FINAL REPORT
A STUDY OF HAZARDOUS WASTE
MATERIALS, HAZARDOUS EFFECTS AND
DISPOSAL METHODS
VOLUME II
For
Environmental Protection Agency
Cincinnati Laboratories
5555 Ridge Avenue
Cincinnati. Ohio 45213
Contract No. 68-03-0032
BAARINC Report No. 9075-003-001
June 30, 1972
\ / / X BOOZ'AllEN APPliCO ' rSC4K'JH WC
WASHINGTON
CHICAGO
LOO ANGELES
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VOLUME II
APPENDIX A INDUSTRIAL DESCRIPTIONS
APPENDK A-1 SIC 10—METAL MINING
SIC 11—ANTHRACITE MINING
SIC 12—BITUMINOUS COAL AND LIGNITE
MINING
APPENDIX A-2 SIC 20—FOOD AND KINDRED PRODUCTS
APPENDK A-3 SIC 22—TEXTILE MILL PRODUCTS
APPENDK A-4 SIC 26—PAPER AND ALLIED PRODUCTS
APPENDK A-5 SIC 28—jCHEMICALS AND ALLIED PRODUCTS
INDUSTRIAL ORGANIC CHEMICALS
INDUSTRIAL INORGANIC CHEMICALS
SIC 282—PLASTIC MATERIALS AND SYNTHETIC
RESINS, SYNTHETIC RUBBER,
SYNTHETIC AND OTHER MANMADE
FIBERS, EXCEPT GLASS
SIC 283—DRUGS
SIC 284—SOAP, DETERGENTS, AND
CLEANING PREPARATIONS.
PERFUMES, COSMETICS, AND
OTHER TOILET PREPARATIONS
SIC 285—PAINTS, VARNISHED, LACQUERS,
ENAMELS, AND ALLIED PRODUCTS
SIC 287—AGRICULTURAL CHEMICALS
SIC 2892—EXPLOSIVES
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VOLUME III
APPENDIX A INDUSTRIAL DESCRIPTIONS
APPENDIX A-6
SIC 29—PETROLEUM REFINING AND RELATED
INDUSTRIES
APPENDIX A-7
APPENDIX A-8
APPENDIX A-9
SIC 31—LEATHER AND LEATHER PRODUCTS
SIC 311—LEATHER TANNING AND FINISHING
SIC 32—STONE, CLAY, GLASS, AND
CONCRETE PRODUCTS
SIC 329—ABRASIVE, ASBESTOS, AND .
MISCELLANEOUS NONMETALLIC
MINERAL PRODUCTS
SIC 33—PRIMARY METAL INDUSTRIES
SIC 331—BLAST FURNACES, STEEL WORKS,
AND ROLLING AND FINISHING MILLS
SIC 333—PRIMARY SMELTING AND REFINING
OF NONFERROUS METALS
APPENDIX A-10 SIC 34—FABRICATED METAL PRODUCTS,
EXCEPT ORDNANCE, MACHINERY,
AND TRANSPORTATION EQUIPMENT
SIC 347—COATING, ENGRAVING, AND
ALLIED SERVICES
APPENDIX A-11 SIC 80—MEDICAL AND OTHER HEALTH
SERVICES
SIC 806—HOSPITALS
APPENDIX A-12 RADIOACTIVE WASTE (ATOMIC ENERGY
COMMISSION)
APPENDIX A-13 WASTE MANAGEMENT (DEPARTMENT OF
DEFENSE)
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VOLUME III (Continued)
APPENDIX A-14 POWER UTILITIES
APPENDIX B CURRENT LISTINGS OF HAZARDOUS
MATERIALS
APPENDIX C HAZARDOUS MATERIAL RATINGS
(COMPOUNDS FOUND HAZARDOUS BY
RATING SYSTEM)
APPENDIX D SUPPORTING DATA
APPENDIX D-l ACCIDENTS INVOLVING HAZARDOUS
SUBSTANCES
APPENDIX D-2 SIC CODE DISTRIBUTION OF TYPICAL
HAZARDOUS CHEMICALS
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VOLUME II
TABLE OF CONTENTS
Page
Number
APPENDIX A
INDUSTRIAL DESCRIPTIONS
APPENDIX A-l SIC 10—METAL MINING A-l-1
1. INTRODUCTION A-l-1
(1) Mine Industry Wastes A-l-2
1. Solid Waste A-l-2
2. Water Wastes A-l-8
3. Air Wastes A-l-13
4. Associated Hazards A-l-19
2. INDIVIDUAL MINERALS A-l-27
(1) SIC 101—Iron Ores A-l-29
1. Description A-l-29
2. Source and Production A-l-29
3. Industrial Consumption A-l-30
4. Future Outlook A-1-31
5. Waste Characteristics A-l-31
6. Associated Hazards A-l-32
(2) SIC 102—Copper Ores A-l-35
1. Description A-1-3 5
2. Source and Production A-l-35
3. Industrial Consumption A-l-36
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Page
Number
4. Future Outlook A-l-37
5. Waste Characteristics A-l-37
(3) SIC 103—Lead and Zinc Ores A-l-38
Lead Ores
1. Description A-l-38
2. Source and Production A-l-39
3. Industrial Consumption A-l-39
4. Future Outlook A-1-40
Zinc Ores
1. Description A-l-41
2. Source and Production A-l-41
3. Industrial Consumption A-l-42
4. Future Outlook A-1-43
5. Lead Zinc Wastes Characteristics A-l-43
6. Associated Hazards A-l-46
(4) SIC 104—Gold and Silver Ores
Gold Ores
1. Description A-1-50
2. Source and Production A-l-50
3. Industrial Consumption A-l-51
4. Future Outlook A-l-51
5. Waste Characteristics A-l-51
Silver Ores
1. Description A-l-54
2. Source and Production A-l-54
3. Industrial Consumption A-1-55
4. Future Outlook A-l-55
5. Waste Characteristics A-l-55
(5) SIC 105—Bauxite and Other Aluminum Ores A-l-56
1. Description A-l-56
2. Source and Production A-l-56
3. Industrial Consumption A-l-57
4. Future Outlook A-1-59
5. Waste Characteristics A-l-59
(6) SIC 106—Ferroalloy Ores, Except Vanadium A-l-60
Manganese
1. Description A-l-60
2. Source and Production A-1-62
3. Industrial Consumption A-1-62
4. Future Outlook A-1-64
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Page
Number
5. Waste Characteristics A-l-64
6. Associated Hazards A-l-64
Tungsten
1. Description A-l-67
2. Source and Production A-l-68
3. Industrial Consumption A-l-68
4. Future Outlook A-l-69
5. Waste Characteristics A-l-69
Chromium
1. Description A-1-71
2. Source and Production A-l-71
3. Industrial Consumption A-l-72
4. Future Outlook A-l-72
5. Waste Characteristics A-l-72
6. Associated Hazards A-l-73
Cobalt
1. Description A-l-75
2. Source and Production A-l-75
3. Industrial Consumption A-l-75
4. Future Outlook A-1-76
5. Waste Characteristics A-l-76
Molybdenum
1. Description A-l-77
2. Source and Production A-l-77
3. Industrial Consumption A-1-78
4. Future Outlook A-1-78
5. Waste Characteristics A-1-78
Nickel
1. Description A-1-80
2. Source and Production A-l-80
3. Industrial Consumption A-l-80
4. Future Outlook A-l-81
5. Waste Characteristics A-l-81
6. Associated Hazards A-l-83
(7) SIC 109—Miscellaneous Metal Ores A-l-85
1. Description A-l-85
2. Source and Production A-l-86
3. Industrial Consumption A-l-86
4. Future Outlook A-l-86
5. Waste Characteristics A-l-89
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Page
Number
Titanium
1. Description A-l-89
2. Source and Production A-l-91
3. Industrial Consumption A-l-91
4. Future Outlook A-l-91
5. Waste Characteristics A-l-92
Vanadium
1. Description A-l-93
2. Source and Pollution A-l-93
3. Industrial Consumption A-l-93
4. Future Outlook A-1-94
5. Waste Characteristics A-1-94
6. Associated Hazards A-l-94
Antimony
1. Description A-l-98
2. Source and Production A-l-98
3. Industrial Consumption A-l-99
4. Future Outlook A-l-99
5. Waste Characteristics A-l-99
Arsenic
1. Description A-l-101
2. Source and Production A-l-101
3. Industrial Consumption A-l-101
4. Future Outlook A-1-102
5. Waste Characteristics A-l-102
6. Associated Hazards A-l-102
Beryllium
1. Description A-l-105
2. Source and Production A-1-106
3. Industrial Consumption A-1-106
4. Future Outlook A-l-106
5. Waste Characteristics A-l-107
6. Associated Hazards A-l-107
Cadmium
1. Description A-l-112
2. Source and Production A-l-113
3. Industrial Consumption A-l-113
4. Future Outlook A-l-113
5. Waste Characteristics A-1-114
6. Associated Hazards A-l-114
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Gallium
1. Description
2. Source and Production
3. Industrial Consumption
4. Future Outlook
5. Waste Characteristics
Germanium
1. Description
2. Source and Production
3. Industrial Consumption
4. Future Outlook
5. Waste Characteristics
Selenium
1. Description
2. Source and Production
3. Industrial Consumption
4. Future Outlook
5. Waste Characteristics
6. Associated Hazards
Tellurium
1. Description
2. Source and Production
3. Industrial Consumption
4. Future Outlook
5. Waste Characteristics
Thallium
1. Description
2. Source and Production
3. Industrial Consumption
4. Future Outlook
5. Waste Characteristics
6. Associated Hazards
SIC 11—Anthracite Mining
1. Description
2. Source and Production
3. Industrial Consumption
4. Waste Characteristics
SIC 12—Bituminous Coal and Lignite Mining
1. Source and Production
2. Industrial Consumption
3. Future Outlook
4. Waste Characteristics
Page
Number
A-l-118
A-l-118
A-l-118
A-l-118
A-l-119
A-l-119
A-l-119
A-l-120
A-l-120
A-l-120
A-l-121
A-l-121
A-l-121
A-l-122
A-l-122
A-l-122
A-l-126
A-l-126
A-l-126
A-l-127
A-l-127
A-l-127
A-l-127
A-l-128
A-l-128
A-l-128
A-l-128
A-l-129
A-l-129
A-l-129
A-l-130
A-l-132
A-l-133
A-l-133
A-l-133
A-l-135
A-l-136
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Page
Number
APPENDIX A-2 SIC 20—FOOD AND KINDRED PRODUCTS A-2-1
1. ECONOMIC STATISTICS A-2-2
(1) SIC Code Classifications and Descriptions A-2-2
(2) Number of Establishments And Locations A-2-5
(3) Major Raw Materials and Annual Production A-2-6
(4) Employment Statistics (Value Added) and A-2-15
Growth Patterns
WASTE CHARACTERISTICS A-2-15
(1) Production Processes and Waste Sources A-2-28
(2) Effluents to Air and Water A-2-37
(3) Hazardous Waste Materials A-2-37
3. WASTE DISPOSAL PROCESSES AND PRACTICES A-2-47
(1) Current Waste Treatment Processes A-2-48
(2) Extent of Utilization of Waste Treatment A-2-53
Processes
(3) Efficiency of Waste Treatment Processes A-2-54
(4) Net Annual Wasteloads and Waste Reduction A-2-57
APPENDIX A-3 SIC 22—TEXTILE MILL PRODUCTS A-3-1
1. INDUSTRY DESCRIPTION A-3-1
(1) SIC 2231—Wool Textile Weaving and A-3-2
Finishing
(2) SIC 2261—Cotton Textile Finishing A-3-2
(3) SIC 2262—Synthetic Textile Finishing A-3-3
(4) SIC 2269—Finishing of Other Textiles A-3-3
(5) Distribution of Establishments A-3-4
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Page
Number
2. MAJOR RAW MATERIALS, ANNUAL A-3-4
PRODUCTION, AND INDUSTRY GROWTH
PATTERN
(1) SIC 2231—^001 Textile Weaving and A-3-4
Finishing
(2) SIC 2261—Cotton Textile Finishing A-3-8
(3) SIC 2262—Synthetic Textile Finishing A-3-9
(4) SIC 2269—Finishing of Textiles Other Than A-3-10
Broad Woven Fabrics
3. PRODUCTION PROCESSES AND WASTE A-3-10
CHARACTERISTICS
(1) Wool Industry A-3-11
1. Production Processes A-3-11
(1) Souring A-3-12
(2) Stock Dyeing A-3-13
(3) Carding A-3-14
(4) Fulling A-3-15
(5) Washing A-3-16
(6) Carbonizing A-3-17
(7) Bleaching and Piece Dyeing A-3-17
2. Waste Characteristics A-3-19
(2) Cotton Industry A-3-22
1. Production Processes A-3-22
2. Waste Characteristics A-3-23
(3) Synthetic Fiber Industry A-3-26
1. Production Processes A-3-26
2. Waste Characteristics A-3-27
4. WASTE DISPOSAL PROCESSES AND PRACTICES A-3-27
(1) Wool Industry A-3-31
1. Production Subprocesses A-3-31
2. Waste Treatment Capability A-3-34
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INDUSTRIAL ORGANIC CHEMICALS
Page
Number
(2) Cotton Industry A-3-40
1. Production Subprocesses A-3-40
2. Waste Treatment Capability A-3-44
(3) Synthetic Fibers Industry A-3-50
1. Production Subprocesses A-3-50
2. Waste Treatment Capability A-3-55
APPENDIX A-4 SIC 26—PAPER AND ALLIED PRODUCTS A-4-1
1. ECONOMIC STATISTICS A-4-1
2. WASTE CHARACTERISTICS A-4-2
3. DISPOSAL PRACTICES A-4-5
(1) Pretreatment A-4-7
(2) Primary Treatment A-4-8
(3) Secondary Treatment A-4-9
(4) Tertiary Treatment A-4-11
(5) Other Methods A-4-12
APPENDIX A-5 SIC 28—CHEMICALS AND ALLIED A-5-1
PRODUCTS
1. GENERAL CHARACTERISTICS A-5-1
(1) SIC 2815—Cyclic Intermediates, Dyes. A-5-2
Organic Pigments (Lakes and
Toners), and Cyclic (Coal Tar)
Crudes
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Page
Number
(2) SIC 2818—Industrial Organic Chemicals. A-5-6
Not Elsewhere Classified
2. PRODUCTION STATISTICS A-5-10
(1) Tar and Tar Crudes A-5-11
(2) Cyclic Intermediates A-5-12
(3) Organic Dyes and Pigments A-5-12
(4) Miscellaneous Organic Chemicals A-5-14
(5) Rubber Processing Chemicals A-5-15
(6) Plasticizers A-5-17
3. PRODUCTION PROCESSES AND WASTE A-5-17
CHARACTERISTICS
(1) Tar and Tar Crudes A-5-19
(2) Cyclic Intermediates A-5-25
1. Aniline A—5-25
2. Alkybenzene, Cumene and A-5-27
Ethylbenzene
3. Chlorobenzene A-5-29
4. Cyclohexane A-5-30
5. Cyclohexanone A-5-31
6. Isocyanates A-5-32
7. Nitrobenzeiies A—5-33
8. Phenol A-5-34
9. Phthalic Anhydride A-5-37
10. Terephthalic Acid and Dimethyl A-5-39
Terephthalate
11. Styrene A-5-40
12. Xylenes A-5-41
(3) Dyes A-5-42
1. Preparation of Intermediates A-5-42
2. Preparation of Dyes A-5-49
(4) Tanning Materials A-5-52
(5) Halogenated Hydrocarbons A-5-52
(6) Phosphorus Compounds A-5-57
(7) Fermentation Reactions A-5-59
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Page
Number
1. Ethyl Alcohol A-5-60
2. Acetone and Butyl Alcohol A-5-60
3. Acetic Acid A-5-61
(8) Animation by Ammonalysis Reactions A-5-61
(9) Aliphatic Acetate Production A-5-62
(10) Methanol A-5-62
(11) Ethylene Oxide A-5-63
4. DISPOSAL PRACTICES AND HAZARDS A-5-64
INDUSTRIAL INORGANIC CHEMICALS
1. ECONOMIC STATISTICS A-5-65
(1) SIC 2812—Alkalies and Chlorine A-5-65
(2) SIC 2813—Industrial Gases A-5-65
(3) SIC 2816—Inorganic Pigments A-5-66
(4) SIC 2819—Industrial Inorganic Chemicals A-5-67
Not Elsewhere Classified
2. WASTE CHARACTERISTICS A-5-70
(1) Composition of Waste Streams A-5-71
1. Gases A-5-72
2. Inorganic Acids A-5-74
3. Phosphorus A-5-79
4. Hydrogen Peroxide A-5-81
5. Calcium Carbide A-5-82
6. Lime A-5-82
7. Aluminum Chloride A-5-83
8. Aluminum Sulfate A-5-83
9. Ammonium Nitrate A-5-84
10. Ammonium Sulfate A-5-84
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Page
Number
3. DISPOSAL PROCESSES A-5-85
SIC 282—PLASTIC MATERIALS AND SYNTHETIC RESINS,
SYNTHETIC RUBBER, SYNTHETIC AND OTHER
MANMADE FIBERS, EXCEPT GLASS
1. ECONOMIC STATISTICS A-5-89
(1) Industry Descriptions A-5-91
(2) Establishment Size and Location A-5-92
2. WASTE CHARACTERISTICS A-5-94
(1) SIC 2821—Plastic and Synthetic Resins A-5-96
(2) SIC 2822—Synthetic Rubber A-5-97
(3) SIC 2823—Cellulosic Manmade Fibers A-5-101
(4) SIC 2824—Synthetic Organic Fibers A-5-102
3. WASTE DISPOSAL PROCESSES A-5-103
(1) Waste Treatment Processes A-5-103
1. Coagulation A-5-103
2. Aeration/Activated Sludge A-5-103
3. Trickling Filter A-5-104
4. Flotation A-5-105
5. Sludge Handling A-5-105
6. Lagoons and Stabilization Ponds A-5-106
7. Sedimentation A-5-110
8. Ion Exchange A-5-112
9. Oxidation-Reduction and Precipitation A-5-112
10. Adsorption A-5-113
11. Reverse Osmosis A-5-113
(2) Waste Treatment Practices A-5-113
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Page
Number
SIC 283—DRUGS
1. ECONOMIC STATISTICS A-5-123
(1) Description and SIC Classification A-5-123
(2) Number of Establishments and Relative A-5-125
Concentration
(3) Major Raw Materials and Annual A-5-127
Production —
(4) Employment and Annual Sales A-5-132
(5) Growth Patterns A-5-134
2.
2. WASTE CHARACTERISTICS A-5-135
(1) Description of Production Processes and A-5-135
Waste Sources
1. Waste Generation During Process and A-5-136
Production
2. Description of Effluents to Air and A-5-138
Water
3. Hazardous Materials in Wastes A-5-139
3. DISPOSAL PRACTICES A-5-141
(1) Current Disposal Technology A-5-141
1. Solid Wastes A-5-141
2. Airborne Wastes A-5-143
3. Water Wastes A-5-145
4. Radiological Wastes A-5-146
5. Animal and Microbiological Wastes A-5-147
6. Solvent Wastes A-5-147
7. Wastes Generated by Research A-5-148
Facilities
4. ESTIMATES OF WASTE PRODUCTION A-5-148
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Page
Number
SIC 284—SOAP. DETERGENTS. AND CLEANING
PREPARATIONS. PERFUMES. COSMETICS.
AND OTHER TOILET PREPARATIONS
1. ECONOMIC STATISTICS A-5-153
(1) SIC 2841—Soap and Other Detergents. A-5-153
Except Specialty Cleaners
(2) SIC 2842—Specialty Cleaning. Polishing. A-5-155
and Sanitation Preparation.
Except Soap and Detergents
(3) SIC 2843—Surface Active Agents. Finishing A-5-157
Agents. Sulfonated Oils and
Assistants
2. DESCRIPTION OF INDUSTRY A-5-159
(1) Soaps A-5-160
(2) Detergents A-5-161
(3) Glycerin A-5-163
3. WASTE CHARACTERISTICS A-5-165
(1) Biodegradability of Surfactants A-5-165
(2) Pollution A-5-166
SIC 285—PAINTS. VARNISHES. LACQUERS. ENAMELS. AND
ALLIED PRODUCTS
1. ECONOMIC STATISTICS A-5-167
2. DESCRIPTION OF INDUSTRY A-5-169
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Page
Number
(1) Paints A-5-169
(2) Varnishes and Enamels A-5-170
(3) Lacquers A-5-172
(4) Pigments A-5-173
3. WASTE CHARACTERISTICS A-5-176
(1) Solvent Emissions A-5-176
(2) Surface Coating Mists A-5-178
SIC 287—AGRICULTURAL CHEMICALS
1. ECONOMIC STATISTICS A-5-179
2. PRODUCTION AND WASTE CHARACTERISTICS A-5-183
(1) Chemical Fertilizers A-5-183
1. Phosphates (Phosphorous) A-5-183
2. Ammonia (Nitrogen) A-5-185
3. Potash (Potassium) A-5-186
4. Storage Problems A-5-188
(2) Pesticides A-5-188
3. DISPOSAL PRACTICES A-5-191
(1) Fertilizer Manufacturing Wastes A-5-191
(2) Pesticide Manufacturing Wastes A-5-197
SIC 2892—EXPLOSIVES
1. COMMERCIAL EXPLOSIVES INDUSTRY A-5-203
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Page
Number
2.
WASTE MATERIALS
A-5-205
3.
MILITARY EXPLOSIVES INDUSTRY
A-5-209
4. SPECIFIC PROCESSES AND PLANTS
(1) TNT Manufacture
(2) RDX/HMX Manufacture
(3) Propellant Manufacture
(4) Primer Materials
(5) White Phosphorus Waste
(5) Contaminated Packaging Disposal
A-5-214
A-5-214
A-5-218
A-5-223
A-5-224
A-5-225
A-5-225
ORDNANCE DISPOSAL
(1) Quantities
(2) Demilitarization
(3) Destructive Disposal
(4) Deep-Water Dumping
(5) Other Proposals
A-5-226
A-5-226
A-5-227
A-5-229
A-5-230
A-5-231
ROCKET PROPELLANTS
(1) Liquid Propellants
(2) Solid Propellants
A-5-232
A-5-232
A-5-233
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APPENDIX A-l
SIC 10—METAL MINING
SIC 11 ANTHRACITE MINING
SIC 12 BITUMINOUS COAL AND LIGNITE MINING
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APPENDIX A-1
SIC 10—METAL MINING
1. INTRODUCTION
Mining as discussed in this section includes the extraction of
naturally occurring, such as solid minerals including coal. Liquids,
such as crude petroleum and natural gas, are treated elsewhere in
this report. The activities of quarrying, milling (crushing, screening.
washing, flotation, etc.), and other preparation needed to render the
material marketable are also included.
It is estimated that, to date, mineral industry solid wastes have
accumulated to a staggering 23 billion tons, and have covered over
1.8 million acres. Those wastes heaped into man made mountains
or impounded behind acres of tailing dams, create serious environ-
mental degradation and land use problems primarily in areas experiencing
urban and industrial growth. In addition air and water pollution
resulting from denuded waste banks and settling ponds, and the emission
of noxious and even toxic gases and smoke from burning coal banks,
have contributed significantly to the degeneration of the environment.
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APPENDIX A-1-2
This section will discuss the mining industry with primary
emphasis being placed on the degree of environmental degradation
contributed by this industry (SIC 10). The discussion is presented
in two parts, as follows:
Mine Industryal Wastes—This section deals generally
with the mining associated wastes, since the type
wastes and the methods in which they are produced are
similar. Mining's contributions to solid, water, and
air pollution are discussed.
Individual Minerals—This section discusses the individual
minerals and includes a brief description of the mineral
and its source, production, and industrial consumption
pattern, future outlook, waste characteristics, and
associated hazards.
The information in this section was mainly obtained from
References 1, 2, and 3.
(1) Mine Industry Wastes
1. Solid Waste
The industrial processes involving the mining,
milling, smelting and refining of minerals produce solid
wastes at each step. The bulk of this solid wastes consists
of discarded material from open pit mines, mills, coal
preparation plants, blast furnaces, smelters, and refineries
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APPENDIX A-1-3
or processing plants. Many of these waste accumulations
contain millions of dollars worth of unrecovered mineral
values, and as such present a challenge to our technology.
Surface mining has disturbed an estimated 3. 2 million
acres (5,000 square miles) in this country. In 1966 along, strip
mining displaced 3. 3 billion tons of overburden. Much of
the overburden and unacceptable ore was redeposited in
mined-out areas, but more than 300 million tons were
dumped on adjacent lands for construction of mill tailings,
ponds, or leading dumps. The remainder was heaped in
piles. Approximately 95 percent of the acreage disrupted
by surface mining involved seven commodites: (1) coal,
41 percent; (2) sand and gravel, 26 percent; (3) stone,
gold, clay, phosphate, and iron together, about 28 percent;
and (4) all others, 5 percent (Reference 4).
Underground mining wastes are attributed to 6, 500
active mines and an estimated 90, 000 abandoned mines in
the United States. About 76 percent are coal mines, 21 per-
cent are metal mines, and 3 percent are nonmetallic mineral
mines. In 1966 subsurface mining accounted for 66 percent
of domestic coal production, 17 percent of the metal ore
tonnage, and 6 percent of the nonmetallic ore tonnage.
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APPENDIX A-1-4
At the present annual rate of mineral production,
strip mining will disrupt 153,000 acres to yield 3.0
billion tons of crude ores, while underground production
will provide an additional 508 million tons of ore. The
solid wastes derived from these activities will accumulate
at a rate of 3.4 billion tons per year by 1985.
The results of this waste accumulation are seen
in the denudation of land, water pollution, alteration of
surface and subsurface drainage patterns, clogging of
stream channels, fish kills, flooding, air pollution,
waste bank fires, land use conflicts, and general dis-
ruption to the total ecological balance. An estimated
dollar figure for reclaiming the mineral industries solid
waste is set in excess of $757 million.
Tables A-1-1 and A-1-2 present sources and magni-
tudes of solid wastes generated by the minerals and fossil
fuel industries up to and including 1968. Table A-1-3
shows the classification methods in terms of physiographic
effects of their resultant solid wastes.
-------
APPENDIX A-1-5
Table A-1-1
Solid Wastes Generated by the Mineral and Fossil Fuel Mining
and Processing Industries in 1968 and Accumulated up to 1968
(1, 000 Short Tons)
Industry
Copper
Iron and Steel
Phosphate Rock
Lead-Zinc
Alumina
Bituminous Coal
Coal Ash
Other
Total
1968
669,683
310,764
411,700
22,246
7,976
97,107
29,735
234,538
1,783,749
Accumulated up to 1968
9,078,544
4,687,858
1,945,144
492,525
61,521
1,849,145
gin 000
455,773
4,576,281
24,055,791
-------
Table A-1-2
Solid Wastes by Type Generated by the Minerals and Fossil
Fuel Industries in 1968""
(1, 000 Short Tons)
Industry
Copper
PKftCnVifl t"a Prt/»1r
Lpad-7-fnr
Coal:
Other
TOTAL
Mine Waste*
AQ? &1A
f 7£ , OJ'»
157 518
OQO 1 QA
^ SO6
7 "*£n
14-'( , C03
1,082,133
Mill Tailings
1 79 7^1
1 /£, / Jl
ITS 798
1 R 577
f.ay
OOf.
90,535
418,343
Washing Plant
Rejects
1 1 n ri7R
07 1 f>7
7/ , J.U/
NA
207,185
Slag
A 900
16 133
4 543
165
NA
25,139
Processing
Plant Wastes
1 315
14 895
6, 9S&
29 715
NA
50,899
Total
fiftQ fifi-l
310 764
411 700
22 24.6
7 976
07 107
29 715
234,538
1,783,749
^Includes overburden moved during surface mining activities and waste
removed from underground mines, excludes overburden displaced by
surface coal mining operations.
NA = Not Available.
w
2J
I
Ol
-------
Table ; i-3
Mining Classification in Terms of PI" siographi Effects
Mining Method Cateajones
Open Cast
Primarily long term operations
exceeding periods of 40 yean, some
extending to 100 or more years
Includes many quarries
Strip Mining
Primarily short mm operations.
some of which are possibly only a
year bl duration but most of them
less than 40 yean maximum
Caving
An underground method of mining
thai may be long or short term, but
leaves glory hotel 01 area of
ground subsidence
Slope and Underground (Mac ) (c)
There arc numerous methods of stop-
Ing which may or may not influence
surface physngnphy except where
back fllUng becomes Involved
Hydraulk Mining
Involves the use of monitor nouses
or water Row Usually not a long
tern method and depends upon an
available water supply and comet-
tag of material being mined
Dredging (a)
Largely historical in U.S.
although there are exceptions.
Requires water and may be done on
small as well as Urge scab.
Usually short term operations lent
than 40 yean.
Special Cases (bl
OU shak mining, Colorado pri-
marily Some llmciiite operations.
inch as In N Land certain types
of operations difficult to classify
Lajuitt Hugh! be Included Augur
or high wall muring would probably
be Included hen but could be
placed In category No 2 Frasch
sulfur operstkmi in Gulf Stales
would also be in this clauJlca-
tion
Metals (d)
r ii.
MesaTMning THInp and Waste
Mosi western porphyry copper Usually extensive
deposits in Arizona. Utah, Nevada, with copper, less
etc Also iron mining in Lake with nan No
Superior region and west senous pollution
problem is a rule
SmaDer copper and iron phs. a few Similar to above but
base metal operations and occasion- on smaOer scale
ally gold. Some uranium mining
Molybdenum mining in Colo. Zinc Tailings vary but
mining in N J . some Inn m Lake can be extensive as
Superior region and Pa. for moly mining in
Colo
Base and precious metal mining m Tailings and waste
general Cour d'Akne. LeadviDe. rock extensive but
Homestake. Suite. Tn-Slate. less fines than m
Tennessee and tungsten mining category No 1
Not loo much being done today Wai Tailings generally
extensive some yean ago In Alaska sluiced down stream.
for gold Some In Colo.. S.O.. Problems largely
and Idaho in past historical
Primarily California and Alaska Coarse spoil piles
ExtcmtaLnCaUfonitiand a problem on Yuba
Colorado before 1900 for gold River and some at
Some in Idaho snd Nevada for pie- Leadville. Favpby
dous metals Tungsten and etc Colorado
Reclaiming of ladings and slag Usually soil have
pro ferns.
Fuels (Pi .isnlyCoal)
Cod ML, SjoiandW,!,
Relatively few really long term Extensive over-
operations although coal ilrippmg burden, male. skte.
has pennled regionally snce and some culm
about 1910m Pa.. West Va. and Scarring of land-
Ohio scape
Extensive in Pa.. West Va.. Ky., Extensive and can
Ohio. Indian, Illinois, and some become s poDudon
m Wyoming, lows, Kansas, Missouri. problem Extensive
Utah. Montana, clc. leaning of area
mined.
Not loo common today although there Large pits left but
was past caving m Pa Some in tailings or waste
Washington kss extensive.
Room and pilkr mining largely and Cob and culm waste
vinous forms of sloping in PL, extensnephis
Illinois. West Vs., Ohio Anthra- ground subsidence
cite mining in N W. Pa. Largely
historical
Not important. Scan left by water
cuts
Some in Ohio and other eastern Largely sediments
men Never loo extensive. relumed to nver
High wen mmmg in Ky and West Same as category No 2
Va (category No 2) Luuite in
Minnesota and N.D
Industrial Minerals (d)
ECaVniaaVrM
Industrial Mbtttstj Sp0" *"d **""
Primarily quirrmg of granite, trap Usually some waste
rock, limestone, marble, etc but not a senous
Exists throughout the nation problem Pits arc..
Some quarries over 110 yean old extensive Pollution
not KHOUI
Borax mmins in Mohave region and Scarring of terrain.
phosphate rock in Western Slates Some waste and polhi-
Abo grand pits, sand phs. and inn may occur on
day pits. small scale
Occasional caving operations such Some waste but no
as Riverside. Cel or Coshocun. senous problems.
Ohio, for cement materials. Large pits left.
Potash mmmg in New Mexico and Not too serious
some days in Mo. and elsewhere.
lak snd gypsum in N Y
Often combined operations. Honda Well controlled and
phosphates an largest. Combined not senous
operations usmg dredge and drag
line techniques Western
phosphates
OU shale not extensive. Ihnemte No) currently
•no rulitc lujcly involve DCACTI senous piobkni.
suds.
Footnotes
"•^ ^~^~
(a) Would include some drag line opaations for precious metals
(bl Solution mining or wells not included
(c) Can be further broken down based on roof support
(d) For exact statistics, see Tsble 8 of U.S.B.M Yearbook (Technologic Trends, etc )
1962 Clsssules surface and underground.
55
O
1-1
X!
-------
APPENDIX A-1-8
2. Water Wastes
Water is basic to man's existence. Presently, there
is a sufficient quantity available for the foreseeable future;
however, quality is a factor. More than 90 percent of the
earth's water is salty, and the remainder fresh. Due to
the accumulative nature of pollutants, only a small
percentage of this fresh water is suitable for municipal,
agricultural, and industrial use without first undergoing
costly treatment. Today, nearly every major fresh water
course or lake suffers to some extent from the cumulative
effects of pollution.
At present about 1 percent of the estimated 99, 000
billion gallons of water used domestically is used by the
mineral industry. However, pollution resulting from
decades of mining and mineral processing has produced
adverse environmental conditions. Industry associated
pollution can be separated into three categories:
(1) physical pollution, (2) chemical pollution, and
(3) combination of both.
-------
APPENDIX A-1-9
Physical Pollutants—Solid participate
material, either mineral or organic, which
enters a stream or pond. These participates
may chemically react with water or other sub-
stances to form even more harmful compounds.
An estimated total of 2, 000 abandoned mine and
mill waste dumps are contributing to water
pollution. Stabilization of these ponds by
planting vegetation is hindered by the high
acidity or alkalinity of the material. Studies
indicate that sediment yields from strip mines
is 1,000 times that derived from forested
areas, and that half of the 4. 2 million gallons
of waste processing water is released untreated
to adjacent streams. This sediment may also
include valuable mineral resources.
Chemcial Pollutants—Acids, alkaline solutions,
mineral salts draining from mines, and waste
heaps accrued from the mining and processing
mineral sulfide ores. This type of pollutant is
more difficult to treat than solids.
The mineral sulfides react chemically
with air and water to form sulfuric acid, which
reacts with water and other minerals to cause
other ions, such as aluminum, manganese,
lead, zinc, and arsenic,.to be added to water.
These could get into water by draining from
spoil material or ground water percolation
through spoil material on its way to nearby
streams. When the concentration of these
pollutants is sufficiently great, "dead water"
which is toxic to living organisms results.
Table A-1-4 compares unpolluted surface
water to some polluted waters of the Eastern
Coal Fields.
-------
APPENDIX A-1-10
Table A-1-4
Comparison of Unpolluted Surface Waters with Polluted Waters
of the Eastern Coal Fields
Parameter
Dissolved Solids
Suspended Solids
Unpolluted
Waters
Kg/liter
0-20
On o
U.J
On ns
- u.uj
0_
—
0_ i sn
~ LJ\J
0 - 250
0 - 100
6Q
• y
Polluted Coal
nOucITcLLcJLy JrOHUbCU
Mg/ liter
21 - 7A.Q
*• A 4H7
OA O O
•H - u.s
On*; _ no
• WO — U«!>
01 n A
• A ~ U.»f
m9AQ
~ A47
251 - 499
101 - 249
5_ A
~ O
L Field Water
Heaullu On11nf-A>4
Ueaviiy roiiucea
Mg/ liter
2504.
1A_i_
.u+
i ru.
* «UT
Oc .
• JT
7SOj-
500+
250+
2_ c
~ 3
pH is neutral on a scale of 14, values higher than 7 indicate
alkalinity and values less than 7 indicate acidity.
-------
APPENDIX A-1-11
Another effect of acid drainage from these
wastes is the formation called "yellow boy, "
a rust-colored precipitate of ferric hydroxide
that accumulates in stream beds. Due to its
coating action it smothers aquatic life (coats
gill structures), and seals stream bottoms to
the extent that water can no longer percolate
through the bed to oxygenate and therefore breeding
areas for aquatic species are reduced.
Physical and Chemical Pollutants—Compounds
such as heavy media and flotation reagents used
in cleaning, milling, and beneficiatiori processes
for the recovery of mineral values are inad-
vertently lost, and reach streams by spills,
direct flushing, or from overflows of natural
leaching of tailing ponds. Normally, they will
be impounded in the settling areas, but
seepage through, or breaks in, the dam permit
these compounds to contaminate ground waters
and streams. Most of these effluents are foul
smelling and discolor the water, and in some
instances they are toxic. Phosphates in water
are believed to stimulate abnormal growth of
algae and other aquatic flora, whose demand
for oxygen is responsible for the suffication of
many forms of stream life.
Physical and chemical pollutants from all types
of mining has adversely affected 18, 000 miles
of streams in the United States. These sources
contribute large volumes of sediment, more
than 4 million tons of sulfuric acid, to the
stream. Surface mining alone has adversely
affected 8, 700 miles of streams. Under-
ground mining is responsible for degrading
approximately 9, 300 miles of stream and 22, 000
acres of lakes and other water bodies in 31
states (Table A-1-5).
-------
APPENDIX A-1-12
Table A-1-5
Fish and Wildlife Habitat Adversely Affected
by Strip and Surface Mining in the United States
State
Alabama
Alaska
Arizona
Arkansas
California
Colorado
Connecticut
Delaware
Florida
Georgia
Hawaii
Idaho
Illinois
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maine
Maryland
Massachusetts
Michigan
Minnesota
Mississippi
Missouri
Montana
Nebraska
Nevada
New Hampshire
New Jersev
New Mexico
New York
North Carolina
North Dakota
Ohio
Oklahoma
Oregon
Pennsylvania
Rhode Island
South Carolina
South Dakota
Tennessee
Texas
Utah
Vermont
Virginia
Washington
West Virginia
Wisconsin
Wyoming
Total
Streams Natural
Miles
275
GO
30
150
320
880
62
(2)
(2)
185
134
GO
90
100
395
1.714
4
115
6
253
~30
330
136
700
41
35
10
100
24
1.200
20
310
34)00
2
640
350
16
32
260
64
755
• •
10
12.898
*£? M.
1,700
500
200
700 2
834 3
J.930
415 2
(2) __
(2)
510
654
350
750
614
7,000
42.500 250
5
500
600
506 16
6
190
2.550
234
21.600
31
1,500
90
1.150
100 2
1.200
73 . .
620
9,100
1
3.Z50
3,983
90 " '".
70
1.015
640
28.015
• • -. ••
200
. Reservoirs and
aKes impoundments
s±e •—
7
200 '.
70 1
13
100
5
10
50
2
100,000
1
1,560 32
1,600
1
2
1
100 . .
1
4
33
1
4
• • . ••
135,970 281 103.630 168
Surface
acres
16,300
4
600
200
390
500
50
72
900
300
6,000
2
120
2,020
9,275
100
4.683
*•
41,516
Wildlife
habitat
Acres
12,000
1,000
30,000
32,400
61,270
21,515
16,783
6.000
41.000
800
355
16,460
132,395
108,744
38,500
66,700
3,000
33,274
7.500
50
30,729
• •
1,900
29,500
10,830
16,915
*•
1,000
• *
47,540
26.350
850
33,140
67.&20
• 28.386
13.6E6
392,000
3!0
SOO
23.000
20,030
146.0S7
11.434
• •
6.000
149.135
NA
l,687.i'8d
NA - Not Available
* Compiled from data obtained from state fish and game personnel.
** Insignificant.
-------
APPENDIX A-1-13
3. Air Wastes
The adverse environmental effects of air pollution
that may be attributed to the production, processing, use,
and disposal of minerals and fossil fuels amount to about
86 percent of the total problem. Table A-l-6 describes
the deleterious effects of mineral-industry-related air
pollution. The two principal categories are:
Dust—Generated during practically every
mining and processing operation, dust poses
a fourfold menace: (1) creates uncomfortable
working conditions; (2) reduces operational life
of equipment; (3) creates unhealthy working
and living conditions; (4) effects are spread
beyond mine or mill site. The principal cause
of dust pollution is neglect, e. g. failure to
return fine spoils to mined-out areas, or
failure to seal the surfaces of waste banks
or settling ponds with chemical soil binders,
or poor site selection for waste by not considering
wind conditions, topography, and proximity of
roads or communities.
Gases— This pollutant results primarily from
the use of fossil fuels and the preparation of
various mineral commodities through smelting.
Sulfur dioxide is emitted by all sources, which
in the presence of sunlight and other mineral
salts, combines with water to produce sulfuric
acid. This combines with other particulates
to produce smog. During smelting of the
various metal ores, the sulfides are driven off
as sulfur dioxide that can be recovered as sulfuric
acid or liquid sulfur dioxide. Table A-1-7 lists
the type of ore and amount of sulfur oxide re-
covered (Reference 5).
-------
APPENDIX A-l-14
Table A-1-6
Deleterious Effects of Mineral-Industry-Related Air Pollution
Nature of
Pollutants
Causes
Deleterious
Effects
Dust
1. Blasting, loading, and
hauling of mine run ore
2. Crushing of ore prepar-
atory to processing
3. Drying up of settling
ponds and tailing dams
4. Overly acid, alkaline, or
sterile nature of fine
wastes
5. Poor waste bank site sel-
ection in relation to pre-
vailing winds
6. Failure to return fine
wastes to mined out
areas
7. Failure to use chemical
soil stabilizers when
wastes will not support
vegetation
8. Failure to cover fine
wastes with coarse
material or top soil
9. Saltation transport
of sand size waste
material
0. Burning of fossil fuels
and combustible solid
wastes
-8. Airborne dust which:
Darkens the sky
Impairs visibility
Creates hazardous driving
and flying conditions
Coats buildings, vegeta-
tion, machinery, mine
and mill structures
Discolors all it falls on
Shortens the operational
life of equipment
Causes respiratory diseases
Creates uncomfortable and
unhealthy working and living
conditions
Smothers and/or poisons
vegetation and those who
feed upon it
Degrades land and aesthetic
values
Pollutes bodies of water
upon which it falls
9. Inundation of surrounding
lands, blockage of nearby
drainages and roads
10. Emission of smoke and other
particulate matter
-------
APPENDIX A-1-15
Table A-1-6
(Continued)
Nature of
Pollutants
Causes
Deleterious
Effects
Gases
Combustion of fossil
fuels and other burnable
solid wastes
Slacking of spoils and
oxidation of pyritic
and carbonaceous
wastes
Smelting of mine run
ores
1. -3. Emission of noxious
and toxic gases:
Sulfur dioxide
Hydrogen sulfide
Carbon monoxide
Carbon dioxide
Hydrocarbons
Nitrogen oxides
Fluorides
Chlorine
Ammonia
These emissions combine
in photochemical reactions
to produce smog, sulfuric
acid, and nitric acid mists
In turn, caustic pollutants
create:
Haze
Corrodes paint and metals
Poisons vegetation
Creates unhealthful living
and working conditions
Contributes to lung cancer
and other respiratory
diseases
Degrades aesthetic and
property values
-------
APPENDIX A-1-16
Table A-l-7
Sulfur Oxide Generation and Recovery in Western Smelters
Type of Smelter
Copper Smelters
Zinc Smelters
Lead Smelters
All Smelters
Generated
(long tons)
1, 565, 000
440, 000
160.000
2, 165,000
Recovered
(long tons)
284, 000
165,000
42, 000
491, 000
Percent
Recovered
18. 1
37.5
26. 3
22.7
Another serious source of mineral-industry-related
air pollution is that generated by the numerous burning
coal refuse banks. This condition results in the emission
of smoke, dust, and poisonous and noxious gases which,
in many instances,have proven fatal to surrounding human
and vegetative life. The amount of identifiable gases
taken from a burning coal refuse bank are listed in
Table A-1-8. The Bureau of Mines has located and
identified 291 burning banks, and 237 outcrop and mine
fires in the United States (See Table A-1-9).
-------
APPENDIX A-1-17
Table A-1-8
Analysis of Air Samples Taken from Two
Boreholes in a Burning Coal Refuse Bank
Gases Identified
Percent of Gas Present
Oxygen, 02
Carbon Dioxide, C02
Carbon Monoxide, CO
Ammonia,
Nitrogen*
7.6 1.0
10.55 20.3
2.15 1.05
0.23 1.01
79.47 76.64
* Determined by substracting percent of other gases from !00.
The location of the refuse sites frequently magnifies
the serious effects from excessive concentration of these
gases. Flames, thermal waves, smoke, fumes or a com-
bination of all these characteristics were observed at the
292 burning coal waste piles. Of these, 260 banks are
located less than five miles from a community of 200 and
13 coal heaps were less than one mile from these popu-
lated areas (Reference 6). A further delineation of the
population of communities to burning coal waste piles is:
Snrroundine Population
Number of Banks (each bank)
138 less than 1,000
123 1,001 - 10,000
25 10,001 - 100,000
6 more than 100,000
-------
Table A-1-9
Environmental Damage of Underground and Surface Mining
Sum
Alabama
Alaska
Arizona
Aikimii
California
Colorado
Connecticut
DeUwuc
Florida
Ceoigia
Hawaii
Idaoh
lUinoa
Indian
lowi
Kanui
Kentucky
Louraana
Maine
Maiybnd
Manachuietii
MKhopn
Mmnoou
Mmmippi
Mauoun
Monlana
Nebraska
Nevada
New Hampthue
New Jersey
New Mexico
NewYoik
NoclhCanUna
North Dakota
Ohio
Oklahoma
Oregon
Penny Ivum
Rbodcldand
South Carolina
South Dakota
Tennenee
Texai
Utah
Vermont
Virginia
WutunglDn
Wat Vupna
WBCOQIID
Wyoming
TOTAL
No. of Barnuf
Coal Refuse
Banb
6
15
4
29
3
6
1
74
4
17
1
132
151
No. of Outcrop and
Underground
MneFma
1
8
18
4
2
39
10
7
6
82
1
17
2
1
16
_2L
237
No. of Canmuniliej
Undermined
1
2
4
6
6
14
22
6
23
2
2
II
6
56
3
2
6
3
I*
21
2
10
1
2
19
10
9
2
292
Acciunubled Miami
Solid Wain
(miUwu of tonf )
161 3
364
382
437 S
334.5
117
73
20
25
78
01
02
96.0
28.5
2441
3142
67.9
87
192.0
1058
12
6.9
477
15.9
II 3
3.2
2.201 1
AcmorURKcUmed
Surface Mined Landi
(dMuondi)
830
69
4.7
166
1079
402
1 1
3.5
143.5
I3J
• •
307
887
276
35.5
50.0
79.2
172
21 j6
181
250
264
7IJ
23.7
43.7
19.6
I6.S
204
5 1
210
20
50.2
22J
229
171.6
222
18.2
229J
22
I9J
25.3
62J
136.4
34
4.2
377
5.5
1114
274
LL
2.0406
Acres of Uke>«POtldi
Affactadby
Surface Muuaj
16.300
200
74
600
100
200
390
500
SO
100.000
100.000
72
2.460
J.600
300
6400
2
100
120
58
2.020
9.275
100
4^83
Trace
fi
2!
d
oo
•Coal mina may underlie aome urban ueu m the anitheaitern poruon of the Stile
••Ua than 1.000 aero
-------
APPENDIX A-1-19
Table A-1-10 details the amount of accumulated
mineral industry solid waste (Reference 7).
4. Associated Hazards
The environmental hazards associated with wastes
derived from the mining and processing of mineral ores
are numerous, and are found throughout the entire process.
Some of these hazards are as follows:
Dust—This hazard accompanies every mining
process and is responsible for uncomfortable,
dirty, and hazardous working conditions. It
fills and blackens the lungs of mine and mill
employees. The resultant respiratory ailments
are known as emphysema, black lung, silicosis,
miners' lung, etc. Symptoms include loss of
strength and vitality, inability to work,
family hardships, and death. Dust concen-
trations in a small closed area are also
subject to disasterous explosions.
Waste Banks—Waste banks constitute a variety
of hazards to people and the environment, de-
pending on the wisdom displayed in the choice
of sites. Many banks block small valleys or
are being used to retain settling ponds.
Flooding causes erosion and failure of the
banks, ehdangering those who inhabit the
vicinity of the waste. In many instances waste
banks exceed the natural angle of repose for
proper stability. The type of material deter-
mines the limits to this angle of repose. The
effects of gravity strain the banks, the addition
of water provides an increase in weight and acts
as a lubricant, and when these effects exceed
the limits of waste banks, dangerous slides
may occur. Slides are also caused when people
remove portions of the material for other uses,
thus upsetting the bank stability.
-------
APPENDIX A-1-20
Table A-l-10
Tonnage and Acreage of Accumulated
Mineral Industry Solid Wastes
State
Alabama
Alaska
Arizona
Arkansas
California
Colorado
Connecticut
Delaware
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
Oregon
Pennsylvania
Rhode Island
South Carolina
South Dakota
Tennessee
Texas
Utah
Vermont
Virginia
Washington
West Virginia
Wisconsin
Wyoming
Antimony
Tons Actes
(mfllioni)
O.S 20
Asbestos
Tons Acres
(mfllioni)
30.0 180
5.4 42
Buiite
Tons Acres
(mOHoni)
8.0 56
2.0 400
96.0 430
0.2 5
4.0 30
1.2 80
Bauxite
Tons Acres
(fnfllkuu)
23.8 134
Beryllium
Tons Acres
(millions)
0.8 200
-------
APPENDIX A-1-21
Table A-1-10
(Continued)
State
Alabama
Alaska
Arizona
Arkansas
California
Colorado
Connecticut
Delaware
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
Oregon
Pennsylvania
Rhode Island
South Carolina
South Dakota
Tennessee
Texas
Utah
Vermont
Virginia
Washington
West Virginia
Wisconsin
Wyoming
Boron
Tom Acres
(millions)
76.0 600
day
Tons Acres
(millions)
18.0 475
9.2 70
Coal
Tons Ad
(millions)
164.0
6.5 1<
0.2
5.2
0.2
222.4
62.8
12.3
157.9
0.1
0.3
22.2
0.8
J
d
!=
3.1 :
i
e
a
84.4 £
1.9 "e
0.1 g
248.4 3
•q
2.3
10.4
49.4
10.0
428.8
res
55
»
•
n
P
Copper Diatomite
Tons Acres Tons Acres
(millions) (millions)
13.6 302
4764.0 20,500
30.0 1,100 64.0 740
2.0 90
1.5 7
431.0 1,150
930.0 5,600
1346.0 9,000 11.5 85
867.0 4,035
0.8 15 75.5 825
0.4 35
3.0 100
2930.5 10.732
12.5 140
-------
APPENDIX A-l-22
Table A-1-10
(Continued)
SUte
Alabama
Alaska
Arizona
Arkansas
California
Colorado
Connecticut
Delaware
Florida
Georgia
Hawaii
Idaho
Illinois
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maine
Maryland
Massachusetts
Michigan
Minnesota
AtlSSlSSIppl
Missouri
Montana
Nebraska
Nevada
New Hampshire
New Jersey
New Mexico
New York
North Carolina
North Dakota
Ohio
Oklahoma
Oregon
Pennsylvania
Rhode Island
South Carolina
South Dakota
Tennessee
Texas
Utah
Vermont
Virginia
Washington
West Virginia
Wisconsin
Wyoming
Feldspv
Tons Acres
(millions)
3.3 24
6.S 500
0.1 2
Fluorspar
Ton Acres
(millions)
2.3 120
2.0 40
3.5 • 350
Gold
Tons Acres
(mfllioni)
161.3 228
34.0 2200
122.0 840
78.7 2715
2.8 120
12.0 1500
196.0 865
6.3 520
S.S 200
98.4 960
6.9 60
4.2 175
Gypsum
Tons Acres
(millions)
16.5 100
3.8 40
Iron & Steel
Tons Acres
(millions)
188.6 696
86.7 640
20.2 121
34.5 120
4.5 45
84.7
32.5
182.2 1326
389.7 5195
6.0 60
28.5 840
12.5 15
1.0 50
290.6 1218
193.4 1510
314.8 1738
23.2 10
28.8
22.0 58
3.1 14
32.0 25
6.0 35
28.5 280
-------
APPENDIX A-l-23
Table A-1-10
(Continued)
State
Alabama
Alaska
Arizona
Arkansas
California
Colorado
Connecticut
Delaware
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
Oregon
Pennsylvania
Rhode Island
South Carolina
South Dakota
Tennessee
Texas
Utah
Vermont
Virginia
Washington
West Virginia
Wisconsin
Wyoming
Lead-Zinc-Silvei
Tons Aczes
(millions)
640.0 2000
9.3 85
330.0 5500
153.5 3160
17.1 349
25.0 2250
42.0 4600
45.9 2160
16.2 485
101.8 5210
7.2 148
12.0 70
53.8 2385
22.5 250
Magnetite
Ton* Acres
(millions)
15.0 90
7.0 200
Manganese
Tons Acres
(millions)
2.0 40
0.3 30
3.4 100
7.9 35
2.3 600
Mercury
Tons Acres
(millions)
0.1 30
21.0 420
0.3 10
1.7 50
1.2 110
Mica
Tons Acres
(millions)
Amount Unknown
5.4 45
-------
APPENDIX A-1-24
Table A-l-10
(Continued)
State
Alabama
Alaska
Arizona
Arkansas
California
Colorado
Connecticut
Delaware
, 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
Oregon
Pennsylvania
Rhode Island
South Carolina
South Dakota
Tennessee
Texas
Utah
Vermont
Virginia
Washington
West Virginia
Wisconsin
Wyoming
Molybdenum
Tons Acns
(millions)
249.5 BOS
68.0 849
Miscellaneous
Tons Acres
(millions)
161.3
161.3 228
36.4 2295
38.2 215
437.5 3780
334.5 4180
12.2 478
7.3 450
2.0 40
2.5 100
7.8 114
0.1 2
0.2 6
96.0 430
28.5 1665
244.1 1232
314.5 3580
67.9 405
8.7 69
18.2 460
192.0 2553
105.8 1680
1.2 80
6.9 60
49.6 344
19.4 243
11.4 395
3.2 63
Nickel
Tons Acns
(millions)
11.5 150
Potash
• Tons Acns
(millions)
233.8 1143
Phosphate
Tons Acres
(millions)
3.4 56
1.4 22
488.8 7566
47.0 230
9.6 158
5.5 91
1.4 22
3.5 58
2.6 42
1.8 80
3.1 774
1.1 18
38.6 590
7.3 121
1.4 20
0.1 10
-------
APPENDIX A-1-25
Table A-l-10
(Continued)
State
Alabama
Alaska
Arizona
Arkansas
California
Colorado
Connecticut
Delaware
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
Oregon
Pennsylvania
Rhode Island
South Carolina
South Dakota
Tennessee
Texas
Utah
Vermont
Virginia
Washington
West Virginia
Wisconsin
Wyoming
Stone
Tons Acres
6.4 25
73.0 360
2.5 100
7.8 114
0.1 2
0.2 6
4.9 75
192.0 2553
0.1 20
40.0 265
1.1 20
3.2 63
Tungsten
Tons Acres
0.3 25
15.0 45
3.7 510
3.7 300
0.9 40
3.9 35
Talc
Tons Acres
2.0 20
0.3 2
0.4 9
Titanium
Tons Acres
63.0 330
11.2 87
Vermiculhe
Tons Acres
12.0 20
-------
APPENDIX A-l-26
Table A-1-10
(Continued)
State
Alabama
Alaska
Arizona
Arkansas
California
Colorado
Connecticut
Delaware
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
Oregon
Pennsylvania
Rhode Island
South Carolina
South Dakota
Tennessee
Texas
Utah
Vermont
Virginia
Washington
West Virginia
Wisconsin
Wyoming
Grand Total
Tons Acres
(millions)
3526
3427
54768
766
10049
10244
696
923
27090
430
9441
13981
14
4888
581
22
7566
1068
2216
3378
2106
4425
587
200
373
2250
1579
55
171
91
235
326
6137
3915
35
2648
10355
2480
5229
58
5562
11170
18627
12454
125
15157
4264
213
15
11614
2028
927
2789
1037
369
9472
1528
5210
805
6844
2116
764
481
30319
954
843
676
4608
124
286
3360
1008
191
13315
660
366
1160
25
161
290
Remarks
-------
APPENDIX A-l-27
Waste Fires—Burning waste banks constitute
a case of potential instability during periods
of heavy participation. Permeating water is
converted in the presence of intense heat into
watergas, which can and sometimes does
explode violently, initiating debris slides.
In addition, if the waste material is on
fire, or thermally hot due to oxidation of
pyritic material, it presents a danger to people
in nearby communities. A number of tragedies
have occurred in the United States in connection
with waste bank fires (Table A-1-11). Burning
banks also produce local smog conditions and
contribute to living hazards as well as dangerous
driving and flying conditions.
2. INDIVIDUAL MINERALS
Wastes associated with the mining of metals are of great volume
for iron, copper, lead, zinc, and aluminum. Other important metals
with lesser waste problems also warrant consideration in the study of
waste, its control, and its subsequent effects on environmental
pollution. The metals discussed in this section are categorized as
follows:
SIC 101 Iron Ores
SIC 102 Copper Ores
SIC 103 Lead and Zine Ores
SIC 104 Gold and Silver Ores
SIC 105 Bauxite and Other Aluminum Ores
SIC 106 Ferroalloy Ores, Except Vanadium
SIC 109 Miscellaneous Metal Ores.
-------
APPENDIX A-1-28
Table A-l-11
Deaths and Accidents Attributed to Coal Waste Fires
(partial list)
Year
Location
Remarks
1928
1928
1940's
1940
1942
1946
1947
1950
1957(?)
1958
1960(?)
1960(?)
1966
Iowa
Iowa
Sagamore,
West Virginia
Lochgelly,
West Virginia
Oakwood,
Virginia
Virginia
Alabama
Mayberry,
West Virginia
Oakwood,
West Virginia
Sharpies,
West Virginia
Hemp Hill,
Kentucky
Rhoda,
Virginia
Amherstdale,
West Virginia
An explosion while excavating a coal
waste bank burned six men; three fatally.
An explosion while excavating a coal
waste bank burned eleven men; three
fatally.
Thirteen killed by an explosion of a burn-
ing coal refuse pile.
One killed by a slide while digging red dog.
Seven killed by an explosion and resultant
slide of a bank.
Burning refuse bank ignited coal seam.
Two killed by an explosion in the mine
while investigating the extent of the fire.
Two killed while excavating burning
refuse material.
One child killed by falling through surface
crust on a burning coal refuse pile.
Two killed by explosion while digging red dog.
Burning coal slide and covered mine opening;
all men were rescued 48 hours later.
Two killed by asphixiation after falling
into burning bank.
Two killed by bank slide.
Explosion and resultant blank slide injured
one child and destroyed several homes.
-------
APPENDIX A-l-29
(1) SIC 101—Iron Ores
1. Description
Iron is the second most abundant element comprising
about 5 percent of the solid rocks of the earth's crust. It
is the most useful of metals because of its abundance and
the ease with which it may be altered by adding small
amounts of other elements. The U. S. is a major con-
sumer of iron, requiring approximately 25 percent of
the world's supply and producing about 13 percent of that
supply.
2. Source and Production
The iron industry is widely distributed geographically.
However, most production is centered in four principal
areas: (1) Northeastern States of New York and Penn-
sylvania; (2) Lake Superior Region of Minnesota and
Michigan; (3) Western States of Montana, Utah, and
Wyoming; and (4) Southeastern States of Alabama and
Georgia. The mines in these areas, together with 13 other
states, were responsible for production of approximately
200 tons of crude ore in 1968, and processing took place in
18 of the states.
-------
APPENDIX A-l-30
In this period there were 109 operating iron ore
mines in the United States, 13 of which were underground.
There were 175 integrated steel plants, 483 steel foundries,
and 2.200 gray, malleable, and ductile iron foundries.
Ore production was valued at $800 million, and revenues
totaled $18. 652 million.
3. Industrial Consumption
In 1968 the domestic availability of iron approxi-
mated 186. 9 million short tons, utilized as follows:
Availability Article
Consumer SIC Codes (short tons) Use (%)
Transportation 371, 372, 373, 30.1 25
374
Construction 331, 343, 344 32.0 27
Products
Machinery and 35, 252, 342. 21; 4 17
Equipment 361-2, 364-9
Containers 341, 349 7.9 7
Oil and Gas 331, 353, 3443, 5.6 5
(pipe & equip.) 3586
Home appli- 251, 342, 363 6. 1 5
ance & equip.
Industry Stocks (as of 56. 3
12/31/68)
Exports 10. 6
Other 16.9 14
-------
APPENDIX A-l-31
4. Future Outlook
Domestic steel averaged about 100 million short tons
from 1964 through 1968; it is anticipated that there will be
an annual growth rate of between 1.0 and 1. 9 percent
compounded. This indicates that the projected demand for
iron for castings and steel finished products in the year
2000 will range between. 162 and 221 million short tons.
5. Waste Characteristics
Waste products are generated at each stage of the
steel conversion process; the most significant are mine
waste, mill tailings, and furnace slags. Wastes accumulated
by this industry up to 1968 exceeded 2 billion tons, covering
approximately 14, 000 acres of land, and is accumulating
at the rate of 157 million tons per year in a 21-state area.
A general breakdown in wastes includes:
Mine Waste—Waste developed during the
exploration, development, and mining of
ore deposits. Approximately 190 million
tons of mine waste, with an additional
500 million tons of lena ore found in 600
mine dumps, cover an estimated 6, 600 acres.
-------
APPENDIX A-1-32
Mill tailings—This reject material is of three
basic types: (1) clay, sand, and fine grained
iron minerals from washing plants; (2) coarse
and fine grained siliceous material from heavy-
media, jig, and magnetic processes; (3) rejects
from tocomite plants. Approximately 720 million
tons of this waste exists, covering about 8, 900
acres of land. The Lake Superior District is
responsible for 80 percent of this material.
Slag—The largest waste contributor in the iron
and steel industry is of two types. The first
type of slag is produced in the conversion of ore
into the metal by means of the blast furnace.
The waste products include metal slag, flue
dust, scrap metal, and gas. About a half-
ton of slag is produced per ton of pig iron.
The second type of slag is produced when
impurities are removed from the pig or scrap
to produce grade steel. This type is a lesser
problem than that generated by the blast furnace
(Reference 8).
Approximately 1 billion tons of slag from both sources
exist in piles covering over 3, 700 acres of land ; Pennsyl-
vania and Ohio account for 3, 000 acres of slag alone.
Flue dust from blast and steel furnace operations,
is another significant pollution source. It is anticipated
that it may exceed 3. 5 million tons per year (Reference 9).
6. Associated Hazards
Inhalation of iron and iron oxides produces a benign
siderosis (or pneumoniosis). In addition to the benign
-------
APPENDIX A-1-33
condition, there may be very serious synergistic effects
as well as other undesirable effects, such as chronic
bronchitis. In the laboratory, iron oxide acts as a vehicle
to transport the carcinogens in high local concentrations
to the target tissue. Similarly, sulfur dioxide is trans-
ported in high local concentrations deep into the lung by
iron oxide particles. The relationships between these
conditions and dose and time are undetermined. There
is no apparent evidence of animal or plant damage.
Soiling of materials by airborne iron or its com-
pounds may produce economic losses. For example, iron
particles seem to produce stains on automobiles, requiring
them to be repainted. Iron oxide participates may also
reduce visibility.
The results from the National Air Sampling Network
3
showed that iron concentrations ranged up to 22 Mg/m >
3
with an average of 1. 6 /Jg/m in 1964. The most likely
sources of iron pollution are from the iron and steel
industry. The validity of this conclusion has been
demonstrated by the decrease in iron concentration
during steel strikes as well as by analysis of iron in the
-------
APPENDIX A-1-34
stack emissions. The iron pollution may be controlled by
particulate removal equipment, such as electrostatic
percipitators, venturi scrubbers, and filters.
Air pollution control cost the steel industry
approximately $102 million in 1968. Fume control
equipment costs for basic oxygen furnaces range between
$3 and $7.5 million. This represents 14 to 19 percent
of the total plant cost. Operating costs average $0.15 to
$0. 25 per ton of steel.
Further studies are suggested in the following areas:
The role of iron and its compounds in carcino-
genesis, especially at the low concentrations
observed in the atmosphere.
The role of iron and its compounds as syner-
gistic agents with other air pollutants (such
as sulfur dioxide) from at least two viewpoints:
catalytic oxidation of pollutant in air and
transport of pollutant into the lungs.
The soiling characteristics of iron and its
compounds as related to particle size, con-
centration, and chemical composition.
-------
APPENDIX A-1-35
(2) SIC 102—Copper Ores
1. Description
Copper is one of the first metals used by humans
because of its natural availability and the ease with which
it can be worked to fashion utensils and weapons of lasting
quality. Although the metal has a wide distribution in
nature, there are relatively few large copper-producing
areas in the world. The most important of these areas
include: (1) Western United States; (2) Northern Michigan;
(3) Western Canada; (4) West Slope of the Andes, Peru,
and Chile; (5) Zambia and the Congo in Africa; and
(6) Urul Mountains and Kazakston, Russia.
2. Source and Production
The United States has been the largest copper-pro-
ducing country since 1883. Approximately 91 percent of
domestic copper is produced in five Western States:
Arizona, Montana, Nevada, New Mexico, and Utah, the
remaining 9 percent is obtained from Michigan and
Tennessee. In 1968, 25 mines accounted for 95 percent
of the U.S. copper output, which was processed in 19
-------
APPENDIX A-1-36
smelters. The major U.S. companies are vertically
integrated and have mining, smelting, refining, and
fabricating facilities and marketing organizations.
3. Industrial Consumption
In 1968 the domestic availability of copper approxi-
mated 3, 615 thousand short tons, utilized as follows:
Availability
Consumer SIC Code (short tons) % Used
Electrical Equip- 36 1,375 50
ment & Supplied
Construction 15, 16 445 16
Industrial Machinery 35 280 10
(except elect.)
Transportation 37 335 12
Ordnance 19 172 6
Misc. (Jewelry, Chemi- 204 7
cal Pigments etc.)
Industry Stocks (as of 563
12/31/68)
Exports 241
Copper ore processing accounts for important
quantities of gold, silver, molybdenum, nickel, selenium,
tellurium, and arsenic, as well as iron, lead, zinc, and
sulfur.
-------
APPENDIX A-1-37
4. Future Outlook
In 1968 the world demand for copper continued high.
In the U.S. the total demand for copper was only slightly
above that of 1967 (2, 811 thousand short tons and a total
supply of 3, 615 thousand short tons). Gains were made in
foreign demand. It is anticipated that the average annual
growth rates between 1968 and the year 2000 will range from
3.7 to 5.2 percent, which amounts to a demand in year 2000
of between 7.6 million to a high of 15.7 million tons.
5. Waste Characteristics
The copper production industy is considered to be
the largest single source of solid waste because of the
copper ore-metal yield ratio 130:1. This means that 99
percent of raw ore is rejected as waste, or about 170
million tons in 1968. Montana, Nevada, Utah, Arizona,
New Mexico, and Michigan are the principal producers,
and smelters in those states provide 40 percent of
domestic refining capability.
-------
APPENDIX A-1-38
The copper wastes, composed of mine waste, mill
tailings, and smelter slags, now total 11. 3 billion tons
of waste, occupying 52, 000 acres of land. These wastes
accumulate at a rate of 492. 6 million tons annually.
A general breakdown of copper wastes include:
Mine Waste—Accounts for 54 percent of total
waste generated largely from open pit operations
in the five Western States. Improved leaching
techniques will permit reprocessing of some
of this ore for copper and by-products. This
waste covers almost 23, 000 acres of land.
Mill Tailings—Five billion tons of this type
of waste is impounded on over 28,000 acres of
land surface.
Copper Slag—Approximately 146 million tons
of copper slag is presently disposed upon an
area covering 1,400 acres.
(3) SIC 103—Lead and Zinc Ores
LEAD ORES
1. Description
Lead is one of the oldest metals used by man, and
many of the ancient applications have persisted through to
the present time. It is a soft, heavy metal, malleable but
-------
APPENDIX A-l-39
only slightly ductile, and is the most corrosion resistant
of any of the common metals. Lead is widely used,alloyed
with other metals. In tonnage produced.it ranks fifth be-
hind steel, aluminum, copper, and zinc respectively.
2. Source and Production
Lead ores are derived from underground mining
methods and beneficiated at mine sites. The concentrates
are shipped to smelters and refineries for processing.
During 1968 lead ores provided 64 percent of primary
domestic lead, lead-zinc ores 26 percent, zinc ores 4
percent, and all other ores 6 percent. Missouri produced
60 percent, Idaho 14 percent, Utah and Colorado 13 per-
cent each. The domestic requirements are supplied
from domestic mine production, imported ore, imported
metal, and domestic secondary.
3. Industrial Consumption
In 1968, the domestic availability of lead approximated
1. 636 thousand short tons, utilized as follows:
-------
APPENDIX A-1-40
Availability
Consumer ! SIC Code (short tons)
i
Transportation 3691, 2911 762
General Building I 1511, 3432. 3341 250
Construction
Small Arms Ammunition 146 81
i
Packaging 3341, 3446 60
Communication equipment 366 87
Printing & publishing 27 32
Industry stocks 12/31/68 179
Exports 8
Other 177
The transportation industry was the major consumer
of lead in 1968, accounting for 53 percent of the total de-
mand. Most of this 53 percent was used in the manufacture
of batteries and 18 percent was used as an additive for
gasoline. Construction required 17 percent, although this
area of lead use is declining. The communication indus-
try is on the decline as a lead user. A slight increase in
the use of lead is found in the small arms ammunition
industry. The use of lead in packaging and publishing is
declining, while the miscellaneous demand remains rather
stable.
4. Future Outlook
The demand for lead in the United States in 1968 was
1,449 thousand short tons. The projected outlook for lead
-------
APPENDIX A-1-41
demand in the year 2,000 shows an average growth rate
of 1.8 to 3.4 percent between 1968 and 2000. This would
show a demand range between 2. 52 to. 4. 4 million tons
of lead, and indicates an increase in each industry
producing end products of lead.
ZINC ORES
1. Description
The ores of zinc were used for making brass for
centuries before it was recognized as a metal in 1746.
It is a bluish-white metal, brittle at ordinary tempera-
tures, but malleable at 100°C. The properties of
being chemically active and alloying readily with other
metals are utilized industrially in preparing a large
number of zinc-containing alloys and compounds.
2. Source and Production
Most zinc is mined using underground mining
methods, principally classed as open shrinkage, cut and
fill, or square set stopping methods. There are 23 mines
classified as zinc mines, 124 as lead-zinc mines, and 60
-------
APPENDIX A-1-42
as lead mines. Oklahoma has the largest number of mines,
47, followed by Idaho with 34, and Colorado with 25.
Tennessee, the leading producing state has 6 large mines.
Twenty-one states produce zinc, with Tennessee producing
more than 20 percent. New York, Idaho, Colorado, and
Pennsylvania together with Tennessee produce more than
60 percent. A total of 7 companies produce more than
75 percent of domestic slab zinc output.
3. Industrial Consumption
In 1968 the domestic availability of zinc approximated
1, 959 thousand short tons, utilized as follows:
Availability
Consumer SIC Code (short tons) % used
Construction 15,16 340 19
Transportation 37 400 23
Electrical equipment 36 210 12
& Supply
Plumbing and heating 3432, 3433 240 13
Industrial Machinery 35 160 9
(exclud. elect)
Pigments & Compounds 2816, 2819 220 13
Rolled zinc, dry cells 2752,3692 50 11
Industry Stocks (as of 12/31/68) 165
Exports 33
Other 141
-------
APPENDIX A-l-43
4. Future Outlook
The 1968 demand in the United States for lead metal
amounted to 1, 761 thousand short tons. The projected
outlook for zinc requirements in the year 2000 is based on
forecasted annual growth rates of between 1. 1 percent to
3. 1 percent, converted into a projected zinc demand of
between 2. 46 million tons to 4. 7 million tons as compared
to the 1968 demand.
5. Lead Zinc Wastes Characteristics
It is estimated that, since the advent of lead-zinc
mining in the U.S., this industry has accounted for more
than 1. 5 billion short tons of crude ore, containing 35. 2
million tons of zinc and 31. 6 million tons of lead. The
three categories (1) mine waste, (2) jig and flotation mill
tailings, and (3) refining slag, accounted for 93 percent
of the total solid waste covering 45 square miles of
surface area (see Table A-1-12).
Mine Waste—There is presently approximately
700 million tons of boulder piles and rock
dumps covering 15,000 acres associated with
lead-zinc mines. At the current production level,
an estimated 3. 5 million tons of mine waste will
be added annually. Some waste piles 40 years
-------
APPENDIX A-1-44
Table A-1-12
Estimated Magnitude of Solid Waste Accumulations
for Lead-Zinc-Silver
State and Type
of Solid Waste
Arizona
Mine waste
Mill tailings
Smelter slag
California
Mine waste
Mill tailings
Smelter slag
Colorado
Mine wastes
Mill tailings
Smf^lt^r* Q! A a
hJAAA^ ALCA. 0 XCLC*
Idaho
Mine -mill-smelter
Illinois -Wisconsin
Mine waste
Mill tailings
Smelter slag
Kansas
Mine waste
Mill tailings
Smelter slag
Missouri
Mine waste
Mill tailings
Smelter slag
Montana
Mine -mill-smelter
Accumulated
through 1968
( thousand tons i
319,000
319,000
2,000
2,300
6,000
1,000
275, 000
55, 000
153,450
1,000
16,050
18
3, 730 [
21. 220 j
8, 860[
33, IIOJ
45, 900
Acres
1, 100
700
200
30
50
5
5, 000
500
3, 160
25
320
4
2. 250
4,600
2, 160
-------
APPENDIX A-1-45
Table A-1-12
(Continued)
State and Type of
Solid Waste
New Mexico
Mine waste
Mill tailings
Smelter slag
New York
Mine waste
Mill tailings
Smelter slag
Oklahoma
Mine waste
Mill tailings
Smelter slag
Pennsylvania
Mine waste
Mill tailings
Smelter slag
Tennessee
1YJT ' 4.
ivime waste
Mill tailings
O It- f* 1 M *w
omeiter siag
Texas
Smelter slag
Utah
Mine waste
Mill tailings
Smelter slag
Washington
Mine waste
Mill tailings
O «-kl4> n 1 n «-*
omeiter siag
Total
Accumulated
through 1968
(thousand tons)
1. 000
15, 000
200
1,190)
100, 570 [
)
7, 150
12, 000
28, 700
14, 500
10,600
2,500
20, 000
1,476,048
Acres
8
465
12
5,210
148
70
1,840
345
200
50
200
28,652
-------
APPENDIX A-l-46
old still do not support vegetation due to
sulfur contents. This pollutant limits the
reclamation of mine wastes.
Jig and Flotation Tailings— Lead and zinc
ores are crushed and ground to permit recovery
of metals. To date there are in existence
740 million tons of mill wastes covering
13, 000 acres. Siliceous dust from dry lead
zinc tailing ponds menaces health and comfort
of nearby communities. Again sulfide contents
limit the reclamation of mill tailing wastes.
Slag— Production of lead and zinc metal has re-
sulted to date in nearly 32 million tons of smelt er
wastes, covering approximately 2, 500 acres of
the earth's surface. Most slag is being retreated
at fuming plants to recover additional lead and
zinc. Slag wastes are accumulating at a rapid
rate as shown in Table A-1-12.
6. Associated Hazards
It is not possible to assess fully the role of zinc and
its compounds as air pollutants. Despite the fact that
specific effects attributable to certain compounds of zinc
have been noted, the common association of zinc with other
metals, and the frequent presence of toxic contaminants
(such as cadmium) in zinc materials, raise questions which
have yet to be answered concerning the synergistic effects
of these metals.
-------
APPENDIX A-1-47
The most common effects of zinc poisoning in humans
are nonfatal metal-fume fever, caused by inhalation of
zinc oxide fumes, and illnesses arising from the ingestion
of acidic foods prepared in zinc-galvanized containers.
Zinc chloride fumes, though only moderately toxic, have
produced fatalities in one instance of highly concentrated
inhalation. Zinc stearate has been mentioned as a possible
cause of pneumonitis. Zinc salts, particularly zinc chloride
produce dermatitis upon contact with the skin.
Accidental poisoning of cattle and horses has occurred
from inhalation of a combination of lead- and zinc-
contaminated air. Zinc oxide concentrations of 400 to 600
/ig/m3 are toxic to rats, producing damage to lung and
liver, with death resulting in approximately 10 percent of
the cases. Although dogs and cats tolerate high concentrations
(up to 1, 000, 000 j*g/day) of zinc oxide for long periods,
glycosuria and damage to the pancreas may result.
3
Concentrations of 40,000 to 50,000 ng/m of zinc ammonium
sulfate produce no appreciable effects on cats.
-------
APPENDIX A-1-48
Some evidence exists of damage to plants from high
concentrations of zinc in association with other metals.
No information was found on damage to materials from
zinc or its compounds in the atmosphere.
The primary sources of zinc compounds in the
atmosphere are the zinc-, lead-, and copper-smelting
industries, secondary-processing operations which re-
cover zinc from scrap are brass-alloy manufacturing and
reclaiming, and galvanizing processing. Average annual
production and consumption of zinc in the U.S. have
increased steadily during this century, and it is predicted
that this trend will continue. As the emission of zinc into
the atmosphere, in most of these operations, represents an
economic loss of the zinc material, control procedures are
normally employed to prevent emission to the atmosphere.
In those industries where zinc is a by-product, control
procedures for zinc are not as effective, and greater
quantities of zinc therefore escape into the environment.
Measurement of the 24-hour average atmospheric
concentrations of zinc in primarily urban areas of the
g
United States reveal an average annual value of 0. 67 pg/m
-------
APPENDIX A-1-49
for the period 1960-1964; the highest value recorded during
g
that period was 58.00 pg/m , measured in 1963 at East
St. Louis, Illinois.
Extensive air pollution abatement methods are in
general use by the zinc industry. Control devices include
precipitator scrubbers, baghouses, and collectors. The
efficiency of the various control methods varies widely.
However, in many instances air pollution control devices
are not used in the general metals industries. Thus, at
present, relatively large quantities of zinc or zinc compounds
are still being emitted into the atmosphere by industrial
plants processing zinc or other compounds containing zinc.
No information has been found on the economic costs of
zinc air pollution or on the costs of its abatement.
Limited means are available for the determination of
concentrations of zinc in the ambient air. These methods
of analyses, however, are not considered adequate for air
pollution monitoring purposes since they do not effectively
discriminate between the zinc and other metals and they
lack sensitivity.
-------
APPENDIX A-1-50
Further studies are suggested in the following areas:
Determination of whether zinc acts either as
an individual air pollutant exerting specific
effects or as a co-pollutant exerting synergistic
effects, or has no adverse effects.
Determination of which zinc compounds are
present as pollutants in the environmental air,
together with the manner in which—and extent
to which—these substances effect human,
animal, and plant life.
(4) SIC 104—Gold and Silver Ores
GOLD
1. Description
Gold is widely distributed, mostly in the metallic
state, and is one of the first metals used by man. It is
the most malleable and ductile, and also one of the softest
of metals. It is a good conductor of electricity and heat,
and is not affected by air and most reagents.
2. Source and Production
At the present time about two-thirds of the gold
produced comes from gold ore and placer mines. The
remaining third is recovered from copper and other base
-------
APPENDIX A-1-51
metals. Three leading good producing mines—two gold mines,
and one copper mine—account for 75 percent of total output.
3. Industrial Consumption
The 1968 total domestic availability of gold was 45. 4
million troy ounces, with an industrial demand of 8 million
troy ounces, as shown in Table A-l-13. Major uses are
jewelry, precious metals, dental equipment, and elec-
tronic components.
4. Future Outlook
The projected annual growth rate for gold demand
between 1968 to the year 2000 has been set between 3. 4
and 4. 8 percent. This converts to a volume demand of
between 23. 1 to 36. 5 million troy ounces.
5. Waste Characteristics
Gold industry related wastes have accumulated to a
point where 15 square miles of land have been covered.
The breakdown is as follows:
Mine waste - 327 million tons, covering
4, 668 acres
-------
APPENDIX A-1-52
Table A-l-13
Estimated Magnitude of Solid Wastes Accumulations from Gold
State and Type
of Solid Waste
Alaska
Mine waste
Mill tailings
omtriLci axdg
Total
Arizona
Mine waste
Mill tailings
Smelter slag
Total
California
Mine waste
Mill tailings
Smelter slag
Total
Colorado
Mine waste
Mill tailings
Smelter slag
Total
Idaho
Mine waste and
Mill tailings
Smelter slag
Total
Montana
Mine waste and
Mill tailings
Smelter slag
Total
Accumulated thru 1968
Tons Acres
(thousands)
67, 300 108
94,000 120
161,300 228
22, 000 1, 200
10,000 800
2, 000 200
34, 000 2, 200
32, 000 200
90, 000 640
122,000 840
26, 000 1, 200
47,650* 1,315
5, 000 200
78,650 2,715
2,800 120
2,800 120
12, 000 1, 500
12,000 1,500
1967
ions
(thousands)
Insignificant
Less than
1, 000 tons
Insignificant
NA
NA
Acres
NA = Not Applicable
* = Data includes 16 million tons of tailings covering 215 acres at
Old Golden Cycle Mill, later used for residential complex.
-------
APPENDIX A-l-53
Table A-l-13
(Continued)
State and Type
of Solid Waste
Nevada
Mine waste
Mill tailings
Smelter slag
Total
New Mexico
Mine waste
Mill tailings
Smelter slag
Total
Oregon
Mine waste
Mill tailings
Smelter slag
Total
South Dakota
Mine waste
Mill tailings
Smelter slag
Total
Utah
Mine waste
Mill tailings
Smelter slag
Total
Washington
Mine waste
Mill tailings
Smelter slag
Total
Accumulated thru 1968
Tons
(thousands)
#$
149, 000
47, 000
196,000
5, 000
1, 000
250
6,250
500
5,000
5,500
20, 000
72, 240
6, 190
98,430
2,300
4,600
6,900
750
3,400
4, 150
Acres
615
250
865
100
400
20
520
100
100
200
250
695
15
960
35
25
60
50
125
175
1967
Tons
(thousands )
7,000
1, 300
8, 300
Insignificant
1, 000
1, 000
400
400
Insignificant
200
200
Acres
21
6
27
20
20
2
2
**Includes about 125 million tons from open-pit operations.
-------
APPENDIX A-1-54
Tailing waste - 384 million tons,
covering 5, 280 acres
Smelter slag - 13 million tons, covering
covering 435 acres.
SILVER
1. Description
Silver normally occurs in deposits associated with
other metals, such as copper, lead, zinc, and gold. It
is pure white with a brilliant luster, a little harder than
gold but only slightly less malleable and ductile.
2. Source and Production
In 1968, about two-thirds of the domestic silver output
came from ores mined chiefly for copper, lead, and zinc.
The remaining third was recovered from ores in which
zinc was the principal metal. Half the domestic supply
came from seven mines in the Coeurd'Alene mining
district in the Idaho panhandle. Other source areas
include Utah, Arizona, and Montana.
-------
APPENDIX A-1-55
3. Industrial Consumption
The 1968 total domestic availability of silver was
628. 8 million troy ounces, with a demand of 182.1 million
troy ounces. The heaviest consumers of silver are silver-
ware and silver plate, photographic equipment, coinage,
with jewelry, refrigeration, household appliances,
batteries, switchgear, etc., using somewhat lesser
amounts.
4. Future Outlook
The projected annual growth rate for silver demand
in the period 1968 to 2000 is 1.4 to 3. 6 percent, which,
when translated to volume, amounts to between 280 to
560 million troy ounces.
5. Waste Characteristics
The silver wastes together with lead and zinc wastes
are shown in Table A-1-12 (see page A-1-44).
-------
APPENDIX A-1-56
(5) SIC 1QS Bauxite and Other Aluminum Ores
1. Description
Aluminum is the most abundant metallic element
in the earth's crust, and ranks third among the elements.
However, it does not appear in a free state. It is found
as the silicate in clays, feldspars, etc., while the com-
mercial ore at present is bauxite, an impure hydrated oxide.
It ranks second among metals in the scale of malleability,
and sixth in ductility. The oxide, alumina, occurs
naturally as ruby, sapphire, corundum, and emery, and is
very hard, ranking next to the diamond. The use of alu-
minum exceeds the use of any other metal in quantity or
value except steel, and its growth rate has been about
three times as great as other metals.
2. Source and Production
The U.S. is the leading producer of aluminum,
producing 37 percent of the 1968 world total. About 95
percent of the bauxite produced domestically comes from
Arkansas, and is processed into alumina at the mines.
The remainder comes from Alabama and Georgia. In addition.
-------
APPENDIX A-1-57
approximately 86 percent of the bauxite consumed
annually in the U. S. is imported primarily from Jamaica
and Surinam. Alumina produced in 1968 at eight plants
located in Alabama, Arkansas, Louisiana, and Texas,
amounted to 6. 4 million tons, requiring 13. 2 million tons
of bauxite and over 6. 5 million tons of alkaline mud waste.
Reduction plants more widely dispersed include Oregon
and Montana (10 plants); West Virginia, Ohio, and Indiana
(3 plants); Tennessee, Alabama, and North Carolina
(4 plants); and New York (2 plants). Three of the largest
aluminum companies account for 76 percent of primary
aluminum in 1968. The remaining five domestic producers
of primary metal also own finished aluminum product
facilities.
3. Industrial Consumption
In 1968 the domestic availability of aluminum metal
approximated 6, 954 thousand short tons, utilized as
follows:
-------
APPENDIX A-1-58
Availability
Consumer SIC Code Jshort tonsj %_TJsed
General Building
Contractors
Motor Vehicles
Aircraft Parts
Ship & Boat Bldg
and repair
Railroad Trans.
Electrical Equip.
and supplies
Fabricated Metal
Prods.
Machinery (except
electric)
Metal Cans.and
containers
Highway & Street
Construction
Other Manufacturing
Abrasives aluminous
Chemical & Allied
products
Non Clay refractories
Industry Stocks (as of 12/31/68)
Exports
Aluminum is in competition with copper, steel,
tinplate, magnesium, lead, wood, plastics, and fiberglass.
1511
371
372
373
40
36, 3352
34
35
3411
1611
399
3291
28
3297
'31/68)
1,000
670
165
20
18
600
470
310
460
60
530
80
160
162
1,441
808
23
10
4
3
3
14
11
14
11
1
2
1
1
1
-------
APPENDIX A-1-59
4. Future Outlook
The 1968 demand in the U. S. for aluminum amounted
to 4,705 thousand short tons. The projected outlook for
aluminum requirements for the year 2000 is based on an
annual growth rate of between 5.1 percent and 7.4 percent.
This converts into a projected aluminum demand of between
21.2 million and 42 million tons.
5. Waste Characteristics
Each of the three types of bauxite (Jamaica, Surinam,
and domestic) used to produce alumina yields a waste with
significantly different physical and chemical properties
requiring different procedures for disposal. The Jamaica
and Surinam bauxite produces metal by the Bayer process,
where aluminum is dissolved from bauxite with caustic
soda. The residue "red mud" is retained in settling ponds.
The "red mud" from domestic bauxite retains appreciable
amounts of alumina, which is removed with lime and soda
ash (combination process). This residue, called "brown
mud", is also pumped into settling ponds.
-------
APPENDIX A-l-60
About 3. 6 million tons, of over 6. 5 million tons of
alkaline muds generated annually, are kept in ponds. The
remaining 2. 9 million tons are discharged into the
Mississippi River. Accumulation of muds over the last
20 years have increased by 8 percent per year (Table A-1-14).
Reclamation is difficult; however, 80 percent of the solids
can be filtered out of the mud wastes.
(6) SIC 106—Ferroalloy Ores. Except Vanadium
The following metals are included in this section:
Manganese
Tungsten
Chromium
Colbalt
Molybdenum
Nickel.
MANGANESE
1. Description
Mananese is a metal resembling chromium and iron,
and is essential for the economical production of cast iron
and steel. This use of manganese far exceeds any other use.
-------
Table A-1-14
Accumulated Mud Wastes from Alumina Refining
Type of
Muds
Red Muds
Alabama
Mobile
Total Alabama
Louisiana
Burn side
Baton Rouge*
Cramer cy*
Total Louisiana
Texas
LaQuinta
Point Comfort
Total Texas
Type of
Bauxite
Surinam
Surinam
Jamaica
Jamaica
Jamaica
(Jamaica)
(Surinam)
Brown Muds (including 15%-18% sand)
Arkansas
Bauxite
Hurricane Creek
Total Arkansas
Inoperative plants
Illinois
East St. Louis
Domestic
(Domestic)
(Jamaica)
(Surinam)
Surinam
Total Generated
Total Deposited in Mud Lakes
Accumulated 1942 - 65
(Thousand Tons)
Diy
Basis
6,500
6,500
1,000
^~
1,000
9,000
3,500
12,500
5,000
9,000
14.000
2,000
36,000
Wet
Settled
13.000
13,000
2,000
™~
2,000
22,500
8.750
31,250
8,300
15,000
23,300
4,000
73.550
Generated 1966 -67
(Thousand Tons)
Dry
Basis
1.000
1,000
430
2,120
1,260
3.810
1,880
1.820
3,700
650
1.120
1.770
10.280
6,900
Wet
Settled
2.000
2,000
860
~™
860
4,700
4,500
9,200
1.080
1,860
T940"
15,000
Accumulated 1942 -67
(Thousand Tons)
Diy
Basis
7^00
1,430
^~
1,430
16.200
15,770
2.000
42,900
Wet
Settled
15,500
2,860
" *
2,860
40.450
26,240
4,000
88,550
TJ
3
* Discharged into Mississippi Rivet
-------
APPENDIX A-1-62
2. Source and Production
The manganese industry in the United States proces-
ses mostly imported manganese ores, since less than 4
percent of the domestic manganese requirement is re-
covered from domestic ores. About 90 percent of the
ores are produced by 10 companies in 15 plants. The
domestic source of low grade ores include Montana,
Colorado, New Mexico, and Minnesota.
3. Industrial Consumption
In 1968 the total availability of manganese approxi-
mated 2, 357 thousand short tons, with a domestic demand
of 1, 180 thousand short tons (Table A-l-15). Nearly 25
percent of the manganese was consumed in production of
cast iron and steels; transportation, machinery and equip-
ment required 17 percent; home appliances, furniture
and pipes and tubing used 15 percent; chemicals, batteries
and other uses accounted for the rest of the manganese
demand.
-------
APPENDIX A-1-63
Table A-l-15
Industrial Consumption Chart
\
SK
15
16
28
29
32
33
34
35
36
37
281
331
334
342
344
353
354
363
371
372
373
2816
2819
2851
3111
3297
3471
3479
3541
3641
3722
V Fenoui
N. Minerdi
Description N.
Contraction (Balding)
Construction (Nonbattdlng)
Chem. And. Pigments etc.
PetroUum Refbuns
Ceramics
Primary Melds
ContaiiiMn
Machinery Nonetocl.
Machinoy BccL
Tfin ipof tstiop
MiK. Chem. Products
Boat Furnaces, Sled Worka
Secondary Smdtuig
Cutlery. Hand Tools
Fibtmtcd SttuctttfU trod.
Construct A Related Mach.
Metahvorkmg Machinery
Home Appliances A Equip.
Motor Vehicles A Equip.
Avenri Parts.
Shm A Boat Budding
Inorganic Pigments
Industnd Chemicals
Punt A Allied Products
Leather Pradu b
tmmin* rluuUCD
Non-day Refractories
Plaong of Melds
Coating A Engraving
Machine^ loota
Lamps
Ancraf I Eng. Parts
Industry Slacks
Exports A Other
Told
Manganese (1000 ST.)
59
see
(28)
651
15
273
1.180
179
2.357
fi
e
650*
2500*
2950*
8250*
.
"
950'
8.287
1.123
25.160
CIS 0001 )«inn«onD
75
1 n
\
85
28
16
see
(33)
22
see
(2816)
345
131
908
fi
300
3654
1576
849
1179
906
3.667
5.888
3.431
21.459
Molybdenum (MO. Ib)
4.5
234
1.4
165
37.9
39.9
1236
NKkd(Mulb)
20.6
(676
49
25 1
40.4
363
440
48.5
182
74.4
54.2
4784
•Eilimated
-------
APPENDIX A-1-64
4. Future Outlook
The projected annual growth rate for manganese
between 1968 and the year 2000 is averaged at 2.25 percent.
The demand volume of metal for the year 2000 is expected
to range between 1.8 and 2. 3 million tons.
5. Waste Characteristics
Solid wastes produced by the manganese industry to
date amount to approximately 15.8 million tons, covering
about 805 acres of land surface. An estimated 3 tons of
rock are derived from each ton of ore produced. Process or
concentrate tailings are currently marketed in Canada,
hence are not accumulating. Estimated manganese wastes
(Reference 10) are shown in Table A-1-16.
6. Associated Hazards
Inhalation of manganese oxides may cause chronic
manganese poisoning or manganic pneumonia. Chronic
manganese poisoning is a disease affecting the central
nervous system, resulting in total or partial disability
if corrective action is not taken. Some people are more
-------
APPENDIX A-1-65
Table A-l-16
Estimated Magnitude of Solid Waste
Accumulations for Manganese
State and Type
of Solid Waste
Arizona
Mine waste
Mine tailings
Smelter slag
Total
Colorado
Mine waste
Mill tailings
Smelter slag
Total
Montana
Mine waste
Mill tailings
Smelter slag
Total
Nevada
Mine waste
Mill tailings
Smelter slag
Total
New Mexico
Mine waste
Mill tailings
Smelter slag
Total
Accumulated thru 1968
...Tons , .
(thousands)
2,000
2,000
250
250
3, 400*
3,400
6,200
1,700
7,900
2, 250*
2,250
Acres
40
40
30
30
100*
100
25
10
35
600*
600
* Total of mine waste and mill tailings.
-------
APPENDIX A-1-66
susceptible to manganese poisoning than others. Manganic
pneumonia is a croupous pneumonia often resulting in
death. The effect of long exposure to low concentrations
of manganese compounds has not been determined.
Manganese compounds are known to catalyze the
oxidation of other pollutants, such as sulfur dioxide, to
more undesirable pollutants—sulfur trioxide, for example*
Manganese compounds may also soil materials.
The most likely sources of manganese air pollution
are the iron and steel industries producing ferromanganese.
Two studies, one in Norway and one in Italy, have shown
that the emissions from ferromanganese plants can signifi-
cantly affect the health of the population of a commuity.
Other possible sources of manganese air pollution are
manganese fuel additives, emissions from welding rods,
and incineration of manganese-containing products, particularly
dry-cell batteries. Manganese may be controlled along with
the pariculates from these sources. Air quality data in the
United States showed that the manganese concentration
3 3
averaged 0.10 /ig/m and ranged as high as 10 pg/m in
1964.
-------
APPENDIX A-1-67
No information was found on the economic costs of
manganese air pollution or on the costs of its abatement.
Further studies in the following areas are suggested:
The effect of inhalation over varying periods
of time of low concentrations of the manganese
compounds found in the atmosphere.
The chemical composition and particle-size
distribution of the manganese compounds in
the atmosphere.
The effect of managanese air pollution on
commercial plants and animals.
Measurement of the concentration of manganese
both near suspected sources and as emitted from
suspected sources.
The economic losses due to mananese air
pollution.
TUNGSTEN
1. Description
Tungsten is a heavy, hard, heat-resistant metal.
At high temperatures (above 3,000°F), it outranks all
other metals in tensile strength. It is chracterized by
good corrosion resistance, good electrical and thermal
conductivity, and low thermal expansion coefficient.
Major industrial application include its use in cutting and
-------
APPENDIX A-1-68
shaping other metals, in alloys, as filaments in electric
lamps, and in ceramics.
2. Source and Production
Most of the tungsten produced in the U. S. in 1968
was recovered as a co-product of molybdenum operations.
Tungsten mines produced minor quantities of co-product
copper, gold, and silver. Most tungsten concentrate
is produced from about 50 mines, most of it derived from
the Pine Creek Mine of Union Carbide Corp. in California
where tungsten is the major product, and the Climax Mine
in Colorado where tungsten is the secondary product. The
U. S. consumes about 20 percent of the world's metal.
3. Industrial Consumption
The 1968 total United States availability of tungsten was
25,160 thousand pounds utilized as shown in Table A-l-15.
The major domestic users of tungsten include: metalworking
machinery, which required 50 percent of the total consumption;
construction, and mining machinery and equipment requiring
18 percent; transportation industry, approximately 15
percent; electrical lamps and other electrical equipment.
-------
APPENDIX A-1-69
about 10. 5 percent; with chemicals and others using
the remaining 6 percent.
4. Future Outlook
The projected annual growth for the tungsten
industry demands between 1968 and the year 2000 has
been set at between 4. 2 and 5. 6 percent. This projec-
tion converts to a volume of between 60 and 93 million
pounds.
5. Waste Characteristics
Solid wastes generated by the tungsten industry
presently total over 12. 3 million tons of coarse material
and 15. 9 million tons resulting from upgrading and milling.
The combined tungsten-related mine and mill wastes
currently cover about 955 acres of land (Reference 10),
as shown in Table A-l-17.
-------
APPENDIX A-1-70
Table A-l-17
Estimated Magnitude of Solid Waste Accumulations for Tungsten
State and Type
of Solid Waste
Arizona
Mine waste
Mill tailings
Smelter slag
Total
California
Mine waste
Mill tailings
Smelter slag
Total
Colorado
Mine waste
Mill tailings
Smelter slag
Total
Idaho
Mine waste
Mill tailings
Smelter slag
Total
Montana
Mine waste
Mill tailings
Smelter slag
Total
Nevada
Mine waste
Mill tailings
Smelter slag
Tola!
Utah
Mine Waste
Mill tailings
Smelter slag
Total
Accumulated thru 1965
Tons
(thousands)
200
50
250
5,000
10, 000
15,000
3,500
200
3,700
2, 500^
1,200
3, 700
850**
850
300
3,600
3, 900
Acres
15
10
25
10
35
45
500
10
510
300
300
40**
40
5
30
35
1967
Tons
(thousands)
Insignificant
350
350
Insignificant
20
20
Insignificant
Inactive
Acres
2
2
3
3
* =
Tailings used for airstrip base ** Total of mine waste & tailings
-------
APPENDIX A-1-71
CHROMIUM
1. Description
Chromium is a steel gray metal prepared by
electrolysis from one of several chromium-containing
electrolytes, or by using the aluminothermic process.
Chromium is chiefly used in alloy form, principally with
iron. Chromite is the only commercial chromium mineral,
and contains varied amounts of its oxides, iron aluminum,
and magnesium. It exists in three grades (metallurgical,
refractory, and chemical), depending largely on chromium
content.
2. Source and Production
Chromite has not been mined in the U. S. since 1961,
therefore, the domestic industry is depended on foreign
supply. The three industries: metallurgical, refractory and
chemical consume about 25 percent of the world's supply.
In 1968, seven companies in 12 locations produced all the
metal alloys. There were 11 principal refactory producers
and four large chemical producers. Chromite was imported
from the U.S.S.R., Republic of South Africa, Turkey,
-------
APPENDIX A-1-72
the Philipines, and Albania, with the U.S.S.R. and South
Africa supplying 75 percent.
3. Industrial Consumption
In 1968, total availability of chromium, was 908 thou-
sand short tons, utilized as shown in Table A-1-15 (page
A-1-63) with the domestic demand being 505 thousand short
tons. The metallurgical companies required approximately
67 percent of the total demand, the refractory industry
consumed 18 percent, and about 15 percent was used in
the chemical industry.
4. Future Outlook
The projected annual growth rate for chromium
between 1968 and the year 2000, falls between 2. 0 and 3. 3
percent, which implies a metal volume between 985 and
1,427 thousand short tons.
5. Waste Characteristics
The only environmental problems are those of
processing; no ore is mined domestically. All major
producers use control measures to control pollution
effects of the OH gases produced during processing.
-------
APPENDIX A-1-73
6. Associated Hazards
The exposure of industrial workers to airborne
chromium compounds and chromic acid mists, particularly
the hexavalent chromates, has been observed to produce
irritation of the skin and respiratory tract, dermatitis,
perforation of the nasal septum, ulcers, and cancer of the
respiratory tract. Chromium metal is thought to be non-
toxic. Hexavalent compounds appear to be much more
harmful than trivalent compounds, with the toxic effects
depending on solubility. Two effects that appear to be
particularly important in relation to air pollution are
hypersensitivity to chromium compounds and induction of
cancers in the respiratory tract. Exposure of industrial
workers in the chromate-producing industry has shown an
incidence of deaths from cancer of the respiratory tract
which is over 28 times greater than expected. Time-
concentration relationships for induction of cancer are not
known.
No evidence of damage by airborne chromium to
animals or plants has been found. Chromic acid mists
have discolored paints and building materials.
-------
APPENDIX A-l-74
In 1964, atmospheric concentrations of total
3
chromium averaged 0.015/ig/m and ranged as high as
g
0.350 /*g/m . Although the exact sources of chromium
air pollution are not known some possible sources are the
metallurgical, refractory, and chemical industries that
consume chromite ore, chemicals and paints containing
chromium, and cement and asbestos dust. Particulate
control methods should be adequate for chromium-
containing particles.
No information has been found on the economic costs
of chromium air pollution or on the costs of its abatement.
Methods of analysis are available to determine the amount
of chromium concentration in the ambient air.
Further studies are suggested in the following areas:
Resolution of the question of toxicity,
hypersensitivity. and cancer induction with
relation to the valence of chromium and
solubility of chromium compounds.
Determination of the concentration and time
of exposure of chromium required to produce
cancer.
Determination of the concentration and time
of exposure of chromium required to produce
allergenic reactions in hypersensitive people
of the general public.
-------
APPENDIX A-1-75
Determination of the concentration and valence
of chromium adjacent to chrome steel plants,
refractory fabricating plants, chromate-
producing plants, chrome-plating operations,
spray-painting operations, cement-making
operations, etc.
COBALT
1. Description
Cobalt is one of the refractory metals of the space
age, and is widely used in electronic devices and certain
paints and ceramics. It is essential in machine tools,
carbides, and high strength permanent magnets.
2. Source and Production
The U. S. produces only a small quantity of cobalt,
and relies principally on imports for its supply of
primary cobalt. The U. S. annually produces 500 to
600 short tons, and it is the principal user of cobalt.
3. Industrial Consumption
In 1968, the total domestic availability of cobalt was
21,459 thousand pounds, the demand being 14,151 thousand
pounds, utilized as shown in Table A-l-15 (page A-l-63).
-------
APPENDIX A-1-76
About 25 percent was used in aircraft and space; 20
percent consumed in electrical equipment; a little more
than 20 percent used in paints, ceramics, chemicals, etc.;
and 10 percent in tools and related machines.
4. Future Outlook
The projected annual growth rate for cobalt demand,
between 1968 and the year 2000, is set between 1. 0 and 2. 4
percent, which means that about 18. 64 to 30. 54 million
pounds of cobalt will be required by the year 2000.
5. Waste Characteristics
The solid wastes associated with the production of
cobalt are insigificant, since only a small amount is
produced domestically.
-------
APPENDIX A-1-77
MOLYBDENUM
1. Description
Molybdenum is a silvery-white metal and is malleable
and ductile when hot. Molybdenite is the principal source
of this metal. It is also found as a by-product or co-product
in the processing of other molybdenum-bearing ores.
2. Source and Production
Molybdenite was mined at three deposits by two
companies in 1968. The largest producer of the metal
produces concentrate at Climax and Urad, Colorado, while
the second largest produces concentrate at Questa, New
Mexico. Approximately 25 percent of the domestic
molybdenum in 1968 derived from molybdenum-bearing
copper, tungsten, and uranium ores, the bulk being from
copper. Nine other companies produce molybdenum as a
by-product. One ton of commercial molybdenum ore
will produce from 2 to 6 pounds of metal.
-------
APPENDIXA-1-78
3. Industrial Consumption
The 1968 total United States availability of molybdenum
was 123.6 million pounds, with an industrial demand of 55. 8
million pounds, utilized as shown in Table A-l-15 (page A-l-63).
The U.S. produced about 75 percent of the world's supply.
The transportation industry accounted for about 30 percent
of the total demand, with about 25 percent required for
production of commercial machinery and equipment. The
pipe and tubing industry accounted for 18 percent of the total,
and chemicals, catalytic, pigment, and lubricants used 8 per-
cent, electrical and electronic compounds utilized 3 percent,
and other industries required the remainder.
4. Future Outlook
The projected annual growth for molybdenum demand,
between 1968 and the year 2000, has been set at approximately
4 percent. This implies an estimated volume of between
151 and 207 million pounds in the year 2000.
5. Waste Characteristics
The accumulation of mine wastes through 1968, total
over 58 million tons. Mill wastes account for 258 million
-------
APPENDIX A-1-79
tons covering an estimated 819 acres. At the present time
there exists nearly 320 million tons of industry-related
solid waste, covering 1, 654 acres of land. An estimate of
accumulated waste per year is in excess of 15. 5 million
tons (Table A-1-18).
Table A-1-18
Estimated Magnitude of Solid Waste
Accumulations for Molybdenum
State and Type
of Solid Waste
Colorado
Mine waste
Mill tailings
Smelter slag
Total*
New Mexico
Mine waste
Mill tailings
Smelter slag
Total**
Accumulated thru 1968
Tons
(thousands)
1,250
248, 250
249, 500
57, 500
10, 500
68, 000
Acres
25
780
805
810
39
849
1967
Tons
(thousands)
15,500
15,500
25, 000
3, 500
28, 500
Acres
60
60
400
10
410
* Total for two underground molybdenum mines
** Total for one open-pit molybdenum mine
-------
APPENDIX A-1-80
NICKEL
1. Description
Nickel is an extremely hard and brilliant metal, which
is resistant to actions of the atmosphere and acids. This
metal has contributed to the advance to civilization almost
as much as copper and iron. Two general types of nickel
ores are found, sulfide and oxide.
2. Source and Production
Production of all domestic nickel ore comes from a
lateritic nickel silicate open pit mine at Nickel Mountain
in Oregon. There was only one metal producer in 1968.
Other nickel is produced as a by-product of copper refining.
The ferronickel produced in 1968 had a market value of
about $28 million.
3. Industrial Consumption
The 1968 total domestic availability of nickel amounted
to about 478. 4 million pounds, with a domestic industrial
demand estimated at 374.1 million pounds, utilized as shown
in Table A-l-15 (page A-l-63). Manufacturers of chemical and
-------
APPENDIX A-1-81
allied products and petroleum refiners are the major
users of nickel. Others are: fabricated metal products,
18 percent; aircraft industry, 26 percent; transportation
and electrical machinery, 22 percent; household appli-
ances and machinery (nonelectrical), 17 percent; con-
tractors, ship building and repair, and others,the re-
maining 12 percent.
4. Future Outlook
The projected annual growth rate for nickel demand,
between 1968 and the year 2000,has been estimated at 2.8
and 4. 0 percent. This converts into a volume figure of
between 895 and 1, 295 million pounds.
5. Waste Characteristics
The accumulation of solid wastes through 1968 in the
nickel industry amounts to greater than 11.5 million tons
of waste, covering an estimated 165 acres, and accumu-
lating at a yearly rate of 1.2 million tons (Reference 10).
Mine Waste—1.8 million tons of crude ore
are handled annually; sorting produces 300, 000
tons of mine waste.
-------
APPENDIX A-1-82
Mill Tailings—There are 200, 000 tons of
mill tailing wastes generated annually, cover-
ing 25 acres of land surface.
Slag—Since 1954, 10 million tons of nickel
generated slag has been produced covering
125 acres of land surface. This is shown in
Table A-1-19.
Table A-l-19
Estimated Magnitude of Solid Waste
Accumulations for Nickel
State and Type
of Solid Waste
Oregon
Mine waste
Mill tailings
Smelter slag
Total
Accumulated thru 1968
Tons
(thousands)
1,500
10,000
11,500
Acres
25
125
150
1967
Tons
(thousands )
200
1,000
1,200
Acres
5
10
15
-------
APPENDIX A-1-83
6. Associated Hazards
Nickel and its compounds are of concern as air
pollutants because harmful effects of exposure to these
materials have been observed among industrial workers.
Exposure to airborne nickel dust and vapors may have
produced cancers of the lung and sinus, other disorders
of the respiratory system, and dermatitis. There is sub-
stantially higher mortality rate among nickel workers due
to sinus cancer—up to 200 times the expected number of
deaths. However, since other metal dusts have also been
present in industrial exposures to nickel, it has not been
possible to determine whether nickel is the carcinogen.
Yet experiments have shown that nickel carbonyl and nickel
dusts can induce cancer in animals. Nickel-contact
dermatitis was found in 77 percent of the females and 10
percent of the males suspected of having allergenic reactions
to metals. No information on the effects of nickel air
pollution on commercial and domestic animals, plants, or
materials was found in the literature.
The most likely sources of nickel in the air appear to
be emissions from metallurgical plants using nickel,
engines burning fuels containing nickel additives, and
-------
APPENDIX A-1-84
plating plants, as well as from the burning of coal and
oil, and the incineration of nickel products. In 1964,
g
urban air concentrations of nickel averaged 0.032 pg/m
3
and ranged up to a maximum of 0. 690 Mg/m in East
Chicago, Indiana.
Emission of nickel in participate form can be
controlled using normal control devices, such as pre-
cipitators, baghouses, and scrubbers. Nickel carbonyl,
which is gaseous, must first be decomposed by heat before
it is removed as a participate.
No information has been found on the economic costs
of nickel air pollution or on the costs of its abatement.
Methods of analysis are available which can be
3
used to detect nickel at the 0.0064 ug/m level and nickel
3
carbonyl at the 7 pg/m level.
Further studies are suggested in the following areas:
Determination of the chemical composition of
nickel compounds in the atmosphere. Measure-
ment of the concentration of nickel near suspected
sources, including metallurgical plants; vehicles'
exhausts; and coal and oil-burning, plating, and
incineration facilities. Measurement and
analysis of the concentration of nickel in the
emissions from these sources.
-------
APPENDIX A-1-85
Determination of the effect of nickel air
pollution on plants and animals.
(7) SIC 109—Miscellaneous Metal Ores
The following metals are included in this section:
Mercury
Titanium
Vanadium
Other metallic minerals:
Antimony
Arsenic
Beryllium
Cadmium
Gallium
Germanium
Selenium
Tellurium
Thallium
1. Description
Mercury is the only metal that is liquid at ordinary
temperatures. It is found in many minerals but is recovered
almost entirely from the red sulfide mineral cinnabar.
-------
APPENDIX A-1-86
2. Source and Production
Domestic output comes from a large number of
small properties. They were 87 active mines in 1968;
53, which accounted for 74 percent of the total output,
were in California. Nevada was second with 17 mines and
17 percent of total product, followed by Oregon with 6 mines
and 3 percent. The remainder comes from 11 mines in
Arizona, Alaska. Idaho, Texas, and Washington.
3. Industrial Consumption
The 1968 total domestic availability of mercury was
105,587 76 pound flasks, with the industrial demand being
75, 422 flasks, utilized as shown in Table A-1-20.
Largest consumers include the manufacturers of fungicides,
dental preparations, electrical apparatus, paints, papers,
Pharmaceuticals, and other products.
4. Future Outlook
We projected annual growth for mercury demand in the
years between 1968 and the year 2000 to be set at 1. 5
and 2.8 percent, which converted into volume will range
between 120,000 to 180,000 flasks in the year 2000.
-------
APPENDIX A-l-87
Table A-1-20
Industrial Consumption Chart
\
SK
28
30
32
33
281
322
333
363
366
367
372
373
1925
2621
2812
2816
2818
2819
2821
2833
2851
2879
2893
2899
3229
3443
3471
3366
3573
3579
3383
SIC 109
>v MJaceuaneoua
X. Metal Ore*
Deacription N.
Chem. A Allied Prod.
Rubber A Plaitfci
Stone, day A CUa
Piiiiiaiy Metal
Induttrial Chem.
GlauA Glaarware
Nonfenoui ADoyi
Houathotd Appliance
Communkatlon Equip.
Elecliunic Component!
Aircraft Pula
Ship A Boal Build.
Guided Mttcilei
Paper MBit
Alkalies A Chlorine
Inorganic Pijmenti
Indiut. Organic Chem.
Induct. Inornnte Chem
Plastki A Ream
Medical Chemicali
PainuAAUedOiem.
Apicultnnl Pciticidci
PrintiB|bik
Miae. Chem. Praducti
GUM 4UIQ Gttuwuc
Fabricated Metal Prod.
Coating A Enfrarinj
Pwt . TiaiuiniuHW
Electronic Computmi
Office Machtoea
Ak Conditioning
j
3600
2300
3100
'See -
(281)
3900
2200
]
4100
700
QAA
300
17900
|
35
35
40'
§
§
1500*
2500*
5900
•
j
7.0
26J
Germanium (1000 tb)
I
1
i
1
Indium (1000 Troy OZ'i)
Mercury (76 Ib Flail)
17453
1914
See
(2833)
S
300
ISO
' See'
.(322).
230
Silver (Ma Troy OZ'i) 1
Tellurium (1000 Ib)
10
24
182
ThiDkira (Ib)
600
1000
§
75
44
243
10
10
|
190
,/ViC*
•
•Estimated
-------
APPENDIX A-1-88
Table A-1-20
(Continued)
X
SIC
3611
3612
3613
3623
3627
3629
3641
3643
36SO
3660
3662
3674
3679
3691
3692
3714
3729
3772
3821
3843
3861
3911
3914
3996
7391
SIC 109
v Miaceflaneooi
N. Metal Ora
Deentptkw X.
Elect Meat buta.
Pwi. Dbtrfbution
Welding Apparatus
Efcc.* Nuclear Det.
Etoc. Indust Apparatus
Electric Lampa
Cunent Canylof Wire
Canwmer Elect.
Communication Equip.
Radio T.V. Equip.
- • - ...
Elect Component!
Stotafe Batteries
Primary rtattakn
Motor Vehldei Parta
Akcraf t Parti
Akenft Eoffcef
Mech. Meat, Equip
Dental Eank>
Ctl| ^
JewefayPnc. Metab
Jcwvby Jk Saatwwv6
1 JimHum AkntiHtf
1 ~
Commercial RAO Labi
liidiiitriil Stock
Export a Othen
Total
1
21000
S.626*
7.901
51427
I
40*
25*
2400
•
23500
c
45
90*
256
111
677
Cadmium (1000 Ib)
400*
1300*
1.069
1,458
14^27
Gallium (Kg'i)
to
to
100
8
to 32
300
to 500
Germanium (1000 Ib)
8.0
37
•
0.5
79
Gold (MO. Troy Oz'l)
2.2
0.8
4.7
13.4
24.3
454
Indium (1000 Troy Oz'l)
200
ISO
400
50
950
Mercury (76 Ib Flaskl)
See
3692
19686
7867
22.466
18475
S
250
See
.3612
428
604
10S.487 1.982
i i
Siher (MIL Troy Oz'l)
5.8
41.6
44
43.6
320.9
170.8
6283
TeDuriiim(lOOOIb)
157
5
378
I
B
4300
25.200
600
31.7U
Titanium (1000 draft ton)
7
8
12
518
7S
1.002
I
3.809
667
10.177
•Estimated
-------
APPENDIX A-1-89
5. Waste Characteristics
Mine wastes generated, to date, by the mercury
industry exceeds 6. 8 million tons. Most mine dumps
are small, averaging less than 150, 000 tons. Volume
of mill tailings and retort furnace rejects presently
amounts to more than 19. 3 million tons, and will increase
to approximately 1. 6 million tons annually. All mercury
wastes, to date, cover about 640 acres of land in sparsely
populated areas (Reference 10) as shown in Table A-l-21.
TITANIUM
1. Description
Titanium is a low-density, silver-white metal and
its importance lies in its lightness, strength, and re-
sistance to corrosion. Titanium alloys possess the
tensile strength and hardness approaching that of many
steel alloys; they have good impact strength and fatigue
resistance.
-------
APPENDIX A-1-90
Table A-1-21
Estimated Magnitude of Solid Waste
Accumulations for Mercury
State and Type
of Solid Waste
Arizona
Mine waste and
Mill tailings
Smelter slag
Total
California
Mine waste
Mill tailings
Smelter slag
Total
Idaho
Mine waste and
Mill tailings
Smelter slag
Total
Nevada
Mine waste
Mill tailings
Smelter slag
Total
Oregon
Mine waste and
Mill tailings*
Smelter slag
Total
Accumulated thru 1968
Tons
(thousands)
60
60
6,000
15,000
21,000
300
300
300
1,400
1,700
150
1,000
1,150
Acres
30
30
420
10
10
50
35
75
110
1967
Tons
(thousands)
Acres
Insignificant
1,000
1,000
15
15
500
500
100
100
10
10
3
3
5
5
5
5
* Furnace rejects
-------
APPENDIX A-1-91
2. Source and Production
Approximately one million tons of titanium con-
centrates are produced yearly from mines in New Jersey,
New York, and Virginia. In 1968, the U. S. received
15 percent of its ilmenite from Canada, its entire rutile
supply from Australia and Sierra Leone, and 25 percent
of titanium metal from the United Kingdom. The U. S.
accounted for half of the world's total, and consumes
about two-thirds that amount.
3. Industrial Consumption
The 1968 total domestic availability of titanium was
1,002 thousand short tons, with an industrial demand of
458 thousand short tons, utilized as shown in Table A-1-20
(page A-l-87). Major users include: paints and allied
products, paper, plastics, floor coverings, aircraft,
fabricated plate work, and others.
4. Future Outlook
The projected annual growth rate for titanium
demand between 1968 and the year 2000 has been set
between 4.1 and 6. 5 percent. These rates imply volume
values between one and 2.4 million tons of metal in the
year 2000.
-------
APPENDIX A-1-92
5. Waste Characteristics
Mine wastes, Essex County, New York, totals over
53 million tons covering 275 acres; milling wastes add an
additional 5 million tons covering 55 acres. In Virginia,
combined mill and mine waste contain 6. 2 million cubic
yards, covering 87 acres. Present production methods
will generate six million tons annually (Table A-1-22).
Table A-1-22
Estimated Magnitude of Solid Waste
Accumulations for Titanium
State and Type
of Solid Waste
New York
Mine waste and
Mill tailings
Smelter slag
Total
Virginia
Mine waste
Mill tailings
Smelter slag
Total
Accumulated thru 1968
Tons
(thousands)
58, 000
5,000
63, 000
11.160
11, 160
Acres
275
55
330
87
87
1967
Tons
(thousands)
5,000
5,000
900
900
Acres
8
8
10
10
-------
APPENDIX A-1-93
VANADIUM
1. Description
Vanadium, a relatively abundant element in the
earth's crust, is recovered principally as a co-product
of other metals. It is chiefly used as an alloying element
for nuclear applications, and as a catalyst.
2. Source and Production
Vanadium oxide is recovered in the U.S. from ores
of domestic or foreign origin by three companies at four
plants. One other company produces a vanadium ferroalloy
principally from imported slag. The U. S. is the principal
producer as well as the principal user of the metal.
3. Industrial Consumption
In 1968,the total domestic availability of vanadium
was 10,177 short tons, with a domestic demand of 5, 770
short tons, utilized as shown in Table A-1-20 (page A-1-87).
Construction products are the principal consumers,
followed by transportation, construction machinery,
metal machinery, and chemical products.
-------
APPENDIX A-1-94
4. Future Outlook
The projected annual growth rate for vanadium
demand has been set at between 4.8 and 6.0 percent
during the period of 1968 to 2000. This rate converts to
a volume range of between 23, 500 to 37, 500 tons in the
year 2000.
5. Waste Characteristics
The solid wastes associated with the production of
vanadium are insignificant.
6. Associated Hazards
Vanadium is toxic to humans and animals; through
inhalation of relatively low concentration (less than 1, 000
3
), it has been found to result in inhibition of the
synthesis of cholesterol and other liquids, cysteine, and
other amino acids, and hemoglobin. Low concentrations
also act as strong catalysts on serotinin and adrenaline.
Chronic exposure to environmental air concentrations
of vanadium has been statistically associated with incidences
of cardiovascular diseases and certain cancers.
-------
APPENDIX A-l-95
Human exposure to high concentrations of vanadium
g
(greater than 1, 000/ig/m ) results in a variety of
clinically observable adverse effects whose severity
increases with increasing concentrations. These effects
include irritation of the gastrointestinal and respiratory
tracts, anorexia, coughing (from slight to paroxysmal),
hemoptysis, destruction of epithelium in the lungs and
kidneys, pneumonia, bronchitis and bronochopneumonia,
tuberculosis, and effects on the nervous system ranging
from melancholia to hysteria.
No information has been found on adverse effects
of atmospheric vanadium concentrations on vegetation
or on commercial or domestic animals.
What is known about the effects of vanadium on
materials related mostly to the corrosive action of
vanadium, acting (together with sulfur dioxide) on oil-
and coal-fired boilers, especially those using vanadium-
rich residual oils and coals.
The major sources of vanadium emissions are the
metallurgical processes producing vanadium metal and
-------
APPENDIX A-l-96
concentrates; the alloy industry; the chemical industry;
power plants and utilities using vanadium-rich residual
oils; and, to a lesser extent, the coal and oil refining
industries. Vanadium production is concentrated in the states
of Colorado, Utah, Idaho, and New Mexico, while the
highest concentration of industries producing vanadium
chemicals is found in New Jersey and New York.
Domestic vanadium consumption has more than doubled
since 1960, and the domestic mine production of ores
and concentrates increased from 1,482 short tons of
vanadium in 1945 to 5, 226 short tons in 1965.
In communities in the U.S. in which vanadium con-
centrations were measured, the average values (quarterly
composites) ranged from below detection (0. 003 jig/m3) to
0.30Mg/m3 (1964), 0.39/Ug/m3 (1966), and 0.90Mg/m3 (1967).
Little information is available on the economic
losses due to vanadium air pollution or on the costs of
abatement. One report indicated that measures taken to
reduce the loss of vanadium to the atmosphere from an
oil-fired steam generator resulted in recovery of
commercially valuable vanadium pentoxide, thereby
-------
APPENDIX A-l-97
producing a profit from air pollution abatement. No other
information was noted in the literature on control procedures
specifically intended to reduce used air pollution caused by
vanadium. However, customary methods used to control
particulate emissions in general are considered suitable
to the industrial processes using vanadium or vanadium-
containing fuels.
Methods of quantitative analysis of vanadium in the
environmental air include colorimetry, atomic absorption
spectroscopy, emission spectrography, and recently
polarography. The trend is toward more use of spectro-
graphic and spectrophotometric methods, some of which
are more sensitive than the other methods and easily
3
automated. Sensitivities on the order of 0. 001 Hg/rn
are reported.
Further study is suggested in the following areas:
. Determination of the relationships of low
concentrations of vanadium in various
oxidation states with enzyme inhibition,
cardiovascular disease, and cancer.
Determination of the concentration and valence
of vanadium near oil and coal burning industries
(especially those burning vanadium-rich oil),
and the vanadium metallurgical and chemical
industries.
Evaluation of the abatement and economics of
vanadium air pollution control.
-------
APPENDIX A-1-98
ANTIMONY
1. Description
Antimony, one of the oldest metals continuously used
by man, is a silvery-white, brittle, crystalline solid which
exhibits poor electrical and heat conductivity. It is chiefly
obtained as a by-product or co-product of base metal ores,
and finds industrial use in batteries and in metal alloys.
It is also used in fire-retardant chemicals, glass, rubber,
plastic, enamels, and small arms ammunition.
2. Source and Production
The current domestic production of antimony comes
as by-product cathode metal from silver ores mined in
the Cour'd Alene District of Idaho from three mines. Over
80 percent of the antimony metal derived from domestic
and imported ores was produced at a single smelter in
Texas, with a small plant in Idaho contributing the remainder
from locally produced concentrates. Antimony metal and
oxide producers are essentially large, vertically integrated
companies.
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APPENDIX A-1-99
3. Industrial Consumption
The 1968 total U. S. availability of antimony amounted
to 51, 527 short tons, with an annual industrial demand of
44, 792 short tons, utilized as shown in Table A-1-20.
(page A-1-87). The principal users of domestic antimony
include: storage batteries, 47 percent of total; fire retardant
chemicals, rubber, and plastics, 17 percent; industrial
chemicals, stone, clay, and glass products, 12 percent;
industrial machinery, 5 percent; communications and others,
the remaining 19 percent.
4. Future Outlook
The projected annual growth rate of antimony de-
mand between 1968 and the year 2000 has been estimated
at an average of 2. 2 percent. This converts to a volume
figure of between 63, 000 and 115, 000 tons in the year 2000.
5. Waste Characteristics
The accumulated mine wastes and mill tailings
attributed to the antimony industry up to the present is
approximately 500, 000 tons, covering a 20-acre land
area (Table A-1-23).
-------
APPENDIX A-l-100
Table A-1-23
Estimated Magnitude of Solid Waste
Accumulations for Antimony
State and Type
of Solid Waste
Idaho
Mine waste and
Mill tailings
Smelter slag
Total
Accumulated thru 1968
Tons
(thousands)
500
500
Acres
20
20
-------
APPENDIX A-l-101
ARSENIC
1. Description
Arsenic is a steel gray, brittle crystalline, semi-
metallic solid which tarnishes in air, and oxidizes
rapidly when heated. The metal is a minor constituent
of copper, gold, and silver. It is extracted from other
ores as a fume or by skimming.
2. Source and Production
Arsenic is produced as a by-product of base-metal
ores. Arsenic smelter segregated from other copper
smelters supplements that recovered at Tacoma. Cur-
rently, U. S. smelter production is about one-fourth of the
domestic supply; the remainder is imported. The world
supply of arsenic exceeds the current demand, with other
materials being used to a greater degree for pesticide
markets.
3. Industrial Consumption
In 1968 the total domestic availability of arsenic
amounted to 26, 200 short tons, with an industrial demand
-------
APPENDIX A-1-102
of 23, 900 short tons utilized as shown in Table A-1-20
(page A-1-87). The agricultural chemicals (pesticides)
industry is by far the greatest user of arsenic (75 percent),
followed by the glass, organic chemicals, nonferrous
alloys, and medical chemical industries.
4. Future Outlook
The projected annual growth rate for arsenic
demand in the period of 1968 to 2000 has been set at
between 0. 8 and 2. 3 percent which, when converted to
volume, amounts to between 31,000 to 32,000 tons in
the year 2000.
5. Waste Characteristics
The solid wastes derived from arsenic are con-
sidered to be insignificant,since it is totally derived
from other base metal ores.
6. Associated Hazards
Arsenic is toxic,to some degree, in most chemical
forms. Arsenical compounds may be ingested, inhaled,
or absorbed through the skin. Industrial exposure to
-------
APPENDIX A-1-103
arsenic has shown that it can produce dermatitis, mild
bronchitis, and other upper respiratory tract irritations
including perforation of the nasal septum. However,
because of the irritant qualities of arsenic, it is doubtful
that one could inhale sufficient amounts to produce
systemic poisoning.
Skin cancer can result from prolonged therapeutic
administration of arsenic. Similar cancers have not been
observed among industrial workers. Moreover, lung
tumors which resulted from inhaling mixed industrial
dusts were often thought to be the result of inhaling
arsenic. Recently, this relationship has been questioned
because animal experiments have failed to demonstrate
that arsenic is a carcinogen. Therefore, the causal
relationship between cancer and arsenic is disputed.
Arsenic is poisonous to both animals and plants, but
no damage to materials was found.
Two air pollution episodes in the U.S. have shown
that there is an arsenical air pollution potential at
every smelter which refines arsenical ores.
-------
APPENDIX A-1-104
Arsenical compounds are used as insecticides and
herbicides. Although the use of arsenical pesticides
declined sharply after the appearance of DDT and 2. 4-D,
arsenical compounds are still used as desiccants, herbicides
and sterilants. Some undetermined amounts of air pollution
take place during spraying and dusting operations with
arsenical pesticides. Pollution from cotton gins and cotton
trash burning has been cited as an important source of
agricultural pollution. While the emission rates from
cotton trash burning have not been determined, as much as
3
1.258,000 Mg/m of exhaust air (580,000 /ig/min) may be
emitted during the ginning operation. This produced
g
concentrations of only 0.14 M g/m of arsenic in the air
150 feet from the gin.
Arsenic is found to the extent of approximately
5Mg/m in coal. Therefore, the air of cities which burn
coal contains some arsenic. Air quality data from 133
sites monitored by the National Air Sampling Network
showed an average daily aresenic concentration of 0.02
Mg/m3 in 1964.
-------
APPENDIX A-l-105
Control of arsenic emissions requires special
attention to the temperature of exhaust gases since arsenic
trioxide sublimes at 192°C. For this reason exhaust
fumes must be cooled to approximately 100 C prior to
removing them as particulates.
No information has been found on the economic costs
of arsenic pollution or on the costs of its abatement.
Analytical methods are available to determine
aresenic at the concentration found in ambient air.
Further studies are suggested in the following areas:
Determination of the carcinogenic effect of
long-term exposure to low concentrations of
arsenic in the atmosphere.
Measurement of the concentration of arsenic
near smelters, pesticide dusting and spraying
operations, cotton gins, and places where
cotton trash is burned.
BERYLLIUM
1. Description
Beryllium metal has a high melting point and is
exceptionally strong, rigid and very light. Beryllium
-------
APPENDIX A-1-106
and its compounds have certain unique properties which,
regardless of cost, promise a growing application in
special uses. The commercial source of beryllium is
beryl, which is hand-sorted from certain pegmatites.
2. Source and Production
The production of hand-sorted beryl in the United
States is negligible, and requirements are met almost
entirely from foreign imports. South Dakota is the
nation's principal producer of beryl, followed by Colorado
and New Mexico. All domestic ores are mined from
small open pit, and underground mines.
3. Industrial Consumption
The 1968 total domestic availability of beryllium was
667 short tons, with a domestic industrial demand of 384
short tons, utilized as shown in Table A-1-20 (page A-1-87).
4. Future Outlook
The projected growth rate for beryllium demand,
between 1968 and the year 2000, indicates a volume demand
in the year 2000 of between 1, 930 and 1, 660 short tons.
-------
APPENDIX A-l -107
5. Waste Characteristics
An accumulation of mine waste for this industry, to
date, amounts to 750,000 tons, covering an area of 2, 000
acres. All of this acreage is in South Dakota. Tonnage
and surface area of mill tailing wastes in other states is
insignificant (Reference 10).
6. Associated Hazards
Inhalation of beryllium or its compounds is highly
toxic to humans and animals, producing body-wide systemic
disease commonly known as beryllium disease. Both
acute and chronic manifestations of the disease are known.
The effects of beryllium intoxication can be mild, moderate,
or severe, and can prove fatal, depending on the duration
and intensity of exposure.
Acute beryllium disease is manifested by a chemical
penumonitis ranging from transient pharyngitis or tracheo-
bronchitis to severe pulmonary reaction. As of June 1966,
215 acute cases had been recorded in the Beryllium Case
Registry.
Chronic beryllium disease generally occurs as
lesions in the lung, producing serious respiratory damage
-------
APPENDIX A-1-108
and even death. However, every organ system may be
involved in response to beryllium exposure, except for
the organs in the pelvic area. The chronic form is
characterized by a delay in onset of disease, which may
occur weeks or even years after exposure. In June 1966,
498 chronic cases had been recorded, plus 47 acute-to-
chronic cases.
Of the total 760 cases recorded in the Beryllium
Case Registry, 210 fatalities, or 27.5 percent, had
occurred by June 1966.
Cancer has been produced experimentally in
animals, and 20 cases of cancer have been found (as
of 1966) in humans afflicted with beryllium disease.
However, insufficient information exists at this time to
causally relate beryllium poisoning to development of
cancer in humans.
Beryllium and its compounds can produce dermatitis,
conjunctivities, and other contact effects; however, these
manifestations are rare.
-------
APPENDIX A-1-109
There is some evidence that beryllium in soil is
toxic to plant life; no evidence was found on the effects
of atmospheric beryllium on plants or on materials.
The major potential sources of beryllium in the
atmosphere are industrial. The processes of extraction,
refining, machining, and alloying of the metal produce
toxic quantities of beryllium, beryllium oxide, and
beryllium chloride, which if allowed to escape into the
atmosphere would cause serious contamination.
Recognition of the serious hazards to health from these
sources has led to adaptation of control procedures
minimizing this potential. However, beryllium in limited
quantity is emitted from these industrial processes, and
danger also exists from accidental discharges. One major
source of beryllium contamination—the use of beryllium
in fluorescent light tubes—was discontinued in 1949.
Other sources could be the use of metallic beryllium
in rocket fuels, and the combustion of coals. Rocket
fuels could present a hazard in the handling and storage
of the powdered metallic beryllium used as an additive
in the fuels. Also, the exhaust fumes, which contain
-------
APPENDIX A-l-110
oxidized beryllium as well as other compounds of
beryllium, would be of significance in local soil and air
pollution if not contained. As beryllium is a normal
constituent (above 2 ppm) of coals, the combustion of coal
may add a significant quantity of beryllium to the
atmosphere.
Measurements are made of the beryllium con-
centration at 100 stations in the U. S. The average 24-hour
g
concentration is less than 0.0005 Mg/m ; the maximum
value recorded during the 1964-1965 period was
3
0.008 Mg/m .
Abatement measures have been implemented
industry-wide, with a very high degree of success.
Conventional air-cleaning procedures have been employed,
including the use of electrostatic precipitators, baghouses,
scrubbers, etc. These procedures have enabled the
beryllium industry to meet the industrial hygiene
standards established for beryllium.
Data on the economic losses resulting from
beryllium air pollution are not available. Court cases
-------
APPENDIX A-l-111
are pending in the State of Pennsylvania, however, which
may provide data on the economic values of impairment to
health resulting from exposure to beryllium. Only one
analysis of the costs for abatement was found. This study
indicated that the added costs for control amounted, in
1952, to approximately 20 percent of the normal cost
of operation for the particular plant analyzed.
Methods of analyzing beryllium in the atmosphere
are available, and are adequate for normal industrial
processes. The most common methods are the Zenia
method. The Zenia method is relatively simple, works
well with high concentrations, and provides sensitivity on
3
the order of 0.5 /ig/m . It can also be used subjectively
to provide a quick spot-check for the presence of beryllium
materials. The morin fluorescent method provides a
3
higher sensitivity range (0.01 /*g/m ) and is suitable
for monitoring out-of-plant concentrations in the vicinity
of beryllium processing plants if a large enough volume
of air is sampled. The spectrographic process gives even
3
higher sensitivities (0.003 /ig/m ) and is suitable for
monitoring concentrations in the general atmosphere.
-------
APPENDIX A-1-112
However, none of the currently available procedures
provides for discrimination between the various compounds
of beryllium, or differentiation between the "low-fired"
(highly-toxic) and the "high-fired" (less toxic) forms of
beryllium oxide.
Further studies are suggested in the following areas:
Further research into the pathogenesis of
beryllium disease, with particular emphasis
upon the effects of protracted exposure to
low concentrations.
Further research into the carcinogenicity of
beryllium compounds.
Analysis of the contribution of coal combustion
to beryllium pollution of the atmosphere.
Development of procedures for analysis of
different compounds of beryllium present in the
atmosphere.
Development of improved methods for
characterization of combustion products of
rocket fuels containing beryllium compounds.
CADMIUM
1. Description
Cadmium is a relatively rare metal whose major
value is its ability to protect more common materials.
-------
APPENDIX A-l-113
It is a soft malleable, silver-white metal when freshly cut,
and dulls due to formation of oxides on exposure to air.
2. Source and Production
The U. S. cadmium-producing industry comprises
nine firms that produce cadmium metal as an integral part
of their zinc operations. In addition, two other plants not
integral to zinc plants produce cadmium from residues,
flue dust, or scrap material.
3. Industrial Consumption
In 1968 the total domestic availability of cadmium
was about 14, 927 thousand pounds, with a demand of
13, 328 thousand pounds utilized as shown in Table A-1-20
(page A-1-87). Cadmium is used in transportation, air-
craft and boats, electroplating, batteris, pigments,
plastics, etc.
4. Future Outlook
The projected annual growth rate for the cadmium
demand for the period 1968 to 2000 has been set at from
1. 4 to 3. 5 percent which, translated into volume, is
from 12. 2 to 39 million pounds by the year 2000.
-------
APPENDIX A-1-114
5. Waste Characteristics
Solid wastes are essentially considered in the zinc
area. Fumes from cadmium are extremely toxic. Fumes
of zinc smelters are collected so there is not too much
cadmium in the air.
6. Associated Hazards
Cadmium and cadmium compounds are toxic sub-
stances by all means of administration, producing acute
or chronic symptoms varying in intensity from irritations
to extensive disturbances resulting in death. However,
despite increasing use of this metal and increasing
attention to its toxic nature, the exact manner in which it
affects human or animal organisms is not yet known.
Cadmium is toxic to practically all systems and functions
of the body, and is absorbed without regard to the levels
of cadmium already present, thereby indicating the
lack of a natural homostatic mechanism for the control
of organic concentrations of cadmium.
Inhalation of cadmium fumes, oxides, and salts
often produces emphysema, which may be followed by
-------
APPENDIX A-1-115
bronchitis. Prolonged exposures to airborne cadmium
frequently cause kidney damage resulting in proteinuria.
Cadmium also affects the heart and liver. Statistical
studies of people living in 28 U.S. cities have shown a
positive correlation between heart diseases and the con-
centration of cadmium in the urban air. Cadmium may
also be a carcinogen. While there is little evidence
to support this conclusion from studies of industrial
workers, animal experiments have shown cadmium may
be carcinogenic. No data were found that indicated
deleterious effects produced by airborne cadmium on
commercial or domestic animals. However, experiments
with laboratory animals have shown that cadmium affects
the kidneys, lungs, heart, liver, and gastro-intestional
organs, and the nervous and reproductive systems. No
data were found on the effects of cadmium air pollution
on plants or materials.
The metals industry is the major source of emissions
of cadmium into the atmosphere. Cadmium dusts and fumes
are produced in the extraction, refining, and processing
of metallic cadmium. Since cadmium is generally produced
-------
APPENDIX A-1-116
as a by-product in the refining of other metals, such as
zinc, lead, and copper, plants refining these materials
are sources of cadmium emissions as well as of the basic
metal. Also, because cadmium is present in small
quantities in the ores of these metals, cadmium emissions
may occur inadvertently in the refining of the basic metal.
Common sources of cadmium air pollution occur
during the use of cadmium. Electroplating, alloying,
and use of cadmium in pigments can produce local con-
taminations of the atmosphere. Also, since cadmium is
added to pesticides and fertilizers, the use of these
materials can cause local air pollution.
In 1964, the average concentration of cadmium in
3
the ambient air was 0.002 /ig/m , and the maximum con-
3
centration was 0. 350 /*g/m .
Air pollution control procedures are employed at
some metal refinery plants in order to recover the valuable
cadmium that would otherwise escape into the atmosphere.
Electrostatic precipitators, baghouses, and cyclones are
effectively used for abatement. However, little information
-------
APPENDIX A-1-117
has been found on the specific application of these
procedures for the purpose of controlling cadmium air
pollution. The procedures for recovering cadmium from
exhaust in a copper extraction plant collected significant
quantities of valuable cadmium, at the same time reducing
local air pollution levels.
No information has been found on the economic costs
of cadmium air pollution or on the costs of its abatement.
Methods are available for the analysis of cadmium in the
ambient air.
Further studies are suggested in the following areas:
Research into the effects of cadmium on human,
animal, and plant health
Research into the carcinogenic effects of
cadmium
Quantitative analysis of the emissions of
cadmium into the atmosphere from industrial
sources.
-------
APPENDIX A-1-118
GALLIUM
1. Description
Gallium is a by-product derived entirely from
processing certain aluminum and zinc ores. It currently
finds application in the electronics industry.
2. Source and Production
Two firms are producing gallium in the U. S.
3. Industrial Consumption
In 1968. the total domestic availability of gallium was
estimated between 300 to 5000 kilograms, with a demand
between 200 to 400 kilogram, utilized as shown in Table
A-1-20 (page A-1-87). Principal users are the electronic
industry, and manufacturers of mechanical measuring devices.
4. Future Outlook
The projected demand for gallium for the year 2000
has been set between 230 and 1,150 kilograms.
-------
APPENDIX A-l-119
5. Waste Characteristics
The solid waste problem due to gallium is essentially
insignificant since it is derived from other base metal ores.
GERMANIUM
1. Description
Germanium is metallic-looking but displays
metallic chracteristics only under special conditions.
It is a semi-conductor ranging between metal and
insulator, and is used chiefly in the electronics industry.
2. Source and Production
Germanium is a minor by-product of ores mined
primarily for zinc. As a primary metal it is wholly due
to domestic production. One domestic refinery produces
the metal by refining residues of zinc. Three secondary
refineries in Pennsylvania and New Jersey process new
scrap from manufacturers of electronic parts.
-------
APPENDIX A-l-120
3. Industrial Consumption
In 1968, the total domestic availability and industrial
demand for germanium was 79 thousand pounds, utilized as
shown in Table A-1-20 (page A-1-87). The largest user was
electronics, with some metal being used in pressed and
blown glass.
4. Future Outlook
The projected annual growth rate for germanium
demand, in the period 1968 to 2000, has been set between
0. 9 and 3. 0 percent, which, when converted to volume,
implies a demand between 97, 000 and 195, 000 pounds of
the metal by the year 2000.
5. Waste Characteristics
Solid wastes are insignificant since the metal is
obtained principally from zinc ores.
-------
APPENDIX A-1-121
SELENIUM
1. Description
Selenium is distributed widely in nature. However,
it is mostly derived from its association with copper,
iron, lead, and other metals.
2. Source and Production
At present selenium is derived domestically as
a by-product of electrolytic copper refining. Five plants
located in New Jersey and Maryland accounted for all
selenium production in 1968.
3. Industrial Consumption
In 1968, the total domestic availability of selenium
was 1,986 thousand pounds, with a demand of 1,100 thou-
sand pounds, utilized as shown in Table A-1-20 (page
A-1-87). Major uses include: electrical power distribu-
tion, glass industry, duplicating machines, pigments, etc.
-------
APPENDIX A-l-122
4. Future Outlook
The projected annual growth rate for selenium
in the period 1968 to 2000 has been set between 0. 3 and
2. 3 percent which, when converted to volume, amounts
to between 1.2 and 2.2 million pounds in the year 2000.
5. Waste Characteristics
Solid wastes due to selenium are insignificant, since
it is derived entirely from other base metal ores.
6. Associated Hazards
Selenium compounds, particularly the water-soluble
compounds, are toxic to humans and animals. In humans,
mild inhalation of selenium dusts, fumes, or vapors
irritate the membranes of the eyes, nose, throat, and
respiratory tract, causing lacrimation, sneezing, nasal
congestion, coughing, etc. Prolonged exposure through
inhalation can cause marked pallor, coated tongue, gastro-
intestinal disorders, nervousness, and a garlicky odor
of breath and sweat. In animals, subacute selenium
poisoning produces pneumonia and degeneration of the
-------
APPENDIX A-1-123
liver and kidneys. Furthermore, experiments with rats
indicate that selenium may cause cancer of the liver.
The biochemical effects of elemental selenium and
its compounds on humans is not as yet thoroughly under-
stood. The selenium deficiency diseases found in animal
species, as well as some of the frank selenium poisoning,
have not been observed in man. Similarly, the carcin-
ogenic hazard of selenium and the antagonistic effect of
arsenic for selenium seen in animals are yet to be shown
in humans. These are important factors that need clarifi-
cation to properly evaluate the role of selenium and its
compounds in air pollution.
There is no information indicating that amospheric
selenium has any detrimental effect on plants or
materials. Some plants contain large amounts of
selenium that can be toxic to the plants themselves,
as well as to humans and animals who ingest the plants.
Samples of snow, rain, and air taken in Boston, Mass.,
(1964-1965) show that the selenium content of the air is
averaging 0. 001 /*g/m3. Based on the selenium-to-sulfur
-------
APPENDIX A-l-124
ratio in these samples, the atmospheric selenium was
probably from terrestrial sources, including the fuels
and ores used by industry. Another source may be the
burning of trash containing paper products. Some papers
when analyzed contain as much as 6 ppm selenium.
Selenium in paper may come from accumulation by the
original tree or plant, or possibly from the manufacturing
of the paper (from the use of pyrites in the process).
Any vegetation which is burned may be a possible source
of atmospheric selenium. Another source could be the
refining of sulfide ores, particularly copper and lead
ores.
Emissions of selenium and its compounds can be
effectively controlled by use of electrostatic precipitators
and water scrubbers.
No information has been found on the economic
costs of selenium air pollution, or on the costs of its
abatement. Methods of analysis are available that can
measure quantitatively in the parts per billion or sub-
microgram region. However, none of the methods is
simple, rapid, or applicable to continuous monitoring.
-------
APPENDIX A-l-125
and many of the methods are not specific for selenium.
A rough estimate as to the magnitude of selenium in the
atmosphere might be made from the concentration of
sulfur in the atmosphere. This method would be valid
if the sources of these two pollutants are sulfide ores,
fossil fuels, or igneous and sedimentary rocks, since
in these materials the average weight ratio of selenium
-4
to sulfur is 1 x 10 .
Further studies are suggested in the following areas:
Further determination of the atmospheric
concentration of selenium coupounds in the
cities of the United States, particularly near
copper refiners and other sulfide ore
refiners, and near trash-burning sites.
Determination of the long-term exposure
effects on humans and animals, particularly
in the concentration range found in the
atmosphere.
Determination of the amount of selenium in
particulates.
Investigation of the possibility of antagonistic,
synergistic, or catalytic effect of selenium
or its compounds with other substances in
the environmental air.
-------
APPENDIX A-1-126
TELLURIUM
1. Description
Tellurium is one of the rarest of elements, ranking
75th in order of abundance in the earth's crust. It
rarely occurs in the native state and is usually assoicated
with copper, lead, silver, gold, mercury, and bismuth ores.
2. Source and Production
Tellurium is a minor by-product of electrolytic
refining of copper and lead, and producers of these com-
modities are producers of tellurium. Some of the tellurium
producers in the United States are located in Carteret, N. J.;
Baltimore, Md.; Perth Amboy, N. J.; Boyertown, Pa.; East
Chicago, Md. ; and Meapeth, N. Y. The U. S. is the world's
leading tellurium producer and consumer.
3. Industrial Consumption
In 1968, the total domestic availability of tellurium
was 378 thousand pounds, with a domestic demand of 221
thousand pounds, utilized as shown in Table A-1-20 (page
A-1-87). Its greatest use is in the primary metals, rubber
and plastics, and chemical industries.
-------
APPENDIX A-l-127
4. Future Outlook
The projected annual growth rate for tellurium demand,
during the period 1968 to 2000, has been set between 0. 3
and 2.4 percent which, converted to volume, reaches
between 240,000 and 485,000 pounds in the year 2000.
5. Waste Characteristics
Since tellurium is totally derived from other ores,
there are no solid waste figures associated with the
metal.
THALLIUM
1. Description
Thallium, a rare metal is recovered entirely as a
by-product of processing certain base-metal ores,
notably zinc. It is very malleable and softer than lead.
2. Source and Production
Thallium is produced domestically by a large
nonferrous metal producing firm. The American Smelting
and Refining Company, which maintains thallium-producing
facilities along with its zinc operation.
-------
APPENDIX A-1-128
3. Industrial Consumption
In 1968 the total domestic availability of thallium
was 31,700 pounds, with a domestic demand of 6,500
pounds, utilized as shown in Table A-l-20 (page A-l-87).
Chief consumers of thallium are the electronics industry
and agricultural pesticides.
4. Future Outlook
The projected annual growth rate for thallium demand
has been set at 1. 6 percent for the period 1968 to 2000;
the volume is expected to range between 6, 000 and
9, 500 pounds.
5. Waste Characteristics
Solid waste from thallium production is insignificant,
since it is derived as a by-product from other base metal
ores.
6. Associated Hazards
Thallium is highly toxic: once ingested it is not
quickly eliminated from the body, and is cumulative.
An antidote for thallium poisoning is not known.
-------
APPENDIX A-1-129
SIC 11—ANTHRACITE MINING
1. Description
Fossil fuels presently account for, and will continue to
account for, the bulk of our energy supply into the year 2000.
These fuels include coal, petroleum and natural gas, and
provide 96 percent of the nation's gross energy input. The
remaining 4 percent is accounted for by hydropower and
nuclear plants. Coal mining includes extraction of
anthracite, bituminous, and lignite.
2. Source and Production
The anthracite industry, located primarily in
Pennsylvania, is comprised of 246 underground mines,
130 strip pits, 127 culm and silt banks, 7 dredges, and
137 preparation plants (including primary screening
stations) in 13 counties in northeastern Pennsylvania.
The coal beds underlie a surface of 484 square miles,
and are separated by geologic conditions into four
distinct fields. The producing area is divided into three
regions.
-------
APPENDIX A-1-130
Organizationally, the industry ranges from small
independent underground mines with as few as two employees,
to large companies with multiple mining operations,
preparation plants, and surface shops. In 1967, 15
of the largest companies produced 64 percent of the total
anthracite output.
3. Industrial Consumption
In 1968,the domestic availability of anthracite coal
amounted to 11, 591 thousand short tons, utilized as
follows:
Availability
Consumer SIC Code (Thousand Short Tons)
Household and 65,70.88 4,759
commercial
Electric Utilities 4911 2,203
Industrial 20. 28, 32 1.872
Primary Metals 33 1,280
U.S. Armed Forces 9189 913
Export 518
Other 99 46
The principal uses of anthracite ore are as an energy
fuel, and as a source of industrial carbon. As an energy
source, the largest use is for space heating, being
-------
APPENDIX A-l -131
specially sized for hand-fired furnaces to large automatic
equipment. It is also heavily used for electric power gen-
eration. In the iron and steel industry, it is used in the
manufacture of coke, sintering, and in place of coke in foundry
processes. Other uses include the manufacture of
briquets, burning cement and lime, in brick and ceramic
kilns, curing agricultural products, and other applications
where the use for a clean steady heat source is necessary.
The railroad as a customer for anthracite has almost
dissappeared.
Anthracite provides a carbon source for use in a
variety of products, including the manufacture of telephone,
water and chemical filtering and purification material,
electrical and electronic equipment, and in the area of
carbide products.
4. Future Outlook
The demand for anthracite in the U.S. is on the
decline. In 1968,this demand approximated 10.2 million
short tons, and is expected to decrease to between 1.0
to 3. 6 million short tons. The most severed decline will
be in the area of space heating, the industries major
-------
APPENDIX A-1-132
market. Since 1949,this decline was at an average annual
rate of 8. 9 percent but is expected to stabilize at about
40 percent of present demand. Decreases in the primary
metal industries are attributed to (1) conversion to natural
gas, (2) substitutions of plastics for some metals, and
(3) increases in electric furnaces requiring less coke. An
increase could be in the need for foundry coke. The future
cost of mined coal will influence its use. Electricity-
generation using anthracite is beginning to stabilize. The
future increase in electric power demand (about 8. 5 percent)
annually) to the year 2000 may result in increased demand
for anthracite near coal-producing regions.
4. Waste Characteristics
Waste characteristics for anthracite mining are in-
cluded with tiiose for bituminous coal and lignite mining
in the following section.
-------
APPENDIX A-1-133
SIC 12—BITNUMINOUS COAL AND LIGNITE MINING
1. Source and Production
The bituminous coal and lignite industry is widely
dispersed throughout the nation. There are currently
5, 300 active mines in the industry, controlled by 3, 800
companies, with the majority of these, small operation.
However, consolidation of smaller operations is the
industry trend. Six leading coal producing states account
for 86 percent of total domestic production, and 14 percent
of the mines are responsible for almost 80 percent of the
total output.
The bituminous industry requires that 73 percent of
total output be transported chiefly by rail; hence, railroad
rates influence the cost of coal and will affect the future
of the industry.
2. Industrial Consumption
In 1968, the domestic availability of bituminous coal
and lignite amounted to 637, 858 thousand short tons,
utilized as follows:
-------
APPENDIX A-l-134
Availability
Consumer SIC Code (thousand short tons)
Household and 651, 70, 88 15,224
Commercial
Electric Utilities 49 294,739
Food and kindored 20 8,480
Products
Paper and Allied 26 14,888
Products
Primary Metal 33 99,313
Industries
Stone, Clay and 32 13.003
Concrete Products
Transportation 40, 44 417
Other Mineral and 39 31,283
Manufacture
Chemical and Allied 28 21,483
Products
Industry Stocks (as of 12/31/68) 87,462
Exports 50,637
Losses 929
The principal use of bituminous coal and lignite is almost
exclusively that of a source of heat and power, with
the major exception being in the production of metallurgical
coke. The largest and most rapid growing market is the
electric utility industry, accounting for 59 percent of total
bituminous and lignite consumption in 1968. The next major
area of importance is the primary metal industry for
-------
APPENDIX A-1-135
production of coke used in blast furnaces, and power for
steel and rolling mills. This accounted for approximately
20 percent of 1968 consumption.
Declines in the use of bituminous coal and lignite
in the past 20 years have occurred in the household and
commercial market, and in the food and allied products
where there has been a trend toward other energy sources,
including oil and natural gas. The stone, clay, and glass
industries other than cement have been declining steadily,
while the paper and allied products showed a slight turn
upward. Railroads and shipping which, we re a large market
for this fuel source, have virtually disappeared.
3. Future Outlook
The demand for bituminous coal and lignite has been
on the decline since the early 1940's; when consumption
ranged around 120 million tons per year, as compared to
15 million tons in 1968. It is anticipated that direct con-
sumption will continue downward, because of shifts to
other energy sources (e. g., electricity, oil, and natural gas).
However, coal will be utilized more and more to produce
-------
APPENDIX A-l-136
electrical power, and an increase in the need for synthetic
gas and liquid fuels will require the additional use of
bituminous coal and lignite.
The demand for these fuels in the U. S., which
approximated 499 million tons in 1968, is expected to
range from 1, 275 million to 2, 639 million tons in the
year 2000.
4. Waste Characteristics
The mining and preparation activities for the
anthracite, bituminous, and lignite industries are widely
distributed in the U. S. A total of 24 states, in 1967,
produced 557 million tons of coal, 95 percent of which
was mined east of the Mississippi River. In the 1960's,
approximately 1.500 strip mines excavated on the average
of 12. 8 cubic yards of overburden per tons of coal.
Unlike other mineral waste, coal wastes from all
sources are most often deposited in the same area. Coal
waste piles vary in size due to differences in mine production,
preparation, and in seams and mining conditions. Although
in some ways different, these culm banks have one
-------
APPENDIX A-1-137
characteristic in common; that is, they contain combustibles
and as such are susceptible to spontaneous combustion.
Anchracite waste materials produced in the coal pro-
duction process are primarily limited to four anthracite
fields in northeastern Pennsylvania. A 1966 in-depth
survey (Reference 11) by the Bureau of Mines regarding
that region's waste showed that there were 863 refuse banks
distributed through the area containing almost 910 million
tons of material, occupying a total of about 12,000 acres.
Bituminous and lignite wastes are generated during
the cleaning, sorting, and sizing of coal. The amount of
raw coal mechanically cleaned and the amount of rejected
waste have steadily increased due to increased efficiency
of coal cleaning and quality demands by the consumer
(Figure A-l-1). It is expected that the percentage of
mechanically cleaned coal will remain essentially cosntant,
but the percentage of waste will increase at a gradual rate
(Figure A-1-2).
In addition to overburden and coal wastes, the com-
bustion of coal produces ash, adding to the disposal
-------
PERCENT
70
60
50
40
30
20
10
PRODUCTION MECHANICALLY CLEANED
REJECT (WASTE TO RAW COAL)
1027 1930
1936
1940
1946
1960
1966
I960
1966
FIGURE A-1-1
Trends in the Portion of Total Production of Coal Which
is Mechanically Cleaned and the Average Reject Percentage
in the United States
TJ
3
00
00
-------
NUMBER OF PLANTS
700
600
600
400
300
200
100
MILLION TONS
1 *
1930 19
MECHANICAL
/^
35 1»
CLEANING PLAN
\
**'
40 19
T7ir/-ir
TS /
^
r
46 191
r T» IT* A i ft
^_
~~7^
1
50 19
A.
*^<
55 19
/
/
* •"•
\-^~
— "*— i^fc^^^1
—
^
BO 191
"
70
»
50
30
»
10 >
^
^
B
o ^
» o
i—i
X
t>
Trends in the Amount of Waste Generated
at Mechanical Coal Cleaning Plants and the Number of Plants
in the United States
co
CD
-------
APPENDIX A-l-140
problem. The electrical power industry consumes vast
amounts of coal and consequently produces more ash than
any other consumer. The combustion process produces
a volume of ash one-tenth the volume of coal consumed.
Power companies pump this residual into settling ponds in
slurry form. In 1965 electric companies were responsible
for over 24, 500,000 tons of ash. This residue is finding
use as a concrete additive, road base stabilizer, and as
agricultural soil conditioners.
-------
APPENDIX A-1-141
REFERENCES
1. Mineral Facts and Problems, U.S. Department of Interior,
Bureau of Mines, Bulletin 650.
2. Mineral Industry Solid Wastes and Our Environment. U. S.
Department of Interior, Bureau of Mines, Staff Report (draft).
3. The Litton Studies of the Toxic Hazards Involved in Mineral
Handling and Utilization, for the Environmental Protection
Agency.
4. Surface Mining and Our Environment, U. S. Department of
Interior, Bureau of Mines, Staff Report, U. S. Government
Printing Office, 1967, p. 39.
5. Environmental Science and Technology, Vol. 4, No. 7, July
1970, p. 555.
6. Burning Coal Refuse Banks and the Associated Environmental
Problems, L. M. McNay, U. S. Department of Interior, Bureau
of Mines, Information Circular, 1970.
7. Mineral Industry Solid Wastes and Our Environment, U. S.
Department of Interior, Bureau of Mines, Staff Report (draft).
8. Mineral Facts and Problems, U. S. Department of Interior,
Bureau of Mines, Bulletin 630, 1965 Edition, p. 1113.
9. Air Pollution Aspects of the Iron and Steel Industry. J.J.
Schueneman, U. S. Department of Health, Education, and
Welfare, Public Health Service, Environmental Health Series
No. 999, Ap. 1, p. 129.
10. Other Metals, Field Office Report, Socorro. New Mexico. U.S.
Department of Interior, Bureau of Mines. Office of Mineral
Resources, 1969.
-------
APPENDIX A-1-142
11. Pennsylvania Anthracite Refuse: A Survey of Solid Waste from
Mining and Preparation, J. C. MacCartney, U. S. Department of
Interior, Bureau of Mines, Information Circular 8409, 1969,
p. 77.
-------
APPENDIX A-2
SIC 20—FOOD AND KINDRED PRODUCTS
-------
APPENDIX A-2
SIC 20—FOOD AND KINDRED PRODUCTS
The Food and Kindred Products industry (SIC code 20) provides
the consumer with his daily sustenance as well as providing a market
place for the rural farming community. Included in this industrial
classification are: establishments which manufacture foods and beverages
for human consumption; certain related products such as manufactured ice,
chewing gum and vegetable and animal fats and oils; and prepared feeds
for animals and fowl. In addition, establishments whose primary concern
is the process and distribution of dairy products (e. g., milk and cream),
and the extraction of animal vegetable oils, are included.
Since this report is designed to explore the production of wastes and
utilization of waste disposal technology for each industry, the Food and
Kindred Products industry appendix includes the following sections:
Economic Statistics (including a description by SIC code
classification)
Waste Characteristics
Disposal Practices
-------
APPENDIX A-2-2
1. ECONOMIC STATISTICS
The Food and Kindred Products industry (SIC code 20) is a vital
part of the economy. The scope of this industry encompasses most
staple commodities from the field and/or manufacturer. This section
covers the following general topics:
SIC Code Classifications and Descriptions
Number of Establishments and Locations
Relative Concentration
. Major Raw Materials and Annual Production
Employment Statistics
Growth Patterns.
(1) SIC Code Classifications and Descriptions
The major SIC code 20 (Food and Kindred Products) includes
nine general categories which are considered in this appendix.
These categories (Reference 1), and a brief description of each,
are as follows:
201 Meat Products—Includes establishments
which slaughter livestock and other animals
(except small game) to be sold or used in canning,
curing, or the making of sausage, lard or other
products on the premises. Establishments which
use prepared carcasses and other materials to
-------
APPENDIX A-2-3
manufacture sausage or prepared meats and meat
specialties by the curing, smoking, canning, and
freezing of meats are also included, as well as
establishments that kill, dress, package, and
can poultry, rabbits, and other'small game.
202 Dairy Products—Includes establishments
which manufacture creamery butter, natural cheese,
condensed and evaporated milk, ice cream and
frozen desserts, and special dairy products such
as processed cheese and malted milk. Establish-
ments that process (pasteurize, homogenize,
vitaminize and bottle) fluid milk and cream for
wholesale or retail distribution are also in this
category.
202 Canned and Preserved Fruits, Vegetables and
Sea Foods—Includes establishments which can
fruits and vegetables and their juices; manufacture
catsup and similar tomato sauces, preserves, jams,
and jellies, sun dry or artificially dehydrate fruits,
vegetables and nuts, or manufacture packaged soup
mixes from dehydrated ingredients; pickle and brine
fruits, vegetables and manufacturing salad dressings,
vegetable relishes, sauces and seasonings; and quick
freeze and pack fruits, fruit juices, vegetables,
and specialties. Also included are those establish-
ments which cook and can fish and other sea foods;
smoke, salt, dry or otherwise cure fish for trade;
prepare fresh and raw or cooked frozen packaged
seafood; and those which can specialty products such
as health foods, baby food, and "nature" foods.
204 Grain Mill Products—Includes establishments
which mill flour or meal from grain; manufacture
prepared feeds for animals and fowls, including
certain feed ingredients and adjuncts; manufacture
cereal breakfast foods and related preparations;
clean and polish rice, and manufacture rice flour
and meal; and prepare blended flours and flour mixes.
Establishments which mill corn or sorghum grain
by the wet process and produce starch, syrup, oil*
sugar and by-products such as gluten feed and meal,
and manufacture starch from other vegetable sources
are also included.
-------
APPENDIX A-2-4
205 Bakery Products—Includes establishments
which make bread, cakes and other perishable
bakery products, as well as dry bakery products such
as biscuits, crackers, and cookies.
206 Sugar—Includes establishments which manu-
facture raw sugar, syrup or finished cane sugar from
sugar cane or sugar beets, as well as those which
refine purchased raw cane sugar and sugar syrup.
207 Confectionary and Related Products—Includes
establishments which manufacture candy including
chocolate, salted nuts, other confections and related
products, solid bars, and chewing gum. Establish-
ments which shell, roast, and grind cocoa beans for
making chocolate liquor are also included.
208 Beverages—Includes establishments which
manufacture malt or malt by-products from barley or
other grains, and all kinds of malt liquors; manu-
facture wines, brandy and brandy spirits (including
bonded storerooms engaged in blending wines);
manufacture alcoholic liquors by distillation and
rectification, and cordials and alcoholic cocktails
by blending processes or by mixing liquors and other
ingredients; manufacture soft drinks and carbonated
waters; and manufacture flavoring extracts, syrups,
and fruit juices for soda fountains, soft drinks, and
colors for bakers and confectioners.
209 Miscellaneous Food Preparations and Kindred
Products—Includes establishments which manu-
facture cottonseed oil and by-product cake, meal,
and linters; manufacture soybean oil and by-product
cake and meal; manufacture animal oils including
fish and other marine animal oils and by-product meal.
and render inedible grease and tallow from animal
fat, bones, and meat scraps; roast coffee, and manu-
facture coffee concentrates and extracts in powder.
liquid, or frozen form; manufacture shortening, table
oils, margarine and other edible fats and oils by
further processing purchased animal and vegetable
oils (no elsewhere classified). Establishments which
-------
APPENDIX A-2-5
manufacture ice for sale (including public utility
operated companies); manufacture dry and canned
macaroni, spaghetti and vermicelli noodles, and
prepared foods and food specialities (not elsewhere
classified) are also included.
(2) Number of Establishments and Locations
Since the Food and Kindred Products industry encompasses
the whole United States, a general discussion of the overall
industrial establishments is divided into four regions (Refer-
ence 2):
Northeastern Region
North Central Region
Southern Region
Western Region.
The major SIC code classifications are also discussed
by region.
There were approxinately 32,518 establishments in 1967,
within the Food and Kindred Products industry. Although it
appears that the major contributor was the North Central
Region with 10,147 establishments, the diversification within
the industry must be considered.
-------
APPENDIX A-2-6
Table A-2-1
National and Regional Establishment Figures for the
Food and Kindred Products Industry*1'
Total Establishments
Geographical Area
10,147
9,114
7,676
5,581
32,518
North Central Region
Southern Region
Northeastern Region
Western Region
United States
(1)1967 data.
For example, in the Canned and Preserved Fruits, Vegetables,
and Seafood classification, the Western Region contains more
establishments than the other regions. The Southern Region
was the main location for establishments in the sugar classifi-
cation. Table A-2-2 gives the number of establishments in
each region for nine industries.
(3) Major Raw Materials and Annual Production
Tables A-2-3 through A-2-10 provide information on
the major raw materials and their 1967 annual production
(Reference 2). Each table represents one of the major classifi-
cations within the Food and Kindred Products industry, and
the products are shown within the applicable processing plant.
-------
Table A-2-2
National and Regional Establishments for the
Major Food Industries (1967)
SIC
Code Industry
201 Meat Products
202 Dairy Products
203 Canned and Preserved
Fruits, Vegetables
and Seafoods
204 Grain Mill Products
205 Bakery Products
206 Sugar
207 Confectionary and
Related Products
208 Beverages
209 Miscellaneous Foods
and Kindred Products
Number of Establishments
Northeastern
Region
901
1,624
758
389
1,615
16
438
1,038
897
North Central
Region
1,633
2,807
746
1,177
1,174
26
316
1,144
1,124
Southern
Region
1.623
957
977
1,140
955
72
254
1,517
1,619
Western
Region
757
800
1,047
406
646
68
232
677
858
United States
Region
4,914
6.188
3.528
3,202
4,390
182
1,240
4,376
4.498
M
to
-------
APPENDIX A-2-8
Table A-2-3
Major Products and Annual Production for Meat Products
Major Product Production/million Ibs
Meat Packing Plant Products
Beef, not canned or made into sausage 17, 866. 5
Pork, fresh and frozen 7, 950.1
Lard 1, 848. 9
Meat Processing Plant Products
Pork, processed or cured (not canned
or made into sausage) 3, 963. 1
Hams and picnics, except canned 1, 349. 7
Sliced bacon 1,163. 1
Sausage and similar products
(not canned) 4, 254. 6
Frankfurters and weiners 1,158. 8
Other sausage, smoked or cooked (e. g.,
bologna, liverwurst, etc.) 1, 649. 8
Canned meats (except dog and cat food)
containing 20 percent or more meat 1, 700. 8
Poultry Dressing Plant Products
Hens (or fowl) and chickens 7,170. 3
Turkeys 1, 564. 1
Canned poultry (sizes other than (1) 10 oz.
and under or (2) 40. 1 oz. to 60 oz.) 2, 057. 1
-------
APPENDIX A-2-9
Table A-2-4
Major Products and Annual Production for Dairy Products
Major Product
Production/million Ibs
Creamery butter, total
National cheese (Italian, grated Cheddar,
brick, Swiss, etc.)
Dry milk products
(Dry skim milk)
Evaporated milk
Bulk fluid milk, and cream
(Fluid whole milk, bulk sales)
(Fluid skim milk, bulk sales)
Packaged fluid milk and related products,
total
(Fluid whole milk packages)
(Partially skim milk, packaged;
approximately 2 percent butter fat)
Buttermilk, chocolate drink, and other
flavored milk products
1,726.8
2,852.9
(1,126.1)
1,618.2
15,830.3
(11,689.7)
(2,640.8)
19,290.8
(16,342.7)
(1,346.5)
1,214.9
-------
APPENDIX A-2-10
Table A-2-5
Major Products and Annual Production for Canned and Preserved
Fruits, Vegetables and Sea Foods
Part I
Major Products
Juices
Canned dry beans, total
Canned fruits (except baby foods), total
Canned vegetables (except hominy and
mushrooms) total
Canned hominy and mushrooms, total
Apple juice
Grape juice (1, 000 cases of 12)
Pineapple juice
Grapefruit juice
Orange juice, single strength
Grapefruit -orange juice blend
Grapefruit-pineapple juice blend
Prune juice (4, 690 in 1, 000 cases of 12)
Other whole fruit juice and mixtures of
whole fruit juices
Nectars (including 1, 000 cases of 40 and 12)
Fruit juices, concentrated, hot pack
(including 1,000 cases of 48 and 1,000
gallons)
Canned vegetable juices, total
Catsup and other tomato sauces, total
Dietetic fruits
Part II
Major Products
Dehydrated fruits, vegetables, and soup
mixes, total
(Dried fruits and vegetables, except soup
mixes)
Potato and potato products (french fries,
patties, puff, etc. )
Frozen Specialties
Production/ 1.000 Cases
9, 400. +
69. 900. +
161,123
243, 164
7,547
9.358
6,407
11,960
14,763
18,288
2,839
6,562
8,718
4,359
3.324
12,457
32,875
96.680
5, 588. 9
Production/ million Ibs
1,442.2
(1,268.8)
1,507.6
2,369.8
-------
APPENDIX A-2-11
Table A-2-6
Major Products and Annual Production for Grain Mill Products
Part I
Manor Products
Wheat flour, except flour mixes
Whole cornmeal
Degermed cornmeal
Corn grits and hominy except for brewer's
use
Corn gruits and flakes for brewer's use
Cornmeal for animal feed
Other corm mill products (corn flour, etc. )
Rye flour
Other flour (excluding wheat, corn, rye)
Pancake and waffle mixes, total
Cake mixes, including gingerbread, total
Biscuit mixes, total
Cookie mixes, doughnut mixes and other
sweet yeast goods mixes, total
Other prepared flour mixes, total
Part II
Mai or Products
Poultry feeds, including supplements
Livestock feeds, including supplements
Dog and cat food
Dehydrated alfalfa meal
Cereal preparations, total
Milled rice, total
Production/ 1,000 Sacks
245,703
6,543
9,867
7,454
13,028
5,700
4,003
2,403
3,577
2,994
9,305
1,121
6,290
3,504
Production/ 1,000 Short Ton
19,002
20, 123
2,300+
1,739
1,059
3,410
-------
APPENDIX A-2-12
Table A-2-7
Major Products and Annual Production for Bakery Products
Production/million Ibs
Major Products (Baked Weight)
Bread and bread-type rolls 14. 371. 4
Sweet yeast goods 1,025. 1
Soft cakes, all types, including pound,
layer, fruit, etc. 1,229.1
Crackers and pretzels 1,496.8
All other cookies and wafers excepting
wafers foi* making ice cream sandwiches 1,448. 6
Production /millions of cones
Ice cream cones and cups 3, 614. 9
Table A-2-8
Major Products and Annual Production for Sugar Products and
Confectionery and Related Products
Major Products Production/1.000 short tons
Raw cane sugar 2, 243. 5
Refined cane sugar:
Shipped in consumer units
(cartons and sacks of 25 pounds
or less) 1,873.3
Shipped in commercial units
(bags and other containers
more than 25 pounds) 1, 227. 0
Shipped in bulk (rail cars, trucks,
or bins) 1. 326. 9
Beet sugar, total 4,611.9
Confectionery products, total 2, 080+
-------
APPENDIX A-2- 13
Table A-2-9
Major Products and Annual Production for Beverage Products
Major Products Production/1, OOP bbl.
Malt liquors and brewing by-products:
Beer, cans (all sizes) 40, 380
Beer, returnable bottles (all sizes) 30, 039
Beer, nonreturnable bottles (all sizes) 18, 576
Beer, barrels and keys (all sizes) 16, 980
Major Products Production /million Ibs
Malt, total 3, 803. 3
Major Products Production/1.000 proof gallons
Whiskey (raw):
Bourbon 123,005
Rye 5, 129
Other 10,948
Spirits (except fruit) 112,607
Other distilled liquors, including gin 33, 327
Bottled in bond:
Whiskey 6,893
Other 2,291
Major Products Production/1.000 wine gallons
Rectified products:
Whiskey, blends of whiskey 2, 560
Whiskey, blends with neutral
spirits and other whiskey 74, 074
Gin 1,969
Cordials, liqueurs, cocktails,
and similar compounds 21, 627
Vodka 16,296
Other rectified products 3, 165
Unrectified products:
Whiskey 79,906
Gin 29,682
Vodka 20,744
Other unrectified products 4,164
Major Products Production/1, OOP cases
Soft drinks and carbonated water, total 1, 759, 900
-------
APPENDIX A-2-14
Table A-2-10
Major Products and Annual Production for Miscellaneous Food
Preparations and Kindred Products
Major Products
Production/million Ibs
Cottonseed oil:
Crude
Once-refined
Soybean oil
Soybean meal
Grease and inedible tallow
Meat meal and tankage
Shortening (baking and frying fats including
bulk shipments of hydrogenated oils to
bakers and fryers)
Hydrogenated oils other than baking or
frying fats (for confectionery fats,
mellorine fats, whipped topping, etc.)
Salad or cooking oil (fully refined and
deodorized oil, produced at this plant)
Soybean cooking or salad oil (consumer
and commercial sizes)
Margarine
Shortening (baking and frying fats)
Hydrogenated oils other than baking and
frying fats
Salad or cooking oils, including olive oil
(refined oils, bleached, deodorized, and/or
unitized)
1,106.7
1,128.0
10,966. 1
26,425.2
5,381.3
7, 594. 0
3,426. 7
1,220.0
3,204. 7
2,230. 1
2,125.6
2,670.2
1,213.2
2,342.1
-------
APPENDIX A-2-15
(4) Employment Statistics (Value Added) and Growth Patterns
Table A-2-11 shows the breakdown of employment statistics
for the nine major classifications within the Food and Kindred
Products industry (Reference 2).
Tables A-2-12 through A-2-16 depict the potential growth
of production within this industry (Reference 3).
2. WASTE CHARACTERISTICS
The most serious problem of the Food and Kindred Products
industry is water pollution. Since the raw materials of this industry
are grown within our country, are processed here, and fulfill our
most vital domestic consumption needs, it is important to be aware of
the waste and waste sources that are inherent within the production
processes. This section is concerned with the following subjects:
Production Processes and Waste Sources
Effluents to Air and Water
Hazardous Waste Materials.
-------
Table A-2-11
Detailed Employment Statistics for
for SIC Codes 201-209 (Annual)
Item
AD employee* (1,000)
Payroll for aO employees (million dollan)
Production Workers (1.000)
Wage* for all production workers (million dollars)
Miateun of production workers (millions)
Value added by manufacture (million dollan)
Establishments1
. with 1-19 employees
. with 2049 employees
. with 100 employees or more
S
201
310.1
1,953.5
248.7
1.435.1
508.0
3,551.0
2,885
1.284
745
202
231.7
1.449.3
107.3
604.5
222.1
3,466.4
3,682
1,880
626
203
259.9
1 ,231.1
226.7
952.3
435.9
3,588.2
1,685
1,161
680
204
111.8
758.2
77.9
480.1
167.5
2,881.9
2,115
887
200
1C Codes
205
264.2
1.664.8
159.6
891.5
320.1
3,494.6
2,582
1.029
779
206
30.9
209.6
24.9
160.9
53.5
652.0
20
57
105
207
83.1
434.2
68.7
312.1
132.4
1048.0
777
279
184
208
220.7
1425.4
1133
725.4
226.8
4,790.1
2.232
1,671
473
209
137.0
850.7
94.3
500.5
193.1
2,948.7
3.026
1.161
309
M
to
i
h-»
o»
-------
APPENDIX A-2-17
Table A-2-12
Projected Per Capita Food Consumption
Total calories per day
Total annual consumption (retail
weight equivalent)
Meat, total (carcass wt. )
Beef (carcass wt. )
Veal (carcass wt.)
Lamb and mutton (carcass
wt.)
Pork (carcass wt.)
Fish (edible wt. equiv. )
Poultry (ready-to-cook basis)
Eggs (number)
(Pounds, except for eggs)
1970
L
M
H
L
M
H
L
M
H
L
M
H
L
M
H
L
M
H
L
M
H
L
M
H
3,130
1,470
164
175
185
83
95
100
7.0
7.8
8.5
3.7
4.9
6.0
60
66
78
9
10
11
35
38
43
330
360
390
1980
3, 120
1,490
170
187
195
85
103
110
7.0
8.5
9.5
3.5
5.5
6.5
60
70
83
9
10
11
35
40
45
330
360
400
1990
3,100
1,490
170
190
205
85
105
115
7.0
9.0
10.5
3.5
6.0
7.0
60
74
85
9
10
11
35
40
45
330
360
400
2000
3,080
1,490
170
195
210
85
105
115
7.0
9.0
11.0
3.5
6.0
7.5
60
75
85
9
10
11
35
40
45
330
360
400
-------
APPENDIX A-2-18
Table A-2-12
Cont
Dairy products (whole milk equiv.
Milk Fat
Non-fat solids
Wheat (grain equiv. )
Corn (grain equiv. )
Potatoes and sweet potatoes
(farm wt. )
Tomatoes (farm wt. )
Other vegetables (farm wt. )
Citrus fruit (farm wt. )
Apples (farm wt. )
nued
(Founds, except for eggs)
1970
L
M
H
L
M
H
L
M
H
L
M
H
L
M
H
L
M
H
L
M
H
L
M
H
L
M
H
L
M
H
590
645
675
22
24
25
44
48
51
135
145
155
35
39
43
95
105
120
70
75
83
175
190
205
90
105
110
22
24
26
1980
550
630
680
20
23
25
44
51
56
120
135
145
31
35
40
85
95
115
70
80
88
175
190
210
100
115
125
20
23
25
1990
5*0
610
680
18.5
22
24
44
53
58
110
125
140
28
32
38
85
95
115
70
80
90
175
195
220
100
115
130
20
23
25
2000
500
610
680
18
22
24
44
53
58
100
120
140
26
31
38
85
95
115
70
80
90
175
195
220
100
115
130
20
23
25
-------
APPENDIX A-2-19
Table A-2-12
Continued
Other fruits and melons (farm
wt. )
Sugar and syrups (refined
equiv. )
Fats and oils (retail wt. )
Coffee, tea, and cocoa (retail
wt.)
(Pounds, except for eggs)
1970
L
M
H
L
M
H
L
M
H
L
M
H
105
117
125
100
105
115
60
65
70
15
17
19
1980
101
115
125
100
105
115
60
65
70
15
17
20
1990
100
115
125
100
105
115
60
65
70
15
17
20
2000
100
115
125
100
105
115
60
65
70
15
17
20
-------
APPENDIX A-2-20
Table A-2-13
Percentage of Food Energy
Contributed by Major Food Groups
Dairy products, excluding butter
Eggs
Meat, poultry, and fish
Fats and oils, including pork fat
cuts and butter
Potatoes and sweet potatoes
Fruits, vegetables and nuts
Flour and cereal products
Sugar and syrups
1970
14.0
2.7
16.5
20.2
2.7
9.9
19.2
14.8
100.0
1980.
14.4
2.8
17.7
20.3
2.5
10.2
17.4
14.8
100.0
1990
14.7
2.8
18.3
20.4
2.5
10.3
16.0
14.9
100.0
2000
14.8
2.8
18.4
20.6
2.5
10.3
15.6
15.0
100.0
-------
APPENDIX A-2-21
Table A-2-14
Aggregate Domestic Consumption of
Principal Food .Items
Beef (carcass wt. )
Veal (carcass wt. )
Lamb and mutton (carcass
wt.)
Pork (carcass wt. )
Fish (edible wt. )
Poultry (ready-to-cook
basis)
Eggs (billions)
Dairy products (whole milk
equiv. )
Milk Fat
(Billion pounds, except for eggs)
1970
L
M
H
L
M
H
L
M
H
L
M
H
L
M
H
L
M
H
L
M
H
L
M
H
L
M
H
16.8
19.8
22.3
1.41
1.62
1.89
.75
1.02
1.22
12.2
13.7
17.3
1.82
2.08
2.45
7.1
7.9
9.6
66.7
74.9
87.0
119
134
151
4.44
4.99
5.58
1980
19.2
25.2
30.6
1.58
2.08
2.65
.79
1.34
1.81
13.6
17. 1
23.1
2.03
2.45
3.07
7.9
9.8
12.6
75
88
112
124
154
190
4.52
5.64
6.97
1990
21.2
30.1
40.1
1.74
2.58
3.66
.87
1.72
2.62
14.9
21.2
29.7
2.24
2.87
3.84
8.7
11.5
15.7
82
103
140
127
175
237
4.61
6.31
8.38
2000
22.8
34.8
49.8
1.88
2.98
4.76
.94
1.99
3.25
16.1
24.8
36.8
2.41
3.31
4.76
9.4
13.2
19.5
88
119
173
134
202
294
4.82
7.28
10.39
-------
APPENDIX A-2-22
Table A-2-14
Continued
Non-fat solids
Wheat (grain equiv. )
Corn (grain equiv. )
Potatoes & sweet potatoes
(farm wt. )
Tomatoes (farm wt. )
Other vegetables (farm wt. )
Citrus fruit (farm wt. )
Apples (farm wt. )
Other fruits and melons
(farm wt.)
Sugar and syrups
(refined equiv. )
(Billion pounds, except for eggs)
1970
L
M
H
L
M
H
L
M
H
L
M
H
L
M
H
L
M
H
L
M
H
L
M
H
L
M
H
L
M
H
8.9
10.0
11.4
27.3
30.1
34.5
7.07
8.11
9.59
19.2
21.8
26.8
14.1
15.6
18.5
35.4
39.5
45.7
18.2
21.8
24.5
4.40
4.99
5.80
21.2
24.3
27.9
20.2
21.8
25.6
1980
9.9
12.5
15.6
27.1
33.0
40.4
7.01
8.57
11. 16
19.2
23.3
32. 1
15.8
19.6
24.6
39.6
46.6
58.6
22.6
28.3
34.9
4.52
5.64
6.98
22.8
28.2
34.9
22.6
25.7
32.1
1990
11.0
15.2
20.2
27.4
35.9
48.9
6.97
9.18
13.26
21.2
27.3
40.1
17.4
23.0
31.4
43.6
56.0
76.8
24.9
33.0
45.4
4.98
6.60
8.72
24.9
33.0
43.6
24.9
30.1
40.1
2000
11.8
17.5
25.1
27.0
39.7
60.6
6.97
10.26
16.45
22.8
31.4
49.8
18.8
26.5
39.0
46.9
64.5
95.3
26.8
38.1
56.3
5.36
7.61
10.80
26.8
38.1
54.1
26.8
34.8
49.8
-------
APPENDIX A-2-23
Table A-2-14
Continued
Fats and oils (retail wt. )
Coffee, tea, and cocoa
(retail wt. )
(Billion pounds, except for eggs)
1970
L
M
H
L
M
H
12.1
13.5
15.6
3.03
3.54
4.24
1980
13.6
15.9
19.5
3.39
4. 16
5.58
1990
14.9
18.7
24.4
3.74
4.88
6.98
2000
16.1
21.5
30.3
4.02
5.63
8.66
-------
APPENDIX A-2-24
Table A-2-15
Projected Combinations of Per Capita
Meat and Poultry Consumption
I. High total consumption.
with emphasis on beef:
Beef and veal
Pork
Lamb and mutton
Poultry
Total
II. High total consumption.
with emphasis on variety:
Beef and veal
Pork
Lamb and mutton
Poultry
Total
III. Medium consumption:
Beef and veal
Pork
Lamb and mutton
Poultry
Total
IV. Low total consumption,
with emphasis on beef:
Beef and veal
Pork
Lamb and mutton
Poultry
Total
(Pounds, carcass weight, for beef
and veal, pork, lamb, mutton;
ready-to-cook weight for poultry)
1970
107
74
4
35
220
101
78
6
35
220
103
66
4.9
38
212
100
60
4
43
207
1980
117
75
3
35
230
105
83
6.5
35
230
111
70
5.5
40
227
107
60
3
45
215
1990
122
79
4
35
240
113
85
7
35
240
114
74
6
40
234
107
60
3
45
215
2000
124
80
6
35
245
118
85
7.5
35
245
114
75
6
40
235
107
60
3
45
215
-------
APPENDIX A-2-25
Table A-2-25
Continued
V. Low total consumption,
with emphasis on variety:
Beef and veal
Pork
Lamb and mutton
Poultry
Total
(Pounds, carcass weight, for beef
and veal, pork, lamb, mutton;
ready-to-cook weight for poultry)
1970
91
68
5
43
207
1980
95
70
5
45
215
1990
95
70
5
45
215
2000
95
70
5
45
215
-------
APPENDIX A-2-26
Table A-2-16
Projected Combination of Aggregate
Meat and Poultry Consumption
I. High total consumption.
with emphasis on beef:
Beef and veal
Pork
Lamb and mutton
Poultry
Total
II. High total consumption.
with emphasis on variety:
Beef and veal
Pork
Lamb and mutton
Poultry
Total
III. Medium consumption:
Beef and veal
Pork
Lamb and mutton
Poultry
Total
IV. Low total consumption.
with emphasis on beef:
Beef and veal
Pork
Lamb and mutton
Poultry
Total
(Billion pounds carcass weight, for
beef and veal, pork, lamb and mutton;
ready-to-cook for poultry)
1970
23.8
16.5
.9
7.8
49.0
22.5
17.4
1.3
7.8
49.0
21.4
13.7
1.0
7.9
44.0
20.2
12.1
.8
8.7
41.8
1980
32.6
20.9
.8
9.8
64.1
29.3
23.2
1.8
9.8
64.1
27.3
17.1
1.3
9.8
55.5
24.2
13.5
.7
10.2
48.6
1990
42.6
27.6
1.4
12.2
83.8
39.4
29.7
2.5
12.2
83.8
32.7
21.2
1.7
11.5
67.1
26.6
14.9
.8
11.2
53.5
2000
53.7
34.7
2.6
15.2
106.2
51.0
36.8
3.2
15.2
106.2
37.7
24.8
2.0
13.2
77.7
28.7
16.1
.8
12.1
57.7
-------
APPENDIX A-2-27
Table A-2-17
Continued
V. Low total consumption,
with emphasis on variety:
Beef and veal
Pork
Lamb and mutton
Poultry
Total
(Billion pounds carcass weight, for
beef and veal, pork, lamb and mutton;
ready-to-cook weight for poultry)
1970
18.4
13.7
1.0
8.7
41.8
1980
21.5
15.8
1.1
10.2
48.6
1990
23.7
17.4
1.2
11.2
53.5
2000
25.5
18.8
1.3
12.1
57.7
-------
APPENDIX A-2-28
(1) Production Processes and Waste Sources
Common to all raw products, the initial processes involve
precleaning, size grading, and sorting. The purpose of these
is to remove unwanted and undesirable material from food before
it undergoes processing.
Wastes from this operation for canned and frozen fruits
and vegetables often include soil, sand, stones, insecticides,
dried plant juices, vegetation, insects, and other residues (Ref-
erence 4). The only waste within this group that might be hazard-
ous is insecticides; however, the concentration is usually low.
Trimming, coring and pitting, cutting, peeling, inspection and
grading are also included in Initial Preparation. However, not
all raw materials are processed by each of these steps. Whether
the harvest was hand- or machine-picked will effect the amount
of impurities. These impurities are removed by soaking, spray
rinsing, or air cleaning (limited use).
The trend is toward the machine-picked harvesting which produces
more soil and other foreign matter wastes and, in turn, requires
higher product specifications and more thorough cleaning.
-------
APPENDIX A-2-29
These techniques produce large wastewater volumes and pollution
loads. Size grading is usually done with screens, belts, or other
separators. Sorting is usually a hand operation and primarily
affects the quantity of solid wastes. Some liquid and solid wastes
originate from trimming which is mainly a hand operation. Coring
and pitting, generally a mechanical process, results in solid
waste. The cutting and peeling operations produce a considerable
volume of wastewater and high loads of BOD: cutting emits liquid
waste from product juices and equipment wash water; peeling
emits most wastes from the chemical peeling operation, although
hand, steam, and machine operations are used. The lye peel
rinse is highly alkaline, hot, and mineralized, and contains a
considerable amount of dissolved organic matter. After grading
and inspection, the final step in initial preparation is transportation
to the Converted Product Handling processes. Transportation is
usually accomplished by belt conveyors or flume. If flume water
is discharged without extended reuse, it represents a large volume
and percentage of the total wastewater, since it contains a
significant amount of the total plant BOD and suspended solids.
-------
APPENDIX A-2-30
These processes, plus plant cleanup from these operations,
contribute about 50 percent of the total plant wastewater volume,
a major portion of the plant BOD, and virtually all of the
suspended solids.
The Converted Product Handling of canned fruits and vege-
tables involves some or all of the following processes: blanching,
mixing and adding syrups and brine solutions, pulping, straining,
cooking in vats, can filling, exhausting and sealing, thermo
processing, can cooling and storage. The equipment and floors
of this portion of the cannery are cleaned regularly, either at
the end of each shift, or at the end of each day. The waste from
blanching is hot and contains a considerable amount of dissolved
organic matter. Only spillages or spoiled solutions cause waste
during the process of mixing and adding syrups and brine solu-
tions. Little waste originates from these processes except when
the equipment is washed. However, when the pulp is wasted, as
in the production of canned fruit juices, disposal of the pulp and
strained solids becomes a solid waste problem. Insignificant
quantities of waste result from the other processes with the excep-
tion of cooling. Since cans are usually cooled in water, consider-
able wastewater is generated.
-------
APPENDIX A-2-31
The Converted Product Handling processes for frozen
fruits and vegetables are categorized as blanching, washing,
cooling, final preparation and inspection, packing, and freezing.
The quantity of wastes from each operation, in terms of both
flow and organic load, is variable and primarily a function of the
raw product being processed. By far the most significant waste
results from the blanching operation. The final steps in preparing
frozen fruit juices are extraction, screening, deoiling, deaera-
tion, pasteurization and concentration, packing and freezing. The
extraction and screening processes are usually mechanical and
result in tremendous quantities of solid residues and some liquid
wastes. Deoiling is accomplished at the same time as deaeration
and, if the steam used in the evacuator is condensed to avoid air
pollution problems, a liquid waste containing dissolved contaminants
results. Canning of juices requires several of the same processes
as freezing, and the quantity and characteristics of the wastes are
similar.
In seafood plants, primarily salmon, where delivered fish
are flumed and/or refrigerated, the largest volume of wastewater
is generated by the flumes and refrigeration tanks (Reference 5).
However, sea water is used in these operations, during which time
-------
APPENDIX A-2-32
the characteristics of the water are not significantly altered.
The largest volume of processing wastewater is from the rinse
sprays provided at the end of the "iron chink." This flow, aug-
mented by water used to flush the gutters, is used to convey
product residuals deposited into the gutter system. Hoses used
to clean the floors and equipment add significantly to the plant
effluent. These streams are consolidated, generally in a central
gutter, screened to remove solids, and discharged from the plant.
The major sources of wastewater from sardine processing
are the delivery pumping system and pickling tanks. Fish scales
are the only residuals contained in these streams. A significant
quantity of processing wastewater is generated to hydraulically
conveyed residuals. Flumes and gutters are continuously flushed,
generally with sea water, to remove residuals from the process-
ing areas. Condensate and fish oils from the steam rooms are
added to the effluent.
Several shrimp processing operations contribute signifi-
cantly to the wastewater volume. The water tanks where the
shrimp are received are provided with a continuous overflow.
Lubricating and cleaning sprays, used in peeling and deveining
machines, contribute significant quantities of organic matter.
-------
APPENDIX A-2-33
Washers provided after the cleaning and deveining operations
discharge large volumes of wastewater. In addition, the vats
used to blanch the shrimp contribute significantly to the organic
load.
The major sources of wastewater from tuna processing
are the flumes (conveying raw fish) and the thawing tanks.
From the product preparation lines, the only continuous source
of wastewater is from the fish washer at the butchering tables.
Additional wastewater flows are discharged during the washing
of tuna trays and racks, as well as the general plant cleanup.
In the meat packing industry, there are five processes
which have a major impact upon the wasteload (Reference 6).
These processes are as follows:
Blood recovery—Either it is recovered, or it
escapes to the sewer. Recovery means 42 percent
reduction in the gross wasteload. Since blood is rich
in protein, it is economically rational to recover it.
However, the very small plant does not produce
tankage and is not located in an area where it can
sell raw blood; therefore, it usually dumps the blood
into the sewer.
-------
APPENDIX A-2-34
Paunch handling—This material becomes a source
of pollution problems if it is dumped into the sewer,
since the total solids concentration becomes so large
that it interferes with the efficient workings of the
traditional waste treatment methods.
Edible rendering—The most polluting and oldest
method is wet rendering without evaporating tank
water. The newer methods, dry rendering and low
temperature rendering, cut wasteloads by 60 percent.
Inedible rendering—The wet rendering method must
be followed by evaporation of tank water in order to
cut wasteloads in half. Both forms of dry rendering,
batch and continuous, will produce 60 percent less
wasteloads than the wasteloads from wet rendering
systems without evaporation of tank water.
Cleanup— The general practice of the industry is using
water from high-pressure hoses to clean up. Pollution
loads could be substantially reduced by the use of dry
cleanup prior to the wet cleanup.
-------
APPENDIX A-2-35
Within the dairy industry, the significant wastes derived
from the fundamental butter process are skim milk from the
separation process, and buttermilk from the. churning operation
(Reference 7). These waste products may be converted into
valuable byproducts through evaporating the moisture and drying
the residue to a powder form for human consumption and /or
animal feed. If the skim milk and buttermilk are treated as wastes,
they become a difficult waste problem because of the high protein
and BOD content: skim milk has a BOD of 7.3 percent and butter-
milk 6. 4 percent. Less significant sources of wastes are:
The spillage which occurs in normal processing and
packaging operations
The wastes incurred with cleaning equipment at the
end of a day* s operation
Some clear water waste occurs in those plants which
use water for once-through cooling in their refrigera-
tion systems.
It should be noted that no water which conies in contact with butter
during the manufacturing process may be reused because of the
danger of contamination.
-------
APPENDIX A-2-36
The significant waste from the fundamental cheese and
fluid milk processes is whey. This waste product may be
converted into valuable byproducts through evaporating the
moisture and drying the residue to a powder form for human
consumption and/or animal feed. As a waste, whey becomes a
most difficult problem because of the high protein and acidic
content. Approximately 54 percent of the solids in the raw mate-
rial remains, resulting in a BOD of 3.2 percent. Less significant
sources are the same three mentioned in the previous paragraph.
The condensed and evaporated milk process produces
wastes from the miscellaneous spillage that occurs in normal
processing and packaging operations, and the loss which occurs
from cleaning equipment at the end of the day. In addition, the
soaps and chemical cleaning solutions used in daily sanitation
procedures contribute to water waste.
Wastes derived from the ice cream and frozen desserts
process are the same three bulleted items mentioned earlier
for the fundamental butter process.
-------
APPENDIX A-2-37
(2) Effluents to Air and Water
Exclusive of containers in which products from the Food
and Kindred Products industry are packaged, the following table
presents those items which are effluents to air and water. This
list also describes the significant hazard at present (Reference 8).
The first four item sections of Table A-2 -17 include wastes from
prunings, or as manure, crop residue, and garbage. These
items are general wastes from two of the nine major industry
classifications. The other item sections are Canning, Meat
Animal Carcasses, Fish Products, Dairy, Brewery and Winery,
and Sugar Refinery. These best examplify the types of produc-
tion which produce air and water effluents.
(3) Hazardous Waste Materials
Table A-2-18 presents the chemicals in the hazardous
wastes of the Food and Kindred Products industry. The mate-
rials and the chemicals created in the waste are itemized
(Reference 8). The items are arranged according to similarity
in chemical breakdown.
-------
Table A-2-17
Effluents to Air and Water
Item
Air Effluent
Water Effluent
Cereal and Grain
Products, Meat Trim-
mings and Wastes, Oils
and Fats, Fruit, Vege-
tables, Egg Shells, Bones,
Tree Leaves, Plants
Manure
Orchards and Groves,
Vineyards
1. CO2* CH4, volatile short-chain
fatty acids, H2S, mercaptans,
N2, NHs, may escape into at-
mosphere
2. Odor nuisance
3. CO, CO2 may appear in stack
discharge as combustion product
1. CO2, CH4, volatile short-chain
fatty acids, H2S, mercaptans,
N2, NHg, may escape into at-
mosphere
2. Odor nuisance
3. CO, CO2 may appear in stack
discharge or combustion pro-
cess
1. CO2, CH4, volatile short-chain
fatty acids, H2S, mercaptans,
N2, NHg, may escape into at-
mosphere
2. Heavy air pollution resulting
from open burning
CO2, aldehydes, ketones,
organic acids, phenol, NH4+,
NO2-, NOg-, plus sulfates,
phosphates, and carbonates
may leach to groundwater
Leaching of nitrogen may lead
to dangerously high NO2-, and
NOg - levels in the groundwater
Contamination with leachates
from stored manures can be
major source of groundwater
CO2, aldehydes, ketones, or-
ganic acids, phenol, NH4+,
NO2~» NOg- may leach to
groundwater
1J
td
GO
00
-------
Table A-2-17 (Continued)
Item
Air Effluent
Water Effluent
DAIRY
Milk Residues, Whey
BREWERY AND WINERY
Spent Hops, Grains,
Grape Pomace,
Fermented Starches,
Yeast and Bacterial
Biomass
SUGAR REFINERY
Beet Wastes and Pulp,
Cane Wastes and Pulp,
Evaporator Residue,
Steffen House Concen-
trates, Beet Washings
1. CO2» CH4, volatile short-chain 1.
fatty acids, I^S, mercaptans,
N2, NH« may escape into at-
mosphere
2. CO, CC>2 may appear in stack
discharge as combustion 2.
products
3. Odor nuisances from decompos-
ing wastes
CO2, CH4 volatile short-chain
fatty acids, H2S, mercaptans,
N2, NH3 may escape into at-
mosphere
CO, CO2 may appear in stack
discharges as combustion
products
Odor nuisances from decompos-
ing wastes
CH, volatile short-chain 1.
fatty acids, ^S, mercaptans,
N2, NH3 may escape into atmos-
phere
CO, CO2 may appear in stack dis-
charges as combustion products 2.
Odor nuisances from decompos-
ing wastes
CO2, aldehydes, ketones,
organic acids, phenol,
NO2-* NO3-, plus sulfates,
phosphates and carbonates
may leach to groundwater
A reservoir wastewater
stream problem
CO2, aldehydes, ketones,
organic acids, phenol, NH4+,
NO2~, NOg-, plus sulfates,
phosphates and carbonates
may leach to groundwater
CO2* aldehydes, ketones,
organic acids, phenol, NH4+,
NO2-, NO3~, plus sulfates,
phosphates, and carbonates
may leach to groundwater
Pesticides contained in the beet
washings may leach into the
groundwater or drain off
into surface water
M
X
to
I
-------
APPENDIX A-2-42
Table A-2-18
Hazardous Waste Materials
Item
Chemical Waste Breakdown
Cereal and Grain Products
Meat Trimmings and Wastes
Oils and Fats
Fruit
Vegetables
Egg Shells, Bones
Tree Leaves
Lawn Trimmings
Plants
Manures
Cattle Manure
(average: 10. 44 lb/1,000 Ib
cow -day
18% total solids
14. 4% volatile
solids)
Swine Manure
(average: 0. 795 lb/100 lb.
pig-day
19% total solids
15% volatile solids)
Protein
Sugars
Starches
Cellulose
Fat
Neutral Fats
Fatty Acids
Lignin
Cellulose
Lignin (20%), cellulose (25%), hemi-
cellulose (18%), fatty and other volatile
acids (3.2% - includes butyric, valeric
and caproic acids), protein, protein-
diamines, NH4, organic N-intermediates
(total N, 3. 79%), P2O5 (1. 1%), CaCOg
Pathogens (not necessarily present)
Salmonella, Mycobacterium bo vis,
Brucella cabustus, Leptospira, E. coli,
viruses
Lignin. cellulose, hemicellulose,
protein, protein-diamines, NH^,
organic N-intermediates (total N,
5. 4%), fatty and other volatile acids
(5.8%), P205 (4.6%), K (2.1%), CaCOg
Pathogens (not always present)
Salmonella, Brucella suis, E. coli,
viruses
-------
APPENDIX A-2-43
Table A-2-18
Continued
Item
Chemical Waste Breakdown
Poultry Manure
(average: 0.20 lb/5 Ib.
bird-day
25% solids
18% volatile solids)
Sheep and Goats
(total solids, 25%)
Horse Manure
(total solids. 25%-30%)
Orchards and Groves
Apple
Apricot
Cherry
Peach
Pear
Plum
Citrus
Walnut
Miscellaneous Fruits
Vineyards
Lignin, cellulose, hemicellulose,
protein, protein-diamines, NH4,
organic N-intermediates (total N,
5. 4%), fatty and other volatile acids
(5.8%), P205 (4. 6%), K (2. 1%), CaCOg
Pathogens (not necessarily present)
Salmonella, E. coli, viruses
Lignin (22%), cellulose (19%), hemi-
cellulose (18. 5%), protein, protein-
diamines, NH4, organic N-inter-
mediates (total N, 4. 0%), fatty and
other volatile acids, P (1.5% as
H3PO4), K2O (1. 9%), CaCOg
Pathogens (not necessarily present)
Salmonella, Brucella melitensils,
E. coli, Leptospira, viruses
Lignin (14%), cellulose (28%), hemi-
cellulose (23. 5%), proteins (7%),
protein-diamines, -NH4, organic N-
intermediates (total N, 2%), P (5% as
H3PO4), K2O (1. 5%), CaCO3
Leaves and wood (cellulose (55%),
lignin (24%), pentosans (18%),
nitrogen (2%)
-------
APPENDIX A-2-44
Table A-2-18
Continued
Item
Chemical Waste Breakdown
Field Crops
Corn Stalks
Wheat and other Grain
Stubble
Sugar Cane Stalks Begasse
Rice Hulls
Truck Garden
Cull Vegetables
Vegetables Trimmings
Cull Berries
Orchards
Cull Fruit
Green Drop
Greenhouse and Nursery
Vegetable Material
Flowering Plant Residue
Fruit
Pulp Press
Peelings
Seeds
Cull Fruit
Oils
Resins
Vegetables
Skins
Cores
Cobs
Shulks
Stalks
Trimmings
Carbohydrates ((80%) (cellulose and
sugars)), protein and fat (20%),
lignin, trace elements
Carbohydrates, protein, lignin,
trace elements
Carbohydrates, protein, lignin,
organic acids, trace elements
Celloluse, lignin, carbohydrates.
trace elements
Canning
Cellulose (55%), lignin (25%), PO4
(as H3P04, 3%), N (2%), K (as K2),
4. 0%)
Plant pathogens
Cellulose (60%), lignin (25%), N (2.5%),
P2O5 (0.7%), K2O (2.0%), S, Mg, ash
(20%), trace metals, pesticide residues
Plant pathogens
-------
APPENDIX A-2-45
Table A-2-18
Continued
Item
Chemical Waste Breakdown
Meat
Stockyards
Manure
Wastes Feed
Slaughtering and Packing Plant
Manure
Blood
Casing
Hair
Paunch Manure
Bones
Grease
Hooves, etc.
Heads
Feathers
Beef and Dairy Herds
Sheep Flocks
Swine Herds
Horse Herds
Poultry Flocks
Entrails
Skins
Scales
Meat
Lignin (20%), celluslose (25%), hemi-
cellulose (18%), fatty and other volatile
acids (3.2% - includes butyric, valeric,
and caproic acids), protein, protein -
diamines, NH^, organic N -intermediates
total N, 3.79%;, P2°s (1-1%). CaCO3
Pathogens (not necessarily present)
Salmonella, mycobacterium bovis,
Brucella caburtus, leptospira, E. coli,
viruses
Volatile matter (80% - 90%), total N
(10%), fibrous protein, fatty acids,
neutral fat, P2O5 (3.5%), K2O (2.5%),
C-14 (17%)
Proteins, fats, glycogen, P, and
trace amounts of minerals
Fish Products
Protein, amino acids, oils, N, P, K
(N+P 7.0%)
-------
APPENDIX A-2-46
Table A-2-18
Continued
Item
Chemical Waste Breakdown
Milk Residues
Whey
Spent Hops
Grains (Culls and Residues)
Oats
Rye
Wheat
Corn
Rice
Grape Pomace
Fermented Starches
Yeast and Bacterial Biomass
Beet Wastes and Pulp
(Most of the pulp disposed
of as livestock feedstuff)
Cane Wastes and Pulp
Evaporatory Residue
Steffen House Concentrate
Beet Washings
Dairy
Proteins, casein, albumin, carbo-
hydrates, lactose, fat, K, P, S
Brewery and Windery
Volatile solids (90%), lignin, cellulose,
carbohydrates, N (3%), P (as H3PO4,
1%), K (as K20, 0. 6%)
Sugar Refinery
Cellulose, lignin, N (0.4%), P(0.6%),
K (as K2O, 0. 6%), Ca, Mg
Cellulose, lignin, N, P, K
Hexoses, pentoses, sugar fragments,
resins, oils, tar, trace elements
Betaine, glutamine, assorted amino
acids, KOH
Soil, pesticides residues
-------
APPENDIX A-2-47
3. WASTE DISPOSAL PROCESSES AND PRACTICES
The Food and Kindred Products industry is one the largest
and most widespread industries within the U.S. economy. Some
product segments of the industry, such as meat products and sea foods,
exist in relatively confined geographical areas, whereas others, such as
dairy products and canned and frozen fruits and vegetables, are found
in almost every state.
Due to the wide variety of food products processed by the industry,
there exists many different processing techniques and, consequently,
many different waste disposal processes and practices. In spite of
these differences, however, there are many waste treatment methods
which are common to many, if not all, food processing industries.
The following sections describe current waste treatment processes
to the food industry, highlighting those problems and processes unique
to a particular industry segment. Examples are given of the com-
position of waste streams from various industry segments, and
the relative efficiencies of waste treatment processes and current
trends affecting these processes.
-------
APPENDIX A-2-48
(1) Current Waste Treatment Processes
Waste treatment processes typical to many segments of
the food industry are briefly described as follows.
In-plant control consists chiefly of arranging
processing operations in such a way that solids
or excessively strong waste streams are isolated
and handled separately. This is done in order to
promote water conservation and reuse.
Screening to remove solids is one of the most com-
mon methods of pretreatment of food processing
waters. Coarse screening is done with bar racks
and fine screening with 10 to 40 mesh. There are
a number of arrangements of fine mesh screening;
the principal ones consist of disc screen, rotating
drum,and vibrating type screen.
Grease recovery is necessary for food processors
who handle a significant quantity of meat or poultry.
Free floating grease can be removed by means of the
simple trap, or surface skimming, and is recovered
as a marketable by-product. Emulsified grease tends
-------
APPENDIX A-2-49
to stay in suspension and is removed and recovered
through air flotation and vacuum flotation systems,
sometimes with the addition of chemicals such as
alum, activated silica, chlorine,and other coagulant
aids.
Biological treatment involves the use of micro-
organisms to remove the organic materials by ad-
sorption and direct metabolism. Biological-oxida -
tion yields carbon dioxide and water as end products
and is achieved by the following processes.
Trickling filters
Activated sludge
Oxidation ditch
Lagooning
Anaerobic digestion
Spray irrigation
Trickling filters are frequently used to treat organic
wastes. These consist of racks, stacked 4 to 7 feet
deep, over an underdrainage system. More recently
plastic filter media have brought about more efficient
-------
APPENDIX A-2-50
systems through higher stacking, increased surface
area and savings in land area. In either system, a
gelatinous film of microorganisms develops on the
filter media which adsorbs the soluble colloidal
organics. Depending upon the composition of the
wasteload, certain precautions must be observed
to ensure sufficient microbial growth on the filter.
Activated sludge process consists of adding a bio-
logically active sludge to the waste water and then
aerating vigorously to supply the organisms with
sufficient oxygen. The variety of activated sludge
processes include the following.
Step aeration process
Contact stabilization process
Modified aeration process
Completely mixed process
Oxidation ditch process
Lagoons consist both of storage and flow -through
lagoons. Most frequently utilized, particularly in
meat packing and food processing plants, is the com-
bination of anaerobic and aerobic lagoons. Some
-------
APPENDIX A-2-51
lagoons rely strictly on natural conditions for re-
oxidation, others achieve increased loading with
mechanical aeration.
Spray irrigation involves the spraying of effluent
over a prepared disposal field with a vegetative
cover such as grass. Purification is accomplished
biologically and is dependent upon the biota and
organic litter on and in the soil.
Anaerobic digestion treatment process is well suited
to wastes of high organic content such as those
from the meat packing industry. This-process in-
volves the heating of an entire stream of waste to
95°F and holding it in an anaerobic digester for
about 12 hours.
Solids disposal has become a mounting problem for the food
industry. For those materials that have no economic recovery
value, there is a constant cost escalation for disposal. Various
methods and associated problems for solids disposal include:
-------
APPENDIX A-2-52
Incineration - creates air pollution.
Landfill and land spraying - limited by available
land and high cost of material hauling to suitable
locations.
Quick composting - results in a humus which is a
satisfactory soil conditioner; however, suitable
markets for the conditioner are not always available.
Ocean dumping - grinding and dumping from barges
beyond a 26 mile point from the nearest mainland
point are available only for food produced near a
coast.
Industry sources indicate that the most satisfactory waste
disposal process would involve the creation of new by-products
from food processing. Until research chemists and engineers
are able to create economical by-products, however, it appears
that most food processing wastes will have to be treated as gar-
bage and hauled away at considerable expense.
-------
APPENDIX A-2-53
(2) Extent of Utilization of Waste Treatment Processes
The waste treatment processes available to the food industry
are utilized to varying extents by different subclassifications within
the industry. Since data is not available for all industry subclassi-
fications, those industries for which data is available will be used
to illustrate broad industry trends.
Generally, the food industry utilizes increasing amounts
of waste treatment for its various effluents. However, the trend
has been to make increasing use of municipal waste treatment fa-
cilities for waste treatment after certain basic in-plant treat-
ments. The following table illustrates this trend for meat products,
dairy products and canned and frozen fruits and vegetables.
Industry Classification
201 Meat Products
202 Dairy Products
2021 Creamery Butter
2022 Cheese
2023 Condensed & Evap. Milk
2024 Ice Cream
2026 Fluid Milk
203 Canned & Frozen Fruits
& Vegetables
Year 1950
35
1
1
Lk 1
50
50
50
1963
50
5
5
5
70
70
60
1967
70
10
10
10
80
80
62
1972
80
32
32
32
90
90
65
1977
85
53
53
53
98
98
69
-------
APPENDIX A-2-54
Tables A-2-19 and A-2-20 illustrate the trend toward in-
creased use of available treatment processes within the meat
products and dairy industries. Since 1950, the total percentage
of plants employing some type of treatment has increased con-
siderably, such that at present virtually every meat and dairy
products plant employs some type of processing prior to dis-
charge at municipal sewers or watercourses.
(3) Efficiency of Waste Treatment Processes
Of the various waste treatment processes employed in
the food industry, the two which have probably received the
greatest attention are not those normally thought of as
waste treatment at all. These include byproduct utilization
and management technique. Both of these techniques reduce
the quantities of waste prior to the implementation of standard
treatment processes.
-------
APPENDIX A-2-55
Table A-2-19
Utilization of Waste Treatment Processes in the
Meat Products Industry
Type of Waste Treatment Estimated Percentage of Plants
Facility Employing Waste Treatment Process
1950 1963 1967 1972 1977
"Catch Basin" Only
(Sedimentation and
Grease Skimming)
Air Flotation
60
0
50
5
46
8
10
20
10
20
It is assumed that a "catch basin" will
precede the following methods of treatment.
Lagoon Systems 10 15 17 20 14
Trickling Filter 13332
Activated Sludge 12331
Anaerobic Contact
(Followed by Lagoons,
Activated Sludge, or
Trickling Filter) 0 5 6 20 25
Channel Aeration
(Pasveer Process) 0 0 2 5 10
Joint Industrial 0 1 2 10 15
Other
(Including Chemical
Treatment) 84482
TOTAL
(Plants With Some Type of
Treatment Facility 80 85 91 99 99
No Treatment Facilities 20 15 10 1 1
TOTAL 100 100 100 100 100
-------
APPENDIX A-2-56
Table A-2-20
Utilization of Waste Treatment
Practices in the Dairy Industry
Treatment Process
Ridge and Furrow
I
i Spray Irrigation
j Aerated Lagoon
Trickling Filter
Activated Sludge
Municipal Sewer
To Waterways
( Utilization as By-product**
Management Technique
% of Plants Employing Listed Processes
1950
u*
u
u
u
u
U-70
26-98
50
40
*U = Under 1%
** Condensed and Evaporated Milk and
have little by-product utilization.
1963
9
5
5
U
U
5-75
21-73
90
50-55
Ice Cream
1967
10
5
10
U
U
10-80
16-58
95
60-65
1972
15
5
15
U
U
32-90
6-30
99
65-75
1977
15
5
25
U
U
53-98
0
100
70-85
and Frozen Desserts
By-product utilization entails the production of marketable
by-products from residual material remaining after processing
the primary product. This practice is particularly applicable
in the meat products industry where virtually every part of the
animal is utilized. The dairy products industry also has a high
level of by-product utilization. Since by-products recovery is
basically a form of raw materials conservation, it retains a
-------
APPENDIX A-2-57
high level of popularity throughout the food industry. In
addition, it reduces the wasteload.
Management technique is also a form of conservation since
it involves the closest possible supervision of production processes
in order to reduce or eliminate processing losses at their source.
This has been of particular benefit to the dairy products industry.
Tables A-2-21 through A-2-23 illustrate the efficiencies
of various waste treatment processes. For most of these
processes, the efficiency is limited by the nature of the process
itself. However, the effective efficiency, as they are actually
employed, is also dependent upon the composition of the waste
streams which they must process. Processes such as spray
irrigation and aerated lagoons have very high efficiencies, but
are often limited by land availability and by sometimes having
a sludge residue which must be disposed of.
(4) Net Annual Wasteloads and Waste Reduction
Fifteen-year net wasteload standards and projections for
several food industry classifications indicate a gradual diminishing
of net wastes discharged to watercourses. In all instances
for which data is available, the gross wasteload in terms of
-------
APPENDIX A-2-58
Table A-2-21
Efficiency of Waste Treatment Processes
in the Meat Products Industry
Treatment Method Theoretical
^.
"Catch Basin" only
Air Flotation Unit
Lagoons
Aerobic and
Facultative (80)
. Anaerobic (80)
Anaerobic-
Aerobic (94)
Trickling Filter
Activated Sludge
Channel Aeration
Anaerobic Contact Plus
. Trickling Filter
. Activated Sludge
Lagoons
Other
(including Chemical
and Joint Industrial)
TOTAL
(1)
All treatment
flotation" arc
(2)
Waste
Reduction
% BOD
Removed
25
50
90
90
95
80-95
95
70
% of Plants Gross Pollution
Employing
Removed by
Method of Waste Treatment
Treatment
50
5
15
3
2
0
5
5
85
methods except Uirf "c.iU
assumed to
ha prcc.edi-..1
l">.\
mil Ibs BOD1 '
135
27
146
29
21
0
48
38
444
M basins only"
•
and
by "catch basins."
Gross pollution load is 1082 million pounds of BOD.
-------
APPENDIX A-2-59
Table A-2-2 2
Efficiency of Waste Treatment Processes
in the Dairy Industry
Removal Method
Ridge and Furrow
Spray Irrigation
Aerated Lagoon
Trickling Filter
Activated Sludge
Municipal Sewer
To Waterways
Utilization as By-product
Management Technique
Normal Removal Efficiency
% of Total Wasteload Removed
Product
95-100
95-100
90-95
90-95
90-95
100
100
99.5
50-75
Soap &
Chemicals
95-100
95-100
90-95
90-95
90-95
100
100
NA
40-75
Wastewater
4*
5*
1*
0
0
100
100
99.5
10-75
* Estimated percent of total evaporated to the atmosphere.
The remainder goes to waterways.
-------
APPENDIX A-2-60
Table A-2-23
Efficiency of Waste Treatment Processes in the Canned and
Frozen Fruits and Vegetables Industry
Method
Screening
20-40 Mesh
Wet Oxidation
Sedimentation
Flotation
Chemical Precipitation
Chemical Oxidation
Activated Sludge
Trickling Filtration
Anaerobic Fermentation
Lagoon ing
Spray Irrigation
Sand Filtration
POLLUTION REDUCTION ft
Flow to
Surface
Water
0
-
0
0
0
-
0
0
0
0-50
50-100
50-100
BOD to
Surface
Water
0-10
-
10-30
10-30
39-89
-
59-97
36-99
40-95
83-99
100
15-85
.)
SS
to Surface
Water
56-80
-
50-80
50-80
70-90
-
90-95
85-90
-
50-99
100
100
-------
APPENDIX A-2-61
BOD, SS and TDS shows a steady increase from 1963 through
1977. However, significantly improved removal processes have
more than compensated for the increase in wasteload. In most
instances, wastes reaching watercourses are materially reduced
as demonstrated in Tables A-2-24 through A-2 -26.
-------
APPENDIX A-2-62
Table A- 2- 24
Summary of Projected Net Wasteloads
for the Meat Products Industry
Year
1963
1968
1969
1970
1971
1972
1977
Gross Wasteload
(million Ibs BOD
1082
1128
1150
1176
1197
1221
1226
Removal* 1}
%
58
74
76
79
81
84
88
Net Waste
Discharged
to Watercourses
(million Ibs BOD)
454
296
274
242
225
198
147
(1)
Includes both in-plant and municipal treatment as well as process
changes and by-product utilization.
-------
APPENDIX A-2-63
Table A-2-2 5
Summary of Projected Net Wasteloads
for the Dairy Industry
Year
1963
1968
1970
1972
1977
Industry
Classification
2021
2022
2023
2024
2026
2021
2022
2023
2024
2026
2021
2022
2023
2024
2026
2021
2022
2023
2024
2026
2021
2022
2023
2024
2026
Gross Wasteload
(million Ibs BOD)
4.142
515
25
18
176
3,716
606
20
20
196
3,309
619
20
20
198
3,931
640
19
20
201
4,243
705
17
20
208
,(D
Removal
%
85
53
16
78
80
91
58
30
85
87
93
67
50
90
91
95
79
68
90
95
99.5
96
99.5
99.5
99.5
Net Waste
Discharged
to Watercourses
(million Ibs BOD)
629
242
21
4
35
340
254
14
3
25
271
204
10
2
18
199
142
6
2
10
22
30
less than 1
less than 1
less than 1
1) . . .
and by-product utilization.
-------
APPENDIX A-2-64
Table A-2-26
Summary of Projected Net Wasteloads for the
Canned and Frozen Fruits and Vegetables Industry
Year
1963
1968
1969
1970
1971
1972
1977
Waste
BOD
SS
TDS
BOD
SS
TDS
BOD
SS
TDS
BOD
SS
TDS
BOD
SS
TDS
BOD
SS
TDS
BOD
SS
TDS
Gross Wasteload
(million lh«>
370
425
395
435
500
465
445
510
475
455
520
485
460
525
490
465
535
495
490
565
525
Removal 1)
57
63
12
64
73
19
65
74
19
66
75
19
67
76
19
68
77
19
73
82
21
Net Quality
Discharged to
Watercourses
(million Ibs)
160
160
350
155
135
375
155
135
385
155
130
390
150
125
395
150
125
400
130
100
415
(I)
Includes both in-plant and municipal treatment as well as nrecess
changes and by-product utilization.
-------
APPENDIX A-2-65
REFERENCES
1. Standard Industrial Classification Manual, prepared by The Office
of Statistical Standards, published U. S. Government Printing
Office, 1967.
2. 1967 Census of Manufacturers, Volume II: Industry Statistics,
Part 1-Major Groups 20-24, prepared by Bureau of the Census,
published U. S. Department of Commerce, January 1971.
3. Resources in America's Future. Patterns of Requirements and
Availabilities. 1960-2000, by H. H. Landsberg, L. L. Fischman
and J. L. Fisher, published The Johns Hopkins Press, 1963.
4. The Cost of Clean Water, Volume III; Industrial Waste Profile,
Number 6 Canned and Frozen Fruits and Vegetables, Federal
Water Pollution Control Administration, U. S. Department of the
Interior, September 1967, FWPCA Publication Number I. W. P. -6.
5. Solid Waste Management in the Food Processing Industry, by
A. M. Katsuyama, N. A. Olson, R. L. Quirk and W. A. Mercer
(National Canners Association), U. S. Environmental Protection
Agency, 1971.
6. The Cost of Clean Water, Volume III:Industrial Waste Profile.
Number 8 Meat Products, Federal Water Pollution Control Admin-
istration, U.S. Department of the Interior, September 1967,
FWPCA Publication Number I. W. P-8.
7. The Cost of Clean Water, Volume III.' Industrial Waste Profile,
Number 9 Dairies, Federal Water Pollution Control Administra-
tion, U.S. Department of the Interior, September 1967, FWPCA
Publication Number I. W. P. -9.
8. Comprehensive Studies of Solid Waste Management. First and
Second Annual Reports, prepared by C. G. Golueke and P. B.
McGauhey, Bureau of Solid Waste Management, U. S. Department
of Health, Education, and Welfare, 1970.
-------
APPENDIX A-3
SIC 22 —TEXTILE MILL PRODUCTS
-------
EPA
APPENDIX A-3
SIC 22 — TEXTILE MILL PRODUCTS
1. INDUSTRY DESCRIPTION
Textile Mill Products is the title for Standard Industrial
Classification (SIC) Major Group 22. This group is subdivided into
the following categories:
221 - Broad Woven Fabric Mills, Cotton
222 - Broad Woven Fabric Mills, Man-Made Fiber
and Silk
223 - Broad Woven Fabric Mills, Wool (Including
Dyeing and Finishing)
224 - Narrow Fabrics and Other Smallwares Mills
(Cotton, Wool, Silk, and Man-Made Fiber)
225 - Knitting Mills
226 - Dyeing and Finishing Textiles, Except Wool
Fabrics and Knit Goods
227 - Floor Covering Mills
228 - Yarn and Thread Mills
229 - Miscellaneous Textile Goods.
-------
APPENDIX A-3-2
To establish a manageable scdpe for dealing with the wastes from
the textile mill industry, it is desirable to concentrate on the processes
within the production of the three principal types of textiles produced
which contribute the most wastes posing the greatest hazard to the pub-
lic health and welfare.
These textiles and processes with their corresponding SIC codes
are described in the following paragraphs.
(1) SIC 2231—Wool Textile Weaving and Finishing
This industry includes those establishments primarily
engaged in weaving fabrics over 12 inches in width, wholly or
chiefly by weight of wool, mohair, or similar animal fibers;
those dyeing and finishing woven wool fabrics or dyeing wool,
tops, or yarn; and those shrinking and sponging wool goods for
the trade. Establishments primarily engaged in weaving or
tufting wool carpets and rags are classified under other codes.
(2) SIC 2261—Cotton Textile Finishing
This industry includes establishments primarily engaged
in finishing purchased cotton broad woven fabrics, or finishing
such fabrics on a commission basis. These finishing operations
-------
APPENDIX A-3-3
include bleaching, dyeing, printing (roller, screen, flock,
plisse), and other mechanical finishing such as preshrinking,
calendering, and napping. This code also includes the shrinking
and sponging of cloth for the trade, and chemical finishing
for water repellency, fire resistance, and mildew proofing.
(3) SIC 2262—Synthetic Textile Finishing
This industry includes establishments primarily engaged
in finishing purchased manmade fiber and silk broad woven
fabrics or finishing such fabrics on a commission basis. These
finishing operations include bleaching, dyeing, printing (roller,
screen, flock, plisse), and other mechanical finishing such as
preshrinking, calendering, and napping.
(4) SIC 2269—Finishing of Other Textiles
This industry includes establishments primarily engaged
in dyeing and finishing of textiles in forms other than broad
woven fabrics such as finishing of raw stock, yarn, braided
goods, and narrow fabrics, except wool and knit fabrics. These
finishing operations include bleaching, dyeing, printing, and
finishing. Establishments classified under this code perform
finishing operations on purchased textiles or on a commission
basis.
-------
APPENDIX A-3-4
(5) Distribution of Establishments
Table A-3-1 shows the distribution of establishments in-
cluded in the SIC codes being considered throughout the various
states. The number of employees and the value added is also
given by state.
Figure A-3-1 provides a graphic presentation of the
relative distribution of major textile mills throughout the United
States.
2. MAJOR RAW MATERIALS. ANNUAL PRODUCTION. AND
INDUSTRY GROWTH PATTERN
(1) SIC 2231—Wool Textile Weaving and Finishing
The American wool market was reasonably stable and
approximated about 400 million clean pounds or roughly 10
percent of the total fibers consumed annually by the U. S.
textile industry in 1966. Industry 2231 shipments of woven wool
fabrics in 1967 represented 96 percent of these products valued
at $896. 6 million shipped by all industries.
Wool mixtures in blend with synthetics and even cotton
are becoming increasingly popular because of their reduced
-------
Table A-3-1
1967 Census of Manufacturers Data
Industry and Geographic Area
SIC 2231 - Weaving & Finishing
Mills, Wool
United States
New England Division
Middle Atlantic Division
East North Central Division
West North Central Division
South Atlantic Division
East South Central Division
West South Central Division
Pacific Division
SIC 2261 - Finishing Plants.
Cotton
United States
New England Division
Middle Atlantic Division
East North Central Division
South Atlantic Division
East South Central Division
West South Central Division
Establishments
Total
Number
310
127
89
12
10
43
7
2
18
216
37
88
14
54
8
5
With 20
Employees
Or More
217
100
48
7
7
38
5
2
10
136
27
43
4
49
7
3
Number of
Employees
(1000)
41.8
16.3
5.9
.9
.5
15.0
1.0 - 2.499
< .25
1.0 - 2.499
35.7
4.2
3.6
.25 - .499
24.1
>2.5
0.25 - 0. 50
Value Added
By Manufacture
(million dollars)
428.6
144.4
63. 1
7.8
3.7
178.4
(D)
(D)
(D)
313.8
35.6
35.7
(D)
211.4
(D)
(D)
w
2
0
H
co
01
-------
Table A-3-1
Continued
Industry and Geographic Area
SIC 2262 - Finishing Plants,
Synthetics
United States
New England Division
Middle Atlantic Division
South Atlantic Division
East South Central Division
Pacific Division
SIC 2269 - Finishing Plants.
NEC
United States
New England Division
Middle Atlantic Division
East North Central Division
South Atlantic Division
East South Central Division
Pacific Division
Establishments
Total
Number
233
43
134
45
1
5
192
18
103
10
46
10
7
With 20
Employees
Or More
167
35
89
38
1
2
105
13
40
6
39
6
3
Number of
Employees
(1000)
25.7
>2. 5
8.7
>2. 5
<0. 25
0.5 - 1.0
12.3
1.0 - 2.50
2.8
1.0 - 2.50
>2.5
1.0 - 2.50
0.3
Value Added
By Manufacture
(million dollars)
271.4
(D)
98.8
(D)
(D)
(D)
124.8
(D)
27.8
(D)
(D)
(D)
2.5
w
a
o
CO
o»
-------
.eft
New England
r -
Estuary
Chesapeake-Susquehanna
:. :-a
y K
-•••-''•--..r \
Florida
cz?
Puerto Rico
o*-
&
Virgin
Islands
t
(a Jt
jj o
*1 £3
So
CD H^>
o g-
a ?•
C CO
o rr
r+ r--
00 £3
-------
APPENDIX A-3-8
cost, improved weight, washability and wear, and other
characteristics. The influence of recent synthetics competition
has assisted in stimulating some technological advancement into
the wool processing industry. There appears to be a trend
toward larger plants to replace older, less efficient operations.
(2) SIC 2261—Cotton Textile Finishing
Cotton fiber is the single most popular and important
fiber in the American textile industry. Its excellent absorptive
and use characteristics, as well as reasonable price, contribute
to the stable market of about 7 to 9 million bales per year con-
sumed during the past decade; this quantity represents approxi-
mately one-half of the total fiber used by our textile industry.
SIC 2261 shipments of cotton broad woven fabric finishing
in 1967 represented 58 percent of these products valued at
$1, 087. 0 million shipped by all industries.
Cotton mixtures in blend with synthetics are becoming
increasingly popular because of the resulting cost, appearance,
and utilitarian features. The U. S. cotton industry has been
traditionally dependent on low labor costs to meet competition
from abroad. Presently, industry leaders are developing newer,
-------
APPENDIX A-3-9
more efficient, larger production yield equipment to replace the
older, less efficient subprocess facilities in order to overcome
domestic labor problems, synthetic fiber, and expanding foreign
competition. It is also interesting to observe that cotton produc-
tion has partially shifted from the Southern United States into the
irrigated lands of the Western United States. The United States
exported over 5 million bales of cotton in 1964 alone. The cotton
industry is expanding in both research and promotion in order to
compete with the well publicized synthetic fibers.
(3) SIC 2262—Synthetic Textile Finishing
Synthetic fibers (namely, those fibers which are man-made
and not found in nature) fall into two main groups, i. e., those
produced from cellulose and those produced synthetically from
organic materials. The cellulose fibers are principally rayon
and acetate. The cellulosic fibers make up approximately 6 per-
cent of the last decade's fiber consumption. The organic fibers
are principally acrylics, polyesters, and nylon. Noncellulosic
synthetic fibers have markedly increased their annual domestic
consumption from approximately 3 million cotton-equivalent
bales in 1957 to some 6 million bales equivalent in 1966.
SIC 2262 shipments of manmade fiber and silk broad woven
-------
APPENDIX A-3-10
fabric finishing in 1967 represented 45 percent of these products,
valued at $1, 022. 7 million, shipped by all industries.
The organic synthetic fiber industry is the most rapidly
growing segment of the textile industry and is continually creating
new and varied fibers to add to the already large number of syn-
thetic fibers now on the market.
(4) SIC 2269 — Finishing of Textiles Other Than Broad
Woven Fabrics
This industry is comprised of establishments primarily
engaged in the finishing of cotton and synthetic textiles which
are not in the broad woven form. Raw stock, yarn, braided
goods, and narrow fabrics are the primary products of this
industry. This industry's 1967 shipments represented 52 per-
cent of these products, valued at $350. 4 million, shipped by all
industries.
3. PRODUCTION PROCESSES AND WASTE CHARACTERISTICS
The production finishing processes and associated wastes dis-
cussed in this section apply to the wool, cotton, and synthetic fiber
industries.
-------
APPENDIX A-3-11
As a general rule, there are four basic subprocesses involved
in the finishing of textiles:
Scouring
Dyeing and /or printing
Bleaching
Special finishing.
Special finishing is meant to include all subprocesses which cannot be
classified in one of the preceding three categories.
(1) Wool Industry
1. Production Processes
Raw sheep wool receives a preliminary wash and
rinse. Then, the fairly clean wool is carbonized with acid
and heating to remove the residual waste. After another
washing, the fibers are ready for carding, fulling, and
weaving. They can be dyed either before or after weaving.
The fundamental processes in the production of
finished wool are scouring, dyeing, carding, fulling, wash-
ing, carbonizing, and bleaching. Although fulling discharges
little direct waste, it contributes to the total wasteload by
-------
APPENDIX A-3-12
the addition of biodegradable chemicals which are removed
in the washing process. Except for carding, all of the re-
maining processes are direct sources of waste.
For each of the fundamental processes, three levels
of technology are described:
Older technology (new in 1950)
Prevalent technology (new in 1963)
Newer, more advanced technology
(new in 1967).
(1) Scouring
Older technology scouring— Grease wool is
scoured in a 3 to 5 bowl scouring train or in 3 to 5
separate bowls in which wool is washed in batches.
Soap and soda ash are used in the first 2 or 3 bowls
with clean water in the remaining bowls. The last
bowl is a continuously running overflow rinse which
is not recirculated or reused in any way.
Prevalent technology scouring—Depending on
the size of the plant, grease wool is initially scoured
in a 3 to 5 bowl train using a low BOD (12 percent
-------
APPENDIX A-3-13
OWC (Other Weight Chemical)) synthetic detergent
in the first 2 or 3 bowls. The rinse water from the
last bowl (or bowls) is recirculated in a counterflow
operation.
Newer technology scouring—The grease wool
is packed into large vacuum kiers and scoured with
methyl alcohol to remove suint salts. The wool is
then scoured with isopropyl or ethyl alcohol to re-
move grease. The spent solvent can be distilled for
reuse and grease recovery. Finally, the wool is
washed in water to remove dirt and other soluble
particles remaining on the fiber.
(2) Stock Dyeing
Older technology stock dyeing — Dyeing is done
in sunken open top kettles containing acetic acid
(62 percent OWC BOD) and dye solution. The wool is
placed in wire mesh baskets with slow moving paddles
and immersed in the solution.
Prevalent technology stock dyeing—The scoured
wool is normally stock dyed in pressure kettles using
-------
APPENDIX A-3-14
ammonium sulfate or sulfuric acid and sodium sul-
fates, plus dye solution. The type of dye used
depends on the color desired, fastness to light and
water, and other properties.
New technology stock dyeing—Scoured wool
is stock dyed by a continuous process using pressure
equipment similar to a scouring train but with eight
compartments and automatic controls to prevent or
control felting. Ammonium sulfate and dye solution
are used in various concentrations in the compart-
ments.
(3) Carding
Older technology carding—Due to shortages,
low BOD carding oils were developed during World
War II and were found to be as good as, or better
than, olive oil. Further improvements in these
synthetic oils had made their use normal practice
by 1950.
Prevalent technology carding—A low BOD oil
(approximately 20 percent OWC) is sprayed onto the
-------
APPENDIX A-3-15
fiber while it is being mixed, in amounts ranging
from 1 to 8 percent. The fiber is then drawn, spun,
and woven into cloth.
Newer technology carding— Low BOD carding
oils (less than 3 percent OWC) are added in amounts
of 1 to 8 percent OWC.
(4) Fulling
Older technology fulling—Soap is generally
used as a fulling agent, often mixed with small
amounts of soda ash. The cloth is immersed in the
fulling solution then passed through squeeze rollers
which remove most excess.
Prevalent technology fulling—The wool cloth
is passed through an impregnating box containing a
synthetic fulling agent of low BOD (about 12 percent
OWC). The amount added (amount remaining in
cloth) depends on the degree of felting desired, and
usually falls in a range of 5 to 10 percent OWC.
Newer technology fulling — The fulling agents
used are either synthetic chemicals or sulfuric acid,
-------
APPENDIX A-3-16
hydrogen peroxide combinations. Fulling is still
done in tubs with beating action rollers. This type
of equipment has been in use for many years.
(5) Washing
Older technology washing — Soap and soda ash
plus softening agents are used in the string washer in
which approximately 46, 000 gallons of water are used
for each 1, 000 pounds of wool. Rinse water is gen-
erally not reused.
Prevalent technology washing—A low BOD
(12 percent OWC) synthetic detergent is used in a
string washer in which the entire wash-rinse cycle
is carried out twice to ensure complete removal of
the oil and fulling agent. Some of the rinse water is
recirculated and used to make the detergent solution.
Newer technology washing—The fulling solution
is completely neutral and contributes no BOD in itself.
Spray rinsing with recirculation or a running rinse in
a continuous piece washer may be used.
-------
APPENDIX A-3-17
(6) Carbonizing
Older technology carbonizing — Carbonizing is
done with a 6 percent sulfuric acid solution and 212°F
oven. Crushing and dusting are done mechanically
and neutralization is achieved by immersion in a soda
ash solution. The wool is rinsed before and after
neutralization with 16,000 + gallons of water /I, 000
pounds of wool.
Prevalent technology carbonizing—The wool is
carbonized with a 6 percent sulfuric acid solution
and oven heating to 212°F. It is neutralized by soak-
ing in a soda ash solution followed by a running rinse
of 16, 000 gallons/1, 000 pounds of wool.
Newer technology carbonizing — Traditional
methods of carbonizing have not been improved to the
extent of reducing the pollution loads; however, some
water reuse in rinsing may be practiced.
(7) Bleaching and Piece Dyeing
Older technology bleaching and piece dyeing-—
Bleaching is done in the dye kettles generally using
-------
APPENDIX A-3-18
hydrogen peroxide. This usually requires
heating to 115°F for at least 3 hours in order to
obtain a good bleach. Piece dyeing is rare, but the
procedure and process chemicals are similar to
those used for stock dyeing of wool fibers.
Prevalent technology bleaching and piece
dyeing—The small percentage of wool cloth which
is to remain white is bleached with sulfur dioxide
or hydrogen peroxide in vats which are also used for
dyeing. Some plants may bleach in the last bowl of
the scouring train before the fiber is woven. Optical
brightening, using acetic acid and fluorescent organic
compounds, is used in many mills. Some mills may
do a small amount of dyeing in small dye lots
following all finishing processes.
Newer technology bleaching and piece dyeing—
Traditional methods of bleaching and piece dyeing are
followed in newer, technologically advanced plants.
-------
APPENDIX A-3-19
2. Waste Characteristics
The major sources of polluting wastes in the wool yarn
and textile production process are scouring, dyeing, and washing.
Of all the textile wastes, wool scouring wastes are gener-
ally considered the most difficult to treat. Raw wool contains
an average of about 50 percent impurities and fibers. Approxi-
mately 50 percent of these impurities are wool grease (lanolin),
20 percent suint (principally potash salts from sweat), 20 percent
inert dirt, and 10 percent vegetable matter. The impurities are
easily dissolved in water, except for the grease. Thus, the
pollution load from the scouring process is extremely high in
BOD and grease, has a turbid brown color due to the large amounts
of dirt and grease, has a generally high alkalinity, and a temperature
between 115°F and 125°F. In an average plant. 50 to 60 pounds
of chemicals (detergents, alkali, softeners, etc.) are used for each
1,000 pounds of scoured wool. The total wasteload is, therefore,
composed of 1, 000 pounds of grease, suint, and dirt plus 50 to 60
pounds of chemicals; or 1, 050 to 1, 060 pounds of total solids for
each 1,000 pounds of scoured wool output.
Costs of treating this effluent by chemical means is
relatively high and treatment by biological means is not feasible
-------
APPENDIX A-3-20
without pretreatment for grease removal. Chemical or mech-
anical methods can be used to remove grease. However, the
process is an economical burden due to the lack of a market for
recovered grease.
Solvent scouring is a technically feasible method of grease
removal. In the solvent scouring method, the grease is removed
in the solvent distillery and the spent solvent is distilled and
reused. However, the lack of a market for grease creates a
financial bias against this process.
Dyeing produces an acid waste which is highly colored and
relatively high in BOD. It may also be slightly toxic depending
on the type of dye used.
Wastes from the wash after fulling contain a high concen-
tration of BOD and oil. In addition, these wastes have tempera-
tures ranging from 110°F to 150°F.
Table A-3-2 lists the substances found in the liquid waste
from a typical finishing mill for wool textiles. The waste analysis
given is for a combination of all the liquid wastes from all pro-
cesses in the mill including scouring, dyeing, and washing.
-------
Table A-3-2
Process Chemical Inventory and BOD Survey—Woolen Mill
Proce** Chemiral Cnmpii-iiinn
Chemical and 1 -e
Soap Fatly ai iH -nap: -murinit. fullmu
Nida A«>h Na.CO,. »rnunn|! fulling
Quailrafo- Na,.P4Olt: wa-hmi!
I'ine Oil I'me Oil. wa-hinv
Hai-apon 500
Proinl T Mineral ml |ilu- nuninnii emul-ifier:
rardinic
Acelir and
84% CH((0()H; dyeing
Olive Sub C3 - Oil; -pinning
Sulfunr acid — H.,SO4; rarlumi/in)!. d)ein|C
Chnmie mordant— ~NA_.< R_.O- + iNH4i_.SO4: dyeint:
Chrome Na_,C-r,O7. dyeing
Glauber call — Na_,SO4; dyeing
Mnnnrhlorn-
hen/ene Q,H -,('!: dveinp
Nnpco InSfi Snluble fatly e-ler: -pinning
IverM.I Rlenrl »f -.nap-. >nlvenl>. anil
determent-. Ka-hmc
Rinxil Determent; oa«hin|!
Sunertex K r"alt\ arid >nap>. -nl\enl. ire-\ln and.
Ha-hin)!
Wool Kmi»h R Ili^h iarlmhydrale> and en/\nie«: fini-h
^uli-liital
\nlnrnl lmininlir\
<>red-e -mill ilirl
(•mini lulal
% OWF*Hsed
Srnunnit
and
CardmfE
2.1
142
0.5
05
0.5
05
04
0
0
0
0
0
0
0
0
0
0
IR7
1500
lftft.7
Fmi-hin|i
55
2.8
0
0 '
0
0
12
0
0.2
04
O.f>
0.4
02
02
1 h
2V
02
2i
185
0
IRS
Total
7.6
17.0
05
0.5
0.5
05
12
04
02
04
Of.
0.4
0.2
02
If.
29
0.2
23
.17.2
1500
IK72
Conc'n
in
Effluent
152
340
10
10
10
10
24
8
4
8
12
8
4
4
32
58
4
4f>
748
WOO
4748
BOD
% .
owe*
155
0
0
108
—
20
62
0
0
0
0
3
12
hO
72
25
57
lfi.7
OWF*
11.7
0
0
0.5
0.1
0.7
0
0
0
0
0
0
1.0
2.1
0.1
1.3
17.5
250
42.5
* % OWC I* HOI) inherent in ilicmual. lia»ed mi il» weight
% OWF i> ROD due In the iliemiial. lia«ed mi weight n( »IHI|
M
2
O
i
CO
to
-------
APPENDIX A-3-22
(2) Cotton Industry
1. Production Processes
Raw cotton is converted to woven cloth or yarn before
any finishing processes are performed. The fundamental
processes for converting raw cotton to finished textile goods
are as follows:
Conversion to cloth
Desizing
Scouring or boil-off
Bleaching
Mercerizing or causticizing
Dyeing
Printing
Finishing.
Conversion to cloth and yarn is usually achieved in
a weaving mill, but this process does not directly produce
any hazardous wastes and is not included in the SIC codes
under consideration. Thus, the wastes from this process
will not be discussed in detail in this section.
-------
APPENDIX A-3-23
2. Waste Characteristics
The major sources of pollutants in a cotton finishing
plant are the desizing, scouring, and dyeing operations.
Wasteloads from other operations are less significant in
strength and volume.
The subprocess wastes which are most likely to
cause difficulty in treatment come from desizing and dyeing,
due to their high concentrations of BOD chemicals and solids.
The BOD chemicals exert an oxygen demand on the receiving
watercourse and may kill fish, produce taste and odor, form
floating scum, and generally be detrimental to beneficial
uses of the watercourse. Dyehouse wastes add aesthetically
objectionable color to the watercourse and, in addition, may
be toxic and either acidic or basic.
Chemical pollutants normally consist of acids, alkalis,
and inorganic salts. They may kill aquatic life, produce
taste and odor, inhibit municipal waste treatment processes,
and render the watercourse unfit for agricultural, municipal,
and industrial uses.
-------
APPENDIX A-3-24
Cotton finishing mills also present waste treatment
problems because wastes from the same plant vary greatly
at different times, especially dyehouse wastes. This pre-
sents a problem because biological waste treatment processes
often do not operate efficiently when subjected to wastewater
influents that vary widely in chemical constituents from day
to day.
In cases where the waste discharge from the plant is
a significant portion of the water flowing in the watercourse,
thermal pollution will result. A temperature rise in the
receiving water may prove detrimental to beneficial uses
downstream.
Table A-3-3 lists the substances found in the liquid
waste from a typical finishing mill for cotton textiles. The
waste analysis given is for a combination of all the liquid
wastes from all processes in the mill, including desizing,
scouring, and dyeing.
-------
Table A-3-3
Process Chemical Inventory and BOD Survey—Cotton Plant*
Chemical
Sla-hing March
Sub-total
Natural Impurities
Sub-total
Pounds
Used
733134
733134
337800
337800
BOD"
OWr Pounds
Drsar Contribution
59 432549
— 432539
SconrfKieri Contribution
— 128364
— 128364
% of
Total
695
69.5
20.6
20.6
Effluent Concentration
p.p.m.
176.0
176.0
81.1
81.1
B.O.D
1033
1033
303
303
Process Chemical BOD. Contribution
Soap
Acetic Acid 56%
Sodium hydruMilfite
I'rea
Rho/yme LA
Tergilol NPX
Detergent MPX
Sub-total
13715
54350
113250
85600
45600
63000
11700
787215
140 19125
35 19023
11 12458
9 7704
2 912
2 1260
8 936
61418
3.7
3.6
2.0
1.2
0.1
0.2
0.1
9.9
3.3
13.1
27.2
20.5
10.9
15.1
2.8
91.9
4.6
4.2
1.5
1.8
0.2
0.3
<0.1
12.6
Process Chemicals with Negligible BOD Contributions
Caustic Soda I 100% I
Sodium bicarbonate
Sidiuni hypochlorile
Sidiuni chloride
Sulfuric acid
Sodium silicate
Sidium tarhonale
Phosphoric acid
llydro|ien (icroxide <30% i
Sidiuni ihlonle
Sub total
(irand Total
2148000
260300
236100
144800
137600
f.7500
56000
44100
27500
23000
3144900
4603049
622331
513.8
62.5
56.6
34.7
32.2
16.0
133
106
6.6
5.5
752.3
1102.2
147.2
* Thi.- plant received h.4JI.OOO pounds of goods during the inventory period il year) and used 2,000,000 gallons of wvler per day.
It de-iied all of the cloth but caustic boiled only 3.378.000 pounds of it The remaining "fancy" cloth, with colored pattern
alread) woven in. 13.053.000 pounds) was peroxide kiered The plant dyed 2.360.000 pounds and left 1.018.000 pour is white.
• * *7< OWC i> BOD inherent in the chemical based on its own weight. Pounds equals the pound? of B O D exrlid by the
rbenuial
-------
APPENDIX A-3-26
(3) Synthetic Fiber Industry
1. Production Processes
Synthetic fibers fall into two main groups; they are
those produced from cellulose and those produced syntheti-
cally from organic materials. The cellulose fibers are
principally rayon and acetate. The organic fibers are
principally acrylics, polyesters, and nylon.
The funadamental processes for finishing rayon and
acetate fabrics are as follows:
Chemical preparation
Scouring and dyeing
Salt bath (rayon only)
Special finishing (optional).
The fundamental processes for finishing nylon,
acrylic, and polyester fabrics usually are as follows:
Scouring
Dyeing or bleaching
Scouring (acrylic and polyester only)
Special finishing (optional).
-------
APPENDIX A-3-27
2. Waste Characteristics
The three key waste-producing steps in the series of
finishing processes for synthetic textiles are scouring,
dyeing or bleaching, and special finishing.
Dyeing of polyester and acrylic fabrics presents a
particularly difficult waste problem due to the odors,
toxic vapors, and high BOD of the carriers, and the heat
of the waste water. Use of pressure dyeing is increasing
as machinery such as Burlington's Hy Press dye machine
comes into use. Where carriers continue to be used,
monochlorobenzene has the advantage of very low BOD in
comparison to other carriers. It has the disadvantage of
requiring venting facilities due to its toxic fumes.
Table A-3-4 lists the substances found in the liquid
waste from the various subprocesses making up the finish-
ing process for the different types of synthetic fibers.
4. WASTE DISPOSAL PROCESSES AND PRACTICES
There are two fundamental principles which may be followed in
order to reduce or eliminate the potential hazards presented to the
-------
APPENDIX A-3-28
Table A-3-4
BOD Contribution of Process Chemicals
Used in Finishing of Synthetic Fibers
Fiber
Rayon
Acetate
Nylon
Process
Chemical
Preparation
Scour
Scour and
Bleach
Salt Bath
Chemical
Preparation
Scour and
Dye
Scour and
Bleach
Scour
Developed
Dispersed
Dye
Bleach
Process Chemical
Antistatic lubricants,
oil, dye, synthetic
detergent
Synthetic detergent
Antistatic lubricants
Oil
Synthetic detergent,
H202
Synthetic detergent,
sodium chloride.
sulfates
Antistatic lubricants,
soap, tetrosodium
pyrophosphate, soda,
fatty esters
Antistatic lubricants
Sulfonated oils
Esters
Synthetic detergent,
H2O2 2£ chlorine
Antistatic lubricants
Soap
Tetrasodium pyro-
phosphate, soda
Fatty esters
Dye, NaN02, HC1,
developer, sulfonated
oils
Peracetic acid
BOD
% owe
14
--
53
--
52
41
--
150
55
56
%OWF
0.4
1.5
1.1
1.5
1.0
0.8
1.5
1.5
0.6
1.7
ppm
612
612
204
-------
APPENDIX A-3-29
Table A-3-4
Continued
Fiber
Acrylic
Polyester
Process
Cuprous Ion,
Phenol Dye
Thermosol
Padding Dye
Bleach
Scour
Scour
Thermosol
Padding
Dye With
Carrier
High Temper-
ature & Pres-
sure Dye
Bleach
Process Chemical
Dye, formic acid
Wetting agent
Phenol
Aromatic amines,
glyoxal, sulfates
Acid
Chlorite
Synthetic detergent
Pine oil
Antistatic lubricants
Chlorite, hypochlor-
ites, non- ionic syn-
thetic detergent
Acid
Dye
Monochlorobenzene o£
orthochlorobenzene
or phenylmethyl
carbinol
or salicylic acid
or benzoic acid
or orthophenylphenol
Dye
Chlorite, NaNO2.
acetic acid, oxalic
acid, nitric acid, bi-
sulfates, proprietary
bleaches
BOD
% owe
20
14
200
4
0
108
--
5
150
141
165
138
% OWF
0.6
0.1
6.0
0.1
0
1. 1
1.5
0.1
45.0
56.4
66.0
13.8
ppm
<480
19,000
25,000
25,000
6,060
-------
APPENDIX A-3-30
public health and welfare by waste materials and effluents from
industry.
Improve production subprocess design by:
Reducing the amount of waste from a subprocess
Recycling the waste from a subprocess to the
same or other subprocesses
Requiring different process compounds less
hazardous than previous compounds when
appearing in the waste stream
Developing new subprocesses which would
require less hazardous compounds
Developing useful purposes for waste materials.
Improve waste treatment capability by:
Construction of new facilities or enlargement of
present facilities to ensure that all wastes are
treated
Installation of new techniques to increase efficiency
in present facilities so that increased wasteloads
can be effectively treated
Installation of new techniques to increase the
effectiveness of present facilities so that treated
wastes pose a lesser hazard to the public health
and welfare.
The following paragraphs describe how these two principles have
been applied to the finishing process industries for the three major
typas of textiles and the degree to which they have been applied.
-------
APPENDIX A-3-31
(1) Wool Industry
1. Production Subprocesses
Table A-3-5 shows the subprocess trends since
1950 and projects them to 1982. Of course, most sub-
process changes are initiated and developed for reasons
other than pollution reduction. However, certain sub-
processes do afford a reduction in waste production when
compared to 1950 technology subprocesses. These waste
reduction figures expressed as a percentage of the wastes
generated in 1950 are presented in Table A-3-6.
By-product utilization depends on economic consider-
ations. It is estimated that 50, 000 to 100, 000 tons of wool
grease and 20, 000 to 40, 000 tons of suint could be utilized
if the market for these products made it economically feasi-
ble. Lanolin is recovered from the wool grease and potash
from the suint.
The amount of process water reused in 1964 was
considerably greater than in 1950 when older methods were
practiced. Counter-current scouring can reduce the amount
of water required by as much as 6, 000 gallons /I, 000 pounds
-------
APPENDIX A-3-32
Table A-3-5
Wool Industry Subprocess Trends
Production Process and
Significant Subprocesses
Scouring
Soap/alkali
Syndet
Non- ionic syndet
Solvent
Dyeing
Sodium Sulfate
Sulfur Dioxide
Hydrogen Peroxide
Acetic Acid
Su If uric Acid
Carding
Olive Oil
Synthetic Oil*
Fulling
Soap
Synthetic Chemicals
Sulfuric Acid
Washing
Soap
Syndet
Carbonizing
Sulfuric Acid
Estimated Percentage of Plants
Employing Process in:
19"iO
80
0
0
20
100
40
40
20
100
20
80
95
0
5
100
0
100
1963
0
80
0
20
100
10
70
20
100
0
100
10
70
20
0
100
100
1967
0
50
40
10
100
5
75
20
100
0
100
0
80
20
0
100
100
1972
0
40
50
10
100
0
85
15
ICO
0
100
0
90
20
0
100
100
1982
0
30
65
5
100
0
95
5
100
0
100
0
100
0
0
100
100
20 percent BOD content by weight.
-------
APPENDIX A-3-33
Table A-3-6
Process Pollution Reduction
Process and
Subprocesses
Scouring
Soap/ Alkali
Syndec
Solvents
>yelng
Acetic Acid
Ammonium Sulfate
Su If uric Acid
lashing
Soap/Alkali
Syndet
Syndet
!arbonlzing
Su If uric Acid plus
Sodium Carbonate
BOD lb/
1000 lb
250
221
10
49
10
70
ISO
64
30
2
Waste Reduction
Effectiveness
(X)
0
11.6
96
30
86
0
0
57.3
80
0
Remarks
Syndet denotes
Synthetic Detergent
20 percent BOD oil used
for carding
BOD reduction due to
use of 3 percent BOD
oil in carding
-------
APPENDIX A-3-34
of wool. Reuse of rinse waters in the wash after fulling
can reduce water requirement by approximately 4,000
gallons/1,000 pounds of wool. It has been estimated that,
in 1964,the wool industry as a whole reused approximately
5 percent of its process water and 95 percent was used
only once.
2. Waste Treatment Capability
Figure A-3-2 is a waste treatment flow chart for the
wool textile finishing industry. The four main subprocesses
involved in wool finishing are depicted, and the possible
treatments for each waste are shown. Treatment practices
vary from finishing mill to finishing mill, so that any treat-
ment process or combinations of processes may prevail at
a given wool finishing mill.
The most common practices of waste treatment in
the wool industry are biological methods, such as sedi-
mentation, activated sludge, trickling filtration, and
lagooning. Screening is almost universally used to remove
fibers which may possibly damage subsequent treatment
facilities. Equalization and holding are generally necessary
-------
APPENDIX A-3-35
FIGURE A-3-2
Wool Textile Production Waste
Treatment Flow Chart-SIC 2231
SCOURING
SUINT
RECOVERY
DECREASING
STOCK DYEING
kSB
RECOVERY
WASHING
AFTER
FULLING
4
NEUTRALIZE
AFTER
CARBONIZING
EQUALIZATION 6 HOLDING
TREATMENT OF
1
(FLOTATION &
SKIMMING/
1
1
COACUUnON
1
TINE MESH
SCREENING
SLUDGE
CONCENTRATION
i
1 EFFLUENT
t
1
i
\
DECREASED I
1
SEDIMENTATION |~
ACTIVATED SLUDGE I
TREATMENT I~~
TRICKLING FILTRATION]
1
(
.IQ1
-
f
JOR.
| LAGOONS
LAGOON
OR
SAND BED
TREATED
DISCHARGE
-------
APPENDIX A-3-36
due to batch dumping of many of the process wastes
creating shock loads and intermittent flows through the
treatment system.
In the past, wool wastes were treated by chemical
precipitation without pretreatment for grease recovery;
however, the present trend is toward biological oxidation
and chemical pretreatment due to economic factors.
Work in recent years by Souther and others indicates
clearly that the activated sludge process with modifications
(primarily extended aeration time and influent pH adjust-
ment) will consistently produce BOD reductions on the order
of 90 percent. As the discharge requirements imposed upon
the textile finishing plants are upgraded, it is probable that
future waste treatment facilities will be predominantly of
the activated sludge type.
The percentage of wool finishing wastes treated by
municipal plants is also increasing steadily as costs of
building and maintaining Inplant treatment facilities in-
crease. Newer finishing mills are being built close to
municipalities rather than in rural areas to take advantage
of the availability of municipal treatment.
-------
APPENDIX A-3-37
Much of this industry's waste is discharged to
municipal sewers because they are often located adjacent
to or within population centers. Industry wastes are
generally pretreated by grease removal techniques and
screening prior to discharge into a municipal system.
Municipal waste treatment plants are not equipped to
easily handle the large amounts of grease produced by
wool mills. Screening for removal of fibers is also
necessary to prevent clogging of biological treatment
equipment and to reduce the quantity of suspended matter.
Carrying rates of waste production require holding tanks
and surge basins to minimize peak discharge and provide
for more or less uniform rates of release to sewers.
Municipal treatment without pretreatment may be feasible
in the case of high capacity chemical coagulation treatment
plants.
Table A-3-7 shows the effectiveness of the various
treatment processes in removing selected pollutants.
Table A-3-8 provides some historical data and some
projections as to the percentage of wool finishing mill
wastes being treated by municipal facilities, industrial
facilities, and that percentage which is not being treated.
-------
APPENDIX A-3-38
Table A-3-7
Treatment Removal Efficiencies
Treatment
Method
Grease Recovery
Acid Cracking
Centrifuge
Evaporation
Screening
Sedimentation
Flotation
Chcrn. Coagulation
CaCl2
Lime + CaCl2
C02- CaCl2
Alum
Copperas
H2S04+ Alum
Urea + Alum
H2S04+ FeCl2
Peso*
Activated Sludge
Trickling Filtration
Lagoons
Normal Reduction Percent
BOD
20-30
20-30
95
0-10
30-50
30-50
40-70
60
15-25
20-56*
20*
21-83*
32-65*
59-84*
50-80
85-90
80-85
0-85
Grease
40-50
24-45
95
0
80-90
95-98
97
0-15
0-10
0-10
Color
0
0
0
0
10-50
10-20
75
10-30
10-30
10-30
Alkal inily
0
0
0
0
10-20
10-20
10-30
10-30
10-20
SS
0-50
40-50
20
50-65
50-65
80-95
80-95
80-95
90-95
90-95
30-70
-------
Table A-3-8
Projected Net Wasteloads
Year
1963
1967
1968
1969
1970
1971
1972
1977
1982
Gross
Waste
Generated
BOD
million Ib
132
132.5
132.8
132.9
,133.0
133.1
133.2
134.2
136
Waste
Treated
Municipally
percent
38.5
40.0
40.5
41.0
41.5
42.0
42.5
45.0
48.0
Average
Reduc-
tion
percent
85
86
86
86
87
87
87
88.5
90
Waste
Treated
By
Industry
percent
21.0
23.0
23.5
24.0
24.5
25.0
25.5
28.0
31.0
Average
Reduc-
tion
percent
70
71
71
71
72
72
73
74
76
Untreated
Wastes
percent
40.5
37.0
36.0
31.0
34.0
33.0
32.0
27.0
21.0
Total
Reduction
percent
47.4
50.7
51.5
52.4
53.7
54.6
55.4
60.6
66.8
Net Waste
Discharged
BOO
million Ib
69.4
65.4
64:5
63.3
61.6
60.4
59.4
52.9
45.1
M
2
D
>
CO
CO
CO
-------
APPENDIX A-3-40
(2) Cotton Industry
1. Production Subproceases
Table A-3-9 shows the subprocess trends in the
cotton finishing industry since 1950 and projects them to
1982. It should be pointed out that which subprocess is
used depends upon such factors as type and color of cotton
cloth being finished, type and size of process machinery
available, skill of available operating personnel, and
length of run.
Table A-3-10 indicates the potential pollution reduc-
tion by substitution of alternate manufacturing subprocesses.
In most cases, the reduction is associated with high-speed
continuous machines or substitution of alternate chemicals.
The economic feasibility of purchasing new machinery or
substituting alternate chemicals is, of course, an individual
decision for each finishing plant. It is anticipated that pollu-
tion reduction will become an increasingly important factor
in future management decisions.
-------
Table A-3-9
Subprocess Trends
APPENDIX A-3-41
Fundamental Process
and Subpirocesses
Desizing
Enzyme
High T° Enzyme
Water (used with CMC)
Scouring
Boil-Off
Kier Boil
Cont. Scouring
Wet Out
Bleaching
Hypochlorite
Hydrogen Peroxide
Continuous
Mercerizing and
Causticiaing
NaOH
Dyeing
Vat
Basic
Direct
Kaphthol
Developed
Sulfur
Aniline Black
Fiber Reactive
Printing
Roller
Screen
Other
7. of Plants Employin
1950
80
20
0
15
70
15
50
50
40
90
10
70
60
70
90
5
10
95
4
1
1963
58
40
2
15
50
20
15
20
80
50
35
90
5
75
55
50
90
5
20
95
4
1
1967
15
80
5
15
20
50
15
20
80
60
30
90
0
80
50
30
90
5
40
95
4
1
e Subprocess
1972
5
85
10
10
5
75
10
10
90
70
25
90
0
80
45
10
85
5
50
90
0
10
1982
0
85
15
5
n
9'.1
r
,i
0
100
80
20
80
0
90
35
0
75
5
70
90
0
10
-------
APPENDIX A-3-42
Table A-3-10
Pollution Reduction by Alternate Subprocesses
Fundamental Processes
and Subprocess
Desizinp:
Enzymes
Water CMC/
Starch Formulation
Scouring;
Boil-off
Con tin. Scour
Bleaching i
Bins
Continuous
Mercerizing end
Caustlclzing
Continuous
Cont. in Recovery
of NaOH
Dyej.ng!
Butch
Continuous
Syn. Dot.
Printing;
: Roller w/soap wash
; Roller with
; Syndat wash
Soap & Syndet
BOD
Lb/1000 Lb
67
20
53
42
4
3
15
6
10 • 60
5-32
5-8
43
19
30
Process Reduction
Efficiency
(7,)
0
70
0
21
0
25
0
60
0
50
80
0
53
30
Remarks
BOD Reduction due
mainly to use of
CMC /Starch Fornu.-
lation in weaving
mill.
NaOH used in both
cases but cont.
process allows use
of less solution.
H202 used
predoninantly
Synthetic detergents
used in wash after
dyeing.
In Prevalent tech.,
both soap and
synthetic detergents
are used.
-------
APPENDIX A-3-43
These waste reduction figures are expressed as a
percentage of the waste generated by a particular subprocess
using 1950 technology. The values shown are generally the
highest reductions for a particular alternate subprocess.
There is no significant by-product use of wastes in
the cotton textile finishing industry. Various researchers
have attempted to develop economically feasible methods
for recovery of the expensive dyeing compounds, but were
unsuccessful. No future by-product use on a significant
scale is predicted.
It is estimated that approximately 16 percent of the
industry process water is reused, and 84 percent is used
only once. It appears that the percentage of process water
reused will increase in the future because newer machinery
is often of continuous or counter-current design. In addition,
because process water is becoming more expensive in many
areas, there will be increased use of instrumentation to
control processes more precisely.
-------
APPENDIX A-3-44
2. Waste Treatment Capability
Figure A-3-3 is a waste treatment flow chart for
the cotton textile finishing industry. Seven principal sub-
processed involved in cotton finishing are depicted, and
the possible treatments for each waste are shown.
Treatment practices vary from finishing mill to finishing
mill so that almost any treatment process or combination
of processes may prevail at a given cotton finishing mill.
Generally, the textile cotton finishing waste treat-
ment process should begin with a holding and equalization
basin. This will level out the volume of flow and pollution
strength to the following treatment units. A reasonably
uniform waste can be treated biologically with much greater
success than can a widely fluctuating waste.
Since the waste is relatively low in suspended solids
and high in dissolved solids, it is often feasible to skip the
primary settling step and begin directly with the aeration
tank. In some cases where the pH is too high, toxic elements
or some other factors inhibiting to the biological treatment
may be present, making chemical pretreatment necessary
prior to the aeration tank.
-------
APPENDIX A-3-45
FIGURE A-3-3
Cotton Textile Finishing Waste
Treatment Flow Chart-SIC 2261
DESIZINC
REPLACE
SLASHING
SIZES H/
LOW POL-
LUTION
CCHPOUNDS
ANAEROBIC
DIGESTION
DEEDED
PLUS
AERATION
REPLACE
SOAP W/
SYNTHETIC
DETERGENT!
IN WASH-
ATION!
2
KXERIHG
AERAnON &
AKOTRALIZA-
TION KIKR
HASTES
BLEACHING
COUNTERFLOW
6 CONTINUOUS
MOVEMENT
HEAT RECOVERY
FOR DIB
HOUSE
MERCERIZING
~STTc5
-------
APPENDIX A-3-46
The activated sludge process for cotton textile waste
is often modified by increasing the aeration time and carry-
ing a higher concentration of mixed liquor suspended solids
in the aeration tank. With careful operation, this process
will produce excellent reduction of BOD and suspended
solids. If some domestic sewage is available to mix with the
textile waste, the efficiency of the plant is generally increased.
To lower construction costs, an aerated lagoon is
sometimes substituted for the activated sludge process.
Properly operated, it is capable of closely approaching the
pollution removal efficiency of the conventional activated
sludge process.
The trickling filter biological treatment is widely
installed, but the trend is away from its use in recent years.
It cannot reach the removal efficiencies of the activated
sludge process and generally lacks operational flexibility.
Where cheap land is available, an inexpensive
tertiary treatment is simple storage in a pond of the second-
ary effluent from the biological treatment process. Simple
storage will often reduce the effluent pollution load an
-------
APPENDIX A-3-47
additional 50 percent, for example, increasing removal
from 90 to 95 percent.
It is estimated, however, that by 1972, 40 percent of
cotton textile finishing mill wastes will be discharged into
municipal sewer systems. Many municipal waste treatment
methods will be susceptible to shock loads from the mills;
therefore, pretreatment should include flow regulation and
equalization holding procedures to ensure waste uniformity.
In a large municipality, the mill waste would be diluted
sufficiently before reaching the treatment facility and would
not harm the operation. Even so, most large municipalities
require finishing plants to provide screening and constant
discharge holding basins. Normally, a cotton finishing plant
waste is easily handled by conventional treatment methods.
Table A-3-11 shows the effectiveness of the various
treatment processes in removing selected pollutants.
Based on a typical waste generated by prevalent plants in
the base year, 1963, the removal efficiencies are expressed
in terms of percentage of gross wasteload removed by the
removal process. It is assumed that the auxiliary units
normally associated with the removal method are included.
-------
Table A-3-11
Treatment Removal Efficiencies
APPENDIX A-3-48
Removal Method
Screening
Plain Sedimentation
Chemical Precipitation
Trickling Filter
Activated Sludge
Lagoon
Aerated Lagoon
Removal Efficiency (Percent)
BOD
0-5
5-15
25-60
40-85
70-95
30-80
50-95
ss
5-20
15-60
30-90
80-90
85-95
30-50
50-95
TDS
0
0
0-50
0-30
0-40
0-40
0-40
Table A-3-12
Waste Treatment Projections
Year
1967
1968
1969
1970
1971
1972
1977
1982
Percent Waste
Treated
Municioally
35
36
37
38
39
40
43
45
Average
Reduction
(Percent)
85
85
85
86
86
86
87
87
Percent Waste
Treated By
Indur.trv
25
27
29
31
33
35
40
45
Average
Reduction
(Percent!
80
80
80
80
80
80
80
80
Total
Reduction
(Percent)
49.5
52.0
54.5
57.5
60.0
62.5
69.5
75.0
-------
APPENDIX A-3-49
For example, the removal efficiencies for the activated
sludge process and trickling filter process assume that
the primary and secondary sedimentation tanks are
included in the process.
Table A-3-12 provides some projections as to the
percentage of cotton finishing mill wastes treated by
municipal facilities and that percentage treated by indus-
trial facilities. The average percent of waste reduction
for these two types of treatment is also projected, and
this affords a prediction of the percentage of total waste
reduction.
The rate of adoption of waste treatment practices
in the textile finishing industry has paralleled, to some
extent, the trends in the municipal sewage treatment area.
As technology has advanced, the attainable standards of
pollution reduction have increased also.
Work in recent years by Souther and others indicates
clearly that the activated sludge process with modifications
(primarily extended aeration time and influent pH adjustment)
will consistently produce BOD reductions on the order of
90 percent. As the discharge requirements imposed upon
-------
APPENDIX A-3-50
the textile finishing plants are upgraded, it is probable
that future waste treatment facilities will be predominantly
of the activated sludge type.
The* rapid increase in treatment predicted in
Table A-3-12 is based on continued strong pressure by
regulatory agencies upon industry to reduce pollution dis-
charged, continued large capital investment to build new
plants and phase out old ones, continued tendency to locate
new plants where a municipal sewer is available for waste
discharge, and advancing technology in waste treatment
processes.
(3) Synthetic Fibers Industry
1. Production Subprocesses
Table A-3-13 shows the subprocess trends in the
synthetic textile finishing industry since 1963 and projects
them to 1982. It should be pointed out that there are often
alternate methods to accomplish a particular operation in
the synthetic textile finishing process. Which method is
used depends upon such factors as type and color of cloth
being finished, type and size of process machinery
-------
APPENDIX A-3-51
Table A-3-13
Subprocess Trends
Textiles and Procesaes
Chemical Preparation
rayon &. acetate
1 . Scour
Scour: nylon, acrylic, polyester
L. Soda Ash
2. Caustic Soda
3. Ammonium Hydroxide
4. Sodium Carboxymethyl
Cellulose
Scour and Dye: rayon
1. Direct
2. Naphthol-
3. Developed
4. Vat
Scour and Bleach: rayon & acetate
1. Hydrogen Peroxide
2. Hypochlorite
3. Sodium Chlorite
Dye Nylon:
1. Dispersed
2. Acid
3. Direct
Dye Acrylic:
1. Cationic w/cationj.c retarder
2. Cationic w/anionic retarder
3. Disperse
4. Basic
Dye Polyester:
1. Conventional
2. w/Orthophenylphenol
3. w/Chlorincted benzenes
4. Benzole? or Salicylic Acid
5. Phenylmethyl carbinol
6. High Temp. 6 Pressure
7. Thermosol Padding
Estimated Percentap? of Plants
Ei-nloyitig Irocsss
1950
1963
100
10
10
60
50
100
30
40
60
50
50
80
60
20
20
50
10
60
60
5
3
2
40
40
5
5
1967
100
5
15
65
60
100
30
50
60
55
45
70
60
20
20
45
10
70
70
5
20
10
20
20
15
10
1972
100
5
20
70
70
100
20
60
70
60
40
60
70
10
20
40
5
80
80
5
20
15
10
10
25
15
1982
100
2
20
70
70
100
20
65
70
65
35
50
70
10
20
30
5
90
90
_
20
25
-
-
35
20
-------
APPENDIX A-3-52
Table A-3-13
Continued
Textiles and Processes
Bleach: nylon, acrylic, polyester
1. Sodium Chlorite
2. Peracetic Acid
3. Hydrogen Peroxide & Sodium
Hypochlorite
Final Scour: acrylic & polyester
1. Soda Ash
2. Caustic Soda
3. Ammonium Hydroxide
4. Sodium Carboxymethyl
Cellulose
Heat Set: all fibers
1. Optional
Finishing: all fibers
1. Optional
Estimated Percentage of Plants
Emplov
1950
1963
30
50
20
10
10
70
30
BO
70
ring Process
1967
20
50
30
5
10
70
40
85
75
1972
10
50
40
2
20
80
50
90
80
1982
10
40
50
2
30
85
60
95
95
-------
APPENDIX Ar3-53
available, skill of available operating personnel, length
of run, and other factors. The primary considerations
in choosing one method over another are production effi-
ciency and product quality, and any decrease in wasteload
produced by the operation is merely a bonus.
Table A-3-14 outlines the relative pollution reduction
potentials of the various alternative subprocesses used in
the synthetic textile industry. The "older" technological
method in each case is used as the basis for comparison.
The values shown are generally the highest reported reduc-
tions for a particular alternate subprocess.
The thermosol dyeing process is an example in that
it produces little liquid waste. Some special finishing
processes use padding to apply the finish and therefore
produce little waste.
There would be an adequate market for wastes
reclaimed in synthetic fiber finishing if economically
feasible methods were developed. This is due to the
fact that all liquid wastes contain chemicals used in the
finishing (or sizing) itself and could be reused if reclaimed.
-------
APPENDIX A-3-54
Table A-3-14
Process Pollution Reduction
Textiles & Processes
Chemical Preparation:
Rayon and Acetate
Lower BOD Chem.
Scour: Nylon, Acrylic
and Polyester
Continuous Scour Machine
Scour and Dye:
Rayon and Acetate
Continuous Machines
Scour and Bleach:
Rayon and Acetate
Continuous Machines
Dye: Nylon
Dye: Acrylic
Dye: Polyester
High temp, pressure dye
machine
Bleach: Nylon, Acrylic »
Polyester
Continuous Bleaching Machine
Final Scour:
Acrylic and Polyester
Continuous Scour Machine
Special Finishing:
All Fibers, Optional
Percent Reduction
Older
0
0
0
0
0
0
0
0
0
0
0
Prevalent
2
10
10
10
Depends
on
Dye
80
5
10
Depends 01
Newer
5
IS
15
IS
Depends
on
Dye
80
10
20
a Finish
-------
APPENDIX A-3-55
The one exception to this is the one percent OWF nylon
extracted in the scour. All carriers presently recovered
are reused. It is not economical to reclaim the other
chemicals, such as spent developed dye bath. Thermal
waste can be reused by heat transfer methods.
It is estimated that the synthetic textile finishing
industry reused approximately 10 percent of its process
water in 1964, and 90 percent was used only once.
2. Waste Treatment Capability
Figure A-3-4 is a waste treatment flow chart for the
synthetic textile finishing industry. Seven principal sub-
processes involved in synthetic textile finishing are de-
picted, and the possible treatments for the wastes from
these subprocesses are shown. Treatment practices vary
from finishing mill to finishing mill, so that almost any
treatment process or combination of processes may prevail
at a given synthetic textile finishing mill.
Synthetic textile wastes have generally been treated
by biological methods with good removal efficiency at
reasonable cost. In the future, it is expected that water
-------
FIGURE A-3-4
Synthetic Textile Finishing Waste
Treatment Flow Chart-SIC 2262
CHEMICAL
PREPA-
RATION
SCOUR
DYE
9LEACH
i <
I
SCOUR
HEAT
SETTXHG
P 1
SPECIAL 1
FINISHES I
r i
1
EQUALIZATION AMD HOLDING
I
PLAIN
SEDIMENTATION
_£
ACTIVATED
SLUDGE
LAGOONDtC
SCREEN INC
CHEMICAL
PRECIPITATION
TRICKLING FILTER
TO
WATERCOURSE
pH CORRECTION
FLOTATION
OXIDATION POND
-------
APPENDIX A-3-57
requirements per unit production will be reduced.resulting
in a plant effluent which will be higher in pollution concen-
tration and lower in volume. Therefore, the adoption of
more elaborate waste treatment facilities utilizing pre-
treatment and tertiary polishing can be expected.
Toxic metallic ions in dye wastes can retard biolo-
gical oxidation when present in high concentrations.
Chemical pretreatment may, therefore,become a require-
ment, or the industry may choose to adopt treatment by
chemical coagulation as the principal method.
Interdependencies among processing techniques
which affect wasteload removal efficiencies or cost are
as follows:
Any heavy metal ions in the waste mill
normally inhibit biological treatment such
as trickling filters or activated sludge. If
a toxic ion is present, it may have to be
removed chemically prior to further treat-
ment or discharge.
Toxic carriers, such as chlorinated benzenes,
may inhibit bacterial growth in biological
treatment. These carriers might be removed
and reused because of their high cost as well
as their toxic effect.
-------
APPENDIX A-3-58
Sequences of treatment due to technical considerations
are as follows:
pH adjustment may precede other chemical
treatment to reduce use of costly chemicals.
Normally, suspended solids removal pre-
cedes biological treatment methods such
as activated sludge or trickling filter,
lagooning, and oxidation ponds. Certain
activated sludge modifications may not
require suspended solids removal.
Sludge treatment and ultimate disposal follow
sludge-producing processes, such as settling.
Substitute techniques may be:
Biological and chemical treatments are,
under certain circumstances, substitutes
for each other. In other situations they may
be part of the same waste treatment process.
Sometimes fine screening may be substituted
for sedimentation basins.
Normally, the activated sludge and the trickling
filter process are not used together in the
same system.
Table A-3-15 shows the effectiveness of the various
treatment processes in removing selected pollutants. Based
on a typical waste generated by prevalent plants in the base
year 1963, the removal efficiencies are expressed in terms
-------
APPENDIX A-3-59
Table A-3-15
Treatment Removal Efficiencies
Treatment Method
Screening
Plain Sedimentation
Chemical Precipitation
Trickling Filter
Activated Sludge
Lagoon
Aerated Lagoon
Removal Efficiency (Percent)
BOD
0 - 5
5-15
25 - 60
40 - 85
70 - 95
30 - 80
50 - 95
SS
5-20
15 - 60
30 - 90
80 - 90
85 - 95
30 - 80
50 - 95
TDS
0
0
0-50
0-30
0-40
0-40
0-40
Table A-3-16
Waste Treatment Projections
Year
1967
1968
1969
1970
1971
1972
1977
1982
Municipally
Treated
Waste
Percent
50
51
52
53
54
55
68
71
Avg BOD
Reduction
Percent
85
85
85
86
86
86
87
88
Industry
Treated
Waste
Percent
25
26
2/
28
29
30
32
34
Avg BOD
Reduction
Percent
65
66
67
68
69
70
73
76
Total
Reduction
Percent
58
60
62
64
66
68
82
88
-------
APPENDIX A-3-60
of percentage of gross wasteload removed by the removal
process.
Table A-3-16 provides some projections as to the
percentage of synthetic textile finishing mill wastes treated
by municipal facilities and the percentage treated by indus-
trial facilities. The average percent of waste reduction
for these two types of treatment is also projected, and this
affords a prediction of the percentage of total waste reduc-
tion.
The tremendous growth rate of the synthetic textile
industry is expected to continue and increase as various
new materials (modifications of existing fibers) and new
fibers are introduced to the public. Concurrent with this
growth, a nearly equal increase in wasteload seems
imminent. This, along with pressures by regulatory
agencies regarding stream pollution, will lead to an
increased rate of adoption of waste treatment practices
in the future.
It is expected, however, that the gross pollution load
produced by the synthetic textile finishing industry will in-
crease significantly because of rapidly increasing production.
-------
APPENDIX A-3-61
The organic and suspended solids pollution reaching
the nation's watercourses will remain essentially constant
because of a greater percentage of waste treated and higher
waste treatment efficiencies. This is not true of the dis-
solved inorganic matter since most prevailing waste treat-
ment methods do not significantly reduce dissolved minerals.
Tertiary treatment techniques capable of removing dissolved
inorganic matter are currently under extensive study, but
it is unlikely that they will come into significant use prior
to 1982.
-------
APPENDIX A-3-62
REFERENCES
"Disposal of Dye and Finishing House Wastes and Similar Materials,"
E.G. Oden, Sr., Water and Sewage Works, September 1967, pp. 367-368.
"Stream Pollution and Effluent Treatment, with Special Reference to
Textile and Paper Mill Effluents, " Dr. L. Klein, Chemistry and
Industry, May 23, 1964, pp. 866-873.
"Waste Treatment Studies at Cluett, Peabody and Company Finishing
Plant, "R.H. Souther, American Dyestuff Reporter, July 28, 1969,
pp. 13-16.
"Sodium Hydroxide Recovery in the Textile Industry, " C. S. Carrique,
L.U. Jauregui, Purdue University - Engineering Extension Series 121,
1966.
"The Treatment and Control of Bleaching and Dyeing Wastes, " A. H.
Little, Water Pollution Control Federation Journal, 1969, pp. 178-189.
"Energy-Induced Changes In An AZO Dyestuff Waste, " A.I. Mytelka,
R. Manganelli, Water Pollution Control Federation Journal, February
1968, pp. 260-268.
"Biological Treatment of Textile Effluents, " A.I. Biggs, Chemistry
and Industry, September 16, 1967, pp. 1536-1538.
"Orion Manufacturing Waste Treatment, " E.F. Taylor et al., Water
Pollution Control Federation Journal, October 1961, pp. 1076-1089.
"Aerobic Treatment of Textile Mill Waste, " E. L. Jones, T. A.
Alspaugh, H. B. Stokes, Water Pollution Control Federation Journal,
May 1962, pp. 495-512.
"The Disposal and Recovery of Textile Wastes, Part I - The Problem;
Preliminary Studies; Experimental Work; Disposal by Chemical
Precipitation, " M. S. Campbell, Textile Research, pp. 490-504.
-------
APPENDIX A-3-63
"Pollution Factors and Treatment of Textile Waste Waters. " P. W.
Sherwood, The Textile Manufacturer, June 1965, pp. 235-238.
Industrial Waste Surveys of Two New England Cotton Finishing Mills,
M. G. Burford and J. W. Masselli, New England Interstate Water
Pollution Control Commission, June 1953.
Pollution Sources from Finishing of Synthetic Fibers, J. W. Masselli
and M. G. Burford, New England Interstate Water Pollution Control
Commission, June 1956.
The Cost of Clean Water, Volume III: Industrial Waste Profile No.
4 - Textile Mill Products, U. S. Department of Interior, Federal
Water Pollution Control Administration, September 1967.
A Simplification of Textile Waste Survey and Treatment, J. W. Masselli
and M. G. Burford, New England Interstate Water Pollution Control
Commission, July 1959.
Reuse of Chemical Fuber Plant Wastewater and Cooling Water
Slowdown, Fiber Industries, Inc., for the Environmental Protection
Agency, Water Quality Office, October 1970.
-------
APPENDIX A-4
SIC 26 —PAPER AND ALLIED PRODUCTS
-------
APPENDIX A-4
SIC 26—PAPER AND ALLIED PRODUCTS
1. ECONOMIC STATISTICS
This classification includes all pulp mills: those which produce
only pulp, and those which produce pulp as a part of the production
of either paper, paperboard, or building papers and boards. The
basic financial and statistical data on the industry for 1967 is shown
below (Reference 1).
E stablishments
SIC Code and Industry
261 - Pulp Mills
262 - Paper Mills, Except
Building Paper
263 - Paperboard Mills
2661 - Building Paper and
Building Board Mills
Total
Value of
Shipments
($ Million)
$ 730.5
4,844.0
2,907.0
341. 1
Total
No.
61
354
283
94
20 or more
Employees
43
313
264
74
$8,822.6
792
694
The 1967 geographic distribution of the industry is given by SIC
code in the following table (Reference 1):
-------
APPENDIX A-4-2
261*
15(9)
11(6)
18(12)
17(16)
262
184(158)
92(87)
48(42)
30(26)
263
36(36)
28(28)
27(27)
16(16)
266
74(62)
64(59)
21(15)
14(10)
The first number indicates the total establishments; the second
number (in parentheses), those with 20 or more employees.
The production of pulp and paper mill products in 1967 is shown
in the following table (Reference 1):
Production
SIC Code and Industry (thousand short tons)
2611 Pulp Mills 37,066
2621 Paper Mills Except 20,938
Building Paper
2631 Paperboard Mills 22,657
2661 Building Paper and 2,754
Building Board Mills
83,415
2. WASTE CHARACTERISTICS
Pulp mill operations include wood preparation, pulping, screen-
ing, washing, thickening, and bleaching. Paper mill operations include
stock preparation, paper machine operation, converting, and finishing.
-------
APPENDIX A-4-3
Wood preparation involves movement of the log from stock
pile to debarking facilities. Pulping converts wood into fibers for
papermaking. Four processes are currently used:
Mechanical—Logs are forced against a grindstone in the
presence of water.
Chemigroundwood—The log is cooked before grinding.
Sulfate (Kraft)—Alkaline solutions dissolve the lignin
(non-cellulose portion of wood cementing cellulose fibers
together).
Sulfite—An aqueous solution containing metallic bisulfite
(Mg, NH3, Na) and sulphur dioxide digests the wood chips.
Wastewaters generated result from spills, leaks, over-
flows, and cooking liquid preparation. They emanate from
the same sources as in the Kraft process. This is also true
for gaseous wastes.
Pulp screening separates coarse and fine fibers and removes
dirt and foreign matter. Coarse screens or centrifugal cleaning is
used.
Thickening (or dewatering) concentrates the screened pulp using
deckers or vacuum filters. Water removed is used to thin fresh stock.
Bleaching brightens the pulp. Two-stage peroxide-hydrosulfite
methods are used. After each stage of the bleaching process, a
washing cycle is needed. Chlorination (followed by alkaline extraction)
and oxidation bleaching are common techniques. Wastewaters are re-
duced by reuse of water in multistage bleaching.
-------
APPENDIX A-4-4
In paper mills, stock preparation involves treating the pulp
mechanically and chemically to form sheets. Water reusage is com-
mon with discharged waste-water contaminated by rejects and cleaners.
The paper machine then converts the fiber suspension into a paper
sheet. Wastewater is usually discharged into the sewer. The by-
products and undesirable wastes are conveyed to an incinerator to
generate power and steam. Other operations in this process include
loading (addition of fillers), sizing, wet strength resins, and coloring.
Most pulp and paper mills reuse water from log plumes and
debarkers, evaporators, washers, bleach plant washers, and paper
machine operations.
Although modifications in fundamental operations do occur, it
is not uncommon for a mill to use older technology in one process and
newer technology in another.
The wastes from mill processes are high in biological oxygen
demand (BOD), while production operations consume large quantities
of water. Typical requirements (Reference 2) include:
-------
APPENDIX A-4-5
Operation
Debarking and Cleaning
Unbleached Kraft Mill
Sulfite - Pulp
Semi-Chemical Pulp
Paper Mills
De -Inking
Jute Rope Rag
Water Required
(gallons/ton)
200 - 1,000
15,000 - 40,000
15,000 - 30,000
20,000 - 30,000
10,000 - 35,000
20,000 - 30,000
65,000 - 80,000
Biological Oxygen
Demand
(Ib/ton)
5 -
10
50
550 - 750
100 - 200
5 - 15
50 - 150
300 - 1,200
Water requirements can be estimated by multiplying the annual
production 83, 500 tons with the estimates of water requirement per
ton of 20,000 - 40,000 gallons. Based on these calculations water
requirements are between 1. 7 and 3. 4 billion gallons. These amounts
compare well with the Census Bureau for 1968 of 2. 2 billion gallons
intake, 6. 5 billion gallons total use (including recirculation) and the
discharge of 2.0 billion gallons.
3. DISPOSAL PRACTICES
A wide variety of processes are available to reduce the solid, or
BOD pollutants, in effluent streams. Economic considerations are
paramount in effluent treatment. Processes which are inherently low
-------
APPENDIX A-4-6
cost or which can produce saleable by-products are needed to econo-
mically reduce the effluent solids with a high BOD.
The effluents from pulp and paper mills, with the exception of
weak wastes and uncontaminated cooling waters, receive some form
of treatment. The waste reduction practices employed are water
reuse, chemical recovery, fiber and solids recovery. The major
pollutants are temperature, BOD (biological oxygen demand),
COD (chemical oxygen demand), color, dissolved solids, SS (suspended
solids) and bacteria. At the present technological level, waste
reductions of 20 to 70 percent can be obtained by water reuse (Reference 3).
Wastewater treatment practices can be divided into four groups:
pretreatment, primary treatment, secondary treatment, and tertiary
treatment. Other treatments may include "strong" waste digester
liquor and pulp wash water handling and disposal, sludge handling
and disposal, and by-product production. Wastewaters may be dis-
charged into separate sewers according to strength and characteristics.
The four major treatment processes are designed to remove as many
contaminants as possible.
-------
APPENDIX A-4-7
(1) Pretreatment
Pretreatment includes the initial operations that prepare
or condition the wastewater prior to primary clarification.
Waste-waters can be either combined mill effluent or segregated
wastewaters.
The most common pretreatment methods used are grit
and debris removal, and wastewater screening. Inorganic ash,
grit from the wood preparation process, and runoff materials
(sand and gravel) must be removed from the wastewaters.
Gravity settling tanks, using a fixed wastewater flow velocity,
remove approximately 70 to 80 percent of the grit. Bar screens
are also used to remove debris.
Neutralization of mill wastewaters is also a pretreatment
process. Wastewater pH can affect conditions in the receiving
stream and cause possible corrosion of mechanical treatment
equipments. Wastewater, after pretreatment, must have a pH
of 6. 5 to 8. 5 to prevent damage to other treatment facilities.
Since wastewater streams vary in pH from 1.5 to 12.0, the
neutralization method is a function of the process of wastewater
separation. Extreme fluctuations in the pH occur and, as a
result, automated systems are used to adjust the pH and lessen
operating costs.
-------
APPENDIX A-4-8
Since waste water temperatures are high compared to
receiving surface waters, wastewater cooling is part of the
pretreatment process. High temperatures result in reduced
efficiency in the biological treatment process. Several cooling
methods are used: towers, spray ponds, cascade channels, and
detention ponds. Cooling towers and cascade channels may,
however, aggravate the foaming problem accompanying pulp
and paper mill wastewater treatment. The foam is controlled
by cold water sprays and antifoam agents.
(2) Primary Treatment
Primary treatment is mainly responsible for the removal of
suspended solids. Certain wastewater colloidal materials and
dispersant-type chemicals inhibit gravity settling of suspended
solids. Flocculation of the wastewater, with or without floccu-
lating chemicals (alum, FeCIS, poly electrolytes), aids in the
removal of suspended solids by gravity settling or dissolved air
flotation. Settling lagoons or gravity clarifiers are used. Very
fine fibers and solids from sulfite mills are removed by air
flotation. The BOD removed is mainly the organic and fibrous
materials that settle out.
-------
APPENDIX A-4-9
Equalization facilities are commonly used between primary
and secondary treatment to control variations in mill wastewater,
flows and characteristics (pH or temperature).
(3) Secondary 'Treatment
Secondary treatment is mainly involved with the removal
of soluble BOD, using biological treatment processes. Prior
to treatment, nutrients vital to the existence of a balanced
biological community are added — mainly N and P in the forms
NHg and Hg PO4- Nutrient starvation could result in lower
removal efficiencies and poor settling characteristics in the bio-
logical sludge.
The activated sludge process for BOD removal is imple-
mented by contacting wastewater with a biological population in
the presence of dissolved oxygen. Organic materials are thus
removed from the water. Gravity settling removes the biological
mass which returns to the beginning of the process to sustain it.
In the contact-stabilization modification of this process, the
biological organisms, after settling out and being transported
to a separate aerated stabilization basin, are returned to the
wastewater and then finally removed.
-------
APPENDIX A-4-10
Eighty-five percent BOD removal is attainable with a
process time of 4 to 6 hours for a mixed liquid having a sus-
pended solids concentration of 2,000 to 3,500 mg/1. The contact-
stabilization modification is particularly applicable to integrated
Kraft mill effluents.
Trickling filters having biological growths remove waste
organics as the wastewater flows through the media. However,
this method has a lower BOD removal efficiency than the process
previously discussed.
Another biological treatment method is the use of lagoons
or stabilization ponds where low concentrations of biological
solids are maintained to remove BOD. An aerated lagoon is
capable of removing 40 to 70 percent of the BOD present.
Irrigation disposal is also used. Operational problems —
runoff, stream pollution, freezing of wastewaters during winter —
limit the applicability of this approach. However, 60 percent
of the BOD can be removed before the wastewater reaches
groundwater levels.
-------
APPENDIX A-4-11
(4) Tertiary Treatment
Tertiary treatment is used to obtain removal of COD and
suspended solids, as well as further removal of BOD, color,
dissolved solids, and bacteria.
From a water pollution standpoint, lignins (as dissolved
color) and bacteria (in concentrated communities) are of pri-
mary consideration. Tertiary treatment has not been very
successful in removing these pollutants.
The most widely used facility for tertiary treatment is the
holding pond. Additional BOD and COD removal by limited bio-
logical activity, as well as the removal of solids by extended
detention and bacterial flocculation, occur. Aerobic conditions
are required. Biological filtration and irrigation methods are
also a part of tertiary treatment.
To date, neither chlorination nor ozonation has been
practical for bacterial removal because of the high chemical
demands and relatively high wastewater flows.
Color removal has been achieved by activated carbon
absorption and foam separation with a 90 percent removal
efficiency.
-------
APPENDIX A-4-12
Inorganic solids removal is achieved by several tertiary
treatment methods: electrodialysis, reverse osmosis, and ion
exchange. Combinations of methods have been proposed.
(5) Other Methods
In addition to the four general treatments of waste-water,
several other treatment operations may be conducted. Among
these is sludge disposal, strong waste disposal, and by-product
recovery.
Sludge Disposal—the handling, dewatering, and
disposal of primary and secondary sludges—either
together or separately. Several dewatering methods
are used: vacuum filtration using conditioning
chemicals, centrifugation, sludge presses, drying
beds, and sludge lagoons. The selection of method
depends on sludge characteristics, land availability,
ultimate disposal considerations, and proportion and
secondary sludges. Landftiling or incineration of
primary and secondary sludges is common.
Strong Wastes Disposal—deep well disposal of
liquor and pulp washer water. The effectiveness
is dependent on geological formations at the mill
location and the amount of waste discharged.
Another method is dilution of spent liquors for
land application — having similar factors as in irri-
gation disposal to define its effectiveness and their
spray application to land. However, runoffs
cause significant damage to receiving stream condi-
tions because of high BOD and solid concentrations.
Waste Treatment By-Products—Several organic by-
products can be recovered from the cooking liquor
-------
APPENDIX A-4-13
resulting from various types of pulping operations.
They include turpentine, oil, yeast, alcohols, and
dimethyl sulfoxide (DMSO). Bark by-products
include roofing felts, thermal insulation materials,
and wrapping paper. The sulfite spent liquor can
be used to produce insecticides, tanning agents,
reinforcing agents, reinforcing agents in rubber,
cement dispersing agents, etc.
By-products are not, at present, obtained from sludges
resulting from mill waste water. However, possible future
by-product development includes: (1) fiber recovery from
primary sludge, (2) drying activated sludge for use as a fuel
supplement, and (3) processing activated sludge as an animal
food supplement or commercial fertilizer.
-------
APPENDIX A-4-14
REFERENCES
1. 1967 Census of Manufactures, U.S. Department of Commerce,
Bureau of the Census, 1971.
2. Industrial Pollution Control Handbook, H. F. Lund, McGraw-Hill
Publishing Co., 1971.
3. Industrial Waste Study of the Paper and Allied Products
Industries, WAPORA, Inc. , for the Environmental Protection
Agency, July 1971.
4. The Cost of Clean Water, Volume III: Industrial Waste Profile
Number 3 - Paper Mills. Except Building, U. S. Department of
Interior, Federal Water Pollution Control Administration,
November 1967.
5. A Paper Industry Environmental Control Technical Program,
National Council of the Paper Industry for Air and Stream
Improvement Inc. , (NCASI).
-------
APPENDIX A-5
SIC 28—CHEMICALS AND ALLIED PRODUCTS
-------
APPENDIX A-5
SIC 28-rCHEMICALS AND ALLIED PRODUCTS
INDUSTRIAL ORGANIC CHEMICALS
1. GENERAL CHARACTERISTICS
The classification of industrial organic chemicals is generally
defined in SIC codes 2815 and 2818. These classifications establish a
middle ground between the processes which produce basic raw mate-
rials from petroleum refining and the industries which use organic
chemicals to produce finished products. The distinction is certainly
not clear cut. The basic processes for production of raw materials
from coal are included in these two classifications,and some of the
outputs are used commercially as finished products.
Any discussion of these two classifications as a separate entity
is further complicated by the fact that the classifications do not define
a given type of industry or plant operation. In the first place, it is
common to find plants which combine products of organic chemicals
in these classifications either with refining operations or production of
final products in a number of other industrial classifications. Secondly,
the range of organic chemicals included is so broad and the production
processes so varied that there are entire industrial groups which
specialize in producing only a few items. Considering that there are
-------
APPENDIX A-5-2
several thousand chemicals of commercial importance produced, the
combination and permutations of combined product lines is quite
large. For example, in 1969. some 1.500 different cyclic-intermedi-
ate organic chemicals were produced by about 215 different companies
in an unspecified number of different plant locations. The number
produced by a given company ranges from more than 10 percent of the
total to a single compound.
(1) SIC 2815—Cyclic Intermediates, Dyes. Organic Pigments
(Lakes and Toners), and Cyclic (Coal Tar) Crudes
This industry comprises establishments primarily engaged
in manufacturing cyclic organic intermediates, dyes, color
lakes and toners, and coal tar crudes. Important products of
this industry include:
Derivatives of benzene, toluene, naphthalene, anthra-
cene, pyridine, carbazole, and other cyclic chemical
products
Synthetic organic dyes
Synthetic organic pigments
Cyclic (coal tar) crudes, such as light oils and light
oil products; coal tar acids; and products of medium
-------
APPENDIX A-5-3
and heavy oil such as creosote oil, naphtholene,
anthracene, and their higher homologues and tar.
Establishments primarily engaged in manufacturing coal tar
crudes in chemical recovery ovens are classified in SIC
3312, and petroleum refineries which produce such products in
SIC 2911.
The industry is concentrated in the east coast area with
65 percent of the firms in this region. As of 1968, the middle
atlantic division, in particular, contains 45 percent of all the
establishments as documented below.
Establishments (1968)
20 or More
Division Total Employees
New England 17 5
Middle Atlantic 78 46
East North Central 26 20
South Atlantic 20 14
East South Central 10 7
West South Central 14 11
Pacific 8 3_
Total 173 106
-------
APPENDIX A-5-4
The total number of establishments has grown considerably
over the past decade. A 50 percent growth has increased the
total number of firms from 115 in 1958 to 173 in 1968. In com-
parison, the total employment has grown relatively little from
28,300 in 1958 to about 30,000 by 1968.
There is a considerable variation in industry size as
indicated below. However. 7 firms, comprising only
4 percent of the total number of firms, employ over 40 percent of
the total industry employees.
Size of Establishment No. of Total No. of
(No. of Employees) Establishments Employees
1
5
10
20
50
100
250
500
1,000
- 4
- 9
- 19
- 49
- 99
- 249
- 499
- 999
- 2,499
26
20
24
27
16
37
13
7
7
177
Less than 50
100
300
900
1,100
5,800
4,500
5,100
12,100
29.950
-------
APPENDIX A-5-5
The industry has experienced a 10-year growth (1958 to
to 1968) in both total value of shipments and value added by manu-
facture. Value of shipments have grown over 70 percent from
$934. 4 million to $1,596. 8 million, while value added has risen
more than 80 percent from $403.1 million to $729. 5 million.
Value of shipments of the cyclic intermediates and crudes
industry in 1967 included shipments of cyclic intermediates and
crudes (primary products) valued at $1,092.1 million, shipments
of other products (secondary products) valued at $412. 7 million,
and miscellaneous receipts of $91.9 million. Secondary products
shipped by this industry in 1967 consisted mainly of industrial
organic chemicals ($168. 4 million) and industrial inorganic
chemicals ($74. 6 million).
Other industries shipping cyclic intermediates and crudes
(primary products) consisted mainly of SIC 2818, Industrial
Organic Chemicals ($360. 2 million), SIC 2911, Petroleum
Refining ($60. 5 million), and SIC 2821, plastic materials and
resins ($42. 8 million).
-------
APPENDIX A-5-6
(2) SIC 2818—Industrial Organic Chemicals, Not Elsewhere
Classified
This industry comprises establishments primarily engaged
in manufacturing industrial organic chemicals, not elsewhere
classified. Important products in this industry include:
Noncyclic organic chemicals such as acetic, chloro-
acetic, adipic, formic, oxalic and tartaric acids
and their metallic salts; chloral, formaldehyde,
and methylamine
Solvents such as amyl, butyl, and ethyl alcohols;
methanol; amyl, butyl and ethyl acetates; ethel ether,
ethylene glycol ether and diethylene glycol ether;
acetone, carbon disulfide and chlorinated solvents
such as carbon tetrachloride, perchloroethylene,
and trichloroethylene
Polyhydric alcohols such as ethylene glycol, sorbitol,
pentaerythritol, synthetic glycerine
Synthetic perfume and flavoring materials such as
coumarin, methyl salicylate, saccharin, citral
citronellal, synthetic geraniol, ionone, terpineol,
and synthetic vanillin
-------
APPENDIX A-5-7
Rubber processing chemicals such as accelerators
and antioxidants, both cyclic and acyclic
Plasticizers, both cyclic and acyclic, such as esters
of phosphoric acid, phthalic anhydride, adipic acid,
lauric acid, oleic acid, sebacic acid, and stearic
acid
Synthetic tanning agents such as naphtalene sulfonic
acid condensates
Chemical warfare gases
Esters, amines, etc, of polyhydric alcohols and fatty
and other acids.
About 46 percent of the total number of establishments are
located on the eastern seaboard and in particular the middle
atlantic division with over 27 percent of the firms. However, a
considerable number of firms are also located in the east north
central, west south central, and pacific divisions as shown on
following page.
-------
APPENDIX A-5-8
Establishments (1968)
Division
New England
Middle Atlantic
East North Central
West North Central
South Atlantic
East South Central
West South Central
Mountain
Pacific
20 or More
Fotal Employees
36
132
80
18
55
25
80
7
55
488
14
75
46
7
30
18
50
3
25
258
The 10-year growth (1957 to 1968) in the number of establish-
ments has been better than 45 percent, from a total of 334 in 1957
to 488 by 1968. During this same period, total employment has
grown over 65 percent, from 508,000 million to 844, 900 million.
Although the large majority of establishments have fewer
than 100 employees, there are a few large firms with over
1,000 employees. Twenty firms, representing only about 4 percent
of the total number of firms, employ over 50 percent of the total
number of employees (about 49,000 persons), as shown on the
following page.
-------
APPENDIX A-5-9
Size of Establishment
(No. of Employees)
1-4
5-9
10 - 19
20 - 49
50 - 99
100 - 249
250 - 499
500 - 999
1,000 - 2,499
2, 500 or more
No. of Total No. of
Establishments Employees
125
49
46
69
50
70
38
21
13
7
488
200
300
600
2,100
3,500
11,100
13,500
15,100
21,800
27,000
95,200
The industry has experienced a 10-year growth (1958 to
1968) of over 100 percent in both total value of shipments and
value added by manufacture. Value of shipments have grown
about 105 percent, from $3,098.0 million to $6,377. 8 million,
while value added has grown about 107 percent from $1, 725. 8
million to $3,575.3 million.
Value of shipments and other receipts of the Industrial
Organic Chemicals Industry in 1967 included industrial organic
chemicals (primary products) valued at $4,461.2 million.
-------
APPENDIX A-5-10
shipments of other products (secondary products) valued at
$1,705.2 million, and miscellaneous receipts of $211.4 million.
2. PRODUCTION STATISTICS
The best available data on the production of synthetic organic
chemicals is contained in the annual reports of the U.S. Tariff Com-
mission (Reference 1), which list chemicals and the companies which
produce them. Production statistics on materials in these SIC code
industries are contained in Table A-5-1.
Table A-5-1
Production Statistics
General
SIC
Code
2815
2815
2818
2815
2815
2818
2818
2818
Material
Classification
Tar
Tar Crudes
Intermediates
Dyes
Pigments
Flavor and Perfume
Materials
Rubber processing
Chemicals
Plasticizers
Miscellaneous Chemi-
cals
Production
1969
millions of
pounds)
7,608
9,845
25,014
226
54
117
313
1,331
67,525
Production
Percent
Change
from 1968
+ 5.4
+ 3.5
+ 9.4
+ 2.9
+ 10.9
-4.8
- 2.7
+ 2.9
+ 14.5
Number of
Producers
13
215
48
35
52
34
59
340
-------
APPENDIX A-5-11
(1) Tar and Tar Crudes
The quantity of tar and tar crudes produced from coal
belongs to SIC code 2815 while that produced from petroleum
is in classification 2900 and discussed elsewhere. Although
the products are essentially the same, the quantity produced
from coal is generally small (except for naphthalene) and the
process is quite different from that used with petroleum.
Comparisons are given in Table A-5-2.
Table A-5-2
Tar and Crude Production
Material
Tar
Benzene
Benzene
Toluene
Xylene
Napthalene
Creosote
Oil
Producer
Coke ovens
Coke ovens
Petroleum
Coke ovens
Petroleum
Coke ovens
Petroleum
Tar distillers and
coke ovens
Petroleum
All
Units
1000 gal
1000 gal
1000 gal
1000 gal
1000 gal
1000 gal
1000 gal
1000 Ibs
1000 Ibs
1000 gal
Production
1969
768,766
101,695
1,083,653
19,603
739,855
5,246
376,596
525,711
375,945
126,895
-------
APPENDIX A-5-12
(2) Cyclic Intermediates
As noted earlier, there are some 1,500 cyclic intermedi-
ates manufactured in commercial quantities. The precursors of
these compounds are primary intermediates produced from
natural gas, petroleum refining, and coal tar distillations,
which are discussed separately. The chemical versatility of
hydrocarbons in modern chemical technology has resulted in a
great deal of conflicting market statistics because it is almost
impossible to avoid counting basic structures more than once as
they enter the market as different products. Thus ethylbenzene
is a standard item of commerce (a cyclic intermediate and a
final product), but so also are the benzene and ethylene from
which it was made.
Of the 1500 cyclic intermediates, 84 percent of the total
pounds produced can be accounted for by 16 companies as shown
in Table A-5-3.
(3) Organic Dyes and Pigments
Domestic synthetic dyes are derived in whole or in part
from cyclic intermediates. About two-thirds of the consumption
is used to dye textiles, about one-sixth to color paper, and the
-------
APPENDIX A-5-13
Table A-5-3
Large Volume Cyclic Intermediates
Material
Ethylbenzene*
Styrene
Cyclohexane
Phenol
Cumene
p -Xylene
Dimethyl terephthalate
Terephthalic acid
O - Xylene
Phthalic anhydride
Cyclohexanane
Chlorobenzene
Straight chain alkylbenzenes
Nitrobenzene
Isocyanates
Aniline
Production 1969,
(million Ibs)
4,907
4,648
2,232
1,691
1,687
1.628
1,537
1,045
850
760
704
602
529
484
421
334
Number of
Producers
16
13
13
13
13
12
4
3
16
12
6
11
7
7
11
7
Does not include ethylbenzene consumed in continuous process
styrene production.
-------
APPENDIX A-5-14
remaining one-sixth to produce pigments and dye leather and plastics.
In 1961. the production was 240 million pounds. Note that this is
two orders of magnitude smaller than production of cyclic
intermediates. In fact,the total production in this category is
less than just the aniline production.
There are several thousand different synthetic dyes known
and more than a thousand are being produced by about 48 manu-
facturing companies. Three chemical classes of dyes account
for two-thirds of the total production:
Azo dyes 31.5%
Anthraquinone dye s 21.6%
Stilbene dyes 17.1%.
Production of organic pigments amounted to 61 million
pounds in 1969, by essentially the same manufacturers.
(4) Miscellaneous Organic Chemicals
This classification (as defined in Reference 1) covers
many of the organic chemicals classified in SIC 2818. Total
production in this classification in 1969 amounted to 76 million
pounds, or three times the amount of cyclic intermediates.
There are 340 companies involved in producing these materials.
-------
APPENDIX A-5-15
The largest classes of cyclic materials were lubricating
oil additives and synthetic tanning materials. In the acyclic groups,
the largest classes were halogenated hydrocarbons, the nitro-
genase compounds, monohydric alcohols, and aldehydes
and ketones. Taken together, these classes represent 2/3 of the
production.
In Table A-5-4,the major classification and the total pro-
duction are shown, together with the members of each class
with the largest production. Of the many hundreds of individual
compounds produced, more than two-thirds of the production
is accounted for in 25 compounds.
(5) Rubber Processing Chemicals
These are the organic compounds added to natural and
synthetic rubbers to provide qualities necessary for conversion
into finished rubber goods. Total production was about 300 mil-
lion pounds in 1969, or less than the production of many indivi-
dual chemicals in the other groups above. Thirty-four companies
are involved in producing these compounds.
In the cyclic materials, which totaled 255 million pounds,
110 million pounds was in amino antioxidant compounds and
42 million pounds of phenolic and phosphite antioxidants.
-------
APPENDIX A-5-16
Table A-5-4
Production of Miscellaneous Organic Compounds
Cyclic, total
Lube oil additives
Tanning materials
Other
Acyclic, total
Cellulose esters and ethers
Cellulose acetate
Lubricating oil additives
Nitrogeneous compounds
Acrylonnitrile
Hexamethylenediamine
Acetone cyanohydrin
Urea
Acids, acyl halides, and anhydrides
Acetic acid
Acetic anhydride
Adipic acid
Salts of organic acids
Aldehydes and ketones
Acetaldehyde
Acetone
Formaldehyde
Alcohols, monohydric
Ethyl alcohol
Isopropyl alcohol
Methanol
Polyhydric alcohols
Ethylene glycol
Propylene glycol
Esters of monohydric alcohols
Halogenated hydrocarbons
Carbon tetrachloride
Chloroethane
1. 2 Dichloroethane
Tetrachloroethylene
Trichloroethylene
Vinyl chloride
All other
Ethylene oxide
Propylene oxide
Phosgene
Rounded Totals
Billions of Ibs
1.90
.83
1.16
.66
.54
5.94
1.77
1.68
1.22
1.65
1.52
4.40
2.36
2.01
4.21
2.57
.46
.58
.40
.92
1.15
.50
13.29
5.75
.25
9.99
11.15
5.53
2.28
16.19
73.81
7.73
75. 7 75. 7
-------
APPENDIX A-5-17
(6) Plasticizers
These are organic chemicals added to plastics and resins
to modify their properties. Total production in 1969 was
1, 382 million pounds. A total of 59 companies were involved
in this production.
Cyclic plasticizers accounted for 1,023 million pounds
of the total. Two compounds, di(2-ethylhexyl) phthalate and
diiso-octal phthalate accounted for 438 million pounds or
42. 8 percent of the cyclic production, or 31.7 percent of all
production.
The acrylic plasticizers accounted for 359 million pounds
of the total. Of this, complex linear polyesters amounted to
54 million pounds and epoxidized esters 104 million pounds.
The production by type material is shown in Table A-5-5.
3. PRODUCTION PROCESSES AND WASTE CHARACTERISTICS
All organic chemicals of industry can be synthesized from hydro-
carbons. In the early years, hydrocarbon materials were obtained
from coal. However, this source is inadequate to support the needs
of a modern industrial economy and since WW II,the primary raw
-------
Table A-5-5
Plasticizer Production
APPENDIX A-5-18
Cyclic, total
Phosphoric acid esters
Phthalic anhydride esters
Trimellitic acid esters
Other
Acryclic, total
Adipic acid esters
Complex linear polyesters
Epoxidized esters
Oleic acid esters
Phosphoric acid esters
Sebacic acid esters
Steric acid esters
Other
Millions
67
884
8
65
66
54
104
13
19
10
10
70
of Ibs
1,022
359
-------
APPENDIX A-5-19
material source is petroleum refining. The oil refining industry has
changed their operations from pure unit operations to one involving
many unit processes for reforming of crudes. Currently, about 5 to
6 percent of the petroleum production is going into organic or petro-
chemicals.
(1) Tar and Tar Crudes
This discussion is limited to coal derived products. Tar
and tar crudes are produced by de tractive distillation of coal,
often in the production of coke for steel making. The products
obtained are dependent on the type of coal used, the method employed,
and the operating conditions. Consequently, the products are
to some degree dependent on product demand. Currently, the
two main objectives in the primary distillates of crude tar are
to obtain a pitch or refined tar residue of the desired softening
point and to concentrate, as far as possible in certain fractions,
those components which are subsequently to be recovered. In
the case of the vertical continuous retort, the main aim is to
concentrate the phenols, cresols, and xylenols in the carbolic
oil fraction, whereas, in the processing of coke-oven tar, the
main objective is to concentrate naphthalene and anthracene in
the napthalene oil and anthracene oil, respectively. The degree
-------
APPENDIX A-5-20
of fractionation employed is generally no better than that required
to achieve these purposes. The number of fractions is usually
be^ow 7. Table A-5-6 indicates typical fractions that
might be taken and the generally recognized product
names. The boiling ranges and yields, however, will vary with
each plant, its design, the nature of the crude, and the secondary
refining operations. It should also be noted that there are no univer-
sally recognized names for the fractions and that the same
term in different plants may refer to two different boiling ranges.
The type products to be derived from each fraction are illustrated
in Figure A-5-1.
In the fraction distilled up to 150°C, one method of further
refining consists of washing with a 2 to 4 percent concentrated
sulfuric acid. This produces a waste acid stream contaminated
with organics which consist of sulfonated non-aromatic s and thio-
phene derivitives* Alternatively the fraction is treated with a cobalt
molybdate-on-alumia catalyst and solvent extraction to remove
these same impurities. The benzol forerunnings contain carbon
disulfide and cyclopentadiene. These forerunnings were formerly
treated to recover the latter products, since cyclopentadiene was the
®(R)
„.— ,^.B .—.— „.„ »„. *~*~+~* and Dieldrin ^y insecticides.
-------
Table A-5-6
Typical Fractions Taken in Continuous Tar Distillation to Medium-Soft Pitch
Type of Tar
Continuous Vertical Retort
Fraction
1
2
3
4
5
6
7
Residue
Liquor and
losses
Names
Crude benzole.
light oil
Naphtha, Car-
bolic oil.
Phenolic oil
Heavy naphtha.
Carbolic oil.
Naphthalene oil
Naphthalene oil
Wash oil,
Benzole
absorbing oil,
light creosote
Creosote
Heavy creosote.
Medium-soft
pitch
Boiling
Range (°C)
106-167
167-194
203-240
215-254
238-291
271-362
285-395
(50%)
Wt (%)
of Crude
Tar
2.4
3.1
9.3
3.5
10.2
11.5
12.1
40.5
7.4
Coke Oven
Names
Crude benzole.
light oil
Naphtha,
light oil.
Naphthalene
oil
Wash oil.
Benzole ab-
sorbing oil,
light creosote
Anthracene
oil.
heavy creosote
heavy oil
Heavy oil
Medium -soft
pitch
Boiling
Range (°C)
99-160
168-196
198-230
224-286
247-355
323-372
(90%)
Wt (%)
of Crude
Tar
0.6
2.9
14.6
2.8
8.0
9.5
56.6
5.0
M
>
en
to
-------
FORE- PITCH
BOOMS RUNNIN6S COKE
CRUDE CRUDE fA*
ANTHRA- NAPHTHA-
LENE
Source: Koppers Co., Inc.
FIGURE A-5-1
Products Derived from Coal
i
en
i
10
-------
APPENDIX A-5-23
These forerunnings are now disposed of as wastes (with
the restrictions on organochlorine insecticides), principally
by burning.
In the fraction distilled in the 150-200°C range, the
pyridine bases, napthas and coumarone resins are produced.
The pyridine bases can be extracted from this fraction with
successive washes of 10 percent aqueous caustic soda (to
remove phenols) followed by slight excess of 25-35 percent
aqueous sulfuric acid in which the bases are soluble. The
acid is neutralized with an alkali base to render the pyridine
fraction insoluble, producing a saturated aqueous solution as
waste. The naptha fraction is sometimes treated with sulfuric
acid which produces a waste. The coumarone resin fraction is
reacted with a boron trifluorine catalyst complexed with acetic
acid or phenol to produce coumarone resin products.
The fraction distilling in the 200 to 250°C range currently
produces the most valuable chemicals, the carbolic and naph-
thalene oils. The carbolic fraction (or tar acids or phenol
fraction) are separated by extraction with an excess of 10 per-
cent aqueous caustic. The carbolic fraction is steam distilled
and then "sprung" in a "springing tower" by treating with a
-------
APPENDIX A-5-24
countercurrent flow of carbon dioxide. The springing tower
product separates into two layers, a layer of crude tar acids
and an aqueous waste solution of sodium carbonate containing
tar acids. The crude tar acid layer is treated with either sul-
furic acid or more carbon dioxide producing more aqueous waste
of either sodium sulfate or bicarbonate. The sodium carbonate/
bicarbonate solution is treated with quicklime (CaO) to recreate
the caustic solution which in turn produces a calcium carbonate
precipitate (lime mud) that is removed by filtration or precipi-
tator. This lime mud is contaminated with tar acids, which are
toxic.
The naphthalene in the 200 to 250°C fraction is the most
abundant single compound in coke oven tar. It is refined in a
number of ways but principally by crystalization and distillation.
Distillation of product destined for production of phthalic anhydride
must be desulfurized by treatment with sulfuric acid, metallic
sodium or catalytic refining, which produce wastes. In any case,
napthalene product is washed with dilute caustic, producing a
toxic waste.
No tar chemicals are extracted commercially from the 250-
300 C distilling fraction. Oil in this range is used in creosote
blends.
-------
APPENDIX A-5- 25
Fractions distilling in the range 300-350°C contain the
anthracene oils composed of 12-25 percent anthracence, 20-35
percent phenanthrene, and 7-15 percent carbazole. The waste
associated with this fraction were not identified in this study.
(2) Cyclic Intermediates
1. Aniline
There are three production processes for aniline
(Reference 2):
Iron reduction of nitrobenzene
Ammonolysis of chlorobenzene
Vapor phase hydrogenation of nitrobenzene.
In the first, or iron reduction process (which is
being superseded by vapor phase hydrogenation)/ 250 pounds
of 30 percent hydrochloric acid solution and 3,200 pounds
of iron borings are consumed per ton of aniline. These
appear as waste liquor solutions of HC1 and ferrous chlor-
ide (FeCl2> and ferric oxide (Fe3O4) sludges. A second
type aniline contaminated waste, tar waste, is produced
as bottoms from the final product distillation purification
-------
APPENDIX A-5-26
step. Yields are 90 to 95 percent. Any waste contaminated
with aniline is poisonous and toxic, and is a problem parti-
cularly because aniline is absorbed through the skin.
In the second process, ammonolysis of chloroben-
zene, an aqueous solution of ammonia is reacted at high
pressure. A by-product of a mole of ammonium chloride
per mole of aniline is produced in aqueous solution, con-
taminated with aniline. The active catalyst is cuprous
chloride made by reacting the by-product ammonium
chloride with cuprous oxide. Consequently, the waste
streams are solutions of ammonium chloride or cuprous
chloride in one to one molar quantities to the aniline com-
pound. Aniline yields are 85 to 90 percent.
The vapor phase hydrogenation of nitrobenzene or
third process is conducted in a fluid bed reactor with a
copper catalyst on SiOg. The process produces a
mole of water per mole of aniline as a by-product which
is an aniline contaminated waste stream. Bottom purges
from the crude aniline still used in product purification,
consist of tars and other materials contaminated with
aniline. Aniline yields are 98 percent.
-------
APPENDIX A-5-27
2. Alkybenzene, Cumene and Ethylbenzene
These three materials are discussed together
because all are produced by alkylation of benzene in
chemically related reactions. All involve the reaction
of an olefin with benzene in reactions catalyzed with a
protenic acid (sulfuric acid, hydrogen fluoride, phosphoric
acid) or by a Friedel-Crafts type of catalyst (aluminum
cloride-hydrogen chloride, boron fluoride). A summary
of the processes, catalysts and yields is given in
Table A-5-7.
Multiple alkylations occur in these reactions. In
the case of ethylbenzene, the polyalkylated material is
recycled for transalkylation, but 2 percent of the feed is
converted to higher polyalkylated products and olefin poly-
mers which are removed as tars. All the alkylation
reactions, therefore, lead to production of high molecular
weight by-product tars resulting from condensation of the
olefin feed and polyalkylation of the benzene. In addition
-------
Table A-5-7
Summary of Alkylation Reactions
Material
Ethylbenzene
Cumene
Dodecylbenzene
Reactants
Ethylene and benzene
Prophylene and benzene
Propylene trimer
and benzene
Catalyst
A1C1.-HC1
•j
H3ro4
Alkar (BFJ
3
H2S04
V°4
HF
AICA..-HCI
H2S04
Catalyst
Consumption
1-3 IDS/ 100 Ibs
product
1 lb/50 gal
product
1 gal H2S04/ 10-12
gal product
1 lb/200 Ib
product
- -
1-3 Ib MCE./
150 Ib product
1 Ib H2S04/
0. 87 Ib product
Yields
92%
High
90%
—
M
01
i
to
00
-------
APPENDIX A-5-29
impurities in the olefin feed stocks (such as propylene or
acetylene with the ethylene) lead to by-products which are
removed as wastes.
Other wastes produced in the processes result from
the catalysts and the water and caustic washes used to
neutralize the product. The aqueous streams are caustic
containing sodium sulfate, sodium chloride and aluminum
chloride contaminated with product and by-products.
3. Chlorobenzene
Production of monochlorobenzene consists of reacting
purified benzene with dry chlorine in the presence of such
chlorination catalysts as ferric, aluminum and antimony
chlorides. The reaction is exothermic,and is always ac-
companied by the production of minor amounts of ortho
and para isomers of dichloro benzenes. In practice, the
chlorination of benzene is always conducted as a three-
product process producing monochlorobenzene and the
two dichlorobenzene isomers.
Production of higher chlorinated benzenes is accom-
plished in related processes with changes in reaction condi-
tions.
-------
APPENDIX A-5-30
The catalyst is not consumed in the process. The
by-product hydrogen chloride is recovered in wash towers
as commercially usable acid and solids.
In efficiently operated continuous processes, the
yield of monochlorobenzene is 95 percent and the by-
product dichlorobenzene is also retained as a usable pro-
duct. Consequently, no significant toxic wastes were
specifically identified in this study, although it can be
hypothesized that reaction residues will contain some
quantities of higher chlorinated benzene which will enter
waste streams.
4. Cyclohexane
Cyclohexane is obtained as a natural product from
petroleum distillation and from hydrogenation of benzene.
Manufacture from benzene is a liquid phase reaction of
benzene and hydrogen on an alumina supported platinum
catalyst containing a small amount of lithium salt. A
nickel catalyst can also be used on sulfur free benzene.
No toxic wastes were identified in this study except spent
catalyst and the reaction produces Cyclohexane of 99.9 per-
cent purity.
-------
APPENDIX A-5-31
5. Cyclohexanone
Cyclohexanone can be produced by catalytic air
oxidation of cyclohexane, catalytic dehydrogenation of
cyclohexanol or by oxidation of cyclohexanol. The oxida-
tion of cyclohexane with manganese and cobalt acetate is
the most common practice, which produces cyclohexanol
as a salable by-product, or the reaction mixture is treated
with aqueous nitric acid to directly produce adipic acid.
The catalytic dehydrogenation of cyclohexanol can
be accomplished with a substance capable of taking up
hydrogen such as phenol. The reaction in the presence of
catalysts produces only quantitative yields of product
since the hydrogenation of the phenol from the hydrogen
liberated from cyclohexanol also produces Cyclohexanone.
The oxidation of cyclohexanol is accomplished by
passing oxygen diluted with inert gas through the liquid
phase at 10 atmospheres pressure and elevated tempera-
tures. Adipic acid is produced as a salable by-product.
Yields were not identified and other oxidation products
would be expected. Degree of commercial use of this
process is not known.
-------
APPENDIX A-5-32
The first two processes for cyclohexanone are not
expected to produce significant toxic wastes beyond the
spent catalysts.
6. Isocyanates
There are a large number of different isocyanates
produced as intermediates in polymeric applications. Most
of the materials are consumed in polyurethane foams,
elastomers and coatings. For economic reasons, the reaction
of amines with phosgene is used almost exclusively for
isocyanate production. Details of processing vary some-
what with the specific aromatic or aliphatic isocyanate,
but all commercial manufacturing processes seem to take
the following approach. The appropriate amine is mixed
with phosgene in an aromatic solvent and the resulting
slurry is digested for several hours at progressively
increasing temperatures. The final solution is fractionally
distilled to recover hydrogen chloride by-product, phos-
gene and solvent for recycling, isocyanate product, and a
distillation residue which is incinerated. The residues are
carbamyl chlorides and ureas which may be polymeric.
The wastes would be hazardous if not incinerated.
-------
APPENDIX A-5-33
It should be noted that the intermediates to this
process are compounds which are toxic, and that produc-
tion of amines produces toxic wastes.
7. Nitrobenzenes
The basic manufacturing process is the classic
nitration reaction of benzene with mixed concentrated nitric
and sulfuric acids. The nitric acid is consumed, the sulfuric
acid becomes diluted and is reconcentrated for recycle. The
yield is 95 to 98 percent based on nitrobenzene. Waste
steams contain toxic and explosive materials including:
The steam strippings of the separated acid
which contain benzene and 0. 5 percent of the
nitrobenzene yield
The water washes of the crude product which
contain nitrobenzene
Residues from product distillation which con-
tain dinitrobenzene and nitrophenol.
Newer production processes are based on techniques to
directly react nitric acid and benzene without the sulfuric
-------
APPENDIX A-5-34
acid to act as a water scavenger. The newer processes
have been operated at 99.3 percent conversion rates.
The wastes in these processes would be as stated above
for residues from product purification distillation.
8. Phenol
Natural phenol is extracted from coal tar but more
than 96 percent of the phenol produced is synthetic. There
are four primary production processes using benzene and
one process using toluene.
About 50 percent of the U. S. production is based on
the cumene process where the cumene is produced from
benzene. Cumene is reacted with air in aqueous solution
to form the hydroperoxide. Cumene is carried out of the
reactor by the nitrogen gas waste stream. Cumene hydro-
peroxide is cleaved by mixing with dilute sulfuric acid to
produce two products, phenol and acetone. The cleavage
reaction mixture is distilled to separate unreacted cumene,
acetone, and phenol, as well as the by-products a-methylstyrene,
acetophenone (which are sold) and tars. The yield of phenol
is 93 percent based on cumene and 84 percent based on
benzene.
-------
APPENDIX A-5-35
The Rashig-Hooker process accounts for about
17 percent of phenol production and is based on oxychlori-
nation of benzene to produce monochlorobenzene, followed
by hydrolysis of the chlorobenzene to phenol. This involved,
self-contained, intricately cyclic process produces phenol
in yields of about 84 percent based on benzene. The only
by-product of this process are high-boiling materials
designated as tars. This process is alleged to be in use
at the Hasker plant at South Shore, Kentucky.
The sulfonation process was the first commercial
synthesis process, and is still in use when the production
plant can be located close enough to a paper plant to con-
sume the by-product sodium sulfite. This process pro-
duces about 16 percent of U. S. production. In this pro-
cess, benzene is reacted with sulfuric acid to form
benzene sulfonate. The sulfonate is reacted with sodium
hydroxide to form the sodium salt of phenol and sodium
sulfite by-product in water solution. The sodium salt of
phenol is reacted with carbon or sulfur dioxide to form
phenol and a solution of sodium bicarbonate or bisulfate.
-------
APPENDIX A-5-36
The product phenol is purified by distillation and the waste
residue contains o-phenylphenol and p-phenylphenol.
The chlorobenzene hydrolysis process, operated by
Dow Chemical, reacts xnonochlorobenzene with aqueous
sodium hydroxide at high temperature and pressure in a
tubular reactor to produce phenol. This process accounts
Cor about 16 percent of U.S. production. The yield of
useful products is about 93 percent based on chlorobenzene.
Significant quantities of diphenyloxide, o-phenylphenol, and
p-phenylphenol are produced as by-products and the
process must be of a scale to enable recovery of these
materials for sale to keep it economically competitive.
The process produces phenol and phenoxide contaminated
sodium chloride brines as wastes.
The Toluene Air Oxidation process is used by Dow
Chemical at Kalama, Washington. In 1964 this plant was
rated at 36 million pounds per year. Toluene is oxidized
to benzoic acid with air using a soluble cobalt catalyst, in
water. This reaction proceeds with 90 percent yield and
produces a formic acid waste stream in water solution.
-------
APPENDIX A-5-37
The benzole acid is purified by distillation and the residue
still bottoms create a waste stream of tars. The benzoic
acid is oxidized with steam and air in the presence of
1 to 2 weight percent copper benzoate and 1 to 2 weight
percent magnesium benzoate. The product phenol, carried
out of the reactor with the steam and air, is purified by
distillation. The reaction of benzoic acid with air is
conducted at yields of 83 percent on benzoic acid and pro-
duces a tar waste stream, separated directly out of the
reactor.
9. Phthalic Anhydride
This material is produced by the air oxidation of
naphthalene or o-xylene. There are four basic reaction
systems; a low and high temperature fixed bed reactor,
fluidized bed and liquid phase reaction. The first three
use vanadium pentoxide catalyst systems, and the fourth
a bromine activated heavy metal catalyst. The low temper-
ature fixed bed process produces relatively small amounts
of by-products with an almost unlimited catalyst life.
Yields are 82 percent of theory with naphthalene, and
73 percent with o-xylene.
-------
APPENDIX A-5-38
The high temperature fixed bed is a U. S. develop-
ment and used by Monsanto and Chevron Oil among
others. By-products are higher, particularly maleic
anhydride, then in the low temperature process. Yield
with o-xylene is 72 percent of theory, and with naphtha-
lene 65 percent.
Fluid bed oxidation accounted for 50 percent of U. S.
production in 1967. In 1967, by-products using o-xylene were
excessive but the problem was being given extensive study.
By-products with naphthalene are small. Catalyst loss
occurs and catalyst life is limited. The process is used by
Badger, American Cyanamid and United Coke and Chemical.
The liquid phase oxidation in acetic acid solvent uses
a mixed xylene feed to simultaneously produce phthalic,
isophthalic and terephthalic acids. Yields of 88 percent
with o-xylene are expected.
Each reaction system loses yield by process combus-
tion of feedstocks. Each purifies the anhydride and the
purification step produces a brittle, solid waste tar residue.
-------
APPENDIX A-5-39
10. Terephthalic Acid and Dimethyl Terephthalate
These compounds are chemically similar to phthalic
anhydride and the production processes correspond. The
primary processes for terephthalic acid are as follows.
Nitric acid oxidation of p-xylene is reported to be
used by DuPont. A liquid phase of p-xylene, 30 to 40
weight percent strength nitric acid and air are reacted to
form terephthalic acid directly. The process converts up
to 2 pounds of nitric acid per pound of p-xylene to oxides
of nitrogen, so a nitric acid plant is required to convert
the oxides back.
In the catalytic liquid phase air oxidation process,
acetic acid is used as a reaction medium with bromine
promoted heavy metal oxidation catalysts such as cobalt
or manganese. This process is used by Amoco Chemicals
Corporation. Eastman Chemical Products utilizes acetal-
dehyde as the catalyst activator. Mobil Chemical Company
uses methyl ethyl ketone as the catalyst activator. This
process produces a more pure product than the nitric acid
system. The purity is better than 997o by weight and con-
tains traces of the reaction intermediates, tolualdehyde,
p-toluic acid, and 4-carboxybenzaldehyde.
-------
APPENDIX A-5-40
Production of dimethyl terephthalate was undertaken
because of the difficulty of converting terephthalic acid to
polymer grade material. Terephthalic acid is reacted
with methanol with a sulfuric acid catalyst to form this
material. The product formed is purified by distillation
or crystallization. It can also be produced by air oxidation
in the liquid phase of p-xylene with a cobalt catalyst, to
produce toluic acid; reaction of this material with methanol;
the methyl toluate product again air oxidized with a cobalt
catalyst; and the acid product again esterified with metha-
nol. This process is used by Hercules.
By-products of dimethyl terephthalate production
are toluate esters. This study did not find mention of
other waste products but it can be hypothesized that
quantities of tars are produced from the purification of
both of these compounds.
11. Styrene
There are a variety of possible methods for reduc-
tion of styrene but all current production is believed to
be based on dehydrogenation processes. The essence of
-------
APPENDIX A-5-41
the process consists of passing ethylbenzene mixed with
superheated steam over a fixed iron oxide-potassium
oxide pebble catalyst bed at high temperature to force
elimination of a hydrogen molecule from the ethyl alkyl
group. Part of the ethylbenzene feed is destroyed by
thermal cracking and the reactor vent stream contains
styrene product, benzene, ethylene, methane, hydrogen
carbon dioxide, water, and other materials. Yields are
about 90 percent, based on moles of product per moles of
ethylbenzene. The styrene is purified by distillation with
removal of benzene, toluene, water and unreacted ethyl-
benzene overhead, and tars and polymeric material
removed as still bottoms. The condensed steam pro-
duces a water waste contaminated with benzene, toluene,
styrene, ethylbenzene, formaldehyde, benzaldehyde,
peroxides and other materials.
12. Xylenes
The xylenes are obtained from petroleum refining
and are produced from reforming of selected naptha
streams. The wastes associated with petroleum refining
operations are discussed under that heading.
-------
APPENDIX A-5-42
(3)
To attempt to define the production processes and wastes
generated in the dye industry within a few pages is a hopelessly
impossible task. Moreover, an accurate assessment and
characterization of the toxic waste processed in this industry
is needed because of the nature and quantity of wastes produced.
This study was not able to satisfactorily address the problem.
A gross summarization of basic characteristics follows.
There are two parts to dye manufacture:
Preparation of intermediates
Preparation of dyes.
The distinction is somewhat arbitrary, particularly since
many of the cyclic intermediates presented in the previous
section are dye intermediates.
1. Preparation of Intermediates
Figures A-5-2 to A-5-6 illustrate typical process-
ing routes based on four key primary raw materials. The
overall processing can be characterized as occurring in
four steps. Step one involves attack on the aromatic
-------
a,
(5
a
h
OH
o°
a
H.SO.
H
a.
•o-
MHO,
MM
MOM
OH
SO.H
6°
a
NH,
«H»:
HM,
* * a a
6a 6 6"°' 6
Cl
a, |
NO,
HNO,
I
Cl
OHO
NO,
CHjOH
H
LI
Cl NH,
}HOf i—O-
«, I
flH
• ' I (P)
'S30'
JMi.
NM
O
.SO,
NMNH.
0
(H)
t
OH
O
OH
?•
NH,
Oa
SO.H
N.HO,
V
I NIN
0 g;
sO'
mm,
?
NH
1
!H*SO
r i'
Jna
NM,
HH,
Orjnftl
i
•
N.N
&,
NM,
GM O
!•«
NH,
OOH
Q-M.M-Q-HMC.H,
H
FIGURE A-5-2
Benzene Derivatives
CJl
-------
INOANTHRENE RED VIOLET RH
BENZOFAST
YELLOW 4GL EX.
FIGURE A-5-3
Toluene Derivatives
H
en
-------
Nlph«MI«CK«l
JMiMSO,
cfe
SO.H
NWKid
OH?
CCrN
SO,N*
An Emint G
(H)
CO
ofr
NH.
nn.
CO
HO,S
liinenfsicid
To'
Pen Idd
HNO,
00
"*
no. «»
NM,
""CC?
NH,
(01
IH.SO.
ISO.H
HO
OH
00-
HO,S
LKid
00
HNO,
°i" aw
H,0
so,
Cine ticidi 1.7)
Htbo BwtfMui BL
00OH~
2-Naphtnol
(See Fig A-5-5)
FIGURE A-5-4
Naphthalene Derivatives
I Kid
I
;H,
7 NO SO,Ni
«soo
CMJmmc G
4
H'SO«
HNO,
HO.S
HK4
NH,
i
*»
01
-------
SO,H
CO°H
OSO.M
(MH'I,SO,
a
"»*>• M.SO.
HWQQ-H.
Sciu«*f-iac>*
|NM,),SO,
JJQ"
MlTl Kid
-"60-
"•WOO"1'
•^ -
|OH
CO'
M.SO.
CO^NiOM
Htcid
Gtcrt
O^CC^/H
r (J*
BWIIO Fast Mordant Y«llow O
BlMFR
Dlimlnogen B
FIGURE A-5-5
Naphthol Derivatives
• OOS5U.
Ar«NHf
ccr
o>
OO-Tao
AS
«.«.«,«.
>
HJ
^
w
2
§
Ol
i
rft
O3
-------
J-.SO,
oo
"•WO,.*
id
0
IN
»«
o
HO
o
JH.SQ,
NO
0
0
NO*
80-"
*°'H
O
K
0
|C.M4I
M
o
I.N d OH
ofo"'"
HO 0 NH2
NHC^H.
0
JmOCH,
0
OCH,
0
JHNO,
0
0
|N
0
OCH,
|c.Mtcoei
0
OCH,
»<.M4«HieiH,iei1.Mi»,
NiOH.(0),vi NH,.(0)
^
°H
IUOH
(0)
Purpurn
Indinihitne Blue RS
0 NHCOCgH,.
O •"•-69
Alizarine Blue SAP Alizarine Direct Blue A Algol Scarlet G
FIGURE A-5-6
Anthraquinone Derivatives
-si
(04
"•
"*•
c-
C9i)
Indanthrene Indanthrana Brown BR
Golden Orange G
W
Z
d
-------
APPENDIX A-5-48
hydrocarbon raw material, introducing one or more
groups. The most frequently used reactions are:
Sulfonation
Nitration
Halogenation
Friedel-Crafts
Oxidation.
These type reactions and the waste stream they produce
were described in the discussion of cyclic intermediates.
Basically, most of those processes were step one activities,
with respect to the dye industry.
Step two reactions involve replacement or conversion
of substituents introduced by step one reactions by groups
of higher reactivity which cannot be introduced directly.
These step two reactions furnish the OH, NH2< CH, OR,
SR and NRR groups. Such reactions produce salt and
brine liquid wastes of Fe2C>3 sludges, ammonium chloride
solutions, zinc hydroxide precipitates, sodium sulfate
solutions, as well as tars from purification steps.
-------
APPENDIX A-5-49
Step three involves further modification or development
of functional groups already introduced. The reactions
used are dependent on the dye to be produced and involve
the organic chemists complete gambit of techniques.
Step four reactions are basically reactions which combine
two intermediates to form products having a skeletal if not
a complete dye structure. Typical reactions include
diazotization and coupling, condensation and dimerization.
2. Preparation of Dyes
The preparation of dyes can be characterized by
type used,by type material to be dyed, or by chemical
similarity. When classed by chemical similarity, three
types comprise two-thirds of all manufacturing:
Azo
Anthraquinone
Stilbene.
Azo dye production involves diazotization of primary
aromatic amines, followed by coupling with hydroxy or
amino aromatic hydrocarbons and other aliphatic compounds.
-------
APPENDIX A-5-50
The generalized procedure for diazotization and coupling
is as follows. Sodium nitrite is added slowly to an acid
solution of the amine. The nitrous acid produced reacts
with the amine to complete the diazotization. The total
mix is run into an acid or alkaline solution of the inter-
mediate to be coupled (depending on the nature of the dye).
After a time period varying from a few minutes to three
days, sodium chloride is added to precipitate the dye,
and the reaction mass is filtered. The solid dye remains
in the filter and the liquid becomes a waste stream. This
stream contains a salt solution of the acid used and can
contain quantities of the organic reactants.
Quantities of wastes produced in azo dye manufacture
can be illustrated by the material balance for producing
1, 800 pounds of Chrome Blue Black U:
Beta-napthol 730 pounds
Sodium hydroxide (40%) 600 pounds
Water 10, 000 pounds
Hydrochloric acid (20%) 500 pounds
l-amino-2-napthol-4-sulfuric 1,200 pounds
acid
-------
APPENDIX A-5-51
•
Sodium chloride 200 pounds
Copper sulfate hydrate 15 pounds
Sodium nitrite 365 pounds
Note that the sum of the two primary reactants,
6-napthaland 1, 2, 4 acid, total 1,930 pounds, which
means that at least 130 pounds of these two reactants
disappeared. Also note that everything except the product
is sewered.
Anthraquinone dyes are based on synthesis of anthro-
quinone from phthalic anhydride. A variety of approaches
are possible. If benzene is used with the anhydride, an-
throquinone is produced directly. If chlorobenzene is
used, chlorinated anthroquinone is produced,etc. Such
reactions can produce aluminum chloride solution wastes,
sulfuric acid wastes, etc. Subsequent processing of the
anthroquinone can proceed in an infinite variety of ways
with creation of large waste streams. For example, to
produce 100 pounds of indanthrene yellow G requires
processing:
Phthalic anhydride 148 pounds
Chlorobenzene (80%) 600 pounds
-------
APPENDIX A-5-52
*
Aluminum chloride 300 pounds
H2S04(100%) 1,500 pounds
Ammonia (28%) 1,500 pounds
Nitrobenzene 2,000 pounds
Antimony pentachloride 700 pounds
The ammonia is 90 percent recovered and the nitrobenzene
can be recovered as aniline, but note the quantities of
other potential wastes.
(4) Tanning Materials
The most used synthetic tanning material is 2-napthalene-
sulfuric acid condensed with formaldehyde. The acid is
prepared by reaction of concentrated sulfuric acid on naphthalene.
The reactor produces the 1-sulfuric acid which is hydrolyzed
back to naphthalene and removed from the product by stream
distillation.
(5) Halogenated Hydrocarbons
1, 2-Dichloroethane, important as a starting material for
vinyl chloride, is produced by reacting chlorine with ethylene.
To obtain high yields of the desired product without various side
-------
APPENDIX A-5-53
reactions, controlled reaction conditions and catalysts such as
ferric, aluminum, copper, or antimony chloride are used. The
reaction is conducted in either the gaseous or liquid phase. A
process reacting a gaseous mixture of anhydrous hydrogen
chloride, ethylene, and air in a fluidized bed of copper chloride
impregnated catalyst, is used in coordination with a continuous
vinyl chloride process and the first process above, to utilize
the hydrogen chloride by-product of vinyl chloride production.
1, 2-dichloroethane is also obtained as a by-product in the
production of ethyl chloride when chlorinating petroleum derived
C2 gases. Waste streams include dilute caustic with sodium chloride
used to wash the product, and heavy ends from the purification
distillation containing poly-chlorinated material.
Vinyl chloride is manufactured by two processes:
Catalyzed hydrochlorination of acetylene
Pyrolytic or alkaline dehydrohalogenation of 1, 2-
dichloroethane.
In the acetylene process, dryed acetylene and anhydrous hydro-
gen chloride are mixed in an activated carbon filled chamber,
and then passed through heated tubes containing mercuric
-------
APPENDIX A-5-54
chloride deposited on carbon to effect the reaction. A variety
of other catalysts are used in mixture with mercury chlorides
such as thorium, cerium, cadmium and potassium chlorides.
Wastes produced include (1) the carbon in the mixing chamber
saturated with chlorine and other impurities, (2) the spent
catalyst suspended in carbon, and (3) ethylidene chloride and
acetaldehyde by-products, as well as hydrated solid potassium
hydroxide used to dry the product before distillation. Yields
on acetylene are 99 percent.
Vinyl chloride is produced by dehydrohalogenation of 1, 2-
dichloroethane. The 1, 2 dichloro is passed through tubes packed
with pumice, or charcoal, or china clay, or titanium oxide,etc.,
at high temperature to effect removal of a hydrogen and a chlorine
atom and produce the product. Wastes produced are hydrogen
chloride which is recovered, and chlorinated tars. Yields are
95 to 96 percent on the 1, 2 dichloroethane.
Carbontetrachloride has many uses but is an important
intermediate for dichlorofluoromethane. Many production
processes are possible. Chlorinalysis, the chlorination of hydro-
carbons at pyrolytic temperatures with simultaneous breakdown
and chlorination of the molecular fragments, is used to produce
-------
APPENDIX A-5-55
this product. Large amounts of higher molecular weight by-
products are formed and yields of carbontetrachloride are about
70 percent. The high temperature chlorinalysis can be operated
to produce perchloroethylene in equal amounts, especially if the
methane and chlorine reactants are run through a fullers earth
catalyst bed. Wastes always include hydrogen chloride, higher
molecular weight chlorinated co-products and chlorinated tars.
Carbontetrathloride can be produced by chlorination of
carbon disulfide dissolved in carbontetrachloride and sulfur
monochloride using an iron filings catalyst. Sulfur is produced
and recovered to make additional carbon disulfide. This
process produces no co-products or by-products.
Ethylchloride production principally occurs by two
processes:
Chlorination of ethane
Hydrochlorination of ethylene
The chlorination of ethane occurs at high temperature and can be
conducted in an inert fluidized bed at about 78 percent yield.
By-products are ethylene which is recycled to produce ethyl
chloride, and HC1. Hydrochlorination of ethylene can be done
-------
APPENDIX A-5-5 6
with HC1 either at high temperature over .thorium oxychloride
catalyst suspended on silica with production of polymeric
materials which eventually destroy the catalyst (waste product)
or at normal temperatures in liquid phase with an aluminum
chloride catalyst in 2 percent solution in ethylchloride.
Trichloroethylene can be produced by three prime processes:
Aqueous alkaline processes
Pyrolytic Processes
Conversion of 1, 2 -dichloroethane.
The starting material is tetrachloroethane (produced from ace-
tylene or ethylene) and the first two processes are dehydro-
chlorination reactions. In the aqueous process,the raw material
is reacted with hot calcium hydroxide, or sodium hydroxide, or
ammonium hydroxide to remove an HC1 molecule. Wastes in-
clude the respective chlorine salts of the hydroxides. Thermal
dehydrochlorination is effected by passing the tetrachloro over
barium chloride catalyst on activated carbon. Spent catalyst
contaminated with chlorinated tarry material is produced as
waste, along with heavy ends and tars from the product purifica-
tion. The conversion of 1, 2dichloroethane is conducted as an
oxychlorination at high temperature with air and chlorine over
-------
APPENDIX A-5-57
copper chloride catalyst on carbon. The reaction produces
spent catalyst contaminated with tarry waste, and chlorinated
tars from product purification.
Tetrachloroethylene for many years was produced by
chlorination of trichloroethylene to pentachloroethane and
dehydrochlorination with cadium hydroxide slurry (or other
strong alkali) as described above, producing similar waste
streams. The pentachloroethane can also be dehydrochlorinated
thermally over thorium or copper chloride catalyst as described
above, with similar wastes, and recovery of the HC1.
(6) Phosphorus Compounds
Phosphorus compounds are widely used as oil additives,
insecticides, plasticizers, gasoline additives, flotation agents,
stabilizers, antioxidants and surfactants. All of these different
end users are based on compounds produced by similar types of
production processes.
Three inorganic phosphorus compounds are principally
used as reactants in commercial productions:
-------
APPENDJX A-5- 58
Phosphorus trichloride
Phosphorus oxychloride
Phosphorus pentasulfide.
Each of these compounds will react with an organic aromatic
or aliphatic alcohol to form mono-, di-, or tri-esters. If
phosphorus trichloride is used, the products are phosphines;
the oxychloride produces phosphates, and pentasulfide thiophos-
phates. When using the chlorides, production of the mono-,
di-, or tri-ester is dependent on the reaction conditions and the
use of a sequesting agent such as an amine, to tie up hydrogen
chloride produced. By-products in reaction with phosphorus
chloride's include the alkyl or aryl chloride, and either HC1
or the alkali salt (such as ammonium chloride). Wastes include
slimy solids which are polymerization products of the reaction.
Similar reactions between the pentasulfide and alcohols pro-
duce diesters, with hydrogen sulfide as a by-product.
Mono- and di-esters produced in the above reactions can
be further processed to add an additional ester group of another
type. This normally involves chlorination (to produce an inter-
mediate) with production of hydrogen chloride as a by-product.
Adding the additional ester can be accomplished either with
-------
APPENDIX A-5-59
production of hydrogen chloride or sodium chloride as by-
product, depending on the mechanism selected.
The product materials are normally purified and separated
from reaction mixtures by distillation. Since the compounds
are subject to thermal degradation, distillation residues include
slimy or glassy polymerization products as wastes.
(7) Fermentation Reactions
Because of similarities in waste disposal processes, the
industrial organic chemicals manufactured by fermentation will
be discussed together. There are five important compounds
produced in this manner:
Ethyl alcohol
Glycerol
Acetic acid
Acetone - butyl alcohol
Amyl alcohol.
Alcohol production by fermentation and from ethylene
compete. Acetone, butyl alcohol, and acetic fermentation pro-
duction have largely been superseded by synthetic processes.
-------
APPENDIX A-5-60
1. Ethyl Alcohol
This compound is produced by yeast fermentation
from a variety of starch and sugar containing natural
products, in either batch or continous processes. The
process consists of fermenting a mash and separation of
the alcohol and related constitutents by distillation. This
first distillation produces a waste known as slop or stillage,
and it contains proteins, residual sugars, and some vita-
min products; it is evaporated and sold as animal feed.
The distilled product fraction contains alcohols and alde-
hydes which are separated in further distillations, pro-
ducing product ethyl alcohol, and impure amyl alcohol and
aldehydes as salable by-products.
2. Acetone and Butyl Alcohol
Production of these materials by fermentation has
virtually ceased with development of synthetic routes and
increased prices of grain and molasses feed stocks. The
bacterium Clostridium acetobutylicum, in its action on
starches produces a series of product compounds in the
route to acetone, butyl alcohol and ethyl alcohol. Among
these are acetyladehyde, acetic acid, acetyl-methyl-carbinol.
-------
APPENDIX A-5-61
and butyric acid, •which are obtained as by-products or
wastes. The three primary products, acetone, butyl
and ethyl alcohol are produced in the ratios of 3:6:1.
The process is as described above for ethyl alcohol, with
the stillage from the fermentation dried and sold as feed.
Other by-products are corn oil, germ meal and corn husks,
all of which are sold, as well as carbon dioxide and hydro-
gen gases.
3. Acetic Acid
This acid can be manufactured by high temperature
oxidation of ethyl alcohol which now is the dominant pro-
cedure. In fermentation production, a dilute solution of
alcohol is converted to dilute (8 percent) acetic acid solu-
tion in 80 to 90 percent yields by Bacterium aceti. The
process is economical only if there is a market for this
dilute acid.
(8) Amination By Ammonalysis Reactions
This procedure is used for production of ethanolamines.
Ethylene oxide is bubbled through aqueous ammonia solutions to
produce the mixed mono-, di-, and tri-ethanol amines in 95 per-
cent yield.
-------
APPENDIX A-5-62
(9) Aliphatic Acetate Production
The acetates are produced by esterification reactions
between the appropriate aliphatic alcohol and acetic acid, or by
esterification of acetylene.
The reaction between the alcohols and acetic acid consists
of reacting the two materials in either a continous process or
batch type reactor in the presence of a small amount of sulfuric
acid catalyst. This process is used to produce these acetates:
ethyl, amyl, butyl, and isoproxyl as well as methyl salicylate,
methyl anthranilate, diethyl phthalate, and dibutyl phthalate.
The esterification of acetylene is used to produce unsat-
urated vinyl type esters by addition of various organic or in-
organic acids. Reactions are conducted in either the vapor
or liquid phase. Products produced are vinyl acetate, vinyl
chloride, acrylonitrile and vinyl fluoride. Yields are high,
80 to 95 percent, and polymerized reaction products are pro-
duced as solid wastes.
(10) Methanol
Methanol is produced principally by zinc oxide catalyzed
air oxidation of methane at high temperature, and by reaction of
hydrogen with carbon monoxide. The average amount of effluents
from this process are (Reference 13):
-------
APPENDIX A-5-63
Waste Ibs. /I, OOP Ibs. of Product
Free Floating Oils 0.17
Heavy Metals
Chromium 0.01
Zinc 0.011
Organic Chlorides 0.18
Phosphates 0.004
(11) Ethylene Oxide
There are two processes for production of the very impor-
tant intermediate, the chlorohydrin and the catalytic oxidation.
Both use ethylene as the raw material.
The oldest process is the chlorohydrin which consists of
reacting ethylene with hypochlorous acid with subsequent dehydro-
halogenation with calcium hydroxide or sodium hydroxide. This
process produces ethylene dichloride as a by-product in the
ratio of 90:10 ethylene oxide to the dichloride. The process
produces a calcium or sodium chloride solution, contaminated
with the two products, as waste.
The catalytic process involves reaction of air (or oxygen)
with ethylene over silver catalyst. Competing side reactions
are combustion of ethylene and formation of a variety of poly-
merized fragments, and isomerization of ethylene oxide to ace-
taldehyde. Waste streams contain water, aldehydes and poly-
merization products or tars. Overall yields are about 60 percent.
-------
APPENDIX A-5-64
4, DISPOSAL PRACTICES AND HAZARDS
The producers of the compounds discussed in this section are
generally classified as being part of the petrochemical industry or
the coal tar products industry. Many producers in these categories
have totally integrated plants, particularly in the petrochemical field.
A single producer is frequently concerned with producing almost all
of the materials discussed. Consequently, a discussion of disposal
practices for these two industries must include discussion of
disposal practices for all materials covered here. To avoid
redundancy and repetition,the entire discussion on disposal practices
and hazards has therefore been incorporated into Appendix A- 6.
-------
APPENDIX A-5-65
INDUSTRIAL INORGANIC CHEMICALS
1. ECONOMIC STATISTICS
According to the .1967 Census of Manufactures (Reference 9),
industrial inorganic chemicals industry can be classified as:
SIC 2812—Alkalies and Chlorine
SIC 2813—Industrial Gases
SIC 2816—Inorganic Pigments
SIC 2819—Industrial Inorganic Chemicals Not Elsewhere
Classified.
(1) SIC 2812—Alkalies and Chlorine
This industry comprises establishments primarily engaged
in manufacturing chlorine, sodium carbonate, sodium hydroxide,
potassium hydroxide, and sodium bicarbonate. Relative size and
distribution of this industry is indicated by the following data
(Reference 9).
Value Added Employees
(106 dollars) Establishment (1,000)
Northeast Region N. A.
North Central Region 109. 7
Southern Region 200. 9
Western Region N. A.
Total United States 419. 2
SIC 2813 — Industrial Gases
5
9
22
8
44
N.A.
7.4
7.5
N.A.
19.2
The products and the 1967 production quantity reported for
this industry is as follows (Reference 9):
-------
APPENDIX A-5-66
Product Quantity Units
Acetylene 14,200 mil. cu. ft.
Carbon Dioxide 1,089 1, 000 short tons
Argon 1,912 mil. cu. ft.
Helium 4,712 mil. cu. ft.
Hydrogen 158,539 mil. cu. ft.
Nitrogen 103,933 mil. cu. ft.
Oxygen 225,191 mil. cu. ft.
Nitrous Oxide 953 million gals.
The geographic distribution is indicated by the number of
establishments shown below:
Number of Establishments
with More Than 20 Employees
United States 156
North East Region 36
North Central Region 45
Southern Region 45
Western Region 30
(3) SIC 2816—Inorganic Pigments
This industry comprises establishments primarily engaged
in manufacturing inorganic pigments such as black pigments
(except carbon black), white pigments and color pigments. The
organic color pigments are classified in SIC 2815. The products
of this industry are:
Titanium pigments
White lead
Zinc oxide pigments
Zinc sulfide
Chrome colors
Chrome oxide green
Chrome yellow and orange
-------
APPENDIX A-5-67
Zinc yellow
Iron oxide pigments
Bed lead
Litharge.
(4) SIC 2819—Industrial Inorganic Chemicals Not Elsewhere
Classified
Important products of this industry include inorganic salts
of sodium (excluding refined sodium chloride) potassium,
aluminum, calcium, chromium, magnesium, mercury, nickel,
silver, tin; inorganic compounds such as alums, calcium
carbide, hydrogen peroxide phosphates, sodium silicate,
ammonia compounds, anhydrous ammonia; rare earth metal
salts and elemental bromine, fluorine, oidine, phosphorus,
and alkali metals (sodium, potassium, lithium, etc.).
Production quantity data from Reference 9 is given below:
1, 000 short tons
Nitric Acid (100% HNOJ 6, 265
Ammonia (100%)
Anhydrous 12,200
Aqua 65
Ammonium Nitrate (100%) 6,005
Ammonium Sulfate (100%) 2,079
Calcium Hypochlorite 40
Sulfuric Acid 28,815
Boric Acid 122
Chromic Acid 22
-------
APPENDIX A-5-68
Hydrochloric Acid 1, 630
Hydrocyanic Acid 126
Hydrofluoric Acid 183
Phosphoric Acid (100%) 5, 066
Aluminum Oxide 6, 046
Aluminum Chloride 60
Aluminum Hydroxide 276
Aluminum Sulfate (17% A10OJ 1, 101
£i O
The relative size and growth of this industrial sector is
indicated by the following data (Reference 9):
1967
1963
1958
Establishments
(20 or more
employees)
358
323
301
Employees
(thousands)
81.2
82.4
89.9
Value Added
(Millions of $)
2295.4
1902.6
1468. 9
This industry is distributed throughout the country. The relative
concentrations by states is indicated by the value added data shown
on the following page:
-------
APPENDIX A-5-69
Massachusetts
New York
New Jersey
Pennsylvania
Ohio
Indiana
Illinois
Michigan
Minnesota
Iowa
Missouri
Nebraska
Kansas
Delaware
Maryland
Virginia
North Carolina
South Carolina
Georgia
Florida
Kentucky
Tennessee
Alabama
Mississippi
Arkansas
Louisiana
Oklahoma
Texas
Montana
Idaho
Colorado
Nevada
Washington
California
Establishments
(20 or More Employees)
5
11
31
19
25
8
23
11
2
7
7
6
5
3
9
5
4
1
11
11
6
17
4
5
7
16
4
30
2
3
4
2
5
36
Value Added
(Millions of $)
11.9
42.9
101.3
86.0
189.6
49. 1
70.8
70.1
7.6
(D)
48.8
(D)
49.8
(D)
40.4
33. 3
(D)
(D)
37. 7
31.2
76. 1
322.9
(D)
(D)
72. 1
121.6
1.8
141.5
(D)
103.4
6. 5
(D)
(D)
110. 7
Region
Totals
Northeast
245.5
North
Central
551.6
South
1149.5
West
348.7
-------
APPENDIX A-5-70
Because there is such a wide variety of products made
within this sector, a limited number of process types have been
selected for review on the basis of availability of data and their
relative importance to hazardous waste problems.
2. WASTE CHARACTERISTICS
Waste streams from inorganic chemical manufacturing vary both
quantitatively and qualitatively depending on the type of compound or
compounds manufactured, processes used, and the raw materials used.
In general, waste streams may be expected to contain variable amounts
of dissolved and suspended solids in the form of acids, alkalies,
troublesome and/or toxic chemicals such as fluorides, phosphates,
sulfates, organic solvents, greases and lubricating oils, metals, and
warm water and/or steam.
Waste waters often consist of both contaminated and relatively
clean effluent streams. In general, contaminated waste waters are
those taken from processes, while the cleaner waste waters are those
used for the purpose of cooling, general washing(etc. Contaminated
waters, on the other hand, result from filter ash washing, waste acid
and alkalie streams, working and process streams. Process waters
are segregated from cooling waters in many plants to reduce the volume
of water which requires treatment prior to discharge.
-------
APPENDIX A-5-71
Clean waste water streams, though basically uncontaminated
may, however, produce adverse thermal effects such as decreased
oxygen solubility, greater oxygen utilization, as well as a list of re-
lated problems, by virtue of their temperature.
Many processes utilized in the manufacture of inorganic chemi-
cals generate large amounts of thermal energy which must be re-
moved by cooling water or air. Of particular significance are the gas
producing plants because of their need to discharge heat extracted fan
air or natural gas during compression and subsequent cooling steps.
Blow down from recirculating systems may also contain substantial
amounts of chemicals added to the cooling water. These include
chromates, zinc, phosphate, bactericides, and organic compounds,
and may constitute pollution,problems. The use of cooling towers may
create ice fogs and other inadvertant weather modifications.
(1) Composition of Waste Streams
The composition of process waste streams is highly
varient, the effluents and treatment procedures for a variety
of manufacturing processes will be discussed. The effluents
from any production complex are dependent on the products which
are in production currently. A wide variation in waste composition
and total waste is possible. To illustrate this point, effluents
-------
APPENDIX A-5-72
from two complex facilities (designated 1 and 2) are given
in Table A- 5- 8 . Complex 1 manufactures sodium sulphate,
sodium thiosulphate, and zinc sulphate. Effluents from this
complex include sulphate, zinc, and sodium bicarbonate.
Effluents from Complex 2 include chlorine, ammonia, iron,
phenol,- and large quantities of dissolved and suspended
solids.
The discussions of individual processes which follow
(Reference 2) should be viewed occurring in a separate facility
or as one process in a plant producing several products. Most
of the inorganic chemicals discussed are for the most part
relatively innocuous. This does not mean that all plants
which produce inorganic chemicals have relatively less hazardous
wastes. Inorganic chemicals may be produced by plants which
produce organic compounds which are highly toxic. In such
cases waste streams may contain substantial amounts of
potentially hazardous compounds.
1. Gases
Nitrogen, oxygen, and other gases are extracted
from air by medium pressure liquification and rectification
of air. Waste problems result from heated cooling water
-------
APPENDIX A-5-73
Table A-5-8
Effluents from Two Complex Facilities
Products of Complex
Effluent Flow Rate (GPD)
Effluent pH
SO3=(ppm)
r, ++
Zn
NaCl (ppm)
NaHCO, 9ppm)
o
Suspended solids (ppm)
Cl'(ppm)
(ppm)
Total soluble solids (ppm)
Fe, soluble (ppm)
Phenols (ppb)
Hardness, equiv. CaCO«
(mg/1)
Complex 1
Sodium sulfite,
sodium thiosulfate
and zinc sulfate
Complex 2
Soda ash, sodium
bicarbonate,
chlorine, caustic
soda, hydrochloric
acid, sodium silicate,
and calcium carbonate
300,000 for process 6, 000,000 total
1.500,000 total
6.5-8.5
20,000
20
45,000
15,000
11
30-50
79,000
4
131,000
0.36
219
76,000
-------
APPENDIX A-5-74
and from waste compressor oils. The quantity of such oil
varies greatly from plant to plant depending on compressor
type, size, and age. Oil emissions are controlled by skimming
and /or biological treatment.
The wastes associated with typical inorganic chemical
production processes are discussed in the paragraphs that
follow. Table A-5-9 summarizes these product-processes, the
significant wastes, and the treatment provided to reduce the
hazards related to these wastes.
2. Inorganic Acids
Effluents from acid manufacturing plants range from a
highly contaminated streams to relatively clean streams
containing small amounts of waste acids. In the manufacture
of hydrochloric acid (about 85 percent of which is obtained as a
by-product of chlorination of hydrocarbons, waste streams
consist primarily of HCl for which neutralization is the best
available treatment method. The highly toxic organic
contaminants such as chlorobenzene and phosgene are also
found in the waste. In plants using the synthetic process, i. e.,
burning of. hydrogen in chlorine gas, HCl waste effluents are
often used to neutralize caustic effluent from adjacent or nearby
chlor-alkali plants.
-------
APPENDIX A
-5-7S
Table A-5-9
Raw Waste and Effluent Data
for Inorganic Chemicals
Product/Process
HC1 (D irect Burning)
HNO_ (Ammonia Oxidation)
H.SO (Contact)
u 4
HF (Reactor with
Florspar)
Effluent
(Ibs/ton)
HC1 - 41
Treatment
Use to neutralize
caustic wastes
HNO_- 6
•5
Phosphoric Acid (Wet
Process)
Phosphoric Acid (Dry
Process)
,- i.o
SO
Recycle wash water
Neutralize with lime
Scrubber exit gases
ti
CaSO - 7100 Settling—water recycle
Lime treatment—settling
Neutralization and ponding
Settling pond
CaF2 - 120
H2SO4 - 500
Silica - 30
CaSO. - 1580 Settling—water recycle
- 68 Lime treatment—settling
A
Phosphates - 45 Lime treatment—settling
Silicates - 170 Settling
Phosphoric - 1 Reuse wash down water
Acid
AS2S3 - 0. 3
Scrubbers, collection,
burial
-------
APPENDIX A-5-75Q.
Table A-5-
Continued
Produce /Process
Effluent
(Ibs/ton)
Treatment
Phosphorus (Electric
Furnace)
Phosphorous-12 Settling—Burial
Soluble - 11
phosphates
Lime treatment,
settling - recycle
water
Fluorides - 8
Lime treatment,
settling, recycle
water
Solid Dry collection and reuse
Phosphates- 115
Hydrogen Peroxide
(Organic Solvent)
Aluminum Chloride
(Molten Aluminum)
Aluminum Sulfate
(Wet Acid)
Organic
Solvents - 4
H2°2 - 4°
Aid, - 32
3
Cl2-8
HC1 - 8
Biodegradable -
activated sludge
Recycle
Wet alkaline scrubbing,
settling
Wet alkaline scrubbing,
settling
Wet alkaline scrubbing,
settling
Silicates - 270 Lime neutralization,
settling
Aluminates - 75 Lime neutralization,
settling
- 10 Lime neutralization,
settling
-11 Lime neutralization,
settling
-------
APPENDIX A-5-76
Table A-5-7
Continued
Effluent
Produce /Process (Ibs/ton) Treatment
Ammonium Nitrate None None
Ammonium Sulfate CaCOg - 1200 Settling pond
(Ammonium Salts)
The typical effluents, amounts per ton of product
and the typical treatment required are shown in
Table A-5-^. This table gives data for a plant repre-
senting about 1 percent of the U.S. //££. production.
Waste sources in the manufacturing of nitric acid
are confined typically to area wash down operations,
cooling water blowdown, and samples taken for quality
control. These small amounts of waste waters are
collected and used as process water to make nitric acid
in most facilities, and in general, there is no discharge
of waste from a nitric acid plant during normal operations.
Waste loads range from 0.1 to 1.0 pound of NHO waste
o
per ton of HNO. produced.
Sulfuric acid, mainly manufactured by the direct
reaction of oxygen and sulfur, is also relatively pollution
free. Since no process water is discharged from newer
-------
APPENDIX A-5-77
plants, the only pollution arises from cooling water
treatment chemicals, spills and wash-downs. In most
plants, the wash-down water is collected and reused to
make sulfuric acid. In older facilities or spent acid
plants, wash-down waters are currently treated with
lime to neutralize the H SO..
& 4
By-product steam can be of economic value in some
instances. To prevent thermal pollution, cooling ponds
and towers are used.
Hydrofluoric acid is manufactured by the reaction of
sulfuric acid with fluorspar (CaF ). By-product gypsum
&
is generally discarded. Effluents from HF plants include
CaSO., CaF2, H SO metal oxides, silica, HgSiF ,
and HF. The standard method of waste treatment
consists of the addition of lime to neutralize the sulfuric
acid, minimize fluoride content to 5 ppm and ponding to
settle out the gypsum.
Eighty percent of the phosphoric acid manufactured
in the U. S. is produced by acidulation of phosphate rock,
while the remainder is made by burning phosphorous
followed by hydrolizing the P O .
i 5
-------
APPENDIX A-5-78
Sources of waste for the acidulation
process include testings from phosphate rock benefication,
and sludges of aluminum and iron phosphate. Scrubber
waters contain large amounts of acid fluorides. The
primary source of waste, however, is waste gypsum from
acidulation. This semisolid waste may contain quantities
of H SO and phosphoric acid.
& 4
Wet processes phosphate and sulphate wastes are
fairly constant, Those for fluoride and silica vary
considerably due to differences in raw materials.
Current treatment of wastes from the acidulation
process consists of settling in ponds to remove insoluble
CaSO. (gypsum), CaF , and SOg. This treatment is
generally followed by two liming operations on ponds to
percipitate soluble fluoride as CaF_. In Florida, water
&
from the ponds is recycled to the process. Water is
discharged from ponds only during the rainy season.
Other locations still discharge wastes from ponds
directly into rivers.
-------
APPENDIX A-5-79
The contribution of flurides to the product, gypsum,
pond water and release to the atmosphere during phosphoric
production processes are presented in Table A-5-10. As
shown in the table (Reference 3), the fluoride emissions
are directly proportional to the quantity of fluorides present
in the phosphate rock.
Phosphoric acid waste from the dry process is
not treated. Arsenic removed in the purification step is
either buried in containers as AS S or ponded. After
2
-------
APPENDIX A-5-80
Table A-5-10
Distribution of Fluorides from
Phosphate Rock
Ib/day F~
Input Rock
73,600
116,300
355,600
CaCO
Charged
(lb/1000 gal)
0
43
67
90
100
112
133
To H PO
o 4
21,500
28,000
105,900
Reaction of
% of
To Gypsum
30,000
39,000
75,100
Table A- 5- 11
To Pond Water To
Atmosphere
21,200
48,500
174,600
12
30
24
Gypsum Pond Water with Lime
pH of
Composition of
(g /liter)
Theoretical Filtrate P9O CaO SO.
ct ID 4
--
50
75
100
110
125
150
1.8 2.00
3.2 1.65
3.4 1.41
4.8 0.59
5.1 0.58
5.1 0.58
5.1 0.58
1.40 2.76
1.20 2.50
1.10 2.30
1.10 2.60
1,10 2.70
1.10 2.60
1.10 2.60
Filtrate
F
2.90
1.00
0.07
0.02
0.02
0.03
0.03
-------
APPENDIX A-5-81
Phosphorous contained in water streams is treated
by clarification methods to settle out and recover some
colloidal phosphorous. Residual water is either fed to
an evaporation pit without discharge, pumped into a
slag pile (which is ultimately buried), or recycled. For
plants recycling their condemnation streams, the phos -
phorous content of the effluent is reduced to 0.05 ppm.
Burial is the best treatment currently in use for
phosphorous settled from phossy streams. Treatment of
the other process water streams generally consists of
lime treatment to reduce fluoride and phosphate content
and settling in ponds to remove insoluble materials.
Water is then discharged, or may be recycled. Air-
borne solids collected by precipitation are generally
recycled.
4. Hydrogen Peroxide
Hydrogen peroxide is made by either the electrolytic
process or by an organic based process using anthra-
quinine dissolved in an organic solvent or liquid iso-
propylalcohol. The organic processes are of major
-------
APPENDIX A-5-82
importance. Waste streams include cooling water,
extraction and purification water, and waste water from
cleanup operations. These effluents contain sulfuric
acid, H0O_ and organic solvents. Treatment is primarily
^ 2
confined to neutralization of the sulfuric acid and
activated sludge treatments to remove the biodegradable
solvents.
5. Calcium Carbide
Calcium carbide is manufactured by the reaction of
quicklime (CAO) and coke in an arc furnace. No water
is used in the process. Wastes result primarily from wet
scrubbing of gaseous effluents and from the washdown of
equipment. The waste steams from scrubbers and wash-
downs consist of lime and dissolved acetylene. 0. 9 pounds
of slaked lime/ton of CaC_ is estimated to be produced.
A
6. Lime
Lime is manufactured by thermal decomposition of
limestone of calcium carbonate in kilns. No process
water is used so that the only waste results from wet
scrubbing of the gaseous effluents to remove particulate
-------
APPENDIX A-5-83
matter. These effluents contain calcium carbonates and
hydroxides and are slightly alkaline. At present, no
treatment of scrubber waste is used; however, problems
associated with wet scrubber effluent may be circumvented
by the use of dry collection methods. The low waste load
from lime plants is estimated to be «0. 9 pounds of CaCO,
plus CaO pound of product.
tt
7. Aluminum Chloride
Aluminum chloride is manufactured by chlorinating
liquid aluminum. The process uses no water, hence all
of the waste water comes from wet scrubbing of gaseous
effluents (HC1, Cl, andHCl,). Scrubbers in the aqueous
O
phase maybe made alkalie to increase efficiency, resulting
in effluent containing Al salts, chlorides, and hypochlorides.
In some plants there is no further treatment of scrubber
efflents. Settling tanks may be used to remove aluminum
salts.
8. Aluminum Sulfate
Aluminum sulfate is made by the reaction of dilute
sulfuric acid with ground bauxite. The liquor is sub-
quently treated with barium sulfide to precipitate iron.
-------
APPENDIX A-5-84
9. Ammonium Nitrate
Ammonium nitrate is manufactured by reacting
preheated ammonia and nitric acid and air drying the
molten product in a cooling chamber. Wash-down
procedures produce substantial amounts of nitrogen rich
waste water. Additional waste quantities are obtained
from scrubber blow downs, and from cooling water.
A potential hazard involved in the manufacture of
NH .NO, is the potentially violently explosive nature of
4 o
concentrated solutions of NH NOQ at high temperatures,
4 u
especially if contaminated with organic material.
10. Ammonium Sulfate
About 35 percent of the ammonium sulfate produced
is manufactured by the direct reaction of ammonium salts
such as carbonates, with sulfuric acid. Some is made using
gypsum in place of sulfuric acid. Major wastes involve
solid discharges of by-product materials. The major
amounts of ammonium sulfate are made during the recovery
of ammonia from coke oven gas. About 40 percent of the
total production is involved with the actual recovery of
by-product ammonia from a variety of other processes.
-------
APPENDIX A-5-85
3. DISPOSAL PROCESSES
A variety of treatment methods and processes are currently
being used by manufacturers of inorganic chemicals (Reference 4)
to control solid, liquid, and thermal wastes including:
Chemical additon
Equalization
Sedimentation
Filtration
Reverse osmosis
Electrodiolysis
Ion exchange
Multiple effect evaporation
Deep well injection
Ocean burial
Dumping and landfill
Lagooning/cooling ponds /solar evaporation ponds
Centrifugation
Cooling towers.
Three typical schemes are indicated in Figure A-5-
for the treatment of (1) waste containing dissolved and suspended
-------
PRE TREATMENT
DILUTE WASTEWATER
1
F
1
CHEMICAL
ADDITION
t
EQUALIZATION
3
OL REMOVAL
i
*
SUSPENDED
SOLID REMOVAL
J
\
4 1
H SEDIMENTATION!*
9
M FILTRATION W
1
1
t
1
DISSOLVED
SOLID REMOVAL
J CHEMICAL A
*] ADDITION ^
T
•IncvERSE OSMOSIS *
.
MELECTROOIALYSIS >
»
M ION EXCHANGE f*
10
^| DISTILLATION [•
1
LIQUID DISPOSAL S
P
ii
* DEEP WELL
It
> LAGOONING
13
> RECEIVING WATERS
' 14
* CONTROLLED
DISCHARGE
IS
• EVAPORATION
I*
* OCEAN DISPOSAL
FIGURE 7
LU06E TREATMENT
13
H FILTRATION
14
» CENT.»UGAT,ON
IS
• THICKENING
h
> SOLID DI1POSAL,
1*
LAND FILL
10
REUSE
II
OCEAN DISPOSAL
+
«-»
NEAT REMOVAL
„
1;,
IT
* COOLMG TOWEnl-»>
It
l*| SPRAT PONDS r*>
^
REUSE
* —
Wastewater Treatment Sequence
•ti
M
21
O
I
CO
en
-------
APPENDIX A-5-87
solids, (2) excess thermal energy discharge, and (3) waste containing
primarily only dissolved solids respectively.
Where waste water contains appreciable dissolved and suspended
solids, a typical treatment process might be 2-3-4-7-11-15 for liquids,
and 15-14-12-17 for solids.
In this sequence, the waste flow is equalized, followed by oil
removal. Clarification is used for suspended solids removal and
the dissolved solids are concentrated and disposed of in deep wells.
Effluent distillate is then discharge or reused. Suspended solids
slurries are thickened, entrifuged, and lagooned. Alternately,
chemical addition could be used for dissolved solids removal if the
dissolved ions have a common insoluble salt. Dissolved solids may
also be concentrated by electrodiolysis or ion exhcange instead of
distillation. These may be recovered and/or converted to a market-
able product.
Where there is excess thermal energy discharge, a treatment
sequence might be 17-6-4-13. Here a cooling tower or pond would be
used, and the cooled effluent reused or discharged. If the water is
recycled, the blowdown from the system may be treated by chemical
additon and clarification to remove undesirable components, especially
CrVI and zinc added for corrosion control. Suspended matter would
-------
APPENDIX A-5-88
then go into a solid disposal sequence. In some cases, such as in
the manufacture of H_SO , by-product steam may be used to economic
advantage.
Where there is -a heavy dissolved solid load but a light suspended
solid load, a sequence for acidic effluents would be 2-1-7-11-13.
Here neutralization would occur after equalization, followed by
reverse osmosis (or distillation, ion exchange or chemical addition),
before alternate disposal such as deep well injection or evaporation
to dry ness.
In general, it is advantageous to keep contaminated and relatively
clean effluent streams segregated, since most methods aim at con-
centrating effluents before discharge, or work better when solutions
are more concentrated.
-------
APPENDIX A-5-89
SIC 282 - PLASTIC MATERIALS AND SYNTHETIC RESINS.
SYNTHETIC RUBBER. SYNTHETIC AND OTHER
MAN-MADE FIBERS. EXCEPT GLASS
1. ECONOMIC STATISTICS
Production of all thermoplastic and thermosetting resins in the
United States was 16 billion pounds in 1968, .of which 12. 3 billion
pounds (over three-fourths of the total) represented thermoplastics.
The statistics for all major resin types are shown in Table A-5-12.
The aggregate growth rate of all thermoplastic resins is expected
to level out at about 11 percent per year over the next decade, com-
pared to an expected rate of about 5 percent per year for thermosets.
Thus, thermoplastics will represent an even greater share of total
resin production in the future.
Three types of thermoplastics—polyolefins (PO), polyvinyl
chloride (PVC), and polystyrene (PS)—have experienced phenomenal
growth, and should continue to do so. Polyolefins include both high-
and low-density polyethylene (PE), and polypropylene (PP). The top
position in thermoplastics is unquestionably held by polyethylene
resins, whose 1968 production of 4. 5 billion pounds was nearly twice
-------
APPENDIX A-5-90
Table A-5-12
PRODUCTION STATISTICS FOR MAJOR RESIN TYPES
Polyethylene (low density)
polyethylene (high density)
1'olj pi-opylcne
Polystyrene (straight and rubber-modified)
Poly vinyl chloride
CVllulosics
Other thermoplastic rosins
(Total thermoplastic resins)
AUyd
Coumn rone - i ndcne
Epoxy
Phenolic
Polyester
Urea and nelaninc
01 her thormobt-tting rer.jns
(Total thcriiu&cttlng resins)
Total resins
1968 Production
Billions
of Pounds
3.3
1.2
0.9
1.8
2.4
0.2
2.5
(12.3)
0.6
0.3
0.2
1.1
0.6
0.7
0.2
11:11
16.0
Percent of
Total Resins
21
7
6
11
15
1
16
(77)
4
2
1
7
4
4
1
(23)
100
U.s?. Tariff Cor.n
-------
APPENDIX A-5-91
that of PVC, about two and a half times that of straight and rubber-
modified PS, and about five times that of PP. Table A-5-13 shows
the estimated distribution of major U. S. thermoplastics production
capacity at the end of 1969.
Arable A-5-13
Distribution of Production Capacity
For Large Volume Thermoplastic Resins
Polymer
LDPE
PE
PO HOPE
PP
PVC
PS
U.S.
Producers
13
13
8
23
15
U.S.
Plants
21
15
8
35
30
Estimated
Capacity
End of 1969
(billion Ib/yr)
4.25
2.11
1.26
3. 72
2.54
13.88
(1) Industry Descriptions
The industries included in this category are:
2821 Plastic Materials, Synthetic Resins - manufacturers
of the resins, cellulose, and casein plastic—not the
users of such materials.
-------
APPENDIX A-5-92
2822 Synthetic Rubber - manufacturers of synthetic
rubber by polymerization or copolymerization,
but not the manufacturers who use such products
to make final products.
2823 Cellulosic Man-Made Fibers - manufacturers of
rayon and similar cellulose fibers.
2824 Synthetic Organic Fibers - manufacturers of all
synthetic fibers other than cellulosic fibers, such
as nylon, acrilon, etc.
(2) Establishment Size and Location
Production data for 1967 and 1958 are shown to illustrate
the magnitude of this industry and its growth rate.
Industry
(SIC Code)
2821
2822
2823
2824
Value Added
(million $)
1967
1635.1
404.9
506.8
1251.8
1958
872.0
197.9
390.3
439.6
Establishments
(20 or more employees]
1967
340
28
20
35
1958
196
18
26
14
-------
APPENDIX A-5-93
The geographic spread of these industrial groups is shown
by the following distribution table.
Number of Establishments
With Over 20 Employees
Industry (SIC Code)
Division 2821 2822 2823 2824
New England
Mid Atlantic
East North Central
West North Central
South Atlantic1
East South Central
West South Central
Pacific
Total 340 28 19 35
A relatively small number of companies manufacture most
of the synthetic rubber and man-made fibers. Resin manufac-
turing is somewhat more widely distributed. The data as of
1967 (Reference 1) is given below:
49
98
69
9
36
16
18
45
-
2
4
-
3
3
14
2
1
4
1
-
7
6
-
-
-
2
-
-
27
6
-
-
-------
APPENDIX A-5-94
Industry (SIC Code)
Percent Accounted for by:
48 20 50
Largest Largest Largest Largest
Companies Companies Companies Companies
2821
2822
2823
2824
27
61
86
84
43
82
99+
94
64
100
100
100
86
-
-
_
2.
The industrial chemical industries (2815 and 2818), the
plastic materials industries (2821, 2822, 2823 and 2824), and
the petroleum industry (2911) are interrelated. Similar products
may be made in each group, while feed stocks, intermediates,
and by-products may be interchanged. Some plastics are also
made in the miscellaneous plastics products industry (3079).
Table A-5-14 illustrates this relationship (Reference 1).
WASTE CHARACTERISTICS
The growth of plastic producting during the past ten years has
continued at an annual rate of 12 to 16 percent. The following
tabulation shows the effect of this growth rate on the production of
the various types of plastics and resins.
-------
Table A-5-14
Shipments by Product Class and Industry, 1967
Material
Plastic Film
Cellulosic, except rayon
Thermoplastic Resins
Thermo setting Resins
Synthetic Resin Protective Coating
Custom Resins
Plastics & Resins (NCC)
Synthetic Rubber
Other Products
Industrial Organic Chemicals
Cyclic Intermediates
Industrial Inorganics
Miscellaneous Plastic Production
Cellulosic Fibers
Non- Cellulosic Fibers
Surface Active Agents
2821
190.1
234.0
1391.0
450.8
223.4
191.3
56.9
(20-50)
577.0
169.6
44.9
12.8
127.2
-
-
18.1
2822
_
-
(5-10)
-
-
(-2)
-
814.4
97.4
(50-100)
(10-20)
-
-
-
-
2823
_
-
-
-
-
-
-
-
-
(50-100)
-
8.1
-
(500-1000)
(50-100)
(+2)
2824
_
-
-
-
-
-
-
-
-
(20-50)
-
(10-20)
(10-20)
(50-100)
1863. 9
3079
792.4
(10-20)
(-2)
(-2)
2.2
(10-20)
2.5
-
-
-
-
-
X
-
-
i
2815
2818
2911
243.0
(50-100)
(500-1000)
('50-100)
60.9
26.6
8.1
(100-250)
-
X
-
-
-
(-2)
(10-20)
w
*
o
tn
i
CO
en
-------
APPENDIX A-5-96
Comparative Production Increases - SIC 2821
(millions of pounds)
1968 1958
Polyethylene 5,445 708
Polyvinylchloride 2,635 689
Styrene 2,896 673
Phenolic and other tar acid resins 1, 096 532
Phthalic alkyd & other alkyd resins 691 523
Coumarone- indene 348 286
Urea and Melamine 816 349
Cellulosic plastic 187 146
Polyester resins 615 96
Epoxy resins 157 47
All other 1.460 424
Total 16,346 4,473
(1) SIC 2821 - Plastic and Synthetic Resins
Production within this category can be broken down into
various classes of plastics and resins. A 1967 study (Reference
1) divided the production processes into nine product areas:
-------
APPENDIX A-5-97
Cellules ics
Vinyl Resins
Polystyrene Resins & Copolymers
Polyolefins
Acrylics
Alkyd & Polyester Resins
Urea & Melamine Resins
Phenolic Resins
Miscellaneous Resins.
The wastes associated with each of these categories
(References 1 and 2) are summarized in Table A-5-15.
(2) SIC 2822 - Synthetic Rubber
The major synthetic rubbers produced include:
Butadiene - styrene copolymers, hot process
Butadiene - styrene copolymers, cold process
Butadiene - acrylonitrite copolymers
Butyl rubber
Neoprene
Silicone rubber
Hypalon.
The waste products from the first three compounds are
similar and vary only because of the differences in raw materials.
Wastes contain minor amounts of raw materials as well as
soaps, catalysts, and modifiers.
Typical reaction products for Butadiene rubbers include:
butadiene, styrene, lorol mercaptan, potassium persulfate,
-------
Table A-5-lfr
Plastic and Resin Associated Wastes
SIC Code
28211
28212
28213
28214
PlulK or Rain
CHLLULOSICS
VINYL RbSINS
POLYSTYRENE
RI.SINS AND
COPOLYMERS
POLYOLLriNS
Type of Product
Cellophane
Acetate Sheets
1 looruig
Wire and table
Sound recordings
Extrusions
Lightweight rigid loams
1 Urns jnd sheets
Insection molding
Type of Waste
Regenerated cellulose-
Cellulose
Sodium hydioxide
Sulfunc acid
Sodium sulfate
Carbon bisulfide
Bisodium suinde
Cellulose esters
Acetic acid
Methylenedichlonde
Magnesium sulfate
Acetic anhydride
SulCunc acid
Cellulose acetate
Mercury chloride
Copper chloride
Surface active agents
Catalysts
Unreacled products
Phenol
Sodium phcnolate
Sodium hydroxide
Cubon telrachloride
Chloroform
Peroxide catalysis
Methyl or ethyl cellulose
Polyacrylic acids
Polyomy dlcohol
Monochlorodimethyl ether
Methylal
Starches
Calcium carbonate
Calcium phosphate
Low pressure polymerization catalysts
Trialk yd Aluminum
Hexavalenl chromium oxide
Titanium chloride
Chromium nitrate
Nickel salts
Colorants
Lubricants
Stabilizers
Solvents such as xylene
Waste (Ib)/
1000 Ib Pnxl.
20
IS
10
NA
Waste Water
(Cal/lb Prod.)
30
1-2
IS
NA
-------
Table A-5-lb
Continued
SIC Code
28215
28216
28217
28218
28219
Plastic or Resin
ACRYLICS
ALKYDAND
POLYESTER RESINS
UREA AND
MELAMINE RESINS
PHENOLIC RESINS
MISCELLANEOUS
RESINS
Polyeura thane
Epoxy
Slbcones
Nylon
TVpe of Product
Fibers
Coalings
Coatings
Rigid foams
Adhesive
Textile and
paper treating
Bonding
Electric insulation
Plywood
Foams
Glues, moldings
Electrical equipment
Textiles, carpeting
Type of Waste
Airyliimuilo
Airylu polymer
Airylu jud
Diniclhylttirnuinidv
UiiniMliyljminv
1 ormii jiid
Duncihyli.jrDunjU'
Monomers
Vinyl jiuljlc
Vinyl chloride
Slyrrnv
Isubutylvnc
Airylamidc
Vinyl pyridmv
Inoriunu sjlls suih js Zmi
Maleic anhydride
Fumaric acid
Styrene
Piopylene glycol
Diethylene glycol
Phthalic anhydride
Adipic acid
Catalysts such as
Benzoyl peroxide
Dicuimf peroxide
Calaum hydroxide
Banum hydroxulr
Vinyl sdtcones
Urea formaldehyde butanol
Dicyanodiamide
Thiourea
Caustic
Phenol
Phenol alcohol
Calcium hydroxide
Sulfunc acid
Formaldehyde
Waste (Ib)/
1000 Ib Prod.
15
6
35
30
Waile Water
(Cal/lb Prod.)
013
2
010
010
01
I
CD
CO
-------
APPENDIX A-5-100
soaps, sodium formaldehyde, sulfoxylate, ethylene diamine tetra-
acetic acid, acrylonitrile, plasticizers, carbon black, caustic.
Neoprene production involves acetylene conversion to
monovinylacetylene utilizing reactions with hydrogen chloride in
a cuprous chloride solution. Other chemicals involved include
such compounds as sodium hydroxide, potassium persulfate, sulfur,
resin.
Most silicone rubbers are derived from dimethyl dichloro-
silane prepared by passing methylchloride over powdered silicone
with copper catalysts. Di-tert-butyl peroxide or dicumyl peroxides
are used for vulcanization.
Typical waste effluents include:
Raw Waste After Waste After
Waste Settlement Filtration
(ppm) (ppm) (mg/L)
Suspended Solids 5000 1000
BOD 700 160 80
COD 10000 1750 600
PV 1200 400 160
Ammoniacal N 8
Oxidized N 35
Total Phosphate (as P) 218
Phosphate in Solution (as P) 15
-------
APPENDIX A-5-101
(3) SIC 2823 - Cellulosic Man-made Fibers
Cellulesic Man-made Fibers are rayon and acetate fibers
made from cellulose, typically wood pulp which is reacted with
sodium hydroxide, the intermediate aged, and then mixed with
carbon disulfide. Titanium dioxide may be added to remove the
shine from the viscose rayon. Dyes are added as desired. The
fiber is then produced by ejecting the polymer through a die into
a zinc sulfate- sulphuric acid solution. Another method uses
cupra ammonium in an ammonia caustic solution to form the
polymer. Cellulose acetate is made by mixing cellulose, treated
with acetic acid, with a mixture of acetic acid and sulfuric acid.
Wastes include cellulose, rayon, sodium hydroxide, mercury,
carbon disulfide, cellulose xanthate, dyes, titanium oxide, zinc
sulfate, sulfuric acid, sodium sulfate, hypochlorite, copper sul-
fate, ammonia, and, for cellulose acetate, acetic anhydride,
methylene chloride, magnesium sulfate, acetic acid.
The characteristics of the waste liquor flowing from a
plant will vary according to the details of operation at each site,
such as the particular type of cellulosic produced (rayon, cupra
ammonium cellulose, cellulosic acetate).
-------
APPENDIX A-5-102
(4) SIC 2824 Synthetic Organic Fibers
Noncellulosic fibers include fibers such as nylon, orlon,
dacron, saran, and similar fibers made from poly amide poly-
ester and alkyd resins. The wastes from these processes will
vary and such wastes may become part of a larger waste stream
which embodies other chemical process wastes from other
operations at the same site.
The wastes for nylon include: hexamethylene adepamide,
monodi- and hydroxycarboxylic acid, dicarboxy acids, cyclo-
hexanol caprolactum, adipic acid, and adiponitrile. For acrylics,
the wastes are dimethylamine, dimethyl formamide, formic acid,
acrylonotrile, dimethyl ammonium,dimethyl carbonate, inorganic
salts, ethylene cyandhydrin, hydroorganic acid, and zinc.
3. WASTE DISPOSAL PROCESSES
In general, the raw waste water from plants in the plastics and
fiber industries contains principally organic contaminants. With few
exceptions, these lend themselves to standard biological treatment for
the purpose of pollution control. Since many of the plants in these
industries operate in states or municipalities which currently regulate
and monitor industrial effluents, considerable experience is available
on the waste reduction treatments.
-------
APPENDIX A-5-103
(1) Waste Treatment Processes
The following descriptions briefly summarize the waste
treatment processes for the plastics and fiber industries
(Reference 3).
1. Coagulation
Coagulation is used to remove colloidal suspended
materials (i. e., non-settling particles in the range of
- 7 - 5
10 to 10 cm in diameter). Coagulants such as organic
poly electrolytes dissolve to form ions. These neutralize
the repelling charges on the colloidal particles permitting
them to agglomerate into larger particles which can be
settled.
2. Aeration/Activated Sludge
Biological oxidation, through the use of micro-
organisms, duplicates portions ofthe natural cycle existing
in bodies of surface waters, yielding carbon dioxide and
water. The treatment plant, therefore, reduces the oxygen
demand of the waste water to a level which can be handled
by the receiving stream.
-------
APPENDIX A-5-104
The principal biological oxidation in use is the acti-
vated sludge process. This consists of a continuous system
in which biological growths are mixed with the waste water
and aerated. The activated sludge (consisting of bacteria,
fungi, protozoa, etc.) is settleable and is separated from
the treated water. Some of the settled material
is recirculated for admixture with the raw waste.
The oxygen required to satisfy the demand of de-
gradable organic matter may be supplied through mechanical
means via surface agitation or submerged air sparging or
diffusion.
3. Trickling Filter
A trickling filter is a packed bed of media (e. g., stone)
covered with a layer of microbial slime (similar in composi-
tion to activated sludge) over which waste water is passed.
As the thin water layer passes over the surfaces, the bio-
degradable ma terial is oxidized. The term "filter" is a
misnomer, because the removal of organic material is not
accomplished with a filtering or straining operation.
-------
APPENDIX A-5-105
4. Flotation
Flotation is used for the removal of suspended solids
from wastes and for the separation and concentration of
sludges. The waste flow or a portion of clarified effluent
is pressurized to 40 to 60 psi in the presence of sufficient
air to approach saturation. When this pressurized air-
liquid mixture is released to atmospheric pressure in the
flotation unit, minute air bubbles are released from solution.
The sludge floes and suspended solids are floated by these
minute air bubbles, which attach themselves to, and become
enmeshed in, the floe particles. The air-solids mixture
rises to the surface, where it is skimmed off. The clarified
liquid is removed from the bottom of the flotation unit. At
this time a portion of the effluent may be recycled back to the
pressure chamber. When flocculent sludges are to be
clarified, pressurized recycle will usually yield a superior
effluent quality since the floes are not subjected to shearing
stresses through the pumps and pressurizing system.
5. Sludge Handling
Sludges from activated sludge treatment frequently
require concentration before they undergo further processing.
-------
APPENDIX A-5-106
Settling ponds, mechanical thickeners or notation equip-
ment may be utilized. Normal sludges of 1 to 2 percent
concentration can be thickened to 5 to 10 percent concen-
tration. The thickened sludge can then be disposed of by
various means: anaerobic digestion with the generation
of methane and sulfides; dewatering of the raw or digested
sludge with subsequent burning or use in land fill; wet
combustion; or by conversion to protein for fertilizer or
animal feed.
6. Lagoons and Stabilization Ponds
The fundamental principle underlying the most used
types of stabilization ponds is that their action depends
upon the simultaneous and continuous functioning of both
sectors of the aerobic cycle of organic growth and decay.
This contrasts with the conventional system which carries
out only the degradation processes and leaves the growth
potential to be exerted in the receiving water. The following
drawing indicates the synergistic activity of bacteria and algae
in photosynthetic oxygenation.
-------
APPENDIX A-5-107
1 Ib
Wastes
1.6 Ib
Aerobic
Dacteria
Excess
Bacteria
(Sludge)^.
1 Ib
Excess
Algae
-- .. Light
C07+NH
£•
Significantly, although the system is internally
self- sufficient, the input is biodegradable dead organic
wastes, and the output is living organic matter at a higher
energy level. The living algae: cells, however, are not
quickly available for biodegradation because of their
tenacity of life. Nevertheless, in terms of water quality,
the stabilization pond effluent may substitute an aesthetic
factor for the quality factors associated with biodegradation
unless algal cells are harvested.
Stabilization basins can be divided into two broad
classifications: the impounding and absorption lagoon, and
the flow-through lagoon. In the impounding and absorption lagoon
there is no overflow or there is intermittent discharge during
-------
APPENDIX A-5-108
periods of high stream flow. The volumetric requirements
of the basin must be equal to the total waste flow less losses
due to evaporation and percolation. In view of the large
area requirements, impounding lagoons are usually limited
to industries discharging low daily volumes of wastes or to
seasonal operations.
The flow- through lagoon can be classified into four
categories depending on the nature of biological activity.
Type I - Aerobic algae ponds. The aerobic
algae pond depends upon algae to provide
sufficient oxygen to satisfy the BOO applied
to the pond. Since sunlight is essential to
oxygen production by algae, the depth of the
pond is limited to that through which light will
penetrate. For most waste systems, this will
not exceed 18 in.
In order to maintain aerobic conditions
in the settled sludge and to provide uniformity
of oxygen, mixing of the basin contents for a
few hours each day is essential. Separation
-------
APPENDIX A-5-109
of the algae from the effluent is necessary to
minimize the oxygen demand on the receiving
waters. The aerobic pond is limited to those
wastes which are not toxic to algae growth.
Type II - Facultative ponds. The facultative
pond is divided by loading and thermal strati-
fication into an aerobic surface and an anaerobic
bottom. The aerobic surface layer will have a
diurnal variation, increasing in oxygen content
during the daylight hours and decreasing during
the night. Sludge deposited on the bottom will
undergo anaerobic decomposition, producing
methane and other gases. Odors will be produced
if an aerobic layer is not maintained. Depths will
vary from 3 to 6 ft.
Type III - Anaerobic ponds. Anaerobic ponds
are loaded to such an extent that anaerobic con-
ditions exist throughout the liquid volume. The
biological process is the same as that occurring
in anaerobic digestion tanks, being primarily
organic acid formation followed by methane
-------
APPENDIX A-5-110
fermentation. The depth of anaerobic ponds
is selected to give a minimum surface area- to-
volume ratio and, thereby, provide maximum
heat retention.
Type IV - Aerated lagoons. These lagoons
have detention periods ranging from a few
days to 2 weeks, depending on the BOD removal
efficiency desired. Oxygen is supplied by
diffused or mechanical aeration systems, which
also cause sufficient mixing to induce a signi-
ficant amount of surface aeration. Depths from
6 to 15 ft. are common.
In some industrial waste applications,
aerobic ponds have been used after anaerobic
ponds to provide a high degree of treatment.
Stabilization basins are also used to "polish"
effluents from biological treatment systems
such as trickling filters and activated sludge.
7. Sedimentation
Settleable solids (particle size greater than 10 cm
in diameter) are handled in lagoons or in clarifiers
-------
APPENDIX A-5-111
(thickeners). Lagoons must be periodically cleaned to re-
move the sediment. Clarifiers continually rake the solids
to a center outlet where they are withdrawn.
An API separator is, in essence, a large-volume
flow- through lagoon which permits free oils or low- density
material to surface and be skimmed off. Similar lagoons
are used in the plastics industry to remove lighter- than-
water plastic particles by a partially submerged drag flight
conveyor.
Three types of heavier-than-wat er sedimentation
occur, depending upon the nature of the solids present:
discrete, flocculent and zone settling. In discrete settling,
the particle maintains its individuality and does not change
in size, shape or density. Flocculent settling occurs when
the particles agglomerate or coagulate during settling with
a resultant change in size and settling rate. Zone settling
involves a flocculated suspension which forms a lattice
structure and settles as a mass, exhibiting a distinct inter-
face.
-------
APPENDIX A-5-112
8. Ion Exchange
Ion exchange, while normally used for influent water
treatment, can also be useful for the removal of undesirable
anions and cations from a waste water stream. Cations can
be replaced by hydroxyl ions. The reactions which occur
depend upon chemical equilibria situations in which one
ion will selectively replace another on the ion exchange
site. Cation exchange on a sodium cycle material can be
illustrated by the following reaction:
Nag • R + Ca** *- Ca-R + 2 Na+
where R represents the exchange resin.
When substantially all the exchange sites have been
replaced with calcium, the resin must be regenerated by
passing a concentrated sodium chloride solution through
the bed. This reverses the equilibrium and replenishes
the sodium content of the resin.
9. Oxidation- reduction and Precipitation.
Through the addition of suitable oxidating or reducing
chemicals, soluble metal ions can be precipitated as the
insoluble hydroxides and removed. pH control is usually
required as well.
-------
APPENDIX A-5-113
10. Adsorption.
Many industrial wastes contain organics in low
concentrations which are difficult or impossible to remove
by conventional biological treatment processes. These can
frequently be removed by adsorption on activated carbon.
After the adsorptive capacity of the carbon has been
reached, it is either replaced or regenerated by heating to
desorb the separated impurity.
11. Reverse Osmosis.
Reverse osmosis is a technique being investigated
for desalination of brackish water. It is also finding appli-
cation in treatment selected industrial wastes.
(2) Waste Treatment Practices.
A wastewater treatment sequence is identified for these
products, as reported by the participating manufacturers to the
Celanese Research Company (Reference 4).
Obviously, the treatment sequence does not present the
entire picture. With similar biological treatment, different
-------
APPENDIX A-5-114
recovery efficiencies are achieved. A perfectly feasible treatment
plant may be hydrauli'cally overloaded with insufficient holdup time.
Proper and adequate design is as important as the selection of
treatment sequence.
For a stream which has undergone biological treatment, the
suspended solids content of the effluent has no relation to the process.
Since solids are created by the biological process, the suspended
solids content of the effluent merely reflects the efficiency of the
polishing lagoon.
Although there are a wide variety of plastics and synthetic
fibers manufactured by various processes and techniques, the quality
of the raw waste water streams can be classified into four general
categories:
Manufacturing processes that do not normally involve
direct contact of water with the ingredients nor con-
tribute pollution in any form to the water used
Manufacturing processes in which the raw waste
water has a very low BOD_, a low-to-intermediate
COD and a relatively low suspended solids content
-------
APPENDIX A-5-115
Processes in which the raw waste water has a high
BODg, a high, but also completely degradable, COD,
and relatively high suspended solids content, and
Raw waste water of moderate BOD_, moderate COD,
U
low- to- intermediate suspended solids content but
specific problems related to the rate of biological
degradation.
Toxic or malodorous chemicals used in the manufacture
of plastic resins or synthetic fibers normally are either recovered
or chemically treated to the extent that they are not allowed to
reach the receiving waters. For each raw waste water classifi-
cation, the current usual treatment procedures are shown below:
Class I
28212 20 Polyvinyl Acetate Resin
28219 30 Urethane Resins
28245 10 Polyolefin Fibers
General Waste Water Characteristics: Either no water is used
in the process or the waste water contains virtually no pollutants.
Usual Treatment: None required. Provision is usually made for
handling leakage of process materials into cooling water.
-------
APPENDIX A-5-116
Class II
28214 11 High-Density Polyethylene (HDPE) Resin
28214 12 Low-Density Polyethylene (LDPE) Resin
General Waste Water Characteristics : Very low BOD_, low-to-
intermediate COD, low suspended solids.
Usual Treatment : API separator (with or without filtration or drag
conveyor to remove oily waste or polymer particles).
Class III
28211 Cellulosic Resins
28211 Cellophane
28214 Polypropylene Resin
28231 Cellulose Acetate Fibers
28232 Rayon Fibers
General Waste Water Characteristics: Intermediate-to-high BODg,
COD and suspended solids. Rayon and cellophane process waste-
waters contain high sulfates, and rayon process wastewater contains
zinc.
Usual Treatment: Preliminary settling lagoon followed by
aeration/activated sludge treatments (AS-Activated Sludge,
-------
APPENDIX A-5-117
AL-Aerated Lagoons, EA-Extended Aeration, and TF-Trickling
Filter) and clarification. BOD, and COD reductions are
o
generally high (80-95'percent). Sulfates are generally not
removed. Zinc is precipitated as the hydroxide where State
regulations mandate.
Essentially all of the COD is biodegradable under normal sewage
conditions. Consequently, adequate sludge holdup time and
extended detention time in polishing lagoons would allow for
more complete biological degradation. Algae growth, however,
could lead to rapid eutrophication. Algae harvest for either
land fill or conversion to protein feed would be mandated.
Sulfate removal is considered uneconomical and not a serious
pollution problem. Zinc removal processes are under development
by two companies, American Enka and FMC's American Viscose
Division. Removal of up to 98% of the zinc is possible.
Class IV
28211 10 Polyvinyl Chloride Resin
28212 30 Polyvinyl Alcohol Resin
28213 10 Polystyrene
-------
APPENDIX A-5-118
28213 20 ABS, SAN Resins
28218 Phenolic Resins
28218 Epoxy Resins
28219 10 Polyacetal Resins
28219 40 Nylon Resins
28241 Nylon Fibers
28243 Acrylic Fibers
28244 Polyester Fibers
General Waste Water Characteristics: Intermediate-to-high
BOD. and COD not readily degradable, low- to- intermediate
o
suspended solids.
Usual Treatment: Preliminary settling lagoon (with or without
neutralization) followed by aeration/activated sludge treatments
(AS, AL, EA, TF) and clarification. Problem metals are gen-
erally coagulated and settled in a separate pond. Reduction or
precipitation units may be used to reclaim zinc, antimony, or
chromium. Absorption units may be used to eliminate toxic or
malodorous chemicals from certain waste water streams. BOD_
reduction is generally high (80- 95 percent), and COD reduction is
generally good (40-90 percent). Most of the BODR and/or COD is
3
-------
APPENDIX A-5-119
generally biodegradable, but under non- normal sewage conditions.
Some of the special problems which exist in the manufacture of
this class of products are outlined below:
28212 10 Polyvinyl Chloride Resin
The raw waste water could contain some emulsion which usually
requires a chemical coagulation step.
28212 30 Polyvinyl Alcohol Resin
Polyvinyl alcohol is extremely inert to biological degradation.
Under the severe oxidation conditions of the COD analysis, it
does show a COD value, but it would not be expected to degrade
in a natural environment.
28218 Phenolic Resins
Phenol which might get into the raw waste water could present a
taste problem if allowed to go out in the effluent. It is usually
removed by an activated carbon absorption or an exchange process
prior to activated sludge treatment.
28218 Epoxy Resins
-------
APPENDIX A-5-120
An appreciable quantity of salt (NaCl) is evolved in the production
of epoxy resins. It is not a toxic material and is usually not re-
moved depending on the receiving water. If removal is necessary,
a solid waste disposal problem would be created.
28213 10 Polystyrene Resin
28213 20 ABS, SAN Resins
28219 10 Polyacetal Resins
28219 40 Nylon Resins
28241 Nylon Fibers
28243 Acrylic Fibers
Principal contributors to process waste water for these products
are monomers such as styrene, formaldehyde, caprolactam,
hexamethylene diamine, adipic acid, low molecular weight
polymers and sizing. These are biodegradable, but have a
gestation time for initial biological attack that is longer than
for normal sewage. These are referred to as "refractory"
organics. Extended detention time in biological treatment
ponds and polishing lagoons will allow for more complete de-
gradation. For these materials, BOD- may not be too significant
«j
a parameter. Titanium pigments (TiO0) used in most nylon textile
£i
compositions and the halogenated flame retardents used in acrylic
carpets may also be found in the processing wastes.
-------
APPENDIX A-5-121
28244 Polyester Fibers
A heavy metal catalyst is used in the manufacture of polyester
fibers. The process waste water is consequently treated in a
reduction unit, prior to biological treatment. This is primarily
for recovery of a valuable material but also accomplishes
pollution control. Complete removal of BOD material is not
possible, even after long periods of aeration, because anto-
oxidation of the sludge results in resolubilization of cellular
material which is subsequently used for synthesis. Therefore,
assuming optimum pH and temperature, adequate oxygen and
nitrogen and phosphate nutrients, a removal efficiency of about
95 percent is theoretically possible.
Field confirmation of data will require close cooperation
of the manufacturers. In many cases, raw waste water from the
plant is not treated by itself. Usually, raw waste water streams
from several process units are combined and treated together.
Polymer solid waste disposal practices presently employed
by the plastics industry were reportedly limited to three: open
dumping, sanitary landfill, and incineration. Resin producers
who have relatively concentrated sources of polymer wastes
-------
APPENDIX A-5-122
typically handled their own waste disposal on company land.
By contrast, plastics processors and fabricators (representing a
much larger number of individual plants, with correspondingly
less waste per plant) typically depended on public agencies or
private contractors for their waste disposal.
-------
APPENDIX A-5-123
SIC 283—DRUGS
1. ECONOMIC STATISTICS
(1) Description and SIC Classification
The term "drug industry" describes that segment of the
manufacturing sector that produces chemicals, pharmaceutical
products and biological and botanical products used for medicinal
purposes. Between 2,000 and 3,000 companies are engaged in
the manufacture of the variety of drug products available.
The Standard Industrial Classification (SIC) Manual
defines the categories of drug manufacturers using the following
four-digit numbers:
SIC 2831 — Biological Products
SIC 2833 — Medicinal Chemicals and Botanical Products
SIC 2834 — Pharmaceutical Preparations.
The assignment of these three industry codes is based
on the following definitions:
SIC 2831—Biological Products: Companies primarily
engaged in the production of bacterial and cirus vaccines,
toxoids and analagous products (i.e., allergenic extracts),
-------
APPENDIX A-5-124
serums, plasmas, and other blood derivatives for
human or veterinary use.
SIC 2833—Medicinal Chemicals and Botanical Products;
Companies primarily engaged in (1) manufacturing bulk
organic and inorganic chemicals and their derivatives,
and (2) processing (grading, grinding, and milling) bulk
botanical drugs and herbs. Establishments engaged in
manufacturing agar-agar and similar products of natural
origin, endocrine products, manufacturing or isolating
basic vitamins, and isolating active medicinal principals
such as alkaloids from drugs and herbs is also included
in this industry.
SIC 2834—Pharmaceutical Preparations: Companies
primarily engaged in manufacturing, fabricating or
processing drugs into pharmaceutical preparations for
human or veterinary use. The greater part of the products
of these establishments is finished in the form intended for
final consumption such as ampoules, tablets, capsules,
ointments, medicinal powders, solutions and suspensions.
Products of this industry consist of two important lines,
namely: (1) pharmaceutical preparations promoted primarily
-------
APPENDIX A-5-125
to the dental, medical, or veterinary professions, and
(2) pharmaceutical preparations promoted primarily to
the public.
(2) Number of Establishments and Relative Concentration
The (1967) Census of Manufacturers (Reference 9)
totals 1,129 establishments as primary producers within SIC
Codes 2831, 2833, and 2834. The relationship between SIC
code and numbers of establishments is as follows:
SIC Number of Companies
2831 128
2833 126
2834 875
This tabulation does not account for companies producing
products within more than one SIC category and is not an accurate
indication of size of the drug industry. The total number of drug-
producing companies is approximately 2,900>with 2,059 of these
producing products in more than one of the three SIC codes (Tables A-5-16
and A-5-17). Companies producing products within more than one SIC
code were listed only once. Manufacturing companies are operating
in 47 States and the District of Columbia.
-------
APPENDIX A-5-12 6
Table A-5-16
Geographical Distribution of Drug Industries
Number of Establishments in Region *
C D E F G H I Total
SIC 2831, 105 712 189 387 57 128 192 32 257 2059
-33, -34
Unknown 57 292 100 141 38 46 66 15 75 830
SIC
Total Drug 162 1004 289 528 95 174 258 47 332 2889
Industries
Percent in Region
C D E
H
SIC 2831, 5.1 34.6 9.2 13; 8 2.8
-33, -34
Unknown 6.9 35.2 12.0 17.0 4.6
SIC
Total Drug 5.6 34.8 10.0 18.3 3.3
Industries
6.2 9.3 1.5 12.5
5.5 8.0 1.8 9.0
6.0 8.9 1.6 11.5
*Regions are defined as follows:
A. New England
B. Middle Atlantic
C. South Atlantic
D. East North Central
E. East South Central
F. West South Central
G. West North Central
H. Mountain
I. Pacific
Table A-5-17
Percent in Five Top Drug-Producing States
SIC 2831,
-33, -34
Unkown SIC
Total Drug
Industries
New York
17.4
21.7
18.7
California
10.8
7.7
9.9
Jfew Jersey
10.5
6.5
9.4
Illinois
8.5
6.4
7.9
Pennsylvania
6.6
7.0
6.7
-------
APPENDIX A-5-127
Number of Companies
Geographic SIC Code
Area 2831 2833 2834
Northeast Region 30 51 326
North Central Region 44 35 262
South Region 30 20 170
West Region 24 20 117
Total (United States) 128 126 875
The percentage distribution of companies in those states
having the largest number of companies is as follows:
Number (Percent) Drug Companies
New
SIC Code New York Calif. Jersey Illinois Penns.
2831 10(7.8) 15(11.7) 9(7) 6(4.7) 6(4.7)
2833 18(14.3) 16(12.7) 21(16.7) 13(10.3) 9(7.1)
2834 137(15.7) 90<10.3) 75(8.6) 72(8.2) 66(7.5)
(3) Major Raw Materials and Annual Production
The drug industry spans the numerous and varied
operations required to produce a packaged product suitable for
administration as a finished, usable medication. The con-
version of raw materials to finished dosage form is concentrated
in companies included in SIC Code 2384. Companies included
in SIC Codes 2831 and 2833 may restrict production processes
to those required for the manufacture of biological, botanical.
-------
APPENDIX A-5-128
or fine chemical substances for bulk distribution or may
extend the scope of operation to include the conversion of
these drug principals to a finished dosage form.
Industry processes begin with biological, botanical
extraction, or chemical synthesis. Further processing includes
milling, grinding, addition and mixing of excipients suited to
the preparation of the final dosage form, depending upon the
manufacturer's product requirement. Products and processes
are briefly summarized as follows:
SIC 2831—Biological Products. Seed cultures (bacterial
or fungal) are innoculated into a suitable medium which is
then permitted to ferment. At the conclusion of the
fermentation process, the bacterial and fungal solids are
extracted from the ferment and discarded. The desired
biological or chemical product is then purified. The
purified product is then readied for bulk distribution or
conversion by the manufacturer into a suitable dosage
form.
SIC 2833—Medicinal Chemicals and Botanical Products.
Products manufactured by companies included in this SIC
code may have as starting materials animal tissues,
-------
APPENDIX A-5-129
botanicals, or synthetic raw materials. Fine chemicals
are derived from animal or botanical sources using
suitable grinding, extraction, and purification procedures.
Fine chemicals are also produced from synthetic raw
materials using appropriate chemical processing
techniques. The derived products may be sold in bulk
or processed by the manufacturer into suitable, finished
dosage forms.
SIC 2834—Pharmaceutical Preparations. Active drug
principals are converted into a variety of dosage forms.
These include:
Formulations for oral administration
Tablets
Capsules
Liquids
Formulations for parenteral administration
Liquids
Pellets
Formulations for topical administration
Liquids
Ointments
Aerosols
-------
APPENDIX A-5-130
Raw material requirements for these varied
operations, although numerous, can be conveniently
described as follows:
Basic active principals including substances
derived from biological, botanical, or
synthetic raw material sources
Solvents and a variety of process chemicals
Excipient materials including gelatin, starch,
lactose, talcum, emulsifiers, coating ma-
terials, flavors, perfumes, and dyes
Packaging items including:
Glass as bottles, vials, and ampoules
Plastic as vials, tubes, bottle caps,
unit packaging
Metal as tubes, unit seals for parenteral
containers and aerosol cans
Cardboard for unit containers and
shipping cartons
Paper for labels, package inserts, and
promotional literature.
One highly specialized area of pharmaceutical manu-
facturing is the preparation of radiological products. The
processing of radioactive substances into pharmaceutical
products is restricted to a very few companies. Although
such products are used chiefly as diagnostic agents, there
are a limited number of palliative products manufactured.
The unique raw materials for this product group are the
radionuclides incorporated into the desired dosage form
-------
APPENDIX A-5-131
(chiefly parenteral) and the specialized shielded (lead)
packaging required for distribution.
The cost of materials utilized by companies included
in the three SIC codes is shown in the following summary:
SIC Number of Cost of Materials Delivered Cost
Code Companies (106 dollars) (106 dollars)
2831 128 56.4 46.7
2833 126 206. 1
2834 875 1,013.7 902.8
Total annual production of the drug industry ranges
between single batch preparation of a few items to con-
tinuous processing of a large number of products. The
value of product shipments taken from the Bureau of
Census statistics (1967) for companies in the three SIC
codes is shown in the following summary:
SIC Number of Value of Shipments
Code Companies (106 dollars)
2831 128 160.0
2833 126 445.2
2834 875 4,696.4
Total 1,129 5.301.6
-------
APPENDIX A-5-132
(4) Employment and Annual Sales
Although in excess of 2, 000 companies are engaged in the
production of drug products, approximately 95 percent of domes-
tic ethical drug sales of dosage form products is attributed to
33 companies.
The global sales of United States pharmaceutical firms
totaled 6.2 billion dollars in 1969. (Table A-5-18, which gives
the sales according to various channels of distribution, was ex-
cerpted from Reference 13.) Of the domestic human-use product
volume (4.03 billion), prescription legend drugs constituted
85 percent, with the remaining 15 percent resulting from sales
of "over-the-counter ethical" products.
To accomplish this total dollar volume, global employment
by the pharmaceutical industry totaled 230,900 people in 1969.
Increases in numbers of employees by domestic-based and
foreign-based firms contributed to a 1. 6 percent increase in
total employment. In spite of the fact that some domestic firms
reported decreases in employment, at least 14 firms reported
employment in excess of 5,000 people, and included six com-
panies employing 15,000 or more persons. Approximately
35 firms have 1,000 or more employees in ethical pharmaceutical
-------
Table A-5-18
Ethical Pharmaceutical Sales
Domestic and Foreign and Shares of End-Use Totals, 1969
(millions of dollars)
Product Fonn
and End Use
Dosage Form:
Human Use ... .
Dosage Form:
Veterinary Use .
Bulk:
Human Use
Dot
Private
Sector
$3.689.9
65.6%
109.9
55.5%
126.0
59.7%
nestic U A Si
Govern-
ments
$31 8.2
5.6%
.7
.5%
.8
.4%
sector i
lies
Total
Domestic
Sales
$4,008.1
77.2%
110.6
55.6%
126.8
60.7%
uesnnanon
1
Sales for
Export to
Other Firms
$65.4
7.2%
1.2
.6%
22.0
70.4%
Foreign Salei
Sales
Abroad*
$1,552.6
27.6%
94.5
45.5%
62.3
29.5%
i
Total
Saks
$1,618.0
2«.S%
95.7
46.4%
84.3
59.9%
TOTAL
$5,626.1
100.0%
206.3
700.0%
211.1
700.0%
Sales for
Export
Intro-Firm
Trans-
actions*
$ 67.2
8.7
115.6
: 105.7
64.2%
$4,031.5
64.9%
.1
.7%
$319.8
5.2%
105.8
64.5%
$4,351.3
70.7%
3.1
7.9%
$91.7
7.5%
55.7
55.5%
$1,765.1
25.4%
58.8
55.7%
$1,856.8
29.9%
164.6
700.0%
$6,208.1
700.0%
14.1
$205.6
Bulk:
Veterinary Use
TOTALS
* "Sales" are before deducting cash discounts and other marketing expenses, but after returns and allowances (domestic returns
and allowances totaled S93.2 million in 1969). Export sales are f.o.b. U.S. port. A large majority of the firms reported most
domestic U.S. sales were made f.o.b. purchaser's location or equivalent. The above domestic U.S. dosage form sales to the private
sector are "gross" at invoice price. For "f.o.b. manufacturer's plant" totals, deduct $126.5 million ($64.4 million transportation out
and $62.1 million company branch or field warehousing).
* "Sales Abroad" refers to sales in a foreign area by subsidiary or other corporate operations and excludes U.S. export sales.
Excluded also are sales outside the U.S. by foreign-owned firms which have subsidiaries in the U.S. as PMA member firms.
• "Sales for Export (intra-flrm transactions)" are sales to own International Division or for export to subsidiary abroad and are
included as part of cost in "Sales Abroad." Addition of the two "Sales for Export" columns will provide the aggregate ethical
pharmaceutical exports reported by PMA member firms.
R
s
I
50
cn
c/i
tn
M
>
I
U1
I
oo
-------
APPENDIX A-5-134
operations. These figures do-not necessarily account for
employees engaged in the manufacture of "proprietary" drug
products.
Although sales are somewhat concentrated within a
restricted number of companies, the industry is not dominated
by any one company. The largest company share of domestic
sales is approximately 7 percent with the 10 largest firms
accounting for 52 percent of the total domestic market.
(5) Growth Patterns
Sales of ethical Pharmaceuticals were expected to reach
7.0 billion dollars by the end of 1970. Exact figures are not
yet available. An increase of 405 million dollars in domestic
sales was forecast for the same period. The industry forecast
of total sales suggested a growth rate of 13 percent compared
to the actual 1968-1969 increase of 9. 6 percent. In excess of
50 percent of companies,for which figures were available,
anticipated an advance of 10 percent or more. Four percent
of the companies forecast an anticipated growth rate of less
than 5 percent. No company anticipated a decline in total
sales.
-------
APPENDIX A-5-135
Thus, based upon sales forecasts of 1970 sales, a
12. 6 percent increase in ethical pharmaceutical sales over that
figure recorded for 1969 global sales is anticipated. An increase
of 9 percent is anticipated in domestic sales. Foreign sales are
expected to increase approximately 11 percent.
The pattern of distribution remains relatively unchanged.
Approximately 19 percent of direct sales are to hospitals with
the remainder distributed to wholesale and retail channels.
2. WASTE CHARACTERISTICS
(1) Description of Production Processes and Waste Sources
The solid waste categories common to the majority of
industrial codes are to be found in the drug industry. The
potential problems of the drug industry, particularly those
identified with the largest companies, parallel those associated
with the chemical industry. Coupled with the chemical and
packaging waste problems, are those wastes originating from
biological, fermentation, botanical and radiopharmaceutical
manufacture and process operations. Identification of the types
of waste materials encountered is presented below. Since
there is a wide variation in types of manufacturing in any one
plant, not all wastes are necessarily found in each plant.
-------
APPENDIX A-5-136
Paper Waste Chemicals
Cardboard Off-quality Products
Plastic Fermentation Solids
Rubber Acid and Alkali Sludges
Glass Sewage Sludge
Metal Geiifcial Construction Trash
Dusts Cafeteria Wastes
Biological Tissue Radioactive Wastes
Botanical Residues Mi>.p«? Production Wastes
Ashes Unidentified)
Production Solids
(lui.iiiferentiated)
The potential for waste-produce generation exists at all
manufacturing and processing steps. In addition to biological
raw material requirements of the industry, research utilization
of animals is great; waste products gftiteration in the category
is greater than that found in most other SIC Codes. In addi-
tion, extensive chemical and microbi /'logical research has the
potential of generating waste products which may be accom-
panied by special disposal problems umque to the research activities.
1. Waste Generation During Process and Production
SIC 2831— Biological Prcuu> is. Bacterial and fungal
solids extracted from fermentation tanks are generally
discarded as solid wastes, l-lpent broth and fermentation
cakes also are wastes requiring disposal.
-------
APPENDIX A-5-137
SIC 2831 — Medicinal Chemicals. Chemical extraction
of animal tissue results in solvent waste and spent
animal tissue. The production of synthetic chemicals
results in solvent waste and chemical solid waste.
SIC 2833—Botanical Products. Botanical products
are manufactured by the extraction and purification of
fine chemicals from botanical materials. The process
results in both solvent wastes and solid waste con-
sisting of bark, leaves, stems, and pulp.
SIC 2834—Pharmaceutical Preparations. Chemicals
are weighed, mixed and channeled into one or more
final dosage forms. These processes result in the
generation of dusts, concentrated tailings, clean-up
residues, off-quality products and returned goods
as wastes. The specific composition of such wastes
varies directly with the product involved and con-
sequently such wastes are impossible to define in
terms of specific material content.
-------
APPENDIX A-5-138
2. Description of Effluents to Air and Water
Effluents to air do not appear to be a problem with
the average small pharmaceutical plant but is more likely
to be the problem of the larger companies. Potentially
greater problems occur within those pharmaceutical
manufacturers operating fermentation plants required for the
production of antibiotics, steroids, and other products of biolo-
gical origin. These problems are discussed in the rest of this section.
Dusts are also of great concern to companies within
the industry. Dust inside a plant may result in "cross-
contamination" of products. This is of major concern
since there are some materials that are capable of
producing extremely toxic reactions to- some individuals
when present in minute quantities (i.e. .penicillin). This*
coupled with the fact that manufacturers within the drug
industry are extremely sensitive regarding their public
image, has resulted in their taking all steps necessary
to minimize the discharge of potentially noxious materials
(including odor) into the air.
Fermentation is an important production process
and represents the basic process for antibiotics and
-------
APPENDIX A-5-139
steroids. The most troublesome waste of the process and
the one most likely to be involved in waste-water problems
is "spent beer". This is the fermented broth from which
the desired product has been extracted and contains a large
amount of organic material, protein and other nutrients.
The direct discharge of such a material into a stream or
other body of water without eliminating or reducing the
quantity of these materials can result in serious problems.
Spills of liquid and solid chemicals and solvents,
both inside the production area as well as in general plant
areas frequently occur and present an effluent water
problem. Spills are washed down the nearest drain in
order to quickly and conveniently clean the area involved.
Thus, a potentially hazardous waste may be introduced
into a storm sewer providing the most convenient drain
was a storm sewer opening.
3. Hazardous Materials in Wastes
Enumeration of all potentially hazardous materials
which appear as wastes generated by the drug industry is
impossible. However, a grouping by descriptive class
is informative. A summary by waste categories follows:
-------
APPENDIX A-5-140
Use
Fine Chemicals Active ingredients
(toxic) in pharmaceutical
formulations
Synthetic raw
materials
(toxic)
Solvents
(toxic -
flammable)
Production of
drug ingredients
Extraction and
purification
Radioactive Preparation of
wastes (toxic, radio phar ma-
radioactive
hazard)
ceuticalsr research
Wastes
Process dusts;
off quality products
returned goods
Process dust;
product tailings;
off-quality products
Product tailings from
recycling process;
may be disposed of
if recycling is not
feasible
Tailings; product
rejects
Animal wastes Production of bio- Tissues; carcasses;
(pathogenic) logicals; research manure
needs
Syringes and
needles
(accident
hazard, reuse)
Biological
wastes
(bacteria,
fungi, etc.)
Glass
(accident
hazard)
Research; product
forms
As such
Production; research Spent broth;
ferment cakes;
residues
Packaging;
research
As such
The desirability of identification of the specific
substances included as fine chemicals, synthetic raw
-------
APPENDIX A-5-141
materials, solvents and radioactive wastes is obvious.
However, the number of chemicals involved coupled with
changes in product type and process operation and the
reluctance of manufacturers to disclose the nature of the
processes used make it impossible to obtain a detailed
inventory.
3. DISPOSAL PRACTICES
(1) Current Disposal Technology
The techniques used by the drug industry in handling
process wastes and the methods of solid waste disposal are
generally similar to those utilized in other industries and by
municipalities (Reference 2). Figure A-5- 8 summarizes the
disposal practices for a number of companies regionally dis-
tributed throughout the U. S.
1. Solid Wastes
Movable containers are used to collect solid wastes
at the source and to transport them to one or more general
collection points. Frequent collections are then made from
the collection point either by contract services or using
company-owned trucks. Land disposal sites, either privately
-------
MA.TEQIM.%
PROCESS
WASTED
WtATfi MMJDUW&
WASTE DISPOSAL.
%ARA6L»
AIMS
MOVAMJb
6OKJTMM&R9
*
I0W8U5.* fe
|
-------
APPENDIX A-5-145
or publicly owned and operated, are the ultimate disposal
areas for all or part of the solid waste generated in the
majority of the plants.
Pretreatment of wastes prior to disposal is practiced
by many companies. This pretreatment may be limited
to selection and sorting of certain solid wastes, wet pulping
and/or dry grinding coupled with compaction. Some
companies (e.g., the Upjohn Company, Kalamazoo,
Michigan) operates on-site incinerators for burning
biological tissues (including animal carcasses), waste
solvents, waste packaging material and waste laboratory
materials. Off-quality products and returned goods are
usually ground, wet or dry and buried at land disposal
sites.
2. Airborne Wastes
Removal of process and production dusts is a concern
of all drug manufacturers. The system employed in
removing airborne dusts are similar to those used through-
out industry in general. One useful method for removing
such substances is the baghouse type dust collector. In
fact, some companies exhaust all air from most manufacturing
-------
APPENDIX A-5-144
operations through this type of dust collector. The use
of this dry filter system is preferred to a scrubber system
if problems of water pollution are anticipated.
In addition to problems with airborne dusts, those
drug companies involved in the manufacture of antibiotics
and other substances produced by fermentation processes
have additional problems with airborne contaminants.
Most of the fermentations carried out are aerobic, that is,
air must be supplied to the fermentation organism. Usually,
compressed air is introduced or sparged into the bottom
of the fermentation tank which may range in volume from
5,000 to 100.000 gallons. Thus, it is necessary to discharge
an equal volume of vent gas from the other end of the tank.
The vent gas scrubs several materials from the fermentation
as it passes through the reaction, notably carbon dioxide
and many complex organic materials which vary with the
type of fermentation. Incineration of this vent gas has
provided a satisfactory solution to a potential problem.
Some companies pipe the vent gas from the fermentor to
the boiler house and use it for combustion air in the boiler.
-------
APPENDIX A-5-145
3. Water Wastes
The material most likely involved in water waste
problems is the spent beer waste generated by fermentation.
This is the fermented broth from which the desired drug
fraction has been extracted. The methods of treatment of
the liquid fermentation waste are generally biological,
trickling filters, or activated sludge. Other techniques
employed in the disposal of this waste are:
Drying by evaporation and sale as animal feed
Spray irrigation requiring approximately
125 acres/100.000 gallons of spent beer
sprayed per day.
An additional type of water waste problem is that associated
with chemical wastes and wash water generated during
manufacture. In dealing with this type of waste, several
techniques are employed. The simplest technique may be
a simple pH adjustment to render the waste amenable to
the bacteria of the waste treatment plant. However, such
wastes and waste water are not always compatible with
the biologic systems of the waste treatment plants. Con-
sequently, more rigorous treatment is often required.
Added effort includes the precipitation of heavy metals.
-------
APPENDIX A-5-146
the elimination of cyanide coupled with the removal of
other toxic elements prior to waste treatment. As an
alternate route of biologic treatment of chemical wastes,
some advances in the acclimation of sewage bacteria to
certain chemicals have been made. However, there are
still many instances where chemical wastes are too
concentrated or too toxic to make this feasible.
4. Radiological Wastes
The preparation of radiopharmaceuticals is a highly
specialized area of pharmaceutical manufacture. Where
nuclear materials are involved, safety standards are,
for the most part, established by the Atomic Energy
Commission. Two major sources of radioactive wastes
exist... (1) water wastes from process washings, and
(2) wastes containing manufacturing residues and off
quality products.
Generally, process washings are piped to high
capacity storage tanks and are allowed to decay to
within safe limits. The storage and decay procedure
usually comprises multiple tank arrangements. When
-------
APPENDIX A-5- 147
one tank is full, additional radioactive waste is directed
to a second tank. When the radiation contained in the full
tanks has decreased to a safe limit level, as determined
by monitoring, the contents are slowly drained into the
sewer system.
In disposing of manufacturing residues and off
quality products, properly license.? AEC disposal services
are normally employed.
5. Animal and Microbiological Wastes
Animal and microbiological wastes are generally
subjected to incineration and the ash residue buried at
disposal sites. In some instances, the microbiological
wastes are sterilized (autoclaving or other suitable
means) and are disposed of as land fill without incineration.
6. Solvent Wastes
The bulk of solvents used in production processes are
reclaimed by purification techniques. Many companies
have installed solvent recovery systems large enought to
recover the wide range of solvents used in the production
of medicinal chemicals and pharmaceutical formulations
-------
APPENDIX A-5-148
One company is known to recycle 99 percent of the hazard-
g
ous solvent substances (>10 gallons/year) used in their
facility. Still-bottom residues are given to a contract
service for further chemical treatment or incineration.
Manufacturing firms using only small volumes of solvent
normally employ a contract service to remove them to a
disposal site.
7. Wastes Generated by Research Facilities
Quantities of waste materials generated by research
operations within the drug industry may be small but
quite toxic. Increasing amount of work involving radiation
emissions has required the installation of special equip-
ment necessary for the prevention of such materials
escaping to the air or water effluent. Wastes are collected
and treated as production wastes. Similarly, microbiological
and animal wastes are incinerated and taken to land fill.
4. ESTIMATES OF WASTE PRODUCTION
Although four site visits were made, useful information re-
garding quantities and ultimate disposal of potentially hazardous
waste materials was obtained from one company. The types and
-------
APPENDIX A-5- 149
quantity of wastes together with the disposal systems employed are
presented in the following summary.
Solid Wastes, exclusive of solid product material but
including cafeteria garbage, construction rubbish, filters
and filter aids are drummed and taken to the municipal
dump. No estimate of quantity was available.
Production Wastes including dusts, off quality products,
packaging materials, returned goods are handled in
one of two ways. A SOMAT process of wet pulping is
used for all materials except plastic which is demolished
by dry-grinding. Approximately 3, 000 cubic yards are
compacted monthly and hauled to a publicly owned sanitary
land fill by company-owned trucks.
Process Water Wastes are emptied into the sewage system,
approximately 1. 6 million gallons per day.
Radioactive Wastes (process washing) are pumped directly
to 10, 000 gallon storage tanks for decay. Manufacturing
residues and product rejects are given to an AEC disposal
service. From 6-12 drums (30 to 55 gallon capacity)
are disposed of each month.
Syringes and Needles are destroyed and taken to a land
fill. From 20 - 50 pounds per month appear as waste.
Hazardous Solvents are reclaimed. Approximately 5, 000
gallons per month may be given to a contract service for
disposal. Additional quantities of solvents (research)
are taken by a service company for reclamation. The
quantity involved is less than 2,000 gallons per month.
Mycelia and Fermentation Residue is emptied into the
municipal sewer system. However, the company pays
for special treatment required to reduce the BOD and
COD load at the treatment site.
-------
APPENDIX A-5-150
The estimated annual cost of waste handling by the company is
$750,000 which includes municipal cost, contract service fees and
maintenance of on-site facilities.
Data describing the waste quantities generated by two of three
SIC codes included in the drug industry are presented in Tables
A-5-19 and A-5-20. No identification of hazardous waste is made.
However, the figures suggest that the drug industry as a whole does
not generate excessive quantities of hazardous waste materials. It
is certainly one industry that is exceedingly aware of and constantly
practicing good housekeeping practices since it is under constant
Federal scrutiny. It follows also, that good housekeeping practices
assist in controlling the indiscriminate generation or disposal of
potentially hazardous wastes. The industry image and Federal
requirements demand cleanliness of the operation. The drug industry
appears to be essentially a "clean" industry.
-------
Table A-5-19
Drug Industry Wastes (Lbs per Day)
1
Employees
Garbage
Mixed
Production
Wastes
Ashes
Street
Refuse
Animal
Remains
Production
Process
Wastes
Manures
Undiff. _
Misc.
Total
SIC 2833
283
269
30
5
60
923 (6.5)
15.411 (25.0)
100 (64.5)
200 (9.1)
5 (3.2)
13.381 (93.5)
46.140 (75.0)
50 (32.3)
41 (100)
2.000 (90.9)
14,304
61,551
155
41.4
2,200
SIC 2834
489
214
1.800
133
119
140
62
177
36
755
214
1.400
736
600
30
150 (7.4)
500 (2.8)
100 (26.8)
20 (3.5)
92.3(66.7)
100 (2.7)
100 (0.3)
10 (1.0
1, BOOSTS. 5)
5.700 (98.3)
16.000 (90.8)
115 (30.8)
150 (93.8)
500 (87.7)
500 (13.3)
600 (80.0)
36.400 (96.4)
750 (73.5)
--4. 860(13.1)--
3.000 (12.8)
11.990 (14.9)
7.500 (32.1)
180" (100)
10 (0.5)
4 (1.1)
50 (1.3)
100 (9.8)
500 (1.3)
20 (0.1)
10 (1.0)
600 (2.6)
78 (3.8)
300 (1.7)
5 (3.1
10 (0.2)
500 (1.3)
240 (1.0)
800 (4.5)
4 (1.1)
5 (3.1
50 (8.8)
46.1 (33.3)
3.000 (79.8)
150 (20.0)
1.230 (3.2
150 (14.7)
17,216 (46.4)
49,971 (62.1)
9,600 (41.1)
200 (9.8)
100 (1.7)
100 (2.7)
14,000(37.8)
2,400 (10.3)
25 (0.2)
150 (40.2)
1"
7-: :
2,038
5.800
17.625
373
160
570
138.4
3.760
750
37. 750
1.020
37.077
80. 468
23.347
180
fc
en
i
i-i
en
'• Combination of various waste types including process wastes.
** Radioactive wastes.
'--'••* Rejects ar.d returned drugs.
-------
APPENDIX A-5- 151A
Table A-5-20
Comparison of Total Solid Waste
Generated with Employment
Employees
475
800
300
489
214
283
269
30
3500
1250
1800
6000
5
60
298
1500
133
119
140
62
177
36
755
214
5846
1400
736
600
30
Production
Employees
275
370
125
192
150
170
216
30
1580
325
5
60
216
729
75
32
77
23
126
17
450
51
2556
398
582
150
18
Total Waste Load
(Pounds /Day)
11.160
24.000
52
2.038
5.800
14.300
61. 550
155
146. 690
7.105
17.625
95.077
46
2.200
Waste Load per
Total Employment
20.3
30.0
0.17
4.2
27.1
50.5
222.9
5.2
41.9
5.7
9.8
15.9
9.2
36.7
1.710(1210)** 5.7(4.1)
32. 100
373
160
570
138
3.760
750
37. 750
1.020
153.969
37,077
80. 468
23. 347
180
21.4
2.8
1.3
4.1
2.22
21.2
20.8
50.0
4.8
26.3
26.5
109.3
38.9
6.0
Waste Load per
Production Employee
40.6
64.9
0.4
10.6
38.7
84.1
284.9
5.2
92.8
54.2
9.2
36.7
7.9 (5.6)
43.9 .
5.0
5.0
7.4
6.0
29.8
44.1
83.9
20.0
60.2
93.2
138.3
155.6
10.0
* Mixed production wastes.
** Recent change from disposal to selling of wood pallets gives the lower figures
In parentheses.
•-:-*•: includes production control employees.
-------
APPENDIX A-5-153
SIC 284—SOAP, DETERGENTS, AND CLEANING
PREPARATIONS, PERFUMES, COSMETICS,
AND OTHER TOILET PREPARATIONS
1. ECONOMIC STATISTICS
(1) SIC 2841—Soap and Other Detergents, Except
Specialty Cleaners
This industry is comprised of establishments primarily
engaged in the manufacture of soap, synthetic detergents, inor-
ganic alkaline detergents, or combinations thereof. In addition,
establishments which produce glycerin from vegetable and animal
fats and oilts are included. Manufacturers producing shampoos
or shaving products from soap or synthetic detergents are clas-
sified in Industry 2844.
This industry is distributed throughout the United States,
with the Middle Atlantic and East North Central Divisions account-
ing for about 50 percent of the total establishments and those
employing 20 or more people (see table below).
-------
APPENDIX A-5-154
Establishments, 1967
20 or More
Division Total Employees
New England 48 8
Middle Atlantic 166 44
East North Central 166 59
West North Central 47 17
South Atlantic 63 28
East South Central 19 5
West South Central 55 11
West Region 106 35
668 207
During the 10-year period 1958 to 1967, the number of
establishments increased from 608 to 688 or about 10 percent,
while the establishments employing 20 or more advanced from
163 to 207 or about 27 percent. Over this 10-year period, the
number of employees in the industry increased only 2 percent,
with a high of seven percent in 1964. Of the 30, 300 employees
in the industry, 28 establishments employ about 58 percent of
the people (see table below).
Size of Establishment No. of Total No.
(No. of Employees) Establishments of Employees
1-4 287 500
5-9 85 600
10 - 19 89 1,300
20 - 49 105 3,500
50 - 99 50 3, 500
100 - 249 24 3,600
250-499 16 6,000
500 - 999 8 5.500
1000 - 2499 4 5, 900
Total 668 30,300
-------
APPENDIX A-5-155
During the period between 1958 and 1967, the industry
experienced a growth in shipment value from $1, 605. 9 million
to $2, 593. 4 million, or about 61 percent. The value added by
the manufacturers increased from $857. 6 million to $1, 403. 7
million, or approximately 63 percent. The value of shipments
and other receipts from the Soap and Other Detergent industry
(in 1967), totaled $2, 593. 4 million. This total was broken down
into three categories: (1) primary products (soaps and other
detergents) at $1,990. 2 million, (2) secondary products at $405. 7,
and (3) miscellaneous receipts at $197.5 million.
(2) SIC 2842—Specialty Cleaning, Polishing, and Sanitation
Preparation, Except Soap and Detergents
This industry is composed of establishments primarily
engaged in the manufacture of furniture, metal and other polishes;
waxes and dressings for fabricated leather and other materials;
household, institutional and industrial plant disinfectants, deodorants
and extermination products; dry cleaning preparations; and other
sanitation preparations.
The Polish and Sanitation industry is distributed over the
entire United States, with the Middle Atlantic and the East North
-------
APPENDIX A-5-156
Central divisions accounting for about 55 percent of the establish-
ments employing over 50 people, and 46 percent of the total
establishments (see table below).
Establishments, 1967
20 or More
Division Total Employees
New England 88 19
Middle Atlantic 247 58
East North Central 211 54
West North Central 99 24
South Atlantic 113 17
East South Central 33 4
West South Central 70 6
West Region 143 21
Total 1,004 203
The 10-year growth period (1958 to 1967) for this industry
shows that the total number of establishments decreased from
1.156 to 1,004, or about 13 percent. However, the establishments
employing 20 or more people rose from 188 to 203, or approxi-
mately 2 percent. The total number of employees in the industry
increased from 16,400 to 19,400, or approximately 18 percent.
The following table shows the relationship between the use of the
establishment and the number of people employed.
-------
APPENDIX A-5-157
Size of Establishment Total No.
(No. of Employees) Establishments of Employees
1-4 527 800
5-9 159 1.000
10 - 19 115 1,600
20 - 49 118 3,500
50-99 41 2,700
100 - 249 30 4.500
250 - 499 12 5,200
500 - 999 2 Not Given
Totals 1,004 19,300+
During the 10 years 1958 to 1967, the Polish and Sanitation
industry experienced a growth in the value of shipments from
$585 million to $1,108 million or about 90 percent, and an increase
in value added by the manufacturer from $295. 6 million to $666.1
million or approximately 122 percent. The value of shipments
and other receipts (in 1967) include: primary products at $810.4
million, other products at $199. 5 million and miscellaneous receipts
at $98.1 million.
(3) SIC 2843—Surface Active Agents, Finishing Agents,
Sulfonated Oils and Assistants
This industry is made up of establishments primarily respon-
sible for the production of surface active preparations used as
wetting agents, emulsifiers and penetrants. Also included in this
category are producers of sulfonated oils and fats, and related
products.
-------
APPENDIX A-5-158
The Surface Active Agents industry is concentrated along
the eastern coast of the United States where approximately 86 per-
cent of the total establishments operate, and 80 percent of these
employ 20 or more people (see table below).
Establishments, 1967
20 or More
Division Total Employees
New England 31 7
Middle Atlantic 64 28
East North Central
West North Central
South Atlantic 31 18
East South Central 10 .
West South Central
West Region 8 5
Totals 164 71
The 10-year period 1958 to 1967, shows a growth in total
number of establishments, from 142 to 164, of about 15 percent.
Those establishments employing 20 or more people grew from
46 to 71 a gain of about 55 percent. The total number of employees
in the industry increased from 3,100 to 5, 700, or about 83. 5
percent. The following table shows the relationship between the
size of the establishments and the number of people employed.
-------
APPENDIX A-5-159
Size of Establishment No. of Total No.
(No. of Employees) Establishments of Employees
1-4 34 100
5-9 31 200
10 - 19 28 400
20 - 49 47 1,500
50 - 99 13 900
100 - 249 9 2,600
500-999 2 Not Given
Totals 164 5,700+
The period between 1958 and 1967 saw the Surface Agent
industry's shipment value grow from $126. 6 million to $294. 2
million or about 130 percent, and the value added by the manu-
facturer grow from $52. 4 million to $129. 5 million, for a 150
percent gain. The value of shipments in this industry includes:
primary products at $219.1 million, secondary products valued
at $59. 2 million, and miscellaneous receipts at $15. 9 million.
2. DESCRIPTION OF INDUSTRY
Although the Washing industry dates back 2,000 years, no other
chemical process industry has experienced such a fundamental reversal
of the chemical raw materials and change in the chemical reactions,
as was caused by the acceptance of detergents in 1940. Soap was never
discovered, but evolved from crude mixtures of alkaline and fatty
-------
APPENDIX A-5-160
materials and became an industry in the Thirteenth Century. Chevreul
showed that soap formation was a chemical reaction instead of a mech-
anical mixture of fat and alkali, as it was previously assumed.
Soap is comprised of the sodium or potassium salts from
various fatty acids such as oceic, stearic, palmitic, lauric, and
myristic acids.
(1) Soaps
Soap, as manufactured by the old kettle process, is now
used only in smaller factories or for special or limited produc-
tion. This process was replaced by a continuous alkaline saponi-
fication process, which can produce as much soap in two hours
as the older batch method could produce in two to five days
(at 300 tons /day). The present method of soap manufacture is
the continuous splitting or hydrolysis process, in which fatty
acids are neutralized into soap after the separation of glycerin.
Raw materials for the manufacture of soap include:
Tallow — This principal fatty material (in soap-
making) represents 75 percent of the fats and oils
consumed.
Grease — This second most important material
represents 20 percent of the consumed materials
obtained from hogs and small domestic animals.
-------
APPENDIX A-5-161
Coconut Oil — This produces a soap that is firm and
lathers well, also contains large proportions of
desirable glycerides of lauric and myristic acids.
Chemicals — These include caustic soda, salt, soda
ash, caustic potash, sodium silicate, sodium bi-
carbonate, and trisodium phosphate. These are
used primarily in the role of soap builders.
Free Fatty Acids — These are the basic materials
for manufacturing wax.
(2) Detergents
Detergents are manufactured by using the continuous
saponification process developed by Sharpies and Lever Brothers
in 1945. The process (sulfonacation-sulfation) starts with alkyl-
benzene being introduced into the sulfonator with the proper
amount of oleum. The dominant bath principle is used to control
heat of sulfonation conversion and to maintain the proper tempera-
ture. Fatty tallow, alcohol, and additional oleum are added to
the sulfonated mixture. All of this is pumped through a sulfatejj,
operating on the dominant bath principle to maintain temperature
and producing a mixture of surfactants. This is followed by a
neutralization process where the sulfonated-sulfated product is
neutralized with a sodium hydroxide solution. The temperature
is controlled to maintain fluidity of the surfactant slurry, which
is conducted to storage.
-------
APPENDIX A-5-162
The surfactant slurry is introduced into the crutcher,
together with the sodium tripolyphosphate and most of the other
additives. Considerable water is removed and the paste is
thickened by a tripolyphosphate hydration reaction. The result-
ing mixture is pumped to an upper story where it is sprayed,
under high pressure, into a spray tower, counter to hot air
from the furnace. Here the granules are formed. These are
transferred again to an upper story by air lift where they become
cool and stabile. Finally, they are separated in a cyclone;
screened, perfumed, and packed.
The raw materials for the manufacture of detergents
include:
Surfactants — These surface active agents include
soaps, detergents, emulsifiers, wetting agents
and penetrants (SIC 2843), and compounds that affect
surface tension when dissolved in water. The
surfactants of both soap and synthetic detergents
act to perform the cleaning and sudsing of the
washing action by reducing surface tension. The
cleaning action consists of three main steps:
(1) wetting the dirt and surface with soap or
detergent, (2) removing dirt from the surface,
and (3) maintaining dirt in the solution until removal
through detergent action and mechanical agitation.
Surfactants are classified as:
Hydrophobic
Hydrophilic
Anionic
Cationic
-------
APPENDIX A-5-163
Nonionic
Z witter ionics
Semipolar.
Suds Regulator a—- This is an ingredient usually used
with a surfactant to stabilize or suppress the genera-
tion of suds. It usually consists of hydrophobic
materials. Examples of suds suppressors are long-
chain fatty acids, silicones, and hydrophobic nonionic
surfactants. Examples of stabilizer surfactant sys-
tems are lauric ethanolamide-alkyl-benzene sulfonate
and lauryl alcohol-alky! sulfate.
Builders—These elements are used to boost deter-
gent power and consist almost exclusively of complex
phosphates such as sodium tripolyphosphate. The
rapid rise in the acceptance of detergents stemmed
from the building action of these polyphosphates.
Additives — These make up about three percent of
the detergents. These include corrosion and tarnish
inhibiters, brighteners, bluings, antimicrobiologicals,
bleaches, perfumes, and colorings.
(3) Glycerin
Glycerin is a clear liquid having a sweet taste but no odor.
It was first prepared by Scheele in 1779; in 1846 Soberero pro-
duced the explosive nitroglycerin; and, in 1868, Nobel made it
as safe to handle as an explosive. These discoveries increased
the demand for glycerin. Glycerin is produced from organic raw
materials and may also be derived synthetically from petrochem-
ical raw materials. In 1962, a total of 549 million pounds was
produced; 118 million pounds (47 percent) was produced
synthetically.
-------
APPENDIX A-5-164
Glycerin is produced by a number of different methods:
(1) saponification of glycerides (oils and fats) in soap production,
(2) hydrolysis, or splitting of fats and oils in the production of
fatty acids, and (3) chlorination and hydrolysis of propylene and
other reactions from petrochemical hydrocarbons. The recovery
of glycerin from the soap plant involves energy, primarily in the
form of heat consumption for evaporation and distillation. The
first step in the production of glycerin from organic raw materials
includes:
Evaporation (multiple effect) for concentration
Purification with settling
Steam vacuum distillation
Partial condensation
Decoloration (bleaching)
Filtration or ion-exchange purification.
Most natural glycerin is produced from natural fats and
oils by the hydrolysis method. The process is carried out,
with a catalyst, in a large continuous reactor at elevated tempera-
ture and pressure. Water flowing countercurrent to fatty acids
extracts glyceral from the fatty phase. The resulting sweet
water, containing about 17 percent glycerol, is fed into a triple-
effect evaporator. Here the glyceral concentration is increased
-------
APPENDIX A-5-165
to 75 or 80 percent (hydrolyzer crude). This concentration,
when settled, contains 78 percent glyceral, . 2 percent fatty
acids, and 22 percent water. After settling, it is distilled.
A small amount of caustic is added to saponify fatty impurities.
Final purification of glycerin is accomplished by carbon bleach-
ing, followed by filtration or by ion-exchange.
3. WASTE CHARACTERISTICS
(1) Biodegradability of Surfactants
Since the surfactants are disposed of into the sewage treat-
ment plants or surface streams, the effect of microbial action
on the surfactant is important. Some of these, such as tetra-
propylene-derived alkyl-benzene sulfonate, degrade slowly with
a persistent residue. Others are more readily decomposable by
micro-organisms and leave practically no persistent residue.
The ease with which surfactants are dissassociated is termed
biodegradability. Tests measuring the die-away rate of surfac-
tants in river waters, or which stimulate the biological process
employed in sewage treatment plants, are being used for biode-
gradability measurements. Work is continuing in this area.
-------
APPENDIX A-5-166
(2) Pollution
The eutrophication of lakes and streams due to soaps,
detergents, and allied products results from too many nutrients
or "fertilizers11 being deposited in our waters. These nutrients,
which feed algal growth, include carbon, nitrogen, iron, and
(depending on the water) some 10 or 15 other chemical elements.
They also include phosphates which come from household laundry
detergents. The detergent industry has undertaken a massive
voluntary program to reduce the phosphate content in its laundry
products, thereby reducing this type of pollution. The magnitude
of this effort is indicated by the fact that, to this date (October 1970),
the industry has reduced the consumption of phosphates by 100
million pounds per year. By early 1972, this figure is estimated
to reach 641. 2 million pounds per year.
(Note:) Information for this section was obtained from References 8
and 9.)
-------
APPENDIX A-5-167
SIC 285 - PAINTS, VARNISHES, LACQUERS, ENAMELS, AND
ALLIED PRODUCTS
1. ECONOMIC STATISTICS
This industry is made up of establishments primarily engaged
in the manufacture of paints (paste or ready-mixed), varnishes, lac-
quers, enamels, shellac, putties and caulking compounds; wood fillers
and sealers, paint and varnish removers, paint brush cleaners and
allied paint products.
The Paint and Allied Products industry is distributed fairly
evenly throughout the North East, North Central, South and Western
regions, with the North East and North Central region containing about
62 percent of the industry (see table below).
Establishments (1967)
20 or More
Division Total Employees
New England 98 30
Middle Atlantic 445 165
East North Central 402 183
West North Central 107 49
South Atlantic 175 70
East South Central 54 28
West South Central 112 47
Mountain 26 8
Pacific 282 100
1.701 680
-------
APPENDIX A-5-168
During the 10-year period from 1958 to 1967, the Paint and
Allied Products industry decreased in total number of establishments
from 1, 709 to 1, 701 or about 0. 5 of 1 percent, while the number of
establishments employing more than 20 people increased from 600 to
680 or about 13 percent. The number of employees during the same
period increased from 58, 800 to 66,100, or approximately 12. 5 percent.
The following table shows the relationship between establishments and
people employed.
Size of Establishment No. of Total
(No. of Employees) Establishments No. of Employees
1-4
5-9
10-19
20-49
50-99
100-249
250-499
500-999
1000-2499
468
242
311
350
171
113
36
8
2
900
1,700
4,300
11,100
12.000
17. 100
11.900
7,100
(NA)
1.701 66.100+
During the 10-year period from 1958 to 1967. the Paint and
Allied Products industry experienced a growth in value of shipment from
$1. 878. 7 million to $2, 911. 4 million or about 55. 5 percent, and an
increase in value added by the manufacturer from $806. 9 million to
$1, 318. 5 million or approximately 64 percent. The value of shipments
and other receipts for this industry (in 1967) totaled $2, 911. 4 million
-------
APPENDIX A-5-169
broken down into primary products of $2, 598. 5 million, secondary
products of $133.0 million, and miscellaneous receipts of $179.8
million.
2. DESCRIPTION OF INDUSTRY
(1) Paints
A paint consists essentially of a pigment, suspended in a
suitable liquid, called a vehicle. This may be a drying oil,
varnish, solution, or a suspension of natural or synthetic resins
in an organic water solvent. When spread in a thin film, the
volatile components evaporate, leaving a mixture of pigment
and binder in the form of a continuous solid coating that is both
decorative and protective.
Oil-based paints dry by oxidation and polymerization of
the vehicle; there are hastened by driers and catalysts consisting
of oleates, resinates, or oxide of cobalt, lead, magnesium,
iron, calcium, zinc or zinconium. Solvents or mineral spirits
are used to decrease viscosity as an aid in application.
Water-based paints were of small importance prior to
World War II, but now hold 20 percent of the do-it-yourself
market. This represents a fifteen-fold increase in the past 10
-------
APPENDIX A-5-170
years. In the next 10 years, water-based paints are expected
to become of major importance for exterior finishes, not only
for houses but for automobiles as well.
There are several methods for preparing paints, but all
require a homogeneous dispersion of the pigment in the vehicle.
This is usually done by grinding methods, such as:
Roller mill—A series of water-cooled, hardened
steel rollers, turned at different speeds and in
opposite directions
Pebble mill-—Pigment and vehicle are placed in a
porcelain-lined water-cooled pebble mill, which is
about half full of pebbles the size of golf balls.
Moorehouse mill—This is a commercial adaptation
of a laboratory colloid mill. Small in size, it is a
high speed continuous mill used for house paints,
flats and water emulsion finishes.
Stone mill—Mixing by grinding between stones, as
has been done for ages, is still used where a fine
grind is desired and capacity is not important.
Sand process—This most recent development for
pigment dispersion, consists basically of a bucket of
sand (controlled particle size) rapidly agitated by
hardened steel discs. A pigment-vehicle mix of low
viscosity is passed through the sand.
(2) Varnishes and Enamels
A varnish differs from an enamel in that it contains no
pigment, and produces a clear transparent coating. Most are
-------
APPENDIX A-5-171
oleoresinous materials made by cooking drying oils and resins,
and then adding drying oils and thinners. Drying oil is generally
tung oil, while the resin is estergum or a special synthetic resin.
However, other oils may be used. The ratio of resin to oil
varies with the different types of varnish used for different pur-
poses (see table below).
Gallons Used per
Oil 100 Ib. Resin Purpose
Short 12-15 Furniture (rubbing)
Moderately Short 15-25 Household enamels
Medium Length 25-35 Spar and floor varnish
Long 35-50 Durable exterior finishes
In making a typical varnish, the gum resin and oil are
heated in a kettle over an oil burner. The temperature rises
rapidly to 500-600° and is maintained until the mixture becomes
homogeneous. Driers are added during the cooking process.
The kettle is pulled from the fire, and its content is cooled and
thinned. Dirt is removed after cooling, and a liquid drier is
added after thinning. The final product, varnish, is then pumped
into storage tanks to await production control tests. (Baking
japans are varnishes made with asphaltum instead of resin.)
-------
APPENDIX A-5-172
Varnishes and enamels are classified as follows:
. Oleoresinous varnishes and enamels
Alkyd varnishes and enamels
. Cellulose clear lacquer and lacquer enamel
Resin lacquers and enamels.
(3) Lacquers
These protective coatings dry by evaporation of volatile
components. The film-forming constituent is usually a cellulose
ester (nitrate, acetate or acetate-butyrate), combined with a
resin. Plasticizers are incorporated to add flexibility to the
film. Acrylics and other thermoplastic polymers are now being
employed in lacquer systems. In addition to nitrated cotton, a
nitro-cellulose lacquer contains: (1) a solvent mixture which
includes a ketone, an alcohol, a volatile ester and an ether-
alcohol; (2) a resin such as alkyd, a phenolic or an ester gum;
(3) a plasticizer for film flexibility, (4) volatile diluents, and,
(5) a dye or pigment.
Lacquer is made by first dissolving the selected resin in
the diluent and then adding this to the cotton-solvent solution.
Finally, the pigment is added, as a suspension, in a nitro-cellulose
solution or in the plasticizer. A tank with an agitator is used for
these operations.
-------
APPENDIX A-5-173
The main uses for lacquers are automobile finishes, wood-
work and furniture, and artificial leather. Artificial leather is
made by coating cotton fabric with a pyroxylin solution and then
embossing it to simulate the grain of leather. The following table
shows amounts of the various components found in paints and
allied products (Reference 9).
Materials Billions of Pounds
Pigments and colors 2.1
Solvents and thinners 2. 0
Resins 0.8
Drying oils 0. 7
Plasticizers, polyols, and 0. 4
miscellaneous
(4) Pigments
Although, the Pigment industry is separate from that of
the Paint and Allied Products industry, almost half of the Pigment
industries' product is consumed in paints and allied products.
Approximately 35 percent of the total Pigment industry materials
(in 1958) were used in the manufacture of paints, varnishes,
enamels and lacquers. Some materials and processes used in
the production of pigments are:
Titanium Dioxide—Produced by mixing sulfuric
acid with concentrated ore. After digestion and
solution, the liquor is filtered. The concentrate
is boiled in sulfuric acid where titanium dioxide
is precipitated. The precipitate is washed, dried,
calcined and ground. This pigment, with controlled
caulking, is used exclusively for house paint.
-------
APPENDIX A-5-174
White Lead—Prepared by several processes:
(1) the Dutch process requiring three months,
(2) the Carter process requiring two weeks, and
(3) the French process requiring two days. The
white lead dust is poisionous and constitutes a
health hazard; hence, it is usually wet ground.
White lead is the sole pigment in oil-based paint
which provides an adherent, tough, elastic and
durable exterior paint.
Zinc Oxide—Prepared by the French process. Zinc
metal is heated, in stoneware retorts, vaporized
and burned in a combustion chamber. The white
dust from this process is collected and prepared as
a pigment. There is a direct process where the
oxide is prepared directly from the ore. Zinc
oxide is also used, primarily for exterior house
paint.
Litharge (Lead Oxide)—Produced by heating metallic
lead in a reverbratory furnace, where it is kept just
above the melting point with large volumes of air
flowing over it. The oxide formed is drawn off the
surface, cooled, ground and levigated.
Red Lead—Produced as a byproduct in the manu-
facture of sodium nitrate, and by calcining litharge
in a muffel furnace. Production of red lead now
surpasses that of white lead.
Iron Oxide—Produced by roasting ferrous sulfate
obtained from the vats used for pickling steel. The
shade of this pigment is varied by altering the firing
time, temperature and atmosphere. It represents
a cheap source of pigment widely used as red barn
paint and metal primer.
Carbon Black—Consists of several different types:
Thermal black—Pigment produced by thermal
decomposition of natural gas.
-------
APPENDIX A-5-175
Channel black—Deposit collected when many
small regulated names impinge on a relatively
cool surface.
Furnace black—Partial combustion of fuel gas
in a furnace; recovery is by cyclone or pre-
cipitator.
Lamp black—Residue as free soot or smoke
collected in chambers burning oils of hydro-
carbon gases.
Prussian Blue—Produced by reacting sodium fer-
rocyanide, ferrous'sulfate and ammonium sulfate.
The precipitate is then oxidized with sodium chlorate
or sodium dichromate.
Phthalocyanine Blue—Produced as greens and blues
with a high tinting strength. They are expensive,
but very effective tinters, and are used in both oil
and water-base paints.
Ultramarine Blue—Produced by heating a mixture
of soda ash, clay and sulfur with charcoal and pitch.
Its use is chiefly in exterior paints.
Chrome Yellows—Produced by precipitating soluble
salts from solution containing sodium or potassium
dichromate. It has high tinting strength. The color
shades are adjusted by varying the pH of the pre-
cipitating solution.
Chrome Greens—Manufactured by co-precipitating
Prussian blue and chrome yellow. The color depends
upon the mixture ratio of the two pigments used.
Natural Pigments—Consist of umber, ochre and
sienna.
Metallic Pigments—Consist of metallic powders
mixed with a suitable vehicle.
-------
APPENDIX A-5-176
Luminescent Pigments—Consist of organic dyes
of the rhodamine, auraxnine and thioflavlng types.
The paints are used in advertising displays and on
aircraft because of their daylight brillance.
3. WASTE CHARACTERISTICS
(1) Solvent Emissions
The emission of organic vapors into the atmosphere is
objectionable because of the photochemical reactions in which
they take part. Certain organic vapors react with oxygen and
nitric oxide to produce smog components which, in turn, produce
eye irritation, plant damage, visibility reduction, etc. Hydro-
carbons are important because they make up about 85 percent
of the organics in the atmosphere. In general, olefins react
rapidly, while aromatics react more slowly. Benzene is unre-
active, while xylene and most substitute-aromatics (common in
solvents) react as rapidly as olefins. Table A-5-19 shows a
breakdown of constituents, with regard to the volatility of
purchased surface coatings.
The concentration of organic solid vapor emissions re-
leased by most surface coating operations, ranges from 100 to
200 parts per million (one pound of solvent vapor per 40, 000
cubic feet of air). There is a hazard of the solvent concentration
-------
APPENDIX A-5-177
building up to explosive proportions, although it is common
practice for industry to limit the concentration to one-fourth of
the lower explosive limit (approximately 2, 500 ppm for common
solvents). The procedure for the recovery and removal usually
involves one of these procedures: (1) condensation, (2) adsorp-
tion, (3) vapor incineration, and (4) adsorption.
Table A-5-1/9
Composition of Commercial Surface Coatings
Type of
Surface
Coating
Paint
Varnish
Enamel
Lacquer
Metal
Primer
Glaze
Resin*
Sealer
Shellac
Stain
Zinc
Chromate
Composition By Percent
Non-
Volatile
44
50
58
23
34
80
50
50
50
20
60
Hydrocarbons
Aliphatic
56
45
10
7
33
-
-
40
-
-
-
Aromatic
_
5
30
30
33
20
-
-
-
80
40
Alcohols
_
-
2
9
_
-
-
-
50
-
-
Ketones
_
-
-
22
_
-
-
-
-
-
-
Esters and
Ethers
—
-
-
9
-
-
-
10
-
-
-
50 percent unspecified solvent type.
-------
APPENDIX A-5-178
(2) Surface Coating Mists
During spray painting operations, the paint becomes
mixed with the atmosphere. Breathing these vapors, many of
which are toxic* constitutes a serious health hazard to anyone in
the surrounding area. In addition, continual use of paint products,
where contact with the products is frequent, leads to certain
medical problems. These may ensue as a result of the toxic
effects of some of the coating constituents, and by inhaling the
paint vapors.
(Note: Information for this section was obtained from References 8 and 9.)
-------
APPENDIX A-5-179
SIC 287 - AGRICULTURAL CHEMICALS
1. ECONOMIC STATISTICS
The agricultural chemicals industry is composed of three
subcategories:
SIC 2871 - Fertilizers
SIC 2872 - Fertilizers. Mixing Only
SIC 2879 - Agricultural Pesticides, and Other Agricultural
Chemicals, Not Elsewhere Classified
SIC 2871 comprises establishments primarily engaged in manu-
facturing mixed fertilizers (mixtures containing nitrogen, phosphoric
acid (PgOg) or potash) from one or more fertilizer materials pro-
duced in the same establishment. When sulfuric, phosphoric, or
nitric acid plants report other activities separately they are classified
as part of SIC 2819 - Industrial Inorganic Chemicals. When separate
data is not provided, captive plants are classified in this industry.
SIC 2879 comprises establishments primarily engaged in the
formulation of ready to use agricultural pest control chemicals.
Establishments primarily engaged in manufacturing basic or technical
agricultural pest control chemicals are in SIC 2871. These chemicals,
including insecticides, fungicides, and herbicides such as lead and
-------
APPENDIX A-5-180
calcium arsenates, copper sulfate, DDT, BHC, 24D, carbonates,
etc., are classified as part of 281 industrial chemicals.
SIC 2872 is engaged in mixing fertilizers manufactured in other
industries.
The geographical distribution and relative size of the various
establishments is shown below:
Division
New England
Mid-Atlantic
East North Central
West North Central
South Atlantic
East South Central
West South Central
Mountain
Pacific
SIC
Estab-
lish-
ments
With 20
or More
Employ-
ees
-
6
39
12
64
29
19
8
5
2871
Value
Added
($ Mil-
lions)
-
(D)
41.7
17.2
179.0*
67.4
53.9
9.3
18.7
SIC
No. of
Estab-
lish-
ments
5
22
44
18
86
15
12
2
6
2872
Value
Added
($ Mil-
lions)
(D)
(D)
66.9
16.5
57.6
10.4
11.9
4.2
9.9
SIC
No. of
Estab-
lish-
ments
21
9
11
25
10
12
6
18
2879
Value
Added
($ Mil-
lions)
53.3
37. 1
41.1
26.5
131. 1
24.4
33.2
28.6
Total
184
434.1
210 195.3
*Florida - $167. 2 million
115
376.3
-------
APPENDIX A-5-181
The interrelationships between these industries and others in
the chemical industry are shown below:
Total Shipments ($Millions)
Totals
Fertilizers
Fertilizers
Mixing Only
Agric. Chemicals
2815
2818
2819
2851
Misc. Receipts
The basic materials consumed (1967) in making fertilizers
are illustrated by the following table:
1000 Delivered
2871 Fertilizers Short Tons Cost ($)
Nitrogenous Materials 1,560 87.4
Phosphatic Materials 430 51.0
Potassic Materials 2.535 69.8
Sulfuric Acid 3,375 50.7
Phosphate Rock 12,485 116.9
Phosphoric Acid 272 45. 8
Sulfur 2,965 108. 1
Containers 14.0
All other materials
& components 123.0
Totals 23,622 667.8
All
Industries
X
982.8
588.2
3 834. 3
X
X
X
X
X
SIC
2871
1196.9
933.6
2
2-5
-
2-5
145.5
-
108.8
SIC
2872
731. 1
12.4
570.1
5-10
-
.6
-
-
137.5
SIC
2879
817.0
2
4.8
598. 5
2
14.9
4.3
10. 2
130. 1
Other
Industries
X
20-50
10-20
223.9
X
X
X
X
-------
APPENDIX A-5-182
2872 Fertilizers
Nitrogenous Materials
Phosphatic Materials
Potassic Materials
Inert Fillers
Sulfuric Acid
Phosphate Rock
Phosphoric Acid
All other materials
Totals
1000
Short Tons
1,122
770
1.482
808
175
80
145
-
-
Delivered
Cost ($)
84.7
89.3
56.5
8.7
4.0
-
15.8
13.0
146.4
4.582
417.4
The sale of pesticidal chemicals in 1967 was:
Fungicides
Herbicides
Insecticides, fumigants
& Rodenticides
Grand Total
178.000.000 Ibs
348. 300. 000 Ibs
504.300.OOP Ibs
1,030,600,000 Ibs
-------
APPENDIX A-5-183
2. PRODUCTION AND WASTE CHARACTERISTICS
The following discussion is divided into the production processes
associated with chemical fertilizers and those associated with the
prodcution of pesticides.
(1) Chemical Fertilizers
The materials used by the fertilizer industry are found in
natural deposits, salvaged from industrial and sewage wastes,
or manufactured synthetically. Each of the primary nutrients,
phosphorus, nitrogen, and potassium, is derived from nature
sources by processes unique to each chemical. The following
paragraphs outline the major extraction processes.
1. Phosphates (Phosphorous).
Processing phosphatic materials is the oldest manu-
facture and actually forms the basis of the industry. Phos-
phate rock is the principal source of phosphorus. Phos-
phatic minerals occur chiefly as amorphous or crystal-
line apatite and its variants such as calcium hydroxyla-
patite. Other sources of phosphorus are basic slag,
bones, and guanos.
Sulfuric acid, used to convert phosphate rock to more
suitable forms, is manufactured by the contact process.
Gaseous SOg and SOg emissions are the principal pollution
-------
APPENDIX A-5-184
sources. There are no inherent water pollutants, but
heat removal using water is essential and, thus, some
cooling treatment is necessary.
Most of the phosphoric acid used is manufactured
by the wet process method, using sulfuric acid, although
nitric and hydrochloric acids may also be used. The sul-
fate component of the sulfuric acid combines with the
calcium according to the following reaction:
Phos. Rock + Sulfuric Acid + Water -» Gypsum and
M-Phosphoric Acid
The insoluble gypsum is then separated. As a result of
the process, water streams may become contaminated
with fluorine which may be liberated in
the reaction.
If nitric acid acidulation is used, the reaction is:
Phos. Rock + Nitric Acid -* Calcium + Phos. Acid
Nitrate
By ammoniation with anhydrous ammonia the calcium
nitrate is then converted to other calcium compounds and
soluble ammonium nitrate (NH.NOq) which are then proc-
essed directly into solid fertilizer. Ammonia (NH3>, HF,
and SIF4 are byproducts released to the atmosphere.
-------
APPENDIX A-5-185
If hydrochloric acid acidulation is used the following
products result
Phos. Rock + Hydrochloric —> Calcium + Phosphoric
Acid Chloride Acid
The updgrading of wet process phosphoric acid to a
more commercially acceptable state involves either con-
centration or the partial removal of impurities. Fluorine
is the principal impurity evolved which contaminates the
water. Settling and/or centrifugation physically separates
precipitated impurities. Due to the high PoOc content of
the impurities, they may be assimilated in the production
of solid fertilizers.
2. Ammonia (Nitrogen)
Ammonia forms the basis for the nitrogen fertilizer
industry. Nearly all ammonia is synthetically produced.
Nitrogen is extracted from the atmosphere and catalytically
reacted with hydrogen. The hydrogen may come from
solid, and heavy liquid feeds (coke, wood, fuel oils) or
light liquid feeds and gases such as natural gas, coke oven
gas, refinery tail gases or electrolytic hydrogen. Over
96 percent of synthetic ammonia produced is from natural
gas. Small traces of sulfur compounds are removed from
-------
APPENDIX A-5-186
the natural gas and vented to the atmosphere. Wastewater
may contain phosphates, sulfates, and s'ulfites. Carbon
dioxide, carbon monoxide, and water vapor are also
produced as side products.
The production of ammonium nitrate involves sever-
al steps. Final nitric acid (HNO«) is produced by the
catalytic oxidation of ammonia with air. Then ammonium
nitrate (NH.NOS) is produced by reacting ammonia and
nitric acid to form ammonium nitrate, a basic fertilizer.
The major source of pollution in all ammonium ni-
trate plants is from floor spellings and ammonium
nitrate dust.
Urea (NHgCONH-) is produced by combining ammonia
and carbon dioxide. Urea plants are located adjacent to
ammonia plants, which supply both the ammonia and the
carbon dioxide requirements of the urea plant. Water
vapor and air, containing traces of urea are vented to the
atmosphere. Spills are recovered.
3. Potash (Potassium)
Potash constitutes one of the major nutrients essen-
tial for plant growth. The element is widely dispersed in
nature, occurring in highly soluble salts such as potassium-
bearing silicates, and in marine and land plants.
-------
APPENDIX A-5-187
Practically all commercial potash is recovered from
potash- bearing brines or from underground deposits of
soluble minerals. Extraction by solution and recrystali-
zation is commonly used. Separation of potash from its
ore by mineral flotation is also widely practiced.
Potassium chloride, or muriate of potash, is the
major source of potash in fertilizers. Potassium sulfate,
also a major component of fertilizers, is made by react-
ing potassium chloride with sulfuric acid to form potas-
sium sulfate and hydrochloric acid. Other potassium
compounds include potassium nitrate and potassium
carbonate.
Potassium nitrate (KNOq) is produced by reacting
potassium chloride and nitric acid to form potassium
nitrate, nitric acid, and hydrochloric acid. Potassium
carbonate (K_CO_) is generally made by the carbonation
of potassium hydroxide.
Generally speaking, with the exception of specialized
crops, one potash fertilizer is as effective as any other as
a source of potash for the plant.
-------
APPENDIX A-5-188
4. Storage Problems
The storage of some fertilizer intermediates and
final products may create pollution problems, especially
with normal superphosphate and triple superphosphate.
The curing of these fertilizers produces fluorine. Fluor-
ine is also released during processing. At that time
scrubbers are used to remove the fluorine.
The physical process of transporting fertilizer
materials—both liquid and solid types—can contribute to
water pollution. Cleaning of a railroad car or tank before
loading and accidental spills create the problems. Ship-
ping losses range between 0. 25-1. 00 percent of the total
material shipped.
(2) Pesticides
Pesticides include a wide range of chemicals used to con-
trol or destroy insects, weeds, etc.
There are approximately 45, 000 pesticide formulations
using some 900 chemicals. Although each is meant to be toxic
to only certain forms of life, they may enter the environment as
a contaminant and may affect other forms of life directly or
indirectly.
-------
APPENDIX A-5-189
Pesticide manufacturers produce many pesticide wastes.
Some are neutralized or degraded at the production site. Minor
amounts are carried by rain and wash water onto the plant site.
The major amounts are found in cleanup wastes. One source
generally overlooked is the pesticide residues in the laundry
waste water from the washing of protective clothing worn during
manufacturing. Unless the waste treatment is a hundred per-
cent effective, the effluent may contain pesticide residues as
high as 1 part per billion. The sludge or settleable matter re-
maining after treatment contains most of the pesticides found in
the influent. The disposal of these solids presents a major
pollution problem. The salvaging of drums which contain emul-
sifiable solutions of pesticides may be another source of con-
tamination if the washwater from drum salvaging is allowed to
enter into a watercourse.
Formulating plants receive pesticide concentrates from
manufacturers. After dilution, the final pesticide formulation
is repackaged, loaded, and shipped to wholesalers. Pesticide
spillage is usually washed or brushed into drains. Also, dust
from formulation methods collects at the plant site.
Wholesale pesticide merchandizing is susceptible to
pesticide spills. Empty drums can continue to retain several
-------
APPENDIX A-5-190
ounces of pesticide, and, as discussed previously, wash-water
from drum salvaging can present a disposal problem.
Air pollution hazards are always present in the manufacture,
formulation, and packaging of pesticides. Pesticides are us-
ually made in closed systems of a continuous-process with
usually a slightly negative pressure to avoid leakage. Little
data exists on the emission rates of pesticides from production
plants.
Drum reconditioning operations may result in occasional
contributions of pesticide residues and wastes to sewage systems
and streams. Usually, 55- gallon drums are spot cleaned,
burned out, or flushed out during the cleaning process. Fre-
quently, informal indisposal of a variety of containers is in open
ditches or other "out-back" locations contributes to water
contamination by pesticides.
-------
APPENDIX A-5-191
3. DISPOSAL PRACTICES
(1) Fertilizer Manufacturing Wastes
The basic pollutants which arise from manufacturing
operations in the fertilizer industry are shown in Table A-5-9,
following this page.
Sulfuric acid mist is removed by precipitators and must elim-
inators. Many of the plants are of the single absorption type which
emit from 1500 to 2500 ppm of sulfur dioxides from their stacks. A
small number of more modern plants are using the double conversion
process which reduces emissions to as low as 500 ppm.
Nitrous oxides are removed by catalytic reducers in many
plants but are not fully successful in eliminating.all emission.
Advanced units are capable of virtually eliminating all oxides
but adequate industrial performance data has not been obtained.
Ammonia gas is captured by acidic scrubbers. Newer
plants have reduced nitrogen oxide losses to less than 0. 5 pound
of nitrogen per ton of ammonia produced, less than 5 percent of
the loss typical of plants built over 25 years ago.
Ammonia losses from urea plants are 2 to 3 pounds per ton of
product. Catalytic reduction and wet scrubbing reduce losses.
Ammonia losses from pressurized containers, when in shipment,
may present a serious hazard.
-------
Table A-5-9
Summary of Fertilizer Production Wastes
Product*
Phosphate .Fertilizers
Sulfunc Acid
Phosphate Rock Grinding
Phosphoric Acid (41%)
Upgrading Phos.Acid to 55-75%
Super Phosphate H2SO4
Phoe. Rock
Triple Super Phosphate
Phos. Rock
H3PO4 Acid
Mono Ammonium Phosphate
(H3PO4 + NH3-»NTH4H2PO4 + Heat)
Di Ammonium Phosphate
2 SO4
with KC1 slurry which is spray dried)
Nitrogen Fertilizers
Natural Gases
Ammonia
Nitric Acid
Ammonium Nitrate
(NH, + HNOs -» NH4NO3)
Urea
(2NHs + CO2 ->NH2CONH2 + H2O)
Summary of Fertilizer Pi oductlon Wastes
Waste Description Quantities
Sulfur Dioxide Gas
Dry Process - Dust
Flourine Gas-
Gypsum (3 CA-SO4- 2 H2O)
Fluorine - Other
w/ Product
S1F4.
SIF,
SK*
Minor L P.O. (Less then)
V.F (2*/Ton)
Recycl e excess NH3
Cl2 NH3 Gases
S02 C02 CO (See Table )
Oil
Catalysts
NH3 - Caustics
Little or none
Little or none
Little or none
Minor
SubHtamUt
Limited
5 Tons Gypsum /Ton H3PO4
Minor
Substantial
Substantial
—
Limited
Limited
Limited
-
~
Waste Process
Scrubbers
Bag Collector
Scrubbers
Sedimentation only or
precipitation with lime
Scrubbers
Scrubbers
Scrubbers
Scrubbers
Sedimentation ponds
Scrubbers
Scrubbers
Slclmminff
Sedimentation
-
—
APPENDIX A-5-]
^™
CO
to
* No commercially proven process for removing N from water solution.
-------
APPENDIX A-5- 193
Fluorine compound emissions as gases ojf particulates
and in scrubbing water is the most difficult hazard to control.
Exit gases from mono and diammonium phosphate and granula-
tion plants are reduced by scrubbing. Fluorine compounds pro-
duced from mixing single and super phosphates are also scrubbed
from emissions. Curing sheds which by and large do not have
ventilation control are major sources of fluorine loss. All
scrubber wastes must be treated with lime to precipitate the
fluorine compounds in settling ponds.
Particulate emissions are particularly heavy from phos-
phate rock drying and grinding operations and from dry proc-
essing and sizing plants. Bag collectors and electrostatic pre-
cipitators currently in use do not meet existing removal
standards.
The major pollutant from phosphate extraction is gypsum.
Approximately 5 tons are accumulated for each ton of super
phosphate produced. Over 20 million tons are generated annually,
most of it in Florida. These slimes are returned to the areas
from which dredged. In the extraction process, the addition of
water increases the bulk of the residuals beyond that of the
original material. Means to effectively dewater such slimes
are needed to restore the land which has been torn up from cut
-------
APPENDIX A-5-194
and fill operations. Rapid de water ing of these sledges would
create compact land fill coupled with lakes, an ideal combination
in Florida.
Raw water is constantly treated to remove sediments and
to cool for reuse in manufacturing operations. The type treat-
ment required by the water wastes associated with the production
of phosphoric acid and phosphorous is shown in Tables A-5-20
and A-5-21.
The effluents from mixed fertilizer operations are largely
made up of fertilizer components which have entered waste
streams. Coagulation and sedimentation are used to remove
wastes. Contamination of water by nitrogen from such opera-
tions occurs. To date there is no commercially proven process
of removing nitrogen from water streams.
Spills are reclaimed as completely as possible. Wet
scrubbers remove pollutants (such as fluorine as SiF^) and the
scrubber effluent is then treated. Drainage collected is either
treated or pumped to a confined area where overall plant pollut-
ants are contained. Dust collection systems prevent minor
product wastes from accumulating.
Generally speaking, solid fertilizer plant effluents are
combined with complex phosphoric acid plant effluents and the
-------
Table A-5-20
Base Levels of Treatment and Best Available Treatment
Wastes from Manufacture of Phosphoric Acid
for
Vocess
Acic'ulotion
it
»
"
Dry
Wastes
CaSC,
(as S)
CaF2
asF*
Phosphates
Silicates
H3P04
As2S3
Jb
SRWL
(Ibs/ton H,PO4)
1580
68
45
170
1.0
0.3
Base Level of Treatment
settling pond, process water
recycle (except during periods
of high rain)
settling pond, process water
recycle, double lime
treatment
settling pond, lime treat-
ment to pH 10
settling pond
use of washdown water
for H3PO4 manufacture
or no treatment
special burial or ponding
with pH control
Resultant
Effluent
0-2000 ppm
CaS04
5-8 ppm
0.5-5 ppm
p24 hour
retention)
same as BLT
with 9-24 hour
retention
same as BLT
use of washdown
H2O for H3PO4
mfg.
special burial
Resultant
Effluent
0-2000 ppm
CaSO4
<5ppm
*0.5 ppm
P04fi
<0.5 ppm
0
0
Hfl
M
en
i
i—•
CO
-------
APPENDIX A-5-196
Table A-5- 21
Base Levels of Treatment and Best Available Treatments for
Wastes from Phosphorous Production
Specific Waste
Phosphoious
Soluble
Phosphates
Fluoiides
Solid
Phosphates
SRWL
(IBs/ton P4)
12
10.5
7.6
115
Base Level
of Treatment
variable, disposal by
burial in various
ways
lime treatment
settling pond
lime treatment and
settling p^na1
dry collection and
recycle
Effluent
0
7.5 mg/l
1.0 mg/l
0
Best Available
Treatment
burial
lime treatment,
settling pond and
recycle of process
water
lime treatment,
settling pond and
recycle of process
H2O
dry collection and
reuse
Effluent
0
0
0
0
-------
APPENDIX A-5- 197
composite is then treated, but it must be remembered that any
chloride ion presence requires separate treatment due to the
possibility of heavy corrosion. Also, chloride ion will solubilize
some water insoluble P2O5 compounds which are present in
plant effluents. Overall, pond areas of sufficient size are used
to permit settling of particulates. Aeration with activated sludge
is a method being tested.
(2) Pesticide Manufacturing Wastes
Control of wastes in the manufacture of pesticides involves
Strict process controls, to reduce to a minimum the wastes which
must be treated, and advanced waste treatment measuret to
successfully treat toxic wastes prior to their release to the air
or water.
Many methods are used to recover plant wastes. Curbs
and collecting sumps are placed around pumping areas. Tanks
are used to collect pump drippings and accidental losses. Such
lost material may be returned to the process. Drain tiles,
connected to a collecting sump, catch contaminants which may
have seeped into the ground. Filters and scrubbers recover
particulates. Industrial vacuum cleaners are used to
immediately clean up spills of dry materials.
-------
APPENDIX A-5-198
Frequently, a buffer unit is placed between the processing
plant and the final waste treatment unit. It is a method of con-
trol, equalization, and stabilization. If the maximum capacity
of the intermediate buffer unit is reached, the waste generating
plant is shut down. The buffer unit serves also as a trap.so
that high process losses can be given additional or different
treatment. Buffer units used may be tanks, receiving ponds,
or sumps.
Empty containers are never abandoned nor allowed to
accumulate in an area accessible to humans or animals. They
are either burned, if combustible, or decontaminated, if non-
combustible. If not contaminated, rinse solutions are burned in
an isolated area away from water supplies.
The treatment of organic phosphorous wastes can vary
from lagooning to incineration. The system used by a manufac-
turer of several varieties of organic phosphorous pesticides was
developed to treat a waste stream containing unreacted raw
materials, partially reacted materials, cleaning products,
solvents and other plant wastes. The steps involved include:
PH adjustment with lime to form calcium phosphate
Primary settlings
Activated sludge processing
Final settlings
Sludge thickening
Sludge dewatering.
-------
APPENDIX A-5-199
The deceleration times may extend to seven to ten days
to ensure the destruction of the toxic compounds by the aerobic
digestion system.
The off-gases from the production of Sigma phosphorus
compounds (which include hydrogen sulfide and mercapetents)
are incinerated. Residual sludges may be landfilled, sea dumped,
or incinerated. In some cases, they are diluted and control fed
to streams.
Chlorinated organic compounds produce pollutant solids
(dust concentrates and powders), liquids (waste solutions), or
gases (vapors and mists). Open burning is not used since the
hydrogen chloride' (HC1) gas released would cause atmospheric
pollution. The HC1 volatilized inorganics or other acid gases
formed are removed by scrubbing towers and/or activated car-
bon towers. Solid waste materials are either buried in an
area designated for disposal of toxic materials, placed in a
permanent stock pile, or sent to a settling pond. Liquid dis-
posal may involve the concentration and incineration of combined
wastes.
Other pesticides and their disposal methods include:
Carbonates are somewhat easier to decompose. They are
lower in toxicity, decompose quickly in soil, are insoluble
in water, breakdown rapidly in alkali, and burn
-------
APPENDIX A-5-200
readily. Mixing with alkali decomposes carbonates. Re-
action products may be sent to a sewage treatment facility.
Caustic treatment in a settling tank is sufficient for water
soluble wastes. Solid wastes, which cannot be easily
treated, are buried using landfill techniques. Empty
containers are burned in unpopulated areas or else are
buried.
Phenoxy Acids. Salts, and Esters - disposal methods in-
clude incineration, chemical treatment (chlorination or
precipitation), or biological treatment (trickling filters,
activated sludge, or sewage lagoons). Deep well disposal
is also used.
Inorganics - three disposal methods are used: (a) burial,
(b) incineration, or (c) municipal sewage system.
Generally speaking, there are five methods of ground
disposal used.
Deep-Well - dug far from fresh water sources. Noxious
fluid wastes are disposed of.
Sanitary Landfill - refuse is reduced to smallest possible
volume, then covered with earth after each day's opera-
tion. There exists here the possibility of ground and
surface water pollution.
-------
APPENDIX A-5-201
Disposal Pits - excavations or dumps for the disposal of
waste materials. They are left open to the air for extended
periods of time. In addition, disposal of waste, both solid
and liquid, is not controlled. Waste is dumped haphazardly,
is not compacted and covered, and is left exposed to the
elements.
Lagoons - shallow excavations or natural topographic de-
pressions used as retention basins or ponds. The waste
is oxidized or degraded biologically, suspended solids
settling to the bottom, and evaporation then reduces the
amount of effluent to be disposed of. However, there
exists the great potential of ground and surface water
pollution because the wastes are already in a fluid state.
Surface - liquid and solid wastes are evenly distributed on
selected soil surfaces for pesticide degradation by oxida-
tion, microbial metabolism, or photochemical transfor-
mation. If the pesticides are not rapidly metabolized, the
possibility for reappearance of the unaltered pesticide in
the environment is high.
Although pesticides are designed for widespread use on
land, careful control of plant effluents is essential to the health
of nearby streams. Unless care is taken to decompose these
-------
APPENDIX A-5-202
compounds by chemical, biological or thermal means, the per-
sistency of some pesticides may permit them to leach into the
underground water system.
Pesticides which enter streams may also enter the eco-
logical chain by being taken up by plankton and subsequently
eaten by higher levels of aquatic life until concentrated into
edible fish species. Regulatory agencies and public interest
will serve to advance the management and handling systems for
these compounds.
-------
APPENDIX A-5-203
SIC 2892 - EXPLOSIVES
1. COMMERCIAL EXPLOSIVES INDUSTRY
The commercial explosives industry comprises all establishments
engaged in production of sporting powder, blasting powders, high ex-
plosives, nitrated carbohydrates,, safety fuses, and detonating caps,
but excluding government -owned /contractor-operated (GOCO) munitions
plants, small arms ammunition manufacturers and pyrotechnic plants.
The SIC code for this category is 2892. Much of the Census data is
based on combination of GOCO plants with the commercial industrial
installations; adjustments have been made in the Census data to suit
the requirements of this part of the report.
The industry includes some 85 establishments, which in 1967
shipped approximately $230 million worth of primary products as
opposed to approximately $17 million worth of secondary products for
a 93 percent specialization rate (relative value of primary shipments
to total shipments). Some 80 of the 85 establishments had specializa-
tion rates of 75 percent or greater. There was a total of 10. 200 em-
ployees in 1967 in the commercial plants; 9, 600 worked in plants
producing primarily explosives, and of these, 9, 000 worked in plants
with specialization rates over 75 percent. Thirty-one plants had
fewer than five employes, 29 more had fewer than 100 employees, and
20 more had fewer than 500 employees.
-------
APPENDIX A-5-204
The product mixture of the commercial explosives industry in
1967 included:
Blasting Caps - 168. 7 million $35, 800, 000
units
Safety fuse and other blasting 28/400, 000
accessories
Permissible high explosives. 237. 5 42, 000, 000
million Ibs. (approved for under-
ground mining)
ANFO explosives, 434. 4 million Ibs. 26,400. 000
Slurried and high explosives, 51, 900, 000
337. 9 million Ibs.
Industrial explosives, black and 29, 800, 000
smokeless powders, propellants
In the period 1963-1967, the total volume of all high explosives
increased by about 20 percent. The volume of blasting caps increased
by roughly 5 percent in this period, but the value shipped increased
about 29 percent. The overall value of shipments for the industry as
a whole increased by about one-third over this period.
-------
APPENDIX A-5-205
The industry consumed in 1967 roughly 226, 000 short tons of
anhydrous ammonia, 107,000 short tons of ammonium nitrate, and
370, 000 short tons of sulfuric acid purchased from other establish-
ments. It is unclear from the published information whether this in-
cludes transfers from one plant within the industry to another, and
whether this includes purchases by GOCO plants. Likewise, there are
incomplete figures for in-plant manufacture and total consumption for
1967. It can be noted, however, that roughly comparable quantities
of materials were produced in-plant as were purchased in the 1963
period, which would indicate that the total consumption of these
materials in 1967 could be of the order of 500,000 short tons each.
This figure is not unreasonable in the light of the increased tonnages
of shipments in 1967, but is only valid as an order of magnitude estima-
tion. The industry also consumes large amounts of various organic
materials (unspecified in the Census data) and some $22 million in
packaging and supplies of other natures not specified, in the 1967
reporting period.
2. WASTE MATERIALS
The general waste material generation characteristics of the
commercial explosives industry is not clearly separable from the
chemical industry as a whole with the exception of two specific kinds
of waste materials:
-------
APPENDIX A-5-206
Waste product materials
Contaminated packaging.
In other respects the waste material generation is identical to that ob-
tained from large commercial chemical establishments producing basic
industrial chemicals such as ammonia, nitric acid, sulfuric acid,
acetic acid and certain common organic chemicals. To avoid repetition
of previously specified data, only wastes characteristic of the explo-
sives industry (as opposed to the basic chemicals industry) are
discussed. Table A-5-22 shows the distribution of materials.
locations, and volumes.
The sole method of waste disposal currently used for these
materials is open burning, except for some primer materials detonated
under water. The frequency of disposal is generally daily, although
some smaller volume wastes are destroyed on a weekly, monthly, or
even annual basis.
As indicative of the types of process wastes obtained in com-
mercial explosives manufacture, the following data for smokeless
powder and for nitroglycerine was taken from "industrial Wastes:
Their Disposal and Treatment, " an ACS Monograph edited by William
Rudolfs. These materials were considered most significant as
-------
APPENDIX A-5-207
Table A-5-22
Distribution, Locations and Volumes
of Explosive Manufacturing Wastes
Federal Region
Quantities in
pounds per day
Waste Material
Nitroglycerine & NG Mixtures
Cont. Waste Packaging
Combined Total
Smokeless Powder
Cont. Packaging
Combined Total
Industrial Exp. & Prop.
Cont. Packaging
Combined Total
Primer Materials & Caps
Cont. Packaging
Combined Total
Regional Total
-
-
-
1
1
2
2
-
1000
3
2003
20
20
220
650
870
3000
830
-
125
750
1705
415
2950
800
800
1600
-
-
-
1600
125
200
325
-;
-
5
2
7
330
10
10
-
100
1000
1100
-
1110
15
15
-
-
X
X
15 +
200
150
1000
-
48
-
1050
10
10
-
50
250
300
—
310
-
;
-
5
5
525
750
1275
\
-
-
1275
X - Materials detonated; quantity unspecified.
Notes: (1) Combined totals exceed sums of specified parts due to variance in
reports from firms.
(2) This table represents reports from four major firms, only, and
is not a complete inventory of rates of generation or locations;
6000 other plant operations are treated in a subsequent section.
*Institute of Makers of Explosives, 420 Lexington Avenue, New York.
-------
APPENDIX A-5-208
representing opposite extremes in explosives manufacturing processes
as regards waste proportion to product, and as representing the prin-
cipal types of explosives manufactured commercially. (ANFO and
slurried blasting agents are not processed compounds as such, but
are mixtures of common industrial chemicals, generally field mixed
or prepared in local mixing plants.)
Pounds Waste per 100, 000 Ibs. of Explosive
Waste Material Smokeless Powder Nitroglycerine
Sulfuric Acid 100,000 5,100
Sulfates 59,800 1,800
Nitrates (N) 108 211
Nitrates (N) 25. 500 5, 740
BOD 2,460 197
Alkalinity (CaCOs) - 4, 740
Hardness (CaCO3) 15,500 1,440
Acid process residue can be xreconcentrated and reused. Acid
wash waters are generally neutralized with an alkaline material such
as dolomitic lime.. Solvents are generally recovered for reuse.
-------
APPENDIX A-5-209
3. MILITARY EXPLOSIVES INDUSTRY
Military explosives manufacturing is conducted principally by
the U. S. Army Munitions Command through the Army Procurement and
Supply Agency, which'has overall production supervision responsibility
over 26 Government-owned /contractor -operated (GOCO) plants located
principally east of the Rocky Mountains (see Figure A-5-10). Produc-
tion capabilities under full mobilization would make this operation the
eighth largest industry in the nation. Under normal circumstances,
the quantities of material produced, while greatly less than full mobili-
zation capability, are still of the order of hundreds of tons daily for
each of the different product lines.
Engineering supervisory control over the GOCO plants is divided
into two basic areas, according to the type of materials or operations
involved. Groups at Picatinny Arsenal, Dover, New Jersey, hold
responsibility for explosives manufacturing and load-and-fill operations,
whereas fabrication of metal parts and manufacture of small arms am-
munition is the responsibility of corresponding groups at Frankford
Arsenal, Philadelphia, Pennsylvania.
The principal categories of waste materials generated in muni-
tions manufacture are:
-------
GATEWAY AAPJ
ST. LOUIS AAP J I
A SUNFLOWER AAP
KANSAS AAP
RIVERBANK AAP
CORNHUSKER AAP
RAVENNA AAP
MAYS AAP A
BURLINGTON AAP
PLANTS - ACTIVE •
PLANTS - INACTIVE A
LAKE CITY AAP
LONE STAR AAP
LONOHORN AAP
LOUISIANA AAP
VOLUNTEER AAP
EXPLOSIVES MANUFACTURINQ PLANTS - +
NUMBERS REFER TO FEDERAL DISTRICTS
FIGURE A-5-10
U. S. Army Munitions Command
Installations and Activities
-------
APPENDIX A-5-211
Metal finishing wastes
Explosives manufacturing process wastes
Off-spec product; contaminated packaging
Metal treatment wastes include free and emulsified oils, acids
(sulfuric, phosphoric, chromic, and hydrochloric), soaps, alkaline
washes, cyanides, nitrates, chlorides, and barrium, lead, chromium,
iron, copper and tin salts. Difficulties in treatment center more on
continuous process modiiications, nonseparability of waste streams,
unavailability of monitoring techniques, and indefinite information on mat-
erials discharged rather than on lack of available abatement technology.
Explosives manufacturing processes produce the most serious
problem in pollution abatement both quantitatively and technologically.
Explosives manufacturing involves production of large quantities of
heavy acids (sulfuric, nitric, acetic), nitration of organic compounds,
and product refinement, washing and drying. The types of waste
generated include: nitrates, acetates, suspended explosive solids,
sulfates, some sludges, red water, and organic explosives and sol-
vents. Acetates are associated with production of RDX and HMX,
red waters with TNT and DNT. The other materials are common to
all explosives manufacturing processes. Both manufacturing plants
and loading plants face the problem of disposing of unwanted
-------
APPENDIX A-5-212
explosives and contaminated packaging. Loading plants also have
difficulties with red waters and with residues from primer compounds
(lead azide, lead styphnate and arsenic compounds).
Efforts have been initiated within the cognizant agencies to cor-
rect the problems of water, air, and land pollution associated with
these operations. Studies have been conducted on the economics of
the various possible approaches, and the decision was made to initiate
an overall modernization program in combination with a pollution abate-
ment program to ultimately eliminate all harmful effluents, however
borne. (Most of the GOCO plants were engineered and constructed
during World War II. Requirements of an intermittent nature since
have resulted in modifications to lines to the extent that some plants
now are geared for 200 percent of design capacity. Design evaluation
studies show that modernization can in most cases be the most effec-
tive and economical means of reducing waste problems.)
Gradually the more active plants (Holston, Radford, Volunteer,
Joliet) have been developing process waste stream treatment schemes
which rely principally on recycling and reclamation steps to reduce
costs and reduce wastes. Incineration techniques for explosive wastes
and contaminated packaging are at various stages of development, but
the primary problem is that of preparation of the waste for incineration,
-------
APPENDIX A-5-213
not that of incineration efficiency. The most common form for disposal
of sensitive wastes is detonation or open burning; contaminated packag-
ing is usually open-burned also. The danger of accidental detonation in
incinerators or pre-treatment units is currently considered too great to
allow use of such methods of disposal without extensive development.
The contractors operating GOCO plants are responsible for all
waste disposal according to terms of the operating agreements. The
supervising agencies, as part of the U.S. Army Munitions Command's
overall modernization and pollution abatement program, are preparing
survey reports detailing the waste treatment problems at all such
plants, however. The survey program is currently expected to be com-
plete by July 1972. At this time, Holston Army Ammunition Plant and
Radford Army Ammunition Plant are most advanced with respect to the
survey. The objectives of the study are fourfold: (1) identify pollutants
(air, water, land); (2) identify sources: (3) specify current practice and
evaluate; and (4) specify proposed abatement program.
Specific information on various mf-ufacturiig processes and
certain plant operating characteristics are pi esented below to provide
a basis for understanding the magnitude, nature, and proposed counter-
measures. Where possible, charts and diagrams have been reproduced
from original material to achieve the data transfer in as efficient a
manner as possible.
-------
APPENDIX A-5-214
4. SPECIFIC PROCESSES AND PLANTS
(1) TNT Manufacture
Manufacturing of TNT via nitration of toluene by a mixture
of sulfuric and nitric acids results in two principal waste mate-
rials. The first is the spent acid stream, which can be reclaimed.
The second waste is the "red water" from the purification process.
The trinitration reactions yield some 95. 5 percent b. w. of the
desired 2, 4, 6 isomer; the remaining 4. 5 percent b. w. is re-
moved by treatment with sodium sulfite, giving a structure of the
form shown below:
+ NaNO2
The characteristic "red water" stream from the selliting process
has the following composition:
Water 77.6% Sodium Sulfite 2.3%
Organics 17.3% Sodium Nitrate 1.7%
Sodium Nitrite 3.5% Sodium Sulfate 0.6%
(Due to conflicting analytical methods, total exceeds 100%.)
There is currently only one disposal technique employed for red
water waste: concentration followed by incineration, producing
-------
APPENDIX A-5-215
NOx and SOx emissions and solid sodium sulfate. After concen-
tration, some of the red water is sold to the paper-manufacturing
industry as a source of sulfite liquor, but this avoidance of in-
cineration is practical at only certain plants located near paper-
producing areas of the country. The sodium sulfate produced by
incineration is currently merely accumulated. The approximate
quantitative relationships in the overall process are:
100 Ibs. TNT produced gives: 34 Ibs. "red water" containing
26. 5 Ibs. water
5. 9 Ibs. organics (nitrotoluene
sulfonic acids)
1. 6 Ibs. dissolved inorganic salts
which on incineration yields approximately 2. 5 Ibs. sodium sulfate.
Although production figures are not readily available, TNT pro-
duction currently results in generation of over 1, 000 tons of
sodium sulfate annually, by estimate based on very incomplete
data (see Figure A-5-11).
Two principal alternatives to incineration have been
proposed:
Regeneration of DNT, renitration to TNT (acidification)
Regeneration of sodium sulfite (fluid bed or Tampella
process).
Acidification recycles the DNT in the waste and eliminates wastes
altogether. Four other exploratory programs are contemplated
-------
WEAK NITRIC ACID
RECYCLE ACID
TOLUENE
STRONG NITRIC ACID
SPENT ACID
YELLOW WATER
(from acid washer)
—MIXED ACID
^MIXED ACID
MIXED ACID
CRUDE TNT ._ _
FIGURE A-5-11
Flow Diagram for Continuous Process
TNT Manufacture*
*From Goldstein, Raymond. Trip Report to Radford Army Amniunition~Plant,
Reference 10
24 October 1968. Picatinny Arsenal.UNCLASSIFIED Report.
a
2
d
CJ1
to
t-«
a»
-------
APPENDIX A-5-217
which are directed towards changing the manufacturing process,
but these are largely untried as yet.
There are two other wastes characteristics of TNT manu-
facture which are quantitatively smaller but still serious. The
first is suspended TNT in waste acid streams and wash waters.
(This waste is also encountered in all loading and formulation
plants using TNT.) Effluent containing more than 5 ppm TNT
is considered deleterious to the environment, and two possible
solutions are being considered:
Liquid/liquid extraction with toluene, TNT recovery
Adsorption of TNT on activated carbon, and sub-
sequently
Toluene wash to regenerate carbon, recover TNT
Thermal regeneration of carbon, destruction of TNT
Thermal regeneration of carbon would require control of NOx/SOx
emissions.
The second of these quantitatively lesser problems is the
disposal of tetranitromethane (TNM) produced as a gaseous by-
product of the trinitration process. TNM is a very dangerous ex-
plosive, alone or with other organic materials, and its vapors are
currently discharged to the air rather than being collected. A
relatively unstable material and sensitive to sunlight, TNM has
-------
APPENDIX A-5-218
not been observed to accumulate on discharge. Some TNM is
found in acid and fume recovery systems, however, and pilot
studies are in progress to determine the feasibility of decom-
posing all TNM produced catalytically to reduce emissions and
simultaneously improve process safety.
(2) RDX/HMX Manufacture
The nitration of hexamine to RDX and HMX occurs by the
action of nitric acid, ammonium nitrate, acetic acid and acetic
anhydride. A process flow sheet based on 100 pounds of reactor
charge is shown on the following page. Although production
figures are again not readily available, an appreciation of the
volume can be obtained by the fact that catch basin figures are
based on 100 tons of explosive per day per building, and at least
one line is normally in operation. The nitration process per se
produces a slurry of explosive in acid; the only wastes are
materials recovered from the acid vapor scrubber stream.
Some NOx, some acetic acid, formic acid and some methylnitrate
escapes from the scrubber.
The next series of processes involves recovery of virtually
all of the by-products of the reaction simultaneously with puri-
fication of the RDX and HMX products. With the exception of
-------
APPENDIX A-5-219
losses through the recovery systems, no wastes are allowed to
be generated. Essentially all of the by-products are recycled
to starting material production plants. The particular plant from
which this data is taken is Holston Army Ammunition Plant, (see
Figures A-5-12, IS, and 14) where acetic arihydrida and nitric acid
are manufactured for use in RDX/HMX production, and the RDX
produced is incorporated with TNT produced elsewhere to form
Composition B. (The wastes from the acid and anhydride manu-
facturing processes are not discussed here, as they are charac-
teristic of chemical manufacturing rather than munitions manu-
facturing. ) Thus, the nitrobodies accumulated in the plant catch
basins include both RDX/HMX (from manufacturing and incorpora-
tion lines) and TNT (from incorporation lines). The current
practice for disposal of materials recovered from catch basins
is open burning; any RDX/HMX found to be contaminated with
glass is also open-burned, as it is too easily initiated when so
contaminated. On a quantitative basis, production of 100 tons of
RDX yields approximately 160 pounds of acetic acid and one pound
of explosive in the catch basin effluent (BOD 878 COD 112) as
opposed to influent of 160 pounds acetic acid and two pounds of
explosive (BOD 979 COD 1177). The balance of catch basin
sludge is a mixture of organic and inorganic salts; essentially
-------
APPENDIX A-5-220
NITRIC ACID - AMMONIUM
NITRATE SOLUTION (603/604)
TNT
ACETIC ACID - HEXAMINE
SOLUTION (601/621)
RDX 0
MANUFACTURED
RDX
WASHED
RDX G
RECRYSTALLIZED
RDX H
DEWATERED
ROX - TNT N
INCORPORATED
COMPOSITION B. K
PACKAGED
FIGURE A-5-12
Process Flow at HAAP
-------
REACTOR MFLUENT
SOI &I7*
521 14.97= (C)
90S W.24 =|T.2«
904 is.ss=
90944JMB
MaP 31= 52)
VENT(M)
ACID VAPORS
VENT(M)
(NEGLIGIBLE LOSS)
ANHYDROOS RDK-ACID SLURRY
(C)
ROX SLURRY
ROX so*)*
NMX I
croc .»•
BSX MS*
904 941*
mm 2jo*
90S i.a»«
800
9tl
CATCH BASIN INFLUENT
N (M)
H^O-4»OOOLB/OAY
(
.OII*ME1HVL-
NrTRATC
.(MB* -
.» * 921
004 •FORHK
AOO
4*
nwM -»•• M iw - „
HMX 2JOXIO-4*
921 3.9XIO-a»
r CATCH BASIN I
DITCH (M)
BOD .187 «
COD .OS *
RDX 2.0 X 10-**
NMX BO X 10-8 *
921 3.9 X I0~* tt
BASIS: 201,600 IBS RDX/DAY/BLD6
E -ESTIMATED VM.UES
C -CALCULATED VALUES
M- MEASURED VALUES
09.69 A6OROX
SLURRY FROll
SECOND REACTOR
FINAL SLURRY
49 IS*
4.42*
croc
904 10.41«
2.70*
921 MS.47*
MgO B7.67*
VENT (M)
2.7XIO-8
DILUTION
LIQUOR
STORAGE
TANK
RDX-AOD SLURRY
TOE-BL00
FIGURE A-5-13
D-Building, Manufacture of RDX
i
en
10
to
-------
Scrubber Vent
3500 PPDN O
49PPD
1S3PPD
533 PPD
17PPD
Main Effluent
Methyl Acetate
Methyl Nitrate
Acetic Acid
Formic Acid
Catch Basin Influent
Catch Basin Effluent
Storage Tank Vents
Negligible
BOD
979
878
COD
RDX
521
1177
112
2.1
.96
160
160
a
i
D
FIGURE A-5-14
D-Building Pollutants
Basis 201,600 PPD RDX Mfg.
I
U1
ro
to
to
-------
APPENDIX A-5-223
all of the catch basin influent comes from equipment cleansing
operations. Design of new explosive waste incinerators for these
materials is now proceeding in conjunction with other efforts
towards biodegradation of nitrobodies.
One waste associated with RDX/HMX manufacture, metyl-
nitrate is both toxic and explosive. Although the quantities
generated are of the order of 200 pounds per 100 tons of RDX
produced, the problem is considered sufficiently serious that a
program of recovery from the gaseous effluents, combination
with amounts recovered from acetic acid purification, and cata-
lytic decomposition or hydrogenation to destroy the nitrate is
scheduled for FY 1973. Design of new explosive waste incinerators
for these materials is underway in conjunction with other efforts
toward* biodegradation of nitrobodies.
(3) Propellant Manufacture
Propellant manufacturing includes a number of processes
involving production of nitroglycerine, nitrocellulose and nitro-
guanidine. The principal wastes in these processes are nitrobodies
of a non-aromatic nature, some of which have been escaping as
losses in wash waters (9000 Ibs. /day nitrocellulose fines are
lost at Radford). The magnitude of the problem is expected to be
-------
APPENDIX A-5-224
greatly lessened by currently planned water purification improve-
ments. The nitrobodies will be reclaimed where possible; where
recovery is unsatisfactory, the material will be treated by bio-
degradation or incinerated.
Current treatment of nearly all explosive wastes not suitable
for reclamation is open-burning. Contaminated nitrogylcerine is
frequently purposely detonated, however, due to its extreme sen-
sitivity, unpredictability and power, it is virtually never put through
a recovery process.
(4) Primer Materials
Lead styphnatel primer manufacture is of the order of 15
tons per month, 35 percent of which is lead styphnate and 77 per-
cent of which is tetrazine. The balance of the primer mix is PETN
(pentaerytritol tetranitrate), aluminum and inorganic salts. The
waste by-products include lead and sodium nitrates and acetates,
styphnic acid (trinitroresorcinol), nitrated sulfonic acids of
resorcinal, aminoguanidine acetate and sodium nitrite. The prin-
cipal current method of treatment is open burning for explosive
materials. Planned process modifications are expected to re-
lieve some problems (changing explosive wastes to non-explosive
wastes), but waste disposal planning is still in its early stages.
-------
APPENDIX A-5-225
(5) White Phosphorous Waste
White phosphorous wastes are a product of shell loading
plants, where the material is carried away primarily in cleaning
and excess removal operations. Treatment is currently unde-
veloped. Current planning is for oxidation to phosphoric oxide
and conversion to usable orthophosphoric acid. No quantitative
data is available at this time.
(6) Contaminated Packaging Disposal
As mentioned previously, current practice for disposal of
all contaminated packaging is open-burning. A program of in-
cinerator development for disposal of such materials has been
initiated, however. Joliet and Cornhusker plants are proceeding
with semi-independent efforts towards equipment of different
capacities. The approximate volumes of contaminated waste
packaging at four major plants are:
Plant Contaminated Waste Non-contaminated Waste
Cornhusker 400, 000 Ibs/month 60,000 Ibs/month
Joliet 60,000 540,000
Radford 160,000 54.000
Volunteer 10,400 0
-------
APPENDIX A-5-226
5. ORDNANCE DISPOSAL
The disposal of unservicable ordnance is a problem common to
all branches of the armed services. As a matter of historical develop-
ment, however, the largest quantities of large-scale ordnance have been
dealt with by the Navy, on behalf of all three services. Earlier forms
of ordnance were relatively easy to desensitize, disassemble and dis-
pose of. In the more recent past, efforts to prevent use of captured
ordnance by enemy forces have resulted in design of "tamper-proof"
munitions. Unfortunately, this design makes disposal of unserviceable
ordnance by "demilitarization" both difficult and dangerous, and the
armed forces established the practice of dumping at sea as the safest
and most effective method of disposal. Efforts to resolve the safety
problem in other forms of disposal have continued, but the amount of
material to be dealt with is enormous and the results of accidents are
extremely serious. No deep water dumping is now permitted, and
current demilitarization facilities are not capable of disposing of the
quantities of material involved, so the ordnance is currently being
accumulated.
(1) Quantities
To exemplify the magnitude of the problem, current estimates
of the backlog of ordnance requiring disposal range between
-------
APPENDIX A-5-227
80, 000 and 120, 000 tons, including:
Explosive Projectiles Firing Devices
Small Arms Ammunition Pyrotechnics
Fuses Ejection Cartridges
Detonators Rockets
Primers Bombs
Grenades Depth Charges
Solid Propellants Rocket Motors.
These items range from small handgun cartridges to
16" shells* Individual items weigh up to several tons in some
cases. Numerically, as examples, some 100, 000, 000 rounds
of ammunition below 20mm are included; no numerical estimates
of the number of other items have been located.
(2) Demilitarization
Time-consuming expensive and dangerous demilitarization
operations could, it is estimated, result in disposal of roughly
50, 000 tons of the total backlog, allowing reclamation of 7, 000
tons of HEX. 6, 000 tons of TNT and 15, 000 tons of smokeless
powder. The procedure varies as a function of the specific type
of ordnance being treated. Small rounds (up to 20mm) are
separated (projectile form cartridge case), the powder is burned
and the projectile and cartridge case "popped" in a retort furnace
("popping" = detonation of primers by heat). The metal is re-
covered for scrap, and it is possible to design the system to
-------
APPENDIX A-5-228
recover and reprocess the powder. Larger units are first de-
fused; the explosive charges are removed by washing, steaming
or drilling. The explosive is then either recovered or burned,
and the metal is recovered for scrap.
The hazards of the demilitarization operations are significant.
A single MK-51 underwater mine contains 3, 200 pounds of TNT,
for example. Successful demilitarization of these mines has re-
sulted in reclamation of over 2, 400 tons of TNT in the immediate
past. The problems of successful demilitarization are apparent
to those who have experience with use of ordnance devices and
explosives and are compounded by the fact that large quantities
of high explosive devices are handled simultaneously. Many ex-
plosives which are easily burned in the open without detonation
are extremely subject to detonation when encased in metal sheaths.
At least one incident has occurred in the fairly recent past in a
20mm demilitarization line where a sudden accumulation of some
20, 000 rounds detonated in a retort furnace. The details of the
incident are not clear, but the entire processing unit was com-
pletely destroyed, leaving a sizable crater.
-------
APPENDIX A-5-223
(3) Destructive Disposal
Two other methods of disposal are currently in use which
involve intentional discharge or detonation of ordnance. Smaller
items are simply dropped into contained fires through tubes, in
the fire they explode and the metal is recovered for scrap. A
second program involves burial of large amounts of ordnance in
pits; these charges are primed and tamped with 10 to 16 feet of
earth and detonated. Roughly 40 pits are detonated daily, dis-
posing of some 40 tons per day. The entire series is detonated
over a 200-second interval. As of September 1971 one such
group was in operation on a five-day week basis. At this rate,
this group would require eight to twelve years to work off the
current inventory; alternatively, ten groups might dispose of the
inventory in one year. Thereafter, however, as much as
20, 000 tons of material would be handled annually, requiring
two groups full time to merely detonate the normal accumulation.
In addition to the problems of manpower, and cost and environ-
mental unpleasantness at the least, the long duration safety and
land use problems are unclear.
At least one incinerator for destruction of some 500 tons of
miscellaneous fuses is under construction at the Earle Naval
-------
APPENDIX A-5-230
Facility. This unit is designed to meet both safety and pollution
regulations, but is as yet a prototype design. The performance
of this unit from both points of view is still undefined.
(4) Deep-Water Dumping
The practice of deep-water dumping, as mentioned above,
has been discontinued. This method of disposal accounted for
some 100, 000 tons of unserviceable ordnance over the period
1964-1971 in the Maritime Administration Hulk Numbered Deep
Water Dumps system alone. According to this system, an ob-
solete vessel (merchantman) was stripped free of all but fixed
elements of the structure and the fuel tanks cleaned thoroughly.
The ordnance was then stowed to give maximum density (more
buoyant items packed in 55-gallon drums filled with concrete),
the hulk was towed at least ten miles from shore and scuttled
in at least 500 fathoms depth. The dumping areas were selected
to reduce the probability of fish kills in the event of detonations,
which were sometimes intentional. Such intentional detonations
were performed at the request of the international scientific
community, occasionally unplanned. In most cases, the hulk
bottomed without detonations, and in no case did detonation occur
prior to scuttling. A dump of this type might range up to 8, 500
tons at a time, but was generally in the broad vicinity of 5, 000 tons.
-------
APPENDIX A-5-231
Small-scale deep water dumping practices were commonly
conducted for many years as ordnance disposal methods. Such
operations involve jettisoning up to 250 tons of material at a time
in sites meeting the ten-mile, 500 fathoms criteria mentioned
above. The actual dumping is performed over a short period of
time, rather than all at once. No detonation has ever been ex-
perienced in operations of this type. Of 13 sites selected for
such dumps in 1971, only one lay less than 20 miles from shore
(12, 000 feet deep). All liquid propellants, industrial chemicals
and chemical agents were excluded from this type of disposal.
(5) Other Proposals
Proposals have been made regarding design of mobile de-
militarization lines to reduce the need for overland transportation
of munitions. The question of safety is not attacked in this par-
ticular solution to part of the problem, but further developments
in both demilitarization technology and new forms of ordnance
construction are expected to alleviate the danger in the future.
Detonation in AEC caverns, in conjunction with AEC tests, and
in abandoned mine shafts has been proposed also. This reduces
the processing danger somewhat but requires substantially more
overland transportation and handling. Biodegradation and more
-------
APPENDIX A-5-232
effective forms of chemical treatment are two possible routes to
safer demilitarization, but we still are very far from achieve-
ment, so far as has been discovered.
6. ROCKET PROPELLANTS
Rocket propellants are broadly divided into two groups: liquid
propellants and solid propellants.
(1) Liquid Propellants
Liquid propellants are fundamentally selected industrial
chemicals which are further divided into oxidizers and fuels.
The bulk of these materials are therefore produced by major
chemical manufacturers. The principal liquid fuels are:
Ammonia Alcohols (prinicpally methanol)
Hydrazine* Nitroparaffins (nitropropane)
Monomethyl Hydrazine (MMH) Hydrocarbons (gasoline, JP4)
Unsymmetrical Dimethyl Liquid Hydrogen
Hydrazine (UDMH) Aerozine 50 (UDMH and hydrazine)
MHF-3 (MMH and hydrazine)
MHF-5 (MMH, hydrazine, hydrazine
nitrate)
The principal liquid oxidizers are:
N2O4 (nitrogen tetroxide) Chlorine trifluoride
RFNA (red fuming nitric acid) Chlorine Pentafluoride
WFNA (white fuming nitric acid) Bromine Pentafluoride
Liquid Oxygen FLOX (liquid oxygen and
Liquide Fluorine liquid fluorine)
Hydrogen Perioxide*
* Also used in catalytic engines as a monopropellant. Detonable in
high strengths.
-------
APPENDIX A-5-233
(2) Solid Propellants
The principal solid propellant used in major missiles is
aluminized ammonium perchlorate, a mixture of 20 percent
finely divided aluminum, 74 percent ammonium perchlorate
and 6 percent organic polymer binder. The entire missile
motor is produced by one manufacturer who formulates and casts
the propellant in the case. Metal parts and component materials
of the propellant may be purchased. Generally, the prime
motor manufacturer conditions the propellant materials, pro-
duces the binder system, formulates the propellant, casts and
cures.
The principal waste material from these operations is ex-
cess propellant and contaminated component materials. When
practical, waste materials are reclaimed. When reclamation is
economically unfeasible, the materials are burned in the open.
The products of combustion include A^OS, H^O, CO, CO2, ^2>
chlorides (HC1), NOx, and carbon. A method of reclaiming am-
monium perchlorate from outdated grains has been patented
(Reference 12) which employs leach water to cool the propellant
during shredding operations. The water dissolves the oxidizer,
-------
APPENDIX A-5-234
leaving aluminum and shredded binder which can be handled as
a "non-hazardous" waste.
Other systems currently in use for smaller missile motors
include: double-based propellants (ordinarily nitrocellulose/
nitroglycerine/binder systems), ammonium nitrate grains
(aluminized and non-aluminzed, similar to preceding discussion),
pressed grains (black power, mixtures of inorganic fuels and
oxidize rs).
The principal constituent materials of solid rocket pro-
pellants are:
Aluminum (power or flake)
Ammonium Perchlorate
Ammonium Nitrate
Sodium Nitrate
Potassium Nitrate
Sodium Perchlorate
Potassium Perchlorate
Magnesium Perchlorate
The principal products of combustion are:
Potassium Permanganate
Sodium Permanganate
Sodium Peroxide
Nitrocellulose
Nitroglycerine
Sulfur (powdered)
Carbon Powder
Binders
Metal Oxides
Water
Nitrogen
Carbon Dioxide
Carbon Monoxide
Hydrogen Chloride
Carbon
NOx
SOx
-------
APPENDIX A-5-235
The principal current method of disposal of solid propel-
lant manufacturing wastes and outdated grains is open burning.
At least one patent (Reference 1) has been issued on a recovery
process involving elation of oxidizer by cooling water during
comminutation of the grain by knives. The oxidizer can be re-
crystallized and reused, and the inert binder and metal fuel can
be further separated for recovery of the metal, either before or
after incineration.
-------
APPENDIX A-5-236
LIST OF REFERENCES
1. U. S. Tariff Commission Report, Synthetic Organic
Chemicals. TC Pub. 412, 1969.
2. National Industrial Solid Waste Management Study, Industrial
Chemical Society, Contract CPE 69-5 for the Environmental
Protection Agency, Research Corporation of New England,
January 1971.
3. Current Industrial Reports, Inorganic Chemicals, Department
of Commerce, 1969
4. Industrial Waste Study of the Plastic Materials and Synthetics
Industry, N. Barson and J. W. Gilpin, Celanese Research Co.
5. A. V. Phosphoric Acid, Vol. 1, Part 2, Huffstuter, K. K.,
and Slack, Marcel Dekker, Inc., New York, 1968.
6. Economics of Clean Water - Inorganic Chemical Industry
Profile, U. W. Department of Interior, March 1970.
7. Industrial Waste Profile No. 10, Plastic Materials and
Rosins - SIC 2821, ITT Research Institute, October 1967.
8. Reigel's Industrial Chemistry, J. A. Kent, ed., Reinhold
Publishing Company.
9. Census of Manufacturers, Vol. II, Part 2, U.S. Department
of Commerce, 1967.
10. Pharmaceutical Manufacturers Association Year Book
1969-1970.
11. American Paint Journal, April 21, 1958.
12. Recovery of Oxidizer from Rocket Propellants, " U. S.
3, 451, 789 to F. Graf to Thiokal Chemical Corporation, 1969.
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