
43
150
8?
6
118
33
136
84
334
26
4
252
.970
,594
i*§Z-
,909
!i.86_l
517
36
JUieJ.
79b !
28
84
69
36
34
30
24
2
15
5
70
34
122
78
101
51
13
41
_J1_
12
226
437
244
15
Total
1,115
_ 136
2,451
16
lib
766
2.187
631
322
1 9.1}!
i,lta
1-Pin
?*;
224
3£__
U_
2,814
750
1,11?
17
478
l,Q9ft
S^llfi
if;
486
.?5?
,197
57
4S6
230
,024
101
34,246
297
1.315
5.680
7.402
5^494
9.727
_7_32_
110
2.484
99R
references cltrd were supplemented by the Industry
See Appendix A for the procedures used to develop these estinw'es
sources listed 1n Table A-l.
NOTE
All production rates except those for SIC 28694 are for CY 1973 The production iates for SIC 28694 are for CV 1972.
HA - Estimates of production rate were not applicable, due to Ijck of appropriate data
4-17
-------
Table 4-5. Process Types Used for Manufacture, by Standard
Industrial Classification -Organic Chemicals
and Technical Pesticides Industries*
Process Type
1. Acylation
2. Alkylation
3. Ammonolysis
4. Carbonylation
5. Coupling
6. Cyclization
7. Dehalogenation
8. Dehydration
9. Dehydrogenation
10. Dehydrohalogenation
11. Distillation
12. Esterification
13. Extraction
14. Halogenation
15. Hydration
16. Hydrogenation
17. Hydrolysis
Process Type
18. Hydroxylation
19. Isomerization
20. Miscellaneous synthesis
21. Neutralization
22. Nitration
23. Oxidation
24. Polymerization
25. Pyrolysis
26. Reduction
27. Sulfonation
28. Multi-step synthesis
29. Dealkylation
30. Fermentation
31. Crystallization
32. Ethylene by-product
33. Condensation
34. Precipitation
See Appendix A for tho procedures used to classify chemical
product-plant site combinations by process type. The process
type names employed were compiled for this study on the basis of
the process chemistries involved in the manufacture of the
individual commodities.
4-18
-------
Table 4-5.
Process Types Used for Manufacture, by Standard Industrial
Classification -Organic Chemicals and Technical
Pesticides Industries (Continued)
EPA
Real op
4
10
9
5
__8_
.1
3
3
__4
4
9
13 1
z8S5o
-
_-
11
—
l
-
l
Z8651
1
__
—
1
1
2
2
2
3
1
1
5
2
2
3
2
1
" 1* ~
1
11
1
1
2
1
1
2
4
1
1
1
2
1
1
5
5
—
2
1
1
2
1
1
4
1
3
2
6
25
6
.._
1
1
1
1
1
1
5
8
1
2
2
9
1
1
4
2
11
...
1
2
9
21
—
2
3
12
-
-
-
1
1
13
2
4
1
1
1
1
-
5
1
4
3
1
2
2
1
iO
14 lib
1
1
2
3
2
4
1
4
5
1
15
17
2
1
1
3
2
64
ZO
1
2! '
i
1
!_(_
I 3
1 ! 1
I
—
3
T"~ '
1
2 35
j_l 3
, 3
1
ZZ
2
2
1
5
1 3U_.
T
i 1
2 |_
1
-4
...
8 1
i
i
2
2
Z
2
4
!
i
71
5
1
18
2J
5
1
1
7
1
2
1
3
2
8
1
4
7
2
6
]
3
3
1
62
24
-
1
1
26
1
1
1
2
5
?7
3
;;
2
i
2
2
—
14
2
3
3
1
4
1
2
1
41
?e
l
l
i
i
4
1
5
1
6
1
11
4
2
6
2
2
2
5
-
1
5
1
63
IS
—
~ T
—
—
i
30
---
—
—
—
-
._
1
1
REGION TOTALS
1
2
3
4
5
6
7
8
9
10
1
2
16
6
S
18
3
0
2
15
6
2
1
1
1
13
4
f,
6
19
3
1
1
1
3
6
3
1
5
8
1
1
1
1
2
1
1
2
5
13
1
3
1
1
5
7
J
3
3
2
4
2
4
32
7
j
13
2
3
4
i
?
3
9
1
1
48
2
S
7
5
5
5
1
3
4
10
11
7
13
9
4
5
3
1
1
I
1
~)
3
16
5
8
9
2
15
9
8
17
10
1
1
1
1
4-19
-------
Table 4-5.
Process Types Used for Manufacture, by Standard Industrial
Classification -Organic Chemicals and Technical
EPA
Real on
4
10
q
i
8
1
3
3
4
9
5
"-*-
7
j
•-]
n
j
9_
1
I
6
,
4
__5
6
10
,
1
4
a
4
6
8
1
10
3
S
8
State
Aiaiara
Alaska
Arum
Arkansas
Colorado
lorjneuu-ut . .
DsliW/e __ _.
District of Columbia
Florida
Bjorjja
Katun
Idajio
JJJj_nois
Indiana
Kansas_
Kentucky
Loul si a na
^lai ne
Maryland
Michigan
Mi nnesota
I Missouri
- —
i New Hampshire
Nfw Jersey
New MexiLO
New York
North Car ol i na
North Dakota
.Ohio _ _ __
QUahoria
Pennsylvania
Puerto Pico
Rhode. Island
South Carol in(!
South Dakota
Tennessee
Texas
Utah
Vermont
Virgin.
Washington
West Vi r^i ma
Wisconsin
Wyonn ng
NATIONAL TOTALS
28652
20
".
..-
,
. ]_.
.
'
27
1
-
--
1
28
2
2
--
4
4
2
0
1
--
19
14
14
12
16
i
5
1
1
3
138
29
-
-
—
1
-
"-
28653
2 20
__.
---
- - -
2
1
1 1
4
2
3
4
- -
)
3
--
- -
HO
15
5
6
8 I
2
1
3 1
101 3
28655
n
5
1
1
5
2
2
2
1
1
1
5
,
6
4
3
9
-
4
2
1
2
2
3
3
1
2
3
11
8
4
t
2
7
0
1
_.
—
-
-
2
5
-
2
-
-
-
i
—
—
i
2
8
— -
__
-
\
1
9 31
1
1 3
2
-
—
1
1
:~
T
1
1
5
1
2
27
—
__
-
-:
—
i
2
1
2
— -
.J
3
^
1
--
1
1
» 3
28691
i n .11 -U. J± .22.
1
1 2
6
-.i.: *-:/:•
3
2 1
1 3
I
............
f"~"
_T
T i
T i
T
T
T
._. ...£_.._.
. _..
""' IT'
"2
1 3 8 24 6
iLii y ?B
_
- '
1
r-2-rr_r
f ;_
4
3
1
t/T
i F |_
r r
i
£J i
1
12 6 314
REGION TOTALS
1
2
3
4
5
6
7
8
9 31
10
1
1
12
63
22
26
13
2
1
1
3
1
7
55
16
7
13
3
2
1
3
2
10
7
15
3
1
1
1
1
5
14
14
19
9
5
4
1
3
1
1
1
2
2
2
1
1
5
5
16
2
3
1
1
1
3
1
3
2
1
1
6
1
3
1
2
2
1
3
1
2
4
1
1
1
16
2
2
2
4
1
1
6
2
3
1
1
2
1
1
1
1
1
1
1
1
1
1
1
4-20
-------
Table 4-5.
Process Types Used for Manufacture, by
Classification - Organic Chemicals and
Pesticides Industries (Continued)
Standard Industrial
Technical
EPA
Realon
4
9
__6 ,
9
8
1
3
3
4
4
9
10
5
5
7
7
4
6
1
_3
]_
5
5
4 _
7
8
_l
9
1
2
6
2
4
8
5
6
10
3
2
\
4
8
4
6
8
1
_3_
10
__3
5
8
State
Alabama
Alaska
Arizona
Arkansas
California
Colorado
Connecticut
Delaware
District of Columbia
Florida
Georgia
Hawai i
Idaho
1 1 1 1 nois
Indiana
Iowa
Kansas
-Kentucky
Louisiana
Mai ne
Maryland
Massachusetts
Michigan
Minnesota
Mi ssouri
Montana
Nebraska
Nevada
New Hampshire
New Jersey
New Mexico
New York
North Carol! na
North Dakota
Ohio
Oklahoma
Oregon
Pefinsyl vama
Puerto Rico
Rhode Island
South Carolina
South Dakota
Tennessee
Texas
Utah
Vermont
Vi njj m a
Washington
^West Virqjma
Wisconsin
Wyoim nq
NATIONAL TOTALS
2869?
2
2
2
2
1
1
1
?
1
1
--
1
1
1
—
J
17
3
1
1
5
1
3
4
6
-
5
2
1
1
14
-2.
1
47
4
-
—
--
2
3
5
—
1
1
1
1
1_
5
6
-
1
1
8
1
1
1
1
1
—
1
2
11
9
1
1
1
4
1
1
1
1
2
3
26
-
1
1
:
i
-
3
12
2
-
4
1
1
2
2
?
2
3
2
14
2
1
5
6
2
3
»
_6
72
13
_J_
2
—
--
4
—
-
7
14
3
1
5
12
1
15
1
1
;
i
i
3
6
4
15
37
1
1
7
—
?5
7
5
1
3
2
1
26
1
15
--
184
2
5
16
1
1
^ 1
32
4
69
16
1
1
1
2
1
5
1
--
[
1
1
8
22
17
1
1
1
1
I
6
3
14
20
1
1
1
1
3
1
1
8
1
2
1
2
4
2
20
4
2
57
21
7
1
3
1
1
1
4
24
9
4
10
5
1
1
2
1
1
76
23
i
2
6
1
1
1
5
2
2
5
15
1
1
2
3
1
12
?
5
6
p.
5
5
4
2
52
2
=
24
2
—
2
1
---
--
3
'I'
159J 8
25
14
4
5
5
2
2
6
19
2
4
1
4
2
3
5
57
1
1
1
138
26
— •
---
—
1
1
27
1
1
—
-
1
1
2
6
f,
28
1
2
1
1
1
2
2
1
4
1
1
1
1
1
12
2
4
7
2
4
19
1
6
77
30
—
1
2
1
1
3
1
T
1
1
12
31
1
-
--
— -
1
2
--
-
-
~7
~3~
5
34
—
—
....
I
--
--
1
REGION TOTALS
1
2
3
4
5
6
7
8
9
10
1
1
4
5
2
2
S
4
10
9
18
1
1
2
1
1
1
1
1
1
5
1
2
1
1
1
2
2
3
i;
1
?
,
J
16
14
10
11
14
4
1
i
,.'
2
35
18
23
21
68
4
"
1
6
6
5
2
4C
2
1
1
3
2
1
13
1
1
3
1
1
1
11
9
1!
3
2J
33
7
8
15
4
1
19
11
22
15
69
I
1
6
10
1
4
3
10
9
6
16
76
4
14
1
1
1
3
l
1
3
14
16
11
7
23
1
1
1
4
1
4
1
1
1
2
3
1
4-2]
-------
Table 4-5.
Process Types Used for Manufacture, by Standard Industrial
Classification - Organic Chemicals and Technical
Pesticides Industries (Continued)
EPA
fteoipn
4
10
6
9
1
3
3
4
4
9
10
b
_ 5
7
7
4
6
1
3
1
b
r,
4
7
8
7
9
?
6
2
4
B
5
6
10
3
1
4
a
4
6
8
1
3
10
1
5
II
State
Alabama
Alaska
JW./2fla_
Arkansas
Cal i forma
Col orado
Connecticut
Delaware
District of Columbia
Florida
Georaia
Hawai i
JJlinojs
^Indiana
Iowa
Kansas
Kentucky
.Louisiana
Mai ne
Marvl and
Massachusetts
Michigan
Minnesota
Mississippi
Mi ssouri
Montana
Nebt aska
Nevada
New Hampshire
New Jersey
New Mexico
New York
North Ca» ul ' na
North Dakota
.-
Ohio
Oklahoma
Oregon
Puerto R'co
Rhode Island
South Carol ina
South Dakota
Tennessee
Texas
Utah
Vermont
Virginia
Washinyton
West Virginia
Wisconsin
Wyom i ng
NATIONAL TOTALS
28693
1
—
2
2
2
1
1
3
2
1
5
1
! !
1
'
]
—
-
.
j
_
-
4
2
4__
1
F
—
^i,
—
r-
1
I 1
1
17
._
1
2
14
i
-
4
6
1
1
11
1
5
1
—
7
2
4
1
8
2
5
1
,
13
1
i
2E
9
6
q
1C
3
-
4
_2
7
lot
2
—
2
14
15
1
1
16
1
1
20
3
2
1
1
1
10
2)
1
3
1
2
7
23
1
1
2
26
28
?
,
1
1
-
1
2
1
30
1
1
1
-
T
1 1
=fz
,
1
-
—
1
?
16
:
2
3
1
1
4
2
1
2
1
3
9
1
1
-
2
69'
2
4
5
i
0
3
2
5
7
3
6
8
12
4
17
11
R
14
40
14
5
8
10
1?
1
R
17
2
7
12
6
30
9
--
30
1
1
33
34
1
1
1
I
•'
L
L
1
1
1
..i
3
1
2
2
12
_
1
14
1
1
|
_JL
1 —
-
--
1
11 1
—
1-
—
1
95
15
1
1
1
1
2
1
2
1
11
5
-L
1
REGION TOTALS
1
•,
3
4
S
6
7
8
9
10
2
2
6
1
1
4
3
2
3
2
2
3
2
2
2
1
6
1
4
37
18
id
2d
7
;
4
2
1
1
1
3
1
2
4
1
1
2
3
1
1
1
3
1
2
1
6
2
1
1
1
1
1
3
5
1
1
1
3
54
30
53
62
34
28
10
16
17
1
1
1
1
2
4
1
1
1
1
4-22
-------
Table 4-1 indicates, for each five-digit SIC product group, the
chemical products(3,4,7-lO) Of the organic chemicals industry covered
in this study.1 It should be noted that SIC 28694 (technical pesti-
cides) covers commodities which are given dual consideration herein,
as the products of the organic chemicals industry, and as the products
of the pesticides industries.
Table 4-2 presents, for each five-digit SIC product group, a
tabulation of the number of p!ant sites(^>12) (industry sources
listed in Table A-l) in each state at which one or more of the chemi-
cals in Table 4-1 for the product group are manufactured. Since
there are numerous plant sites at which chemicals in each of several
five digit SIC product groups are manufactured, the tabulation is
partially redundant. Excluding double accounting, the true aggregate
number of organic chemical plant locations covered in this study was
899.
For comparison, the true aggregate number was 1204 for locations where any
"commercial scale" organic chemical was manufactured^ ' ' (commercial
scale here indicates a United States production total in 1973 of 1 million
P
pounds or more ). The study thus encompassed about 75 percent of the com-
mercial scale production sites.
The three states with the greatest concentrations of plant sites
covered in this study were: New Jersey (137), Texas (98), and Ohio (61).
The three product groups with the largest number of plant sites were SIC
28692, miscellaneous acyclic chemicals (424); SIC 28651, cyclic intermediates
(247); and SIC 28694, technical pesticides (134).
o
The distribution of plant sizes for each of the 12 production groups,
rated in terms of aggregate daily production capacity for the chemicals in
the group, is given in Table 4-3. Roughly 65 percent of the product
group-plant site combinations were rated at less than 100 metric tons per
day. At the upper end of the scale, only one combination in 16 was rated
at 1000 or more metric tons per day.
See Appendix A for the criteria used to select organic chemicals covered
in this study.
p
Organic chemicals (other than pesticides) which were not listed by the
U.S. International Trade Commission (Reference 3) because there was only
one manufacturer were also excluded. Polychlorobiphenyl (PCB) and other
chemicals with potentially hazardous waste streams were therefore ex-
cluded on this basis.
See Appendix A for the procedures employed to obtain the estimates of
individual plant sizes, and the references used as data sources.
4-23
-------
Table 4-4 lists the distribution of production for the organic
chemicals industry. The figures given are composited from production
capacity and production rates for 1972 and 1973. They indicate that the
two product groups which account for more than 90% of the organic chemical
production covered in this study are SIC 28692, miscellaneous acyclic
chemicals, and SIC 28651, cyclic intermediates. The miscellaneous acyclic
chemicals amount to almost three-fourths of the total organic production
given in Table 4-4. The locales with the greatest concentrations of pro-
duction are Texas, Louisiana, and Puerto Rico.
3
The distribution of process types used for manufacture of organic
chemicals for each Standard Industrial Classification product group is
given in Table 4-5. Approximately 2700 of the 3206 chemical product-plant
site combinations covered in this study have been classified by process
type in Table 4-5. Each such combination represented a production line
which manufactured an organic chemical commodity. Due to the adaptability
of much of the organic chemical process equipment and unit operations, the
same physical equipment, in many cases, was used to produce different
chemicals at different times of the year. This was true for both batch
operations and continuous production systems.
4.3 PESTICIDES INDUSTRIES
The data presented in this section are subject to the limitations noted
in Section 3 "Methodology" and in "Appendix A" on the pesticide preparations
and formulations industry. To round out the picture of the pesticides
industries, a portion of the data presented earlier in Section 4.2 on
SIC 28694 (the technical pesticides product group) has been repeated.
See Appendix A for the procedures and references used to develop these
estimates.
9
In some cases, wastes generated at plant sites located in Puerto Rico
are shipped to sites located within the United States for treatment and
disposal. In addition, EPA considers Puerto Rico as part of Region II
and treats it as such in its studies. For these reasons, Puerto Rico
was also included in this study.
3See Appendix A for the procedures used to classify chemical product-plant
site combinations by process type. The process type names employed were
compiled for this study on the basis of the process chemistries involved
in the manufacture of the individual commodities.
4-24
-------
Table 4-6 presents data^ ' ' on the distribution by state of plants
in the technical pesticide manufacturing (SIC 28694) and formulating (SIC
2879) industries. The national total number of production sites for the
two industries are 134 and 388, respectively. With the exception of plants
producing certain highly dangerous products, the listing of production
sites for SIC 28694 covers only those facilities producing at least one
pesticide for which the annual total national production is close to or in
excess of 453 metric tons (1 million pounds). In Table 4-6, the formulat-
ing plants are further divided into the following four product group SIC
subcategories:^ '
t SIC 28791; Establishments engaged in the formulation of insecticidal
preparations for agriculture, garden and health service.
• SIC 28792; Establishments engaged in the formulation of herbicidal
preparations for agriculture, garden and health service.
• SIC 28793; Establishments engaged in the formulation of agricultural
chemicals, fungicides, soil fumigants, and products not elsewhere
classified.
• SIC 28794; Establishments engaged in the formulation of household
insecticides and repellants.
• SIC 28790; Establishments engaged in the formulation of agricultural
chemicals not specified by kind.
The national totals for the formulation sites in SIC 28791, 28792, 28793,
28794 and 28790 are 155, 97, 110, 158 and 307, respectively. These numbers
and the plant distribution data for the states are based on an advance copy
of the information which will be published in the "1972 Census of Manu-
facturers" by the Census Bureau. Since pesticides in each of several of
the above subcategories may be formulated at a formulation site, the total
number obtained by adding sites for each of the five subcategories exceeds
that shown for the parent SIC 2879 (827 vs. 388). Although some pesticide
manufacturing plants are operated as integrated facilities for both pesti-
cide production and formulation, in general, pesticide formulation is con-
ducted at a separate site and often by an independent formulator.
4-25
-------
Table 4-6. Number of Plant Sites by Standard Industrial
Classification - Pesticides Industries(6»H)
EPA
Rfalpn
4
ja
3L
A.
_i
3
3
4
4
5
JiL
5
5
7
7
4
6
1
3
1
5
5
4
7
8
7
9
1
2
6 ,
2
4
8
6
10
3
2
1
4
8
4
6
8
1
3
10
3
5
8
SUtt
Alibau
Alaska.
Arl^pna
California
Colorado
Connecticut __ .
Pelaware
District of Columbia
Florida
Georoia
Jdiho
Illinois
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maine
Maryland
Massachusetts
Michigan
Minnesota
Mississippi
Missouri
Montana
Nebraska
Nevada
New Hampshire
New Jersey
New Me* ico
New York
North Carolina
North Dakota
Ohio
Pennsylvania
Rhode Island
South Carol 1 na
South Dakota
Tennessee
Texas
Utah
Vermont
Vi rgi ma
Washington
West Virginia
Wisconsin
Wyoming
NATIONAL TOTALS
Technical
Pestitides
SIC 28694 T
7
2
9
2
3
1
1
3
8
3
4
3
8
2
4
1
4
7
16
5
3
6
2
4
1
5
9
1
4
5
1
134
Pesticides Preptnttoni and Formulations - SIC 2879 4
SIC 28791 Z
7
4
21
3
6
8
8
3
5
1
2
7
2
2
4
1
6
5
1
2
6
4
6
5
2
4
5
3
17
1
2
1
155
SIC 2S792 r
4
1
12
2
M->
4
4
4
2
3
3
1
4
1
2
3
2
3
4
1
3
2
4
4
2
3
3
1
12
2
1
97
SIC 28793 '
4
1
18
2
6
8
7
1
2
1
1
1
3
4
3
3
1
4
<
5
5
2
3
3
1
13
1
2
1
110
SIC 28794 '
1
16
1
5
15
1
17
4
2
1
1
1
3
3
4
3
1
10
2
2
11
13
10
2
6
1
3
2
9
3
4
158
SJC J8790 r
2
1
3
46
L
2
1
22
8
2
1
16
9
6
3
1
7
••
5
5
3
8
16
2
2
2
9
13
9
17
1
5
17
5
7
23
1
3
7
1
4
307
ToUl J
8
1
8
53
8
2
1
25
14
1
1
18
5
10
3
1
15
6
6
S
4
10
23
2
3
2
1
5
17
12
13
3
5
15
NA
9
9
35 .
1
4
8
1
5
^,38?,-,
NA - Estimate of number of plant sites not applicable, due to lack of appropriate data
Number of olant sites at which Technical Organic Pest Control Chemicals, whose total national annual production was in excess of 1 million
puunds, were manufactured
Number of manufacturing establishments which reported shipments in this" product class in the Bureau of the Census "1972 Census of Manufacturers"
Number of manufacturing establishments classified within this industry in the Bureau of Census "1972 Census of Manufacturers".
rhe Pestiiides Preparations and Formulations Industry is divided into five product groups:(7)
SIC 28791 Insecticidal preparations for agriculture, garden and health service
SR 28792 Herbicidal preparations for agriculture, garden and health service.
SIC 28793 Agricultural chemicals, fungicides, soil fumigants, and NEC.
SIC 28794 Household insecticides and repellants.
SIC 28790 Agricultural Chemicals NSK - (Data includes companies with <10 employees)
NEC - not elsewhere classified
NSK - not specified by kind
4-26
-------
The commodities manufactured under product group SIC 28694 are listed
in Table 4-1. The production capacities for plants manufacturing technical
pesticides (SIC 28694) are given in Table 4-3. Data on production capacities
for plants engaged in pesticide preparation and formulation manufacture are
not available.
Table 4-7^ ' ' ' ' presents estimates* of production for calendar
year 1972, in thousands of metric tons, for the pesticides industries.
California, Texas, and New Jersey are the states which led the nation in
1972 in overall pesticide production.
The process type designations for technical pesticide manufacturing
plants (SIC 28694) are given in Table 4-5. Data on process types employed
in formulation and preparation plants is not available, although the
majority engage in simple dry ingredient blending and/or solution prepara-
tion operations.
4.4 EXPLOSIVES INDUSTRIES
Establishments included in SIC 2892 are subclassified into SIC 28921
and SIC 28922.^ ' The first subclassification covers privately owned and
operated establishments engaged in the manufacture of explosives for com-
mercial uses and, in limited cases, under special contracts, for military
and space applications. Commercial uses of explosives are primarily in
mining and construction activities. SIC 28922 covers all GOCO facilities
engaged in the manufacture/formulation of explosives for military uses.
4.4.1 Commercial Explosives Industry
Major explosives of commercial importance are listed in Table 4-8.
From the usage standpoint, commercial explosives may be grouped into fixed
high explosives and blasting agents. Table 4-9 lists the quantities of
various fixed high explosives and blasting agents which were sold for con-
sumption in the United States in 1973.* ' In the absence of actual pro-
duction data, the sale-for-consumption data in this table (and in related
*
See Appendix A for the procedures used to develop these estimates. The
references cited were supplemented by the industry sources listed in
Table A-l.
4-27
-------
Table 4-7.
Production Rate, Thousand Metric Tons Per Year, CY 1972
by Standard Industrial Classification - Pesticides
Industries(3,6,ll)*
TECHNICAL PESTICIDES
SIC 28694
PESTICIKS PREPARATIONS
AND FORMULATIONS
SIC 2879
Iff.
itaitUL
4
19- .
.__!.,
-J_
9
8
1
_J
3
4
4
19
s
i
;
4 ,
«
1
3
1
5
5
4
7
R
7
9_ [
2
e ,
4
-;
. *—
?
4
• v
6
1
nr
—
e
T
SUte
Al«b»M
Alaska
Arizona
Arkansas
California
Colorado
Connecticut
Delawre
District of Columbia
Honda
Georgia
Idaho
Illinois
Indiana
Iowa
Kansas
Kentucky
Louisiana
"ame
Maryland
Massachusetts
Hichiqan
"innesota
Mississippi
P'SSOurl
Montana
Nebraska
fiew Ha-Dshire
'*ex Jersey
New Mexico
New vcrk
'iorth Carolina
Ohio
»"odf .OjrH
'e»as
._ 1
• er"<'t J
- — 4-—
64
8
41
13
5
0.3
7
21
1
24
4
35
2
30
2
27
23
59
11
65
17
4
2
0.5
23
58
-
0.1
7
30
7
516
26
3
26
174
26
7
3
82
46
3
3
59
16
33
1(1
3
49
20
20
]fi
13
33
76
7
in
7
3
40
Ifi
3Q
A3
in
le
49
30
30
115
3
13
26
3
16
Lffi
in
•)
34
?15
19
12
R?
1
1
an
17
^7
14
•a
»a
77
?n
4fi -
K
fin
7
in
7
,
108
C7
qn
60
]0 .
?n
51
30
53
173
3
a
31
33
__23 . _
1,791
-t •, '--> ,
-
i
>
-------
Table 4-8. Major Commercial Explosives
PRIMARY EXPLOSIVES AND INITIATING AGENTS
Blasting Caps
Detonating Cords
Electric Matches
Lead Azide
Mercury Fulminate
Safety Fuses
HIGH EXPLOSIVES
Dynami tes
Nitroglycerin
Pentaerythritol Tetranitrate (PETN)
NITROCELLULOSE
Amine Nitrates (RDX, HMX)
Dinitrotoluene (DNT)
Trinitrotoluene (TNT)
BLASTING AGENTS AND PROPELLANTS
Ammonium Nitrate (Prilled or Grained)
Ammonium Nitrate-Fuel Oil Mixtures (ANFO)
Black Powder
Ni trocarboni trates
Smokeless Powder
Water Gels and Slurries
4-29
-------
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4-30
-------
subsequent tables) are assumed to be close to actual production. This is
based on private explosives industry practice, which is to maintain rela-
tively small constant inventories of explosives (other than ANFO* blasting
agents), to prevent safety hazards due to degradation and quantity. ANFO
blasting agents are generally formulated one day or less prior to use.
The data in Table 4-9 indicate that ANFO blasting agents account for close
to 89 percent of all the commercial explosives sold. Table 4-10 contains
data on the estimated production of industrial explosives^ ' by state,
EPA Region and explosives class.
Plants in the commercial explosives industry fall into two general
categories: (1) large and often complex facilities manufacturing explo-
sives and many of the necessary chemical feedstocks and (b) small plants,
usually located on or near the use site (mining field, etc.). Table 4-11
presents data on the number of licensed commercial explosives manufacturers
in each state and EPA region, based on the information provided by the
Bureau of Alcohol, Tobacco and Firearms (ATF), U.S. Treasury Department, '
and by listings included in the SRI directory of Chemical Producers/ '
(12)
and by Dun and Bradstreet. ' The companies listed in the latter two
sources were contacted by telephone to verify that they were indeed involved
in actual manufacturing of explosives. Those which were distributors or
were no longer involved in explosives manufacturing were omitted from
further consideration. Based on the data received from ATF, the size and
production capability at each site could not be determined. Most of the
facilities included in the ATF listing, however, are believed to be small
ANFO formulators operating near the use site.
4.4.2 Military Explosives
The basic explosives for military use are manufactured by the U.S.
Army. The basic explosives which are produced in volume quantities include
trinitrotoluene (TNT), nitroglycerine, nitrocellulose, cyclotrimethylene-
trinitramine (RDX) and cyclotetramethylenetetranitramine (HMX).
*
Ammonium nitrate-fuel oil
4-31
-------
Table 4-10.
Estimated Production Rate, Metric Tons for CY
By Explosive Class -Private Explosives
1973,
**J fc- ^ f i v* j i v ^ WIUOO r I
Industry SIC 2892l(15)
C- »«•
4 Alabama
10 Alaska
9 Arizona
6 Arkansas
9 California
6 Colorado
1 Connecticut
3 Dela»are
3 District of Columbia
* I Florida
4 j ueorqia
9 Ham 11
Idaho
5 1 Illinois
5 Indiana
j Iowa
. _; | 'ansas
' , fentuck.
f | Lou siana
1 +.»ane
J 1 Maryland
1 ''assacnusetts
I I Mich:qan
fj Minnesota
4 ._, MISSISSIPPI
' M-ssourl
c Montana
7 _,Jiebraska
» J Nevada
Ne» Harfpshlre
2 I New .ersev
£ , New Mexico
New York
~ ' North Carolina
j Net th Dakota
1 : n < o
r - ----
1- Vej"r -^
. j'^:;:-;v
_; I j.ur,r^ ! „ 3
- •- a*"'
~rr' fcV f e
, ->.;; • '"
1 _ • -•
" *' • .-,
.
V '.i_ - -«i'.
.' J s' •"'- J*e'1
Fixed High
Perm1ss1bles
2,454
23
3
29
.5
210
25
101
.9
6,847
5
5
.9
1
64
24
.9
6
5
677
5
1,508
365
' '•" ' 128 "
5
2.369
3
5, -95
5
10
?0.081
Explosives
Other
Hlah Exn1oi1»«
3,426
1,949
2,605
938
2,333
3,819
2.854
55
11.352
2.527
209
1,474
5,933
1,141
3,758
730
5,801
803
702
2,151
1,613
1,583
851
915
5,942
1,419
291
196
775
1,444
1,779
3,608
2,908
3,695
1,046
2.319
11.417
102
637
129
5,828
2,977
777
660
4,989
2,122
2,721
1,343
394
119.042
CyHndrlolly
Packaoed
12,217
88
108
235
191
61
424
5
2.198
1.209
9
80
26,076
16,985
286
917
24,712
79
402
133
1.085
2.175
6
2.682
134
110
3
148
9
495
760
8,375
1.387
19
6.427
90
2.839
212
21
5
2.184
135
9.460
131
1,039
126.396
Blasting Agtntl
Uifcr'TSeV"
and Slurries
575
265
23,362
777
6.451
314
I,™
4.260
2.920
151
118
2.868
1.714
1.047
900
1.200
4
105
1.913
199
8.995
31.700
18
2.236
63
4
282
10
782
3.293
1.515
1.332
1.096
1.235
?21
4.740
332 _
59
1.039
1,105
3,814
3
1,935
116
410
1,497
1,186
119.541
tKr Blauino—
aents i AHFQ
68,236
59.325
6,139
21.208
5,765
4.449
3. 105
8. ,36
1.17?
3,592
It, 242
35,564
9.12!
1,713
116.564
1.602
2.285
1.422
14.355
41
21.103
1.219
685
11.634
296
865
24.062
6.163
7.452
367
58.183
12.301
3,676
105 fi44
277
S65
7R?
16,283
13,221
171
34, 0,?!
',108
52,196
6,293
2,345
364.554
45,776
Total
86^908
2.325
85.400
8,091
30,184
9.989
14 79?
1 44 1
5.263
51.330
14.312
155 125
2.409
1.772
6.751
3.368
26.026
52.193
979
2.859
981
12.???
1.084
29.143
11.7SB
17.456
I 72,026
«,Q7n
fi.PT,
I J?Q 71fi
| 379
J_ i o?4
, Qfiq
',-. . 1U3£6__ _
20,577
17,964
844
45j49B
7,489
69j_981
9,321
4,978
1,249.614
! 49,776
Or- • -,,, -r,-^| -
i
i
^
5
6
9.C72
9.672
327
4
'67
196
32
6,706
5,052
21,333
33,395
14,546
7,543
10,722
6,538
5,343
7,864
644
643
18.478
44,031
54,877
1,843
3.685
1,255
418
322
1.697
2,297
8.998
11,676
47.870
6,414
4.187
5,436
30,246
720
7.500
7,028
194.145
235,632
148,102
60,386
32.621
23,700
93,289
12,375
IS. 55.2 _
15.026
252.026
334,406
26". 322
"6,190
51.532
37,125
129,296
21,313
4-32
-------
Table 4-11.
Number of Plant Sites by Standard Industrial
Classification - Explosives Industry
PRIVATE EXPLOSIVES INDUSTRY - SIC 28921
SOCO PLAKTS* - SIC 28922
EPA
lUlttL
4
10
9
«
9
_a ,
j
3
3
4
4
-9
10
5
5
7
7
4
6
1
3
1
:
5
4
7
6
7
9
1
2
6
2
4
e
5
6
10
3
2
1
4
8
4
e
8
1
3
10
3
5
8
NATION/
REGION
1
2
3
4
5
e
7
8
9
10
SUtt
Alibau
Alaska
Arizona
Arkansas .
California
Colorado
Connecticut
Delaware
District of Columbia
Florida
Georoia
Huutl
Idaho
Illinois
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maine
Maryland
Massachusetts
Hlchfaan
Minnesota
MISSiSSlDDl
Missouri
Montana
Nebraska
Nevada
New Hampshire
New Jersey
New Mexico
New York
North Carolina
North Dakota
Ohio
Oklahoma
Oregon
Pennsylvania
Puerto R1co
Rhode Island
South Carolina
South Dakota
Tennessee
Texas
Utah
Vermont
Virginia
Washington
West Virginia
Wisconsin
riyomi ng
L TOTALS
TOTALS
ATF Data("i)
11
0
22
7
43
19
9
0
1
11
11
1
6
23
14
17
7
21
4
2
5
2
12
11
1
17
12
2
9
4
6
13
16
8
0
30
8
3
72
0
0
2
0
12
35
9
0
7
12
22
IV
6
576
17
22
107
77
101
67
43
46
75
21
Additional Data
from TRH(ll.lZ)
1
1
2
1
1
1
1
1
1
10
1
2
1
1
2
2
1
Total
11
0
23
7
43
19
9
0
1
11
11
1
6
24
14
17
7
21
4
2
5
2
12
11
1
17
12
2
9
4
8
13
16
9
0
31
9
3
7J
0
0
?
0
12
36
9
1
7
12
23
11
6
586
18
24
108
78
103
69
43
46
76
?1
Total
1
0
0
1
2
1
0
0
0
0
0
0
0
1
2
2
2
0
1
0
1
0
0
1
0
2
0
1
0
0
2
2
0
0
0
2
0
0
3
0
0
0
0
3
3
0
0
1
0
0
1
0
35
0
2
5
4
7
7
7
1
7
n
Active
0
0
0
1
1
0
0
0
0
0
0
0
0
1
2
1
1
0
1
0
1
0
0
0
0
0
0
0
0
0
)
2
0
0
0
1
0
0
0
0
0
0
0
3
3
0
0
1
0
0
1
0
21
0
1
2
3
4
7
1
0
1
n
•Includes six AE.C plants, one each In Iowa, Texts, California and Ohio, snd two in New Mexico, ihr Army GOCO and
&OGO plants""; and does not Include commercial plants In Utah and California manufacturing propel 1 ant for the
US Air Force
4-33
-------
In addition to manufacturing explosives, the Army operates facilities for
formulation of various explosives compositions and for loading, assembly
and packing (LAP) of munitions. Manufacture and formulation of explosives
and the LAP operations are conducted at GOCO Army ammunition plants (AAP's)
and. to a negligibly small scale, at Army arsenals. Although not involved
in large scale explosives manufacturing, the Navy and the Energy Research
and Development Agency (ERDA; formerly Atomic Energy Commission) operate
a number of LAP, explosive formulation, and research and development
facilities which generate explosive-containing wastes.
The data on the distribution by state and EPA region of all 60GO and
GOCO AAP's and arsenals are presented in Table 4-11. Because of current
peacetime operation and the decline in demands for munitions, many of
these facilities were inactive in 1973. Some of the AAP's (e.g., Scranton
AAP in Pennsylvania and Riverbank AAP in California) are involved mainly
in metal parts manufacturing and metal finishing operations and do not
generate explosive-containing wastes. The distribution by state and EPA
region for active facilities producing explosive-containing wastes are
also shown in Table 4-11.
Nearly all Army ammunition plants were constructed during World War II
(1940-45). These facilities still utilize much of the original equipment
and processes. In recent years, the Army has initiated an extensive plant
modernization program involving equipment replacement and construction of
facilities which incorporate the latest advances in automation and chemical
process technology. Some of the specific modernization projects have
already been completed at a number of AAP's. Other modernization programs
are currently either in the design construction stage or are awaiting fund-
ing considerations.
The 1973 quantities of basic explosives (TNT, DNT, NG, RDX, HMX, and
tetryl), high explosive compositions (Composition B, etc.), propellants
(NC), propellant formulations (single base, double base, etc., propellant)
and munition items produced at Army facilities are presented in Table 4-12.
These production quantities represent only the 1973 operation which is pro-
bably representative of the peacetime activities. During World War II, the
Korean War, and the Vietnam operation, most of the AAP's (including those
4-34
-------
Table 4-12.
Production Rate, Metric Tons1 for CY 1973, GOCO Plants,(18)
Explosives Industry (SIC 28922)
CPA
talon
_J
10
9
6
9
8
1
3
3
4
4
9
10
_i
5
7
7
4
6
1
3
1
5
5
-4
7
8
7
9
1
2
6
2
4
8
5
6
10
3
2
1
4
8
4
6
8
1
3
10
3
5
8
suit
Allbou
AlMlU
Arllona
Arkinus
California
Colorado
Connecticut
Delaware
District of Columbia
Florida
Qeorala
Hawaii
Idaho
Illinois
Indiana
Kansas
Kentucky
Louisiana
Maine
Maryland
Massachusetts
Michigan
Minnesota
Mississippi
Missouri
Montana
Nebraska
Nevada
New Hampshire
New Jersey
New Mexico
New York
North Carolina
North Dakota
Ohio
Oklahoma
Oreqon
Pennsylvania
Puerto R1co
Rhode Island
South Carolina
South Dakota
Tennessee
Texas
Utah
Vermont
Virginia
Washington
West Virginia
Wisconsin
Wyoming
NATIONAL TOTALS
BiS 1C
High Explosives
109,7Bn
71.40.11
50,352
4,271
235,803
Mtfln1 t^lbsiVff
Composi tions
— ,
74,™
74,580
Propel lants
29.940
... 9.027
38.967
Formulations
13,750
16.190
b9,940
LAP Items
(1 000 rounds)
1. 403
^.760
19.704
2*419.
31.876
6.165
312
712
7q ,„
160.291
304,894
REGION TOTALS
1
2
3
4
5
6
7
8
9
10
50,352
71,400
114,051
74,580
29,940
9,027
43,750
16,190
712
312
79,252
22,464
167, 851
34,29!
LAP items are in 1,000 round units
4-35
-------
now inactive) were in full production. The fluctuations in the production
of TNT and tetryl at one AAP (Joliet, Illinois) from January 196& to
February 1974 are presented in Figures 4-1 and 4-2, respectively. The
fluctuations are representative of the variability of production in
response to Department of Defense demand. Since waste generation at explo-
sive plants is directly proportional to production, the fluctuations also
indicate the variability in waste quantities generated at the AAPs.
Many of the explosive-producing AAP's operate on-site facilities for
the production and/or recovery from spent solutions of inorganic chemical
feedstocks (e.g., nitric and sulfuric acids). These satellite operations
are essentially identical to those in the commercial inorganic chemicals
industry and were not included in the present study.
4-36
-------
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5. WASTE CHARACTERIZATION
5.1 GENERAL
This section presents process flow diagrams and mass balances for
typical plants of the organic chemicals, pesticides and explosives indus-
tries; short narrative descriptions of these typical plants and their haz-
ardous waste streams; estimates of the quantities of land^clesttned hazardous
wastes generated to land disposal by the industries in 1973; projections of
the impact of air pollution control regulations and of the Federal Water
Pollution Control Act Amendments on the industries' hazardous wastes destined
for land disposal in 1977 and 1983; and listings of the highly dangerous
waste stream components.
The process flow diagrams are schematic and have been deliberately
chosen to represent a single-product process system - a typical "depart-
ment" in the terminology used by many companies. This was done to simpli-
fy the process descriptions and the identification and characterization of
hazardous waste streams. The norm for the industries, however, is a plant
complex, composed of many departments, frequently interrelated, with inter-
dependent feedstocks, intermediates, products and process waste streams.
The process waste streams are often combined prior to treatment and
disposal.
The quantities, compositions, and properties of the hazardous waste
streams were determined, where possible, from the industry and government
agency sources listed earlier in Table A-l, in the Appendix. Working process
models were developed, based on the literature referenced, where such
definitive data were absent.
The diagrams follow a uniform format. Feedstocks (raw materials) are
on the reader's left; products are on the right. All quantities are based
on unit weight of product. Miscellaneous water uses have not been included
in the material balance. The use of process and cooling water varies so
widely with location, climate, time of year, and specific equipment selec-
tion that presentation of data in a typical process flow diagram would be
misleading.
5-1
-------
5.? ORGANIC CHEMICALS INDUSTRY
The major commercial products of the organic chemicals industry are
almost 400 in number as indicated in Table 4-1. Of this total, approxi-
mately 100 are industrially significant - the 100 most important chemi-
(19)
calsv ' with a manufacturing rate of approximately 23,000 metric tons
(50 million pounds) or more per year. Twenty-one hypothetical typical
plants, each using a single process, were selected on the basis of the
significance of their products and process waste streams to character-
ize the organic chemicals industry. The selection had, as partial basis
(with two exceptions*), the 23,000 metric ton or more per year production
criterion for industrial significance. Consequently, all of the organic
chemicals selected are products of the two major industry classifications
(SIC 2865, cyclic crudes and intermediates and SIC 2869, industrial organic
chemicals NEC) which represent the bulk of all organic chemical production.
The products selected constituted approximately 9 percent by weight of the
total 1973 production of the industry. The total process wastes (dry basis)
discharged to land in 1973 by plants producing these products represented
about 52 percent by weight of the total process wastes (dry basis) discharged
to land by the industry. The processes were selected on the basis of
generating significant quantities of land-destined wastes, and hence had
a higher "waste discharge factor."
5.2.1 Typical Plant Process and Waste Stream Descriptions
It should be noted that no process flow diagram in this section repre-
sents an individual actual plant department or process line. The features ^
presented represent a hypothetical typical case, and give a composite pic-
ture of usual operations in the single process selected to represent the
manufacture of the product involved. Descriptions of these typical indus-
trially significant processes are presented below.
Perch!oroethylene SIC 28692^°' 21' 22' 23^
Production of perchloroethylene ("tetrachloroethylene") in 1973 totaled
320,000 metric tons (706 million pounds). There were eight major producers
- Diamond Shamrock Corporation, Dow Chemical Company, E. I. duPont de
*Benzoyl peroxide and the synthetic pyridines, which were selected as rep-
resentatives of the important acyl peroxide (RC(0)00(0)CR),and heterocyclic
groups of chemical products, respectively.
5-2
-------
Nemours and Company, Inc., Vulcan Materials Company (Chemical Division),
Hooker Chemical Corporation (Division of Occidental Petroleum), PPG
Industries, Inc., Stauffer Chemical Company (Industrial Division), and
Ethyl Corporation. Typical plant sizes are in the range of 32,000 to
45,000 metric tons (50 to 100 million pounds) per year.
About 20 percent of the perchloroethylene manufactured uses chlorine
and acetylene as starting materials. The chemistry of the reactions is as
follows:
SbCl,
2C12 + HC=CH 8QOg) C2H2C14
C2H2C14 a3c>- C1-CH=CC12 + HC1
Fed 3
C1CH=CC12 + C12 7o_80oc > C12CHCC13
2Cl«CHCClo + Ca(OH)~ °" > 2C1?C=CC1? + CaCl? + 2H20
f_ j t. u. C. i— C-
Chlorine and acetylene, each individually premixed with a reaction medium
of recycled tetrachloroethane and antimony trichloride catalyst, are fed to
a packed chlorination tower. The reaction product (Figure 5-1) is fed to a
still and separated into spent antimony chloride catalyst, tetrachloroeth-
ane, and vent gas. The spent antimony trichloride catalyst is sent to re-
covery; overall catalyst loss is smair ' and estimated at 1 kg/1 million
kg product.
The tetrachloroethane is split into a recycle stream, and a dehydro-
chlorinator feed stream. The dehydrochlorination of the tetrachloroethane
takes place in a packed tower, filled with activated carbon catalyst, at
300°C. The reaction products, trichloroethylene and hydrogen chloride are
cooled and the liquid and gas phases are separated. The gaseous phase hy-
drogen chloride is absorbed in water and sold as commercial grade muriatic
acid.
The condensate trichloroethylene is fed to a degasser and then to a
distillation column for purification. The tails from the purification col-
umn constitute a "heavy ends" process waste stream. The combined heavy
ends from this purification column and the perchloroethylene purification
column are approximately 0.30 kg per kg product; they are sent to land
disposal.
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The purified trichloroethylene is fed to a chlorination tower where
chlorination to pentachloroethane takes place at 70° to 80°C in the pres-
ence of a ferric chloride catalyst. The product pentachloroethane is
dehydrochlorinated, using aqueous slaked lime suspension, in a heated
packed tower maintained at 80°C. The aqueous phase, containing unreacted
slaked lime, calcium chloride and trace quantities of chlorinated solvents,
is discharged, after separation from the perchloroethane, through an indus-
trial outfall.
The crude perchloroethylene, after phase separation, is fed to a puri-
fication column. Product refined "perc" (perchloroethylene) is sent to
storage. The column bottoms, or "heavy ends," are sent to land disposal.
As noted earlier, the combined heavy ends from the trichloroethylene and
perchloroethylene columns are about 0.30 kg per kg perchloroethylene prod-
uct; analysis is about 77 percent hexachlorobutadiene, 7 percent chloro-
benzenes, 7 percent tars and residues, 3 percent chloroethanes, and 3 per-
cent chlorobutadienes. These heavy ends constitute a hazardous waste
stream to land disposal; the constituents are bioaccumulative and are
therefore classified as highly dangerous. Other losses of chlorinated
hydrocarbons take place to the air at low levels from the reflux condenser
(distillation column), the hydrochloric acid absorber, and the chlorination
reaction reflux condenser. These losses total slightly less than 0.008 kg/
kg product.
Nitrobenzene SIC 28651^20> 25' 26^
Nitrobenzene, classified as a "cyclic intermediate," was produced at
(A)
the rate of 140,000 metric tons in 1973V . The major producers reported
were Allied Chemical Company,* American Cyanamid Company, E. I. duPont de
Nemours and Company, Inc., First Chemical Corporation, Mobay Chemical Com-
/3)
pany, Monsanto Company, and Rubicon Chemicals Inc. ' Typical plant capac-
ities range from 4,500 metric tons (10 million pounds) to 38,000 metric tons
(84 million pounds) per year.
The process employed is typical of many liquid phase organic nitration
reactions. It is dependent upon the use of a large quantity of sulfuric
acid to promote substitution rather than oxidation, to serve as a mutual
solvent for the reactants, and to add to the heat-absorbing capability
*
No longer a manufacturer.
5-6
-------
(heat capacity) of the reaction system. The mixed acid used for this
reaction typically has the following composition: 50-60 percent HpSO*,
30-40 percent HN03, and about 8 percent water. The reaction which takes
place is, typically:
C6H6 + HN03 T07 C6H5N02 + H2°
The overall production of nitrobenzene in a batch plant (Figure 5-2) is
relatively simple. Benzene and mixed acid are fed in sequence to a jacketed,
cooling coil-equipped, cast-iron or steel reaction kettle equipped with an
efficient agitator. The time of reaction is temperature dependent and
varies from 3 to 40 minutes^ . The temperature ranges (dependent upon
process and company) from 45° to 95°C.
After completion of the reaction, the reaction mixture is separated
into an upper (nitrobenzene) and a lower (spent acid) phase in a liquid/
liquid separator.
The spent acid phase, diluted due to the water produced as a reaction
product, is recycled and reused after concentration or regeneration. The
nitrobenzene phase, after discharge from the separator, is washed with
dilute sodium carbonate and purified by distillation. The washer wastes
contain a small portion of nitrobenzene (0.00004 kg/kg product), sodium
sulfate, and residual sodium carbonate. The purification column wastes
contain nitrobody heavy ends (unknown nitro substituted aromatic compounds).
They are considered highly dangerous on the basis of the generic physiologi-
cal effects of nitro substituted aromatic compounds and this process waste
stream is classified as a hazardous waste stream discharged to land. It is
believed that the Federal Water Pollution Control Act Amendment will require
the removal of the nitrobenzene currently discharged in washer waste water
to industrial outfall .
l-Chloro-4-Nitrobenzene SIC 28651^24' 27^
Estimated production capacity for l-chloro-4-m'trobenzene is approxi-
mately 52,000 metric tons (118 million pounds) per year. There were two
(3)
major producers reported in 1972V ': E. I. duPont de Nemours and Company,
Inc., and the Monsanto Company. Typical plant capacities are in the
10,000 to 40,000 metric ton per year range. The product is basically an
5-7
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intermediate used for the manufacture of such chemicals as p-nitro-aniline,
p-anisidine and 3,4-dichloro-l-nitro benzene; these are, in turn, used as
intermediates in the manufacture of dyes, drugs, pesticides and
photochemicals.
The reaction involves a simple nitration using sulfuric acid as the
solvent for trichlorobenzene and the nitric acid. Two major competing reac-
tions take place in the ratio shown:
2
CCHCC1 + HNO
H0SO, P - W°2C1 + H2° 65%
'65 U3 40-70°C
o - CHN0C1 + H0 34%
Overall reaction yields are above 98 percent. The major cost element in
the production of the desired para-isomer is separation from the ortho-
isomer (which is recovered as a by-product, for other in-plant uses). Man-
ufacture follows the flow diagram shown in Figure 5-3.
Chlorobenzene is reacted with mixed acid in a jacketed, agitated,
cooling-coil equipped nitration kettle. Reaction takes place (in batch
processes) over time intervals that range up to 9 hours. The charge is
allowed to settle after reaction, and the spent acid layer is sent to the
sulfuric acid plant for regeneration and rinse. The upper layer or mixture
of crude chloronitrobenzenes, is washed with dilute sodium carbonate solu-
tion and vacuum dried. The mixture of chloronitrobenzenes is subjected to
fractional crystallization and vacuum distillation to effect separation
into ortho, meta and para (1,2-, 1,3-, and 1,4-) isomers . The tars and
residues are concentrated in the residues from vacuum distillation for pur-
ification of the l-chloro-2-nitrobenzene. These are composed of polyaro-
matic tars and unknown nitro substituted aromatic polymers (estimated at
about 0.172 kg/kg of product l-chloro-4-nitrobenzene). The polyaromatic
tars and nitro substituted aromatic polymers are considered hazardous com-
ponents on the basis of the physiological effects of these classes of mate-
rial. This process waste stream is, therefore, considered a hazardous
waste stream to land disposal, with moderately dangerous components.
5-9
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Chlorinated Solvents (Chloromethanes) SIC 28692^21)
United States total production for the Chloromethanes in 1973 was as
follows:^
Carbon tetrachloride 517,000 metric tons (1,047 million pounds)
Chloroform 115,000 metric tons (253 million pounds)
Methyl chloride 247,000 metric tons (544 million pounds)
Dichloromethane 236,000 metric tons (520 million pounds)
There were 12 major manufacturers reported^ ': Allied Chemical, Continen-
tal Oil Company, Diamond Shamrock, Dow Corning Corporation, Dow Chemical
Company, Vulcan Materials Company, FMC Corporation, E. I. duPont de Nemours
and Company, Inc., PPG Industries, Inc., Stauffer Chemical Company, and
Union Carbide Corporation. One typical plant has a production capacity of
close to 50,000 metric tons per year of the various Chloromethanes. The
proportion of each produced is a function of sales demand. There are seve-
ral major processes employed using chlorine, methane or methanol as
feedstocks.
Figure 5-4 presents a flow diagram for a hypothetical typical plant
using methanol and chlorine as raw materials. During start-up operation
(not shown), the plant uses an external supply of HC1 to react with metha-
nol to produce methyl chloride. Subsequent to start-up, the plant gener-
ates the hydrogen chloride needed for the conversion of methanol to methyl
chloride via the reaction of chlorine with methyl chloride and methyl
chloride's chlorination products recycled from the various purification
towers.
The reactions taking place concurrently in the thermal chlorination
reactor are:
CH3C1 +
CH2C12
CHC13
ci2 —
+ ci2 —
+ ci2_
-+ CH2C12 -
— v CHC13 -
— v CC14 4
^ HC1
i- HC1
HC1
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The system produces an excess of hydrogen chloride over that required in
the second reactor of Figure 5-4 to produce methyl chloride from methanol :
CH3OH + HC1 Liquidise' CH3C1 + H2°
The excess hydrogen chloride is separated, dried, compressed and sold as
anhydrous HC1 .
The methyl chloride vapor phase produced in the second reactor is
quenched, washed with caustic soda solution to remove traces of hydrogen
chloride, and dried with sulfuric acid prior to transfer as liquid to prod-
uct storage. The weak acid produced in the quench tower may be fortified
with hydrogen chloride gas and sold as commercial hydrochloric acid. The
spent caustic soda solution and spent sulfuric acid "bleeds" are neutral-
ized and discharged through an industrial outfall.
The mixed chloromethane cuts from the thermal chlorination reactor,
after separation of hydrogen chloride, are fractionated to recover the
chlorinated hydrocarbon solvents. A portion of the methyl chloride, methyl-
ene chloride, and chloroform cuts from the fractionation towers is recycled.
The remainder is sent to storage as product. The carbon tetrachloride after
rectification goes to storage as product. The heavy ends, composed of
higher chlorinated hydrocarbons (predominantly crude hexachlorobenzene and
hexachlorobutadiene) , are the distillation residues from the carbon tetra-
chloride tower. These wastes (0.006 kg/kg product) are sent to land dis-
posal. Due to the toxicity of the hexachlorobenzene and hexachlorobutadiene
(both rated as highly dangerous), the stream is considered to be a hazardous
waste.
Chlorobenzene SIC ^4> 25'
Monochlorobenzene production in the United States during 1973 was
approximately 180,000 metric tons (397 million pounds)^ . The majority of
this production was used as the starting material for other compounds. The
(3)
major manufacturers reportedv ' were Allied Chemical Corporation, Dow Chem-
ical Company, Dover Chemical Corporation, Hooker Chemical Corporation, the
Monsanto Company, Montrose Chemical Company, PPG Industries, Inc., and
Standard Chlorine of Delaware, Inc. Both batch and continuous processes
are employed, with conditions varied based on the percentages of mono- and
5-13
-------
di-chloroberizenes required. A typical plant has a capacity of 32,000 metric
tons (70 million pounds) per year.
Figure 5-5 presents a flow diagram for a hypothetical typical batch
plant, selected as representative of older plants operating in 1973.* Iron
turnings, retained in the glass-lined reaction kettle, are used to catalyze
the reaction in the vessel between liquid phase dry benzene and gaseous
chlorine, bubbled in at a rate which maintains a temperature of about 50°C.
The product manufactured varies with the quantity of chlorine added to the
reactors; for monochlorobenzene only, the chlorination is stopped when
60 percent of the theoretical chlorine requirements have been charged to
the kettle.
The hydrogen chloride produced is scrubbed with benzene or chloroben-
zene to remove entrained organics, and absorbed in water to produce commer-
cial grade hydrochloric acid. The vent gas from the absorber/scrubber con-
tains a low amount of residual HC1 .
The product crude chlorobenzene from the reactor kettle is agitated in
a steam-jacketed neutral izer with warm dilute (10 percent) sodium hydroxide
solution to remove residual acidity. After neutralization, the chloroben-
zene is settled in a separator. The bulk of the dichlorobenzenes settle out
in a sludge which is sent to recovery by distillation. The supernatant liq-
uor from the separator is distilled and separated into several fractions,
which are in turn sent to batch fractionating towers for recovery of ben-
zene, monochlorobenzene and dichlorobenzene. The distillation residues dis-
charged from the fractionating columns contained about 0.044 kg of poly-
chlorinated aromatic resinous materials per kilogram of monochlorobenzene
product. These were discharged to land disposal. Because of the toxicity
and bioaccumulation characteristics of the polychlorinated aromatic compo-
nents, the waste stream is considered hazardous.
Ethyl Chloride SIC 28692^22' 25' 27' 30^
Ethyl chloride production in the United States during 1973 totaled
299,000 metric tonsv '. Of this quantity, approximately 128,000 metric
tons were sold . Three-fourths of ethyl chloride production is normally
^Proprietary information protection considerations and the nonavailability
of data precluded the selection of the continuous process facility.
5-14
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(27}
used for the manufacture of tetra-ethyl leadv . There are seven companies
(American Chemical Corporation, Dow Chemical Company, E. I. duPcnt de
Nemours and Company, Inc., Hercules, Inc., PPG Industries, Inc., Shell Chem-
ical Company Division of Shell Oil Company, and Ethyl Corporation) listed
as najor manufacturers. A typical process line size is 90,000 metric tons
(200 million pounds) of ethyl chloride production per year.
A continuous hydrochlorination process (presented in Figure 5-6) account-
(27 30)
ed for about 88 percent of productionv ' ' in 1973. Anhydrous hydrogen
chloride, in the presence of aluminum chloride, reacts with ethylene in
both liquid and vapor phases to give 90 to 95 percent yields of ethyl
(22 30)
chloridev ' . The yield of polychloro compounds is reduced by the
addition of ethylene dichloride to the reaction mixture^ . The chemistry
of the reaction is:
A1C13
C2H4 + HC1 I5-4QOC' C2H5C1
In addition to ethyl chloride, the reaction produces a hydropolymer oil by-
product (0.02 kg per kg of ethyl chloride) from the separator, chlorinated
hydrocarbon tails (0.093 kg per kg of ethyl chloride) from the fractionat-
ing column, and spent catalyst from the reactor. The spent catalyst is
regenerated and recycled. The by-product hydropolymer oil is sold. The
fractionating column tails are sent to chlorinated solvent manufacture;
they are composed of 3 percent ethyl chloride, 22 percent dichloroethanes,
32 percent trichloroethylene, and 43 percent heavy chlorinated organics.
While there are, apparently, no process wastes sent directly to land
disposal as a result of ethyl chloride production, a process waste is sent
to land disposal from the chlorinated solvent production facility asso-
ciated with ethyl chloride production. The "heavy chlorinated organics"
portion of the fractionating column wastes sent to the plant site's chlori-
nated solvent process line is discharged as a part of the solvent process
(22)
line distillation residues sent to land disposal. ' These distillation
residues are mixed heavy chlorinated hydrocarbons (77 percent hexachloro-
butadiene, 7 percent chlorobenzenes, 3 percent chloroethanes, 3 percent
chlorobutadienes, 7 percent tars and residues). These wastes constitute a
hazardous waste stream because of the toxicity and bioaccumulability of the
hexachlorobutadiene, chlorobenzene, and chloroethane components.
5-16
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Epichlorohydrin SIC 28692^20' 25>
Estimated 1974 active capacity for the production of epichlorohydrin
(l-ch!oro-2,3-epoxy propane) was 225,000 metric tons (495 million pounds)
per year. Major uses of epichlorohydrin include the manufacture of epoxy
resins and glycerin manufacture. There were two active producers report-
(3)
ed : Dow Chemical Company and Shell Chemical Company (a division of
Shell Oil Company). Plant sizes ranged from 27,000 to 125,000 metric tons
per year for the three producing plants. The typical plant size selected
was 75,000 metric tons per year.
The major process used for the manufacture of epichlorohydrin is shown
in Figure 5-7. Ally! chloride, chlorine, and slaked lime are the major raw
materials. Yields based on allyl chloride consumption are between 85 and
90 percent. There are two steps in the chemistry of the process. The
first is chlorohydroxylation of ally! chloride to dichlorohydrin:
C1CH2— CH=CH2 + HOC1 30_4QOc > C1CH2— CHC1— CH2OH
The second reaction is the conversion of dichlorohydrin to epichlorohydrin
(dehydrochlorination and epoxide formation):
2C1CH2— CHC1— CH2OH + Ca(OH)2 60_7QOc > 2C1CH2— CH-Ch? + CaCl2 + 2H20
0
Allyl chloride is fed continuously to a stirred tank where it reacts at
atmospheric pressure at 30-40°C in the liquid phase with a solution of
hypochlorous acid. The hypochlorous acid is produced in a packed tower by
dissolving chlorine in water. The reaction tank effluent is fed to a sep-
arator; the upper layer (aqueous phase) is recycled to the hypochlorous
acid tower. The underflow, chiefly dichlorohydrins, is fed to the second
agitated reactor, where virtually quantitative conversion to epichlorohydrin
by reaction with lime slurry takes place. Trichloropropane is used as a
solvent for the epichlorohydrin. The effluent from the second reactor is
steam stripped, removing epichlorohydrin as the water azeotrope. The under-
cut (calcium chloride solution, and the excess lime, in suspension) is sent
to by-product recovery, or discharged through an industrial outfall. The
distillate's water and organic phases are separated, with the undercut fed
to a fractionating tower for recovery of epichlorohydrin and solvent. The
5-18
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purified epichlorohydrin cut is sent to storage. The recovered solvent is
recycled.
The small amount of dichlorohydrins carried over from the steam strip-
per in the epichlorohydrin-water azeotrope is largely discharged in the
water phase from the second separator. The heavy ends discharged as still
bottoms from the fractionator contain some epichlorohydrin, 10 percent
dichloropropanol , 14 percent chloroethers, and 70 percent trichloropropane
in the 0.053 kg/kg product discharged to land. The heavy ends constitute a
hazardous waste discharge to land disposal; the constituents are currently
rated as moderately dangerous.
Ethanol amines SIC 28692^21' 25^
The three ethanolamines —mono-, di-, and triethanolamine —had a total
reported 1973 production^ ' of 133,000 metric tons (293 million pounds).
Monoethanolamine (MEA) production was 40,000 metric tons. The major manu-
facturers of MEA were Dow Chemical Company, Glyco Chemicals Incorporated,
Jefferson Chemical Company, Koch Chemical Company, 01 in Corporation, and
Union Carbide Corporation; with the exception of Glyco Chemicals Incorpo-
rated these companies were also major manufacturers of diethanolamine (DEA)
and triethanolamine (TEA). DEA production in 1973 was 48,000 metric tons;
TEA production for the same year was 45,000 metric tons. A typical plant
size is 14,000 metric tons per year.
The ethanolamines are made by reacting ethyl ene oxide and excess
ammonia. Yields are generally of the order of 80 percent, based on ethyl ene
oxide conversion to ethanolamines. A hypothetical typical plant flow dia-
gram is presented in Figure 5-8. Ethylene oxide, aqueous ammonia solution,
and recycled amines are fed continuously to a reactor. Ammonolysis of the
ethyl ene oxide takes place exothermally. The ratio of MEA, DEA and TEA
formed is dependent upon the ratio of the reactants. The reactions taking
place concurrently are:
MEA
DEA
TEA
5-20
CHo— CH9 H
V
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The reactor effluent is stripped of its excess ammonia in the ammonia
stripper. The overhead (excess ammonia) from the stripper, plus make-up
ammonia, is fed to an absorber for the production of the aqueous ammonia
fed to the reactor.
The ethanolamines are recovered from the bottoms of the ammonia strip-
per by evaporation of the water, followed by drying in a drying
column. The water evaporated is condensed and used as feed to the ammonia
absorber. The dried ethanolamines are fractionated in a product distilla-
tion train to produce recycle amines, product MEA, DEA, and TEA, and
rejected high boiling distillation residues.
The rejected distillation residues from the TEA column are estimated
to be 0.08 kg per kg of product, and contain equal amounts of TEA and tars
of unknown composition. The distillation residues are considered a hazard-
ous waste stream due to their moderately dangerous amine and tar components,
and are discharged to land disposal.
Furfural SIC 28692^' 24^
Furfural (2-furaldehyde) currently has only one major manufacturer
(the Quaker Oats Companyr . Capacity for furfural in 1974 was estimated
as 68,000 metric tons per year^ '. Typical plant capacity is estimated at
35,000 metric tons per year. The production of furfural, as presented in
Figure 5-9, is dependent upon the hydrolysis of the pentosans present in
corncobs, rice hulls, cottonseed bran, and oat hulls. The reaction, with
xylose as an example, is as follows:
5-10% HySQ. HC—CH
HOCH?— (CHOH),— CHO irn 17fLr " II II + 3H0
t J luU-l/CM, HC C
\l
0
The reaction is carried out, batchwise, in rotating digesters, under steam
q p
pressures of 4.5 - 7.9 x 10 newton/meter (50-100 psig) for approximately
2 hours. The steam distilled furfural is further purified by fractional
distillation. Methanol is produced and sold as a by-product. The stripped
hulls are burned as an energy source or sold as a by-product for use as a
fertilizer conditioner. Wastes to land include still bottoms (0.5 kg tars
and polymers/kg furfural and 0.06 kg sulfuric acid/kg furfural) and filter
5-22
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solids (0.005 kg fines and participates from stripped hulls/kg furfural).
The tars and polymers, because of their furfural content, are presumed to
be a hazardous waste.
^32)
Benzoyl Peroxide SIC 28691
Benzoyl peroxide was for a long period of time the most important
industrial aromatic diacyl peroxide. Production in 1973 was 4,000 metric
tons' '. Manufacturers included Dart Industries (Aztec Chemicals Division),
Noury Chemical Corporation, Norac Company, Inc. (Mathe Chemical Company
Division), Reichhold Chemicals Inc., Witco Chemical Company, Inc., and
PennwaK Corporation (Lucidol Division). Typical plant capacities are
estimated to range from 500 metric tons (1.1 million pounds) to 2,000 metric
tons (4.4 million pounds) per year. The product has been known to be explo-
sive when subject to fire/thermal shock.
Benzoyl peroxide (Figure 5-10) is produced by the step condensation of
benzoyl chloride with hydrogen peroxide to yield perbenzoic acid, which
reacts further with benzoyl chloride to yield benzoyl peroxide. The hydro-
gen chloride formed is continuously removed by in-situ reaction with 50 per-
cent sodium hydroxide solution, shifting the equilibrium in favor of the
benzoyl peroxide. The reactions are:
0 0
/~V_c__d + H202 + NaOH *• /~\-C— 0—0—H + NaCl + H20
0 0
all A \ II
C—0—0—H + ( VC —C1 + NaOH
+ NaCl + H20
The product is removed by centrifuging and is washed, stored wet, or pack-
aged after drying.
The major waste stream is wastewater which includes backwash, and is
lagooned, skimmed, and sent to water treatment. The excess sodium hydroxide
(0.07 kg/kg product) and the sodium chloride reaction product (0.48 kg/kg
5-24
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product) constitute the bulk of the process waste; residual hydrogen
peroxide (0.03 kg/kg product) and benzole acid and other aromatic compounds
(0.01 kg/kg product) are the minor portions of the process wastes. The
Federal Water Pollution Control Act Amendments will require that the ben-
zoic acid and other aromatic compounds be removed from the waste stream
prior to discharge to receiving water courses or municipal sewer systems.
The solids separated as sludges in the lagoons are treated by biological
sludge digestion, and the residues are incinerated.
Pyridines (2-Methyl, 5-Ethyl Pyridine and g-Picoline) SIC 28651^23> 25' 34^
Because of increased demands which could not be satisfied by pyridines/
pyridine bases produced from the coking process, commercial production of
these compounds by synthesis has increased sharply. Total capacity in 1973
was about 18,000 metric tons (40 million pounds). The major producer of
methyl ethyl pyridine (MEP) and a-picoline was the Union Carbide Corpora-
tion; other producers of a-picoline included Koppers Company, Inc., Nepara
Chemical Company, Inc., and Reilly Tar and Chemical Corporation. The type
of plant shown in Figure 5-11 accounted for over 50 percent of synthetic
pyridines production. Typical plant capacity was 35,000 metric tons/year.
Paraldehyde and ammonia are reacted in the presence of an aluminum oxide
catalyst and ammonium acetate to give yields in the range of 70 percent of
pyridine compounds — mainly 2-methyl, 5-ethyl pyridine, containing
about 10 percent a-picoline (methyl pyridine). The two concurrent reac-
tions are:
4 23 /^-CH2CH3 + 4H20
3 ^"a^'S ' m'3 NH4(CH3C02) H
3 n
2-methyl, 5-ethyl pyridine
and:
_ lru run\ 4. MU —« >• (i ^^ "*" 3HoO + CH^CHoOH
T ^n^unu;7 f INH^ MU ^ru PQ j || I ^ o t
' 2 H3C~^N^
2-methyl pyridine (a-picoline)
5-26
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The paraldehyde used as raw material is produced at the plant site by
polymerizing acetaldehyde with an acid catalyst:
H2SO.
3CH3CHO > (CH3CHO)3
Overall, the manufacturing process involves polymerizing acetaldehyde to
the trimer, and then feeding ammonia, acetic acid and preheated crude par-
aldehyde to the reactor. The reactor effluent is fed to an ammonia strip-
ping tower for recovery and recycle of unreacted ammonia. The stripped
mixture is separated in a decanter into an upper layer, containing the
pyridine and by-products, and a lower layer, containing soluble acetates,
amides, and other impurities. The decanted crude "pyridine" is refined in
a batch still. The higher boiling fraction is refined methyl ethyl pyri-
dine. The overhead, composed mainly of picoline, other pyridines, ammonia
and paraldehyde, is distilled again into an overhead cut, stored for fur-
ther recovery of by-products, a recovered benzene fraction, and refined
picolines. The decanter water layer is batch distilled in a stripping
still, with the overhead "cut" going to storage prior to further process-
ing, and the tails constituting the major process waste stream. Other proc-
ess wastes include a very small quantity of still tails from the batch still
used to produce by-product refined paraldehyde, and the methyl sthyl pyri-
dine (MEP) residues from the batch still producing refined MEP.
The stripping still tails quantity is approximately 0.038 kg/kg refined
MEP; the major contaminants are paraldehyde (0.03 kg/kg MEP), sulfuric acid
(0.003 kg/kg MEP), pyridines and picolines (0.0025 kg/kg MEP) and soluble
acetates (0.0025 kg/kg MEP). These constituents currently go to waste
water treatment; they are hazardous components which must be removed from
waste water treatment effluent, as per the Federal Water Pollution Control
Act Amendments. The MEP residues from the refined MEP still are about
0.02 kg/kg MEP product; they are currently fed to the powerhouse as a fuel.
Because of the heterocyclic compounds present, the MEP residues are consid-
ered a hazardous process waste.
Fluorocarbons SIC 28692^25> 35> 36^
The production of fully substituted fluorochloromethanes in the United
States in 1973^ totaled 373,000 metric tons (823 million pounds). Of this
5-28
-------
quantity, 222,000 metric tons was dichlorodlfluoromethane; the remainder
was trichlorofluoromethane. Major manufacturers for both products Included
E. I. duPont de Nemours and Company, Inc., Allied Chemical Corporation,
Kaiser Aluminum and Chemical Corporation, Pennwalt Corporation, Racon, Inc.,
(4)
and Union Carbide Corporation. ' Typical plant sizes ranged to as high
as 80,000 metric tons capacity per year. The fluorocarbons of this series
are used as aerosol propellants, refrigerants, and solvents.
A hypothetical characteristic continuous production system is shown in
Figure 5-12. An initial catalyst charge of antimony trichloride (equiva-
lent to all of the antimony chloride which will be discharged as spent cat-
alyst during the next year of operation) has been placed in the reactor and
chlorinated prior to the start-up. Carbon tetrachloride (both fresh feed
and recycle) and anhydrous hydrogen fluoride are fed continuously to the
reactor system. They react as follows:
CC1. + HF ——> CC13F + HC1 20%
c-,+5
CC14 + 2HF ——> CC12F2 + 2HC1 80%
Other reactions which may take place are:
+5
CC14 + 3HF ——y CC1F3 + 3HC1
and
The crude fluorocarbon product passes through a stripping still, with
hydrogen chloride removed and sent to by-product sales or use, and carbon
tetrachloride bottoms recycled to the reactor. The partially purified
product stream is next stripped of its HF, which is sent to recovery.
The fluorocarbon stream is washed with caustic soda solution to remove
traces of acid and dried with sulfuric acid. The fluorocarbons are then
separated in a fractionating column and sent to storaye.
The sodium hydroxide and sulfuric acid bleed streams are neutralized
and sent to the plant industrial outfall. The spent catalyst is discharged
5-29
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from the reactor of the typical plant twice per year, at the "rate" of
0.00022 kg/kg product. It contains antimony pentachloride, which is con-
sidered a highly dangerous component, and is discharged to the land. Due
to the toxicity of the antimony chloride constituent, the waste discharge
Is deemed hazardous.
Toluene Diisocyanate SIC 28651^20> 23' 25' 36^
Mixed toluene diisocyanates (the 80/20 mixture of toluene-2,4-diiso-
cyanate and toluene-2,6-diisocyanate) production in the United States in
1973' ' was 230,000 metric tons (506 million pounds). The total for all
isocyanic acid derivatives was 395,000 metric tons. The major producers
(3)
of the mixed toluene diisocyanatesv ' in 1973 were Allied Chemical Corpo-
ration (Specialty Chemicals Division), BASF Wyandotte Corporation, E. I.
duPont de Nemours and Company, Inc., General Tire and Rubber Company, Mobay
Chemical Company, 01 in Corporation, Rubicon Chemicals Inc., and Union Car-
bide Corporation. The toluene isocyanates (TDIs) are major intermediates
for the production of the polyurethanes. A typical TDI continuous process
plant capacity is 27,500 metric tons (60 million pounds) per year.
Starting raw materials for the hypothetical typical continuous process
plant flow diagram of Figure 5-13 are a solution of toluene-2,4-diamine (in
mixture with toluene-2,6-diamine) and gaseous phosgene. These compounds
are fed to two jacketed, agitator-equipped reactor kettles, in series,
along with recycled "inert" solvent (in this instance, o-dichlorobenzene
containing dissolved recycled phosgene), where the following reactions take
place:
CH, CH-
+ COC1
2 25-30°C
(Reactor 1)
NH2-HC1
COC12 180-l90°c'
CH3 NHCOC1
NHCOC1
+ 2HC1
(Reactor 2)
NHCOC1
NHCOC1
(Note: For ease of presentation, only the preparation of 2,4-TDI is shown
throughout this text. The 2,6-TDI isomer preparation 1s similar
to the preparation of thp 2,4-TDI.
5-31
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An excess of phosgene is used; the unreacted phosgene and the hydrogen
chloride liberated constitute the major components of the gas stream exit-
ing the second reactor. The reactor exit gas goes to a phosgene recovery/
by-product hydrochloric acid recovery system. Because of the extreme tox-
icity of phosgene, stringent safety measures are used throughout the manu-
facturing process. Degassers, seal pots, vent kettles, scrubbers and flare
towers are used to recover and reuse phosgene, recover/abate hydrogen
chloride discharge, and prevent escape of vent phosgene gases to the
atmosphere.
The phosgene recovered is recycled in solution in recovered solvent
and fed to the first reactor. The by-product hydrochloric acid (2.32 kg
37.5 percent HCl/kg TDI product) is recovered from the gas stream after
removal of the phosgene and is sent to storage or sales. The waste gas
scrubber effluent contains the residual hydrogen chloride (0.025 kg/kg TDI
product) dissolved in water; it is sent to neutralization and then to the
plant industrial outfall.
The conversion to TDI takes place after the reactor liquid has been
fed to the degasser, in accordance with the following reaction:
NHCOC1 (^ ^ NCO
Inert Gas
95-11QOC
NHCOC1
Inert Gas^ | | A 2HC1 j
An inert gas (natural gas) is blown through the solution to "degas" the
evolved HC1. The degasser vent gas is sent to the "phosgene and HC1 recov-
ery system", where the HC1, as noted above, is recovered as by-product
hydrochloric acid, and the natural gas is recycled to the vent gas
compressor.
The crude solution of TDI's from the degassers is fed to the stills
and evaporators to recover solvent and purify the TDI's. The purified TDI
is sent to storage. The recovered solvent is recycled for use in recovery
of phosgene and as a solvent for the toluene diamine feed. The evaporator
residue is processed and centrifuged; the centrifugate is recovered TDI
which is sent to storage, and the centrifuge residue is a process waste
5-33
-------
sent to land disposal, at the rate of approximately 0.021 kg per kg of TDI
product. The material contains 90 percent polymers and tarry matter, 6 per-
cent ferric chloride (largely from process impurities) and 3 percent waste
isocyanates. It is considered a hazardous waste stream, containing highly
dangerous components (the waste isocyanates).
Vinyl Chloride Monomer SIC 28692^20> 21' 25' 37^
The production rates in 1973 for vinyl chloride monomer (VCM) and for
ethylene dichloride (EDC), the intermediate used in the majority of manu-
facturing processes, were 2,432,000 metric tons (5,351 million pounds) and
4,215,000 metric tons (9,293 million pounds)'3^. In 1973 there were ten
major producers^ . Allied Chemical Corporation (Specialty Chemicals Divi-
sion), American Chemical Company, B. F. Goodrich Company (B. F. Goodrich
Chemical Company Division), Continental Oil Company, Dow Chemical Company,
Tenneco Chemicals Incorporated, Monochem Incorporated, PPG Industries, Inc.,
Shell Oil Company (Shell Chemical Company Division) and Ethyl Corporation.
A typical plant size can produce 136,000 metric tons per year. Plant capac-
ities ranged from 27,000 metric tons to 317,500 metric tons per year for the
(21)
major process system employed/ '
The process flow diagram of Figure 5-14 is a composite typical opera-
tion for the production of vinyl chloride from ethylene and chlorine. Eth-
ylene dichloride is produced continuously by the liquid phase catalyzed
addition chlorination reaction between ethylene and chlorine, fed as gaseous
reactants to a pressurized vessel. The reaction which takes place is:
FeCK
H2C=CH2 + C12 0J ' C1H2C—CH2C1 (EDC)
I UU \s
The catalyst employed is ferric chloride suspended in liquid ethylene di-
chloride. The product ethylene dichloride is liquefied, scrubbed with
dilute caustic soda solution, filtered and distilled. The heavy ends from
the still (0.0104 kg per kg product VCM) are a hazardous process waste sent
to land disposal. The heavy ends contain highly dangerous components -
ethylene dichloride (23 percent), 1,1,2-trichloroethane (38 percent) and
tetrachloroethane (38 percent) -which are bioaccumulative.
5-34
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VENT ON REFLUX CONDENSOR (GAS)
ETHANE 0.0049
ETHYLENE DICHLORIOE 0-012
METHANE 0.0049
®
HEAVY ENDS
ETHYLENE OICHLORIDE 0.0024
1,1,2 TRICHLOROETriAHE 0.004
TETRACHLOROETIIA.JE 0.004
TARS TRACE
TO AIR
TO LA;JO
HEAVY ENDS
HEAVY ENDS 0.037
ETHYLENE DICHLORIDE 0.0008
TARS 0.00005
SOLIDS ASH 0.0002
TO LAND
Figure 5-14. Vinyl Chloride Monomer Manufacture (Continued)
5-36
-------
The purified EDC from the still is fed to the pyrolysis furnace for
the production of vinyl chloride monomer, in accordance with the following
reaction:
C1CH2CH2C1 ' HC1 + CH=CHC1 (VCM)
The reaction takes place in the vapor phase, at 450-620 x 10 newtons/
n
meter (50-75 psig). The catalysts employed may be activated carbon or
pumice. When mercuric chloride is employed as a catalyst for this reaction,
lower temperatures (450°C) and higher pressures (520-930 x 10^ newtons/
o
meter ) are used. Conversion per pass through the reactor is 50 percent;
with recycle, the reactor pyrolysis yield is 95 to 96 percent.
The product gas stream from the furnace, containing VCM, EDC and HC1 ,
is quenched with recycled liquid EDC and condensed. The hydrogen chloride
is separated in the condenser since it remains (as the sole constituent) in
the gas phase, and is sent to recovery or to use in an oxychlorination
unit for the production of EDC by reaction with ethylene.
The liquid effluent from the condenser is sent to a still where it is
separated into VCM product, recycle EDC, and heavy ends (about 0.038 kg/kg
VCM product). The heavy ends are a hazardous process waste sent to land
disposal. In this case they are composed of 97 percent higher halogenated
hydrocarbons, 2 percent EDC and 1 percent tars, and are considered highly
dangerous. When mercuric chloride is used as catalyst, there is also a
discharge of mercuric "hydroxide" (hydrated oxide) to land in the filter
solids, estimated at 5 x 10~6 kg/kg VCM.
Methyl Methacrylate Monomer SIC 28692^°' 37^
Production reported for methyl methacrylate monomer in 1973 was
(3)
320,000 metric tons (706 million pounds). The major producers were
American Cyanamid Company, E. I. duPont de Nemours and Company, and Rohm
and Haas Company. Virtually all of the production was converted to polymer.
A typical plant size for the production of monomer is 55,000 metric
tons per year.
5-37
-------
All of the methyl methacrylate produced commercially in the United
States is based upon the use of acetone, hydrogen cyanide and methanol as
raw materials in the acetone cyanohydrin process. The flow diagram of
Figure 5-15 presents a typical production flow based on the acetone cyano-
hydrin process used for commercial production in this country. Acetone
cyanohydrin is produced from the acetone and hydrogen cyanide fed continu-
ously to the cyanohydrin reactor in accordance with the following reaction:
CH3COCH3 + HCN NaQH> (CH3)2C(OH)CN
Sodium hydroxide is employed as the alkaline catalyst in a cooled reaction
kettle. The excess base is neutralized in the reactor effluent stream with
sulfuric acid. Sodium sulfate crystallizes from the neutralized crude ace-
tone cyanohydrin stream and is removed by filtration. The sodium sulfate,
after washing, is sent to land disposal (0.1 kg/kg product). The crude
acetone cyanohydrin is fed to a two-stage distillation unit for concentra-
tion. The acetone and water overhead of the first still are recycled to
the cyanohydrin reactor, and the rest of the water is removed from the
cyanohydrin in the second still.
The acetone cyanohydrin is then blended with concentrated sulfuric
acid in a cooled hydrolysis kettle, and heated after blending to form
methacryl amide sulfate:
(CH3)2C(OH)CN + H2S04 125.155oc'
CH3 0
H2C NH4S04
The effluent from the hydrolysis kettle is reacted continuously with metha-
nol in an esterification column to produce methyl methacrylate:
CH, 0 CH, 0
\ II \ II
C— C + CH3OH - »> C— C-0-CH3
Inhibitors, such as hydroquinone, are added during the process to prevent
polymerization.
5-38
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The esterification column effluent is transferred continuously to the
acid stripper column, where the stream is split into an overhead containing
crude methyl methacrylate, methanol and water, and an acid residue. The
acid residue, on a water-free basis, is about 2.28 kg per kg of product
methyl methacrylate; it contains (water-free basis) 55 percent ammonium
acid sulfate, 42 percent residual sulfuric acid, and 3 percent "organics"
(ammonium methacrylate, methanol, polymers and ammonium cyanide). It con-
stitutes a hazardous process waste which is either sent to a recovery unit
(37)
or discharged to sewer.v '
The recovery unit is either an ammonium sulfate recovery plant (where
the majority of the organics present are adsorbed on the crystals of ammo-
nium sulfate produced) or a spent sulfuric acid recovery plant. The spent
sulfuric acid recovery plant would be required to operate a pyrolysis unit
at temperatures over 1000°C, decomposing the organics and the ammonium com-
pounds to give a gas stream containing S02, C02, N2, H20 and 02. The gas
stream would be dried and "converted" to S03 and then to H2$04 for reuse.
The overhead from the acid stripper column is distilled in the "metha-
nol recovery" column. Methyl methacrylate containing some methanol is
taken off as a mid-cut; the overhead cut is methanol which is recycled to
the rectifier. The bottoms from this column are about 0.086 kg/kg product
and constitute a hazardous waste stream to land disposal containing 87 per-
cent polymers and 13 percent hydroquinone.
The mid-cut of crude methyl methacrylate is stripped of its last
traces of methanol by water extraction. The water-methanol extract is
cycled to the methanol recovery column. The washed monomer is distilled to
yield dry methyl methacrylate product. The light ends from the first rerun
column (about 0.029 kg/kg product) go to the plant industrial outfall.
They contain hazardous components whose removal via land-based treatment
techniques would be required by the Federal Water Pollution Control Act
Amendments. The hazardous components would be destined for land disposal.
Acrylonltrile SIC 28692(20> 21'
Production of acrylonitrile in the United States during 1973 was
(3)
614,000 metric tons (1,354 million pounds). ' The major producers were:
American Cyanamid Company, B. F. Goodrich Company (B. F. Goodrich Chemical
5-41
-------
Company Division), the duPont Company, the Monsanto Company, and Vistron
Corporation (Standard Oil Company of Ohio)/ ' The major part of the acryl-
onitrile produced is used in the manufacture of synthetic fibers, in acrylo-
nitrile plastics, and in cyanoethylation of cotton to improve its wear and
life characteristics.
The Sohio process presented in Figure 5-16 is used for production of
acrylonitrile by more than 35 plants throughout the world. Aggregate pro-
duction by this process worldwide exceeds 1,360,000 metric tons. Typical
production lines range in size from 4,500 metric tons to about 160,000 met-
ric tons per year.
Propylene, fertilizer grade anhydrous ammonia, and air are fed continu-
ously to a fluid bed catalytic reactor operating at relative low pressure
(138 to 310 kilonewtons per square meter or 20 to 45 pounds per square inch)
and temperatures between 400 and 510°C, (752 and 950°F).
The catalyst used currently is a solid antimony-uranium oxide mixture;
older plants use a 50-60 percent bismuth phosphomolybdate catalyst on sil-
ica. In the vapor phase, a number of concurrent reactions take place, pro-
ducing acrylonitrile, hydrogen cyanide, acetonitrile, water, carbon monox-
ide, and propane as major products. These may be summarized as follows:
4H2C=CHCH3 + 4NH3 + 502
CH2=CHCN + C3Hg + 2CH3CN + 9H20 + CO + HCN
Heat is absorbed from the highly exothermic reaction by generating high
pressure steam from boiler feedwater. Steam may also be added to the reac-
tor as a diluent. The reactor effluent is scrubbed with water in a counter-
current absorber. The off-gas from the absorber contains, as major impuri-
ties, carbon monoxide, propylene and propane, with a lesser quantity of
acrylonitrile, and traces of ammonia and acetonitrile; it is flared as a
safety measure. The water solution of organic materials (acrylonitrile,
acetonitrile, hydrogen cyanide, and heavy ends) goes to an acrylonitrile
recovery column where wet acrylonitrile-hydrogen cyanide is taken off as an
overhead stream. Acetonitrile bottoms from the column are purified by dis-
tillation. The bottoms from the first acetonitrile purification distillation
5-42
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step consist mainly of water with some acetonitrile (0.002 kg per kg product
acrylonitrile). The overhead from the second acetonitrile purification dis-
tillation (not shown in the flow diagram) contains about 0.001 kg hydrogen
cyanide per kg of acrylonitrile product and is flared as a safety measure.
About 0.015 kg of acetonitrile per kg acrylonitrile is recovered for sales
or in-plant use. The bottoms from the second acetonitrile distillation col-
umn are heavy ends (about 0.003 kg per kg of product acrylonitrile) which
are probably nitrile polymers, and constitute a hazardous process waste dis-
charge to land.
The wet acrylonitrile-hydrogen cyanide overhead from the acrylonitrile
recovery column is separated by fractional distillation into a crude HCN
overhead and a crude acrylonitrile higher boiling cut. The crude HCN is
sent to HCN recovery where about 0.10 kg of hydrogen cyanide per pound of
product acrylonitrile is recovered for by-product sales or in-plant use.
The light impurities from HCN recovery are low in quantity and are flared.
The higher boiling cut of crude acrylonitrile is purified by distilla-
tion to produce specification grade product and heavy impurity bottoms.
The heavy bottoms (0.002 kg per kg acrylonitrile) are probably higher mole-
cular weight nitriles and polymers and are a hazardous process waste sent
to land disposal.
Maleic Anhydride SIC 28692^°' 21» 25^
Maleic anhydride production in the United States during 1973 was
128,000 metric tons (282 million pounds). ' The seven manufacturers in
1973^ were Allied Chemical Corporation (Specialty Chemicals Division)*,
Tenneco Chemicals Incorporated, Koppers Company Incorporated (Organic Mate-
rials Division), the Monsanto Company, Petro-Tex Chemical, Reichhold Chemi-
cals, Incorporated, and USS Chemicals Division of U.S. Steel Corporation.
Typical plant sizes ranged from 9,000 to 13,600 metric tons per year.
The process flow diagram for the manufacture of maleic anhydride shown
in Figure 5-17 is based on the vapor phase catalytic oxidation of benzene
with air, at pressures of 300-400 kilonewtons per square meter (43.5 to 58.0
pounds per square inch). Reactor temperatures are maintained at 400 to
450°C by the use of fused salt cooler with molten salt circulation to produce
''No longer a manufacturer.
5-44
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5-45
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high pressure steam. The reaction utilizes a solid vanadium pentoxide cata-
lyst supported on an inert porous carried (diatomaceous earth) and is
extremely exothermic. It is as follows:
C6H6 * 402
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The overall yield of maleic anhydride is approximately 67 percent. The hot
reaction gases are cooled and the crude maleic anhydride is partially con-
densed. The remaining gases, containing 40-50 percent of the maleic anhy-
dride, are passed through a waste gas scrubber where virtually all of the
maleic anhydride is washed out to form a maleic acid solution. The residual
gas is flared.
The crude maleic anhydride and the concentrated maleic acid solution
exiting from a thin film evaporator are continuously dehydrated in the spe-
cial dehydrator to yield a relatively pure maleic anhydride and a residue.
The dehydrator residue is washed and recycled to the concentrator. The
final step taken in purification is to vacuum distill the maleic anhydride
to obtain specification grade product, an overhead water condensate, and
vacuum column bottoms.
The water condensate from the vacuum still overhead contains 0.0006 kg
of maleic anhydride per kg product. The vacuum still bottoms contain in
excess of 0.03 kg of moderately dangerous components (12 percent maleic
anhydride and 88 percent fumaric acid, chromogenic compounds and tars) per
kilogram of product and constitute a hazardous process waste discharge
to land.
Lead Alkyls SIC 28692^22> 25' 37"39^
Tetraethyl lead (TEL) production in the United States during 1973 was
(3)
160,000 metric tons (353 million pounds).v ' There were 346,000 metric
tons of other organo-lead compounds (tetramethyl lead, tetra (methyl-ethyl)
lead) produced. Manufacturers reported^ ' were E. I. duPont de Nemours and
Company, Inc., the Nalco Chemical Company, PPG Industries, Inc., and Ethyl
Corporation. The almost exclusive use for these compounds was as motor fuel
5-46
-------
additives - "anti-knock" fluid for blending with gasoline. Typical lead
alkyl production plant sizes ranged from 18,000 to 100,000 metric tons per
year.
Generally, some version of the 40-year old original batch process is
used to produce TEL from the reaction between ethyl chloride and sodium-
lead alloy. Figure 5-18 presents a composite of typical process flows. A
90:10 weight ratio lead:sodium alloy is prepared in an alloy pot and cooled
under an atmosphere of nitrogen and then charged to an autoclave. An excess
of ethyl chloride is charged to the autoclave reactor, which is equipped
with a reflux condenser. The reaction takes place at 520-525 kilonewtons/
square meter and 65-70°C. It is as follows:
4C2H5C1 + 4PbNa - » 3Pb + 4NaCl + Pb(C2H5)4 (TEL)
Waste hydrocarbons produced by side reactions between the sodium and the
ethyl chloride are discharged to the atmosphere.
The mixture, after completion of the reaction, is fed to a still, where
the TEL is stripped from the lead and sodium chloride. The TEL and water
vapor are condensed and sent to a decanter from which the TEL is withdrawn
as a bottoms stream. The upper layer containing unreacted ethyl chloride
and organic by-products is transported via an open ditch to the next treat-
ment step.
The TEL in the bottoms stream is washed, settled, and blended with
ethylene dichloride (EDC), ethylene dibromide (EDB) and dyes prior to
storage/shipment as product. The salt-containing sludge bottoms from the
still are decanted to separate the bulk of the lead from the solution. The
lead sludge is washed free of sodium chloride, dried, and remelted before
being recycled for reuse. The salt solution, containing some suspended
lead, goes to a sludge pit. The bottoms from the sludge pit are periodi-
cally sent to lead recovery. The overflow from the sludge pit is combined
with the overflow from the TEL decanter. This stream next has sodium car-
bonate solution added and ozone bubbled through to precipitate the remaining
lead. This lead precipitate is separated in a settling basin; it amounts to
0.1 kg of lead precipitate per kg TEL. It is a highly dangerous process
waste discharge (currently recovered in many plants).
5-47
-------
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5-48
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The settling basin overflow is discharged to a process outfall. The
charge to the outfall has 0.007 kg ethyl chloride per kg TEL product, and
an unknown quantity of complex, partially chlorinated organic by-products
as its hazardous components. The Federal Water Pollution Control Act
Amendments will require the removal of these materials, and their disposal
to the land.
g-Chlorotoluene SIC 28651^25> 27^
Total United States production of a-chlorotoluene (benzyl chloride) in
1972 was 36,500 metric tons (80 million pounds). ' There were only three
known manufacturers in 1972: Stauffer Chemical Company (Specialty Products
Division), Monsanto Company, and Velsicol Chemical Corporation. Typical
process facility sizes are estimated to range in capacity from 10,000 to
15,000 metric tons per year. The material is used as an intermediate for
the manufacture of plasticizer (butyl benzyl phthalate) and as a benzylating
agent.
Figure 5-19 presents a typical process flow diagram for the manufacture
of a-chlorotoluene. Dry chlorine reacts with an excess of refluxing toluene
in a glass-lined reactor kettle, as follows:
Cl,
> HC1 + C6H5CH2C1 (a-chlorotoluene)
The hydrogen chloride produced comes off as an overhead from the condenser
and is sent to by-product recovery.
The excess of toluene is removed from the benzyl chloride in a frac-
tionating column and recycled. The undercut, crude benzyl chloride, is dis-
tilled to produce the refined product and a bottom cut. The still bottoms are
a hazardous process waste discharge to land disposal and contain 0.001 kg of
highly dangerous components (benzyl chloride and benzotrichloride) per kg of
product benzyl chloride.
Methylene Chloride SIC 28692^°' 25"28^
Methylene chloride (dichloromethane) production in the United States
/ o}
in 1973 was 236,000 metric tons (520 million pounds)/ ' There were six
major manufacturers: Allied Chemical Corporation (Specialty Chemicals Divi-
sion), Diamond Shamrock Corporation, Dow Chemical Company, E. I. duPont de
5-49
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Nemours and Company, Inc., Vulcan Materials Company (Chemical Division),
and Stauffer Chemical Company (Industrial Division). Major uses are as a
paint remover solvent and aerosol propel 1 ant. The typical production facil-
ity size is 15,000 metric tons per year.
The major process employed for methylene chloride production is the
continuous noncatalytic chlorination of methane-methyl chloride mixture.
Figure 5-20 presents a typical process flow diagram. Gaseous methane,
chlorine, and a recycled stream of methyl chloride are preheated and fed
to a reactor equipped with mercury arc lamps. Residence times in the reac-
tor are controlled to maintain a temperature of 447° to 472°C. All of the
chlorine, all of the methyl chloride and about 65 percent of the methane
react. The reactions which take place are:
CH4 + C12 »• HC1 + CH3C1 (Methyl chloride)
CH3C1 + C12 »• HC1 + CH2C12 (Methylene chloride)
CH2C12 + C12 >• HC1 + CHC13 (Chloroform)
CHC13 + C12 * HC1 + CC14 (Carbon tetrachloride)
The exit gases from the reactor contain unreacted methane in addition to
the chloromethane products shown above. The chloromethanes are separated
from the methane and HC1 by scrubbing the reactor effluent gases with a
mixture of refrigerated liquid chloromethanes whose major constituents are
chloroform and carbon tetrachloride. Methane and HC1 are discharged as
gases and transferred to a water absorber, which produces by-product liquid
hydrochloric acid solution. The gaseous methane is not absorbed, and is
recycled to the reactor.
The chloromethane absorber liquid effluent is fed to a stripper. The
overheads from the stripping column are the methyl chloride and methylene
chloride. These are condensed, washed with hot water to remove residual
HC1, then washed with alkali solution, and finally dried with concentrated
sulfuric acid. Methyl chloride is taken off as the overhead in a fraction-
ation column and recycled. The high boiling fraction is redistilled in an
additional column to yield methylene chloride product and chloroform/carbon
5-51
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tetrachloride bottoms which are recycled for use as solvent in the absorber
or sent to the CHC13-CC14 manufacturing facility.
Process waste discharges include:
• Purge gas to air from the methane recycle system contain-
ing, per kilogram of product methylene chloride,
0.001 kg methane, 0.013 kg methyl chloride, 0.002 kg of
methylene chloride, 0.001 kg of chloroform, and 0.001 kg
of carbon tetrachloride.
• Neutralizer liquid wastes (spent alkali bleed) to the
industrial outfall from the alkali wash tower containing,
per kg of product methylene chloride, 0.00002 kg each
of methyl chloride, methylene chloride, chloroform, car-
bon tetrachloride and perchloroethylene.
• Drying column liquid wastes (spent drying acid bleed) to
the industrial outfall from the drying tower containing,
per kg of product methylene chloride, 0.00003 kg each of
methyl chloride, methylene chloride, chloroform, carbon
tetrachloride and perchloroethylene.
The hydrogen chloride solution coming from the hot water wash tower is
stripped of its chloromethane content and used as feed to the HC1 absorber.
There are no process wastes to land disposal. The Federal Water Pol-
lution Control Act Amendments will require removal of the chlorinated hydro-
carbons currently present in the liquid wastes sent to the industrial
outfall.
1,1.1-Trichloroethane SIC 28692^20> 22^
Production of 1,1,1-trichloroethane (methylchloroform) in 1973 was
just under 250,000 metric tons (548 million pounds). Major producers were
the Dow Chemical Company, Vulcan Materials Company (Chemical Division),
PPG Industries, Inc., and Ethyl Corporation. A typical process line capac-
ity is 18,000 metric tons (40 million pounds) per year.
Figure 5-21 presents a typical process flow diagram for the production
of 1,1,1-trichloroethane from vinyl chloride and chlorine. The process
emits no hazardous wastes to land, currently. Vinyl chloride, make-up
and recycled hydrogen chloride, recycled dichloroethane and recycled
5-53
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trichloroethane are fed to a tower reactor for the catalyzed
hydrochlorination reaction which produces the dichloroethane intermediate:
FeCU
HC1 + CH2=CHC1 35_40oc> C2H4C12 (Dichloroethane)
The dichloroethane cut is taken overhead from the purification column, and
chlorinated in the chlorinator reactor:
C12 + C2H4C12 40Qoc* CH3CC13 + HC1 (1,1,1-Trichloroethane)
The crude trichloroethane, the hydrogen chloride produced, and the excess
dichloroethane are recycled to the hydrochlorination reactor. Product
crude trichloroethane is taken as the high boiling fraction from the puri-
fication column, steam stripped, and distilled to produce 1,1,1-trichloro-
ethane for storage and sales.
5.2.2 Annual Process Stream Discharge to Land Disposa]
The estimated total quantities (dry weight basis) of process waste
streams generated and discharged to land-based disposal in calendar year
1973 for those portions of the organic chemical industry covered in this
study are presented in Table 5-1 by Standard Industrial Classification
product group for each state. Land-based disposal, as used herein, covers
landfill, land burial, deep-well disposal, deep-sea disposal, lagooning
and incineration.
The estimated national total quantity (dry weight basis) of process
waste streams discharged to land-based disposal in 1973 by organic chemical
plants was 2.18 million metric tons.* The majority of these process waste
streams were low in water content or were nonaqueous, based on the sample
of the industry described in Section 6.2. Based on this sample, the high-
water-content process waste streams which went to deep wells, lagoons, and
evaporation ponds constituted only 13 percent of the number of waste
streams sent to land disposal by the organic chemicals industry. The water
content of the wastes sent to deep wells, lagoons, and evaporation ponds
*Includes wastes from technical organic pest control chemical plants, and
thus differs from the figures presented in the Executive Summary.
5-55
-------
Table 5-1.
Total Process Waste Stream* Discharge to Land Disposal,
Metric Tons for CY 1973 by Standard Industrial
Classification,0rganic Chemicals and Technical
Pesticides Industries
EM
B*9_Laa
4
10
9
6
9
6
1
3
3
4
4
9
10
5
5
7
7
j
6
i
j
;
i
7
9
1
2
£
2
4
,,
,
*
-r
,
2
1
4
t
4
6
-,
,
,0
5
VION
-E',10'
"
~7
State
Alabama
Alaska
Arizona
Arkansas
California
Colorado
Connecticut
Delaiure
District of Columbia
Florida.
Gtorola
Ha.a1 <
Idaho
Illinois
Indiana
I ova
Kansas
'entuclu
Louisiana
"aine
"ardamJ
Massachusetts
"icMoar
"innescta
"iSSlSS'COi
"1 ssouri
"on tana
Sebraska
New Hampshire
•.» Jerse,
New Mexico
New lor*
North Carolina
North Da rota
Ohio
OHahora
Puerto Pico
°hode Island
Sojtl- Carolina
South Dakota
Texas
Utah
Washington
•yo-ilng
AL TOTALS
TOTALS
4
a
28610
¥17
#75
5493 -
29610
5493
,
28611
(J214
485
295
6994
28611
6699
295
28612
325
163
2,213
325
3,026
28612
2701
325
28651
12667
1731
14
22,200
9509
1295
1.3
83413
565
.8
1V76
1,288
2/49
37,094
69
27,709
1,160
2?970
7,349
22^11
29600
167471
151
3,634
2,963
9031
483621
28651
1
44512
58400
93476
27445
250884
4044
165
1731
2963 J
28652
51
)1
10
11
101
.4
1571
538
434
115
193
27
138
6
7
34
3,247
28652
128
2109
245
639
115
11
28653
7
3
9
3
217
45
47
12
9
3
46
401
28653
12
262
55
50
15
7
28655
330
46
100
167
183
417
343
46
46
739
46
289
76
12606
77
46
15,557
28655
46
752
506
1478
12606
77
46
46
28691
2
788
197
2
136
337
197
1^12
83
382
5
1023
1559
6,628
28691
5
2000
1.559
«05
721
136
2
28692
54)4
7,928
7394
5734
1474
604
179
¥48
60.232
2689
6830
5,991
2808
10,506
1^378
8597
73B49
ns^oo
10
171,766
1.476.56
28692
17396
260156
292^69
15,275
876032
7009
7928
28693
815
749
5
2
12
503
1691
116
49
940
746
5628
28693
815
2194
795
867
945
12
?8694
35,153
3492
16J53
794
842
93
449
5,395
190
42«5
1524
22/29
255
7514
90
7012 1
6931
9629
1,15'
109
1,732
1.524
407
146
6,432 ..
186S7
18
2,449
52CS
170.953
26694
842
20780
680
49.394
20129
44,906
12/00
794
16753
1 jsg,. ,
2K95
122
122
28695
122
TOTAL
52 2s7
3,492
26,478 '
808
1,657
22,208
26,927
9,178
17,296
977
4.245
2,998
95.262
267,135
1,248
111
27,664
136
8,497
16.522
66,963
6,390
28,299
14,764
1,570
112.295
16,068
35
22.495
210,986
915,504
228
3,669
5,412
163.230
5,208
Z.178,;35
1,803
£9,421
322.642
453,932
66,045
.116.131
73.765
1,043
26.471
6.982
te'-free b<
Industry
isis using the procedures given in Section 3 and Appendix A The data'for the calculations were obtained
irces listed in Table A-l and References 3, 4, 8. 11, 12, 19-49.
5-56
-------
was very high - so high that it raised the ratio between actual tons (wet
basis) and dry basis tons for the entire sample to 3.17. Calculated on the
basis of this ratio, the estimate of the wet-basis weight of the process
waste streams sent to land in 1973 by the organic chemicals industry was
6.9* million metric tons. Analogous estimates of the process wastes which
will be sent to land by the industry in 1977 and 1983 were 11.1* and 12.2*
million metric tons, respectively.
Dry weight of the process waste streams has been used as the basis of
the estimates presented below for the organic chemicals industry.
The major industry product groups which discharge the highest quanti-
ties of process waste streams to the land nationally are:
t SIC 28692, the miscellaneous acyclic chemicals and chem-
ical products group of the industrial organic chemicals
industry, with just under 1.5 million metric tons
t SIC 28651, the cyclic intermediates product group of the
cyclic crudes and intermediates industry, with approxi-
mately 0.5 million metric tons
t SIC 28694 (also covered in Section 5.3), the pesticides
and other synthetic organic agricultural chemicals prod-
uct group of the industrial organic chemicals NEC indus-
try, estimated at slightly less than 0.2 million metric
tons.
SIC 28692 and SIC 28651 combined account for approximately 90 percent of
the total estimate of wastes destined for land disposal from the organic
chemicals industry. These two product groups are, as shown in Table 4-4,
the bellwethers of the industry in production with over 02 percent of the
industry's total. Product group total waste generation factor weighted
averages** are 0.024 kg of process waste to land per kg of production for
SIC 28692, and 0.031 kg of process waste to land per kg of production for
SIC 28651; the industry-wide factor is 0.026.
The states which have the highest total estimated process waste dis-
charge to land are Texas, Tennessee, and West Virginia for SIC 28692, and
*Includes wastes from technical organic pest control chemical plants, and
thus differs from the figures presented in the Executive Summary.
**0btained by dividing the estimated total dry-basis process weight dis-
charge to land for the product group by the estimated total production
rate for the product group (from Table 4-4).
5-57
-------
Texas, Louisiana and New Jersey for SIC 28651. Texas, with its tremendous
concentration of organic chemical industry manufacturing, has almo'st one-
•
half of the total national process waste discharge to land for SIC 28692
and one-third of the national figure for SIC 28651.
The projections for total process waste discharge to land by the
organic chemicals industry in 1977 and 1983 are presented in Tables 5-2 and
5-3. The estimated total process waste discharged to land for the industry
in 1977 goes up by over 67 percent from the 1973 figure. The average total
waste generation factor for the industry rises to 0.039 kg of process waste
per kg of production in 1977. The reason for this increase in the esti-
mated waste discharge to land is the impact projected for the Federal Water
Pollution Control Act Amendments.
Roughly 90 percent of the increase in the "water-free basis" weight of
total process waste stream discharges to land* for the industry is a result
of the following assumption: Land disposal processes will be impievented
in 1977 for those hazardous wastes currently discharged to water whose
presence in industrial outfalls will not be permitted in 1983 by the Fed-
eral Water Pollution Control Act as amended. This is, of course, a worst-
case assumption for 1977; most probably the actual figures will be some-
where between the least impact assumption of only a 10 percent increase
(based on increased production), and the worst-case assumption. There was
no basis available for determining a more realistic number at the time of
this study.
The figures for 1983 reflect the impact of the legal requirements as
amended for 1983, and the much lesser impact of a 21.6 percent increase in
production. The estimated total "dry weight" process waste discharge to
land for the industry in 1983 is 3.9 million tons. The associated process
waste discharge factor is 0.038 kg of waste per kg of production; the
increase here reflects strictly the assumed impact of the enforced removal
of hazardous materials from industrial outfalls.
The manufacture of the SIC 28692 and SIC 28651 product groups will
still provide over 90 percent of the total industry process waste discharged
*As defined for this study, "discharge to the land" includes landfill, land
burial, deep-well disposal, lagooning, and incineration.
5-58
-------
Table 5-2.
Total Process Waste Stream* Discharge to Land Disposal,
Metric Tons for CY 1977 by Standard Industrial
Classification,Organic Chemicals and Technical
Pesticides Industries
EPA
Rwlon
4
_lfl
- i
6
9
a
l
3
3
4
4
15-
5
7 _,
7
4
_ 6
1
3
-J
5
4
7
7
9
1
2
6
2
4
8
5
10
2
1
4
8
4
6
a
1
3
10
3
5
8
State
Alabama
Alaska
Ar1 zona
Arkansas
California
Colorado
Connecticut
Delaware
District of Columbia
Florida
Hawal t
Jdjfco
Kansas
Kentucky
Louisiana
Maine
Maryland
.Baisachuietts
Minnesota
Missouri
Nebraska
New Hampshire
New Jersey
New Mexico
New fork
Ohio
Puerto R1co
Rhode Island
South Carolina
Tennessee
Texas
Utah
Vermont
Virginia
Washington
Wisconsin
NATIONAL TOTALS
28610
1539
2503
28611
__68JI6_
533
_Ji5_
1
6042
7694
REGION TOTALS
2
3
4
5
6
7
8
9
0
6042
7369
325
28612
358
179
2434
_ 358
-y
28651
27453
28652
54
6445 • 12
32
210 '
25278
28653
7
19329
345
. . 1 -
2864 |
663 11 _j 3
_9753_2__
1900 , 11
0.9 ' 107
10
21535 0.4 1 3
" 1 *~ J-
3,329
2971
358
3046
"t i
1 335
62675
646
28655
370
51
28691
JJJ_
190
f1 _ 868
217
.- 184-. i 161
201 1
... .__
1-60- _
- 459 4
- 1 "
5J_
28692
,.„
1JI54
41161
1888
21)868
3Z4L
. 17,134
. 1495.-
916
28693 28694
3841
16 18591
978
925 1247
122
500
I
90S 1 5^52
- 43. .! . 211 -
IHb
1214.42 '• I
. 343826 -
7
549. 26Q3J5
"
-.IHzIL 28-_ |
-1Z78. . 37- -4621 .
! ''.91
671 L 4u7 1D.425
- .-.I.. .. S6BO
,
1670 234 ."1 . 112-
^ 563 1 49. 1
33985 i 462
1637 1 122
T
j
42171
20612
24439
32;il
205
29
146
7
208^84 ]
356
5826
4904
17,284
825
665.874
7
37
3,443
51
18
1C
3
49
437
r 712
1337
- 51.
918
85
14683
85
767
20,812
211 j 136
..83,933 _
92/59 i
122,002 |
260
680
43671 122
305,616 1
5912 L
388 i
6780 1 12
4904 1
.13 |
,592 1
1
44^473 1
18J
1^1
153,0/3
,_ 113,21!
630
26j220
260,461
1,491. 97J
441
6,223
8.74:
228.630
7,257
3,190,254
1546 1247
3599 26445
L 1426 914
1160 63594
1291 23409
1324 55120
570 J7078
[ ','78
16 j 18511
45 PO
13o
55°1
10809
6057
373
^_ .4,919.
210,602
41 7 »30
569,871
149,388 j
1,968,234 j
14^569
i ,898
'Estimated «»ter-free basis, using the procedures gfyen in Section 3 and Appendix « The data for '.he calculation-,
were obtained from the private industry sources listed in Table A-l and Reference, ', 1, 6. 11. <•>. 19-51
5-59
-------
Table 5-3. Total Process Waste Stream* Discharge to Land Disposal,
Metric Tons for CY 1983 by Standard Industrial
Classification.Organic Chemicals and Technical
Pesticides Industries
Reuion
4
10
9
4
9
0 _
1
3
3
4
4
9
D
b
4
I
]
4
H
q
}
6
a
H
6
1U
1
}
4
8
4
6
8
1
)
ID
3
5
jj
'•MtF
Al?bam,i
AJaste _ .
MiDJli)
tiljfflrnia
ifllpradjj
icnneitjtut
JJg 1 4WJ r g_
District of Columbia
JdiLhp
111 ing 15
Ind_idna
Kansas
r e n t u c k_y
LO.U i s_'_an
-------
to land in 1977 and 1983. Texas, Louisiana and Tennessee are the states
with the highest total process waste discharge to land in 1977 and 1983 for
SIC 28692. For SIC 28651, Texas, Louisiana and New Jersey are projected to
be the states with the highest total process waste discharge to land in 1977
and 1983.
The data on estimated total process discharge by the organic chemicals
industry to land disposal for hazardous waste streams are presented in
Tables 5-4, 5-5 and 5-6 for calendar years 1973, 1977 and 1983, respectively.
It will be noted that waste streams rated as hazardous account for almost
98 percent of total process waste discharges to land. The relative quanti-
ties of wastes for the SIC product groups remain the same - SIC 28692 first,
at just under 1.5 million metric tons, SIC 28651 second, at just under
0.5 million metric tons, and SIC 28694 third, at just under 0.2 million
metric tons. Similarly, in SIC 28692 the greatest quantities of total haz-
ardous waste stream discharges will be in the states of Texas, Tennessee
and West Virginia in 1973, and Texas, Louisiana and Tennessee in 1977 and
1983. For SIC 28651 the states discharging the greatest quantities of haz-
ardous waste streams to land are unchanged — Texas, Louisiana and New
Jersey for all 3 years for which estimates were made.
The hazardous component contents, in metric tons, of the process waste
streams discharged to the land by the organic chemicals industry in calen-
dar years 1973, 1977 and 1983 are presented in Tables 5-7, 5-8 and 5-9,
respectively. The product group with the greatest quantity of hazardous
components in 1973 was SIC 28651, the cyclic intermediates, with slightly
over 0.4 million metric tons; SIC 28692 was second with 0.3 million metric
tons; and SIC 28694 was third with under 60,000 metric tons. The hazardous
component content discharge factors* wsre 0.027 kg per kg of product for
SIC 28651, 0.0048 kg per kg of product for SIC 28692, and 0.010 kg per kg
of product for the industry as a whole. The two high hazardous component
discharge product groups (SIC 28651 and SIC 28692) account for 88 percent
of the industry's total.
*0btained by dividing the estimated total hazardous component content for
the product group by the estimated total production rate for the product
group (from Table 4-4).
5-61
-------
Table 5-4. Total Process Discharge to Land Disposal, Hazardous Waste
Streams? Metric Tons for CY 1973 by Standard Industrial
Classification,Organic Chemicals and Technical Pesticides
Industries
EPA
Real on
4
10
9
6
$
_ 3.
3
4.
4
__i_
_10_._
5
_5
7
7
4
6
1
3
] _j
5
5
4
7
B
7
9
1
2 ^
6 ,
2
4
8
_j>
6 _,
10
3
I ,
1
4
8
4
6
8
1
j
10
3
5
8
State
Alabama
Alaska
Arizona
Arkansas
California
Colorado
Connecticut
Delaware
District of Columbia
Florida
Georgia
Hawai i
Idaho
Illinois
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maine
Maryland
Massachusetts
Michigan
Minnesota
Mississippi
Ml SSOurl
Montana
Nebraska
Nevada
New Hampshire
New Jersey
New Mexico
New York
North Carolina
North Dakota
Ohio
Oklahoma
Oregon
Pennsylvania
Puerto Rico
Rhode Island
South Carolina ^
South Dakota
Tennessee
Texas
Utah
Vermont
Virginia
Washi ngton
West Virginia
Wi sconsf n
Wyoming
NATIONAL TOTALS
28610
3/17
2275
5492
28611
6214
485
, 295
6994
28612
325
163
2213
325
3,026
2,8651
12K7
1,731
14
_2g200_
9509
_!£95
1 3
83413
565
.8
16776
_l288
2749
LJZ?94
69
_2j£OJL
1,160
22£70
7349
23211
29,600
167471
151
3,634
2,963
9031
183,621
28652
51
11
10
11
101
.4
iJ£?'
538
434
115
193
27
138
6
7
34
3,247
28653
7
3
9
3
217
4~i,
47
12
9
3
46
401
28655,
330
4S_
100
167
183
417
343
46
46
301
720
46
289
76
12606
77
46
5,839
28691
768
197
2
136_
337
197
_ 1912
88
_._3_82_
5
1023
1559
6,628
28692
544
7928
17,165
5734
1046
u 336
179
94311
58869
2601
117
4555
2808
0,312
85,021
8,597
173^49
707080
izqutL
1444482
28693
_8Ji
749
u -5
2^
12
u_ 51U
1651
116
49
940
746
5j628
28694
35153
3,492
^¥53
842
93
44_9_
5395
190
4245
1524
22729
.255_
7514
an
-JUU2.
. 643L
10/69
1151
109
-L7JZ
1S?4
4QZ_
14fi
6432
14468
18
2449
567
153,233
7R&45
—122—
122
TOTAL
52,287
3,492
;6,478
80S
1,657
; 2,200
i6,69B
9,178
16,868
709
4,245
2,998
<4,325
2(5,772
1 ,248
111
27,576
136
8,49/
9.80J
!3,6t;
6,691
;8,299
10,549
1,570
1C8.938
16,068
35
^2,495
210,986
902,565
228
3,659
5,412
HI, 89?
567
2.128.713
REGION TOTALS
1
2
3
4
5
6
7
8
9 _j
10
5492
6699
295
2701
325
1
44512
58401
93475
27445
250884
4044
165
1731
2963
128
2109
245
639
0.4
115
11
12
262
55
50
15
7
347
752
506
1.459
12606
77
46
46
5
2,000
1559
2,205
721
136
2
12>0
[255451
291,603
10295
865949
296
7,928
815
2194
795
867
945
I?
842
H920
680
49^94
1^488
4Q689
12700
794
16,753
3973
122
1.803
76.4^6
317,9,™
4SP.764
_ i£.29£L . ..
1.1/1.R79
L_ 17J)i2. —
.1,1-il
Z6.471 .
t 000
Estimated, water-free basis, using the procedures given 1n Section 3 and Appendix A. The data for the calculations were obtained
from the private Industry sources listed in Table A-l and References 3, 4, 11, 12, 19-54
Defined as process waste streams containing one or more components classified as "Moderately Dangerous" or "Highly Dangerous"
in this study.
5-62
-------
Table 5-5. Total Process Discharge to Land Disposal, Hazardous Waste
Streams, Metric Tons for CY 1977 by Standard Industrial
Classification, Organic Chemicals and Technical Pesticides
Industries
EPA
tedafl.
4
_lfl_
_S
_£..
2
. 8
- L_
J
3
_J
4
s
.IS...
_i _
5
7
7
4 _
.6
1
_3_._
1
s
4
H
7
9
\
2
6
2 1
4
__B
5
6
10
3
2
1
4
8
4
6
8
1
3
JO
3
^
8
Stats
Alabama
Alaska
Arizona
Arkansas
California
Colorado
Connecticut
Delaware
District of Columbia
Georgia
Ha«a11
Idaho
111 inois
Iowa
Kansas
Kentucky
Louisiana
Maryland
Massachusetts
Michigan
Mjnnesota
Mississippi
M^sj 0 u r J
Montana
Nebraska
Nevada
New Hampshire
New Jersey
New Me«ico
New fork
North Carolina
_Nprth_rjakc»ta
Ohio
Oklahoma
Oregon
Pennsylvania
Puerto Rico
Rhode Island
South Carolina
South Dakota
Tennessee
Texas
Utah
Vermont
/i^ini*
Washington
west Virginia
Wlsconsl n
Wv omi nq
NATIONAL TOTALS
28610
3J539
2503
6,042
UMON TOTALS
]
2
3
4
5
6
7
3
S
10
6042
28611
6036
533
325
7694
7350
325
28612
358
179
2434
358
|
3,329
? 971
15R
28651
27453
6445
32
210
25278
19^329
345
2864
663
975JJ2
1900
0 9
21535
2751
3046
335
62675
646
33985
1637
42171
20612 ~1
24439
02/11
!08P84
356
_5826
4,904
17,284
825
665,874
211
83933
92459
17PCK1?
43K71
305616
5910
3Rft
67RO
4904
28652
54
12
11
11
107
0 4
— - -
1,670
563
462
122
205
29
146
7
7
37
3,443
28653
7
3
10
3
234
49
51
18
10
3
49
437
28655
370
51
110
184
201
459
i_ 636
51
112
712
1316
51
918
85
4683
85
767
20,791
JJ6_
??M
6fln
1??
JP
;j
?H3
- ZL
t -Z-
823
2,144
565
2,388
1J683
85
51
51
28691
133
190
868
217
161
150
217
129
2473
362
521
605
5
1544
295
1829
9,699
134
_4S35_
1829
3,500
766
445
190
28692
1462
77
1454
41161
I888.
20616
9741
16664
6235
1495
836
126412
342327
I 7
1662
4484
671
1296_
447
15938
7030
VA7~
33162
189
5560
99384
92464
1414
16,089
229,245
353
620
206J41
6TT"
,491 ,642
1.662
_115431_
307973
61216"
15732J5_
3627
447
41J61
6257
28693
16
925
90b
43
549
28
37
467
570 _
USD
181'
167
306
575
593
S26
775
851
10,927
]5«
3,594
1426
1160
1291
• 1324
570
16
28694
42668
3£41
18591
978
..m-
122
500
5952
211
6^49
1676
r
26J36
361
_8A2-3 .
191
10,425
9,1 53
15281
1418
159
2671
1676
527
22!
9499
20,602
26
2844
656
92,404
28695
10809
3
4591
135
6p57
J73
22,968
1
MXL
16699
914
6_J594
18,304
50479
VJ078
_978
18591
IS2 1)
IIP
5591
10809
5057
(7i
TOTAL
76.037
77
5,295
66,473
1 ,010
2,382
27.166
31.124
13,536
54,004
7,035
7,744
5,376
12', 089
467,277
2,738
1.808
3b,3lfc
24 1
14.131
"11^065
447
335
129
100,166
12,594
39,592
39.837
189
7,287
149,31,1
113.211
630
26,220
260,461
i .479.741
441
6,212
8,741
?2' ,IB8
2,152
3,435,250
4,949
225,970
41Jj6_55
588.589
138.588
1.952.502
- . 27Jfi5L._
1 J9S
- <>iAO!i .
16.105
Estimated, water-free basis, using the procedures given in Section 3 and Appendix A The data for the rMiulations were ubta
from the private industry sources 'isted in Table A-l and Reference? 3, 4, y, I!, 12, 19-54.
Defir.ed ds process waste streams containing one or more components classified as "Moderately Dangerous" or "Highly Dangerous"
m this study
5-63
-------
Table 5-6. Total Process Discharge to Land Disposal,1 Hazardous Waste
Streams,2 Metric Tons for CY 1983 by Standard Industrial
Classification,Organic Chemicals and Technical Pesticides
Industries
EPA
Heal on
4
10
-i—
3
^a
i
3
4
4
)
Jfi-
5
5
7
7
a
6
1
3
}
5
tj
4
8
7
9
,
^
6
2
4
8
5
6
10
1
2
]
4
8
4
e
8 j
1
3 '
10
J
5 |
8
State
Alabama
AJiSii
Arilona
Arkansas
Colorado
Connecticut
Sslimre
"iiLrict of Columbia
Florida
Geocgij
Hawaii
Idaho
Illinois
Indiana
_lfiwa_
Kentucky
Maine
Maryland
Massachusetts
Michigan
Minnesota
Mississippi
Missouri
Nebraska
Nevada
New Hamjjshire
New Jersey
New Mexico
New York
North Carolina
North Dakota
Ohio
Oklahoma I
Oregon
Puerto Rico
Rhode Island
South Carolina
South Dakota
Tennessee
Te«as
Utah
Vermont
Virginia
Washington
West Virginia
Wisconsin
Wyoming
NATIONAL TOTALS
REGION TOTALS
2
3
4
S
6
7
8
9
10
28610
3912
2767
6679
$679
28611
7556
589
359
5504
8145
359
28612
396
198
2690
396
3680
3,284
396
28651
30349
7125
36
232
27943
21367
381
3166
732
107817
2101
1
23805
3041
3367
370
69284
714
37569
1809
46618
22786
27016
36160
230028
394
6440
5421
19106
912
736.WO
233
92784
102208
134,867
48274
337845
6,533
430
7495
5421
28652
58
12
12
12
114
4
1785
613
494
131
219
31
156
7
8
39
$95
145
2,398
278
727
135
12
28653
8
3
10
3
250
52
54
^ 19
10
3
53
465
13
302
63
57
22
8
28655
409
66
121
203
222
507
703
56
124
787
1455
56
1015
93
16,231
93
848
22J79
911
2,370
623
2639
16,231
93
56
56
28691
147
210
959
240
178
166
409
240
142
2733
400
576
668
6
1707
326
4
2022
11133
148
3133^
2022
3869
1255
492
4
210
28692
1616
85
1,608
45.501
2087
22790
10768
18422
6892
1651
924
139,742
378427
8
1837
4957
741
1433
494
17618
7772
4695
36658
209
6147
109864
102215
1563
238876
1 358874
390
685
228100
741
2.754392
1,837
127605
340449
420,791
67,670
1,739,118
4010
494
45,501
6,917
28693
18
1023
1,000
48
607
31
40
516
630
1990
2011
185
338
636
655
582
857
941
12,108
1709
4001
1577
1283
1,426
1464
630
18
28694
47162
4246
20551
1081
1378
135
553
6580
233
6908
1853
28782
377
9531
211
jns_24
10119
16893
1567
176
2952
1853
583
244
10500
22,775
29
3,144
726
212666
1378
18460
989
70294
20233
55803
18880
1081
20,551
4,997
28695
11949
4
6180
149
6695
412
25,389
0
153
6180
11949
6.695
412
TOTAL
84,049
85
5,854
73,481
1,117
2,633
30 ,030
34,405
14,961
59,699
7,776
8,561
5.943
140.489
516,554
3,005
1,993
39,452
267
16,062
15,549
494
370
142
110,681
13,916
43,749
44,030
209
8,056
165,125
125,150
695
28,979
287,925
1 .635,786
491
6,867
9,662
251 ,109
2,379
3,797,780
5,463
249,747
456 , 1 36
650,619
153,603
2,158,403
30,053
2,102
73,851
17,803
1 tstimated, water-free basis, using the procedures given in Section 3 and Appendix A. The data for the calculations were obtained
from the private industry sources listed In Table A-l and References 3, 4, 8, 11, 12, 19-54.
2 Defined as process waste streams containing one or more components classified as "Moderately Dangerous" or "Highly Dangerous"
in this study
5-64
-------
Table 5-7. Hazardous Component Content*, Process Waste Stream Discharge to
Land Disposal, Metric Tons for CY 1973 by Standard Industrial
Classification -Organic Chemicals and Technical Pesticides
Industries
EP»
Rmton
4
Jfi_.
2
9
a
i
3
--3 _^
4
-A.._
3
-JJL
5 ...
i _,
7
7
4
6
__1
3
1
5
5
4
7
8
7
9
1
t
e.
2
^
a
5
6
10
3
2
\
4
8
4
6
8
1
1
10
3
5
8
Stitf
Alabama
Alaska
Arl/pna
Arkansas
California
Colprado
Connecticut
Delaware
District of Columbia
Florida
Georgia
Hawaii
-Uiba.
jLUlnflii
Indiana
Iowa
Kentucky
Louisiana
Maine
Maryland
Massachusetts
Michigan
Minnesota
MISSISSIPPI
Missouri
Montana
Nebraska
Nevada
New Hampshire
New Jersey
New Mexi co
New York
North Carolina
North Dakota
Ohio
Oklahoma
Pennsylvania
Puerto Rico
Rhode Island
South Carolina
South Dakota
Tennessee
Texas
Utah
Vermont
Virginia
Washington
West Virginia
Wisconsin
Wyomi ng
NATIONAL TOTALS
REGION TOTALS
1
2
3
4
5
6
7
8
9
10
28610
3217
2275
5,493
5493
?8611
6214
485
295
6994
2861!
325
163
_£L3
325
3,026
7B651
12646
1731
14
22^00
5509
1295
1
68,820
565
0 2
14,586
1288
949
34693
62
27/09
650
22^70
6,984
22.203
9600
42/04
151
3,245
?963
5667
34,607
2865?
41
8
10
11
100
.4
U 1,537
508
423
98
192
27
137
6
7
24
3,129
6699
295
2701
325
0.2
41,739
54,247
93,449
24.745
Zl 1.524
4.044
165
1,731
2.963
127
_ 2.045
234
617
98
8
28653
6
2
9
3
212
44
47
12
9
3
45
392
2B6S5
330
46
100
__I67_ __
183
417
343
46
46
301
720
46
289
77
11,699
77
46
14,933
12
2i&_
54
49
15
SL .
347
752
_M2_
1.459
1 .699
J2_
46
4fi
28611
2
789
197
2
137
13
197
1912
87
382
5
387
?fl69?
544
7683
14,203
5121
884
13
179
14154
51604
2421
r n7
139!
2797
6312
4649
8597
12J?6
58,180
?(»91
815
749
5
2
7
503
1456
116
49
705
- t" -p
1,560 J1011J |
_._ J^.._ -
" T "
5,670 (iOl ,093
_i ,
1.999 __
1.560--
1.570
397
137
_2_
12.785
(4,767
46,148
9.630
ZflSLZM
296
JJB3 ...
746
5,153
- aii.
1.959
-Z35
8fc7
_ao_
2B694
15586.
664
3258
386
24
31
19
965
36
562
290
15283
255
1804
71
2597
4073
4565
210
0 1
96
290
148
55
254J!
5/39
0 1
552
91
)6.160
2W45
122
122
10TAI
32,681
664
12,734
400
839
22,200
23,737
8,135
12,276
_232
562 .
1J64
:4,167
13^469
1 ,248
109
19,172
"' H
4,082
6t946
45,759
5j465
28.J79
3J86
3J6.
2? ^06
. li,/M. -
J5
22J95
44J44
319,027
22B
3,252
3,515
18,206
91
836,771
.21
5,675
__4fl3
2Q,fi98
l.nfil
Ifi.fiflfi
4,175
1R6
122.
„
-------
Table 5-8. Hazardous Component Content* Process Waste Stream Discharge to
Land Disposal, Metric Tons for CY 1977 by Standard Industrial
Classification -Organic Chemicals and Technical Pesticides
Industries
EPA
Real on
4
IS
..5
-i_
.3 -
. .8
3
J
4
4
9
10
b
5
1
7
a
6
1
1
1
5
5
4
;
3
,
9
1
t
6
2
4
8
5
6
10
3
2
1
4
y
4
6
B
1
3
10
3
b
8
State
Alabama
AJasM . .. .
Jrlifllli
Arkansas
California
Colorado
Delaware
JLuiriiLoL CiUatU.
norms
Hawaii
Idaho
JLLu3ojs_
Indiana
Iowa
Kansas
Kentucky
loyisjana
Maine
Nirylind
Massachusetts
Michigan
Minnesota
Mississippi
Missouri
Montana
Nebraska
Nevada
New Hampshire
,Nw Mexico
New Vork
North Dakota
Ohio
Oklahoma
Oregon . j
Pennsylvania
Puerto Rico
Rhode Island
South Carol ina
South Dakota
Tennessee
Texas
Utah
Vermont
Virginia
Washington
West Virginia
Wisconsin
Wyoml nq
NATIONAL TOTALS
REGION TOTALS
1
2
3
4
6
6
7
B
9
10
28610
3539
2503
6,042
28611
6836
533
325
7.694
6,042
__ £l6i
125
28612
358
179
2434
'
358
3,329
28651
27433
6445
32
210
25278
19329
345
2864
662
81481
1900
0.2
19,126
2,751
3046
335
60P34
638
33985
1076
41732
20210
24429
327JJ
181,516
356
S826
4,904
13583
825
613,062
P971
.158
210
8qBB2
88319
121971
40701
267997
591(1
3Sfl
fi/nn
4904
28652
44
8
n
n
107
0.4
1634
540
450
103
204
29
146
7
7
26
3,327
136
2174
248
658
103
8
28653
7
3
10
3
228
48
51
18
10
3
48
429
13
276
R«
14
n
7
2865S
370
51
110
184
201
459
636
51
112
712
1316
51
918
85
13686
85
767
19,794
28691
133
190
868
217
161
150
14
217
129
2473 '
361
521
605
5
846
296
1829
9,015
824
?144
565
JIM
llfftfi
S5
51
51
134
2834
1^29
2^02
780
446
190
28692
1462
77
1454
40864
I.B88
24057
9741
16486
5878
1495
834
38Z37
224385
7
1662
4484
67n
1296
447
15760
7022
4247
33161
189
5560
10949
92464
1414
38074
634575
353
620
29^97
671
1,250,48
1^62
115246
43194
1 1 7,903
-fiflfiBL.
86q60i
36?5
447
40^64
fi?57
28693
16
907
886
43
549
28
37
166
467
564 j
1800
1819
168
u 287
575
t_ 593
526
775
851
11,057
28694
21127
730
3635 '
V 3
115
122
23
1078
41
1477
319
12325
361
2344
5577
5758
9347
432
9
447
319
192
121
5226
11013
1
807
107
83,676
1^28
3619
1426
1161
1/119
V*?4
564
16
135
9779
55'
32,205
4pl7
?lnfiR
7554
543
3,695
11 76
286(5
10809
3
5591
135
6,057
373
22.968
138
5,591
irymo
f"
173
TOTAL
64,466
77
2,184
51.276
575
1,252
27,166
34.565
13,058
4E.933
6,508
2,972
4,017
38,913
319,573
2,738
1,807
26,644
217
9,683
10,664
447
335
129
91,391
11,572
39,431
37,013
189
5,930
60,171
112,809
630
2,611
77,475
847,918
441
6,187
6,704
47,101
1.603
2,030,874
3,818
215,772
143JS3
__J2UO'-
_lfflJLl8_
1.169,864
17.653
1.463
__5L.6_U_
12.711
Estima
given
and K,
ted water-
In Section
ferences 3
free basis, for
3 and Appendix
, 4, 8, 11, 12,
components cl
A. The data
19-54
assified as "Moderately Dangerous" or "Highly Dangerous" in this study, using the procedures
for the calculations were obtained from the private Industry sources listed 1n Table A-l
5-66
-------
Table 5-9. Hazardous Component Content Process Waste Stream Discharge to
Land Disposal, Metric Tons for CY 1983 by Standard Classifica-
tion — Organic Chemicals and Technical Pesticides Industries
tPA
Real on
. 4 .
-UL--
S. -„
.6...
_.9 ..
8.
. J --
- J -
- 1_
-A —
4
5
..UL
_ 5__
5 _.
/_
7
4
-J---
1
3
1
5
_5
4
J
B
7 __
9-.-.
__ 1__
,1.
..2. .-
4
___8
_L_-
.6,
.Jfi- -
3
_ 2
1
4
H
4
6
JL
1
3
10
_J
5
8
State
A lab. una
Alaska
Arizona
.ArJWPiAS
California
Color Adfl
Connecticut
JltlajurjL.. . ...
District jf.tjjluBtli
Florida
Georgia
KM* 11
Jdjho.. ,
.-Lltou. . _.
JMldiy
IBM . .
Kjnjjs
JSsnXucky . . _
.LfiiiiSJin* . ..
HJJJS--
JtoJjnd
MjiSachusettj
J1Jchjgin_
.MjSntSptii . ..
-*.'5.sissippi_
Missouri
Montana
.NrtrjiU.
to.d.1
.Nej«.Hdi'tp>hire
.New_J«rsey
New. Mexico
Jjew_ York
NorJ:_h_ Carol ind
North Da l(p u
OUto
pklahpriM
.Oregon
j^erto Rico
Rhode Island
South Carolina
_Sputh Dakota
Tennessee
Texas
JHah
_V ei_mon t
VjrtMnia__
Jtasjiinjttpn
Wes^^Vir^inid
J«. ',
--J.4'
IOUL%[
i2,;;i
,43^570
40,yi2
:os_ _
_. . li.lii.. .
oUOt . 1
124,704 I
6?5
.28,H59.
f5,643
937.33?
at;/
6,840 1
/.410
'j^.UCb
1,771
1.V40.9U3
-- ..l^li.
.2M.4J4 _..
158.166
32SL66L. .
_ aU.6611
--LS-i.12- .
L -Uili -.
L .i7-Jli4 .
4]j| 11.IM1
tstlmated, uater-free basis, for components classified as "Moderately Dangerous" or "Highly Dangerous" In this study, using the procedures
jlven 1n Section 3 and Appendix A. The data for the calculations were obtained from the private industry sources listed In Table A-l and
References 3, 4, 8, 11, 12. 19-54
5-67
-------
The situation changes very sharply based on projections of the effects
of the Federal Water Pollution Control Act as amended. The quantity of
hazardous components discharged to land by the SIC 28692 product group in
1977 was estimated to be 1.25 million metric tons, an increase of 850,000
metric tons. The increase in hazardous component discharge to land for 1977
by SIC 28651 is less than 200,000 metric tons, bringing the total to 0.6
million metric tons. In 1977, SIC 28692 and SIC 28651 hazardous component
discharges to land constitute 92 percent of the 2.0 million tons of such
components discharged by the industry. The hazardous component content
discharge factors projected are 0.022 kg per kg of product for the industry,
0.018 kg per kg product for product group SIC 28692, and 0.036 kg per kg
product for product group SIC 28651.
The projections of hazardous component quantities discharged to land
for 1983 are of the same relative order and magnitude as those for 1977;
product group SIC 28692, 1.4 million metric tons, hazardous components dis-
charge factor 0.018 kg per kg product; product group SIC 28651, 0.7 million
metric tons, hazardous components discharge factor 0.036; and overall
organic chemical industry, 2.2 million metric tons, hazardous components
discharge factor 0.022 kg per kg product.
Table 5-10 lists the highly dangerous components in the process waste
streams discharged to the land by the organic chemicals industry. Tables
5-11, 5-12, and 5-13 present estimates of the total quantities of these
highly dangerous components discharged to land disposal for the years 1973,
1977 and 1983, tabulated for each state and region by the individual prod-
uct groups of the organic chemicals industry.
The manufacturers of the miscellaneous acyclic chemicals and chemical
products of SIC 28692 discharge the greatest quantities of highly dangerous
components to land disposal in each of the 3 years for which estimates were
made. In each year, the discharges of the three highest product groups
(SIC 28692, SIC 28651, and SIC 28694) amount to 98 percent or more of the
total industry discharge to land of highly dangerous components. In each
of the 3 years, Texas and Louisiana are the states highest in quantity of
highly dangerous waste components to land disposal.
The quantities and highly dangerous waste component discharge factors
for 1973 for the two most pollution prone product groups and for the
5-68
-------
Table 5-10. Highly Dangerous Waste Stream Components by Standard
Industrial Classification.Organic Chemicals and
Technical Pesticides Industries
SIC Highly Dangerous Component
^8651 Aluminum oxide (DPA contaminated catalyst)
Amines
Ammonia
Azobenzene
Benzidine
Benzidine hydrochloride
Chlorinated aromatics
Chlorotoluene and phenol
Cyclopentadiene
Dichloroanilines
Dichloroethane
Dicyclopentadiene
Dinitrotoluenes
Diphenylamine
Heavy metal catalyst from melamine manufacture
Heavy organics from p-nitroaniline manufacture
Hydrazobenzene
Hydroquinone
Isocyanates
Manganese oxides
Melamine
Methyl aniline
a-naphthylamine
B-naphthylamine
Nitrobenzene
Nitrobenzene sulfonic acid
Nitrotoluene
N-phenylhydroxylami ne
N,N-diethylaniline
Phenol
Phenolics
Phenylenediamines
Phosgene
Phthalic anhydride
Polymeric matter, phenol contaminated
Polymers and tarry matter from isocyanates manufacture
p-chlorophenol
p-hydroxybenzoic acid
p-nitroaniline
p-ni trochlorobenzene
p-nitrotoluene sulfonic acid
Quinone
Resorcinol, phenol and cresol
Resorcinol
Sodium phenoxide
Spent catalyst and support
Sulfuric acid
Tars from diphenylamine manufacture
5-69
-------
Table 5-10. Highly Dangerous Waste Stream Components by Standard
Industrial Classification.Organic Chemicals and
Technical Pesticides Industries (Continued)
SIC Highly Dangerous Component
28651 Tars and naphthylamine from a and 6 naphthylamine manufacture
Toluene diamine
Toluidine
2-naphthylamine
2,4 dimethyl aminoazo benzene
3,3'-dichlorobenzidine
28652 Aminotoluene
Chloroacetic acid
Dinitrophenol
Phenol
p-anisidine
p-formamidoanisole
p-hydroxyaniline
o-anisidine
o-formamidoaniso"!e
o-hydroxyaniline
o-nitrophenol
2-aminotoluene
2-amino, 4-nitrophenol
2-nitro, 4-aminophenol
2-nitro, 4-amino anisole
2,4-diaminotoluene
4-aminotoluene (paren-toluidine)
28653 Naphthylamine
N-ethylnaphthylamine
p-toluidine
p-toluidine-2-sulfonic acid
p-toluidine-3-sulfonic acid
3,3'-dichlorobenzidine
28655 Phenols
28691 Acetylamino fluorene
Ferric chloride
Napthenic acid
Napthenic acid salts
Phenol
Phenolic salts
p-cresol
Thionyl chloride
Zinc dust
2,6 di-tert-butyl-p-cresol
28692 Acetonitrile
Acrolein
Acrylic acid
5-70
-------
Table 5-10. Highly Dangerous Waste Stream Components by Standard
Industrial Classification,0rganic Chemicals and
Technical Pesticides Industries (Continued)
SIC Highly Dangerous Component
28692 Acrylonitrile
Ally! alcohol
Allyl chloride
Ammonia
Ammonium cyanide
Ammonium methacrylate
Antimony oxide
Antimony pentachloride
B-propiolactone
Carbon tetrachloride
Chlorinated aldehydes
Chlorine
Chloroacetic acid
Chloroamino ethanes
Copper (recov) from acetaldehyde manufacture
Crotonaldehyde
Crude hexachlorobenzene
Dichloroethane
Dichloroethylene
Diethyl amine
Dimethyl ethers
Epichlorohydrin
Ethyleneamines
Ethylene diamine
Ethylene dichloride
Ethylene oxide
Ethyleneimine
Ethyl acrylate
Fluorocarbons
Heavy ends from acetic anhydride manufacture
Heavy metal catalyst from n-paraffins manufacture
Heavy tars from vinyl chloride manufacture
Hexamethyleneimine
Hydrogen chloride
Hydrogen cyanide
Hydroquinone
Lead sludge
Mercuric tin hydroxide
Metallic fluorinating agent
Methylch1oromethylether
Methyl ethyl ketone
Methyl methacrylate
Mixed heavy chlorinated hydrocarbons
Na salt of EDTA
Nickel from hexylene glycol manufacture
Nickel chloride
N-chlorodimethyl amine
N-nitrosodimethyl amine
5-71
-------
Table 5-10. Highly Dangerous Waste Stream Components by Standard
Industrial Classification,Organic Chemicals and
Technical Pesticides Industries (Continued)
SIC Highly Dangerous Component
28692 Phenols
Pentachloroethane
Perch1oroethy1ene
Phenol/am" line
Polymers from acrylic acid/acrylates manufacture
Polymers and hydroquinone from methyl methacrylate manufacture
Propionic acid
Propylene oxide
Propyl aldehyde
Sodium acrylate
Sodium cyanide
Sodium fluoride
Sodium formate
Stearic acid
Stearic acid salts
Tars from ethylene diamine manufacture
Tetrachloroethane
Tetrachloroethy1ene
Trichloroethane
Trichloroethy1ene
Trichloropropane
Vinyl chloride
Vinyl chloride contam. solids
Vinylidene chloride
Zinc acetate/on coke
1,1,2-tri chloroethane
28693 Alkylated phenol
Benzyl chloride
Dodecylmercaptans
Myristic acid
Myristic acid ester
Organic mercaptan salts
Partial phosphate esters
Phenols
Spent activated carbon from phosphoric acid ester manufacture
Stearic acid and esters
Tars from benzothiazole manufacture
Unreacted phenol
28694 Acrolein
Aldicarb
Aldrin
Alpha-naphthylthiourea
Arsenic trioxide
Atrazine
Bis(chloromethyl ether)
Chlorinated methyl ethers
5-72
-------
Table 5-10. Highly Dangerous Waste Stream Components by Standard
Industrial Classification,0rganic Chemicals and
Technical Pesticides Industries (Continued)
SIC Highly Dangerous Component
28694 Captan
Carbofuran
Carbaryl
Carbophenothion
Chlordane
2,4-Dichlorophenol
2,6-Dichlorophenol
2,2-Dichlorovinyl dimethyl phosphate
Dieldrin
0,0-Diethyl 0-(3-chloro-4 methyl-2-oxo-2H-l-benzopyran-7-yl)
phosphorothioate
0,0-Diethyl S-[2-ethylthio)ethyl] phosphorodithioate
0,0-Diethyl 0-2-pyrazinyl phosphorothioate
Dimethoate
0,0-Dimethyl 0-p-nitrophenyl phosphorothioate
0,0-Dimethyl S-[(4-oxo-l,2,3-benzotriazin-3(4H)-yl methyl]
phosphorodithioate
Dimethyl phosphate ester with 3-Hydroxy-N,N-Dimethyl-cis-
crotonamide
Dimethyl phosphate of 3-Hydroxy N-methyl-cis-crotonamide
Dinoseb
Dioxathion
Diphacinone
Diuron
Endothall
Endrin
Ethyl hexanediol
Ethyl thiocarbonate
Ethion
0-Ethyl S-phenyl ethylphosphorodithioate
S-[2-(Ethylsulfinyl)ethyl]0-0-Dimethyl phosphorothioate
Heavy carbamate residues
Hydrazine
Hydrogen sulfide
Heptachlor
Ma, lath ion
Methomyl
Methyl chloroacetate
Methyl fluoroacetate
Methyl isocyanate
1-Naphthylamine hydrochloride
Nicotine
Phenol
Phenolic resins from 2,4-dichlorophenoxyacetic acid manufacture
Parathion
Polymers and tars, pesticide contaminated from warfarin
manufacture
Phosphamidon
5-73
-------
Table 5-10. Highly Dangerous Waste Stream Components by Standard
Industrial ClassificationgOrganic Chemicals and
Technical Pesticides Industries (Continued)
SIC Highly Dangerous Component
28694 Sodium p-nitrophenolate
Tarry residues, pesticide contaminated from malathion manufacture
Sodium fluoroacetate
Tetraethyl pyrophosphate
2,4,6-trichlorophenol
Toxaphene
Warfarin
5-74
-------
Table 5-11. Highly Dangerous Component Content*, Process Waste Stream
Discharge to Land Disposal, Metric Tons for CY 1973 by
Standard Industrial Classification - Organic Chemicals
and Technical Pesticides Industries
£M
Reaion
4
.19 _,
9 ,
6
_3
8 .
J .
3
4
4
--*—
c
State
Alabama
Alaska
Arizona
Arkansas
California
Connecticut
Delaware
District of Columbia
Florida
Hawdi i
4 1 1 1 no i S
5 1 Indiana
-,
,
6
1 _
t
Louisiana
Maryland
Massachusetts
5 IjnnesoU
4
' | Kissojri
8 Montana
.......
7 i Nebraska
9 1 Nevada
'
2
4
P
5
6
10
2
1
4
t
4
6
-- - -
1 j
•.'-::••.
28610 Z8611
1
j
j
1
28612
i ,
~*
28651
2£00
1^08
478
2808
966
1
10J35
0 1
1,951
762
i 20
i
'
New York '
North Carolina
Ohio
" T
" - ;p
8003
6
595
355
|
i
I 1 j
10247
4,137
479
637
14526
tflti | j '
,'er-ont I i L
- - -J 1 " \
nasnnnton j 1 J i 22?2
IL TfjTALS
-EW. -CTSLS
4
_
J 1 , 3618
1 1
66p54
28652
.1
1
3
22
1
256
100
85
16
38
6
23
1
550
28653
2
1
28655
324
46
100
167
183
417
3
.5 139
46
|
JB691
191
2
2
117
j
69 46 ! ?7
,4
11
6
3
1
15
306
46
139
77
541
77
14
375
1 - ..
1
1
46
i
126 | 2700
I |
1 L
1 j
i |
I
I i
:~~_".i.ir~
1
12146
14343
5,274
5114
24661
9B6
, 1308
1 2222
28
356
41
109
16
1
4
83
18
12
6 5
2
46
602
501
841
541
728
27
see
16
117
11 L. ...
46 I 2
46 1
28692
544
2J322
SplO
279
179
8441
298=0
170
681
1542
4734
3281
4,092
6,555
28693
62
13
2
i '
i
71 -
88
33
59,920 705
|
I
T
7981 ] 10
|
13.1,082 1 1.630
6315
11262
17550
5183
89£771
179
2822
62
716
43
103
705
1
28694
9837
582
2,780
52
11
9
836
32
417
254
6,131
4
1^53
34
2,391
521
2,357
197
1 1
21)695
46
254
22
53
2096 "*
4,468
.1
499
79
35,315
11
2554
26
14386
2380
11181
1192
52
2780
f '753
TOIAl
1575!
582
6,960
52
73
478
2.010
109
~"
4.105
215 ^
417
1.399 J
8,444
46,234
i
424 H
25 1
3,616 1
80 |
3,?53
542
11,440
2,574
691
5,565
300
13,763
8,229
7
555
9,740
80,160
77
1
2,721
11,670
T)
240,185
105
22,243
26.335
38,398
13,660
2^358
i.Ot'i
"[,1 "ateo water-free bas!S, for components classTfied as "Highly Dangerous" in Wns study, using the procedures given in Section 3 and
tppprOK i The data for the calculations were obtained from the private industry sources listed in Table A-l and References i, 4, 8,
5-75
-------
Table 5-12. Highly Dangerous Component Content Process Waste Stream
Discharge to Land Disposal, Metric Tons for CY 1977 by
Standard Industrial Classification - Organic Chemicals
and Technical Pesticides Industries
1 PA
Reaion
4
10
q
6
')
8 . _
J .
4
4
't
5
7
fi
1
5.
4
J
1
6
_2
4
f>
1
1
:
F
4
6
»
.1
10 _,
3
5
8
State
A.lahantf _ _
Alaska _ -
Arizona
Aj-J- Carolina
South Dakota
Te«a',
Utati
Ve'nont
ViiJinia
Washington
West Virginia
Wisconsin
Wyoming
NATIONAL TOTALS
RIGION TOTALS
2
3
4
b
6
8
9
0
28610
--
- - -
281)11
- --•
.... _..
- -- -
28612
- -
- --
- - —
28651
3134
1999
525
_420»
255
1083
659
12599
3
0.2
2J86
1P39
22
12656
13
657
533
12^53
5477
532
712
18847
2498
6226
69
88,885
28652
0 02
2
3
24
0 1
273
106
90
17
41
6
24
0 1
586
18,146
19/07
6733
7251
31446
i;os
1999
Z498
30
379
44
116
17
28653
?
~
1
-- -
3
0 6
73
15
12
7
3
1
16
134
28655
357
51
110
184
201
— -
459
153
51
52
337
51
163
85
595
84
68
3,748
28691
11
3
3
129
11
60
22
44
158
632
10
1,283
4
88
19
13
8
2
52
690
552
926
595
64
51
51
11
82
10
887
161
129
3
2869?
607
1454
16871
1J56
413
117
7626
|056
1299
626
24868
124168
3
810
97
6099
1556
7265
164
5J68
49459
8,651
231457
235
14141
505,366
28693
77
21
7
28
17
46
793
6
119
51
775
42
1,982
57114
20703
346%
16757
357243
2022
— i
16871
77
839
93
6
168
782
17
281)94
4760
640
3153
58
24
^U
10
920
Jb
434
279
7638
84
1753
30
5804
1776
- -
5551
237
0 1
68
27a
/?
119
47^9
JJ478
0 1
569
87
58,557
24
5788
106
25442
2893
17756
2489
58
3153
,...W
28695
__..
TOTAL
18,869
2,094
22.079
58
101
1,681
41J
23'
12,162
l7i47
1,7)3
1 ,988
25,530
144,541
552
27
4,931
81
6,843
1,012
11
24,810
2,74:
809
8.504
11)4
3JO
18.401
54,936
675
15,009
" i'sf.Tsz
84
235
3,067
20.503
156
659,794
146
82,488
_ 41J72.__ .
68^405
aj£L.
«fl7-ii5l-
_.W«3. ..
142
22J« __
3.397
Estimated, water-free basis,
Appendix A The data for thi
11, 12. 19-54
for components classified as "Highly Dangerous" in this study, using the procedures given in Section 3 and
e calculations were obtained from the private industry sources listed in Table A 1 and References 3, 4, 8,
5-76
-------
Table 5-13.
Highly Dangerous Component Content* Process Waste Stream
Discharge to Land Disposal Metric Tons for CY 1983 by
Standard Industrial Classification - Organic Chemicals
and Technical Pesticides Industries
TBT
IttlM.
4
10
9
6
9
8
1 -
3
3
4
.,«.
9
10
5
5
.7
7
4
6
1
3
1
5
5
4
7
8
7
9
1
2
6
2
4
e
5
6
10
3
2
1
4
8
4
6
8
1
3
10
3
5
8
State
AlabMia
Alukl
ArllDIU
Ark.nia,
CillfornU
Colorado
Conn.cn cut
Dtlaur*
DUtrfct of Columbia
Florida
G«orn1l
Ha«a11
Idaho
Illinois
Indiana
IBM ..
Kansas
Kentuckv
Loulslani
Maine
Maryland
Massachusetts
Michigan
Minnesota
MISSlSSlDOl
Missouri
Montana
Nebraska
Nevada
Nm Kamoshtre
New Jersey
New Mexico
Nen York
North Carolina
North Dakota
Ohio
Oklahoma
Oreoon
Pennsylvania
Puerto R1co
Rhode Island
South Carolina
South Dakota
Tennessee
Texas
Utah
Vermont
Virginia
Washington
West Virginia
W1 scons rn
NATIONAL TOTALS
28610
REGION TOTALS
1
2
3
4
5
6
8
9
IS . „
J8«ll
2W12
28651
'J'4641
#10
581
4(52
282
1197
7Zi
13927
4
.1
2416
1149
24
13,990
14
726
589
14319
6055
588
787
2t)B35
2/61
^882
77
98,258
28652
.1
Z
3
25
.1
291
113
97
19
43
6
26
.1
625
28651
2
1
4
.6
78
16
13
8
4
1
17
145
0.1
20,059
21,786
7,443
3,016
34,762
1.221
2,210
._. 2,761
31
104
46
125
19
0.1
5
94
21
14
9
?_
28*55
394
56
121
203
222
507
169
56
58
372
56
180
93
657
93
76
3,313
28691
12
3
3
142
12
67
25
48
174
919
11
1,416
28692
671
18650
1?78
456
129
8430
1167
1436
692
27490
137262
3
895
108
6,742
1720
8031
lai
5713
54675
9563
55865
260
1 5632
57,049
58
763
608
1,022
657
93
56
56
12
92
11
979
177
142
3
63.137
22,886
38,309
18.523
393.308
2.236
18.650
28693
85
24
8
31
19
51
876
7
131
57
857
46
2,192
85
927
103
7
186
865
19
28694
16316
707
3486
64
27
22
11
1017
39
480
309
6444
93
1?38
33
5863
l?64
6U5
262
.1
75
309
25
131
5227
10477
.1
628
96
64.178
27
6.397
118
27.570
3.198
19.628
2.753
64
3.486
1 337 — 1
28t»5
TOTAL
20.857
707
24,407
64
112
1,859
478
261
14,329
1,710
1,916
2,198
28,222
159,783
610
29
5,450
89
7,012
2,115
12
27.412
3.026
891
9.399
181
365
20.341
60.730
7
745
16. MS
288,691
93
260
3,389
22 ,664
173
727,176
160
91,168
45.734
75.055
31.150
449.362
6.229
157
__14.4W •
3.754
Estimated, Mter-fre« basis, for exponents classified as "Highly Dangerous" 1n this study, using the procedures given In Section 3 and
Appendix A. The data, for the calculations iwe obtained from the private Industry sources listed In Table A-l and References 3, 4, 8,
11, 12, 19-54.
5-77
-------
industry are as follows: SIC 28692, 133,000 metric tons, 0.0021 kg per kg
product; SIC 28651, 66,000 metric tons, 0.0042 kg per kg product; organic
chemicals industry, 249,000 metric tons, 0.0028 kg per kg product. The
statistics for 1977 and 1983 are based on the assumptions stated earlier
on the increase in discharge to land predicated as the result of the re-
quirements of the FWPCA as amended; the estimated waste discharges differ
considerably from those presented for 1973.
The increase in the quantity of highly dangerous components discharged
to land disposal is greatest in 1977 for SIC 28692, in both absolute ton-
nage and relative rise. The tonnage of highly dangerous waste stream con-
stituents for SIC 28692 in 1977 is projected as 0.5 million metric tons, an
increase of 280 percent over the 1973 estimate. Similar figures for SIC
28651 are an increase to 89,000 metric tons, which is only 35 percent higher
than the 1973 estimate for the product group. The highly dangerous compo-
nent waste discharge factors projected for 1977 are: SIC 28692, 0.0074 kg
per kg product; SIC 28651, 0.0052 kg per kg product; organic chemicals
industry, 0.0071 kg per kg product.
The projections for 1983 of highly dangerous component quantities dis-
charged as waste to land reflect only the increases above 1977 due to in-
creases in production. The order and magnitudes of the highly dangerous
component waste discharges for the product groups are, therefore, the same
for 1983 as for 1977; the component waste discharge factors are identical.
The overall projection for the organic chemicals industry in 1983 is a
highly dangerous components discharge to waste of 0.7 million metric tons;
three-fourths of this results from the manufacture of the products of SIC
28692.
5.3 PESTICIDES INDUSTRIES
The pesticides industries are treated throughout this study as two
entities: technical pesticides manufacture (SIC 28694), and pesticides
preparations and formulations production (SIC 2879).
Emphasis has been placed in the characterization of wastes from the
pesticides industries on the discharges and technologies of the technical
pesticides manufacturing industry (SIC 28694). The reasons, as noted in
Section 3 and in Appendix A, are twofold: First, and most important, are
5-78
-------
the much higher quantities of hazardous wastes anticipated from technical
pesticides plants, as opposed to the relatively low quantities estimated
for pesticides formulations and preparations production. Second is that
this study's lack of access to quantitative data other than gross national
statistics on pesticides formulations and preparations production caused
problems. Detailed information on the annual production of each formula-
tion at each plant site was treated as proprietary by the companies in-
volved and was not available from trade publications.
Because of the very sensitive nature of the pesticide manufacturing
and formulation industries, very little information is available on spe-
cific details of production and formulation operations for a large number
of individual pesticides and pesticide preparations. Most manufacturers
and formulators are extremely reluctant to reveal technical process data.
Several pesticide manufacturers and formulators were contacted for data.
One major manufacturer, who in recent years had received some adverse pub-
licity on its waste disposal practices, flatly refused to discuss their
operation or to provide pertinent data for use in this study. Some of the
other manufacturers who allowed production-site interviews did not permit
their personnel to elaborate beyond what is common technical knowledge and
had been published in the literature. The list of pesticide company head-
quarters and plants which were visited, shown in Table A-l, has been ex-
panded to show the products for which data were obtained and is presented
as Table 5-14.
As a result of the lack of published data and a lack of full coopera-
tion from the majority of the manufacturers contacted, specific data on the
manufacturing processes, mass balances, and nature and quantities of raw
materials used and wastes generated were not available for many of the tech-
nical pesticides considered. Accordingly, the simplified approach, noted in
Section 3 for grouping the technical pesticides into "chemical" classes and
selecting one to three pesticides from each class as group representatives
for more in-depth analysis, was used for process technology review, and for
estimation of waste quantities. This approach was deemed adequate since
many of the pesticides in each group share similar process chemistries and
are produced from the same starting raw materials. For example, as indi-
cated in Figure 5-22, cyanuric chloride is the starting material for the
5-79
-------
3
O
u_
Dl
si
13
4->
O
C
ro
5:
ai
-a
1/5
CD
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O
E to
s- -a
o o
14- JC
c •*->
K-i a)
en
E i—
•r- (O
T3 l/l
•r- O
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O to
S_ T-
Q_ Q
to Q)
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CX
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cu
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(1)
ex.
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j_
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synthesis of triazine pesticides and the synthesis involves reaction of
cyanuric chloride with alkyl or aryl amines.
The 127 technical pesticides considered in this study (i.e., as indi-
cated in Appendix A, those with national production quantities close to
or in excess of 453 metric tons/year, and those produced at somewhat
smaller quantities but considered extremely hazardous) are listed in
Table 5-15, grouped into 17 classes. Based on this chemical classifica-
tion system, these pesticides consist of 19 chlorinated aromatics, eight
chlorinated polycyclics, five halogenated aliphatics, five ureas, one
thiourea, six phosphate and pyrophosphates, 11 phosphorothioates, 14 phos-
phorodithioates, eight carbamates, ten amides and imides, two arsenicals,
15 biological and natural products, three triazines, two uracils, six nitro
compounds, six thiocarbamates, and 12 miscellaneous products. The pesti-
cides selected as class representatives (a total of 32) are marked by an
asterisk in Table 5-15. Selection of class representatives was based on
the extent of data available, production volume, number and distribution of
manufacturing sites, and hazard characteristics of the waste streams, prod-
ucts, raw materials and intermediates.
5.3.1 Typical Plant Process and Waste Stream Descriptions
Five of the 32 class representatives for the technical pesticides
group have been selected for presentation of process flow diagrams, mass
balances, and waste stream descriptions. Combined total production in 1972
for the five technical pesticides selected was estimated to constitute
approximately 26 percent of the national total for production of all tech-
nical organic pest control chemicals. Combined total process wastes dis-
charged to land (dry weight basis) for the five technical pesticides
are estimated to constitute 19 percent of the national total dry weight of
process wastes discharged to land by all technical organic pesticides
plants. The five technical pesticides selected were, therefore, adequately
representative of product group SIC 28694. A brief description of the
production operations of a hypothetical plant for each of these five
pesticides follows. Again, it should be noted that the descriptions pre-
sented are composites, rather than any single plant.
5-82
-------
Table 5-15. Pesticides Considered in SIC 28694 and Their Grouping
into Chemical Classes1 (Pesticides Marked by Asterisks
are Class Representatives)
Group 1 - Chlorinated Aromatics
Barban
l,l-Bis(chlorophenyl)-2,2,2-trichloroethanol
Chloramben
Di camba
*Dichloro diphenyl trichloroethane
2,6-Dichloro-4-nitroaniline
*2,4-Dichlorophenoxyacetic acid
Dimethyl tetrachloroterephthalate
Ethyl 4,4'-dichlorobenzilate
Isopropyl 4,4'-dichlorobenzilate
Lindane (gamma isomer of benzene hexachloride)
Linuron
Methoxychlor
Pentachloronitrobenzene
Pentachlorophenol
Si 1 vex
2,3,6-Trichlorobenzoic acid and related polychlorobenzoic acids,
dimethyl amine salts
*2,4,5-Trichlorophenoxyacetic acid
Group 2 - Chlorinated Polycyclics
*Aldrin
*Chlordane
*Dieldrin
Dodecachlorooctahydro-1,3,4-metheno-lH-cyclobuta[cd]pentalene
Endosulfan
Endrin
Heptachlor
*Toxaphene
*The nomenclature employed is taken from Reference 13.
5-83
-------
Table 5-15. Pesticides Considered in SIC 28694 and Their Grouping
into Chemical Classes1 (Pesticides Marked by Asterisks
are Class Representatives) (Continued)
Group 3 — Halogenated Aliphatics
*Dalapon
l,2-Dibromo-3-chloropropane
*Methyl bromide
Sodium fluoroacetate
Trichloroacetic acid
Group 4 — Ureas
Chloroxuron
*Diuron
Maloran
*Norea
Siduron
Group 5 — Thioureas
*A1pha-naphthylthiourea
Group 6 - Phosphate and Pyrophosphates
Crufornate 4-tert-butyl-2-chlorophenyl methyl methylphosphoramidate
2,2-Dichlorovinyl dimethyl phosphate
*Dimethyl phosphate ester with 3-Hydroxy-N,N-dimethyl-cis-crotonamide
*Dimethy1 phosphate of 3-Hydroxy-N-methyl-cis-crotonamide
Phosphamidon
Tetraethyl pyrophosphate
Group 7 — Phosphorothioates
Chloropyrifos,
0-(2,4-Dichlorophenyl)0,0-diethyl phosphorothioate
0,0-Diethyl 0-(3-chloro-4 Methyl-2-oxo-2H-l-benzopyran-7-yl)
phosphorothioate
0,0-Diethyl 0-(2-isopropyl-6-methyl-4-pyrimidinyl)phosphorothioate
*0,0-Dimethyl 0-p-nitrophenyl phosphorothioate
S-[2-(Ethylthio)ethyl] 0,0-dimethyl phosphorodithioate
!The nomenclature employed is taken from Reference 13.
5-84
-------
Table 5-15. Pesticides Considered in SIC 28694 and Their Grouping
into Chemical Classes1 (Pesticides Marked by Asterisks
are Class Representatives) (Continued)
*Parathion
Ronnel
O.O.O.O'-Tetramethyl 0,0'-thiodi-p-phenylene phosphorothioate
0,0,0,0-Tetrapropyl dithiopyrophosphate
Group 8 - Phosphorodithioates
Carbophenothion
0,0-Diethyl 0-[-p(methy1sulfinyl)pheny1]phosphorothioate
*0,0-Diethyl S-[2-(ethylthio)ethyl]phosphorodithioate
Dimethoate
0,0-Dimethyl S-[(4-oxo-l,2,3-benzothiazin-3(4H)-yl)methyl]
phosphorodithioate
3-(0,0-Diisopropyl phosphorodithioate)ester of N-(2-mercaptoethyl)
benzenesulfonamide
Dioxathion
Ethion
0-Ethyl S,S-dipropyl phosphorodithioate
0-Ethyl S-phenyl ethylphosphorodithioate
Haled
*Malathion
S,S,S-Tributyl phosphorotrithioate
Tributyl phosphorotrithioite
Group 9 — Carbamates
*Aldicarb
Benomyl
*Carbaryl
Carbofuran
2,6-Di-tert-butyl-p-tolyl methylcarbamate
0-Ethyl hexahydro-lH-azepine-1-carbothioate
M-(l-Ethylpropyl)phenyl methylcarbamate mixture with M-(l-methylbutyl)
phenyl methylcarbamate
Methomyl
iThe nomenclature employed is taken from Reference 13.
5-85
-------
Table 5-15. Pesticides Considered in SIC 28694 and Their Grouping
into Chemical Classesl (Pesticides Marked by Asterisks
are Class Representatives) (Continued)
Group 10 - Amides and Imides
*Alachlor
*Captan
2-Chloro-N-isopropylacetanilide
N,N-Diallyl-2-chloroacetamide
3',4'-Dichloropropionanilide
N,N-Diethyl-meta-toluamide
Diphenamid
N-1-Naphthylphthalamic acid
N-Octyl bicycloheptenedicarboximide
Cis-N-[(l,1,2,2-Tetrachloroethyl)thio]-4-cyclohexene-l,2-dicarboximide
Group 11 - Arsenicals
*Cacodylic acid
Disodium methanearsonate; Monosodium acid methanearsonate
Group 12 - Biological and Natural Products
*Bacillus thuringiensis
Nicotine
Polyhedrus virus
*Pyrethrins
Rotenone
Group 13 — Triazines
*Atrazine
2-Chloro-4,5-bis(isopropyl amino)-S-triazine
Simazine
Group 14 - Uracils
*Bromacil
Terbacil
iThe nomenclature employed is taken from Reference 13.
5-86
-------
Table 5-15. Pesticides Considered in SIC 28694 and Their Grouping
into Chemical Classes* (Pesticides Marked by Asterisks
are Class Representatives) (Continued)
Group 15 - Nitro Compounds
Binapacryl
N-Butyl-N-ethyl-alpha,alpha,alpha-trifluoro-2,6-dinitro-p-toluidine
2,4-Dinitro-6-octyl phenyl crotonate;2,6-dinitro-4-octyl phenyl
crotonate
Dinoseb
4-(Methylsulfonyl)-2,6-dinitro-N,N-dipropyl-anil ine
*Trifluralin
Group 16 — Thiocarbamates
2-chloroallyl diethyldithiocarbamate
S-(2,3-Dichloroallyl)diisopropylthiocarbamate
S-Ethyl cyclohexylethylthiocarbamate
*S-Ethyl diisobutylthiocarbamate
S-Propyl butyl ethylthiocarbamate
*S-Propyl dipropylthiocarbamate
Group 17 -Miscellaneous
Acrolein
Amitrole
*l,2-Dihydro-3,6-pyridazinedione
Diphacinone
Dipropyl isocinchomeronate
Dodine
Endothall
Ethyl hexanediol
Piperonal,bis[2-butoxyethoxy)ethyl]acetal
Piperonyl butoxide
2-(p-Tert-butylphenoxy)cyclohexyl 2-propynyl sulfite
*Warfarin
nomenclature employed is taken from Reference 13.
5-87
-------
' 47)
Aldrin is a chlorinated hydrocarbon used for control of a broad spec-
trum of insects. Pure aldrin is a white crystalline substance with a melt-
ing point of 104-104.5°C. In the soil, plants, insects and invertebrates
aldrin is convered to dieldrin which is environmentally persistent. It is
a highly toxic bioaccumulative substance with reputed toxicity data indicat-
ing a 96-hour TLm of less than 0.1 ppm and an oral LDcn (male rat) of
r (-^\ '" 3(J
39 mg/kg.v ' The production of aldrin has been discontinued, and the
pesticide has been deregistered. In 1972, production of aldrin was esti-
mated as 4,500 metric tons (19 million pounds); the sole producer reported
was Shell Chemical . ^
Technical grade aldrin is a brown substance with a melting point in
the 45°-60°C range and contains about 82 percent endo-exo isomer of 1,2,3,-
4,10 JO-hexachloro- 1,4,5, 8-diendomethylene- 1,4, 4a, 5,8, 8a-hexahydronaphtha-
lene, 12-13 percent analogs, and about 5 percent various other compounds.
Commercial-scale production of aldrin is a semicontinuous process involving
reaction between excess bicyclo [2.2.1] heptadiene-2,5 and hexachlorocyclo-
pentadiene at 100°C. The aldrin yield is about 80 percent based on the
hexachlorocyclopentadiene. The excess bicycloheptadiene is recovered and
reused. Bicycloheptadiene may be purchased from outside or produced on-site
by the reaction of cyclopentadiene with acetylene at 250-360°C and 400-
2000 kilonewtons/square meter (60-300 psi) pressure. The reaction is car-
ried out either in an organic solvent (e.g., pentane) or with nitrogen as a
diluent for acetylene. The yield of bicycloheptadiene is about 30-60 per-
cent with toluene, tricycline and a number of other compounds formed as by-
products. Acetylene used in aldrin production is generally produced on
site from calcium carbide (process yield is estimated at 95 percent). Hex-
achlorocyclopentadiene is produced by chlorination of cyclopentadiene which
can be obtained from cracking of dicyclopentadiene. Production of chemical
aldrin can be summarized as follows:
CaC2 + 2H20 - v Ca(OH)2 + C2H2
r H Cracking t r H
C10H12 - ^ C5H6
5-*
-------
C5H6 + 6C12
C5H6
C2H2
+ 6HC1
Hexachlorocyclopentadiene
Bicycloheptadiene
Aldrin
Figure 5-23 presents a schematic flow diagram for the production of
(41)
aldrin, based on data reported by Lawless, et al. ' A typical plant size
is approximately 4,500 metric tons per year. The mass balance data were
estimated based on the production chemistry discussed above. The major
land-destined wastes from the process are lime sludge from acetylene pro-
duction (estimated at 0.73 kg of Ca(OH)2 per kg of technical grade aldrin),
tars from production of bicycloheptadiene and cyclopentadiene (estimated at
a total of 0.5 kg/kg of product), damaged containers containing aldrin, and
chemical spills. No liquid process waste containing aldrin is generated.
Wastewater from floor washing and spill clean-up, however, would contain
some aldrin.
Atrazine/41' 52^
Atrazine is a selective herbicide of the triazine class. Production
of atrazine in 1972 was 41,000 metric tons (90 million pounds). ' It is
a white crystalline substance with a melting point of 173-175°C and a water
5-89
-------
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5-90
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solubility of less than 0.01 percent. The major producer n the United
States was Ciba-Geigy Corp. Atrazirie is generally considered to be
toxic and environmentally persistent, loxicity data compiled by Hann and
(53)
Jensen ' indicate an aquatic tcxicity rating corresponding to a 96-hour
TL of 1-10 ppm and an L!)rn {oral rat) in excess of 2000 ing/kg.
ill -JU
Commercial atrazine production is a two-stage operation involving
reaction of cyanuric chloride with ethyl amine and sodium hydroxide to pro-
duce 2,4-dichloro-6»ethylarnino-3--triazint: whi^h is then reacted with iso~
propyl amine and sodium hydroxide to prod-jre :*t.raz5r:e. The cyanuric chlo-
ride necessary for the synthesis of tns-.iii;! can be prepared in a number
of ways, including catalytic polymerization of cyanogen chloride (with a
yield in excess of 90 percent) using ch'iorine and nydrcgen cyanide as the
starting raw material. The polymerization reaction may be carr.ed out in
the gas phase at. 350-400°C using activated carbon as a catalyst or in the
liquid phase under pressure in an organic solvent using either anhydrous
(47)
aluminum chloride, boron fluoride, or HC1 , as catalyst. ' ' '
3HCN + 3C12 "CalalysT 3HU
Cyanuric Chloride
Cl Cl
+ C2HcNHn + NaOH
CT'
H
2,4-dichloro-6-
ethylamino-5-
triazine
+ NaCl + HoO
5-91
-------
Cl Cl
+ (CH3)2CHNH2 + NaOH > ( } T
fl" "^N^ ^NHC H ^N^^^f
25 | ' |
H H
Atrazine
+ NaCl + H20
Figure 5-24 is the schematic flow diagram for the production of atra-
zine by the continuous process, based in part on data reported by Lawless,
(41)
et al. ' for a production facility in St. Gabriel, Louisiana. Estimated
mass balance data shown on the figure are for the production of 1.00 kg of
technical grade atrazine. The 5 percent impurities in the technical grade
product are assumed to consist mainly of water insoluble heterocyclic by-
products produced during amination and inorganics such as NaOH and NaCl.
Atrazine losses resulting from the filtration step are estimated at 0.1 per-
cent. An efficiency of 90 percent was assumed on the basis of the litera-
ture for the production of cyanuric chloride. The data on Figure 5-24 indi-
cate that liquid wastes from atrazine production would be high in salt
content and would contain such hazardous constituents as atrazine and
cyanide-related compounds. A typical plant size is approximately 20,000
metric tons per year.
Trifluralin^41'42)
Trifluralin is a selective herbicide belonging to the nitroaromatic
pesticide class. It is a yellow-orange crystalline substance with a melting
point of 48.5-49°C and a water solubility of about 40 ppm. Production esti-
mates for 1972 were 11,000 metric tons (25 million pounds) for the sole
(43)
manufacturer, Eli Lilly and Company/ ' Trifluralin is considered to be
of low toxicity (LDgQ is greater than 10,000 mg/kg) and environmentally
nonpersistent. Production of trifluralin involves nitration of p-chloro-
benzotrifluoride followed by amination with dipropyl amine:
,5-92
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3 0?N
solution e-
+ NaCl + NaHCO,
3,5-dinitro-4-chloro-
benzotrifluoride
p-Chlorobenzotrifluoride
H7C3 C3H7
Trifluralin
Figure 5-25 is the schematic flow diagram for the production of
trifluralin, based in part on discussions with the technical personnel at
Eli Lilly and Company (producer of trifluralin) and data compiled by
Lawless, et al. ' The spent acid (dilute HN03/H2S04) from the nitration
reaction undergoes denitrification treatment for the recovery of residual
nitric acid which is concentrated and returned to the first nitrator. With
the exception of a portion which is recycled, the dilute sulfuric acid that
is recovered is sold to acid suppliers. Storage and transfer of the inter-
mediate product (3,5-dinitro-4-chlorobenzotrifluoride) is in chloroform,
which is recovered from the final product and reused.
Estimated mass balance data for trifluralin production are shown on
Figure 5-25. The technical grade trifluralin is assumed to contain 5 per-
cent impurities (consisting mainly of inorganic salts, NaCl, NaHCO-, Na^CO-),
moisture, and chemical intermediates and side products. The major aqueous
wastes from the process are salt water from amination/purification steps and
scrubber wastewater from gas cleaning operation. The major pollutants and
their relative quantities in the process gas before scrubbing for the Eli
Lilly plant in Lafayette, Indiana, are shown in Table 5-16a. The scrubbing
system has a pollutant removal efficiency in excess of 90 percent. Typical
analysis of the brine waste from this plant before and after waste treatment
by activated carbon adsorption is also shown in Table 5-16b. Because the
production data and wastewater volumes were not available, the data in
Tables 5-15 and 5-16 cannot be expressed in terms of waste generation fac-
tors to check the accuracy of the calculated mass balance data shown on Fig-
ure 5-25. At this plant, the spent carbon from waste brine treatment is
currently stored in plastic-lined steel drums. The effluent liquids from
5-94
-------
-------
Table 5-16a. Trifluralin Production - Process Exhaust
Before Scrubbing
Compounds Emitted
Particulates
Gases
Sulfur Dioxide
Sulfur Trioxide
Hydrogen Fluoride
Hydrogen Chloride
Nitrogen Oxides
Nitrate
Sulfate
Chloride
<0.5 kg/hr
<0.5 kg/hr
<0.5 kg/hr
Ib/hr)
Ib/hr)
Ib/hr)
<1.5 kg/hr (< 3 Ib/hr)
<0.5 kg/hr (< 1 Ib/hr)
<0.5 kg/hr (< 1 Ib/hr)
<4.5 kg/hr (<10 Ib/hr)
<1.5 kg/hr (< 3 Ib/hr)
Table 5-16b. Analysis of Typical Aqueous Brine from
Trifluralin Manufacture Before and
After Treatment with Activated Carbon
Color, units
COD, ppm
Fluoride, ppm
PH
Raw Waste
100,000
14,000
1,000
9
Treated Waste
1,000
1,200
75
8
gas scrubbing and carbon adsorption units are treated in a biological waste
treatment system before final disposal.
Parathion and Methyl Parathion
Parathion (0,0-diethyl 0-p-nitrophenyl phosphorothioate) and methyl
parathion (0,0-dimethyl 0-p-nitrophenyl phosphorothioate) are two of the
most widely used organophosphate insecticides. Annual production capacity
in 1973 for the parathions was estimated at 62,000 metric tons (137 million
5-96
-------
pounds). ' There were six major producers in 1973: Arn< • ican Cyanamid
Company, Hercules Incorporated, Kerr-McGee Corporation, Monsanto Company,
Stauffer Chemical Company, and Vicksburg Chemical Company. Production
facility sizes ranged from 6,000 to 23,000 metric tons per year capacity.
Because of its lower toxicity to mammals, methyl parathion is gradually
displacing parathion and is currently produced in a larger quantity. Except
for the use of ethanol instead of methanol as one of the starting raw mate-
rials, the industrial synthesis of parathion is essentially identical to
that for methyl parathion. The synthesis of parathion involves (1) reaction
of phosphorus pentasulfide with ethanol to produce diethyl dithiophosphoric
acid, (2) chlorination of diethyl dithiophosphoric acid to obtain diethyl-
chlorothiophosphate, and (3) reaction of diethylchlorothiophosphate with
sodium p-nitro phenolate in an organic solvent (e.g., acetone) to produce
parathion:
4(C2H5OH)
S
HC1
S
ii
(C2H50)2PC1 + NaO
NaCl
Table 5-17 presents some general characteristic data for parathion and
methyl parathion. The schematic process flow diagram and estimated mass bal-
ance data for a parathion production plant are shown in Figure 5-26. At this
plant the by-product hydrogen sulfide gas is flared, and the sulfur generated
in the chlorinator is disposed of by incineration. Part of the hydrochloric
acid produced in the chlorinator is recovered and the rest is neutralized
with sodium carbonate and discharged to the biological waste treatment plant.
Sodium chloride (possibly containing small quantities of the product and chem-
ical intermediates) is in the waste stream from the parathion unit which is
5-97
-------
Table 5-17. Some General Characteristics of Parathicn
and Methyl Parathion(47,53)
T
Pa rath ion
Methyl Parathion
Physical nature (pure
substance)
(technical grade)
Melting point, °C
Boiling point, °C
Solubility in water, ppm
LD(-n, mg/kg
96-hr TL , ppm
Environmental persistence
Purity of technical
grade, %
Main organic impurities
in the technical
grade
Clear oily liquid
Dark brown 1iquid
6.1
113*
24
6-12
Nonpersistent**
98
0-ethyl 0,0-bis
(4-nitrophenyl)
thiophosphate;
p-nitrophenol;
triethyl
thiophosphate
White crystalline substance
35-36
109*
55
25-50
Nonpersistent**
96-98
0-methyl 0,0-bis
(4-nitrophenyl)
thiophosphate;
p-nitrophenol;
trimethylthiophosphate
*At 7 newtons/meter (0.05
**Persistent in soil 1 to 3 months
mm of Hq]
™^'
also discharged to the plant waste treatment system. Parathion concentra-
tion in the effluent from the biological treatment system is reported to be
less than 1 ppm.
Malathion is a nonsystemic organophosphate insecticide and acaricide.*
The pure substance is a colorless liquid with a boiling point of 150°C and a
water solubility of 145 mg per liter (at 20°C). The technical grade product
is a brownish liquid of 95-98% purity. Malathion is considered to be of
"low" toxicity and environmentally nonpersistent. The 1050 reported for var-
ious experimental animals is in the 500-1500 mg/kg range. W) The aquatic
toxicity rating for malathion corresponds to a 96-hour TL of less than
* m
10
*A type of pesticide having the power to kill acarlds
(i.e., mites and ticks)
5-98
-------
og in in m
oo o O o
•— o o o
o o o d
oo
ui
oo
o
!± o o
F °t
\~ \~ a:
o S S it)
0.
V
z:
o
a
^
<0
o
=5
C
t— 00
S LU
< |-
—I K-I
OL OO
o; LU
UJ (-
F ^
t «c
o 3:
0
0
uj
o:
<:
P
o:
-
3:
cj
LU
>-
CQ
t-
z
LU
CS4
CO
0
<->
.
UJ
(_)
ce
LU
CL.
o
CX3
X
o
a:
a.
Q.
(O
3
-J.
OT
-r-
u_
in
oo
cj
Q.
5-99
-------
Malathion capacity reported for 1972 was 14,000 metric tons (30 million
pounds) per year. ' The manufacturers reported were American Cyanamid
Company, Blue Spruce Company, and Prentiss Drug and Chemical Company.
Commercial production of malathion involves the addition of dimethyl -
dithiophosphoric acid to diethylmaleate. The reaction is usually conducted
in an organic solvent and in the presence of a proprietary basic catalyst:
S CHCOOC0HC S
II 25 H
(CH30)2P-SH + -(CH30)2P-SCHCOOC2H5
CHCOOC9H, CH9COOC9H,
L. 0 £ f. 0
The dimethyldithiophosphoric acid required for malathion synthesis is obtained
by the reaction of methanol with phosphorus pentasulfide:
2(CH30)2P-SH
Impurities (2-5 percent) in the technical grade malathion include trimethyl-
dithiophosphate, diethylmaleate, and residual solvent. The hydrogen sulfide
gas generated in the reaction of phosphorus pentasulfide with methanol is
generally processed for sulfur recovery.
A schematic flow diagram, including estimated mass balance for the pro-
duction of malathion, is shown in Figure 5-27. The technical grade malathion
was assumed to contain 3 percent impurities consisting primarily of diethyl-
(47)
maleate, trimethyldithiophosphoric acid and toluene. ' The flow diagram
(41 )
shown is from Lawless, Rumker and Fergusonv ' for a plant where the liquid
process wastes are barged to the sea.* Solid wastes from the filtration
step are disposed of in an approved landfill. The hydrogen sulfide-containing
product gas is processed for sulfur recovery. The total hazardous constituents
of the wastes are estimated at 0.084 kg per kg of technical grade product.
*0cean disposal regulations will probably forbid continuation of this prac-
tice and require a change to land-based treatment and disposal techniques.
5-100
-------
o i—<
ce
UJ
2
§
-------
5.3.2 Annual Process Stream Discharge to Land Disposal
Total Quantities
The estimated total quantities to land of process wastes, hazardous
wastes, hazardous components, and highly dangerous components for the pesti-
cides industries are presented in Tables 5-18, 5-19, and 5-20. The general
procedures used were those cited in Section 3 and Appendix A. More specifi-
cally, based on the data available in the literature and information obtained
through site visits and discussions with technical personnel in the industry,
estimates were made of the waste generation factors for "land-destined"
wastes for each of the 32 pesticides selected to represent the 17 pesticide
groups of SIC 28694. In cases where more than one pesticide was used to
represent a pesticide class, the waste factor for the class was calculated
as the average of the waste factors for the class representatives. These
class waste factors were then used to estimate waste quantities for each
class and the total waste generated in the pesticide manufacturing industry
(SIC 28694). Estimates of waste quantities for 1977 and 1983 were based on
assumed production increases of 10 percent (over 1973) and 21.6 percent
(over 1983), respectively,* and consideration of potential impacts of the
Federal Air and Water Pollution Control laws. In evaluating such impacts,
inputs were solicited from industry and their responses were considered in
estimating future waste quantities.
The "land destined" waste quantities for the pesticide formulation
industry (SIC 2879) were assumed to be 0.0033 kg of waste per kg of produc-
(28)
tion. ' The wastes were assumed to have the average composition of the
(28)
pesticide formulations/ ' which contained about 40 percent active ingre-
dients. This value for the weighted average composition was obtained by
determining, from Table 4-7, the ratio between the total production of tech-
nical organic pest control chemicals (SIC 28694) and the total production of
pesticide preparations and formulations (SIC 2879).
*The basis for the production increases assumed were the increases in gross
natic
Bank.
national product projected from the data published by the United California
5-102
-------
Table 5-18.
Process Waste Discharge to Und Disposa;
CY 1973, by Type and Standard Industrial
Pesticides Industries
ic Tons for
Tiassification,
EPA
4
10
£_
9
6
1
3
3
4
4
9
10
5
5
7
7
4
6
3
5
5
4
SUte
Alibana
Alalka
Arizona
Arkansas
California
Color adi)
Connecticut
Delaware
District of Columbia
Florida
Georgia
Hawaii
Idaho
Illinois
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maine
Maryland
Massachusetts
Michigan
Minnesota
Mississippi
7 Missouri
8
7
9
1
2
6
2
4
5
6
10
3
2
1
Montana
Nebraska
Nevada
New Hampshire
New Jersey
Mew York
Qklahona
Rhode Island
South Dakcta
6 : Texas
i
1C
V.T.«-
Total Process
Waste Streams
SIC 28694
35153
3492
16753
794
842
93
449
5,395
190
4245
1524
22729
255
7514
90
7012
6.931
19629
1151
109
1732
1524
407
146
6432
18687
Vermont
18
.... —V*-
5203
170,953
SIC 2879
88
11
88
580
88
22
11
274
153
11
11
197
55
110
33
11
165 ...
66
66
55
44
13
252
22
33
22
11
165
186
131
142
33
55
165
;w
99
99
383
11
44
11
55
4,159
Hazardous
Waste Streams
SIC 28694
35153
3492
16753
794
842
93
449
_5J395_
190
4245
1524
2272.9
255
7,514
90
7012
6,931.
10769
' 1151
109
1732
1,524
407
146
6432
14468
18
567
153,233
SIC 2879
88
11
88
580
88
22
11
274
153
11
11
197
K
no
... 33 .
11
165
66
51
. 44.
- „ .. 13
252 .
33
22
11
165..
136
131
142
33
.. 55
165
NA
99
99
383
11
44
as.
11
55
4,159
Hazardous Coinpon* r
SIC 286S4
15586
664
3258
386
24
93
19
965
36
562
2J2_
1Q283
1S6_
iaa.4 .
71
2,597
-4P73
5,465
210
0 1
96
290
148
55
2548
L 5739
0 1
552
91
56,161
SIC MX
35
4
35
232
35
9
4
no
61
4
4
79
22
44
13
4
65-
26
26
... .!?.._
18
S_
10!
9
1J_
. . 9 .
4
, . —46—-
74
b2
57
13
22
6o.__
40
40
153
4
18
35
4
22
1,638
H lyh Jy Dangeroui
Components
SIC 28694
9837
s re
^780
52
11
9
836
32
»I7
254
.___fim .
4
Ji'-4
34
_ JU2.I. .
..
.._ _aM_ ..
197
0. i
-. . «
7 •;.«:-.
63
209f
4468
0 1
W9
79.
35,316
SIC 2b79
?!
3
139
21
t
3
66
37
3
-1.3
26
3
. ... .1. .
. -10 -
16.
16.
Ji. ._
U .
J. .
.._ ..i. ..
. --S.
. __, 1
..J
.40. .
t5
32
.14 .
i
.13
. . .. 10
.24 . _
24
92
- '--
12
. 1' 1.
3
1,003
'EG:™ TOTALS
i
2
3
4
e
9
842
20780
680
49394
20,129
44908
r 13700
794
16753
3373
99
351
297
868
548
669
428
121
624
154
8420
11920
680
49394
15488
40689
12700
794
16,753
3973
99
^ 351
297
868
548
669
428
L izi
t" 624
154
24
5675
404
20898
J263
16686
- 1H1
386
3258
842
40 .
142
120
351
222
271
1 173
r 49
253
62
-.. _U.__.
2J.54
37
14J86
23nO
I'lBl
1192
52
2780
751. .
li-
89
75
?21
_..i.40_
PO
109
31
159
19
•rstt«ted, «ter-free basis, using the procedures given in Section 3 Section 5 3.2, and Appendix A The data for the calculations were
stained from the private industry sources listed in Table A-l and References 3-6, 10, 11, 37, 41, ,2, 52-5°..
5-103
-------
Table 5-19.
Process Waste Discharge to Land Disposal, Metric Tons for
CY 1977, by Type and Standard Industrial Classification,
Pesticides Industries
EPA
Heal on
4
10
9
6
9
_8
1
3
3
4
4
_5
_LQ
5
5
7_
7
4
6
1
3
]
5
b
4
1
8
7
9
1
2
6
2
4
8
5
6
ID
3
2
1
4
a
4
6
8
1
3
10
3
5
8
State
Alibaiu
Alaska
Arizpn*
Arkansas
California
Colorado
Connecticut
Delaware
District of Columbia
Georgia
Hawaii
Idaho
1 1 1 1 no i s
Indiana
Iowa
Kansas
Kentucky
Maine
Maryland
Massachusetts
Michiqan
Minnesota
Mississlooi
Mi ssouri
Montana
Nebraska
Nevada
New Hampshire
New Jersey
New Mexico
New York
North Carolina
North Dakota
Ohio
Oklahoma
Oregon
Pennsylvania
Puerto Rico
Rhode Island
South Carolina
South Dakota
Tennessee
Texas
Utah
Vermont
Virginia
Washington
West Virginia
Wisconsin
Wyom 1 ng
NATIONAL TOTALS
Total Process
Waste Streams
SIC 28694
42)568
3841
18591
978
1247
122
500
5952
211
6249
1676
26036
361
8623
191
10425
9153
Z5027
1418
159
2671
1676
527
221
9499
25/43
26
2844
5761
211,896
SIC 2879
97
12
97
638
38
24
12
301
168
12
12
217
60
121
36
12
181
73
;s
60
48
14
277
24
36
24
12
182
205
144
156
36
60
182
109
109
421
12
48
97
12
60
4,575
Hazardous
Waste Streams
SIC 28694
«2f68
3841
18,591
978
1247
122
500
5952
211
6.249
1676
26036
361
8623
191
10425
9153
15^81
1418
159
2671
1676
527
221
9499
20602
26
2844
666
•J^. 192,404
SIC 2879
"7
12
97
638
97
24
12
301
168
12
12
217
60
121
36
.12
181
73
73
60
48
.. . H. .
277
24
,.36
24
12
182
205
144
156
36
60
182
109
109
421
12
48
,97 ...
12
60
-f 4,575
Hazardous Components
SIC 28694
JM177
730
3695
543
135
122
23
1078
41
1477
319
12325
361
2^44
5,577
.. ,. 5^758
9347
432
9
447
319
192_
121
5226
11013
1
807
107
83,676
SIC 2879
Id
5
39
255
39
10
5
122 .
68
5
5
88
24
49
15
5
73
30
30
24
19
6
11?
10
15
10
5
74
83
58
63
1".
74
74
44
170
5
19
39
5
24
1,870
Highly Dangerous
Components
SIC 28694
640
3151
58
24
20
10
920
35
434
___2Z9_
7638
84
1753
30
5.804
[776
5551
237
779
77
119
4729
9478
0.1
569
87
58,557
SIC 2879
25
3
23
153
23
3
73
41
3
3
55
15
9
3
46
19
19
15
17
4
... . 70
,
fi
1
47
52
4fl
Q
47
28
28
107
3
__L2
25
3
15
1,112
REGION TOTALS
1
2
3
4
5
6
7
8
9
10
1247
26445
914
63,594
23409
55,120
17078
978
18591
4520
109
386
327
955
603
736
471
133
686
169
1,247
16699
914
63594
18,304
50,479
17078
978
18591
4,530
109
386
327
955
603
736
471
133
686
169
135
9,779
554
27413
4017
24068
7554
543
3695
1126
44
156
132
386
244
297
190
54
277
68
?4
5788
106
25,442
2893
17756
24811
. 58
3153
848
31J .
as _
83
243
153
____jaz
IL9 .
24
174
43
'Estimated, water-free basis, using the procedures given in Section 3, Section 5.3.2, and Appendix A, The data for the calculations were
obtained from the private industry sources listed in Table A-l and References 3-6, 10, 11, 37, 41, 42, 51-55.
5-104
-------
Table 5-20.
Process Waste Discharge to Land Oispos;.,
CY 1983, by Type and Standard Industria
Pesticides Industries
i%tn'c Tons for
" lastnfication,
EM
Stalsu.
4
10
9
6
9
8
1
3
. 3
4
4
9
10
5
5
7
7
4
6
1
3
1
5
5
4
7
8
7
9
1
2
e
2
4
8
5
6
10
3
2
1
4
8
4
6
8
1
3
10
3
5
8
State
ll.K^i
Al.lk.
AHUM
4rkaiuit
C.Hfornl.
Colorado
Coring tl cut
Delaware.
District of Columbia
Florid.
Georoia
Hu»1 1
Idaho
Illinois
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maine
Maryland
Massachusetts
Michigan
Minnesota
M1ss1ss1po1
Missouri
Montana
Nebraska
Nevada
New Hawshlre
New Jersey
New Mexico
New York
North Carolina
North Dakota
Ohio
Oklahoma
Oreoon
Pennsylvania
Puerto R1co
Rhode Island
South Carolina
South Dakota
Tennessee
Texas
Utah
Vermont
Virginia
Washington
West Virginia
Wisconsin
Wvomi nq
NATIONAL TOTALS
Total Process
Waste Streams
SIC 28694
47162
' 4246
20551
1081
1378
135
553
teSO
233
6908
1853
28782
399
9531
21!
11524
10119
27666
1567
176
2952
1853
583
244
10500
27905
29
3J44
- 6^69
232,800
SIC 2879
107
13
107
702
97
27
13
331
185
13
13
239
66
133
40
13
122.
SO
80
66
53
15 .
305
26
40
26
13
200
226
158
172
40
66
200
NA
120
120
463
13
53
107
13
66
5,054
Ha<:»idf
SIC 28694
2.435^
.83' _J
4P85
600
149
135
2n
H9I
4j>
liii.
&Z-.
J46Zi-
J2i
_ _._3531_
i 1B1
6 itiij
6^64
. . 10333 __|
47J . .
10.
m H
i ji2_
~ tLtZ
..
120
120
463
13
ll
107
n
66
5,054
___ 13-L-J
i//-'
12174
t
tn
I'S
93,1 ft
SI-_ 2"
6
43
280
43
11
6
134
zs
ft
6
97
JS
54
li
6
50
Jl
. _Ji
~Z6
Zl
J_
i2J
11
... .16. . -
Highly Dangerous
Components
SIC 28694
707
3486
§4
22
LL.
-401L
39
480
i09
L J1444
JU
1933
10
>>,%.!
JJIC4
.. Jl .,_ _
J)l
.31
t>f. . .
£2
. _ J6_. _
[_ ,.a
81
it
f\
12' .
- 47. _
'Estimated, water-free basis, using the procedures given in Section 3, Section 5.3.2. and Appendix A. The data for the calculat
obtained from the private Industry sources listed 1n Table A-l and References 3-6, 10, 11, 37, 41, 42, 51-ff.
5-105
-------
The method employed for estimating the waste quantities discharged to
land in each state for SIC 2879 (multiplying the waste generation factor
cited above by the national production prorated on the basis of the number
of establishments in the state) was the best procedure option which could
be used with the data available. The data required for the most accurate
approach were not available for use. The most accurate approach would have
been to obtain and use production information for each pesticide's prepara-
tion and formulation facility, summing the individual estimates by geograph-
ical area to yield state and regional totals.
The data presented in Table 5-20 indicate the far greater discharge of
process wastes to land disposal from the technical pesticides manufacturing
portion (SIC 28694) of the pesticides industries. The pesticide prepara-
tions and formulations industry (SIC 2879) process waste discharges to land
are generally less than 3 percent of those of the technical pesticides
industry.
The actual ("wet-basis") volumes of process wastes sent to land dis-
posal by the pesticides industries have been estimated by using the factor
3.17 (see Section 5.2.2 for derivation) for the ratio between wet-basis
wastes and dry-weight basis wastes discharged to the land. On this basis,
the pesticide industries wet-weight volumes of process wastes to the land
were estimated as 554,000 metric tons for 1973, 684,000 metric tons for 1977,
and 753,000 metric tons for 1983. The dry weight of the process waste
streams has been used as the basis for the estimates presented below for the
pesticides industries.
The projected impact on the pesticides industries of changes in waste
disposal practices in 1977 to meet the requirements of the Federal Water
Pollution Control Act, as amended, is far less, relatively,.than the impact
projected for the organic chemicals industry. The increase in estimated
waste discharge factors (e.g., hazardous waste stream discharge to land for
the technical pesticides industries from 0.297 kg per kg of product in 1973
to 0.339 kg per kg of product in 1977) is the best indicator since it elim-
inates the effect of increases in production. The major reason for the
decreased impact of the Act as amended is undoubtedly the extremely high
proportion of pesticide industry wastes discharged to the land currently
5-106
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due to the high toxicity of these wastes. Since, general t.oxicity had
ruled out discharge to water in the past, the amended Act ^ requirements
for removal of hazardous materials from outfalls would not cause the type
of increase to land disposal for pesticides t:hat is projected for the
organic chemicals industry.
The state which has the highest estimated totals in 6U process waste
discharge categories (total process waste streams, Hazardous waste streams,
hazardous components, and highly dangerous components) to* 1373, 1977, and
1983 is Alabama; Louisiana and New Jersey rank sei,;,-:-! tir.-i third in total
process waste discharged to land in 1973. ft is anticipated that Louisiana
and Texas will rank second and third in 197/ and 19^3 in total process waste
sent to land.
Louisiana and California discharged the second and third highest totals
of hazardous waste streams to land in 1973. Jn 1977 c*nd 1983, Louisiana and
Texas are projected to be second and third highest in hazardous process waste
discharges. Louisiana and Texas, whose quantities of hazardous components
discharged to land were second and third highest in 19/5, are also projected
to be second and third in this category of wasU> discharge in 1977 and 1983.
The same states are estimated to have discharged the second and third largest
quantities of highly dangerous components to lano in K'/3- The projections
for 1977 and 1983 indicate that Texas will be second and Louisiana third in
quantities of highly dangerous components seat to land disposal.
Approximately 90 percent of estimated arid projected process wastes dis-
charged to land are classified as hazardous waste streams, for all three years
in the study (1973, 1977 and 1983). Approximately 37 percent of the weight
(water-free basis) of these hazardous waste streams, was composed of hazardous
components in 1973. In 1977 and 1983, this quantity will increase to about
43 percent. Highly dangerous components constituted 23 percent of the esti-
mated gross "dry" weight of the pesticide industries' hazardous waste streams
in 1973, and will constitute 30 percent of the gross dry weight projected for
1977 and 1983.
Pesticide Formulation^47'48^
Successful use of pesticides depends to a larye extent on the formula-
tion of the product into a preparation which can be used directly or can be
5-107 : ,
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reformulated and brought most effectively into contact with the target pests
in a safe and environmentally acceptable manner. The most important types
of formulations are powders, dusts, wettable powders, emulsifiabls concen-
trates, granules, and aerosols. The type of formulation most suitable for
a specific application is dependent on a large number of factors, including
physicochemical properties and biological efficiency of the active ingre-
dient, host-pest relationship, characteristics of the available production/
application equipment, and economic and environmental considerations.
Dusting is frequently the most inexpensive and simplest method for
applying pesticides. Pesticidal dusts consist of a physical mixture of
active ingredients with fine particles (3-30y) of an inert carrier/diluent.
The concentration of active ingredient may range from 0.1 to 20 percent.
The carriers most widely used are organic flour, sulfur, silicon oxides,
lime, gypsum, talc, pyrophyllite and bentomite. In making dusts, the
ingredients are usually ground in a hammer, impact, vertical roller, or
fluid-energy mill.
Wettable powders are solid formulations which can be dispersed in water
to produce stable suspensions for more effective application by spraying. A
surface active agent (1-2 percent) is usually used to impart wettability and
suspendibility of the powder. Wettable powders are usually formulated in a
manner similar to that for dust production. Wettable powders, however, are
generally more concentrated in the active ingredient (15-95 percent). Emul-
sifiable concentrates are pesticide formulations which upon dilution with
water yield stable emulsions suitable for spraying plants and surfaces. The
concentrates are prepared by dissolving the active ingredients (15-80 percent)
and a surface active agent (less than 5 percent) in a water-emulsifiable
organic solvent. The surface active emulsifiers commonly used include cal-
cium sulfonates, polyethylene and polypropylene glycols, various soaps, and
salts of naphthenic acids.
Granulated pesticide formulations are prepared by impregnating granular
(0.2-1 mm particle size) inert carriers with liquid pesticides or their solu-
tions. The inert carriers most commonly used include clay, vermiculite, ben-
tomite and diatomaceous earth. The impregnation involves mixing or spraying
of the inert granules with the active ingredient in a liquid form. Solid
pesticides are usually melted or dissolved in a solvent prior to use.
5-108
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For applications as aerosols, the active ingredient i',; commonly dissolved
in water or a suitable organic solvent and then packaged with a propellent
into various types of pressurized containers. The pesticides solution usually
contains less than 2 percent active ingredient and may also contain a number
of special purpose additives (e.g., for odor-masking or for enhancing the
effectiveness of the active ingredient).
The most important unit operations in pesticide formulation are dry mixing
and grinding of solids, dissolving or melting of solids, and blending. Virtu-
ally all formulations are batch-type operations. Depending on the location of
the site, the operation may be conducted in the open or it may be enclosed
within a building. In a formulation plant, the same production equipment is
generally used for the formulation of more than one product. The possibility
of cross-contamination is a serious problem which can only be minimized by
adequate cleaning prior to product "switch-over". A schematic presentation
of a typical liquid formulation unit is presented in Figure 5-28.
Wastes from formulation of the pesticides originate from spills, "off-
spec" batches, equipment clean-up and mixing and grinding operations. The
exact quantity of the waste is affected to a large extent by the in-plant
management practices of good housekeeping. As was indicated earlier in this
section, the quantity of land-destined wastes generated in the pesticide for-
mulation industry is estimated at 0.0033 kg of waste per kg of production,
with the waste containing about 40 percent active ingredients.
5.4 EXPLOSIVES INDUSTRY
As was indicated in Section 4.4.2, explosives-containing wastes origi-
nate from the manufacture of basic explosives, from explosives formulation,
and from loading, assembling, and packing (LAP) operations. Basic explosives
which were manufactured in significant quantities in 1973 were TNT, nitro-
cellulose, nitroglycerin, RDX, and HMX. Section 5.4.1.1 contains brief
descriptions of the manufacturing process for each of these basic explosives.
The production of Composition B, dynamites, and a double-base propellant are
described in Section 5.4.1.2 as examples of formulation operations. The
description of a typical LAP operation is also presented in Section 5.4.1.3.
Quantitative data on land-destined hazardous wastes for the explosives indus-
try are presented in Section 5.4.2.
5-109 i ,
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5.4.1 Typical Plant Process and Waste Stream Descriptions
5.4.1.1 Manufacture of Basic Explosives
TNT Production
TNT manufacture involves the nitration of toluene with a mixture of
nitric acid and fuming sulfuric acid (oleum). The sulfuric acid acts as a
catalyst and a dehydrating agent, absorbing and reacting with the water which
is formed by the nitration reactions. The operation may be batch type ("old"
technology) or continuous ("new" technology). Although in 1973 both methods
were being used for TNT production, plant modernization programs planned for
the Army ammunition plants (AAPs) call for replacement of all the remaining
existing batch TNT lines with the new Canadian Industries Limited (CIL) con-
tinuous TNT lines.
Figure 5-29 is the schematic flow diagram for the batch TNT process and
the associated satellite operations.* (The flow diagram is for the Joliet
AAP which was the largest TNT producer in 1973). The nitration reactions
are carried out in three consecutive batch units referred to as "mono-",
"bi-", and "tri-" houses. The feed chemicals to the mono-house are toluene
and the waste acid from the bi-house which is fortified with 60% HNCL. The
charge is allowed to settle, the waste acid is transferred to a storage tank
(for subsequent recovery), and the partially nitrated toluene (mono oil) is
pumped to the bi-house where further nitration is effected in the presence
of waste acid from the tri-house fortified with 60% HN03. The nitrated
product (bi oil) from the bi-house is pumped to the tri-house where the feed
acid is a mixture of 98% nitric acid and oleum. The nitrated product from
this third-stage operation is crude TNT containing a-TNT (2,4,6-trinitro-
toluene) which is the desired product, and TNT isomers which are the impu-
rities. The crude TNT is gravity fed to the wash house for purification.
The purification of crude TNT involves crystallization in water, neu-
tralization of free acid with soda ash and solubilization and removal of
undesirable nitrated products by treatment with a solution of sodium sulfite
*The satellite operations, with the exception of Red Water Disposal, will
not be considered in this study. (Red Water Disposal is discussed in
Section 6.4.1.)
5-111
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(sellite). The wastewater from the sellite purification =tage is the "red
water" which is sent to the red water treatment plant for disposal by
evaporation/concentration and concentrate incineration. The TNT slurry is
transferred to a filter tank where it is washed and filtered on a screen
leaving layers of TNT crystals. The crystals are reslurried with water and
pumped to a melt tank where TNT is melted and most of the water is removed
by evaporation. The molten product is run into hot air driers for the
removal of residual water. The water-free product is solidified on a water-
cooled flaker drum and the resultant film is removed in the form of small
flakes by scraping with a beryllium blade scraper. The flake TNT is boxed
and sent to a packing house for transfer to the magazine storage area.
Continuous TNT lines were in operation at Radford AAP (Va.) in 1973.
As of September 1974, when Joliet AAP was visited, three continuous TNT
lines were expected to become operational soon and three additional lines
were under construction.* In the production of TNT by the continuous proc-
ess, the nitration of toluene is carried out in six nitrator-separator
stages with the organic phase (toluene-nitrobody mixture) flowing counter-
current to the acid phase. Nitric acid fortification is provided at inter-
mediate points in the process. The first and third nitration stages have
two nitration vessels per separator, whereas the remaining four stages have
only one nitration vessel per separator. Extensive instrumentation pro-
vides for safe operation and automatic process control. If the process
temperature in a nitrator vessel exceeds a pre-set level, the feed to the
nitrator is automatically shut off and the contents of the nitrator and
separator are automatically discharged into drowning tubs. For TNT purifi-
cation, the crude TNT first passes through a mixer-settler washer where five
separate countercurrent water washes remove the free acids. The acid wash
is returned to the second nitrator as acid make-up. The TNT flows through
two sellite washers in series where it is neutralized with soda ash and
treated with sodium sulfite. Each of the sellite washers is followed by a
separator which separates the aqueous phase (red water) from the purified
*Flow diagrams for TNT production by the continuous process have .not been
given due to time and effort constraints
5-113
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TNT phase. The dilute red water from the second separator is returned to the
first separator, and the more concentrated red water from the first separator
is sent to the red water treatment plant. The sellite-treated TNT receives
final countercurrent water washes and is slurried and pumped to the finishing
building for drying, flaking and packaging.
The major sources of aqueous wastes in TNT manufacturing are reo water,
spent acids, acid spills, TNT spills, cooling water, and overflows from catch
basins and drowning tubs. As indicated in Figure 5-29, the red water is dis-
posed of in the red water treatment plant and the spent acids are treated in
the acid recovery facilities. The remaining wastewaters from TNT manufac-
turing are treated (usually in combination with other plant wastewaters)
prior to final disposal. The major objectionable constituents of these
wastes are TNT particles, nitrobodies, sulfate, nitrate, acidity (low pH),
and color (due to the presence of nitrobodies). The gaseous wastes in the
TNT manufacturing are acid fumes which evolve from the nitration and separa-
tion vessels. These fumes are withdrawn by the application of a constant
suction above the tanks and sent to the fume recovery facility (see Fig-
ure 5-29) for treatment/disposal. The solid wastes associated with TNT
manufacturing are scrap TNT, and settled TNT sludges collected in sumps in
the TNT wash and recovery houses. As discussed in Section 6.4.1, the current
disposal method for waste explosives is open-burning.
Table 5-21 presents the material balance for batch TNT production and
associated satellite operations. The data are for Joliet AAP and are based
on 1969 production and operating conditions. From the standpoint of pollu-
tant discharges to the environment, somewhat lower values would be expected
for the present-day operation due to improvements in process control and
housekeeping and increased environmental awareness on the part of operating
personnel and plant management. Material balance data for the continuous
TNT lines are presented in Table 5-22. These data were obtained from Radford
AAP (Radford, Va.) which in 1973 operated three CIL continuous TNT lines.
Nitrocellulose (NC) Production
Nitrocellulose is produced by nitration of cellulose (wood pulp or cot-
ton linters). A mixture of nitric and sulfuric acids is used for nitration,
with the sulfuric acid acting as a catalyst and dehydrating agent. A block
5-114
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Table 5-22. Mass Balance Data for TNT Production by the Continuous
Process (Radford AAP, Radford, Virginia)
Process Input
kg per kg of TNT
Process Output
kg per kg of TNT
TNT/Nitrobody Losses
Toluene 0.48
Weak Nitric Acid 0.53
Strong Nitric Acid 0.80
Oleum 2.5
Sellite 0.085
Purified TNT 1.00
Red Water 0.50
Spent Acid 3.70
Total: 15% based on
toluene feed (6% iso-
mers and a-TNT in red
water; 6-8% oxidation
products in fume
gases; 1-3% isomers
and oxidation prod-
ucts in spent acid).
flow diagram of the batch NC production at Radford AAP is presented in
Figure 5-30. In the nitrator house, a charge of wood pulp fibers (or cot-
ton 1 inter, depending on the type and grade of NC desired) are treated with
a nitric-sulfuric acid mixture. After nitration, the spent acid is removed
and crude NC is transferred in the form of a water slurry to the boiling tub
house where it is stabilized by an acid boil, two neutral boils and three
water washes. In the beater house the NC is cut to desired size. In the
poacher house, the NC slurry is pumped into wooden tubs where it receives
a neutralization treatment (a soda (sodium carbonate solution) "boil"),
three neutral "boils", and three wash cycles. The NC is then screened and
transferred to the blender house where NC of various analyses are mixed to
produce the specific blend desired. The final purification operation is
performed in the wringer house where NC is wrung through centrifugal
wringers to obtain a product containing a small and uniform amount of
moisture.
Aqueous wastes from NC production originate from washing, boiling and
dewatering. The neutral boil wastewater from the boiling tub house contains
most of the NC fines lost during operations and processing. This and other
wastewaters are currently collected in special pits where most of NC fines
settle out and are periodically removed and returned to the process for
reuse. The quantity of NC fines currently lost in the overflow is estimated
at 1 metric ton (2200 lbs)/day/line, or about 0.072% of the NC output. In
5-116
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the future this loss of NC fines will be significantly reduced when the
neutral boil wastewater is isolated and treated separately by centrifuga-
tion. Based on data for Radford AAP, for a production rate of 66,000 kg/day
and with a considerable amount of water recirculation, the total volume of
3
the final wastewater effluent from NC production is estimated at 9500 m
per day (2.5 million gallons per day). The major solid waste from the
process is contaminated NC which is estimated at 1-2 percent of the NC
production. Acid fumes are the major air pollutants from NC production.
Plant modernization program for Radford AAP calls for the replacement
of the batch operation with a continuous NC production process. Table 5-23
presents mass balance data for the proposed continuous lines. The data are
based on the production of 50 percent 1 inters NC and the use of Delaval centri-
fuges for the removal of NC fines from wastewaters.
Nitroglycerin (NG) Production
Nitroglycerin is manufactured by a closely controlled reaction between
glycerin and a mixture of nitric and sulfuric acids. The reactor is equipped
with cooling coils through which a cold brine solution is circulated. Both
batch and continuous (Biazzi) processes are in current use. One commercial
nitroglycerin manufacturing plant uses a mixture of glycerin and ethylene
glycol as the starting material; the product obtained in this plant is a mix-
ture of nitroglycerin and ethylene glycol dinitrate.
Following nitration, the NG is separated from the spent acid by gravity
separation and purified by washing with water and with a solution of sodium
carbonate. Most facilities are equipped with settling pits and catch basins
for the capture and return to process of most of the nitroglycerin particles
entrained in the wastewaters. At Radford AAP, the spent acids are recovered
and reused. Steam is used for denitrifying the spent acid at one commercial
facility. At this facility, the effluent steam containing nitric acid is dis-
charged directly to the atmosphere, and the sulfuric acid is stored in a
lagoon for sale as a by-product. A block flow diagram for NG production is
presented in Figure 5-31. Table 5-24 presents the material balance for NG
production (based on operating conditions at Radford AAP).
5-118
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Table 5-23. Mass Balance Data for Modernized Nitrocellulose
Production (kg per kg of NC Produced)
Feedstocks
Cellulose 0.61
HN03 1.67
H2S04 0.50
Products/losses
Cellulose in NC
Cellulose lost
HNOo recovered
HNOo consumed
HNO- lost in fumes and to wastewater
HpSO, recovered
HpSO. lost to wastewater
0.60
0.01
0.76
0.91
0.41
0.46
0.04
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Production (kg per kg NG Produced)
Mixed Spent Acid Input
Glycerin
Soda Ash
Spent Acid
Waste water
NG Lost to Waste water
2.13
0.42
0.12
0.15
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5-121
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HMX and RDX Production
HMX (cyclotetramethylenetetranitramine) and RDX (cyclotrimethylene-
trinitramine) are used in the formulation of a variety of explosives compo-
sitions for ballistic use (see Section 5.4.1.2). A schematic flow diagram
for the production of HMX and RDX at Holston Army Ammunition Plant is shown
in Figure 5-32. Except for some differences in reaction conditions (e.g.,
reaction temperature), solution strength, and the handling method in the
purification stage, the production steps for RDX and HMX are essentially
identical. In fact, a small quantity of RDX is produced as an undesirable
side-product in the production of HMX, and vice versa.
RDX/HMX manufacture is essentially a batch operation involving nitra-
tion of hexamine. The starting raw chemicals are nitric acid, ammonium
nitrate, acetic acid, acetic anhydride, and hexamine. Following nitration,
the crude production is vacuum filtered and washed until the residual acid
content is less than 1 percent. Initial filtrates which contain about 60
percent acetic acid and 2-3 percent nitric acid are sent to an acid recovery
facility and the secondary filtrates are combined and returned to the nitra-
tion building for reuse in slurrying the product. Washed explosives are re-
slurried with water and pumped to the finishing building. There RDX is
recovered directly in dissolvers where solvent, either acetone or cyclohexanone,
is added to effect dissolution prior to recrystallization. HMX is received in
a tank where the solids settle out and the water is decanted to a filtration
unit ("neutch"). HMX is then pumped to dissolvers where solvent is added
for dissolution. The product is recrystallized from the solvent and the sol-
vent is recovered for reuse. The objective of recrystallization is to remove
residual acidity, to control particle stze, and to improve product stability.
The spent acid from filtration of the crude RDX/HMX contains about
60 percent acetic acid, 2-3 percent nitric acid and some RDX/HMX. The spent
acid is neutralized with sodium hydroxide and sent to the primary evaporators
where about 80 percent of the acetic acid is recovered as a 60 percent solution.
The residual "sludge" is then removed, diluted, heated and cooled to effect
crystallization of RDX/HMX. To aid and promote recrystallization, a slurry
of purified RDX/HMX is added to the solution during cooling. The crystallized
product is then recovered in cyclone separators and sent to the process for
5-122
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reuse. A portion of the resulting liquid is recycled to the primary
evaporators and the rest is sent to secondary evaporators for further
recovery of acetic acid. The "sludge" from the secondary evaporator is
treated with sodium hydroxide to decompose residual RDX/HMX and to recover
ammonia for reuse. The final sludge from the causticizing operation is
neutralized with 61 percent nitric acid and evaporated to recover sodium
nitrate which can be sold as a fertilizer.
The acetic acid (60 percent) recovered in primary and secondary evap-
orators is concentrated to 99 percent strength by azeotropic distillation.
The operation generates about 5,400 kg (12,000 lb)/month of a wastewater
(at 40 percent operating capacity) containing methyl nitrate (10 percent),
nitromethane, methyl acetate, propyl formate, propyl acetate and other
esters and alcohols. At present, the wastewater is subject to biological
degradation in a treatment lagoon. A portion of the concentrated (99 per-
cent) product acetic acid is sent to process for reuse; the remaining quan-
tities are used for the production of acetic anhydride.
5.4.1.2 Explosives Formulation
Production of propellents and explosive compositions, and "packing"
the explosive products into munition items (LAP operations) are considered
here as formulation operations. Wastes requiring treatment/disposal origi-
nate from spillage of ingredients and final products, materials not meeting
specifications, and from general equipment clean-up. At Army ammunition
plants, the production of propellants, explosive compositions, and munition
items are versatile operations with the production facilities capable of
producing a wide variety of products for different applications.
Propellants
Most of the propellants produced currently are of two basic types:
solvent and solventless. Depending on the number of explosive ingredients,
solvent-type propellants may be single-base, double-base, or triple-base.
Typical compositions for a single-base, a double-base and a triple-base
propel 1 ant are shown in Table 5-25. Solvent propellants are produced by
mixing the ingredients in a suitable organic solvent (ethyl alcohol, acetone,
5-124
-------
Table 5-25. Typical Composition of Propellants (Percent)
Major Ingredients
Nitrocellulose
Nitroglycerin
Nitroquanidine
Dinitrotoluene
Dibutyl phthalate
Diphenylamine
Potassium sulfate
Ethyl central ite (symmetrical
di ethyl diphenyl urea)
Barium nitrate
Potassium nitrate
Graphite
Cryolite
Single Base
84
—
—
10
5
<1
:1
—
—
—
—
Double Base
67
25
—
—
—
—
—
6
0.75
0.70
0.3
—
Triple Base
48
28
22
—
—
—
—
1.5
—
—
—
0.3
ether, etc.) to obtain the desired blend. The mixture then undergoes a
series of operations for shaping into cylindrical blocks, extruding into
strands and cutting to desired size. The operation is batch process and in
general most of the solvent is recovered and reused. Production of solvent-
less propellants ("rolled powder") is similar to that for solvent propellents
except that no organic solvent is used in the mixing step. The operation is
a batch process in which nitrocellulose, nitroglycerin and other ingredients
are slurried in water, wrung to a wet cake, and dried to a paste. The paste
is then rolled into sheets and wound into a "carpet roll" for extrusion into
small rocket grains, or processed into "mortar increments".
Based on the operation at Radford AAP, the quantity of explosive wastes
generated in the manufacturing of propellents is estimated to range from 4-10
percent of the finished product. In the production of double-base propel-
lants, approximately 0.125 kg of ethyl alcohol and 0.1 kg of acetone are lost
to the atmosphere per kg of propellant manufactured.
Explosive Compositions
Holston AAP (Kingsport, Tennessee) formulates a variety of explosive
compositions for use by the military with minor use by the National Aeronautic
and Space Administration. These explosive compositions have specified ballistic
5-125
-------
properties and contain RDX or HMX as their prime Ingredient. The production
operation involves addition of RDX (or HMX) to various explosives (e.g., TNT),
and nonexplosive (e.g., wax) compounds to produce a plastic bonded material
or a solidified end product. The make-up of a number of major military
explosive compositions are presented in Table 5-26.
Based on the weekly Burning Ground record for May 20 to July 22, 1974, '
(18)
and the 1973 production data/ ' the solid waste generated in the formula-
tion of Composition B is estimated at 0.0005 kg of waste per kg of final
product.
Dynamites
Although there are many different dynamite formulations, most commercial
dynamites contain nitroglycerin and sodium and/or ammonium nitrate as their
major ingredients. Many dynamites are formulated to the customer's specifi-
cations and some also contain a number of proprietary ingredients. The most
common ingredients of dynamites are listed in Table 5-27. Typical composi-
tion for "straight" dynamite with "active" base (sodium nitrate) is presented
in Table 5-28.
Dynamite formulation involves, first, mixing ammonium and/or sodium
nitrate with various nonexplosive ingredients. Nitroglycerin is then added
and the product is transported to a cartridge house for packaging into
waxed cardboard boxes or plastic tubes for final shipment or storage in
magazines.
Wastes from dynamite formulation originate from spills, off-spec prod-
ucts, and equipment clean-up. A waste generation factor of 0.3 percent of
(57)
the production rate is estimated for the formulation of dynamite. '
Ammonium Nitrate-Fuel Oil Mixture (ANFO)
In 1973 ANFO compositions accounted 'for close to 70 percent of all com-
mercial explosives used. ANFO is a mixture of ammonium nitrate (about 94 per-
cent) and fuel oil (about 6 percent) to which may be added a variety of minor
ingredients such as aluminum powder, ferrophosphate, coal, calcium silicate,
Atticote, and mineral oils. Some ANFO compositions may contain up to 5 per-
cent aluminum powder. ANFO formulation may be a batch or a continuous
5-126
-------
Table 5-26. Makeup of Major Explosive Compositions
Explosive
Composition
Principal Ingredients
Composition A-3
Composition B
Composition C-4
Cyclotol 70/30
Octol 70/30
Octol 75/25
RDX (91%), Wax (9%)
RDX (60%), TNT (39%), Wax (1%)
RDX (91%), Polyisobut-lene (2.1%), Motor
oil (1.6%), di(2-ethylhexyl) sebacate (5.3%)
RDX (70%), TNT (30%)
HMX (70%), TNT (30%)
HMX (75%), TNT (25%)
Table 5-27. Common Ingredients of Dynamites
Nitroglycerin
Ammonium Nitrate
Sodium Nitrate
Sodium Chloride
Calcium Carbonate
Sulfur
Nitrocellulose
Phenolic Resin Beads
Bagasse
Sawdust and Wood Pulp
Coal
Corn Meal and Corn Starch
Trace Inorganic Salts
Grain and Seed Hulls and Flours
5-127
-------
Table 5-28. Typical Composition of "Straight" Dynamite with "Active" Base
Component
Nitroglycerin
Sodium Nitrate
Wood Meal
Calcium Carbonate
Percent, Weight
40
44 - 45
12 - 15
1 - 3
blending operation, with waste originating mainly from spillage and equipment
clean-up. Solid waste generated in the formulation of blasting agents (ANFO
and water gels and slurries) is estimated as approximately 0.1 percent of the
production. Large, centrally located ANFO formulators market their products
in bulk or in bags or cylinders. Occasionally, the fuel oil is "dyed" prior
to mixing with the nitrate salt to identify specific formulations. Many of
the small ANFO formulators are located near mine use areas. These on-site
facilities receive ammonium nitrate and fuel oil in bulk quantities, blend the
ingredients to customer specifications and transport the finished ANFO by
trucks to the mine.
5.4.1.3 LAP Operations
Most of the Army ammunition plants which conduct LAP operations do not
have on-site explosive manufacturing capabilities. In these plants, the
explosives are shipped in from other AAP's. Most LAP operations involve
melting of the explosives and loading the molten product into metal shells
of projectiles. The loaded projectiles are cooled, transferred to an assem-
bly area for the installation of end items, inspected, and the acceptable
rounds are packed for shipment and/or storage. The operational flow chart
for a loading line at Louisiana AAP (Shreveport, La.) is shown in Figure 5-33.
Solid wastes generated in LAP operations include contaminated and rejected
explosives, floor sweepings containing spilled explosives, and explosive-
containing sludges from wastewater collection sumps. Wastewaters originate
5-128
-------
RECEIVE EMPTY
PROJECTILES
RECEIVE
EXPLOSIVES
RECEIVE
CLFAN SCRAP
EXPLOSIVES
FEED TO MELT
UNIT GRID
POSITION
PROJECTILES
UNDER POUR
OBTAIN DESIRED
TEMPERATURE
EXPLOSIVE
DRAW MOLTEN
EXPLOSIVE INTO
HOLDING TANK
EXPLOSIVE
WASTES
SCRAP
EXPLOSIVE
EXPLOSIVE
-»•
WASTES
EXPLOSIVE
WASTES
WATER TO SUMPS
PACK & SHIP
PROJECTILES
Figure 5-33.
Operational Flow Chart for a
Projectile Loading Line
5-129
-------
mainly from "steam-out" and wash-out of rejected bombs and from washing of
equipment and floors. Since TNT is usually an ingredient of the explosives
used, the wastewaters from LAP operation are characteristically pinkish in
color and are referred to as "pink water". Carbon adsorption is an effective
method for the removal of nitrobodies from pink water; disposal of spent car-
bon is a problem in solid waste management. Very little air pollution is
associated with the LAP operation.
There are significant variations in waste generation factors for differ-
ent LAP operations, depending on the specific items loaded, method and equip-
ment used for loading, and extent of in-plant waste management and housekeeping,
Two typical waste generation factors are 0.0132 and 0.0416 kg waste explosives
per kg of explosives in product ordnance items. Material balance for two
LAP operations at Joliet Army ammunition plant is shown in Table 5-29.
Modernization programs, which are planned for this plant and for other AAP's,
are expected to result in significant improvements in the operational effi-
ciency of the LAP lines and, hence, in a reduction in the quantity of waste
generated.
5.4.2 Annual Process Stream Discharge to Land Disposal
Table 5-30 contains a summary of the estimated quantities of hazardous
wastes generated in the production of commercial explosives. The following
assumptions were used in arriving at these estimates: (1) The quantity of
explosives produced in each state or EPA region is equal to the quantity of
explosives sold for consumption in that state or region (Table 4-10). (2)
Waste generation factors for fixed high explosives and blasting agents are
0.003 and 0.001 (weight per weight of product), respectively. ' These
assumptions and estimated production increases (over the 1973 level) of
10 percent by 1977 and 21.6 percent by 1983 were used to estimate waste
quantities for 1977 and 1983. The production increases reflect the increases
in the GNP projected for 1977 and 1983.^51^
The 'wet-basis" quantities of process waste sent to land disposal
by private explosives industry were estimated assuming that the ratio
between wet-basis wastes and dry-weight basis wastes discharged to the
land, is the same as that for the organic chemicals industry, (i.e., by
using a factor of 3.17 - see Section 5.2.2). On this basis the private
5-130
-------
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5-131
-------
Table 5-30. Explosive Wastes Discharged to Land Disposal, Metric Tons
for CY 1973 for the Private Explosives Industry (SIC 28921)
(With Comparative Totals for CY 1977 and CY 1983)
EM
Imaia,
'
10
9
6
9
a
1
3
3
4
4
9
10
.. 5
5
7 .
7
4
6
1
3
I
_5
5
4
7
e
7
9
1
. 2
6
2
4
8
5
6
10
3
Z
1
4
a
4
6
a
i
3
10
3
5
8
State
JUjhM
Alaikl
Arizona
Arkansas
California
Colorado
Connecticut
Delaware
District of Columbia
Florida
Georoia
Hani 11
Idaho
Illinois
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maine
Maryland
Massachusetts
Michigan
Minnesota
HISslsSlOOl
Missouri
Montana
Nebraska
Nevada
New Hampshire
New Jersey
New Mexico
New York
North Carolina
North Dakota
Ohio
Oklahoma
Oreaon
Pennsylvania
Puerto Rico
Rhode Island
South Carolina
South Dakota
Tennessee
Texas
Utah
Vermont
Vlrqlnla
Washington
West Virginia
Wisconsin
Wyoming
NATIONAL TOTALS
Fixed HE
18
6
e
3
7
12
9
0 17
34
8
0 63
4
18
3
12
2
38
2
2
6
5
5
3
3
IB
4
0.87
0.59
2
4
5
11
9
13
3
7
39
0.30
2
0 39
19
9
3
2
22
6
24
4
1
41 72
Blasting Agents
81
0.35
83
7
28
6
6
0.005
10
12
1
4
45
S4
10
3
142
2
1
5
2
24
51
0.006
26
1
0.69
12
0.31
2
27
8
10
.... . 0,37
6S
15
4
117
0.28
1
0.84
35
18
17
0 18
38
5
62
8
5
mi2
Total His Us
N
6
91
10
35
18
15
0 18
44
20
2
8
63
57
22
5
180
4
3
11
7
29
54
3
44
5
2
13
2
6
32
19
19
0.37
81
18
11
156
0.58
3
1
54
27
20
2
60
11
86
12
6
1528*
Total - 197/
109
6
100
11
38
19
16
0.2
48
22
}
9
70
64
24
6
198
4
3
12
7
32
59
3
48
6
2
14
3
5
36
21
20
0.4
89
20
12
171
0.6
4
1
59
29
22
2
66
13
95 _
13
6
16812
Total - 1983
120
8
110
12
42
22
18
0.2
53
24
2
10
77
70
27
7
219
5
4
13
8
36
66
3
54
7
2
15
3
5
40
23
22
0.4
98
22
... 13
0.7
4
1
65
32
24
3
73
14
105
IS
'
18582
REGIONAL TOTALS
1
2
3
4
5
6
7
8
9
10
20
15
91
131
46
22
33
20
16
23
Estimated, water-free basis, using the proce<
The data for the calculations w>s obtained f
Includes undistributed production (that port
allocation was possible).
11
10
222
291
250
69
40
30
124
13
31
25
313
422
296
91
73
50
140
36
34
27
344
463
327
100
80
54
154
40
37
28
380
570
362
111
90
66
169
45
ures given in Section 5.4.2 and Appendix A "Methodology Details."
-on References 7, 16, 51 and 57.
on of the national total reported for wnlch no state or region
5-132
-------
explosives industry was estimated to have discharged approximately 5,000 met-
ric tons (wet-basis) of process waste to land in 1973. The figures projected
for 1977 and 1983 were 5,500 metric tons and 6,000 metric tons (wet-basis).
Estimates of the 1973 waste quantities for the manufacture of military
explosives are shown in Table 5-31. The data are based on:(l) a 1974
Resource Recovery Information survey by U. S. Army Material Command Installa-
tion and Service Agency, ' (2) visits to several Army ammunition plants
and arsenals, and (3) the TRW data file on operations at various AAP's.
Historically, the production at ammunition plants has varied significantly
in response to the fluctuating demand for munitions. As an example, Joliet
AAP was first placed in operation during World War II. In August 1945 all
production of explosives was halted, the sulfuric acid and ammonium nitrate
plants were leased out, and the remaining production facilities were put in
lay-away status. In August 1965, reactivation of the explosives manufacturing
area was initiated and production of chemicals and explosives commenced in
April 1966. In the LAP area, the operation was also halted in August 1945.
The facility, however, was reactivated in 1951 for the Korean action. Sub-
sequent curtailment of the operation was started in 1956 although the AAP
was in a high state of readiness until it was reactivated in October 1966.
Since early 1969 there has been a general gradual decrease in the production
rate with current (1974) production level close to the minimum for the period.
Because of the extreme unpredictability of future political and military
conditions, it is exceedingly difficult, if not impossible, to estimate muni-
tion production for 1977 or 1983. This was indeed the response received from
plant managers and Army personnel during site visits and interviews. The
prediction of the quantity of wastes requiring final disposal is even more
difficult in the light of planned pollution control and modernization pro-
grams. These programs, which will result in significant reductions in pollu-
tion generation, are at various stages of design, construction, planning, and
funding consideration. Although tentative target dates have been established
for most of the projects, in the past the target dates have not always been
met and some of the programs have been cancelled or modified.Because of these
uncertainties which influence both production and waste generation, 1977 and
1983 waste production were assumed to remain at the 1973 level, which reflects
peacetime operations.
5-133
-------
Table 5-31
Explosive and Explosive Contaminated Wastes Discharged to
Land Disposal, Metric Tons for CY 1973 - GOCO Plants,
Explosive Industry (SIC 28922)*
EM
talon
«
10
9
6
9
a
1
3
3
4
4
9
10
5
5
7
7
4
6
1
3
1
5
5
4
7
B
_7
9
1
2
6
2
4
a
5
6 ,
10
3
2
1
4
8
4
e
e
i
3
10
3
5
8
SUtt
AJlfelL-
AlUl*..-_
»riz( u
Arkansas
Calliornla
Coloi ado
Connecticut
Delauare
District of Columbia
Florid.
Georufa
Hawaii
Idaho
illilBli.
IraUf/a
Iowa
Kanses
Kentucky
Louisiana
Maine
Mary 'and
Massachusetts
Mich. dan
Minnesota
Mlsslsslpol
Missouri
Mont,.na
Nspniska
Hevatla
Me» Hampshire
Ney Jersey
Nm Mexico
New "ork
North Carolina
North Dakota
Ohio
Oklahoma
OreQW
Pennsylvania
Puer .0 RHo
Rhodp Island
South Carolina
South Dakota
Tennessee
Texa:
Utah
Verm int
Virginia
Wash ington
Uest Virginia
Wisconsin
Hyom mq
NATIONAL TOT'LS
REGION TOTALS
]
2
3
4
5
6
7
8
9
in
txplollve Wastes
Open Burned
^60
163
119
204
76
454
147
69
1
335
472
739
1078
646
'
47b3
1078
335
929
995
427
739
260
Sold
78
58
136
78
58
Explosive Contaminated
Inert Ujstet
Open BurnwJ
27
900
49
71
762
692
890
24
7776
54
BS
2,370
13701
2370
7776
949
770
1723
86
27
Land Filled
536
253
218
1006
218
535
253
Other Hazardous Wnstei
Sold
19
19
19
Open purnad
80
0
9 .
89
9
80
Land Filled
0
136
136
136
Covers active AAP's, AEC facilities and two conmercial plants, one in Utah and one in California, manufacturing propellants under
Air Force contracts Quantities were estimated on a water-free basis, in accordance with the procedures given 1n Appendix A,
The data fcr t*ie calculations were obtained from the U.S. Army and Army Ammunition Plant sources listed In Table A-l and
References 17, 18, 56, 58 and 59.
5-134
Z.I-,
-------
The great majority of explosives wastes discharged by the GOCO plants
(in excess of 93 percent) were treated/disposed of on-site because of their
highly dangerous character. These wastes were either dry or of very low
moisture content (less than 10 percent). The small quantities of GOCO
plant process wastes which were sold or land-filled were also low in water
content. The "wet-basis" national total estimated for GOCO plant process
waste streams sent to land in 1973 was the same, therefore, as the dry
weight basis estimate, 19,850 metric tons.
5-135
-------
6. TREATMENT AND DISPOSAL TECHNOLOGY
6.1 GENERAL
The technologies used for treatment and disposal of the land-destined
hazardous waste streams from the explosives industries are so markedly dif-
ferent from those common to the organic chemicals and pesticides industries
that the results of this study are reported under two separate headings.
The organic chemicals and pesticides industries, which differ only slightly
in treatment and disposal technology, are covered in Section 6.2. The explo-
sives industries' techniques, which historically stem from the concern of
the ordnance industry with plant equipment and plant personnel safety rather
than environmental impact, are discussed in Section 6.3.
Three treatment and disposal technology levels are identified in this
study. Level I technology represents the practice currently employed by
typical facilities — broad, average, present treatment and disposal prac-
tice. Level II is the best technology currently in commercial use in at
least one location for the same or a similar application — "best" here
referring to the adequacy of the process from an environmental and health
standpoint. Level III is the technology necessary to provide adequate envi-
ronmental protection, and may include pilot or bench scale processes.
Level I, II, and III technology may be identical in those cases where the
broad, average, present treatment is both the best technology currently in
use and is environmentally adequate.
Company and Government agency-supplied information, used in this study,
which covered treatment and disposal technologies employed at 52 major
plant sites, was obtained by visits to 34 plants and/or company headquarters,
and to 4 off-site contractor disposal sites, and through other direct con-
tacts. For the organic chemicals and pesticides industries, the data em-
braced the technology for disposal of just under 200 hazardous waste streams.
Data were received from the U. S. Army Armament Command on land disposal
activities at all of the Army ammunition plants, in addition to the personal
observations made at three of the four active basic high explosives manu-
facturing plant sites and the information furnished on treatment and dis-
posal development projects.
6-1
-------
Fifteen land-destined hazardous waste streams (one each from 15 of the
26 hypothetical typical plants chosen to represent the organic chemicals and
technical organic pesticides industries) were selected to give composite pic-
tures of characteristic treatment and disposal technologies employed in the
two industries. The number of hazardous waste streams, for which disposal
technologies could be subjected to detailed analysis in this study, had time
and cost limitations in addition to the limitations imposed by data avail-
ability; the 15 hazardous waste streams were, therefore, chosen on the basis
of product significance and hazardous waste significance. Production in 1973
of the ten organic chemicals selected constituted just over 7 percent of the
total production of the organic chemicals industry. The discharge of the ten
process waste streams investigated in depth from plants manufacturing the ten
organic chemicals totaled close to 16 percent of the aggregate dry weight of
all hazardous wastes discharged to land in 1973 by the organic chemicals
industry. The production total (excluding pesticide formulations and prep-
arations) in 1973 for the five technical organic pesticides selected was
just under 26 percent of the national total production for all technical
organic pesticides. The dry weight of the five technical pesticide waste
streams studied (from all plants producing these five technical pesticides)
constituted approximately 21 percent of the dry weight of all hazardous wastes
discharged to land tn 1973 by this industry.
The technology used in 1973 for disposal of the three major types of
process waste streams sent to land by the plants of the military explosives
industry is described in Section 6.3.1. The limited data available on the
waste treatment and disposal techniques used in 1973 by the private explo-
sives industry are summarized in Section 6.3.2.
6.2 ORGANIC CHEMICALS AND PESTICIDES INDUSTRIES
Summaries of the specific information on land-destined hazardous waste
treatment and disposal practices in the organic chemicals and pesticides
industries, collected from companies cooperating in this study, are presented
in Tables 6-1, 6-2 and 6-3. Tables 6-1 and 6-3 contain data on waste treat-
ment and disposal methods used in the organic chemicals and pesticides
industries, respectively. Table 6-2 presents data on treatment/disposal
technology distribution for selected organic chemicals plant sites.
6-2
-------
Table 6-1. Hazardous Waste Treatment/Disposal Methods
at Selected Organic Chemical Plant Sites
Individual Hazardous Waste Stream Disposal Process
Liquid tars, still bottoms and
process residues
Liquid tars and oils (still
bottoms)
Liquid tars (still bottoms)
Waste water, condensate
Liquid tars
Liquid tars and oils
Liquid, tars and oils
Liquid, tars and oils
Liquid, oils (distillation
residue)
Semi-solid phenolic wastes
Solid, spent activated carbon
Liquid process wastes (phenols,
alcohols, etc.)
Liquid, dispersed in water
organicsl with metal catalyst
3
Liquid, mixed process waste
slurry in water
Liquid tars, reactor byproduct
Liquid tars, byproduct
Liquid organic wastes
Solid organic wastes and trash
Fluid residues
Fluid residues, miscellaneous
Sludge, filter residues
Solid reactor residues
Incineration, uncon-
trolled, energy
recovery
Landfill
Incineration,
controlled
Incineration,
controlled
Landfill
Landfill
Landfill
Landfill
Landfill
Landfill, drummed
Recovery
Incineration,
controlled
Incinerator
control!ed^
Landfill, drummed
Deep well
Incinerator,
uncontrolled
Incinerator,
uncontrolled
Contractor landfill
Contractor landfill
Incineration,
uncontrolled,
energy recovery
Landfill
Landfill
Actual Quantity,
metric tons/yr
17,800
300
300
7,600
50
140
90
50
50
70
"lot Available
1,600
> 21,800
254,OOO4
1,800
500
200
200
14,100
1,600
360
160
6-3
-------
Table 6-1. Hazardous Waste Treatment/Disposal Methods at Selected
Organic Chemical Plant Sites (Continued)
Individual Hazardous Waste Stream Disposal Process
Solid residual pitch
Solid, spent metal oxide
catalyst
Fluid, reactor residue
Fluid, reactor recycle
Fluid, still heads
Solid, spent metal catalyst
Liquid (thick), reactor residue
Semi-sol id residue
Liquid, wash water waste
Liquid, activated sludge from
wash water waste
Liquid, activated sludge, tar
Liquid, activated sludge
Solids, filter residues
Liquid reaction waste
Liquid purification waste
Liquid activated sludge from
water-phase wastes
Liquid still bottoms
Liquid still bottoms
Liquid, contaminated steam
condensate
Liquid, contaminated wash water
Liquid, activated sludge from
aqueous chloroaromatic wastes
Liquid, activated sludge from
aqueous chloroaromatic wastes
Landfill
Recovery and
byproduct sales
Incineration,
uncontrolled,
energy recovery
Recovery and
recycle
Incineration,
uncontrolled,
energy recovery
Landfill
Activated sludge
and lagoon5
Incineration,
controlled
Incinerator,
controlled
Incineration,
controlled
Incineration,
controlled
Deep well injection
Deep well injection
Incineration,
controlled
Incineration,
controlled
Incineration,
controlled
Deep well injection
Deep well injection
Incineration,
controlled
Incineration,
controlled
Actual Quantity,
nietric tons/yr
830
60
170
60
130
14
680
16
1,000
90
36
70
22,700
11
800
800
90
30
20
80
6-4
-------
Table 6-1. Hazardous Waste Treatment/Disposal Methods at Selected
Organic Chemical Plant Sites (Continued)
Individual Hazardous Waste Stream Disposal Process
Liquid still heavy ends
Liquid, phenolic contaminated
wash water
Liquid, activated sludge from
wash water waste
Liquid still bottoms
Liquid, reprocessing tars
Liquid, neutralization products
Liquid, scrubber waste
Semi-sol id, filter cake
Liquid, still bottoms
Liquid, wash water
Liquid, activated sludge from
wash water waste
Liquid, contaminated condensate
Liquid, activated sludge from
contaminated condensate
Semi-sol id, filter cake
Liquid, wash-down wastes
Liquid, activated sludge from
wash-down wastes
Solid, spent ion exchange resin
Solid, spent charcoal
Solid, wastes/residues
Incineration,
controlled
Activated sludge
and lagoon
Incineration,
controlled
Incineration,
controlled
Incineration,
control led
Deep well injection
Incineration,
controlled (salt
ash to industrial
outfall)
Landfill
Incineration,
controlled (salt
ash to industrial
outfall)
Activated sludge
and lagoon
Incineration,
control led
Activated sludge
and lagoon
Incineration,
controlled
Landfill
Activated sludge
and lagoon
Incineration,
controlled
Landfill
Thermal regeneration
(recovery)
Incineration,
uncontrolled
Actual Quantity,
metric tons/yr
500
90
70
200
6,000
400
280
1,100
600
100
20
500
100
20
1
50
Jot Available
6-5
-------
Table 6-1. Hazardous Waste Treatment/Disposal Methods at Selected
Organic Chemical Plant Sites (Continued)
Individual Hazardous Waste Stream Disposal Process
Liquid, activated sludge from
wastewater
Liquid, neutralized Al salt
solution
Liquid wastes, toxic
Liquid, oil sludge from waste
water
Solid, catalyst residue,
Ni compounds
Solid, catalyst residue,
Cr compounds
Solid, catalyst residue,
SiC compounds
Liquid, distillation residue
Solid, catalyst residue,
Ni compounds
Solid, catalyst residue,
Cr compounds
Solid, catalyst residue,
SiC compounds
Fluid, aromatic residues
Solid, spent catalyst, Sb salt
Solid, spent catalyst,
Cu and oxides
Solid, spent catalyst (mol-sieve) Landfill
Liquid, viscous
Evaporation (spread
on farm land)
Contractor deep
well, landfill and
incineration
Contractor disposal
Contractor disposal
Recovery (Ni - 100%)
Recovery (Cr - 100%)
Recovery
Incineration,
uncontrolled
energy recovery
Recovery (Ni - 100%)
Recovery (Cr - 100%)
Recovery
Incineration,
uncontrolled
energy recovery
Landfill
(encapsulated)
Recovery (Cu - 100%)
Solid, spent catalyst,
Ni compounds
Solid, spent catalyst,
Cr compounds
Incineration,
uncontrolled
energy recovery
Recovery (Ni - 100%)
Recovery (Cr - 100%)
Actual Quantity,
metric tons/yr
Not Available
Nr* Available
f!ot Available
Not Available
20
2,700
20
260
20
3
5
8,200
20
6-6
-------
Table 6-1. Hazardous Waste Treatment/Disposal Methods at Selected
Organic Chemical Plant Sites (Continued)
Individual Hazardous Haste Stream
Solid, spent catalyst,
SiC compounds
Solid, spent catalyst,
Co compounds
Solid, waste Na metal
Fluid, organic residue
Fluid, organic cyclic gums
Liquid, dryer waste, Ca salts
Liquid, dryer waste, Ca salts
Liquid, activated sludge
Solid, filter wastes
Liquid, vent scrubber wastes
Liquid, tar dump
Liquid, organics/acid
Liquid, residues
Semi-solid, chlorinated
hydrocarbon heavies
Semi-solid, lead compound
siudge
Fluid, reactor byproduct
Solid, copper compound residues
Solid, Cr compound residues
Disposal Process
Recovery
Incineration,
uncontrolled,
energy recovery
Landfill
Incineration,
uncontrolled
energy recovery
Deep well injection
Deep well injection
Incineration,
controlled
Incinerator
Activated sludge
and lagoon'
Activated sludge
and lagoon''
Activated sludge
and lagoon7
Activated sludge
and lagoon7
Deep well injection
Recovery furnace
Incineration,
controlled,
energy recovery
Recovery
Recovery
Actual quantity,
metric tons/yr
20
3
1
300
9,000
14
5
230
4
6,500
45
2,300
90
13,600
9,100
1,600
3
1
6-7
-------
Table 6-1. Hazardous Waste Treatment/Disposal Methods at Selected
Organic Chemical Plant Sites (Continued)
8
Actual Quantity,
Composite Hazardous Waste Streams Disposal Process metric tons/yr
4 Liquid hazardous waste
streams
5 Liquid hazardous waste
streams
10 Liquid hazardous waste
streams
14 Liquid hazardous waste
streams
23 Solid hazardous waste
streams
4 Liquid or solid hazardous
waste streams
5 Liquid or solid hazardous
waste streams
5 Liquid or solid hazardous
waste streams
Recovery
Incineration,
controlled
Incineration,
uncontrolled
Landfill
Landfill
Lagooned
Contractor
incineration
Contractor landfill
2,350
3,860
10,000
1,1009
5,8009
Not Available
2,100
4,700
1. 90% organics.
2. Metal recovered from incinerator ash.
3. About 0.5% organics in water.
4. Highly dangerous compound — 700 metric tons/year.
Moderately dangerous compound — 600 metric tons/year.
5. Salts to outfall.
6, Soluble salts to industrial outfall, silicates to landfill
7. Salts to industrial outfall.
8. Data composited to protect proprietary information.
9. Includes 800 metric tons stored hazardous wastes.
6-8
-------
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6-9
-------
Table 6-3. Hazardous Waste Treatment/Disposal Methods at
Selected Pesticides Industries Plant Sites
Product
Technical
Pesticides
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Preparations
Formulations
X
X
X
X
Individual Hazardous
Waste Stream
Combined naphthol residues
Spent catalyst (Ni, Cr, SiC)
Waste sodium metal
Dilute aqueous wastes
Liquid wastes ("Autothermal") **
Dilute aqueous wastes
Liquid. wastes**
Solid wastes (containers, bags, etc)
Dilute acid solution, contaminated
with phenols
Spent carbon from acid purification
Methyl chloride ^
Organic wastes >
Still bottoms J
Brine, contaminated with low
concentration of pesticides,
intermediates and solvent-
Sulfur byproduct from intermediate.
HgS byproduct gas.
HC1 byproduct from intermediate.
Dust from collectors and bag houses.
Dryer dump.
Waste brine.
Contaminated condensate.
Solid filter cake residues
Acidic reactor wastes
Neutralization products (intermediate]
Scrubber bleed (intermediate)
Phenolic tars
Aqueous wastes
Brine solution from pesticide unit.
J>pent activated carbon.
Alkaline scrubber bleed.
Solid wastes (filter elements,
packaging materials, empty
containers, etc).
Treatment/Disposal Methods
Incineration, uncontrolled*
Metal and SiC recovery.
Controlled landfill
Evaporation ponds
Incineration, controlled
Evaporation ponds.
Incineration, controlled.
Classified, state-approved
contractor landfill site.
Discharge to large bog (a biolog-
ical waste water treatment has beer
constructed and will be used).
Open pile storage.
Incineration-ash to municipal
solid waste.
Deep well injection (1067 m. zone).
On-site landfill.
Incineration, uncontrolled.
Recovery and merchant sales.
Contractor-operated state-1 i censed
landfill .
Deep well injection.
Deep well injection.
Biological treatment/polishing
lagoon.
Incineration, controlled.
Deep well injection.
Deep well injection.
Incineration, controlled.
Storage in drums
Activated carbon adsorption,
followed by biological treatment
and discharae to industrial outfall
Activated carbon adsorption,
followed by biological treatment
and discharge to industrial outfall
On-site storaciej drummed.
Biological treatment and discharge
to industrial outfall .
Contractor-operated state- licensed
landfill.
*energy recovery
**capable of self-sustained combustion
6-10
-------
The data in Table 6-1, for selected organic chemical plant sites, include
hazardous waste stream and disposal process descriptions for 104 land-destined
streams covered individually, and 70 land-destined streams covered collectively,
to safeguard proprietary information. The majority of the streams were non-
aqueous liquids, sludges or slurries; less than 30 percent were true solids.
From the statistical summary presented in Table 6-2, it is evident that on-
site landfill and incineration were the most prevalent practices, numerically,
for the reporting organic chemical manufacturers, and were used to dispose of
approximately 32 and 33 percent, respectively, of the hazardous waste streams
examined. The disposal processes employed on the remaining hazardous wastes,
with one exception, were divided numerically, in descending order, between
recovery, contractor disposal, biological treatment and lagooning, and deep
well injection. Land farming was employed for disposal of only one waste
stream generated by one of the reporting companies. On-site incineration
practices were split fairly evenly numerically between "controlled" and
"uncontrolled" incineration. Contractor disposal practices reported were
also split somewhat evenly between landfill and incineration.
Uncontrolled incineration is defined for this study as the disposal of
wastes by combustion in facilities which lack treatment processes adequate
for the protection of the environment from the combustion wastes. Controlled
incineration is defined as the disposal of wastes by combustion, using the
technology necessary to provide adequate environmental protection. The treat-
ment processes and technology currently used in controlled incineration for
protection of the environment from the combustion wastes include (but are not
limited to):
Properly designed and operated afterburners and secondary combustion
systems to abate NOx emissions; settling chambers, impingement and
cyclone separators, bag filters, electrostatic precipitators, packed
towers, and s.pray chamber, venturi and cyclone scrubbers for the
removal of particulate and gaseous contaminants from the incinerator
vent gases; and evaporators, ponds, lagoons, land farms and chemical
landfill for ash, collected particulate material, and scrubber liquid
wastes not suitable for recovery or reuse.
The picture of organic chemicals industry practices presented in Table 6-2
under the headings "Annual Volume, Actual Tons" and "Percent of Total Annual
Actual Tons" is distorted by the dilution with water used in certain instances
6-11
-------
for deep well injection. Normal biological treatment and lagooning, of
course, are restricted to relatively low salinity aqueous wastes. A more
accurate appraisal of the relative volumes of hazardous wastes (and their
components) treated by each technique may be obtained from the data presented
in Table 6-2 under the headings "Annual Volume, Estimated Dry Tons" and "Per-
cent of Total Annual 'Dry' Tons". Uncontrolled on-site incineration was the
Level I practice used to dispose of almost one-half (48 percent) of the dry
weight of the hazardous waste streams at the selected organic chemical plant
sites. Controlled on-site incineration, considered to be Level II and III
technology, was employed for disposal of approximately 22 percent of the
land-destined process waste dry-tonnage, on-site landfill close to 15 per-
cent, recovery about 8 percent, contract disposal slightly over 5 percent,
and deep well injection only 2 percent by weight. Biological treatment and
lagooning as a practice was used in less than one percent of the dry weight
total of the hazardous waste streams of the reporting plant sites.
The disposal technology statistics reported are for a sampling of the
organic chemicals industry, with a bias towards companies who were willing
to furnish data for use in this study. Such companies represented many of
the major producers, with multiproduct, high volume output at their plant
sites. Some of these respondents have had an above average record of
,employing proper hazardous waste management technology. The somewhat
high proportion of on-site incineration facilities engaged in energy
recovery, and a similarly high percentage for resource recovery are possible
indications of this type of bias. The proportion of "dry" discharge handled
by contract disposal is thought to be somewhat lower in the sample due to
this bias, than the norm for the industry, nationally. The estimated
140,000 metric tons ("dry" basis) of hazardous process wastes to the land
covered in the sample are about 7 percent of the estimated organic chemicals
industry national total for 1973 (2 million metric tons for process discharge
of hazardous waste streams to land disposal), and are considered statistically
significant from that standpoint. The geographical dispersion of the plants
in the sample is also sufficient to avoid bias due to strictly local con^
sideratjons.
Table 6-3 covers a similar sample of treatment and disposal practices
employed in the pesticides manufacturing and formulation industries. The
treatment/disposal practices listed for the 25 hazardous waste streams from
6-12
-------
pesticides manufacturing and formulation operations indicate ten of the waste
streams (40 percent of the total»waste streams listed) are directly or
indirectly disposed of in landfills; the next three prevalent practices are
incineration (16 percent), storage in drums or open piles (13 percent) and
resource recovery (8 percent).
The wide variety of treatment and disposal systems in current use
reflectsthe differences in:(l) waste stream characteristics, (2) manufac-
turing and formulating methods, (3) size and geographic location of the
plants, and (4) applicable environmental regulations. Because of differ-
ences in waste quantities and characteristics and in plant locations and
operations, it was extremely difficult to arrive at a "broad average" waste
treatment/disposal method representative of the current practice at a "typi-
cal" plant within the constraints imposed on this study. It is impossible
to define or prescribe a practical treatment/disposal system which would be
applicable to the management of wastes at all organic chemical production
sites or pesticides manufacturing/formulating plants. For example, deep
well disposal which has been used successfully in some locations for the
disposal of organic chemicals and pesticides wastes may not be suitable for
use in other locations because of geological considerations or regulatory
restrictions. Many individual pesticides and organic chemicals are manu-
factured at large complex cnemical production facilities which also manufac-
ture a large number of other chemicals and generate significant quantities
of a variety of other wastes containing hazardous components.* In such
facilities, the management of waste from a specific production operation is
not usually an isolated problem requiring a separate solution, but rather
an element in the total waste management plan for the facility.
With the above-mentioned limitations in mind, the analyses of the exist-
ing and applicable-waste treatment/disposal technologies for 15 hypothetical
"typical" plants, each producing a single commodity, are presented in Sec-
tion 6.2.1. As indicated in Section 6.2, ten of the plants are samples
*Approximately 92 percent of the total production of organic chemicals and
technical organic pesticides in 1973 took place at the 539 plant sites
which manufactured more than one organic chemical or technical organic
pesticide.
6-13 - ..
-------
selected from the organic chemicals industry; five are examples chosen from
the pesticides manufacturing industry. For each hypothetical plant, one
land-destined waste stream has been selected for detailed treatment/disposal
technology evaluation in Section 6.2.1 and for cost analysis in Section 7.
The assumed plant capacities and the selected waste streams and their charac-
teristics are listed in Table 6-4.
The use of off-site waste management agencies for off-site treatment/
disposal of wastes is a common practice in both the pesticides and organic chem-
icals industries. The operation of off-site waste management centers is
briefly reviewed in Section 6.2.2. The data presented in Sections 6.2.1 and
6.2,2 indicate that, for the examples selected, landfill disposal, incinera-
tion, deep well injection, lagooning, resource recovery, and chemical detoxi-
fication are the methods most widely used at on-site and off-site waste
treatment/disposal facilities. A brief, general review of these treatment/
disposal methods, and of the activated carbon adsorption technique (used for
the removal of hazardous organic constituents from aqueous waste streams)
is presented in Section 6.2.3.
It is believed that many of the described applications of ultimate dis-
posal techniques represented real or potential hazards to the environment.
The following waste management technologies, as applied to the hazardous
waste streams of the sample, are considered either inadequate or of dubious
adequacy for environmental protection:
1. Uncontrolled incineration. This technique was used in 1973
on almost one-half of the hazardous wastes of the organic
chemicals and pesticides industries plants in the sample.
It thus represents Level I technology for these industries.
It afforded no protection against discharge to the atmo-
sphere of such noxious pollutants as nitrogen oxides, sul-
fur oxides, carbon monoxide, hydrogen halides, residual
chlorinated organics, and polynuclear aromatic hydrocarbons.
2. Landfilling at insufficiently characterized sites. Two-thirds
of the hazardous wastes Hisnosed of by landfill at the organic
chemicals and pesticides plants in the sample were disposed at
sites for which there was inadequate knowledge of subsurface
6-14
-------
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6-15
-------
geology, ground water course locations, leaching characteristics,
and run-off and drainage protection requirements. The protec-
tion afforded the environment against contamination by water-
soluble or dispersible toxic materials was therefore doubtful
or insufficient.
3. Deep well injection of hazardous process wastes. This method
for disposal was used on 2 percent by weight of the sample
plants' hazardous process wastes. The data supplied by these
sample plants indicated, in general, that there was little or
no knowledge of the-capabilities of the injection strata to
serve as adequate permanent liquid storage reservoirs or to
protect developed and undeveloped mineral resources, includ~
ing ground water. There was a similar lack of knowledge
on the migration and chemical change characteristics of the
hazardous materials injected.
The Level I treatment and disposal technologies for the 15 land-destined
hazardous waste streams selected to give the composite pictures of practices
in the organic chemicals and pesticides industries were heavily dependent
upon the techniques described above. Uncontrolled incineration was the
disposal method which represented the broad average of processes used on
the hazardous wastes at typical vinyl chloride monomer, methyl methacrylate,
acrylonitrile, lead alkyl and parathion plants. Landfill was the Level
I technology for the typical chloromethane solvents, toluene diisocyanate,
and maleic anhydride production facilities. Level I treatment for the
hazardous waste streams of the typical perchloroethylene plant and of the
single atrazine producer was deep well disposal.
6.2.1 Waste Stream Treatment/Disposal Technologies
The three levels of treatment/disposal technologies identified for the
15 selected hazardous waste streams are listed in Table 6-4. A brief descrip-
tion of the treatment/disposal technologies identified for each waste stream
will follow. Estimates of the prevalence of safeguards used in disposal are
contained in the descriptions, and are based upon the company supplied infor-
mation (cited in Section 6.1). These estimates and data presented
on treatment/disposal technolgles are based on Information obtained
for 1972-1974.
Waste Stream No. 1, Perchloroethylene Manufacture
This waste stream is composed of heavy ends from the perchloroethylene
purification column (Figure 5-1). It is discharged from the process as a
6-16
-------
nonaqueous liquid. For a plant producing 35,000 metric tons of
perchloroethylene, the estimated annual production of this waste is
10,500 metric tons. As indicated in Table 6-4, the major hazardous com-
ponents of this process discharge are hexachlorobutadiene, hexachlorobenzene,
chloroethanes, chlorobutadienes, and tars and residues. The Level I
treatment/ultimate disposal method for this waste is admixture with a large
volume of water to obtain a 0.5 percent suspension which is then injected
into subsurface formations using deep wells. Desirable features and limita-
tions and shortcomings of waste disposal by deep well injection are reviewed
in Section 6.2.3. In general, deep well disposal is currently viewed by many
companies and some regulating agencies as a temporary approach to waste man-
agement, and in the future, deep well disposal may have to be abandoned in
favor of more ecologically acceptable alternatives. Specific limitations of
deep well injection for the disposal of Waste Stream No. 1 include: (1)
requirements for pretreatment, (2) uncertainties regarding the movement and
ultimate fate of the waste in underground formations, (3) potential for ground-
water contamination, and (4) geological requirements.
Level II technology for the disposal of Haste Stream No. 1 is controlled
incineration* in combination with other organic wastes (or hydrocarbons) serv-
ing as fuels and hydrogen sources. In the presence of hydrogen-containing
organics, the organic chloride in the raw waste is converted to hydrochloric
acid which is captured effectively by countercurrent aqueous scrubbing of the
product gas stream. Because of the chemical nature of the waste, control equip-
ment* is included in the disposal system to abate emissions of air pollutants
(e.g., hydrochloric acid fumes, particulates, etc.). Only a very small quan-
tity of ash results from incineration of this waste. This ash is disposed
of in a landfill.
Level III technology for ultimate disposal of Waste Stream No. 1 is the
same as Level II technology.
The plants which produce perchloroethylene via the typical process shown
in Figure 5-1 do not use plastic/concrete encapsulation or leachate treatment
"'As defined on p. 6-11.
6-17
-------
and collection as safeguards in landfill disposal of the heavy ends waste
stream discussed above. It is estimated, based on the responses received
for this study, that steel drums are used as safeguards in the disposal
of approximately 20 percent of the total quantity of the heavy ends waste
streams generated.
The use of deep well injection (Level I technology) is not considered
environmentally adequate, (Section 6.2.3.) The Level II (and Level III)
disposal technique employed (controlled incineration)* is considered
environmentally adequate. Required implementation times for complete
controlled incineration systems for heavy ends are estimated as approx-
imately 2 to 3 years, based on engineering study requirements, equipment
lead time, installation and construction periods, and anticipated start-up
problems. Controlled incineration technology is suitable for retrofit to
the majority of installations using Level I technology, with no impact on
air, and noise problems and a possible decrease in groundwater pollution.
The sampling, testing and surveillance techniques required to adequately
monitor controlled incineration disposal facility operations are state-of-
the-art (References 60 through 63), and are within the capabilities of
current contract disposal facilities and the organic chemical companies
manufacturing perchloroethylene.
Waste Stream No. 2, Nitrobenzene Manufacture
The heavy ends from the final purification step in nitrobenzene pro-
duction (Figure 5-2) constitute Waste Stream No. 2. The process waste is
discharged as a nonaqueous liquid containing primarily nitrated aromatics
and possibly some residual inorganic salts. For an annual nitrobenzene
production of 20,000 metric tons, the waste quantity is estimated at 50
metric tons per year. The waste is placed in plastic-lined drums and
disposed of in an on-site landfill. This method of waste disposal, how-
ever, is not available for use in all locations. Because of the hazardous
nature of the waste, only secured landfills (i.e., those which are designed
and operated in a manner which provides for adequate protection against
environmental contamination, Section 6.2.3) should be used.
As defined in p. 6-11.
6-18
-------
As with Waste Stream No. 1, controlled incineration is,the Level II and
Level III treatment/disposal method for Waste Stream No. 2. Auxiliary organic
fuels are not a requirement in this case. Incineration may permit recovery
of thermal energy for in-plant use.
The plants which produce nitrobenzene via the typical process
shown in Figure 5-2 do not use plastic/concrete encapsulation or leachate
treatment and collection as safeguards in disposal of the heavy ends gener-
ated by purification of nitrobenzene. It is estimated that steel drums are
used as safeguards in the disposal of approximately 30 percent of the total
quantity of nitrobenzene purification column wastes sent to land disposal-
Disposal of nitrobenzene purification wastes in on-site landfills
(Level I technology) is considered of dubious adequacy for environmental
protection on the basis of the discussion in Section 6.2.3. Controlled
incineration (the Level II and Level III technology) is considered environ-
mentally adequate for disposal of the nitrobenzene wastes. The required
implementation times for complete controlled incineration systems for
nitrobenzene purification column wastes are estimated as approximately
2 to 3 years without energy recovery, and 3 to 5 years with energy
recovery. There would be no impact on air and noise pollution problems
and a possible decrease in water pollution as the result of the use of
controlled incineration for disposal of nitrobenzene purification heavy
ends, and the technology is suitable for retrofit to the installations
now using Level I (landfill)technology. Current contract disposal
operators and the organic chemical companies manufacturing nitrobenzene
have the capabilities needed for the sampling, testing and surveillance
techniques cited in References 60 through 63 for adequate monitoring
of controlled incineration.
Waste Stream No. 3, Chlorinated Solvents Manufacture
Waste Stream No. 3 is the solid tails from the solvent recovery system
in the production of methyl chloride, methylene chloride, chloroform, and
carbon tetrachloride from methanol and chlorine (Figure 5-4). The waste is
essentially crude hexachlorobenzene which cannot be further refined eco-
nomically, and which also contains small quantities of hexachlorobutadiene
6-19
-------
and other chlorinated paraffins. The estimated annual quantity of waste
resulting from a 50,000 metric tons per year manufacturing capability is
300 metric tons.
The Level I technology disposal method for Waste Stream No.3 .is contract
disposal at an off-site landfill. Level II and Level III technologies for a
waste of this nature are controlled incineration, in combination with other
organic wastes (or hydrocarbons) serving as auxiliary fuel and hydrogen
source.
The plants which produce methyl chloride, methylene chloride, chloroform
and carbon tetrachloride (the chloromethanes) from methanol and chlorine .
do not use plastic/concrete encapsulation or leachate collection as
safeguards in the disposal of the solid tails from the solvent recovery
system. It is estimated that steel drums are used as safeguards in the dis-
posal of 30 percent of the solvent recovery wastes sent to land disposal.
Disposal of solvent recovery wastes generated in chloromethanes produc-
tion by contract disposal at off-site landfills (Level I technology) is con-
sidered to be of dubious environmental adequacy if the disposal sites do not
utilize adequate safeguards to prevent environmental contamination. Controlled
incineration, the Level II and III technology employed, is considered environ-
mentally adequate for disposal of the solid tails waste stream. The required
implementation times for complete controlled incineration systems for solvent
recovery wastes are estimated as 2 to 3 years. Controlled incineration is a
technique suitable for retrofit to existing plants using contract disposal
(Level I technology) with no impact on air and noise pollution problems, and
a possible decrease in water pollution. The sampling, testing and surveillance
techniques cited in References 60 through 63 for monitoring of emissions
from controlled incineration facilities are within the capabilities of current
contract disposal operators and the companies which manufacture the chloromethanes,
Waste Stream No. 4. Epichlorohydrin Manufacture
Waste Stream No. 4 Is the liquid heavy ends from the fractionation column
in the production of epichlorohydrin (Figure 5-7). Approximately 3,975 metric
6-20
-------
tons of this waste are produced in the production of 75,000 metric tons of
epichlorohydrin. Major constituents of the waste are 1,2,3-trichloropropane,
tetrachloropropyl ethers, dichloropropyl alcohols, epichlorohydrin and chlorinated
aliphatics and alcohols. Level I disposal technology for this waste is
storage in on-site storage facilities. A waste of this kind, however, can be
effectively destroyed by incineration with proper control to eliminate air
pollution. Level II and Level III technology for handling this waste is
controlled incineration as defined on p. 6-11. The ash content from
incineration would be low, and can be discharged to landfill.
The plants which use the ally! chloride process for the manufacture of
epichlorohydrin do not use plastic/concrete encapsulation, leachate treatment and
collection, or steel drums as safeguards in disposal of liquid heavy ends from the
fractionating column. Large steel tanks are employed for storage of this waste at
the plant sites.
Long-term storage in on-site facilities is environmentally adequate,
but presents potential problems due to possible corrosion of the steel tanks.
The use of controlled incineration* for disposal of the fractionation column
heavy ends is considered environmentally adequate. The required implementa-
tion times for complete Level II/III systems for fractionation column heavy
ends are estimated as approximately 2 to 3 years. Controlled incineration
technology can be used at installations using long term storage, with no impact
on air, water and noise problems. The companies which manufacture epichlorohydrin
and the contract disposal site operators have the capabilities to perform the
sampling, testing and surveillance (References 60 through 63) required to
adequately monitor controlled incineration operations.
Waste Stream No. 5, Toluene Diisocyanate Manufacture
Waste Stream No. 5 is the thick liquor/semi sol id waste from processing
and centrifugation of still bottoms and residues from the production of
toluene diisocyanate. For a production rate of 27,500 metric tons per year,
*As defined on D. 6-11.
6-21
-------
the estimated annual quantity of waste generated is 588 metric tons. The
wastes consist primarily of polyurethane low polymers and tars, ferric
chloride, and isocyanates. Level I technology for the disposal of this waste
is containerization in drums and burial in landfills. Controlled incineration
in a steam generating plant (to recover thermal energy) is the Level II and
Level III technology for the management of this waste stream.
The plants which manufacture toluene diisocyanate via the typical process
shown in Figure 5-13 do not use plastic/concrete encapsulation as a safeguard
in the disposal of wastes from the process. Leachate collection is employed
as a safeguard on approximately 15 percent (estimated) of the wastes sent to
land after centrifugation of the production stillbottoms and residues. Steel
drums are employed as safeguards on approximately 25 percent (estimated) of
these wastes.
Disposal of the centrifugation wastes by containerization in drums and
burial in landfills is of dubious environmental adequacy if the disposal site
does not utilize adequate safeguards to prevent environmental contamination.
The Level II and III technology is considered environmentally adequate. The
required implementation times for Level II/III disposal systems using controlled
incineration in steam generating plants are estimated as 3 to 5 years. The
Level II/III disposal systems can be employed in existing installations usinq
Level I technology and will have no impact on air and noise pollution problems,
and will result in a possible decrease in water pollution. The sampling, test-
ing, and surveillance techniques required to monitor the Level II/III disposal
system operations adequately are standard, current state-of-the-art, available
from the literature, * ~ ' and within the capabilities of the toluene diisocy-
anate manufacturers.
Waste Stream No. 6, Vinyl Chloride Monomer Production
Waste Stream No. 6 is the liquid heavy ends from the ethylene dichloride
recovery still used in the production of vinyl chloride monomer (shown as
Stream No. 4 in Figure 5-14). For a production rate of 100,000 metric tons/
year, the estimated annual quantity of this waste is 3,800 metric tons. The
major hazardous components of the waste are 1,1,2-trichloroethane, 1,1,1,2-
tetrachloroethane, 1,2-dichloroethane, and tars. Contractor incineration*
is the Level I technology for the disposal of this waste. Controlled incfner-
* Uncontrolled incineration, as defined on p. 6-11.
6-22
-------
ation either on-site or off-site (by a disposal contractor) is the Level II
and III technology for the management of this waste stream.
None of the plants which manufacture vinyl chloride monomer by the use
of the typical process shown in Figure 5-14 employ plastic/concrete encapsu-
letion or leachate collection as disposal safeguards. The disposal of approxi-
mately 30 percent (estimated) of the liquid heavy ends discharged from the
ethylene dichloride recovery stills is protected by the use of steel drums.
The Level I technology (uncontrolled incineration by a disposal contractor)
is not considered environmentally adequate. The Level II/III technology,
controlled incineration, is considered environmentally adequate for use at
either on-site or off-site disposal facilities. The required implementation
times for complete controlled incineration systems for recovery still
residues are estimated as 2 to 3 years. Level II/III disposal systems can
be retrofitted to existing installations using Level I technology and will
have no impact on water and noise pollution problems, and will cause a
decrease in air pollution. The sampling, testing and surveillance techniques
required to monitor the Level II/III disposal system operations adequately
are standard, current state-of-the-art, available from the literature (60-63)
and are within the capabilities of disposal contractors and vinyl chloride
monomer manufacturers.
Waste Stream No. 7, Methyl Methacrylate Manufacture
This waste stream is the liquid heavy ends from the methanol recovery
section of the methyl methacrylate production unit (Figure 5-15.) The waste
consists of methacrylate polymeric matter and hydroquinones. For a plant
with a production capacity of 55,000 metric tons per year, the annual quantity
of waste produced is estimated at 4,730 metric tons per year. The Level I
technology for the disposal of this waste is uncontrolled incineration.
Controlled incineration is the Level II and Level III technology used for
management of this waste.
6-23
-------
As indicated in Figure 5-15, a major waste stream in the production of
methyl methacrylate is the spent sulfuric acid from acid stripper columns.
The spent acid is neutralized with ammonia and processed to recover ammo-
nium sulfate. However, if the spent acid can be pyrolyzed (using auxiliary
fuel) to recover sulfuric acid for reuse, it may be possible to dispose of
Waste Stream No. 7 by combustion in the sulfuric acid regeneration system.
It is not known whether this approach has been tried, and sufficient analyt-
ical data are not available to evaluate the technical and economic feasibility
of such an approach.
Plastic/concrete encapsulation and leachate treatment are not used
as safeguards in the disposal of heavy ends from the methanol recovery
sections of methyl methacrylate production units. It is estimated that
steel drums are used as safeguards in the disposal of approximately 20
percent of these wastes.
Uncontrolled incineration (Level I disposal technology) is not considered
environmentally adequate, on the basis of the discussion cited in Section
6.2.3 . The Level II/III technology employed (controlled incineration*)
is considered environmentally adequate. Required implementation times for
controlled incineration systems for methanol recovery wastes are estimated
as 2 to 3 years. The Level II/III technology can be retrofitted to installa-
tions which use Level I technology, with no impact on water and noise pollu-
tion problems, and a decrease in air pollution. The techniques needed for
sampling, testing, and surveillance required to adequately monitor con-
trolled incineration facilities are known, state-of-the-art, and are within
the capabilities of the companies which manufacture methyl methacrylate.
Waste Stream No. 8, Acrylonitrile Manufacture
Waste Stream No. 8 is the liquid heavy ends from the product column
in the manufacture of acrylonitrile by the Sohio Process (Figure 5-16).
Approximately 160 metric tons of this waste are produced in the manufacture
of 80,000 metric tons of acrylonitrile. The waste stream contains polymeric
*As defined on p. 6-11.
6-24
-------
matter and higher nitriles. The Level I technology for the disposal of
this waste is incineration without the use of control equipment. Level II
and Level III technology is incineration with the use of adequate con-
trol equipment* to remove air pollutants.
The plants which use the Sohio Process for the manufacture of acrylo-
nitrile do not employ plastic/concrete encapsulation or leachate collection
as safeguards in the disposal of product column heavy ends. It is estimated
that steel drums are used as safeguards in the disposal of approximately
50 percent of these wastes.
Uncontrolled incineration, the Level I technology, is not
considered environmentally adequate for disposal of product column
heavy ends, on the basis of the discussion in Section 6.2.3. Controlled
incineration,* employed as the Level II and III technology, is considered
environmentally adequate. Required implementation times for complete
controlled incineration systems for heavy ends from the product columns
are estimated as 2 to 3 years. Controlled incineration techniques can
be retrofitted to the plants which use Level I technology, with no impact
on water and noise pollution problems, and a decrease in air pollution.
References 60 through 63 describe the sampling, testing and surveillance
techniques required to adequately monitor controlled incineration systems;
these techniques are within the capabilities of the companies which man-
ufacture acrylonitrile.
Waste Stream No. 9, Haleic Anhydride Manufacture
This waste stream is the bottoms from the distillation column in the
production of maleic anhydride (Figure 5-17). Maleic anhydride, tar,
fumaric acid and chromogenic compounds are the major constituents of this
waste. The quantity of waste generated is estimated at 333 metric tons
per year for a plant with an annual maleic anhydride production of 11,000
metric tons. The Level I technology for the disposal of this waste
is landfill ing.
*As defined on p. 6-11,
6-25
-------
The waste, however, Is suitable for combustion. Controlled combustion 1s
the Level II and Level III technology for the management of this waste. A
new maleic anhydride production facility, which is being constructed by
one chemical company, will use a proprietary solid catalyst. Butane is
used as the raw chemical feedstock and the system design reportedly in-
corporates a "built-in" incinerator which will dispose of waste "internally."
Details of the process and the design criteria for the system are not dis-
closed.
The plants which produce maleic anhydride by vapor phase catalytic
oxidation of benzene do not employ plastic/concrete encapsulation or
leachate collection as disposal safeguards. It is estimated that steel
drums are used as a safeguard in handling 5 percent of the distillation
column residues (bottoms).
The landfill disposal technique (Level I technology) used on distilla-
tion column residues is not considered environmentally adequate on the
basis of the discussion in Section 6.2.3. Controlled incineration* for
disposal of these maleic anhydride process wastes is considered environ-
mentally adequate. The required implementation times for complete con-
trolled incineration systems are estimated as approximately 2 to 3 years.
Controlled incineration for disposal is a technology suitable for use at
installations currently using Level I technology, with no impact on air
and noise pollution problems, and a possible decrease in ground water
pollution. The sampling, testing and surveillance techniques required to
monitor controlled incineration disposal facility operations are described
in the literature. These techniques are current state-of-the-art
and are within the capabilities of contract disposal operators and the
companies which manufacture maleic anhydride.
Waste Stream No. 10, Lead Alkyls Manufacture
Waste Stream No. 10 is the sludge precipitated after alkaline ozoniza-
tion of the aqueous effluent from steam stripping purification of lead alkyls
*As discussed on p. 6-11.
6-26
-------
(tetraethyl lead and tetramethyl lead, Figure 5-18). The highly dangerous
components of this waste stream are the inorganic and organic lead salts
(present in the precipitate). This sludge, which contains close to 80 per-
cent water, is dewatered and incinerated to recover lead for reuse. The
operation is incorporated into the main lead recovery system for the process
or is conducted in a separate furnace. The sludge incineration process
in Level I technology does not utilize equipment for control of air pollutant
emissions. Particulate emission recovery and control equipment* is in-
cluded in Level II and Level III technologies.
It is believed that none of the plants which produce lead alkyls use
plastic/concrete encapsulation, leachate collection, or steel drums as
safeguards in disposal of the sludge precipitated by ozonization.
The uncontrolled incineration process used for Tead recovery (Level
I technology) is not considered environmentally adequate due to the dis-
charge of lead and lead oxide particulates to the atmosphere. Controlled
incineration* (Level II and Level III technology) is environmentally
acceptable. The Level II/III technology is suitable for retrofit to
existing installations using Level I technology with no impact on water
and noise pollution problems, and a decrease in air pollution. The samp-
ling, testing and surveillance techniques required to adequately monitor
controlled incineration are described in the literature • These
are current state-of-the-art, and are within the capabilities of the lead
alky! manufacturers.
Haste Stream No. 11, Aldrin Manufacture
Waste Stream No. 11 is the land-destined aqueous waste water resulting
from floor washing and spill clean-up activities in the aldrin manufacturing
plant (currently inactive). For a plant capacity of 4,500 metric tons per
year, the average rate at which this wastewater is generated is estimated
at 550 liters per minute. Since aldrin is practically insoluble in water,
nearly all aldrin in this waste stream (estimated at 0.01 percent) is
present as a suspension. Nonhazardous constituents of this waste stream include
*As discussed on p. 6-11.
6-27
-------
water and the inorganic dissolved solids originally present. The Level I
disposal technology for the waste stream is solar evaporation in an asphalt-
lined evaporation basin. When a sufficient quantity of sludge is accumulated
in the pond, the sludge is removed and disposed of by incineration. The area
surrounding the pond is contoured to prevent the surface runoff from entering
the pond. The use of lined evaporation ponds is also considered to represent
Level II and Level III treatment/disposal technology for the one plant which
formerly manufactured aldrin. The plant is located in an area with a high
rate of evaporation, and has an adequate amount of reasonably inexpensive
land for the use of this technique.
The plant which produced aldrin did not use plastic/concrete encap-
sulation, collection of leachate, or steel drums as disposal safeguards
for Waste Stream No. 11. ( The wash-down and spill clean-up waste water
which constituted Waste Stream No. 11 is not considered leachate). Disposal
of the wastewater by evaporation in lined ponds is considered environmentally
adequate for the site where the technique was used. Aldrin is no longer manu-
factured, and there will be no need for retrofit, or the use of sampling,
testing and surveillance methods to monitor adequacy of disposal.
Waste Stream No. 12, Atrazine Production
Waste Stream No. 12 is the aqueous brine solution from neutralization
and scrubbing of the effluent waste stream from the cyanuric chloride unit
in atrazine production (Figure 5-24). Approximately 224,600 metric tons
per year of this waste are produced in a plant with an annual atrazine output
of 20,000 metric tons. The major hazardous constituents of the waste stream
are cyanuric acid (resulting from alkaline hydrolysis of cyanuric chloride),
insoluble by-product residues (cyamellde, etc.) from cyanuric chloride
hydrolysis and excess sodium hydroxide. The treatment/disposal method
employed as Level I and Level II technology for this waste stream is pre-
liminary treatment (pH adjustment and filtration) followed by deep-well
injection. The very high concentration of sodium chloride in the waste
stream results mainly from the neutralization of hydrochloric acid fumes
from the cyanuric chloride unit. Chemical detoxification by ozonization
6-28
-------
followed by deep well injection is considered Level III technology.
Due to the extremely large volume of Waste Stream No. 12, and the locations
of the atrazine plants (Louisiana and Alabama), the use of lined evaporation
ponds is not feasible.
It is believed that none of the plants that produce atrazine employ
plastic/concrete encapsulation, leachate collection, or steel drums as dis-
posal safeguards for Waste Stream No. 12.
The Level I/II treatment/disposal method (deep well injection subsequent
to pH adjustment and filtration) is considered of dubious environmental ade-
quacy on the basis of the discussion in Section 6.2.3. Complete detoxifi-
cation by ozonization followed by deep well injection of the neutral, filtered
brine into a suitable geological strata would be considered environmentally
acceptable. Times required for implementation of Level III technology are
1 to 2 years. The Level III technology is suitable for retrofit to existing
atrazine plants which use Level I/II technology, with no impact on air and
noise pollution problems, and a possible decrease in groundwater contamination.
The sampling, testing, and surveillance techniques required for adequate
(2)
monitoring would involve drilling monitor wells v , and periodically
testing composite samples taken from the wells , for increases in sodium
chloride contents as evidence of undesirable waste brine migration. In
addition, daily composite control samples would be required of the
well-feed to check for complete detoxification. The company currently man-
ufacturing atrazine has the capabilities needed for sampling and testing;
drilling monitor wells would provide the means for surveillance.
Waste Stream No. 13, Trifluralin Manufacture
Waste Stream No. 13 is the spent activated carbon resulting from acti-
vated carbon absorption treatment of the brine wastewater from trifluralin
production (Figure 5-25). The spent carbon is not regenerated and is
stored in plastic-lined steel drums. It is estimated that for an annual
trifluralin production of 10,000 metric tons, approximately 600 metric
tons of spent carbon is produced which contains about 93 metric tons of
trifluralin and related fluoroaromatic compounds and 453 metric tons of un-
reacted intermediates and solvents.
6-29
-------
On-site storage of spent carbon in steel drums (Level I technology)
is only a short-term solution for the one plant which produces trifluralin.
Until thermal regeneration of spent carbon (Level III technology — see
below) is successfully demonstrated on a pilot-scale or full-scale unit,
an interim solution involving disposal of carbon in a secured landfill (as
defined in Reference 2) or secured storage area (e.g., tn concrete trenches)
represents Level II technology.
As discussed later in this section, activated carbon used for the ' oat-
ment of municipal wastewaters and most industrial liquid wastes can be re-
generated thermally with very little loss in adsorption capacity and no more
than 10 percent loss of carbon. Spent carbon from treatment of trifluralin
waste should be amenable to thermal regeneration, provided that the regener-
ation furnace and its auxiliary equipment are constructed of suitable mate-
rial to withstand the corrosive hydrogen fluoride fumes which are released.
Adequate control equipment* should also be provided to scrub the effluent
gases from the furnace. Some pilot-plant studies may be needed to define
optimum operating conditions and abatement needs for carbon regeneration.
Regeneration and reuse of spent carbon thus may be considered as Level III
technology for the management of Waste Stream No. 13.
The plant which manufactures trifluralin does not use leachate collection
or plastic/concrete encapsulation as safeguards in the disposal of spent
activated carbon. All of the spent activated carbon wastes are placed in
steel drums as a disposal safeguard.
The Level I disposal technology used on the spent activated carbon is
considered environmentally adequate, but impractical from a long-term stand-
point. Disposal of activated carbon by storage in concrete trenches is also
considered environmentally adequate, but represents only an interim solu-
tion. Recovery of the activated carbon by thermal regeneration, using the
equipment described on p. 6-11 for control of pollution from incinera-
tors, is considered environmentally adequate and the long-term technique.
*As defined for controlled incineration on page 6-11
6-30
-------
The period required for implementation of Level III technology is
estimated as 3 to 5 years. The thermal regeneration technology can be retro-
fitted to the existing plant, without impact on air, water, and noise pol-
lution problems. The sampling, testing and surveillance techniques required
for adequate monitoring of thermal regeneration are described in the litera-
ture/ " and are within the capabilities of the company manufacturing
trifluralin.
Waste Stream No. 14t Parathion Manufacture
Waste Stream No. 14, the sludge discharged from the chloHnator unit
in the production of parathion (Figure 5-26), is an acidic sludge containing
elemental sulfur and organophosphorus compounds as major impurities. This
sludge is disposed of by incineration (Level I technology) without any
controls for abatement of SO? and phosphorus oxide emissions. For a
production rate of 20,000 metric tons per year, the quantity of sulfur in
the sludge is estimated at 2,300 metric tons per year.
Direct recovery of sulfur from the sludge is uneconomical. Abatement
of air pollutant emissions by conventional techniques is also unattractive
since it produces a different type of sludge or an aqueous waste which has
to be processed and disposed of. Addition of excess alkali (lime) to the
waste sludge and disposal of the product in a properly designed and operated
landfill represent the Level II and III technologies.
The plants which produce parathion do not use plastic/concrete encap-
sulation or leachate collection as safeguards in the disposal of chlorinator
waste sludges. It is estimated that steel drums are used as safeguards
in the disposal of 15 percent of Waste Stream No. 14.
The use of incineration without controls for abatement of S02 and phos-
phorus oxide emissions to the atmosphere is not considered environmentally
acceptable. The Level II/III disposal technology (detoxification with ex-
cess lime followed by disposal in a secured landfill) is considered
environmentally adequate. Required times for implementation of Level II/III
technology is estimated as less than 1 year. The detoxification-secured
landfill technology is suitable for use by existing plants which use Level
I technology, with no impact on water and noise pollution problems, and a
6-31
-------
decrease in air pollution. The sampling, testing and surveillance techniques
are given in part in Reference 2. Monitor wells peripheral to the landfill
sites are also required, as are routine, periodic chemical tests of composite
samples taken daily from the wells. The companies manufacturing parathion
have the required capabilities and sampling and testing facilities.
Waste Stream No. 15, Malathion Manufacture
This waste stream is a semi sol id filter cake waste resulting fro1" ,e
filtration of dimethyldithiophosphoric acid. For an annual production rate
of 14,000 metric tons per year, the quantity of the filter cake waste is
estimated at 1,826 metric tons per year, consisting of 1,000 metric tons of
filter aids, 70 metric tons of dimethyldithiophosphoric acid and 756 metric
tons of toluene and insoluble reaction products. The practice for management
of this waste stream involves detoxification by treatment with sodium hydroxide
and burial in an secured landfill (Level I technology). Level II and III
technologies for the management of this waste are considered to be the same
as that of Level I.
The plants producing malathion do not use plastic/concrete encapsula-
tion or leachate collection as safeguards in the disposal of the filter
cake wastes from filtration of dimethyldithiophosphoric acid. Use of
steel drums as safeguards is estimated to be used for approximately 10
percent of the waste.
The common disposal technology used for Level I, II and III is environ-
mentally acceptable. The time required for substitution to plants using
other techniques is estimated as less than .1 year. The detoxification-
landfill disposal method would be without impact on air, water and noise
pollution problems. The sampling, testing and surveillance techniques
are given in part in Reference 2. Monitor wells peripheral to the
landfill sites are required with routine, periodic chemical tests of com-
posite samples taken from each well to determine the leaching characteristics
from the site. The companies manufacturing malathion have the required
capabilities and sampling and testing facilities.
6-32
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6.2.2 "Off-Site" Contract Disposal 1n the Organic Chemicals and Pesticides
Industries
Many of the plants in the organic chemicals and pesticides industries
dispose of at least a portion of their wastes at off-site facilities
operated by private waste management agencies and contractors. Some
of these waste management contractors also operate a fleet of trucks and
provide services for waste collection and transfer to the disposal site.
Depending on the processing/disposal/recovery technologies used, nearly
all "off-site" waste management centers place certain restrictions on the
types of wastes which they accept. Table 6-5 presents distributions by
state of the off-site disposal sites and the type of wastes accepted. '
A variety of treatment/disposal methods are employed at off-site facil-
ities. Some sites specialize in the recovery of salable products from
certain classes of wastes (e.g., heavy metal sludges, oily wastes); the re-
sidual wastes from the recovery operation are forwarded to another facil-
ity for further processing and/or ultimate disposal. The treatment/disposal
methods at some sites are fairly elaborate and consist of a variety of
operations including chemical treatment, deep well disposal, landfill, bio-
logical treatment, resource recovery and incineration.
Table 6-6 lists distribution by states of treatment/disposal methods
employed at off-site hazardous waste management sites. The data in this
table indicate that disposal in landfills is by far the most prevalent
method of ultimate disposal and is practiced at an estimated 32 sites. In-
cineration and deep well disposal are practiced at 20 and 6 sites, respec-
tively. The estimated number of sites which practice some sort of resource
recovery is 22; 23 sites provide some sort of chemical processing (neu-
tralization, precipitation, oxidation, etc.). Biological treatment, lagoon-
ing, and ocean disposal are practiced by ten, four, and two facilities,
respectively. An estimated total of 17 off-site facilities act merely as
transfer agents and do not provide for ultimate disposal of the waste.
These transfer agents may possibly employ certain preliminary processing steps
(blending, concentrating, neutralizing, etc.) to obtain a product or prod-
ucts which can be transported more easily or sold to other agencies/sites
for treatment/disposal.
6-33
-------
Table 6-5. Off-Site Contract Disposal Sites and Types of
Wastes Accepted(64)
EPA
fleaiaa
4
ID
9
6
9
8
1
3
3
4
- 4
9
10
5
5
7
7
4
6
1
3
1
5
5
4
7
8
7
9
1
2
6
2
4
8
5
6
10
3
2
1
4
8
4
6
8
1
3
10
3
S
8
State
Alabama
Alaska
ArllOM
Arkansas
California
Colorado
Connecticut
Delaware
District of Columbia
Florida
Georata
Hawaii
Idaho
Illinois
Ifltiti11?
Iowa
Kansas
Kentucky
Louisiana
Maine
Maryland
Massachusetts
Michigan
Minnesota
Mississlnol
Missouri
Montana
Nebraska
Nevada
New Hampshire
New Jersey
New Mexico
New York
North Carolina
North Dakuta
Ohio
Oklahoma
Oreqon
Pennsylvania
Puerto Rico
Rhode Island
South Carolina
South Dakota
Tennessee
Texas
Utah
Vermont
Virginia
Washington
West Virginia
Wisconsin
Wyomt ng
NATIONAL TOTALS
REGION TOTALS
2
3
4
5
6
7
8
g
10 . _
NUMBER OF OFF-SITE
HAZARDOUS WASTE MANAGEMENT
FACILITlfcb
11
1
2
3
3
]
1
2
2
S
1
2
2
1
5
5
3
2
2
4
]
3
2
64
3
10
5
3
16
7
2
2
12
4
CAUSTICS 1
6
1
1
2
1
I
1
1
3
2
2
2
2
2
2
1
30
Nl
O
u
6
2
1
1
3
2
2
2
3
j
3
2
33
2
4
1
8
5
2
6
2
2
4
4
1
e
6
2
6
2
HEAVY METAL PI
SOLUTIONS |=|
7
1
2
1
1
]
3
1
2
1
2
3
2
2
1
3
2
35
2
3
3
12
3
2
7
3
CYANIDES E
2
1
1
1
3
]
2
1
3
2
2
1
2
22
4
1
8
5
2
7
£s
il
6
1
2
1
1
1
2
_2
3
2
1
3
3
2
2
3
1
3
2
41
3
6
3
1
10
6
2
7
3
HALOGENATED fel
HYDROCARBONS^
5
1
2
1
1
1
1
2
3
3
1
2
23
2
6
4
2
2
R
2
S
§1=
Q
UJ
7
1
2
]
1
1
•
1
i
1
1
2
20
EXaOSIVES
1
1
3
4
1
4
6
6
2
2
4
4
8
1
Used by the organic chemicals and pesticides Industries
6-34
-------
Table 6-6. Treatment/Disposal Methods at "Off-Site" Disposal Sites
•xiloi
1
10
«
6
9
_8
1
3
3
4
4
9
10
5
5
7
7
4
6
1
3
1
5
5
4
7
8
7
9
1
2
6
2
4
8
5
g
10
3
2
1
4
8
4
6
8
3
10
3
5
8
St)U
A'ltiM
Alaska
Arizona
Arkansas
California
Colorado
Connecticut
n«i«»r»
District of Coluriila
Florida
Georala
Hawaii
Idaho
Illinois
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maine
Maryland,
Massachusetts
M1ch1oan
Minnesota
Mlssllstoot
Missouri
Montana
Nebraska
Nevada
Men Hannshlre
New Jersey
New Mexico
Hex York
North Carolina
North Dakota
Ohio
Oklahoma,
Oreoon
Pennsylvania
Puerto R1cq
Rhode Island
Texas
Utah
Virginia
Washington
Vest Virginia
Wisconsin
Hvonflns
NATIONAL TOTALS
LAWT1U
10
1
2
1
1
1
1
2
2
1
2
1
1
2
3
1
32
INCIKMTIOI
1
1
2
1
1
2
1
2
1
2
1
4
1
20
SITES CMHOYIM
So
1
2
1
1
1
e
RESOURCE
RECOVERY
1
3
1
1
1
2
2
4
1
1
2
2
1
22
INDICATED PERTINENT/DISPOSAL METHOD
CHEMICAL
TREATMENT
1
1
1
1
1
1
1
4
2
3
1
2
1
3
1
1
25
BIOLOGICAl
TKEATNBIT
1
1
1
1
1
1
1
3
10
fl
2
1
1
4
ojsmftu
1
i
2
3
1
3
3
1
1
17
* i
O a
1
1
2
Rffijr* TQTAt 5
1
2
3
4
5
6
7
8
9
10
1
2
2
1
7
5
2
11
1
3
2
1
e
5
2
1
1
1
2
2
1
6
2
6
2
_1
1
i._
2
5
1
9
4
2
1
1
2
1
3
4
1
1
2
3
e
i
6
1
1
1
•Used by the organic chemicals and pesticides Industries.
6-35
-------
The fees charged for the disposal of wastes at off-site facilities
vary considerably, reflecting differences in the capital invested in the
facility, volume of waste handled, and operation and maintenance costs.
Depending on the treatment/disposal method employed, the users charge could
be based on wastewater characteristics (water content; solids content;
concentration and type of specific ingredients such as cyanides, heavy
metals, oil, etc.), value of the recovered product, volume of f!.2 waste,
and the frequency of required service. For aqueous wastes, the unit
service charge could vary from less than $0.00264 per liter to over $0.396 per
liter.* Some facilities, which also provide collection/handling services, com-
bine the, transportation and treatment/disposal costs into a single user
charge for a certain radius within their service area. Other facilities
separate the two items of cost in their rate quotations. For example, one
company which operates burial sites for the disposal of extremely hazardous
wastes (certain pesticides, heavy metals, and radioactive wastes) charges a
transportation fee of $0.62 per kilometer for 18.1 metric ton truck loads, and
a burial fee of $0.44 per liter.** The hauling of certain hazardous wastes
requires special handling equipment and/or prior containerization/packaging.
In general, the transportation cost for hazardous wastes are higher than
those for nonhazardous materials due to the requirements for additional
precautionary measures. When the distance to an off-site waste treatment/
disposal center is significant, the transportation cost may account for a
significant portion of the disposal cost.
In collecting data for use in this study, three off-site hazardous
waste management facilities were visited. The three facilities (located in
California) are: Omar Industrial Pumping in Chula Vista, Environmental Pro-
tection Corporation -Bryant-Park & Associates, Inc. in Bakersfield, and
Fresno County Department of Public Works in Coalinga. The three facilities
specialize, respectively, in handling hazardous liquid, oily, and pesticide
wastes. The treatment/disposal methods employed at these sites are;(l) evap-
oration ponds and sludge disposal by landfilling at the Chula Vista site,
(2) land spreading and microbial degradation in the soil at the Bakersfield
site, and (3) landfill at the Coalinga site. The techniques used for site
selection, operation and monitoring represent examples of good practices
*$0.01 per gallon to over $1.50 per gallon
**Respectively, $1.00 per mile, 40,000 pound and $1.25 per cubic foot
6-36
-------
for all operators of lagoons, evaporative ponds, land farms, and landfills
for the organic chemicals and pesticides industries. The techniques and
their applications at the three sites are as follows.
The Omar Industrial Pumping disposal site (now about 15 years old)
handles only liquid wastes, approximately 98 percent of which are picked up
at the source by Omar-owned trucks. The waste materials include industrial
process acids, alkalies, and oily wastes; company policy is to avoid more
hazardous materials such as pesticides, beryllium, cyanides, flammables,
explosives and radioactive substances. However, certain of these materials
(liquid or solid) are picked up by the company and transferred to the San
Diego County disposal site or the Nuclear Engineering Company site in Beatty,
Nevada. The total quantity of wastes handled at the Omar facility averages
988,400 liters per month (261,100 gallons per month.) There are six disposal
lagoons which have been either sunk in natural bentonite or lined with a 0.9-
meter thickness of that material. Each lagoon has a capacity of about
1,590,000 liters (420,000 cubic feet). A series of observation holes which are
located downhill from the lagoon and extend to a level be'low the base of
tha lagoon are routinely monitored for the detection of any waste which
may infiltrate into the subsurface formations, Regional Water Quality Board
monitors the observation boreholes, and to date, no fluid has been detected
in any of these holes. Solidified waste from the filled lagoons is land-
filled in an adjacent area underlain with an 18.29-meter (60-foot) seam
of impermeable clay. The site's 15-year operation has been trouble-free;
there have been no fires, explosions or spills at the site.
The Bryant-Park Associates Westside site and the Environmental Protec-
tion Corporation Eastside site have both been developed to handle liquid
organic wastes from the oil industry. These wastes are grouped into six
categories: oil sump sludge, oil field brine, rotary mud, tank bottom
sediment, service station waste and "other." No pesticides or inorganic
wastes are accepted by either site, and both are licensed as California
Class I (Appendix B) with additional development. As the Eastside site
has significant potential for later development as a residential area,
operations are geared to this objective and include filling of canyons with
stabilized soil. The disposal farming technique practiced at the Westside
site involves spreading the liquid wastes on the land directly from tank trucks
The earth is then disked under and the waste is worked into the soil.
6-37
-------
The farming technique at the Eastside site uses the "flooding" method
whereby a plot of land (0.4 to 1.6 hectares) is flooded with the waste-
water and allowed to remain idle until most of the water is evaporated.
The area is then plowed, and replowed as necessary thereafter, to assure
adequate aeration and rapid degradation of the oily waste. Waste-receiving
plots are rotated to assure continuity of operation. In both the "flooding"
and "spreading" methods, the quantities of wastes applied to tne soil are
carefully controlled to assure the maintenance of aerobic conditions , 1(,nin
the disposal layer (generally, the upper 15 centimeters (6 inches) of soil).
The state of degradation of the waste is assessed through changes in soil
texture and provides a good indication of the readiness of the land for
reuse. The quantities of wastes which have been handled at the two sites
are 85,200,000 liters (536,000 barrels) and 36,000,000 liters (230,000
barrels) for Eastside and Westside, respectively.* Of these totals, the
majority has been sump sludges and drilling muds with very little in the
way of service station wastes and "other" wastes.
The Fresno County Department of Public Works site near Coalinga was
established to provide a central location for the disposal of discarded/
reject pesticides and related agricultural chemicals and the empty contain-
ers which would otherwise accumulate throughout the loca'i San Joaquin
farming area. The site is California Class I (as described in Appendix B)
and consists of a 130,000 square meter (32-acre) parcel on the eastern slope
of the Pacific Coast Range; the underlying strata are classified as being
of "moderate to low" permeability and are not in hydraulic continuity with
fresh water-bearing zones in adjacent areas. The site is only open 4 weeks
per year (2 weeks in the fall and 2 weeks in the spring). The disposal pro-
cedure consists of excavating a 6-meter (20rfoot) deep trench, emptying the
waste material into the trench and leveling and compacting it with a bulldozer.
At the end of each working day, the waste is covered with 15 centimeters
(6 inches) of dirt. A dirt cover of 0.6 meters (2 feet) is provided when
the site is closed for the season. The gross capacity of the site is estimated
at 460,000 cubic meters (600,000 cubic yards), of which only a small fraction
has been used. A typical operational period (October 21 - November 1, 1974)
involved the disposal of 5000 cubic meters (6600 cubic yards) of various
pesticide containers; 180 metric tons (198 tons) of zinc sludge waste;
*Based on data obtained for 1974
6-38
-------
15.4 metric tons (17 tons) of diluted pesticide residue; and 24 cubic
meters (31 cubic yards) of mercury-contaminated seed. The wastes
handled are from both Fresno County and adjacent counties.
6.2.3 Prevalent Treatment/Pispgsaj^ Technologies
As indicated above, the most prevalent methods for the
processing/disposal of hazardous wastes from the organic chem'cals and
pesticides industries are landfill disposal, incineration, deep well in-
jection, lagooning, and activated carbon absorption. The following is a
brief general review of each of these methods as applied to the wastes of
the industries covered in this study.
Landfill Disposal
The use of landfills is a common method for the disposal of solids,
semisolids and concentrated liquid wastes from the organic chemicals and
pesticides industries. In general, there are two methods of landfill
disposal. In the "trench" method, a bulldozer or front-end digger is used
to make trenches (about 1 to 4 meters (4 to 12 feet) deep, 4.5 to 17 meters (15
40 feet wide) in which the waste is deposited. The excavated material is
then used as cover after the deposited material is compacted. The "area
method" of landfilling is generally used when the site is considerably
lower in elevation than the surrounding land. The material is deposited
and compacted in the fill and covered daily with a minimum of 15 centimeters
(6 inches) of compacted earth. The cover material is usually obtained
from borrow pits. Most liquid wastes and some semisolid and solid wastes
are "buried" in landfills in containers (e.g., 208 liter (55-gallon) drums).
In some cases, liquid wastes are also disposed of in a landfill by spray-
ing over them over the fill area or by injection into the body of the previously
completed fill. Many of the highly dangerous wastes are placed in steel
containers or treated to produce chemically and mechanically stable solids
prior to burial in a landfill. Some liquid wastes are also containerized.
Landfills for the disposal of hazardous wastes must be located at sites
with little or no possibility for groundwater contamination. Where the sub-
surface geological formations are not favorable, the site will have to be
6-39
-------
lined with a nonpermeable material (e.g., clay), and protected against
surface runoff from the surrounding land. Depending on the nature of the
wastes, soil conditions, rainfall and temperature, the waste material in
a landfill may undergo chemical and biological degradation. Some landfills
(the so-called "chemical" landfills) are specifically designed and operated
to promote biodegradation and accelerated waste stabilization, These land-
fills are usually provided with a system for leachate collection. The
leachate is then processed in a conventional wastewater treatment facility
(e.g., an activated sludge plant) prior to final disposal.
Landfills for the disposal of hazardous wastes are generally operated
under some form of a permit from a state agency. The regulations and re-
strictions vary greatly from state to state. The California system of
landfill classification and restrictions on the kind of wastes which can
be placed in each type of landfill is presented in Appendix B, In the
California system, pesticides and other toxic and hazardous wastes can only
be deposited in Class I disposal sites which are located in geologically
suitable areas and which are designed and operated in a manner which pro-
vides for maximum environmental protection. Section 6.2.2 contains the
description of a California Class I disposal site handling primarily agri-
cultural wastes (pesticides and pesticide containers).
Incineration
Incineration is widely used in the organic chemicals and
pesticides industries for the disposal of combustible solids, semisolids
and concentrated liquid wastes. Properly designed and operated incinerators
can provide for effective waste disposal in an environmentally acceptable
manner. Incineration of most wastes results in the production of an inor-
ganic ash, which has to be disposed of, and generation of air pollutants
which must be controlled by the use of appropriate emission control equip-
ment. Certain incineration operations are aimed at recovery of by-products
for reuse. Examples of such an application include recovery of hydrogen
chloride from chlorinated organic wastes and recovery of lead as slag from
the lead-containing sludge obtained as wastes in the manufacture of lead
alkyls. In some facilities, concentrated wastes high in calorific value
are burned in the on-site power plant, thereby effecting a partial recovery
6-40
-------
of energy for in-plant use. Incineration of dilute aqueous wastes and
sludges require the use of supplementary fuels to promote and sustain
combustion.
To achieve complete destruction of the waste material, design and
operation of incinerators should provide for'. (1) adequate residence time,
(2) effective mixing and turbulence, (3) sufficiently elevated temperature
(760°C to over 1000°C), and (4) adequate amounts of oxygen for combustion.
A variety of incinerator types and designs are available for the disposal
of industrial hazardous wastes. Table 6-7 lists the incinerators used for
the disposal of chemical plant wastes and summarizes the applications,
advantages, and limitations of each type of incinerator.
Equipment requirements for control of air pollutant emissions vary
for different applications, reflecting differences in waste characteristics,
incinerator performance, and air pollutant emission regulations. Emissions
of particulate pollutants can most effectively be controlled by the use of
such devices as cyclones, bag filters, electrostatic precipitators and ven-
turi scrubbers. Airborne emissions from combustion of wastes containing
halogens, and sulfur and phosphorous compounds require the use of aqueous
gas scrubbing (with water or an alkaline solution). Commonly used scrubbing
devices include packed towers, spray towers, plate towers, and venturi
scrubbers. For incinerators fed phosphorus compounds, particulate emission
control devices must be used in series with the gas scrubbing equipment.
Figure 6-1 is a schematic presentation of a new 76 billion joule
(72 million Btu) per hour stationary liquid waste burner at the Dow Chemical
Plant in Midland. The unit is capable of burning tars (still residues,
waste solvents, chemical by-products, etc,) at a rate of 34 liters per
minute (9 gallons per minute). The tars are pumped to four low-pressure
atomizing oil burner nozzles in a box-type combustion chamber maintained at
1080°C (1800°F). The hot combustion gases travel through a baffled quench
chamber where they are cooled to 150°C (300°F). A 448 kilowatt, 2.3 meter
(600 horsepower,190-inch) fan then pulls them through a high pressure drop
venturi scrubber. After passing through a packed tower, the scrubbed gases
are discharged to the atmosphere through a 30-meter (lOO-foot)stack. More
than 9,500 liters per minute (2500 gallons per minute) of water (the effluent
from the primary clarification of the plant liquid wastes) are used in the
scrubber to remove acid fumes and particulates.
6-41
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Table 6-7. Incinerators for the Disposal of Chemical Plant Wastes*
Type
Uses and Advantages
Ulsadvantayrs ,uid Limitations
Solid Stationary Hearth
1. Low c.ipi tJl.
?.. Potential of tt>iht air ccntTol with
an airlock feeder.
3. Used for incineration of solids.
4. Can be designed to Include liquid
Incineration.
No t;irbul»ncp. mixing or aeration.
Slow burning rjtes.
3. Batch operation.
1. llanual ash removal.
5. Ooes not '"nd if..'If to aood air
pollution curfol
Solid Hearth (Rotary Hearth or
Rabble Arms)
1. Continuous ash oischarae.
2. Capable of incinerJtina waste solids
Independently or liquids and solids
1n combination.
3. Widest practical turn down ratio.
(Maximum to minimum operating range)
4. Incinerating materials will not tall
through hearth.
5. Adaptable for use with a gas scrubbing
System.
1. Rabble arms or plows are susceptible
to damage.
Limited turbulence and air contai.
Partly combus'ed materials may flow
out ash discharge.
Solid wastes fed at Intervals. An
air lock system snould L>e used to
Improve combustion characteristics
and control.
Arched, stlf-supported multiple hearths
made of refractory material are vulner-
able to abrupt tenperature variations
with resultant downtime and cost Increas
Rotary Kiln
1. Will Incinerate a wide variety of
liquid and solid wastes.
2. Capable of receiving liquids and
Solids Independently or in combination
3. Not hampered by materials passing
through a melt phase.
4. Feed capability for drums and bulk
containers.
5. Wide flexibility in feed mechanism
design.
6. Provides high turbulence and air
exposure of solid wastes.
7. Long inventory time for slow burning
refuse.
8. Continuous ash discharge.
9. No moving parts within the kiln.
10. Adaptable for use with a wet gas
scrubbing system.
High capital cost installation for low
feed rates.
Cannot utilize suspended brick 1n kiln.
j. Operating care necessary to prevent
refractory damage.
Airborne particles may be carried out of
kiln before conplete combustion.
Spherical or cylindrical items mjy roll
through kiln before complete combustion
Kiln Incinerators frequently require
excess air intake to operate ouc to air
leakage into the kiln via the kiln end
seals and feed chute, which lowers fuel
efficiency.
Drying or Ignition grates, If used
prior to rotary kiln, can cause problems
with plastics melt plugging grates and
gr ate n.tchiinism:,.
Fluid Bed
1. Capable ot incinerating a moderate
range of liquid and solid wastes.
2. Rapid heat transfer from gas to
solid.
3. High combustion rate. High turbu-
lence and air exposure.
4. Low excess air requirements.
5. Large heat sink to smooth out
fluctuations in feed rate or fuel
value.
Requires fluid bed preparation and
maintenance.
Feed selection must avoid bed damage.
May require special operating procedures
to avoid bed damage.
Incineration temperatures limited to a
maximum of about 315°C (1500°F).
Stationary Liquid Waste
Burner
1. Capable of incinerating a wide range
of 1(quid wastes.
2. Hay use suspended brick.
3. No continuous ash removal system
required other than air pollution
controls.
Must be able to atomize tars or liquids
through a burner nozzle except for
certain limited application:,.
Heat content of ]'-]uids must r>aintdin
adequate temperatures or a supplemental
fuel must be provided.
Must provide for complete combustion
and prevent flame impingement on
refractory.
"A Guide for Incineration of Chemical Plant Wastes", Manufacturing Chemists Association, Technical Guide SW-3,
adopted April 1974.
6-42
-------
ewriGCMCT ve
Figure 6-1. Cross Section of the New Tar Burner
at Dow Chemical Midland Facility
Figure 6-2 is a schematic presentation of one of the two rotary kiln
incineration systems at the Shakopee, Minnesota, facility of Pollution Con-
trols, Inc. (a chemical waste management firm). The systems have been used
for contract incineration of a variety of hazardous wastes from chemicals
manufacturing plants. Each kiln is 2.4 meters ( 8 feet) in diameter and 12.2 meters
(40 feet) long with separate venturi scrubbers followed by a Universal Oil
Products Company floating bed ("bouncing ball'1) scrubber. The scrubbed
bed exit gases go through blowers for discharge to a common stack. The
kilns are unlined carbon steel shells which are cooled by external water
sprays. The cooling water falls from the outer surface of the kilns
directly into a sump. This water is supplemented with makeup water and
returned to the spray although a portion overflows to the basins receiving
water discharged from the scrubbers. The scrubber water basins are operated
in a series so that the water from the second basin is recycled to the
scrubbers, Scrubber water from both incinerators is discharged into the
first basin and recycled from the second basin. Consequently, it will be
necessary to operate only one incinerator if the changing conditions in the
scrubber water system are determined. Because lime is usually used
to control the pH in the scrubber loop, the basins contain large quantities
of sludge which are removed periodically. This sludge is accumulated in
6-43
-------
WASTE
SPRAY HEADER
"AA'AAAAAAAATV
AIR-
GAS-
ROTARY KILN
MAKE UP T7~ T1 TT1 , ,'., • T777T
WATER 1, II,, i_ '..-; '. ' •, ,' • •', '. ', .
KII-NCOOUNG
WATER CIRC.
PUMc
Figure 6-2. Rotary Kiln Incinerator and Control Equipment
at an "Off-Site" Disposal Facility
lined pits, prior to feeding to the incinerators. Solids discharged from
the incinerators are sent to local landfills.
The wastes can be pumped into the feed end of the kiln, and solids and
sludges can be introduced through an opening at the feed end of the kiln.
Gas is burned as an auxiliary fuel at both the feed and exit ends of the
rotary kiln. Consequently, the temperatures in the unlined rotary sections
are usually maintained under 650°C (1200°F), whereas in the large run of
ducting following the burner at the exit end, the temperatures may reach
1040° to 1320°C (1900° to 2400°F). The residence times in the high tempera-
ture zones are reported to be up to 2 seconds. Waste feed rates are reported
to be from 2 to 4 cubic meters per hour {500 to 1000 gallons per'Fiour); 'presumably
feed rates could be virtually any value below the maximum rate at which
complete combustion occurs, limited essentially by the automatic safety control
of the burners and the temperature measurements taken at a few points in the
off-gas system.
6-44
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Deep Well Injection
Deep wells, in recent years,.have provided an economically attractive
alternative to surface treatment/disposal of wastes. Although deep wells
have been extensively used in the oil and gas industry for the disposal
of brine and enhancement of gas and oil yields, their use for the disposal
of chemical industry liquid wastes is a relatively new practice which grew
substantially in the past decade. In 1964 there were approximately 30
chemical process waste injection wells; in 1973, there were 280 chemical proc-
ess waste injection wells in the United States.^ Most of the wells are located
in Texas (about 25 percent of the total),Louisiana, and Michigan, Because
of uncertainties involving future regulations concerning deep well disposal,
few new disposal wells are currently being constructed and some large chemi-
cal companies which used deep wells for the disposal of some of their wastes
are considering alternative approaches to waste management.^ ' Figure 6-3
is a schematic presentation of an injection well which is used by one com-
pany for the disposal of a concentrated organic chemical waste (14 percent
organics, consisting mainly of dibasic organic acids and-salts, alcohols,
and aromatic compounds). '
A deep well disposal system can only be successful if a porous, per-
meable formation of wide areal extent and thickness is available at suffi-
cient depth to insure continued, permanent storage of the injected liquid.
The disposal layer should also;(l) contain no minerals'of commercial value,
(2) be below the lowest ground water aquifiei; (3) be confined above and be-
low by impermeable zones, and (4) contain no extensive faults or.other
natural fractures of formations. The liquid waste to be disposed of by-
deep well injection must also be physically and chemically compatible with
the formation. It should be completely detoxified by chemical and physical
treatment prior to injection. Wastes containing significant concentrations
of suspended solids or constituents which may result in the formation of
precipitates and plugging of the pores in the disposal stratum require
pretreatment (e.g., sedimentation, pH adjustment, filtration, etc.) prior
to injection. Well construction should provide adequate protection against
groundwater contamination and should include provisions for continuous mon-
itoring of well performance and movement of the waste underground, including
6-45
-------
16-inch conductor pipe
103/4-inch sgrfoce pip*
Pocker
4-inch screen liner
Grovel pock
Per foro tions
Shale —
Figure 6-3, Injection Well Completion^6 )
6-46
-------
continuous sampling of subsurface water courses by monitor wells. Very few
of the deep well treatment and disposal systems in current use meet all of
these requirements.
State laws concerning deep well injection are varied. Some states
(e.g., Idaho and Arizona) strictly prohibit underground waste disposal.
Texas, Michigan and Ohio are the only states that have specific regulations
for underground waste injection. Other states have added regulations in-
volving underground waste injection to existing laws, or have liberally
interpreted their surface and groundwater pollution laws, and in a few cases
their oil and gas laws, to include subsurface injection of industrial wastes.
In California, deep well injection is regulated by the State Water Resources
Control Board and by the Division of Oil and Gas. Permits for deep well
disposal are granted on a case-by-case basis. The Injection Well Act of
the State of Texas "is reproduced in Appendix B.
A 1974 U.S. Bureau of Mines Information Circular^ ' provides case
histories for 15 subsurface injection wells in the United States. General
information on 13 of these wells handling wastes from the organic chemicals
industry are summarized in Table 6-8. The systems listed in this table
employ a variety of waste treatment schemes prior to subsurface injection.
Significant differences also exist in the geology, well construction, in-
jection rate and operating pressure at each site.
Evaporation Ponds
Evaporation ponds (lagoons) are used by the organic chemicals
and pesticides industries for the containment/disposal of liquid wastes.
These ponds are, either used alone or as a final polishing step after the
wastewater is processed by other methods of treatment (e.g., biological
oxidation). A recent study of the pollution control technology in the pesti-
cides formulating industry^ ' indicates that solar evaporation is the most
widely employed treatment technique. This same survey^ ' also identifies
evaporative systems with no discharge of water as the best practicable tech-
nology for the management of aqueous wastes from most pesticides formulating
plants.
6-47
-------
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-------
Depending on the wastewater volume, evaporation ponds consist of
small concrete tanks, large earthen depressions or excavation basins. Un-
less the natural soil is reasonably impervious, earthen ponds are lined
with an impervious material such as bentonite clay, asphalt, concrete, or
plastic liners to prevent subsurface percolation and possible contamination
of the groundwater. For larger ponds, the runoff from the surrounding areas
is kept away by the use of diversion structures. Some pondr are provided
with observation wells (test holes) drilled at strategic locations away
from the pond for routine monitoring and detection of possible leakage into
the underlying subsurface formations.
In addition to the loss of water by evaporation, and depending on waste-
water characteristics, a number of other processes could be operative in an
evaporation pond. These include sedimentation, biochemical oxidation, pre-
cipitation, and chemical oxidation. To increase the rate of evaporation,
some ponds are provided mechanical surface aeraters or sprayers. The
wastewater discharged to an evaporation pond is often subjected to pre-
treatment. Depending on the nature of the wastewater, the pretreatment
methods used include deemulsification, oil removal and pH adjustment.
Off-site disposal contractors which handle a variety of wastes originating
from different industrial operations are concerned with waste compatibility
and usually either operate "segregated" ponds or require proper pretreat-
ment at the source prior to waste pick-up. When significantly large quanti-
ties of sludge accumulate in a pond, such sludge is removed and
disposed of (e.g., by landfilling). When several ponds are available for
use, the ponds can be operated on a "rotational" basis to provide uninter-
rupted operation when one or more ponds are being serviced.
Evaporation ponds can be employed most successfully in areas where
relatively inexpensive land is available and where climatic conditions are
conducive to a high rate of evaporation during most of the year. Possible
problems associated with evaporation ponds include the potential for odor
development and air pollution, seepage into the ground, and possible hazard
to the wildlife. Evaporation ponds in current use in the pesticide indus-
try vary significantly in size, depending on the wastewater volume and
annual rate of evaporation.
6-50
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Detailed descriptions of an "off-site" contract disposal facility in
Southern California which uses evaporation ponds and disposes of the sludge
by landfilling were presented in Section 6.2,2.
Activated Carbon Adsorption
Activated carbon adsorption is an effective method for the removal of
organic material from a variety of industrial wastewaters. The greatest
applicability of carbon adsorption is in processing waste streams which are
not amenable to biological treatment because of their content of toxic
chemicals and/or the refractory nature of their organic constituents. Use
of activated carbon for the treatment of aqueous wastes from the organic
chemicals and pesticides industries is expected to become more widespread
in the future as higher levels of pollutant removal become necessary to
meet stringent effluent discharge requirements. Activated carbon adsorp-
tion has been identified as the best available technology for the treat-
ment of wastewaters from pesticides formulating plants. ' Activated
carbon adsorption can be regarded as a "land-related1' waste treatment/
disposal method since in some applications (e.g., processing of the brine
wastewater from trifluralin manufacture) the spent carbon is disposed of
by containerization and surface storage. Furthermore, the conventional
thermal method of spent carbon regeneration, whereby the adsorbed or-
ganics are destroyed by pyrolysis/oxidation in a multiple hearth furnace,
may be regarded as an incineration method for the destruction of organic
wastes.
Both granular and powdered activated carbons have been used for waste
water treatment. Powdered carbon application involves mixing the carbon
with the wastewater, flocculation by the addition of a polyelectrolyte,
and separation of the spent carbon from wastewater by filtration. Granular
carbon adsorption essentially involves passing the wastewater through a
columnar bed of carbon in an upflow or downflow fashion. Powdered carbons
cannot be regenerated economically. Unless the necessary technology is
developed, the application of powdered carbon to wastewater treatment will
be on a once-used throwaway basis. For most applications, granular carbons
can be regenerated for reuse with almost 100 percent restoration of ad-
sorptive capacity and not more than 10 percent loss per cycle. It is
6-51
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because of this regeneration possibility that granular carbon is more
economical than powdered carbon for wastewater treatment.
Adsorption of pollutants on activated carbon is affected by a large
number of factors related to the adsorbate-adsorbent-solution properties.
Because properties of activated carbon vary among different commercially
available carbons, the selection of a carbon for a particular application
is generally based on laboratory and pilot column tests in which the adsorp-
tive capacity of different carbon products are evaluated and compared.
Of the several techniques tested for the regeneration of organic
compound-contaminated granular carbons, thermal regeneration under controlled
conditions has been found to be most economical. Thermal regeneration is
usually considered a three-step process, involving: (1) drying which results
in evaporation of the free water, (2) baking or pyrolysis of adsorbed or-
ganics which results in the evolution of gases and formation of carbon
residues in the micropores of the activated carbon, and (3) activation or
destruction of the carbon residues formed in the baking step. Drying can
be accomplished at 100°C (212°F), baking between 100° to 815°C (212° to
1500°F), and activation at carbon temperatures between 815° to 900°C (1500°
to 1650°F). All three steps can be carried out in a direct-fired multiple
hearth furnace, which is currently regarded as the best commercially avail-
able equipment for the regeneration of carbon used in treatment of domestic
and certain industrial wastewaters.
Figure 6-4 presents a schematic diagram of the carbon adsorption system
at the Chipman Division of Rhodia, Inc., in Portland, Oregon. The system
handles phenolic wastewaters from the manufacturing and formulation of
chlorinated pesticides (see Table 6-9 for wastewater analysis). The removal
efficiency for the toxic phenols is reported to be close to 99 percent.
Because of the low pH of the wastewater (pH = 0.5), the carbon columns are
of wood construction. Corrosion-resistant material, such as glass, fiber-
reinforced plastic, special metals and acid-proof brines, 1s also used in
certain sections of the system. Carbon regeneration 1s conducted in a
multiple-hearth furnace with a carbon loss of about 5 percent. The exhaust
gases leave the furnace at 315°C (600°F) and pass through an afterburner
6-52
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Table 6-9. Analysis of Wastewater*
(67)
Concentration
Component (mg/1)
Phenol and cresol 10
Chlorophenols and chlorocresols 100
Chlorophenoxyacetic acids :"0
Alcohols (primarily octyl) 1,000
Chlorides (as Nad) 50,000
Sulfates (as Na2$04) 8,000
Biochemical oxygen demand (BOD) 2,000
Chemical oxygen demand (COD) 3,600
Total solids 62,000
Suspended solids 10
*pH = 0.5
which operates at 980° C (1800° F) and insures complete destruction of all
organics prior to discharge to the atmosphere. The effluent from the car
bon column is neutralized with lime prior to discharge into municipal
sewers.
6.3 EXPLOSIVES INDUSTRY
6.3.1 Military Explosives Industry
Table 6-10 summarizes the treatment/disposal technologies which are
currently used or are being developed for the management of the "land-
destined" hazardous wastes in the military explosives industry. The
hazardous wastes of greatest importance are waste explosives, explosives-
contaminated inerts (bulk metal and wooden materials, nonreusable boxes
and containers, etc.), spent activated carbon from processing
aqueous hazardous wastes, red water from TNT purification, organic sol-
vents from propel 1 ant manufacture, and wastewaters containing dissolved
and suspended RDX/HMX. Based on the technology classification system
6-54
-------
Table 6-10. Treatment Disposal Technologies for Major Land-Destined
Wastes in the Military Explosives Industry
Hazardous
Waste
Technology Level
Typical
(Level I)
Best Current
(Level II)
Environmentally Acceptable
(Level III)
Waste Explosives
Explosives -
Contaminated
Inert Wastes
Spent Activated
Carbon
Red Water
Open burning
"Flashing" (for
equipment and
noncombustibles);
open burning (for
combustibles)
Open burning
Concentration by
evaporation and
incineration of
the concentrate
(Same as Level I)
(Same as Level I)
(Same as Level I)
Concentration by
evaporation and sale
for paper company use
Controlled Incineration:
Rotary Kiln
Fluidized Bed
Closed Pit
Soil Disposal
Composting
Controlled Landfill
Use in Commercial Blasting Agent Formulations
Controlled Incineration
Controlled Incineration
Thermal Regeneration
Solvent Regeneration
Fluidized bed reduction
Tampella Process
Red Water Acidification and Steam Stripping
6-55
-------
discussed in Section 3, waste treatment/disposal technologies for the
processing of major hazardous wastes in SIC 28922 are grouped fnto
Levels I, II and III technologies, as shown in Table 6-10.
Waste Explosives
The most common method for the disposal of waste explosives
is open burning. Waste material is spread over concrete pads and initiated
(ignited) remotely. Major environmental drawbacks of the open burning
techniques are: (1) the emission of significant quantities of air pc1"
tants (particulates, NO , etc.), (2) the hazards associated with stockpiling
/\
a dangerous waste material, (3) the inefficient and uncontrollable nature
of the operation, and (4) the potential for water pollution, Open burning
is not considered environmentally adequate.
Controlled combustion for the disposal of explosives wastes has been
successfully tested in pilot plant and prototype operations. Figure 6-5
presents a block flow diagram for explosive waste incineration. The two
types of incinerator designs which have been tested are the rotary kiln and the
catalytic fluidized bed. The test results and conclusions, which are sum-
marized in a "Design Guide for Propellant and Explosive Waste Incinera-
(68)
tion'a ', indicate that, though both designs provide for safe operation
with emissions meeting the regulatory standards, the fluidized bed system
appears to be superior. Both techniques are considered environmentally
adequate.
A third controlled combustion method which has been successfully
tested in a prototype operation is the closed-pit batch incineration
developed under AEC sponsorship. ' Forced air circulation is used to
decrease combustion temperature, improve performance and decrease NO
A
formation. A gravel and dirt top is included in the design to provide for
the removal of particulates and absorption of gaseous pollutants from the
combustion gases,
A number of other promising concepts for explosives waste disposal are
under consideration for pilot-plant testing and possible large-
scale utilization. These include the use of scrap military explosives
6-56
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in commercial blasting agent formulations, and controlled soil disposal
to effect biodegradation.
The GOCO explosive plants do not use plastic/concrete encapsulation,
leachate collection, or steel drums as safeguards in the disposal of
waste explosives. The Level I technology, open burning, is also Level
II technology; it is not considered environmentally adequate
The Level III technologies for the disposal of waste explosives are
all in the pilot plant stage. Required Implementation times for compile
Level III disposal systems are estimated as 2-3 years, ^ ' and the systems
can be substituted for open burning at existing GOCO explosive plants.
The sampling, testing and surveillance techniques required
for adequate monitoring are available, and are within the capabilities
of the GOCO facilities. The Level III technology systems will have no
impact on water and noise pollution problems, and will decrease air pollution.
Explosive-Contaminated Inert Wastes
Open burning is used for the destruction of explosive-contaminated
combustible materials such as: (1) large timbers, plywood and other materials
of construction, and (2) nonreusable packaging and container items. Non-
combustible contaminated materials such as equipment and metallic items,
including process tanks, hoods, ducts and large unloaded ordnance items
containing residual explosives, are thermally decontaminated by "flashing".
Open burning and flashing are considered environmentally objectionable
from the standpoint of generating air pollutants.
Incinerators have been developed for controlled combustion of contaminated
inert wastes. A 270 kilogram ( 600 pound) per hour prototype unit has been
constructed and successfully tested at Joliet Army Ammunition Plant. A
schematic diagram of this prototype unit is shown in Figure 6-6. Monitoring
of the stack effluent during the prototype testing has indicated compliance
with applicable regulations. Based on the results of the operation at Joliet
and of other engineering feasibility studies, a "Design Guide for Explosive
Contaminated Inert Waste Incineration" * ' has been published.
6-58
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Activated carbon adsorption has been shown to be an effective method
for the removal of dissolved nitrobodies and a number of other explosive
contaminants from wastewaters. Full-scale activated carbon adsopption
units are in operation at a number of AAP's for the removal of nitro-
bodies from LAP waste waters. Activated carbon adsorption has also been
considered for treatment of condensate from red water evaporation and for
processing other aqueous wastes containing hazardous organic1. Cpent
carbon is disposed of by open burning. Controlled combustion ir1 an ex-
plosive waste incinerator is considered as a more desirable alternative.
Regeneration of carbon for reuse is also being evaluated in laboratory
studies. Two regeneration methods considered are thermal treatment in
a fluidized bed, and elution with organic solvents.
The GOCO explosives plants do not use plastic/concrete encapsulation,
leachate collection or steel drums as safeguards in the disposal of
explosives-contaminated inert wastes.
The Level I and Level II technologies used for disposal of explosives-
contaminated inert wastes and spent activated carbon wastes are identical;
both Level I and Level II technologies are not considered environmentally
adequate.
The Level III technologies for the disposal of explosives-contaminated
inert wastes and spent activated carbon wastes are all in prototype or
pilot plant stages. Required implementation times for complete Level III
disposal systems are estimated as 3 to 5 years, * ' and the systems can
be utilized by existing GOCO plants. The sampling, testing, and surveillance
techniques required for adequate monitoring are available, and have been
('70)
used in pilot and prototype units ^ ' and are described in the
literature' . The use of Level III disposal systems will have
no impact on water and noise pollution problems and will decrease
water pollution.
Red Water
The purification of crude TNT by neutralization with soda ash and
washing with sellite (a solution of sodium sulfite) results in the generation
of an alkaline red colored aqueous waste containing TNT impurities
6-60
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(sodium salts of dinitrotoluenesulfonic adds) and other organic and
inorganic salts. The red water from batch TNT production is considerably
more dilute than that from the new continuous TNT lines (3 to 5 percent
vs. 30 to 35 percent solids). Because of a very low current rate of TNT
production, the quantity of red water generated at the TNT plants is
relatively small and is "disposed" of through sale to kraft pulp mills.
Because of the small market, this method of disposal is viewed as only a
temporary solution^ and other potential alternatives are under active
consideration. In the past, the voluminous quantities of red water generated
were disposed of by incineration. The red water was neutralized with
sulfuric acid, concentrated- by evaporation, and the concentrate was
incinerated in a rotary kiln (Figure 6-7). Since the quantity of ash
produced was significant (0.19 kilograms per kilogram of TNT manufactured)
large piles of ash have accumulated at some TNT production sites. At one
plant the ash has been disposed of by land burial.
Because of the environmental inadequacies of the disposal methods,
a considerable amount of effort is directed toward developing methods
for the utilization and recycle of red water ash. Three of the most
promising methods under investigation are fluidized bed reduction, the
TampeTIa Process, and red water acidification.
In fluidized bed reduction (Figure 6-8) the ash is ground and reacted
with carbon monoxide which also serves to fluidize the solids. Carbon
monoxide is generated by reacting coke with carbon dioxide. The process
produces sodium carbonate and H^S which can be used (after conversion of
HpS to S02) to produce sellite solution for recycling. The fluidized bed
reduction process has been evaluated in laboratory bench-scale tests.
In the Tampella Process, pulverized coal is added to the concentrated
red water and the mixture is incinerated to produce a sodium carbonate
smelt plus gaseous hydrogen sulfide; these are used to produce sellite for
recycling. This process has been tested in pilot-plant studies.
In red water acidification, the wastewater pH is lowered by the addition
of acid. Steam is then added to convert the nitrotoluene sulfonates in
the red water to such useful compounds as diaminotoluene and dinitrotoluene.
The red water acidification process is in the laboratory bench-scale evaluation
stage.
6-61
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In addition to the red water treatment/disposal technologies discussed
above, a number of other approaches have been Investigated to reduce waste-
water volume and strength. Conversion of the batch TNT lines to the new and
more efficient continuous lines was discussed in Section 5.4.1.1. Low temp-
erature nitration of toluene, which results in a higher yield of a-TNT and
hence production of a smaller quantity of undesirable Isomers, is another
attractive possibility for reducing waste quantities. Full-^ale testing
of the low-temperature nitration concept underway at one of the AAP's in
1974 when a halt in production resulted 1n discontinuation of the experi-
ment. Adequate data were not available on the low temperature nitration
method in 1974 to permit process evaluation.
Plastic/concrete encapsulation, leachate collection, and steel drums
were not used by the GOCO plants as safeguards in the disposal of red water
wastes from TNT production.
The Level I technology (concentration by evaporation, followed by
incineration and open storage of the ash) is not considered environmentally
adequate. The Level II technology (concentration by evaporation, and sale
of the concentrated liquor to paper companies) which is considered environ-
mentally acceptable can be applied to only a snail portion of the red water
wastes because of the limited marketability. The Level III technologies
listed in Table 6-10 are all in the pilot plant stage. Required imple-
mentation plans for Level III technologies are estimated at 5 to 8 years. '
The Level III techniques can be used at existing GOCO TNT plants. The
sampling, testing, and surveillance techniques required for adequate mon-
itoring of the fluidized bed reduction, Tampella and red water acidification/
steam stripping processes are available and are within the capabilities
of the GOCO plants. The Level III techniques will have no impact on air and
noise pollution problems, and will decrease water pollution problems.
6.3.2 Commercial Explosives Industry
Compared to the military explosives industry, for which an extensive
volume of data are available on waste treatment technologies, very little
data are available on the commercial explosives industry. Although in some
instances the nature of the problems and the required abatement methodology
are the same for both industries, the pollution control effort in the military
6-64
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explosives industry is significantly more advanced because of the greater
emphasis on development and installation of pollution control techniques
in Federal installations.
Based on a search of the published literature^2' 20' 72~74^and visits
to eight plant, sites, the following are identified as the land-related
waste treatment/disposal technologies used in the commercial explosives
industry: (1) open burning of scrap explosives and contaminated wastes,
(2) chemical detoxification, (3) contract disposal, (4) sale of scrap
explosives or product waste to vendors for reclamation/reuse, (5) deep
well disposal, and (6) spray irrigation or lagooning. Based on the available
data and the technology classification defined in Section 2.3, for the
commercial explosives industry open burning of scrap explosives is con-
sidered Level I technology, and the sale of scrap explosives or product
waste to vendors for reclamation or reuse, and spray irrigation or
lagooning of the aqueous wastes are considered as Level II and III
technologies.
Open burning, the Level I technology, is generally conducted under
special state permits which specify under what conditions the material
can be air burned. Burning is usually conducted on concrete pads or in
open pits. One commercial plant which manufactures propellents for the
Air Force has seven concrete pads, each of which can be loaded with a
maximum of 110 kilograms of materials. Another facility utilizes 12
"burning pits" which can each be loaded with 270 to 320 kilograms of
waste propellents as needed. Except for safety considerations, and unless
stipulated otherwise in the permit, there is generally no limit on the
quantity of wastes which can be disposed of by open burning.
One particular application of open burning is the "open-top" incinerator
developed by Du Pont ^ , which is used at one of the plants visited
for the disposal of nitrocellulose wastes. Wood is ad^d to the wet nitro-
cellulose as fuel. The principal feature of the open-top incinerator
is the admission of air for burning through closely spaced, high-velocity
nozzles. The advantages claimed for this design include: (1) high flame
temperature and turbulence which result in more complete combustion, (2)
simplicity of loading and cleaning, and (3) lower maintenance cost than the
conventional incinerators.
6-65
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Chemical treatment with an alkali such as lime or limestone is used
in some facilities for the deactivation of explosive-containing sludges
such as those from the production of nitroglycerin and smokeless powder.
One plant disposes of the treated sludge by discharge into a lagoon which
overflows into a nearby river.
Concentrated acid wastes from manufacturing operations are usually
either purified on-site and reused or sold to outside compares for reuse.
At one nitroglycerin production site, the spent HN03/H2S04 acid is denitri-
fied by treatment with steam and the product sulfuric acid (30 percent acid
content) is discharged to a temporary storage lagoon prior to sale to an
outside acid supplier. The nitric acid contained in the steam effluent
is not recovered and is discharged to the atmosphere. The quantity of
nitric acid discharged to air at this site is estimated at 200 metric
tons/year.
In the Level II and III technology used at one facility in northern
California, the process wastewater is neutralized and disposed of on
"percolation" land. Shallow and deep test wells are provided for monitoring
the subsurface waste movement. Some of the waste at this facility has also
been taken to a Class 1* disposal site. A deep well facility was constructed
at this sfte for future waste injection into subsurface formations between
298 and 427 meters (980 and 1400 feet). The well is expected to operate
under a well head pressure of less than 480 kilonewtons per square meter
(55 pounds per square inch). In the event of well plugging, malfunction
of the pH adjustment system or other contingency, the wastewater is to be
diverted to a cement-lined basin which has a 15-day hold-up capacity.
In connection with a study of water pollution control in the commercial
explosives industry, Patterson and Minear ^75\isited a number of cormiercial
explosives-manufacturing sites and found several applications of waste manaqe-
ment by land irrigation and by storage in evaporation lagoons. These Level II
and III methods of land treatment or disposal appear especially attractive for
use by on-site explosive formulators and by plants located in arid and semi-
arid regions. Land disposal data reported by Patterson and Minear'75^are
summarized in Table 6-11.
* See Appendix B for definition of "Class 1 disposal site".
6-66
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Table 6-11.
Use of Spray Irrigation and Evaporation Lagoons for Waste
Disposal(75; in the Commercial Explosives Industry
site
Des iqna tion
A
B
f
D
1 E
F
Genera]
Location
An arid
region
Upper
Midwest
Southeast
An arid
region
Northern
Midwest
Central
Southeast
Nature of
Production Operation
Complex production
facil ity producing
ANFO, dynamites,
various intermediates
and specialty products
Complex production
facility
On-site small water
gel formulation
Complex production
facil ity
On-site facility
On-site water gel
formulator
Waste
Pretreatment
Sedimentation and
oil skimming
Activated sludge
and lagooning
None
None
None
None
Disposal Method and
Site Characteristics
Spray irrigation on a 48 K(mr pasture
of bermuda grass. Application rate
^
0.11 liter/(nrln.m ) . Site used to qrazt
cattle. Expansion of the irrigation
area to additional 80-160,000 m2
underway.
Spray irrigation at a rate of 4.4 x
10"4 liter/(min.mZ). Only about half
of the waste percolates into the ground
the remainder appears as surface
runoff.
Flow very small (95-114 liter/day); it
is collected in a tank truck, and as
necessary, sprayed onto an abandoned
mine overburden disposal site on
plant property.
Only waste streams from clean-up of
ANFO-blasting equipment and NG
neutralization disposed of by storage
in evaporation/percolation lagoon,
All waste waters (17,600 liter/day in
winter, 23,300 liter/day in summer)
discharged to a natural basin; most
of losses by percolation.
All process waste waters (3.8 liter/min.
discharged to a lagoon having a
capacity of 26,500m .
6-67
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The commercial explosives Industry does not use plastic/concrete
encapsulation or leachate collection as safeguards in the disposal of
its land-destined process wastes. There is insufficient data on which to
base an estimate of the use of steel drums as safeguards in process waste
disposal.
The Level I technology (open burning) is not considered environmentally
adequate because of the factors cited in Section 6.3.1 for tht use of this
technique. The Level II and Level III treatment and disposal techno!^ .tis
employed by the commercial explosives plants are considered environmentally
adequate. The Level III technologies of the military explosives industry,
described in Section 6.3.1, are suitable for application to the disposal
of the process wastes of the commercial explosives industry.
The sale of scrap explosives or product waste to vendors for sale and
reuse and the military industry's Level III disposal technologies can be
used at existing commercial explosives industry plants. The estimated
required times for the implementation are from 5 to 8 years. The Level III
technologies will decrease air and water pollution, and will have no effect
on noise pollution problems. The sampling, testing, and surveillance tech-
niques required for adequate monitoring are available and are within the
plants' capabilities.
6-68
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7. COST ANALYSIS
Because of the similarities in the treatment/disposal technologies
used for management of wastes from the organic chemicals and pesticides
industries and because of differences between these technologies and those
employed in the explosives industries, the cost analysis in this section is
presented in two separate subsections. Section 7.1 presents the cost data
for treatment/disposal of 15 selected land-destined hazardous waste streams
from the organic chemicals and pesticides* industries. The cost data per-
taining to the explosives industry are presented in Section 7.2.
7.1 ORGANIC CHEMICALS AND PESTICIDES* INDUSTRIES
The hazardous waste streams and the three levels of treatment/disposal
technologies for which cost estimates are made are listed in Table 6-4 and
discussed in detail in Section 6.2. Except as noted in individual cases,
the general basis for cost estimates and the criteria used are those listed
in Table 7-1, and those contained in the discussions of the costs of indi-
vidual treatment and disposal methods. All cost estimates have been adjusted
to December 1973 dollars using the "CE Plant Cost Index" as reported each
month in Chemical Engineering. The unit costs used for estimating capital
and operating costs were obtained from the following sources: (1) direct
contact with the industry, (2) published literature,(74'76'79) anc] (3) tech-
nical discussions with equipment manufacturers. The estimated capital cost
was depreciated over the estimated service life of the equipment system
using the straight-line depreciation approach. In cases where the land area
devoted to on-site waste processing/disposal was appreciably large, the land
value was considered as a capital cost item. For "off-site" land disposal,
*
Since the results of this study (as presented in Table 5-18) indicate that
the hazardous waste tonnages discharged to land by the technical organic
pest control chemicals product group (SIC 28694} were many times higher
than the quantities of hazardous wastes discharged to land by the pesti-
cides preparations and formulations industry (SIC 2879), the treatment
and disposal cost analyses performed for the pesticides industries dealt
exclusively with the practices of SIC 28694.
7-1
-------
Table 7-1. Bases and Criteria for Cost Estimation
Private debt financing assumed for treatment and disposal facilities investment.
Cost of capital = annual interest on investment = 10 percent.
Depreciation - straight line over estimated life for initial cost less salvage value.
Estimated life for equipment and systems:
2
Lagoons - 25 years 2
Landfill/other mobile equipment - 5 years 2
Incinerators, air pollution abatement devices, landfill serviced life, etc., - 10 years
Land value = $14,800/hectare3
2
Labor (includes supervision, fringe benefits, and overhead) = $7.50/hour
2
Maintenance (labor and materials) = 6 percent of investment
Chemical Engineering Plant Cost Index, December 1973 index value of 144.1 (1957-59 = 100)
2
Incineration at 125"' of stoichiometn'c air requirements.
Sodium hydroxide used at 110% of stoichiometric requirements in scrubbing acid gaseous wastes.
2
Waste/supplies shipment for 420 km (250 mi)
Unit Costs:
4
Industrial power $0.02/kw hr
Freight cost, 420 kg (250 mi) $35.30/metric ton ($32/ton)4
Sodium hydroxide, 50% liquid, 76% Na20 basis $126/metric ton ($114/ton)
Activated carbon $0.66/metric kg ($0.30/lb)4
Fuel oil $84/metric ton ($12/bbl)4
Clay $8.85/metric ton ($8/ton)4
3 4
Steel drums, lined (0.21 m or 55 gal capacity) $15 each
-> 4
Steel drums, used (0.21 m° or 55 gal capacity) $7.50 each
Water $7.93/k(m3) ($30/Mgal)4
Concrete $26.20/mJ ($20/cu. yd)4
Excavation-shallow $0.89/m3 ($0.68/cu. yd)2
Excavation-deep (landfill) $2.60/m3 ($1.98/cu. yd)2
2 2
Surface finishing (leaching) $44/m ($0.37/sq. yd)
Cost of capital and depreciation were those prevalent in December 1973 and used as a common
basis for this series of studies.
Estimated by TRW on the basis of information from private industry sources.
Cost estimated by TRW on an experience basis for industrial land in the Texas Gulf Coast area
in December 1973.
4
Quotations obtained by TRW from various private industry sources.
the cost for land investment was assumed to be included in the contractor's
fee for waste handling and disposal. The typical plant site was assumed
to be in the Gulf Coast region of EPA Region VI since this area contains
the greatest concentration of organic chemicals production plants (as
indicated in Table 4-4). For this area, the capital cost of land used for
on-site waste processing/disposal was assumed to be $14,800 per hectare
($6,000 per acre).
7-2
j • '
-------
The techniques and costs of many of the landfill disoosal operations
servicing the organic chemicals and pesticides industries are very similar
to the techniques and costs for solid waste disposal in sanitary landfills.
Figure 7-1 presents some estimates for solid waste disposal in sanitary
landfills as reported by Heaney and Keane in 1970.^ ' The factors which
affect landfill disposal costs for the organic chemicals and pesticides
industries include the size of the operation, the value of the land, the
type of wastes (i.e., hazardous versus nonhazardous), and location
characteristics including on-site availability of cover material.
The costs of disposal by incineration are varied, depending on the
size of the operation, waste characteristics, type of incinerator, and
emissions control requirements. Figure 7-2 gives some perspective of the
10
9
8
7
TOTAL COST PER TON (T.VER IWTERIAI.
PURCHASED AT S1.96/M3
4-
TOTAL COST PL'R TOfl COVE". I'/iTERIAL
•\\ i / 0" SITE
COVER IVTERIAL PURCHASED AT
S1.96/M3
- LA'IUFILL LQUIPIlL.'iT
LC'IDFILL LABOR
0 200 400 600 800 10UO
SOLID WASTES, METRIC TONS/WEEK (SIX-DAY OPERATION)
Figure 7-1. The Cost of Solid Waste Disposal in
Sanitary Landfills(Q0)
(Note: The techniques and costs of landfill disposal operations for the
organic chemicals and pesticides industries are very similar to those given
for solid waste disposal in sanitary landfills.)
7-3
-------
INCINERATOR CAPACITY, KG/HOUR
100 ZOO 300 400
_L
j l
Incinerator
(Multiple-Chambers)
J I I I
_L
J
0 100 200 300 400 500 600 700 800 900 1000
INCINERATOR CAPACITY (#/HOUR)
Figure 7-2. Cost of Small Scrubber-Equipped
Incineration Systems in 1971 (8u
capital costs for smaller size incinerator systems equipped with wet scrub-
bers for pollution control/ ' The capital investment for the new tar
incinerator at Dow Chemical Midland facility (illustrated in Figure 6-2)
was reportedly close to $2.25 million dollars. The operating costs for this
unit and other incinerators which handle a total of 2460 cubic meters (650,000
gallons) of liquid waste tars and more than 700 drums of burnable chemicals
each month are reported as $94,000 per month. The operating costs con-
sist of $25,000 for labor (12 hourly operators, 1 foreman, and 1 super-
intendent), $20,000 for maintenance, $22,000 for utilities, $15,000 for
general services ( including landfill disposal costs), and $12,000 for mis-
cellaneous items (materials, factory expense, technical projects, etc.).(49)
Because of the differences in the geological conditions in various
regions of the country and in pretreatment requirements for different types
of wastes, the capital investment for deep well injection varies at dif-
ferent locations and for different wastes. In 1971, the average cost for
drilling and completing oil wells in the contiguous United States was $57.61
per meter of depth, with actual values ranging from a low of $13.97 in
Nebraska to a high of $95.09 in one location 1n California.(65)(The Correspond-
ing costs for waste injection wells should be somewhat higher.) A 1961 survey
(65)
7-4
-------
indicated that the total costs of underground-waste-injection systems ranged
from $30,000 (for a system without surface equipment for pretreatment of the
waste) to $1,400,000, for one with elaborate equipment and a well 3660 meters
(12,000 feet) deep. The average cost was $200,000. The operating cost for
deep well injection Is dependent on the pretreatment requirements and the
operating pressure at the well head. The well pressures reported for exist-
ing facilities range from near vacuum to over 6900 kilonewtons per square meter
(1000 pounds per square inch).
Estimates of the costs for new deep well disposal systems should be
made on a case-by-case basis and require a detailed knowledge of the sub-
surface geology and physical and chemical characteristics of the waste.
The following data are a statistical breakdown of costs for the example
given in Section 6.2.3, including drilling and equipment costs for a
"typical" disposal well completed by casing perforation at the disposal
zone.'66'
Dimensions, meters (feet):
Depth of well 914 (3,000)
Surface casing, 2.67 cm (10-1/2 in.) 91 (300)
Injection casing, 17.8 cm (7 in.) 914 (3,000)
Tubing, 7.6 cm (3 in.) 91 (300)
Costs, dollars:
Drilling and completion costs 50,000
Tests 10,000
Engineering 20,000
Surface equipment 120,000
Total 200,000
The capital cost of an evaporation pond is determined primarily by
the land value and the costs of excavation, construction of runoff diversion
structures, and any additional equipment which is used for supplemental
mixing and aeration. The operating costs are essentially those for pond
maintenance, power consumption (in cases of supplemental mixing and aeration)
and laboratory analysis for wastewater characterization and monitoring.
Ferguson' ' reported on a preliminary design and cost analysis for an
7-5
-------
evaporation system handling an annual wastewater volume of 1,892 cubic
meters (0.5 million gallons) from a pesticide formulating plant (18,120
metric tons or 40,000,000 pounds per year formulation rate). The data
indicated that a system consisting of a pump, a surge tank (15,000 liter
capacity), a concrete evaporation pad (4.57 meters wide, 9.14 meters long
and 0.91 meters deep) with a roof, and an aeration pump, could probably
be constructed with a capital investment of less than $10,QOi' and could
be operated at an annual cost of close to $3,000. The reported^ '
capital cost did not include the value of the land.
The cost of activated carbon adsorption is dependent on a large
number of factors including wastewater characteristics, pretreatment needs,
size of the operation, desired removal efficiency, and emission control
requirements for the regeneration furnace. The quantity of carbon required
for the treatment of biologically processed municipal wastewaters is in
the 30 to 42 kilogram per 1000 cubic meter (250 to 350 pounds per million
gallons) range. Higher carbon dosages would be required for raw municipal
or industrial wastewaters which contain a significantly higher concentra-
tion or organlcs. For a 28,400 cubic meter per day (7.5 million gallons
per day) advanced municipal waste treatment facility, the capital and
operating costs of carbon adsorption have been reported as C.57<£ and 0.87i£
per cubic meter of wastewater ($21.5 and $32.91 per million gallons),
(82)
respectively/ ; The total capital expenditure for the pesticides industry
activated carbon adsorption plant of the Chipman Division of Rhodia, Inc.
(discussed in Section 6.2.3) Is reported to be $300,000, and the operating
cost is estimated at 9.4tf per cubic meter (35.Sit/1000 gallons). The plant
treats 568 cubic meter per day (150,000 gallons/day) of a phenolic waste-
water.
A summary of cost estimates for the three levels of treatment/disposal
technology for the 15 selected waste streams of the organic chemicals and
pesticides industries is presented in Table 7-2. The cost items shown in
this table include total investment cost, total annual operating cost
(excluding energy cost), annual energy cost, and total disposal cost per
metric ton of product and of hazardous waste. Table 7-3 presents a compara-
tive listing of current costs (including transportation) for the disposal
of land-destined organic chemical wastes, obtained from a private industry
source which supplied information to TRW on a proprietary basis.
7-6
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Table 7-3. Comparative Data - Current Costs of Chemical Waste
Treatment and Disposal for a Typical Organic
Chemical Plant
Disposal Practice
Contractor secured unlined landfill, drummed wastes
Contractor off-site incineration, drummed wastes
Contractor secured lined landfill, drummed wastes
On-site lined landfill, drummed wastes
On-site controlled incineration, components
Cost/Metric Ton'
$49.60
$66.10
$79.40
$20.00
$60.00
*Quantities above 4000 metric tons per year; includes transportation
for off-site disposal.
*
The weighted averages of the cost estimates given in Table 7-2 for
Levels I,II and III treatment and disposal technology are as follows:
Level I: $13.36/metric ton of waste (wet basis); $48.32/metric
ton of waste (dry weight basis);
Level II: $30.56/metric ton of waste (wet basis); $110.54/metric
ton of waste (dry weight basis);
Level III: $30.69/metric ton of waste (wet basis); $111.02/metric
ton of waste (dry weight basis).
The costs of treatment and disposal of the selected waste streams from manu-
facture of the 15 commodities, calculated as percent of 1973 sales values
from Reference 30, have weighted averages of 0.9 percent for Level I treat-
ment and disposal technology, and 2.2 percent for Level II and III tech-
nologies. The total national cost projected for the use of Level I tech-
nology for treatment and disposal of the 2.19 million metric tons (dry
basis) of land-destined wastes discharged by the organic chemicals and
pesticides industries is approximately $106,000,000. The basis used for
calculation of this figure is the weighted average estimate of $48.32 per
Weighted in accordance with the quantity estimated as the national total
discharge in 1973 of each of the 15 selected waste streams.
7-11
-------
metric ton of waste (dry weight basis) given above. The value of organic
chemicals and pesticides sales in 1973 is estimated (based on extrapolation
of the data of Reference 30) as approximately $21.4 billion.
The general discussion which follows is concerned with the sources of
the major changes which can occur in the costs estimated for the applica-
tions of treatment and disposal technology to the industry subcategories
shown in Figure 7-2. The discussion will include the effects o* the con-
ditions causing the major cost changes, and how these major cost chanrpr
may be estimated.
There are 13 different major types of treatment and disposal methods
associated with the 15 industry subcategories and the three technology
levels shown in Table 7-2. These 13 disposal methods and the major factors
which affect the treatment and disposal costs for their application to the
industry subcategories are shown in Table 7-4. As indicated in Table 7-4,
the factors with major cost impact vary with the nature of the industry,
the nature of the waste stream, and the technology used. These major factors
(each of which is not necessarily applicable in all cases) include:
Pretreatment requirements, site subsurface geology, waste stream
discharge rate, emission control requirements, cost of land,
availability/cost of cover material, transportation distances,
contractor capital and operating costs, cost of drums, and cost
of tanks.
The above factors are those which must be considered in estimating disposal
costs for other plants and locations from the costs shown in Table 7-2 for
specific waste treatment and disposal technology applications to typical
plants located in the Gulf Coast area. For each treatment/disposal method,
the effect of these factors may be estimated as follows:
1) The extent and nature of pretreatment required prior to
final disposal of a waste is dependent on the waste
characteristics, ultimate disposal method (e.g., incinera-
tion, deep well injection, landfilling, etc.) and appli-
cable environmental regulations. The impact of differences
in pretreatment is to change capital outlay,* and to
change costs per metric ton of waste as a function of
Capital outlay, as used throughout this discussion, is synonymous with
investment, as used in Figure 4-2.
7-12
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7-13
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change in capital outlay. The change in capital outlay must
be estimated based on engineering and cost studies. Changes
in disposal costs per metric ton for the baseline typical
plant size can be estimated by multiplying the factors for
annual capital cost, depreciation, and maintenance (which
total about 0.26)* by the change in capital outlay, and
dividing the result by the baseline typical waste stream
discharge rate.
2) For deep-well injection, in addition to its impact ^n prp-
treatment costs, differences in subsurface geology ai"o affects
well depth and hence drilling costs and operating energy rcbts.
An individual site survey must be performed at each site to
determine well depth and energy consumption requirements. The
effect of changes in well depth may be estimated for the typical
Gulf Coast site by multiplying the depth change in meters by
$70. Changes in drilling cost for sites other than Gulf Coast
will require individual estimation based on the survey; they range
from $75 per meter to $125 per meter.(65) These revised costs
will change capital outlay and disposal costs per metric ton
of waste. The change in disposal costs per metric ton of waste
due to changed capital outlay can be calculated in the same
fashion as for pretreatment costs. The effect of operating
energy requirement changes is to change energy costs. The
changed energy costs can be calculated by determining change
in pump horsepower required and assuming 60 percent pump
efficiency.
3) The effect of waste stream discharge rate changes is to change
capital outlay requirements from those shown for the typical
plant. The new capital outlay may be estimated by multiplying
the baseline typical plant capital outlay by the factor
(New waste stream discharge rate \
Baseline typical plant waste stream discharge rate)
The effect of the changed capital outlay requirements on disposal
cost per metric ton of waste may be approximated by multiplying
the change in capital outlay by the factor 0.26, and dividing the
result by the new waste stream discharge rate. These estimation
procedure's can be used for all of the noncontractor-performed
on-site treatment/disposal methods.
4) Emission control requirements have a major impact on the costs
of controlled incineration, and are dictated by local, state and
Federal regulations. The costs shown for capital outlay, opera-
ting (excluding energy) and energy in Table 7-2 for controlled
incineration are based on maximum equipment requirements.
Changes must be estimated on a case-by-case basis.
10 percent cost of capital, 10-year straight line depreciation, and
6 percent maintenance. 7 ...
-------
5) Cost of land has its major impact on the capital outlay
requirements for landfill, evaporation ponds, and on-site
storage. The effect on change in costs per metric ton of
waste is a factor of the chanqe in capital outlay. The approxi-
mate change in capital outlay may be calculated by multiplying
the total land in acres required for the disposal facility by
the difference between new land cost figure per acre and $6,000*
The change in cost of disposal per metric ton of waste may be
estimated by multiplying thn factors for annual cost of capital
and depreciation**(which total about 0.20) by the change in
capital outlay, and dividing the product by the baseline typical
plant waste stream discharge rate.
6) Availability/cost of cover material impact the cost of landfill
disposal, and must be determined on an individual site basis.
A rough rule of thumb is that change in cost of cover material
per cubic meter is approximately equal to change in cost of
disposal per metric ton of waste, based on sanitary landfill
practice.(80)
7) Waste transportation distance changes from the 402 kilometers
(250 miles) used as baseline have a direct impact on the costs
of contractor disposal via incineration or landfill. The chanqe
in cost per metric ton of waste must be determined by individual
rate quotation, based on actual location, actual transportation
distances, and actual waste quantities to be hauled.
8) Contractor capital and operating costs have a direct impact on
the rates quoted for contract disposal via landfill and incinera-
tion. The rates quoted are also dependent upon quantity of
waste disposal per unit time and the term of the contract.
Contractor quotations must be obtained on a case-by-case basis.
9) Site geology has a major impact on the cost of disposal in
secured landfills, storage in concrete trenches and evaporation
ponds. The cost of protection required, which is a major cost
factor, is directly dependent upon distance to groundwater,
subsurface geology, climate (including rainfall and evaporation
rate), topography, and monitoring requirements. Estimation
of changes in cost must be on a case-by-case basis, with
individual site surveys. The impact is generally a change in
capital outlay, which results in a change in cost per metric
ton of waste. The change in cost per metric ton of waste may
be estimated by the method used for estimating changes in costs
for pretreatment requirements.
10) The effect of changes in the cost of drums is major on costs for
the contract landfill disposal of chloronethane solvent wastes,
*
A land cost of $6000 per acre has been used in the cost estimates shown
in Table 7-2 (See also page 7-2).
**
The land is assumed non-usable for other purposes due to the hazardous
character of the wastes.
7-15
-------
and for on-site lined drum storage of trifluralin spent carbon
wastes. Changes in cost of disposal per metric ton of waste may
be estimated as follows:
For chloromethane solvent wastes, change in cost per
metric ton of waste is equal to approximately the new
cost of drums minus $7.50 times 3.1.
*
For trifluralin spent carbon wastes, change in cost per
metric ton of waste is equal to approximately t"2 new
cost of drums minus $15.00 times 11.8.**
11) Changes in the cost of the steel tanks used for on-site storage
of epichlorohydrin still liquid residues have a major impact
on the capital outlay, and are reflected in changes in cost per
metric ton of waste. The change in capital outlay will have to
be estimated on a case-by-case basis. The change in cost per
metric ton of waste may be estimated by multiplying the change
in capital outlay by factors covering the cost of capital
(10 percent), depreciation (15-year straight line) and mainten-
ance (3 percent).
7.2 EXPLOSIVES INDUSTRY
As indicated in Section 5 explosives and explosives-contaminated wastes
are the major land-destined hazardous wastes in the explosives industry.
Currently these wastes are disposed of by open burning. Major cost elements
for disposal by open burning are land value, transportation cost and the
cost of operation and maintenance.
In the military explosives industry, the burning grounds are located
on military reservation property and as such are carried at no cost to the
plant operating contractors. Most waste-generating facilities in the com-
mercial explosives industry (especially the large number of on-site
ammonium nitrate-fuel oil (ANFO) formulators) are located in areas where the
land is relatively inexpensive and the value of the land accounts for a very
small fraction of the total disposal cost. Table 7-5 lists the cost for
open burning at a selected number of Army ammunition plants based on a 1973
Based on 320 kilograms of waste (dry basis) per drum,
1000 kg/metric ton ~ i/ drum \
320 kg/drum J' ' Wtric ton '
**Based on 85 kilograms of waste (dry basis) per drum,
1000 kg/metric ton ,, q/ drum \
85 kg/drum " "^metric ton'
7-16
-------
Table 7-5. Cost of Waste Disposal by Open Burning at
Selected Army Ammunition Plants(58)
Location
Nebraska
Tennessee
Tennessee
Tennessee
111 i no is
Missouri
Louisiana
Iowa
$/lb
0.1907
0.0218
0.012
0.2555
0.0101
0.2909
0.0264
0.0013
$/kg
0.4204
0.0481
0.0265
0.5633
0.0223
0.6413
0.0502
0.0029
/ rn\
survey. The variations in the reported costs reflect the differences in
the size of the operation and in the costs for operation, maintenance, and
waste transportation.
As indicated in Section 6, open burning is not an environmentally
acceptable method for the disposal of explosives and explosives-contaminated
wastes. Controlled incineration which provides for safe disposal of wastes
is being developed as an alternative to open burning. Pilot plant studies
which were conducted have resulted in the development of auxiliary com-
ponents and techniques for waste preparation, handling, and incineration.
The fluidized bed being considered for full-scale utilization is currently
in advanced development and an economic assessment of the system is under-
way. ' Preliminary data from this economic evaluation were not available
to TRW for use in this study.
Based on data, for the prototype unit shown in Figure 6-6, studies have
been made of capital costs of systems for the disposal of contaminated inert
waste by incineration.^ ' Table 7-6 presents a summary of the capital cost
data for three incineration systems having capacities of 2,300, 5,900, and
11,800 kilograms per day. The capital cost breakdown for the 5,900
kilograms per day system is shown in Table 7-7. The breakdowns for the
7-17
-------
Table 7-6. Explosive Contaminated Inert Waste
Incineration(71)
Capital Cost Summary
Facility Capacity (kg/day)
Item
Arch. & Struct.
Electrical
Mechanical
10% Contingency
8.5% Engr. Support
5% S&A
Sub Total
Equipment
8% Engr. & Plant Support
Sub Total
Total
2,300
$153,300
59,300
40,900
$253,500
25,350
$278,850
23,702
$302,552
15,127
$317,679
$304,400
24,352
$328,752
$646,431
$
$
$
$
$
$
$
$1
5,900
207,000
73,000
45,500
325,500
32,550
358,050
30,434
388,484
19,424
407,908
619,200
49,536
668,736
,076,644
$
$
$
$
$
$
$
$1
11,800
237,700
81,100
48.90U
367,700
36,770
404,470
34,379
438,849
21,942
460,791
746,700
59,736
806,436
,267,227
7-18
-------
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7-19
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projected operating costs were not available. TRW estimates of total
disposal costs* are $360 per metric ton of waste for the 2,300 kilogram per
day incineration unit, $214 per metric ton of waste for the 5,900-kilograms
per day incineration unit, and $133 per metric ton of waste for the
11,800-kilogram per day incineration unit.
Includes costs of capital, operating costs (excluding energy), and
energy.
7-20
-------
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May 1974.
Report to Congress, Disposal of hazardous wastes. Office of Solid Waste
Management Programs. Washington, Superintendent of Documents,
SW-115. U. S. Government Printing Office, 1974. 110 p.
Slover, E. E. Union Carbide chemical landfill institute, West Virginia.
Prepublication copy 2. Charleston, West Virginia, Union Carbide
Corporation, June 28, 1971. 79 p.
Swift, W. H., et al. Program for the management of hazardous wastes.
Richland, Washington, Battelle Memorial Institute, Pacific
Northwest Laboratories, Contract No. 68-01-0762. July 1973.
385 p.
The Form of hazardous waste materials, Northeast Region, and Gulf Coast
Region. Wilmington, Delaware, Rollins Environmental Services.
September 7, 1972. 52 p.
Versar off-site disposal processor questionnaire. Hazardous Waste
Assessment. Springfield, Virginia, Versar, Inc. 3 p. 1974.
Worley, R. D. Disposal of waste or excess high explosives. Progress
Report. Amarillo, Texas, Mason and Hanger — Silas Mason
Company, Inc. MHSMP-74-31. Atomic Energy Commission,
Albuquerque Operations Office, April-June 1974. 31 p.
8-10
-------
Worley, R. D., T. K. Mehrhoff and J. E. Wichmann. Disposal of waste or
excess high explosives — progress report. Amarillo, Texas,
Mason and Hanger - Silas Mason Company, Inc. MHSMP-74-14.
Atomic Energy Commision, Albuquerque Operations Office,
January-March 1974. 37 p.
1972 Census of manufacturers. Washington, U. S. Department of Commerce,
Bureau of Census. MC 72(P)-28F. January 1974.
1972 Census of Manufactures. Numerical list of manufactured products
(new (1972) SIC Basis). U. S. Department of Commerce, Bureau
of the Census. MC 72-1.2. May 1973.
8-11
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APPENDIX A
METHODOLOGY DETAILS
Page
DATA ACQUISITION ..... A-2
DATA COLLATION AND ANALYSIS V-9
HAZARDOUS WASTES - IDENTIFICATION AND ESTIMATION A-12
TREATMENT AND DISPOSAL TECHNOLOGY EVALUATION A-18
COST ANALYSIS A-19
A-l
-------
DATA ACQUISITION
The data used in this study were acquired predominantly from the open
literature, prior EPA studies, industry and government sources, and prior
TRW studies. The trade associations (e.g., Manufacturing Chemists Associa-
tion, Synthetic Organic Chemical Manufacturing Association, and the National
Agricultural Chemicals Association) were extremely cooperative, but were
unable, because of charter restrictions, to function as intermediaries to
obtain "hard" data on production, waste discharge, and waste treatment from
their member companies. The data acquisition methodology varied somewhat
between industries; each industry will, therefore, be treated separately.
Table A-l lists companies and agencies which supplied information on
production and/or waste disposal methods.
Organic Chemicals Industry
The information acquired for the organic chemicals industry formed the
data base from which estimates were made of production rates, processes,
waste quantities, waste components, waste stream destination, and waste
hazard classification for the individual chemicals produced at each plant
site. The data acquisition methodology was keyed to these objectives.
The open literature, including prior studies on hazardous wastes,
hazardous spills, and hazardous materials, furnished a majority of the in-
formation used as the "hard" data basis for estimation. A substantial
minority of the data base on processes, wastes, and waste disposal, however,
was obtained from industry sources, via meetings with industry personnel at
company headquarters and production sites, and via correspondence requesting
specific data. The organic chemicals industry facilities for which data
were obtained directly from industry sources are included in the listing
of Table A-l. As .noted earlier, production rate information was regarded
as proprietary by most companies. In addition, company policy in some cases
required proprietary information protection agreements before any data could
be released for use in this study.
The United States Tariff Commission was an extremely valuable source of
information for assignment of the synthetic organic chemicals to the proper
Standard Industrial Classification, and for key production data. The Com-
mission's "Synthetic Organic Chemicals —United States Production and Sales"
annual report for 1972/ ' and preliminary annual reports for
A-2
-------
Table A-1. Companies and Agencies Supplying Information
on Production and/or Disposal
Plants
Aerojet Solid Propulsion Company, Sacramento, California
*Allied Chemical Corp., Frankford Plant, Philadelphia, Pennsylvania
*Allied Chemical Corp., Ironton, Ohio
Badger Army Ammunition Plant, Wisconsin
Baychem Corp., Chemagro Division, Kansas City, Missouri
Commercial Solvents Company, Trojan U.S. Powder Division, Tacoma,
Washington
Crown Zellerhach, Chemical Products Division, Camas, Washington
Diamond Shamrock Corporation, Greens Bayou, Texas
Dow Chemical USA, Midland Division, Midland, Michigan
Dow Chemical USA, Texas Division, Freeport, Texas
*E. I. duPont de Nemours and Co., Chambers Works, Deepwater,
New Jersey
Edgewood Arsenal, Maryland
Ethyl Corporation, North Baton Rouge, Louisiana
Georgia Pacific, Albany, Oregon
*B. F. Goodrich Chemical Co., Akron, Ohio
*B. F. Goodrich Chemical Co., Henry, Illinois
Hercules, Inc., Bacchus, Utah
Hercules, Inc., Kenvil, New Jersey
Hercules, Inc., Parlin, New Jersey
Holston Army Ammunition Plant, Kingsport, Tennessee
Covered by proprietary rights/trade secrets protection agreements,
A-3
-------
Table A-l. Companies and Agencies Supplying Information
on Production and/or Disposal (Continued)
Hooker Chemical and Plastics Corp., Niagara Falls, New York
*ICI United States Inc., Atlas Point, New Castle, Delaware
Joliet Army Ammunition Plant, Joliet, Illinois
*Eli Lilly and Co., Tippecanoe Laboratory, Lafayette, Indiana
*Monsanto Industrial Chemicals Co., Sauget, Illinois
*Monsanto Commercial Products Co., Anniston, Alabama
*Monsanto Commercial Products Co., Muscatine, Iowa
*The Naval Ammunition Depots and Naval Propellant Plants
Pennwalt Corp., Lucidol Division, Genesco, New York
Picatinny Arsenal, Dover, New Jersey
Radford Army Ammunition Plant, Radford, Virginia
Reichold Chemicals Inc., Pacific Northwest Division, Tacoma,
Washington
Rhodia Inc., Chipman Division, Portland, Oregon
Rhodia Inc., Chipman Division, St. Joseph, Missouri
Rubicon Chemicals, Geismar, Louisiana
Shell Oil Company, Shell Chemical Co., Axis, Alabama
Standard Oil of California, Chevron Chemical Co., Richmond,
California
Standard Oil of California, Chevron Chemical Co., South Plainfield,
New Jersey
Standard Oil of California, Chevron Chemical Co., Orlando, Florida
Standard Oil of California, Chevron Chemical Co., Fort Madison, Iowa
Standard Oil of Indiana, Amoco Chemicals Corporation
Chocolate Bayou, Texas
Decatur, Alabama
A-4
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Table A-1. Companies and Agencies Supplying Information on
Production and/or Disposal (Continued)
Joliet, Illinois
Wood River, Illinois
Texas City, Texas
Stauffer Chemical Co., Louisville, Kentucky
Stauffer Chemical Co., Mt. Pleasant, Tennessee
Stauffer Chemical Co., Omaha, Nebraska
Tenneco Chemicals Inc., Long Beach, California
Thiokol Chemical Co., Wasatch Division, Brigham City, Utah
Union Carbide Corp., Institute, West Virginia
Volunteer Army Ammunition Plant, Tennessee
Off-site Disposal Contractor Facilities
County of San Diego Public Works Agency, San Diego, California
Environmental Protection Corp., Bakersfield, California
Fresno County Disposal Site, Fresno, California
Omar Industrial Pumping, Chula Vista, California
A-5
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covered national total statistics, where publlshable, on United States
production and sale of all synthetic organic chemicals and, with certain
exception, identified the companies which manufactured each chemical. The
Commission's reports do not, however, contain data on the amounts pro-
duced by each company, or on the plant sites at which the individual
chemicals are manufactured.
The Bureau of Census "Preliminary Report - 1972 Census of Manufac-
(18)
tures"v ' was the source of the total United States production data for
gum and wood chemicals, and statistics on the number of establishments
producing gum and wood chemicals.
To acquire the base from which to estimate the statistics on individual
chemical production at each plant site, this study used the 1974 Directory
of Chemical Producers - United States of America," Chemical Information
Services, Stanford Research Institute/ ' other open literature sources,
and some limited private industry input. The Directory indicated, under
the pertinent company headings, the location of each organic chemical plant
site, and the chemicals manufactured at the plant site. For many of the
major commercial organic chemical commodities, plant production capacity
estimates these capacity figures were available^ ' *nd utilized.
Data used to furnish the base for estimates of waste quantities and
components were obtained from the prior EPA studies and other literature
sources cited as references throughout the body of this report, and from
the industrial sources cited in Table 3-1. Most industrial companies pro-
ducing organic chemicals do not monitor either the quantity of process
wastes sent to land for disposal or the components of the process waste
streams. In consequence, much of the information received on process waste
from industrial sources represented "best estimates" based on old/partial
data on the part of knowledgeable personnel responsible for production and/
or environmental control —waste processing and disposal. Where the indus-
trial sources provided information under the cover given by proprietary
rights/trade secret protection agreements, use was in part restricted to
serve as a check upon the estimates made.
A-6
-------
The data covering typical hazardous waste processing and disposal
practices were to a large extent obtained from the industry sources cited
in Table A-l and from the open literature.
( 7R fil fiR)
The standard cost literaturev ' °°~03' in conjunction with data from
the prior EPA studies served as a basis for cost estimation. The indices
reported periodically in Engineering News Record and Chemical Engineering
were also employed as information sources.
Pesticides Industries
The pesticides industries, discussed in this study, include both the
manufacture of technical organic pesticides*, normally included among the
organic chemicals under Standard Industrial Classification 28694, and the
manufacture of pesticide preparations and formulations — Standard Industrial
Classification 2879. Data acquisition for SIC 28694 followed the methodolgy
given above under Organic Chemicals Industry. Data acquisition for SIC
2879 was as follows.
The major comprehensive sources of industry-wide information on pro-
duction for the pesticides preparations industry were the Bureau of the
(Of. \
Census, and the Farm Chemicals Handbook. ' The remaining production data
were either considered proprietary (by the private industry sources in-
volved), or presumed protected against disclosure by public law** (for ma-
terial in the files of the EPA Pesticide Registration Division), or were so
fragmented that their acquisition would involve much additional time and be
too costly. Based on a preliminary evaluation of the relative importance of
hazardous waste streams discharged to land disposal by the pesticide prepa-
ration portion of the industries, which indicated a relatively low tonnage,
it was decided to acquire statistics sufficient to yield production estimates
at the state level, for the industry as a whole.
The Bureau of the Census furnished the information needed for these
estimates. The "Preliminary Report, 1972 Census of Manufacturers, Industry
Service, Agricultural Chemicals, N.E.C."' ' covered sufficient material
*Bureau of the Census' ' terminology used at times in this text is
"technical organic pest control chemicals."
Federal Insecticide, Fungicide, and Rodenticide Act.
A-7
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statistics on quantities and values of preparations (formulations) shipped
or manufactured to permit an estimate to be made of total quantity pro-
duced for the industry as a whole. A private communication from the Census
Bureau^ furnished data on the geographical distribution of the manufac-
turing establishments.
Information on characteristic pesticide preparation waste stream
quantities, contents, and disposal practices was obtained from the industry
sources listed in Table 3-1 and from prior EPA studies. Data acquisition
for cost analysis followed the methodology employed for the organic chemi-
cal industry.
Explosives Industry
In general, the explosives Industry has been treated as a two-segment
industry (Sections 4.4 and 6.3): the military explosives industry which
manufacture explosives for defense, and the commercial explosives industry
which product explosives for use by the private sector of the economy.
The great majority of explosives produced for defense are manufactured
at the Army ammunition plants. The United States Army Armament Command
furnished detailed reports, or arranged meetings at the Army ammunition
plants, to cover individual explosive production and hazardous waste data
at each plant. The data furnished included cost information. Hhere infor-
mation was missing, prior TRW studies of environmental pollution abatement
activities at the Army ammunition plants furnished the basis for estimation.
Additional detailed information was obtained from the plants manufacturing
propellant for the Air Force, from the Naval ammunition depots load-
assemble-pack operations, and from other defense activities.
Data acquisition for the privately operated sector of the industry,
because of the paucity of the product and production information base, was
on the basis of state-by-state statistics for explosive product groups. A
survey by the Bureau of Mines^ ' included statistics on the apparent con-
sumption of industrial explosives and blasting agents. A private communica-
tion from the Alcohol, Tobacco and Firearms Bureau of the Treasury
Department ' provided the geographical location of all the private sector
A-8
-------
plants. Data from a prior TRW study, ' and from the private sector
companies listed in Table 3-1 was used as the primary basis for the
remainder of the estimates made.
DATA COLLATION AND ANALYSIS
Plant characterization matrix forms (Figure A-l is a specimen form)
i
were developed for this study to collect and record prr.Huction and process
information extracted from the literature as well as statistics and des-
criptions obtained from industrial sources. Data forms of this t/he were
completed for 899 plant sites for the organic chemicals industry. Based on
the criteria given below 373 organic chemicals were included in the study.
The criteria used in the study were to include:
1) Individual organic chemical compounds whose production in the
United States was 10 million pounds per year or more.
2) Groups of closely related organic compounds for which production
data were readily accessible, or for which group production was
10 million pounds per year or more.
3) Organic chemical compounds closely related to the compounds of
(1) above.
4) Suspected carcinogens, 14 of which were not included under (1),
(2), and (3) above.
5) Technical organic pesticides for which United States production
was 1 million pounds per year or more.
A highly significant sample representing 90 percent of the tonnage
produced in 1973 by the industry was obtained under these criteria.
The organic chemicals industry was divided into 12 five-digit Standard
Industrial Classification product groupings for statistical summary pur-
poses. For most of the organic chemicals, each entry made in the plant
characterization matrices was then examined to determine what production
data were missing. The portions of the total annual national production of
each chemical not accounted for in the known production capacity entries
were prorated (distributed equally) among the remaining companies listed as
manufacturers for the chemicals in question, and further prorated (by the
same method) among the individual company plant sites listed as production
sites.
A-9
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A-10
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Two organic chemical product groups (SIC's 28652 and 28653 -dyes
and pigments, respectively) were divided into product categories for
estimating production data, and for process analysis and statistical sum-
maries. Seven categories of dyestuffs, on the basis of category production
in excess of 10 million pounds per year, were considered to represent SIC
28652. The synthetic organic pigments product group (SIC 28653) included
four major pigment categories for which production (with one exception)
was more than 10 million pounds per year. The estimation of production
rates for the dye and pigment categories was handled in a manner analogous
to that cited for the bulk of the organic chemicals.
Technical organic pest control chemicals (SIC 28694) for which indi-
vidual production figures were available were divided into 17 chemical
groups for process and waste generation analysis.
A process description was written, using the data base assembled, to
describe the manufacture of each criteria organic chemical, and to describe
the manufacture of dyes, pigments and technical pesticides representative
of each group. Each process description was then classified as one of the
31 process types used in this study, and the appropriate entry made in all
of the pertinent plant characterization matrices.
For each plant characterization matrix, the production estimates for
all organic chemicals in each five-digit SIC product group were summed.
This yielded the figures descriptive of "plant size" for each of the indi-
vidual five-digit SIC product groups manufactured at the plant site. A
plant site could thus have several "plant size" ratings.
For each state, the production estimates of all organic chemicals in
each five-digit SIC product group manufactured at plant sites within the
state were added. , The sums represented the annual production rates of each
of the SIC's produced within the state.
No entries were made to cover "plant age" for the organic chemicals
industry, since almost all of the industrial sources listed in Table A-l
had indicated that their production processes had been modified so frequently
that start-up date was meaningless, technically. These statements were in
accord with the extremely competitive character of the organic chemicals
A-ll
-------
industry, and the rapidity of technical and process system advances in
that industry.
The pesticides preparations and formulations industry production
statistics presented on a state-by-state basis for the preparations industry
as a whole were obtained by prorating the estimated total national produc-
tion. Prorating was on the basis of the fraction of total establishments
(c)
reported for each state by the Bureau of the Census. ;
The detailed GOCO explosives industry data furnished by the United
States Army Armament Command, supplemented by data from a prior TRW
(87)
report^ ' was used for the production statistical summaries. The statis-
tical summaries of production on a state-by-state basis for the private
sector of the explosives industry assumed that production in each state was
equal to the consumption reported for the state by the Bureau of Mines. '
HAZARDOUS WASTES - IDENTIFICATION AND ESTIMATION
Criteria were developed to enable proper identification and estimation
of hazardous wastes (See Table 3-1). The criteria divided waste streams
into two major categories on the basis of the characteristics of their
components — hazardous wastes and other wastes. Hazardous wastes were
separated further into two classes -Moderately dangerous and highly
dangerous.
The major bases used to assess the waste streams were:
• Potential to cause human death, injury, illness, or harm to
wildlife/beneficial biota.*
• Possible paths for harmful entry into the environment, throughout
the entire cycle of waste management.**
*
See Table 3-1 for the quantitative basis used to rate components of the
waste streams.
**
Based on consideration of the solubility, dispersibility, physical form
and concentration of all components rated as hazardous by the methods
shown in Figure A-2.
A-12
-------
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A-13
-------
Under the considerations noted above, hazardous wastes was the
designation for all waste streams which contained one or more components
which were:
• Classified as moderately dangerous or highly dangerous by the
standards of Table 3-1.
• Any of the following specific substances or types of substances:
asbestos, arsenic, beryllium, cadmium, chromium,1 copper, cyanides,2
lead, mercury, halogenated hydrocarbons, pesticides, selenium
and zinc.
• Assessed as explosive (as defined below), carcinogenic, oncogenic
(tumor forming), teratogenic, mutagenic, subject to bioaccumula-
tion to toxic level3, strongly corrosive or a strong sensitizer.
In addition, where the physical characteristics of the waste stream
iteself were such as to endanger, actually or potentially, life or limb,
the stream was classified as a hazardous waste, e.g., waste streams dis-
charged directly to the environment at high temperature or high pressure
could be classified as hazardous wastes.
The term"other wastes"was applied to all waste streams not classified
as hazardous wastes.
The definitions given below for previously used terms are cited in
part from the California Hazardous Waste Law and the California Hazardous
Substances Labeling Act:
Strongly Corrosive: Any substance which by contact with living
animal tissue will cause destruction of the
tissue by chemical action.
Explosive: Any substance which generates a sudden, rapid
rise in pressure through decomposition, heat,
or other means, and may be initiated by self-
reaction, mechanical, electrical or thermal
shock.
Strong Sensitizer: A substance which will cause in normal living
tissue through an allergic or photodynamic
process, a hypersensitivity which becomes
evident on reapplication of the same substance.
Hexavalent chromium compounds only
2
Except ferrocyanide compounds
All bioconcentratable materials were raised to the next higher Hazard
Classification.
A-14
-------
Waste components were classified 1n accordance with the standards of
Table 3-1, and the procedure and sequence shown in Figure A-2. The sub-
stances and 1on1c species listed above (asbestos, arsenic, beryllium, etc.),
were classified as highly dangerous components.
The detailed process descriptions cited earlier in this section were
performed for each of the 373 organic chemicals and technical pesticides.
This study derived for each product the identity of the Wor>le components
discharged in process waste streams, their destination, and the w _ gene-
ration factors for the individual components. Information on the chemical
processes used for production was obtained from the references cited, but
actual quantities of the chemical components in the waste streams were
available for only 50 percent of the commodity chemicals in this study.
For those process waste streams on which no literature or production
source data were available, this study used information on the chemistry
and unit operations of the production process, and on related chemicals,
related chemical reactions, and related processes as the bases for estima-
tion. Analogous reactions (e.g., esterification) were assumed to yield anal-
ogous waste stream components and waste generation factors and to require the
use of like process equipment. The quantities of dissolved solids in the
waste streams per pound of product were calculated from simple molar rela-
tionships. Hhere products were water-soluble, and distillation, flashing
and the like were used as the final purification step, it was assumed that
purification was complete. Where products were only slightly water soluble,
a small amount over and above the quantity in solution was assumed to be
mechanically entrained in the process waste stream.
To summarize: A listing of process waste components were developed
for each of the air, water and land process waste streams of each organic
chemical and technical pesticide. A waste generation factor (metric tons
per metric ton of product) was derived for each waste component. Each
waste component was subjected to a hazard analysis, in accordance with the
"Hazard Evaluation System" of Figure A-2, and rated as other wastes,
A-15
-------
moderately dangerous or highly dangerous. The 1977 (and 1983)* land
disposal probability, based on the Federal Water Pollution Control Act
Amendments (P.L.92-500), and pertinent air pollution regulations, was assessed
for each hazardous-rated component now disposed of to water or to air.
Production increase factors (based on projected growth in Gross National
Product)**of 1.10 and 1.216 were applied to the 1973 factors to obtain the
1977 and 1983 factors. For each organic chemical or group, colligative
waste generation factor sets for land disposal in the three categories (other
wastes, moderately dangerous and highly dangerous) were compiled for 1973,
1977 and 1983.
The colligative waste generation factors in the three hazard classes
noted for each chemical were multipled by the rates of production of the
chemical in each state as described in Figure A-3, and the products summed
by SIC listing for the chemicals for each of the time frames (1973, 1977
and 1983). The results of these calculations were the statistical summaries
presented on process waste streams destined for land disposal.
The procedure used for the pesticides preparations and formulations
industry was much simpler because less data were available. Based on pro-
duction-source supplied information, pesticide preparation and formulation
wastes destined for land disposal were estimated as 1 metric ton for each
300 metric tons of product. Based on the ratio of total technical organic
pesticides produced nationally in 1973 to the estimate of total pesticide prep-
arations produced nationally, approximately 40 percent of this land-destined
waste was estimated to be active pesticide ingredients, and therefore,
hazardous components of this total. Based on an analysis of this fraction
(the hazardous components) in the active ingredients, 60 percent was
classified as highly dangerous. The statistical summaries shown for SIC
2879 are the results of the use of these factors and the production increase
factors for 1977 and 1983 against the state production totals for pesticide
preparations and formulations.
The land disposal probability for 1977 was presumed to be the same as
for 1983, since, for simplification of calculations it had been assumed
that the industries would meet the 1983 requirements of the Water
Pollution Control Act as amended.
There has been a close correlation between GNP and organic chemicals
production for the past 10 years.
A"* I D
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The calculation of process wastes going to land disposal for the
technical organic pesticides product group (SIC 28694) was similar to that
used for the remainder of the organic chemicals. For each of the 17 groups
of analogous pesticides, representative members were chosen for process
analyses and waste generation factor determination. Each member of the
group was assumed to have the same product component and non-product com-
ponent waste generation factors as the average of the group^ representative
members. The colligative waste generation factors for each technical pesti-
cide were calculated on this basis, and the remaining calculations were
identical with those performed on the rest of the organic chemicals.
The components and quantities of hazardous wastes generated by each
plant in the GOCO portion of the explosives industry were available from
(18)
reports furnished by the U.S. Army Armament Command^ , or from prior
studies by TRW^ ' ' . The hazard evaluation system cited earlier
was employed for rating the waste components, and the quantities were sum-
marized for each state with an active Army ammunition plant or other
defense sector explosives industry plant.
For the private sector of the explosives industry, the waste generation
factors obtained from the Institute of Makers of Explosives for a prior EPA
study were employed to calculate the quantities of waste explosive for
each state from the production statistics. The only hazardous wastes
reported in this study for the nondefense explosives industry are the waste
explosives, since the data obtained from the literature and from the private
plant visits were deemed insufficiently representative of the more than
600 plants in the United States.
TREATMENT AND DISPOSAL TECHNOLOGY EVALUATION
The treatment, and disposal technology used for hazardous wastes destined
for land disposal was identified and described on the basis of the following
standards:
Level I The typical broad average practice(s) for the industry
or product group.
Level II The best technology available in current commercial
practice.
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Level III Technology currently known and assessed as providing
adequate health and environmental protection. The
interpretation of currently known technology included
technology now available only at the bench or pilot
plant level.
COST ANALYSES
Cost estimates for the treatment processes applied to the typical and
actual plants chosen as representative of the industry or product group
were developed. The standard cost engineering techniques utilized
included:
• Cost of capital was assumed to be 10 percent.
• Straight-line depreciation based upon estimated life and capital
outlay less salvage value was used on capital items.
• Operating and maintenance costs used were the normal costs for
these functions, excluding power and energy costs, which were
stated separately.
• Land costs took into account reduced market value where required
due to disposal operations.
A-19
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APPENDIX B
TEXAS AND CALIFORNIA STATE ACTS AND
REGULATIONS ON TREATMENT AND DISPOSAL
Page
INJECTION WELL ACT, STATE OF TEXAS B-2
HASTE DISPOSAL TO LAND REGULATIONS, STATE OF CALIFORNIA B-6
HAZARDOUS WASTE LAW, STATE OF CALIFORNIA B-12
HAZARDOUS WASTE REGULATIONS, STATE OF CALIFORNIA B-14
B-l
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INJECTION WELL ACT
STATE OF TEXAS
Article 7621b, V.T.C.S.
as amended by 61st Legislature,
Regular Session, 1969
Section 1. SHORT TITLE. This Act may be cited as the Injection Well Ac*
Section 2. DEFINITIONS. As used in this Act, unless the context requires
a different definition:
(a) "board" means the Texas Water Quality Board;
(b) "commission" means the Texas Railroad Commission;
(c) "Person" means individual, corporation, organization,
government or governmental subdivision or agency, business trust,
partnership, associatiation, or any other legal entity;
(d) "Pollution" means the alteration of the physical,
chemical, or biological quality of, or the contamination of, water that
renders the water harmful, detrimental, or injurious to humans, animal
life, vegetation or property, or to public health, safety, or welfare, or
impairs the usefulness or the public enjoyment of the water for any lawful
or reasonable purpose;
(e) "Industrial and municipal waste" is any liquid, gaseous,
solid or other waste substance or a combination thereof resulting from any
process of industry, manufacturing, trade, or business or from the develop-
ment or recovery of any natural resources, or resulting from the disposal
of sewage, or other wastes of cities, towns, villages, communities, water
districts and other municipal corporations, which may cause or might
reasonably be expected to cause pollution of fresh water;
(f) "fresh waters" means waters whose bacteriological,
physical and chemical properties are such that they are suitable and
feasible for beneficial use for the purposes permitted by law;
(g) "casing" means any material utilized to seal off strata
at and below the earth's surface;
(h) "injection well" means an artificial excavation or opening
into the ground, made by means of digging, boring, drilling, jetting, driving
or otherwise, and made for the purpose of injecting, transmitting, or dis-
posing of industrial and municipal waste into a subsurface stratum; also a
well initially drilled for the purpose of producing oil and gas when used
B-2
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for th«-- purpose of transmitting, injecting, or disposing of industrial and
municipal waste into a subsurface stratum; but "injection well" does not
include any surface pit, excavation or natural df-press ion used to dispose
of industrial and municipal waste.
(i) Notwithstanding any provisions of Subsection (e) of
this section, '"waste arising out of or incidental to the drilling for or the
producing of oil or gas" includes, but is not limited to, the following
items when they result from such drilling or producing activities; salt
wattJi, brine, sludge, drilling mud, and other liquid or semi-liquid
waste materials.
Section 3. INDUSTRIAL AMD MUNICIPAL WASTES; APPLICATIONS TO BOARD,
(a) Before any person commences the drilling of an injection
well, or before any person converts any existing well into an injection
well, for the purpose of disposing of industrial and municipal waste, other
than waste arising out of or incidental to the drilling for or the producing
of oil or gas, a permit therefore shall be obtained from the board. The
board shall be available upon request without cost. The board shall
require the furnishing of such information by an applicant as the board
may deem necessary to discharge properly the duties imposed by this Act.
An application for a permit to drill an injection well, or to convert any
existing well to an injection well, shall be accompanied by a fee of
$25. 00 which shall be collected by the board for the benefit of the state.
(b) Upon receipt by the board of an application in proper
form and accompanied by the necessary fee for a permit to drill an injec-
tion well, or to convert an existing well to an injection well, the board
shall cause an inspection to bo made of the location of the proposed
injection well to determine local conditions and the probable effect of
the injection well, and shall cause an evaluation to be made to determine
the requirements for the setting of casing, as provided in Section 5 of
this Act.
(c) The board shall also send copies of every application
received in proper form to the Texas Water Development Board, the Texas
State Department of Health, the Texas Water Well Drillers Board, and to
such other persons as the board may designate. The agencies and other
persons to whom a-copy of the application is sent may make recommenda-
tions to the board concerning any aspect of the application, and shall
have such reasonable time to do so as the board may prescribe.
(d) The board may hold a public hearing upon an application
if it is deemed necessary and in the public interest, but otherwise, a pub-
lic hearing is not required. Notice of any public hearing and its procedure
shall be under such terms and conditions as the board may prescribe.
B-3
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(e) Any person applying to the board for a permit to inject
industrial and municipal waste, other than waste arising out of or inci-
dental to the drilling for or the producing of oil or gas, into a subsurface
stratum shall submit with the application a lutter from the commission
stating that the drilling of the injection well and the injection of indus-
trial and municipal waste into the subsurface stratum will not endanger
or injure any oil or gas formation.
Section 4. ISSUANCE OF PERMIT; CASING OF WILL; RULES AND REGULATIONS,
If the board or commission, as the case may be, finds that
the installation of the injection well is in the public interest, will not
impair any existing rights, and that by requiring proper safeguards both
ground and surface fresh waters can be protected adequately from pollu-
tion, the board or commission, as appropriate, may grant the application
in whole or in part and Issue a permit with such terms, provisions, condi-
tions and requirements as are reasonably necessary to protect fresh waters
from pollution by industrial and municipal waste. Specifically, the board
or commission shall require that the injection well shall be so cased as to
protect all fresh waters from pollution by the intrusion of industrial and
municipal waste. The casing shall be set at such depth, with such mate-
rials, and in such manner as the board or the commission may require.
The board or the commission, in establishing the depth to which casing
shall be installed, shall consider known geological and hydrological
conditions and relationships, the foreseeable future economic develop-
ment in the area, and the foreseeable future demand for the use of the
fresh waters in tht? locality. The board or commission may also require
the permittee to keep and furnish a complete and accurage record of the
depth, thickness and character of the different strata penetrated in the
drilling of the well. In the event an existing well is to be converted to
an injection well, the board or commission may require that the applicant
furnish an electric log or a drilling log of the existing well. A copy of
every permit issued by the board shall be furnished by the board to the
commission, the Texas Water Development Board, the Texas State
Department of Health, and the Texas Water Well Drillers Board. A copy
of every permit issued by the commission shall be furnished by the com-
mission to the board, which shall in turn forward copies to the other
agencies named in the preceding sentence. The board and the commission
each shall adopt rules, regulations and procedures reasonably required
for the performance of the duties, powers and functions prescribed for
each by this Act. Copies of any rulos or regulations under this Act pro-
posed by the board or the commission shall, before their adoption, be
sent by each of these agencies to the other agency, and also to the
B-4 Vi!
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Texas Water Development Board, the State Department of Health, tho
Texas Water Well Drillers Board, and such other persons as the origi-
nating agency may designate. Any agency or person to whom the copies
of proposed rules and regulations are sent may submit comments and
recommendations to tho agency proposing the rules and regulations, and
shall have such reasonable time to do so as the originating agency may
prescribe.
Section 5. WILLING COPY OF PERMIT. Any person receiving a permit
to inject industrial and municipal waste, shall, before injection opera-
tions are begun, file a copy of the permit with the health authorities of
the county, city and town where the well is located.
Section 6. ENFORCEMENT. Any person who fails to comply with the
provisions of this Act, or with any rule or regulations promulgated by
the board or the commission under this Act, or with any term, condi-
tion or provision in his permit issued pursuant to this Act, shall be
subject to a civil penalty in any sum not exceeding One Thousand
Dollars ($1,000.00) for each day of non-compliance and for each act of
non-compliance, as the court may deem proper. The action may be
brought by the board or the commission, as appropriate, in any court
of competent jurisdiction in the county where the offending activity is
occurring or where the defendant resides. Full authority is also given
the board or commission, as appropriate, to enforce by Jurisdiction in
the county where the offending activity is occurring, any and all reason-
able rules and regulations promulgated by it which do not conflict with
any law, and all of the terms, conditions and provisions of permits
issued by the board or commission pursuant to the provisions of this
Act. At the reguest of the board or the commission, the attorney general
shall institute and conduct a suit in the name of the State of Texas for
injunctive relief or to recover the civil penalty, or for both the injunctive
relief and civil penalty, authorized in this section. Any party to a suit
may appeal from a final judgment as in other civil cases. The obtaining
of a permit under the provisions of this Act by a person shall not act to
relieve that person from liability under any statutory law or the Common
Law.
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REGULATIONS
STATE OF CALIFORNIA
Subchapter 15
Waste Disposal to Land
Article I
General Provisions
Section 2500 DEFINITION OF TERMS, (a) "Disposal site" moans any
place used for the disposal of solid or liquid wastes. It does not include
sowage treatment ponds or locations of waste disposal from pipes or
ditches into waters of the state.
(b) "Disposal Area" is the actual area of the site which
has received or is receiving wastes.
(c) "Percolate" is fluid resulting from the percolation or
draining of a liquid through a waste substance.
(d) "Usable" ground or surface water includes potentially
usable water.
(e) "Hydraulic continuity" is a condition existing when
fluid occupying an interstice of a saturated material is able to move,
under a head differential imposed by gravity, to adjoining interstices
and/or surface channels containing fluid.
(f) "Capillary fringe" is the partly saturated zone immediately
above the water table in which water is held by capillary forces.
Section 2501. DISPOSAL AT CLASSIFIED SITES. Disposal of either solid
or liquid wastes at disposal sites shall be only at those sites which have
been classified by the appropriate regional water quality control board in
the establishment of waste discharge requirements in conformity with this
subchapter unless requirements are waived by the regional board pursuant
to Section 2530 (c).
Article 2
Classification of Waste Disposal Sites
Section 2510. CLASS I DISPOSAL SITES. Class I disposal sites are
those at which protection is provided for the quality of ground and
B-6
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surface waters from all wastes as determined by the following criteria:
(a) The disposal area is underlain by non-waterbearing
geological formations or by unusable groundwnter which is isolated from
other usable waters.
(b) Geological conditions must be naturally capable of
preventing both vertical and lateral continuity between liquids and gases
from waste in the site and usable groundwaters, or have been modified
to ar-hleve such capability in a manner acceptable to the regional board.
(c) Underlying geological formations which contain rock
fractures or fissures of questionable permeability must be sealed to pro-
vide a competent barrier to the movement of liquids or gases from the
disposal site.
(d) Surface drainage from tributary areas outside the site
must be precluded from entering areas of the site which have received or
are receiving wastes until the site is closed in accordance with require-
ments of the regional board.
(e) Subsurface flow into the disposal area and percolate
resulting from internal drainage shall be contained within the site unless
other disposition is made in accordance with requirements of the regional
board.
(f) Class I sites made suitable for use by man-made
physical barriers shall not be located where improper operation or main-
tenance of man-made physical containment structures will impair usable
ground or surface water quality or create a hazard to public health.
(g) Class I sites shall not be located over zones of active
faulting or where other forms of geological change would reduce the cap-
ability of natural or man-made features to prevent continuity with usable
groundwaters.
(h) Class I sites for unlimited use must not be subject to
washout or inundation by floods.
(i) Sites which comply with a ,b,c,e,f, and g but would
be subject to inundation by a flood of greater than 100 year frequency may
ho classified by the regional board as a limited Class I Disposal Site
subject to waste discharge requirements which would include limits on
(1) the typo and quantity of material entering the site, (1!) the concentra-
tion of ma)oriil in the waste deposited on the site, (3) the amount of
residue present r>r remaining on the site after evaporation of the liquid.
Section 2S11 CLASS IT DISPOSAL SITES. Class II disposal sites are those
at which protection is provided to water quality from Group 2 and Group 3
wastes as determined by the following criteria:
(a) If the site has hydraulic continuity with usable ground
or surface water, there must be physical features to prevent degradation
B-7
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of groundwater quality due to liquid or gases emanating from the waste.
The types of physical features and the extent of protection of groundwater
quality further divides Class II sites into two general categories.
(1) A Class II-1 site is isolated from vertical
hydraulic continuity with usable groundwater by natural
impervious geological formations or artificial barriers,
or it is underlain by non-waterbearing rocks, but it may
have lateral hydraulic continuity with qroun.Hwater basins
containing usable groundwater.
(2) A Cla3S II-l' cite may have vertical hydrauH^
continuity with usable groundwater but it is either modi-
fied by artificial barriers or has natural geological and
hydraulic features, such as soil type and depth to ground-
water, which prevent degradation of the quality of usable
groundwater underneath the site.
(b) Class II disposal sites located in flood plains shall be
protected by natural or artificial features so as to assure protection from
washout and.flooding which could occur as a result of floods having a
predicted frequency of once in 100 years.
(c) Surface drainage from tributary areas shall be precluded
from contacting waste in the site.
(d) Gases emanating from waste in the site will bo prevented
from degrading groundwater during the predictable life of the site by physi-
cal features or rate of groundwater movement in hydraulic continuity with
the site.
(e) Internal drainage of the site or subsurface flow into
the site and the depth at which water soluble materials are placed shall
be controlled during construction and operation of the site to minimize
percolate and assure that the waste material will be above the highest
anticipated elevation of the capillary fringe of the groundwater. Such
control may include discharge from the.site subject to waste discharge
requirements proscribed by the regional board. '•
Section 2512 CLASS III DISPOSAL SITES. Class Til disposal sites are those
at which protection is provided for water quality from Group '.'< wastes as
determined by the lollowing criteria:
(a) Each site is located and constructed to prevent erosion
or transport of deposited material.
(b) Operation or construction of the site shall not result
in degradation of surface water quality due to erosion of adjacent land
areas.
B-8
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Section 2513 WASTE WELLS. Wells suitable for the disposal of wastes
shall provide protection to usable groundwater from wastes of Groups 1
or 2 in any form as determined by the following conditions:
(a) The receiving formation shall not be in hydraulic
continuity with any usable groundwater.
(b) The construction and injection procedure will be such
that no paths of percolation are developed which will permit the movement
of the wor;te to a usable aquifer or to the surface.
(c) Certification has been provided by the California
Division of Oil and Gas that construction and operation of waste wells
under its jurisdiction will conform to regulations of the Division.
(d) Wells used for the disposal of wastewater and the
resultant recharge of groundwater, or for the disposal of used irrigation
water, under requirements adopted by the regional board may be exempted
{torn provisions a, b, and c.
(e) Construction and operation of sewer wells shall be in
conformation witli applicable regulations for the protection of public health.
Article 3
Classification of Wastes Discharged to Land
Sootion 2520 GROUP I WASTES. Group I wastes consist of or contain
substances directly harmful or dangerous to the health and safety of man
r>r other living organisms during disposal operations or in the event of
mixing with usable water, or substances which may significantly impair
UK- quality of usable waters. Examples include but are not limited to
the following;
(a) Municipal Wastes
(1) Saline fluids from water or waste treatment and
reclamation processes .
(2) Community incinerator ashes .
(b) Industrial Wastes
(1) Saline brine from food processing, oil well
production, water treatment, industrial processes
and goothermal plants.
(2) Toxic or hazardous fluids from industrial processes
or resulting from spills, or blowdown. These fluids
may include spent cleaning fluids, petroleum
fractions, chemicals, acids, alkalies, phenols,
and spent washing fluids.
B-9
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(3) Substances from which toxic materials can leach
such as process ashes, chemical mixtures, and
mine tailings.
(c) Agricultural Wastes
(1) Agricultural chemicals such as herbicides,
insecticides, fungicides, and chemical fertil-
izer and their containers to the extern *hey are
actually toxic or hazardous to human health or
water quality after mixing wtth water.
(d) Other toxic wastes such as compounds of arsenic or
mercury, chemical warfare agents, etc.
Section 2521 GROUP 2 WASTES. Group 2 wastes consist of or contain
decomposable organic material which does not include substances which
are toxic or significantly impair the quality of usable water. Group 2
wastes may be deposited in either a Class II-l or II-2 site unless spe-
cifically limited by the regional board or the regulations of other appro-
priate authorities. Examples include but are not limited to the following:
(a) Municipal and industrial wastes
(l) Garbage consisting of putresciblc wastes from
processing, preparation, cooking, and serving
of food
(2) Market wastes from handling, storage, and
processing of produce
(3) Construction and demolition materials containing
paper, cardboard, tin cans, wood, glass, bedding,
rubber products, roofing paper, wallpaper, stumps,
and other materials
(4) Rubbish and street refuse consisting of putrescible
and non-putrescible material such as sweepings,
dirt, leaves, catch basin dirt, litter, yard clippings,
glass, paper, wood and metals in various forms or
combinations.
(5) Dead animals
(6) Abandoned vehicles
(7) Sewage treatment residue including solids from
screens and grit chambers and sludge
(8) Water treatment residue including solid organic
matter collected on screens and in settling tanks
(9) Ashes from household burning
B-10
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(10) Infectious materials and hospital or laboratory
wastes authorized for disposal to land by official
agencies charged with control of plant, animal,
or human disease.
(11) Magnesium and other highly flammable or pyrophoric
materials
(12) Miscellaneous industrial wastes such as metals and
metal products, wood and paper materials, oils,
chemicals and sludges which are not toxic or
hazardous within the definition of Group 1 wastes.
(b) Agricultural wastes
(l) Stalks, vines, green drops, culls, stubble, hulls,
lint and seed from field and seed crops
(2) Vines, stalks, roots, green drops, and culls from
vegetable crops
(3) Stumps, prunings and trimmings, culls, and green
drops from fruit and nut crops
(4) M anures
(5) Dead animals or materials of animal origin.
Section 2523 DISPOSAL OF GROUP I WASTES IN CLASS II - I SITES.
Regional board may allow the disposal of certain Group I
wastes in a Class II-l site when, in the judgment of the board, such
disposal will not constitute a threat to water quality. Such selected
disposal of specific Group I wastes shall be subject to terms and condi-
tions considered appropriate by the regional board.
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APPENDIX I (From State of California Statutes of 1972, Vol. 1, p. 2387-2393).
Assembly Bill No. 596
CHAPTER 1236
i act to add C'hapttr 6.S (commencing with Section 25100) tn
Division HO of the Health and Safety Code, relating to waste
(Apptovod by Governor December 13. IB7I Filed with
Sec-civy of Suit December II. I«7J |
I .F.UbLATIVE COUNSEL'S DIGEST
An 198, [>•_• u«p Industrial waste.
Requires the State Department of Public Health to adopt
{illations for the handling, processing, and disposal of hazardous and
tremely hazardous wastes, as defined, to protect against hazards to
z public health, to domestic livestock, and to wildlife Specifies
ocedure for such adoption. Makes it unlawful to dispose of any such
iste except as provided for in such regulations.
Requires the department to prepare a listing of wastes determined
be hazardous and extremely hazardous.
Requires any producer of a material which he may reasonably
nsider to be an extremely hazardous waste and which he does not
end to recycle for rouse to notify the department of his intent to
.pose of such waste
Requires after January 1, 1974, the person producing a hazardous
iste listed by the department to provide operators of transportation
uipment with a list setting forth specified information. Requires
:h list to be released to person responsible for disposal and to be
awn to department officials, officers of the California Highway
Irol upon demand, or any local public officer as designated by the
•ector
Requires the department to adopt and enforce rules and regulations
such lists Specifies documents required by other state or federal
encies meeting specified conditions shall meet such requirement
Creates a hazardous waste technical advisory committee and
rnfies membership and duties of such committee
Jrovides civil enforcement procedures for provisions of act,
ithorizes state health officials to enter at a reasonable hour of the day
?cified facilities in order to carry out the purposes of the act
Requires the director to establish as specified, and operators of
.posal sites where wastes subject to such provisions are disposed to
y to the director, fees sufficient for, but not in excess of, amounts
cessary for administration of provisions re such wastes.
Specifies related powers and duties of the department
Operative July 1, 1973.
if people of the State of California do enact as follows
>ECTION 1 Chapter 6.3 (commencing with Section 29100) it
ed to Division 20 of the Health and Safety Code, to read:
CHAPTER 6 5. HAZAHDOUS WASTE COHTHOL
Article 1 Finding) and Declarations
3100 The legislature finds that increasing quantities of
ardoiu wastes arc being generated in the state and that without
<|iiatc ufcRuurds for handling and disposal, such wastes can create
ditions which threaten the public health and safety and create
urcli to wildlife
HOI The Legislature therefore declares that in order to prevent
i hazardous conditions it is in the public interest to establish
ulations and to maintain a program to provide for the safe handling
disposal of hazardous wastes.
Article 2. Definitions
110 Unless the context indicates otherwise the definitions in this
:le govern the construction of this chapter.
Ill "Department" means the State Department of Public
Jth
112 Director" means the Director of Public Health
1 13 "Disposal" means to abandon, deposit, intern or otherwise
discard waste as a final action after their use has been achieved or a
use is no longer intended.
29114. "Disposal site" means the location where any final
deposition of solid waste occurs.
29113. "Extremely hazardous waste" means any hazardous v^jte
or mixture of hazardous wastes which, if human oxpow.ce old
occur, may likely result in death, disabling personal injury or iiuiesr
during, or as a proximate result of. any disposal of such warte or
mixture of wastes because of its quantity, concentration, or chemical
characteristics.
23116 "Handling" means the transport, transfer from one place to
another, or packaging of hazardous and extremely hazardous witte
23117. "Hazardous w&»t>." rn«*i -a any waste material or mixtux-e of
wastes which is toxic, corrosive, narrrnaole, en Irritrnt, • tirc-nts
sensitizcr, which generates pressure .hrough decomposition. h»at or
other means, if such a waite or mixture o»" -vartca imsy ~" w *ii-jsUn(:n'
personal injury, serious illness or harm to wild. Coring, or .c «
proximate result of any disposal of such wastes or mixhi-c of wi-jttes
The terms "toxic," "corrosive," "flammable," "irritant," an«J ' s>ror:j
sensitizer" shall be given the same meaning as in the Oa!if..>-.o*
Hazardous Substances Act (Chapter 13 (commencing with Section
28740) of Division 21).
85118. "Person" also includes any city, county, district, thf «tt t•
any department or agency thereof
25119. "Processing" means to treat, detoxify, 'icutr .!•///•
incinerate, biodegrade, or otherwise process a hazardous wa>;< to
remove its harmful properties or characteristics for disposi-S in
accordance with regulations established by the department in
conjunction with any 6Uw agency authorized to regulate or control
hazardous waste.
29120. "Processing facility" means any facility or location where
any final treatment, incineration, processing or deposition of
hazardous waste occurs.
25121. "Recycle" means to process, alter, or otherwise treat a
hazardous watte for subsequent use?
25122. "Waste" means any material for which no use or reuse u
intended and which is to be discarded.
Article 3. Hazardous Waste Technical Advisory Committee
25130. The department shall establish a hazardous waste technical
advisory committee to provide consultation to the department
concerning matters covered by the chapter. The committee shall
advise the department on the development of standards, rules, and
regulations for hazardous waste management, and shall supply
recommendations concerning methods by which existing hazardous
waste management practices and the laws regulating them may be
supplemented and improved and their administration financed.
25131. The committee shall consist of seven members appointed
by the director who shall be knowledgeable in hazardous waste
management. The members shall insofar as possible represent the
interests of the public, local and regional government, agriculture,
manufacturing industry, local health departments, and the waste
management industry.
25132. At least two members of the committee shall represent the
interests of the public and shall have no financial interest in any of the
recommendations or studies of the committee. Such financial interest
shall include, but not be limited to, service as a consultant to any
person specializing in waste disposal, as a tenant or landlord of
property used for waste disposal, or as an attorney of a party with a
direct financial interest in hazardous waste disposal.
25133. Members of the hazardous waste technical advisory
committee shall serve without compensation, but shall be entitled to
per diem and reimbursement for travel expenses incurred as a result
of official committee business.
Article 4 Listings
25140. The department shall prepare, adopt and may revise when
appropriate, a listing of the wastes which are determined to be
hazardous, and a listing of the wastes which are determined to be
extremely hazardous When identifying such wastes the department
shall consider, but not be limited to, the immediate or persistent toxic
effects to man and wildlife and the resistance to natural degradation
or detoxification of the wastes.
B-12
-------
APPTNDIX I (Continual;.
Article 5 Standards
25150 The depaihni.'iit shall adopt, and may revise when
appropriate, minimum standards und regulation) for the handling,
processing and disposal of hazardous and extremely hazardous wastes
N> protect against hazards to the public health, to domestic liveitock,
.11: J to wildlife Before adoption of such standard] and regulations the
department shall consult with all agencies of mteretted local
govftuni'-nts and secuie technical assistance from the Department of
Agriculture, the Department of the California Highway Patrol, the
Department of Fish and Game, the Department of Industrial
Relation?, D vision of Industrial Safety, the State Air Resources Board,
the State W&rer fl'-sources Control Board and the State Fire Marshal.
25151 1 he department may adopt varying standards for different
arem of mr tiai • "Vending on population density, climate, geology
end ether , i: 'ors lelevunt to hazardous waste processing and disposal
^5152 Hefore adopting or revising minimum standards and
legislations (or the handling, processing, and disposal of hazardous and
extremely lui/ardous wastes, the department shall hold at least one
public hearing in .Sacramento, 01 in a city within the area of the state
lu be uffocled by the proposed regulations. The department shall
adopt the proposed regulations alter making changes or additions that
are uppr^pnate in view of the evidence and testimony presented at
the public hearing or hearings
25153 Any person who is producing a waste material which he
m.iv ,-easonably consider to be an extremely hazardous waste, and
which he d'>es not intend to recycle for reuse and intends to dispose
of as iva.ite, shall notify the department of his intent to dispose of such
waste rraterial
25154 After the effective date of the regulations adopted by the
department pursuant to this article, it shall be unlawful for any person
to dispose of any hazardous or extremely hazardous waste except of
provided for in such regulations
25153 After January 1. 1974, no eAt.^..^l/ hazardous waste as
listed by the department pursuant to Section 28140, may be disposed
of without prior processing to remove its harmful properties or a*
specified by the regulations of the department for the handling and
dispose of the particular extremely hazardous waste.
Article 6 Transportation
25100 After January 1, 1974, the person producing a hazardous
waste luted by the department pursuant to Section 25140 shall provide
the driver of any truck, a crew member of any train, or the captain
of any vessel carrying such hazardous wastes with a list setting forth
the rmr.ardous wastes carried, the amount of such waste, the general
chemical and mineral composition of such waste hsted by probable
maximum and minimum percentages, and the origin and destination
of an) such waste carried Such list, when appropriate, may include
information on antidotes, first aid, or safety measures to be taken in
c«*e of accidental contact with the particular hazardous waste being
earned The person carrying, or handling the hazardous waste shall
have the list m his possession while carrying or handling the hazardous
waste and ihall release the list to a person responsible for disposal of
the hazardous waste at the time of delivery Such list shall be shown
upon demand to any department official, officer of the California
Highway Patrol, or tny local public officer as designated by the
director
251IH Trie department shall adopt and enforce all rules and
regulations, including the form and content of the list, necessary and
appropriate to accomplish the purposes of Section 25160.
25182 Documents required by other agencies of the state or the
federal government which describe the character and amount of
hazardous wastes being carried shall satisfy the requirement of
Section 25160
Article 7 Other Provisions
25170 The department In performing its duties under this chapter
•hall
(u) Kstabtlsh procedure* for evaluation and coordination ol
research and development regarding methods of hazardous waste
handling and disposal and may conduct appropriate studies relating to
hazardous wastes.
(b) Maintain a technical reference center on Ka/ardoiu waste
disposal, recycling practices, and related information for public and
private us«
(c) Render technical assistance to state and local agencies in the
planning and operation ol hazardous waste pro-trains
(d) Provide for appropriate surveillance oV hazur.Jous w,
processing and disposal practices in the jtnte
25171 No provision of this chapter shall oc construed to teqi
disposal of hazardous waste at the site of production, provided.
the transportation of luch wosite conforms to all applicable ri!gulnti<
25172. No provision of this chapter slioli limit the authority of
state or local agency in the enforcement or administration of
provision of law which it is specifically poimitten or requir't)
enforce and administer
25173 The department shall establish procedures to 'mure t
trade secrets used by H person regarding methods of ruvj&.-sj'Uis -*j
handling and disposal are utilized by the director, tli» tJ.-MjAi 'mer.t
any authorized representHtive of the department on!> in < uruiect
with the responsibilities of the dep^rtrnen" j>uisu»nf to Uus ; oup
and that such trade secrets ure not othet*ise i"
director, the department, or any authorised ieprr.en;-.-m- t
department without the consent of the person iimk- rrrr- '•..
used in this section, muy mciu'ie. bu. ife not [united ;,., uu, !"!, mt-chiinijm, r-cr.ip..m,.'j ft** •!>
production dutu, or compilation of information winch i- u> ^ i ; :n
which is known only to certain individual-- within u . :vni',«'r
concern who are using it to fabricate, produce, or c<>n>p«> wl us M'_
of trade or a service having commercial viJue, wid whu h s '• * 't> >
on opportunity to obtain a business ndvantage <,vsr i.-omp'liK'i. v
do not know or use it.
25174. Beginning January i, 1974, each opeiatoi of anv >jui '-JRII
Article 6 (commencing with Section MIC'J, The director i
establish a schedule of the fees to be caid to the director by s
operator for each disposti of hazardous waste luted ./•. such a iis
document, which shall prov -^ revalue* which ihkll not e-xcted
amount necessary, but shall be sufficient, io cover ail <-r>-,tr. mcurre<
the administration of this chapter. Such fees shall U.- deposited e
month in the Hazardous Waste Control Account in the Genera! Ft
Article 8 Enforcement
25180. The minimum standards and regulations ao vtr\i In
department pursuant to Section 25150 shall be enforn-d by
department or any local health officer or any local public oifice
designated by the director.
25181. Whenever, in the judgment of the department, air pei
has engaged In or is about to engage in any acts ->r practice' w
constitute or will constitute a violation of any provision ol tins' '<*l
or any rule, regulation, or order issued thereunder, and at the i eq
of the department, the district attorney of the county in which •
acts or practices occur or will occur or the Attorney Generol
imke application to the superior court for an order enjoining such
or practices, or for an order directing compliance, and upon a shov
by the department that such person has engaged in or is aboi
engage in any such acts or practices, a permanent or tempo
injunction, restraining order, or other order may be granted
25182. Every civil action brought under the provisions of
chapter at the request of the department shall be brought b\
district attorney or Attorney General in the name of the people o
State of California and any such actions relating to the sam? proces
or disposal of hazardous wastes may be joined or consolidated
25183. Any civil action brought pursuant to this chapter roce
or disposed of, In order to carry out the purposes ot thu cliapte
SEC. 2. This act shall become operative on July 1. 1973
B-13
-------
HAZARDOUS WASTE REGULATIONS, STATE OF CALIFORNIA
Till...- :>.;>
IJi.vision 'i. Knvironmental Health
Chapter 1. Introduction
Article 1. Definitions
OOQOl. Department. Whenever the term "department" is used in this
divi::ion, it means the State Department of Health, unless otherwise specified.
60003. Director. Whenever the term "director" is used in this division,
it means the Director, State Department of Health, unless otherwise specified.
B-14
-------
Chapter 2. Hazardous Waste
Article 1. General
60100. Definitions. The definitions set forth in Article 2. (commencing
with Section 25110) of Chapter 6.5 of Division 20 of the Health and Safety Cod-.
:,'ifUl govern the construction of this chapter.
60105. Minimum Standards. Nothing in this chapter shall be construed aq_
relieving any person involved in the management of hazardous waste from the
obligations of obtaining all required permits, licenses, or other clearances,
and complying with al.1 orders, laws, regulations, or other requirements of
duly authorized and constituted regulatory or enforcement agencies, such as,
bij-c rr'.t limited to, health authorities, state and local water and air pollution
control agencies, local land use authorities, fire authorities, etc.
B-15
-------
/VrMcJ.
l.'1/.ardou.'j Waste;;
:: Wrx;;t«' Jiir;l. (u.) 'Hie i'ujlowin/r, i r. a ,J i:;l,in/^ oi' mal.fri,-il
./Mch, n..; d(.-fined in LJeetion 'd.'j.L22 of the- Health ?uid Safely Code ?u wact.t;, h.-i.v(
I en determined to be hazardous as defined in Section 2^117 of the Health and
.'J-.fotv Code:
(l) Toxic
Acetone cyanhydrin
2-Acetylaminofluorene
Aldrin
Ailyl alcohol_
Aluminum fluoride
' i~ Ami n odiphenyl
Ammonium arsenate, solid
Ammonium bifluoride
Ammonium fluoride
Ammonium picrate
Aniline oil, liquid
Antimony
Antimony potassium tartrale
Antimony ^ulfn.te
Antimony trichloride
Antimony trifluoride
Antimony trioxide
Arsenic acid, liquid or solid
Arsenic bromide, .solid
Arsenic chloride, liquid
Arsenic iodide, :;olid
Arsenic pentaselenid"
Arsenic pentoxide, .solid
Arsenic, solid
Arsenic sulfide, solid
Arsenic trichloride, liquid
Arsenic trioxide, solid
Arsenical compounds or mixtures
Arsenical dip, liquid
Arsenical dust
Arsenous acid, solid
Arsenous and mercuric iodide
solution, liquid
Arsines
Asbestos
Barium carbonate
B-16
-------
Barium chloride
Barium cyanide, solid
Barium fluoride
Barium sulfide
Benzene_ sulf onic acid
Benzene hexachloride
Benz,id_ine_
Beryllium compounds
Bidrin
Bomyl
Boranes, Di-? Penta-, Trichloro-
Bordeaux arsenites,, liquid or
solid
Boron trifluoride
Brucine, solid
Cacodylic acid, solid
Cadmium
Cadmium chloride
Cadmium cyanide
Cadmium fluoride
Cadmium oxide
Cadmium phosphate
Cadmium potassium cyanide
Cadmium sulfate
Calcium arsenate, solid
Calcium arsenite, .solid
Calcium fluoride
Carbanolate, Tennik
Carbolic acida liquid or sqlia
Carbon tetrachloride
Carbophenpthion, TriIhl- n i
Chloracetojhenone i 1 ijiui d. or
solid
Chloral hydrate
Chlordane
Chlorine
Chloracetaldehyde
Chlordinitrobenzol
Chloroform
bis-Chloromethyl ether
Chloro-o-toluidiue hydri'chloride
Chlorpicrin and methyl chloride
mixture
Ghlorpicrin
Chromic fluoride
Cocculus, solid
Compound ^072
Copper acetoarseniter solid_
B-17
-------
Copper arsenate
Copper arsenite, solid
Copper cyanide
Cyanide of calcium or mixtures,
solid
Cyanides of copper, zinc, lead
and silver
Cyanides or cyanide mixtures,
dry
Cyanide of potassium, liquid or
solid_
Cyanide of sodium, liquid or
solid
Cyanoacetic acid
Cyanogen bromide
Cycloheximide, Acti-Dione
2.U-D
DDT
DDVP
Demeton, Systox
3,3'-Dichlorobenzidine
Dichloroethyl ebher
Pichlorome thane
1,3-Cichlorprppene
D_ieldrin_
Diglycidyl ether
U-Dime bhylaminoazobenzei^e
Dimethyl sulf at e
2 , ^-Dinitr oaniline
Dinitrobenzol, solid or liquid
Jinitrochlorbenzol, solid
Dinitrocresol, Sinox, Egetol 3Q
Dinitrophenol solutions
Dinitrotoluene
Dioxathion, Delnav
Diphenylaminechlorarsine^ liquid
or golid
Diphenylchlorarsine , solid
Pi sulf ot on. Disyston
Dowicide 7, PGP Penchlorq
Endosulfan, Thiodan
Endrin
Epi chlor ohydr in
EPN
Ethion. Nialate
Ethyldichloroarsine
Ethylene_ bromide
B-18
-------
Ethylene cyanohydrin
Ferric arsenate, solid
Ferrous arsenate, solid
Fluoride
Fluoroacetic acid, sodium salt,
compound 1080
Furadan
GB.l
' juthi on
Heptachlor
Hexaethyl tetraphosphate mixture
Hydrocyanic acid solution^
Lead
Lead acetate
Lead arsenate, solid
Lead arsenite. solid
Lead carbonate
Lead cyanide.
Lead oxide
Lewi_sltg_
London purple^ solid
Magnesium arsenate^ soli_d
Magnesium arsenite
Manganese arsenate
Manganese methylcyclopentadienyj.-
tricarbonyl
Mercury or Mercurial liquid
Mercuric acetate
Mercuric-arnmonium chloride, so_lid
Mercuric benzoate3 solid
Mercuric bromide, solid
Mercuric chloride
Me_rcuric__cyanide, sol id
Mercuric iodidf'; solid i.>
Mej-cui'ic _oleai,('j SL'lid
Mercuric oxide Iredj sol it.
Mercuri c oxide ( y elJxw ) 3 s o i i d
Mercuric oxycyanide , solid
Mercuric-potassium cyanide, solid
Mercuric-potassium iodide, solid
Mercuric salicylate, solid
Mercuric subsuljfat_e_j s_olid
Mercuric suLfatej solid
Mercuric thiocyanate, solid
Mci-curol (mercury jiucleatc-), ;joli' i
Mej-curous bromide, s,olid
Mercurous gluconatej _sol_id
Mercurous iodide, soli_d
Mercurous nitrate, solid
Mercurous oxide (black)^ solid
Mercurous sulfate, solid
Mercury
B-19
-------
Mercury acetate, solid
Mercury bisulfate, solid
Mercury compounds (organic)
Mercury cyanide, solid
n-Methylaniline
Methyl bromide and chlorpicrin
mixture
Methyl bromide_and ebhy_lene
dibromide mixture
Methyl bromide, liquid
Methyl chloromethyl ether
Me_thyldichl or ar sine
h±h' -Methylunc bis (2-Chloro-
aniline)? Mq£a
Methyl parathion? liquid
Methyl parathionjnixt.ure, dry_ or
liquid
Mevinphos, Ph< • sdrin
I^ionochlor icetone, stabilized
al pha- Naj)h thyl .• trane
L' ..-?-.:apholiyl;irriine
Ni c kel_ antimonide
Mckel arsenide
Nickel cyanide, GOli
Nic:k>'I neJenide
Nicotine hydrochloride
Nicotine j liquid
Nicotine s alicylate
Nicotine sulfabe, liquid or stol
tartrat e
Ni Lroaniline
^i^HP^?1!?0-^ liquid
Ni tr ochl orb en zen e , ortho^ 1 iquia
U-Nitrodiphenyl
Nitrogen mustard
U-Nitrophenol
n-Nitr o s odime thyl ami ne
Nitroxylol
Oxalic acid
Parani t r oisui 1 i nt- ? s ol i d
Parathion, liquid
Parathion, mixture^ dry or liquid
Paris green, solid
PCS
Pe ntachlorophenol
Perchloroethylene
Perchloro-methyl-mercaptan
Perchloryl fluoride
I^enol
Rienyldichlorarsine, _ liquid
B-20
-------
Phenylhyjdrazine _hydrochlgrlde
Phorate, Thimet
Phosgene
Phorrphamidon, bimecrun
Pho;jphiiie_
Potassium arsenate, ;;olid
Potassium arsenite, solid
Potas slum bifluoride
Potassium Jainoxalate
Potassium_flupride
beta-Propiolactone
SeleniouG acid, and salts
Selenium \
So] eriium f J uoride
LJhradanz_CMiJA
Sodium arsenate, solid
Sodium arsenit^j liquid
Sodium azide
Sodium bifluoride
eacodylate3 s
-------
(2) Corrosive or Irritant
Acetyl chloride
Acridine
Allyl chlorocarbonate
Allyl chloroformate
Allyl trichlorosilane
Ammonium hydroxide
Ammonium_ sulfide
A^iyl trichlorosilane
Anisoyl chloride
Antimony pentachloride
Antimony pentafluoride
Benzene phosphorous dichloride
Benzoyl chloride
Benzyl bromide
Benzyl chloride
Benzyl chlorformate
Boron chloride
Boron trichloride
Mromic arid
Hromint!
Bromine pentafluoride
Bromine trifluoride
Butyl trichlorosilane
Caustic potash, liquid
Caustic soda, .Liquid
Chloracetyl chloride
Chlorine trifluorid0
Chlorosulfonic acid
Chlorosulfonic acid-sulfurtriqxide
mixture
Chromyl chloride
Cupriethylene-diamine ::pint'••>:_!
Cyclohexenyl trich.Iorosila_ue
Cyclohexyl trichlQrosil.arie
o-Dichlorobenzene
p-Dichlorobenzene
Diethyl dichlorosilane
Difluorophpsphoric acid, anhydrous
Dimethylsulfate
Diphenyl dichlorosilane
Ethyl chloroformate
Ethyl phenyl dichlorosilane
Ji i. X g . -—-
Flyorosulfonic acid •
Formic acid
Hexadecyl trichlorosilane
Hexafluorophosphoric acid
Hexamethylene diamine solutioa
'6-22
-------
Hexyl trichlorosilane
Hydrazine
Hydriodic acid
Hydrobromic acid
Hydrochloric acid
Hydrofluoric acid
Hydrof Luoro.'iilicic acid
Hydrogen peroxide
Ilypochlorite solutions containing
more than 7$ available chlorine
Iodine monochloride
Isopropyl percarbonate stabilized
Memtetrahydrophthalic anhydride
Methyl chloroj'ormate
Monochloroacetic acid^ liquid
Monofluorophusphoric acid, anhydrous
Nitric acid
Nitrohydrochloric acid
IJonyl trichlorosilane
Octadecyltrichlorosilane
Qctyl trichlorosilane
Perchloric ,u
Phenyl bricnlorosilarie
PhoGphoric.. acid
Pho.sphorous oxybromicl.e
Phosphorous oxychlori do
Phosphorous tribromide
Phosphorous trichloride
Potassium oxalate
Propyl trichloroG.ilane
Pyrosulfuxyl chloride
Silicon chloride
Silicon tetrachloride
Sodium alviminal'.' liquid
Sodium chlorite solution
Sodium oxide
Sodium sulfide
Stannic chloride
Sulfur chloride
Sulfur trioxide, stabilized
Sulfuric acid
Sulfurous acid
Sulfuryl chloride
Thionyl chloride
Thiophosphoryl chloride
Tin tetrachloride, anhydrous
Titanium sulfate solutio;.
Titanium tetrachloride
Iris (l-aziridinyl) phosphine oxide
Vanadium oxytrichloride
Vanadium tetrachloride
Zinc chloride
B-23
-------
(3) Flammable
Acetaldehyde
Acfctg.no
Acutpni'.riJ.fc
Acetyl beuzu.vJ peroxide
Acetyl peroxide
Acrolein, inhibited
Acrylonitrile
Alkyl aluminum halides
Allyl bromide
Allyl chloride
Aluminum nitrate
Aluminum phosphide
Ammonium bichromate
Ammonium nitrate
Ammonium nitrate-carbonate mixtures
Ammonium perchlorate
Ammonium persulfate
Ammonium permanganate
Amyl acetate
Amyl chloride
Amyl merraptan
Barium chlorate, dry or wet
Barium nitrate
Barium perchlorale
J^arixun permangonal
Barium peroxide
Benzene
Benzine
Benzoyl peroxide
Butyl acetate
Butyl mere apt an
Butyl aldehyde
Calcium chlorate
Calcium chlorite
Calcium hypochlorite , compout ids ,
dry, containing more than
available chlorine
Ant uuoiiy pcntaMUl.rid.o
Hariuro azide. 50^ of more water, wet
Calcium metallic
Calcium nitrate
Calcium permanganate
Calcium peroxide
Calcium phosphide
Calcium resinate
Caprylyl peroxide solution
Carbon bisulfide
Chlorate of potash
B-24
-------
Chlorate of soda
f ^ oxide
C_hlorobenzene_
Chlorobenzoyl peroxide
Chy oiH
Chromic anhydride
Cobalt nitrate
Cobalt recinate, precipitated
Collodion
Copper nitrute
Grot onaldehyde
Cumene hydroperoxide
Cyclohexane
Cyclohexangne peroxide
Cycloperitane
Cycl open bane, methyl
Decaborane
Diborane
Dichlorethylene
iJichloroiGpcyanttric acid, dry,
containing more than 39$
available chlorine
Dicurayl peroxide
Die thylamine
Diisopropylbenzene hydroperoxide
Dimethylaminet aqueous solution
Dimethyldi chlor o s ilane
Dimethylhexane dihydroperoxide
Dimethyldydrazine
Dimetliylsulfide
Dioxane
Ether
Ethyl acetate
Ethyl chloride
Ethyl dichlorosilane
Ethylene dichloride
Ethyleneimine, inhibited
Ethylene oxide
Ethyl formate
Ethyl mercaptan
Ethyl methyl ether
Kthyl methyl ketone
Ethyl nitrate
Ethyl nitrite
Ethyl trichlorosilane
Gasoline
Guanidine nitrate
Hafnium metal, dry
Heptane
B-25
-------
Hexane
Isouctaruj
Isooctcne
1 uopeatane
Icopropanol
Isopropyl acetate
Isopropyl ether
Isopronyl mercaptan
Isopropyl percarbonate, unstabilized
Lauroyl peroxide
Lead nitrate
aluminum hydride
Lithium Aluminum hydride, ethereal
Lithium amide, powdered
Lithium ferro silicon
Lithium hydride,
Lithium hypochlorite compounds, dry
containing more than 39$
available chlorine
metallic -
Lithium peroxide
Lithium silicon
Mar.nesium chlorate,
Magnesium nitrate
Magnesium perchlorate
Magnesium peroxide,_ solid
Mercuric nitrate
Jfej-rhyl acetate
Methyl acetone
Methyl aluminum .t;ut;.'
Methyl aluminum sesjjuichluride
Methyl chloride
Methyl chloromethyl ether, anhydrous
Methyl dichlorosilane
Methyl ethyl ketone
Methyl formate
Methyl hydrazine
Methyl iso-propenyl ketone, inhibite 1
Methyl magnesium bromide in ethyl
ether in concentrations not
over
Methyl mercaptan
Methyl methacrylate monomer
Methyl trichlorosilane
Methyl vinyl ketone,, inhibited
Monoethylamine, aqueous solution
Naptha
Meohexane
Nickel carbonyl
B-26
-------
Nickel catalyst , finely divided
Nitro carbo nitrate
Paramethane hydroperoxide
Pentaborane
Fentane
Pentane ., methyl
Peracctic acid
Permanganate of potash
Permaii;r/unab'' of soda
Petroleum ether
Phosphoric anhydride
Phosphorus a amorphous, red
Phosphorus pentachloride
Phosphorus _ pentasulfide
Phosphorus sesguisulfide
Phosphorus . white or yellow
Picric acid , _weji_
Potassium bromaLe
Pota^siuin dichloroitiocyanurate^ dry,
containing more than 39^ avail-
able chJ orine
Potassium dlchromate
Putassium? metallic
PotaGsiuru_ nitrate
osium nitrate mixed with sodium
Potassium nitrite
Potassium perchlorate
Potassium permanganate
Potassium peroxide
Potassium sulfide
Propylene imine, inhaJbited
PropyJLmercaptan
PropyJeiK,' uxidc
Pyridiuu
Pyroxylin plastics
Silver nitrate
Sodium aluminum hydride
Sodium amide
Sodium brornate
Sodium carbonate peroxide
Sodium chlorate
Sodium chlorite
nitrate
Sodium diehJ orolsoryanuratej dry
containing more than J9/'
available chlorine
Sodium hydride
S odium hydr o sulfi t e
Sodium, metallic
Sodium, metallic< dispersion in
organic solvent
Sodium methylabe. dry
-------
Sodium nitrate
Sodium nitrite
nodium_ nitrite mixed with potassium
nitrate
Uodium permanganate
L; odium peroxide
C odium picramate, vet
Sodium potassium alloys
Spirits of nitroglycerin
Strontium chlorate, wet or dry
Strontium nitrate
Strontium peroxide^
Succinic acid peroxide
Tertiary butyl!sopropyl benzene
hyjdrop er oxi do
'J 'ctrahyxir ofuran
'^-iZ3-!1! trome thane
l"horium metal,_p_ovdered
Titanium metal powder; dry
Titanium metal powder, wet
Toluol
T_richlpr ob»r anc
'Irichloroi ^pc^cumric _acid
containing more than
availiible chlorine
Trichlorosilarie
Triaethylamine, agueous solution
Trimethylchlorosilane
Trinitrobenzene, wet
Trial ir_ob( Ti^oic' aci'";', we I.
' 'rini tro I o_lu.enc , w r L_
! fraijy_l_J.i i \f r ate } j; o J. id
Vinyl acetate
VinyJLidene chloride ; inliibiLed
YiSTA trichlorosilane
Wet nitrocellulose
Wet nitrostarch-20^ _water
Wet nitrostarch-jQ^' so.lvenl
Wood alqohol
Zinc_ ammonium nitrite
Zinc chlorate
Zinc nitrate
Zinc permanganate
Zinc peroxide
Zirconium metal
Zirconium, metallic, solutions
Zir cpnlxun. picramate? wet
Zirconium scrap
B-28
-------
Strong Sensitiaer
Epoxy resin systems containing in any concentration, ethylene-
diamlne, diethylenetriamine, and diglycidyl ethers of_
molecular weight of less than 200.
Formaldehyde _and ^rodjL^ct£;_^onta.iriiiTg_l_J3ercent_ or...more of'
formaldehyde.
Glutaraldehyde
Oil of bergamot and products containing 2 percent or more of
oil of bergamot.
Paraphenylenediamine and products containing it.
Powdered orris root and products containing it.
Toluene 2,k - Diisocyanate
\
Waste epoxy resins
(3) Pressure Reneratinp; material through, decomposiblon3 heat or
other means
Ammonium chrornate
Antimony trisulflde
1,2,^-Butanetriol trirdtrate
Cadmium nitrate
Calcium carbide
C; ulcium hydride
Chlorine pentafluoridu
Copper acetylide
Copper chlorotetrazole
Gyanuric triazide
Diazodinitrophenol
Diethylene glycol dinitrate
Dipentaerybhrlotol hexanitrate
Fulmiriate of-mercury
B-29
-------
Glycerolmonolacetate trlnitrate
Glycgl dinltrate
0 qld_ fuijrri nate
Guanyl nitro:',rimino guanylidenc'
hydrazine
Hydr a. zi ne azj.de
Hydrazoic acid
Lead azide
Lead chlorite
Lead 2 , k- Dinitrore scorcinate
i.ead monomitroresorcinate
Lead styphnate
^4alu ii toi hexanitrate
Nickel nitrate
Nitrog.lyceri ri
Nitrom«.nr)ite
i !pgu;_ut l< iim-
J Lc
Polyvinyl nilr-at t
Potassium dini trobenaf urox?
Silver ace byiide
Silver azide
Silver tetra/.eiie
Sodivim perchlorat c
v inyl chloride
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6U121. Wastes Not lasted. A waste will be considered ha:-,?.• d<
if it meets the definition given in Section 25117 of the Heali fch a/id
Safety Code even though said waste is not listed in ^eoiicr bU.f
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Article 3- Extremely Hazardous Waste
60130. Extremely Hazardous Waste. The following is a listing of
the hazardous wastes as listed in Section 60120 which have been deter-
mined based on their toxicities to be extremely hazardous as defined
in Section 25115 of the Health and Safety Code:
_A.eroltan, Aqualin
j-'-Acety.l aminufluorenc
Aldrin
Aluminum phosphide, Phostoxin
^--Aminodiphenyl
Arsines
Benzidine, and salts
Beryllium
Bidrin
Bomyl
Boranes, Di-, penta-, Irichloro-
Carbanolate, Temik
Carbophenothion, Trithion
Chioroacetaldehyde
Compound 40?2-
Cyanide salts
Cycloheximide, Acti-dione
DDVP, dichlorvos, vapona
Dunn;ton, Systox
l ilckl ordben/.idine
i^Jyc Idy.l a
Dimethyl aminoa^oben/.i.'iiv
J)imethylsulfate
Dinitrocresol, Sinox,_Elff.
Dinitrophenol
Dioxathion, Delnav
Disulfoton, Disyston
Dowieide 7. POP, Pencil! on
Endosulfrui, 'L'hiodari
lilndr Ln
KPN
Ethion, JMialate
Ethylene imine
Fluorine
Fluoroacetio acid, sodium salt,
compound 1060
Furadan
Hydrocyanic acid, Hydrogen cyanic! •
Hydrofluoric acid, hydrogen fluoridf
arsenate
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Mercury
Methyl chloromethyl ether
U_jk_ '_-Me thyleng b_is _J 2 - chloro-
anlline), Moca
Methyl parathion
Mevinpho.'j, Phosdrin
• iJ-pha- IN •• iphlhy I amjm •
i > >-• I,- 1.- !' l.'iphthy-l .-unini •
k - NitrodiphenyJ^
n -• Nitroaodimethylamine
Parathi on
^tgj ThjLioet
beta-Propiolactone
Sel enioits a ci d a and .salt .o_
Seleni urn f luori de
.? ^.QC?.^£i L1? i ' '• LJ ^ Jjla- ' f: u 5 •' ' ' J ' 1 ! -!
phradruij CMPA
'ii.'^ ?liL' ' tl'iyJ J (-' ad . ; 1 1 1 1 1 1 1 1 , 1 u; r
'i-'-'t'hy I j)yri 'plu^^.''
di bli
Tetrauitrome lhaiie
Thionazin, Zinophos
Phoaphatnldt ui^ JJimocron
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60131. Hazardous Wastes Not Listed. A hazardous waste will be
considered extremely hazardous if it meets Jthe_de_firdtion given in
Section 25115 of the Health arid Safety Code even though said hazard-
om; waste ir, not li:;ted in faction CJOI'JO.
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6013H.__ Disposal, (a) No extremely hazardous waste shall be disposed
of in California except at _ an eligible disposal site acceptable for sueh wfi;,1'- ;u
defined in Subchapter 1^ commencing with Section 2500 of Title 23 of the
California Administratiye__Cod.e and as_ approved by the Department.
(b) lio person shrill dispose of a waste materinl whieh he may reasonably
eun elder to be ari i 'xt rf 'me J y ha /.ardous waste without prior approvaJ uf l.h'.1
Department. Requests for approval shall be sent to the Department by <-erlJ-
f i e d mai 1 at least f i f t e e n ( 15 ) day_s_p_r_ior_ tq_ the intended date(s) of di;j-
posal of such waste material. Such notification shall include, but not be
limited to, data on amount and type of material, date(s) of intended. .dls.-
posal arid the proposed disposal site. The Department shall_ reply by Certi-
fied Mail within ten ( 10) days of the receipt of notifica t i_on } e_i^t her grantir i^,
approval of the proposed disposal method or detailing alternate acceptable
methodn. In the event that notification to the Departme^nt fifte_en (l'j) da.\c
prior to the intend£d ^J^el.'"')--!^' dlGpoii.n.1 i:: impracticabJe or_ I'esulta in
undue hardship;;, the Department may^upon request } __ waive th:lr> requlremc-ritj,
(c) In the event of an emergency, accident, or dLi_sast_er which _re sult_s
in a need for the immediate processing or jiisposal of an extremely hazardous
waste, the required fifteen (15) daynotification_^all^e_j£aived._ As ..s_oon
an poLisible _ thereafter, the Department shall be_notified f Irst^ b^r telephone
or telegraph and subsequently by certified mail as to the ^amount and type _cf
thf extremely hazardous waste and the processing orjiisposal method used.
if th'- method of processing or disposal of the extremely hazardous waste
i;; not acreptable to the Department, subsequent action may be required to
re-proee^s or remove and re-dispose of the extremely hazardous waste. If_
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this action is necessary, the Department will reply within one working day
.after receiving notification.
(d) 'Jhc' Department may grant blanket approval up to twelve (l_'d) month;
for processing and disposal methods for reoccurring waste material.
(e) Hazardous wastes being legally disposed of directly to sanita"-,
sewers are exempt from these regulations.
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Article U. Waste Mixtures
60lUQ. Hazardous Waste Mixtures. For a mixture of wastes, the
determination of whether the mixture is a hazardous waste as defined by
Section 25117 of the Health andSafety Code should be based on the physical,
fhemical and pharmacological characterise OR of the mixture. A mixture o!'
wastes may therefore be less hay.ardous or more hazardous than 1 t.n Componentr.
because of synergistir or antagonistic reactions. It may not be possible
to rea^h B decision concerning the toxic, irritant, corrosive, flammable,
rensiti7Jng or pressure-generating properties of B waste from whet i.s
known about its components or ingredients. The mixture itself shall then
be tested by the producer and the analytical data shall be submitted to
'.he Department for determination as to whether the mixture is hazardous.
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Article 5. Transportation
60150. Manifest Form and Content. The forms approved by the State
Water Resources Control Board for the records bo be maintained by waste
haulers, as defined in Subchaptcr 13 (commencing with Section glfOO) of
Title 23 of the California Administrative Code, shall serve a.-; the manifest
pursuant to Section 25162 of the Health and Safety Code. The form and cun-
tent of the State Water Resources Control Board's California Liquid Waste
Haulers Record shall satisfy the requirements_of Section 25161 of the
Health and Safety Code,
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Article 6. Records
60170. Records. Operators of disposal sites which receive
hazardous waste ahull submit monthly records to the director as
1'olJ ows:
(;i) An arrountin,''; of the IVr;; <'oj loci,, 'd.
(b) A copy of the manifests received. Said man i ('• -st shaij
include, but need not be limited Lo, the type, .pajuitity and lh" L'i> , '•
disposal method of the waste, whether by ponding, spreading, iandfiJJ
or Jther.
(c) A summary of the deviations from the standard operating
procedure. The summary shall include a brief description L'f <.[\r:
d( • v La ti> >ns and reasons thorf.'for.
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