United States
Environmental Protection
Agency
Solid Waste
Office of
Solid Waste
Washington, D.C. 20460
EPA/530-SW-86-056
November 1986
Best Demonstrated Final
Available Technology
(BOAT) Background
Document for
F001 - F005 Spent
Solvents
Volume 1
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BEST DEMONSTRATED AVAILABLE TECHNOLOGY (BOAT)
BACKGROUND DOCUMENT FOR F001-F005 SPENT SOLVENTS
VOLUME l
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Solid Waste
401 M Street, S.W.
Washington, D.C. 20460
James R. Berlow, Chief David Pepson
Treatment Technology Section Project Manager
November 7, 1986
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BOAT BACKGROUND DOCUMENT FOR
F001-F005 SPENT SOLVENT WASTES
TABLE OF CONTENTS
VOLUME 1 Page
Executive Summary xx
SECTION 1: Background and General Description
1.1 Legal Background 1-1
1.2 EPA' s Approach to Developing BOAT 1-2
1.2.1 Waste Treatability Groups 1-3
1.2.2 Determination of "Demonstrated" Treatment
Technologies 1-3
1.2.3 Determination of "Available" Treatment
Technologies 1-4
(1) Treatment technologies that present greater
total risks than land disposal methods 1-5
(2) Proprietary or Patented Processes 1-5
(3) Substantial Treatment 1-5
1.2.4 Collection and Analysis of Performance Data 1-6
(1) Collection of Performance Data 1-6
(2) Treatment Design and Operation 1-7
1.2.5 Identification of "Best" Demonstrated Available
Treatment 1-8
1.2.6 Variance from the Treatment Standard 1-8
SECTION 2: Industries Affected
2.1 Introduction 2-1
2.2 Classification of Waste as F001-F005 Spent Solvents 2-1
2.3 Industries Which Use Listed Solvents 2-1
2.4 Spent Solvent Waste Generation 2-10
2.4.1 Surface Cleaning 2-10
2.4.2 Equipment Cleaning 2-11
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TABLE OF CONTENTS (Continued)
Page
SECTION 2 (continued)
2.5 Geographical Distributions 2-12
REFERENCES 2-45
SECTION 3: Waste Characterization
3.1 Introduction 3-1
3.2 Waste Characterization Data 3-1
3.2.1 Furniture Manufacturing 3-3
3.2.2 Plastics and Resins Industry 3-7
3.2.3 Fiber Industry 3-10
3.2.4 Pharmaceuticals Manufacturing 3-11
3.2.5 Paint Formulation 3-15
3.2.6 Dyes and Pigments Manufacturing 3-16
3.2.7 Organic Chemicals Manufacturing 3-17
3.2.8 Organic Pesticides Manufacturing 3-21
3.2.9 Printing Industry 3-24
3.2.10 Can Coating Industry 3-26
3.2.11 Membrane Production Industry 3-31
REFERENCES 3-32
SECTION 4: Applicable Treatment Technologies 4-1
4.1 Introduction 4-1
4.2 Carbon Adsorption 4-1
4.2.1 Applicability 4-1
4.2.2 Underlying Principles of Operation 4-2
4.2.3 Description of Activated Carbon Manufacture and
Carbon Regeneration 4-3
(1) Activated Carbon Manufacture 4-3
(2) Carbon Regeneration 4-5
4.2.4 Design and Operating Parameters Affecting
Performance 4-6
(1) Design Parameters 4-6
(2) Operating Parameters 4-9
11
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TABLE OF CONTENTS (Continued)
SECTION 4: (continued)
4.2.5 Bench-Scale Testing 4-10
4.2.6 Pilot-Scale Testing 4-11
Carbon Adsorption References 4-13
4.3 Distillation 4-14
4.3.1 Steam Stripping 4-14
(1) Applicability 4-14
(2) Underlying Principles of Operation 4-14
(3) Description of Steam Stripping 4-17
(4) Design and Operating Parameters Affecting
Performance 4-17
4.3.2 Batch Distillation 4-20
(1) Applicability 4-20
(2) Underlying Principles of Operation 4-21
(3) Description of Batch Distillation 4-21
(4) Design and Operating Parameters Affecting
Performance 4-21
4.3.3 Thin Film Evaporation 4-23
(1) Applicability 4-23
(2) Underlying Principles of Operation 4-23
(3) Description of Thin Film Evaporation 4-24
(4) Design and Operating Parameters Affecting
Performance 4-24
4.3.4 Fractionation 4-24
(1) Applicability 4-24
(2) Underlying Principles of Operation 4-26
(3) Description of Fractionation 4-26
(4) Design and Operating Parameters Affecting
Performance 4-26
Distillation References 4-29
4.4 Biological Treatment 4-30
4.4.1 Applicability 4-30
4.4.2 Underlying Principles of Operation 4-30
(1) Anaerobic Biological Treatment 4-31
(2) Aerobic Biological Treatment 4-31
111
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TABLE OF CONTENTS (Continued)
SECTION 4: (continued)
4.4.3 Description of Biological Treatment 4-32
(1) Activated Sludge 4-32
(2) Aerated Lagoons 4-34
(3) Trickling Filters 4-35
(4) Rotating Biological Contactors 4-37
4.4.4 Design and Operating Parameters Which Affect
Performance 4-39
(1) Equalization 4-39
(2) Nutrients 4-39
(3) Aeration/Oxygen Supply 4-40
(4) Wastewater-Biomass Contact 4-41
(5) Microorganism Growth Phase 4-43
(6) Temperature 4-43
(7) ph 4-44
(8) Selection of Microorganisms 4-45
Biological Treatment References 4-46
4.5 Incineration 4-47
4.5.1 Applicability 4-47
4.5.2 Underlying Principles of Operation 4-47
4.5.3 Description of Incinerators 4-48
(1) Liquid Injection 4-48
(2) Rotary Kiln 4-48
(3) Fluidized Bed 4-51
(4) Hearth 4-51
4.5.4 Design and Operating Parameters Affecting
Performance 4-51
(1) Design Parameters 4-51
(2) Operating Parameters 4-59
Incineration References 4-61
4.6 Wet Air Oxidation 4-62
4.6.1 Applicability 4-62
4.6.2 Underlying Principles of Operation 4-62
4.6.3 Description of Wet Air Oxidation 4-63
(1) Conventional Wet Air Oxidation 4-63
(2) Catalyzed Wet Air Oxidation 4-65
IV
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TABLE OF CONTENTS (Continued)
SECTION 4: (continued)
4.6.4 Design and Operating Parameters Affecting
Performance 4-65
Wet Air Oxidation References 4-67
4.7 Air Stripping 4-68
4.7.1 Applicability 4-68
4.7.2 Underlying Principles of Operation 4-68
4.7.3 Description of Air Stripping 4-68
(1) Mechanical Surface Aerators 4-70
(2) Diffused Aerators 4-70
Air Stripping References 4-71
4.8 Fuel Substitution 4-72
4.8.1 Applicability 4-72
4.8.2 Underlying Principles of Operation 4-72
4.8.3 Description of Fuel Substitution 4-72
(1) Industrial Boilers 4-73
(2) Industrial Kilns 4-73
4.8.4 Design and Operating Parameters Affecting
Performance 4-74
Fuel Substitution References 4-76
v
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TABLE OF CONTENTS (Continued)
VOLUME 2
SECTION 5: Treatment Performance 5-1
5.1 Introduction 5-1
5.2 Summary of Treatment Performance Data 5-2
5.3 Data Editing Rules 5-5
5.4 Statistical Methods for Establishing BOAT 5-7
5.4.1 Variability Factor Calculation 5-7
5.4.2 Outlier Test 5-9
5.4.3 Analysis of Variance 5-9
5.5 Development of BOAT Treatment Standards for Wastewaters
Containing F001-F005 Spent Solvent Wastes 5-12
5.5.1 Transfer of Treatment Data for Wastewaters
Containing F001-F005 Spent Solvent Wastes 5-14
5.5.2 Derivation of Average Variability Factors for
Wastewater Treatment 5-17
5.5.3 Acetone Wastewaters 5-20
5.5.4 n-Butyl Alcohol Wastewaters 5-21
5.5.5 Carbon Disulfide Wastewaters 5-22
5.5.6 Carbon Tetrachloride Wastewaters 5-23
5.5.7 Chlorobenzene Wastewaters 5-27
5.5.8 Cresols (Cresylic Acid) Wastewaters 5-34
5.5.9 Cyclohexanone Wastewaters 5-37
5.5.10 1,2-Dichlorobenzene Wastewaters 5-38
5.5.11 Ethyl Acetate Wastewaters 5-44
5.5.12 Ethylbenzene Wastewaters 5-45
5.5.13 Ethyl Ether Wastewaters 5-57
5.5.14 Isobutanol Wastewaters 5-58
5.5.15 Methanol Wastewaters 5-59
5.5.16 Methylene Chloride Wastewaters 5-62
5.5.17 Methyl Ethyl Ketone Wastewaters 5-71
5.5.18 Methyl Isobutyl Ketone Wastewaters 5-73
5.5.19 Nitrobenzene Wastewaters 5-77
5.5.20 Pyridine Wastewaters 5-83
5.5.21 Tetrachloroethylene Wastewaters 5-84
5.5.22 Toluene Wastewaters 5-91
5.5.23 1,1,1-Trichloroethane Wastewaters 5-110
5.5.24 l,l,2-Trichloro-l,2,2-Trifluoroethane Wastewaters. 5-115
5.5.25 Trichloroethylene Wastewaters 5-116
VI
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TABLE OF CONTENTS (Continued)
SECTION 5: (Continued)
5.5.26 Trichlorofluoromethane Wastewaters 5-123
5.5.27 Xylene Wastewaters 5-126
5.6 Development of BOAT Treatment Standards for
F001-F005 Spent Solvent Wastes (Other Than Wastewater) .. 5-129
5.6.1 Transfer of Incineration Treatment Data 5-130
5.6.2 Derivation of An Average Variability Factor for
Incineration 5-133
5.6.3 Acetone (Other Than Wastewater) 5-135
5.6.4 n-Butyl Alcohol (Other Than Wastewater) 5-139
5.6.5 Carbon Disulfide (Other Than Wastewater) 5-140
5.6.6 Carbon Tetrachloride (Other Than Wastewater) 5-143
5.6.7 Chlorobenzene (Other Than Wastewater) 5-144
5.6.8 Cresols (Cresylic Acid) (Other Than Wastewater)... 5-147
5.6.9 Cyclohexanone (Other Than Wastewater) 5-148
5.6.10 1,2-Dichlorobenzene (Other Than Wastewater) 5-149
5.6.11 Ethyl Acetate (Other Than Wastewater) 5-152
5.6.12 Ethylbenzene (Other Than Wastewater) 5-153
5.6.13 Ethyl Ether (Other Than Wastewater) 5-156
5.6.14 Isobutanol (Other Than Wastewater) 5-157
5.6.15 Methanol (Other Than Wastewater) 5-158
5.6.16 Methylene Chloride (Other Than Wastewater) 5-159
5.6.17 Methyl Ethyl Ketone (Other Than Wastewater) 5-163
5.6.18 Methyl Isobutyl Ketone (Other Than Wastewater) 5-166
5.6.19 Nitrobenzene (Other Than Wastewater) 5-170
5.6.20 Pyridine (Other Than Wastewater) 5-173
5.6.21 Tetrachloroethylene (Other Than Wastewater) 5-174
5.6.22 Toluene (Other Than Wastewater) 5-177
5.6.23 1,1,1-Trichloroethane (Other Than Wastewater) 5-181
5.6.24 l,l,2-Trichloro-l,2,2-Trifluoroethane (Other Than
Wastewater) 5-184
5.6.25 Trichloroethylene (Other Than Wastewater) 5-185
5.6.26 Trichlorofluoromethane (Other Than Wastewater) ... 5-188
5.6.27 Xylene (Other Than Wastewater) 5-189
REFERENCES 5-192
VI1
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TABLE OF CONTENTS (Continued)
Page
VOLUME 3
APPENDIX I 1-1
APPENDIX II II-l
VI11
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LIST OF TABLES
Table Page
BDAT Treatment Standards xxii
2-1 Constituents of Listed.Hazardous Spent Solvent Wastes .. 2-2
2-2 Industries Using Solvents Listed as F001-F005 2-3
2-3 Industries Involved in Surface Cleaning and
Degreasing 2-9
2-4 Census Data (1977) for Number of Facilities in Each
State and EPA Region
Wood Furniture Manufacturing 2-14
2-5 Census Data (1977) for Number of Facilities in Each
State and EPA Region
Metal Furniture Manufacturing 2-15
2-6 Census Data (1977) for Number of Facilities in Each
State and EPA Region
Plastics and Resins Manufacturing 2-16
2-7 Census Data (1977) for Number of Facilities in Each
State and EPA Region
Fiber Manufacturing 2-17
2-8 Census Data (1977) for Number of Facilities in Each
State and EPA Region
Pharmaceutical Manufacturing 2-18
2-9 Census Data (1977) for Number of Facilities in Each
State and EPA Region
Paint Manufacturing and Application 2-19
2-10 Census Data (1977) for Number of Facilities in Each
State and EPA Region
Cyclic Crudes and Intermediates Including Dyes
Manufacturing 2-20
2-11 Census Data (1977) for Number of Facilities in Each
State and EPA Region
Pigments Manufacturing 2-21
2-12 Census Data (1977) for Number of Facilities in Each
State and EPA Region
Organic Chemicals Manufacturing 2-22
IX
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LIST OF TABLES
(Continued)
Table Page
2-13 Census Data (1977) for Number of Facilities in Each
State and EPA Region
Agricultural Chemicals Manufacturing 2-23
2-14 Census Data (1977) for Number of Facilities in Each
State and EPA Region
Printing Industry 2-24
2-15 Census Data (1977) for Number of Facilities in Each
State and EPA Region
Commercial Testing Laboratories 2-25
2-16 Census Data (1977) for Number of Facilities in Each
State and EPA Region
Electronic Components Manufacturing 2-26
2-17 Census Data (1977) for Number of Facilities in Each
State and EPA Region
Semiconductors and Related Devices Manufacture 2-27
2-18 Census Data (1977) for Number of Facilities in Each
State and EPA Region
Synthetic Rubber Industry 2-28
2-19 Census Data (1977) for Number of Facilities in Each
State and EPA Region
Tire Industry 2-29
2-20 Census Data (1977) for Number of Facilities in Each
State and EPA Region
Textiles Industry 2-30
2-21 Census Data (1977) for Number of Facilities in Each
State and EPA Region
Leather and Tanning Industry 2-31
2-22 Census Data (1977) for Number of Facilities in Each
State and EPA Region
Transportation Vehicles Manufacturing 2-32
2-23 Census Data (1977) for Number of Facilities in Each
State and EPA Region
Paper Coating Industry 2-33
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LIST OF TABLES
(Continued)
Table Page
2-24 Census Data (1977) for Number of Facilities in Each
State and EPA Region
Adhesives and Sealants Industry 2-34
2-25 Census Data (1977) for Number of Facilities in Each
State and EPA Region
Food Industry - Beer, Edible Fats, and Butter 2-35
2-26 Census Data (1977) for Number of Facilities in Each
State and EPA Region
Dry Cleaning Industry 2-36
2-27 Census Data (1977) for Number of Facilities in Each
State and EPA Region
Wool Weaving and Finishing Industry 2-37
2-28 Census Data (1977) for Number of Facilities in Each
State and EPA Region
Petroleum Refining Industry 2-38
2-29 Census Data (1977) for Number of Facilities in Each
State and EPA Region
Primary Metals Manufacturing 2-39
2-30 Census Data (1977) for Number of Facilities in Each
State and EPA Region
Fabricated Metals Manufacturing 2-40
2-31 Census Data (1977) for Number of Facilities in Each
State and EPA Region
Non-Electric Machinery Manufacture 2-41
2-32 Census Data (1977) for Number of Facilities in Each
State and EPA Region
Electric Eguipment Manufacture 2-42
2-33 Census Data (1977) for Number of Facilities in Each
State and EPA Region
Instruments and Clocks Manufacture 2-43
XI
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LIST OF TABLES
(Continued)
Table Page
2-34 Census Data (1977) for Number of Facilities in Each
State and EPA Region
Automotive Repair Shops 2-44
3-1 Summary of Industries for Which Spent Solvent Waste
Characterization Data Are Available 3-2
3-2 Waste Characterization Data for Spent Thinner and
Solvent from Furniture Manufacturing - Plant A 3-3
3-3 Waste Characterization Data for Spent Thinner and
Solvent from Furniture Manufacturing - Plant B 3-4
3-4 Waste Characterization Data for Spent Thinner and
Solvent from Furniture Manufacturing - Plant C 3-5
3-5 Waste Characterization Data for Spent Thinner and
Solvent from Furniture Manufacturing - Plant D 3-6
3-6 Waste Characterization Data for Still Bottoms and
Caustic from Plastics and Resins Manufacturing 3-7
3-7 Waste Characterization Data for Epoxy Resin Waste
from Plastics and Resins Manufacturing 3-7
3-8 Waste Characterization Data for Phenolic and Polyester/
Alkyd Resin Waste from Plastics and Resins
Manufacturing 3-9
3-9 Waste Characterization Data for Solvent Recovery
Bottoms, Laboratory Solvents and Chrome Plating
Solution from Fiber Industry 3-10
3-10 Waste Characterization Data for Solvent Recovery
Bottoms from Pharmaceutical Manufacturing 3-11
3-11 Waste Characterization Data for Solvent Recovery
Bottoms from Pharmaceutical Manufacturing 3-13
3-12 Waste Characterization Data for Paint Tank Wash from
Paint Manufacturing 3-15
XII
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LIST OF TABLES
(Continued)
Table Page
3-13 Waste Characterization Data for Spent Thinner from
Paint Manufacturing 3-15
3-14 Waste Characterization Data for Dyes and Pigments
Waste from Dyes and Pigments Manufacturing 3-16
3-15 Waste Characterization Data for Still Bottoms and
Caustic from Organic Chemicals Manufacturing 3-17
3-16 Waste Characterization Data for Isocyanates
Manufacturing Wastes from Organics Chemicals
Manufacturing 3-19
3-17 Waste Characterization Data for Diphenyl Methane and
Isocyanate Manufacturing Wastes from Organic
Chemicals Manufacturing 3-19
3-18 Waste Characterization Data for Alkenes Manufacturing
Wastes from Organic Chemicals Manufacturing 3-20
3-19 Waste Characterization Data from Aldehyde Furan
Manufacturing Waste from Organic Chemicals
Manufacturing 3-20
3-20 Waste Characterization Data from Organic
Pesticides Manufacturing 3-21
3-21 Waste Characterization Data from Organic
Pesticides Manufacturing 3-21
3-22 Waste Characterization Data from Organic
Pesticides Manufacturing 3-22
3-23 Waste Characterization Data from Organic
Pesticides Manufacturing 3-22
3-24 Waste Characterization Data from Organic
Pesticides Manufacturing 3-23
3-25 Waste Characterization Data from Organic
Pesticides Manufacturing 3-23
Xlll
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LIST OF TABLES
(Continued)
Table Page
3-26 Waste Characterization Data for Solvent Recovery
Bottoms from Printing Industry 3-24
3-27 Waste Characterization Data for Spent Ink Wash from
Printing Industry 3-25
3-28 Waste Characterization Data for Spent Can Coating
Residue from Can Coating Industry 3-26
3-29 Waste Characterization Data for Spent Solvents and
Organics from Membrane Production Industry 3-31
5-1 Quantification Levels for F001-F005 Solvents 5-6
5-2 BOAT Treatment Standards (as Concentrations in the
Treatment Residual Extract) 5-13
5-3 Grouping of Spent Solvent Constituents for Transfer
of BOAT Wastewater Treatment Data 5-15
5-4 Variability Factors for All Full-Scale Wastewater
Treatment Data Sets Used in the Derivation of the
BOAT Treatment Standards 5-18
5-5 Treatment Performance Data for Carbon Tetrachloride .... 5-25
5-6 Calculation of BOAT for Carbon Tetrachloride 5-26
5-7 Treatment Performance Data for Chlorobenzene 5-30
5-8 Calculation of BOAT for Chlorobenzene 5-33
5-9 Treatment Performance Data for Cresols (Cresylic
Acid) 5-36
5-10 Treatment Performance Data for 1,2-Dichlorobenzene 5-40
5-11 Calculation of BOAT for 1,2-Dichlorobenzene 5-43
5-12 Treatment Performance Data for Ethylbenzene 5-47
5-13 Calculation of BOAT for Ethylbenzene 5-56
xiv
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LIST OF TABLES
(Continued)
Table Page
5-14 Treatment Performance Data for Methanol 5-61
5-15 Treatment Performance Data for Methylene Chloride 5-65
5-16 Calculation of BOAT for Methylene Chloride 5-70
5-17 Treatment Performance Data for Methyl Ethyl Ketone 5-72
5-18 Treatment Performance Data for Methyl Isobutyl Ketone .. 5-75
5-19 Calculation of BOAT for Methyl Isobutyl Ketone 5-76
5-20 Treatment Performance Data for Nitrobenzene 5-79
5-21 Calculation of BOAT for Nitrobenzene 5-82
5-22 Treatment Performance Data for Tetrachloroethylene 5-86
5-23 Calculation of BOAT for Tetrachloroethylene 5-90
5-24 Treatment Performance Data for Toluene 5-94
5-25 Calculation of BDAT for Toluene 5-109
5-26 Treatment Performance Data for 1,1,1-Trichloroethane ... 5-112
5-27 Calculation of BDAT for 1,1,1-Trichloroethane 5-114
5-28 Treatment Performance Data for Trichloroethylene 5-118
5-29 Calculation of BDAT for Trichloroethylene 5-122
5-30 Treatment Performance Data for Trichlorofluoromethane... 5-125
5-31 Treatment Performance Data for Xylene 5-128
5-32 Grouping of Spent Solvent Constituents for Transfer
of BDAT Treatment Data for All Other F001-F005
Spent Solvents 5-131
5-33 Variability Factors for Incineration Data 5-134
5-34 Incineration Data for Acetone 5-137
xv
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LIST OF TABLES
(Continued)
Table Page
5-35 Incineration Data for Carbon Bisulfide 5-142
5-36 Incineration Data for Chlorobenzene 5-146
5-37 Incineration Data for 1,2-Dichlorobenzene 5-151
5-38 Incineration Data for Ethylbenzene 5-155
5-39 Incineration Data for Methylene Chloride 5-161
5-40 Incineration Data for Methyl Ethyl Ketone 5-165
5-41 Incineration Data for Methyl Isobutyl Ketone 5-168
5-42 Incineration Data for Nitrobenzene 5-172
5-43 Incineration Data for Tetrachloroethylene 5-176
5-44 Incineration Data for Toluene 5-179
5-45 Incineration Data for 1,1,1-Trichloroethane 5-183
5-46 Incineration Data for Trichloroethylene 5-187
5-47 Incineration Data for Xylene 5-191
xvi
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LIST OF TABLES
(Continued)
Table Page
1-1 Index of Plant Treatment Data 1-1
II-l Analysis of Variance Results for Comparing Biological
and Combined Biological and Activated Carbon Treatments
at Plant 246 (Chlorobenzene) II-2
II-2 Summary Statistics for the Transformed Data at
Plant 246 (Chlorobenzene) II-2
II-3 The Outlier Test Results for the Biological Treatment
Performance Data at Plant 246 (1,2-Dichlorobenzene) .... II-3
II-4 Analysis of Variance Results for Comparing Biological
and Combined Biological and Activated Carbon Treatments
at Plant 246 (1,2-Dichlorobenzene) II-4
II-5 Summary Statistics for the Transformed Data at
Plant 246 (1,2-Dichlorobenzene) II-4
II-6 Analysis of Variance for Comparing Steam Stripping
of Pharmaceuticals Industry Treatment Data and
Biological Treatment Data at Plant 265 (Methylene
Chloride) II-5
II-7 Analysis of Variance Results for Comparing Air
Stripping Treatment and Steam Stripping Pilot-Scale
Treatments (Methyl Isobutyl Ketone) II-6
II-8 The Outlier Test Results for the Combined Steam
Stripping and Activated Carbon Treatments at Plant 297
(Nitrobenzene) II-6
II-9 Analysis of Variance Results for Comparing Steam
Stripping and Combined Steam Stripping and Activated
Carbon Treatments at Plant 297 (Nitrobenzene) II-7
11-10 Summary Statistics for the Transformed Data at
Plant 297 (Nitrobenzene) II-7
11-11 The Outlier Test Results for the Biological Treatment
Data at Plant 225 (Tetrachloroethylene) II-8
xvi i
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LIST OF TABLES
(Continued)
Table Page
11-12 The Outlier Test Results for the Biological Treatment
Data at Plant 234 (Toluene) II-9
11-13 Analysis of Variance Results for Comparing Biological
Treatment and Combined Biological and Activated
Carbon Treatments at Plant 246 (Toluene) 11-10
11-14 Summary Statistics for the Transformed Data at
Plant 246 (Toluene) 11-10
11-15- Analysis of Variance Results for Comparing Pilot-Scale
Air Stripping and Pilot-Scale Steam Stripping Data
(1,1,1-Trichloroethane) 11-11
11-16 Summary Statistics for the Transformed Data of the
Pilot-Scale Air and Steam Stripping Treatments
(1,1,1-Trichloroethane) 11-11
11-17 The Outlier Test Results for the Steam Stripping
Treatment Data at Plant 284 (Trichloroethylene) 11-12
xvi 11
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LIST OF FIGURES
Figure
2-1 EPA Regions 2-13
3-1 Resin Production Process 3-8
3-2 Organic Phosphate Ester Production Process 3-18
3-3 Litho Pressing of Three Piece Cans 3-27
3-4 Production of Two Piece Can Bodies 3-28
3-5 Pressing of Can Ends 3-29
3-6 Assembly of Three Piece Cans 3-30
4-1 Plot of Breakthrough Curve 4-4
4-2 Moving Bed Carbon Adsorption 4-8
4-3 Isotherms for Carbon Adsorption 4-12
4-4 Steam Stripping 4-18
4-5 Batch Distillation 4-22
4-6 Thin Film Evaporation 4-25
4-7 Tray Fractionation Column 4-27
4-8 Activated Sludge 4-33
4-9 Trickling Filter 4-36
4-10 Rotating Biological Contactor 4-38
4-11 Liquid Injection Incinerator 4-49
4-12 Rotary Kiln Incinerator 4-50
4-13 Fluidized Bed Incinerator 4-52
4-14 Hearth Incinerator 4-53
4-15 Wet Air Oxidation 4-64
4-16 Air Stripping 4-69
xix
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EXECUTIVE SUMMARY
The final rule for the Land Disposal Restrictions of F001-F005 Spent
Solvent Wastes establishes technology-based treatment standards
representative of Best Demonstrated Available Technology (BOAT). These
standards will, to the .extent possible, reflect well designed and
operated treatment systems and account for variations in treatability due
to waste matrix effects.
For the F001-F005 spent solvent rule, EPA identified two broad
categories of wastes consisting of wastewater and non-wastewater. Within
the wastewater treatability group, the Agency identified a separate
treatability subgroup for methylene chloride wastewater generated at
pharmaceutical plants.
The treatment standards are summarized in the following table. The
technologies used as the basis for BOAT as well as the treatment data
used to develop the specific performance levels are presented in Section
5 of this document.
The BOAT Background Document for F001-F005 Spent Solvents consists of
three volumes. The first volume contains Sections 1 through 4.
Section 1 summarizes the legal background and general approach to the
development of BOAT; Section 2 characterizes the principal industries
that generate wastes subject to this rule; Section 3 presents waste
characterization data for F001-F005 spent solvents; and Section 4
discusses the technologies found to be demonstrated for treatment of
F001-F005 spent solvents. The second volume consists of Section 5 as
previously described. The third volume contains complete data sets for
all data considered in the development of the treatment standards.
xx
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BOAT TREATMENT STANDARDS
(As Concentrations in the Treatment Residual Extract)
Constituent
Acetone
n-Butyl alcohol
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Cresols (cresylic acid)
Cyclohexanone
1,2-Dichlorobenzene
Ethyl acetate
Ethylbenzene
Ethyl ether
Isobutanol
Wastewaters
Containing
Spent Solvents
(mg/L)
0.05
5.0
1.05
0.05
0.15
2.82
0.125
0.65
0.05
0.05
0.05
5.0
Non-Wa s t ewa t e r
Spent Solent
Wastes
(mg/L)
0.59
5.0
4.81
0.96
0.05
0.75
0.75
0.125
0.75
0.053
0.75
5.0
Methanol 0.25
Methylene chloride 0.20
Methylene chloride generated 12.7
at Pharmaceuticals plants
Methyl ethyl ketone 0.05
Methyl isobutyl ketone 0.05
Nitrobenzene 0.66
Pyridine 1.12
Tetrachloroethylene 0.079
Toluene 1.12
1,1,1-Trichloroethane 1.05
l,l,2-Trichloro-l,2,2- 1.05
trifluoroethane
Trichloroethylene 0.062
Trichlorofluoromethane 0.05
Xylene 0.05
0.75
0.96
0.96
0.75
0.33
0.125
0.33
0.05
0.33
0.41
0.96
0.091
0.96
0.15
xxi
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1. BACKGROUND AND GENERAL DESCRIPTION
1.1 Legal Background
This rulemaking sets the regulatory framework for implementing the
land disposal restrictions and establishes treatment standards and
associated effective dates for certain solvent- and dioxin-containing
wastes. This action is responsive to amendments to the Resource
Conservation and Recovery Act (RCRA), enacted through the Hazardous and
Solid Waste Amendments of 1984 (HSWA). These amendments impose
substantial new responsibilities on those who handle hazardous waste.
In particular, the amendments prohibit the continued land disposal of
untreated hazardous wastes beyond specified dates, "unless the
Administrator determines that the prohibition ... is not required in
order to protect human health and the environment for as long as the
wastes remain hazardous . . ." (RCRA sections 3004(d)(l), (e)(l), (g)(5),
42 U.S.C. 6924(d)(l), (e)(l), (g)(5)). Congress established a separate
schedule in section 3004(f) for making determinations regarding the
disposal of dioxins and solvents in injection wells.
Wastes treated in accordance with treatment standards set by EPA
under section 3004(m) of RCRA, are not subject to the prohibitions and
may be land disposed. The statute requires EPA to set "levels or methods
of treatment, if any, which substantially diminish the toxicity of the
waste or substantially reduce the likelihood of migration of hazardous
constituents from the waste so that short-term and long-term threats to
human health and the environment are minimized" (RCRA section 3004(m)(l),
42 U.S.C. 6924(m)(l».
Land disposal prohibitions are effective immediately upon
promulgation unless the Agency sets another effective date based on the
earliest date that adequate alternative treatment, recovery, or disposal
capacity which is protective of human health and the environment will be
available (RCRA sections 3004(h) (1) and (2), 42 U.S.C. 6924(h) (1) and
(2)). However, these effective date variances may not exceed 2 years
beyond the applicable statutory deadline. In addition, two 1-year
case-by-case extensions of the effective date may be granted under
certain circumstances.
For the purposes of the land disposal restrictions program, the
legislation specifically defines land disposal to include, but not be
limited to, any placement of hazardous waste in a landfill, surface
impoundment, waste pile, injection well, land treatment facility, salt
dome or salt bed formation, or underground mine or cave (RCRA section
3004(k), 42 U.S.C. 6924(k)).
1-1
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Congress also has prohibited the storage of any hazardous waste that
is subject to a prohibition from one or more methods of land disposal
unless "such storage is solely for the purpose of the accumulation of
such quantities of hazardous waste as are necessary to facilitate proper
recovery, treatment or disposal" (RCRA section 3004(j), 42 U.S.C.
6924(j)).
There also is a statutory exemption from the land disposal
restrictions for the treatment of wastes in a surface impoundment,
provided that the impoundments meet minimum technological requirements
(with limited exceptions) and that treatment residues that do not meet
the treatment standard(s) are removed within 1 year of the entry of the
waste into the impoundment (RCRA section 3005( j) (11) (A)(B) , 42 U.S.C.
The legislation sets forth a series of deadlines for Agency action.
At certain deadlines, further land disposal of a particular group of
hazardous wastes is prohibited if the Agency has not set treatment
standards under section 3004(m) for such wastes or determined, based on a
case-specific petition, that there will be no migration of hazardous
constituents from the unit for as long as the wastes remain hazardous.
Other deadlines cause conditional restrictions on land disposal to take
effect if treatment standards have not been promulgated or if a petition
has not been granted. In any case where EPA does not set a treatment
standard for a waste by the statutory date, it is not precluded from
later promulgating a treatment standard for that waste. Similarly, where
EPA has set a treatment standard, it is not precluded from revising that
standard after the statutory date through rulemaking procedures.
The above discussion is meant to serve as a summary of the legal
background of the final rule. See the preamble to the final rule for a
detailed discussion.
1.2 EPA's Approach to Developing BOAT
This section establishes the framework under which treatment
standards based on the Best Demonstrated Available Technology (BOAT) will
be developed in accordance with 3004(m). Development of waste
treatability groups is discussed in subsection 1.2.1. Determination of
"Demonstrated" treatment technologies is discussed in subsection 1.2.2.
Determination of "Available" treatment technologies is discussed in
subsection 1.2.3. Collection and analysis of performance data is
discussed in subsection 1.2.4. Identification of "Best" demonstrated
available treatment is discussed in subsection 1.2.5.
1-2
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1.2.1 Waste Treatability Groups
Fundamental to waste treatment is the concept that the type of
treatment technology used and the level of treatment achieved depend on
the physical and chemical characteristics of the waste. The Agency will
establish broad "waste treatability groups" based on similar physical and
chemical properties (e.g., metal-bearing sludges or wastes containing
cyanides; etc.) in order to account for differences in types of treatment
used and effectiveness of treatment on different wastes. Because it may
not be possible to fully account for the full range of chemical and
physical characteristics of a waste with these broad groups, EPA
recognizes that treatability groups could require further subdivision to
more fully account for these effects. However, further subdivision must
be reasonably limited by the availability of sufficient time and
resources necessary to conduct the various analyses required in the
proposed standard setting process.
The legislative history to Section 3004(m) supports this general
approach by providing that treatment determinations do not have to be
made only by waste code and by authorizing EPA to establish "generic"
treatment standards for similar wastes (Volume 130 Congressional Record
S9179 (daily edition July 25, 1984). EPA believes grouping and
subgrouping wastes by industry or manufacturing process may be used to
account for waste matrix effects on treatment performance (i.e., similar
manufacturing operations appear to generate waste with similar
treatability characteristics). For example, in this rulemaking, EPA has
sufficient data to form a separate treatability subgroup for wastewaters
containing spent methylene chloride generated by the pharmaceutical
industry.
However, while the Agency believes that industry-specific analyses
will generally account for waste matrix effects, some wastes (e.g., spill
contaminated soils) are not amenable to categorization by industry
because the wastes are generated independent of routine manufacturing
operation. Therefore, EPA also may establish additional treatability
groups for wastes from unknown or miscellaneous sources.
1.2.2 Determination of "Demonstrated" Treatment Technologies
To be considered a "demonstrated" treatment technology, a full scale
facility first must be known to be in operation for the waste or a waste
judged to be similar. EPA will not, during this first step of its
methodology, examine data to see if the data from the treatment
facilities represent a well-designed and operated system. This factor is
more appropriately taken into account later when evaluating the
performance of the treatment operations. If no full scale treatment
operations are known to exist for a waste or wastes with similar
1-3
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treatability characteristics, the Agency will be unable to identify any
"demonstrated" treatment technologies for the waste and, accordingly, the
waste will be completely prohibited from continued placement in RCRA land
disposal units (unless handled in accordance with the exemption and
variance provisions of the rule). The Agency is, however, committed to
establishing new treatment standards as soon as new or improved treatment
processes become demonstrated as full scale operations.
Pilot- and bench-scale operations will not be considered in
identifying "demonstrated" treatment technologies for a waste. EPA
believes that this approach will ensure that currently used technologies
will be considered. This approach is consistent with legislative history
providing that "[t]he requisite levels of [sic] methods of treatment
established by the Agency should be the best that has been demonstrated
to be achievable" and not a "BAT-type process which contemplates
technology-forcing standards." (Vol. 130 Cong. Rec. S9178 (daily ed.,
July 25, 1984). In certain circumstances data from such operations may
be used by the Agency in evaluating the performance of demonstrated full
scale treatment operations for certain wastes. A more detailed
discussion of the circumstances that would prompt the use of data from
pilot- or bench-scale operations in assessing treatment performance, as
well as the manner in which such data will be used, is presented below in
subsection 1.2.4.
1.2.3 Determination of "Available" Treatment Technologies
EPA will use the following criteria for "available" treatment
technologies: 1) the technology does not present a greater total risk
than land disposal; 2) if the technology is a proprietary or patented
process, whether it can be purchased or licensed from the proprietor; and
3) the technology provides substantial treatment.
EPA will not set treatment standards based on a technology that does
not meet the above criteria. Thus, the decision to classify a technology
as "unavailable" may have a direct impact on the treatment standard. If
the best technology is unavailable, the treatment standard would have to
be based upon the next best treatment technology that was determined to
be available. To the extent that the resulting treatment standards are
less stringent, greater concentrations of hazardous constituents in the
treatment residuals could be placed in land disposal units.
There also may be circumstances where EPA concludes that for a given
waste none of the demonstrated treatment technologies are "available" for
purposes of establishing the 3004(m) treatment performance standards.
Subsequently, these wastes will be prohibited from continued placement in
or on the land unless managed in accordance with the exemption and
1-4
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variance provisions. The Agency is, however, committed to establishing
new treatment standards as soon as new or improved treatment processes
become "available".
(1) Treatment technologies that present greater total risks than
land disposal methods. EPA will evaluate the risks associated
with treatment technologies relative to land disposal methods. Based on
a comparative risk assessment, those technologies that are found to
present greater total risks than land disposal of the untreated waste
will be excluded (jL.e., considered "unavailable") as a basis for
establishing treatment standards.
If all demonstrated treatment technologies are determined to present
greater risks than land disposal for the waste treatability group, the
Agency will not be able to identify any "available" treatment
technologies and, accordingly, will not set a treatment standard for that
group. As a result of such a determination, the waste will be prohibited
from land disposal (unless managed in accordance with the exemptions and
variance provisions) unless a new or improved technology emerges that is
determined not to pose greater total risks than direct land disposal.
Treatment technologies identified as riskier than land disposal and,
therefore, classified as unavailable for purposes of establishing
standards may still, however, be used by facilities in complying with
treatment standards expressed as performance levels. EPA is committed to
developing sufficient regulatory controls or prohibitions over the design
and operation of these technologies to ensure that their use in complying
with the treatment standards do not result in increased risks to human
health and the environment.
(2) Proprietary or patented processes. If the demonstrated
treatment technology is a proprietary or patented process that is not
generally available, EPA will not consider the technology in its
determination of the treatment standards. EPA will consider proprietary
or patented processes available if it determines that the treatment
method can be purchased or licensed from the proprietor or is
commercially available treatment. The services of the commercial
facility offering this technology often can be purchased, although the
technology itself cannot.
Treatment technologies classified as proprietary are unavailable for
the purposes of establishing the treatment standards but may still be
used by facilities in complying with treatment standards expressed as
performance levels.
(3) Substantial treatment. In order to be considered "available", a
demonstrated treatment technology must "substantially diminish the
1-5
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toxicity" of the waste or "substantially reduce the likelihood of
migration of hazardous constituents" from the waste in accordance with
section 3004(m). By requiring that substantial treatment be achieved in
order to set a treatment standard, the statute ensures that all wastes
are adequately treated before being placed in or on the land, and that
the Agency does not require a treatment method that provides little or no
environmental benefit. Treatment will always be deemed substantial if it
results in nondetectable levels of the hazardous constituents of concern
in the TCLP extract. EPA will evaluate whether a treatment technology
provides substantial treatment on a case-by-case basis when the treatment
technology does not achieve nondetectable constituent concentrations in
the residual. This approach is necessary due to the difficulty in
establishing a meaningful guideline that can be applied broadly to the
many wastes and technologies that will be considered. EPA will consider
the following factors in an effort to evaluate whether a technology
provides substantial treatment on a case-by-case basis:
(a) Number and types of constituent treated;
(b) Performance (concentration of the constituents in the treatment
residuals); and
(c) Percent of constituents removed.
If none of the demonstrated treatment technologies achieve
substantial treatment of a waste, the Agency cannot establish treatment
standards for the constituents of concern in that waste.
1.2.4 Collection and Analysis of Performance Data
(1) Collection of performance data. Once the demonstrated available
treatment technologies have been determined for a waste treatability
group, the Agency will collect data representing treatment performance
and information on the design and operation of the treatment system. In
developing technology-based standards, treatment performance is evaluated
using the TCLP. The Agency, in future land disposal restrictions
rulemakings, may consider using a total waste analysis on the
constituents of concern as the basis for determining treatment standards.
Wherever possible, the Agency will evaluate treatment technologies
using full scale systems. If performance data from properly designed and
operated full scale treatment methods for a particular waste or waste
judged to be similar are not available, EPA may use data from pilot-scale
operations. Similarly, where pilot-scale data cannot be obtained EPA may
use data from bench-scale treatment operations. Whenever bench- and
pilot-scale data are used, EPA will explain the use of such data in the
1-6
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preamble or background document and will request comments on the use of
such data. When data on treatment performance for a particular waste or
similar wastes are judged by EPA to be insufficient, EPA will generate
data and information through sampling and analysis regarding the design
and operational parameters and performance of the demonstrated available
treatment technologies.
The Agency recognizes that in some instances all wastes represented
by a particular waste code may not be included in the studies. EPA,
therefore, recognizes the possibility that unique waste matrices may not
be considered in establishing the treatment standard. EPA is providing
the opportunity for interested parties to petition the Agency for
variances to the treatment standards based on a demonstration that the
promulgated treatment standards for a particular waste cannot be
attained. In essence, the variance process allows the applicant to
present information which, if properly considered when the treatment
standard was originally developed, would have required EPA to create a
separate treatability subgroup for the waste.
(2) Treatment design and operation. The Agency will not establish
treatment standards using performance data that are determined not to be
representative of a well designed and operated treatment system. The
effectiveness of a particular treatment technology will depend, to a
significant extent, on how well the system is designed and operated. EPA
will explain the parameters considered in the determination of proper
design and operation with each rulemaking, because the parameters that
comprise a well designed and operated system will vary for each
technology. However, by way of example, some of the critical design and
operating parameters for steam stripping include the number of
equilibrium stages in the column, the temperature at which the unit is
designed to operate, and how well the design temperature is controlled.
In evaluating performance data from a steam stripping operation, the
Agency would examine the design specifications (e.g., the basis for
selecting the number of stages and design temperature) for the treatment
unit in order to determine the extent to which the hazardous constituents
could be expected to volatilize. After the design specifications are
established, the Agency would collect data (e.g. , hourly readings of the
column temperature) throughout the operation of the treatment process
demonstrating that the unit was operating according to design
specifications. If the data collected varies considerably from the
design requirements, it could form the basis of a determination that the
treatment was improperly operated. If the temperature data show, for
example, that for significant periods of time the temperature varied
considerably from the design requirements, the Agency would not use this
data to determine the levels of performance achievable by BDAT.
1-7
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Ideally, for all treatment data, EPA will have associated design and
operating data. However, when treatment performance data are limited,
EPA may use treatment performance data for which there are few or no
associated design and operating data. In these instances, EPA will use
engineering judgment based on a comparison of constituent concentrations
before and after treatment to determine whether the data reflect a well
designed and operated treatment system. The Agency will also use a
statistical outlier analysis to confirm the engineering analysis. An
outlier in a data set is an observation that is significantly different
from the trend in the data. (Refer to Section 5.4.2 for further
discussion of the outlier analysis.) The Agency believes this approach
is reasonable in view of statutory time constraints.
1.2.5 Identification of "Best" Demonstrated Available Treatment
After deleting data representing treatment from systems that are not
well designed or operated, EPA will calculate average performance values
for each specific waste treated with a particular technology.
In cases where the Agency has data on treatment of the same or
similar wastes using more than one technology, we will perform an
analysis of variance test to determine if one of the technologies
performs significantly better. In cases where a particular treatment
technology performs better, the treatment standard will be based on the
best technology. If one of the technologies does not perform
significantly better, we will average the performance values and multiply
this value by the highest variability factor associated with any of the
accepted technologies to derive the treatment standard.
Where the Agency has data from the treatment of different wastes
containing the same constituent of concern but achieving significantly
different levels of performance, the Agency will establish a separate
treatability group in cases where the data and information on the waste
are sufficient to do so. Within any treatability group, however, the
Agency will use the highest treatment value reflecting well designed and
operated treatment to establish BDAT. EPA believes that this approach
ensures that the treatment standard can be achieved by all facilities
within a treatability group.
1.2.6 Variance from the Treatment Standard
The Agency recognizes that there may exist unique wastes that cannot
be treated to the level specified as the treatment standard. In such
cases, generators or owners/operators may submit a petition to the
Administrator requesting a variance from the treatment standard. A
particular waste may be significantly different from the wastes
considered in establishing treatability groups because the waste contains
1-8
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a more complex matrix which makes it more difficult to treat. For
example, complex mixtures may be formed when a restricted waste is mixed
with other waste streams by spills or other forms of inadvertent mixing.
As a result, the treatability of the restricted waste may be altered such
that it cannot meet the applicable treatment standard.
Variance petitions must demonstrate that the treatment standard
established for a given waste cannot be met. This demonstration can be
made by showing that attempts to treat the waste by available
technologies were not successful, or through appropriate analyses of the
waste which demonstrate that the waste cannot be treated to the specified
levels. Variances will not be granted based on a showing that adequate
BOAT treatment capacity is unavailable. (Such demonstrations can be made
according to the provisions in §268.5 for case-by-case extensions of the
effective date.) The Agency will consider granting generic petitions
provided that representative data are submitted to support a variance for
each facility covered by the petition.
Petitioners should submit at least one copy to:
The Administrator
U.S. Environmental Protection Agency
401 M Street, S.W.
Washington, D.C. 20460
An additional copy marked "Treatability Variance" should be submitted
to:
Chief, Waste Treatment Branch
Office of Solid Waste (WH-565)
U.S. Environmental Protection Agency
401 M Street, S.W.
Washington, D.C. 20460
Petitions containing confidential information should be sent with only
the inner envelope marked "Treatability Variance" and "Confidential
Business Information," and the contents marked in accordance with the
requirements of 40 CFR Part 2 (41 FR 36902. September 1, 1976, amended by
43 FR 40000).
The petition should contain the following information:
(1) The petitioner's name and address;
(2) A statement of the petitioner's interest in the proposed action;
1-9
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(3) Name, address, and EPA identification number of the facility
generating the waste, and the name and telephone number of the plant
contact;
(4) The process(es) and feed materials generating the waste and an
assessment of whether such process(es) or feed materials may produce a
waste that is not covered by the demonstration;
(5) A description of the waste sufficient for comparison with the
wastes considered by the Agency in developing BDAT, and an estimate of
the average and maximum monthly and annual quantities of waste covered by
the demonstration; (Note: The petitioner should consult the appropriate
BDAT background document for determining the characteristics of the
wastes considered in developing treatment standards.)
(6) If the waste has been treated, provide a description of the
system used for treating the waste, including the process design,
operating conditions and an explanation of the reasons the treatment
standards are not achievable or are based on inappropriate technology for
treating the waste; (Note: The petitioner should refer to the
appropriate BDAT background document as guidance for determining the
design and operating parameters that the Agency used in developing
treatment standards.)
(7) A description of the alternative treatment systems examined by
the petitioner (if any), a description of the treatment system deemed
appropriate by the petitioner for the waste in question, and, as
appropriate, the concentrations in the treatment residual or extract of
the treatment residual (using the TCLP) that can be achieved by applying
such treatment to the waste;
(8) The dates of the sampling and testing;
(9) A description of the methodologies and equipment used to obtain
representative samples;
(10) A description of the sample handling and preparation techniques,
including techniques used for extraction, containerization, and
preservation of the samples; and
(11) A description of the tests performed (including results).
After receiving a petition for a variance, the Administrator may
request any additional information or waste samples which he may require
to evaluate and process the petition.
1-10
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Additionally, all petitioners must certify that the information
provided to the Agency is accurate under §268.4(b).
In determining whether a variance would be granted, the Agency will
first look at the design and operation of the treatment system being
used. If EPA determines that the technology and operation are.consistent
with BDAT, the Agency will evaluate the waste to determine if the waste
matrix and/or physical parameters are such that BDAT properly reflects
treatment of the waste.
In cases where more than one technology is applicable to a waste, the
petitioner would have to demonstrate that the treatment standard cannot
be met using any of the technologies, or that none of the technologies is
appropriate for treatment of the waste. After the Agency has made a
determination on the petition, the Agency's findings will be published in
the FEDERAL REGISTER, followed by a 30-day period for public comment.
After review of the public comments, EPA will publish its final
determination in the FEDERAL REGISTER as an amendment to the treatment
standards in Part 268 Subpart D.
1-11
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2. INDUSTRIES AFFECTED
2.1 Introduction
A list of industries which use listed F001-F005 solvents is presented
in Section 2.3. Spent solvent wastes included in the F001-F005 hazardous
waste testing are presented in Section 2.2. A discussion of how spent
solvent wastes are generated in industry is presented in Section 2.4.
Geographical data for industries generating spent solvent waste are
presented in Section 2.5 by state and by EPA region.
2.2 Classification of Waste as F001-F005 Spent Solvents
The classification of a waste as an F001-F005 spent solvent waste is
based upon two criteria: the concentration of solvent in the virgin
solvent mixture and the manner in which the solvent is used. The virgin
solvent must have been comprised of any solvent mixture or blend which
contains at least, in total, 10 percent by volume of one or more listed
solvents. Also, the solvent must have been used for its "solvent"
properties. Still bottoms from operations performed to recover listed
solvent constituents are also classified as spent solvents. A solvent is
considered "spent" when it has been used and is no longer fit for use
without being regenerated, reclaimed, or otherwise reprocessed.
Commercial chemical products, off-specification commercial chemical
products, and manufacturing intermediates are not considered to be spent
solvents under the F001-F005 hazardous waste listings. These residuals
are regulated by the solvent-associated "P" and "U" hazardous waste
listings that will be the subject of later standards. Also excluded from
the listing are solvents used as reactants or ingredients in the
formulation of commercial chemical products, solvents which are
impurities in feed streams, and manufacturing process wastes which are
contaminated with solvents.
The compounds included in hazardous waste codes F001-F005 are listed
in Table 2-1. Wastes designated F001, F002, and F004 are listed based on
their toxicity. Wastes designated as F003 are listed for ignitability,
and wastes designated as F005 are listed for both ignitability and
toxicity.
2.3 Industries Which Use Listed Solvents
A list of industries known by EPA to use solvents included in the
F001-F005 hazardous waste listings is presented in Tables 2-2 and 2-3.
However, there may be other industries and other solvent uses which have
not been identified by EPA at this time and hence are not included in
2-1
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Table 2-1. Constituents of Listed
Hazardous Spent Solvent Wastes
FOOT
Tetrachloroethylene
Trichloroethylene
Methylene chloride
1,1,1-Tnchlorethane
Carbon tetrachloride
Chlorinated fluorocarbons
F002
Tetrachloroethylene
Methylene rhloride
Trichloroethylene
1,1,1-Trichloroethane
Chlorobenzene
1,1,2-Trichloro-l,2,2-trifluoroethane
1.2-Dichlorobenzene
Trichlorofluoromethane
F003
Xylene
Acetone
Ethyl acetate
Ethyl benzene
Ethyl ether
Methyl isobutyl ketone
n-Butyl alcohol
Cyclohexanone
Methanol
F004
Cresols
Cresylic acid
Nitrobenzene
F005
Toluene
Methyl ethyl ketone
Carbon disulfide
Isobutanol
Pyridine
2-2
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2-8
-------
Table 2-3. Industries Involved in Surface
Cleaning and Degreasing
Textile Industry
Metal Furniture Manufacturing
Primary Metals Manufacturing
Fabricated Metal Products
Non-Electrical Machinery Manufacture
Electrical Equipment Manufacture
Transportation Vehicles Manufacturing
Instruments and Clocks Manufacture
Automotive Repair Shops
Gasoline Stations*
Listed Hazardous Solvents Used in Oegreasing
Chlorobenzene
Cyclohexanone
Methylene chloride
1,2-Dichlorobenzene
Toluene
1.1,1-Trichloroethane
Tr ichloroethylene
Tetrachloroethylene
Trichlorofluoromethane
1,1,2-Trichloro-l,2,2-trifluoroethane
Xylene
•Georgraphic distribution data not available.
Reference: Organic Solvent Use Study - Final Report.
2-9
-------
Tables 2-2 and 2-3. The tables present information on solvent use in
industry for permit writers, enforcement personnel and the regulated
community. It is not intended to establish the applicability of the
regulation.
The primary industries that generate spent solvents through surface
cleaning and degreasing operations are presented in Table 2-3. Table 2-3
also includes a list of solvents commonly used for degreasing.
2.4 Spent Solvent Waste Generation
There are many ways in which spent solvent wastes are generated in
industry. In processes which involve reactions, solvents are sometimes
used to solubilize reactants or products to keep the reaction
single-phased or to aid in the purification or drying of products. Spent
solvent wastes can be generated in subsequent product purification or
solvent recovery steps. Typical spent solvent wastes generated in
solvent recovery operations include distillation bottoms or wastewater
from steam stripping and other types of treatment. In addition, if no
recovery processes are employed, solvents that are no longer useful as
solvents are themselves spent solvent wastes.
Many industries such as the paint, ink, and dye industries
manufacture solvent-containing products. Solvents are used to solubilize
active ingredients and to aid in the application of the product. Solvent
waste is usually generated during cleaning of the above products. For
example, a printer may use solvent to clean printing presses between jobs
requiring different batches of ink. A paint plant may use solvents to
clean paint residue from tanks and equipment. Industrial applicators of
paints or other solvent-containing coatings may have solvent vapor
recovery systems or water-scrubber systems to reduce solvent emissions to
the atmosphere.
2.4.1 Surface Cleaning
Surface cleaning includes both industrial degreasing of metal
products and repair work. Degreasing operations occur in all of the
industries presented in Table 2-3. Solvent cleaning is used to remove
oily dirt, grease, smears, and fingerprints from metal workplaces before
the final finishing operation, such as porcelain enameling, is performed
(Reference 7). Solvent cleaners are also used to remove oil and grease
based lubricants that have been applied to the surface of nonferrous
metals during mechanical forming operations (Reference 8). Repair work
encompasses degreasing operations with respect to industrial maintenance
and repair of manufacturing equipment, commercial service and repair, and
consumer-performed maintenance and repair.
2-10
-------
Establishments that practice surface cleaning may use one of four
types of degreasing operations: cold cleaning, open top vapor
degreasing, conveyorized degreasing, and fabric scouring. These
degreasing operations are described below. Spent solvents can be
generated from all four types of degreasing operations. In cold cleaning
operations, the solvent is maintained below its boiling point. The item
to be cleaned may either be immersed in an agitated solvent or suspended
above the solvent tank and sprayed with the solvent. Cold cleaning can
also consist of a solvent-filled tank where items to be cleaned are
simply dipped in the tank. Spent solvents will be generated when the
solvent is too contaminated to do further useful cleaning.
Solvents used in cold degreasing include halogenated solvents,
aliphatic and aromatic non-halogenated solvents, and oxygenated compounds
(Reference 2). The halogenated solvents include trichloroethylene,
1,1,1-trichloroethane, tetrachloroethylene, methylene chloride, and
trichlorotrifluoroethane. The non-halogenated solvents are petroleum
products including naphtha, kerosene, benzene, toluene, xylene,
cyclohexane, and heavy aromatics. Oxygenated solvents include acetone,
methyl ethyl ketone, butyl alcohols, and ethers.
In open top vapor degreasing an item is cleaned as it is suspended
over a boiling solvent in a vat. Solvent vapor condenses on the dirty
object until the temperature of the object reaches that of the solvent.
The object may also be sprayed with liquid solvent for additional
cleaning. Halogenated solvents are used for vapor degreasing. Petroleum
products are too flammable and their boiling points are too low to safely
use them for vapor degreasing. The same halogenated compounds named
above for use in cold degreasing operations are used in vapor degreasing.
Conveyorized degreasing consists of vapor degreasing or cold
degreasing. Objects to be cleaned are continuously moved through the
solvent spray.
Fabric scouring operations use conveyorized degreasing machines to
clean fabric. Tetrachloroethylene is the solvent predominantly used for
scouring. Scouring solvents are removed from the fabric with an aqueous
solution of alcohol (Reference 4).
2.4.2 Equipment Cleaning
Listed F001-F005 solvents are used in virtually every industry for
equipment and process cleaning. Spent solvent wastes are generated when
equipment such as reaction vats, storage tanks, pumps, and process lines
2-11
-------
are cleaned. Process equipment is often cleaned between production of
different types of products that contain solvents and during general good
housekeeping procedures. Equipment cleaning may be synonymous with
surface cleaning or degreasing in some instances (e.g., degreasing of a
pump).
2.5 Geographical Distributions
Included in Tables 2-4 through 2-34 are state and EPA regional
distribution data for many of the industries listed in Table 2-2. A
United States map (Figure 2-1) is included to illustrate the EPA region
boundaries.
2-12
-------
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2-13
-------
Table 2-4
CENSUS DATA (1977) FOR NUMBER OF FACILITIES
IN EACH STATE AND EPA REGION
Wood Furniture Manufacturing*
State
Facilities
State
Facilities
EPA Region Totals
AL (IV)
AK (X)
AZ (IX)
AR (VI)
CA (IX)
CO (VIII)
CT (I)
DE (III)
DC (III)
FL (IV)
GA (IV)
HI (IX)
ID (X)
IL (V)
IN (V)
IA (VII)
KS (VII)
KY (IV)
LA (VI)
ME (I)
MD (III)
MA (I)
MI (V)
MN (V)
MS (IV)
MO (VII)
71
38
44
661
39
34
214
79
7
92
101
3
20
27
18
25
22
103
86
33
57
53
MT (VIII)
NE (VII)
NV (IX)
NH (I)
NJ (II)
NM (VI)
NY (II)
NC (IV)
ND (VIII)
OH (V)
OK (VI)
OR (X)
PA (III)
RI (I)
SC (IV)
SD (VIII)
TN (IV)
TX (VI)
UT (VIII)
VT (I)
VA (III)
WA (X)
WV (III)
WI (V)
WY (VIII)
I
2 II
III
31 IV
81 V
VI
322 VII
236 VIII
IX
66 X
19
44
129
23
116
139
24
67
57
38
217
403
281
823
416
220
78
39
706
1C1
"Includes Data for SIC codes 2521, 2517, and 2511
Reference: 1977 Census of Manufacturers
2-14
-------
Table 2-5
CENSUS DATA (1977) FOR NUMBER OF FACILITIES
IN EACH STATE AND EPA REGION
Metal Furniture Manufacturing*
State
Facilities
State
Facilities
AL (IV)
AK (X)
AZ (IX)
AR (VI)
CA (IX)
CO (VIII)
CT (I)
DE (III)
DC (III)
FL (IV)
GA (IV)
HI (IX)
ID (X)
IL (V)
IN (V)
IA (VII)
KS (VII)
KY (IV)
LA (VI)
ME (I)
MD (III)
MA (I)
MI (V)
MN (V)
MS (IV)
MO (VII)
13
4
116
4
1
39
14
42
11
2
2
7
4
17
19
3
4
15
MT
NE
NV
NH
NJ
NM
NY
NC
ND
OH
OK
OR
PA
RI
SC
SD
TN
TX
UT
VT
VA
WA
WV
WI
WY
(VIII)
(VII)
(IX)
(I)
(II) 26
(VI)
(II) 104
(IV) 26
(VIII)
(V) 29
(VI)
(X)
(III) 46
(I)
(IV)
(VIII)
(IV) 13
(VI) 22
(VIII)
(I)
(III) 10
(X)
(III) 1
(V) 10
(VIII)
I
II
III
IV
V
VI
VII
VIII
IX
X
•Includes data for SIC codes 2522 and 2514
Reference: 1977 Census of Manufacturers
EPA Region Totals
21
130
116
2-15
-------
Table 2-6
CENSUS DATA (1977) FOR NUMBER OF FACILITIES
IN EACH STATE AND EPA REGION
Plastics and Resins Manufacturing*
State
Facilities
State
Facilities
EPA Region Totals
AL (IV)
AK (X)
AZ (IX)
AR (VI)
CA (IX)
CO (VIII)
CT (I)
DE (III)
DC (III)
FL (IV)
GA (IV)
HI (IX)
ID (X)
IL (V)
IN (V)
IA (VII)
KS (VII)
KY (IV)
LA (VI)
ME (I)
MD (III)
MA (I)
MI (V)
MN (V)
MS (IV)
MO (VII)
48
10
7
9
11
31
8
2
9
13
3
24
10
5
8
4
MT
NE
NV
NH
NJ
NM
NY
NC
ND
OH
OK
OR
PA
RI
SC
SD
TN
TX
UT
VT
VA
WA
WV
WI
WY
(VIII)
(VII)
(IX)
(I)
(ID
(VI)
(ID
(IV)
(VIII)
(V)
(VI)
(X)
(III)
(I)
(IV)
(VIII)
(IV)
(VI)
(VIII)
(I)
(III)
(X)
(III)
(V)
(VIII)
I
II
III
IV
45 V
VI
15 VII
11 VIII
IX
26 X
8
21
5
6
31
3
3
5
6
34
70
39
59
86
44
6
48
11
•Includes data for SIC Code 2821
Reference: 1977 Census of Manufacturers
2 -16
-------
Table 2-7
CENSUS DATA (1977) FOR NUMBER OF FACILITIES
IN EACH STATE AND EPA REGION
Fiber Manufacturing*
State
Facilities
State
Facilities
EPA Reeion Totals
AL (IV) 5
AK (X)
AZ (IX)
AR (VI)
CA (IX)
CO (VIII)
CT (I) 2
DE (III) 1
DC (III)
FL (IV) 3
GA (IV) 2
HI (IX)
ID (X)
IL (V)
IN (V)
IA (VII)
KS (VII)
KY (IV)
LA (VI)
ME (I)
MD (III) 4
MA (I)
MI (V)
MN (V)
MS (IV)
MO (VII)
MT
NE
NV
NH
NJ
NM
NY
NC
ND
OH
OK
OR
PA
RI
SC
SD
TN
TX
UT
VT
VA
WA
WV
WI
WY
(VIII) I
(VII) II
(IX) III
(I) IV
(ID V
(VI) VI
(II) VII
(IV) 13 VIII
(VIII) IX
(V) 1 X
(VI)
(X)
(III) 3
(I) 1
(IV) 15
(VIII)
(IV) 9
(VI)
(VIII)
(I)
(III) 9
(X)
(III) 1
(V)
(VIII)
3
18
47
1
•Includes data for SIC Codes 2823 and 2824
Reference: 1977 Census of Manufacturers
2-17
-------
Table 2-8
CENSUS DATA (1977) FOR NUMBER OF FACILITIES
IN EACH STATE AND EPA REGION
Pharmaceutical Manufacturing*
State
Facilities
State
Facilities
EPA Resion Totals
AL (IV)
AK (X)
AZ (IX)
AR (VI)
CA (IX)
CO (VIII)
CT (I)
DE (III)
DC (III)
FL (IV)
GA (IV)
HI (IX)
ID (X)
IL (V)
IN (V)
IA (VII)
KS (VII)
KY (IV)
LA (VI)
ME (I)
MD (III)
MA (I)
MI (V)
MN (V)
MS (IV)
MO (VII)
5
96
7
16
3
20
12
60
19
14
6
7
17
22
29
11
6
30
MT (VIII)
NE (VII)
NV (IX)
NH (I)
NJ (II)
NM (VI)
NY (II)
NC (IV)
ND (VIII)
OH (V)
OK (VI)
OR (X)
PA (III)
RI (I)
SC (IV)
SD (VIII)
TN (IV)
TX (VI)
UT (VIII)
VT (I)
VA (III)
WA (X)
WV (III)
WI (V)
WY (VIII)
I
3 II
III
IV
82 V
VI
98 VII
12 VIII
IX
23 X
8
47
4
13
30
4
12
2
8
38
180
81
67
150
30
53
11
101
8
•Includes data for SIC Code 2834
Reference: 1977 Census of Manufacturers
2-18
-------
Table 2-9
CENSUS DATA (1977) FOR NUMBER OF FACILITIES
IN EACH STATE AND EPA REGION
Paint Manufacturing and Application*
State
Facilities
State
Facilities
EPA Region Totals
AL
AK
AZ
AR
CA
CO
CT
DE
DC
FL
GA
HI-
ID
IL
IN
IA
KS
KY
LA
ME
MD
MA
MI
MN
MS
MO
(IV)
(X)
(IX)
(VI)
(IX)
(VIII)
(I)
(III)
(III)
(IV)
(IV)
(IX)
(X)
(V)
(V)
(VII)
(VII)
(IV)
(VI)
(I)
(III)
(I)
(V)
(V)
(IV)
(VII)
13
8
232
10
21
4
78
37
142
32
14
7
22
10
24
48
67
20
9
51
MT
NE
NV
NH
NJ
NM
NY
NC
ND
OH
OK
OR
PA
RI
SC
SD
TN
TX
UT
VT
VA
WA
WV
WI
WY
(VIII)
(VII)
(IX)
(I)
(ID
(VI)
(ID
(IV)
(VIII)
(V)
(VI)
(X)
(III)
(I)
(IV)
(VIII)
(IV)
(VI)
(VIII)
(I)
(III)
(X)
(III)
(V)
(VIII)
I
II
III
IV
146 V
VI
133 VII
22 VIII
IX
97 X
16
18
61
4
23
87
5
14
26
31
69
279
103
208
389
121
72
15
232
44
•Includes data for SIC Code 2851
Reference: 1977 Census of Manufacturers
2-19
-------
Table 2-10
CENSUS DATA (1977) FOR NUMBER OF FACILITIES
IN EACH STATE AND EPA REGION
Cyclic Crudes and Intermediates Including Dyes Manufacturing*
State
Facilities
State
Facilities
EPA Region Totals
AL
AK
AZ
AR
CA
CO
CT
DE
DC
FL
GA
HI
ID
IL
IN
IA
KS
KY
LA
ME
MD
MA
MI
MN
MS
MO
(IV) 4
(X)
(IX)
(VI)
(IX) 8
(VIII)
(I) 2
(III) 2
(III)
(IV)
(IV)
(IX)
(X)
(V) 16
(V)
(VII)
(VII)
(IV) 1
(VI) 3
(I)
(III)
(I) 3
(V) 6
(V) 4
(IV)
(VII)
MT
NE
NV
NH
NJ
NM
NY
NC
ND
OH
OK
OR
PA
RI
SC
SD
TN
TX
UT
VT
VA
WA
WV
WI
WY
(VIII) I
(VII) II
(IX) III
(I) IV
(II) 42 V
(VI) VI
(II) 12 VII
(IV) 7 VIII
(VIII) IX
(V) 13 X
(VI)
(X)
(III) 14
(I) 2
(IV) 8
(VIII)
(IV) 2
(VI) '13
(VIII)
(I)
(III)
(X)
(III) 7
(V)
(VIII)
10
54
26
22
33
16
8
•Includes data for SIC Code 2865
Reference: 1977 Census of Manufacturers
2-20
-------
Table 2-11
CENSUS DATA (1977) FOR NUMBER OF FACILITIES
IN EACH STATE AND EPA REGION
Pigments Manufacturing*
State
Facilities
State
Facilities
EPA Reeion Totals
AL
AK
AZ
AR
CA
CO
CT
DE
DC
FL
GA
HI
ID
IL
IN
IA
KS
KY
LA
ME
MD
MA
MI
MN
MS
MO
(IV)
(X)
(IX)
(VI)
(IX) 11
(VIII)
(I)
(III) 1
(III)
(IV)
(IV) 3
(IX)
(X)
(V) 8
(V)
(VII)
(VII)
(IV)
(VI)
(I)
(III)
(I) 4
(V)
(V)
(IV) 1
(VII) 5
MT
NE
NV
NH
NJ
NM
NY
NC
ND
OH
OK
OR
PA
RI
SC
SD
TN
TX
UT
VT
VA
WA
WV
WI
WY
(VIII) I
(VII) II
(IX) III
(I) IV
(II) 18 V
(VI) VI
(II) 7 VII
(IV) VIII
(VIII) IX
(V) 11 X
(VI)
(X)
(III) 11
(I)
(IV)
(VIII)
(IV) 3
(VI)
(VIII)
(I)
(III)
(X)
(III)
(V)
(VIII)
4
25
12
7
19
5
11
"Includes data for SIC Code 2816
Reference: 1977 Census of Manufacturers
2-21
-------
Table 2-12
CENSUS DATA (1977) FOR NUMBER OF FACILITIES
IN EACH STATE AND EPA REGION
Organic Chemicals Manufacturing*
State
Facilities
State
Facilities
EPA Region Totals
AL
AK
AZ
AR
CA
CO
CT
DE
DC
FL
GA
HI
ID
II
IN
IA
KS
KY
LA
ME
MD
MA
MI
MN
MS
MO
(IV)
(X)
(IX)
(VI)
(IX)
(VIII)
(I)
(III)
(III)
(IV)
(IV)
(IX)
(X)
(V)
(V)
(VII)
(VII)
(IV)
(VI)
(I)
(III)
(I)
(V)
(V)
(IV)
(VII)
9
6
42
5
13
4
6
15
28
6
3
6
11
32
10
20
11
MT
NE
NV
NH
NJ
NM
NY
NC
ND
OH
OK
OR
PA
RI
SC
SD
TN
TX
UT
VT
VA
WA
WV
WI
WY
(VIII)
(VII)
(IX)
(I)
(II)
(VI)
(ID
(IV)
(VIII)
(V)
(VI)
(X)
(III)
(I)
(IV)
(VIII)
(IV)
(VI)
(VIII)
(I)
(III)
(X)
(III)
(V)
(VIII)
I
II
III
2 IV
73 V
VI
39 VII
14 VIII
IX
31 X
23
4
12
12
72
5
14
11
29
112
46
79
96
110
20
15
42
•Includes data for SIC Code 2869
Reference: 1977 Census of Manufacturers
2-22
-------
Table 2-13
CENSUS DATA (1977) FOR NUMBER OF FACILITIES
IN EACH STATE AND EPA REGION
Agricultural Chemicals Manufacturing*
State
Lit i es
State
Facilities
•Includes data for SIC Code 2879
Reference: 1977 Census of Manufacturers
EPA Region Totals
AL (IV)
AK (X)
AZ (IX)
AR (VI)
CA (IX)
CO (VIII)
CT (I)
DE (III)
DC (III)
FL (IV)
GA (IV)
HI (IX)
ID (X)
IL (V)
IN (V)
IA (VII)
KS (VII)
KY (IV)
LA (VI)
ME (I)
MD (III)
MA (I)
MI (V)
MN (V)
MS (IV)
MO (VII)
8
7
56
2
25
16
18
5
6
13
8
19
MT (VIII) I
NE (VII) II
NV (IX) III
NH (I) IV
NJ (II) 18 V
NM (VI) VI
NY (II) 20 VII
NC (IV) 13 VIII
ND (VIII) IX
OH (V) 12 X
OK CVI)
OR (X)
PA (III) 12
RI (I)
SC (IV)
SD (VIII)
TN (IV) 6
TX (VI) 42
UT (VIII)
VT (I)
VA (III)
WA (X) 10
WV (III)
WI (V)
WY (VIII)
i
2
38
12
76
35
62
25
56
10
2-23
-------
Table 2-14
CENSUS DATA (1977) FOR NUMBER OF FACILITIES
IN EACH STATE AND EPA REGION
Printing Industry*
State
Facilities
State
Facilities
EPA Region Totals
AL
AK
AZ
AR
CA
CO
CT
DE
DC
FL
GA
HI
ID
IL
IN
IA
KS
KY
LA
ME
MD
MA
MI
MN
MS
MO
(IV)
(X)
(IX)
(VI)
(IX)
(VIII)
(I)
(III)
(III)
(IV)
(IV)
(IX)
(X)
(V)
(V)
(VII)
(VII)
(IV)
(VI)
(I)
(III)
(I)
(V)
(V)
(IV)
(VII)
563
46
503
436
7,647
959
1078
43
456
2,497
1,209
129
176
4,202
1,291
1,137
822
650
617
202
941
1,959
2,162
1,567
401
1,719
MT
NE
NV
NH
NJ
NM
NY
NC
ND
OH
OK
OR
PA
RI
SC
SD
TN
TX
UT
VT
VA
WA
WV
WI
WY
(VIII)
(VII)
(IX)
(I)
(ID
(VI)
(ID
(IV)
(VIII)
(V)
(VI)
(X)
(III)
(I)
(IV)
(VIII)
(IV)
(VI)
(VIII)
(I)
(III)
(X)
(III)
(V)
(VIII)
199
537
150
248
2,548
210
8,313
1,097
182
2,613
769
601
2,746
196
401
277
1,150
3,658
242
152
995
844
292
1,513
88
I 3,835
II 10,861
III 5,473
IV 7,968
V 13,348
VI .5,690
VII 4,215
VIII 1,947
IX 8,429
X 1,667
*Includes data for SIC Codes 2711 through 2795 and 2893
Reference: 1977 Census of Manufacturers
2-24
-------
Table 2-15
CENSUS DATA (1977) FOR NUMBER OF FACILITIES
IN EACH STATE AND EPA REGION
Commercial Testing Laboratories*
State
Facilities
State
Facilities
EPA Region Totals
AL (IV)
AK (X)
AZ (IX)
AR (VI)
CA (IX)
CO (VIII)
CT (I)
DE (III)
DC (III)
FL (IV)
GA (IV)
HI (IX)
ID (X)
IL (V)
IN (V)
IA (VII)
KS (VII)
KY (IV)
LA (VI)
ME (I)
MD (III)
MA (I)
MI (V)
MN (V)
MS (IV)
MO (VII)
28
7
25
14
247
52
29
4
3
100
33
3
5
89
28
20
18
26
68
7
23
53
64
29
22
28
MT
NE
NV
NH
NJ
NM
NY
NC
ND
OH
OK
OR
PA
RI
SC
SD
TN
TX
UT
VT
VA
WA
WV
WI
WY
(VIII)
(VII)
(IX)
(I)
(ID
(VI)
(ID
(IV)
(VIII)
(V)
(VI)
(X)
(III)
(I)
(IV)
(VIII)
(IV)
(VI)
(VIII)
(I)
(III)
(X)
(III)
(V)
(VIII)
10 I
6 II
6 III
6 IV
81 V
11 VI
113 VII
27 VIII
14 IX
81 X
40
20
82
9
12
3
32
200
17
1
33
38
12
36
9
105
194
157
280
327
333
72
105
281
70
•Includes data for SIC Code 7397
Reference: 1977 Census of Service Industries
2-25
-------
Table 2-16
CENSUS DATA (1977) FOR NUMBER OF FACILITIES
IN EACH STATE AND EPA REGION
Electronic Components Manufacturing*
State
Facilities
State
Facilities
EPA Region Totals
AL (IV)
AK (X)
AZ (IX)
AR (VI)
CA (IX)
CO (VIII)
CT (I)
DE (III)
DC (III)
FL (IV)
GA (IV)
HI (IX)
ID (X)
IL (V)
IN (V)
IA (VII)
KS (VII)
KY (IV)
LA (VI)
ME (I)
MD (III)
MA (I)
MI (V)
MN (V)
MS (IV)
MO (VII)
19
53
1
964
44
117
128
15
265
76
28
25
7
14
47
226
85
8
5
36
MT (VIII)
NE (VII)
NV (IX)
NH (I)
NJ (II)
NM (VI)
NY (II)
NC (IV)
ND (VIII)
OH (V)
OK (VI)
OR (X)
PA (III)
RI (I)
SC (IV)
SD (VIII)
TN (IV)
TX (VI)
UT (VIII)
VT (I)
VA (III)
WA (X)
WV (III)
WI (V)
WY (VIII)
5
43
276
15
339
37
113
27
29
180
14
7
6
25
156
2
38
39
57
I 416
II 615
III 265
IV 243
V 676
VI 199
VII 94
VIII 50
IX 1,017
X 68
•Includes data for SIC Codes 3675, 3676, 3677, 3678, and 3679
Reference: 1977 Census of Manufacturers
2-26
-------
Table 2-17
CENSUS DATA (1977) FOR NUMBER OF FACILITIES
IN EACH STATE AND EPA REGION
Semiconductors and Related Devices Manufacture*
State
Facilities
State
Facilities
EPA Region Totals
AL
AK
AZ
AR
CA
CO
CT
DE
DC
FL
GA
HI
ID
IL
IN
IA
KS
KY
LA
ME
MD
MA
MI
MN
MS
MO
(IV)
(X)
(IX)
(VI)
(IX)
(VIII)
(I)
(III)
(III)
(IV)
(IV)
(IX)
(X)
(V)
(V)
(VII)
(VII)
(IV)
(VI)
(I)
(III)
(I)
(V)
(V)
(IV)
(VII)
16
180
8
13
19
1
5
3
46
3
4
MT
NE
NV
NH
NJ
NM
NY
NC
ND
OH
OK
OR
PA
RI
SC
SD
TN
TX
UT
VT
VA
WA
WV
WI
WY
(VIII)
(VII)
(IX)
(I)
(II)
(VI)
(II)
(IV)
(VIII)
(V)
(VI)
(X)
(III)
(I)
(IV)
(VIII)
(IV)
(VI)
(VIII)
(I)
(III)
(X)
(III)
(V)
(VIII)
I
II
III
IV
34 V
VI
59 VII
VIII
IX
13 X
3
4
31
4
1
36
3
2
68
93
31
20
21
39
4
11
196
5
•Includes data for SIC Code 3674
Reference: 1977 Census of Manufacturers
2-27
-------
Table 2-18
CENSUS DATA (1977) FOR NUMBER OF FACILITIES
IN EACH STATE AND EPA REGION
Synthetic Rubber Industry*
State
Facilities
State
Facilities
EPA Region Totals
AL (IV)
AK (X)
AZ (IX)
AR (VI)
CA (IX)
CO (VIII)
CT (I)
DE (III)
DC (III)
FL (IV)
GA (IV)
HI (IX)
ID (X)
IL (V)
IN (V)
IA (VII)
KS (VII)
KY (IV) 2
LA (VI) 4
ME (I)
MD (III)
MA (I)
MI (V) 7
MN (V)
MS (IV) 1
MO (VII)
MT
NE
NV
NH
NJ
NM
NY
NC
ND
OH
OK
OR
PA
RI
SC
SD
TN
TX
UT
VT
VA
WA
WV
WI
WY
(VIII) I
(VII) II
(IX) III
(I) IV 3
(II) V 11
(VI) VI 14
(II) VII
(IV) VIII
(VIII) IX
(V) 4 X
(VI)
(X)
(III)
(I)
(IV)
(VIII)
(IV)
(VI) 10
(VIII)
(I)
(III)
(X)
(III)
(V)
(VIII)
"Includes data for SIC Code 2822
Reference: 1977 Census of Manufacturers
2-28
-------
Table 2-19
CENSUS DATA (1977) FOR NUMBER OF FACILITIES
IN EACH STATE AND EPA REGION
Tire Industry*
State
Facilities
State
Facilities
EPA Region Totals
AL
AK
AZ
AR
CA
CO
CT
DE
DC
FL
GA
HI
ID
IL
IN
IA
KS
KY
LA
ME
MD
MA
MI
MN
MS
MO
(IV)
(X)
(IX)
(VI)
(IX)
(VIII)
(I)
(III)
(III)
(IV)
(IV)
(IX)
(X)
(V)
(V)
(VII)
(VII)
(IV)
(VI)
(I)
(III)
(I)
(V)
(V)
(IV)
(VII)
9
6
21
2
12
7
5
5
1
4
1
1
4
3 '
3
4
MT
NE
NV
NH
NJ
NM
NY
NC
ND
OH
OK
OR
PA
RI
SC
SD
TN
TX
UT
VT
VA
WA
WV
WI
WY
(VIII) I
(VII) II
(IX) III
(I) IV
(II) V
(VI) VI
(II) 5 VII
(IV) 9 VIII
(VIII) IX
(V) 21 X
(VI) 6
(X)
(III) 13
(I)
(IV) 4
(VIII)
(IV) 11
(VI) 12
(VIII)
(I)
(III) 6
(X)
(III)
(V) 2
(VIII)
7
5
20
52
38
24
10
21
•Includes data for SIC Code 3011
Reference: 1977 Census of Manufacturers
2-29
-------
Table 2-20
CENSUS DATA (1977) FOR NUMBER OF FACILITIES
IN-EACH STATE AND EPA REGION
Textiles Industry*
State
Facilities
State
Facilities
EPA Region Totals
AL (IV)
AK (X)
AZ (IX)
AR (VI)
CA (IX)
CO (VIII)
CT (I)
DE (III)
DC (III)
FL (IV)
GA (IV)
HI (IX)
ID (X)
IL (V)
IN (V)
IA (VII)
KS (VII)
KY (IV)
LA (VI)
ME (I)
MD (III)
MA (I)
MI (V)
MN (V)
MS (IV)
MO (VII)
10
2
95
34
2
6
104
13
11
6
120
7
2
MT (VIII)
NE (VII)
NV (IX)
NH (I)
NJ (II)
NM (VI)
NY (II)
NC (IV)
ND (VIII)
OH (V)
OK (VI)
OR (X)
PA (III)
RI (I)
SC (IV)
SD (VIII)
TN (IV)
TX (VI)
UT (VIII)
VT (I)
VA (III)
WA (X)
WV (III)
WI (V)
WY (VIII)
I
II
III
14 IV
215 V
VI
235 VII
160 VIII
IX
22 X
6
125
61
85
29
8
32
1
5
240
450
165
396
47
10
95
7
•Includes data for SIC Codes 2231, 2261, 2262, 2269, and 2295
Reference: 1977 Census of Manufacturers
2-30
-------
Table 2-21
CENSUS DATA (1977) FOR NUMBER OF FACILITIES
IN EACH STATE AND EPA REGION
Leather and Tanning Industry*
State
Facilities
State
Facilities
EPA Region Totals
AL
AK
AZ
AR
CA
CO
CT
DE
DC
FL
GA
HI
ID
IL
IN
IA
KS
KY
LA
ME
MD
MA
MI
MN
MS
MO
(IV)
(X)
(IX)
(VI)
(IX)
(VIII)
(I)
(III)
(III)
(IV)
(IV)
(IX)
(X)
(V)
(V)
(VII)
(VII)
(IV)
(VI)
(I)
(III)
(I)
(V)
(V)
(IV)
(VII)
36
3
14
6
2
13
2
110
8
5
3
MT
NE
NV
NH
NJ
NM
NY
NC
ND
OH
OK
OR
PA
RI
SC
SD
TN
TX
UT
VT
VA
WA
WV
WI
WY
(VIII)
(VII)
(IX)
(I)
(ID
(VI)
(ID
(IV)
(VIII)
(V)
(VI)
(X)
(III)
(I)
(IV)
(VIII)
(IV)
(VI)
(VIII)
(I)
(III)
(X)
(III)
(V)
(VIII)
I
II
III
14 IV
31 V
VI
85 VII
3 VIII
IX
7 X
19
2
11
10
1
2
2
24
138
116
25
21
58
10
9
36
"Includes data for SIC Code 3111
Reference: 1977 Census of Manufacturers
2-31
-------
Table 2-22
CENSUS DATA (1977) FOR NUMBER OF FACILITIES
IN EACH STATE AND EPA REGION
Transportation Vehicles Manufacturing*
State
Facilities
State
Facilities
EPA Region Totals
AL (IV)
AK (X)
AZ (IX)
AR (VI)
CA (IX)
CO (VIII)
CT (I)
DE (III)
DC (III)
FL (IV)
GA (IV)
HI (IX)
ID (X)
IL (V)
IN (V)
IA (VII)
KS (VII)
KY (IV)
LA (VI)
ME (I)
MD (III)
MA (I)
MI (V)
MN (V)
MS (IV)
MO (VII)
97
81
64
1,905
86
151
6
631
165
5
17
278
444
88
152
70
203
78
114
173
599
120
45
183
MT
NE
NV
NH
NJ
NM
NY
NC
ND
OH
OK
OR
PA
RI
SC
SD
TN
TX
UT
VT
VA
WA
WV
WI
WY
(VIII)
(VII)
(IX)
(I)
(II)
(VI)
(ID
(IV)
(VIII)
(V)
(VI)
(X)
(III)
(I)
(IV)
(VIII)
(IV)
(VI)
(VIII)
(I)
(III)
(X)
(III)
(V)
(VIII)
22
5
212
3
407
150
3
465
174
185
340
41
43
5
126
623
34
2
125
332
11
171
I 450
II 619
III 596
IV 1,327
V 2,077
VI 1,067
VII 450
VIII 128
IX 1,991
X 534
*Includes data for SIC Codes 3711 through 3799
Reference: 1977 Census of Manufacturers
2-32
-------
Table 2-23
CENSUS DATA (1977) FOR NUMBER OF FACILITIES
IN EACH STATE AND EPA REGION
Paper Coating Industry*
State
Facilities
State
Facilities
EPA Region Totals
AL
AK
AZ
AR
CA
CO
CT
DE
DC
FL
GA
HI
ID
IL
IN
IA
KS
KY
LA
ME
MD
MA
MI
MN
MS
MO
(IV)
(X)
(IX)
(VI)
(IX)
(VIII)
(I)
(III)
(III)
(IV)
(IV)
(IX)
(X)
(V)
(V)
(VII)
(VII)
(IV)
(VI)
(I)
(III)
(I)
(V)
(V)
(IV)
(VII)
59
10
10
9
45
11
8
2
4
41
22
10
2
10
MT
NE
NV
NH
NJ
NM
NY
NC
ND
OH
OK
OR
PA
RI
SC
SD
TN
TX
UT
VT
VA
WA
WV
WI
WY
(VIII)
(VII)
(IX)
(I)
(ID
(VI)
(ID
(IV)
(VIII)
(V)
(VI)
(X)
(III)
(I)
(IV)
(VIII)
(IV)
(VI)
(VIII)
(I)
(III)
(X)
(III)
(V)
(VIII)
I
II
III
4 IV
40 V
VI
48 VII
10 VIII
IX
40 X
3
31
9
4
10
28
5
21
64
88
31
47
149
32
18
59
8
•Includes data for SIC Code 2641
Reference: 1977 Census of Manufacturers
2-33
-------
Table 2-24
CENSUS DATA (1977) FOR NUMBER OF FACILITIES
IN EACH STATE AND EPA REGION
Adhesives and Sealants Indi/stry*
State
Facilities
State
Facilities
EPA Region Totals
AL
AK
AZ
AR
CA
CO
CT
DE
DC
FL
GA
HI
ID
IL
IN
IA
KS
KY
LA
ME
MD
MA
MI
MN
MS
MO
(IV)
(X)
(IX)
(VI)
(IX) 78
(VIII)
(I) 10
(III)
(III)
(IV)
(IV) 20
(IX)
(X)
(V) 54
(V)
(VII)
(VII)
(IV) 6
(VI)
(I)
(III) 8
(I) 36
(V) 28
(V)
(IV)
(VII) 19
MT
NE
NV
NH
NJ
NM
NY
NC
ND
OH
OK
OR
PA
RI
SC
SD
TN
TX
UT
VT
VA
WA
WV
WI
WY
(VIII) I
(VII) II
(IX) III
(I) IV
(II) 45 V
(VI) VI
(II) 49 VII
(IV) 11 VIII
(VIII) IX
(V) 42 X
(VI)
(X) 11
(III) 27
(I)
(IV)
(VIII)
(IV) 10
(VI) 32
(VIII)
(I)
(III)
(X)
(III)
(V) 14
(VIII)
46
94
35
47
138
32
19
78
11
•Includes data for SIC Code 2891
Reference: 1977 Census of Manufacturers
2 -34
-------
Table 2-25
CENSUS DATA (1977) FOR NUMBER OF FACILITIES
IN EACH STATE AND EPA REGION
Food Industry - Beer, Edible Fats, and Butter*
State
Facilities
State
Facilities
EPA Reelon Totals
AL
AK
AZ
AR
CA
CO
CT
DE
DC
FL
GA
HI
ID
IL
IN
IA
KS
KY
LA
ME
MD
MA
MI
MN
MS
MO
(IV)
(X)
(IX)
(VI)
(IX)
(VIII)
(I)
(III)
(III)
(IV)
(IV)
(IX)
(X)
(V)
(V)
(VII)
(VII)
(IV)
(VI)
(I)
(III)
(I)
(V)
(V)
(IV)
(VII)
9
53
14
11
13
27
18
19
14
2
17
6
5
8
17
44
6
15
MT
NE
NV
NH
NJ
NM
NY
NC
ND
OH
OK
OR
PA
RI
SC
SD
TN
TX
UT
VT
VA
WA
WV
WI
WY
(VIII)
(VII)
(IX)
(I)
(ID
(VI)
(ID
(IV)
(VIII)
(V)
(VI)
(X)
(III)
(I)
(IV)
(VIII)
(IV)
(VI)
(VIII)
(I)
(III)
(X)
(III)
(V)
(VIII)
I
16 II
III
1 IV
20 V
VI
28 VII
14 VIII
IX
21 X
1
42
2
16
44
12
20
40
18
48
59
71
167
61
64
14
53
21
•Includes data for SIC Codes 2021, 2077, 2082
Reference: 1977 Census of Manufacturers
2-35
-------
Table 2-26
CENSUS DATA (1977) FOR NUMBER OF FACILITIES
IN EACH STATE AND EPA REGION
Dry Cleaning Industry*
State
Facilities
State
Facilities
EPA Region Totals
AL (IV)
AK (X)
AZ (IX)
AR (VI)
CA (IX)
CO (VIII)
CT (I)
DE (III)
DC (III)
FL (IV)
GA (IV)
HI (IX)
ID (X)
IL (V)
IN (V)
IA (VII)
KS (VII)
KY (IV)
LA (VI)
ME (I)
MD (III)
MA (I)
MI (V)
MN (V)
MS (IV)
MO (VII)
984
61
488
580
5,615
695
690
113
182
2,453
1,349
158
186
2,661
1,323
619
578
750
873
191
842
1,106
1,803
727
672
1,179
MT
NE
NV
NH
NJ
NM
NY
NC
ND
OH
OK
OR
PA
RI
SC
SD
TN
TX
UT
VT
VA
WA
WV
WI
WY
(VIII)
(VII)
(IX)
(I)
(ID
(VI)
(ID
(IV)
(VIII)
(V)
(VI)
(X)
(III)
(I)
(IV)
(VIII)
(IV)
(VI)
(VIII)
(I)
(III)
(X)
(III)
(V)
(VIII)
186
323
176
156
1,712
277
4,458
1,347
144
2,267
716
476
2,138
190
773
179
1,029
3,518
232
88
1,158
754
340
900
104
I 2,421
II 6,170
III 4,773
IV 9,357
V 9,681
VI 5,964
VII 2,699
VIII 1,540
IX 6,437
X 1,477
•Includes data for SIC Codes 7215, 7216, and 7217
Reference: 1977 Census of Service Industries
2-36
-------
Table 2-27
CENSUS DATA (1977) FOR NUMBER OF FACILITIES
IN EACH STATE AND EPA REGION
Wool Weaving and Finishing Industry*
State
Facilities
State
F_acilili_es
EPA Region Totals
AL (IV) 1
AK (X)
AZ (IX)
AR (VI)
CA (IX)
CO (VIII)
CT (I) 2
DE (III)
DC (III)
FL (IV)
GA (IV) 4
HI (IX)
ID (X)
IL (V)
IN (V)
IA (VII)
KS (VII)
KY (IV)
LA (VI)
ME (I) 11
MD (III)
MA (I) 24
MI (V)
MN (V) 3
MS (IV)
MO (VII)
MT (VIII) I
NE (VII) II
NV (IX) III
NH (I) 6 IV
NJ (II) V
NM (VI) VI
NY (II) 23 VII
NC (IV) VIII
ND (VIII) IX
OH (V) 2 X
OK (VI)
OR (X) 6
PA (III) 13
RI (I) 17
SC (IV) 4
SD (VIII)
TN (IV)
TX (VI) 8
UT (VIII)
VT (I)
VA (III) 6
WA (X) 1
WV (III)
WI (V)
WY (VIII)
60
23
19
5
2
8
7
•Includes data for SIC Code 2231
Reference: 1977 Census of Manufacturers
2-37
-------
Table 2-28
CENSUS DATA (1977) FOR NUMBER OF FACILITIES
IN EACH STATE AND EPA REGION
Petroleum Refining Industry*
State
Facilities
State
Facilities
EPA Region Totals
AL (IV)
AK (X)
AZ (IX)
AR (VI)
CA (IX)
CO (VIII)
CT (I)
DE (III)
DC (III)
FL (IV)
GA (IV)
HI (IX)
ID (X)
IL (V)
IN (V)
IA (VII)
KS (VII)
KY (IV)
LA (VI)
ME (I)
MD (III)
MA (I)
MI (V)
MN (V)
MS (IV)
MO (VII)
6
4
41
4
1
2
17
9
12
5
26
7
3
5
4
MT
NE
NV
NH
NJ
NM
NY
NC
ND
OH
OK
OR
PA
RI
SC
SD
TN
TX
UT
VT
VA
WA
WV
WI
WY
(VIII)
(VII)
(IX)
(I)
(ID
(VI)
(ID
(IV)
(VIII)
(V)
(VI)
(X)
(III)
(I)
(IV)
(VIII)
(IV)
(VI)
(VIII)
(I)
(III)
(X)
(III)
(V)
(VIII)
7
II
III
IV
8 V
4 VI
7 VII
VIII
3 IX
10 X
16
18
2
76
7
3
7
3
2
10
15
25
18
48
126
16
31
43
7
•Includes data for SIC Code 2911
Reference: 1977 Census of Manufacturers
2-38
-------
Table 2-29
CENSUS DATA (1977) FOR NUMBER OF FACILITIES
IN EACH STATE AND EPA REGION
Primary Metals Manufacturing*
State
Facilities
State
Facilities
EPA Region Totals
AL
AK
AZ
AR
CA
CO
CT
DE
DC
FL
GA
HI
ID
IL
IN
IA
KS
KY
LA
ME
MD
MA
MI
MN
MS
MO
(IV)
(X)
(IX)
(VI)
(IX)
(VIII)
(I)
(III)
(III)
(IV)
(IV)
(IX)
(X)
(V)
(V)
(VII)
(VII)
(IV)
(VI)
(I)
(III)
(I)
(V)
(V)
(IV)
(VII)
156
35
23
50
908
30
280
8
22
91
2
672
344
67
41
73
26
1
46
285
637
102
49
142
MT
NE
NV
NH
NJ
NM
NY
NC
ND
OH
OK
OR
PA
RI
SC
SD
TN
TX
UT
VT
VA
WA
WV
WI
WY
(VIII)
(VII)
(IX)
(I)
(II)
(VI)
(ID
(IV)
(VIII)
(V)
(VI)
(X)
(III)
(I)
(IV)
(VIII)
(IV)
(VI)
(VIII)
(I)
(III)
(X)
(III)
(V)
(VIII)
17
1
28
370
3
561
78
750
62
42
710
100
50
38
363
16
10
67
14
45
233
1
I 704
II 931
III 876
IV 557
V 2,738
VI 504
VII 267
VIII 47
IX 932
X 93
•Includes data for SIC Codes 3312 through 3399
Reference: 1977 Census of Manufacturers
2-39
-------
Table 2-30
CENSUS DATA (1977) FOR NUMBER OF FACILITIES
IN EACH STATE AND EPA REGION
Fabricated Metals Manufacturing*
State
Facilities
State
Facilities
EPA Recion Totals
AL (IV)
AK (X)
AZ (IX)
AR (VI)
CA (IX)
CO (VIII)
CT (I)
DE (III)
DC (III)
FL (IV)
GA (IV)
HI (IX)
ID (X)
IL (V)
IN (V)
IA (VII)
KS (VII)
KY (IV)
LA (VI)
ME (I)
MD (III)
MA (I)
MI (V)
MN (V)
MS (IV)
MO (VII)
418
194
149
4,368
255
988
21
3
808
428
3
4
2,635
923
1,205
243
294
212
35
286
1,178
2,406
583
107
606
MT
NE
NV
NH
NJ
NM
NY
NC
ND
OH
OK
OR
PA
RI
SC
SD
TN
TX
UT
VT
VA
WA
WV
WI
WY
(VIII)
(VII)
(IX)
(I)
(ID
(VI)
(ID
(IV)
(VIII)
(V)
(VI)
(X)
(III)
(I)
(IV)
(VIII)
(IV)
(VI)
(VIII)
(I)
(III)
(X)
(III)
(V)
(VIII)
84
3
41
1,533
7
2,525
451
3
2,371
354
365
1,929
377
216
16
518
1,915
92
5
261
387
92
771
I 2,624
II 4,058
III 2,592
IV 3,240
V 9,689
VI 2,637
VII 2,138
VIII 366
IX 4,568
X 756
•Includes data for SIC Codes 3411 through 3499
Reference: 1977 Census of Manufacturers
2-40
-------
Table 2-31
CENSUS DATA (1977) FOR NUMBER OF FACILITIES
IN EACH STATE AND EPA REGION
Non-Electric Machinery Manufacture*
State
Facilities
State
EPA Reeion Totals
AL (IV)
AK (X)
AZ (IX)
AR (VI)
CA (IX)
CO (VIII)
CT (I)
DE (III)
DC (III)
FL (IV)
GA (IV)
HI (IX)
ID (X)
IL (V)
IN (V)
IA (VII)
KS (VII)
KY (IV)
LA (VI)
ME (I)
MD (III)
MA (I)
MI (V)
MN (V)
MS (IV)
MO (VII)
444
236
278
6,383
414
1,258
36
912
559
99
3,452
1,332
535
514
380
345
92
285
1,539
3,929
1,047
203
852
MT (VIII)
NE (VII)
NV (IX)
NH (I)
NJ (II)
NM (VI)
NY (II)
NC (IV)
ND (VIII)
OH (V)
OK (VI)
OR (X)
PA (III)
RI (I)
SC (IV)
SD (VIII)
TN (IV)
TX (VI)
UT (VIII)
VT (I)
VA (III)
WA (X)
WV (III)
WI (V)
WY (VIII)
201
38
177
2,097
121
2,794
787
3,663
564
493
2,464
263
356
11
535
2,702
136
45
374
535
180
1,479
37
I 3,374
II 4,891
III 3,334
IV 4,176
V 14,902
VI 4,010
VII 2,102
VIII 598
IX 6,657
X 1,127
•Includes data for SIC Codes 3511 through 3599
Reference: 1977 Census of Manufacturers
2-41
-------
Table 2-32
CENSUS DATA (1977) FOR NUMBER OF FACILITIES
IN EACH STATE AND EPA REGION
Electric Equipment Manufacture*
State
Facilities
State
Facilities
EPA Region Totals
AL
AK
AZ
AR
CA
CO
CT
DE
DC
FL
GA
HI
ID
IL
IN
IA
KS
KY
LA
ME
MD
MA
MI
MN
MS
MO
(IV)
(X)
(IX)
(VI)
(IX)
(VIII)
(I)
(III)
(III)
(IV)
(IV)
(IX)
(X)
(V)
(V)
(VII)
(VII)
(IV)
(VI)
(I)
(III)
(I)
(V)
(V)
(IV)
(VII)
80
104
72
3,027
100
381
1
455
133
3
1 ,068
310
73
70
85
21
39
153
667
451
250
57
218
MT
NE
NV
NH
NJ
NM
NY
NC
ND
OH
OK
OR
PA
RI
SC
SD
TN
TX
UT
VT
VA
WA
WV
WI
WY
(VIII)
(VII)
(IX)
(I)
(II)
(VI)
(II)
(IV)
(VIII)
(V)
(VI)
(X)
(III)
(I)
(IV)
(VIII)
(IV)
(VI)
(VIII)
(I)
(III)
(X)
(III)
(V)
(VIII)
1
19
8
73
908
27
1,514
181
634
82
92
767
43
55
6
221
636
32
7
149
147
9
292
I 1,210
II 2,422
III 1,079
IV 1,267
V 3,005
VI 838
VII 380
VIII 139
IX 3,139
X 242
"Includes data for SIC Codes 3612 through 3699
Reference: 1977 Census of Manufacturers
2-42
-------
Table 2-33
CENSUS DATA (1977) FOR NUMBER OF FACILITIES
IN EACH STATE AND EPA REGION
Instruments and Clocks Manufacture*
State
Facilities
State
Facilities
EPA Region Totals
AL (IV)
AK (X)
AZ (IX)
AR (VI)
CA (IX)
CO (VIII)
CT (I)
DE (III)
DC (III)
FL (IV)
GA (IV)
HI (IX)
ID (X)
IL (V)
IN (V)
IA (VII)
KS (VII)
KY (IV)
LA (VI)
ME (I)
MD (III)
MA (I)
MI (V)
MN (V)
MS (IV)
MO (VII)
33
26
19
1,458
88
209
7
222
35
12
484
96
19
31
23
7
63
435
251
119
8
89
MT (VIII)
NE (VII)
NV (IX)
NH (I)
NJ (II)
NM (VI)
NY (II)
NC (IV)
ND (VIII)
OH (V)
OK (VI)
OR (X)
PA (III)
RI (I)
SC (IV)
SD (VIII)
TN (IV)
TX (VI)
UT (VIII)
VT (I)
VA (III)
WA (X)
WV (III)
WI (V)
WY (VIII)
24
3
33
430
4
855
56
326
20
41
409
38
15
3
47
332
19
6
70
28
3
106
I 728
II 1,285
III 552
IV 406
V 1,382
VI 375
VII 163
VIII 110
IX 1,487
X 81
•Includes data for SIC Codes 3811 through 3873
Reference: 1977 Census of Manufacturers
2-43
-------
Table 2-34
CENSUS DATA (1977) FOR NUMBER OF FACILITIES
IN EACH STATE AND EPA REGION
Automotive Repair Shops*
State Facilit'
AL (IV)
AK (X)
AZ (IX)
AR (VI)
CA (IX)
CO (VIII)
CT (I)
DE (III)
DC (III)
FL (IV)
GA (IV)
HI (IX)
ID (X)
IL (V)
IN (V)
IA (VII)
KS (VII)
KY (IV)
LA (VI)
ME (I)
MD (III)
MA (I)
MI (V)
MN (V)
MS (IV)
MO (VII)
2,192
315
1,525
1,871
14,226
1,989
1,431
299
156
5,756
3342
547
742
5,796
3,469
2,488
2,030
2,218
2,234
1,072
1,823
3,552
3,934
2,583
1,509
3,575
State
MT (VIII)
NE (VII)
NV (IX)
NH (I)
NJ (II)
NM (VI)
NY (II)
NC (IV)
ND (VIII)
OH (V)
OK (VI)
OR (X)
PA (III)
RI (I)
SC (IV)
SD (VIII)
TN (IV)
TX (VI)
UT (VIII)
VT (I)
VA (III)
WA (X)
WV (III)
WI (V)
WY (VIII)
Facilities
770
1,439
447
789
4,027
909
8,130
4,176
452
5,575
2,355
1,886
8,718
587
2,008
607
2,719
9,891
905
480
2,683
2,617
923
2,616
383
EPA Reeion Totals
I
II
III
IV
V
VI
VII
VIII
IX
X
7,911
12,157
14,602
23,920
23,973
17,260
9,532
5,106
16,745
5,560
"Includes data for SIC Codes 7538, 7531, 7535 and parts of 7539
including transmission repair shops, auto electrical and fuel
system services, and other automotive repair shops.
Reference: 1977 Census of Service Industries
2-44
-------
REFERENCES - SECTION 2
1. Executive Office of the President, Office of Management and Budget.
Standard Industrial Classification Manual 1972. Washington, D.C.:
U.S. Government Printing Office, 1972.
2. Goodwin, D.R. and D.G. Hawkins. Organic Solvent Cleaners -
Background Information for Proposed Standards. Research Triangle
Park, North Carolina: U.S. Environmental Protection Agency
EPA-450/2-78-045a, October 1979.
3. Lee, B.B., G.E. Wilkins and E.M. Nichols. Organic Solvent Use Study
- Final Report. Washington, D.C.: U.S. EPA 560/12-79-002 (PB 301
342), 1979.
4. Pope-Reid Associates, Inc. Draft Report, Background Document for
Solvents Land Disposal Restrictions Volumes I, II, and III. Prepared
for U.S. Environmental Protection Agency, EPA Contract No.
68-01-6892, 7 January 1986.
5. U.S. Department of Commerce, Bureau of the Census. 1977 Census of
Manufacturers. August 1981.
6. U.S. Department of Commerce, Bureau of the Census. 1977 Census of
Service Industries, Volume 1. September 1981.
7. U.S. Environmental Protectin Agency. Final Development Document for
Effluent Limitations Guidelines and Standards for the Porcelain
Enameling Point Source Category. Washington, D.C.: U.S.
EPA/440/1-82/072, November 1982.
8. U.S. Environmental Protection Agency. Nonferrous Metals Forming and
Metal Powders Point Source Category Development Document
Administrative Record, pp. 46,001-48,209. Washington, D.C.: U.S.
EPA, August 1985.
2-45
-------
3. WASTE CHARACTERIZATION
3.1 Introduction
Characterization data for spent solvent wastes from several
industries are presented in this section. Table 3-1 lists industries for
which characterization data are available to EPA. Data are presented in
tabular form with a description of the process generating the spent
solvent waste.
The characterization data were obtained from delisting petitions, the
Industrial Technology Division of the Office of Water, the Industry
Studies Data Base compiled by the Characterization and Assessment
Division of the Office of Solid Waste, a Hazardous Waste Treatment
Workshop, and other literature sources. Sampling data which were
collected by EPA in support of the land disposal restrictions for
solvents are also presented.
3.2 Waste Characterization Data
Characterization data for spent solvent wastes are presented in
Tables 3-2 through 3-29. Process flowsheets, where available to EPA, are
included. Sample points are indicated on the flowsheet by an X.
3-1
-------
Table 3-1
SUMMARY OF INDUSTRIES FOR WHICH SPENT SOLVENT WASTE
CHARACTERIZATION DATA ARE AVAILABLE
Industry
Furniture Manufacturing
Plastics and Resins
Manufacturing
Fiber Manufacturing
Pharmaceutical Manufacturing
Paint Manufacturing
Dyes and Pigments
Manufacturing
Organic Chemicals
Manufacturing
Agricultural Chemicals
Manufacturing
Printing Industry
Can Coating Industry
Membrane Production Industry
Description of the Spent Solvent Waste
Spent thinner and solvent
Still bottoms and caustic
Epoxy resin waste
Phenolic and polyester/alkyd resin waste
Solvent recovery bottoms, laboratory sol-
vents, and chrome plating solution
Solvent recovery bottoms
Paint tank wash
Spent thinner
Dyes and pigments waste
Still bottoms and caustic
Isocyanates manufacturing wastes
Alkenes manufacturing waste
Aldehyde furan manufacturing wastes
Pesticide manufacturing waste
Spent recovery bottoms
Spent ink wash
Spent can coating residue
Spent solvents and organics
3-2
-------
3.2.1 Furniture Manufacturing
Waste characterization data for spent solvent wastes generated by the
furniture manufacturing industry are presented in Tables 3-2 through 3-5.
Table 3-2
Waste Description: Dirty, reclaimed lacquer thinner used to rinse
solvent-based furniture finishing material (F001, F003, and F005) from
spray lines between color changes. The spent thinner is also used to
wash off culled or miscolored pieces of wooden casegood furniture.
Constituent
Cyclohexanol
Methylene chloride
Chloroform
Toluene
Styrene
Suspended solids
Dissolved solids
Constituent
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Selenium
Silver
Endrin
Lindane
Methoxychlor
Toxaphene
Dichlorophenoxyacetic acid
Trichlorophenoxyproprionic acid
Flash Point (cc): <100°F
pH: acid
Reference: Delisting petition number 488 for Plant A.
Concentration
(% by weight)
20
43
10
17
10
<5
4
Cone entration
(ppm)
<0.001
0.009
0.002
0.007
0.01
<0.001
<0.001
<0.01
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
3-3
-------
Table 3-3
Waste Description: Dirty, reclaimed lacquer thinner used to rinse
solvent-based furniture finishing material (P001, F003, and F005) from
spray lines between color changes. The spent thinner is also used to
wash off culled or miscolored pieces of wooden casegood furniture.
Constituent
Aliphatic naphtha
Methylene chloride
Xylene
Toluene
Carbitol
Suspended solids
Dissolved solids
Constituent
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Selenium
Silver
Endrin
Lindane
Methoxychlor
Toxaphene
Dichlorophenoxyacetic acid
Trichlorophenoxyproprionic acid
Flash Point (cc): <100°F
pH: acid
Reference: Delisting petition number 488 for Plant B.
Concentration
(% by weight)
31
6
8
14
38
<5
8
Concentration
(ppm)
<0.001
0.04
0.01
0.002
0.1
<0.01
<0.001
<0.01
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
3-4
-------
Table 3-4
Waste Description: Dirty, reclaimed lacquer thinner used to rinse
solvent-based furniture finishing material (F001, F003, and F005) from
spray lines between color changes. The spent thinner is also used to
wash off culled or miscolored pieces of wooden casegood furniture.
Constituent
Aliphatic naphtha
Methylene chloride
Xylene
Toluene
Methyl ethyl ketone
1,1,1-Trichloroethane
Suspended solids
Dissolved solids
Constituent
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Selenium
Silver
Endrin
Lindane
Methoxychlor
Toxaphene
Dichlorophenoxyacetic acid
Trichlorophenoxyproprionic acid
Flash Point (cc): <100°F
pH: neutral
Reference: Delisting petition number 488 for Plant C.
Concentration
(% by weight)
51
2
4
34
6
1
5-20
6
Concentration
(ppm)
<0.001
0.11
<0.005
0.03
0.02
<0.001
<0.001
<0.01
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
3-5
-------
Table 3-5
Waste Description: Dirty, reclaimed lacquer thinner used to rinse
solvent-based furniture finishing material (F001, F003, and F005) from
spray lines between color changes. The spent thinner is also used to
wash off culled or miscolored pieces of wooden casegood furniture.
Constituent
Aliphatic and aromatic hydrocarbon solvents
Adipate plasticizer
Suspended solids
Dissolved solids
Constituent
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Selenium
Silver
Endrin
Lindane
Methoxychlor
Toxaphene
Dichlorophenoxyacetic acid
Trichlorophenoxyproprionic acid
Flash Point (cc):
pH:
<100°F
neutral
Concentration
(% by weight)
90
10
<5
8
Concentration
(PPM)
<0.001
0.007
<0.005
<0.005
0.007
<0.001
<0.001
<0.001
<0.005
<0.005
<0.005
<0.005
<0.005
<0.005
Reference: Delisting petition number 488 for Plant D.
3-6
-------
3.2.2 Plastics and Resins Industry
Waste characterization data for spent solvent wastes generated by the
plastics and resins industry are presented in Tables 3-6 through 3-8.
Table 3-6
Waste Description: Methanol concentrations contained in plant wastewater
from the production of alkyd resins are presented here. Alkyd resin is
produced via a polymerization reaction and is recovered by a stripping
system (see Figure 3-1). Methanol is used as a solvent in the
production of one of the resins produced at this plant; therefore, the
product recovery stripping bottoms contain methanol (F003). The
stripping bottoms are mixed with caustic rinsewater from cleaning
kettles and mixtures between different batches.
Date
09/16/81
11/09/81
12/23/81
01/12/82
05/10/82
06/09/82
08/12/82
08/31/82
01/24/83
03/16/83
04/06/83
04/14/83
Methanol
0.60
0.80
0.54
1.96
0.74
0.41
13
.43
0.29
0.62
1.24
0.70
Flash Point
NR
NR
>200°F
NR
>200°F
NR
>200°F
NR
>200°F
>200°F
>200°F
>200°F
NR = Not Reported
Reference: Delisting petition number 476.
Table 3-7
Waste Description: Spent solvent waste from the manufacture of epoxy
resin. Methyl ethyl ketone (F003) is used as a solvent to purify epoxy
resins.
Constituent
Epoxy resin
Methyl ethyl ketone
Surfactant
Water
Concentration
(ppm)
1-10
>50
0.1-1
1-10
Reference: Industry Studies Database. Prepared for US EPA, Office of
Solid Waste, Waste Identification Branch, 1985.
3-7
-------
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3-8
-------
Table 3-8
Waste Description: Data are for a waste stream generated from the
production of polyester/alkyd resin. Alkyd resins are produced using a
condensation polymerization reaction. Methanol (F003) is used as a
solvent to maintain a single-phase system which permits the
condensation reaction to proceed rapidly. Solvents such as xylene
(F003) or toluene (FQ05) are also added to the reactor to form an
azeotrope with the water. The azeotrope leaves the reactor as a vapor
and is condensed and settled in a decanter. The solvent layer is
recycled. The water layer from the decanter comprises the spent
solvent waste stream.
Concentration
Constituent (% by weight)
Hydroxyl dialkyl ether 0.01-0.1
Diether 1-10
Ether 0.01-0.1
Alkyl hetero-aliphatic compound 1-10
Alkyl benzene <0.01
Acetaldehyde 0.1-1
Acetone 0.01-0.1
Diethylene glycol 0.1-1
Ethanol 0.1-1
Ethylene glycol 0.1-1
Methanol >50
Methyl acetate <0.01
o-Xylene 1-10
Toluene 0.1-1
Water 1-10
1,4-Dioxane 0.1-1
Reference: Industry Studies Database. Prepared for US EPA, Office of
Solid Waste, Waste Identification Branch, 1985.
3-9
-------
3.2.3 Fiber Industry
Waste characterization data for spent solvent wastes generated in
the fiber industry are presented in Table 3-9.
Table 3-9
Waste Description: This waste is generated by a fiber company which
produces cellulose acetate resin, yarn, and tow. Resin is made from
wood pulp, acetic acid, and acetic anhydride using sulfuric acid as a
catalyst. The plant uses a solvent extraction system consisting of
benzene, methyl ethyl ketone (F005), and ethyl acetate (F003) to
recover acetic acid. A distillation column recovers the acetic acid,
and a second column recovers the solvents. The still bottoms from the
solvent recovery column form part of the plant's spent solvent waste
stream. After the cellulose acetate resin is produced, it is-dissolved
in acetone (F003), filtered, and extruded through spinnerets into yarn
or tow. Acetone vapors are recovered using a carbon adsorption system
along with distillation. The still bottoms from this column are the
second source of spent solvent in the plant waste stream. Also present
in the waste stream are small amounts of laboratory solvents including
acetone, benzene, methylene chloride (F002), ethyl acetate, methyl ethyl
ketone, and small amounts of chrome plating solution from a chrome
plating system for jet spinnerets.
Constituent
Sample
1
Concentration (mg/L)
Sample
2
Sample
3
Sample
4
Acetone
Benzene
Ethyl acetate
Methylene chloride
Methyl ethyl ketone
Methanol
Chloroform
Ethyl ether
Trichlorotrifluoroethane
Pyridine
Toluene
Xylenes
54
43
0.56
0.007
0.56
4.5
0.0009
0.0009
<0. 00007
<0.004
0.002
<0. 00004
24
8.5
12
<0.0003
26
0.61
0.0003
<0.0002
<0. 00007
<0.004
<0. 00008
<0. 00004
24
2.7
6.1
0.008
15
5.8
<0.0004
<0.001
<0. 00006
<0.019
<0.006
<0.0005
52
2.4
8.8
<0.010
15
<1.0
<0.01
<0.019
<0.01
<0.01
<0.01
<0.01
Reference: Delisting petition number 0254.
3-10
-------
3.2.4. Pharmaceutical Manufacturing
Waste characterization data for spent solvent wastes generated in the
Pharmaceuticals manufacturing industry are presented in Tables 3-10 and
3-11.
Table 3-10
Waste Description: Pharmaceutical manufacturing operations at this
facility involve chemical reactions which occur in solvents (F002,
F003, and F005). Both batch and continuous operations are performed.
Products are recovered from the solvent using crystallization,
filtration, and centrifugation. Solvents and reaction by-products are
further treated by evaporation and/or fractionation to recover
solvents. The spent solvent waste is comprised of various still
bottoms and fractionator cuts from solvent recovery. The hazardous
liquid wastes are segregated into primary and secondary waste before
being incinerated on-site. Primary waste contains less than 15
percent water, and secondary waste contains greater than 15 percent
water. The following data are for primary waste.
Average
Concentration
Constituent (% by weight)
Acetone 10.8289
Acetonitrile 3.2735
Benzene ND
Bromodichloromethane ND
Bromoform ND
Bromomethane ND
Carbon disulfide ND
Carbon tetrachloride ND
Chlorobenzene 0.0015
Chlorodibromomethane ND
Chloroethane ND
2-Chloroethylvinylether ND
Chloroform 0.0889
Chloromethane ND
Cyclohexanone 0.1350
1,2-Dibromoethane ND
1,2-Dichlorobenzene ND
1,3-Dichlorobenzene ND
1,4-Dichlorobenzene ND
Dichlorodifluoromethane ND
ND = Not Detected
3-11
-------
Table 3-10 (Continued)
Constituent
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethylene
t-1,2-Dichloroethylene
1,2-Dichloroethylene
c-1,2-Dichloropropene
t-1,2-Dichloropropene
Ethyl acetate
Ethyl -benzene
Ethyl ether
Isobutanol
Methanol
Methylene chloride
Methyl ethyl ketone
Methyl isobutyl ketone
n-Butanol
Pyridine
1,1,2,2-Tetrachloroethane
1,1,2,2-Tetrachloroethylene
Toluene
1,1,1-Trichloroethane
1,1,2-Trichloroethane
1,1,2-Trichloroethylene
Trichlorofluoromethane
Trichlorotrifluoroethane
Vinyl chloride
Xylene
ND = Not Detected
Reference: Delisting petition number 559.
Average
Concentration
(% by weight)
0.0006
0.6628
0.0015
ND
0.0006
ND
ND
9.5240
0.0169
0.7256
0.0271
12.7553
4.4733
0.0518
0.1130
2.8430
<0.2500
0.1523
0.0029
4.0435
0.0029
0.4630
0.0010
ND
ND
ND
0.0697
3-12
-------
Table 3-11
Waste Description: Pharmaceutical manufacturing operations at this
facility involve chemical reactions which occur in solvents (F002,
F003, and F005). Both batch and continuous operations are performed.
Products are recovered from the solvent using crystallization,
filtration, and centrifugation. . Solvents and reaction by-products are
further treated by evaporation and/or fractionation to recover
solvents. The spent solvent waste is comprised of various still
bottoms and fractionator cuts from solvent recovery. The hazardous
liquid wastes are segregated into primary and secondary waste before
being incinerated on-site. Primary waste contains less than
15 percent water, and secondary waste contains greater than 15 percent
water. The following data are for secondary waste.
Constituent
Acetone
Acetonitrile
Benzene
Bromodichloromethane
Bromoform
Bromomethane
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chlorodibromomethane
Chloroethane
2-Chloroethylvinylether
Chloroform
Chloromethane
Cyclohexanone
1,2-Dibromoethane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Dichlorodifluoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethylene
t-1,2-Dichloroethylene
1,2-Dichloroethylene
c-1,2-Dichloropropene
t-l,2-Dichloropropene
Ethyl acetate
Average
Concentration
(% by weight)
2.1428
0.7550
ND
ND
ND
ND
ND
ND
0.0001
ND
ND
ND
0.0013
ND
0.0028
ND
ND
ND
ND
ND
0.00000625
0.0007
0.0001
ND
<0.00000625
ND
ND
0.1609
ND = Not Detected
3-13
-------
Table 3-11 (Continued)
Constituent
Ethylbenzene
Ethyl ether
Isobutanol
Methanol
Methylene chloride
Methyl ethyl ketone
Methyl isobutyl ketone
n-Butanol
Pyridihe
1,1,2,2-Tetrachloroethane
1,1,2,2-Tetrachloroethylene
Toluene
1,1,1-Trichloroethane
1,1,2-Trichloroethane
1,1,2-Trichloroethylene
Trichlorofluoromethane
Trichlorotrifluoroethane
Vinyl chloride
Xylene
Average
Cone ent ra t i on
(% by weight)
0.000015
0.0157
0.0413
0.6115
0.2361
0.0039
0.0028
0.0404
0.0078
0.0008
0.00000625
0.0854
0.0001
0.0004
0.00000625
ND
ND
ND
0.0001
ND = Not Detected
Reference: Delisting petition number 559.
3-14
-------
3.2.5 Paint Formulation
Waste characterization data for spent solvent wastes generated by the
paint formulation industry are presented in Tables 3-12 and 3-13.
Table 3-12
Waste Description: Wastewater stream from paint tank washing. The waste
contains sodium hydroxide and spent solvent (F003) from paint residue.
Concentration Detection Limit
Constituent (ug/L) (ug/L)
Bis(2-ethylhexyl)phthalate 27,953 NR
Ethylbenzene 6,336 MR
Phenol 20,009 MR
NR = Not Reported in data base
Reference: Development Document for Effluent Limitations Guidelines for
Paint Formulation Point Source Category.
Table 3-13
Waste Description: Spent paint thinner (F003 and F005).
Concentration
Constituent (% by weight)
Toluene 9.4
Isopropyl acetate 9.1
Ethanol 6.9
Methyl ethyl ketone 6.8
Acetone 3.8
Isopropanol 3.1
Butyl acetate 2.4
Methanol 3.0
Ethyl acetate 3.0
Xylene 2.8
Cellosolve acetate 1.6
n-Propanol 1.2
Ethylbenzene 1.2
Methyl isobutyl ketone 0.7
Other trace organics 2.9
Non-distillable constituents 42.1
Reference: Treatment and Recovery of Ignitables, Solvents, and Solvent
Bearing Wastes. Hazardous Waste Treatment Workshop #3,
April 9, 1984. Sample Number 820930.
3-15
-------
3.2.6 Dyes and Pigments Manufacturing
Waste characterization data for a spent solvent waste generated in
the dyes and pigments industry are presented in Table 3-14.
Table 3-14
Waste Description: Spent solvent waste (F003) from the production of
dyes and pigments.
Concentration
Constituent (% by weight)
Di/triester 0.01-0.1
Di/triester 0.01-0.1
Di/triester 0.01-0.1
Diphenyl ether 0.1-1
Biphenyl 0.1-1
Ethanol >50
Methanol 10-50
Reference: Industry Studies Database. Prepared for US EPA, Office of
Solid Waste, Waste Identification Branch, 1985.
3-16
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3.2.7 Organic Chemicals Manufacturing
Waste characterization data for spent solvent wastes generated by the
organic chemicals manufacturing industry are presented in Tables 3-15
through 3-19.
Table 3-15
ORGANIC CHEMICALS MANUFACTURING
Waste Description: Solvent waste containing pyridine (F005) is generated
at an organic chemical manufacturing plant which produces an organic
phosphate ester used as an additive in the preparation of flame
retardant, flexible polyurethane foams. The product is produced in a
three-step process using phosphorus trichloride and ethylene oxide as
starting materials. Chlorine, ethylene glycol, and hydrogen chloride
are introduced at intermediate stages of the process. Following a
chlorination step, the reaction intermediate undergoes esterification
to produce the crude product. The crude product is then refined and
stored. The solvent pyridine is used in the esterification step and is
later recovered by distillation for reuse in the production process, as
shown in Figure 3-2. The pyridine still bottoms are mixed with vent
scrubber water, residuals from product recovery processes, and other
plant wastewater before being pumped to biological treatment.
Concentration (ppm)
Month (1981) Pyridine
January 23
February 37
March 28
April 24
May 32
June 13
July 22
August Plant not operating
September 28
October 23
Reference: Delisting petition number 381.
3-17
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Raw
Materials
Pyridine
Solvent
Solvent
Recycle
Product
Synthesis
Product
Recovery
Products to
Storage
Caustic
Pyridine
Recovery
Distillation
Unit
Product Recovery
Residuals
Pyridine Recovery
Still Bottoms (F005)
Process
Wastewater
Biological
Treatment
Figure 3-2
ORGANIC PHOSPHATE ESTER PRODUCTION PROCESS
3-18
-------
Table 3-16
Waste Description: Spent solvent waste (P002) from the production of
isocyanate alkane.
Concentration
Constituent (% by weight)
Carbon tetrachloride <0.01
Chlorobenzene >50
Hydrochloric acid 1-10
Phosgene 1-10
Polymer <0.01
Trichloromethane <0.01
Reference: Industry Studies Database. Prepared for US EPA, Office of
Solid Waste, Waste Identification Branch, 1985.
Table 3-17
Waste Description: Spent solvent waste (F002) from the production of
diphenyl methane, isocyanate.
Concentration
Constituent (% by weight)
Carbon tetrachloride <0.01
Chlorobenzene >50
Hydrochloric acid <0.01
Phosgene 1-10
Polymer <0.01
Trichloromethane <0.01
Reference: Industry Studies Database. Prepared for US EPA, Office of
Solid Waste, Waste Identification Branch, 1985.
3-19
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Table 3-18
Waste Description: Spent solvent waste (F003) from the production of
alkenes.
Concentration
Constituent (% by weight)
Inorganic sulfide 0.1-1
Calcium chloride 1-10
Hydrochloric acid 1-10
Iron chloride 0.1-1
Methanol 1-10
Water >50
Reference: Industry Studies Database. Prepared for US EPA, Office of
Solid Waste, Waste Identification Branch, 1985.
Table 3-19
Waste Description: Spent solvent waste (F003) from the production of
aldehyde furan.
Concentration
Constituent (% by weight)
Acetic acid 1-10
Ethanol 10-50
Ethyl acetate 1-10
Furfural 1-10
Methanol 10-50
Water 10-50
Reference: Industry Studies Database. Prepared for US EPA, Office of
Solid Waste, Waste Identification Branch, 1985.
3-20
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3.2.8 Organic Pesticides Manufacturing
Waste characterization data for spent solvent wastes generated by the
organic pesticides manufacturing industry are presented in Tables 3-20
through 3-25. Toluene (F005) is listed as a constituent in four of the
following six data sets. The Industry Studies Data Base from which these
six data sets were obtained includes 40 waste streams from the organic
pesticide industry. Fifteen of these 40 waste streams listed toluene as
a constituent. Other constituents commonly occurring in spent solvent
waste streams from the pesticide industry are methanol (F003), methylene
chloride (F001), and xylene (F003). The 34 data sets which are not
included here did not list specific composition or concentrations of
spent solvents.
Table 3-20
Waste Description: Spent solvent waste (F003) from the production of
cyclic ester.
Cone entration
Constituent (% by weight)
Cyclic ester 10-50
Non-cyclic aliphatic alcohol 0.1-1
Ethyl acetate 10-50
Xylene 10-50
Reference: Industry Studies Database. Prepared for US EPA, Office of
Solid Waste, Waste Identification Branch, 1985.
Table 3-21
Waste Description: Spent solvent waste (F005) from the production of
phosphoroamidothioate.
Concentration
Constituent (% by weight)
Phosphoroamidothioates 1.1-11
Reaction/decomposition product #1 1-10
Reaction/decomposition product #2 0.1-1
Toluene >50
Reference: Industry Studies Database. Prepared for US EPA, Office of
Solid Waste, Waste Identification Branch, 1985.
3-21
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Table 3-22
Waste Description: Spent solvent still bottoms (F002) from a
distillation process in the production of phosphoroamidothioate.
Concentration
Constituent (% by. weight)
Cyano, nitrile alkane 1-10
Phosphoroamidothioate 1-10
Polymer 10-50
Reaction/decomposition product #1 1-10
Reaction/decomposition product #2 1-10
Reaction/decomposition product #3 1-10
Dimethyl sulfide 10-50
Dimethyl sulfate - 1-10
Methylene chloride 1-10
Toluene 0.1-1
Reference: Industry Studies Database. Prepared for US EPA, Office of
Solid Waste, Waste Identification Branch, 1985.
Table 3-23
Waste Description: Spent solvent waste (F003 and F005) from the
production of chloroimide.
Cone ent rat i on
Constituent (% by weight)
Dichloroalkane 1-10
Amide 1-10
Chloroimide <0.01
Methanol 10-50
Sodium chloride 0.1-1
Toluene >50
Reference: Industry Studies Database. Prepared for US EPA, Office of
Solid Waste, Waste Identification Branch, 1985.
3-22
-------
Table 3-24
Waste Description: Spent solvent solid residue (F005) from the
production of n-alkyl carbamate.
Cone ent rat ion
Constituent (% by weight)
n-Alkyl carbamate 10-50
Hydroxyl naphthalene 10-50
Toluene 10-50
Reference: Industry Studies Database. Prepared for US EPA, Office of
Solid Waste, Waste Identification Branch, 1985.
Table 3-25
Waste Description: Spent solvent waste (F005) from the production of
ketocarbamate.
Concentration
Constituent (% by weight)
Alkane, isocyanate 0.1-1
Ketocarbamate 10-50
Methyl ethyl ketone 10-50
Reference: Industry Studies Database. Prepared for US EPA, Office of
Solid Waste, Waste Identification Branch, 1985.
3-23
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3.2.9 Printing Industry
Waste characterization data for spent solvent wastes generated by the
printing industry are presented in Tables 3-26 and 3-27.
Table 3-26
Waste Description: Data presented are from a plastics facility which
performs decorative printing of polyvinyl chloride film which is used
primarily in the furniture industry. The printing solution is a 95
percent methyl ethyl ketone (F003) solvent containing pigment
suspension. Toluene (F005) is used as a solvent in vinyl coating
preparations. Cyclohexanone (F003) is used in minute guantities in
some products as a drying retardant ingredient in the coating
preparations. The plant operates a direct contact steam distillation
system to recover F003 and F005 solvents. Solvents are recovered from
waste printed polyvinyl chloride film, from waste cleanup solvent
(methyl ethyl ketone) used to clean printing eguipment, drums, and
containers, and from waste inks which cannot be reused. The waste
polyvinyl chloride is fed to the distillation system in granular form.
The solvent recovery bottoms on which the analysis is performed is
essentially polyvinyl chloride in granular form with printing ink
solids and cleanup solutions encapsulated in the polyvinyl chloride.
Concentration
Constituent (mg/L)
Arsenic 0.02
Barium 0.80
Cadmium 0.06
Chromium <0.10
Lead 2.40
Antimony 0.11
Zinc 1.50
Xylene <0.10
Cyclohexanone <0.10
Toluene 1.40
Methyl ethyl ketone 8.80
Methyl isobutyl ketone <0.10
Reference: Delisting petition number 0032.
3-24
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Table 3-27
Waste Description: Ink wash residual spent solvent waste (F003).
Concentration
Constituent (% by weight)
Ethyl acetate 30
Ethanol 21.5
Propyl acetate 8.1
Methanol 2.1
Isopropyl acetate 1.7
Isopropanol 1.4
Other trace organics 3.2
Non distiliable constituents 32.0
Reference: Treatment and Recovery of Ignitables, Solvents, and Solvent
Bearing Wastes. Hazardous Waste Treatment Workshop #3,
April 9, 1984, presented by Chemical Waste Management, Inc.
Sample Number 840169.
3-25
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3.2.10 Can Coating Industry
Waste characterization data for a spent solvent waste generated by
the can coating industry are presented in Table 3-28.
Table 3-28
Waste Description: Spent solvents are generated at a can assembly plant
from cleaning coating and ink residues (varnishes, lacquers and sealing
compounds) from applicators and machinery. Clean-up solvents include
methyl ethyl ketone (F005), toluene (F005), cellosolve acetate, butyl
cellosolve, mineral spirits, ethyl alcohol, and n-butyl alcohol (F003).
This plant cuts, decorates, assembles, and coats many different types
of cans. Figures 3-3, 3-4, 3-5, and 3-6 illustrate the processes
which generate spent cleanup solvents.- Clean-up solvents contain
coating residue from equipment cleaning. The coatings are composed of
non-hazardous food grade solids blended with various carrier solvents
(F003 and F005). The plant lists 24 different coatings and the primary
carrier solvent constituents. The following analysis gives the
approximate quantities of carrier solvents that would be contained in
an "average" blend of coating residues.
Concentration
Constituent (% by weight)
Xylene 6.7
Cellosolve acetate 4.4
n-Butyl alcohol 3.9
Butyl cellosolve 3.6
Mineral spirits 2.9
Methyl isobutyl ketone 1.5
Methyl ethyl ketone 1.3
Hexane 1.2
Isopropyl alcohol 1.0
Diacetone alcohol 0.8
Reference: Delisting petition number 597.
3-26
-------
Presses
Cleanup Solvents w/
Coating Residues
Cleanup Solvents w/
Varnish Residues
Spent Cleanup
Solvents (F003
and F005)
Temporary
Storage
Figure 3-3
LITHO PRESSING OF THREE PIECE CANS
3-27
-------
Cupper
(Cut i Draw)
Bodymaker
iRedraw & Iron)
Waste
Lubricating
Oil
Temporary
Storage
Can Washer
Can Decorator
Varnish
Applicator
Curing Oven
Cleanup Solvent w/
Varnish Residue
Coatiig SorayLnz
Cleanup w/
Solvent
Residue
ilven
Spent Cleanup
So 1 vents
(FOOT md "0051
Temporarv
i c o r a e e
Figure 3-4
PRODUCTION OF TWO PIECE CAN BODIES
3-28
-------
Sheet Feed
Scroll Shear
End Presses
Cleanup Solvents w/
End Sealing Compound
Residues (F003 and F005)
Conversion
Presses
In-Plant
Storage
Figure 3-5
PRESSING OF CAN ENDS
3-29
-------
Assembly of
Soldered Cans
Assembly of
'Velded Cans
Cleanup Solvents w/
Side Stripe Residues
Cleanup Solvents w/
Coating Residues
Spent Cleanup
Solvents (F003
and F005)
Cleanup Solvents w/
.Coating Residues
Temporary
Storage
Figure 3-6
ASSEMBLY OF THREE PIECE CANS
3-30
-------
3.2.11 Membrane Production Industry
Waste characterization data for a spent solvent generated by the
membrane production industry are presented in Table 3-29.
Table 3-29
Waste Description: Presented are characteristics of waste generated by a
plant which manufactures and markets membranes for precision separation
for the Pharmaceuticals, microelectronics, and health care industries.
The raw wastewater stream contains spent solvents (P003). This data
set was presented in an article on the performance of an activated
sludge treatment system designed to treat this waste. Based upon the
results of a pilot study and the projected waste load, a full-scale
pretreatment system was designed and constructed.
Constituent Concentration (mg/L)*
Methanol 180-2,900 (1,140)
Ethanol 240-4,400 (1,458)
Butanol 190-2,000 (958)
Acetone 49-2,700 (571)
Dimethylacetamide 5-200 (80)
Dimethylsolf oxide «10)
Dimethylformamide <3-190 (23)
Influent solvents (total) 1,900-10,900 (4,230)
Influent COD 3,100-10,000 (6,700)
*Average values are presented in parentheses.
Reference: Marston, Kurt B. and Franklin E. Woodard. "Treatment of High
Strength Wastewater Containing Organic Solvents". Purdue
Industrial Waste Conference, Vol. 39. 1985.
3-31
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REFERENCES
1. Chemical Waste Management, Inc. "Treatment and Recovery of Ignitables,
Solvents and Solvent-Bear Wastes." Hazardous Waste Treatment Workshop
#3, EPA Communication. April 9, 1984.
2. U.S. Environmental Protection Agency. Proposed Development Document
for Effluent Limitations Guidelines for Paint Formulating Point Source
Category. EPA 400/1-79/049-b.
3. Marston, Kurt R. and Franklin E. Woodard. "Treatment of High Strength
Wastewater Containing Organic Solvents." Purdue Industrial Waste
Conference, Vol. 39. 1985.
4. Industry Studies Data Base. Prepared for U.S. EPA, Office of Solid
Waste, Waste Identification Branch. 1985.
5. Delisting Petition 0032, Intex Plastics, Inc., Corinth, MS.
6. Delisting Petition 0254, Celanese Fibers, Narrows, VA.
7. Delisting Petition 0381, Olin Chemicals Group, Lake Charles, LA.
8. Delisting Petition 0476, CE Cast Industrial Products, Muse, PA.
9. Delisting Petition 0488, Stanley Furniture Company, Stanleytown, VA.
10. Delisting Petition 0559, Eli Lilly and Company, Clinton, IN.
11. Delisting Petition 0597, Continental Can Company, Milwaukee, WI.
3-32
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4. DEMONSTRATED TREATMENT TECHNOLOGIES
4.1 Introduction
Treatment technologies that are demonstrated for F001-F005 spent
solvent wastes are discussed in this section. Five treatment
technologies demonstrated for wastewaters containing F001-F005 spent
solvents are carbon adsorption, distillation (steam stripping),
biological treatment, wet air oxidation and air stripping. Carbon
adsorption is discussed in Section 4.2; distillation is discussed in
Section 4.3, biological treatment is discussed in Section 4.4, wet air
oxidation is discussed in Section 4.6 and air stripping is discussed in
Section 4.7. Three technologies demonstrated for non-wastewater spent
solvent wastes are distillation, incineration and fuel substitution.
Incineration is discussed in Section 4.5 and fuel substitution is
discussed in Section 4.8. Incineration and fuel substitution are not
demonstrated for wastewaters containing F001-F005 spent solvents.
4.2 Carbon Adsorption
4.2.1 Applicability
This technology is demonstrated for the F001-F005 spent solvent
wastewater. For purposes of the F001-F005 spent solvent rulemaking,
wastewaters contain by definition less than one percent total organic
carbon (TOG). EPA analyzed full-scale carbon adsorption treatment
performance data from four plants and pilot-scale data from two plants.
At one of these full-scale plants, carbon adsorption is used after
biological treatment. The Agency obtained data on chlorobenzene,
1,2-dichlorobenzene, methylene chloride, nitrobenzene, toluene, and
trichloroethylene from this facility. At another full-scale plant,
carbon adsorption follows steam stripping. The Agency obtained data on
nitrobenzene and toluene from this facility. In the third case, EPA has
full-scale data from a plant in the pesticides industry which generates
wastewater containing cresols. EPA has full-scale data for process
wastewater containing cresol at the fourth plant. Pilot-scale data for
trichloroethylene are available on treatment of contaminated drinking
water. Pilot-scale data are also available for methylene chloride,
toluene, and xylene on treatment of runoff water from a waste disposal
site. The Agency believes that these data represent treatment of wastes
which are similar to wastes that will be subject to this rule. The data
are presented in Section 5 of this document. This section also discusses
the use of data relative to the development of the treatment standards.
Activated carbon adsorption is a widely recognized technology for the
removal of organic compounds from wastewaters. The concentrations of
4-1
-------
organics which can be effectively removed vary widely depending on the
overall chemical and physical characteristics of the wastewater.
Literature citations for treatment applicability range from several
hundred parts per million to five percent organic content in the
wastewater. For treatment effectiveness of spent solvent wastewaters not
similar to those evaluated in Section 5 of this document, facilities need
to conduct bench- and pilot-scale evaluations as discussed in subsections
4.2.5 and 4.2.6. They should also review the "underlying principle"
section and the section on design and operating parameters affecting
performance for identification of other factors that should be considered
in applying this technology to a particular wastewater.
The underlying principles of operation for carbon adsorption are
presented in subsection 4.2.2. A description of activated carbon
adsorption is presented in subsection 4.2.3. Parameters which affect the
performance of activated carbon adsorption are presented in
subsection 4.2.4. Bench-scale and pilot-scale tests commonly used to
determine design and operating parameters for treatment of a specific
waste are discussed in subsections 4.2.5 and 4.2.6, respectively.
4.2.2 Underlying Principles of Operation
Adsorption is the collection and concentration of a molecule onto a
solid surface from a liquid or gas. The activated carbon selectively
adsorbs hazardous constituents by surface attraction within the internal
pores of the carbon granules. The principal factor which affects carbon
adsorption is the chemical affinity between the carbon and the organic
compound. Other characteristics such as solubility, temperature and pH
also influence the effectiveness of carbon adsorption.
The rate o£ adsorption is dependent upon three distinct steps:
transport, diffusion and binding. The first step is transport of the
constituent to be removed from the solvent waste solution through a
surface film to the exterior of the carbon. Second, the constituent
molecule to be removed must diffuse into the pores of the activated
carbon. This step is very important since most of the active surface
area for activated carbons used in wastewater treatment occurs within the
particle pores. The final step is the physical or chemical binding of
the constituent of concern to the surface of the activated carbon.
The effectiveness of adsorption generally improves with increasing
contact time. Exceptions to this rule include chemical compounds which
are not preferentially adsorbed onto the carbon surface. These compounds
can be desorbed from adsorption sites in favor of compounds that have a
higher affinity for the carbon.
4-2
-------
Typically, the wastewater to be treated is passed downward through a
stationary bed of carbon. The constituent to be removed is adsorbed most
rapidly and effectively by the upper few layers of fresh carbon during
the initial stages of operation. These upper layers are in contact with
the wastewater at its highest concentration level. The small amounts of
the constituent to be removed which escape adsorption in the first few
layers of the activated carbon are then removed from solution in the
lower or down stream portion of the bed. Initially, none of the
constituent to be removed escapes from the adsorbent.
As the waste stream continues to flow into the bed, the top layers of
carbon become saturated with the constituent being removed and less
effective for further adsorption. As the adsorption zone moves downward,
more and more of the constituent to be removed escapes in the effluent.
As the adsorption zone moves downward to the end of the bed, the
concentrations in the effluent increase rapidly approaching the influent
concentration. This point in the operation is referred to as
breakthrough. A breakthrough curve is the plot of the ratio of effluent
to influent concentrations versus time of operation. This curve shows
how the ratio of effluent to influent concentrations increases as the
adsorption zone moves through the column (See Figure 4-1). Breakthrough
on this curve represents the point in operation where all of the carbon
in the column is in equilibrium with the influent water and beyond which
little additional removal of the constituent will occur. At this stage
of operation, the spent carbon is either replaced or reactivated. The
time to reach breakthrough is generally decreased by increased particle
size of the carbon, increased concentration of the constituent to be
removed in the influent, increased pH of the water, increased flow rate,
and decreased bed depth. In application, breakthrough is determined by
measuring the effluent concentration of the constituent of concern. In
situations where the constituent can not be measured directly by
continuous monitoring instruments, an operating curve determined by
initial pilot-scale calibration of the adsorption system is used to
predict breakthrough (see Section 4.2.6 for discussion of pilot-scale
testing).
4.2.3 Description of Activated Carbon Manufacture and Carbon
Regeneration
(1) Activated Carbon Manufacture. Wastewater treatment by activated
carbon adsorption utilizes specially prepared carbon granules or
powder^ to adsorb and thereby remove organic contaminants from the
wastewater. The term "activated carbon" refers to any amorphous form of
carbon that has been treated to increase the surface area to volume ratio
of the carbon.
•'•This section addresses the use of granular carbon only.
4-3
-------
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-------
Activated carbon is derived from virtually any carbonaceous material
including wood, coal, coke, peat, lignin, nut shells, sugar cane pulp,
sawdust, lignite, bone, and petroleum residues. Pores are formed on the
carbon surface during activation processes by burning away carbon
layers. The surface area of the carbon is greatly increased through the
formation of the surface porosity.
In general, carbon used in wastewater treatment is activated through
thermal activation processing. There are three steps involved in the
thermal activation process: dehydration, carbonization, and activation.
Dehydration of the starting material is accomplished by heating at
temperatures of up to 170°C. Carbonization converts the organic material
to primary carbon and occurs as the temperature is increased above
170°C. In this step, the material is degraded, releasing CO, CQ>2>
acetic acid, methanol, and tar. When the temperature reaches 400 to
600°C, the organic material has been converted to approximately
80 percent primary carbon. High temperature steam (750 to 950°C) is
generally used to activate the carbon by exposing and widening pores
plugged by tars and other decomposition products.
(2) Carbon Regeneration. The most common method of carbon
regeneration is thermal regeneration. This process is performed in a
multiple hearth furnace or a rotary kiln at temperatures of approximately
850°C. The carbon can be regenerated with minimal carbon losses. Virgin
carbon is added to replace that which is lost through the regeneration
process. Other regeneration processes, termed "nondestructive
processes," include treating the spent carbon with chemicals (e.g., acids
and alkali), hot water or steam. There is a loss of performance with
each regeneration step; therefore, the activity is never restored to its
original level. The number of times that the carbon can be regenerated
is determined by the extent of physical erosion and the loss of
adsorptive capacity. Isotherm tests on the regenerated carbon can be
used to determine adsorptive capacity, thereby aiding in the prediction
of the number of times the carbon can be regenerated.
Environmental emissions can result from the carbon regeneration
processes. For example, if carbon is regenerated by high temperature
heating in a multiple hearth furnace or a rotary kiln, aqueous wastes can
be generated from wet air pollution control devices on the furnace or
kiln stack. Aqueous wastes can also be generated from nondestructive
carbon regeneration processes. The aqueous wastes from regeneration may
require further treatment prior to discharge or disposal. For carbon
adsorption of very toxic or hazardous materials, the carbon may be
incinerated or disposed rather than regenerated.
4-5
-------
4.2.4 Design and Operating Parameters Affecting Performance
There are a number of design and operating parameters which must be
considered in the selection of an effective carbon adsorption system to
treat a specific waste. An integral part of the design usually includes
the process bench-scale or pilot-scale evaluation of these parameters.
Further description of bench-scale tests and pilot-scale tesing are
presented in subsections 5 and 6, respectively.
(1) Design parameters. The design parameters to consider include
carbon properties, equipment configuration, contact time, and hydraulic
loading. As contact time and hydraulic loading are also the key
operating parameters, these parameters are discussed below under
operating parameters.
(a) Carbon properties. When applying carbon adsorption
technology, there are several properties of the activated carbon which
must be considered to ensure that adequate system performance is
achieved. The properties include surface area, pore size, particle size,
the iodine number, and the hardness number.
(i) Surface area. Because adsorption occurs on the surface
of the carbon, highly porous or permeable carbon is used. Typical
particle surface area to mass ratios range from 500 to 1,400 square
meters per gram (Reference 4). The total surface area of a particle is
dependent upon pore size and to a lesser extent, particle size.
(ii) Pore size. The optimal pore size for a specific
application is dependent upon the sizes of the waste constituent
molecules that the column is designed to adsorb. The greatest binding
force occurs when the molecule size and the pore size are equal.
Exceptions to this rule include wastes having high solvent concentrations
where slightly larger pores are most efficient (pores quickly fill with
the constituent to be removed making them too small for further
adsorption).
(Hi) Particle size. Activation of carbon is performed to
increase the surface area to volume ratio. As the particle size
diminishes, more of the internal pore surface area is exposed and
available for adsorption. This increased area affects the rate of
adsorption rather than the adsorptive capacity because all of the pore
volume is eventually used regardless of the surface area. This occurs
because the constituents diffuse throughout the particle. As a practical
matter, selection of particle size is limited because very small
particles can be carried out of the bed by the fluid stream. Very small
particles do not readily settle from the effluent.
4-6
-------
(iv) Iodine number. The iodine number is defined as the
ratio of the mass (in milligrams) of iodine adsorbed by one gram of
activated carbon when the iodine concentration of the effluent filtrate
reaches 0.02N in a bench-scale test. This number correlates to the
capacity of a specific carbon to adsorb iodine (molecular weight 254).
The test is useful to evaluate the adsorptive capacity of low molecular
weight organics.
(v) Hardness Number. The hardness number is a measure of a
specific carbon's resistance to degradation. This value is derived from
a bench-scale test and used to indicate the carbon's ability to withstand
repeated regeneration cycles and the physical stresses encountered during
operation without damage to the adsorption surface.
(b) Column Configuration. Column configuration can also be an
important consideration in the performance of an adsorption treatment
system. Granular activated carbon systems can be operated as fixed bed
(downflow) or moving or expanded bed (upflow) systems.
(i) Fixed bed. Fixed bed adsorbers operate in a downflow
direction. Downflow operation acts to filter suspended solids from the
influent wastewater. However, solids filtered by the carbon bed result
in pressure drop build-up and must be periodically removed by backwashing
the bed. Backwash water may require treatment prior to disposal. Most
fixed bed carbon adsorption columns must be taken off-line for carbon
regeneration. To keep adequate carbon capacity on-line, fixed bed
processes may use two carbon columns, one on-line for treatment, and one
off-line undergoing carbon regeneration. For large flow rates, columns
can be placed in parallel and rotated as they become exhausted. Several
columns can also be placed in series so that carbon exhaustion in one
column will not significantly affect the quality of the overall
effluent. Also, this series configuration can be used to improve
treatment performance by designing each column to selectively adsorb
different organic compounds. Since fixed-bed carbon columns are not
replenished, they do not achieve steady state operation, and, thus, the
effluent concentration is continually changing.
(ii) Moving bed. In a moving bed system, the carbon
adsorbent continuously moves down the column and is drawn off at the
bottom of the column for regeneration (Figure 4-2). Virgin or
regenerated carbon enters the column at the top. These units operate
with approximately 10 percent void space between the particles to allow
movement of the particles.
4-7
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Virgin and
Regenerated
Carbon
Influent
Waste
Effluent
Moving Bed
Carbon
Adsorber
Carbon
Effluent
Waste
Influent
Figure 4-2
Moving Bed
Carbon Adsorption
4-8
-------
The moving bed systems do not have the ability to filter suspended
solids because the void space allows the solids to flow through the
column. Thus, solids will not be removed from the wastewater in this
mode of operation. Wastewaters containing suspended solids should be
filtered or clarified prior to carbon treatment in upflow systems to
prevent discharge of solids in the treatment effluent. As discussed
under "fixed bed," moving bed systems can also be run in series with
different carbon beds to remove compounds with different adsorption
characteristics.
(c) Flow distribution. Uniform flow distribution over the
carbon bed insures maximal contact between the waste and the carbon and
results in effective constituent removal. Non-uniform flow distribution
can occur from a number of phenomena such as channelling or flooding.
These occur from improper design of the column or packing and will vastly
reduce the surface area available for adsorption and column capacity.
Channelling, where an uneven carbon distribution results in the fluid
bypassing a portion of the carbon bed, produces an effluent that exceeds
the desired composition. Uniform flow distribution is achieved in the
design through proper selection of the flow distribution mechanisms
including incoming fluid distribution devices (e.g., rings, plates, or
nozzles), carbon loading procedures, and bed support materials.
(2) Operating Parameters. Operating parameters include several
related variables such as carbon bed volume, contact time, hydraulic
loading, temperature, and pH.
(a) Carbon bed volume. A fixed contact time at a given
hydraulic loading establishes the minimum required bed volume. Excess
bed volume can be provided to increase the time between regeneration
cycles. The bed size is optimized by balancing costs associated with
pumping reguirements against the frequency and associated costs of carbon
regeneration.
(b) Contact time. A minimum contact time is required to obtain
a desired effluent concentration for a fixed hydraulic loading.
Insufficient contact time can result in poor treatment performance.
(c) Hydraulic loading. Hydraulic loading directly affects the
rate and efficiency of adsorption. For a fixed bed volume, an increase
in flow rate increases the rate of adsorption while the contact time is
reduced. At too high a flow rate, the contact time is inadequate and
adsorbate removal is adversely affected. At very low flows, the mass
transfer becomes diffusion-limited, and the mass transfer rate is so
adversely affected that the adsorbate removal is not complete. Thus, the
4-9
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flow rate is selected to avoid the above ranges of poor operation. The
optimization of flow is a function of bed geometry (cross-sectional area
and bed height) and required treatment rate.
(d) Temperature. In general, since adsorption reactions are
exothermic, lower temperatures should favor adsorption (Reference 3).
The effects of operating temperature are investigated during bench-scale
testing.
(e) pH. The effect of pH on adsorbability can vary
significantly from compound to compound. Adsorption is most effective at
the pH which imparts the least polarity to the molecules. A weak acid,
such as phenol, is adsorbed best at low pH values. For amines (a weak
base) adsorption favors higher pH values (Reference 3).
4.2.5 Bench-Scale Testing
Bench-scale tests can be a valuable tool in determining the
applicability of different carbons for adsorption of specific
constituents from a given waste stream.
Adsorptive capacity is measured by the adsorption isotherm of the
waste stream. An isotherm is a graph relating the amount of solute
adsorbed at a given temperature to the mass of carbon used for the
adsorption. The plot is usually derived from bench-scale tests where
premeasured amounts of activated carbon are placed in a measured amount
of the wastewater at a constant temperature for a specified period of
time. By measuring contaminant concentration in solution before and
after treatment, the amount which has been adsorbed can be determined.
Plots are generated from several test points taken at the same
temperature. Operating parameters can be varied in generation of each
test point, e.g., plots generated at various temperatures or pH.
Isotherm plots are usually fitted with a smooth curve using the
Freundlich Equation which describes the adsorbability characteristics of
a constituent for a given carbon. The equation is usually written as
follows:
X/m = KC1/n
where, X = amount of contaminant adsorbed, mg
m = weight of carbon, kg
C = equilibrium concentration of contaminant left in
solution, ppm
K = empirical constant, dimensionless
n = empirical constant, dimensionless
4-10
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Plotting the log of the Freundlich Equation will generate a straight
line with 1/n representing the slope. The constant "K" is a measurement
of relative adsorption capacity. A large value of "K" indicates high
carbon adsorptivity (Reference 4). The value "n" is a measure of the
effects of concentration on adsorption capacity. Typical carbon
adsorption isotherms are shown in Figure 4-3 for two different types of
carbon. Isotherms obtained under identical conditions using the same
test solutions for two test carbons can be compared to reveal the
relative effectiveness of the carbons.
4.2.6 Pilot-Scale Testing
Although the treatability of a particular wastewater by activated
carbon adsorption and the relative capacity of different types of
activated carbon for treatment may be estimated from adsorption
isotherms, activated carbon performance and design criteria are best
determined by pilot-scale tests. Adsorption isotherms are determined in
a batch test, but the treatment of wastewaters by granular activated
carbon most often is accomplished in a continuous system involving packed
beds. Pilot-scale tests provide more accurate estimates of the actual
performance of a full-scale unit.
Pilot-scale granular activated carbon column tests are performed for
the purpose of obtaining design data for full-scale plant construction.
Pilot-scale column tests allow a wide range of testing necessary to
establish the design of a full-scale plant including the following:
compare the performance of different carbon types under the same dynamic
flow conditions; determine the minimum contact time required to produce
the desired quality of carbon column effluent can be; verify the
manufacturer's data for pressure drop at various flow rates through
different bed depths; verify the backwash flow rate necessary to expand
the carbon bed for cleaning purposes; establish the carbon bed volume
required which will also determine the necessary capacity of the carbon
regeneration furnaces and auxiliaries; the effect of various methods of
pretreatment (influent water quality) upon carbon column performance,
carbon dosage and overall plant costs; evaluate the practical advantages
and disadvantages for alternatives such as use of upflow or downflow
carbon columns or the particle size of carbon to be used. In all of the
pilot-scale plant tests, the pH and temperature should be observed to be
certain that they correspond to the values for the full-scale plant
operation, since their values are influential to proper operation of the
activated carbon adsorption unit.
4-11
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O>
JC
D>
E
x £
Carbon A
Slope = —
Carbon B
Concentration, C (ppm)
Key:
Freundlich Equation
j_
x/m=KC n
x = Amount of Waste Constituent Adsorbed, mg
m = Weight of Carbon, kg
C = Concentration of Waste Constituent Left in Solution, ppm
K = Empirical Constant, Dimensionless
n = Empirical Constant, Dimensionless
Figure 4-3
Isotherms for Carbon Adsorption
4-12
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CARBON ADSORPTION REFERENCES
1. Perry, Robert H. and Cecil H. Chilton. Chemical Engineer's Handbook,
5th ed. McGraw-Hill Book Company, New York. 1973.
2.. U.S. EPA. Process Design Manual for Carbon Adsorption. Contract
Number EPA 625/l-71-002a, October 1973.
3. Liptak, Bela G. Environmental Engineers' Handbook, Volume 1; Water
Pollution. Chilton Book Company, Radnor, Pennsylvania. 1974.
4. McCabe, Warren L., Julian C. Smith, and Peter Harriott. Unit
Operations of Chemical Engineering, 4th ed. McGraw-Hill Book
Company, New York, 1985.
5. Montgomery, James W., Consulting Engineers, Inc. Water Treatment
Principles and Design, John Wiley & Sons, New York. 1985.
6. Weber, Walter J., Jr. Physiochemical Processes for Water Quality
Control. Wiley-Interscience, New York. 1972.
4-13
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4.3 Distillation
This subsection presents a general discussion of four types of
distillation systems used to treat F001-F005 spent solvent wastes. These
are steam stripping, batch distillation, thin film evaporation, and
fractionation. There is a section for each technology that contains a
discussion of the applicability of the technology to F001-F005 spent
solvent wastes, a discussion of the underlying principles of operation, a
description of the technology, and finally a discussion of the design and
operating parameters affecting performance.
4.3.1 Steam Stripping
(1) Applicability. Steam stripping is a demonstrated technology for
wastewaters containing the F001-F005 spent solvent wastes. The Agency
has full-scale steam stripping treatment performance data from 4 plants
and pilot-scale data on treatment of contaminated ground water. The full
scale data represent treatment of F001-F005 spent solvent wastewater at
one plant; the remaining three plants were treating wastewater containing
F001-F005 constituents generated as process contaminants. The Agency
believes that these data represent treatment of wastes which are similar
to wastes that will be subject to this rule. The Agency analyzed steam
stripping data on ethylbenzene, methylene chloride, methyl isobutyl
ketone, nitrobenzene, toluene, 1,1,1-trichloroethane, and
trichloroethylene. These data are presented in Section 5 of this
document.
Steam stripping is a widely recognized technology for the removal of
organic compounds from wastewaters. The concentrations of organics which
can be effectively removed vary widely depending on the overall chemical
and physical characteristics of the wastewater. Literature citations for
treatment applicability range from several parts per million to one
percent organic content in the wastewater. For treatment effectiveness
of spent solvent wastewaters not similar to those evaluated in Section 5
of this document, facilities need to conduct bench- and pilot-scale
evaluations. They should also review the "underlying principles of
operation" section and the section on "design and operating parameters
affecting performance" for identification of other factors that should be
considered in applying this technology to a particular wastewater.
(2) Underlying Principles of Operation.
(a) General. Distillation is broadly defined as the separation of
more volatile materials from less volatile materials by a process of
vaporization and condensation. Distillation involves application of heat
4-14
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to a liquid mixture to vaporize part of the mixture and subsequent
removal of heat from the vaporized portion. The resultant condensed
liquid, the distillate (overhead), is richer in the more volatile
components and the residual unvaporized bottoms are richer in the less
volatile components.
Central to the concept of distillation is the phenomena of
vapor-liquid equilibium which is the relationship between the composition
of the vapor phase and the composition of the liquid phase. When a
liquid mixture of two or more components is brought to the boiling point
of the mixture, a vapor phase is created above the liquid phase. The
composition of the vapor phase is different from the composition of the
liquid phase and is a function of the concentrations of the constituents
in the liquid phase and the vapor pressures that the pure components
would exhibit at the temperature corresponding to the boiling point of
the mixture. If the vapor pressures of the pure components are different
(which is usually the case), then the consituent(s) having the higher
vapor pressure will be more concentrated in the vapor phase than the
constituent(s) having the lower vapor pressure. If the vapor phase above
the liquid phase were cooled to yield a liquid called the condensate a
partial separation of the constituents would result. The degree of
separation would depend on the relative differences in the vapor
pressures of the constituents; the larger the difference in the vapor
pressures, the larger the separation.
However, unless the difference between the vapor pressures is
extremely large, a single separation cycle or single equilibrium stage of
vaporization and condensation would not achieve a significant separation
of the constituents. In order to achieve greater separations multiple
equilibrium stages are used. In practice, the multiple equilibrium
stages are obtained by stacking trays or packing into a column. The
vapor phase from a tray rises to the tray above it and the liquid phase
falls to the tray below it. In simplistic terms, each tray represents
one equilibium stage. In a packed distillation column, the individual
equilibrium stages are not discernible, but the number of equilivalent
trays can be calculated from mathematical relationships.
To facilitate distillation calculations, the vapor liquid equilibrium
is expressed as relative volatility or the ratio of the vapor to liquid
concentration for a constituent divided by the ratio of the vapor to
liquid concentration of the other constituent. The relative volatility
is a direct measure of the ease of separation. If the numerical value is
1, then separation is impossible because the constituents have the same
concentrations in the vapor and liquid phases. Separation by
distillation becomes easier as the value of the relative volatility
becomes increasingly greater than unity.
4-15
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With some combinations of constituents an azeotropic condition can be
reached during distillation. An azeotrope is defined as a mixture that
will vaporize continuously without change in composition, i.e. without
separation of the constituents. Thus, such a system is called a constant
boiling mixture. Usually, the azeotrope exists over a limited range of
concentration for the constituents so that separation of the constituents
can be made until the composition of the liquid in the still reaches the
azeotropic concentration range.
Distillation processes can be classified into three general
categories, simple or batch distillation, stripping, and fractionation.
The differences between these three categories can best be explained by
the basic steps that take place in the distillation process. These steps
are summarized below and discussed in greater detail under the sections
for the individual distillation technologies.
In the batch distillation process, the mixture is vaporized in the
boiler and the vapor is cooled and condensed to a liquid in a condenser.
Since the batch distillation process uses only one equilibrium stage the
degree of separation is very limited unless there is a great difference
in the relative volatilities.
The stripping process uses multiple equilibrium stages with the
initial waste mixture entering the uppermost equilibrium stage. The
boiler is located below the lowermost equilibrium stage so that vapor
generated moves upward in the column coming into contact with the falling
liquid. As the vapor comes into contact with the liquid at each stage,
the more volatile components are stripped from the liquid by the vapor
phase, thus giving the process the name stripper. The concentration of
the emerging vapor is slightly enriched (as it is in equilibrium with the
incoming liquid), but the bottoms in the boiler are considerably
concentrated in the lower vapor pressure constituent. The process of
stripping is very effective for wastewaters where the relative
volatilities are large.
The fractionation process uses multiple equilibrium stages with the
initial waste feed entering the column at a point between the first and
last equilibrium stages. The stages at and below the point of entry are
called the stripping section because the stages function as described
above under the stripping process. The stages located above the point of
feed are called the rectification section. These additional stages allow
the vapor to become further enriched in the volatile components compared
to incoming feed. A portion of the condensed vapor is returned as liquid
to the uppermost stage to aid in rectification. This step of returning a
portion of the condensed vapor to the column is called reflux.
4-16
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(b) Steam Stripping. The underlying principle for steam
stripping is the same as described above for a stripper except that steam
(introduced directly at the bottom of the stripping section or generated
from the wastewater through indirect heating in the boiler) is used to
strip the organic volatiles from the wastewater. The water effluent from
the bottom of a well designed and operated unit is considerably reduced
in organic content and usually can be discharged in compliance with NPDES
requirements or municipal treatment standards. The vapors at the top of
the column containing steam and organics are condensed. Organics in the
condensate which form a separate phase in water can be physically
separated. Depending upon the concentration of soluble organics in the
remaining condensate, it is either recycled to the stripper, disposed, or
treated further with another technology (e.g. biological treatment).
(3) Description of Steam Stripping. A steam stripping unit consists
of a boiler, a stripping section, a condenser and a product receiver.
Figure 4-4 is a schematic showing the major components of a steam
stripper. The boiler is a device that provides the heat required to
vaporize the liquid fraction of the waste. The stripping section is
composed of a set of trays or packing in a vertical column. The feed
enters at the top of the stripping section. In the stripping section,
vapor rising from the boiler is contacted with the downflowing liquid
feed. Through this contacting, the lower boiling point constituents are
concentrated in the vapor. The rising vapor is collected at the top of
the column, cooled and condensed. The cooled liquid product stream is
then routed to a product receiver.
(4) Design and Operating Parameters Affecting Performance. Unlike
the other distillation processes discussed below, steam stripping is not
generally designed and operated from a perspective of product recovery
but rather for the purpose of removing contaminants from wastewater to
comply with NPDES requirements or municipal treatment standards.
There are a number of design and operating parameters which must be
considered in the selection of an effective steam stripping system to
treat a specific waste.
(a) Design Parameters. The design parameters to consider
include: vapor liquid equilibrium data (required to determine the number
of equilibrium stages and the liquid and vapor flow rates), column
temperature and pressure, column internals and condenser temperature.
4-17
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Waste
Influent
Vent of
Non-Condensed Vapors
Condenser
Stripped
Effluent
Receiver
Figure 4-4
Steam Stripping
4-18
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(i) Vapor Liquid Equilibrium Data. The vapor liquid
equilibrium data are determined in laboratory tests unless already
available. The use of these data are required for several reasons.
First, they are used to calculate the number of theoretical stages
required to achieve the desired separation. Using the theoretical number
of stages, the actual number of stages can then be determined through the
use of empirical tray efficiency data supplied by an equipment
manufacturer (refer to column internals discussion below).
Secondly, the vapor liquid equilibrium data are used to determine the
liquid and vapor flow rates that ensure sufficient contact between the
liquid and vapor streams. These rates are in turn used to determine the
column diameter.
(ii) Column Temperature and Pressure. These parameters are
integrally related to the vapor liquid equilibrium conditions. The
design column temperature is calculated by developing an enthalpy (heat)
balance around the steam stripping unit, accounting for the heat removed
in the condenser, heat input in the feed, heat input from steam injectors
and heat loss from the column. Column pressure influences the boiling
point of the liquid. For example, the column temperature required to
achieve the desired separation can be reduced by operating the system
under vacuum. These parameters are also critical to operation of the
system and will be discussed in the following section, operating
parameters.
(iii) Column internals. Column internals are designed to
accommodate the physical and chemical properties of the wastewater to be
stripped. Two types of internals may be used in steam stripping: trays
or packing. Tray types include bubble cap, sieve, valve and turbo-grid.
Trays have several advantages over packing. Trays are less susceptible
to blockage by solids or polymerization products, they have a lower
capital cost for large diameter columns (greater than or equal to 3
feet), and they accommodate a wider range of liquid and vapor flow
rates. A comparison of various tray types can be found in the Chemical
Engineer's Handbook (3) and Distillation Design in Practice (5). Packing
types include raschig rings, pall rings, saddles and sulzer-structures.
Compared to trays, packing has the advantages of having a lower pressure
drop per theoretical stage, being more resistant to corrosive materials,
having a lower capital cost for small diameter column (less than 3 feet),
and finally being less susceptible to foaming because of a more uniform
flow distribution. A comparison of various packing types can be found in
the Chemical Engineer's Handbook (3) and Distillation Design in Practice
(5).
4-19
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As indicated above, the different types of trays and packing have
associated with them different separation efficiencies. Efficiency needs
to be accounted for in determining the actual number of trays or height
of packing required. Efficiency data can be supplied by the manufacturer.
(iv) Condenser Temperature. The condenser temperature is
calculated in the design to ensure that the overhead product recovery
rate is maximized and emissions from the condenser venting are
minimized. In practice, the design condenser temperature is achieved by
balancing the size of the condenser with the cooling or chilled water
throughput.
(b) Operating Parameters. The parameter that requires control
to ensure that the steam stripper is properly operated is the temperature
at the top of column before the vapor exits to the condenser (the
uppermost stage). There are a number of operating parameters that can be
adjusted to maintain the design specification for temperature. These
include condenser temperature, column pressure, steam rate and feed rate.
From the perspective of minimizing air emissions it is important to
control the temperature of the liquid leaving the condenser. The higher
that this temperature is, the greater the amount of vapor that could
potentially be discharged to the atmosphere in the absence of further
emission controls. In practice, the temperature of the condenser must be
matched with the other parameters that affect the column temperature.
4.3.2 Batch Distillation
(1) Applicability. Batch distillation is a demonstrated technology
for F001-F005 spent solvent wastes, other than wastewaters, as
wastewaters are defined for purposes of this rulemaking (i.e., less than
one percent total organic carbon (TOG)). It is estimated that at least
400 facilities perform full scale batch distillation for on-site or
commercial treatment of these wastes. This technology is sometimes
referred to as pot distillation, "cooking", still pot distillation, or
simple distillation. In general, it is applied to spent solvent wastes
where a crude separation is acceptable and the wastes are highly
concentrated and yield significant amounts of recoverable material upon
separation. For wastes with constituents having a large relative
volatility, batch distillation is capable of providing a good
separation. Batch distillation is particularly applicable for wastes
with high solids concentrations since the more volatile constituents are
separated leaving the solids in the still bottoms. In this way it may
also be effective to reduce the quantity of waste requiring subsequent
land disposal or incineration.
4-20
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Batch distillation processes yield a residue (the still bottoms) that
may contain a high amount of suspended solids and may be quite viscous.
Whether this residue can be land disposed directly or requires further
treatment depends upon the level of F001 - F005 constituents in the TCLP*
extract of this residue.
(2) Underlying Principles of Operation. The underlying principles
of operation for batch distillation are discussed generally in the
general subsection under steam stripping.
In the batch distillation process, the mixture is vaporized in the
boiler and the vapor is cooled and condensed to a liquid in a condenser.
Since the batch distillation process uses only one equilibrium stage the
degree of separation is very limited unless there is a great difference
in the relative volatilities.
(3) Description of Batch Distillation. A batch distillation unit
consists of a boiler, a condenser, and a product receiver. Figure 4-5 is
a schematic showing the major components of a batch distillation unit.
The boiler is a device that provides the heat required to vaporize the
liquid fraction of the waste. The rising vapor is collected at the top
of the column, cooled and condensed. The liquid product stream is then
routed to a product receiver.
(4) Design and Operating Parameters Affecting Performance.
(a) Product Recovery. To establish the efficiency for product
recovery, the design and operating parameters are optimized between the
amount of product recovered and the energy and equipment sizing
requirements. In consideration of these factors, facilities will adjust
operating temperature, duration of the process, sizing of the condenser,
and finally the temperature of the condenser cooling water.
(b) Environmental Considerations. In optimizing a batch
distillation unit from the perspective of minimizing releases to the
environment, many of the same factors are considered but the optimal
operating conditions can be quite different. For example, the optimal
temperature out of the condenser may need to be significantly lower from
*TCLP is the Toxicity Characteristic Leaching Procedure. This procedure
is referenced as Appendix I in 40 CFR 268.41, Treatment Standards
Expressed as Concentrations in Waste Extract. In some cases it may be
possible to further reduce the F001 - F005 constituent concentrations
by increasing the operating temperature or duration of the batch.
4-21
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Vent of
Non-Condensed
Vapors
Waste
Influent
Condenser
Product
Receiver
Heated
Jacket
Still
Bottoms
(Batch)
Figure 4-5
Batch Distillation
4-22
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the perspective of minimizing air emissions than for achieving cost
effective product recovery. Additionally, the optimal temperature and
duration of a batch distillation run may be different from the
perspective of minimizing organics in the batch distillation residue than
from the standpoint of cost effective product recovery. It is important
to point out that facilities may find in some instances that higher
temperatures and longer distillation runs may result in a residual that
could be land disposed directly rather than require incineration. The
amount of noncondensable vapor in the waste feed can also influence the
amount of vapor vented.
4.3.3 Thin Film Evaporation
(1) Applicability. Thin film evaporation is also a demonstrated
distillation technology for F001-F005 spent solvent wastes other than
wastewater, as wastewater is defined for the purposes of this rulemaking
(i.e., less than one percent total organic carbon). It is also used to
treat highly concentrated wastes; it differs, however, from batch
distillation in that the feed stream to a thin film evaporator must
contain considerably lower suspended solids concentrations. Use of this
technology results in a product stream which almost always can be reused
as a solvent directly or after further treatment, and a bottoms stream
which often is used as fuel for incinerators. Because the waste feeds
are usually concentrated and contain little or no suspended solids,
treatment using thin film evaporation rarely results in a residue that
requires land disposal.
(2) Underlying Principles of Operation. As discussed previously in
this section in reference to steam stripping, the basic principle of thin
film evaporation is the separation of a liquid mixture into various
components by a process of vaporization-condensation. As in batch
distillation, the vapors are removed as they are formed, so that
thin-film units contain only one-equilibrium stage and are thus limited
in the degree of separation by the relative volatilities of the
constituents.
The principal objective of this type of thin film apparatus is to
provide the heat and surface area for separation to occur. The cylinder
walls are heated by steam from the outside as the feed trickles down the
inside walls. The feed rate of waste is controlled to allow the solvent
material adequate time to vaporize. The heat transfer from the steam to
the waste is determined by their relative temperatures and the heat
transfer coefficient of the vessel materials.
4-23
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As in a batch distillation unit, as more of the volatiles are
removed, the temperature must be continually raised to vaporize the
remaining waste. Thus the highly volatile components escape near the top
of the evaporator while heavier components fall to the bottom of the
evaporator.
(3) Description of Thin Film Evaporation. Thin film evaporation
consists of a steam jacketed cylindrical vessel, a condenser, and a
product receiver. Figure 4-6 is a schematic showing the major components
of a thin film evaporator. The steam heated surface of the cylindrical
vessel provides the heat required to vaporize the liquid fraction of the
waste. The rising vapor is collected at the top of the column, cooled
and condensed. The cooled liquid product stream is then routed to a
product receiver. The significant feature of this technology is the
distribution device that spreads a thin film over the heated surfaces.
(4) Design and Operating Parameters Affecting Performance.
(a) Product Recovery. To establish the efficiency for product
recovery, the design and operating parameters are optimized between the
amounts of the various products recovered and the energy usage and
equipment sizing requirements. In consideration of these factors,
facilities will adjust operating temperature, sizing of the condenser,
and the temperature of the condenser cooling water.
(b) Environmental Considerations. The vapors which result from
thin film evaporation are collected and condensed for reuse or for
further purification. The recovery of solvents from the unit is similar
to batch distillation in regard to the final temperature of the product
leaving the condenser. The higher the temperature of the product, the
greater the amount of solvents that will be vented into the atmosphere
unless controlled by air emission devices such as secondary condensers.
The amount of uncondensed vapor potentially vented to the atmosphere
depends on the temperature of the product leaving the condenser. The
amount of non-condensibles in the waste feed can also influence the
amount of vapor vented.
4.3.4 Fractionation
(1) Applicability. Fractionation is another demonstrated
distillation technology for F001-F005 spent solvent wastes other than
wastewater, as wastewater is defined for the purposes of this rulemaking
(i.e., less than one percent total organic carbon). It differs from
batch distillation, steam stripping and thin film evaporation in that it
is designed to achieve the highest degree of distillate purity of any of
these treatment technologies. Fractionation can be operated to produce
4-24
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Rotating
Drive
Waste
Influent
Liquid
Film
Vent of
Non-Condensed
Vapors
Condenser
I 1 Product
\^
Receiver
^•Bottoms
Figure 4-6
Thin Film Evaporation
4-25
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multiple product streams for recovery of more than one solvent
constituent from a waste, while generating minimal amounts of residue to
be land disposed. In general, this technology is used where recovery of
multiple constituents is desired and where the waste contains minimal
amounts of suspended solids. It is frequently used as a recycle/reuse
operation within manufacturing processes.
(2) Underlying Principles of Operation. The underlying principles
of operation for fractionation are discussed generally in the general
subsection under steam stripping. Fractionation processes use multiple
equilibrium stages with the initial waste feed entering at a point
between the first and last equilibrium stages. The stages at and below
the point of entry are called the stripping section because the stages
function as described above. The stages located above the point of feed
are called the rectification section. These additional stages allow the
vapor to become further enriched in the volatile components compared to
the incoming feed mixture. A portion of the condensed vapor is returned
as liquid to the uppermost stage to aid in rectification. This step of
returning a portion of the condensed vapor to the column is called
reflux.
(3) Description of Fractionation. A fractionation unit consists of
a boiler, a stripping section, a rectification section, a condenser, a
reflux system, and a product receiver. Figure 4-7 is a schematic showing
the major components of a fractionation unit. The boiler is a device
that provides the heat required to vaporize the liquid fraction of the
waste. The stripping section is composed of a set of trays or packing in
a vertical column. In the stripping section, vapor rising from the
boiler is contacted with the downflowing liquid feed. Through this
contacting, the lower boiling point constituents are concentrated in the
vapor. In the rectification section, the vapor rising above the feed
tray is contacted with downflowing condensed liquid product (reflux).
Through this contacting, further enrichment of the vapor is achieved.
The rising vapor is collected at the top of the column, cooled, and
condensed. The liquid product stream is then routed to a product
receiver.
(4) Design and Operating Parameters Affecting Performance.
(a) Product Recovery. To establish the efficiency for product
recovery, the design and operating parameters are optimized between the
amounts of the various products recovered and the energy usage and
equipment sizing requirements. In consideration of these factors,
facilities will adjust operating temperature, sizing of the condenser,
and the temperature of the condenser cooling water.
4-26
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Vent of
Non-Condensed
Vapors
t
Waste ^
1 nfli • A •**
inTiuent
^-L.
— — — — «. —
x^__^^x
^ Reflux V
^ f
1 _}'
Rectifier 1 1 ometn^t
• •w>iiiwi L_>^J^J rrOUUCI
section \s^ i Receiver
, i
Stripper
Section
i
+ \
Reboil
^1 1 ^ rtnll^mj
Reboiler
Figure 4-7
Tray Fractionation Column
4-27
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(b) Environmental Considerations. The vapors which result from
thin film evaporation are collected and condensed for reuse or for
further purification. The recovery of solvents from the unit is similar
to batch distillation in regard to the final temperature of the product
leaving the condenser. The higher the temperature of the product, the
greater the amount of solvents that will be vented into the atmosphere
unless controlled by air emission devices such as secondary condensers.
The amount of uncondensed vapor potentially vented to the atmosphere
depends on the temperature of the product leaving the condenser. The
amount of non-condensibles in the waste feed can also influence the
amount of vapor vented.
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DISTILLATION REFERENCES
1. Van Winkle, Matthew. Distillation. McGraw-Hill Book Company, New
York. 1967.
2. McCabe, Warren L., Julian C. Smith, and Peter Harriot. Unit
Operations of Chemical Engineering. McGraw-Hill Book Company, New
York. 1985.
3. Perry, Robert H. and Cecil H. Chilton. Chemical Engineer's Handbook,
5th ed. McGraw-Hill Book Company, New York. 1973.
4. Water Chemical Corporation. Process Design Manual of Stripping of
Organics, PB84-232628. Prepared for the Industrial Environmental
Research Laboratory Office of Research and Development, U.S.
Environmental Protection Agency. August, 1984.
5. Rose, L. M. Distillation Design in Practice. Elsevier, New York.
1985.
6. Kirk-Othmer. Encyclopedia of Chemical Technology. 2nd ed., Vol. 7,
John Wiley and Sons, New York. 1965.
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4.4 Biological Treatment
4.4.1 Applicability
This technology is demonstrated for wastewaters containing the
F001-F005 spent solvents. The Agency has full scale biological treatment
performance data from 28 plants in the organic chemicals, plastics, and
synthetic fibers industries which manufacture, in total, over 200
different products. These data were from treatment of wastes containing
F001-F005 constituents as a result of process contamination. While the
wastes are not included in EPA's definition of spent solvent wastes, the
Agency believes that these wastes are similar to spent solvent wastes.
The Agency has biological treatment data on carbon tetrachloride,
chlorobenzene, cresols, 1,2-dichlorobenzene, ethylbenzene, methylene
chloride, nitrobenzene, tetrachloroethylene, toluene, trichloroethylene,
1,1,1 trichloroethane, and trichlorofluoromethane. These data are
presented in Section 5 of this document.
Biological treatment is a widely recognized technology for the
removal of organic compounds from wastewaters. The concentrations of
organic constituents that can be effectively removed vary widely
depending on the overall chemical and physical characteristics of the
wastewater. Treatment applicability ranges from 0.01 to several hundred
parts per million in the wastewater. For treatment effectiveness of
spent solvent wastewaters not similar to those evaluated in Section 5 of
this document, facilities should review the "underlying principles of
operation" section and the "design and operating parameters affecting
performance" section for identification of other factors that should be
considered in applying this technology to a particular wastewater.
The underlying principles of biological treatment are presented in
subsection 4.4.2 below. Descriptions of biological treatment processes,
including activated sludge, aerated lagoons, trickling filters, and
rotating biological contactors, are presented in subsection 4.4.3.
Parameters which affect the performance of biological treatment are
presented in subsection 4.4.4.
4.4.2 Underlying Principles of Operation
Biological treatment involves the use of naturally occurring,
acclimated or genetically-altered microorganisms to degrade organic
contaminants in wastewater. During aerobic (presence of oxygen)
biological treatment, organic constituents are converted by
microorganisms to carbon dioxide, water, and cell protein. In anaerobic
(absence of oxygen) biological treatment, wastes are converted by
microorganisms to methane, carbon dioxide, and cell protein.
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(1) Anaerobic biological treatment. While anaerobic biological
processes have been shown to be effective in treating complex organic
wastes that generally cannot be treated aerobically, these are still in
developmental stages. Since the anaerobic processes currently find
limited application for the treatment of hazardous wastes, only aerobic
biological- treatment will be discussed in detail.
(2) Aerobic biological treatment. Aerobic processes use
microorganisms which require oxygen (as air or oxygen containing
compounds) for biodegradation of organic contaminants. In addition,
nutrients are needed in the form of nitrogen and phosphorous. The
aerobic biodegradation process can be represented by the following
generic equation:
Microorganisms
Cx Hy + Q£ - >• H20 + C02 + cellular biomass
nutrients
The aerobic bacteria degrade the organic waste to obtain energy for
cell metabolism and cell growth. A fraction of the waste is also
oxidized to products such as nitrates (N03>, sulfates (804),
and carbon dioxide
Biological oxidation of wastewaters containing organic constituents
will result in the net accumulation of a biomass of expired
microorganisms consisting mainly of cell protein. However, the cellular
biomass or sludges may also contain entrained constituents of the
wastewater, partially degraded constituents, or intermediate products
which have not been degraded. If biological treatment is carried out in
a land-based, unlined impoundment or lagoon with no drain-collection
system, such as aerated lagoons, any underlying soil materials may be
contaminated by leachate from the overlying sludges or the wastewater
itself.
Biological oxidation sludges must be periodically wasted in order to
maintain proper operation of the wastewater treatment system. Waste
biological sludges may be routed to a clarification tank where they are
allowed to settle. Settled sludges may be further dewatered on sludge
drying beds or by mechanical dewatering. The final dewatered, settled
waste sludge is a residual which must be disposed. If a TCLP analysis of
the waste for compliance purposes shows the leachate from the sludge to
contain F001-F005 solvents in excess of the BOAT treatment standard, it
would most likely have to be incinerated. At present, land disposal is
one of the methods of disposition for residuals generated from biological
wastewater treatment.
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For the application of biological treatment to industrial wastes, it
is important that the wastes be compatible with the physical-chemical
needs of the microorganisms, including consideration of the
physical-chemical and nutritional needs of the microorganisms, and the
effects of any toxic constituents on the microorganisms. Treatment
process modifications and/or waste pretreatment may be reguired to
provide the proper environment necessary for maintaining an active
microbial population.
4.4.3 Description of Biological Treatment
There are four types of biological treatment processes:
• Activated sludge,
• Aerated lagoons,
• Trickling filters, and
• Rotating biological contactors (RBCs).
(1) Activated sludge. The activated sludge process is currently the
most widely used biological treatment process. This is due in part to
the fact that recirculation of the biomass, which is an integral part of
the process, allows microorganisms to adapt to changes in wastewater
composition by relatively short acclimation processes and also allows a
greater degree of control over the acclimated bacterial population.
A schematic diagram of the activated sludge process is shown in
Figure 4-8. Wastewater which contains organic contaminants enters a
basin or tank where an aerobic bacterial population is maintained in
suspension and aeration is provided. The contents of the basin are
referred to as the mixed liguor.
Oxygen is supplied to the aeration basin by mechanical or diffused
aeration. A portion of the mixed liguor is continuously discharged from
the aeration basin into a clarifier, where the biomass is separated from
the treated wastewater by sedimentation. A portion of the biomass is
recycled to the aeration basin in order to maintain an optimum
concentration of acclimated microorganisms in the aeration basin. The
remainder of the separated biomass is discarded or "wasted" and the
clarified effluent is discharged. The recycled biomass is referred to as
activated sludge. The term "activated" is used because the recycled
biomass contains living and acclimated microorganisms which will
metabolize and assimilate organic material at a high rate when returned
to the aeration basin. This is because of the low food to microorganism
ratio in the sludge from the clarifier.
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Oxygen
and
Nutrients
Waste
Influent
Equalization
Tank
i
Aeration
Basin
Basin
Effluent
Sludge Recycle
Treated
Effluent
Waste
Sludge
Figure 4-8
Activated Sludge
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An important variation on the activated sludge process is the PACT®
process, developed by DuPont Corporation and licensed by Zimpro, Inc.
This process offers a combined treatment and pre-treatment unit whereby
non-compatible and toxic constituents are adsorbed onto activated carbon
and microorganism compatible waste remains in solution. Powdered
activated carbon is added directly to the .aeration basin of the activated
sludge treatment system. Overall removal efficiency is improved because
compounds which are not readily biodegradable or which are toxic to the
microorganisms are adsorbed onto the surface of the powdered activated
carbon. The carbon is removed from the wastewater in the final clarifier
along with the biological sludge. Both the carbon and the biological
sludge must be treated further or disposed. Generally, the activated
carbon is recovered, regenerated, and recycled.
(2) Aerated lagoons. Aerated lagoons are another form of aerobic
biological wastewater treatment. An aerated lagoon is a large pond or
tank which is eguipped with mechanical aerators to maintain an aerobic
environment and to avoid settling of the suspended biomass. In the
beginning, the population of microorganisms in an aerated lagoon is much
lower than in an activated sludge system because there is no sludge
recycle. A significantly longer residence time is therefore reguired in
order to achieve a specified effluent quality. However, this longer
residence time may be an advantage when complex organic chemicals are to
be degraded. Biodegradation of the organic contaminants in the
wastewater occurs throughout the lagoon. The effluent from the lagoon
may flow to a secondary sedimentation unit for removal of suspended
solids. Alternatively, the mechanical aerators may be shut off in the
aerated lagoon for a period of time to facilitate settling and
sedimentation prior to discharge of the effluent.
Aerated lagoons are exposed to variations in ambient air temperature
and thus perform better in warmer climates. This is due to the fact
that, as the temperature of the lagoon drops, the activity of the
microorganisms decrease and the efficiency with which the microorganisms
degrade organic material declines. Because there is usually no mechanism
for increasing the number of microorganisms in a lagoon (recycle is not
usually practiced), the performance of a lagoon may suffer at low
temperatures. The microorganisms used in aerated lagoons are also more
resistant to upsets by organic influent and pH shock loads compared to
activated sludge and fixed biomass processes because of longer detention
times and larger tank volume. Aerated lagoons also perform like cooling
towers, so no additional cooling is required to treat wastes with
relatively high temperatures. Compared to other biological treatment
systems, aerated lagoons are easy to operate and require little
maintenance. However, aerated lagoons require a large land area, are
susceptible to hydraulic shock loads, and there is little operational
control for adjustment to sustained changes in influent loading.
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(3) Trickling filters. The trickling filter biological treatment
process involves contact between wastewater containing organic
contaminants and a population of microorganisms which are fixed or
attached to the surface of filter media. Rocks or synthetic material
such as plastic rings and saddles are typically used as filter media.
The wastewater is distributed over the top of the filter by a rotating
distribution arm or a fixed distributor system. Wastewater forms a thin
layer as it flows downward through the filter and over the microorganism
layer on the surface of the media. As the distribution arm rotates, the
microorganism layer is alternately exposed to a flow of wastewater and
air. In the fixed distributor system, the wastewater flow is cycled on
and off at a specified dosing rate to ensure that an adequate supply of
oxygen is available to the microorganisms. A schematic diagram of a
trickling filter is shown in Figure 4-9.
The microorganism layer on the filter media is commonly called the
slime layer. The slime layer consists of a variety of organisms
including aerobic, anaerobic, and facultative bacteria, fungi, algae and
protozoans. Worms, insect larvae and snails may also be present. These
higher animal forms feed on the slime layer in the trickling filter,
thereby maintaining the bacterial population in a state of rapid growth
and food utilization. The presence of the varied organisms limits the
overgrowth of any particular type of organism.
Oxygen from the air reaches the microorganisms through the void
spaces in the media. Oxygen is necessary for aerobic degradation of the
organic contaminants in the wastewater. Trickling filters have an
underdrain system to collect the treated wastewater and any biological
solids which have become detached from the media. This underdrain system
acts both as a collection unit and as a structure through which air can
reach the void space of the filter media.
Organic material present in wastewater is adsorbed onto the
biological film or slime layer. Near the surface of the biological slime
layer, the attached microorganisms are exposed to oxygen. In this zone,
organic material is degraded by aerobic microorganisms. This degradation
of organic material causes the microorganisms to grow, resulting in an
increase in the thickness of the slime layer. The oxygen that diffuses
into the slime layer is consumed before it can fully penetrate the entire
slime layer. Therefore, an anaerobic environment is established near the
surface of the support media.
Eventually, as the slime layer continues to increase in thickness,
the adsorbed organic material is fully metabolized before it reaches the
microorganisms at the support media surface. Because no organic material
is present to feed the microorganisms at the support media surface, they
4-35
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Waste
Influent
Waste Distributor
Trickling Filter
Waste Effluent
Figure 4-9
Trickling Filter
4-36
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enter into an endogenous phase of growth (a state of reduced respiration
and metabolism) and lose their capability to cling to the surface. The
wastewater washes the slime from the media, and a new slime layer begins
to grow. This process is referred to as sloughing and is primarily a
function of the organic and hydraulic loading on the filter. The organic
loading affects the rate of metabolism in the slime layer while the
hydraulic loading determines shear velocities on the slime layer. Based
on the hydraulic and organic loading rates, trickling filters are
classified as low-rate or high-rate filters. Maintenance of a regulated
flow rate is very crucial in this process. Any fluctuation in the flow
rate would result in the sloughing off effect where the slime layer will
get detached from the support.
Trickling filter systems are typically used as a roughing filter, to
reduce the organic loading on a downstream activated sludge process.
Trickling filters can be used for the treatment of wastewaters which
produce bulking sludge (a sludge with poor settling characteristics and
poor compactibility) in an activated sludge process because the microbial
film which sloughs off the trickling filter is relatively dense and can
be readily removed by sedimentation.
Trickling filter biological treatment has been demonstrated in the
organic chemicals, plastics, and synthetic fibers industries. A
trickling filter system is used to treat aqueous waste containing toluene
and ethylbenzene at one plant.
(4) Rotating biological contactors. The rotating biological
contactor (RBC) consists of a series of closely spaced, parallel disks
which are rotated while partially immersed in a trough of wastewater.
The disks are constructed of polystyrene, polyvinyl chloride, or similar
materials. Rotating biological contactors can be customized depending on
the type of influent waste requiring biodegradation. Each disk is
covered with a biological slime which degrades dissolved organic matter
present in the wastewater. The rotation of disks facilitates exposure of
microorganisms to the air. As the disk is rotated out of the tank, it
carries a film of the wastewater into the air where oxygen is available
for aerobic biological decomposition. As excess biomass is produced, it
sloughs off the disk and is separated from the process effluent in a
final clarifier. The sloughing off process is similar to what occurs in
a trickling filter, which was described above. A schematic diagram of a
rotating biological contactor is shown in Figure 4-10.
RBCs can be used to treat dilute aqueous wastes containing
biodegradable organics, including solvents. The large amount of
biological cell mass permits the system to withstand organic and
hydraulic surges effectively. RBCs allow a greater degree of control
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Waste
Influent
Rotating Discs
(fill
V V
T7\
\\\l
Clarifier
. Waste
Effluent
Sludge
Figure 4-10
Rotating Biological Contactor
4-38
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over treatment variables than trickling filters. The rate of contact
between the microorganisms, the organic waste, and atmospheric oxygen can
be controlled by adjusting the depth to which the disks are submerged in
the wastewater and the rate at which the disks rotate. RBCs tend to be
susceptible to operational problems; deflection of the central shaft and
difficulty in controlling growth (slime layer tends to overgrow or slough
off completely) are common problems.
4.4.4 Design and Operating Parameters Affecting Performance
There are a number of parameters affecting the performance:
Equalization,
Nutrients,
Aeration/oxygen supply,
Wastewater-biomass contact,
Microorganism growth phase.
Temperature,
pH, and
Selection of microorganisms.
These parameters are discussed in the following paragraphs. The way
in which these parameters are controlled is specific to the type of
biological treatment process employed.
(1) Equalization. Equalization is important because biological
treatment systems are very sensitive to variations in influent flow rate
and organic loadings. Sudden changes can cause process upsets, toxic
effects or reduced dissolved oxygen levels, all of which will result in
diminished treatment efficiency. The treatment influent should be
monitored to detect variations in organic loadings and sufficient
equalization time should be provided to yield a relatively constant
loading to the treatment system.
(2) Nutrients. Nutrient addition is important in controlling the
growth of microorganisms as insufficient nutrients will result in poor
microbial growth with poor removal of organic compounds. The principal
inorganic nutrients required are nitrogen and phosphorus. It has been
shown that the percentage distribution of nitrogen and phosphorus in
microbial cells varies with the age of the cell and environmental
conditions. The total amount of nutrients required will depend on the
net mass of organisms produced. In addition to the major nutrients,
trace amounts of potassium, calcium, sulfur, magnesium, iron and
manganese are required for optimum microbial growth.
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(3) Aeration/Oxygen Supply. An adequate supply of oxygen is
critical to maintain an environment in which aerobic microorganisms can
grow and metabolize dissolved organic material. The way in which oxygen
is supplied to the microorganisms varies with the type of biological
treatment process used.
The oxygen can be provided as atmospheric oxygen or in the form of
sulfates, nitrates, nitrites or other oxygen-containing organic compounds
such as sugar or starch.
(a) Activated sludge. The suspended microorganisms in the aeration
basin of an activated sludge treatment system obtain oxygen directly from
the wastewater being treated. For this reason, the dissolved oxygen
(D.O.) concentration in the aeration basin should be maintained close to
the saturation level (approximately 8 mg/L) at all times. Ideally, the
D.O. level should be monitored continuously to detect process upsets or
deterioration of aeration efficiency. The D.O. level is controlled by
adjusting the aeration rate. Mechanical and diffused aerators are both
commonly used with activated sludge systems. Theoretical oxygen
requirements are determined from biochemical oxygen demand (BOD) of the
waste and the influent wastewater flow rate. The air supply must be
adequate to satisfy the BOD of the waste, provide adequate mixing (i.e.,
to keep microbial population in suspension), and provide dissolved oxygen
in the aeration basin as close to the saturation level as possible.
(b) Aerated lagoons. The suspended microorganisms in an aerated
lagoon also obtain oxygen directly from the wastewater. The D.O. level
in an aerated lagoon is controlled by adjusting the aeration rate and
should be kept as high as possible at all times. Since the waste
retention time is longer, aeration is accomplished by use of mechanical
aerators because diffused aerators tend to become fouled with bottom
sediment. Aeration performs the two functions of oxygen transfer and
mixing.
(c) Tricking filters. The microorganisms in a trickling filter are
attached to the filter media and obtain oxygen from air which permeates
the void space in the media. The organisms are alternately exposed to
the flowing layer of wastewater or air. If the organisms do not have a
sufficiently long period of exposure to air between passes of the
distribution arm or cycle times, efficient aerobic degradation of the
waste is not possible. The only way to ensure an adequate supply of
oxygen is to control the wastewater feed rate (hydraulic loading rate).
The hydraulic loading rate (gallons per minute per square foot) will be
affected by a number of variables including the biological oxygen demand
of the wastewater and the characteristics of the support media.
4-40
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particularly the void space. An increased void space will permit a
higher hydraulic loading as well as enhanced oxygen transfer to the
biological slime. Synthetic support media have more void space and
surface area per unit volume than do conventional rock media.
Trickling filters are classified according to their hydraulic and
organic loading rates as low-rate or high-rate filters. High-rate
filters operate with hydraulic and organic loading rates of 0.156 to 0.47
gallons per minute per square foot and 90 pounds of BOD per day per 1,000
cubic feet of media, respectively. High-rate hydraulic loading rates of
trickling filters with synthetic media are even higher, at 2.3 gallons
per minute per square foot. The corresponding organic loading rates for
low rate filters are 0.063 gallons per minute per square foot and 10 to
20 pounds of BOD per day per 1,000 cubic feet of media.
Recirculation is another important factor in the efficient operation
of a trickling filter, especially for concentrated wastewaters.
Recirculation of the effluent is often used to dilute the trickling
filter influent and thereby reduce the organic loading to the filter. It
also provides additional residence time in the unit that facilitates
further degradation of organic constituents.
(d) Rotating biological contactors. The microorganisms in a rotating
biological contactor system are attached to the rotating disks and obtain
oxygen primarily through exposure to air. A portion of the disk is
submerged in the wastewater at all times. As the disk rotates, a given
area of organisms on the disk will alternatively be submerged and exposed
to the air. In order for aerobic biodegradation to effectively occur,
the portion of the disk which is submerged and the disk rotation rate
must be adjusted to ensure that during each disk rotation cycle the
organisms do not spend an excessive amount of time submerged, and an
adequate exposure time to the air is provided. The optimal disk
submergence time and rotation speed will primarily be a function of disk
size and the biological oxygen demand of the wastewater. For treatment
of concentrated wastewaters supplemental aeration may be required.
(4) Wastewater-Biomass Contact. In order for a specified amount of
biodegradation of organic contaminants to be achieved, a sufficient
amount of contact between the wastewater and microorganisms must occur.
The amount of contact required is a function of the concentration of
organic contaminants in the wastewater. The way in which this contact is
achieved varies with the type of biological treatment system used.
(a) Activated sludge. An important parameter in the activated sludge
process which is related to wastewater-biomass contact is the food to
microorganisms (F/M) ratio. The F/M ratio is defined as the quantity
4-41
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of organic material metabolized per day in the system divided by the
total active biomass in the system. That is, the F/M ratio is a measure
of the amount of biomass available to metabolize the influent organic
loading to the system. The F/M ratio is controlled by adjusting the
biomass recirculation rate.
The mixed liquor volatile suspended solids {MLVSS) concentration is a
measure of the active microbial mass in the treatment system. As such,
it is one of the process parameters which determines the food to
microorganism ratio. The sludge wasting rate is important because it is
the operating parameter which controls the MLVSS concentration in the
aeration basin and consequently the F/M ratio.
(b) Aerated lagoon. In an aerated lagoon, sludge is neither removed
(wasted) nor recycled. Therefore, the total active biomass in the system
cannot be controlled. However, the amount of time that the wastewater
spends in contact with the biomass is a variable operational parameter.
The hydraulic detention time of the wastewater, defined as the volume of
the lagoon divided by the influent wastewater flow rate, determines the
contact between the wastewater and the suspended microorganisms in the
system. A longer hydraulic detention time increases the wastewater
biomass contact.
(c) Trickling filter. The amount of contact between the wastewater
and the microorganisms in a trickling filter is a function of the
hydraulic loading rate (gpm per foot). This rate will be affected by the
specific surface area and depth of the support media. The type of media
and the depth are design variables and are not operational parameters
that can be controlled.
The type of media which is used in a trickling filter significantly
impacts the operation of the filter. Greater surface area allows for the
presence of a larger mass of microorganisms per unit volume. This in
turn permits greater biodegradation of organic constituents in
wastewater. A higher hydraulic loading is possible with an increased
void space as well as enhanced oxygen transfer to the biological slime.
Synthetic media have more void space and surface area per unit volume
than do conventional rock media.
In addition to the type of media, the depth of a trickling filter bed
is important in determining its performance. A filter with rock media
usually has a bed depth between 0.9 and 2.5 meters (three and eight
feet). The rock media have a lower percent void space which restricts
the use of a deeper bed due to oxygen transfer requirements. The
lighter-weight synthetic media allows for deeper beds, ranging in depth
from 9 to 12 meters (30 to 40 feet). As mentioned above, the
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synthetic-media filters also have greater void space and surface area
than rock-media trickling filters, permitting greater oxygen transfer,
and, hence, higher hydraulic loadings. These factors allow aerobic
bacteria to be present throughout the depth of the bed. Organic
degradation therefore occurs throughout the depth of the filter when
synthetic media is used.
(d) Rotating biological contactors. Contact between wastewater and
the microorganisms in a rotating biological contactor system is a
function of the hydraulic loading rate (gpm/ft^) which is defined as
the total wastewater flow rate through the system divided by the total
area of submerged disk in the system.
The total area of submerged disk in the system can be controlled by
adjusting the depth of the disks submerged under wastewater and by adding
or bypassing disk units. Like trickling filter media, RBC disk media are
characterized by a specific surface area. The total surface area per
stage and the number of stages in series are key design parameters for
RBC systems.
(5) Microorganism Growth Phase. The growth phase of the microbial
population in a biological treatment system is an important parameter in
the performance of the system. This parameter can only be controlled,
however, in the activated sludge process where biomass (sludge) wasting
and recycle are practiced. In the activated sludge process, the mean
cell residence time (MCRT), or sludge age, directly determines the growth
phase of the microorganisms in the aeration basin.
In order to maintain a low level of dissolved organic material in the
effluent, the bacterial population in the aeration basin must be kept in
an endogenous or declining growth phase. This is accomplished by
controlling the residence time of the biomass in the system. Also, to
ensure that microorganisms will grow, they must be allowed to remain in
the system long enough to reproduce. This period depends on their growth
rate which is directly related to the rate at which they metabolize or
utilize the waste. Sludge age is defined as the total active microbial
mass in the treatment system divided by the total quantity of microbial
mass withdrawn daily (wasted) from the treatment system.
(6) Temperature. Microbial growth can occur under a wide range of
temperature, although the majority of the microbial species are active
between 20° and 35°C. Kinetic rate parameters are sensitive to
fluctuations in temperature. The rate of biochemical reactions in cells
increase with temperature up to a maximum above which the rate of
activity declines as enzyme denaturation occurs and microorganisms either
die off or become less active.
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(a) Activated sludges. Because of the ability to control the
quantity of biological solids by sludge recycle and short residence time,
the temperature in the activated sludge basins can be be controlled
effectively. As a result, the quality of effluent from activated sludge
processes has been found to be relatively insensitive to changes in
ambient temperature. The effect of increases in temperature will be to
increase the amount of excess sludge produced and the amount of aeration
required. An increase in rate of wasting will compensate for this
effect. Decreases in temperature can be offset by increasing the sludge
recycle rate.
Activated sludge aeration basins are typically sized to perform up to
a critical summer temperature and down to a critical winter temperature.
Temperature deviations outside of the design range can affect performance.
(b) Aerated lagoons. Aerated lagoons are more susceptible to
temperature variations than activated sludge systems, primarily due to
the large surface area available for heat transfer and the additional
heat losses due to agitation. Estimation of the critical lagoon
operating temperature is an important design factor. At long hydraulic
residence times, mesophillic bacteria are relatively insensitive to
temperature; however, sludge production and settleability will be
affected.
(c) Trickling filters. In trickling filters, as in other biological
treatment processes, temperature fluctuations cause changes in the rate
of substrate removal and consequently affect the effluent quality. It is
common to cover or enclose small trickling filters located in extreme
climates to dampen temperature variation.
(d) Rotating biological contactors. As with trickling filters, low
temperatures have an adverse effect upon RBC performance but the use of
enclosures can essentially eliminate any heat loss. As a result, the
temperature which controls process efficiency is the influent wastewater
temperature.
(7) pH. In general, neutral or slightly alkaline pH favors
bacterial growth. The optimum range for most microorganisms found in
biological treatment systems is between 6 and 8. Treatment effectiveness
is generally insensitive to changes within this range. However,
excursions outside the range can lower treatment performance. The pH of
the influent should be monitored and adjusted at the preliminary
treatment or equalization step and in the aeration basin of activated
sludge systems, and at the influent for aerated lagoons, trickling
filters and RBCs.
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(8) Selection of microorganisms. The nature and quantities of the
toxic constituents in a waste affect the biodegradability of the waste.
Microorganisms differ substantially in their tolerance to toxics and
their ability to degrade compounds at differing concentrations and
indifferent physico-chemical environments. In all biological treatment
systems, the microorganisms naturally undergo a selection process by
which organisms which are capable of efficient biodegradation under the
given circumstances increase their numbers, and other microorganisms are
killed or washed out.
Recently, microorganism additives have been developed which are
essentially freeze-dried cultures of special microorganisms. These
cultures can be added to the biological treatment system in order to
enhance the population of specific microorganisms. For example, cultures
of organisms that degrade hydrocarbons as well as specific pollutants are
available.
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BIOLOGICAL TREATMENT REFERENCES
1. Liptak, Bela G. (editor). Environmental Engineers' Handbook. Volume
1 Water Pollution. Radnor, Pennsylvania; Chilton Book Company, 1974.
2, Metcalf and Eddy. Wastewater Engineering: Treatment, Disposal,
Reuse. McGraw-Hill Book Company, New York. 1979.
3. Grady, C.P. Leslie, Jr, and Henry C. Lim. Biological Wastewater
Treatment: Theory and Applications. Marcel Dekken, Inc. 1980.
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4.5 Incineration
4.5.1 Applicability
This technology is widely demonstrated for treatment of F001-F005
spent solvent wastes. The Agency estimates that there are over 200 full
scale facilities, many of which incinerate F001-F005 spent solvents. The
Agency has data for analyses of the TCLP extract of incinerator ash for
ten incinerators at nine full scale facilities. All incinerators were
operating treating a variety of wastes including spent solvents. The
F001-F005 constituents for which data were available are acetone, carbon
disulfide, chlorobenzene, 1,2-dichloro-benzene, ethylbenzene, methylene
chloride, methyl ethyl ketone, methyl isobutyl ketone, nitrobenzene,
tetrachloroethylene, toluene, 1,1,1-trichloroethane, trichloroethylene
and xylene. The Agency believes that these data represent treatment of
wastes which are the same or similar to wastes which will be subject to
this rule. The data are presented in Section 5 of this document.
The underlying principles of incineration are presented in
subsection 4.5.2. Descriptions of types of incinerators, including
liguid injection, rotary kiln, fluidized bed, and hearth incinerators are
discussed in subsection 4.5.4. Design and operating parameters which
affect the performance of incinerators are presented in subsection 4.5.4.
4.5.2 Underlying Principles of Operation
Incineration is a controlled oxidation destruction process that uses
flame combustion to destroy hazardous wastes with oxygen by converting
the wastes to carbon dioxide, water and other combustion products. The
specific products of incineration (combustion) vary depending on the
types of wastes that are burned.
Incineration of simple, non-halogenated organic wastes involves the
oxidation of carbon and hydrogen-containing molecules to form carbon
dioxide and water. As in any chemical reaction, the proportion of
reactants, in this case, oxygen, hydrogen, and carbon, should be balanced
so that combustion reactions can go to completion. When the proportion
of oxygen to hydrocarbon waste is balanced, the fuel to air ratio is said
to be "stoichiometric." In practice, an excess of oxygen is used to
ensure that all of the hydrocarbon is oxidized or burned. If the
proportion of oxygen and hydrocarbon feed is sub-stoichiometric or oxygen
deficient, carbon monoxide is also formed, and depending on the severity
of the oxygen deficiency, products of incomplete combustion (PICs) can be
formed. Too low a combustion temperature and inadequate dwell or
residence time in the flame or high temperature zone are other factors
that can lead to incomplete combustion and the possible formation of PICs.
4-47
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The generation of carbon monoxide and PICs can be minimized by
controlling temperature, residence time, and oxygen during combustion.
Combustion reactions proceed most efficiently at high temperatures, with
a correct stoichiometry or balance of oxygen (as air) and fuel, and with
a sufficient residence time to match the kinetic rates of combustion.
The relationship of these factors to the design and operation of
incinerators is discussed in subsection 4.5.4. below.
4.5.3 Description of Incinerators
All waste incinerators consist of a waste feed system, an air or
oxygen-feed burner system, a combustion chamber, combustion monitoring
systems, and, if required, equipment for air pollution control, and ash
removal. These elements are applied somewhat differently in the various
types of incinerators. Four types of incineration systems are discussed
in this section: liquid injection, rotary kiln, fluidized bed, and
hearth incinerators.
(1) Liquid Injection. The liquid injection system is capable of
incinerating a wide range of gases and liquids. The combustion system
has a very simple design with virtually no moving parts. A burner or
nozzle atomizes the liquid waste and injects it into the combustion
chamber where it burns in the presence of air or oxygen. A forced draft
system supplies the combustion chamber with air to provide oxygen for
combustion and turbulence for mixing. The combustion chamber is usually
a cylinder lined with refractory (i.e., heat resistant) brick, and may be
fired horizontally, vertically upward, or vertically downward. The
specific configurations are designed to satisfy the needs of the owner.
Figure 4-11 illustrates a liquid injection incineration design.
(2) Rotary Kiln. Rotary kiln systems are capable of incinerating
solid, liquid, and gaseous hazardous wastes either separately or
simultaneously. In general, rotary kiln operations utilize high Btu
liquid wastes in conjunction with lower Btu solids in order to enhance
combustion. Because of their versatility, rotary kilns have been used
for treatment in large commercial facilities. A rotary kiln is a slowly
rotating, refractory-lined cylinder that is mounted at a slight incline
from the horizontal (see Figure 4-12). Solid wastes enter at the high
end of the kiln, and liquid or gaseous wastes enter through atomizing
nozzles in the kiln or afterburner section. Rotation of the kiln exposes
the solids to the heat, vaporizes them, and allows them to combust by
mixing with air. The rotation then causes the ash to move to the lower
end of the kiln where it can be removed. Rotary kiln systems usually
have a secondary combustion chamber or afterburner following the kiln to
ensure more complete combustion of the volatilized components of solid
wastes.
4-48
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Gas to
Air Pollution
Control
Auxiliary
Fuel
Solid Waste
Influent
Feed
Mechanism
Afterburner
Combustion
Gases
Liquid or
Gaseous
Waste Injection
Ash
Figure 4-12
Rotary Kiln Incinerator
4-50
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(3) Fluidized Bed. A fluidized bed incinerator consists of a column
containing inert particles such as sand which is referred to as the bed
(see Figure 4-13). Air, driven by a blower, enters the bottom of the bed
to fluidize the sand. Air passage through the bed promotes rapid and
uniform mixing of the injected waste material within the fluidized bed.
The fluidized bed has an extremely high heat capacity (approximately
three times that of flue gas at the same temperature), thereby providing
a large heat reservoir. The injected waste reaches ignition temperature
quickly and transfers the heat of combustion back to the bed. Continued
bed agitation by the fluidizing air allows larger particles to remain
suspended in the combustion zone.
(4) Hearth. Hearth incinerators, also called controlled air or
starved air incinerators, are another major technology used for hazardous
waste incineration. Hearth incineration is basically a two-stage
combustion process (see Figure 4-14). Waste is ram-fed into the first
stage, or primary chamber, and burned at roughly 50-80 percent of
stoichiometric air requirements. This starved air condition causes most
of the volatile fraction to be destroyed pyrolytically, with the required
heat provided by the oxidation of the carbonaceous fraction in the
waste. The resultant smoke and pyrolysis products, consisting primarily
of volatile hydrocarbons and carbon monoxide, along with products of
combustion, pass to the second stage, or secondary chamber. Here,
additional air is injected to complete the combustion, which can occur
either spontaneously or through the addition of supplementary fuels. It
is this two-stage process that generally allows low stack emissions. The
primary chamber combustion reactions and turbulent velocities are
maintained at low levels by the starved air conditions so that
particulate entrainment and carryover is minimized.
4.5.4 Design and Operating Parameters Affecting Performance
(1) Design Parameters. Excess air, temperature, residence time,
mixing, chemical thermodynamic properties of the waste, burner design,
and atomization are the primary variables affecting combustion efficiency
in any incinerator design.
(a) Excess Air. The most basic requirement of any combustion
system is a sufficient supply of air to completely oxidize the feed
material. The stoichiometric, or theoretical air requirement is
calculated from the chemical composition of the feed material. If
perfect mixing could be achieved and the waste burned instantaneously,
then only the stoichiometric requirement of air would be needed. Neither
of these phenomena occur in real-world applications, however, so some
excess air is always required to ensure adequate waste/air contact.
4-51
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Auxiliary
Fuel
Waste
Injection
Burner
Afterburner
(Secondary
Combustion
Chamber)
Sand Bed
t
Gas to Air
Pollution Control
Fluidized
Bed
Incinerator
Make-up
Sand
Fluidized
Air
Ash
Figure 4-13
Fluidized Bed Incinerator
4-52
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Air
Waste
Injection
Burner
Primary
Combustion
Chamber
Grate
Air
I
Gas to
Air Pollution
Control
t
Secondary
Combustion
Chamber
Auxiliary
Fuel
2-Stage Hearth
Incinerator
Ash
Figure 4-14
Hearth Incinerator
4-53
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Excess air is usually expressed as a percentage of the stoichiometric air
requirement. For example, 50 percent excess air implies that the total
air supplied to the incinerator is 50 percent greater than the
stoichiometric requirement.
The amount of excess air used or needed in a given application
depends on the degree of air/waste mixing achieved in the primary
combustion zone and the desired degree of combustion gas cooling. Since
excess air acts as a diluent in the combustion process, it reduces the
temperature in the incinerator (i.e., maximum theoretical temperatures
are achieved at zero percent excess air). This temperature reduction is
desirable when readily combustible, high heating value wastes are being
burned in order to limit refractory degradation. When low heating value
waste is being burned, however, excess air should be minimized to keep
the system temperature as high as possible. Even with highly combustible
waste, it is desirable for equipment design considerations to limit
excess air to some extent so that combustion chamber volume and
downstream air pollution control system capacities can be limited.
(b) Temperature. Three basic questions should be considered in
evaluating whether or not a proposed operating temperature is sufficient
for waste destruction:
• Is the temperature high enough to heat all waste components
(and combustion intermediates) above their respective
ignition temperatures and to maintain combustion?
• Is the temperature high enough for complete reaction to
occur at the proposed residence time?
• At what point in the combustion chamber is the proposed
temperature to be measured?
Complete waste combustion requires a temperature and heat release
rate in the incinerator high enough to raise the temperature of the
incoming waste constituents above their respective ignition temperatures
(i.e., to provide energy input in excess of their respective activation
energies so that combustion will occur). In cases where combustion
intermediates are more stable than the original waste constituents,
higher temperatures are required for complete combustion of the
intermediates than for parent compound destruction.
Since heat transfer, mass transfer, and oxidation all require a
finite length of time, temperature requirements must also be evaluated in
relation to the proposed residence time in the combustion chamber. Heat
transfer, mass transfer, and kinetic reaction rates all increase with
increasing temperature, lowering the residence time requirements.
4-54
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After addressing the temperature requirements for waste destruction,
it is also necessary to determine whether the proposed temperature is
within normal limits for the incinerator design, whether this temperature
can be attained under the proposed firing conditions.
When identifying a minimum temperature acceptable for waste
destruction, it is also important to identify the location in the
combustion chamber at which this temperature should be measured.
Temperature varies tremendously from one point to another in the
combustion chamber, being highest in the flame and lowest at the
refractory wall or at a point of significant air infiltration (e.g., in
the vicinity of secondary air ports). Ideally, temperature should be
measured in the bulk gas flow at a point after which the gas has
traversed the combustion chamber volume that provides the specified
residence time for the unit. It should not be measured at a point of
flame impingement or at a point directly in sight of radiation from the
flame.
(c) Residence Time. In addition to temperature and excess air,
residence time is a key factor affecting the extent of combustion. This
variable, also referred to as retention time or dwell time, is the mean
length of time that the waste is exposed to the high temperatures in the
incinerator. It is important in designing and evaluating incinerators
because a finite amount of time is required for each step in the heat
transfer/mass transfer/reaction pathway to occur.
In waste combustion, discrete (although short) time intervals are
required for heat transfer from the gas to the surface of the atomized
droplets or solids, for liquid evaporation, for mixing with oxygen in the
gas stream, and for reaction which itself involves a series of individual
steps depending on the complexity of the waste's molecular structure.
The total time required for these processes to occur depends on the
temperature in the combustion zone, the degree of mixing achieved, and
the size of the liquid droplets. Residence time requirements increase as
combustion temperature is decreased, as mixing is reduced, and/or as the
size of discrete waste particles is increased.
(d) Mixing. Temperature, oxygen, and residence time
requirements for waste destruction all depend to some extent on the
degree of mixing achieved in the combustion chamber. This parameter is
difficult to express in absolute terms, however. Many of the problems
involved in interpreting burn data (i.e., data from previous incinerator
tests) relate to the difficulty involved in quantifying the degree of
mixing achieved in the incinerator, as opposed to the degree of mixing
achieved in another incinerator of different design.
4-55
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In liquid waste incinerators, the degree of mixing is determined by
the specific burner design (i.e., how the primary air and waste/fuel are
mixed), combustion product gas and secondary air flow patterns in the
combustion chamber, and turbulence.
In rotary kiln.incineration systems, both the solids retention time
in the kiln and the gas residence time in the afterburner must be
considered. Afterburner residence time considerations are essentially
the same as those for liquid injection incinerators.
Air/solids mixing in the kiln is primarily a function of the kiln's
rotational velocity, assuming a relatively constant gas flow rate. As
rotational velocity is increased, the solids are carried up higher along
the kiln wall and showered down through the air/combustion gas mixture.
Since solids retention time is also affected by rotational velocity,
there is a tradeoff between retention time and air/solids mixing. Mixing
is improved to a point by increased rotational velocity, but the solids
retention time is reduced. Mixing is also improved by increasing the
excess air rate, but this reduces the kiln operating temperature.
(e) Waste Chemical and Thermodynamic Properties. Chemical and
thermodynamic properties of the waste that need to be considered in
incinerator design evaluation are its elemental composition, its net
heating value, and any special properties (e.g., explosive properties)
that may interfere with incinerator operation or require special design
considerations. The percentages of carbon, hydrogen, oxygen, nitrogen,
sulfur, halogens, and phosphorus in the waste, as well as its moisture
content, need to be known to calculate stoichiometric combustion air
requirements and to predict combustion gas flow and composition. Once
the weight fraction of each element in the waste has been determined, the
stoichiometric oxygen requirements and combustion product yields can be
calculated. The stoichiometric air requirement is determined directly
from the stoichiometric oxygen requirement via the weight fraction of
oxygen in air.
The heating value of a waste corresponds to the quantity of heat
released when the waste is burned, commonly expressed as Btu per Ib.
Since all organic wastes have some finite heating value, all combustion
reactions are exothermic. However, the magnitude of this heating value
must be considered in establishing an energy balance for the combustion
chamber and in assessing the need for auxiliary fuel firing. To maintain
combustion, the amount of heat released by the burning waste must be
sufficient to heat incoming waste up to its ignition temperature and to
provide the necessary activation energy for the combustion reactions to
occur. Activation energy is the quantity of heat needed to destabilize
4-56
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molecular bonds and create reactive intermediates so that the exothermic
combustion reaction with oxygen will proceed.
Waste heating values needed to sustain combustion without auxiliary
fuel firing depend on the following criteria:
• physical form of the waste (i.e., gaseous vs. liquid vs. solid),
• temperature required for refractory waste component destruction,
• excess air rate, and
• heat transfer characteristics of the incinerator.
In general, higher heating values are required for solids vs. liquids
vs. gases, for higher operating temperatures, and for higher excess air
rates, if combustion is to be sustained without auxiliary fuel
consumption.
When an organic waste exhibits a low heating value, it is usually due
to high concentrations of moisture or halogenated compounds. An increase
in the moisture content of an organic waste proportionately decreases the
overall heating value on a Btu/lb waste basis.
The heating value of a waste also decreases as the chlorine (or other
halogen) content increases, although there is no simple mathematical
relationship.
(f) Burner design. For incineration of liquids, the liquid
wastes are injected through burners, atomized to fine droplets, and
burned in suspension. To heat the unit to operating temperature before
waste is introduced, all incinerator designs should also include an
auxiliary fuel firing system. This may consist of separate burners for
auxiliary fuel, dual-liquid burners, or single-liquid burners equipped
with a premix system whereby fuel flow is gradually turned down and waste
flow is increased after the desired operating temperature is attained.
If auxiliary fuel firing is needed during routine operation the same
types of systems are needed: fuel/waste premix, dual-liquid burners, or
separate auxiliary fuel burners.
Each burner, regardless of type, is generally mounted in a refractory
block or ignition tile. This is necessary to confine the primary
combustion air introduced through the burner, to ensure proper air/waste
mixing, and to maintain ignition. The shape of the ignition tile cavity
also affects the shape of the flame and the quantity of primary air which
must be introduced at the burner. Some burners and tiles are arranged to
4-57
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aspirate hot combustion gases back into the tile, which aids in
vaporizing the liquid and increasing flame temperature more rapidly.
The dimensions of the burner block, or ignition tile, vary depending
on the burner design. Each manufacturer has his own geometrical
specifications, which have been developed through past experience.
Therefore, it is not possible to specify a single burner block geometry
for design evaluation purposes. However, this aspect of the design can
be checked to eliminate systems that do not provide for any flame
retention.
The location of each burner in the incinerator and its firing angle,
relative to the combustion chamber, should also be checked. In axial or
side-fired nonswirling units, the burner is mounted either on the end
firing down the length of the chamber or in a sidewall firing along a
radius. Such designs, while simple and easy to construct, are relatively
inefficient in their use of combustion volume. Improved utilization of
combustion space and higher heat release rates can be achieved with the
utilization of swirl or vortex burners or designs involving tangential
entry. Regardless of the burner location and/or gas flow pattern,
however, the burner is placed so that the flame does not impinge on
refractory walls. Impingement results in flame quenching, and can lead
to smoke formation or other forms of incomplete combustion. In multiple
burner systems, each burner should be aligned so that its flame does not
impact on other burners.
In a rotary kiln incinerator, both the afterburner and kiln are
usually equipped with an auxiliary fuel firing system to bring the units
up to the desired operating temperatures. As was discussed earlier, the
auxiliary fuel system may consist of separate burners for auxiliary fuel,
dual-liquid burners designed for combined waste/fuel firing, or
single-liquid burners equipped with a premix system, whereby fuel flow is
gradually turned down and liquid waste flow is increased after the
desired operating temperature is attained.
If liquid wastes are to be burned in the kiln and/or afterburner,
additional considerations are:
• flame retention characteristics of the burners,
• burner alignment to avoid flame impingement on refractory walls,
and
• in multiple burner systems, burner alignment to avoid interference
with the operation of other burners.
4-58
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(g) Atomization. Before a liquid waste can be combusted, it
must be converted to the gaseous state. This change from a liquid to a
gas occurs inside the combustion chamber and requires heat transfer from
the hot combustion gases to the injected liquid. To cause a rapid
vaporization (i.e., increase heat transfer), it is necessary to increase
the exposed liquid surface area. Most commonly the amount of surface
exposed to heat is increased by finely atomizing the liquid to small
droplets. Good atomization is particularly important when low heating
value wastes are being burned. It is usually achieved in the liquid
burner directly at the point of air/fuel mixing.
The degree of atomization achieved in any burner depends on the
kinematic viscosity of the liquid and the amount of solid impurities
present. Liquids should generally have a kinematic viscosity of 10,000
Saybolt Seconds Universal (SSU) or less to be satisfactorily pumped and
handled in pipes. For atomization, they should have a maximum kinematic
viscosity of about 750 SSU. If the kinematic viscosity exceeds this
value, the atomization may not be fine enough. This may cause smoke or
other unburned particles to leave the unit. However, this is only a rule
of thumb. Some burners can handle more viscous fluids, while others
cannot handle liquids approaching this kinematic viscosity.
Solid impurities in the waste can interfere with burner operation via
pluggage, erosion, and ash buildup. Both the concentration and size of
the solids, relative to the diameter of the nozzle, need to be
considered. Filtration may be employed to remove solids from the waste
prior to injection through the burner.
(2) Operating Parameters. The major factors governing incineration
efficiency that can be directly controlled during operation are
temperature and excess air. As discussed earlier, other factors affect
incinerator effluent (e.g., turbulence) but these factors are not easily
monitored and controlled.
(a) Temperature. Incinerator temperature is monitored on a
continuous basis to assure that the minimum acceptable temperature for
waste destruction is maintained. This requires one or more temperature
sensors in the hot zone and a strip chart recorder or equivalent
recording device.
Generally, wall temperature and/or gas stream temperatures are
determined using shielded thermocouples as sensors. Thermocouples are
the most commonly used contact sensors for measuring temperatures above
1,000°F.
4-59
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Optical pyrometers are not recommended for these measurements due to
spectral bias factors present in the combustion area which can cause
unacceptable measurement error.
The location at which temperature measurements are taken is
important, due to possible variations in temperature from one point to
another in the combustion chamber. Temperatures are highest in the flame
and lowest in the refractory wall or at a point of significant air
infiltration. Ideally, temperatures are measured in the bulk gas flow at
a point after which the gas has traversed the combustion chamber volume
that provides the specified residence time for the unit. Generally,
temperature measurement at a point of flame impingement or at a point
directly in sight of radiation from the flame is not recommended.
(b) Excess Air. Instrumentation is available to measure and
control oxygen and carbon monoxide (CO) concentrations in the combustion
gas to ensure proper excess air levels.
Oxygen and CO concentrations in the combustion gas are usually
measured at a point of high turbulence, after the gas has traversed the
full length of the combustion chamber. A good location for measurement
is at the inlet to the duct leading from the combustion chamber to the
quench zone.
Oxygen and CO measurements are made on a continuous basis. Whichever
type of sensor is used, it is typically equipped with a gas conditioning
system specified by the manufacturer for the gas environment in which the
instrument is used.
When measuring oxygen or CO concentration directly in the
high-temperature flow, some difficulty can be experienced because of
molten slag impingement on the probe. Trial-and-error solutions of
location and probe length can minimize this problem. A redundant system
for scheduled maintenance is desirable.
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INCINERATION REFERENCES
1. Bonner, T.A., et al. Engineering Handbook for Hazardous Waste
Incineration. Prepared by Monsanto Research Corporation for U.S.
Environmental Protection Agency, PB81-248163. June 1981.
2. Brunner, Calvin R. Incineration Systems: Selection and Design. New
York, New York. Von Nostrand Reinhold Company, Inc. 1984.
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4.6 Wet Air Oxidation
4.6.1 Applicability
This technology is demonstrated for the F001-F005 spent solvent
wastewaters. The Agency has treatment performance data for pilot-scale
wet air oxidation treatment for methylene chloride, methanol, methyl
ethyl ketone, tetrachloroethylene, toluene, 1,1,1-trichloroethane, and
xylene. We believe these data represent treatment of wastes which are
the same as or judged to be similar to spent solvent wastes that will be
subject to this rule. The data are presented in Section 5 of this
document.
The underlying principles of wet air oxidation are presented in
subsection 4.6.2. Descriptions of conventional and catalyzed wet air
oxidation are presented in subsection 4.6.3. Design and operating
parameters affecting performance are discussed in subsection 4.6.4.
4.6.2 Underlying Principles of Operation
Wet air oxidation is a controlled oxidation destruction process
conducted in a water solution at moderate temperatures (175-340°C) and
elevated pressures (300-3000 psi) to destroy organic constituents in
wastewater. The oxidation process converts organic compounds into carbon
dioxide, water and simple organic acids. The specific end products of
wet air oxidation vary depending on the chemical composition of the
organics.
The chemistry of the wet air oxidation reaction includes several
intermediate reaction steps that involve the formation and participation
of free radicals:
RH + 02 -» R» + »OOH
R« + 02 •> ROO*
ROO* + RH -» ROOH + R»
The reactions above will not occur at room temperature and pressure
because of the low solubility of oxygen in water at these conditions.
Consequently, the wet air oxidation reaction is conducted at moderate
temperatures and elevated pressures where the solubility of oxygen is
much greater.
Pressurization of the reactor also keeps the water in a liquid state
at the operating temperature of the system and prevents excess
evaporation of the liquid phase. The oxygen partial pressure required
depends on the oxidation reaction kinetics and the mass balance
characteristics of the reactor.
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In general, high molecular weight compounds are oxidized before lower
molecular weight compounds; however, the ease of oxidation also depends
on molecular structure. Electron donating functional groups, such as OH
and NH2, will enhance oxidation. The presence of electron withdrawing
groups, such as halogens, will result in lower oxidation rates. With
halogenated organics it may be necessary to use a cupric ion catalyst in
the oxidation process.
The main advantage of wet air oxidation is that it allows the
oxidation in water media at a lower temperature than other thermal
treatment methods.
4.6.3 Description of Wet Air Oxidation
There are two types of wet air oxidation commercially available:
conventional wet air oxidation and catalyzed wet air oxidation.
Catalyzed wet air oxidation allows for either a higher destruction
efficiency than conventional at the same temperature or the same
destruction efficiency at a lower temperature.
(1) Conventional Wet Air Oxidation. A wet air oxidation system (see
Figure 4-15) consists of a compressor, a heat exchanger, reactor vessel,
and a vapor liquid separator. Wastewater containing the organic
contaminants is pumped into the system using a high pressure pump to
maintain pressure at a high enough level so that at the operating
temperature, system pressure exceeds the steam pressure.
The waste stream is preheated to the reaction conditions by indirect
heat exchange with the hot oxidized effluent. This enables the process
to be thermally self-sufficient; the heat of combustion released in the
reactor is used to preheat the influent and thereby sustain the
reaction. In cases where the heat of combustion is insufficient to
sustain the reaction (due to a low influent concentration of organics),
additional heat may be necessary. This extra heat is added either by
inserting start-up steam into the reactor, or by placing a start-up heat
exchanger between the reactor and the effluent heat recovery exchanger.
Air or pure oxygen, used as the oxidant, is injected either into the
feed line before the heat exchanger, or directly into the reactor
vessel. The amount of oxygen which can be dissolved in the water
increases with both temperature and pressure.
As the oxidation progresses, the heat of combustion is liberated
increasing the temperature in the reactor. The reaction time varies from
a few minutes to several hours depending on the waste type and the
desired effluent concentrations.
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Gaseous Effluent
Waste
Influent
Pressurized
Air
Start-up.
Steam
High
Pressure
Reactor
Gas to
Air Pollution
Control
1
Separator
Waste
Effluent
Figure 4-15
Wet Air Oxidation
4-64
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After cooling, the oxidized effluent is reduced to atmospheric
pressure through a pressure control valve. A gas liquid separator is
then used to separate the gaseous and liguid elements of the effluent
stream.
Wet air oxidation.is not necessarily a "stand-alone" process. The
vapor stream is normally sent to some type of air pollution control
system such as a scrubber, activated carbon treatment, or a gas
incinerator. The aqueous stream may require further treatment, such as
biological treatment to remove low molecular weight acids or hydrochloric
acid if chlorinated organics are oxidized.
(2) Catalyzed Wet Air Oxidation. The major impact of a catalyst on
the system is either to lower the reaction temperature or increase the
destruction efficiency. A catalyst has three roles in the reaction:
oxygen fixation, generation of free radicals and organic oxidation. Two
catalysts are mentioned in the literature: bromide-nitrate and cupric
ion. The bromide-nitrate catalyst increases the transfer of oxygen to
the aqueous phase at low temperature and accelerates the reactions.
Cupric ion has shown high levels of catalytic activity over a wide range
of conditions; it is particularly effective for halogenated compounds.
Catalytic wet air oxidation using bromide nitrate catalyst usually
requires a reactor design different from the conventional design. A
continuously stirred tank reactor (CSTR) contains the catalyst solution.
Air and waste containing organics are pumped into the reactor and
oxidized, with the heat of reaction driving off water. The water and any
condensible organics are condensed and returned to the reactor.
Inorganic salts or acids formed during the oxidation may have to be
removed by treatment in a closed loop stream. The operating temperature
of a catalytic wet air oxidation system ranges from 165°C to 275°C.
(Reference 4).
4.6.4 Design and Operating Parameters Affecting Performance
There are four parameters which affect the performance of wet air
oxidation systems:
• Temperature,
• Pressure,
• Residence time, and
• Waste type.
The temperature is the most important parameter affecting the
system. The temperature must be high enough to allow the oxidation
reactions to reach completion. The pressure affects the performance of
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the system by causing dissolution of oxygen into solution. It also must
be high enough to keep the water in the aqueous phase at the operating
temperature. If the water is not kept in the aqueous phase the oxidation
reactions will be slowed or stopped.
The residence time is important in assuring that the wastes are in
the reactor long enough for the oxidation reactions to reach completion.
Typically, the reaction rates are relatively fast for the first 30
minutes; after 60 minutes, the rates become slow. There is little
increase in overall oxidation with extended reaction time. (Reference 3).
The operating conditions of the system {temperature, pressure, and
residence time) need to be selected based on the type of waste being
treated. Some wastes (such as aliphatics or chlorinated aliphatics) are
relatively easy to oxidize; others (such as high molecular weight
chlorinated species) require extreme operating conditions or a catalyst
(such as CuCl2) to achieve adequate destruction.
The effluent from the wet air oxidation unit primarily consists of
carbon dioxide and water. For some complex wastes, the aqueous effluent
may also contain simple organic acids. If very volatile chemicals are
oxidized, some volatilization may occur during treatment producing low
concentration organics in the vapor stream. If chlorinated compounds are
oxidized, the vapor stream may contain HC1. The vapor stream may require
further treatment such as by activated carbon adsorption or a scrubber to
collect HC1 and any residual organics. The aqueous effluent is usually
treated biologically to destroy the organic acids.
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WET AIR OXIDATION REFERENCES
1. Baillord, C. Robert and Faith, Bonnie M. Wet Oxidation and Ozonation
of Specific Organic Pollutants. Prepared for USEPA under Grant
No. R805565-010. EPA-600/2-83-060. August 1983.
2. Dietrich, M.J., Copa, W.M., and Cannery, P.J. Demonstration of Full
Scale Wet Air Oxidation of Hazardous Waste. Prepared for State of
California Depart of Health Services under Contract No. 83-82053
ORR-54 A-l. November 1984.
3. Freeman, H. Innovative Thermal Hazardous Waste Treatment Processes.
U.S. Environmental Protection Agency, Hazardous Waste Research
Laboratory, Office of Research and Development. 1985.
4. Dietrich, M.J., Randall, T.L., and Cannery, P.J. Wet Air Oxidation
of Hazardous Organics in Wastewater. Environmental Progress Vol 4,
No.3, pp 171-177. August 1985.
5. Schultz, David W., Editor. Incineration and Treatment of Hazardous
Waste. Proceedings of 8th Annual Research Symposium at Fort
Mitchell, K.Y. EPA Contract No. 600/9-83-003. March 8-10 1982.
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4.7 Air Stripping
4.7.1 Applicability
This technology is demonstrated for wastewaters containing F001-F005
spent solvents. The Agency has pilot-scale air stripping treatment
performance data from treatment of ground water contaminated with
1,1,1-trichloroethane, methyl isobutyl ketone, toluene,
tetrachloroethylene, and ethylbenzene and from treatment of tap water
spiked with tetrachloroethylene and trichloroethylene. Though these data
are not included in EPA's definition of spent solvent wastes, the Agency
believes that such wastewaters are similar to spent solvent wastes that
will be subject to this rule. The data are presented in Section 5 of
this document.
The underlying principles of air stripping are presented in
subsection 4.7.2. Descriptions of air stripping technologies are
presented in subsection 4.7.3.
4.7.2 Underlying Principles of Operation
Air stripping is a mass transfer process in which an "organic"
constituent dissolved in wastewater is transferred to the gas phase,
air. Since air is a noncondensable medium, it does not directly
influence the vapor liquid equilibrium relationship. The relative
volatility of the organic constituents in water determines the ease with
which the organic constituents are separated. The air effluent is
generally not recovered because the concentrations of the organics are
very low, and for recovery of the organics it would be necessary to cool
the constituents to their respective dew points using mechanical
refrigeration. In some instances, the air effluent may be routed to a
catalytic combustor which is fed by auxiliary fuel or to carbon
adsorption. The liquid effluent is generally discharged under an NPDES
permit or to a municipal wastewater treatment system. With highly
volatile constituents the system may be operated at ambient conditions.
The wastewater feed may be preheated to enhance the vaporization of less
volatile components.
4.7.3 Description of Air Stripping
Air stripping is accomplished in a packed column or through the use
of aeration devices. In a packed column configuration, the wastewater
feed is introduced at the top of the column and the air is drawn or blown
into the bottom of the column. A schematic diagram of a packed air
stripping column is shown in Figure 4-16.
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Waste
Influent
Vent
to
Atmosphere
Distributor
Air Inlet
Waste Effluent
Figure 4-16
Air Stripping
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The principal types of aeration devices used to strip volatiles from
water are: mechanical surface aerators and diffused aerators.
(1) Mechanical Surface Aerators. These types of aerators are the
simplest. Aeration is accomplished by submerged or partially submerged
impellers that agitate the water vigorously. The turbulence entrains air
in the wastewater and rapidly changes the air-water interface to
facilitate solution of the air. Air stripping of volatiles within the
water is also achieved by the agitation and increased air-water contact.
(2) Diffused Aerators. Air stripping is accomplished in diffused
aeration by injecting air bubbles into water through submerged diffusers
or porous plates. Ideally, the process is conducted counterflow, with
the untreated water entering the top and the treated water exiting the
bottom. Exhausted air leaves the top. Gas transfer can be improved by
increasing the basin depth, improving contact basin geometry, and using a
turbine to reduce the bubble size and increase bubble retention time.
Diffused aeration is commonly used to strip volatiles prior to or during
biological treatment processes.
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AIR STRIPPING REFERENCES
1. Canter, L.W. and R.C. Knox. Ground Water Pollution Control. Lewis
Publishers, Inc., Chelsea, Michigan. 1986.
2. Treybal, Robert E. Mass-Transfer Operations, Third Edition.
McGraw-Hill, Inc., New York. 1980.
3. Roach, Andrew P. and Wayne E. Sisk, "Pilot Demonstration of an Air
Stripping Technology for the Treatment of Groundwater with Volatile
Organic Compounds," in Proceedings of the American Defense
Preparedness Association, 14th Environmental Systems Symposium, Omega
International Hotel, Baltimore, Maryland, October 23-25, 1985.
4. Water Chemical Corporation, Process Design Manual of Stripping of
Organics, EPA 600/2-84-139, PB84-232628, August, 1984. Prepared for
the U.S. Department of Commerce, National Technical Information
Service.
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4.8 Fuel Substitution
4.8.1 Applicability
This technology is demonstrated for F001-F005 spent solvent wastes
other than wastewater. According to a 1983 EPA survey, 4,934 industrial
boilers and 868 industrial furnaces and kilns burned waste-derived fuel.
A large volume of the hazardous wastes burned in these devices contained
chlorinated and nonchlorinated solvent constituents. Data indicate that
many of the solvent constituents listed in F001 and F005 wastes have been
present in hazardous wastes burned as fuel substitutes. In cases where
F001-F005 spent solvents contain high concentrations of chlorine, wastes
must be blended with other organic wastes or fuel prior to burning to
minimize corrosivity caused by the formation of hydrochloric acid vapor.
In conclusion, fuel substitution is we11-demonstrated for most boilers
for wastes that are highly concentrated and that contain minimal amounts
of suspended solids.
The underlying principles of operation for fuel substitution are
presented in subsection 4.8.2. Descriptions of appropriate technologies
are presented in subsection 4.8.3. Design and operating parameters
affecting performance are discussed in subsection 4.8.4.
4.8.2 Underlying Principles of Operation
Fuel substitution involves the use of combustible organic wastes as
substitutes for conventional fuels that are burned in high temperature
industrial processes. As in incineration, the organic waste is destroyed
in flame combustion yielding essentially carbon dioxide and water. If
halogenated organics are burned, acid and free halogen are also among the
products of combustion, e.g., combustion of chlorinated wastes yield
hydrogen chloride and chlorine in the flue gas streams.
The underlying principles of operation for incineration are in large
part equally applicable for fuel substitution. See Section 4.5 for a
discussion of these principles.
4.8.3 Description of Fuel Substitution
There are many high temperature industrial processes with
temperatures and residence time sufficient to destroy solvent wastes. In
most cases, the organic waste is used to supplement primary fuels such as
natural gas, fuel oil, or coal, thus lowering the total fuel cost
required for the process, and providing an inexpensive means of
destroying wastes. The more predominant industrial applications for this
technology are discussed below (Reference 1).
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(1) Industrial Boilers. A boiler is a closed vessel in which water
under pressure is transformed into steam by the application of heat.
Typically, heat is supplied by the combustion of pulverized coal, fuel
oil, or gas. These fuels are fired into a combustion chamber with
nozzles and burners that provide mixing with air. Liquid wastes, and
granulated solid wastes in the case of grate-fired boilers, can be burned
as fuels in a boiler by using these wastes as auxiliary fuels. However,
it has been reported that few grate-fired boilers burn hazardous wastes.
These boilers are not often used in the types of industries that produce
combustible hazardous wastes.
In general, burning of solvent-containing wastes in industrial
boilers is economically attractive when the waste possesses a heat
content greater than or equal to 8,000 to 10,000 Btu per pound.
Viscosity is also an important physical parameter for waste liquid
injection systems, as discussed previously in the section on liquid
injection incinerators.
Deposition of fly ash and slag on heating surfaces in a boiler can
lead to serious fouling and potential burn-out of boiler tubes.
Therefore, facilities may reject wastes if they contain unacceptable
levels of ash content. Generally, oil-fired boilers are designed to be
fired with oils containing less than 0.2 percent ash. Boilers fired with
coal are reportedly designed to handle fuels containing roughly 8 to 20
percent ash.
Another important waste characteristic that should be taken into
consideration is the chlorine content of the waste. Excess quantities of
chlorine may lead to unacceptable corrosion of the unprotected metal
surfaces within the boiler. Modern boilers operating at supercritical
steam conditions are especially susceptible to chloride stress (corrosion
failure of boiler tubes). Acceptable chloride levels in the fuel/waste
mixture vary with type of boiler and owner preference.
(2) Industrial Kilns. Combustible wastes may also be used as fuel
in industrial kilns. Three types of kilns are particularly applicable:
(1) cement kilns, (2) lime kilns, and (3) light-weight aggregate kilns.
There are other types of high-temperature industrial processes, such as
blast furnaces, sulfur recovery furnaces, and brick ovens that may also
be used.
Combustible waste liquids are often used to co-fire industrial
kilns. Coal-fired kilns are capable of handling solid wastes if particle
size is reduced.
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Clinker, a primary additive of cement, is manufactured in a cement
kiln, which is an application of rotary kiln technology. The cement kiln
is a refractory-lined steel shell used to calcine a mixture of calcium,
silicon, aluminum, iron, and magnesium. These raw materials are crushed,
blended, and fed to the kiln as either a slurry or a dry mixture, thus
the terms wet and dry kilns. In the wet process, water is added to the
raw materials before they are ground. Over 50 percent of the cement
kilns in the United States use the wet technology. The kiln is usually
fired by coal or oil; liquid and solid combustible wastes then serve as
auxiliary fuel. Temperatures within the kiln are typically between
1,380°C and 1,540°C (2,500°F and 2,800°F).
Lime (CaO) is manufactured in a calcination process using limestone
(CaCC>3) or dolomite (CaCC>3 • MgCC>3). These raw materials are also
heated in a refractory-lined rotary kiln to temperatures of 982°C to
1,260°C (1,800°F to 2,300°F). Light-weight aggregate kilns heat clay to
produce an expanded lightweight inorganic material, which is used in
Portland Cement formulations and other applications. The kiln has a
temperature range of 1,100°C to 1,150°C (2,000°F to 2,100°F) with a
residence time of 1.5 seconds.
As with industrial boilers, industrial kilns will generally accept
wastes with sufficient heat content to promote combustion. For cement
and lime kilns, product quality may degrade as the chlorine content of
the fuel increases. For cement kilns, this level is about 0.7 percent of
the total fuel feed; for lime kilns, about 0.5 percent. However, wastes
with higher chlorine content may be blended with fuels of lower chlorine
content to obtain a fuel that will not affect product quality.
4.8.4 Design and Operating Parameters Affecting Performance
The principal design and operating parameters affecting performance
of industrial processes are the same as for incinerators, e.g., fuel/air
stoichiometry, temperature, and residence time. However, for industrial
processes these parameters are fixed by the requirements of the
industrial process. Thus, the industrial processes that are suitable for
burning wastes are those processes where the design and operating
parameters match or exceed the equivalent specifications required for
incineration wastes.
Temperatures are monitored and controlled in industrial boilers in
order to provide the needed quality and flowrate of steam. The
efficiency of combustion in industrial boilers is monitored by CO and
02 instrumentation to ensure efficient utilization of fuel and to meet
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air pollution standards. In larger boilers, it is also common to monitor
flame stability, flame shape, and flame quality by means of video cameras
and monitors.
Wastes should not be co-fired until temperature reaches the minimum
needed for destruction of the wastes. Temperature, CO, and 02
instrumentation and control should be designed to stop waste co-firing in
the event of process upsets.
Monitoring and control of temperature in industrial kilns is critical
to the production of quality product, i.e., lime, cement, or aggregrate
production requires minimum temperature for calcination. Kilns have very
high thermal inertia in the refractory and in-process product, high
residence times and high air flow rates, so that even in the case of
momentary stoppage of fuel flow to the kiln, residual wastes would
continue to be destroyed. The main operational control required for
waste burning in kilns is to stop waste flow in the events of low kiln
temperature, loss of the electrical power to the draft air fan, and loss
of primary fuel flow.
Industrial boilers and kilns generally employ some means of
particulate control, such as electrostatic precipitation or bag house.
The ash or product fines collected by these devices are generally land
disposed and, as a result, will have to meet any applicable land disposal
restriction regulations in the future.
The Agency is currently developing regulations that will govern the
use of hazardous waste as fuel. These standards are likely to control
hydrogen chloride emissions. (The Agency already controls these
emissions for incinerators.) To meet the emission standard,
owner/operators could limit the chlorine levels in the waste or rely on
emission control equipment, such as scrubbers. EPA believes that most
industrial furnaces, and some boilers, will be able to meet these
standards when burning hazardous solvent wastes as fuel.
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FUEL SUBSTITUTION REFERENCES
1. Westat, Inc. Final Report for the Survey of Waste As Fuel: Track II
(Survey of Burners of Used or Waste Oil and Waste-Derived Fuel
Material). Prepared for U.S. EPA, OSW under EPA Contract No.
68-01-6621. November 1985.
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