United States
Environmental Protection
Agency
AIR
Office of Air Quality
Planning And Standards
Research Triangle Park, NC 27711
EPA-454/R-98-006
May 1998
EPA
LOCATING AND ESTIMATING
AIR EMISSIONS FROM
SOURCES OF LEAD AND LEAD COMPOUNDS
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EPA-454/R-98-006
Locating And Estimating Air Emissions
From Sources of Lead and Lead Compounds
Office of Air Quality Planning and Standards
Office of Air and Radiation
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
May 1998
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This report has been reviewed by the Office of Air Quality Planning and Standards, U.S.
Environmental Protection Agency, and has been approved for publication. Mention of trade
names and commercial products does not constitute endorsement or recommendation for use.
EPA-454/R-98-006
in
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TABLE OF CONTENTS
Section Page
LIST OF TABLES xiii
LIST OF FIGURES xviii
EXECUTIVE SUMMARY xxi
1.0 PURPOSE OF DOCUMENT 1-1
2.0 OVERVIEW OF DOCUMENT CONTENTS 2-1
3.0 BACKGROUND 3-1
3.1 PHYSICAL AND CHEMICAL NATURE OF LEAD AND
LEAD COMPOUNDS 3-1
3.1.1 Organolead Compounds 3-3
3.1.2 Lead Oxides 3-10
3.1.3 Lead Sulfides 3-11
3.1.4 Lead Salts 3-11
3.2 OVERVIEW OF PRODUCTION AND USE 3-12
4.0 EMISSIONS OF LEAD AND LEAD COMPOUNDS FROM THE
METALLURGICAL INDUSTRY 4-1
4.1 PRIMARYLEAD SMELTING 4-1
4.1.1 Process Description 4-2
4.1.2 Emission Control Techniques 4-4
4.1.3 Emissions 4-5
4.2 SECONDARY LEAD SMELTING 4-5
4.2.1 Source Location 4-5
4.2.2 Process Description 4-5
Reverberatory Furnaces 4-10
Blast Furnaces 4-12
Rotary Furnaces 4-15
Electric Furnaces 4-17
4.2.3 Emission Control Techniques 4-19
4.2.4 Emissions 4-20
IV
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TABLE OF CONTENTS, (CONTINUED)
Section Page
4.3 PRIMARY COPPER PRODUCTION 4-23
4.3.1 Source Description 4-23
4.3.2 Process Description 4-23
4.3.3 Emissions 4-24
4.3.4 Emission Control Techniques 4-27
4.4 SECONDARY COPPER PRODUCTION 4-31
4.4.1 Source Description 4-31
4.4.2 Process Description 4-31
4.4.3 Emission Control Techniques 4-34
4.4.4 Emissions 4-36
4.5 PRIMARY ZINC SMELTING 4-36
4.5.1 Source Description 4-36
4.5.2 Process Description 4-38
4.5.3 Emissions 4-44
4.6 SECONDARY ALUMINUM OPERATIONS 4-45
4.6.1 Source Description 4-45
4.6.2 Process Description 4-45
4.6.3 Emissions and Emission Control Techniques 4-50
4.7 IRON AND STEEL FOUNDRIES 4-52
4.7.1 Source Location 4-52
4.7.2 Process Description 4-52
Metal Melting Process 4-56
Mold and Core Production 4-57
4.7.3 Emission Control Techniques 4-57
4.7.4 Emissions 4-57
4.8 ORE MINING, CRUSHING, AND GRINDING 4-57
4.8.1 Source Description 4-57
4.8.2 Process Description 4-59
4.8.3 Emissions 4-61
4.8.4 Emission Control Techniques 4-61
4.9 BRASS AND BRONZE PROCESSING 4-61
4.9.1 Source Description 4-61
4.9.2 Process Description 4-64
4.9.3 Emissions 4-66
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TABLE OF CONTENTS, (CONTINUED)
Section Page
5.0 EMISSIONS OF LEAD AND LEAD COMPOUNDS FROM
COMBUSTION SOURCES 5-1
5.1 STATIONARY EXTERNAL COMBUSTION 5-1
5.1.1 Source Location 5-3
5.1.2 Residential Heating 5-4
Residential Coal Combustion 5-4
Process Description 5-4
Emissions 5-5
Residential Distillate Oil Combustion 5-5
Process Description 5-5
Emissions 5-7
Residential Natural Gas Combustion 5-7
Process Description 5-7
Emissions 5-7
5.1.3 Process Descriptions for Utility, Industrial, and
Commercial Fuel Combustion 5-9
Utility Sector 5-9
Tangentially-fired Boiler 5-9
Wall-fired Boiler 5-11
Cyclone-fired Boiler 5-11
FluidizedBed Combustion Boiler 5-11
Stoker-fired Boiler 5-14
Emission Control Techniques 5-14
Industrial/Commercial Sector 5-16
Stoker-fired Boiler 5-17
Water-tube Boilers 5-17
Fire-tube and Cast Iron Boilers 5-18
Wood Waste Boilers 5-18
Waste Oil Combustion 5-20
Coal Combustion 5-21
Emission Control Techniques 5-21
5.1.4 Emission Factors for Utility, Industrial, and
Commercial Fuel Combustion 5-22
Wood Waste Combustion 5-23
Natural Gas Combustion 5-28
Coal Combustion 5-30
Oil Combustion 5-38
Solid Waste Combustion 5-38
Miscellaneous Combustion 5-38
VI
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TABLE OF CONTENTS, (CONTINUED)
Section Page
5.2 STATIONARY INTERNAL COMBUSTION SOURCES 5-44
5.2.1 Source Description 5-44
5.2.2 Emissions 5-45
5.3 MUNICIPAL WASTE INCINERATION 5-45
5.3.1 Source Location 5-45
5.3.2 Process Description 5-46
Mass Burn Combustors 5-46
RDF-Fired Combustors 5-53
Modular Combustors 5-53
Emission Control Techniques 5-56
5.3.3 Emissions 5-57
5.4 INDUSTRIAL AND COMMERCIAL WASTE
INCINERATION 5-57
5.4.1 Source Location 5-57
5.4.2 Process Description 5-61
5.4.3 Emissions 5-62
5.5 SEWAGE SLUDGE INCINERATORS 5-62
5.5.1 Source Location 5-62
5.5.2 Process Description 5-63
Multiple-Hearth Furnaces 5-63
Fluidized-Bed Combustors 5-65
Emission Control Techniques 5-67
5.5.3 Emissions 5-68
5.6 MEDICAL WASTE INCINERATION 5-68
5.6.1 Source Location 5-71
5.6.2 Process Description 5-71
Controlled-Air Incinerators 5-71
Excess-Air Incinerators 5-73
Rotary Kiln Incinerators 5-75
Emission Control Techniques 5-77
Combustion Control 5-78
APCD Control 5-78
.3 Emissions 5-78
5.7 HAZARDOUS WASTE INCINERATION 5-82
5.7.1 Source Location 5-83
5.7.2 Process Description 5-83
Liquid Injection Incinerators 5-85
vn
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TABLE OF CONTENTS, (CONTINUED)
Section Page
Rotary Kiln Incinerators 5-85
Fixed-Hearth Incinerators 5-88
Fluidized-Bed Incinerators 5-88
Fume Injection Incinerators 5-90
Emission Control Techniques 5-90
5.7.3 Emissions 5-91
5.8 DRUM AND BARREL RECLAMATION 5-91
5.8.1 Source Location 5-91
5.8.2 Process Description 5-91
5.8.3 Emissions 5-92
5.9 SCRAP TIRE INCINERATION 5-92
5.9.1 Source Location 5-92
5.9.2 Process Description 5-94
5.9.3 Emissions 5-95
5.10 OPEN BURNING OF SCRAP TIRES 5-95
5.10.1 Source Location 5-95
5.10.2 Process Description 5-95
5.10.3 Emissions 5-96
5.11 CREMATORIES 5-96
5.11.1 Source Location 5-96
5.11.2 Process Description 5-96
5.11.3 Emissions 5-99
5.12 PULP AND PAPER INDUSTRY 5-99
5.12.1 Kraft Recovery Furnaces and Smelt Dissolving
Tanks 5-101
Source Location 5-101
Process Description 5-101
Emissions 5-107
5.12.2 Lime Kilns 5-108
Source Location 5-108
Process Description 5-108
Emissions 5-111
5.12.3 Sulfite Recovery Furnaces 5-111
Source Location 5-111
Process Description 5-111
Emissions 5-115
Vlll
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TABLE OF CONTENTS, (CONTINUED)
Section Page
5.13 PORTLAND CEMENT MANUFACTURING 5-115
5.13.1 Source Location 5-115
5.13.2 Process Description 5-117
5.13.3 Emission Control Techniques 5-125
5.13.4 Emissions 5-126
6.0 EMISSIONS OF LEAD AND LEAD COMPOUNDS FROM
OTHER SOURCES 6-1
6.1 PRESSED AND BLOWN GLASS 6-1
6.1.1 Source Description 6-1
6.1.2 Process Description 6-2
6.1.3 Emissions 6-5
6.2 LEAD-ACID BATTERY PRODUCTION 6-7
6.2.1 Source Description 6-7
6.2.2 Process Description 6-8
6.2.3 Emissions 6-14
6.3 LEAD OXIDES IN PIGMENTS 6-17
6.3.1 Source Location 6-17
6.3.2 Process Description 6-17
Lead Oxides 6-17
Lead Monoxide 6-17
Black Oxides 6-20
Lead Dioxide 6-20
Lead Pigments 6-23
Red Lead 6-23
White Lead 6-23
Lead Chromate 6-23
Leaded Zinc Oxides 6-23
6.3.3 Emissions 6-24
Lead Oxides 6-24
Lead Pigments 6-24
Red Lead 6-24
6.4 LEAD CABLE COATING 6-25
6.4.1 Source Description 6-25
6.4.2 Process Description 6-27
6.4.3 Emissions 6-28
6.5 FRIT MANUFACTURING 6-30
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TABLE OF CONTENTS, (CONTINUED)
Section Page
6.5.1 Process Description 6-30
6.5.2 Emissions 6-31
6.6 CERAMICS AND GLAZES 6-33
6.6.1 Process Description 6-37
6.6.2 Emissions 6-38
6.6.3 Piezoelectric Ceramics 6-38
Process Description 6-41
Emissions 6-41
6.7 MISCELLANEOUS LEAD PRODUCTS 6-41
6.7.1 Ammunition 6-43
Emissions 6-43
6.7.2 Type Metal Production 6-43
Process Description 6-45
Emissions 6-45
6.7.3 Other Metallic Lead Products 6-46
Process Description 6-46
Emissions 6-47
6.7.4 Abrasive Grain Processing 6-47
Process Description 6-47
Emissions 6-50
6.8 SOLDER MANUFACTURING 6-51
6.8.1 Source Description 6-51
6.8.2 Process Description 6-51
6.8.3 Emissions 6-52
6.9 ELECTROPLATING (INCLUDING PRINTED CIRCUIT
BOARDS) 6-53
6.9.1 Source Description 6-53
6.9.2 Process Description 6-53
6.9.3 Emissions 6-58
6.10 STABILIZERS IN RESINS 6-58
6.10.1 Process Description 6-60
6.10.2 Emissions 6-64
6.11 ASPHALT CONCRETE 6-64
6.11.1 Source Location 6-64
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TABLE OF CONTENTS, (CONTINUED)
Section Page
6.11.2 Process Description 6-65
Emission Control Techniques 6-71
6.11.3 Emissions 6-72
6.12 APPLICATION OF PAINTS 6-72
6.12.1 Source Description 6-74
Automotive Industry and Automobile Refmishing 6-74
Industrial Applications 6-75
Machinery Finishes/Traffic Paints 6-75
Artists Paints 6-75
Marine Coatings 6-75
6.12.2 Process Description 6-76
6.12.3 Emissions 6-77
6.13 SHOOTING RANGES AND EXPLOSIVE ORDINANCE
DISPOSAL SITES 6-77
6.13.1 Source Description 6-77
6.13.2 Emissions 6-78
6.14 RUBBER PRODUCTS 6-80
6.14.1 Process Description 6-81
6.14.2 Emissions 6-83
7.0 EMISSIONS OF LEAD AND LEAD COMPOUNDS FROM
MOBILE SOURCES 7-1
7.1 GENERAL 7-1
7.1.1 Leaded Fuels 7-2
7.1.2 Unleaded Fuels 7-6
.2 EVAPORATIVE EMISSIONS FROM FUEL
DISTRIBUTION FOR MOBILE SOURCES 7-6
7.3 COMBUSTION EMISSIONS 7-8
7.4 ROAD DUST 7-9
7.4.1 Paved Roads 7-9
7.4.2 Unpaved Roads 7-11
8.0 SOURCE TEST PROCEDURES 8-1
8.1 AMBIENT AIR SAMPLING METHODS 8-1
XI
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TABLE OF CONTENTS, (CONTINUED)
Section Page
8.2 STATIONARY SOURCE SAMPLING METHODS 8-5
8.2.1 EPA Method 12 - Methodology for the
Determination of Metals Emissions in Exhaust
Gases from Hazardous Waste Incineration and
Similar Combustion Sources 8-5
8.2.2 EPA Draft Method 29 - Determination of Metals
Emissions from Stationary Sources 8-7
8.3 ANALYTICAL TECHNIQUES FOR THE
MEASUREMENT OF LEAD 8-9
8.3.1 Direct Aspiration (Flame) Atomic Absorption
Spectroscopy 8-9
8.3.2 Graphite Furnace Atomic Absorption Spectroscopy 8-10
8.3.3 Inductively Coupled Plasma Atomic Emission
Spectroscopy 8-10
9.0 REFERENCES 9-1
APPENDICES
Appendix A - Emission Factor Summary Table A-l
xn
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LIST OF TABLES
Table Page
3-1 Physical Properties of Lead 3-2
3-2 Physical Properties of the Principal Lead-Ore Compounds 3-3
3-3 Uses of Lead Alloys 3-4
3-4 Lead Compounds 3-6
4-1 Domestic Primary Lead Smelters and Refineries 4-1
4-2 Lead Emission Factors for Primary Lead Smelting Facilities 4-6
4-3 U.S. Secondary Lead Smelters Grouped According to Annual Lead Production
Capacity 4-7
4-4 Lead Emission Factors for Secondary Lead Smelting 4-21
4-5 Lead Emission Factors for Primary Copper Smelting Facilities 4-28
4-6 Chemical Characteristics of Fugitive Particulate Emissions from Various Sources
at Primary Copper Smelters 4-30
4-7 Domestic Secondary Copper Producers 4-32
4-8 Lead Emission Factors for Secondary Copper Smelting Facilities 4-37
4-9 Domestic Primary Zinc Producers 4-38
4-10 Lead Emission Factors for Secondary Aluminum Production 4-51
4-11 Lead Emission Factors for Iron and Steel Foundries 4-58
4-12 Lead Emission Factors for Leadbearing Ore Crushing and Grinding 4-62
4-13 Emission Sources and Control Devices 4-63
4-14 Characteristics of Uncontrolled Exhaust Gas from a Brass and Bronze
Reverberatory Furnace 4-67
4-15 Brass and Bronze Production and Lead Emissions in 1992 4-67
5-1 Lead Emission Factors for Residential Coal Combustion 5-6
xiii
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LIST OF TABLES, (CONTINUED)
Table Page
5-2 Emission Factors for Residential Distillate Oil-fired Furnaces 5-8
5-3 Lead Emission Factors for Wood Waste-fired Utility Boilers 5-24
5-4 Lead Emission Factors for Wood Waste-fired Industrial Boilers 5-25
5-5 Lead Emission Factors for Wood Waste-fired Commercial/Institutional Boilers . . . 5-27
5-6 Lead Emission Factors for Natural Gas-fired Utility Boilers from AP-42 5-29
5-7 Lead Emission Factors for Natural Gas-fired Utility Boilers
from Utility Study 5-29
5-8 Lead Emission Factors for Coal-fired Utility Boilers 5-31
5-9 Lead Emission Factors for Coal-fired Utility Boilers from Utility Study 5-33
5-10 Lead Emission Factors for Coal-fired Industrial Boilers 5-34
5-11 Lead Emission Factors for Coal-fired Commercial/Institutional Boilers 5-36
5-12 Lead Emission Factors for Oil-fired Utility Boilers 5-39
5-13 Lead Emission Factors for Oil-fired Utility Boilers from Utility Study 5-40
5-14 Lead Emission Factors for Oil-fired Industrial Boilers 5-40
5-15 Lead Emission Factors for Oil-fired Commercial/Institutional Boilers 5-41
5-16 Lead Emission Factors for Waste Oil-fired Industrial Boilers 5-41
5-17 Lead Emission Factors for Waste Oil-fired Commercial/Institutional Boilers 5-42
5-18 Lead Emission Factors for Solid Waste-fired Utility Boilers 5-43
5-19 Lead Emission Factors for Miscellaneous Industrial Boilers 5-43
5-20 Summary of Geographical Distribution of MWC Facilities 5-47
5-21 Lead Emission Factors for Municipal Waste Combustion Sources 5-58
XIV
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LIST OF TABLES, (CONTINUED)
Table Page
5-22 Lead Emission Factors for Sewage Sludge Incinerator Sources 5-69
5-23 Lead Emission Factors for Medical Waste Combustion Sources 5-79
5-24 Lead Emission Factors for Drum And Barrel Reclamation Sources 5-93
5-25 Lead Emission Factors for Open Burning Of Scrap Tires 5-97
5-26 1991 U.S. Crematory Locations by State 5-98
5-27 Lead Emission Factor for Crematories 5-100
5-28 Distribution of Kraft Pulp Mills in the United States (1997) 5-102
5-29 Lead Emission Factors for Kraft Process Recovery Furnaces and Smelt Dissolving
Tanks 5-109
5-30 Lead Emission Factors for Lime Kilns 5-112
5-31 Distribution of Sulfite Pulp Mills in the United States (1997) 5-113
5-32 Lead Emission Factors for Sulfite Process Recovery Furnaces 5-116
5-33 Portland Cement Production Facilities 5-118
5-34 Lead Emission Factors for Portland Cement Manufacturing Facilities 5-127
6-1 Glass Manufacturers (SIC 3229) in the United States Reporting Lead and Lead
Compound Emissions Under SARA 313 6-3
6-2 Lead Emission Factor for Glass Manufacturing 6-7
6-3 Lead-Acid Battery Production Facilities 6-9
6-4 Lead Emission Factors for Lead-acid Battery Production 6-16
6-5 U.S. Facilities Manufacturing Lead Oxides in Pigments 6-18
6-6 Characteristics of Uncontrolled Exhaust Gas from Lead Oxide Ball Mill and
Barton Pot Processes 6-25
6-7 Performance Test Results on Baghouses Serving Lead Oxide Facilities 6-26
XV
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LIST OF TABLES, (CONTINUED)
Table Page
6-8 Lead Emission Factors for Manufacture of Lead Oxide in Pigments 6-27
6-9 Lead Emission Factor for Lead Cable Coating 6-29
6-10 Manufacturers of Ceramicware 6-35
6-11 Decorative Ceramic Tile Manufacturers 6-36
6-12 Manufacturers of Enamels for Stove and Range Use 6-37
6-13 Lead Emission Factor for Ceramic/Glaze Application 6-39
6-14 Manufacturers of Lead Zirconate Titanate (PZT) and Manufacturers of
Piezoelectronics 6-40
6-15 Lead Emission Factors for Miscellaneous Lead Products 6-44
6-16 Lead Emission Factor for Type Metal Production 6-46
6-17 Lead Emission Factor for Solder Manufacturing Facilities 6-53
6-18 Lead Electroplating Manufacturers 6-54
6-19 Manufacturers of Heat Stabilizers Containing Lead 6-60
6-20 Manufacturers of Resins and Plastics Reporting Lead and Lead Compound
Emissions in the 1992 Toxic Chemicals Release Inventory 6-61
6-21 Poly vinyl Chloride Manufacturers in the United States 6-63
6-22 Lead Emission Factors for Batch-Mix Hot-Mix Asphalt Plants 6-73
6-23 Lead Emission Factor for Drum-Mix Hot-Mix Asphalt Plants 6-74
6-24 Uncontrolled Lead Emission Factors for EOD Activities 6-79
6-25 End Uses of Rubber that may Contain Lead 6-81
6-26 Rubber Product Manufacturing Facilities in the United States Reporting Lead And
Lead Compound Emissions in 1992 Under SARA 313 6-82
7-1 Lead Content Of Motor Vehicle Fuels 7-3
xvi
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LIST OF TABLES, (CONTINUED)
Table Page
7-2 Fuel Sales 7-4
7-3 Composition and Properties of TEL and TML 7-5
7-4 Industrial Paved Road Silt Loadings 7-10
7-5 Typical Values for Paved Road Industrial Augmentation Factor (I) 7-11
7-6 Typical Silt Content Values of Surface Material on Industrial and Rural Unpaved
Roads 7-13
A-l Summary of Emission Factors by Source Classification Codes A-l
XVll
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LIST OF FIGURES
Figure Page
3-1 Consumption of Lead in the United States in 1992 3-14
4-1 Typical Primary Lead-Processing Scheme 4-3
4-2 Simplified Process Flow Diagram for Secondary Lead Smelting 4-9
4-3 Cross-Sectional View of a Typical Stationary Reverberatory Furnace 4-11
4-4 Cross-Section of a Typical Blast Furnace 4-13
4-5 Side View of a Typical Rotary Reverberatory Furnace 4-16
4-6 Cross-Sectional View of an Electric Furnace for Processing Slag 4-18
4-7 Typical Primary Copper Smelter Flowsheet 4-25
4-8 Copper Converter 4-26
4-9 Fugitive Emission Sources at Primary Copper Smelters 4-29
4-10 Secondary Copper Smelting Processes 4-33
4-11 Electrolytic Primary Zinc-Smelting Process 4-39
4-12 Pyrometallurgical Primary Zinc-Smelting Process 4-43
4-13 Typical Process Diagram for Pretreatment in the Secondary Aluminum Processing
Industry 4-46
4-14 Typical Process Flow Diagram for the Secondary Aluminum Processing Industry . . 4-47
4-15 Process Flow Diagram for a Typical Sand-Cast Iron and Steel Foundry 4-54
4-16 Emission Points in a Typical Iron and Steel Foundry 4-55
4-17 Process Diagram for Ore Mining and Crushing 4-60
4-18 Brass and Bronze Alloys Production Processes 4-65
5-1 Simplified Boiler Schematic 5-10
5-2 Single Wall-fired Boiler 5-12
xviii
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LIST OF FIGURES, (CONTINUED)
Figure Page
5-3 Simplified Atmospheric Fluidized Bed Combustor Process Flow Diagram 5-13
5-4 Spreader Type Stoker-fired Boiler 5-15
5-5 Typical Mass Burn Waterwall Combustor 5-50
5-6 Simplified Process Flow Diagram, Gas Cycle for a Mass Burn/Rotary Waterwall
Combustor 5-51
5-7 Mass Burn Refractory-Wall Combustor with Grate/Rotary Kiln 5-52
5-8 Typical RDF-Fired Spreader Stoker Boiler 5-54
5-9 Typical Modular Starved-Air Combustor with Transfer Rams 5-55
5-10 Typical Multiple-Hearth Furnace 5-64
5-11 Fluidized-Bed Combustor 5-66
5-12 Controlled-Air Incinerator 5-72
5-13 Excess-Air Incinerator 5-74
5-14 Rotary Kiln Incinerator 5-76
5-15 Typical Process Component Options in a Hazardous Waste Incineration Facility ... 5-84
5-16 Typical Liquid Injection Combustion Chamber 5-86
5-17 Typical Rotary Kiln/Afterburner Combustion Chamber 5-87
5-18 Typical Fixed-Hearth Combustion Chamber 5-89
5-19 Typical Kraft Pulping and Recovery Process 5-103
5-20 Direct Contact Evaporator Recovery Boiler 5-105
5-21 Non-direct Contact Evaporator Recovery Boiler 5-106
5-22 Process Flow Diagram for Lime Kiln 5-110
XIX
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LIST OF FIGURES, (CONTINUED)
Figure Page
5-23 Process Diagram for Magnesium-Based Sulfite Pulping and Chemical Recovery . . 5-114
5-24 Process Flow Diagram of Portland Cement Manufacturing Process 5-123
6-1 Glass Manufacturing Process 6-4
6-2 Process Flow Diagram for Lead-Acid Battery Production 6-12
6-3 Barton Pot Process for Lead Oxide Manufacture 6-21
6-4 Ball Mill Process for Lead Oxide Manufacture 6-22
6-5 Process Flow Diagram for Frit Manufacturing 6-32
6-6 Multilayer Ceramic Capacitor Manufacturing Process 6-42
6-7 Flow Diagram for Abrasive Grain Processes 6-49
6-8 General Electroplating Process Flow Diagram 6-55
6-9 General Process Flow Diagram for Batch-Mix Asphalt Paving Plants 6-67
6-10 General Process Flow Diagram for Drum-Mix Asphalt Paving Plants 6-69
6-11 General Process Flow Diagram for Counterflow Drum-Mix Asphalt Paving Plants . 6-70
8-1 Components of a High-Volume Ambient Air Sampler for Lead 8-2
8-2 Air Flow through a High-Volume Sampler in a Shelter 8-4
8-3 Method 12 Sampling Train 8-6
8-4 Method 29 Sampling Train 8-8
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EXECUTIVE SUMMARY
The 1990 Clean Air Act Amendments contain a list of 188 hazardous air pollutants
(HAPs) which the U.S. Environmental Protection Agency (EPA) must study, identify sources of,
and determine if regulations are warranted/ Of these HAPs, lead and lead compounds are the
subject of this document. This document describes the properties of lead and lead compounds as
air pollutants, defines their production and use patterns, identifies source categories of air
emissions, and provides lead emission factors. The document is a part of an ongoing EPA series
designed to assist the general public at large, but primarily federal, state, and local air agencies,
in identifying sources of HAPs and developing emissions estimates.
Lead is primarily used in the manufacture of lead-acid batteries, lead alloys, lead oxides
in pigments, glass, lead cable coating, and a variety of lead products including ammunition and
radiation shielding. Lead is emitted into the atmosphere from mining and smelting; from its use
as a feedstock in the production of lead alloys, lead compounds and other lead-containing
products; from mobile sources; and from combustion sources.
In addition to the lead and lead compound sources and emission factor data, information
is provided that specifies how individual sources of lead and lead compounds may be tested to
quantify air emissions.
Caprolactam was delisted from the list of HAPs (Federal Register Volume 61, page 30816, June 18, 1996).
XXI
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SECTION 1.0
PURPOSE OF DOCUMENT
The Environmental Protection Agency (EPA) and state and local air pollution
control agencies are becoming increasingly aware of the presence of substances in the ambient air
that may be toxic at certain concentrations. This awareness has led to attempts to identify
source/receptor relationships for these substances and to develop control programs to regulate
toxic emissions.
To assist groups interested in inventorying air emissions of various potentially
toxic substances, EPA is preparing a series of documents that compiles available information on
sources and emissions. Existing documents in the series are listed below.
Substance or Source Category EPA Publication Number
Acrylonitrile EPA-450/4-84-007a
Arsenic EPA-454/R-98-011
Benzene EPA-450/4-84-007q
1,3-Butadiene EPA-454/R-96-008
Cadmium EPA-454/R-93-040
Carbon Tetrachloride EPA-450/4-84-007b
Chlorobenzenes (revised) EPA-454/R-93-044
Chloroform EPA-450/4-84-007c
Chromium EPA-450/4-84-007g
Chromium (supplement) EPA-450/2-89-002
1-1
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Substance or Source Category
Coal and Oil Combustion Sources
Cyanide Compounds
Dioxins and Furans
Epichlorohydrin
Ethylene Oxide
Ethylene Bichloride
Formaldehyde
Lead
Manganese
Medical Waste Incinerators
Mercury and Mercury Compounds
Methyl Chloroform
Methyl Ethyl Ketone
Methylene Chloride
Municipal Waste Combustors
Nickel
Organic Liquid Storage Tanks
Perchloroethylene and Trichloroethylene
Phosgene
Polychlorinated Biphenyls (PCB)
Polycyclic Organic Matter (POM)
Sewage Sludge Incineration
Styrene
Toluene
Vinylidene Chloride
Xylenes
EPA Publication Number
EPA-450/2-89-001
EPA-454/R-93-041
EPA-454/R-97-003
EPA-450/4-84-007J
EPA-450/4-84-0071
EPA-450/4-84-007d
EPA-450/2-91-012
EPA-454/R-98-006
EPA-450/4-84-007h
EPA-454/R-93-053
EPA-453/R-93-023
EPA-454/R-93-045
EPA-454/R-93-046
EPA-454/R-93-006
EPA-450/2-89-006
EPA-450/4-84-007f
EPA-450/4-88-004
EPA-450/2-90-013
EPA-450/4-84-007i
EPA-450/4-84-007n
EPA-450/4-84-007p
EPA-450/2-90-009
EPA-454/R-93-011
EPA-454/R-93-047
EPA-450/4-84-007k
EPA-454/R-93-048
This document deals specifically with lead and lead compounds. Its intended
audience includes federal, state and local air pollution personnel and others who are interested in
locating potential emitters of lead and lead compounds and making gross emissions estimates.
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The reader is strongly cautioned against using the emissions information contained
in this document to try to develop an exact assessment of emissions from any particular facility.
This document is intended to be used as a tool to assist in inventorying lead air emissions from
source categories, rather than specific facilities. Available data are insufficient to develop
statistical estimates of the accuracy of these emission factors, so no estimate can be made of the
error that could result when these factors are used to calculate emissions from any given facility.
The public's misinterpretation of these figures can lead to a gross exaggeration of lead air
emissions. It is possible, in some cases, that order-of-magnitude differences could result between
actual and calculated emissions, depending on differences in source configurations, control
equipment, and operating practices.1 Thus, in situations where an accurate assessment of lead
emissions is necessary, source-specific information should be obtained to confirm the existence of
particular emitting operations, the types and effectiveness of control measures, and the impact of
operating practices. A source test should be considered as the best means to determine air
emissions directly from a facility or operation.
A national ambient air quality standard (NAAQS) for lead of 1.5 micrograms per
cubic meter (j^g/m3) averaged over a calendar quarter was established in 1978. The EPA used
health effects criteria as the basis for arriving at this level for the NAAQS. As such, a large
amount of health-related information does exist in available literature for lead.
Since establishing the NAAQS for lead in 1978, EPA has periodically reviewed the
standard, again focusing on the health effects of lead. Although the NAAQS limit has remained
unchanged at 1.5 |^g/m3, evaluation of the standard is ongoing at EPA, generating additional
health-related and ambient air concentration data. However, data collected through ambient air
studies do not reveal specific lead emission contributions from individual sources, which is the
focus of this document.
With the 1990 Amendments to the CAA, lead and lead compounds were both
recognized for their toxic characteristics and included on the list of hazardous air pollutants
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(HAPs) presented in Section 112(d) to be evaluated in the development of maximum achievable
control technology (MACT) standards. In addition, many states also recognize lead and lead
compounds as toxic pollutants, and some states may impose their own regulations, which can be
more stringent than federal standards. For example, under the state of California's air toxic
identification and control program, the California Air Resources Board (CARB) is proposing to
identify inorganic lead as a toxic air contaminant. The identification or risk assessment process
includes assessing the exposure and health effects of toxic air contaminants. Once a toxic air
contaminant is identified by the Board, it enters into the control or risk management phase of the
program. In this phase, the need for an appropriate degree of controls is evaluated with full
public participation.2
Lead air emissions have also been affected by regulatory activity from other
agencies, including: the Occupational Safety and Health Administration (OSHA), which has
enacted regulations for reducing lead exposure to a variety of worker categories; the U.S.
Consumer Product Safety Commission, which has prohibited lead paints on toys and furniture; the
Food and Drug Administration (FDA) has guidelines for levels of lead that can leach out of
ceramics; and the Toxic Substances Control Act (TSCA) which proposed reducing lead in the
manufacture of certain products, such as fishing sinkers.
The MACT standards development program at the Office of Air Quality Planning
and Standards (OAQPS) has served as a means of providing source-specific information on lead
and lead compound emissions. A concerted effort was made during the development of this
document to coordinate with the work underway at OAQPS. Data were available through this
program for the metallurgical industry, which is a significant emitter of lead. However, many of
the MACT standards were in the preliminary stages (e.g., secondary aluminum, iron and steel
foundries), and emissions information was not available.
As a result of California's "Hot Spots" source testing program and other state
source testing efforts, data were available for incorporation into this document. Information and
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test data from these reports are maintained in EPA's Source Test Information Retrieval System
(STIRS) database and the Factor Information Retrieval (FIRE) System.3'4 However, despite the
data generated by these programs, the available data on some potential sources of lead emissions
are limited and the configurations of many sources will not be the same as those described in this
document. Therefore, this document is best used as a primer to inform air pollution personnel
about the following: (1) the types of sources that may emit lead, (2) process variations that may
be expected within these sources affecting emissions, and (3) available emissions information that
indicates the potential for lead to be released into the air from each operation. This document
does not contain any discussion of health or other environmental effects of lead, nor does it
include any discussion of ambient air levels.
As standard procedure, L&E documents are sent to government, industry, and
environmental groups wherever EPA is aware of expertise. These groups are given the
opportunity to review a document, comment, and provide additional data, where applicable.
Although this document has undergone extensive review, there may still be shortcomings.
Comments subsequent to publication are welcome and will be addressed based on available time
and resources. In addition, any comments on the contents or usefulness of this document are
welcome, as is any information on process descriptions, operating practices, control measures,
and emissions information that would enable EPA to update and improve the document's
contents. All comments should be sent to:
Group Leader
Emission Factor and Inventory Group (MD-14)
Office of Air Quality Planning and Standards
U. S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
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SECTION 2.0
OVERVIEW OF DOCUMENT CONTENTS
This section briefly outlines the nature, extent, and format of the material
presented in the remaining sections of this report.
Section 3.0 provides a brief summary of the physical and chemical characteristics
of lead and lead compounds and an overview of its production, uses, and emission sources. This
background section is useful in developing a general perspective on lead, how it is manufactured
and consumed, and identifies potential sources of lead emissions.
Section 4.0 focuses on air emissions of lead from the metallurgical industry. For
each major production source category described in Section 4.0, a list of individual companies
identified in that particular industry is provided, where available. An example process
description and a flow diagram with potential lead emission points are given. Emission factors
for potential lead emissions, before and after controls employed by industry, are given where
available.
Section 5.0 describes various combustion source categories where lead emissions
have been reported. For each type of combustion source, a description(s) of the combustor is
given and potential lead emission points are identified on diagrams. Emission factors for
potential lead emissions, before and after controls, are given where available.
Section 6.0 summarizes other source categories that use and potentially emit lead.
The manufacture of lead-acid batteries is discussed in this section. The majority of the other
source categories discussed use lead as an additive in various products such as glass, paint,
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pigments, glazes, solders, and stabilizers. Limited information on many of these sources is
available; therefore, varying levels of detail on the processes, emissions, and controls are
presented. Locations of facilities in each source category are provided, where available.
Section 7.0 discusses lead emissions from mobile sources. Both on-road and
off-road sources, as well as aircraft are addressed. This section also includes a discussion of
emissions from lead deposited in soil by mobile sources and reentrained in road dust.
Section 8.0 summarizes available procedures for source sampling, ambient air
monitoring, and analysis of lead. This section provides an overview of applicable sampling
procedures and cites references for those interested in conducting source tests. References for
the entire document are listed in Section 9.0.
Appendix A presents a summary table of the emission factors contained in this
document. This table also presents the factor quality rating and the Source Classification Code
(SCC) or Area/Mobile Source (AMS) code associated with each emission factor.
Each emission factor listed in Sections 4.0 through 7.0 was assigned an emission
factor rating (A, B, C, D, E, or U) based on the criteria for assigning data quality ratings and
emission factor ratings as required in the document Procedures for Preparing Emission Factor
Documents.5 The criteria for assigning the data quality ratings to source tests are as follows:
A - Tests are performed by using an EPA reference test method, or when not
applicable, a sound methodology. Tests are reported in enough detail for
adequate validation, and, raw data are provided that can be used to
duplicate the emission results presented in the report.
B - Tests are performed by a generally sound methodology, but lacking
enough detail for adequate validation. Data are insufficient to completely
duplicate the emission result presented in the report.
C - Tests are based on an unproven or new methodology, or are lacking a
significant amount of background information.
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D - Tests are based on generally unacceptable method, but the method may
provide an order-of-magnitude value for the source.
Once the data quality ratings for the source tests had been assigned, these ratings
along with the number of source tests available for a given emission point were evaluated.
Because of the almost impossible task of assigning a meaningful confidence limit to industry-
specific variables (e.g., sample size vs. sample population, industry and facility variability,
method of measurement), the use of a statistical confidence interval for establishing a
representative emission factor for each source category was not practical. Therefore, some
subjective quality rating was necessary. The following quality ratings were used in the emission
factor tables in this document:
A - Excellent. Emission factor is developed primarily from A- and B-rated
source test data taken from many randomly chosen facilities in the industry
population. The source category population is sufficiently specific to
minimize variability.
B - Above average. Emission factor is developed primarily from A- or
B-rated test data from a moderate number of facilities. Although no
specific bias is evident, it is not clear if the facilities tested represent a
random sample of the industry. As with the A rating, the source category
population is sufficiently specific to minimize variability.
C - Average. Emission factor is developed primarily from A-, B-, and C-rated
test data from a reasonable number of facilities. Although no specific bias
is evident, it is not clear if the facilities tested represent a random sample
of the industry. As with the A rating, the source category population is
sufficiently specific to minimize variability.
D - Below average. Emission factor is developed primarily form A-, B-, and
C-rated test data from a small number of facilities, and there may be
reason to suspect that these facilities do not represent a random sample of
the industry. There also may be evidence of variability within the source
population.
E - Poor. Factor is developed from C- rated and D-rated test data from a very
few number of facilities, and there may be reasons to suspect that the
facilities tested do not represent a random sample of the industry. There
also may be evidence of variability within the source category population.
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U - Unrated (Only used in the L&E documents). Emission factor is developed
from source tests which have not been thoroughly evaluated, research
papers, modeling data, or other sources that may lack supporting
documentation. The data are not necessarily "poor," but there is not
enough information to rate the factors according to the rating protocol.
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SECTION 3.0
BACKGROUND
3.1 PHYSICAL AND CHEMICAL NATURE OF LEAD AND LEAD
COMPOUNDS
Pure lead is a silvery-white metal that oxidizes and turns bluish-gray when
exposed to air. It is soft enough to be scratched with a fingernail. It is dense, malleable, and
readily fusible.6 Its properties include a low melting point; ease of casting; high density; low
strength; ease of fabrication; acid resistance; electrochemical reaction with sulfuric acid;
chemical stability in air, water, and earth; and the ability to attenuate sound waves, atomic
radiation and mechanical vibration.7 The physical properties of lead are presented in Table 3-1.
Lead in its elemental or pure form rarely occurs in nature. Lead most commonly
occurs as the mineral galena (lead sulfide [PbS]), and is sometimes found in other mineral forms,
which are of lesser commercial importance, such as anglesite (PbSO4) and cerussite (PbCO3).6
Table 3-2 presents properties of these three mineral compounds.
Lead is hardened by alloying it with small amounts of arsenic, copper, antimony,
or other metals.6 These alloys are frequently used in manufacturing various lead-containing
products. A list of typical end uses for lead alloys is given in Table 3-3.
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TABLE 3-1. PHYSICAL PROPERTIES OF LEAD
Property
Value
Atomic weight
Melting point
Boiling point
Specific gravity
20°C
327 °C (solid)
327 °C (liquid)
Specific heat
Latent heat of fusion
Latent heat of vaporization
Vapor pressure
980°C
1160°C
1420°C
1500°C
1600°C
Thermal conductivity
28°C
100°C
327 °C (solid)
327 °C (liquid)
Thermal conductivity
(relative to Ag = 100)
Coefficient of linear expansion, at 20 °C per °C
Surface tension at 360°C, mN/m (= dyn/cm)
207.2g
327°C
1770°C
11.35g/cm3
ll.OOg/cm3
10.67 g/cm3
130 J/(kg-K)a
25 J/ga
860 J/ga
0.133kPab
1.33kPab
13.33 kPab
26.7 kPab
53.3 kPab
34.7 W/(m-K)
33.0 W/(m-K)
30.5 W/(m-K)
24.6 W/(m-K)
8.2
29.1xlO-6
442
Source: Reference 8
a To convert J to cal, divide by 4.184.
b To convert kPa to mm Hg, multiply by 7.5.
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TABLE 3-2. PHYSICAL PROPERTIES OF THE PRINCIPAL LEAD-ORE
COMPOUNDS
Formula
Lead, percent
Hardness, Mohs scale
Luster
Color
Density, g/cm3
Galena
PbS
86.6
2.5 to 2.75
Metallic
Lead gray
7.58
Cerussite
PbCO3
77.5
3 to 3.5
Adamantine to
vitreous, resinous
Colorless to white
6.55
Anglesite
PbSO4
68.3
2.5 to 3
Adamantine to
vitreous, resinous
Colorless to white
6.38
Source: Reference 9
Lead in its compound form also has many uses in manufacturing processes,
primarily as pigments. Lead compounds can be classified into the following general categories:
• Organolead compounds;
• Lead oxides;
• Lead sulfides; and
• Lead salts.
Each of these classes of lead compounds is discussed briefly below. Table 3-4 presents a
summary of the chemical formulas and end uses of the most commonly used lead compounds.
3.1.1 Organolead Compounds
Organolead compounds are distinctive with at least one lead-carbon bond. Only
two types of organolead compounds have found large-scale commercial applications:
tetramethyllead (TML) and tetraethyllead (TEL). However, with the removal of lead from
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TABLE 3-3. USES OF LEAD ALLOYS
Alloy
Uses
Lead - Copper
<0.10% copper by wt.
60 to 70% copper by wt.
(leaded brass or bronze)
Lead - Antimony
Lead - Antimony - Tin
Lead - Tin
Lead - Calcium
Lead - Calcium - Aluminum
Lead sheet
Lead pipes
Sheathings for electric power cables
Wire and other fabricated lead products
Tank linings
Tubes for acid-mist precipitators
Steam heating pipes for acid-plating baths
Bearings and bushings
Lead-acid battery positive grids, posts, and connectors
Flashings and roofing materials
Cable sheathings
Ammunition
Tank linings, pumps, valves, pipes, and heating and cooling coils in chemical
operations using sulfuric acid or sulfate solutions at elevated temperatures
Lead sheet
Anodes in metal-plating and metal-electrowinning operations
Collapsible tubes
Wheel-balancing weights for automobiles and trucks
Special weights and castings
Battery cable clamps
Printing-type metals
Bushing and sleeve bearings
Journal bearings in freight cars and mobile cranes
Decorative, slush, and special castings (e.g., miniature figures, casket trim, belt
buckles, trophies, and holloware)
Solders for sealing and joining metals (e.g., electronic applications including
printed circuit boards)
Automobile radiators
High-temperature heat exchangers
Terne-steel sheets for radio and television chassis, roofs, fuel tanks, air filters,
oil filters, gaskets, metal furniture, gutters, and downspouts
Coating of copper sheet used for building flashings
Coating of steel and copper electronic components
Electroplating
Grids for large stationary stand-by power, submarine, and specialty sealed
batteries
Original equipment automotive batteries
Negative grids for replacement batteries
Electrowinning anodes
Cable sheathing, sleeving for cable splices, specialty boat keels, and lead-alloy
tapes
Negative battery grids
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TABLE 3-3. USES OF LEAD ALLOYS (CONTINUED)
Alloy
Uses
Lead - Calcium - Tin
Lead - Silver
Lead - Silver - Antimony
Lead - Silver - Calcium
Lead - Strontium - Tin
Lead - Tellurium
Fusible (lead, cadmium,
bismuth, and tin in varying
compositions)3
Lead - Idium
Lead - Lithium and
Lead - Lithium - Tin
Maintenance-free automotive battery grids
Electrowinning anodes
Insoluble anodes for zinc and manganese electroplating
Anodes in the d-c cathodic protection of steel pipe and structures used in fresh,
brackish, or seawater
Solder in high pressure, high temperature cooling systems
Positive grids of lead-acid batteries
Soft solders
Production of thin copper foil for electronics
Zinc electrowinning
Maintenance-free battery grids
Bearings
Used in pipes and sheets for chemical installations
Shielding for nuclear reactors
Cable sheathing
Fuses
Low-melting sprinkler systems
Foundry patterns
Molds, dies, punches, chucks, cores, mandrels, flexible tubing, and low-
temperature solder
Used to solder metals to glass
Battery grids
Bearings
Source: Reference 10
a Alloys that melt at very low temperatures (i.e., 32°F to 361.4°F [0°C to 183°C]).
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TABLE 3-4. LEAD COMPOUNDS
Compound
Chemical Formula or Description
Uses
Lead acetate
Lead alkyl, mixed
Lead antimonate
Lead arsenate
Lead arsenite
Lead azide
Lead borate
Lead borosilicate
Lead carbonate, basic
Lead chloride
Lead chromate
Lead cyanide
Lead dimethyldithiocarbamate
Lead dioxide
Lead fluoborate
Pb(C2H3O2)2-3H2O
A mixture containing various methyl and ethyl
derivatives of tetraethyl lead and tetramethyl lead
Pb3(Sb04)2
Pb3(AsO4)2
Pb(AsO2)2
Pb(N3)2
Pb(BO2)2-H2O
Composed of a mixture of the borate and silicate of
lead
2PbCO3-Pb(OH)2
PbCl2
PbCrO4
Pb(CN)2
Pb[SCSN(CH3)2]2
PbO2
B,FR-Pb
Dyeing of textiles, waterproofing, varnishes, lead driers,
chrome pigments, gold cyanidation process, insecticide,
anti-fouling paints, analytical reagent, hair dye
Anti-knock agents in aviation gasoline
Staining glass, crockery, and porcelain
Insecticide, herbicide
Insecticide
Primary detonating compound for high explosives
Varnish and paint drier, waterproofing paints, lead glass,
electrically conductive ceramic coatings
A constituent of optical glass
Exterior paint pigments, ceramic glazes
Preparation of lead salts, lead chromate pigments,
analytical reagent
Pigment in industrial paints, rubber, plastics, ceramic
coatings; organic analysis
Metallurgy
Vulcanization accelerator with litharge
Oxidizing agent, electrodes, lead-acid storage batteries,
curing agent for polysulfide elastomers, textiles (mordant,
discharge in dyeing with indigo), matches, explosives,
analytical reagent.
Salt for electroplating lead; can be mixed with stannous
fluoborate to electroplate any composition of tin and lead
as an alloy
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TABLE 3-4. LEAD COMPOUNDS (CONTINUED)
Compound
Chemical Formula or Description
Uses
Lead fluoride
Lead fluosilicate
Lead formate
Lead hydroxide
Lead iodide
Lead linoleate
Lead maleate, tribasic
Lead molybdate
Lead (3-naphthalenesulfonate
Lead naphthenate
Lead nitrate
Lead oleate
Lead oxide, red
Lead phosphate
Lead phosphate, dibasic
PbF2
PbSiF6-2H2O
Pb(CHO2)2
Pb(OH)2
PbI2
Pb(C18H3102)2
C4H605-Pb
PbMoO4
Pb(C10H7S03)2
C7H12O2-xPb
Pb(NO3)2
[CH3(CH2)7CH:CH(CH2)7COO]2Pb
Pb304
Pb3(P04)2
PbHPO4
Electronic and optical applications, starting materials for
growing single-crystal solid-state lasers, high-temperature
dry film lubricants in the form of ceramic-bonded coatings
Solution for electrorefining lead
Reagent in analytical determinations
Lead salts, lead dioxide
Bronzing, printing, photography, cloud seeding
Medicine, drier in paints and varnishes
Vulcanizing agent for chlorosulfonated polyethylene.
Highly basic stabilizer with high heat stability in vinyls
Analytical chemistry, pigments
Organic preparations
Paint and varnish drier, wood preservative, insecticide,
catalyst for reaction between unsaturated fatty acids and
sulfates in the presence of air, lube oil additive
Lead salts, mordant in dyeing and printing calico, matches,
mordant for staining mother of pearl, oxidizer in the dye
industry, sensitizer in photography, explosives, tanning,
process engraving, and lithography
Varnishes, lacquers, paint drier, high-pressure lubricants
Storage batteries, glass, pottery, and enameling, varnish,
purification of alcohol, packing pipe joints, metal-
protective paints, fluxes and ceramic glazes.
Stabilizing agent in plastics
Imparting heat resistance and pearlescence to polystyrene
and casein plastics
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TABLE 3-4. LEAD COMPOUNDS (CONTINUED)
Compound
Chemical Formula or Description
Uses
oo
Lead phosphite, dibasic
Lead phthalate, dibasic
Lead resinate
Lead salicylate
Lead sesquioxide
Lead silicate
Lead silicate, basic
Lead silicochr ornate
Lead sodium thiosulfate
Lead stannate
Lead stearate
Lead subacetate
Lead suboxide
Lead sulfate
Lead sulfate, basic
2PbO-PbHPO3-l/2H2O
C6H4(COO)2Pb-PbO
Pb(C20H2902)2
Pb(OOCC6H4OH)2-H2O
PbA
PbSiO3
A pigment made up of an adherent surface layer of
basic lead silicate and basic lead sulfate cemented to
silica
A yellow lead-silicon pigment
PbS2O3-2Na2S2O3
PbSnO3-2H2O
Pb(C18H3502)2
2Pb(OH)2Pb(C2H3O2)2
Pb2O
PbSO4
PbSO.-PbO
Heat and light stabilizer for vinyl plastics and chlorinated
paraffins. As a UV screening and antioxidizing stabilizer
for vinyl and other chlorinated resins in paints and plastics
Heat and light stabilizer for general vinyl use
Paint and varnish drier, textile waterproofing agent
Stabilizer or costabilizer for flooring and other vinyl
compounds requiring good light stability
Ceramics, ceramic cements, metallurgy, varnishes
Ceramics, fireproofing fabrics
Pigment in industrial paints
Normal lead silicon chrornate is used as a yellow prime
pigment for traffic marking paints. Basic lead silicon
chromate is used as a corrosive inhibitive pigment for metal
protective coatings, primers, and finishers. Also for
industrial enamels requiring a high gloss
Matches
Additive in ceramic capacitors, pyrotechnics
Varnish and lacquer drier, high-pressure lubricants,
lubricant in extrusion processes stabilizer for vinyl
polymers, corrosion inhibitor for petroleum, component of
greases, waxes, and paints
Decolorizing agent (sugar solutions, etc.)
In storage batteries
Storage batteries, paint pigments
Paints, ceramics, pigments
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TABLE 3-4. LEAD COMPOUNDS (CONTINUED)
Compound
Chemical Formula or Description
Uses
Lead sulfate, blue basic
Lead sulfate, tribasic
Lead sulfide
Lead telluride
Lead tetraacetate
Lead thiocyanate
Lead titanate
Lead tungstate
Lead vanadate
Lead zirconate titanate
Litharge
Composition: Lead sulfate (min) 45%, lead oxide
(min) 30%, lead sulfide (max) 12%, lead sulfite (max)
5%, zinc oxide 5%, carbon and undetermined matter
(max) 5%
3PbO-PbSO4-H2O
PbS
PbTe
Pb(CH3COO)4
Pb(SCN)2
PbTiO3
PbWO4
Pv(V03)2
PbTiZrO3
PbO
Components of structural-metal priming coat paints, rust-
inhibitor in paints, lubricants, vinyl plastics, and rubber
products
Electrical and other vinyl compounds requiring high heat
stability
Ceramics, infrared radiation detector, semi-conductor,
ceramic glaze, source of lead
Single crystals used as photoconductor and semiconductor
in thermocouples
Oxidizing agent in organic synthesis, laboratory reagent
Ingredient of priming mix for small-arms cartridges, safety
matches, dyeing
Industrial paint pigment
Pigment
Preparation of other vanadium compounds, pigment
Element in hi-fi sets and as a transducer for ultrasonic
cleaners, ferroelectric materials in computer memory units
Storage batteries, ceramic cements and fluxes, pottery and
glazes, glass, chromium pigments, oil refining, varnishes,
paints, enamels, assay of precious metal ores, manufacture
of red lead, cement (with glycerol), acid-resisting
compositions, match-head compositions, other lead
compounds, rubber accelerator
Source: Reference 11
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gasoline, these compounds are no longer produced in the United States, although they are
imported for special applications such as use in aircraft fuel.
3.1.2 Lead Oxides
Lead oxide is a general term and includes lead monoxide or "litharge" (PbO); lead
tetraoxide or "red lead" (P\)3O^>; and black or "gray" oxide, which is a mixture of 70 percent lead
monoxide and 30 percent metallic lead. Litharge is used primarily in the manufacture of various
ceramic products. Because of its electrical and electronic properties, litharge is also used in
capacitors and electrophotographic plates, as well as in ferromagnetic and ferroelectric materials.
It is also used as an activator in rubber, a curing agent in elastomers, a sulfur removal agent in the
production of thiols and in oil refining, and an oxidation catalyst in several organic chemical
processes. It also has important markets in the production of many lead chemicals, dry colors,
soaps (i.e., lead stearate), and driers for paint. Another important use of litharge is the production
of lead salts, particularly those used as stabilizers for plastics, notably polyvinyl chloride
materials.12
Lead tetraoxide or red lead is a brilliant orange-red pigment. It is used as a
pigment in anticorrosion paints for steel surfaces. It is also used in lead oxide pastes for tubular
storage batteries, in ballistic modifiers for high-energy propellants, in ceramic glazes for
porcelain, in lubricants for hot pressing metals, in radiation-shielding foam coatings in clinical
x-ray exposure, and in rubber adhesives for roadway joints.10 Black lead is made for specific use
in the manufacture of lead acid storage batteries.12
Lead dioxide (PbO2) is a brownish, black powder. Because of its strong oxidizing
properties, it is used in the manufacture of dyes and to control burning in incendiary fires. It is
also used as a curing agent for liquid polysulfide polymers and low molecular weight butyl and
polyisopropane.13
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Lead titanate (PbTiO3) and lead zirconate (PbZrO3) are two lead oxides that are
frequently mixed, resulting in highly desirable piezoelectric properties that are used in
high-power acoustic radiating transducers, hydrophones, and specialty instruments.14
3.1.3 Lead Sulfides
Lead sulfide (PbS) or galena is one of the most common lead minerals, appearing
black and opaque. It is an efficient heat conductor and has semiconductor properties, making it
desirable for use in photoelectric cells. Lead sulfide is used in ceramics, infrared radiation
detectors, and ceramic glaze.14'15
3.1.4 Lead Salts
Most lead salts are white or colorless and are used commercially as pigments.
Basic lead carbonate (Pb(OH)2-2PbCO3), basic lead sulfate (Pb(SO4)-PbO), and basic lead
silicates (3PbOSiO2) are well known white pigments. Basic lead carbonate is used as a
component of ceramic glazes, as a curing agent with peroxides to form improved polyethylene
wire insulation, as a color-changing component of temperature-sensitive inks, as a component of
lubricating greases, and as a component of weighted nylon-reinforced fish nets made of
polyvinylchloride (PVC) fibers.10
Basic lead sulfate helps provide efficient, long-term, economic heat stability to
flexible and rigid PVC. It can be dispersed easily, and has excellent electrical insulation
properties. It is also an effective activator for azodicarbonamide blowing agents for vinyl
foams.10
Basic lead silicates are used by the glass, ceramic, paint, rubber, and plastics
industries. Lead monosilicate (3PbO3SiO2) is used in formulating lead-bearing glazes for the
ceramics industry and as a source of PbO in the glass industry. Lead bisilicate
(PbOOO3Al2O3-1.95SiO2) was developed as a low solubility source of lead in ceramic glazes for
foodware. Tribasic lead silicate (3PbOSiO2) is used primarily by glass and frit producers.10
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Lead chromates (PbCrO4), colored salts, are used frequently as orange and yellow
pigments.11
Lead borates [Pb(BO2)2H2O], germanates (PbOGeO2), and silicates (PbOSiO2)
are glass-forming compounds that impart unique properties to glasses, enamels, glazes, and other
ceramics. Other salts are used as stabilizers for plastics and rubbers, explosives, and in
electroplating.10'11
3.2 OVERVIEW OF PRODUCTION AND USE
Lead is produced in one of two ways: either by primary production through
mining of ores or secondary production through recycling. According to the U.S. Bureau of
Mines, the 1992 domestic production of recoverable lead from lead ores was 437,715 tons
(397,923 Mg), or 22 percent of the total lead produced domestically. The 1992 domestic refined
lead recovered from lead scrap was 1,008,257 tons (916,597 Mg), or 78 percent of the total lead
produced domestically.16
In 1992, domestic lead ore mining in the United States accounted for about
13 percent of the total world lead mine production for that year. Australia, Canada, China, and
Kazakhstan (formerly part of the U.S.S.R.) accounted for nearly 47 percent of the world's lead
mine production in 1992. Other major lead ore producing countries include Mexico, North
Korea, Morocco, Peru, South Africa, Sweden, and other nations part of the former U.S.S.R.16
Most of the lead ore mined in the United States comes from the "lead-belt" in
southeast Missouri. The recoverable lead mine production from Missouri was about 76 percent
of the total lead mine production in the United States in 1992. In Missouri, lead is primarily
recovered from lead, zinc, and lead-zinc ores. Lead is also mined in Alaska, Arizona, Colorado,
Idaho, Illinois, Montana, New Mexico, New York, and Tennessee. In these states, lead is
recovered from zinc, lead-zinc, copper, gold, and fluorspar ore deposits.16
3-12
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Lead ore is mined underground except when it is mined with copper ores, which
are typically mined in open pits. The lead content of ores typically ranges from 3 to 8 percent.
The ores are processed at the mine site to produce a lead ore concentrate of 55 to 70 percent lead.
Once dried, the lead-ore concentrates are shipped to primary lead smelter/refinery plants for
further processing.
Lead ore concentrates are processed at primary lead smelter/refinery plants to
produce lead metal or alloys. In 1992, primary lead smelter/refinery plants operating in the
United States produced 335,270 tons (304,791 Mg) of refined lead.16 These smelters/refineries
were the following: ASARCO (with smelter located in East Helena, MT, and refinery located in
Omaha, NE); ASARCO (with both smelter and refinery located in Glover, MO); and Doe Run
(with both smelter and refinery located in Herculaneum, MO).
Lead is among the most recycled nonferrous metals in the world. Secondary
production (from recycled materials) has risen steadily, such that in 1992, secondary output
surpassed primary output in the United States by about a factor of three. This growth reflects the
favorable economic conditions associated with lead recycling and the ability of lead to retain its
physical and chemical properties when recycled.17
Secondary lead smelters and refineries recover and refine metal from lead-bearing
scrap materials and residues to produce lead and lead alloy ingots, lead oxide, and lead pigments.
About 86 percent of recycled scrap was from lead-acid battery plates.16
In 1992, 1,330,228 tons (1,236,571 Mg) of lead were consumed by product
manufacturing sectors in the United States. Figure 3-1 shows the various manufacturing sectors
consuming lead in 1992.16
As shown in Figure 3-1, the manufacture of storage batteries is the major end use
of lead (accounting for 81 percent of domestic lead use). About 63 percent of the total storage
battery consumption is for manufacturing battery posts and grids, and 37 percent was for
manufacturing lead oxides used in battery paste.16
3-13
-------
United States Lead Use in 1992
1,360,228 tons (1,236,571 Mg)
Storage batteries
SIC 3691
1,098,002 tons (998,184 Mg)
Ammunition
SIC 3482
71,330 tons (64,845 Mg)
Other oxides: paint, glass, and ceramic products, other
pigments and chemicals
SIC 285, 32, 28
69,548 tons (63,225 Mg)
Sheet lead
SIC 15, 3443, 3693
23,107 tons (21,006 Mg)
Casting metals
SIC 36, 371,37, 3443
18,822 tons (17,1 HMg)
Cable covering
SIC 36
17,591 tons (15,992 Mg)
Solder
SIC 15, 341,367, 36, 371
14,870 tons (13,518 Mg)
Miscellaneous uses
14,310 tons (13,009 Mg)
Pipes, traps, other extruded products
SIC 15, 3443
12,817 tons (11,652 Mg)
Brass & bronze: billets and ingots
SIC 3351
10,093 tons (9,175 Mg)
Bearing metals
SIC 35, 36, 37
5,264 tons (4,785 Mg)
Other metal products: foil, type metal, collapsible tubes,
annealing, galvanizing, plating, and fishing weights
SIC 27, 34
3,326 tons (3,024 Mg)
Calking lead: building construction
SIC 15
1,150 tons (1,045 Me)
Figure 3-1. Consumption of Lead in the United States in 1992
Source: Reference 16.
3-14
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The manufacture of ammunition and "other oxides" are the next largest uses of
lead, each accounting for 5 percent of the total domestic lead consumption in 1992. "Other
oxides" include the manufacture of pigments and chemicals, paints, glass, and ceramic products.
The manufacture of pigments and chemicals account for 16 percent, and the manufacture of
paints and glass and ceramics account for 84 percent of the total lead consumption for the "other
oxides" category.16
The manufacture of casting materials, solder, sheet metal, and cable covering each
accounted for 1 to 2 percent of total lead consumption in 1992.16
Some uses of lead experiencing increased growth over the past few years with
continued growth expected are the use of lead in cathode ray tubes for television and computer
screens (to protect viewer and service technicians from harmful radiation), and use of lead solder
in the microelectronics industry.17
3-15
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SECTION 4.0
EMISSIONS OF LEAD AND LEAD COMPOUNDS FROM THE METALLURGICAL
INDUSTRY
4.1 PRIMARY LEAD SMELTING
Lead is recovered from a sulfide ore, primary galena (lead sulfide), which also
contains small amounts of copper, iron, zinc, and other trace elements. A description of the
process used to manufacture lead and a discussion of the emissions resulting from the various
operations are presented below.
A list of primary lead smelters currently in operation within the United States is
given in Table 4-1. Primary lead smelters produced 449,800 tons (408,000 Mg) of refined lead
in 1990.19
TABLE 4-1. DOMESTIC PRIMARY LEAD SMELTERS AND REFINERIES
1990 Production
Smelter Refinery tons (Mg)
ASARCO, East Helena, MT ASARCO, Omaha, NE 72,500 (65,800)
ASARCO, Glover, MO Same site 123,200 (112,000)
Doe Run (formerly St. Joe), Same site 254,100 (231,000)
Herculaneum, MO
Source: Reference 19
4-1
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4.1.1 Process Description
Figure 4-1 presents a typical process flow diagram for primary lead smelting.
The recovery of lead from the lead ore consists of three main steps: sintering, reduction, and
refining.20
Sintering is carried out in a sintering machine, which is a large oven containing a
continuous steel pallet conveyor belt. Each pallet consists of perforated grates, and beneath the
grates are wind boxes, which are connected to fans to provide a draft through the moving sinter
charge. Depending on the direction of the draft, the sinter machine is characterized as either an
updraft or downdraft machine. Except for the draft direction, all machines are similar in design,
construction, and operation. Capacities range from 1,000 to 2,500 tons (910 to 2,270 Mg) per
day. Lead concentrates account for 30 to 35 percent of the input material for the sintering
process. The balance of the charge consists of fluxes such as limestone and large amounts of
recycled sinter or smelter residues.18
The blast furnace reduces the lead oxide produced in the sintering machine to
elemental lead and removes undesirable impurities as a slag. Reduction reactions to elemental
lead occur around 2,900°F (1,600°C). The resulting metal, called bullion, assays 94 to
98 percent lead. The furnace is a rectangular, water-cooled steel shell or shaft atop a
refractory-lined crucible or hearth. Both sides are equipped with tuyeres through which
pressurized combustion or blast air is introduced. Furnace capacities range from 500 to
1,000 tons (454 to 910 Mg) per day. The charge to the furnace includes sinter, coke, slags from
dressing and refining processes, silica, limestone, and baghouse dust. About 80 percent of the
charge consists of sinter that may contain from 28 to 50 percent lead. Blast air is introduced
through the side-mounted tuyeres, resulting in partial combustion of coke and formation of
carbon monoxide, and providing the heat required to reduce lead oxide to lead bullion.
Most of the impurities react with the silica and limestone and form a slag. The
slag is skimmed continuously from the furnace and is treated either at the smelter or is shipped
4-2
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O
GO
00
(L)
O
O
ctf
(L)
h-1
ctf
.a
fin
"3
o
00
O
4-3
-------
elsewhere for recovery of the metal content. Slags that are high in zinc are generally treated at
the smelter in a zinc forming furnace to recover zinc oxide.18
The lead bullion is tapped from the furnace periodically, and is usually treated in
a dressing kettle before undergoing final refining. In the kettle, the bullion is cooled and the
higher melting impurities, primarily copper, float to the surface and form a dross which is
skimmed off and subsequently treated in a reverberatory furnace. The bullion undergoes a final
refining in a series of cast iron kettles. The final lead product, typically 99.99 percent or more
pure, is then cast into pigs or ingots for shipping.18
The function of the dross reverberatory furnace is to separate lead bullion carried
over in the dross from other metals of economic value or contaminants in the dross. The dross
lead content may be as high as 90 percent. Although much smaller, the reverberatory furnace
used is similar in construction to the reverberatory furnace used in copper smelting. Where
applied, end-products usually include lead bullion, which is recycled; matte, which is rich in
copper and usually sent to a copper smelter for copper recovery; and speiss, which is high in
arsenic and antimony.18
4.1.2 Emission Control Techniques
Emission controls on primary lead smelter operations are used for controlling
(PM) and sulfur dioxide (SO2) emissions resulting from the blast furnace and sintering machines.
Centrifugal collectors (cyclones) may be used in conjunction with fabric filters or electrostatic
precipitators (ESPs) for PM control. Because lead emissions generally are associated with PM
emissions, devices used to control PM emissions should also control lead emissions. However,
no data on the effectiveness of fabric filters and ESPs in controlling lead emissions are
available.20
4-4
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4.1.3 Emissions
Lead can potentially be emitted from each unit operation within a primary lead
smelting facility. Table 4-2 presents lead emission factors for specific primary lead operations.
Since lead is generally emitted as PM, lead will be some fraction of total PM. The lead content
of particulate emissions ranges from 20 to 65 percent. For blast furnaces, the lead content of
total PM ranges from 10 to 40 percent. The lead content of parti culate emissions from dross
reverberatory furnaces ranges from 13 to 35 percent. For processes where the operating
temperature is near the boiling point of lead, such as the sinter machine, lead fume may be
emitted.
4.2 SECONDARY LEAD SMELTING
4.2.1 Source Location
In 1990, primary and secondary smelters in the United States produced
1,380,000 tons (1,255,000 Mg) of lead. Secondary lead smelters produced 946,000 tons
(860,000 Mg) or about 69 percent of the total refined lead produced in 1990.21 Table 4-3 lists
U.S. secondary lead smelters according to their annual lead production capacity.
4.2.2 Process Description
The secondary lead smelting industry produces elemental lead and lead alloys by
reclaiming lead, mainly from scrap automobile batteries. Blast, reverberatory, rotary, and
electric furnaces are used for smelting scrap lead and producing secondary lead. Smelting is the
reduction of lead compounds to elemental lead in a high-temperature furnace, which requires
higher temperatures (2200 to 2300°F [1200 to 1260°C]) than those required for melting
elemental lead (621 °F [327°C]). Secondary lead may be refined to produce soft lead (which is
nearly pure lead) or alloyed to produce hard lead. Most of the lead produced by secondary lead
smelters is used in the production of lead-acid batteries.21
4-5
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TABLE 4-2. LEAD EMISSION FACTORS FOR PRIMARY LEAD SMELTING FACILITIES
SCC Emission Source
3-03-010-02 Blast Furnace
3-03-010-04 Ore Crushing
3-03-010-25 Sinter Machine Leakage
3-03-010-28 Tetrahedrite Drier
3-03-010-29 Sinter Machine (weak
gas)
3-03-010-32 Ore Screening
Control Device
None
Baghouse
Spray
Tower/FF
None
Baghouse
ESP/Scrubber
Baghouse
ESP/Scrubber
Baghouse
Average Emission
Factor
in Ib/ton (kg/Mg)
l.OxlO'4
(5.0xlO'5)a
6.7xlO'2
(3.4xlO'2)b
1.7xlO'2
(S.SxlO'Y
S.OxlO'1
(l.SxlO'1)0
2.0xlO'3
(1.0xlO-3)d
3.2xlO'2
(1.6xlO'2)e
6.0xlO'4
(3.0xlO'4)f
1.9xlO'2
(9.5xlO'3)e
2.0xlO'3
(1.0xlQ-3)f
Emission Factor Range Emission
in Ib/ton (kg/Mg) Factor Rating
U
E
U
U
E
E
E
E
E
Reference
22
20
22
23
20
20
20
20
20
a Emission factors are expressed in Ib
b Emission factors are expressed in Ib
0 Emission factors are expressed in Ib
d Emission factors are expressed in Ib
e Emission factors are expressed in Ib
f Emission factors are expressed in Ib
(kg) of pollutant emitted per ton (Mg) of lead produced.
of pollutant emitted per ton bullion processed.
of pollutant emitted per ton of ore crushed.
(kg) of pollutant emitted per ton (Mg) of lead in ore.
(kg) of pollutant emitted per ton (Mg) of sinter produced.
(kg) of pollutant emitted per ton (Mg) of ore processed.
"—" means data not available.
-------
TABLE 4-3. U.S. SECONDARY LEAD SMELTERS GROUPED ACCORDING TO
ANNUAL LEAD PRODUCTION CAPACITY
Smelter
Location
Small-Capacity Group:"
Delatte Metalsb
General Smelting and Refining Company
Master Metals, Inc.b
Metals Control of Kansas'3
Metals Control of Oklahoma13
Medium-Capacity Group:c
Doe Run Company
East Penn Manufacturing Company
Exide Corporation
GNB, Inc.
Gulf Coast Recycling, Inc.
Refined Metals Corporation13
RSR Corporation
Schuylkill Metals Corporation
Tejas Resources, Inc.13
Large-Capacity Group :d
Exide Corporation
Gopher Smelting and Refining, Inc.
GNB, Inc.
RSR Corporation
Sanders Lead Company
Schuylkill Metals Corporation
Ponchatoula, LA
College Grove, TN
Cleveland, OH
Hillsboro, KS
Muskogee, OK
Boss, MO
Lyon Station, PA
Reading, PA
Columbus, GA
Frisco, TX
Tampa, FL
Beech Grove, IN
Memphis, TN
City of Industry, CA
Middletown, NY
Forest City, MO
Terrell, TX
Muncie, IN
Eagan, MN
Vernon, CA
Indianapolis, IN
Troy, AL
Baton Rouge, LA
Source: Reference 21, 24
a Less than 22,000 tons (20,000 Mg).
b These facilities were not operating as of January 1995.
c 22,000 to 82,000 tons (20,000 to 75,000 Mg).
d Greater than 82,000 tons (75,000 Mg).
4-7
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Lead-acid batteries represent about 90 percent of the raw materials used at a
typical secondary lead smelter, although this percentage may vary from one plant to the next.
These batteries contain approximately 18-20 Ib (8.2-9.1 kg) of lead per battery consisting of
40 percent lead alloys and 60 percent lead oxide. Other types of lead-bearing raw materials
recycled by secondary lead smelters include drosses (lead-containing byproducts of lead
refining), which may be purchased from companies that perform lead alloying or refining but
not smelting; battery plant scrap, such as defective grids or paste; and scrap lead, such as old
pipes or roof flashing. Other scrap lead sources include cable sheathing, solder, and babbitt-
metal.21
As illustrated in Figure 4-2, the normal sequence of operations in a secondary
lead smelter is scrap receiving, charge preparation, furnace smelting, lead refining, and alloying
and casting. In the majority of plants, scrap batteries are first sawed or broken open to remove
the lead alloy plates and lead oxide paste material. The removal of battery covers is typically
accomplished using an automatic battery feed conveyor system and a slow-speed saw. Hammer
mills or other crushing/shredding devices are then used to break open the battery cases.
Float/sink separation systems are typically used to separate plastic battery parts, lead terminals,
lead oxide paste, and rubber parts. The majority of lead smelters recover the crushed plastic
materials for recycling. Rubber casings are usually landfilled or are incinerated in the smelting
furnace for their fuel value, and in many cases, lead is reclaimed from the casings.
Paste desulfurization, an optional lead recovery step used by some secondary lead
smelters, requires the separation of lead sulfate and lead oxide paste from the lead grid metal,
polypropylene plastic cases, separators, and hard rubber battery cases. Paste desulfurization
involves the chemical removal of sulfur from the lead battery paste. The process improves
furnace efficiency by reducing the need for fluxing agents to reduce lead-sulfur compounds to
lead metal. The process also reduces sulfur dioxide (SO2) furnace emissions. However, SO2
emissions reduction is usually a less important consideration because many plants that perform
paste desulfurization are also equipped with SO2 scrubbers. About one-half of smelters perform
paste desulfurization.21
4-8
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Batteries Arrive
by Truck
Polypropylene
Plastic to
Recycling
Acid to
Water Treatment
or Recycling
Other Lead-
Bearing Materials
and Scrap
Disposal
Finished
Product
Figure 4-2. Simplified Process Flow Diagram for Secondary Lead Smelting
Source: Reference 21
4-9
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After removing the lead components from the batteries, the lead scrap is
combined with other charge materials, such as refining drosses and flue dust, and is charged to a
reverberatory furnace. Reverberatory furnace slag, coke, limestone, sand, and scrap iron are fed
to a blast, rotary or electric smelting furnace. Smelting furnaces are used to produce crude lead
bullion, which is refined and/or alloyed into final lead products. In 1994, there were
approximately 15 reverberatory furnaces, 24 blast furnaces, 5 rotary furnaces, and 1 electric
furnace operating in the secondary lead industry in the United States.21 Blast and reverberatory
furnaces are currently the most common types of smelting furnaces used in the industry,
although some new plants are using rotary furnaces.
Reverberatory Furnaces
A reverberatory furnace (Figure 4-3) is a rectangular refractory-lined furnace
operated on a continuous basis. Natural gas- or fuel oil-fired burners located at one end or at the
sides of the furnace are used to heat the furnace and charge material to an operating temperature
of about 2200 to 2300°F (1200 to 1260°C).21 Oxygen enrichment may be used to decrease the
combustion air requirements. Reverberatory furnaces are maintained at negative pressure by an
induced draft fan.
Reverberatory furnace charge materials include battery grids and paste, battery
plant scrap, rerun reverberatory furnace slag, flue dust, drosses, iron, silica, and coke. A typical
charge over one hour may include 9.3 tons (8.4 Mg) of grids and paste to produce 6.2 tons
(5.6 Mg) of lead.21
Charge materials are often fed to a natural gas- or oil-fired rotary drying kiln,
which dries the material before it reaches the furnace. The temperature of the drying kiln is
about 400°F (200°C), and the drying kiln exhaust is drawn directly into the reverberatory
furnace or ventilated to a control device. From the rotary drying kiln, the feed is either dropped
into the top of the furnace through a charging chute, or fed into the furnace at fixed intervals
with a hydraulic ram. In furnaces that use a feed chute, a hydraulic ram is often used as a stoker
to move the material down the furnace.
4-10
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E
n;
o:
CD
D)
o
o
-D
CO
"CD
n;
0>
O
PH
O
-4—1
I
>
(S
§
n
X
H
o
8
o
I
GO
Source: Reference 21
o
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-------
Reverberatory furnaces are used to produce a soft, nearly pure lead product and a
lead-bearing slag. This is done by controlling the reducing conditions in the furnace so that lead
components are reduced to metallic lead bullion while the alloying elements (antimony, tin,
arsenic) in the battery grids, posts, straps, and connectors are oxidized and removed in the slag.
The reduction of PbSO4 and PbO is promoted by the carbon-containing coke added to the charge
material:
PbSO4 + C - Pb + CO2 + SO2 (1)
The PbSO4 and PbO also react with the alloying elements to form lead bullion and oxides of the
alloying elements, which are removed in the slag.
The molten lead collects in a pool at the lowest part of the hearth. Slag collects in
a layer on top of this pool and retards further oxidation of the lead. The slag is made up of
molten fluxing agents such as iron, silica, and lime, and typically has significant quantities of
lead. Slag is usually tapped continuously and lead is tapped intermittently. The slag is tapped
into a mould. The slag tap and crucible are hooded and vented to a control device.
Reverberatory furnace slag usually has a high lead content (as much as 70 percent by weight)
and is used as feed material in a blast or electric furnace to recover the lead. Reverberatory
furnace slag may also be rerun through the reverberatory furnace during special slag campaigns
before being sent to a blast or electric furnace. Lead may be tapped into a mold or directly into a
holding kettle. The lead tap is usually hooded and vented to a control device.21
Blast Furnaces
A blast furnace (Figure 4-4) is a vertical furnace that consists of a crucible with a
vertical cylinder affixed to the top. The crucible is refractory-lined and the vertical cylinder
consists of a steel water-jacket. Oxygen-enriched combustion air is introduced into the furnace
through tuyeres located around the base of the cylinder.
4-12
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Charge Hopper
Exhaust Offtake to Afterburner
Charge
Cool Water
Average Level of Charge
Working Height
of Charge
2.4 to 3.0 m
Lead Spout
Diameter at Tuyeres
— 68 to 120 cm —
Hot Water -*
Cool Water
Slag Layer
Slag Spout
Drain Tap Lead Layer |
Figure 4-4. Cross-Section of a Typical Blast Furnace
(5
tr
ui
Source: Reference 21.
4-13
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Charge materials are pre-weighed to ensure the proper mixture and then are
introduced into the top of the cylinder using a skip hoist, a conveyor, or a front-end loader. The
charge fills nearly the entire cylinder. Charge material is added periodically to keep the level of
the charge at a consistent working height while lead and slag are tapped from the crucible. Coke
is added to the charge as the primary fuel, although natural gas jets may be used to start the
combustion process. Combustion is self-sustaining as long as there is sufficient coke in the
charge material. Combustion occurs in the layer of the charge nearest the tuyeres.
At plants that operate only blast furnaces, the lead-bearing charge materials may
include broken battery components, drosses from the refining kettles, agglomerated flue dust,
and lead-bearing slag. A typical charge over one hour may include 4.8 tons (4.4 Mg) of grids
and paste, 0.3 tons (0.3 Mg) of coke, 0.1 tons (0.1 Mg) of calcium carbonate, 0.07 tons
(0.06 Mg) of silica, 0.5 tons (0.4 Mg) of cast iron, and 0.2 tons (0.2 Mg) of rerun blast furnace
slag, to produce 3.7 tons (3.4 Mg) of lead. At plants that also have a reverberatory furnace, the
charge materials will also include lead-bearing reverberatory furnace slag.21
Blast furnaces are designed and operated to produce a hard (high alloy content)
lead product by achieving greater furnace reduction conditions than those typically found in a
reverberatory furnace. Fluxing agents include iron, soda ash, limestone, and silica (sand). The
oxidation of the iron, limestone, and silica promotes the reduction of lead compounds and
prevents oxidation of the lead and other metals. The soda ash enhances the reaction of PbSO4
and PbO with carbon from the coke to reduce these compounds to lead metal.
Lead tapped from a blast furnace has a higher content of alloying metals (up to
25 percent) than lead produced by a reverberatory furnace. In addition, much less of the lead
and alloying metals is oxidized and removed in the slag, so the slag has a low metal content
(e.g., 1 to 3 percent) and may qualify as a nonhazardous solid waste.
Because air is introduced into the blast furnace at the tuyeres, blast furnaces are
operated at positive pressure. The operating temperature at the combustion layer of the charge is
4-14
-------
between 2200 and 2600°F (1200 and 1400°C), but the temperature of the gases exiting the top
of the charge material is only between 750 and 950 °F (400 and 500 °C).
Molten lead collects in the crucible beneath a layer of molten slag. As in a
reverberatory furnace, the slag inhibits the further oxidation of the molten metal. Lead is tapped
continuously and slag is tapped intermittently, slightly before it reaches the level of the tuyeres.
If the tuyeres become blocked with slag, they are manually or automatically "punched" to clear
the slag. A sight glass on the tuyeres allows the furnace operator to monitor the slag level and
ensure that the tuyeres are clear of slag. At most facilities, the slag tap is temporarily sealed
with a clay plug, which is driven out to begin the flow of slag from the tap into a crucible. The
slag tap and crucible are enclosed by a hood, which is vented to a control device.
A weir dam and siphon in the furnace are sometimes used to remove the lead
from beneath the slag layer. Lead is tapped from a blast furnace into either a crucible or directly
to a refining kettle designated as a holding kettle. The lead in the holding kettle is kept molten
before being pumped to a refining kettle for refining and alloying. The lead tap on a blast
furnace is hooded and vented to a control device.
Rotary Furnaces
As noted previously in this section, rotary furnaces, sometimes referred to as
rotary reverberatory furnaces, (see figure 4-5), are used at only a few recently constructed
secondary lead smelters in the United States.21 Rotary furnaces have two advantages over other
furnace types: the ease of adjusting the relative amount of fluxing agents (because the furnaces
are operated on a batch rather than a continuous basis), and better mixing of the charge
materials.
A rotary furnace consists of a refractory-lined steel drum mounted on rollers with
a variable-speed motor to rotate the drum. An oxygen-enriched natural gas or fuel oil jet at one
end of the furnace heats the charge material and the refractory lining of the drum. The
connection to the flue is located at the same end as the jet. A sliding door at the end of the
4-15
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Hygiene Hood
Rotary Furnace Shell
Drive Train
Figure 4-5. Side View of a Typical Rotary Reverberatory Furnace
Source: Reference 21.
4-16
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furnace opposite the jet allows charging of material to the furnace. Charge materials are
typically placed in the furnace using a retractable conveyor or charge bucket, although other
methods are possible.
Lead-bearing raw materials charged to rotary furnaces include broken battery
components, flue dust, and drosses. Rotary furnaces can use the same lead-bearing raw
materials as blast furnaces. They usually produce slag that is relatively free of lead, less than
2 percent. As a result, a blast furnace is not needed for recovering lead from slag, which can be
disposed of as a nonhazardous waste.
Fluxing agents for rotary furnaces may include iron, silica, soda ash, limestone,
and coke. The fluxing agents are added to promote the conversion of lead compounds to lead
metal. Coke is used as a reducing agent rather than as a primary fuel. A typical charge may
consist of 12 tons (11 Mg) of wet battery scrap, 0.8 tons (0.7 Mg) of soda ash, 0.6 tons (0.5 Mg)
of coke, and 0.6 tons (0.5 Mg) of iron, and will yield approximately 9 tons (8 Mg) of lead
product.21
The lead produced by rotary furnaces is a semi-soft lead with an antimony
content somewhere between that of lead from reverberatory and blast furnaces. Lead and slag
are tapped from the furnace at the conclusion of the smelting cycle. Each batch takes 5 to
12 hours to process, depending on the size of the furnace. Like reverberatory furnaces, rotary
furnaces are operated at a slight negative pressure.
Electric Furnaces
An electric furnace consists of a large, steel, kettle-shaped container that is
refractory-lined (Figure 4-6). A cathode extends downward into the container and an anode is
located in the bottom of the container. Second-run reverberatory furnace slag is charged into the
top of the furnace. Lead and slag are tapped from the bottom and side of the furnace,
respectively. A fume hood covering the top of the furnace is vented to a control device.
4-17
-------
C/
GO
'55
o
8
I
PL,
O
o
o
(U
O
^
(U
I
-^J
o
(U
C/3
O
O
(U
Source: Reference 24
O
CO
-------
In an electric furnace, electric current flows from the cathode to the anode
through the scrap charge. The electrical resistance of the charge causes the charge to heat up and
become molten. There is no combustion process involved in an electric furnace.
There is only one known electric furnace in operation in the United States for the
secondary lead industry. It is used to process second-run reverberatory furnace slag, and it
fulfills the same role as a blast furnace used in conjunction with a reverberatory furnace.
However, the electric furnace has two advantages over a blast furnace. First, because there are
no combustion gases, ventilation requirements are much lower than for blast or reverberatory
furnaces. Second, the electric furnace is extremely reducing, and produces a glass-like, nearly
lead-free slag that is nonhazardous .21
Refining, the final step in secondary lead production, consists of removing
impurities and adding alloying metals to the molten lead obtained from the smelting furnaces to
meet a customer's specifications. Refining kettles are used to purify and alloy molten lead.
4.2.3 Emission Control Techniques
Three main strategies are used to control lead emissions and provide worker
protection in secondary lead smelters. These three control strategies involve engineering
measures, work practices, and personal protection. Engineering measures are the most effective
means of lead emissions abatement. Included in this category are control devices, material
substitution, process and equipment modification, isolation and automation, and local and
general ventilation. Good work practices and personal hygiene have become important in
reducing worker lead exposure. Included in these categories are housekeeping, administrative
controls, and the use of personal protective equipment such as respirators, gloves, goggles, and
aprons.25
Control devices used in secondary lead smelters include afterburners, baghouses,
and scrubbers for furnace emissions control, and hooding and ventilation to a baghouse for
process fugitive emissions control.26
4-19
-------
4.2.4 Emissions
In secondary lead smelting operations, lead is emitted in some degree from each
unit operation. Measuring the level of lead in the blood of workers in each area is the most
readily available method of determining the operations that contribute the most to lead
emissions. Blood lead levels were highest among workers in the furnace area, clean-up area,
welding operations area, and the alloying and sawing areas. The lowest blood lead levels were
found in workers in the shipping area.25
Hazardous air pollutants and criteria air pollutants are emitted from secondary
lead smelters as process emissions from the main smelting furnace exhaust, process fugitive
emissions from smelting furnace charging and tapping and lead refining, and fugitive dust
emissions from materials storage and handling and vehicle traffic. Lead emission factors for
these processes are shown in Table 4-4.
The largest sources of process fugitive emissions are furnace charging, slag
tapping, and agglomerating furnace operation. Lesser sources are lead tapping and kettle
refining. Battery breaking and lead casting have fewer emissions. Lead casting is not a
substantial source of emissions because the temperature of molten lead is well below the fuming
temperature of lead.
Fugitive dust emissions contain lead emissions but are dependent upon the size of
the facility and the fugitive dust controls and practices in place at each facility. These emissions
cannot be measured and can only be roughly estimated using emission factors and facility
specific data.21
4-20
-------
TABLE 4-4. LEAD EMISSION FACTORS FOR SECONDARY LEAD SMELTING
Average Emission Factor Emission Factor Range
sec
Number
3-04-004-03
3-04-004-04
3-04-004-13
3-04-004-02
3-04-004-26
3-04-004-14
Emission Source
Blast Furnace (Cupola)
Rotary Sweating
Furnace
Smelting Furnace
Fugitives
Reverberatory Furnace
Kettle Refining
Kettle Refining
Fugitives
Control Device
None
Wet Scrubber/FF/
Cyclone/Settling
Chamber/Demister
None
Baghouse
Baghouse/scrubber
None
Baghouse
None
None
None
Afterburner/FF/
Venturi Scrubber/
Demister
in Ib/ton
(kg/Mg)a
1.04xl02
(5.2x10')
2.9x10-'
(1.5x10-')
2.8xlO-2
(1.4xlO-2)
1.9xlQ-2
(9.5xlQ-3)
1.2xlQ-2
(6.0xlQ-3)
6.5x10'
(3.3x10-')
LOxlO'2
(6.0xlQ-3)
6.00xlO-4
(S.OOxlO-4)
2.4
(1.2)
in Ib/ton
(kg/Mg)a
6.4x10' - 1.4xl02
(3.1x10' -7.0x10')
S.OxlO-2 -6.4x10-'
(2.0xlO-2 - 3.2x10-')
7.0 - 1.6x10'
(4.0 - 8.0)
1.6xlO-2 - 5.2xlO-2
(S.OxlO-3 - 2.6xlO-2)
1.7xlO-2-2.1xlO-2
(8.5xlQ-3- l.lxlO-2)
2.0x10-' -6.0x10-'
(1.0x10-' -3.0x10-')
7.4xlO-3-2.1xlQ-2
(3.7xlQ-3- l.lxlO-2)
3. 5x10' -9.7x10'
(1.7x10' -4.8x10')
—
Emission
Factor
Rating
C
C
E
D
D
E
U
C
C
E
U
Reference
28
28
28
29
29
28
30
28
28
28
22
-------
to
to
TABLE 4-4. LEAD EMISSION FACTORS FOR SECONDARY LEAD SMELTING (CONTINUED)
sec
Number
3-04-004-09
3-04-004-25
Average Emission Factor
in Ib/ton
Emission Source
Casting
Casting Fugitives
Control Device
None
None
(kg/Mg)a
LOxlO'2
(5.0xlO-3)
7.0xlO'4
(3.5xlO'4)
Emission Factor Range Emission
in Ib/ton Factor
(kg/Mg)a Rating
C
E
Reference
28
28
a Emission factors are expressed in Ib (kg) of pollutant emitted per ton (Mg) of lead produced.
"—" means data not available.
FF = Fabric Filter.
-------
4.3 PRIMARY COPPER PRODUCTION
4.3.1 Source Description
Seven primary copper smelters were operating in the United States in 1995 and
one additional was closed for modifications.27 The combined production capacity in 1995 for
the seven plants in operation was 1,728,043 tons (1,570,623 Mg).
4.3.2 Process Description
The pyrometallurgical process used to extract copper from sulfide ore
concentrates is based upon copper's strong affinity for sulfur and its weak affinity for oxygen as
compared to that of iron and other base metals in the ore. The purpose of smelting is to separate
the copper from the iron, sulfur, and commercially worthless mineral materials. All eight of the
primary copper smelters currently produce anode copper from sulfur-bearing ores with the same
basic processes:
• matte smelting;
• converting; and
• refining in an anode furnace.
Copper concentrates received by the smelter typically contain 24 to 30 percent copper,
30 percent sulfur, 25 percent iron, and 10 to 20 percent oxides of silicon, calcium, aluminum,
magnesium, and zinc. (Copper-bearing ores typically contain 0.5 to 1 percent copper by mass.
A froth-flotation process is utilized to produce the "concentrate." This froth-flotation process
may or may not be performed at the smelter site.) Concentrates also contain input impurities,
such as lead, arsenic, antimony, cadmium, chromium, cobalt, manganese, mercury, nickel, and
selenium. These input impurities are typically found in combined concentrations of less than
one percent. The smelter may also receive copper scrap (for direct input into the converters), or
may receive other non-concentrate inputs, such as precipitates, or copper "speiss."
4-23
-------
Incoming concentrates are typically dried before input into a smelting furnace or
reactor. Several types of smelting furnaces/reactors are currently utilized in the United States,
including flash furnaces, CONTOP reactors, Noranda reactors, and IsaSmelt reactors.
Figure 4-7 illustrates basic smelting operations.
The smelting furnace/reactor produces molten copper matte, typically containing
55-75 percent copper, which is tapped from the furnace, and transferred by ladles to converters.
The smelting furnace/reactors also produces slag, containing relatively low amounts of copper
(typically less than two percent). This slag may be discarded directly, if less than 1 percent
copper, or may be transferred to an electric slag-cleaning vessel (for further copper removal), or
may be cooled and reconcentrated (in an attempt for further copper removal).
Molten copper matte is transferred by ladles from the furnace/reactor, and poured
into the converters. In the converters, further sulfur is removed from the matte, and in addition,
iron is oxidized and separated by skimming. The output from the converters is "blister" copper,
generally containing greater than 98 percent copper. Figure 4-8 illustrates a typical converter.
Molten blister copper is poured from the converter, and transferred by ladles to
anode furnaces, where further refining by removal of oxygen and other impurities takes place.
The resulting "anode" copper is generally greater than 98.5 percent pure. It is cast into anodes
for use in the final electrolytic refining step.
Further refining of "anode" copper into "cathode" copper (greater than
99.9 percent purity) is performed by electrolytic means in a "tank house." Production of cathode
copper may or may not take place at the smelter site.
4.3.3 Emissions
Particulate matter and SO2 are the principal air contaminants emitted from
primary copper smelters. Actual emissions from a particular smelter will depend upon the
smelting configuration (type and mix of equipment used), control devices applied, and the
4-24
-------
Ore Concentrates with Silica Fluxes
Fuel
Air
Drying
(SCC 3-03-005-06)
Converter Slag (2% Cu)
Fuel
Air
Offgas
Calcine
Smelting
(SCC 3-03-005-03)
Slag
(0.5% Cu)
to Dump
Slag to
Electric
Cleaning
Vessel
(<2% Cu)
Air
Offgas
Matte (55-75% Cu)
Scrap
Copper
Converting
(SCC 3-03-005-04)
Converter
Slag
Green Poles or Gas
Fuel —
Air -
-+• Offgas
Blister Copper (>98% Cu)
Anode Furnaces
and Fire Refining
(SCC 3-03-005-05)
Slag to Converter
-+• Offgas
Anode Copper (>98.5% Cu)
1
To Electrolytic Refinery
Figure 4-7. Typical Primary Copper Smelter Flowsheet
Source: Reference 27.
4-25
-------
OFF-GAS
TUYtRE PIPES
PNEUWTI
PUNCHERS
SILICEOUS
FLUX
AIR
Source: Reference 31.
Figure 4-8. Copper Converter
4-26
-------
operating and maintenance practices employed. Typically, lead will be emitted as PM. In
addition, actual lead emissions will vary depending on the quantity of lead introduced to the
smelter with the copper-bearing feed materials. The available emission factors for smelting and
converting are presented in Table 4-5. No factors are available for refining.
In addition to process emissions, significant quantities of fugitive emissions are
also generated during material handling operations and furnace charging and tapping.
Fugitive particulates emitted from primary copper smelting consist primarily of metallic oxides
and dust. Major sources of fugitive emissions are shown in Figure 4-9. Principal sources
include ore concentrate unloading and handling, calcine transfer operations, furnace tapping
operations, and converter charging and skimming operations. Information on chemical
characteristics of fugitive paniculate, including lead content, from a variety of these sources is
presented in Table 4-6. The data illustrated in the table suggest that the principal source of
fugitive lead emissions may be the converters, with fugitive particulate emissions containing 2 to
6 percent lead.18
4.3.4 Emission Control Techniques
Control devices for particulate emissions from smelting and converting operations
typically consist of a dry (plate/wire) ESP, baghouses, scrubbers, and a wet (tube/wire) acid mist
ESP (to remove sulfuric acid and volatile heavy metals that condense during the cooling
process).
The control techniques applied vary depending on smelter configuration, process
equipment mix, emissions characteristics, and feasibility for SO2 control. Off-gases from
smelting equipment that produce relatively high concentrations of SO2 (greater than 4 percent;
includes fluidized-bed roasters, non-reverberatory smelting furnaces, and converters) are
generally treated in single- or double-contact sulfuric acid plants for SO2 removal.
4-27
-------
TABLE 4-5. LEAD EMISSION FACTORS FOR PRIMARY COPPER SMELTING FACILITIES
SCC Number
Emission Source
Control Device
Average Emission Factor1
in Ib/ton (kg/Mg)
Emission Factor Rating
3-03-005-03
3-03-005-04
Smelting
Converter
None
None
7.2xlO'2
(3.0xlO'2)
2.7x10-'
(0.135)
Source: Reference 32
a Emission factors are expressed in Ib (kg) of pollutant emitted per ton (Mg) of concentrated ore processed and represent total process and fugitive emissions.
to
oo
-------
RAILCAR
SILICA
FLUXES '
(IT REOL-IRED)
to
CONCEN-
TRATES
STORAGE
(25Z Cu)
KLUX
AND
SILICA
ROASTER
,-'" CALCINE
FLUE DUST
COPPEK PRECIPITATES—
FLUX-
T
REVERB EKATORY
FURNACE
(SMELTER)
f t
1 I
^ONVERTO®
•^ SLAC. l!i
AIR n/ET. (ur
SLAG
HATTE
(35Z^u)71
SLAG
CONVERTER
ELECTROLYTICALLT
REFINED
COPPER (>99.5Z Cu)
ELECTROLYTIC
PLANT
[lj)
X
SILICA AI». tiAHO
FLl'K 6R OXYGEN
EHRICHED
A1R
TAP
FIRE
REFINING
FURNACE
(ANODE FURNACE)
ANODE
CASTING
AIR
I OTHERS
"-"* NATURAL CE.C., GREEN
(IF REQUIRED) GAS LOGS)
Figure 4-9. Fugitive Emission Sources at Primary Copper Smelters
Source: Reference 27.
-------
TABLE 4-6. CHEMICAL CHARACTERISTICS OF FUGITIVE PARTICIPATE
EMISSIONS FROM VARIOUS SOURCES AT PRIMARY COPPER SMELTERS
Process Step
Ore concentrate storage and handling
Slag handling
Roaster loading and operation
Reverberatory furnace loading
and operation
Matte transfer
Converter loading and blowing
Cu Fe
28 24
0.5 40
5
5
42 32
1
Composition (%)
S SiO7 Zn Cd
32 11
1.5 38
16
16
25 1
8 4
Pb
0.3
0.3 - 18
0.3 - 18
0.4- 18
0.25
2-6
Other
5
20
0.5
0.5
Source: Reference 18
Fugitive emissions produced by the majority of smelter fugitive sources,
including ore concentrate handling, calcine transfer, and furnace tapping (matte and slag), are
controlled by enclosing the fugitive emission points in a hood and exhausting the captured
emissions to a control device for collection. Fugitive emissions associated with converter
operations are much more difficult to control. These emissions are substantial and occur during
charging, skimming, or pouring operations when the converter mouth is rotated out from under
the primary hood. They also result from primary hood leakage. Control techniques for
converter fugitive emissions include secondary hoods of various designs and ventilating the
converter building to a control device. All plants currently operating have hooding at all
smelting furnace/vessel matte and slag tapping points. Six of the eight plants in operation have
both primary and secondary hoods on Fierce-Smith converters.27
4-30
-------
4.4 SECONDARY COPPER PRODUCTION
4.4.1 Source Description
The secondary copper industry processes scrap metals to recover copper.
Products include refined copper or copper alloys in forms such as ingots, wirebar, anodes, and
shot. Copper alloys are combinations of copper and other materials, commonly tin, zinc, and
lead. Also, for special applications, combinations include such metals as cobalt, manganese,
iron, nickel, cadmium, and beryllium, and non-metals such as arsenic and silicon. A list of
secondary copper smelters currently operating within the United States is provided in Table 4-7.
Secondary copper capacity totaled 529,100 tons (479,000 Mg) in 1992.33 Except where
otherwise indicated, this section is derived from Section 12.9 of AP-42.34
4.4.2 Process Description
The principal processes involved in copper recovery are scrap metal pretreatment
and smelting. Pretreatment includes cleaning and concentration to prepare the material for the
smelting furnace. Smelting involves heating and treating the scrap to achieve separation and
purification of specific metals.
The feed material used in the recovery process can be any metallic scrap
containing a useful amount of copper, bronze (copper and tin), or brass (copper and zinc).
Traditional forms are punchings, turnings and borings, defective or surplus goods, metallurgical
residues such as slags, skimmings, and drosses, and obsolete, worn-out, or damaged articles,
including automobile radiators, pipe, wire, bushings, and bearings.
The type and quality of the feed material determines the processes the smelter
will use. Due to the large variety of feed materials available, the method of operation varies
greatly among plants. Generally, a secondary copper facility deals with less pure raw materials
and produces a more refined product, whereas brass and bronze alloy processors take cleaner
scrap
4-31
-------
TABLE 4-7. DOMESTIC SECONDARY COPPER PRODUCERS
Smelter 1992 Capacity, tons (Mg)
Cerro Copper Products, Sauget, IL 77,000 (70,000)
Chemetco (Concorde Metals), Alton, IL 148,000 (135,000)
Franklin Smelting and Refining, Philadelphia, 17,600 (16,000)
PA
Gaston Recycling Industries, Gaston, SC 121,000 (110,000)
Scrapwire Co., Carrolton, GA 115,500 (105,000)
Cyprus Casa Grande Corp., Lakeshore, AZ 49,500 (45,000)
Source: Reference 33
and do less purification and refining. Figure 4-10 is a flowsheet depicting the major processes
that can be expected in a secondary copper-smelting operation.
Pretreatment of the feed material can be accomplished using several different
procedures, either separately or in combination. Feed scrap is concentrated by manual and
mechanical methods, such as sorting, stripping, shredding, and magnetic separation. Feed scrap
is sometimes briquetted in a hydraulic press. Pyrometallurgical pretreatment may include
sweating, burning off insulation (especially from wire scrap), and drying (burning off oil and
volatiles) in rotary kilns. Hydrometallurgical methods include floatation and leaching, with
chemical recovery.
In smelting, low-grade scrap is smelted in a cupola furnace, producing "black
copper" (70 to 80 percent Cu) and slag; these are often separated in a reverberatory furnace.
From here, the melt is transferred to a converter or electric furnace to produce "blister" copper,
which is 90 to 99 percent Cu. The actual temperature at which the smelting takes place is not
known. However, the operating temperatures are probably not significantly different from that
of primary copper-smelting operations (1200°F [650°C]).
4-32
-------
ENTERING THE SYSTEM
LEAVING THE SYSTEM
LOW GRADE SCRAP,
(SLAG, SKIMMINGS,
DROSS, CHIPS, BORINGS)
FUEL
AIR
FLUX
FUEL
AIR
FLUX
FUEL
AIR
FLUX
FUEL
AIR
PYROMETALLURGICAL
PRETREATMENT
(DRYING)
|SCC 3-04-002-07)
TREATED
SCRAP
CUPOLA
(SCC 3-04-002-10)
BLACK
COPPER
SMELTING FURNACE
(REVERBERATORY)
(SCC 3-04-002-11)
SEPARATED
COPPER
SLAG'
CONVERTER
(SCC 3-04-002-50)
BLISTER
COPPER
AIR
FUEL
REDUCING MEDIUM
(POLING)
SLAG
FIRE REFINING
BLISTER
COPPER
GASES, DUST, METAL OXIDES
TO CONTROL EQUIPMENT
CARBON MONOXIDE, PARTICULATE DUST,
METAL OXIDES, TO AFTERBURNER AND
PARTICULATE CONTROL
-»- SLAG TO DISPOSAL
GASES AND METAL OXIDES
TO CONTROL EQUIPMENT
CASTING AND SHOT
PRODUCTION
(SCC 3-04-002-39)
GASES AND METAL OXIDES
TO CONTROL EQUIPMENT
FUGITIVE METAL OXIDES FROM
POURING TO EITHER HOODING
OR PLANT ENVIRONMENT
GASES, METAL DUST,
TO CONTROL DEVICE
REFINED COPPER
Figure 4-10. Secondary Copper Smelting Processes
Source: Reference 34.
4-33
-------
Blister copper may be poured to produce shot or castings, but is often further
refined electrolytically or by fire refining. The fire-refining process is essentially the same as
that described for the primary copper-smelting industry. The sequence of events in fire refining
is the following: (1) charging, (2) melting in an oxidizing atmosphere, (3) skimming the slag,
(4) blowing with air or oxygen, (5) adding fluxes, (6) "poling" or otherwise providing a reducing
atmosphere, (7) reskimming, and (8) pouring.
To produce bronze or brass, rather than copper, an alloying operation is required.
Clean, selected bronze and brass scrap is charged to a melting furnace with alloying metals to
bring the resulting mixture to the desired final composition. Fluxes are added to remove
impurities and to protect the metal against oxidation by air. Air or oxygen may be blown
through the melt to adjust the composition by oxidizing excess zinc.
With zinc-rich feed, such as brass, the zinc oxide concentration in the exhaust gas
is sometimes high enough to make recovery for its metal value desirable. This process is
accomplished by vaporizing the zinc from the melt at high temperatures and then capturing the
oxide downstream in a process fabric filter.
The final step is always casting the alloyed or refined metal into a desired form,
e.g., shot, wirebar, anodes, cathodes, ingots, or other cast shapes. The metal from the melt is
usually poured into a ladle or a small pot (which serves as a surge hopper and a flow regulator)
and then continues into a mold.
4.4.3 Emission Control Techniques
The principal pollutant emitted from secondary copper smelting activities is PM
in various forms. Removing insulation from wire by burning produces particulate emissions of
metal oxides and unburned insulation. Drying chips and borings to remove excess oils and
cutting fluids can result in large amounts of dense smoke consisting of soot and unburned
hydrocarbons. Particulate emissions from the top of a cupola furnace consist of metal oxide
fumes, dirt, and dust from limestone and coke.
4-34
-------
The smelting process uses large volumes of air to oxidize sulfides, zinc, and other
undesirable constituents of the feed. This procedure generates considerable particulate matter in
the exhaust gas stream. The wide variation among furnace types, charge quality, extent of
pretreatment, and size of the charge is reflected in a broad spectrum of particle sizes and variable
grain loadings in the exhaust gases. One major factor contributing to differences in emission
rates is the amount of zinc present in scrap feed materials; due to its low boiling point, zinc
evaporates and combines with oxygen, producing zinc oxide fumes.
Metal oxide fumes from furnaces used in secondary copper smelters may be
controlled by fabric filters, ESPs, or wet scrubbers. Control efficiency by fabric filters may be
higher than 99 percent, but cooling systems are needed to prevent the hot gases from damaging
or destroying the bag filters. A two-stage system using both water jacketing and radiant cooling
is common. Electrostatic precipitators are not as well suited to this application, having a
low-collection efficiency for dense particulates, such as oxides of lead and zinc. Wet scrubber
installations also are relatively ineffective in the secondary copper industry. Scrubbers are
useful mainly for particles larger than 1 micron, but the metal oxide fumes are generally
submicron in size.
Particulate emissions associated with drying kilns can be similarly controlled.
Drying temperatures up to 302°F (150°C) produce relatively cool exhaust gases, requiring no
precooling for control by fabric filters.
Wire burning generates large amounts of parti culate matter, primarily unburned
combustibles. These emissions can be effectively controlled by direct-flame afterburners, with
an efficiency of 90 percent or better if the afterburner combustion temperature is maintained
above 1,800°F (1,000°C). If the insulation contains chlorinated organics, such as polyvinyl
chloride, hydrogen chloride gas will be generated and will not be controlled by the afterburner.
One source of fugitive emissions in secondary smelter operations is charging
scrap into furnaces containing molten metals. This often occurs when the scrap being processed
is not sufficiently compacted to allow a full charge to fit into the furnace prior to heating. The
4-35
-------
introduction of additional material onto the liquid metal surface produces significant amounts of
volatile and combustible materials and smoke, which can escape through the charging door.
Briquetting the charge offers a way to avoid fractional charges. When fractional charging
cannot be eliminated, fugitive emissions are reduced by shutting off the furnace burners during
charging. This reduces the flow of exhaust gases and enhances the ability of the exhaust control
system to handle the emissions.
Metal oxide fumes are generated not only during melting, but also during pouring
of the molten metal into the molds. Other dusts may be generated by the charcoal, or other
lining used in association with the mold. Covering the metal surface with ground charcoal is a
method used to make "smooth-top" ingots. This process creates a shower of sparks, releasing
emissions into the plant near the furnace and the molds being filled.
4.4.4 Emissions
Lead may be present in the scrap metals that are processed to recover secondary
copper, therefore, lead emissions can be expected from secondary copper-smelting operations.
Generally, lead will be emitted as particulate matter. Lead emission factors are presented in
Table 4-8.
4.5 PRIMARY ZINC SMELTING
4.5.1 Source Description
Zinc is found primarily as the sulfide ore sphalerite (ZnS). Its common coproduct
ores are lead and copper. Metal impurities commonly associated with ZnS are cadmium and
minor quantities of germanium, gallium, indium, and thallium.35
Four primary zinc smelters were in operation in the United States in 1992. Three
of the smelters employed the electrolytic smelting process and one employed a pyrometallurgical
4-36
-------
TABLE 4-8. LEAD EMISSION FACTORS FOR SECONDARY COPPER SMELTING FACILITIES
sec
Number
3-04-002-42
3-04-002-43
3-04-002-44
3-04-002-xx
Emission Source
Reverberatory Furnace
(charge with other alloy
[7%])
Reverberatory Furnace
(charge with high lead
[58%])
Reverberatory Furnace
(charge with red/yellow
brass)
Secondary Copper -
smelting
Control Device
None
None
None
Baghouse
Average Emission Factor
in Ib/ton (kg/Mg)a
5.0
(2.5)
5.0x10'
(2.5x10')
1.32x10'
(6.6)
l.OOxlO'3
(5.00xlO'4)b
Emission Factor Range Emission
in Ib/ton (kg/Mg)a Factor Rating
B
B
B
B
Reference
34
34
34
37
a Emission factors are expressed in Ib (kg) of pollutant emitted per ton (Mg) of product, except as noted.
b Emission factor is expressed in Ib (kg) of pollutant emitted per ton (Mg) of material processed.
"—" means data not available.
-------
process. Table 4-9 lists the four U.S. smelters according to their process type and slab zinc
production.36
4.5.2 Process Description
A general diagram of the electrolytic process is presented in Figure 4-11.
Electrolytic processing involves four major steps: roasting, leaching, purification, and
electrolysis.
Roasting is common to both electrolytic and pyrometallurgical processing.
Calcine is produced by the roasting reactions in any one of three types of roasters:
multiple-hearth, suspension, or fluidized-bed. Multiple-hearth roasters are the oldest
technology; fluidized-bed roasters are the most modern. Fluidized-bed roasters are currently the
only type of roasting process used in the United States. The primary zinc-roasting reaction
occurs between 1,184 and 1,832°F (640 and 1,000°C), depending on the type of roaster used.
The reaction is the following:
2 ZnS + 3 O2 - 2 ZnO + 2 SO2 (2)
TABLE 4-9. DOMESTIC PRIMARY ZINC PRODUCERS
Company
Big River Zinc Co.,
Sauget, IL
Jersey Miniers Zinc Co.,
Clarksville, TN
Zinc Corporation of America,
Bartlesville, OK
Zinc Corporation of America,
Monaca, PA
Type of Process
Electrolytic
Electrolytic
Electrolytic
Pyrometallurgical
1992 Slab Zinc Production
Capacity, ton (Mg)
90,200
(82,000)
107,800
(98,000)
56,100
(51,000)
135,300
(123,000)
Source: Reference 36
4-38
-------
SOa
Dust and Fume
J^.
I
VO
Roasting
Leach
Solution
Concentrated
Ore
Sulphuric Acid
Limestone
Zinc Oxide
Thickener
Cyanide
Spent Electrolyte
Electrolyte
Mist
Fume
Zinc
Solution
Cathode
Zinc
Zinc Dust
Purifying Additives
Sulphuric Acid
Colloidal Additives
Barium Hydroxide
(or Sodium Carbonate)
Figure 4-11. Electrolytic Primary Zinc-Smelting Process
Source: Reference 35.
-------
In a multiple-hearth roaster, the concentrate is blown through a series of nine or
more hearths stacked inside a brick-lined cylindrical column. As the feed concentrate drops
through the furnace, it is first dried by the hot gases passing through the hearths and then
oxidized to produce calcine. The reactions are slow and can only be sustained by the addition of
fuel.
In a suspension roaster, the feed is blown into a combustion chamber, which is
very similar to that of a pulverized coal furnace. Additional grinding, beyond that required for a
multiple-hearth furnace, is normally required to ensure that heat transfer to the material is fast
enough to initiate desulfurization and oxidation reactions in the furnace chamber. Hearths at the
bottom of the roaster capture the larger particles, which need more time in the furnace to
complete the reactions.
In a fluidized-bed roaster, finely ground sulfide concentrates are suspended and
oxidized within a pneumatically supported feedstock bed. This technique achieves the lowest
sulfur content calcine of the three roaster designs.
Suspension and fluidized-bed roasters are superior to multiple-hearth roasters for
several reasons. Although they emit more particulate, their reaction rates are much faster,
allowing greater process rates. Also, the SO2 content of the effluent streams of these two
roasters is significantly higher, permitting more efficient and economical use of acid plants to
control SO2 emissions.
Leaching is the first step of electrolytic reduction. In this step, the zinc oxide
reacts with sulfuric acid to form aqueous zinc sulfate in an electrolytic solution.
ZnO + H2SO4 - Zn+2 (aq) + SO;2 (aq) + H2O (3)
Single- and double-leach methods can be used, although the former exhibits
excessive sulfuric acid losses and poor zinc recovery. In double leaching, the calcine is first
leached in a neutral solution. The readily soluble sulfates from the calcine dissolve, but only a
4-40
-------
portion of the zinc oxide enters the solution. The calcine is then leached in the acidic
electrolysis recycle electrolyte. The zinc oxide is dissolved as shown in reaction (3), as are
many of the impurities, especially iron. The electrolyte is neutralized by this process and it
serves as the leach solution for the first stage of calcine leaching. This recycling also serves as
the first stage of refining because much of the dissolved iron precipitates out of the solution.
Variations on this basic procedure include the use of progressively stronger and hotter acid baths
to bring as much of the zinc into solution as possible.
Purification is a process in which a variety of reagents are added to the zinc-laden
electrolyte to force impurities to precipitate. The solid precipitates are separated from the
solution by filtration. The techniques that are used are among the most advanced industrial
applications of inorganic solution chemistry. Processes vary from smelter to smelter and the
details are proprietary and often patented. Metallic impurities such as arsenic, antimony, cobalt,
germanium, nickel, and thallium interfere severely with the electrolytic deposition of zinc, and
their final concentrations are limited to less than 4xlO"7 Ib/gal (0.05 mg/L).
Electrolysis takes place in tanks, or cells, containing a number of closely spaced
rectangular metal plates that act as anodes (made of lead with 0.75 to 1.0 percent silver) and as
cathodes (made of aluminum). A series of three major reactions occurs within the electrolysis
cells:
H9SO,
2 H70 -2—i* 4H + (aq) + 4e - + O, (4)
anode
2Zn+2 +4e_ cathode^ Zno
4 H+ (aq) + 2 SO;2 (aq) , 2 H2SO4 (6)
4-41
-------
Oxygen gas is released at the anode, metallic zinc is deposited at the cathode, and
sulfuric acid is regenerated within the electrolyte.
Electrolytic zinc smelters contain a large number of cells-often several hundred.
A portion of the electrical energy released in these cells dissipates as heat. The electrolyte is
continuously circulated through cooling towers, both to lower its temperature and to concentrate
the electrolyte through the evaporation of water. Routinely, half of the cathodes in a cell are
disengaged for removal of zinc from the plates. The other half carry a higher current load.
Occasionally, a complete cell shutdown occurs, such as when a cell is bypassed (using a Buss
Bar to reroute current) for cleaning or repairing.
The final stage of electrolytic zinc smelting is the making and casting of the
cathode zinc into small slabs (59 Ib [27 kg]) or large slabs (1,408 to 2,420 Ib [640 to 1,100 kg]).
A general diagram of the pyrometallurgical process is presented in Figure 4-12.
Pyrometallurgical processing involves three major steps: roasting, sintering, and retorting.
Sintering is the first stage of the pyrometallurgical reduction of zinc oxide to slab
zinc. Sintering removes lead and cadmium impurities by volatilization and produces an
agglomerated permeable mass suitable for feed to retorting furnaces. Down-draft sintering
machines of the Dwight-Lloyd type are used in the industry. Grate pallets are joined together
for a continuous conveyor system. Combustion air is drawn down through the grate pallets and
is exhausted to a particulate control system. The feed is a mixture of calcine, recycled sinter,
and coke breeze, which is low-sulfur fuel. Having a low boiling point, oxides of lead and
cadmium are volatilized from the sinter bed and are recovered in the particulate control system.
In retorting, because of the low boiling point of metallic zinc (1,663°F [906°C]),
reduction and purification of zinc-bearing minerals can be accomplished to a greater extent than
with most minerals. The sintered zinc oxide feed is brought into a high-temperature reducing
atmosphere of 1,652 to 2,730°F (900 to 1,499°C). Under these conditions, the zinc oxide is
simultaneously reduced and volatilized to gaseous zinc:
4-42
-------
S02
Dust and Fume
Roasting
Concentrated
Ore
SO2
Dust and Fume
Sintering
Sand
Coke
Zinc Sulfate
Sinter
Fume
Recycled Blue Powder
Coal or Coke
Silica
Fume
J
L
Retorting
Molten
Zinc
j
L
Casting
^
Slab Zinc
Figure 4-12. Pyrometallurgical Primary Zinc-Smelting Process
Source: Reference 35.
-------
ZnO + CO - Zn (vapor) + CO2 (7)
Carbon monoxide regeneration also occurs:
CO2 + C - 2 CO (8)
The zinc vapor and carbon monoxide that are produced pass from the main
furnace to a condenser, where zinc recovery is accomplished by bubbling the gas mixture
through a molten zinc bath. Retorting furnaces can be heated either externally by combustion
flames or internally by electric resistance heating. The latter approach, electrothermic reduction,
is the only method currently practiced in the United States, and it has greater thermal efficiency
than do external heating methods. In a retort furnace, preheated coke and sinter, silica, and
miscellaneous zinc-bearing materials are fed continuously in the top of the furnace. Feed coke
serves as the principal electrical conductor, producing heat; it also provides the carbon monoxide
required for zinc oxide reduction. Further purification steps can be performed on the molten
metal collected in the condenser. The molten zinc finally is cast into small slabs (59 Ib [27 kg])
or large slabs (1,408 to 2,420 Ib [640 to 1,100 kg]).35
4.5.3 Emissions
All four smelters treat the SO2-rich roaster exhaust gases in a sulfuric acid plant
for SO2 removal. As a result, paniculate and lead emissions are negligible. The balance of the
processes performed at the electrolytic plants are wet and do not produce emissions.
Uncontrolled emissions from electrothermic reduction furnaces are also negligible. Thus, the
only potentially significant source of particulate and lead emissions from primary zinc smelting
operations in the United States is the one sinter machine operated at the pyrometallurgical plant.
The sinter machine at this plant is currently controlled by three ESPs and one baghouse in
series.18 Lead emission factors for primary zinc production are not available.
4-44
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4.6 SECONDARY ALUMINUM OPERATIONS
4.6.1 Source Description
Secondary aluminum operations involve the cleaning, melting, refining, alloying,
and pouring of aluminum recovered from scrap, foundry returns, and dross. The processes used
to convert scrap aluminum to secondary aluminum products such as lightweight metal alloy for
industrial castings and ingots are presented in Figures 4-13 and 4-14. Production involves two
general classes of operations: scrap treatment and smelting/refining. Except where otherwise
indicated, this section is derived from Section 12.8 of AP-42.38
4.6.2 Process Description
Scrap treatment involves receiving, sorting, and processing scrap to remove
contaminants and prepare the material for smelting. Processes based on mechanical,
pyrometallurgical, and hydrometallurgical techniques are used, and those employed are selected
to suit the type of scrap processed.
The smelting/refining operation generally involves the following steps:
a. charging f demagging
b. melting g. degassing
c. fluxing h. skimming
d. alloying i. pouring
e. mixing
All of these steps may occur at each facility, with process distinctions being the
furnace type used and emissions characteristics. However, as with scrap treatment, not all of
these steps are incorporated into the operations at a particular plant. Some steps may be
combined or reordered, depending on furnace design, scrap quality, process inputs, and product
specifications.
4-45
-------
PRETREATMENT
A
INSPECTION]
SORTING
r\ i r\ P u r r T
X CASTINGS > » CRUSHING „"
'CLIPPINGS ' 'SCREENING "*
.NEW CLIPPINGS,
FORCINGS
SHREDDING/
* UAULL 'CLASSIFYING '
RORINRS CRUSHING, BURNING
TURNINGS 'SCREENING > DRYING
[SCC 3-04-001-081 HSCC 3-04-001-09)
HEAVY METALLIC
SKIMS
FUEL > HOT DROSS < FLUX
PROCESSING
[SCC 3-04-001-07)
RESIDUES
[SCC 3-04-001-16)
>i LEACHING
(SCC 3-04-001 -18)
WATER t pFUEL
> HIGH IRON > SWEATING >
SCRAP (SCC 3-04-001 -01)
t
TREATED
ALUMINUM
SCRAP
FUEL
Figure 4-13. Typical Process Diagram for Pretreatment in the Secondary Aluminum
Processing Industry
Source: Reference 38.
4-46
-------
SMELTING/REFINING
PRODUCT
I:
CHLORINE
FLUX
FUEL
REVERBERATORY
(CHLORINE)
SMELTING/REFINING
(SCC 3-04-001-04)
— FLUORINE
— FLUX
r-FUEL
REVERBERATORY
(FLUORINE)
SMELTING/REFINING
(SCC 3-04-001-05)
FLUX
FUEL
CRUCIBLE
SMELTING/REFINING
(SCC 3-04-001-02
INDUCTION
SMELTING/REFINING
HARDENERS
FLUX
ELECTRICITY
Figure 4-14. Typical Process Flow Diagram for the Secondary Aluminum
Processing Industry
Source: Reference 38.
4-47
-------
Purchased aluminum scrap undergoes inspection upon delivery and is sorted into
the categories shown in Figure 4-13. Clean scrap requiring no treatment is transported to storage
or is charged directly into the smelting furnace. The bulk of the scrap, however, must be
manually sorted as it passes along a steel belt conveyor. Free iron, stainless steel, zinc, brass,
and oversize materials are removed. The sorted scrap then goes to appropriate scrap treating
processes, if necessary, or is charged directly to the smelting furnace. The more common scrap
treatment processes are discussed in the following paragraphs.
Sorted scrap is conveyed to a ring crusher or hammer mill where the material is
shredded and crushed, and the iron is torn away from the aluminum. The crushed material
passes over vibrating screens to remove dirt and fines, and tramp iron is removed by magnetic
drums and/or belt separators. Baling equipment compacts bulky aluminum scrap into bales.
Pure aluminum cable with steel reinforcement or plastic insulation is cut by
alligator-type shears and granulated or further reduced in hammer mills to separate the iron core
and the plastic coating from the aluminum. Magnetic processing removes the iron and air
classification separates the insulation. Borings and turnings, in most cases, are treated to remove
cutting oils, greases, moisture, and free iron. The processing steps involved are (1) crushing,
(2) drying to remove oil and moisture, (3) screening to remove aluminum fines, (4) removing
iron magnetically, and (5) storing the clean dried borings in tote boxes.
Several types of residue from primary and secondary aluminum plants contain
recoverable amounts of aluminum. Aluminum is recovered from hot and cold drosses by batch
fluxing in rotary furnaces. In the dry milling process, cold aluminum dross and other residues
are processed by milling, screening, and concentrating to reduce oxides and non-metallic
materials to fine powders, yielding a product which is 60 to 70 percent aluminum.
Drosses, skimmings, and slags are treated by leaching to remove fluxing salts and
other nonrecoverable materials. First, the raw material is fed into a long, rotating drum or an
attrition or ball mill, from which soluble contaminants are leached. The washed material is then
screened to remove fines and dissolved salts and is dried and passed through a magnetic
4-48
-------
separator to remove ferrous materials. The non-magnetic materials are then stored or charged
directly to the smelting furnace.
Aluminum foil is treated by roasting to separate carbonaceous materials
associated with the aluminum.
Sweating is a pyrometallurgical process using open-flame reverberatory furnaces
to recover aluminum from scrap with high iron content. The aluminum and other constituents
with low-melting temperatures melt, trickle down the hearth, through a grate, and into molds or
collecting pots. The materials with higher-melting temperatures, including iron, brass, and
oxidation products formed during the sweating process, remain in the furnace until they are
removed. Treated aluminum scrap is transferred to the smelting/refining operations for
refinement into finished products.
In smelting/refining operations, reverberatory furnaces are commonly used to
convert clean, sorted scrap, sweated pigs, or untreated scrap to ingots, shot, or hot metal. The
scrap is first mechanically charged to the furnace, often through charging wells designed to
introduce chips and light scrap below the surface of a previously melted charge ("heel"). Batch
processing is generally practiced for alloy ingot production, and continuous feeding and pouring
are generally used for products having less strict specifications.
Cover fluxes are used to prevent oxidation of the melt caused by air contact.
Solvent fluxes react with non-metallic materials, such as burned coating residues and dirt, to
form insoluble materials that float to the surface as part of the slag. Alloying agents are charged
to the furnace in amounts determined by product specifications. Nitrogen or other inert gases
can be injected into the molten metal to help raise dissolved gases (typically hydrogen) and
intermixed solids to the surface.
Demagging reduces the magnesium content of the molten charge from
approximately 0.3 to 0.5 percent (typical scrap value) to about 0.1 percent (typical product line
alloy specification). When demagging with chlorine gas, chlorine is injected under pressure
4-49
-------
through carbon lances to react with magnesium and aluminum as it bubbles to the surface. Other
chlorinating agents or fluxes, such as anhydrous aluminum chloride or chlorinated organic
compounds, are sometimes used.
In the skimming step, contaminated semi-solid fluxes (dross, slag, or skimmings)
are ladled from the surface of the melt and removed through the forewell. The melt is then
cooled before pouring.
The reverberatory (fluorine) process is similar to the reverberatory (chlorine)
smelting/refining process, except that aluminum fluoride (A1F3) is employed in the demagging
step instead of chlorine. The A1F3 reacts with magnesium to produce molten metallic aluminum
and solid magnesium fluoride salt, which floats to the surface of the molten aluminum and is
skimmed off.
The crucible smelting/refining process is designed to produce harder aluminum
alloys by blending pure aluminum and hardening agents in an electric induction furnace. The
process steps include charging scrap to the furnace, melting, adding and blending the hardening
agent, skimming, pouring, and casting into notched bars.
4.6.3 Emissions and Emission Control Techniques
Each processing step in the secondary aluminum industry is a potential source of
lead emissions, which are generally emitted as PM. Lead emissions will be a small fraction of
total particulate emissions and will vary with the lead content of the scrap. Table 4-10 presents
lead emission factors for specific processing units.
Data for lead emissions from secondary aluminum processing facilities was
extremely limited. Currently, emissions data from secondary aluminum facilities are being
4-50
-------
TABLE 4-10. LEAD EMISSION FACTORS FOR SECONDARY ALUMINUM PRODUCTION
SCC Number Emission Source Control Device
3-04-001-09 Burning/Drying Venturi Scrubber
Baghouse
Multiple Cyclones
3-04-001-14 Reverberatory Baghouse
Furnace
Emission Factor
in Ib/ton
(kg/Mg)a
4.36xlO-3
(2.18xlO-3)
1.04xlO'5
(S.lSxlO'6)
2.16xlO-2
(l.OSxlO-2)
1.4xlO'3
(7.0xlO'4)b
Emission Factor Range
in Ib/ton (kg/Mg)a
2.02xlO-3 - 7.04xlO-3
(l.OlxlO-3 - 3.52xlO-3)
6.76X10'6 - 1.48xlO'5
(3.38xlO-6-7.40xlO-6)
2.10xlO-2-2.26xlO-2
(l.OSxlO-2 -1.13xlO-2)
1.0xlO-3-2.2xlO-3
(S.OxlO'4- l.lxlQ-3)b
Emission
Factor
Rating
U
U
U
D
Reference
39
39
40
41
a Emission factors are expressed in Ib (kg) of pollutant emitted per ton (Mg) of aluminum produced, except as noted.
b Emission factors are expressed in Ib (kg) of pollutant emitted per ton (Mg) of aluminum processed.
-------
collected for inclusion in the secondary aluminum MACT, which may augment the information
provided here.
There is potential for particulate emissions from several processing steps,
including crushing/screening, shredding/classifying, bailing, burning/drying, dross processing,
roasting, smelting/refining, and demagging. Particulate emissions may also be released by
leaching operations during drying. Fumes may be emitted from fluxing reactions. Lead
emission levels from each of these processes depend on the lead content of the feed introduced
to each unit step.
Typical control devices at secondary aluminum operations include baghouses,
multicyclones, scrubbers, and local ventilation. Although, these have been designed primarily
for PM control, in controlling PM, lead emissions are controlled.
4.7 IRON AND STEEL FOUNDRIES
4.7.1 Source Location
There were approximately 756 iron and steel foundries in the United States in
1992 based on a survey conducted by the EPA to support development of the iron and steel
foundry Maximum Achievable Control Technology (MACT) standard.42 In general, foundries
are located in areas of heavy industry and manufacturing, especially areas where iron and steel
are produced (e.g., the Great Lakes States).
4.7.2 Process Description
Iron and steel foundries can be defined as those that produce gray, white, ductile,
or malleable iron and steel castings. Both cast irons and steels are solid solutions of iron,
carbon, and various alloying materials. Although there are many types of iron and steel, groups
can be distinguished by their carbon content. Cast iron typically contains 2 percent carbon or
greater; cast steel usually contains less than 2 percent carbon.40
4-52
-------
Iron castings are used in most types of mechanical equipment, including motor
vehicles, farm machinery, construction machinery, petroleum industry equipment, electrical
motors, and iron and steel industry equipment.
Steel castings are used in motor vehicles, railroad equipment, construction
machinery, aircraft, agricultural equipment, ore refining machinery, and chemical manufacturing
equipment.43 Steel castings are classified on the basis of their composition and heat treatment,
which determine their end use. Classifications include carbon, low-alloy, general-purpose-
structural, heat-resistant, corrosion-resistant, and wear-resistant.
The following four basic operations are performed in all iron and steel foundries:
• Storage and handling of raw materials;
• Melting of scrap or ingot metal;
• Transfer of the hot molten metal into molds; and
• Preparation of the molds to hold the molten metal.
Other processes present in most, but not all, foundries include:
• Sand preparation and handling;
• Mold cooling and shakeout;
• Casting cleaning, heat treating, and finishing;
• Coremaking; and
• Pattern making.
A generic process flow diagram for iron and steel foundries is shown in Figure 4-15.
Figure 4-16 identifies the emission points in a typical iron and steel foundry.
4-53
-------
New
Sand
Additives
Preparation
i '
Molding
New
Sana
Chemical Resins,
Binders & Catalysts
Sand
Preparation
Core
Making
Hot Metal
Transfer,
Slagging and
Treatment
Mold
Pouring
and
Cooling
Melting
and
Alloying
Scrap Metal
and Ingot
(Also Fuel
and Flux)
Return Sand
Transfer,
Processing and
Storage
Shakeout
Charge
Preparation
Cleaning
and
Finishing
Finished Casting
(Product)
Figure 4-15. Process Flow Diagram for a Typical Sand-Cast Iron and Steel Foundry
Source: Reference 43.
-------
Fugitive
Partlculates
Fugitive
Dust
I
Raw Materials,
Unloading, Storage,
Transfer
• Flux
• Metals
_ Carbon Sources
"Sand
• Binder
t
Scrap
Preparation
Fumes and
Fugitive Dust
Fugitive
Dust
Hydrocarbons,
Co, and Smoke
Furnace
Vent
Fugitive
Dust
Furnace
» Cupola
» Electric Arc
. Induction
* Other
Tapping,
Treating
Fugitive
. Fumes and
Dust
Fugitive
Fumes and
Dust
Fugitive
Dust
Core Making
Oven
Vent
Mold Pouring,
Cooling
Core Baking
Sand
Casting
Shakeout
Cooling
Cleaning, Finishing
Fugitive
Dust
Fumes and
Fugitive
Dust
Fugitive
Dust
Shipping
Figure 4-16. Emission Points in a Typical Iron and Steel Foundry
Source: Reference 44
4-55
o
Q.
OL
LU
-------
Metal Melting Process
The highest amount of metal (by volume) in iron and steel foundries is melted in
cupolas. Electric arc furnaces (EAFs) and induction furnaces are also commonly used. Cupolas
are charged with alternate layers of coke, metallics, and fluxes. Combustion air is introduced
into the cupola through tuyeres located at the base. The heat produced by the burning coke
melts the iron, which flows down and is tapped from the bottom of the cupola. Fluxes combine
with non-metallic impurities in the charge and form slag, which is removed through tap holes
located above the level of the metal tap hole. Cupola capacities range mostly from 1 to 30 tons
(1 to 27 Mg) per hour, with a few large units capable of producing close to 100 tons (90 Mg) per
hour. Larger furnaces are operated for several days at a time with inspections and cleanings
between melt cycles.45
Iron and steel castings are produced in a foundry by injecting or pouring molten
metal into cavities of a mold made of sand, metal, or ceramic material. The use of EAFs and
induction furnaces is increasing. Steel foundries rely almost exclusively on EAFs or induction
furnaces for melting purposes.
In all types of foundries, when the poured metal has solidified, the molds are
separated and the castings removed from the mold flasks on a casting shakeout unit. Cutoff,
abrasive (shotblasting) cleaning, grinding, and heat treating are performed as necessary. The
castings are then inspected and shipped to plants of other industries for machining and/or
assembly into final products.43
In a typical foundry operation, charges to the melting unit are sorted by size and
density and cleaned (as required) prior to being put into the melter. Charges consist of scrap
metal, ingot, carbon (coke), and flux. Prepared charge materials are placed in crane buckets,
weighed, and transferred into the melting furnace or cupola. The charge in a furnace or cupola
is heated until it reaches a certain temperature and the desired product chemistry of the melt has
been attained. After the desired product is obtained, the molten metal is poured out of the
furnace into various-size transfer ladles and then into the molds holding furnaces.
4-56
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Mold and Core Production
The casting or mold pouring and cooling operations in iron and steel foundries
are suspected to be a source of lead emissions. In addition to casting, mold preparation and
casting shakeout (removal from the mold) activities are also suspected as lead emission sources.
Lead emissions from these processes are believed to be small, although test data are not available
to quantify actual lead emissions.
4.7.3 Emission Control Techniques
Lead emissions depend mostly on the scrap metal quality and control
technologies. Control technologies commonly used to control lead emissions from iron and steel
foundry metal melting operations include baghouses and wet scrubbers. Additionally, lead
emissions due to coke combustion may be reduced by substituting natural gas for coke as a heat
source. Potential lead emissions from molding, casting, and shakeout are fugitive in nature.
Fugitive emissions from such sources are generally controlled with local hooding or building
ventilation systems that are ducted to a control device (predominantly baghouses).45
4.7.4 Emissions
Lead emission factors for several iron foundry processes were available. These
emission factors are presented in Table 4-11.
4.8 ORE MINING, CRUSHING, AND GRINDING
4.8.1 Source Description
Lead emissions are generated by the mining, crushing, and grinding of three
primary nonferrous metal ores: lead, zinc, and copper. Lead and zinc ores are normally mined
underground, whereas copper ores are normally mined in open pits.46 Lead, zinc, and copper
occur in various amounts in all three ore types. If the metal content of two or more metals is
high
4-57
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TABLE 4-11. LEAD EMISSION FACTORS FOR IRON AND STEEL FOUNDRIES
SCC Number Emission Source
3 -04-003-0 1 Iron Foundry - Cupola
3-04-003-02 Iron Foundry -
Reverberatory Furnace
f' 3-04-003-03 Iron Foundry - Electric
ro Induction Furnace
3 -04-003-20 Iron Foundry - Casting
Control Device
None
Afterburner/
Venturi
Scrubber
Baghouse
None
None
Afterburner/
Venturi
Scrubber
Emission Factor Emission Factor Range Emission
in Ib/ton in Ib/ton Factor
(kg/Mg)a (kg/Mg)a Rating
LOOxlO-'-l.lO B
(5.00xlO-2-1.10)
1.56xlO'3 — U
(7.80xlO'4)b
2.67xlO-3 1.39xlO-3-4.45xlO-3 U
(1.34xlO-3) (6.95xlO-4 - 2.23X10'3)
1.20X10'2 - 1.40x10-' B
(6.00xlO'3 - 7.00xlO'2)
9.00xlO-3 - l.OOxlO-1 B
(4.45xlO-3 - S.OOxlO'2)
4.80xlO'3 — U
(2.40xlO'3)b
Reference
47
3
48
47
47
3
a Emission factors are expressed in Ib (kg) of pollutant emitted per ton (Mg) of iron/steel produced, except as noted.
b Emission factors are expressed in Ib (kg) of pollutant emitted per ton (Mg) of material processed.
"—" means data not available.
-------
enough for economical extraction, the ore is listed as a mixed ore (e.g., lead-zinc, copper-lead).
Except where otherwise indicated, this section is derived from Control Techniques for Lead Air
Emissions.1*
4.8.2 Process Description
Lead, zinc, and copper ores are generally concentrated in a liquid medium using
settling and flotation. In all but a few cases, the metal is combined with sulfur and/or oxygen in
the ore. Lead, zinc, and copper are usually found together in varying percentages in ore
deposits.46 Depending on the amount of each of these metals in the ore and on the potential
economic return, the metals are either separated from the ore or discarded in the tailings.
The ore in the underground mines is disintegrated by light-weight percussive and
rotary-percussive drilling machines. Power shovels, front-end loaders, scrapers, and mucking
machines load the pulverized ore into electric or diesel-powered motorized trains operating on
heavy-gauge tracks, or into trackless shuttle cars. The ore is commonly run through a primary
crusher underground and then conveyed by skip loader, rail tram, or conveyor belt (depending
on the mine depth) to the surface, where classifying and additional grinding occur. Figure 4-17
illustrates a typical ore crushing and grinding operation.
Lead and zinc ores are concentrated to 45 to 75 percent before going to the
smelter. Depending on the mineral and gauge material, the ore is crushed and ground to a size
based on an economic balance between the recoverable metal values and the cost of grinding.
Standard jaw, gyratory, and cone crushers, vibrating or trommel screens, and rod and ball mills
are used to reduce the ore to powder in the 65- to 325-mesh range. Through gravity and/or
selective flotation, the finely divided particles of copper, lead, and zinc are separated from the
gangue and are cleaned, thickened, filtered, and dried.
Copper ores are handled in essentially the same manner as zinc and lead ores.
Open-pit mining for copper, copper-lead, copper-zinc, and copper-lead-zinc ores is centered
4-59
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Ore
Mining
Primary Crushing
Secondary Crushing
Tertiary Crushing
Grinding
Beneficiation
Drying
Packaging
and
Shipping
Storage
Storage
Tailings
Figure 4-17. Process Diagram for Ore Mining and Crushing
Source: Reference 46.
4-60
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primarily in the Western U.S. in arid or semi-arid areas. The ore and gangue are loosened and
pulverized by explosives, scooped up by power shovels or other mechanical equipment, and
loaded into trucks, rail trains, or cars for transport to the concentrator. The ore is then processed
in the same manner as lead and zinc ores.
4.8.3 Emissions
Lead emissions are basically fugitive in nature and are caused by drilling,
blasting, loading, conveying, screening, unloading, crushing, and grinding operations.46 The
emissions from actual ore mining operations are contained in underground mines. Lead
emission factors from available literature sources are presented in Table 4-12. Lead emissions
from lead, copper, or zinc ore mining are dependent upon the lead content of the ore. Ores with
greater lead content produce greater lead emission factors. Mixed-ore mining produces
relatively constant emission rates, although the lead content of the ore varies.
4.8.4 Emission Control Techniques
Because of the diversity of particulate emission sources in ore mining and
operations, a variety of control methods and techniques have been used. Dust-suppression
techniques are the most commonly used. They are designed to prevent PM from becoming
airborne and are applicable to both process and fugitive dust sources. Particulate emissions such
as those generated by crushing operations can be captured using local hooding and ventilation
and collected in control devices. Emission sources and applicable control options are listed in
Table 4-13.
4.9 BRASS AND BRONZE PROCESSING
4.9.1 Source Description
Brass and bronze are generally considered to be copper-based alloys, with zinc,
tin, and other metals such as lead, aluminum, manganese, and silicon as secondary components.
4-61
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TABLE 4-12. LEAD EMISSION FACTORS FOR LEADBEARING ORE CRUSHING AND GRINDING
ON
to
sec
Number
3-03-031-01
3-03-031-02
3-03-031-03
3-03-031-04
3-03-031-05
3-03-031-06
3-03-031-07
Emission Source
Lead Ore (5.1% Pb content)
Zinc Ore (0.2% Pb content)
Copper Ore (0.2% Pb content)
Lead-Zinc Ore (2.0% Pb content)
Copper-Lead Ore (2.0% Pb content)
Copper-Zinc Ore (0.2% Pb content)
Copper-Lead-Zinc Ore (2.0% Pb
content)
Control
Device
None
None
None
None
None
None
None
Emission Factor
in Ib/ton (kg/Mg)a
S.OOxlO'1
(l.SOxlO'1)
1.20X10'2
(6.00xlO'3)
1.20X10'2
(e.OOxlO'3)
1.20X10'1
(e.OOxlO'2)
1.20X10'1
(e.ooxio-2)
1.20X10'2
(e.ooxio-3)
1.20X10'1
(e.ooxio-2)
Emi s si on F actor Range Emi s si on
in Ib/ton (kg/Mg)a Factor Rating
B
B
B
B
B
B
B
Source: Reference 49
a Emission factors are expressed in Ib (kg) of pollutant emitted per ton (Mg) of ore processed.
"—" means data not available.
-------
TABLE 4-13. EMISSION SOURCES AND CONTROL DEVICES
Operation or Source
Control Options
Drilling
Blasting
Loading
Hauling (emissions from roads)
Crushing
Screening
Conveying (transfer points)
Stockpiling
Conveying
Windblown dust from stockpiles
Windblown dust on roads
Liquid injection (water or water plus a wetting agent)
Capturing and venting emissions to a control device
No control
Good blasting practices
Water wetting
Water wetting
Treatment with surface agents
Soil stabilization
Paving
Traffic control
Wet-dust suppression systems
Capturing and venting emissions to a control device
Same as for crushing
Same as for crushing
Stone ladders
Stacker conveyors
Water sprays at conveyor discharge
Covering
Wet-dust suppression
Water wetting
Surface active agents
Covering
Windbreaks
Oiling
Surface active agents
Soil stabilization
Paving
Sweeping
Source: Reference 18
4-63
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In 1987, the production of brass and bronze ingots totalled 203,934 tons (185,058 Mg).18 Of this
total, about 19 percent consisted of tin bronze, aluminum bronze, and nickel bronze, which do
not contain appreciable amounts of lead. The remaining 81 percent consisted of leaded red and
semi-red brass, high-leaded tin bronze, yellow brass, and manganese bronze, all of which
contain significant amounts of lead. Except where otherwise indicated, this section is derived
from Control Technologies for Lead Air Emissions.18
4.9.2 Process Description
Figure 4-18 illustrates the processes involved in the production of brass and
bronze alloys. The principal processes include scrap metal pretreatment and smelting. Feed
materials consist primarily of high-grade copper and copper alloy (brass and bronze) scrap.
Scrap pretreatment can be accomplished using several different techniques in
combination or separately, depending on the type and grade of scrap to be treated. Mechanical,
pyrometallurgical, and hydro-metallurgical processes may be used. Generally, the feed scrap is
first concentrated by manual and mechanical means, including manual sorting, stripping,
shredding, magnetic separation, and briquetting. Pyrometallurgical processes may include
sweating to remove low-melting metals such as lead, solder, and babbitt; burning to remove
insulation from wire or cable scrap; and drying to eliminate volatile oils and cutting fluids from
machine shop scrap. Hydro-metallurgical processes include floatation and leaching.34
Melting, smelting, and alloying are performed in a variety of furnace types,
including stationary and rotary reverberatory furnaces, electric furnaces, and crucible or pot
furnaces. First, the pretreated and clean scrap, along with fluxes, are charged to the melting
furnace. The charge materials are then melted by direct or indirect heat supplied by gas or oil
combustion in fossil fuel-fired furnaces, and by electric arc resistance or induction in the electric
furnaces. Metal oxides and other impurities in the melt react with fluxes to form a slag, which is
skimmed off and generally discarded. Alloying metals are added as required to bring the
mixture to the desired final composition. In addition, air and oxygen may be blown into the
smelt to
4-64
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ENTERING THE SYSTEM
LEAVING THE SYSTEM
HIGH GRADE SCRAP,
(WIRE, PIPE, BEARINGS,
PUNCHINGS, RADIATORS)
MANUAL AND MECHANICAL
PRETREATMENT
(SORTING)
DFSIBFn R
k
JARS
» FUGUTIVE DUST TO ATMOSPHERE
(SCC 3-04-002-30)
UNDESIRED
TO SALE
DESIRED
COPPER SCRAP
AND BRONZE SCRAP
1
1
GASES, METAL OXIDES
TO CONTROL EQUIPMENT
LEAD, SOLDER, BABBITT METAL
FLUX-
FUEL-
ALLOY MATERIAL-
(ZINC, TIN, ETC.)
MELTING AND
ALLOYING FURNACE
ALLOY MATERIAL
CASTING
(FINAL PRODUCT)
_>. PARTICULATES, HYDROCARBONS,
ALDEHYDES, FLUORIDES, AND
CHLORIDES TO AFTERBURNER
AND PARTICULATE CONTROL
METAL OXIDES TO
CONTROL EQUIPMENT
-4
SLAG TO DISPOSAL
FUGITIVE METAL OXIDES GENERATED
DURING POURING TO EITHER PLANT
ENVIRONMENT OR HOODING
(SCC 3-04-002-39)
Figure 4-18. Brass and Bronze Alloys Production Processes
Source: Reference 34.
4-65
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oxidize excess zinc. After the desired final composition is reached, the refined metal product is
poured or tapped into ingots or other cast shapes.34
4.9.3 Emissions
Scrap treatment by mechanical and hydrometallurgical processes at brass and
bronze manufacturing facilities produces little or no emissions. Pyrometallurgical treatment
processes may generate substantial emissions, including combustion products and contaminants,
but few metal oxides such as lead oxide. Wire burning generates much PM, consisting largely of
unburned combustibles. Lead may be emitted as PM from wire burning depending on the lead
content of the charge. Scrap drying and cutting produces large amounts of soot and
hydrocarbons but little or no metal oxides such as lead oxide. Sweating operations may produce
small amounts of metal oxides, which are typically controlled by baghouses.
Air pollutants emitted from brass and bronze smelting furnaces consist of
products of combustion, dusts, and metallic fumes resulting from the oxidation and condensation
of the more volatile metals such as lead, zinc, and others. The lead fraction of the PM generated
will vary according to fuel type, alloy composition, furnace type, smelting temperature, and
other operational factors. Exhaust gas parameters for an uncontrolled brass and bronze
reverberatory furnace are presented in Table 4-14. Table 4-15 shows production data and
emission factors.
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TABLE 4-14. CHARACTERISTICS OF UNCONTROLLED EXHAUST GAS FROM
A BRASS AND BRONZE REVERBERATORY FURNACE
Parameters Standard International Units English Units
Gas flow ratea 4.5 m3/s*Mg*h"1 product 8600 acfm/tph product
Temperature13 925 - 1315 C 1700 - 2400 °F
Grain loading 0.12 - 9.4 g/m3 0.05 - 4.1 gr/scf
Particle size distribution 0.03-0.5 mm (majority)
Lead content of particulate high-leaded 58% wt
yellow and red 15% wt
other brass and bronze 7% wt
Source: Reference 18
a Flow rates can vary according to the hooding arrangement. Volume given is at 250°F (120°C).
b Temperature is usually reduced to 250°F (120°C).
TABLE 4-15. BRASS AND BRONZE PRODUCTION AND LEAD EMISSIONS IN 1992
Product
High-leaded alloys0
Red and Yellow lead alloys'1
Other alloys6
Total
Productiona
tons (Mg)
21,285 (19,309)
119,986(108,880)
21,803 (19,785)
163,073 (147,974)
Pb Emission Factor*3
Ib/ton (kg/Mg)
50 (25)
13.2(6.6)
5.0(2.5)
The U.S. Bureau of Mines provided total lead alloy production for 1992. The breakdown of production for
each alloy type was not available. Therefore, the 1992 production estimates for each alloy type are based on
the breakdown of total lead production for each alloy type in 1986. Total lead alloy production was estimated
to be 163,073 tons (147,974 Mg). Source: Reference 18, 53
Source: Reference 18
Includes all production of high-leaded tin bronze; 90 percent of production for manganese bronze; and silicon
brass and bronze.
Includes all production of leaded red brass, semi-red brass, and yellow brass.
Includes all production for copper-base hardness and master alloys, miscellaneous alloys, 10 percent of
manganese bronze, and silicon brass and bronze.
4-67
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SECTION 5.0
EMISSIONS OF LEAD AND LEAD COMPOUNDS FROM COMBUSTION SOURCES
This section contains process descriptions, available emission factor data, and
source locations for source categories that emit lead and lead compounds during combustion.
These source categories include fuel combustion in external and internal combustion engines;
incineration of various types of waste, including municipal waste, industrial waste, sewage sludge,
medical waste, hazardous waste, and scrap tires; and drum and barrel reclamation and
crematories.
There are few emission controls that are dedicated solely to reducing lead
emissions from combustion sources. However, the control strategies used to reduce PM
emissions have been found to be effective in controlling lead emissions in particulate form. Where
a specific emission control strategy has been identified to reduce lead emissions from a particular
combustion source discussed in this section, that control strategy is discussed as part of the
process description for that source. In many cases throughout this section, emission factor data
are provided for both controlled and uncontrolled combustion units that are typically found in a
particular source category.
5.1 STATIONARY EXTERNAL COMBUSTION
The combustion of solid, liquid, and gaseous fuels such as coal, wood, fuel oil, and
natural gas has been shown to be a source of lead emissions. Lead emission rates depend on both
fuel characteristics and combustion process characteristics. Emissions of lead originate from lead
compounds contained in fuels and emitted during combustion.51'52'53 Because metals such as lead
only change forms (chemical and physical states) during combustion and are never destroyed, the
5-1
-------
amount of lead in the original fuel or waste will be equal to the amount of lead found in the ash or
emitted in the effluent gas.54'55
Lead concentrations in coal depend on the type of coal. Example specific lead
concentrations in coal are as follows: anthracite coal contains approximately 7 ppm lead;
bituminous coal contains 14 ppm lead; subbituminous coal contains 6 ppm lead; and lignite coal
contains 7 ppm lead.56 Likewise, the lead concentration in fuel oil also depends on the type of oil.
Residual oil averages about 1 ppm lead by weight, while the lead content of distillate oil ranges
from 0.1 to 0.5 ppm lead by weight.57'58 Wood has been reported to have a lead content of
20 ppm.59
Lead and lead compound emissions may be reduced from combustion sources by
using PM control devices, lower combustion and control device temperatures, and controlling
feed chlorine content.60 Each of these lead reduction techniques is discussed briefly below.
In general, use of PM control devices in combustion/air pollution control systems
can be viewed as a surrogate for controlling emissions of lead (and other metals).55 The most
effective means of controlling lead emissions to the atmosphere are minimizing lead vaporization
in the combustion zone and maximizing small particle collection in the Air Pollution Control
Device (APCD). Lead compounds, like many heavy metal compounds, vaporize at elevated
temperatures and, as temperatures drop, only a fraction of the vaporized metal condenses. The
remaining vaporized metal can escape through the PM APCD.
During the combustion process, lead and other metals volatilize and then, upon
cooling, condense on all available particulate surface area. The submicrometer particles with very
high surface areas can carry a very high concentration of condensed lead. This phenomenon is
known as "fine particle enrichment." There are three general factors favoring fine particle
enrichment of lead:55
• High particulate surface area;
• Large number of particles; and
5-2
-------
• Low flue gas temperatures.
There is some evidence that fine particle enrichment of lead on PM is not as
prevalent at higher flue gas temperatures. It is believed that as long as the flue gas temperatures
remain high, the metals tend to remain volatilized, such that they do not condense and bond with
PM.55
Another factor that influences the extent of lead emissions is chlorine content. The
chlorine content of the combusted fuel or waste increases the sensitivity of lead emissions to bed
temperature. When a high chlorine content is present, lead will volatilize at lower temperatures
due to the high volatility of lead chlorides (PbCl2) versus oxides (PbO). Monitoring and limiting
the feed chlorine content reduces the volatility of lead, allowing more lead to condense onto PM
for more effective lead emissions control.
The primary stationary combustion sources emitting lead compounds are boilers,
furnaces, heaters, stoves, and fireplaces used to generate heat and/or power in the residential,
utility, industrial, and commercial use sectors. A description of combustion sources, typical
emission control equipment, and lead emission factors for each of these major use sectors is
provided in the sections that follow.
5.1.1 Source Location
Fuel economics and environmental regulations affect regional use patterns for
combustion sources. Most of the utility coal-firing capability in the United States is east of the
Mississippi River, with the significant remainder being in the Rocky Mountain region. Natural gas
is used primarily in the South Central States and California. Oil is predominantly used in Florida
and the Northeast. Information on precise utility plant locations can be obtained by contacting
utility trade associations, such as the Electric Power Research Institute in Palo Alto, California
(415-855-2000), the Edison Electric Institute in Washington, B.C. (202-828-7400), or the
U.S. Department of Energy (DOE) in Washington, D.C. Publications by EPA and DOE on the
utility industry are useful in determining specific facility locations, sizes, and fuel use.
5-3
-------
Industrial and commercial coal combustion sources are located throughout the
United States, but tend to be concentrated in areas of industry and larger population. Most of the
coal-fired industrial boiler sources are located in the Midwest, Appalachian, and Southeast
regions. Industrial wood-fired boilers tend to be located almost exclusively at pulp and paper,
lumber products, and furniture industry facilities. These industries are concentrated in the
Southeast, Gulf Coast, Appalachian, and Pacific Northwest regions. Trade associations such as
the American Boiler Manufacturers Association in Arlington, Virginia and the Council of
Industrial Boiler Owners in Fairfax Station, Virginia can provide information on industrial boiler
locations and trends.61'62
Section 5.1.2 presents process descriptions and available emission factors for
residential heating. Section 5.1.3 presents process descriptions for utility, industrial, and
commercial fuel combustion. Section 5.1.4 presents available emission factors for utility,
industrial, and commercial fuel combustion.
5.1.2 Residential Heating
The residential sector includes furnaces and boilers burning coal, oil, and natural
gas, stoves and fireplaces burning wood, and kerosene heaters. All units in this sector are
designed to heat individual homes. Residential combustion sources generally are not equipped
with PM or gaseous pollutant control devices. With coal- and wood-fired residential sources,
changes in stove design and operating practice in recent years have lowered PM, CO, and
hydrocarbon emissions from these sources. Changes include modified combustion air flow
control, greater thermal control and heat storage, and the use of combustion catalysts. Such
changes are also expected to reduce lead emissions.63'64
Residential Coal Combustion
Process Description—Coal is not widely used for residential heating in the United
States. Only 0.3 percent of the total coal consumption in 1990 was for residential use.65
5-4
-------
Although combustion units burning coal are minor sources of lead emissions, they may be
important local sources in areas where a large number of residences rely on coal for heating.
There are a wide variety of coal-burning stoves in use. These include boilers,
furnaces, and stoves that are designed to burn coal, and wood-burning stoves that burn coal.
These units may be either hand-fed or automatically-fed. Boilers and warm-air furnaces are
usually stoker-fed and are automatically controlled by a thermostat. Stoves are less sophisticated,
generally hand-fed, and less energy efficient than boilers and furnaces. Lead emissions from all of
these units depend on the concentration of lead in the coal.
Emissions-A 1979 EPA study reported average lead emission factors for a
residential coal-burning boiler and furnace. These emission factors, shown in Table 5-1, represent
total lead particulate emissions. Although these factors are dated, they should be representative
of current lead emissions from these sources for two reasons. First, these emissions depend on
the concentration of lead in the coal used and, second, emission controls still remain uncommon
among these sources.66
Residential Distillate Oil Combustion
Process Description—Distillate oil is the second most important home heating fuel
behind natural gas. (Residual oil is seldom used in the residential sector.)67 The use of distillate
oil-fired heating units is concentrated in the Northeast. In 1991, Connecticut, Maine,
Massachusetts, New Hampshire, Rhode Island, Vermont, Delaware, District of Columbia,
Maryland, New Jersey, New York, and Pennsylvania accounted for approximately 72 percent of
residential distillate oil sales.68
Residential oil-fired heating units are available in a number of design and operating
variations. These variations include burner and combustion chamber design, excess air, and
heating medium. Residential systems typically operate only in an "on" or "off mode and at a
constant fuel-firing rate, unlike commercial and industrial applications, where load modulation is
the general practice.70 In distillate oil-fired heating units, fuel oil is atomized into
5-5
-------
TABLE 5-1. LEAD EMISSION FACTORS FOR RESIDENTIAL COAL COMBUSTION
SCC Number
A2 1-04-002-000
A2 1-04-00 1-000
Emission Source Control Device
Bituminous/ None
Subbituminous Coal - All
Combustor Types
Anthracite Coal - All None
Combustor Types
Average Emission
Factor
in Ib/ton
(kg/Mg)a
2.00x1 0-2
(l.OOxlO-2)
i.eoxio-2
(8.00x1 0-3)
Emission Factor Range
in Ib/ton
(kg/Mg)a
—
—
Emission Factor Rating
U
U
Source: Reference 69
a Emission factors are expressed in Ib (kg) of pollutant emitted per ton (Mg) of coal combusted.
"—" means data are not available.
-------
finer droplets for combustion. Finer droplets generally result in more complete combustion and
less PM formation.
Emissions-Lead emissions from oil combustion depend primarily on the grade,
composition of the fuel, and the level of equipment maintenance. Secondary contributions would
be the type and size of the combustion equipment and the firing and loading practices used. The
extent of particulate and lead emissions depends directly on the grade of oil fired. The lighter
distillate oils result in significantly lower particulate formation than do the heavier and dirtier
residual oils. In addition, residual oils typically contain substantially higher lead levels than do
distillate oils.
Residential combustion units are less sophisticated than utility and industrial
combustion units. For this reason, they normally burn distillate oil to keep emissions to a
minimum.57'58 Average emission factors for residential distillate oil-fired furnaces are presented in
Table 5-2.
Residential Natural Gas Combustion
Process Description—Natural gas is the most widely used fuel for home heating
purposes. More than half of all homes in the United States are heated by natural gas
combustion.71 Gas-fired residential heating systems are generally less complex and easier to
maintain than oil-burning units because the fuel burns cleaner and no atomization is required.
Residential gas burners typically are built of the same basic design. Natural aspiration is used
where the primary air mixes with the gas as it passes through the distribution pipes. Secondary air
enters the furnace around the burners. Flue gases then pass through a heat exchanger and a stack.
As with oil-fired systems, there is usually no APCD installed on gas systems. Excess air,
residence time, flame retention devices, and maintenance are the key factors in controlling PM
(including lead) emissions from these units.
Emissions—Emissions testing data for lead from gas-fired residential units have
been extremely scarce, probably because the expected emissions are low and this source has not
5-7
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TABLE 5-2. EMISSION FACTORS FOR RESIDENTIAL DISTILLATE OIL-FIRED FURNACES
SCC Number
Emission Source
Average Emission Factor
Control in Ib/MMBtu
Device (kg/Joule)a
Emission Factor Range
in Ib/MMBtu
(kg/Joule)a
Emission
Factor Rating
A21-04-004-000 Distillate (No. 2 oil)
Oil-fired Furnaces
None
2.2xlQ-4
(9.5xlQ-14)
2.44xlQ-2 - 3.08xlQ-2
(2.92xlQ-6 - 3.96xlQ-6)
U
Source: Reference 72
a Emission factors are expressed in Ib (kg) of pollutant emitted per MMBtu (Joule) of heat input.
oo
-------
been identified as a priority for testing. As a result, there are no available emission factors for this
source.
5.1.3 Process Descriptions for Utility. Industrial, and Commercial Fuel Combustion
Utility Sector
Utility boilers burn coal, oil, natural gas, and wood to generate steam for
electricity generation. Fossil fuel-fired utility boilers comprise about 72 percent [or
497,000 megawatts (MW)] of the generating capacity of U.S. electric power plants. Of these
fuels, coal is the most widely used, accounting for approximately 60 percent of the U.S. fossil
fuel-powered electricity generating capacity. Natural gas represents about 25 percent and oil
represents the remaining 15 percent.73
A utility boiler consists of several major subassemblies, as shown in Figure 5-1.
These subassemblies include the fuel preparation system, air supply system, burners, the furnace,
and the convective heat transfer system. The fuel preparation system, air supply, and burners are
primarily involved in converting fuel into thermal energy in the form of hot combustion gases.
The last two subassemblies transfer the thermal energy in the combustion gases to the superheated
steam that operates the steam turbine and produces electricity.73
Utility boilers are generally identified by their furnace configuration. Different
furnace configurations used in utility boilers include tangentially-fired, wall-fired, cyclone-fired,
stoker-fired, and fluidized bed combustion (FBC) boilers. Some of these furnace configurations
are designed primarily for coal combustion, while others are also used for oil or natural gas
combustion. The furnaces types most commonly used for firing oil and natural gas are the
tangentially-fired and wall-fired boiler designs.74 Each of these furnace types is described below.
Tangentially-fired Boiler—The tangentially-fired boiler is based on the concept of a
single flame zone within the furnace. The fuel-air mixture in a tangentially-fired boiler projects
from the four corners of the furnace along a line tangential to an imaginary cylinder located
5-9
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Superheaters and Reheaters
Furnace
Secondary Air
Burners
1
<
•—
0.
^
•c
a.
V
Fuel Prep
Flue Gas
Air
Fuel
Figure 5-1. Simplified Boiler Schematic
Source: Reference 73.
s
o
a.
5-10
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along the furnace centerline. When coal is used as the fuel, the coal is pulverized in a mill to the
consistency of talcum powder (i.e., so that at least 70 percent of the particles will pass through a
200 mesh sieve), entrained in primary air, and fired in suspension.75 As fuel and air are fed to the
burners, a rotating "fireball" is formed. By tilting the fuel-air nozzle assembly, this "fireball" can
be moved up and down to control the furnace exit gas temperature and to provide steam
temperature control during variations in load. Tangentially-fired boilers commonly burn
(pulverized) coal. However, oil or gas may also be burned.73
Wall-fired Boiler—The wall-fired boiler, or normal-fired boiler, is characterized by
multiple, individual burners located on a single wall or on opposing walls of the furnace
(Figure 5-2). As with tangentially-fired boilers, when coal is used as the fuel it is pulverized,
entrained in primary air, and fired in suspension. In contrast to tangentially-fired boilers that
produce a single flame zone, each of the burners in a wall-fired boiler has a relatively distinct
flame zone. Various wall-fired boiler types exist, including single-wall, opposed-wall, cell,
vertical, arch, and turbo. Wall-fired boilers may burn (pulverized) coal, oil, or natural gas.73
Cyclone-fired Boiler—In the cyclone-fired boiler, fuel and air are burned in
horizontal, cylindrical chambers, producing a spinning, high-temperature flame. Cyclone-fired
boilers are almost exclusively (crushed) coal-fired. The coal is crushed to a 4-mesh size and
admitted with the primary air in a tangential fashion. The finer coal particles are burned in
suspension, while the coarser particles are thrown to the walls by centrifugal force.74 Some units
are also able to fire oil and natural gas.73
Fluidized Bed Combustion Boiler—Fluidized bed combustion is a newer boiler
technology that is not as widely used as the other, more conventional boiler types. In a typical
FBC, crushed coal in combination with inert material (sand, silica, alumina, or ash) and/or sorbent
(limestone) are maintained in a highly turbulent suspended state by the upward flow of primary air
(Figure 5-3). This fluidized state promotes uniform and efficient combustion at lower furnace
temperatures, between 1,575 and 1,650°F (860 and 900°C), compared to 2,500 and 2,800°F
(1,370 and 1,540°C) for conventional coal-fired boilers. Fluidized bed combustors have been
developed to operate at both atmospheric and pressurized conditions.73
5-11
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Burner B
Burner A
AirA-
AirB-
AirC-
Air'D-
Fuel A
FuelB
FueIC
FuelD
Burner D
Burner C
Of
LU
Figure 5-2. Single Wall-fired Boiler
Source: Reference 73.
5-12
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Flue Gas
Convection ,
Pass
Coal Limestone
Freeboard
Splash
Zone
Bed
Transport Air
Forced Draft Air
Compressor
Cyclone
Fluldlzlng Air
Recycle
Distributor
Plate
Plenum
Waste
Waste
o
CL
Figure 5-3. Simplified Atmospheric Fluidized Bed Combustor Process Flow Diagram
Source: Reference 73.
5-13
-------
Stoker-fired Boiler—Instead of firing coal in suspension as in the boilers described
above, the mechanical stoker can be used to burn coal in fuel beds. Mechanical stokers are
designed to feed coal onto a grate within the furnace. The most common stoker type used in the
utility industry is the spreader stoker (Figure 5-4). In the spreader stoker, a flipping mechanism
throws crushed coal into the furnace and onto a moving fuel bed (grate). Combustion occurs
partly in suspension and partly on the grate.75
Emission Control Techniques—Utility boilers are highly efficient and are among the
best controlled of all combustion sources. Existing emission regulations for total PM have
necessitated controls on coal- and oil-fired utility sources. Emission controls are not required on
natural gas boilers because, relative to coal and oil units, uncontrolled emissions are inherently
low.64 Baghouses, ESPs, wet scrubbers, and multicyclones have been used to control PM in the
utility sector. As described in other source category sections, lead condenses on PM, which is
easily controlled by PM control technologies. Particulate lead, specifically fine particulate, is
controlled most effectively by baghouses or ESPs. Depending on their design, wet scrubbers are
potentially effective in controlling particulate lead. Multicyclones are ineffective at capturing fine
particles of lead and, therefore, are a poor control system for lead emissions.63'64
Lead emissions from utility boilers are commonly controlled using an SO2 control
technology known as lime/limestone flue gas desulfurization (FGD). This technology employs a
wet scrubber for SO2 removal and is often preceded by an ESP, which accomplishes the bulk of
PM control. Wet FGD/ESP systems, while controlling lead condensed on PM at the entrance to
the ESP, are relatively inefficient for control of vapor-phase lead. However, most lead emissions
are condensed on PM and are not emitted in the vapor phase.63'64
A more recently applied SO2 control technique for utility boilers is spray drying.
In this process, the gas stream is cooled in the spray dryer, but it remains above the saturation
temperature. A fabric filter or an ESP is located downstream of the spray dryer, thus controlling
both particulate-phase lead emissions and vapor-phase lead emissions that condense before they
reach the baghouse or ESP.63'64
5-14
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Tangential Overfire Air
Distributors
Drive Shaft
Grates
Return Rails
Tangential Overfire Air
A /
Drag Seals Idler Shaft
Carbon-Recovery Nozzles
Back-Stop Assembly
Take-Up
Sittings Hopper
Figure 5-4. Spreader Type Stoker-fired Boiler
Source: Reference 73.
-------
Industrial/Commercial Sector
Industrial boilers are widely used in manufacturing, processing, mining, and
refining, primarily to generate process steam, electricity, or space heat at the facility. Only a
limited amount of electricity is generated by the industrial sector; only 10 to 15 percent of
industrial boiler coal consumption and 5 to 10 percent of industrial boiler natural gas and oil
consumption are used for electricity generation.76 Commercial boilers are used to provide space
heating for commercial establishments, medical institutions, and educational institutions.
In collecting survey data to support its Industrial Combustion Coordinated
Rulemaking (ICCR), the EPA compiled information on a total of 69,494 combustion boiler units
in the industrial and commercial sectors.259 While this number likely underestimates the total
population of boilers in the industrial and commercial sectors (due to unreceived survey responses
and lack of information on very small units) it provides an indication of the large number of
sources included in this category.
Of the units included in the ICCR survey database, approximately 70% were
classified in the natural gas fuel subcategory, 23% in the oil (distillate and residual) subcategory,
and 6% in the coal burning subcategory. These fuel subcategory assignments are based on the
units burning only greater than 90% of the specified fuel for that subcategory. All other units
(accounting for the other 1% of assignments) are assigned to a subcategory of "other fossil
fuel."259
Other fuels burned in industrial boilers are wood wastes, liquified petroleum gas,
and kerosene. Wood waste is the only non-fossil fuel discussed here since most lead emissions
are attributed to the combustion of wood fuel. The burning of wood waste in boilers is confined
to those industries where it is available as a by-product. It is burned both to obtain heat energy
and to alleviate possible solid waste disposal problems. Generally, bark is the major type of wood
waste burned in pulp mills. In the lumber, furniture, and plywood industries, either a mixture of
wood and bark, or wood alone, is frequently burned. As of 1980, the most recent data identified,
5-16
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there were approximately 1,600 wood-fired boilers operating in the United States with a total
capacity of over 100,000 MMBtu/hr (30,000 MW thermal).78
Many of the same boiler types used in the utility sector are also used in the
industrial/commercial sector; however, the average size boiler used in the industrial/ commercial
sector is substantially smaller than the average size boiler used in the utility sector. In addition, a
few boiler designs are used only by the industrial/commercial sector. For a general description of
the major subassemblies and key thermal processes that occur in boilers, refer to Figures 5-1 to
5-4 in the section on Utility Sector Process Description and the accompanying discussion.
Stoker-fired Boiler—Instead of firing coal in suspension (like the boilers described
in the Utility Sector Process Description section), mechanical stokers can be used to burn coal in
fuel beds. All mechanical stokers are designed to feed coal onto a grate within the furnace. The
most common stoker types in the industrial/commercial sector are overfeed and underfeed
stokers. In overfeed stokers, crushed coal is fed from an adjustable gate above onto a traveling or
vibrating grate below. The crushed coal burns on the fuel bed as it progresses through the
furnace. Conversely, in underfeed stokers, crushed coal is forced upward onto the fuel bed from
below by mechanical rams or screw conveyors.73'75
Water-tube Boilers-In water-tube boilers, water is heated as it flows through
tubes surrounded by circulating hot gases. These boilers represent the majority (i.e., 57 percent)
of industrial and commercial boiler capacity (70 percent of industrial boiler capacity).76
Water-tube boilers are used in a variety of applications, from supplying large amounts of process
steam to providing space heat for industrial and commercial facilities. These boilers have
capacities ranging from 9.9 to 1,494 MMBtu/hr (2.9 to 439.5 MW thermal), averaging about
408 MMBtu/hr (120 MW thermal). The most common types of water-tube boilers used in the
industrial/commercial sector are wall-fired and stoker-fired boilers. Tangentially-fired boilers and
FBC boilers are less commonly used.77 Refer to Figures 5-1 to 5-4 and the accompanying
discussion in the section on Utility Sector Process Description for more detail on these boiler
designs.
5-17
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Fire-tube and Cast Iron Boilers—Two other heat transfer methods used in the
industrial/commercial sector are fire-tube and cast iron boilers. In fire-tube boilers, hot gas flows
through tubes that are surrounded by circulating water. Fire-tube boilers are not available with
capacities as large as water-tube boilers, but they are also used to produce process steam and
space heat. Most fire-tube boilers have a capacity between 1.4 and 25 MMBtu/hr (0.4 to 7.3 MW
thermal). Most installed fire-tube boilers burn oil or gas and are used primarily in
commercial/institutional applications.77
In cast iron boilers, the hot gas is also contained inside the tubes that are
surrounded by the water being heated, but the units are constructed of cast iron instead of steel.
Cast iron boilers are limited in size and are used only to supply space heat. Cast iron boilers range
in size from less than 0.34 to 9.9 MMBtu/hr (0.1 to 2.9 MW thermal).77
Wood Waste Boilers—The burning of wood waste in boilers is primarily confined
to those industries where wood is available as a by-product. Wood is burned both to obtain heat
energy and to alleviate solid waste disposal problems. Wood waste may include large pieces such
as slabs, logs, and bark strips as well as cuttings, shavings, pellets, and sawdust.78
Various boiler firing configurations are used to burn wood waste. One
configuration that is common in smaller operations is the dutch oven or extension type of furnace
with a flat grate. This unit is used widely because it can burn very high-moisture fuels. Fuel is fed
into the oven through apertures in a firebox and is fired in a cone-shaped pile on a flat grate. The
burning is accomplished in two stages: (1) drying and gasification, and (2) combustion of gaseous
products. The first stage takes place in a cell separated from the boiler section by a bridge wall.
The combustion stage takes place in the main boiler section.78
In another type of boiler, the fuel-cell oven, fuel is dropped onto suspended fixed
grates and is fired in a pile. The fuel cell uses combustion air preheating and positioning of
secondary and tertiary air injection ports to improve boiler efficiency.78
5-18
-------
In many large operations, more conventional boilers have been modified to burn
wood waste. These modified units may include spreader stokers with traveling grates or vibrating
grate stokers, as well as tangentially-fired or cyclone-fired boilers. Refer to Figures 5-1 to 5-4
and the accompanying discussion in the section on Utility Sector Process Description for more
detail on these types of boilers. The spreader stoker, which can burn dry or wet wood, is the
most widely used of these configurations. Fuel is dropped in front of an air jet that casts the fuel
out over a moving grate. The burning is carried out in three stages: (1) drying, (2) distillation
and burning of volatile matter, and (3) burning of fixed carbon. These operations often fire
natural gas or oil as auxiliary fuel. Firing an auxiliary fuel helps to maintain constant steam when
the wood supply fluctuates or to provide more steam than can be generated from the wood supply
alone.78
Sander dust is often burned in various boiler types at plywood, particle board, and
furniture plants. Sander dust contains fine wood particles with a moisture content of less than
20 percent by weight. The dust is fired in a flaming horizontal torch, usually with natural gas as
an ignition aid or as a supplementary fuel.78
A recent development in wood-firing is the FBC (refer to Figures 5-1 to 5-4 and
the accompanying discussion in Utility Sector Process Description for more detail on this boiler
type). Because of the large thermal mass represented by the hot inert bed particles, FBCs can
handle fuels with high moisture content (up to 70 percent, total basis). Fluidized bed combustors
can also handle dirty fuels (up to 30 percent inert material). Wood material is pyrolyzed faster in
a fluidized bed than on a grate due to its immediate contact with hot bed material.78
The composition of wood waste is expected to have an impact on lead emissions.
The composition of wood waste depends largely on the industry from which it originates. Wood
waste fuel can contain demolition debris like plastics, paint, creosote-treated wood, glues,
synthetics, wire, cable, insulation, etc., which are potential sources of lead emissions. Pulping
operations, for example, produce great quantities of bark along with sand and other
noncombustibles. In addition, when fossil fuels are co-fired with wood waste, there is potential
for additional lead emissions from the lead content of the fossil fuel.79
5-19
-------
Waste Oil Combustion—Waste oil is another type of fuel that is burned primarily in
small industrial/commercial boilers and space heaters. Space heaters (small combustion units
generally less than 250,000 Btu/hr [0.1 MW] heat input) are common in automobile service
stations and automotive repair shops where supplies of waste crankcase oil are available.80 Waste
oil includes used crankcase oils from automobiles and trucks, used industrial lubricating oils (such
as metal working oils), and other used industrial oils (such as heat transfer fluids). Due to a
breakdown of the physical properties of these oils and contamination by other materials, these oils
are considered waste oils when they are discarded.81
The federal government has developed regulations for waste oil fuel under the
Resource Conservation and Recovery Act (RCRA). The EPA has determined that as long as
used oil is recycled (which includes burning it for energy recovery as well as re-refining it or other
processes), it is not considered a hazardous waste under RCRA 40 CFR 261.1.82 However, if a
facility does burn used oil, that facility is subject to certain requirements under RCRA.
EPA has established two categories of waste fuel: "on-specification" and
"off-specification." If the lead levels of the waste oil are 100 ppm or less, the waste oil is
classified as "on-specification;" if the lead levels are greater than 100 ppm, the waste oil is
classified as "off-specification" (40 CFR 279.II).83
If a facility is burning "on-specification" waste oil for energy recovery, that facility
is only subject to certain reporting and recordkeeping requirements (40 CFR 279.11).86 If a
facility burns the waste oil in a space heater with heat input capacity less than 0.5 million Btu/hr
(0.15 Mg) and vents the exhaust to the ambient air, that facility is not subject to any requirements
(40 CFR 279.23).84
A facility burning "off-specification" waste oil for energy recovery must comply
with additional requirements, including verification to EPA that the combusted oil was not mixed
with other hazardous wastes (40 CFR Subpart G).88
5-20
-------
Boilers designed to burn No. 6 (residual) fuel oils or one of the distillate fuel oils
can be used to burn waste oil, with or without modifications for optimizing combustion. As an
alternative to boiler modification, the properties of waste oil can be modified by blending it with
fuel oil to the extent required to achieve a clean-burning fuel mixture.
Coal Combustion—A very small amount of coal is used in the industrial/
commercial sector. Coal accounts for only 18 percent of the total firing capacity of fossil fuel
used. The majority of coal combustion occurs in the utility sector. Refer to Figures 5-1 to 5-4
and the accompanying discussion in Utility Sector Process Description for more detail about these
boiler types.
Emission Control Techniques—The amount of lead emissions from
industrial/commercial boilers depends primarily on two factors: (1) the type of fuel burned, and
(2) the type of boiler used. The secondary influences on lead emissions are the operating
conditions of the boiler and the APCD used.
Fly ash injection, one type of control commonly used in large wood-fired boilers to
improve fuel efficiency, may increase particulate lead emissions. With fly ash injection, a greater
amount of carbon is introduced into the boiler which, in turn, increases the amount of fine PM.
Fine PM is more difficult to collect with the APCD; the fine PM escapes through the APCD
uncontrolled, thereby increasing lead emissions.75
Emission controls for industrial boilers and their effectiveness in reducing lead
emissions are very similar to those previously described for utility boilers. PM control in the
industrial sector is achieved with baghouses, ESPs, wet scrubbers, and multicyclones. FGD
systems for SO2 control are used less frequently in the industrial sector than in the utility sector.
Generally, in the industrial sector, SO2 regulations are met by burning lower-sulfur-content
fuels.63'64
PM emissions from oil-fired industrial boilers generally are not controlled under
existing regulations because emission rates are low. Some areas may limit SO2 emissions from
5-21
-------
oil-firing by specifying the use of lower-sulfur-content oils. Natural gas-fired industrial boilers are
also generally uncontrolled because of very low emissions.63'64
Wood-fired industrial boilers are typically controlled by multicyclones followed by
venturi or impingement-type wet scrubbers for PM control. Some wood-fired boilers use ESPs
for PM control. The effect of both control systems on lead emissions reduction is estimated to be
similar to that obtained at coal-fired units using the same technology (i.e., potentially effective PM
and vaporous lead control with scrubbers, and effective PM lead control but no vaporous lead
control with ESPs).63'64
5.1.4 Emission Factors for Utility. Industrial, and Commercial Fuel Combustion
Extensive lead emissions data for utility, industrial, and commercial stationary
external combustion sources are available in the literature. Because state and federal air pollution
regulations often require emissions testing for toxic air pollutants, a current database of lead
emissions from these fuel combustion sources exists.
Emission factors for utility, industrial, and commercial stationary external
combustion source categories, grouped according to the type of fuel burned, are presented in
Tables 5-3 to 5-19 and discussed under the following sub-headings:
• Wood waste combustion:
Utility boilers (Table 5-3),
Industrial boilers (Table 5-4),
Commercial/institutional boilers (Table 5-5);
• Natural gas combustion:
Utility boilers (Tables 5-6 and 5-7);
5-22
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• Coal combustion:
Utility boilers (Tables 5-8 and 5-9),
Industrial boilers (Table 5-10),
Commercial/institutional boilers (Table 5-11);
• Oil combustion:
Utility boilers (Table 5-12 and 5-13),
Industrial boilers (Table 5-14),
Commercial/institutional boilers (Table 5-15);
• Waste oil combustion:
Industrial boilers (Table 5-16),
Commercial/institutional boilers (Table 5-17);
• Solid waste combustion:
Utility boilers (Table 5-18);
• Miscellaneous combustion:
Industrial boilers (Table 5-19).
Wood Waste Combustion
Lead emission factors for wood waste combustion in utility, industrial, and
commercial boilers are presented in Tables 5-3, 5-4, and 5-5, respectively. These emission factors
are widely applicable to all utility, industrial, and commercial wood waste combustion SCC
categories.73 However, a wide range of boiler sizes, boiler and control device configurations, and
fuel characteristics is reflected by these composite emission factors. For this reason, if site-
specific information is available to characterize an individual combustion source more accurately,
it is recommended that the reader locate the appropriate process-specific emission factor
presented in the applicable table.
5-23
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TABLE 5-3. LEAD EMISSION FACTORS FOR WOOD WASTE-FIRED UTILITY BOILERS
Ul
to
sec
Number Emission Source Control Device
1-01-009-01 Wood Waste-fired None
Boiler (Bark-fired)
1-01-009-02 Wood Waste-fired ESP
Boiler (Wood/Bark-
fired)
Scrubber
Multiple Cyclone with Flyash
Reinjection
Multiple Cyclone without Flyash
Reinjection
1-01-009-03 Wood Waste-fired ESP
Boiler (Wood-fired)
Multiple Cyclone without Flyash
Reinjection
None
Limestone Injection, Thermal
de- NOX with Ammonia
Injection, Water Treatment,
Multi-Cyclone, Fabric Collector
Average Emission Factor
in Ib/ton
(kg/Mg)a
2.90x1 0'3
(1.45xlO-3)
1.60xlO-5
(8.00x1 0-6)
3.50xlO-4
(1.75xlO-4)
3.20xlO'4
(1.60xlO-4)
3.20xlO'4
(i.eoxio-4)
LlOxlO-3
(5.50x1 0-4)
3.10xlO-4
(1.55xlO-4)
2.9x1 0-3
(1.45xlO-3)
4.49x1 0'6lb/MMBtub
(1. 93x1 0-15 kg/Joule)
Emission Factor Range Emission
in Ib/ton Factor
(kg/Mg)a Rating
D
D
D
D
D
D
D
U
1.4xlO-7-9.41xlQ-6 U
lb/MMBtub
(6.00xlO-17-4.10xlO-15
kg/Joule)
Reference
86
86
86
86
86
86
86
87
88
a Emission factors are expressed in Ib (kg) of pollutant emitted per ton (Mg) of wood waste combusted, except as noted. Emission factors are based on wet, as-
fired wood waste with 50 percent moisture and a higher heating volume of 4,500 Btu/lb.
b Emission factors are expressed in Ib (kg) of pollutant emitted per MMBtu (Joule) of heat input.
"—" means data are not available.
ESP = Electrostatic Precipitator.
-------
TABLE 5-4. LEAD EMISSION FACTORS FOR WOOD WASTE-FIRED INDUSTRIAL BOILERS
Ul
to
sec
Number
1-02-009-01
1-02-009-02
Emission Source
Wood Waste-fired
Boiler (Bark-fired,
>50,000 Ib steam)
Wood Waste-fired
Boiler (Wood/Bark-
fired, >50,000 Ib
steam)
Control Device
ESP - Medium Efficiency
None
Multiple Cyclone with Flyash
Reinjection
ESP
Scrubber
Multiple Cyclone without
Flyash Reinjection
Average Emission Factor
in Ib/ton
(kg/Mg)a
1.50xlO-6lb/MMBtub
(6.46x1 0-16 kg/Joule)
2.90x1 0-3
(1.45xlO-3)
3.20xlO'4
(1.60xlO-4)
i.eoxio-5
(8.00x1 0-6)
3.50xlO-4
(1.75xlO-4)
3.20xlO'4
(1.60xlO-4)
Emission Factor Range
in Ib/ton
(kg/Mg)
IJOxlO'6- IJOxlO'6
lb/MMBtub
(5.60xlO-16-7.33xlO-16
kg/Joule)
—
—
...
—
___
Emissio
n Factor
Rating
U
D
D
D
D
D
Reference
89
86
86
86
86
86
1-02-009-03 Wood Waste-fired
Boiler (Wood-fired,
>50,000 Ib steam)
Wet Scrubber - Medium
Efficiency
Multiple Cyclone without
Flyash Reinjection/Wet
Scrubber - Medium
Efficiency
1.60xlQ-5lb/MMBtub
(6.89x10-15 kg/Joule)
4.00x10'5lb/MMBtub
(1.72xlO-14 kg/Joule)
1.1 OxlO'5-2.50x10'5
lb/MMBtub
(4.74x10'15- l.OSxlO'14
kg/Joule)
3.20xlO-4-5.00xlO-4
lb/MMBtub
(1.38xlO-13-2.15xlQ-13
kg/Joule)
U
U
90
91
Multiple Cyclone without
Flyash Reinjection
ESP
3.10xlO-4
(1.55xlO-4)
LlOxlO'3
(5.50x1 0-4)
D
D
86
86
-------
TABLE 5-4. LEAD EMISSION FACTORS FOR WOOD WASTE-FIRED INDUSTRIAL BOILERS (CONTINUED)
Ul
to
sec
Number
1-02-009-03
(continued)
1-02-009-04
1-02-009-05
1-02-009-06
Emission Source
Wood Waste-fired
Boiler (Wood-fired,
>50,000 Ib steam)
Wood Waste-fired
Boiler (Bark-fired,
<50,000 Ib steam)
Wood Waste-fired
Boiler (Wood/Bark-
fired, <50,000 Ib
steam)
Wood Waste-fired
Boiler (Wood-fired,
<50,000 Ib steam)
Control Device
Multiple Cyclone without
Flyash Reinjection/ESP -
Medium Efficiency
None
Multiple Cyclone with Flyash
Reinjection
ESP
Scrubber
Multiple Cyclone without
Flyash Reinjection
Multiple Cyclone without
Flyash Reinjection
ESP
Scrubber
Average Emission Factor Emission Factor Range
in Ib/ton in Ib/ton
(kg/Mg)a (kg/Mg)
2.25x1 0'6 lb/MMBtub 2.10xlQ-6 - 2.40x1 0'6
(9.70x1 0-16 kg/Joule) lb/MMBtub
(9.05xlO-16-1.03xlO-15
kg/Joule)
2.90x1 0-3
(1.45xlO-3)
3.20xlO'4
(1.60xlO-4)
i.eoxio-5
(8.00x1 0-6)
3.50xlO-4
(1.75xlO-4)
3.20xlO'4
(1.60xlO-4)
3.10xlO-4
(1.55xlO-4)
LlOxlO'3
(5.50x1 0-4)
1.14xlQ-5lb/MMBtub
(4.91xlO-15 kg/Joule)
Emissio
n Factor
Rating
U
D
D
D
D
D
D
D
U
Reference
92
86
86
86
86
86
86
86
93
a Emission factors are expressed in Ib (kg) of pollutant emitted per ton (Mg) of wood waste combusted, except as noted. Emission factors are based on wet, as-
fired wood waste with average properties of 50 percent moisture and 4,500 Btu/lb higher heating value.
b Emission factors are expressed in Ib (kg) of pollutant emitted per MMBtu (Joule) of heat input.
"—" means data are not available.
ESP = Electrostatic Precipitator.
-------
TABLE 5-5. LEAD EMISSION FACTORS FOR WOOD WASTE-FIRED COMMERCIAL/INSTITUTIONAL BOILERS
Average Emission Factor
in Ib/ton
SCC Number Emission Source Control Device (kg/Mg)a
1-03-009-01 Wood/Bark-fired Boiler None
(Bark-fired)
1-03-009-02 Wood/Bark-fired Boiler Multiple Cyclone with
(Wood/Bark-fired) Flyash Reinjection
Scrubber
ESP
Multiple Cyclone
without Flyash
ui _. . . :
^ ,, Reinjection
1-03-009-03 Wood/Bark-fired Boiler Multiple Cyclone
(Wood-fired) without Flyash
Reinjection
ESP
2.90x1 0-3
(1.45xlO-3)
3.20xlO'4
(1.60xlO-4)
3.50xlO-4
(1.75xlO-4)
1.60xlO-5
(8.00x1 0-6)
3.20xlO'4
(i.eoxio-4)
3.10xlO-4
(1.55xlO-4)
LlOxlO'3
(5.50x1 0-4)
Emission Factor Range
in Ib/ton Emission Factor
(kg/Mg)a Rating
D
D
D
D
D
D
D
Source: Reference 86
a Emission factors are expressed in Ib (kg) of pollutant emitted per ton (Mg) of wood waste combusted. Emission factors are based on wet, as-fired wood
waste with 50 percent moisture and a higher heating value of 4,500 Btu/lb.
"—" means data are not available.
ESP = Electrostatic Precipitator.
-------
The average emission factors for utility wood waste-fired boilers are presented in
Table 5-3. The emission factors represent a range of control configurations and wood waste
compositions.86
Average emission factors for industrial wood waste-fired boilers are presented in
Table 5-4. Several of the emission factors are based on a comprehensive toxic air emission testing
program in California. The study, conducted by the Timber Association of California (TAG),
tested boiler types with capacities greater than 50,000 Ib (22,680 kg) of steam per hour, including
fuel cell, dutch oven, stoker, air injection, and fluidized bed combustors. The summarized results
of the study were used to obtain the average lead emission factors. The emission factors
represent a range of boiler designs and capacities, control configurations, and wood waste
compositions. The range of control devices represented in the sample set included multiple
cyclones, ESPs, and wet scrubbers. Sampling was conducted using CARB Method 431, which
captures particulate lead.89'90'91
Wood waste-fired commercial/institutional boilers average emission factors are
presented in Table 5-5. These emission factors represent a range of control configurations and
wood waste compositions.86 Many of these same emission factors can be found in the utility,
commercial/institutional, and industrial wood waste-fired tables. This duplication is expected
because the same types of boilers and waste composition are found in all three industry
categories.
Natural Gas Combustion
There were few data available for deriving lead emission factors for natural gas-
fired utility boilers. Based on the limited data available, it is unclear whether there are significant
lead emissions from these boilers. Tables 5-6 and 5-7 present lead emission factors for natural gas
fired boilers.
5-28
-------
TABLE 5-6. LEAD EMISSION FACTORS FOR NATURAL GAS - FIRED UTILITY BOILERS FROM AP-42
Control Average Emission Factor Emission Factor Range Emission
SCC Number Emission Source Device in Ib/ton (kg/Mg)a in Ib/ton (kg/Mg)a Factor Rating Reference
1-01-006-04 Natural Gas Boiler " 2.71xlQ-4 — E 94
a To convert from Ib/million ft3 to Kg/million m3 multiply by 16.0.
b Data for boilers controlled with overfire air and flue gas recirculation.
TABLE 5-7. LEAD EMISSION FACTORS FOR NATURAL GAS - FIRED BOILERS FROM UTILITY STUDY
Control Median Factor Emission Factor
Emission Source Device (Ib/trillion BTU Rating Reference
V1 Gas Fired Units None 0.37 U 95
to ^^^^— ——
-------
Coal Combustion
Lead emission factors for coal-fired utility boilers are presented in Tables 5-8 and
5-9. The tables include composite emission factors for anthracite, bituminous pulverized
wet-bottom, and bituminous pulverized dry-bottom boilers. The emission factors include
particulate lead.55
Lead emission factors for coal-fired industrial and commercial/institutional boilers
are listed in Tables 5-10 and 5-11, respectively. Composite emission factors for two industrial
boiler design categories, pulverized bituminous dry-bottom boilers and bituminous stokers, are
presented. Control configurations include uncontrolled and multicyclone controlled. Both sets of
lead emission factors represent particulate lead emissions.76'98'99
AP-42, Section 1.1 also includes an equation for bituminous coal, subbituminous
coal and lignite combustion. This equation can be used for both controlled and uncontrolled
boilers. The equation is also applicable to all typical firing configurations of utility, industrial and
commercial/industrial boilers. The equation for lead is as follows:
Lead emissions (lb/1012 BTU) =3.4
— * PM
A
, 0.8
where: C = concentration of metal in the coal, parts per million by weight
(ppmwt)
A = weight fraction of ash in the coal. For example, 10% ash is 0.1 ash
fraction
PM = site-specific emission factor for total particulate matter, lb/106 Btu.
The factors produced by the equation should be applied to heat input.97
5-30
-------
TABLE 5-8. LEAD EMISSION FACTORS FOR COAL-FIRED UTILITY BOILERS
SCC Number
1-01-001-02
1-01-002-01
1-01-002-02
1-01-002-03
1-01-002-04
1-01-002-05
1-01-002-21
Emission Source
Anthracite Coal Traveling Grate
Overfeed Stoker
Bituminous Coal: Pulverized:
Wet Bottom
Bituminous Coal: Pulverized:
Dry Bottom
Bituminous Coal: Cyclone
Furnace
Bituminous Coal: Spreader
Stoker
Bituminous Coal: Traveling
Grate (Overfeed) Stoker
Subbituminous Coal:
Pulverized: Wet Bottom
Control
Device
None
None
None
ESP, FF or
venturi
scrubber
None
ESP, FF or
venturi
scrubber
None
None
None
Average Emission
Factor Emission Factor Range
in Ib/ton in Ib/ton Emission
(kg/Mg)a (kg/Mg)a Factor Rating Reference
8.90x1 0-3
(4.45x1 0-3)
5.07x1 0'4 lb/MMBtub
(2.1 8x1 0-13 kg/Joule)
5.07x1 0-4lb/MMBtub
(2.1 8x1 0-13 kg/Joule)
4.20x1 Q-4lb/tonc
(2.10xlO-4kg/Mg)
5.07x1 0-4lb/MMBtub
(2.1 8x1 0-13 kg/Joule)
4.20x1 Q-4lb/tonc
(2.10xlO-4kg/Mg)
5.07x1 0-4lb/MMBtub
(2.1 8x1 0-13 kg/Joule)
5.07x1 0'4 lb/MMBtub
(2.1 8x1 0-13 kg/Joule)
5.07x1 0-4lb/MMBtub
(2.1 8x1 0-13 kg/Joule)
E 96
E 97
E 97
A 97
E 97
A 97
E 97
E 97
E 97
-------
TABLE 5-8. LEAD EMISSION FACTORS FOR COAL-FIRED UTILITY BOILERS (CONTINUED)
SCC Number Emission Source
1-01 -002-22 Subbituminous Coal:
Pulverized: Dry Bottom
1-01-002-23 Subbituminous Coal: Cyclone
Furnace
Lf\
to 1-01-002-24 Subbituminous Coal: Spreader
Stoker
1-01-002-25 Subbituminous Coal: Traveling
Grate (Overfeed) Stoker
Control
Device
None
ESP, FF or
venturi
scrubber
None
ESP, FF or
venturi
scrubber
None
None
Average Emission
Factor Emission Factor Range
in Ib/ton in Ib/ton Emission
(kg/Mg)a (kg/Mg)a Factor Rating
5.07x1 0'4 lb/MMBtub — E
(2.1 8x1 0-13 kg/Joule)
4.20x1 0-4lb/tonc — A
(2.10xlO-4kg/Mg)
5.07x1 0'4 lb/MMBtub — E
(2.1 8x1 0-13 kg/Joule)
4.20x1 0-4lb/tonc — A
(2.10xlO-4kg/Mg)
5.07x1 0'4 lb/MMBtub — E
(2.1 8x1 0-13 kg/Joule)
5.07x1 0-4lb/MMBtub — E
(2.1 8x1 0-13 kg/Joule)
Reference
97
97
97
97
97
97
a Emission factors are expressed in Ib (kg) of pollutant emitted per ton (Mg) of coal combusted, except as noted.
b Emission factors are expressed in Ib (kg) of pollutant emitted per MMBtu (Joule) of heat input.
c Emission factor should be applied to coal feed, as fired.
"—" means data are not available.
-------
TABLE 5-9. LEAD EMISSION FACTORS FOR COAL-FIRED BOILERS FROM UTILITY STUDY
Emission Source
Control
Device
Median Factor
(Ib/trillion BTU)
Emission Factor
Rating
Reference
Coal Fired Units
PM Control
PM/SO2
Control
4.8
5.8
U
U
95
95
-------
TABLE 5-10. LEAD EMISSION FACTORS FOR COAL-FIRED INDUSTRIAL BOILERS
sec
Number
1-02-001-04
1-02-002-01
1-02-002-02
1-02-002-03
1-02-002-04
1-02-002-05
1-02-002-06
1-02-002-13
1-01-002-21
Emission Source
Anthracite Coal Traveling Grate
(Overfeed) Stoker
Bituminous Coal Pulverized: Wet
Bottom
Bituminous Coal Pulverized Coal:
Dry Bottom
Bituminous Coal Cyclone Furnace
Bituminous Coal Spreader Stoker
Bituminous Coal Overfeed Stoker
Bituminous Coal Underfeed Stoker
Bituminous Coal Wet Slurry
Subbituminous Coal: Pulverized:
Wet Bottom
Control
Device
None
None
None
ESP, FF, or
venturi
scrubber
None
ESP, FF, or
venturi
scrubber
None
None
None
None
None
Average Emission
Factor
in Ib/ton (kg/Mg)a
8.90x1 Q-3 (4.45x1 Q-3)
5.07x1 0-4lb/MMBtub
(2.1 8x1 0-13 kg/Joule)
5.07x1 0-4lb/MMBtub
(2.1 8x1 0-13 kg/Joule)
4.20x1 Q-4lb/tonc
(2.10xlO-4kg/Mg)
5.07x1 Q-4 lb/MMBtub
(2.1 8x1 0-13 kg/Joule)
4.20x1 0-4lb/tonc
(2.10xlO-4kg/Mg)
5.07x1 0-4lb/MMBtub
(2.1 8x1 0-13 kg/Joule)
5.07x1 Q-4 lb/MMBtub
(2.1 8x1 0-13 kg/Joule)
2.24x10-' (1. 12x10-')
9.89x1 0-3 (4.95x1 0-3)
5.07x1 0-4lb/MMBtub
(2.1 8x1 0-'3 kg/Joule)
Emission Factor Range Emission
in Ib/ton (kg/Mg)a Factor Rating
E
E
E
A
E
A
E
E
U
U
E
Reference
96
97
97
97
97
97
97
97
76
93
97
-------
TABLE 5-10. LEAD EMISSION FACTORS FOR COAL-FIRED INDUSTRIAL BOILERS (CONTINUED)
SCC Number
1-01-002-22
1-01-002-23
1-01-002-24
1-01-002-25
Emission Source
Subbituminous Coal:
Dry Bottom
Subbituminous Coal:
Furnace
Subbituminous Coal:
Subbituminous Coal:
(Overfeed) Stoker
Control
Device
Pulverized: None
ESP,FF, or
venturi
scrubber
Cyclone None
ESP, FF, or
venturi
scrubber
Spreader Stoker None
Traveling Grate None
Average Emission
Factor
in Ib/ton (kg/Mg)a
5.07x1 0'4 lb/MMBtub
(2.1 8x1 0-13 kg/Joule)
4.20x1 0-4lb/tonc
(2.10xlO-4kg/Mg)
5.07x1 0-4lb/MMBtub
(2.1 8x1 0-13 kg/Joule)
4.20x1 0'4lb/tonc
(2.10xlO-4kg/Mg)
5.07x1 0'4 lb/MMBtub
(2.1 8x1 0-13 kg/Joule)
5.07x1 0-4lb/MMBtub
(2.1 8x1 0-13 kg/Joule)
Emission Factor Range Emission
in Ib/ton (kg/Mg)a Factor Rating
E
A
E
A
E
E
Reference
97
97
97
97
97
97
a Emission factors are expressed in Ib (kg) of pollutant emitted per ton (Mg) of coal combusted, except as noted.
b Emission factors are expressed in Ib (kg) of pollutant emitted per MMBtu (Joule) of heat input.
c Emission factor should be applied to coal feed, as fired.
"—" means data are not available.
-------
TABLE 5-11. LEAD EMISSION FACTORS FOR COAL-FIRED COMMERCIAL/INSTITUTIONAL BOILERS
sec
Number
1-03-001-02
1-03-002-08
1-03-002-03
1-03-002-05
1-03-002-06
1-03-002-07
1-03-002-09
1-03-002-21
Emission Source
Anthracite Coal Traveling
Grate (Overfeed) Stoker
Bituminous Coal Underfeed
Stoker
Bituminous Coal Cyclone
Furnace
Bituminous Coal Pulverized:
Wet Bottom
Bituminous Coal Pulverized
Coal: Dry Bottom
Bituminous Coal Overfeed
Stoker
Bituminous Coal Spreader
Stoker
Subbituminous Coal:
Pulverized: Wet Bottom
Control Device
None
Multiple Cyclone
without Flyash
Reinjection
None
ESP, FF, or venturi
scrubber
None
None
ESP, FF, or venturi
scrubber
None
None
None
Average Emission
Factor
in Ib/ton
(kg/Mg)a
8.90x1 0-3
(4.45x1 0-3)
1.21xlO-3
(6.05x1 0-4)
5.07x1 0-4lb/MMBtub
(2.1 8x1 0-13 kg/Joule)
4.20x1 0-4lb/ton
(2.10xlO-4kg/Mg)c
5.07x1 0-4lb/MMBtub
(2.1 8x1 0-13 kg/Joule)
5.07x1 0-4lb/MMBtub
(2.1 8x1 0-13 kg/Joule)
4.20x1 0-4lb/ton
(2.10xlO-4kg/Mg)c
5.07x1 0-4lb/MMBtub
(2.1 8x1 0-13 kg/Joule)
5.07x1 0-4lb/MMBtub
(2.1 8x1 0-13 kg/Joule)
5.07x1 0-4lb/MMBtub
(2.1 8x1 0-13 kg/Joule)
Emission Factor Range Emission
in Ib/ton Factor
(kg/Mg)a Rating
E
U
E
A
E
E
A
E
E
E
Reference
96
98
97
97
97
97
97
97
97
97
-------
TABLE 5-11. LEAD EMISSION FACTORS FOR COAL-FIRED COMMERCIAL/INSTITUTIONAL BOILERS (CONTINUED)
sec
Number
1-03-002-22
1-03-002-23
1-03-002-24
1-03-002-25
Emission Source
Subbituminous Coal:
Pulverized: Dry Bottom
Subbituminous Coal: Cyclone
Furnace
Subbituminous Coal: Spreader
Stoker
Subbituminous Coal:
Traveling Grate (Overfeed)
Stoker
Control Device
None
ESP, FF, or venturi
scrubber
None
ESP, FF, or venturi
scrubber
None
None
Average Emission
Factor
in Ib/ton
(kg/Mg)a
5.07x1 0'4 lb/MMBtub
(2.1 8x1 0-13 kg/Joule)
4.20xlO'4 Ib/ton
(2.10xlO-4kg/Mg)c
5.07x1 0'4 lb/MMBtub
(2.1 8x1 0-13 kg/Joule)
4.20xlO'4 Ib/ton
(2.10xlO-4kg/Mg)c
5.07x1 0'4 lb/MMBtub
(2.1 8x1 0-13 kg/Joule)
5.07x1 0'4 lb/MMBtub
(2.1 8x1 0-13 kg/Joule)
Emission Factor Range Emission
in Ib/ton Factor
(kg/Mg)a Rating
E
A
E
A
E
E
Reference
97
97
97
97
97
97
a Emission factors are expressed in Ib (kg) of pollutant emitted per ton (Mg) of coal combusted, except as noted.
b Emission factors are expressed in Ib (kg) of pollutant emitted per MMBtu/Joule of heat input.
c Emission factor should be applied to coal feed, as fired.
"—" means data are not available.
-------
Oil Combustion
Lead emission factors for oil-fired utility boilers are presented in Tables 5-12 and
5-13. Lead emission factors for oil-fired industrial and commercial/institutional boilers are
presented in Tables 5-14 through 5-17.
Emission factors for specific utility boiler and control device configurations are
also listed in Table 5-12, as are emission factors for residual oil and distillate oil combustion.
Lead emission factors for oil-fired industrial boilers are presented in Table 5-14.
The data used in factor development came from the testing of two uncontrolled units. Testing
was conducted using CARB Method 436. The emission factors represent particulate lead.100
A lead emission factor for oil-fired commercial/institutional boilers is provided in
Table 5-15. The average emission factor is based on a boiler with a rated capacity of less than
10 MMBtu/hr (2.9 MW).101
Lead emission factors for industrial and commercial/institutional waste oil
combustion are shown in Tables 5-16 and 5-17, respectively. Emission factors are available for
two basic types of uncontrolled space heaters: a vaporizing pot-type burner and an air atomizing
burner. The use of both blended and unblended fuels is reflected in these factors.
Solid Waste Combustion
Lead emission factors for solid-waste fired utility boilers are presented in
Table 5-18.
Miscellaneous Combustion
Lead emission factors for industrial boilers firing other fuel types (i.e., solid waste
refuse-derived fuel) are presented in Table 5-19.
5-38
-------
TABLE 5-12. LEAD EMISSION FACTORS FOR OIL-FIRED UTILITY BOILERS
SCC Number
1-01-004-01
1-01-004-04
1-01-004-05
1-01-005-01
Emission Source
Residual Oil-fired
Boiler: No. 6 Oil,
Normal Firing
Residual Oil-fired
Boiler: No. 6 Oil,
Tangential Firing
Residual Oil-fired
Boiler: No. 5 Oil,
Normal Firing
Distillate Oil Grades
1 and 2 Oil
Control Device
None
Flue Gas
Recirculation
None
None
None
Average Emission Factor Emission Factor Range
in Ib/MMBtu in Ib/MMBtu
(kg/Joule)a (kg/Joule)a
LOxlO'5
(4.33x1 0-15)
2.17xlO-5 1.26xlO-5-2.83xlO-5
(9.35xlO-15) 5.43x1 0-15- 1.22x1 0-14)
LOxlO'5
(4.33x1 0-15)
1.60xlO-5
(6.89x1 0-15)
8.90x1 0-6
(3.84xlO-15)
Emission
Factor
Rating
C
u
C
u
E
Reference
102
103
102
104
102
a Emission factors are expressed in Ib (kg) of pollutant emitted per MMBtu (Joule) of heat input.
"—" means data are not available.
-------
TABLE 5-13 LEAD EMISSION FACTORS FOR OIL-FIRED UTILITY BOILER FROM UTILITY STUDY
Emission Source
Oil-Fired Units
Control
Device
PM Control
PM/SO2
Control
Median Factor
(Ib/trillion BTU)
2.6
9.0
Emission Factor
Rating
U
U
Reference
95
95
TABLE 5-14. LEAD EMISSION FACTORS FOR OIL-FIRED INDUSTRIAL BOILERS
sec
Number
1-02-004-01
1-02-005-01
Emission Source Control Device
Residual Oil Grade 6 Oil None
Distillate Oil Grades 1 None
and 2 Oil
Average Emission Factor
in Ib/MMBtu
(kg/Joule)a
l.OOx 10-5(b)
(4.33xlO-15)
8.90xlO-6
(3.84xlO-15)
Emission Factor Range
in Ib/MMBtu Emission
(kg/Joule)a Factor Rating
C
E
Source: Reference 102
a Emission factors are expressed in Ib (kg) of pollutant emitted per MMBtu (Joule) of heat input.
b Emission factor is in Ib x 103 gal, to convert to kb/103 L, multiply by 0.12.
"—" means data are not available.
-------
TABLE 5-15. LEAD EMISSION FACTORS FOR OIL-FIRED COMMERCIAL/INSTITUTIONAL BOILERS
SCC Number Emission Source Control Device
1-03-004-01
1-03-005-01
Residual Oil None
Grade 6 Oil
Distillate Oil None
Grades 1 and 2 Oil
Average Emission Factor
in Ib/MMBtu
(kg/Joule)a
l.OOx 10-5(b)
(4.33xlO-15)
8.90xlO-6
(3.84xlO-15)
Emission Factor Range
in Ib/MMBtu Emission
(kg/Joule)a Factor Rating
C
E
Source: Reference 102
a Emission factors are expressed in Ib (kg) of pollutant emitted per MMBtu (Joule) of heat input.
b Emission factor is in lb/103 gal, to convert to kg/103 L, multiply by 0.12.
"—" means data are not available.
TABLE 5-16. LEAD EMISSION FACTORS FOR WASTE OIL-FIRED INDUSTRIAL BOILERS
SCC
Number
1-02-013-02
1-05-001-13
Emission Source
Waste Oil
Waste Oil Air Atomized
Burner
Control Device
None
None
Average Emission Factor
inlb/lOOOgal
(kg/kL)a
1.68
(2.01x10-')
50Lb
(6.0L)
Emission Factor Range
inlb/lOOOgal
(kg/kL)a
—
Emission
Factor
Rating
U
D
Reference
105
106
a Emission factors are expressed in Ib (kg) of pollutant emitted per 1000 gallons (kL) of oil combusted.
b L=weight % lead in fuel. Multiply numeric value by L to obtain emission factor.
"—" means data are not available.
-------
TABLE 5-17. LEAD EMISSION FACTORS FOR WASTE OIL-FIRED COMMERCIAL/INSTITUTIONAL BOILERS
SCC Number
1-01-013-02
1-05-002-13
Emission Source
Waste Oil
Waste Oil Air Atomized
Burner
Control Device
None
None
Average Emission
Factor
inlb/lOOOgal
(kg/kL)a
1.68
(2.01x10-')
50Lb
(6.0L)
Emission Factor Range Emission
inlb/lOOOgal Factor
(kg/kL)a Rating
U
D
Reference
23
106
a Emission factors are expressed in Ib (kg) of pollutant emitted per 1000 gallons (kL) of oil combusted.
b L=weight % lead in fuel. Multiply numeric value by L to obtain emission factor.
"—" means data are not available.
Ul
to
-------
TABLE 5-18. LEAD EMISSION FACTORS FOR SOLID WASTE-FIRED UTILITY BOILERS
SCC Number Emission Source
1-01-012-01 Solid Waste
Control Device
None
ESP
Spray
Dryer/Absorber/ESP
Average Emission Factor
in Ib/ton
(kg/Mg)a
2.65x10-'
(1.33x10-')
1.24xlO-4lb/MMBtu
(5.34x1 0-'4kg/Joule)b
<2.66xlO'4
(<1.33xlO-4)
Emission Factor Range
in Ib/ton
(kg/Mg)a
2.00x10-' -3.40x10-'
(1.00x10-'- 1.70x10-')
8.15xlO-5 - 2.04x1 0-4 Ib/MMBtu
(1.51xlO-'4-3.78xlO-14
kg/Joule)b
<1.30xlO-4-3.66xlO-4
(<6.50xlO-5-1.83xlO-4)
Emission
Factor
Rating
U
C
U
Reference
108
108
109
a Emission factors are expressed in Ib (kg) of pollutant emitted per ton (Mg) of waste combusted, except as noted.
b Emission factors are expressed in Ib (kg) of pollutant emitted per MMBtu (Joule) of heat input.
"—" means data are not available.
ESP = Electrostatic Precipitator.
TABLE 5-19. LEAD EMISSION FACTORS FOR MISCELLANEOUS INDUSTRIAL BOILERS
SCC Number
1-02-012-02
Emission Source
Solid Waste Refuse-derived
Fuel
Control Device
None
Average Emission Factor in
Ib/ton (kg/Mg)a
1.30x10-'
(6.50x1 0-2)
Emission Factor Range in
Ib/ton (kg/Mg)a
...
Emission
Factor Rating
U
Source: Reference 23
a Emission factors are expressed in Ib (kg) of pollutant emitted per ton (Mg) of waste combusted.
"—" means data are not available.
-------
5.2 STATIONARY INTERNAL COMBUSTION SOURCES
5.2.1 Source Description
Internal combustion sources for electricity generation and industrial application are
grouped into two types: gas turbines and reciprocating engines.
Stationary gas turbines are applied in electric power generators, in gas pipeline
pump and compressor drives, and various process industries. Gas turbines greater than 3 MW are
used in electricity generation for continuous, peaking, or standby power. The primary fuels used
are natural gas and distillate (No. 2) fuel oil.107
Reciprocating internal combustion engines may be classified as spark ignition and
compression ignition. Spark ignition engines are fueled by volatile liquids such as gasoline, while
compression ignition engines use liquid fuels of low volatility, such as kerosene and distillate oil
(diesel fuel).110
In compression ignition engines, combustion air is compression-heated in the
cylinder and diesel fuel oil is then injected into this hot air. Ignition is spontaneous because the air
is above the autoignition temperature of the fuel. Spark ignition engines initiate combustion with
an electrical discharge. Usually, fuel is mixed with air in a carburetor (for gasoline) or at the
intake valve (for natural gas), but fuel can also be injected directly into the cylinder.111
The rated power of gasoline and diesel internal combustion engines covers a
substantial range: up to 250 hp (186 kW) for gasoline engines and greater than 600 hp (447 kW)
for diesel engines. The primary domestic use of large stationary diesel engines (greater than
600 hp) is in oil and gas exploration and production. These engines supply mechanical power to
operate drilling (rotary table), mud pumping, and hoisting equipment and may also operate pumps
or auxiliary power generators.112 Stationary natural gas-fired spark ignition engines of over
5,000 hp and natural gas-fired turbines of over 10,000 hp exist.
5-44
-------
5.2.2 Emissions
Air emissions from the flue gas stack are the only emissions from electricity
generation, industrial turbines, and reciprocating engines. Turbines firing distillate or residual oil
may emit trace metals carried over from the metals content of the fuel.
An emissions assessment study of internal combustion sources developed in 1979
presents a lead emission factor for distillate oil-fired gas turbines of 5.8xlO~5 Ib/MMBtu
(25 picogram/joule [pg/J]).no More recent test results for distillate oil-fired gas turbines indicate
an average lead emission factor of 2.9xlO~5 Ib/MMBtu.113 The data used to develop these
emission factors are limited and may not be representative of a specific source or population of
sources. However, the emission factors provide order-of-magnitude levels of lead emissions for
turbines fired with distillate oil. Emissions of trace elements, including lead, from the gas-fired
gas turbine tested during the 1979 study were insignificant.110
If the fuel analysis is known, the metals content of the fuel should be used for flue
gas emission factors, assuming all metals pass through the turbine.107 The average fuel analysis
result can be used to calculate emissions based on fuel usage or stack exhaust flow measurements.
Potential emissions based on the trace element content of distillate oils have been calculated and
compared with measured stack emissions.110 In almost all cases, the potential emissions were
higher than the measured emissions. Limited lead emissions and lead emission factors were
available for the other emission sources indicated in this section.
5.3 MUNICIPAL WASTE INCINERATION
5.3.1 Source Location
As of January 1992, there were 160 municipal waste combustor (MWC) plants
operating in the United States with capacities greater than 40 tons/day (36 Mg/day), with a total
capacity of approximately 110,000 tons/day (100,000 Mg/day) of municipal solid waste (MSW).
It is projected that by 1997, total MWC capacity will approach 165,000 tons/day
5-45
-------
(150,000 Mg/day), which represents approximately 28 percent of the estimated total amount of
MSW that will be generated in the United States by the year 2000.m Table 5-20 lists the
geographical distribution of MWC units and statewide capacities.115
5.3.2 Process Description
MWCs burn garbage and other nonhazardous solid waste, commonly called MSW.
Three main types of combustors are used to combust MSW: mass burn, refuse-derived fuel-fired
(RDF), and modular. Each type is discussed in this section.
Mass Burn Combustors
In mass burn units, MSW is combusted without any preprocessing other than
removal of items too large to go through the feed system. In a typical mass burn combustor,
refuse is placed on a grate that moves through the combustor. Combustion air in excess of
stoichiometric amounts is supplied both below (underfire air) and above (overfire air) the grate.
Mass burn combustors are erected at the site (as opposed to being prefabricated) and range in size
from 50 to 1,000 tons/day (46 to 900 Mg/day) of MSW throughput per unit. Mass burn
combustors can be divided into mass burn/waterwall (MB/WW), mass burn/rotary waterwall
(MB/RC), and mass burn/refractory wall (MB/REF) designs.
The walls of a MB/WW combustor are constructed of metal tubes that contain
pressurized water and recover radiant heat for production of steam and/or electricity. A typical
MB/WW combustor is shown in Figure 5-5. With the MB/RC combustor, a rotary combustion
chamber sits at a slight angle and rotates at about 10 revolutions per hour, causing the waste to
advance and tumble as it burns. The combustion cylinder consists of alternating water tubes and
perforated steel plates. Figure 5-6 illustrates a simplified process flow diagram for a MB/RC.
MB/REF designs are older and typically do not include any heat recovery. One type of MB/REF
combustor is shown in Figure 5-7.
5-46
-------
TABLE 5-20. SUMMARY OF GEOGRAPHICAL DISTRIBUTION OF MWC FACILITIES
State
Alabama
Alaska
Arkansas
California
Connecticut
Delaware
District of Columbia
Florida
Georgia
Hawaii
Idaho
Illinois
Indiana
Iowa
Maine
Number of MWC
Facilities
2
2
5
3
9
1
1
14
1
1
1
1
1
1
4
State MWC Capacity Percentage of Total
in tons/day U.S. MWC
(Mg/day) Capacity
990 1
(900)
170 <1
(150)
380 <1
(350)
2,560 2
(2,330)
6,660 6
(6,050)
600 <1
(550)
1,000 1
(910)
17,350 16
(15,770)
500 <1
(450)
2,760 2
(2,510)
50 <1
(45)
1,600 1
(1,450)
2,360 2
(2,150)
200 <1
(180)
1,870 2
( 1,700)
5-47
-------
TABLE 5-20. SUMMARY OF GEOGRAPHICAL DISTRIBUTION OF MWC FACILITIES
(CONTINUED)
State
Maryland
Massachusetts
Michigan
Minnesota
Mississippi
Missouri
Montana
New Hampshire
New Jersey
New York
North Carolina
Ohio
Oklahoma
Oregon
Pennsylvania
Number of MWC
Facilities
3
10
5
13
1
1
1
4
6
15
4
4
2
3
6
State MWC Capacity
in tons/day
(Mg/day)
3,810
(3,460)
10,340
(9,400)
4,820
(4,380)
5,330
(4,850)
150
(140)
78
(71)
72
(65)
860
(780)
5,820
(5,290)
12,510
(11,370)
780
(710)
4,800
(4,360)
1,230
(1,120)
810
(740)
7,200
(6,550)
Percentage of Total
U.S. MWC
Capacity
3
9
4
5
<1
<1
<1
1
5
11
1
4
1
1
6
5-48
-------
TABLE 5-20. SUMMARY OF GEOGRAPHICAL DISTRIBUTION OF MWC FACILITIES
(CONTINUED)
State
Puerto Rico
South Carolina
Tennessee
Texas
Utah
Virginia
Washington
Wisconsin
TOTAL
Number of MWC
Facilities
1
2
4
4
1
9
5
9
160
State MWC Capacity
in tons/day
(Mg/day)
1,040
(950)
840
(760)
1,480
(1,350)
240
(220)
400
(360)
6,840
(6,220)
1,500
(1,360)
1,360
(1,240)
111,400
(101,200)
Percentage of Total
U.S. MWC
Capacity
1
1
1
<1
<1
6
1
1
100
Source: Reference 115
5-49
-------
Ul
o
Forced Draft
Fan
Overhead
Crane
Dl
G
1 \
•ying
rate
^
Corr
G
; I
Secondary
Fan
Riddling
Conveyor
Total
Ash
Discharge
Figure 5-5. Typical Mass Burn Waterwall Combustor
Source: Reference 114.
-------
Figure 5-6. Simplified Process Flow Diagram, Gas Cycle for a Mass Burn/Rotary Waterwall
Combustor
Source: Reference 114.
-------
Stack
Overhead
Crane
Emergency
Stack
Air
Pollution
Control
Device
L/l
to
Waste Tipping floor
Refuse
Pit
Mixing r
Chamber//]
/v
S?rays9 Cooling Conveyors
Bottom Chamber
Forced Overfire Vibrating
Draft Air Conveyor
Fan Fan f°r Bottom
Ash
u"encn Conveyor
Figure 5-7. Mass Burn Refractory-Wall Combustor with Grate/Rotary Kiln
Source: Reference 114.
-------
RDF-Fired Combustors
RDF-fired combustors burn processed waste that varies from shredded waste to
finely divided ftiel suitable for co-firing with pulverized coal. Combustor sizes range from 320 to
1,400 tons/day (290 to 1,300 Mg/day). There are three major types of RDF-fired combustors:
dedicated RDF combustors, which are designed to burn RDF as a primary fuel; coal/RDF co-fired
combustors; and fluidized-bed combustors (FBCs), where waste is combusted on a turbulent bed
of limestone, sand, silica or aluminum.
A typical RDF-fired combustor is shown in Figure 5-8 . Waste processing usually
consists of removing noncombustibles and shredding, which generally raises the heating value
and provides a more uniform fuel. The type of RDF used depends on the boiler design. Most
boilers designed to burn RDF use spreader stokers and fire fluff RDF in a semi-suspension mode.
Modular Combustors
Modular combustors are similar to mass burn combustors in that they burn waste
that has not been pre-processed, but they are typically shop-fabricated and generally range in size
from 5 to 140 tons/day (4 to 130 Mg/day) of MSW throughput. One of the most common types
of modular combustors is the starved-air or controlled-air type, which incorporates two
combustion chambers. A process diagram of a typical modular starved-air (MOD/SA) combustor
is presented in Figure 5-9. Air is supplied to the primary chamber at sub-stoichiometric levels.
The incomplete combustion products (CO and organic compounds) pass into the secondary
combustion chamber, where additional air is added and combustion is completed. Another design
is the modular excess air (MOD/EA) combustor, which consists of two chambers, similar to
MOD/SA units, but is functionally like the mass burn unit in that it uses excess air in the primary
chamber.
5-53
-------
Superheater
Air
Pollution
Control
Device
Steam Coil
Air Preheater
Source: Reference 114.
Figure 5-8. Typical RDF-Fired Spreader Stoker Boiler
-------
L/l
To Stack ex-
Waste Heat Boiler
Secondary
Air
Primary
Gas Burner
Feed
Chute
Ram
Feeder
Charge
Hopper
Secondary
Chamber
Fire Door Pnmary Chamber
Transfer Rams
Ash Quench
Primary Air
Figure 5-9. Typical Modular Starved-Air Combustor with Transfer Rams
Secondary
Gas Burner
"S
O
D.
CfL
Source: Reference 114.
-------
Emission Control Techniques
Lead is present in a variety of MSW streams, including paper, inks, batteries, and
metal cans, but is most prevalent in plastics. Lead is used to make dyes and stabilizers that
protect plastics from thermal and photo degradation. Because of the wide variability in MSW
composition, lead emissions are highly variable and are independent of combustor type. Because
the vapor pressure of lead is such that condensation develops onto particulates in the flue gas,
lead can be effectively removed by a PM control device.114
Because lead is usually emitted from MWCs in particulate form, the control of lead
is most frequently accomplished through the use of an ESP or fabric filter (FF), which are
common PM control techniques. Although other PM control technologies (e.g., cyclones,
electrified gravel beds, and venturi scrubbers) are available, they are not as effective as the ESP or
FF at removing PM and so are seldom used on existing systems.114 Well-designed ESPs and FFs
operated at 450°F (230°C) or less remove over 97 percent of lead and other metals.116
The most common types of ESPs are plate-and-wire units, in which the discharge
electrode is a bottom-weighted or rigid wire, and flat plate units, which use flat plates rather than
wires as the discharge electrode. As a general rule, the greater the amount of collection plate
area, the greater the PM collection efficiency. After the charged particles are collected on the
grounded plates, the resulting dust layer is removed from the plates by rapping or washing and
collected in a hopper. As the dust layer is removed, some of the collected PM becomes
re-entrained in the flue gas. To ensure good PM collection efficiency during plate cleaning and
electrical upsets, ESPs have several fields located in series along the direction of flue gas flow that
can be energized and cleaned independently. Particles re-entrained when the dust layer is
removed from one field can be recollected in a downstream field. Because of this phenomenon,
increasing the number of fields generally improves PM removal efficiency.114
5-56
-------
5.3.3 Emissions
Available lead emission factor data for several types of MWCs are provided in
Table 5-21. The column labeled "Emission Source" identifies the main characteristics of each
incinerator type. For some types of incinerators, a range of factors is provided that represents
different sample test runs of the same source. Generally, there is a wide range in the emission
factors associated with MWCs. This range is attributable to the variability of waste compositions
and to the operating practices and effectiveness of control devices.117 Waste composition can
differ from one MWC unit to another, especially where the permit specifications for the accepted
waste are different. For example, an MWC with a permit that prohibits the burning of lead-acid
batteries will have lower lead emissions than an MWC with a permit that does not prohibit such
burning. Because of this variability, the factors shown in Table 5-21 must be used cautiously and
may not be representative of other MWCs.
5.4 INDUSTRIAL AND COMMERCIAL WASTE INCINERATION
5.4.1 Source Location
Commercial waste incinerators are generally located in urbanized, metropolitan
areas with highly concentrated populations. Locations of industrial waste incinerators parallel
those of the industries that use them for waste disposal. The lumber and wood products, primary
metals, and printing industries are the greatest users of incinerators for waste disposal. Lumber
and wood producers are primarily in the Southeast and Northwest. Primary metals plants are
predominantly in the Midwest, the Mideast, and the Southwest. The printing industry is
essentially distributed nationwide.64 There are numerous industrial and commercial waste
incinerators across the country; no specific information on locations of individual incinerators was
identified.
5-57
-------
TABLE 5-21. LEAD EMISSION FACTORS FOR MUNICIPAL WASTE COMBUSTION SOURCES
Average Emission Factor
SCC in Ib/ton
Number Emission Source Control Device (kg/Mg)a
5-01-001-01 Starved-Air: Multiple- None
Chamber
ESP
5-01-001-02 Mass Burn: Single- None
Chamber
5-01-001-03 Refuse-derived Fuel None
ESP
Lf\
00 Spray Dryer/FF
Spray Dryer/ESP
5-01-001-04 Mass Burn: Refractory None
Wall Combustor
Spray Dryer/FF
Spray Dryer/ESP
Dry Sorbent
Injection/FF
Dry Sorbent
Injection/ESP
ESP
1.20x10-'
(6.00x1 0-2)
2.82x1 0-3
(1.41xlO-3)
1.80x10-'
(9.00x1 0-2)
2.01x10-'
(1.00x10-')
3.66xlO'3
(1.83xlO-3)
1.04xlO-3
(5.20xlO-4)
1.16xlQ-3
(5.80xlO-4)
2.13x10-'
(1.07x10-')
2.61xlQ-4
(1.31xlO-4)
9.15xlO-4
(4.58x1 0-4)
2.97x1 Q-4
(1.49xlQ-4)
2.90x1 0-3
(1.45xlO-3)
3.00xlO-3
n.soxio-3)
Emission Factor Range Emission
in Ib/ton Factor
(kg/Mg)a Rating
U
C
U
C
A
D
B
A
A
A
C
E
A
Reference
23
114
23
114
114
114
114
114
114
114
114
114
114
-------
TABLE 5-21. LEAD EMISSION FACTORS FOR MUNICIPAL WASTE COMBUSTION SOURCES (CONTINUED)
Average Emission Factor
SCC in Ib/ton
Number Emission Source Control Device (kg/Mg)a
5-01-001-05 Mass Burn: Waterwall None
Combustor
Spray Dryer/FF
Spray Dryer/ESP
Dry Sorbent
Injection/FF
Dry Sorbent
Injection/ESP
ESP
5-01-001-06 Mass Burn: Rotary None
Waterwall Combustor
Spray Dryer/FF
Spray Dryer/ESP
Dry Sorbent
Injection/FF
Dry Sorbent
Injection/ESP
ESP
2.13x10-'
(1.07x10-')
2.61xlO-4
(1.31xlO-4)
9.15xlO-4
(4.58x1 0-4)
2.97x1 0-4
(1.49xlQ-4)
2.90x1 0-3
(1.45xlO-3)
S.OOxlO'3
(1.50xlO-3)
2.13x10-'
(1.07x10-')
2.61xlO-4
(1.31xlO-4)
9.15xlO-4
(4.58x1 0-4)
2.97x1 Q-4
(1.49xlQ-4)
2.90x1 0-3
(1.45xlO-3)
S.OOxlO'3
fLSOxlO-3)
Emission Factor Range Emission
in Ib/ton Factor
(kg/Mg)a Rating
A
A
A
C
E
A
A
A
A
C
E
A
Reference
114
114
114
114
114
114
114
114
114
114
114
114
-------
TABLE 5-21. LEAD EMISSION FACTORS FOR MUNICIPAL WASTE COMBUSTION SOURCES (CONTINUED)
Average Emission Factor
SCC in Ib/ton
Number Emission Source Control Device (kg/Mg)a
5-0 1 -00 1 -07 Modular Excess Air None
Combustor
Spray Dryer/FF
Spray Dryer/ESP
Dry Sorbent
Injection/FF
Dry Sorbent
LT\ Injection/ESP
o ESP
2.13x10-'
(1.07x10-')
2.61xlO-4
(l.SlxlQ-4)
9.15xlO-4
(4.58x1 0-4)
2.97x1 0-4
(1.49xlQ-3)
2.90x1 0-3
(1.45xlO-3)
S.OOxlO'3
(1.50xlO-3)
Emission Factor Range Emission
in Ib/ton Factor
(kg/Mg)a Rating Reference
A 114
A 114
A 114
C 114
E 114
A 114
a Emission factors are expressed in Ib (kg) of pollutant emitted per ton (Mg) of waste incinerated.
"—" means data are not available.
ESP = Electrostatic Precipitator.
FF = Fabric Filter.
-------
5.4.2 Process Description
Similar to municipal waste incinerators, some solid waste is also incinerated in
industrial and commercial facilities. Most individual waste incinerators at these sites are subject
to State and local air quality regulations, such that these units have varying degrees of emissions
control. Most incinerators are equipped with afterburners, and newer incinerators may have
scrubbers or ESPs.64
Industrial wastes combusted in incinerators consist primarily of processing wastes
and plant refuse containing paper, plastic, rubber, textiles, and wood. Because of the variety of
manufacturing operations, waste composition is highly variable among plants, but may be fairly
consistent within a plant. Industrial waste incinerators have basically the same design as small
municipal waste incinerators. Available data indicate that approximately 91 percent of the units
are multichamber designs, 8 percent are single-chamber designs, and 1 percent are rotary kiln or
fluidized bed design.
About 1,500 of the estimated 3,800 industrial incinerators are used for volume
reduction, 640 units (largely in the petroleum and chemical industries) are used for toxicity
reduction, and the remaining 1,700 units are used for resource recovery, primarily at copper wire
and electric motor plants.64
Commercial waste incinerators, typically small, multichamber incinerators, are used
to reduce the volume of wastes from large office and living complexes, schools, and commercial
facilities. Over 90 percent of such units require firing of an auxiliary fuel. Emissions controls are
generally not present on commercial units.64
Lead emissions from industrial and commercial waste incineration are a function of
waste composition, incinerator design and operating practices, and incinerator emissions control
equipment. Both the incineration of wastes and the combustion of incinerator auxiliary fuel may
be sources of lead emissions. Incinerator design and operating practices affect waste mixing,
residence time in the flame zone, combustion stoichiometry, and other factors that contribute to
5-61
-------
the amount of lead emissions generated. The type of emissions control used dictates whether lead
in the form of PM or a gaseous pollutant is controlled and to what extent. Generally, lead
emissions exist in both particulate and some gaseous forms, with available data indicating that
particulate lead emissions often predominate. Incinerators with emission controls designed
primarily for PM collection may be accomplishing most of the lead emissions control.
5.4.3 Emissions
At the time this report was compiled, there were no available emission factors for
lead emissions from industrial/commercial waste incinerators. Most of the incinerators used by
commercial and industrial facilities are multichamber designs. The process and control device
configurations for incinerators at industrial and commercial facilities are the same as those used by
municipalities. The emission factors for municipal incinerators, however, would not be accurate
to use for industrial and commercial facilities because these two types of facilities incinerate
different types of waste. The waste streams at industrial and commercial sites are highly variable.
One plant might burn wood protected with lead-based paint, which would yield high lead
emissions. Another plant might burn wooden boxes and pallets that have low lead content. As a
result, very little data has been developed that accurately characterizes lead emissions from
industrial/commercial incinerators.
5.5 SEWAGE SLUDGE INCINERATORS
5.5.1 Source Location
There are approximately 200 sewage sludge incineration plants operating in the
United States.118 Most sewage sludge incinerators (SSIs) are located in the eastern United States,
although there are a significant number on the West Coast. New York has the largest number of
facilities with 33; Pennsylvania and Michigan have the next largest number with 21 and 19 sites,
respectively.119
5-62
-------
5.5.2 Process Description
The first step in the process of sewage sludge incineration is dewatering the
sludge. Sludge is generally dewatered until it is about 15 to 30 percent solids, at which point it
will burn without supplemental fuel. After dewatering, the sludge is sent to the incinerator for
combustion. The two main types of SSIs currently in use are the multiple-hearth furnace (MHF)
and the fluidized-bed combustor (FBC). Over 80 percent of the identified operating SSIs are
MHFs and about 15 percent are FBCs. The remaining SSIs co-fire MSW with sludge.120
Multiple-Hearth Furnaces
A cross-sectional diagram of a typical MHF is shown in Figure 5-10. The basic
MHF is a vertically oriented cylinder. The outer shell is constructed of steel and lined with
refractory material and surrounds a series of horizontal refractory hearths. A hollow cast iron
rotating shaft runs through the center of the hearths. Cooling air is introduced into the shaft,
which extends above the hearths. Attached to the central shaft are the rabble arms, which extend
above the hearths. Each rabble arm is equipped with a number of teeth approximately 6 inches in
length and spaced about 10 inches apart. The teeth are shaped to rake the sludge in a spiral
motion, alternating in direction from the outside in to the inside out between hearths. Burners,
which provide auxiliary heat, are located in the sidewalls of the hearths.
In most MHFs, partially dewatered sludge is fed onto the perimeter of the top
hearth. The rabble arms move the sludge through the incinerator by raking the sludge toward the
center shaft, where it drops through holes located at the center of the hearth. In the next hearth,
the sludge is raked in the opposite direction. This process is repeated in all of the subsequent
hearths. The effect of the rabble motion is to break up solid material to allow better surface
contact with heat and oxygen. A sludge depth of about 1 inch is maintained in each hearth at the
design sludge flow rate.
Under normal operating conditions, 50 to 100 percent excess air must be added to
an MHF to ensure complete combustion of the sludge. Besides enhancing contact between the
5-63
-------
Furnace Exhaust
to Afterburner
Product
> .'^, ~ W | I
Cooling and Combustion Air vf V \ '
Feed Material
Figure 5-10. Typical Multiple-Hearth Furnace
Source: Reference 120.
5-64
-------
fuel and the oxygen in the furnace, these relatively high rates of excess air are necessary to
compensate for normal variations in both the organic characteristics of the sludge feed and the
rate at which it enters the incinerator. When an inadequate amount of excess air is available, only
partial oxidation of the carbon will occur, with a resultant increase in emissions of CO, soot, and
hydrocarbons. Too much excess air, on the other hand, can cause increased entrainment of
particulate and unnecessarily high auxiliary fuel consumption.120
Fluidized-Bed Combustors
Figure 5-11 shows the cross-section diagram of an FBC. FBCs consist of a
vertically oriented outer shell constructed of steel and lined with refractory material. Tuyeres
(nozzles designed to deliver blasts of air) are located at the base of the furnace within a
refractory-lined grid. A bed of sand approximately 2.5 feet (0.75 meters) thick rests upon the
grid. Two general configurations can be distinguished based on how the fluidizing air is
injected into the furnace. In the hot windbox design, the combustion air is first preheated by
passing it through a heat exchanger, where heat is recovered from the hot flue gases.
Alternatively, ambient air can be injected directly into the furnace from a cold windbox.
Partially dewatered sludge is fed into the lower portion of the furnace. Air injected
through the tuyeres at a pressure of 3 to 5 pounds per square inch gauge (20 to 35 kilopascals)
simultaneously fluidizes the bed of hot sand and the incoming sludge. Temperatures of 1,400 to
1,700°F (750 to 925°C) are maintained in the bed. As the sludge burns, fine ash particles are
carried out of the top of the furnace. Some sand is also removed in the air stream and must be
replaced at regular intervals.
Combustion of the sludge occurs in two zones. Within the sand bed itself (the first
zone), evaporation of the water and pyrolysis of the organic materials occur nearly simultaneously
as the temperature of the sludge is rapidly raised. In the freeboard area (the second zone), the
remaining free carbon and combustible gases are burned. The second zone functions essentially as
an afterburner.
5-65
-------
Exhaust and Ash
Thermocouple
Sludge
Inlet
Fluidizing
Air Inlet
Pressure Tap
Sight
Glass
Burner
Tuyeres
1=
FT — J
Arch
J
_, Windbox ^
^_
_J
Fuel Gun
Pressure Tap
Startup
Preheat
Burner
for Hot
Windbox
Source: Reference 120.
Figure 5-11. Fluidized-Bed Combustor
5-66
-------
Fluidization achieves nearly ideal mixing between the sludge and the combustion
air; the turbulence facilitates the transfer of heat from the hot sand to the sludge. A FBC
improves the burning atmosphere, such that a limited amount of excess air is required for
complete combustion of the sludge. Typically, FBCs can achieve complete combustion with 20 to
50 percent excess air, about half the excess air required by MHFs. As a consequence, FBCs
generally have lower fuel requirements than MHFs.120
Emission Control Techniques
The emission rates of lead in SSIs are affected by the following conditions:
• Sludge metal content;
• Operating bed temperature;
• Sludge chlorine content;
• Flow patterns leading to solids drop-out ahead of APCD; and
• APCD control efficiency as a function of particle size.
Clearly, the quantity of lead in the feed sludge is the basic scalar of emissions.
Lead in sludge arises from several sources, including industrial discharges (especially plating
wastes), corrosion of outtake plumbing materials, street runoff (especially deposited lead
compounds from lead-containing paints), and numerous lesser domestic and industrial activities.
The lead content varies from day to day, reflecting a diversity of waste types.
The temperature of the combustion environment influences the behavior of lead
emissions because of the following sequence of events during incineration:
1. At elevated temperatures, many heavy metal compounds (including lead)
vaporize. The higher the temperature, the larger the fraction of lead that is
vaporized.
2. As temperatures drop, a fraction of the lead condenses. Condensation
takes place in proportion to available surface area.
5-67
-------
3. Collection of the lead condensed on the PM occurs while passing through
the APCD system.
Sludge chlorine content increases the sensitivity of lead emissions to bed
temperature, such that the lead volatilizes at a lower temperature than if there were no chlorine in
the sludge. This behavior is due to the high volatility of the metal chlorides (PbCl2) versus metal
oxides (PbO).60 Monitoring and limiting the sludge chlorine content allows more lead to
condense onto PM for more effective lead emissions control.
Lead emissions may be reduced by using PM control devices, reducing incinerator
and APCD temperatures, and controlling sludge chlorine content. The types of existing SSI PM
controls include low-pressure-drop spray towers, wet cyclones, high-pressure-drop venturi
scrubbers, and venturi/impingement tray scrubber combinations. A few ESPs and baghouses are
employed, primarily where sludge is co-fired with MSW. The most widely used PM control
device applied to an MHF is the impingement tray scrubber. Older units use the tray scrubber
alone; combination venturi/impingement tray scrubbers are widely applied to newer MHFs and
some FBCs.120
5.5.3 Emissions
Table 5-22 presents lead emission factors for SSIs. The factors presented cover
the two main incinerator types: MHFs and FBCs. Again, as the emission factor tables for the
other types of incinerators (previously discussed) show, PM type control technologies offer the
greatest efficiency for reducing lead emissions.
5.6 MEDICAL WASTE INCINERATION
Medical waste incinerators (MWIs) burn both infectious ("red bag" and
pathological) medical wastes and non-infectious general hospital wastes. The primary purposes of
MWIs are to (1) render the waste innocuous, (2) reduce the volume and mass of the waste, and
(3) provide waste-to-energy conversion.
5-68
-------
TABLE 5-22. LEAD EMISSION FACTORS FOR SEWAGE SLUDGE INCINERATOR SOURCES
SCC Number Emission Source Control Device
5-01-005-15 Multiple-hearth None
Furnace
Single Cyclone/Venturi
Scrubber
Single Cyclone
ESP
Venturi Scrubber
Venturi Scrubber/Wet ESP
Venturi Scrubber/
Impingement-type Wet
Scrubber
Venturi Scrubber/
Impingement-type Wet
Scrubber/Afterburner
Impingement-type Wet
Scrubber
Single Cyclone/Venturi
Scrubber/Impingement
Scrubber
Average Emission Emission Factor Range
Factor in Ib/ton in Ib/ton
(kg/Mg)a (kg/Mg)a
l.OOxlO-1
(5.00x1 0-2)
6.00x1 0-3
(S.OOxlO'3)
6.00x1 0-2
(S.OOxlO-2)
2.00x1 0-3
(l.OOxlO-3)
l.SOxlO'3
(9.00x1 0-4)
l.SOxlO'4
(9.00x1 0-5)
6.00x1 0-2
(S.OOxlO-2)
l.OOxlO'1
(5.00x1 0-2)
4.00x1 0-2
(2.00x1 0-2)
2.20x1 0-2
(l.lOxlO'2)
Emission
Factor
Rating
B
E
E
E
E
E
B
E
E
E
Reference
120
120
120
120
120
120
120
120
120
120
-------
TABLE 5-22. LEAD EMISSION FACTORS FOR SEWAGE SLUDGE INCINERATOR SOURCES (CONTINUED)
--j
o
SCC Number Emission Source Control Device
5-01-005-16 FludizedBed None
FF
Impingement-type Wet
Scrubber
Venturi Scrubber
Impingement-type Wet
Scrubber
Venturi Scrubber/
Impingement-type Wet
Scrubber/ESP
Average Emission Emission Factor Range
Factor in Ib/ton in Ib/ton
(kg/Mg)a (kg/Mg)a
4.00x1 0-2
(2.00x1 0-2)
LOOxlO'5
(5.00x1 0-6)
6.00x1 0-3
(S.OOxlQ-3)
1.60x10-'
(8.00x1 0-2)
2.00x1 0-6
(LOOxlO-6)
Emission
Factor
Rating
E
E
E
E
E
Reference
120
120
120
120
120
-------
5.6.1 Source Location
There are an estimated 6,000 MWIs in the United States, located at such facilities
as hospitals, pharmaceutical companies, research facilities, nursing homes, and other institutions
and companies that incinerate medical waste.55 It is estimated that 90 percent of the nation's
6,872 hospitals (where the majority of MWIs are located) have some type of on-site incinerator, if
only a small unit for incinerating special or pathological waste.55
5.6.2 Process Description
Three main types of incinerators are used as MWIs: controlled-air or starved-air,
excess-air, and rotary kiln. The majority (>95 percent) of incinerators are controlled-air units. A
small percentage (<2 percent) are excess-air, and less than 1 percent were identified as rotary kiln.
The rotary kiln units tend to be larger and typically are equipped with air pollution control
devices. Approximately two percent of all MWIs are equipped with air pollution control
devices.121
Controlled-Air Incinerators
Controlled-air incineration is the most widely used MWI technology, and now
dominates the market for new systems at hospitals and similar medical facilities. This technology
is also known as two-stage incineration or modular combustion. Figure 5-12 presents a schematic
diagram of a typical controlled-air unit.1
121
Combustion of waste in controlled-air incinerators occurs in two stages. In the
first stage, waste is fed into the primary, or lower, combustion chamber, which is operated with
less than the stoichiometric amount of air required for combustion. Combustion air enters the
primary chamber from beneath the incinerator hearth (below the burning bed of waste). This air is
called primary or underfire air. In the primary (starved-air) chamber, the low air-to-fuel ratio
dries and facilitates volatilization of the waste and most of the residual carbon in the ash burns.
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Carbon Dioxide,
— Water Vapor
and Excess
Oxygen and Nitrogen
to Atmosphere
Air
Main Burner for
Minimum Combustion
Temperature
Volatile Content
is Burned in
Upper Chamber
Excess Air
Condition
Starved-Air
Condition in
Lower Chamber
Controlled
Underfire Air
for Burning
Down Waste
Figure 5-12. Controlled-Air Incinerator
Source: Reference 121.
5-72
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At these conditions, combustion gas temperatures are relatively low (1,400 to 1,800°F [760 to
980°C]).m
In the second stage, excess air is added to the volatile gases formed in the primary
chamber to complete combustion. Secondary chamber temperatures are higher than primary
chamber temperatures-typically 1,800 to 2,000°F (980 to 1,095°C). Depending upon the
heating value and moisture content of the waste, additional heat may be needed. Additional heat
can be provided by auxiliary burners located at the entrance to the secondary (upper) chamber to
maintain desired temperatures.121
Waste feed capacities for controlled-air incinerators range from about 75 to
6,500 Ib/hr (0.6 to 50 kg/min) (at an assumed fuel heating value of 8,500 Btu/lb [19,700 kJ/kg]).
Waste feed and ash removal can be manual or automatic, depending on the unit size and options
purchased. Throughput capacities for lower-heating-value wastes may be higher because feed
capacities are limited by primary chamber heat release rates. Heat release
rates for controlled-air incinerators typically range from about 15,000 to 25,000 Btu/hr-ft3
(430,000 to 710,000 kJ/hr-m3).121
Excess-Air Incinerators
Excess-air incinerators are typically small, modular units. They are also referred to
as batch incinerators, multiple-chamber incinerators, or "retort" incinerators. Excess-air
incinerators are typically a compact cube with a series of internal chambers and baffles. Although
they can be operated continuously, they are usually operated in batch mode.121
Figure 5-13 presents a schematic for an excess-air unit. Typically, waste is
manually fed into the combustion chamber. The charging door is then closed, and an afterburner
is ignited to bring the secondary chamber to a target temperature (typically 1,600 to 1,800°F
[870 to 980°C]). When the target temperature is reached, the primary chamber burner ignites.
The waste is dried, ignited, and combusted by heat provided by the primary chamber burner, as
well as by radiant heat from the chamber walls. Moisture and volatile components in the waste
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Flame Port
Stack
Charging
Door
Ignition^
Chamber
Hearth
Secondary
Air Ports
Secondary
Burner Port
Mixing
Chamber
First
Underneath Port
Secondary
Combustion
Chamber
Side View
Mixing
Chamber Flame Port
Cleanout
Doors
Charging Door
Hearth
Primary
Burner Port
Secondary
Underneath Port
Figure 5-13. Excess-Air Incinerator
CO
CD
0)
CD
OL
LU
Source: Reference 121.
5-74
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are vaporized and pass (along with combustion gases) out of the primary chamber and through a
flame port that connects the primary chamber to the secondary or mixing chamber. Secondary air
is added through the flame port and is mixed with the volatile components in the secondary
chamber. Burners are also installed in the secondary chamber to maintain adequate temperatures
for combustion of volatile gases. Gases exiting the secondary chamber are directed to the
incinerator stack or to an air pollution control device. After the chamber cools, ash is manually
removed from the primary chamber floor and a new charge of waste can be added.121
Incinerators designed to burn general hospital waste operate at excess air levels of
up to 300 percent. If only pathological wastes are combusted, excess air levels near 100 percent
are more common. The lower excess air helps maintain higher chamber temperature when
burning high-moisture waste. Waste feed capacities for excess-air incinerators are usually
500 Ib/hr (3.8 kg/min) or less.121
Rotary Kiln Incinerators
Rotary kiln incinerators are also designed with a primary chamber, where the waste
is heated and volatilized, and a secondary chamber, where combustion of the volatile fraction is
completed. The primary chamber consists of a slightly inclined, rotating kiln in which waste
materials migrate from the feed end to the ash discharge end. The waste throughput rate is
controlled by adjusting the rate of kiln rotation and the angle of inclination. Combustion air enters
the primary chamber through a port. An auxiliary burner generally is used to start combustion
and maintain desired combustion temperatures.
Figure 5-14 presents a schematic diagram of a typical rotary kiln incinerator.
Volatiles and combustion gases pass from the primary chamber to the secondary chamber. The
secondary chamber operates at excess air. Combustion of the volatiles is completed in the
secondary chamber. Because of the turbulent motion of the waste in the primary chamber, solids
burnout rates and particulate entrainment in the flue gas are higher for rotary kiln incinerators than
for other incinerator designs. As a result, rotary kiln incinerators generally have add-on gas-
cleaning devices.121
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Exhaust Gas to Stack or
Air Pollution Control Device"
Waste Feed
Ul
--J
Auxiliary Fuel
Ash Removal
Figure 5-14. Rotary Kiln Incinerator
Source: Reference 121.
-------
Emission Control Techniques
Medical waste contains toxic metals such as lead. Lead is found in many materials,
including plastics, paper, inks, and electrical cable insulation. However, the primary source of
lead appears to be plastics. Lead is used to make dyes and stabilizers that protect plastics from
thermal and photo-degradation. The dyes made from lead are used to color plastic bags; thus,
some of the lead emissions from MWIs could be due simply to the "red bags" that infectious
waste is placed in. During incineration, lead only changes forms (chemical and physical states)
but is not destroyed. Lead can be emitted from incinerators on small particles capable of
penetrating deeply into human lungs.122
A majority of lead and other metal emissions is in the form of PM, and a minority
is in vapor form. Particulate emissions of lead from the incineration of medical wastes are
determined by three major factors:
1. Suspension of noncombustible inorganic materials containing lead;
2. Incomplete combustion of combustible lead materials; and
3. Condensation of lead-based vaporous materials (these materials are mostly
inorganic matter).
Emissions of noncombustible materials result from the suspension or entrainment
of ash by the combustion air added to the primary chamber of an incinerator. The more air that is
added, the more likely that noncombustibles become entrained. Particulate emissions from
incomplete combustion of combustible materials result from improper combustion control of the
incinerator. Condensation of vaporous materials results from noncombustible substances that
volatilize at primary combustion chamber temperatures with subsequent cooling in the flue gas.
These materials usually condense on the surface of other fine particles.122
Typically, two strategies are used to minimize metals emissions: (1) combustion
control in the primary chamber so as to inhibit vaporization or entrainment of metals, and
5-77
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(2) capture of any metals that do escape by APCDs. Both of these strategies are discussed below.
The key APCD parameters used are specific to the device that is used.
Combustion Control—Most MWIs are simple single-chamber units with an
afterburner located in the stack. The ability of batch incinerators to control lead emissions is
limited because only the temperature in the stack is usually monitored.
Most new incinerators are starved-air units. The primary chamber is designed to
operate at low temperatures and low gas flow rates. This minimizes the amount of materials
entrained or vaporized.
To ensure that lead emissions are minimized, operators must maintain the primary
chamber at the temperatures and gas flow rates for which it was designed. Usually the only
parameter that system operators can directly control is feed rate. High feed rates can lead to high
temperatures and high gas velocities. Thus, many operators carefully control the feed rate. The
feed rate is reduced when primary temperatures increase. Keeping the temperature low enables
the lead to condense on different sizes of particles, which are then easily trapped by PM control
devices.
APCD Control—When lead reaches the APCD, it is present in one of three forms.
Non-volatile lead is present on large entrained particles. Lead that has vaporized and recondensed
is usually enriched on fly-ash particles with diameters less than 1 micron. Extremely volatile lead
is present as vapor.122 The majority of lead emissions are in the first two forms and are controlled
by PM control devices. Generally, particulate control is a surrogate for lead control in an
incinerator/air pollution control system.55
5.6.3 Emissions
The available lead emission factors for MWIs are presented in Table 5-23. As with
the other types of incinerators, waste composition is a critical factor in the amount of lead emitted
from MWIs.
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TABLE 5-23. LEAD EMISSION FACTORS FOR MEDICAL WASTE COMBUSTION SOURCES
Ul
--J
sec
Number Emission Source Control Device
5-01-005-05 Other Incineration None
Pathological/Rotary
Kiln
5-01-005-05 Other Incineration None
Pathological/
Controlled Air
5-01-005-05 Other Incineration Wet Scrubber - High
Pathological Efficiency
Wet Scrubber -
Medium Efficiency/FF
FF
Spray Dryer/ FF
Spray Dryer/Carbon
Injection/FF
Dry Sorbent Injection/
ESP
Dry Sorbent
Injection/FF
Dry Sorbent Injection/
Carbon Injection/FF
Dry Sorbent
Inj ection/FF/S crubber
Wet Scrubber - Low
Efficiency
Average Emission
Factor in Ib/ton
(kg/Mg)a
1.24x10-'
(6.20x1 0-2)
7.28x1 0-2
(3.64xlO-2)
6.98x1 0-2
(3.49xlO'2)
1.60xlO-3
(8.00x1 0-4)
9.92x1 0-5
(4.96x1 0-5)
1.89xlO'4
(9.45x1 0-5)
7.38xlO-5
(3.69xlO'5)
4.70x1 0'3
(2.35x1 0-3)
6.25x1 0-5
(3.12x10')
9.27x1 0-5
(4.64x1 0'5)
5.17xlO-5
(2.59x1 0-5)
7.94x1 0-2
G.97X10-2)
Emission Factor Emission
Range in Ib/ton Factor
(kg/Mg)a Rating
E
B
E
E
E
E
E
E
E
E
E
E
Reference
121
121
121
121
121
121
121
121
121
121
121
121
-------
TABLE 5-23. LEAD EMISSION FACTORS FOR MEDICAL WASTE COMBUSTION SOURCES (CONTINUED)
oo
o
sec
Number Emission Source Control Device
5-02-005-05 Commercial - None (Rotary Kiln
Incineration - Incinerator)
Pathological . . ,
Afterburner
FF
Wet Scrubber - High
Efficiency
Wet Scrubber -
Medium Efficiency/FF
Spray Dryer/FF
Spray Dryer/Carbon
Injection/FF
Dry Sorbent
Injection/ESP
Dry Sorbent
Injection/Carbon
Injection/FF
Dry Sorbent
Injection/FF
None (Controlled Air
Incinerator)
Dry Sorbent Injection/
FF/Scrubber
Average Emission
Factor in Ib/ton
(kg/Mg)a
1.24x10-'
(6.20x1 0-2)
6.50x1 0-4
(3.30xlO'4)
9.92x1 0-5
(4.96x1 0-5)
6.98x1 0-2
(3.49xlO'2)
1.60xlO-3
(8.00x1 0-4)
1.89xlO-4
(9.45x1 0-5)
7.38xlO-5
(3.69xlO-5)
4.70x1 0-3
(2.35x1 0-3)
9.27x1 0-5
(4.64x1 0'5)
6.25x1 0-5
(3.13xlO-5)
7.28x1 0-2
(3.64xlO-2)
5.17xlO-5
(2.59x1 0-5)
Emission Factor Emission
Range in Ib/ton Factor
(kg/Mg)a Rating
E
5.30xlO-4-7.60xlO-4 E
(2.70x1 0-4 -
3.80xlO'4)
E
E
E
E
E
E
E
E
B
E
Reference
121
123
121
121
121
121
121
121
121
121
121
121
-------
TABLE 5-23. LEAD EMISSION FACTORS FOR MEDICAL WASTE COMBUSTION SOURCES (CONTINUED)
sec
Number
5-02-005-05
(continued)
Emission Source
Commercial -
Incineration -
Pathological
Control Device
Wet Scrubber - Low
Efficiency
Average Emission
Factor in Ib/ton
(kg/Mg)a
7.94x1 0'2
(3.97xlO-2)
Emission Factor
Range in Ib/ton
(kg/Mg)a
—
Emission
Factor
Rating
E
Reference
121
a Emission factors are expressed in Ib (kg) of pollutant emitted per ton (Mg) of waste incinerated.
"—" means data are not available.
ESP = Electrostatic Precipitator.
FF = Fabric Filter.
oo
-------
The lead emission factors were developed from tests at facilities burning red bag
waste, pathological waste, and/or general hospital waste. Red bag waste is defined as any waste
generated in the diagnosis or immunization of human beings or animals; pathological waste is
defined as any human and animal remains, tissues, and cultures; and general hospital waste was
defined as a mixture of red bag waste and municipal waste generated by the hospital.
As with other combustion sources, the presented emission factors are highly
dependent upon the composition of the waste. For example, the difference in the emission factors
presented in Table 5-23 for both a high efficiency and medium efficiency wet scrubber applied to
an MWI is expected to be more a function of the lead content of the waste burned than scrubber
efficiency.
5.7 HAZARDOUS WASTE INCINERATION
Hazardous waste, as defined by 40 CFR Part 261, includes a wide variety of waste
materials.124 Hazardous wastes are produced in the form of liquids (e.g., waste oils, halogenated
and nonhalogenated solvents, other organic liquids, and pesticides/herbicides) and sludges and
solids (e.g., halogenated and nonhalogenated sludges and solids, dye and paint sludges, resins,
and latex). The lead content of hazardous waste varies widely, but lead could be emitted from the
incineration of any of these types of hazardous waste. Based on a 1986 study, total annual
hazardous waste generation in the United States was approximately 292 million tons (265 million
metric tons).125 Only a small fraction of the waste (less than 1 percent) was incinerated. MACT
standards for hazardous waste combustors and Portland cement manufacturing were proposed
May 2, 1997 and March 24, 1998, respectively. These proposed standards should reduce lead
emissions.
Based on an EPA study conducted in 1983, the major types of hazardous waste
streams incinerated were spent nonhalogenated solvents and corrosive and reactive wastes
contaminated with organics. Together, these accounted for 44 percent of the waste incinerated.
Other prominent wastes included hydrocyanic acid, acrylonitrile bottoms, and nonlisted ignitable
wastes.126
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Industrial kilns, boilers, and furnaces are used to burn hazardous waste. They use
the hazardous waste as fuel to produce commercial products such as cement, lime, iron, asphalt,
or steam. In fact, the majority of hazardous waste generated in the United States is currently
disposed of in cement kilns. Lead emissions from cement kilns are discussed in Section 5.13.
Hazardous waste, which is an alternative to fossil fuels for energy and heat, is used at certain
commercial facilities as a supplemental fuel. In the process of producing energy and heat, the
hazardous wastes are subjected to high temperatures for a sufficient time to volatilize metals in
the waste.
5.7.1 Source Location
Currently, 162 permitted or interim status incinerator facilities, having 190 units,
are in operation in the United States. Another 26 facilities are proposed (i.e., new facilities under
construction or permitting).127 Of the above 162 facilities, 21 facilities are commercial facilities
that burn about 700,000 tons of hazardous waste annually.128 The remaining 141 are on-site or
captive facilities and burn about 800,000 tons of waste annually.
5.7.2 Process Description
Hazardous waste incineration employs oxidation at high temperatures (usually
1,650°F [900°C] or greater) to destroy the organic fraction of the waste and reduce volume. A
diagram of the typical process component options in a hazardous waste incineration facility is
provided in Figure 5-15. The diagram shows the major subsystems that may be incorporated into
a hazardous waste incineration system: waste preparation and feeding, combustion chamber(s),
air pollution control, and residue/ash handling.
Five types of hazardous waste incinerators are currently available and in operation:
liquid injection, rotary kiln, fixed-hearth, fluidized-bed, and fume injection.129
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Waste Preparation
Combustion
Air Pollution Control
Blending
Screening
Shredding
Heating
Atomlzatlon
Ram
Gravity
Auger
Lance
Liquid Injection
Rotary Win
Fixed Hearth
Fluldlzed Bed
Quench
Heat
Recovery
Venturl
Wet ESP*
IWS*
Fabric Filter
Packed Tower
Spray Tower
Tray Tower
IWS
Wet ESP
I
oo
IWS = Ionizing Wet Scrubber
ESP = Electrostatic Predpltator
POTW = Publlcally Owned
Treatment Works
Dewaterlng
Chemical
Stabilization
Secure Landfill
Return to
Process
POTW*
Neutralization
Chemical Treatment
Residue
and Ash
Handling
Figure 5-15. Typical Process Component Options in a Hazardous Waste Incineration Facility
Source: Reference 125.
-------
Additionally, a few other technologies have been used for incineration of hazardous waste,
including ocean incineration vessels and mobile incinerators. These processes are not in
widespread use in the United States and are not discussed below.
Liquid Injection Incinerators
Liquid injection combustion chambers are used for pumpable liquid waste,
including some low-viscosity sludges and slurries. Liquid injection units are usually simple,
refractory-lined cylinders (either horizontally or vertically aligned) equipped with one or more
waste burners. The typical capacity of liquid injection units is about 8 to 28 million Btu/hour
(8.4 to 29.5 GJ/hour). Figure 5-16 presents a schematic diagram of a typical liquid injection
unit.125'129
Rotary Kiln Incinerators
Rotary kiln incinerators are used for destruction of solid wastes, slurries,
containerized waste, and liquids. Because of their versatility, these units are most frequently used
by commercial off-site incineration facilities. Rotary kiln incinerators generally consist of two
combustion chambers: a rotating kiln and an afterburner. The rotary kiln is a cylindrical
refractory-lined shell mounted on a slight incline. The primary function of the kiln is to convert
solid wastes to gases, which occurs through a series of volatilization, destructive distillation, and
partial combustion reactions. The typical capacity of these units is about 10 to 60 million
Btu/hour (10.5 to 63.3 GJ/hour).
Figure 5-17 presents a schematic diagram of a typical rotary kiln unit. An
afterburner is connected directly to the discharge end of the kiln. The afterburner is used to
ensure complete combustion of flue gases before their treatment for air pollutants. A tertiary
combustion chamber may be added if needed. The afterburner itself may be horizontally or
vertically aligned, and functions on much the same principles as the liquid injection unit described
above. Both the afterburner and the kiln are usually equipped with an auxiliary fuel-firing system
to control the operating temperature.
5-85
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Ul
oo
Aqueous
Waste
Steam
Auxiliary
Fuel
Liquid
Waste
Atomizing
Steam or
Air
120-250%
Excess Air
Primary
Combustlc
Air
Ion
2600 P= - 30003 F
0.3 - 2.0 Seconds
Mean Combustion
Gas Residence Time
Discharge
to Quench or
Waste Heat Recovery
1500 9= - 220(9 F
Figure 5-16. Typical Liquid Injection Combustion Chamber
-------
Discharge to
Quench or
Heat Recovery
Air
Combustion
Air
oo
120200%
Excess Air
Waste Liquids
Ash
Ash
Afterburner
Rotary Kiln
Figure 5-17. Typical Rotary Kiln/Afterburner Combustion Chamber
1.0-3.0 Seconds
Mean Gas
Residence Time
Refractory
Source: Reference 125.
ERG PB S17.ds4
-------
Fixed-Hearth Incinerators
Fixed-hearth incinerators (also called controlled-air, starved-air, or pyrolytic
incinerators) are the third major technology used for hazardous waste incineration. Figure 5-18
presents a schematic diagram of a typical fixed-hearth unit.125'129 This type of incinerator may be
used for the destruction of solid, sludge, and liquid wastes. Fixed-hearth units tend to be of
smaller capacity (typically 5 million Btu/hour [5.3 GJ/hour]) than liquid injection or rotary kiln
incinerators because of physical limitations in ram feeding and transporting large amounts of
waste materials through the combustion chamber.
Fixed-hearth units consist of a two-stage combustion process similar to that of
rotary kilns. Waste is ram-fed into the primary chamber and burned at about 50 to 80 percent of
stoichiometric air requirements. This starved-air condition causes most of the volatile fraction to
be destroyed pyrolitically. The resultant smoke and pyrolysis products pass to the secondary
chamber, where additional air and, in some cases, supplemental fuel, is injected to complete the
combustion.125
Fluidized-Bed Incinerators
Fluidized-bed incinerators (combustors), which were described in Section 5.5.2 of
this report, have only recently been applied to hazardous waste incineration. FBCs used to
dispose of hazardous waste are very similar to those used to incinerate sewage sludge except for
their additional capability of handling liquid wastes.
FBCs are suitable for disposing of combustible solids, liquids, and gaseous wastes.
They are not suited for irregular or bulky wastes, tarry solids, or other wastes that leave residues
in the bed.130 Fluidized-bed combustion chambers consist of a single refractory-lined combustion
vessel partially filled with inert granular material (e.g., particles of sand, alumina, and sodium
carbonate).125 The typical capacity of this type of incinerator is 45 million Btu/hour (47.5
GJ/hour).
5-88
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Ul
oo
Auxiliary Fuel
Feed
Ram
100-200%
Excess Air
Discharge to
Quench or
Heat Recovery
0.25-2.5 Seconds
Mean Residence Time
Secondary
f Chamber
1400"F-2000°F
Steam
Auxiliary Fuel or
Uquld Waste
Air
50-80%
Excess Air
Refractory
Transfer
Ram
Ash Discharge
pgm Ash Discharge
Figure 5-18. Typical Fixed-Hearth Combustion Chamber
ER3_PB_518.ljs4
Source: Reference 125.
-------
Fume Injection Incinerators
Fume injection incinerators are used exclusively to destroy gaseous or fume
wastes. The combustion chamber is comparable to that of a liquid-injection incinerator
(Figure 5-16) in that it usually has a single chamber, is vertically or horizontally aligned, and uses
nozzles to inject the waste into the chamber for combustion. Waste gases are injected by pressure
or atomization through the burner nozzles. Wastes may be combusted solely by thermal or
catalytic oxidation.
Emission Control Techniques
The types of incinerators used for hazardous waste combustion are similar to the
incinerators used by the other combustion sources discussed earlier in this section. However, the
components in the hazardous waste stream vary extensively. The hazardous waste stream may
include a variety of liquid, solid, or sludge wastes considered hazardous by RCRA. The
hazardous waste stream may also include wastes generated by a variety of sources (e.g., medical,
municipal, and sewage sludge).
Controlling lead emissions is partly accomplished by monitoring the temperature of
the combustion bed and the feed chlorine content. Lead compounds vaporize at elevated
temperatures. The higher the temperature, the larger the fraction of lead vaporized. As the
temperature drops, a fraction of the lead condenses. Collection of lead condensed on PM occurs
in the APCD. Controlling lead emissions is accomplished using the same type of PM control
devices described in Section 5.3.
Chlorine content increases the sensitivity of lead emissions to bed temperature,
causing the lead to volatilize at a lower temperature than if there were no chlorine present in the
feed. This behavior is due to the high volatility of lead chlorides (PbCl2) versus lead oxides
(PbO). Monitoring and limiting the sludge chlorine content allows more lead to condense onto
PM for more effective lead emissions control.60 The PM is then easily captured by ESP or fabric
filter control devices.
5-90
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5.7.3 Emissions
The composition of the hazardous waste varies tremendously in the hazardous
waste incineration industry, causing the lead content of the waste stream to vary widely. For
example, burning lead-based paint may result in significant lead emissions, while burning
halogenated solvents may result in no lead emissions. The lead content of the waste being
combusted dictates whether or not significant lead emissions occur.
Because of limited data available on hazardous waste incineration emissions, no
emission factors for lead are reported here. However, lead emissions are expected from this
source because lead-containing components comprise part of the hazardous waste stream. The
variability of the waste is too great to produce any factors that could represent an average
incinerator scenario.
5.8 DRUM AND BARREL RECLAMATION
5.8.1 Source Location
Approximately 2,800,000 to 6,400,000 55-gallon drums are incinerated annually in
the United States.131 This estimate is based on the assumptions that there are 23 to
26 incinerators currently in operation, with each incinerator handling 500 to 1,000 drums per day,
and operating 5 days a week with 14 days down time for maintenance. The exact locations of
these incinerators could not be determined from the available data.
5.8.2 Process Description
Lead emissions have been detected in the stack gases from drum reclamation
facilities.132 These facilities typically consist of a furnace that is used to heat the drums to an
elevated temperature in order to destroy any residual materials in the containers. The drums are
then repaired, repainted, relined, and sold for reuse. The drums processed at these facilities come
from a variety of sources, such as the petroleum and chemical industries.133
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The furnaces are fired by an auxiliary fuel such as oil or natural gas. The used
drums are typically loaded onto a conveyor, which carries them through the heat treatment zone.
As the drums proceed through this process, any residual contents, paint, and interior linings are
burned off or disintegrated. Lead formation can occur from either the heat treatment of the
barrels or from the combustion of the auxiliary fuel.
5.8.3 Emissions
Only one test report was found that measured emissions of specific lead
compounds from a drum reclamation facility.132 The tested facility recycles 55-gallon drums. No
information was available concerning the physical or chemical characteristics of the residual waste
in the drums or of the auxiliary fuel type used to fire the furnace. The drum furnace consists of a
boiler at 1400°F (760°C) and an afterburner at 1600°F (871 °C) as an emissions control device.
Table 5-24 shows the lead emission factor developed for this facility.
The emission factor for drum reclamation should be used cautiously because the
nature of the residual waste product can vary greatly from facility to facility, which will likely
affect lead emissions. The type of auxiliary fuel used can also have a significant effect on lead
emissions from these facilities.
5.9 SCRAP TIRE INCINERATION
Most facilities that burn scrap tires use the tires to supplement a primary fuel, such
as wood. This section addresses only those facilities that burn scrap tires as their sole fuel. The
primary purpose of these facilities is to recover energy from the combustion of scrap tires.
5.9.1 Source Location
The EPA's Office of Solid Waste has estimated that approximately 26 million scrap
tires were incinerated in the United States in 1990.134 This equates to approximately
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TABLE 5-24. LEAD EMISSION FACTORS FOR DRUM AND BARREL RECLAMATION SOURCES
SCC Number
3-09-025-01
Emission Source
Drum Reclamation: Drum
Burning Furnace
Control Device
None
Average Emission Factor in
llVbarrel (g/barrel)a
3.50xlO-4
(1.59x10-')
Emission Factor Range
in Ib/barrel (g/barrel)a
—
Emission Factor
Rating
E
Source: Reference 132
""Emission factors are expressed in Ib (g) of pollutant emitted per barrel of waste incinerated.
"—" means data are not available.
-------
11 percent of the 242 million scrap tires generated in 1990. The use of scrap tires as fuel
increased significantly during the late 1980s, and is expected to continue to increase.134
In December 1991, there were two operational, dedicated tire-to-energy facilities
in the United States: the Modesto Energy Project in Westley, California, and the Exter Energy
Company in Sterling, Connecticut. In 1993, the Erie Energy Project was built in Lackawanna,
New York. The total capacity for all three plants combined could approach almost 25,000,000
tires per year (4,500,000 at the Modesto plant, and 10,000,000 each at the Exter and Erie
plants).135
5.9.2 Process Description
The following process description is based on the operations at the Modesto
Energy Facility in Westley, California. The Modesto facility consists of two whole-tire boilers
that generate steam from the combustion of the scrap tires. Tires from a nearby supply pile are
fed into a hopper located adjacent to the pile. Tires are then fed into the boilers at a rate of
350 to 400 tires per hour for each boiler. The boilers can accommodate tires as large as 4 feet in
diameter made of rubber, fiberglass, polyester, and nylon.
The tires are burned on reciprocating stoker grates in the combustion chamber at
the bottom of the boilers. The grate configuration allows air flow above and below the tires,
which aids in complete combustion. The boilers are operated above 2,000°F (1,093°C) to ensure
complete combustion of organic compounds emitted by the burning tires. The heat generated by
the burning of the tires causes the water contained in the pipes of the refractory brickwork that
lines the boiler to turn into steam. The high-pressure steam is then forced through a turbine for
the generation of power. After exiting the boiler chamber, exhaust gases pass through the large
fabric filter.
5-94
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5.9.3 Emissions
Although no lead emission factors were identified specifically for scrap tire
incinerators, this source category is included as a potential source of lead emissions. Lead
emission factors for open burning of scrap tires are identified in Section 5.10, "Open Burning of
Scrap Tires." The data presented in that section show that lead is a component of tires and, as a
result, is emitted from the combustion of tires. It is expected that lead emissions are also present
in emissions from incinerators that burn scrap tires. However, because of differences in the
combustion and APCD design and operation, emission factors from open burning of scrap tires
are not representative of scrap tire incinerators.
5.10 OPEN BURNING OF SCRAP TIRES
5.10.1 Source Location
Open burning of scrap tires can occur at permitted landfills that stockpile scrap
tires, at closed landfills that already contain scrap tires, and at illegal dumpsites where tires are
discarded. The fires can start by accident or are intentionally set by arsonists, and thus are often
unpredictable as to where and when they will occur.
5.10.2 Process Description
Approximately 240 million vehicle tires are discarded annually.136 Although viable
methods for recycling exist, less than 25 percent of discarded tires are recycled; the remaining
175 million are discarded in landfills, stockpiles, or illegal dumps.136 Although it is illegal in many
States to dispose of tires by open burning, fires often occur at tire stockpiles and through illegal
burning activities. These fires generate a huge amount of heat and are difficult to extinguish
(some tire fires continue for months). Lead is a component of tires and is emitted from the
combustion of these tires.
5-95
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5.10.3 Emissions
Table 5-25 contains emission factors for the open burning of tires.137 The average
emission factor presented represents the average of tests performed on the simulated open burning
of chunk (defined as one-quarter or one-sixth of an entire tire) and shredded tires. When
estimating emissions from an accidental tire fire, note that emissions from burning tires are
generally dependent on the burn rate of the tire.
5.11 CREMATORIES
5.11.1 Source Location
In 1991, there were about 400,000 cremations in more than 1,000 crematories
located throughout the United States. Table 5-26 lists the number of crematories located in each
State and the estimated number of cremations performed in each State.138
5.11.2 Process Description
Crematory incinerators used for human cremation at funeral homes, mortuaries,
cemeteries, and crematories are normally of an excess air design. They utilize secondary chamber
(afterburner) and primary chamber (ignition) burners fueled by liquified petroleum (LP) gas or
natural gas. Burner capacities are generally between 750,000 and 1,500,000 BTUs per hour per
burner. Late model units have burner modulation capability to regulate chamber temperatures and
conserve fuel. Incineration rates range from 100 to 250 pounds of remains per hour.
Preheating and a minimum secondary chamber temperature, typically ranging from
1,400°F to 1,800°F, may be requirements. Although not suitable for this batch load type of
incinerator, the same requirements are occasionally applied to the primary chamber.
5-96
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TABLE 5-25. LEAD EMISSION FACTORS FOR OPEN BURNING OF SCRAP TIRES
SCC Number
5-03-002-03
Emission Source
Open Burning of Shredded
Automobile Tires
Burning of Chunk
Automobile Tires
Control Device
None
None
Average Emission Factor
in Ib/ton (kg/Mg)a
2.00x1 0-4
(l.OOxlO-4)
6.70x1 0-4
(3.35xlO'4)
Emission Factor Range
in Ib/ton (kg/Mg)a Emission Factor Rating
C
C
Source: Reference 137
a Emission factors are expressed in Ib (kg) of pollutant emitted per ton (Mg) of waste incinerated.
"—" means data are not available.
-------
TABLE 5-26. 1991 U.S. CREMATORY LOCATIONS BY STATE
State
Alabama
Alaska
Arizona
Arkansas
California
Colorado
Connecticut
Delaware
District of Columbia
Florida
Georgia
Hawaii
Idaho
Illinois
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maine
Maryland
Massachusetts
Michigan
Minnesota
Mississippi
Missouri
No. of
Crematories
6
6
31
13
142
27
10
4
0
97
15
8
13
47
25
14
10
6
5
4
18
13
40
20
4
23
No. of
Cremations
1,313
860
13,122
2,435
89,233
9,537
5,528
1,062
NA
59,213
4,786
3,937
2,637
17,557
4,743
3,042
2,029
1,548
2,466
3,469
6,300
10,611
17,460
7,296
693
6,105
State
Montana
Nebraska
Nevada
New Hampshire
New Jersey
New Mexico
New York
North Carolina
North Dakota
Ohio
Oklahoma
Oregon
Pennsylvania
Rhode Island
South Carolina
South Dakota
Tennessee
Texas
Utah
Vermont
Virginia
Washington
West Virginia
Wisconsin
Wyoming
No. of
Crematories
15
7
12
6
16
10
38
27
1
42
10
36
46
5
12
3
9
39
6
5
26
49
6
28
3
No. of
Cremations
3,234
1,710
6,343
2,348
16,557
3,140
24,625
6,884
NA
16,109
2,120
11,272
16,867
2,446
2,422
NA
2,451
13,795
1,210
1,902
7,738
18,466
762
7,293
NA
Source: Reference 138
NA = not available.
5-98
-------
The human remains and cremation container, generally made of cardboard or
wood, are loaded onto the primary chamber hearth and the primary burner is ignited to begin the
cremation process. The remains may be raked at the midpoint of the cremation to uncover
unburned material and speed the process. The average cremation takes from 1 1/2 to 3 hours,
after which the incinerator is allowed to cool for a period of at least 30 minutes so that the
remains can be swept from the hearth.139
5.11.3 Emissions
Evaluation tests on two propane-fired crematories at a cemetery in California were
conducted through a cooperative effort with the Sacramento Metropolitan Air Quality
Management District to determine HAP emissions from a crematory.140 The units were calibrated
to operate at a maximum of 1.45 MMBtu per hour. Emissions testing was performed over a
two-week period. Thirty-six bodies were cremated during the test period. The body, cardboard,
and wood process rates for each test were reported.
Sampling, recovery, and analysis for lead were performed in accordance with
CARB Method 436. Emission factors developed from these data are presented in Table 5-27.
5.12 PULP AND PAPER INDUSTRY
Chemical wood pulping involves the extraction of cellulose from wood by
dissolving the lignin that binds the cellulose fibers. Kraft pulping is the major form of chemical
wood pulping in the United States, accounting for approximately 85 percent of pulp production141
and is expected to continue as the dominant pulping process.142'143 Semi-chemical and acid sulfite
pulping constitute 6 and 4 percent of domestic pulp production, respectively.141
Four processes associated with the pulp and paper industry have been identified as
potential sources of lead emissions: chemical-recovery furnaces, smelt-dissolving tanks, lime
kilns, and power boilers. The following sections focus on the pulp mill thermal chemical-recovery
processes associated with potential lead emissions. Lead emissions from wood waste
5-99
-------
TABLE 5-27. LEAD EMISSION FACTOR FOR CREMATORIES
Average Emission Factor in
Ib/body
SCC Number Emission Source Control Device (kg/body)? Emission Factor Rating
3-15-021-01 Crematory Stack None 6.62xlQ-5 U
qoixio-5)
Source: Reference 140
Note: Average weight per body incinerated: body = 141 Ib (64 kg); wrapping material = 4 Ib (2 kg) cardboard, 3 Ib (1.4 kg) wood.
a Emission factors are in Ib (kg) per body.
o
o
-------
and fossil fuel-fired industrial power boilers are not specific to the pulp and paper industry; see
Section 5.1.
5.12.1 Kraft Recovery Furnaces and Smelt-Dissolving Tanks
Source Location
The distribution of kraft pulp mills in the United States in 1997 is shown in
Table 5-28. Kraft pulp mills are located primarily in the southeast, whose forests provide over
60 percent of U.S. pulpwood.
Process Description
The kraft pulping process involves the cooking or digesting of wood chips at an
elevated temperature (340 to 360°F [about 175°C]) and pressure (100 to 135 psig) in white
liquor, which is a water solution of sodium sulfide (Na2S) and sodium hydroxide (NaOH). The
lignin that binds the cellulose fibers is chemically dissolved by the white liquor in a tall, vertical
digester. This process breaks the wood into soluble lignin and alkali-soluble hemicellulose and
insoluble cellulose or pulp. A typical kraft pulping and recovery process is shown in Figure 5-19.
Two types of digester systems are used in chemical pulping: batch and continuous.
In a batch digester, the contents of the digester are transferred to an atmospheric tank (usually
referred to as a blow tank) after cooking is completed (2 to 6 hours). In a continuous digester,
wood chips and white liquor continuously enter the system from the top while pulp is
continuously withdrawn from the bottom into a blow tank. In both types of digesters, the entire
contents of the blow tank are diluted and pumped to a series of brownstock washers, where the
spent cooking liquor is separated from the pulp. The pulp, which may then be bleached, is
pressed and dried into the finished product.
5-101
-------
TABLE 5-28. DISTRIBUTION OF KRAFT PULP MILLS IN THE
UNITED STATES (1997)
State
Alabama
Arizona
Arkansas
California
Florida
Georgia
Idaho
Kentucky
Louisiana
Maine
Maryland
Michigan
Minnesota
Mississippi
Montana
New Hampshire
New York
North Carolina
Ohio
Oklahoma
Oregon
Pennsylvania
South Carolina
Tennessee
Texas
Virginia
Washington
Wisconsin
Total
Number of Mills
14
1
7
2
7
12
1
2
10
7
1
3
2
6
1
1
1
6
1
1
7
3
6
2
6
4
6
4
124
Source: Reference 144
5-102
-------
POTENTIAL
EMISSIONS
CHIPS
RELIEF
NONCONOENSABLES
t
TURPENTINE
CONTAMINATED WATER
STEAM, CONTAMINATED WATER
CONTAMINATED
-*• WATER
PULP
ON
R
1
EVAPORAl
o
1 .
BLACK LIQUOR
50% SOLIDS
DIRECT CONTACT
EVAPORATOR
BLACK
LIQUOR 70% SOLIDS
-*<
1 ^
c
n
i
WATER
i
RECOVERY
FURNACE
OXIDIZING
ZONE
REDUCTION
ZONE
4
MJ LI-UK
t *
GREEN
LIQUOR
SMELT |
Na2S + Na2CC
AIR
Figure 5-19. Typical Kraft Pulping and Recovery Process
o
Q_
Source: Reference 145.
-------
The balance of the kraft process is designed to recover the cooking chemicals and
heat. The diluted spent cooking liquor, or weak black liquor, which is 12 to 18 percent dissolved
solids, is extracted from the brownstock washers and concentrated in a multiple-effect evaporator
system to about 55 percent solids. The liquor is then further concentrated to 65 percent solids
(strong black liquor) in a direct contact evaporator (DCE) or a nondirect contact evaporator
(NDCE), depending on the configuration of the recovery furnace in which the liquor is
combusted. DCE and NDCE recovery furnace schematics are shown in Figures 5-20 and 5-21,
respectively.
In older recovery furnaces, the furnace's hot combustion gases concentrate the
black liquor in a DCE prior to combustion. NDCEs include most furnaces built since the early
1970s and modified older furnaces that have incorporated recovery systems that eliminate
conventional DCEs. These NDCEs use a concentrator rather than a DCE to concentrate the
black liquor prior to combustion. In another type of NDCE system, the multiple-effect
evaporator system is extended to replace the direct contact system.
The strong black liquor is sprayed into a recovery furnace with air control to
create both reducing and oxidizing zones within the furnace chamber. The combustion of the
organics dissolved in the black liquor provides heat for generating process steam and, more
importantly, for reducing sodium sulfate (Na2SO4) to Na2S to be reused in the cooking process.
Na2SO4, which constitutes the bulk of the particulates in the furnace flue gas, is recovered and
recycled by an ESP. After combustion, most of the inorganic chemicals present in the black
liquor collect as a molten smelt (containing sodium carbonate [Na2CO3] and Na2S) at the bottom
of the furnace, where they are continuously withdrawn into a smelt-dissolving tank. Molten smelt
in the smelt-dissolving tank is contacted with mill water or weak wash (the filtrate from lime mud
washing) to form green liquor.
In addition to straight kraft process liquor, semi-chemical pulping process spent
liquor, known as brown liquor, may also be recovered in kraft recovery furnaces. The
semi-chemical pulping process is a combination of chemical and mechanical pulping processes
5-104
-------
Electrostatic
Precipitator
Air
I \_
Recovery Boiler
Combustion Gas
60-70% Solids
Direct Contact
Evaporator
Smelt
Black Liquor
50% Solids
Figure 5-20. Direct Contact Evaporator Recovery Boiler
Source: Reference 146.
-------
—{
k
Recovery Boiler
Combustion Gas
Steam
Electrostatic
Precipitator
72% Solids
i
Indirect Contact
Evaporator
Black Liquor
50% Solids
Stack
Figure 5-21. Non-direct Contact Evaporator Recovery Boiler
Source: Reference 146.
-------
that was developed to produce high-yield chemical pulps. In the semi-chemical process, wood
chips are partially digested with cooking chemicals to weaken the bonds between the lignin and
the wood. Oversize particles are removed from the softened wood chips and the chips are
mechanically reduced to pulp by grinding them in a refiner. The most common type of
semi-chemical pulping is referred to as neutral sulfite semi-chemical (NSSC). The major
difference between the semi-chemical process and the kraft/sulfite pulping process is that the
semi-chemical digestion process is shorter and wood chips are only partially delignified. Some
semi-chemical pulp mills are, as of 1997, using chemical recovery.144 Also, as mentioned above,
some mills combine spent liquor from the on-site semi-chemical process with spent liquor from
the adjacent kraft process for chemical recovery.141
Particulate emissions from the kraft recovery furnaces consist primarily of Na2SO4
and Na2CO3, with some sodium chloride. Particulate emissions also contain lead, but only in
minute quantities because lead is found as a contaminant in process chemicals and in trace
amounts in wood. Particulate control and, therefore, lead control on recovery furnaces is
achieved with ESPs, including both wet- and dry-bottom and, to a lesser extent, with scrubbers.
Further particulate control is necessary for DCEs equipped with either a cyclonic scrubber or a
cascade evaporator because these devices are generally only 20 to 50 percent efficient for
particulates.145 Most often in these cases, an ESP is employed after the DCE for an overall
particulate control efficiency range of 85 percent to more than 99 percent. At existing mills,
auxiliary scrubbers may be added to supplement older and less efficient primary particulate control
devices. No specific data were available in the literature documenting lead control efficiencies for
ESPs and scrubbers on kraft black liquor recovery furnaces.
Emissions
Emission factors for lead from kraft recovery furnaces were developed from data
provided by the National Council for Air and Stream Improvement, an industry environmental
research organization.147'148 Kraft furnace/control configurations represented included a DCE
recovery furnace equipped with an ESP and scrubber in series, a DCE recovery furnace equipped
5-107
-------
with only an ESP, an NDCE recovery furnace equipped with an ESP and scrubber in series, and
an NDCE recovery furnace equipped with only an ESP. Emissions data were also provided for
smelt-dissolving tanks (3). Lead emission factors for kraft black liquor recovery furnaces and
smelt-dissolving tanks are presented in Table 5-29.
5.12.2 Lime Kilns
Source Location
Lime kilns are located at kraft process pulp mills. (See Table 5-28 for kraft pulp
mill source locations reported in 1993.)
Process Description
In the kraft process, green liquor from the smelt-dissolving tanks is clarified and
reacted with burnt lime (CaO) in a lime slaker. Following a series of causticizing vessels, the
resultant white liquor is clarified to yield Na2S + NaOH (aqueous white liquor) and lime mud or
calcium carbonate (CaCO3). The white liquor is recycled to the digestion process and the lime
mud is calcined in a lime kiln to regenerate CaO.146
A lime kiln is a counter current, inclined tube process heater designed to convert
lime mud (CaCO3) to CaO for reuse in the causticizing of kraft liquor. A process flow diagram
for a lime kiln is shown in Figure 5-22. The rotary kiln is the most common lime kiln design used
in the kraft pulp and paper industry. Rotary lime kilns range from 8 to 13 ft (2.4 to 4.0 m) in
diameter, and from 100 to 400 ft (30 to 120 m) in length. Lime kilns predominantly fire natural
gas, with some units firing distillate and/or residual fuel oil. Many facilities incinerate
non-condensible gases (NCG) from pulping source vents in lime kilns to control total reduced
sulfur (TRS) emissions. Temperatures in the kiln can range from 300 to 500°F (150 to 260°C) at
the upper or wet end to 2200 to 2400°F (1200 to 1300°C) at the hottest part of the calcination
zone near the lower or dry end.146'149
5-108
-------
TABLE 5-29. LEAD EMISSION FACTORS FOR KRAFT PROCESS RECOVERY FURNACES AND
SMELT DISSOLVING TANKS
SCC Number
3-07-001-04
3-07-001-10
3-07-001-05
Emission Source
Direct Contact Evaporator
Kraft Recovery Furnace
Nondirect Contact
Evaporator Kraft Recovery
Furnace
Smelt Dissolving Tank
Control Device
ESP, ESP/Wet
Scrubber
ESP, ESP/Wet
Scrubber
Demister, Venturi
Scrubber
Average Emission Emission Factor Range
Factor in lb/1 06 ton in lb/1 06 ton
(kg/106Mg)a (kg/106Mg)a
9.5x10'
(4.8x10')
1.2xl02
(5.9x10')
2.3x10'
(1.2x10')
Emission Factor
Rating
D
D
D
Source: Reference 147,148
aEmission factors are in Ib (kg) of pollutant emitted per million tons (Mg) of black liquor solids (BLS) processed.
"—" means data are not available.
ESP = Electrostatic Precipitator.
-------
Potential
Emissions
Baghouse IJ-^. . Baghouse
Vent ^ J 1
Bucket
Elevator
Conveyor
Vent To
Baghouse
Conveyor \
Figure 5-22. Process Flow Diagram for Lime Kiln
To Green
Liquor
Tank
Source: Reference 146.
-------
Emissions of concern from lime kilns include PM, largely in the form of calcium
salts; some of the PM also contains lead. Emissions of lead from lime kilns are likely due to the
lead content of the lime mud with some contribution from the combustion of fossil fuel (natural
gas or fuel oil). The most common PM control technologies used on lime kilns are scrubbers
(some ESPs are also used). Scrubbers on lime kilns use either fresh water or clean condensates
from pulping sources as a scrubbing medium. Small amounts of caustic solution may be added to
the scrubbing solution to scrub TRS & SO2. Lime kiln scrubber designs include impingement,
venturi, and cyclonic scrubbers.150
Emissions
Lead emission factors for uncontrolled and scrubber-controlled lime kilns are
presented in Table 5-30.
5.12.3 Sulfite Recovery Furnaces
Source Location
Sulfite recovery furnaces are located at sulfite process pulp mills. Table 5-31
shows the distribution of sulfite pulp mills in the United States in 1997 according to information
compiled in support of EPA's pulp and paper industry MACT standard development.
Process Description
Although not as commonplace, the acid sulfite pulp production process is similar
to the kraft process except that different chemicals are used for cooking. Sulfurous acid is used in
place of a caustic solution to dissolve wood lignin. To buffer the cooking solution, a bisulfite of
sodium, magnesium, calcium, or ammonium is used. Digestion occurs under high temperature
and pressure, as in the kraft process, in either batch mode or continuous digesters. Following
digestion and discharge of the pulp into an atmospheric blow pit or dump tank, the spent sulfite
5-111
-------
TABLE 5-30. LEAD EMISSION FACTORS FOR LIME KILNS
Average Emission Factor Emission Factor Range
in Ib/ton in Ib/ton Emission
SCC Number Emission Source Control Device (kg/Mg) (kg/Mg) Factor Rating Reference
3-07-001-06 Lime Kiln None 1.09xlQ-4
(5.44xlO-5)a
Scrubber 1.41 xlO4
(7.07x1 03)b
1.86xlO-5-1.21xlO-4 U 151
D 147,148
a Emission factors in Ib (kg) per air dry ton (Mg) of pulp produced.
b Emission factors in Ib (kg) per million tons (Mg) of calcium oxide (lime) produced.
"—" means data are not available.
-------
TABLE 5-31. DISTRIBUTION OF SULFITE PULP MILLS IN THE UNITED STATES
(1997)
State
Alaska
Florida
Maine
New York
Pennsylvania
Washington
Wisconsin
Total
Number of Mills
1
1
1
1
1
5
4
14
Source: Reference 144
liquor, known as red liquor, may be treated and discarded, incinerated, or sent through a recovery
process for recovery of heat and chemicals. Additionally, chemicals can be recovered from
gaseous streams such as those from red stock washers. The cost of the soluble bases, with the
exception of calcium, makes chemical recovery economically feasible.141'145 A simplified process
schematic of magnesium-based sulfite pulping and chemical recovery is shown in Figure 5-23.
Chemical recovery in the sulfite process involves the concentration of weak red
liquor in multiple effect evaporators and DCEs to strong red liquor (55 to 60 percent solids).
This liquor is sprayed into a furnace and burned, producing steam for mill processes. When
magnesium-base liquor is burned, magnesium oxide is recovered from the flue gas in a
multicyclone. The collected magnesium oxide is then water-slaked and used as circulation liquor
in a series of venturi scrubbers designed to absorb SO2 from the flue gas to form bisulfite solution
for use in the cook cycle.
5-113
-------
Wood
Chips Digester
Relaf
^vJ
Digester
\Y
pit/
Dump Tank
Exhaust
I ^
1 Blow
1 Pltf
Dumi
.-» Tank
rv
R
A
/- — I
Fornication
Tower
[-*-] Add
kryJ Filter
Cooking
Add
Storage
v Hot Water
i^3^
f
•y 1 Pulp Washers
-J ^
• «"i
• V_2 —
Weak
Red
Uquor
Potential POM
Emissions
ecovery Furnace/
bsorptlon Stream
Exhaust
Evaporative
J Exhaust
1 F| 1 I 1 Recovery
1 ' 1 Direct-Contact Furnace
\~7 Evaporator Exhaust
'-J32 -^
L. Absorpflon I J MgC
U I I f^-S
L ^rrJ iff- r-C
| •.. .... (j ^ My(OII
Water
Makeup
rLTHZ-"
1 — 1 ' — 1 Sulfur
^as Burner Strong
Cooler Red
Uquor "
Storage
Condensate
Screens
•m
Unbleached
Pulp
Storage
Weak Red Uquor
Mechanical , ^ Steam for
Dust Process and Power
Collector
6b '
__ || r\ (^ «
II II 1
^mP ( I
' Uquor *>
Heater
-------
Several processes for chemical recovery from sodium-base liquor are based upon
the combustion of concentrated liquor in a kraft-type recovery furnace. The resultant smelt is
similar in composition to that produced by combustion of kraft liquor. The commercial
approaches to convert sodium-base smelt chemicals into regenerated cooking liquor include
Sivola-Lurgi, Tampella, Storm, Mead, and Rayonier.152 Sulfite mills that do not practice chemical
recovery require an acid plant to fulfill total sulfite demand. This is accomplished by rotary or
spray sulfur burners equipped with heat exchangers and SO2-absorbing scrubbers.
Emissions
As with the kraft process, lead exists only as a contaminant in process chemicals
and in trace amounts in wood and is, therefore, found in minute quantities. Only one emission
factor was available in the literature for lead from an uncontrolled sulfite recovery furnace. The
lead emission factor is presented in Table 5-32.
5.13 PORTLAND CEMENT MANUFACTURING
Two processes, the wet and dry processes, can be used to manufacture Portland
cement. Based on 1990 U.S. cement kiln capacity data, an estimated 68 percent of Portland
cement is manufactured using the dry process. A description of the wet and dry processes and the
emissions resulting from the various operations is presented below.
5.13.1 Source Location
In 1990, there were a total of 212 U.S. cement kilns with a combined total clinker
capacity of Sl.lxlO6 tons (73.5xl06 Mg). Of this total, 11 kilns with a combined capacity of
2.0xl06 tons (l.SxlO6 Mg) were inactive. More than 30 raw materials are used to manufacture
Portland cement. These materials can be classified into four basic classes of raw materials:
calcarious, siliceous, argillaceous, and ferriferous. The 201 active kilns had a clinker capacity of
5-115
-------
TABLE 5-32. LEAD EMISSION FACTORS FOR SULFITE PROCESS RECOVERY FURNACES
SCC Number
Emission Source
Control Device
Average Emission Factor
inlb/106ton
(kg/106Mg)a
Emission Factor Range
inlb/106ton
(kg/106Mg)a
Emission Factor
Rating
3-07-002-22
Sulfite Recovery Furnace
None
1.70x10'
(8.5)
D
Source: Reference 147,148
""Emission factors in Ib (kg) per million tons (Mg) of red liquor solids (RLS) processed.
"—" means data are not available.
-------
79.1x106 tons (71.8xl06 Mg). The name, location, and clinker capacity of each kiln is presented
in Table 5-33.
5.13.2 Process Description
Figure 5-24 presents a basic flow diagram of the Portland cement manufacturing
process. The process can be divided into four major steps: raw material acquisition and handling,
kiln feed preparation, pyroprocessing, and finished cement grinding.
The initial step in the production of Portland cement manufacturing is raw
materials acquisition. Calcium, which is the element of highest concentration in Portland cement,
is obtained from a variety of calcareous raw materials, including limestone, chalk, marl, sea shells,
aragonite, and an impure limestone known as "natural cement rock." The other raw
materials—silicon, aluminum, and iron—are obtained from ores and minerals such as sand, shale,
clay, and iron ore. Lead is expected to be present in the ores and minerals extracted from the
earth. The only potential source of lead emissions from raw material acquisition would be due to
wind-blown particulate-containing lead from the quarry operations. Lead emissions are expected
to be negligible from these initial steps in Portland cement production.
The second step involves preparation of the raw materials for pyroprocessing
(thermal treatment). Raw material preparation includes a variety of blending and sizing
operations designed to provide a feed with appropriate chemical and physical properties. The raw
material processing differs for wet processes and dry processes. At facilities where the dry
process is used, the moisture content in the raw material, which can range from less than
1 percent to greater than 50 percent, is reduced to less than 1 percent. Lead emissions can occur
during this drying process, but are anticipated to be very low because the drying temperature is
much below the boiling point of lead. At some facilities, heat for drying is provided by the
exhaust gases from the pyroprocessor. At facilities where the wet process is used, water is added
to the raw material during the grinding step, thereby producing a pumpable slurry containing
approximately 65 percent solids.
5-117
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TABLE 5-33. PORTLAND CEMENT PRODUCTION FACILITIES
Company and location
Alamo Cement Co.
San Antonio, TX
Allentown Cement Co., Inc.
Blandon, PA
Armstrong Cement & Sup. Co.
Cabot, PA
Ash Grove Cement Co.
Nephi, UT
Louisville, NE
Durkee, OR
Foreman, AR
Montana City, MT
Chanute, KS
Inkom, ID
Blue Circle, Inc.
Ravena, NY
Atlanta, GA
Tulsa, OK
Calera, AL
Boxcrow Cement
Midlothian, TX
Calaveras Cement Co.
Redding, CA
Tehachapi, CA
California Portland Cement
Mojave, CA
Colton, CA
Rillito, AZ
No. /type of kiln
1-Dry
2-Dry
2-Wet
1-Dry
2-Dry
1-Dry
3-Wet
1-Wet
2-Wet
2-Wet
2-Wet
2-Dry
2-Dry
2-Dry
1-Dry
1-Dry
1-Wet
1-Dry
2-Dry
4-Dry
Clinker
103Mg/yr
680
844
281
544
872
454
857
254
450
191
1,390
555
544
544
907
591
386
943
680
966
capacity3
103tons/yr
750
930
310
600
961
500
945
280
496
210
1,532
612
600
600
1,000
651
425
1,039
750
1,065
Capitol Cement Corporation
Martinsburg, WV
Capitol Aggregates, Inc.
San Antonio, TX
Carlow Group
Zanesville, OH
Centex
Laramie, WY
La Salle, IL
Fernley, NV
3-Wet
1 -Dry/1 -Wet
2-Wet
1-Dry
1-Dry
2-Dry
746
456/319
547
418
372
376
822
503/352
603
461
410
415
5-118
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TABLE 5-33. PORTLAND CEMENT PRODUCTION FACILITES (CONTINUED)
Company and location
Continental Cement Co., Inc.
Hannibal, MO
Dixon-Marquette
Dixon, IL
Dragon Products Company
Thomaston, ME
Essroc Materials
Nazareth, PA
Speed, IN
Bessemer, PA
Frederick, MD
Logansport, IN
Florida Crushed Stone
Brooksville, FL
Giant Cement Company
Harleyville, SC
Gifford-Hill & Co., Inc.
Harleyville, SC
Oro Grande, CA
Riverside, CA
Glens Falls Cement Co.
Glens Falls, NY
Hawaiian Cement Company
Ewa Beach, HI
Heartland Cement Company
Independence, KS
Hercules Cement Company
Stockertown, PA
No. /type of kiln
1-Wet
4-Dry
1-Wet
1-Dry
2-Dry
1 -Dry/1 -Wet
2-Wet
2-Wet
1 -Dry
4 -Wet
1 -Dry
7 -Dry
2-Dry
1-Dry
1-Dry
4-Dry
3-Drv
Clinker
103Mg/yr
544
475
413
874
863
295/191
336
367
518
789
560
1,041
100
450
239
305
656
capacity3
103tons/yr
600
524
455
963
951
325/211
370
404
571
870
617
1,148
110
495
263
336
723
5-119
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TABLE 5-33. PORTLAND CEMENT PRODUCTION FACILITES (CONTINUED)
Company and location
Holnam, Inc.
Theodore, AL
Clarksville, MO
Holly Hill, SC
Mason City, IA
Florence, CO
Fort Collins, CO
Dundee, MI
Artesia, MS
Seattle, WA
Three Forks, MT
Ada, OK
Tijeras, NM
Saratoga, AR
Morgan, UT
Independent Cement Corp.
Catskill, NY
Hagerstown, MD
Kaiser Cement Corp.
Permanente, CA
Keystone Cement Company
Bath, PA
Kosmos Cement Co.
Louisville, KY
Pittsburgh, PA
LaFarge Corporation
New Braunfels, TX
Buffalo, IA
Demopolis, AL
Grand Chain, IL
Alphena, MI
Whitehall, PA
Sugar Creek, MO
Paulding, OH
Fredonia, KS
Lehigh Portland Cement
Mason City, IA
Leeds, AL
Cementon, NY
Union Bridge, MD
Mitchell, IN
York, PA
Waco, TX
No. /type of kiln
1-Dry
1-Wet
2-Wet
2-Dry
3-Wet
1-Dry
2-Wet
1-Wet
1-Wet
1-Wet
2-Wet
2-Dry
2-Wet
2-Wet
1-Wet
1-Dry
1-Dry
2-Wet
1-Dry
1-Wet
1-Dry
1-Dry
1-Dry
2-Dry
5-Dry
3-Dry
2-Dry
2-Wet
2-Wet
1-Dry
1-Dry
1-Wet
4-Dry
3-Dry
1-Wet
1-Wet
Clinker
103Mg/yr
1,308
1,190
991
806
780
448
880
457
429
283
544
448
335
298
464
452
1,452
546
657
357
865
778
655
1,076
1,773
689
437
445
347
689
591
506
900
689
90
73
capacity3
103tons/yr
1,442
1,312
1,092
888
860
494
970
504
473
312
600
494
369
328
512
498
1,600
602
724
394
954
858
722
1,186
1,954
760
482
490
382
760
651
558
992
760
99
81
5-120
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TABLE 5-33. PORTLAND CEMENT PRODUCTION FACILITES (CONTINUED)
Company and location
Lone Star Industries
Cape Girardeau, MO
Greencastle, IN
Oglesby, IL
Pryor, OK
Nazareth, PA
Sweetwater, TX
Medusa Cement Co.
Charlevoix, MI
Clinchfield, GA
Wampum, PA
Mitsubishi Cement Corp.
Lucerne Valley, CA
Monarch Cement Company
Humboldt, KS
Des Moines, IA
National Cement Company
Ragland, AL
Natl. Cement Co. of California
Lebec, CA
North Texas Cement
Midlothian, TX
Phoenix Cement Company
Clarkdale, AZ
Rinker Portland Cement Corp.
Miami, FL
River Cement Company
Festus, MO
RMC Lonestar
Davenport, CA
Roanoke Cement Company
Cloverdale, VA
Signal Mountain Cement Co.
Chattanooga, TN
South Dakota Cement
Rapid City, SD
No. /type of kiln
1-Dry
1-Wet
1-Dry
3-Dry
4-Dry
3-Dry
1-Dry
1 -Dry/1 -Wet
3-Dry
1-Dry
3-Dry
2-Wet
1-Dry
1-Dry
3-Wet
3-Dry
2-Wet
2-Dry
1-Dry
5-Dry
2-Wet
l-Drv/2-Wet
Clinker
103Mg/yr
1,002
649
422
623
565
449
1,237
508/187
638
1,514
611
272
767
590
816
640
512
1,070
726
1,013
408
408/287
capacity3
103tons/yr
1,104
715
465
687
623
495
1,364
560/206
703
1,669
674
300
845
650
900
705
564
1,179
800
1,117
450
450/316
5-121
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TABLE 5-33. PORTLAND CEMENT PRODUCTION FACILITES (CONTINUED)
Clinker capacity3
Company and location
Southdown, Inc.
Victorville, VA
Brooksville, FL
Knoxville, TN
Fairborn, OH
Lyons, CO
Odessa, TX
St. Mary's Peerless Cement Co.
Detroit, MI
Tarmac Florida, Inc.
Medley, FL
Texas Industries
New Braunfels, TX
Midlothian, TX
Texas-Lehigh Cement Co.
Buda, TX
Total capacity reported
Source: Reference 153
a Kilns reported as inactive in 1990:
Ash Grove Cement
California Portland Cement
Holnam, Inc.
Lone Star Industries
Medusa Cement Company
Monarch Cement Company
Tarmac Florida
No. /type of kiln 103Mg/yr
2-Dry 1,406
2-Dry 1,089
1-Dry 544
1-Dry 553
1-Dry 408
2-Dry 499
1-Wet 533
3-Wet 933
1-Dry 689
4- Wet 1,139
1-Dry 895
135-Dry/79-Wet 73,532
103tons/yr
1,550
1,200
600
610
450
550
610
1,028
759
1,256
987
81,056
Clinker capacity
1 03 Mg/year 1 03 tons/year
Foreman, AR 1 kiln 246
Rillito,
AZ 2 kilns 245
Florence, CO 2 kilns 334
Sweetwater, TX 1 kiln 150
Clinchfield, GA 1 kiln 187
Des Moines, IA 2 kilns 272
Medby,
FL 2 kilns 334
Total active capacity 71,764
271
270
368
165
206
300
368
79,108
5-122
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to
o
Od-JDCUD.-
QIS^
oaf
ri
AZ
1-0
CCCM1
Uoam-
Figure 5-24. Process Flow Diagram of Portland Cement Manufacturing Process
Source: Reference 154,155.
-------
Pyroprocessing of the raw material is carried out in the kiln, which is the heart of
the Portland cement manufacturing process. During pyroprocessing, the raw material is
transformed into clinkers, which are gray, glass-hard, spherically shaped nodules that range from
0.125 to 2.0 in. (0.32 to 5.1 cm) in diameter. The chemical reactions and physical processes that
take place during pyroprocessing include the following:
1. Evaporation of uncombined water from raw materials as material
temperature increases to 212°F (100°C).
2. Dehydration as the material temperature increases from 212°F (100°C) to
approximately 800°F (430°C) to form the oxides of silicon, aluminum, and
iron.
3. Calcination, during which carbon dioxide (CO2) is evolved between
1,650°F (900°C) and 1,800°F (982°C) to form calcium oxide.
4. Reaction of the oxides in the burning zone of the rotary kiln to form
cement clinker at temperatures of about 2,750°F (1,510°C).
The rotary kiln is a long, cylindrical, slightly inclined, refractory-lined furnace. The
raw material mix is introduced into the kiln at the elevated end, and the combustion fuels are
usually introduced into the kiln at the lower end in a countercurrent manner. The rotary motion
of the kiln transports the raw material from the elevated end to the lower end. Fuel such as coal
or natural gas, or occasionally oil, is used to provide energy for calcination. Lead is present in
coal and oil. Use of other fuels such as chipped rubber, petroleum coke, and waste solvents is
becoming increasingly popular.
Combustion of fuel during the pyroprocessing step contributes to potential lead
emissions. Lead may also be present in the waste-derived fuel mentioned above. Because lead
evaporates at 2,950°F (1,620°C), which is above normal kiln operating temperatures, much of the
lead present in the raw materials is expected to be incorporated into the clinker. Most of the lead
that is volatilized in the hot end of the kiln condenses onto PM upon cooling and is either
removed in the downstream equipment, such as the APCD, or removed in the bypass gases or the
preheater.
5-124
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Pyroprocessing can be carried out using one of five different processes: wet, semi-
dry, dry, dry with a preheater, and dry with a preheater/precalciner. These processes essentially
accomplish the same physical and chemical steps described above. The last step in the
pyroprocessing is the cooling of the clinker. This step recoups up to 30 percent of the heat input
to the kiln system, locks in desirable product qualities by freezing mineralogy, and makes it
possible to handle the cooled clinker with conventional conveying equipment. Finally, after the
cement clinker is cooled, a sequence of blending and grinding operations is carried out to
transform the clinker into finished Portland cement.
5.13.3 Emission Control Techniques
With the exception of the pyroprocessing operations, the emission sources in the
Portland cement industry can be classified as either process emissions or fugitive emissions. The
primary pollutant resulting from the fugitive sources is PM, which contains a fraction of lead. The
control measures used for these fugitive dust sources are comparable to those used throughout
the mineral products industries.
Process fugitive emission sources include materials handling and transfer, raw
milling operations in dry process facilities, and finish milling operations. Typically, particulate
emissions from these processes are captured by a ventilation system vented to fabric filters.
Because the dust from these units is returned to the process, they are considered to be process
units as well as air pollution control devices. The industry uses shaker, reverse air, and pulse jet
filters, as well as some cartridge units, but most newer facilities use pulse jet filters. For process
fugitive operations, the different systems are reported to achieve typical outlet PM loadings of
0.02 grains per actual cubic foot (gr/acf) (45 milligrams per cubic meter [mg/m3]). Because the
lead is in particle form, the performance of these systems relative to lead control is expected to be
equivalent to this overall particulate performance. However, no data are available on lead
performance of fugitive control measures.
In the pyroprocessing units, PM emissions are controlled by fabric filters (reverse
air, pulse jet, or pulse plenum) and ESPs. The reverse air fabric filters and ESPs typically used to
5-125
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control kiln exhausts are reported to achieve outlet PM loadings of 0.02 gr/acf (45 mg/m3).
Clinker cooler systems are controlled most frequently with pulse jet or pulse plenum fabric filters.
A few gravel bed filters have been used on clinker coolers.
5.13.4 Emissions
Lead emission factor data are presented in Table 5-34. The principal source of
lead emissions is expected to be from the kiln. The majority of the lead input from the raw
materials and fuels is incorporated into the clinker. Lead volatilized from the kiln is either
removed in the bypass gases, the preheater, or the APCD. Small quantities of emissions would be
expected during raw materials processing and mixing in the form of fugitive dust containing
naturally occurring quantities of lead compounds in raw materials.
Processing steps that occur after the calcining process in the kiln would be
expected to be a much smaller source of emissions than the kiln. Emissions resulting from all
processing steps include particulate matter. Additionally, emissions from the preprocessing step
include other products of fuel combustion such as sulfur dioxide (SO2), nitrogen oxides (NOX),
carbon dioxide (CO2), and carbon monoxide (CO). Carbon dioxide from the calcination of
limestone will also be present in the flue gas.
5-126
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TABLE 5-34. LEAD EMISSION FACTORS FOR PORTLAND CEMENT MANUFACTURING FACILITIES
to
Average Emission Emission Factor Range Emission
SCC Number
3-05-006-06
3-05-006-13
3-05-006-17
3-05-006-22
3-05-006-23
3-05-007-06
Emission Source
Dry Process Kilns
Dry Process Raw
Material Grinding or
Drying
Dry Process Clinker
Grinding
Dry Process Preheater
Kilns
Dry Process Preheater/
Precalcinator Kiln
Wet Process Kilns
Control Device
FF
ESP
None
None
None
FF
ESP
FF
ESP
ESP
FF
None
Factor Ib/ton (kg/Mg)
7.50xlO'5
(3.75xlO'5)a
7.10xlO-4
(3.55xlO'4)a
1.20x10-'
(6.00x1 0'2)b
4.00x1 0-2
(2.00x1 0'2)a
4.00x1 0-2
(2.00x1 0'2)b
7.50xlO'5
(3.75xlO'5)a
7.10xlO'4
(3.55xlO'4)a
7.50xlO'5
(3.75xlO'5)a
7.10xlO'4
(3.55xlO'4)a
7.10xlO-4
(3.55xlO'4)a
7.50xlO'5
(3.75xlO'5)a
l.OOxlO'1
(5.00x1 0'2)b
Ib/ton (kg/Mg) Factor Rating
D
D
U
U
U
D
D
D
D
D
D
U
Reference
155
155
23
23
23
155
155
155
155
155
155
23
-------
to
oo
TABLE 5-34. LEAD EMISSION FACTORS FOR PORTLAND CEMENT MANUFACTURING FACILITIES (CONTINUED)
sec
Number
3-05-007-17
Emission Source
Wet Process Clinker
Grinding
Control Device
None
Average Emission
Factor Ib/ton (kg/Mg)
2.00x1 0-2
(l.OOxlO-2)"
Emission Factor Range
Ib/ton (kg/Mg)
—
Emission
Factor Rating
U
Reference
23
a Emission factors are expressed in Ib (kg) of pollutant emitted per ton (Mg) of cement produced.
b Emission factors are expressed in Ib (kg) of pollutant emitted per ton (Mg) of clinker produced.
"—" means data are not available.
ESP = Electrostatic Precipitator.
FF = Fabric Filter.
-------
SECTION 6.0
EMISSIONS OF LEAD AND LEAD COMPOUNDS FROM OTHER SOURCES
6.1 PRESSED AND BLOWN GLASS
6.1.1 Source Description
The most recent estimate available for the amount of lead used in the manufacture
of glass and ceramics in the United States is from 1986. During that year, 44,960 tons
(40,800 Mg) of lead were consumed.156 Based on an average lead content of 28 percent for
leaded glasses, an estimated 160,500 tpy (145,700 Mg/yr) of leaded glass were produced.
Adding lead to glass imparts unique qualities, including the following:
• Brilliance;
• High refractive index/high dispersion without coloring;
• Economic melting temperatures, which allows a long working range
suitable to traditional methods of handworking and machining;
• High density;
• Softness, to permit cutting and decorating;
• Chemistry suitable to acid polishing; and
High durability.157
6-1
-------
Lead glass is basically composed of silica sand and lead oxide. The lead oxide content usually
ranges from 12 to 60 percent, although some types may contain as much as 92 percent lead oxide.
Lead-containing glasses are used primarily in optical glasses (such as binoculars,
microscopes, telescopes), lead crystal, and cathode ray tubes for televisions, computers, and video
game screens. Demand for lead for use in glass has remained stable over the past few years for
most applications, with the exception of cathode ray tubes, where growth in use reflects an
increased demand for video and computer terminals.158 The 1992 TRI listed pressed and blown
glass as the third largest category for lead air emissions. The 15 facilities reporting lead emissions
in the 1992 TRI are listed in Table 6-1.159
6.1.2 Process Description
The following three basic operations are performed in all leaded glass
manufacturing facilities:
• Raw material preparation;
• Melting; and
• Forming.
A generic process flow diagram for leaded glass manufacturing facilities is shown in Figure 6-1.
First, raw material, including silica sand, limestone, soda ash, and litharge (PbO)
are received separately at a production facility called a batch plant. The coarse materials are
crushed and stored in segregated bins, transferred to a weigher, and then mixed with cullet
(recycled glass) to ensure homogeneous melting. Batch weighing and mixing systems may be
operated manually or may be fully automated. In preparing the high-density components for
manufacturing leaded glass, most plants use high-intensity, rotating-barrel type mixers, which
tumble the batch upon itself in a revolving drum or double cone. The mixture is held in a batch
storage bin until it is fed to the melting furnace.
6-2
-------
TABLE 6-1. GLASS MANUFACTURERS (SIC 3229) IN THE UNITED STATES
REPORTING LEAD AND LEAD COMPOUND EMISSIONS UNDER SARA 313
Facility Location
Corning Asahi Video Products Co.a State College, PA
Corning Inc. Fall Brook Plant Corning, NY
Corning Inc. Stueben Plant Corning, NY
Corning, Inc. Danville, VA
General Electric Company Niles, OH
GTE Products Corporation Central Falls, RI
Versailles, KY
Lancaster Glass Corporation13 Lancaster, OH
Lenox Crystal, Inc. Mount Pleasant, PA
OI-NEG TV Products, Inc.3 Columbus, OH
Perrysburg, OH
Pittston, PA
Schott Glass Technologies, Inc. Duryea, PA
St. George Crystal Ltd. Jeannette, PA
Thomson Consumer Electronics3 Circleville, OH
Total
Source: Reference 159
a This source manufactures components for cathode ray tubes.
b The only glass manufacturer (SIC 3229) in the 1992 TRI that reported lead compound emissions instead of lead
emissions.
6-3
-------
en
II
o
o
&
00
I
-4—'
o
O
I
o
CD o
0>
o
o
cw
6-4
-------
Next, these raw materials are melted in a melting furnace to form glass.
Production of leaded glass requires heat to convert the raw material litharge to a homogeneous
melt that turns to a rigid glass upon cooling. Lead that has been melted at a high temperature is
introduced into the raw material, where it becomes incorporated into the glass matrix.157 The
glass furnaces are charged continuously or intermittently by means of manual or automatic
feeders. Production of low-viscosity glass—such as crystal, which requires special production
techniques—is carried out in day tanks. These tanks, usually built from refractory brick, are
typically heated rapidly by one to three pairs of oil or gas burners.161 In addition, electric
"boosting" may or may not be employed to add control over glass composition.161 In the furnace,
the mixture of materials is held in a molten state at about 2,800°F (1,540°C) until it acquires the
homogenous character of glass. It is then cooled gradually in other sections of the furnace to
about 2,200°F (1,200°C) to make it viscous enough to form.
Finally, the molten material is drawn from the furnace and worked on forming
machines by a variety of methods, including pressing, blowing, drawing, or rolling to produce the
desired product.
The end product undergoes finishing (decorating or coating) and annealing
(removing unwanted stress areas in the glass). Any damaged or undesirable glass is transferred
back to the batch plant to be used as cullet.
6.1.3 Emissions
Air emissions from leaded glass manufacturing occur in three areas: raw material
blending and transport, melting, and forming and finishing. Fugitive dust is produced by the
blending and transport process. In most cases, fabric filters are used on silos and the transport
system to confine the particulate emissions. Lead emissions from the raw material preparation
and forming and finishing operations are generally considered to be negligible.
The glass melting furnace is the principal source of lead emissions from a glass
plant. The main lead compounds found in the furnace discharges are lead carbonates from
6-5
-------
gas-heated fornaces and lead sulfates from liquid fuel-fired furnaces.162 The composition and rate
of emissions from glass melting furnaces vary considerably, depending upon the composition of
glass being produced and, to a lesser extent, upon the design and operating characteristics of the
furnace. Emissions consist primarily of products of combustion and entrained PM.
The use of fully electric furnaces is estimated to reduce lead compound emissions
by a factor of 4 to 10.162 Other methods used to control emissions include:
• Use of raw materials with a lower content of fines;
• Maintenance of free moisture of the batch at about 4 to 5 percent;
• Control of the air-to-fuel ratio;
• Reduction of air flow rate on the furnace.163
Emissions can be further reduced by lowering furnace temperature by such means
as increasing broken glass ratios, modifying batch preparation, and by increasing the amount of
electrical boosting.163
If these techniques are inadequate for meeting desired emission levels, a baghouse
provides the most effective means of controlling particulate emissions. Collection efficiencies
have exceeded 99 percent on certain types of glass furnaces. Full-scale units are operating with
filtering velocities of 1 to 2 fpm (0.5 to 1 cm/s). Precautions must be taken, however, to address
problems associated with acid gases and high temperatures. SO2 and SO3 in the furnace exhaust
may cause severe acid corrosion, and hot off-gases cause deterioration of the bag material. Bags
made of felted Nomex, silicone-treated glass fiber, and Dacron have been used effectively in these
applications.163
Wet scrubbers have proven relatively ineffective in collecting submicron-size
particulate that are characteristic of glass furnace emissions. Test of a low-pressure-drop wet
centrifugal scrubber showed an overall efficiency of only 52 percent. Higher-energy venturi
6-6
-------
scrubbers require a pressure drop of over 50 in. H20 (13 kPa) to achieve an efficiency of
approximately 97 percent.163
Tests on certain glass furnaces controlled by ESPs showed efficiencies between
80 and 90 percent.163
The composition and rate of emissions from glass melting furnaces vary
considerably, depending on the composition of glass being produced and, to a large extent, on the
design and operating characteristics of the furnace. Emissions consist primarily of products of
combustion and entrained PM.
One emission factor for uncontrolled lead emissions from leaded glass
manufacturing is presented in Table 6-2.16° Based on the type of controls currently used in the
glass manufacturing industry (baghouses, venturi scrubbers, ESPs), an overall control efficiency
of at least 90 percent is expected.
TABLE 6-2. LEAD EMISSION FACTOR FOR GLASS MANUFACTURING
Average Emission
Emission Factor in Emission
SCC Number Source Control Device Ib/ton (kg/Mg) Factor Rating
3-05-014 All processes Uncontrolled 5(2.5) B
Source: Reference 160.
6.2 LEAD-ACID BATTERY PRODUCTION
6.2.1 Source Description
Today's major use of lead is in lead-acid storage batteries. The electrical systems
of vehicles, ships, and aircraft depend on such batteries for start-up and, in some cases, batteries
provide the actual motive power. The battery industry is divided into two main production
sectors: starting, lighting, and ignition (SLI) batteries and industrial/traction batteries.
6-7
-------
The Battery Council International (BCI) reported a 1992 SLI battery production
of 81.07 million units. This total includes both original equipment market and replacement market
automotive-type batteries. Using the BCI estimate of about 18-20 Ib lead per unit, the lead
consumption for this sector was 768,600 tons. The industrial/traction (stationary/motive power)
sector was estimated to have consumed 220,500 tons of lead.50
There are 65 lead-acid battery manufacturing facilities in the United States.164'165
Table 6-3 lists these battery manufacturing facilities and their location.
6.2.2 Process Description
166
Figure 6-2 presents a flow diagram for lead-acid battery production. Lead-acid
storage batteries are produced from lead alloy ingots and lead oxide. The lead oxide may be
produced by the battery manufacturer or may be purchased from a supplier. Lead oxide is
produced either by the ball mill process or the Barton process. Both processes incorporate a
baghouse for product recovery and to control air emissions.
Battery manufacturing begins with grid casting and paste mixing. Battery grids are
manufactured by either casting or stamping operations. In the casting operation, lead alloy ingots
are charged to a melting pot; the molten lead then flows into molds that form the battery grids.
These grids may be connected in a continuous strip (concast) or cast into doublets. The stamping
operation consists of cutting or stamping the battery grids from lead sheets. The paste mixing
operation is conducted in a batch-type process to make paste for application to the grids. A
mixture of lead oxide powder, water, and sulfuric acid produces a positive paste. The negative
paste is made with the same ingredients in slightly different proportions with the addition of an
expander (generally a mixture of barium sulfate, carbon black, and organic fibers). Pasting
machines then force these pastes into the interstices of the grids to make plates. Concast plates
are then cut apart into single plates for curing in a controlled atmosphere.
6-8
-------
TABLE 6-3. LEAD-ACID BATTERY PRODUCTION FACILITIES
Company
Location3
Battery Builders Inc.
C&D Charter Power Systems, Inc.
Daniell Battery Mfg. Co.
Douglas Battery Mfg. Co.
Eagle-Picher Ind. Inc.
East Penn Manufacturing Co., Inc.
Enpak, Inc.
Exide Corp.
Hawker Energy Prods. Inc.
GMC Delco Remy Division
Naperville, IL
Leola, PA
Conyers, GA
Attica, IN
Hugeunt, NY
Baton Rouge, LA
Winston-Salem, NC
North Kansas City, MO
Socorro, NM
Lyon Station, PA
Memphis, TN
Burlington, IA
Frankfurt, IN
Laureldale, PA
Harrisburg, PA
Manchester, IA
Salina, KS
Greer, SC
Bristol, TN
Warrenburg, MO
Fitzgerald, GA
Anaheim, CA
Olathe, KS
Muncie, IN
New Brunswick, NJ
6-9
-------
TABLE 6-3. LEAD-ACID BATTERY PRODUCTION FACILITIES (CONTINUED)
Company
Location3
GNB Inc.
GNB Inc. ABD
GNB Inc. Battery Technologies Inc.
GNB Industrial Battery Co.
Industrial Battery Eng.
Interspace/Concorde Battery Corp.
Johnson Controls Battery Group, Inc.
KW Battery Co.
Power Battery Co., Inc.
Powerflow Sys. Inc.
Power Source Inc.
Ramcar Batteries Inc.
Standard Ind. Inc.
Superior Battery Mfg. Co., Inc.
City of Industry, CA
Farmers Branch, TX
Florence, MS
Kankakee, IL
Columbus, GA
Fort Smith, AR
Shreveport, LA
Dunmore, PA
Kansas City, KS
Sun Valley, CA
West Covina, CAb
Canby, OR
Holland, OH
Middletown, DE
Geneva, IL
Forton, CA
Tampa, FL
St. Joseph, MO
Winston-Salem, NC
Milwaukee, WI
Skokie, IL
Paterson, NJ
Terrell, TXb
Ooltewah, TNb
City of Commerce, CA
San Antonio, TXb
Russell Springs, KY
6-10
-------
TABLE 6-3. LEAD-ACID BATTERY PRODUCTION FACILITIES (CONTINUED)
Company Location3
Surrette America Northfield, NH
Teledyne Battery Prods. Redlands, CA
Trojan Battery Co. Santa Fe Springs, CA
Lithonia, GA
Universal Tool & Engineering Co. Indianapolis, INb
U.S. Battery Mfg. Inc. Evans, GA
U.S. Battery Mfg. Co. & Battery Corona, CAb
Voltmaster Co., Inc. Corydon, IAb
Yuasa-Exide Inc. Hays, KY
Richmond, KY
Laureldale, PA
Sumter, SC
Source: Reference 24,164,165
a These facilities reported lead emissions during 1993, unless otherwise noted. Lead emissions are in the form of
compounds, most often lead oxides. Lead emissions are not emitted to the air as elemental lead, but they are
measured as lead.
b Facility reported emissions of lead compounds.
6-11
-------
0>
o
O
6-12
-------
After the plates are cured, they are sent to the three-process operation of plate
stacking, plate burning, and element assembly into the battery case. In this operation, the doublet
plates are first cut apart and, depending on whether they are dry-charged or to be wet-formed,
they are stacked in an alternating positive and negative block formation with insulators between
them. These insulators are made of non-conductive materials such as plastic or glass fiber.
During the burning operation, leads are welded to tabs on each positive or negative plate,
fastening the assembly (element) together. An alternative to this operation is the cast-on strap
connection, where molten lead is poured around and between the plate tabs to form the
connection. Then a positive tab and negative tab are independently welded to produce an
element. The completed elements are then automatically placed into battery cases either before
formation (wet batteries) or after formation (dry batteries). A top is placed on the battery case.
The posts on the case top are welded to two individual points that connect the positive and
negative plates to the positive and negative posts, respectively.
During formation, the inactive lead oxide-sulfate paste is chemically converted into
an active electrode. Lead oxide in the positive plates is oxidized to lead peroxide; in the negative
plates it is reduced to metallic lead. The unformed plates are placed in a dilute sulfuric acid
solution. The positive plates are connected to the positive pole of a direct current (dc) source and
the negative plates are connected to the negative pole of the dc source. In the wet formation
process, the elements are assembled into the battery case before forming. After forming, the spent
acid may be dumped and fresh acid added, and a boost charge is added to complete the battery.
In the dry formation process, the individual plates may be assembled into elements first, and then
formed in large tanks of sulfuric acid or formed as individual plates. The formed elements from
either method are placed in the battery cases, the positive and negative parts of the elements are
connected to the positive and negative terminals of the battery, and the batteries are shipped dry.
Defective parts are either reclaimed at the battery plant or are sent to a secondary
lead smelter for recycling. Lead reclamation facilities at battery plants are generally pot-type
furnaces for non-oxidized lead. Approximately 1 to 4 percent of the lead processed at a typical
lead-acid battery plant is recycled through reclamation as paste or metal.
6-13
-------
6.2.3 Emissions
165,166
Lead oxide emissions result from the discharge of air used in the lead oxide
production process. Fabric filtration is generally used as part of the process control equipment to
collect particulate emissions from lead oxide facilities.
Lead and other particulate matter are generated in several operations within
storage battery production, including grid casting, lead reclamation, slitting, small parts casting,
and during the three-process operation. These particulates are usually collected by ventilation
systems and ducted through fabric filters (baghouses).
Significant emissions of lead oxide may result during the first step of the paste
mixing operation when dry ingredients are charged to the mixer. These emissions are usually
collected and ducted through a baghouse (or impingement wet scrubber). Also, during the second
step, when moisture is present in the exhaust stream from acid addition, emissions from the paste
mixer are generally collected and ducted to either an impingement scrubber or fabric filter.
Emissions from grid casting machines, lead reclamation facilities, and the three-process operation
are sometimes processed by impingement wet scrubbers, but normally through a baghouse.
Sulfuric acid mist emissions are generated during the formation operation. These
emissions are significantly higher for dry formation processes than for wet formation processes
because wet formation takes place in battery cases and dry formation is conducted in open tanks
(a practice which is decreasing within the industry). Wet formation processes usually do not
require control. Emissions of sulfuric acid mist from dry formation processes can be reduced by
more than 95 percent by the use of mist eliminators or scrubbers. Also, acid mist emissions from
dry formation are commonly controlled by the application of surface foaming agents over the acid
baths or receptacles. Other emission control practices are water sprays and good work practices
in general.
Emission reductions of 99 percent and above can be obtained when fabric filters
are used to control slitting, paste mixing, and three-process operations. The use of scrubbers to
6-14
-------
control emissions from paste mixing and grid casting operations, and at lead reclamation facilities,
can result in emissions reductions of 85 percent or better.
Many lead-acid battery manufacturing plants use central vacuum systems for
general housekeeping practices. However, these units may be subject to the New Source
Performance Standards (NSPS) for lead-acid battery manufacture as an "other lead emitting
source." The industry typically uses fabric filters to control exhaust emissions from these vacuum
systems.
Fabric filters have become an accepted method for controlling emissions from grid
casting and lead reclamation. Also, since the original NSPS development project, two new lead
control techniques have been applied to various facilities manufacturing lead-acid batteries. These
are the use of cartridge collectors as primary control devices and the use of high efficiency
particulate air (HEPA) filters for secondary collection. Specifically, cartridge collectors and
HEPA filters can be used in grid casting, paste mixing, lead oxide manufacturing, the
three-process operation, or lead reclamation.
Table 6-4 presents lead emission factors for lead-acid battery manufacturing
operations and lead oxide production. The emission factors presented include lead and its
compounds, expressed as elemental lead. Controlled emission factors expressed in terms of lead
emissions per lead processed or production were not readily available. Therefore, the appropriate
control efficiency should be applied to the uncontrolled factors. Bag filters and scrubbers are the
most commonly used controls for lead acid batteries.24 Emissions data for lead-acid battery
manufacturing facilities, including grid casting, paste mixing, lead oxide manufacturing, three-
process operation, lead reclamation, and formation are presented in the EPA document Review of
New Source Performance Standards for Lead-Acid Battery Manufacture.^65
6-15
-------
TABLE 6-4. LEAD EMISSION FACTORS FOR LEAD-ACID BATTERY PRODUCTION
SCC Number
3-04-005-05
3-04-005-06
3-04-005-07
3-04-005-08
3-04-005-09
3-04-005-10
3-04-005-11
3-04-005-12
Emission Source
Total Production
Grid Casting
Paste Mixing
Lead Oxide Mill
(Baghouse Outlet)
Three-process
Operation
Lead Reclaiming
Furnace
Small Parts Casting
Formation
Average Emission Factor Emission Factor Range
in lb/1 000 batteries in lb/1 000 batteries
Control Device (kg/1 000 batteries)3 (kg/1 000 batteries)3
None
None
Rotoclone
None
Wet Scrubber -
Medium Efficiency
FF
None
FF
None
Scrubber
None
None
—
—
6.73x1 0-2
(3.06xlO-2)
—
4.00x1 0-4
(2.00x1 0'4)b
—
—
3.77x10-'
(1.71x10-')
—
1.01x10-'
(5.05x1 0-2)b
1.00x10-'
(4.60x1 0-2)
—
1.53x10'-
(6.95 -
7.70x10-'-
(3.50x10-'-
6.10xlO-2-
(2.77x1 0-2-
1.10-
(5.00x10
-
1.10x10-'-
(5.00x1 0-2-
1.06x10'-
(4.82 -
2.40x10-'-
(1.09x10-'-
7.70x10
(3.50x10-'-
6.40x1 0-2 -
(3. 20x1 0-2-
-
-
1.77x10'
8.05)
9.00x10-'
4.09x10-')
8.00x1 0-2
3.64xlO'2)
2.49
-'-1.13)
-
1.20x10-'
5.50x1 0-2)
1.46x10'
6.64)
4.59x10-'
2.09x10-')
-'-1.38
6.27x10-')
1.42x10-'
7.10xlO-2)b
-
-
Emission
Factor
Rating
U
B
U
B
U
C
B
U
B
U
C
Reference
166
166
92
166
22
166
166
92
166
168
166
166
a Emission factors are expressed in Ib (kg) of lead emitted per 1000 batteries produced, except where noted.
b Emission factors are expressed in Ib (kg) of lead emitted per ton (Mg) of lead produced.
"—" means data are not available.
-------
6.3 LEAD OXIDES IN PIGMENTS
Lead oxide is used primarily in the manufacture of lead-acid storage batteries (see
Section 6.2). It is also useful as a pigment in paints and ceramic glazes. The principal oxides of
lead include litharge, lead dioxide, and red lead. Black oxide, the most widely used form of lead
oxide, consists of a mixture of litharge and finely divided metallic lead. Red lead is a major lead
pigment. Other lead pigments include white lead, lead chromates, and leaded zinc oxides. Total
lead oxide production in the United States in 1995 was 68,013 tons, excluding lead oxide used in
batteries (61,700 Mg).167
6.3.1 Source Location
The distribution of facilities manufacturing lead oxides in lead pigments in the
United States is presented in Table 6-5.
6.3.2 Process Description
Lead Oxides
Lead Monoxide-Most lead oxides and many of the major lead pigments are
derived from lead monoxide, in a form called litharge. There are four principal processes for
producing high-grade litharge:
• Metallic lead is partially oxidized and milled to a powder, which is charged
into a reverberatory furnace at about 1,100°F (590°C) to complete the
oxidation to ordinary "chemical litharge;"
• Pig lead is oxidized and stirred in a reverberatory furnace or rotary kiln to
form lead monoxide;
• Molten lead is run into a cupelling furnace held at about 1,800°F
(1,020°C), and molten litharge is produced; and
• Molten lead at about 950°F (510°C) is atomized into a flame where it
burns vigorously, producing "sublimed" or "fumed" litharge.
6-17
-------
TABLE 6-5. U.S. FACILITIES MANUFACTURING LEAD OXIDES IN PIGMENTS
Lead Oxides
Lead Monoxide
Admiral Chemical Co.
ASARCO Incorporated
Eagle-Picher Industries, Inc., Electronics Division,
Chemicals Department
Great Western Inorganics
Hammond Lead Products, Inc.
Johnson Matthey, Inc., Aesar/Alfa
Micron Metals, Inc., Atlantic Equipment Engineers Division
Oxide & Chemical Corporation
Pacific Dunlap
Quenell Enterprises, Inc., Daelco Division
Lead Dioxide
Aithaca Chemical Corporation
Eagle-Picher Industries, Inc., Electronics Division,
Chemicals Department
Hammond Croton, Inc.
PSI Chemicals Division, Pluess & Staufer International, Inc.
Spectrum Chemical Manufacturing Corporation
Lead Pigments
Red Lead
Hammond Lead Products, Inc.
Oxide & Chemical Corporation
Spectrum Chemical Manufacturing Company
Robert I. Webber Co., Inc.
White Lead
Hammond Lead Products, Inc., Halstab Division
National Chemical Co., Inc.
Peabody, Massachussetts
Denver, Colorado
Joplin, Missouri
Golden, Colorado
Hammond, Indiana
Pottstown, Pennsylvania
Wardhill, Massachusetts
Bergenfield, New Jersey
Brazil, Indiana
Lancaster, Ohio
Columbus, Georgia
City of Commerce, California
Uniondale, New York
Joplin, Missouri
South Plainfield, New Jersey
Stamford, Connecticut
Gardena, California
Hammond, Indiana
Pottstown, Pennsylvania
Brazil, Indiana
Gardena, California
City of Commerce, California
Stamford, Connecticut
Hammond, Indiana
Chicago, Illinois
6-18
-------
TABLE 6-5. U.S. FACILITES MANUFACTURING LEAD OXIDES IN PIGMENTS
(CONTINUED)
Lead Chromate
Althaea Chemical Corporation
ALL-Chemic, Ltd.
Cookson Pigments, Inc.
Engelhard Corporation, Pigments and Additives Division
Kikuchi Color & Chemicals Corp. U.S.A.
Mineral Pigments Corporation, Chemical Color Division
National Chemical Co., Inc.
Spectrum Chemical Manufacturing Company
Wayne Pigment Corporation
Lead Antimonate Yellow Pyrochlore
Ferro Corporation, Coatings, Colors & Electronic Materials
Group, Color Division
Uniondale, New York
Fort Lee, New Jersey
Newark, New Jersey
Louisville, Kentucky
Paterson, New Jersey
Beltsville, Maryland
Chicago, Illinois
Gardena, California
Milwaukee, Wisconsin
Cleveland, Ohio
Source: References 169,170,171
6-19
-------
In all cases, the product must be cooled quickly to below 570°F (300°C) to avoid formation of
red lead.163
Black Oxides-Black oxide typically contains 60 to 80 percent litharge and 20 to
40 percent finely divided metallic lead. It is used exclusively in the manufacture of lead-acid
storage batteries, specifically in the production of battery paste. It is usually produced by the
Barton process, but is also produced by the ball mill process. In both processes, a baghouse is
used for product recovery.
The Barton process is shown in Figure 6-3. Lead ingots are first melted and then
fed into a vessel or pot, where the molten lead is rapidly stirred and atomized into small droplets.
The droplets of molten lead are then oxidized by air drawn through the pot and conveyed to a
product recovery system, which typically consists of a settling chamber, cyclone, and baghouse.
In the ball mill process, shown in Figure 6-4, lead pigs or ingots are charged with
air into a ball mill. Oxidation is initiated by the heat generated by the tumbling lead ingots.
During milling, the lead oxide that forms on the surface of the ingots and fine particles of
unoxidized lead are broken off, forming a fine dust that is removed from the mill by a circulating
air stream. Air flow through the mill, the temperature of the charge, and the weight of the charge
are controlled to produce a specified ratio of lead oxide to finely divided metallic lead.
Centrifugal mills and/or cyclones are used to collect large particles, while the finer particles are
collected in a baghouse.
Lead Dioxide-Lead dioxide is a vigorous oxidizing agent used in a number of
chemical process industries. It decomposes to lower oxides rather easily, releasing oxygen. It is
commercially produced either by the treatment of an alkaline red lead slurry with chlorine, or by
anodic oxidation of solutions of lead salts. The amount of lead dioxide produced is insignificant
and of little commercial importance.163
6-20
-------
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6-22
-------
Lead Pigments
Red Lead—Red lead, also called minium, is used principally in ferrous metal
protective paints. The manufacture of red lead begins by charging litharge into a reverberatory
furnace held at 900 to 950°F (480 to 510°C). The litharge is oxidized until a specified amount of
lead monoxide is converted to Pb3O4. A typical red lead manufacturing plant will produce 30 tons
(27 Mg) of red lead per day.
White Lead—The commercial varieties of white lead include basic carbonate white
lead, basic sulfate white lead, and basic lead silicate. Manufacture of basic carbonate white lead is
based on the reaction of litharge with acetic acid. The product of this reaction is then reacted
with carbon dioxide to form lead carbonate, which is contained in a slurry and recovered by wet
filtration and drying. Other white leads are made either by a chemical or a fuming process. The
chemical process is like that described above except that other mineral dioxides are used in place
of carbon dioxide. The fuming process differs in that the product is collected in a baghouse rather
than by wet slurry filtration and drying.
Lead Chromate—Chromate pigments are generally manufactured by precipitation
or calcination. A commonly used process is the reaction of lead nitrate solution with sodium
chromate solution:
Pb(NO3)2 + Na2 (CrO4) = PbCrO4 + 2NaNO3
The lead nitrate solution can be made using either lead monoxide or by reacting molten lead with
nitric acid.
Leaded Zinc Oxides—Leaded zinc oxides are used almost entirely as white
pigments for exterior oil-base paints. Leaded zinc oxides are produced either by smelting and
cofuming combinations of zinc and lead sulfide ores or by mechanically blending separately
6-23
-------
prepared fractions of zinc oxide and basic lead sulfate. The first process involves heating the two
materials to produce a fume, which is cooled and collected in a baghouse.
6.3.3 Emissions
Lead Oxides
Exhaust gas characteristics typical of those associated with the manufacture of
litharge and black oxide, using the ball mill and Barton processes, are summarized in Table 6-6.
Based on an average lead emission rate of 0.44 Ib/ton (0.22 g/kg) product and consumption of
65,600 tons (59,600 Mg) of lead for other oxides, an estimated 14 tons (13 Mg) of lead was
emitted into the atmosphere by lead oxide production facilities (other than storage battery
production) in 1991.172
Lead Pigments
Red Lead—Collection of dust and fume emissions from the production of red lead
is an economic necessity. Consequently, particulate emissions are minimal. Particulate emissions
after a baghouse have been measured at 1.0 Ib/ton (0.5 g/kg) product.163 Only lead monoxide and
oxygen go into the production of red lead, so most of the particulate emissions can be assumed to
be lead.
Data on emissions from the production of white lead pigments, leaded zinc oxides,
and chrome pigments are not available.
Baghouses, usually preceded by dry cyclones or settling chambers, are the
universal choice for the recovery of lead oxides and most pigments. The baghouses used are
generally mechanical shaker types, and are operated at air-to-cloth ratios ranging from 1 to 3 fpm
(0.5 to 1.5 cm/s). Other types, including pulse jet units, have also been used. Dry cyclones
and/or settling chambers are usually installed upstream of the baghouse to capture larger particles
and provide cooling. Performance data on several baghouse installations servicing lead oxide
6-24
-------
TABLE 6-6. CHARACTERISTICS OF UNCONTROLLED EXHAUST GAS FROM LEAD
OXIDE BALL MILL AND BARTON POT PROCESSES
Parameters English Units Standard International Units
Gas flow rate 2,300 acfm/tph Pb charged 1.2 rrrVs.Mg.h"l Pb charged
Temperature 250°F 120°C
Grain loading 3 to 5 gr/scf 7 to 11 g/m3
Particle size distribution, 0 to 1 jam - 4% 4%
wt% 1 to 2 nm-11% 11%
2 to 3 urn - 23% 23%
Lead emission factor3 0.44 Ib/ton product 0.22 g/kg product
Source: Reference 173
a Emissions are after a baghouse, which is considered process equipment.
production facilities are presented in Table 6-7. Collection efficiencies in excess of 99 percent are
generally considered achievable.
Lead emission factors found in the literature for the manufacture of lead oxides
and lead pigments are presented in Table 6-8. The emission factors for lead oxide production
were assigned an E rating because of high variabilities in test run results and nonisokinetic
sampling.
6.4 LEAD CABLE COATING
6.4.1 Source Description
About 90 percent of the lead cable covering produced in the United States is on
lead-cured jacketed cables and 10 percent is on lead-sheathed cables.174 Approximately
7,000 tons of lead were consumed for lead cable sheathing production in 1996.175 Today, lead
sheathing is only being used on power cables with voltage levels generally greater than 10 kV.
6-25
-------
TABLE 6-7. PERFORMANCE TEST RESULTS ON BAGHOUSES SERVING LEAD
OXIDE FACILITIES
Barton Pot
Hammermill Furnace Hammermill Furnace
Control system
Settling chamber/
cyclone/baghouse
Cyclone/baghouse Cyclone/baghouse
Test point
Particulate emissions:
Lead
Source:
gr/dscf
g/m3
Ib/ton product
gr/kg product
emissions:
gr/dscf
g/m3
Ib/ton product
gr/kg product
Reference 173
Outlet
0.032 - 0.056
0.074-0.13
0.41 -0.85
0.21 -0.43
0.024 - 0.046
0.055-0.11
0.30 - 0.69
0.15 -0.35
Outlet
0.012
0.028
0.057
0.028
0.008
0.018
0.042
0.021
Inlet
32.9
75.7
30.3
69.7
6-26
-------
TABLE 6-8. LEAD EMISSION FACTORS FOR MANUFACTURE OF LEAD OXIDE IN
PIGMENTS
SCC Number Emission Source
Lead Oxide Production
3-01-035-06 Barton pot
3-01-035-07 Calciner
Pigment Production
3-01-035-10 Red Lead
3-01-035-15 White Lead
3-01-035-20 LeadChromate
Control
Device
None
None
Baghouse
None
None
None
Average Emission
Factor in Ib/ton
(kg/Mg)a
4.40X10-1
(2.20X10-1)
1.40X101
(7.0)
5.00xlQ-2
(2.50xlO-2)
9.00X10-1
(4.50X10-1)
5.50X10-1
(2.75X10-1)
l.SOxlO-1
(6.50xlO-2)
Emission
Factor Rating
E
E
E
B
B
B
Source: Reference 12
a Emission factors are expressed in Ib (kg) of pollutant emitted per ton (Mg) of oxide/pigment produced.
6.4.2
Process Description
The manufacture of cured jacketed cables involves a stripping/remelt operation
because an unalloyed lead cover that is applied in the vulcanizing treatment during the
manufacture of rubber-insulated cable must be stripped from the cable and remelted. Lead
coverings are applied to insulated cable by hydraulic or screw-type presses. Molten lead is
continuously fed into the press, where it solidifies as it is extruded onto a cable.174 Continuous
extruders are the most prevalent means of producing lead-sheathed power cable. Continuous
extruders have largely replaced the ramp-press equipment widely used prior to 1950.176
6-27
-------
Extrusion rates for typical presses are 3,000 to 15,000 Ib/hr (1.3 to 6.8 Mg/hr). A
lead melting kettle supplies lead to the press, which is heated either electrically or with a
combustion-type burner.
6.4.3 Emissions
The melting kettle is the only source of atmospheric lead emissions in lead
sheathing production. Fumes from these kettles are exhausted to the atmosphere. Table 6-9
presents uncontrolled lead emission factors for cable covering.
Cable sheath reliability and quality relate directly to the oxide content of the
sheath. Because of lead density, flotation of lead oxides from the melting and holding kettles used
to feed the extruder is possible. To minimize introduction of oxygen into the lead bath, modern
melting pots use pneumatically operated lids and splash prevention devices on the ingot loading
mechanism.176
Further control is provided by controlling the height of the overflow channel from
the melting pot to the holding pot by properly spacing the baffles to prevent oxide movement
along the direction of metal flow and bottom tapping of the holding pot.176
Emissions data from facilities with any type of emission controls are scarce or
unavailable. Also, the percentage of facilities having any type of controls in place is unknown.
Cable covering processes do not usually include particulate collection devices.
However, fabric filters, scrubbers, or cyclones can be installed to reduce lead emissions at
different control efficiency levels. Process modifications to minimize emissions include lowering
and controlling the melt temperature, enclosing the melting unit, and using fluxes to provide a
cover on the melt.
6-28
-------
TABLE 6-9. LEAD EMISSION FACTOR FOR LEAD CABLE COATING
SCC Number
3-04-040-01
Process/Emission
Source
Cable Covering
Control
Device
None
Average Emission Factor
Ib/ton (kg/Mg)a
S.OOxlQ-1
(2.50X10-1)
Emission Factor Range
Ib/ton (kg/Mg)a
—
Emission Factor
Rating
C
Source: Reference 57,174
a Emission factors are expressed in Ib (kg) of lead emitted per ton (Mg) lead processed.
"—" means data are not available.
to
-------
6.5 FRIT MANUFACTURING
Frit is a homogeneous melted mixture of inorganic materials that is used in
enameling iron and steel and in glazing porcelain and pottery. Frit renders soluble and hazardous
compounds (such as lead) inert by combining them with silica and other oxides. Frit also is used
in bonding grinding wheels, to lower vitrification temperatures, and as a lubricant in steel casting
and metal extrusion.177
6.5.1 Process Description
Frit is prepared by fusing a variety of minerals in a furnace and then rapidly
quenching the molten material. The constituents of the feed material depend on whether the frit is
to be used as a ground coat or as a cover coat. For cover coats, the primary constituents of the
raw material charge include silica, fluorspar, soda ash, borax, feldspar, zircon, aluminum oxide,
lithium carbonate, magnesium carbonate, and titanium oxide. The constituents of the charge for a
ground coat include the same compounds plus smaller amounts of metal oxides such as cobalt
oxide, nickel oxide, copper oxide, and manganese oxide.177
To begin the process, raw materials are shipped to the manufacturing facility by
truck or rail and are stored in bins. Next, the raw materials are carefully weighed in the correct
proportions. The raw batch is then dry mixed and transferred to a hopper prior to being fed into
the smelting furnace. Although pot furnaces, hearth furnaces, and rotary furnaces have been used
to produce frit in batch operations, most frit is now produced in continuous smelting furnaces.
Depending on the application, frit smelting furnaces operate at temperatures of 1700° to 2700°F
(930° to 1480°C). If a continuous furnace is used, the mixed charge is fed by screw conveyor
directly into the furnace. Continuous furnaces operate at temperatures of 2000° to 2600°F
(1090° to 1430°C). When smelting is complete, the molten material is passed between
water-cooled metal rollers that limit the thickness of the material, and then it is quenched with a
water spray that shatters the material into small glass particles called frit.177
6-30
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After quenching, the frit is milled by either wet or dry grinding. If the latter, the
frit is dried before grinding. Frit produced in continuous furnaces generally can be ground
without drying, and it is sometimes packaged for shipping without further processing. Wet
milling of frit is no longer common. However, if the frit is wet-milled, it can be charged directly
to the grinding mill without drying. Rotary dryers are the devices most commonly used for drying
frit. Drying tables and stationary dryers also have been used. After drying, magnetic separation
may be used to remove iron-bearing material. The frit is finely ground in a ball mill, into which
clays and other electrolytes may be added, and then the product is screened and stored. The frit
product then is transported to on-site ceramic manufacturing processes or is prepared for
shipping. In recent years, the electrostatic deposition spray method has become the preferred
method of applying frit glaze to surfaces. Frit that is to be applied in that manner is mixed during
the grinding step with an organic silicon encapsulating agent, rather than with clay and
electrolytes. Glaze application to ceramics is discussed in more detail in Section 6.6. Figure 6-5
presents a process flow diagram for frit manufacturing.177
6.5.2 Emissions
When frit containing lead oxides is being manufactured, lead emissions are created
by the frit smelting operation in the form of dust and fumes. These emissions consist primarily of
condensed lead oxide fumes that have volatilized from the molten charge.177
Lead emissions from the furnace can be minimized by careful control of the rate
and duration of raw material heating, to prevent volatilization of the more fusible charge
materials. Lead emissions from rotary furnaces also can be reduced with careful control of the
rotation speed, to prevent excessive dust carryover. Venturi scrubbers and fabric filters are the
devices most commonly used to control emissions from frit smelting furnaces, and fabric filters
are commonly used to control emissions from grinding operations. No information is available on
the type of emission controls used on quenching, drying, and materials handling and transfer
operations.177 Also, no lead emission factors for frit manufacturing were identified.
6-31
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CLAYS, OTHER
ELECTROLYTES
WET
MILLING
(GRINDING)
PACKAGING
RAW MATERIALS
STORAGE
1
WEIGHING
(SCC 3-05-013-02)
CD
JL
©
J.
(7) PM EMISSIONS
(2) GASEOUS EMISSIONS
MIXING
(SCC 3-05-013-03)
FURNACE
CHARGING
(SCC 3-05-013-04)
SMELTING FURNACE
(SCC 3-05-014-05,-06)
QUENCHING
(SCC 3-05-013-10)
TO CERAMIC
MANUFACTURING
PROCESS
(1)
(I)
(T)©
M
11
DRYING
(SCC 3-05-013-11)
,
DRY MILLING
(GRINDING)
(SCC 3-05-013-15)
i
SCREENING
(SCC 3-05-013-16)
) |
CLA^
^ ELECT
ENC
©
J.
AGENT
Figure 6-5. Process Flow Diagram for Frit Manufacturing
6-32
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6.6 CERAMICS AND GLAZES
Glazes are applied to clay-based ceramic products to provide a shiny, generally
smooth surface and to seal the clay.178 Adding lead to glazes dramatically improves their chemical
durability and heightens color, helping them to withstand detergent attack. Lead gives a smooth,
durable hygienic surface that resists scratching. Lead also allows the glaze to be melted and
fluxed easily. Lead increases the strength of the bond between glaze and substrate.179
Basic carbonate white lead [2PbCO3»Pb(OH)2] has been the preferred leaded glaze
used in ceramic manufacture for hundreds of years. White lead has varied applications in
whiteware glazes, particularly for fine china and commercial artware. White lead has a small
particle size and lower particle density, making it capable of suspending a glaze without the
presence of clays or organic binders. However, white lead and other lead oxides are more soluble
than other forms of lead, and because the lead leaches out over time, they are being phased out by
the ceramic industry.14
The ceramics industry is addressing this solubility problem by adding lead to glaze
in frit form. The frit is a ground mixture of two or more compounds. For example, lead
monosilcate (PbO0.67SiO2), which is considered one of the most economical methods for
introducing lead into a glaze, contains 85 percent PbO and 15 percent SiO2. The frit form
desolubilizes and detoxifies the lead compounds. The frit also allows the glazes to be fired at
lower temperatures and creates a more uniform glaze. The fritted glaze usually includes clay or
organic binders, which ensure that the glaze adheres to the ceramic and does not dust off prior to
firing.14 Frits are usually manufactured by frit manufacturers rather than ceramic manufacturers.
(See Section 6.3 for a list of frit manufacturers.)
Since the 1970s, attention has been focused on the use of lead glazes in china
dishes and the tendency for lead from the glaze to leach into food. This tendency toward
leachability depends upon several factors, including glaze composition, firing conditions, pH
(e.g., orange, tomato juices, vinegar), temperature, and physical state of food (liquid, moist),
duration of food contact.
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The following presents a brief history of the regulatory drivers influencing lead
reduction in ceramics. The U.S. Food and Drug Administration (FDA) set informal guidelines in
1971 for levels of lead leaching from ceramic products. These levels were tightened in 1979.
They are now being further reduced because new information shows that lead can pose health
hazards. The guideline levels for lead leaching from ceramic waste are being reduced as follows:
• From 7.0 to 3.0 ppm for plates, saucers, and other flatware;
• From 5.0 to 2.0 ppm for small hollowware, such as cereal bowls (but not
cups and mugs);
• From 5.0 to 0.5 ppm, for cups and mugs;
• From 2.5 to 1.0 ppm for large (greater than 1.1 liters) hollowware such as
bowls (but not pitchers).180
These guideline levels for ceramics are expected to reduce lead emissions from
ceramic manufacturers. However, the leaded glaze content of certain non-food ceramic products
(such as tiles) is not expected to be affected. A list of ceramicware manufacturers in the United
States is presented in Table 6-10; a list of ceramic tile manufacturers in the United States is
presented in Table 6-11.
In addition to lead in ceramic glazes, metal cookware is often enameled because of
the heat resistance, ease of cleaning, permanent color, and corrosion resistance of enamel.
Typical enamel compositions for aluminum cookware contain 35 to 42 percent lead monoxide.14
A list of manufacturers of enamels for stove and range use is presented in Table 6-12.
A breakout of U.S. consumption of lead specific to ceramic products is not
available. However, total consumption of lead oxides in glass and ceramic products and paint was
estimated at 59 tons (53 Mg) in 1992.50
6-34
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TABLE 6-10. MANUFACTURERS OF CERAMICWARE
Facility
Location
Bennington Potters, Inc
Buffalo China, Inc.3
Burden China Co., Inc.
Ebaz Systems, Inc.
Frankoma Pottery3
Haeger Potteries, Inc.3
Homer Laughlin China Co.
Innovative Ceramic Corporation
Kingwood Ceramic, Inc.
Lenox Inc.b
Mayer China Co.
Nelson McCoy Ceramic Co.
Pewabic Pottery
Sterling China Co.c
Syracuse China Corporation
Bennington, VT
Buffalo, NY
El Monte, CA
Williamsburg, VA
Sapulpa, OK
Dundee, IL
Newell, WV
East Liverpool, OH
East Palestine, OH
Pomona, NJ
Kinston, NC
Beaver Falls, PA
Roseville, OH
Detroit, MI
Wellsville, OH
Syracuse, NY
Source: Reference 181
a Listed in the 1992 TRI under SIC code 3269
b Listed in the 1992 TRI under SIC code 3262
c Listed in the 1992 TRI without an SIC code.
(Pottery Products, NEC). Source Reference 159
(Vitreous China Table & Kitchenware). Source Reference 159.
Source Reference 159.
6-35
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Facility
TABLE 6-11. DECORATIVE CERAMIC TILE MANUFACTURERS
Location
Acme Brick Co.
American Clean Tile Co., Inc.a/Dal-Tile
Corporation13
Dai-Tile Corporation
Florida Tileb
Monarch Tileb
American Marazzib
Bennington Potters, Inc.
Lone Star Ceramics Co.
Mannington Ceramic Tile, Inc.
Metropolitan Ceramics, Inc.
Pewabic Pottery
Stark Ceramics, Inc.c
Winburn Tile Manufacturing Co.
Fort Worth, TX
Lansdale, PA
Dallas Texas
Lakeland, FL
Florence, AL
Sunnyvale, TX
Bennington, VT
Dallas, TX
Lexington, NC
Canton, OH
Detroit, MI
East Canton, OH
Little Rock, AR
Source: Reference 181.
a Listed in the 1992 TRI under SIC code 3253 (Ceramic Wall and Floor Tile) with reported lead compound
emissions of 2 Ib/yr. Source Reference 159.
b Source: Reference 184
c Listed in the 1992 TRI under SIC code 3251 (Brick and Structural Clay Tile). Source Reference 159.
6-36
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TABLE 6-12. MANUFACTURERS OF ENAMELS FOR STOVE AND RANGE USE
Facility Location
A.O. Smith, Protective Coatings Division Florence, KY
Randolph Products Co. Carlstadt, NJ
Schenectady Chemicals Schenectady, NY
Ferro Corporation, Frit Division Cleveland, OH
Chit-Vit Corporation Urbana, OH
Sterling Group Sewickley, PA
Source: Reference 183
6.6.1 Process Description
Prior to glaze application, the frit and other glaze materials are ground in a ball mill
until they reach a particular size distribution that will permit uniform application, but not so fine
that the lead exceeds solubility standards.14
Leaded glaze is applied to ceramics either by spraying or dipping.178 Spraying is
probably the most common method of glaze application in the ceramic industry. Various types of
automatic glaze sprayers have been developed. These sprayers may be circular or a straight
conveyor line. They are generally capable of rotating the ware and have multiple spray guns,
which can be oriented according to the item being sprayed, allowing even application of glaze
thickness.14
Dipping is an older process for glaze application, and is generally used only on
shapes that are not conducive to spraying. Flat surfaces (such as wall tile) can be glazed using a
waterfall technique—passing the tiles under a thin falling sheet of glaze.14
6-37
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6.6.2 Emissions
When leaded glazes are used, lead is emitted during the glaze spraying phase. One
uncontrolled emission factor for lead measured from a spray booth stack during ceramic glaze
spraying is presented in Table 6-13. The glaze being used during this test contained 28.3 weight
percent lead monosilicate. The test was conducted using combined EPA Methods 5 and 12
sampling trains.184 Although no lead emission factors were identified for other steps in the
ceramic process, lead emissions can also occur during the firing of glazes.185 Two emission
control options frequently used at ceramic kilns are (1) the limestone gravel-bed filter, and (2) dry
scrubbing.185
Because of the special properties that lead imparts to ceramic glazes, it will
continue to be used in the ceramic industry. However, work is continuing in the United States to
identify ways to lower the lead solubilities of commercial ceramic frits.14
6.6.3 Piezoelectric Ceramics
Lead-based ceramics are reported to be "critically important" to the electronics
industry. These are piezoelectric materials, which are used to convert mechanical to electrical
energy. Currently, the most widely used piezoelectric ceramic is lead zirconate titanate (PZT).
Some of the applications for piezoelectric ceramics include igniters for gas appliances, cigarette
lighters, remote control of appliances, tone generators, and electronic displays. These ceramics
contain 60 to 64 percent lead (65 to 69 percent lead oxide).14 Multilayer ceramic capacitors are
becoming more widely used in electronic circuits, especially with the trend toward miniaturization
and surface-mount technology.186 A list of PZT manufacturers as well as manufacturers using
PZT in electronic applications is presented in Table 6-14.
6-38
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TABLE 6-13. LEAD EMISSION FACTOR FOR CERAMIC/GLAZE APPLICATION
Average Emission Factor in Emission Factor
SCC Number Emission Source Control Device Ib/ton (kg/Mg)a Rating
3-09-060-01 Ceramic Glaze Spraying - None 3.0 B
Spray Booth (1.5)
Source: Reference 184
a Emission factors are expressed in Ib (kg) of pollutant emitted per ton (Mg) of ceramic glaze applied.
-------
TABLE 6-14. MANUFACTURERS OF LEAD ZIRCONATE TITANATE (PZT) AND
MANUFACTURERS OF PIEZOELECTRONICS
Facility
Location
American Piezo Ceramics, Inc.
Bullen Ultrasonics, Inc.
Cerac Inc.
Channel Products, Inc.
Channel Technologies, Inc.
Edo Corp., Electro Ceramic Division3
Enprotech Corporation
Hoechst CeramTec North America, Inc.
International Transducer, Inc.
Materials Research & Analysis (MRA)
Laboratories, Inc.
Motorola, Inc. Ceramics Products3
NTK Technical Ceramics
Piezo Kinetics, Inc.
Radio Materials Corporation
Tarn Ceramics, Inc.
Ultran Labs, Inc.
Ultrasonic Powders, Inc.
Vernitron Corp., Piezoelectric Division
Mackeyville, PA
Eaton, OH
Milwaukee, WI
Chesterland, OH
Santa Barbara, CA
Salt Lake City, UT
Pittsburgh, PA
Mansfield, MA
Santa Barbara, CA
North Adams, MA
Albuquerque, NM
Springfield, NJ
Mesa, AZ
Bellefonte, PA
Attica, IN
Niagara Falls, NY
State College, PA
South Plainfield, NJ
Cleveland, OH
Source: Reference 181
a Listed in the 1992 TRI under SIC code 3679 (Electronic Components, NEC). Source: Reference 159.
6-40
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Process Description
The process for manufacturing a multilayer ceramic capacitor (MLCC) is shown in
Figure 6-6. The process begins with casting a ceramic film on a removable substrate, such as a
plastic film. When the film is dry, it is punched into squares, and multiple internal electrode
patterns are screened onto it. These films are then stacked and laminated by applying heat and
pressure to form a green MLCC bar. This bar is cut into individual MLCC chips and then fired.
End termination electrodes are applied by dip-coating both ends of the chip and firing at 1472°F
(800°C) to connect the internal electrodes.186
Emissions
Lead emissions are expected to occur during PZT manufacture, handling of raw
materials, casting, and ceramic firing. Because these PZT ceramics require no glazing, lead
emissions are expected to be much lower than those from manufacture of ceramics and decorative
tiles. No lead emission factors were identified for PZT ceramic manufacturers.
6.7 MISCELLANEOUS LEAD PRODUCTS
The following categories (in decreasing order of lead usage) are the most
significant sources of lead emissions in the miscellaneous lead products group: ammunition, type
metal, and other metallic lead products (including bearing metals, and pipe and sheet lead). Since
1992, U.S. can manufacturers no longer use lead solder. Also, the EPA has recently proposed a
regulation under the Toxic Substances Control Act to prohibit the manufacture of lead-containing
fishing sinkers.187 Therefore, neither can solder nor fishing sinkers are included as miscellaneous
lead products in this section. Also, information on abrasive grain processing is included in this
section. Available information indicates that this process is likely to emit metals (including lead)
as constituents of the feed material.
6-41
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Raw materials
1 Mixing
Calcination
Powder and water
Ceramic binder
Electrode ink
Electrode ink ,
Slurry
'Casting
A.
Printing and laminating
/Cutting
Firing
External electrode
Slurry
Plastic carrier film
Dipped T Lead attachment
HK and resin coating
Lead wire resin
Resin
(inspection : Inspection
t
Chip
Internal electrode
a:
o
Lead wire
Figure 6-6. Multilayer Ceramic Capacitor Manufacturing Process
6-42
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6.7.1 Ammunition
Lead is consumed and emitted in the manufacture of ammunition. Approximately
58,000 tons of lead were consumed for ammunition production in 1996.175 Lead used in the
manufacture of ammunition is processed by melting and alloying before it is cast, sheared,
extruded, swaged, or mechanically worked in the production of lead shot or lead-filled
ammunition. Some lead is also reacted to form lead azide or lead styphnate, a detonating agent.
Emissions
A lead emission factor for ammunition production is presented in Table 6-15. The
emission factor represents a manufacturing scenario where little or no air pollution control
equipment was used. Lead emissions from ammunition manufacturing are controlled by fabric
filters, wet scrubbers and/or cyclone separators, depending on the manufacturing situation.188
A total of 206 facilities manufacturing small arms ammunition (Standard Industrial
Classification - 3482) nationwide were identified as being potential sources of lead emissions.189
There is not enough evidence to indicate that large weapons manufacturing
facilities (Standard Industrial Classification - 3483) emit significant amounts of lead.189
6.7.2 Type Metal Production
Lead type has been used primarily in the letterpress segment of the printing
industry. However, in the late 1980s, the printing industry started phasing out the use of lead
type. The use of lead type has decreased in the last few years, but still continues to be used at
some facilities. Lead typemaking processes are classified according to the methods of producing
the final product: linotype, monotype, and stereotype. Because type metal is recycled many times
before it is spent, the quantity of type metal actually processed in a particular year can not be
calculated.
6-43
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TABLE 6-15. LEAD EMISSION FACTORS FOR MISCELLANEOUS LEAD PRODUCTS
sec
Number
3-04-051-01
3-04-051-02
3-04-051-03
3-05-035-05
Process/Emission Source Control Device
Ammunition None
Bearing Metals None
Other Metallic Lead Processes None
Abrasive Grain Wet Scrubber
Processing/Washing/Drying
Average Emission
Factor
in Ib/ton (kg/Mg)
(<5.0xlO-')
Negligible
1.5
(7.5x10-')
4.4x1 0-3
(2.2x1 0-3)
Emission
Factor
Range in
Ib/ton
(kg/Mg)
—
—
—
—
Emission
Factor Rating
C
C
C
E
Reference
57,174
57,174
57,174
190
"—" means data are not available.
Based on 1973 data.
-------
Process Description
Linotype and monotype processes produce a mold; the stereotype process
produces a plate. All three processes are closed-cycle. The type is cast from a molten lead alloy
and then remelted after printing. A small amount of virgin metal is added periodically to the
melting pot to adjust the alloy and meet make-up requirements.
All type metal is an alloy consisting mainly of lead and much smaller amounts of
antimony and tin. Each constituent provides a desired metallurgical characteristic for a slug (a
solid bar with raised letters in a line) or other form of type-casting. Lead constitutes 60 to 85
percent of the type metal because it has a low melting point. Antimony lends hardness to the alloy
and minimizes contraction as the metal cools. The antimony expands as the slug solidifies,
providing a clear type face. Tin gives both strength and fluidity to the type metal and provides a
smooth and even surface to the slug.
174
Emissions
The melting pot is the major source of emissions in type metal production.
Melting the dirty recycled type metal, contaminated with printing ink, paper, and other impurities,
generates smoke that contains hydrocarbons as well as lead particulates. Only small quantities of
particulates are created by the oxidation of lead after the meltdown because of the protection
afforded by the layer of dross on the metal surface. Limited test data indicate that lead may
comprise as much as 35 percent of the total amount of PM emitted.191'192 Table 6-16 presents lead
emission factors for type metal production.
The transferring and pouring of the molten metal into the molds may produce
fuming because of surface oxidation of the metal. The trimming and finishing operations emit lead
particles. However, the particles are typically large in size and tend to settle out in the vicinity of
the trimming saws and finishing equipment.
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TABLE 6-16. LEAD EMISSION FACTOR FOR TYPE METAL PRODUCTION
SCC Number
3-06-001-01
Emission Source
Type Metal
Production/
Remelting
Control
Device
b
Average Emission
Factor in Ib/ton
(kg/Mg)a
2.5x10-'
(1.3x10-')
Emission Factor Range
in Ib/ton
(kg/Mg)a
—
Emission
Factor Rating
C
Source: References 31,173,194
a Emission factor is expressed in Ib (kg) of pollutant emitted per ton (Mg) of lead processed.
b The emission factor is an industry average. Typical control devices utilized by the industry are cyclones, wet
scrubbers, fabric filters, and electrostatic precipitators, which may be used in various combinations.
"—" means data are not available.
The most frequently controlled sources at hot metal printing facilities are the main
melting pots and dressing areas. Linotype melting pots and finishing equipment do not require
emission controls when they are operated properly. Emission control devices in current use
include wet scrubbers, baghouses, and electrostatic precipitators. These can be used in various
combinations. During dressing, the enclosure doors are opened and pot emissions may enter the
plant atmosphere unless vented to a control device or to the outside.
6.7.3
Other Metallic Lead Products
Lead is also consumed and emitted in the manufacture of other metallic lead
products such as bearing metals, caulking lead, pipe and sheet lead, casting metals, solder, and
terne metal. Lead is also used for galvanizing, annealing, and plating. Approximately 68,100 tons
of lead were consumed in the manufacturing operations of these metallic lead products in 1991.193
Process Description
Lead is used in the manufacture of bearing metals by alloying it with copper,
bronze, antimony, and tin to form various alloys. Bearings are used in electric motors, machines,
6-46
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and engines. In the manufacturing of other metallic lead products, lead is usually processed by
melting and casting, followed by mechanical forming operations.
Emissions
Table 6-15 presents a lead emission factor for manufacturing processes of
miscellaneous metallic lead products. Uncontrolled emissions from bearing metals operations are
considered negligible. There is little or no published information on control techniques or
practices used for these sources.
6.7.4 Abrasive Grain Processing
Abrasive grain manufacturers produce materials for use by bonded and coated
abrasive product manufacturers during production of abrasive products.
190
Process Description
The most commonly used abrasive materials for abrasive grain manufacturing are
silicon carbide and aluminum oxides. These synthetic materials account for as much as 80 to
90 percent of the abrasive grains produced domestically. Other materials used for abrasive grains
are cubic boron nitride (CBN), synthetic diamonds, and several naturally occurring minerals such
as garnet and emery. The use of garnet as an abrasive grain is decreasing. CBN is used for
machining the hardest steels to precise forms and finishes. The largest application of synthetic
diamonds has been in wheels for grinding carbides and ceramics. Natural diamonds are used
primarily in diamond-tipped drill bits and saw blades for cutting or shaping rock, concrete,
grinding wheels, glass, quartz, gems, and high-speed tool steels. Other naturally occurring
abrasive materials (including garnet, emery, silica sand, and quartz) are used in finishing wood,
leather, rubber, plastics, glass, and softer metals.
Silicon carbide is manufactured in a resistance arc furnace charged with a mixture
of approximately 60 percent silica sand and 40 percent finely ground petroleum coke. A small
6-47
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amount of sawdust is added to the mix to increase its porosity so that the CO formed during the
process can escape freely. Common salt is added to the mix to promote the carbon-silicon
reaction and remove impurities in the sand and coke. During the heating period, the furnace core
reaches approximately 4,000°F (2,200°C), at which point a large portion of the load crystallizes.
At the end of the run, the furnace contains a core of loosely knit silicon carbide crystals
surrounded by unreacted or partially reacted raw materials. The silicon carbide crystals are
removed to begin processing into abrasive grains.
Fused aluminum oxide is produced in pot-type electric arc furnaces with capacities
of several tons. Before processing, bauxite, the crude raw material, is calcined at about 1,740°F
(950°C) to remove both free and combined water. The bauxite is then mixed with ground coke
(about 3 percent) and iron borings (about 2 percent). An electric current is applied and the
intense heat, on the order of 3,700°F (2,000°C), melts the bauxite and reduces the impurities that
settle to the bottom of the furnace. As the fusion process continues, more bauxite mixture is
added until the furnace is full. The furnace is then emptied and the outer impure layer is stripped
off. The core of aluminum oxide is then removed to be processed into abrasive grains.
CBN is synthesized in crystal form from hexagonal boron nitride, which is
composed of atoms of boron and nitrogen. The hexagonal boron nitride is combined with a
catalyst such as metallic lithium at temperatures in the range of 3,000°F (1,650°C) and pressures
of up to 1,000,000 pounds per square inch (psi) (6,895,000 kilopascals [kPa]).
Synthetic diamond is manufactured by subjecting graphite in the presence of a
metal catalyst to pressures in the range of 808,000 to 1,900,000 psi (5,571,000 to
13,100,000 kPa) at temperatures in the range of 2,500 to 4,500°F (1,400 to 2,500°C).
Figure 6-7 presents a process flow diagram for abrasive grain processing.
Abrasive grains for both bonded and coated abrasive products are made by graded crushing and
close sizing of either natural or synthetic abrasives. Raw abrasive materials first are crushed by
primary crushers and then reduced by jaw crushers to manageable size, approximately
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Abrasives
Material
Washing/Drying
(Optional)
(SCC 3-05-035-05)
Primary Crushing
(SCC 3-05-035-01)
Screening
(SCC 3-05-035-04)
©
PM emissions
Secondary Crushing
(SCC 3-05-035-02)
v
Final
Crushing
(SCC 3-05-035-03)
v :
Separating
(SCC 3-05-035-08)
i
Screening
(SCC 3-05-035-06)
>.
Classification
(fine sizes)
(SCC 3-05-035-07)
Figure 6-7. Flow Diagram for Abrasive Grain Processes
Source: Reference 190.
6-49
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0.75 inches (in) (19 millimeters [mm]). Final crushing is usually accomplished with roll crushers
that break up the small pieces into a usable range of sizes. The crushed abrasive grains are then
separated into specific grade sizes by passing them over a series of screens. If necessary, the
grains are washed in classifiers to remove slimes, dried, and passed through magnetic separators
to remove iron-bearing material before they are again closely sized on screens. This careful sizing
is necessary to prevent contamination of grades by coarser grains. Sizes finer than 250 grit
(0.10 mm) are separated by hydraulic flotation and sedimentation or by air classification.
Emissions
190
Little information is available on emissions from the manufacture of abrasive grains
and products.
Emissions from the production of synthetic abrasive grains, such as aluminum
oxide and silicon carbide, are likely to consist primarily of PM, PM10, and CO from the furnaces.
Aluminum oxide processing takes place in an electric arc furnace and involves temperatures up to
4,710°F (2,600°C) with raw materials of bauxite ore, silica, coke, iron borings, and a variety of
minerals that include chromium oxide, cryolite, pyrite, and silane. This processing is likely to emit
fluorides, sulfides, and metal constituents of the feed material.
The primary emissions from abrasive grain processing consist of PM and PM10
from the crushing, screening, classifying, and drying operations. PM is also emitted from
materials handling and transfer operations. Table 6-15 presents a lead emission factor developed
from the results of a metals analysis conducted on a rotary dryer controlled by a wet scrubber in
an abrasive grain processing facility.
Fabric filters preceded by cyclones are used at some facilities to control PM
emissions from abrasive grain production. This configuration of control devices can attain
controlled emission concentrations of 37 micrograms per dry standard cubic meter (0.02 grains
per dry standard cubic foot) and control efficiencies in excess of 99.9 percent. Little other
information is available on the types of controls used by the abrasives industry to control PM
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emissions. However, it is assumed that other conventional devices such as scrubbers and
electrostatic precipitators can be used to control PM emissions from abrasives grain and products
manufacturing.
6.8 SOLDER MANUFACTURING
6.8.1 Source Description
A small fraction of the total lead produced is transformed into solder. Lead
content in solder can range from 0 to over 50 percent. Industrial trends are showing an increased
demand for lead-free solder, partially in response to the June 1988 amendments to the Safe
Drinking Water Act, which set limits of 0.02 percent lead in solders and fluxes and 8 percent lead
in pipe and fittings used in public water supply systems and facilities connected to them. Lead
used in soldered food and soft drink cans declined steadily through the 1980s. As of November
1991, cans made with lead-containing solder were no longer manufactured in the United States.195
In 1989, the solder manufacturing industry was comprised of 175 facilities
involved in melting and realloying solder into ingots, extruding or stamping solder, and/or paste
solder production. Lead emissions from the solder manufacturing industry are estimated as
negligible.196
6.8.2 Process Description
Lead and tin pigs are melted and blended in a kettle. The alloy is cast into billets in
the slug molds and put into a press, where it is hydraulically extruded at 15,000 psi through holes
1/2 inch in diameter. The solder is wire-spooled and put through a drawing machine to produce
threads of varying diameters. After extrusion, wire stock can go to the rolling mills (rather than
being spooled), where it is formed into a solder ribbon from which washers are stamped.197
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Paste solder is produced by alloying various amounts of tin and lead or silver or
lead oxide. The alloy is put into a powder form by centrifuging or spraying. The solder powder
is mixed with a vehicle (water-based or other solvents plus additional ingredients).197
The main processes of solder manufacturing—melting and paste solder
production—are similar to the melting phase and paste production, respectively, in lead-acid
battery production. Refer to Section 6.2 for the process description of lead-acid battery
production.196
6.8.3 Emissions
Studies conducted by EPA concluded that the solder manufacturing industry is a
minimal source of lead emissions. This research identified two areas of solder manufacturing as
potential sources of lead emissions, the lead melting process and solder paste production. Lead
emissions from these sources occur by the same mechanism as lead emissions from lead-acid
battery production, but the amount of lead released is expected to be much less because of the
lower lead content of the alloy produced by solder manufacturing. Uncontrolled lead emissions
from paste solder production are estimated to be small because the size and density of the
particles have settling velocities sufficient to prevent migration to the atmosphere.196
Lead emissions from solder manufacturing facilities are estimated to be decreasing
because of a higher demand for lead-free solder. Many solder producers are substituting
tin/antimony or tin/antimony/silver solders for the previously manufactured lead solders.
Table 6-17 presents a controlled emission factor that was developed from emissions test data.
Lead will generally be emitted in particulate form from solder manufacturing
facilities. Therefore, control devices effective for PM removal include fabric filters and scrubbers.
Refer to Section 6.2.3 for a more detailed description of devices used to control emissions from
lead-acid battery facilities, which are similar in process to solder manufacturing facilities.
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TABLE 6-17. LEAD EMISSION FACTOR FOR SOLDER MANUFACTURING FACILITIES
SCC Number
3-04-004-14
Emission
Source
Lead
Melting Pot
Control Device
Afterburner/
Scrubber
Average Emission
Factor in Ib/ton
(kg/Mg)a
4.6x1 0-2
(2.3x1 0-2)
Emission Factor
Range in Ib/ton
(kg/Mg)a
—
Emission
Factor
Rating
D
Source: Reference 198
a Emission factors are expressed in Ib (kg) of lead emitted per ton (Mg) of materials processed.
"—" means data are not available.
6.9 ELECTROPLATING (INCLUDING PRINTED CIRCUIT BOARDS)
6.9.1 Source Description
Electroplating is used to coat base materials with lead or to act as a means of
soldering printed circuit boards. With advances in the electronics industry creating complex parts,
the use of electroplating has grown dramatically. Currently, electroplating can easily and
efficiently complete 30,000 or more connections on a single circuit board. Table 6-18 presents
those companies that are involved with lead electroplating operations.
6.9.2 Process Description
A flow diagram for a typical electroplating process for the coating of parts other
than printed circuit boards is presented in Figure 6-8. Prior to plating, the parts undergo a series
of pretreatment steps to smooth the surface of the part and to remove any surface soil, grease, or
oil. Pretreatment steps include polishing, grinding, and/or degreasing of the part to prepare for
plating. The part being plated is rinsed after each step in the process to prevent carry-over of
solution that may contaminate the baths used in successive process steps.
Polishing and grinding are performed to smooth the surface of the part.
Degreasing is performed either by dipping the part in organic solvents or by vapor degreasing the
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Company
TABLE 6-18. LEAD ELECTROPLATING MANUFACTURERS
Location
CP Chemicals Inc.
CuTech Inc.
Enthone-OMI Inc.
GSP Metals & Chemicals Corp.
General Chemical Corp.
Harstan Div., Chemtech Industries Inc.
JacksonLea, A Unit of Jason Inc.
LeaRonal Inc.
MacDermid Inc.
Maclee Chemical Co., Inc.
McGean-Rohco Inc.
Pitt Metals & Chemicals Inc.
Quin-Tec Inc.
Shipley Co., Inc.
Taskem Inc.
Technic Inc.
Transene Co., Inc.
Fort Lee, NJ
Hatfield, PA
New Haven, CT
Los Angeles, CA
Parsippany, NJ
St. Louis, MO
Conover, NC
Freeport, NY
Waterbury, CT
Chicago, IL
Cleveland, OH
McDonald, PA
Warren, MI
Newton, MA
Brooklyn Heights, OH
Pawtucket, RI
Rowley, MA
Source: Reference 199.
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Substrate
to be
Plated
Pretreatment
Step
Polishing & Degreasing
Cleaning
Rinse
Acid Dip
Rinse
Lead
Electroplating
Rinse
Electroplated
Product
Post
Treatment
Potential
Lead
Emissions
Figure 6-8. General Electroplating Process Flow Diagram
Source: Reference 200.
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part using organic solvents. The exact pretreatment steps used depend upon the amount of soil,
grease, or oil on the parts. Following pretreatment, the parts are transferred to the plating tank.
In lead plating, the part(s) is placed in a tank and connected into the electrical
circuit as the cathode. If small parts are to be plated, the parts are first placed in a plating barrel
or on a plating rack. The plating barrel or plating rack is then placed in the tank and connected
into the electrical circuit. As current is applied, lead ions in solution are drawn to the negatively
charged cathode where they undergo reduction, resulting in the deposition of lead onto the part.
The efficiency of the plating bath is based on the amount of current that is consumed in the
deposition reaction versus the amount of current that is consumed by other side reactions.
Following plating, the part is thoroughly rinsed. Post-treatment of the part may be
necessary.
Tin/lead solder is used in the production of circuit boards in two ways:
• Tin/lead solder is applied to the boards in the manufacturing process to
protect the copper from etching during production and from oxidizing,
allowing the circuit board to be stored for long periods of time.
• Tin/lead solder is used to attach components to the circuit board.
The American Electronics Association (AEA) advises that a major reason that
tin/lead solder is used is because it is a conductive material that bonds aggressively. The low
melting point of tin/lead solder is often preferred because of the reduced probability of thermal
shock to soldered assemblies during high speed soldering operations. In addition to its ability to
bond aggressively at a relatively low temperature, tin/lead solder has other advantageous physical
properties, including: good wicking tendencies, i.e., the tendency to produce strong bonds by
traveling up the holes to mount components to some printed circuit boards; pliancy to resist
breakage from vibration; and good electrical conductivity.
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Manufacturing circuit boards involves the application of tin/lead solder to maintain
the circuit boards' solderability by protecting the copper boards from oxidizing. The oldest
manufacturing technique employs the application of tin/lead plating to the circuit board. This
process begins with a copper clad circuit board-a laminate such as fiberglass or epoxy that has
been coated with copper on one or both sides. Tin/lead solder is used as a protective pattern of
"etch resist," which is deposited on the copper surface, and the unwanted copper is etched away.
This technique produces a copper clad circuit pattern protected by tin/lead plating.
Manufacturers of circuit boards now employ a solder-mask-over-bare copper
technique that reduces the amount of solder needed in basic circuit board production. This
technique is referred to as "hot air leveling." Using this technique, a solder mask, which is an
organic coating such as epoxy, is applied to the bare copper board. The circuit board is then
dipped into liquid tin/lead solder and forced air is used to blow excess solder back into the liquid
solder (hence the term, "hot air leveling"). With this process, tin/lead solder is applied only to the
joints where the components will be attached, which is about 25 percent of the exposed copper on
the board, as compared to covering 100 percent of the exposed copper on the board with the
tin/lead plating method.
Both tin/lead plating and hot air leveling are presently in use in the electronics
manufacturing industry; however, a comparison of the frequency of use of each process is not
available.
In both types of manufacturing, additional solder is applied to the circuit boards to
attach the components. The soldering process is defined as a metallurgical joining method using a
filler metal (the solder) with a melting point below 600°F (316°C). According to AEA, the most
common soldering technique for both printed circuit board manufacturing and electronic
component assembling is wave soldering. This process employs a bath of solder through which
the circuit boards pass. In the assembly operations, automated equipment places electronic
components on or in the printed circuit boards prior to soldering.
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Surface mount assembly and through-hole assembly are two technologies used to
attach electrical components to the circuit boards. With surface mount technology, components
are attached directly to the circuit boards without drilling or punching holes. Without holes, the
components can be densely packed on the board, thereby reducing the size of the board. Texas
Instruments cites a 40 percent reduction in size of the printed circuit board assembly over
through-hole technology when surface mount technology is used. With through-hole technology,
the leads of the electrical components are placed in holes that have been drilled in the circuit
board. Usually, the circuit board is soldered on the side from which the leads protrude.201
For the purposes of electroplating solder on printed circuit boards, stannous
fluoborate, lead fluoborate, and fluoborate acid, in various proportions, can be used for plating all
percentages of tin-lead (solder), 100 percent lead and 100 percent tin. The bath requires boric
acid for stability and an addition agent, usually a liquid peptone or a non-protein liquid. The
addition agent provides the following advantages: (a) the solution remains clear, (b) the grain
structure of the deposit is improved, (c) the throwing power of the bath is improved, and
(d) better rinsing is possible and drag-out is reduced.202
6.9.3 Emissions
Lead emissions potentially occur from the plating stage of the electroplating
process. However, these emissions are estimated to be low.
6.10 STABILIZERS IN RESINS
Due to its excellent insulation properties, lead is used as a component of heat
stabilizers in resins. Heat stabilizers prevent the thermal degradation of resins that are exposed to
elevated temperatures or ultra-violet light and weathering during end use. Lead-containing
stabilizers are usually lead salts of long-chain organic acids. Typical lead stabilizers include the
following compounds:203
Diabasic lead stearate [3PbOPB(C17H35COO)2],
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Hydrous tribasic lead sulfate (3PbOPbSO4H2O),
Dibasic lead phthalate [2PbOPb(OCO)2C6H4], and
Dibasic lead phosphate (2PbOPbHPO3^/l/2H2O).
These lead-containing stabilizers are used primarily in polyvinyl chloride (PVC), vinyl chloride
copolymers, and PVC blends.204 PVC is generally regarded as one of the most versatile of
polymers because of its compatibility with many other materials, such as plasticizers, fillers, and
other polymers. A list of manufacturers of heat stabilizers containing lead is presented in
Table 6-19.
The major use of lead-stabilized PVC is in construction applications with a long
life—for cable jacketing, conduits, and other building applications (such as siding, rainwater-
resistant products, window framing, and general trim).158 Lead-stabilized PVC is also used for
various types of piping and fittings, including larger diameter drain and sewer pipe.205'206
Other likely applications of lead-stabilized PVC include consumer products (such
as appliance housings, sporting and recreational items, footwear, luggage, credit/bank cards,
floppy disk jackets, window shades, blinds and awnings, industrial and garden hoses) and
transportation applications (such as automobile upholstery and tops).205
Demand for lead stabilizers in plastics increased steadily during the 1980s due to
increased demand for PVC products related to construction activity.206 Since that time, demand
has remained relatively stable. In the 1992 Toxic Release Inventory, there were 53 facilities
reporting lead and lead compound emissions from the manufacture of resins and plastics.159 These
facilities are listed in Table 6-20 and probably represent some of the major lead-stabilized resin
and plastic manufacturers in the United States.
Products used in residential and commercial construction currently account for
70 percent of all PVC sold.206 Because lead is primarily used as a heat-stabilizer in these
products, a list of PVC manufacturers in the United States is presented in Table 6-21.
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TABLE 6-19. MANUFACTURERS OF HEAT STABILIZERS CONTAINING LEAD3
Facility Location
Akzo Chemical Division New Brunswick, NJ
Hammond Lead Products, Halsted Division Hammond, IN
Mooney Chemicals, Inc. Cleveland, OH
M-R-S Chemicals Inc. Maryland Heights, MO
Synthetic Products Co. Cleveland, OH
RT Vanderbilt Co., Inc. Norwalk, CT
Source: Reference 207.
a Includes dibasic lead phthalate, dibasic lead phosphite, and tribasic lead sulphate.
Due to increasing pressure from state and federal agencies, U.S. manufacturers of
heavy-metal heat stabilizers (including lead) are focusing research and development on finding an
acceptable alternative. Some of these replacement heat stabilizers under development include
magnesium-zinc, barium-zinc, and tin stabilizers.208
6.10.1 Process Description
Lead stabilizer production can be a highly variable process because many of the
stabilizers are custom-blended for specific applications. Probably the most commonly used lead
stabilizer is tribasic lead sulfate, a fine white powder that is made by boiling aqueous suspensions
of lead oxide and lead sulfate. The anhydrous compound decomposes at 1,643°F (895 °C). The
addition of 2 to 7 percent tribasic lead sulfate to flexible and rigid PVC provides efficient, long-
term, economical heat stability.209
Addition of the heat stabilizer additives occurs as part of the overall production of
the formulated PVC resins. Formulation of the resin normally uses a blender system and,
depending upon the particular PVC product, may be a batch or continuous operation.
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TABLE 6-20. MANUFACTURERS OF RESINS AND PLASTICS REPORTING LEAD AND
LEAD COMPOUND EMISSIONS IN THE
1992 TOXIC CHEMICALS RELEASE INVENTORY
Facility
Location
SIC 2821: Plastics Materials and Resins
Ampacet Corporation
BF Goodrich Company, Geovinyl Division
BF Goodrich Company
North American Plastics Inc.
Synergistics Inc.
Union Carbide Chemicals and Plastics
Vista Chemical Company, Polymers Division
Deridder, LA
Pedricktown, NJ
Louisville, KY
Avon Lake, OH
Madison, MS
Prairie, MS
Howell Township, NJ
Texas City, TX
Aberdeen, MS
SIC 3089: Plastics Products
American Wire & Cable Company
Conex of Georgia Inc.
KW Plastics of California
Lancer Dispersions Inc.
RIMTEC Corporation
WITCO Richardson Battery Parts
WITCO Corporation, Richardson Battery
Olmsted Township, OH
Greensboro, GA
Bakersfield, CA
Akron, OH
Burlington, NJ
Philadelphia, MS
Indianapolis, IN
SIC 3087: Custom Compound Purchased Resins
Allied Products Corporation Coz Division
Crown Wire & Cable Company
Gary Chemical Corporation
Heller Performance Polymers Inc.
KW Plastics
Lynn Plastics Corporation
Northbridge, MA
Taunton, MA
Leominster, MA
Visalia, CA
Troy, AL
Lynn, MA
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TABLE 6-20. MANUFACTURERS OF RESINS AND PLASTICS REPORTING LEAD AND
LEAD COMPOUND EMISSIONS IN THE 1992 TOXIC CHEMICALS RELEASE
INVENTORY (CONTINUED)
Facility
Location
Manner Plastic Materials Inc.
Pantasote Inc., Plastic & Materials, Vinyl Compounds
Plastics Color Chip Inc.
PMS Consolidated
Reed Plastics Corporation, Sandoz
Spectra Polymer Company Inc.
Teknor Color Company
Teknor Apex Company
Vista Performance Polymers
Rancho Dominguez, CA
Passaic, NJ
Asheboro, NC
Somerset, NJ
Elk Grove Village, IL
Saint Peters, MO
Holden, MA
Grand Prairie, TX
Ashburnham, MA
Henderson, KY
Pawtucket, RI
Mansfield, MA
Jeffersontown, KY
SIC 3079: Miscellaneous Plastics Products
PVC Compounders, Inc.
Kendallville, IN
SIC 3081: Unsupported Plastic Films & Sheet
Gencorp Polymer Products - Rigid Plastics Division
Newcomerstown, OH
Source: Reference 159.
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TABLE 6-21. POLYVINYL CHLORIDE MANUFACTURERS IN THE UNITED STATES
Facility
Borden Chemicals and Plastics
Partnership
CertainTeed Corporation
Formosa Plastics Corporation U.S.A.
The BFGoodrich Company, BFGoodrich
Chemical Group
Georgia Gulf Corporation
The Goodyear Tire & Rubber Company,
General Products Division
Keysor-Century Corporation
Occidental Chemical Corporation,
Polymers & Plastics, Vinyls Division
Shintech Incorporated
Union Carbide Corporation, Solvents &
Coatings Materials Division
Vista Chemical Company, Olefins &
Vinyl Division
Vygen Corporation
Westlake PVC Corporation
Total
Location
Geismar, LA
Illiopolis, IL
Lake Charles, LA
Baton Rouge, LA
Delaware City, DE
Point Comfort, TX
Avon Lake, OH
Deer Park, TX
Henry, IL
Louisville, KY
Pedricktown, NJ
Delaware City, DE
Plaquemine, NJ
Niagara Falls, NY
Saugus, CA
Baton Rouge, LA
Burlington, NJ (south)
Pottstown, PA
Pasadena, TX
Freeport, TX
Texas City, TX
Aberdeen, MS
Oklahoma City, OK
Ashatbula, OH
Pensacola, FL
Capacity
(millions of Ib)
500
350
260
865
130
1,050
300
325
60
400
370
150
840
115
60
450
150
250
1,400
2,400
140
440
400
125
200
12,030
Source: Reference 169, 206.
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The primary process used to manufacture lead-stabilized PVC in the United Sates
is suspension polymerization. In this process, the vinyl chloride monomer is finely dispersed in
water with vigorous agitation. At this point, monomer-soluble initiators and lead stabilizers in
suspension are used. The particular sequence of stabilizer addition depends upon the processing
method to be used (e.g., calendaring, extrusion, injection molding). The molecular weight of the
PVC can be controlled by varying the temperature, where the molecular weight increases as the
temperature increases.206
6.10.2 Emissions
No information is available for the specific types of emission control devices used
to control lead emissions resulting from production of lead stabilizers or lead-containing PVC
products. One potential source of lead emissions is materials handling, especially since lead
stabilizers are used in powder form. Lead emissions may occur when lead stabilizers are added to
the PVC resins during formulation and prior to processing the PVC resin.
Lead emissions may also be present during subsequent phases: drying, extruding,
molding, grinding, weighing, packaging. However, emissions from these sources are expected to
be minimal since temperatures necessary to volatilize significant quantities of lead compounds
would thermally destroy the resin and other organic constituents.
No emission factors are published for this process, and no test data are available to
allow calculation of an emission factor.
6.11 ASPHALT CONCRETE
6.11.1 Source Location
In 1983, there were approximately 2,150 companies operating an estimated
4,500 hot-mix asphalt plants in the United States.210 More recently, the number has fallen to
about 3,600 plants.211 Approximately 40 percent of these companies operate only a single plant.
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Plants are usually located near the job site, so they are concentrated in areas with an extensive
highway and road network.210 Additional information on the location of individual hot-mix
asphalt facilities can be obtained by contacting the National Asphalt Pavement Association in
College Park, Maryland.
6.11.2 Process Description
To produce hot-mix asphalt (also referred to as asphalt concrete), aggregate,
which is composed of gravel, sand, and mineral filler, is heated to eliminate moisture and then
mixed with hot asphalt cement. The resulting hot mixture is pliable and can be compacted and
smoothed. When it cools and hardens, hot-mix asphalt provides a waterproof and durable
pavement for roads, driveways, parking lots, and runways.
There are three types of hot-mix asphalt plants operating in the United States:
batch-mix, continuous-mix, and drum-mix. Batch-mix and continuous-mix plants separate the
aggregate drying process from the mixing of aggregate with asphalt cement. Drum-mix plants
combine these two processes. Production capacities for all three types of plants range from 40 to
600 tons (36 to 544 Mg) of hot mix per hour. Almost all plants in operation are of either the
batch-mix or drum-mix type. Less than 0.5 percent of operating hot-mix plants are of the
continuous-mix design.211
Aggregate, the basic raw material of hot-mix asphalt, consists of any hard, inert
mineral material. Aggregate typically comprises between 90 and 95 percent by weight of the
asphalt mixture. Because aggregate provides most of the load-bearing properties of a pavement,
the performance of the pavement depends on selection of the proper aggregate.
Asphalt cement is used as the binding agent for aggregate. It prevents moisture
from penetrating the aggregate and acts as a cushioning agent. Typically, asphalt cement
constitutes 4 to 6 percent by weight of a hot-mix asphalt mixture.210 Asphalt cement is obtained
from the distillation of crude oil. It is classified into grades under one of three systems. The most
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commonly used system classifies asphalt cement based on its viscosity at 140°F (60 °C). The
more viscous the asphalt cement, the higher its numerical rating.
The asphalt cement grade selected for different hot-mix asphalts depends on the
type of pavement, climate, and type and amount of traffic expected. Generally, asphalt pavement
bearing heavy traffic in warm climates requires a harder asphalt cement than pavement subject to
either light traffic or cold climate conditions.
Another material used significantly in the production of new or virgin hot-mix
asphalt is recycled asphalt pavement (RAP), which is pavement material that has been removed
from existing roadways. RAP is now used by virtually all companies in their hot-mix asphalt
mixtures. The Surface Transportation Assistance Act of 1982 encourages recycling by providing
a 5-percent increase in Federal funds to State agencies that recycle asphalt pavement. Rarely does
the RAP comprise more than 60 percent by weight of the new asphalt mixture.
Twenty-five percent RAP is typical in batch plants, and 40 to 50 percent RAP mixtures are typical
in drum-mix plants.210
The primary processes of a typical batch-mix hot-mix asphalt facility are illustrated
in Figure 6-9.211 The moisture content of the stockpiled aggregate at the plant usually ranges
from 3 to 5 percent. The moisture content of recycled hot-mix asphalt typically ranges from 2 to
3 percent. The different sizes of aggregate are typically transported by front-end loader to
separate cold-feed bins and metered onto a feeder conveyor belt through gates at the bottom of
the bins. The aggregate is screened before it is fed to the dryer to keep oversize material out of
the mix.
The screened aggregate is then fed to a rotating dryer with a burner at its lower
(discharge) end that is fired with fuel oil, natural gas, or propane. In the production of hot-mix
asphalt, the majority of lead emissions can be expected from the rotating dryer. The dryer
removes moisture from the aggregate and heats the aggregate to the proper mix temperature.
Lead emissions occur primarily from fuel combustion. Aggregate temperature at the discharge
end of the dryer is about 300°F (149°C). The amount of aggregate that a dryer can heat depends
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on the size of the dram, the size of the burner, and the moisture content of the aggregate. As the
amount of moisture to be removed from the aggregate increases, the effective production capacity
of the dryer decreases.
Vibrating screens segregate the heated aggregate into bins according to size. A
weigh hopper meters the desired amount of the various sizes of aggregate into a pugmill mixer.
The pugmill typically mixes the aggregate for 15 seconds before hot asphalt cement from a heated
tank is sprayed into the pugmill. The pugmill thoroughly mixes the aggregate and hot asphalt
cement for 25 to 60 seconds. The finished hot-mix asphalt is either loaded directly into tracks or
held in insulated and/or heated storage silos. Depending on the production specifications, the
temperature of the hot-mix asphalt product mix can range from 225 to 350°F (107 to 177°C) at
the end of the production process.
Continuous-mix plants are very similar in configuration to batch plants. Asphalt
cement is continuously added to the aggregate at the inlet of the mixer. The aggregate and
asphalt cement are mixed by the action of rotating paddles while being conveyed through the
mixer. An adjustable dam at the outlet end of the mixer regulates the mixing time and also
provides some surge capacity. The finished mix is transported by a conveyor belt to either a
storage silo or surge bin.210
Dram-mix plants dry the aggregate and mix it with the asphalt cement in the same
dram, eliminating the need for the extra conveyor belt, hot bins and screens, weigh hopper, and
pugmill of batch-mix plants. The dram of a dram-mix plant is much like the dryer of a batch
plant, but it typically has more flights than do batch dryers to increase veiling of the aggregate and
to improve overall heat transfer. The burner in a dram-mix plant emits a much bushier flame than
does the burner in a batch plant. The bushier flame is designed to provide earlier and greater
exposure of the virgin aggregate to the heat of the flame. This design also protects the asphalt
cement, which is injected away from the direct heat of the flame.210
Initially, dram-mix plants were designed to be parallel-flow, as depicted in
Figure 6-10. Recently, the counterflow dram-mix plant design shown in Figure 6-11 has become
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popular.211 The parallel flow drum-mix process is a continuous-mixing type process using
proportioning cold feed controls for the process materials. Aggregate, which has been
proportioned by gradations, is introduced to the drum at the burner end. As the drum rotates, the
aggregates and the combustion products move toward the other end of the drum in parallel.
Liquid asphalt cement flow is controlled by a variable flow pump that is electronically linked to
the virgin aggregate and RAP weigh scales. The asphalt cement is introduced in the mixing zone
midway down the drum in a lower temperature zone along with any RAP and PM from collectors.
The mixture is discharged at the end of the drum and conveyed to a surge bin or storage silos.
The exhaust gases also exit the end of the drum and pass on to the collection system.211
In a counterflow drum-mix plant, the material flow in the drum is opposite or
counterflow to the direction of the exhaust gases. In addition, the liquid asphalt cement mixing
zone is located behind the burner flame zone so as to remove the materials from direct contact
with hot exhaust gases. Liquid asphalt cement flow is still controlled by a variable flow pump and
is injected into the mixing zone along with any RAP and PM from primary and secondary
collectors.211
Of the 3,600 active hot-mix asphalt plants in the United States, approximately
2,300 are batch-mix plants, 1,000 are parallel-flow drum-mix plants, and 300 are counterflow
drum-mix plants. About 85 percent of plants being constructed today are of the counterflow
drum-mix design; batch-mix plants and parallel-flow drum-mix plants account for 10 percent and
5 percent respectively.211
Emission Control Techniques
Emissions of lead from hot-mix asphalt plants most likely occur because of fuel
combustion in the aggregate rotary dryers, but some emissions from the aggregate during the
drying process are possible. These emissions are most often controlled by wet scrubbers or
baghouses.211
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6.11.3 Emissions
Emissions from hot-mix asphalt plants were reexamined recently for the purpose of
updating the information contained in the EPA's Compilation of Air Pollutant Emission Factors,
commonly referred to as AP-42. Representative batch-mix and drum-mix plants (both parallel
and counterflow) were selected for testing. Emissions from hot-oil heaters used to warm stored
asphalt concrete were also evaluated. Lead emissions from hot-mix plants can result from fuel
combustion, aggregate mixing and drying, and asphalt heating. The only lead emissions found
from these tests were from the drying process. These lead emission factors are provided in
Tables 6-22 and 6-23.212
6.12 APPLICATION OF PAINTS
Leaded house paints were common up until the mid-1950s. In 1971, the
Lead-Based Paint Poisoning Prevention Act prohibited the use of paints containing more than
1 percent lead by weight in the nonvolatile portion of liquid paints or in the dried film on all
interior and exterior surfaces accessible to children in residential structures. In 1972, the FDA
ordered a reduction of the lead content of paints used in and around households to 0.5 percent in
1973 and 0.06 percent in 1975. Further legislation in 1976 required the Department of Housing
and Urban Development to prohibit lead-based paint in residential structures built or rehabilitated
with federal assistance. Also, the Department of Health, Education, and Welfare banned lead
paints from cooking and eating utensils, and the Consumer Products Safety Commission
prohibited lead paints on toys and furniture. As a result, the use of white lead in paints for these
consumer applications has plummeted in recent years.213
Although the use of lead paint has dramatically decreased in these consumer
products, leaded paint is still used in certain applications. The major uses of lead-based paints
today are as metal primers in automobile refinishing, as anti-corrosive undercoating in the
automobile industry, for public works applications (such as bridges and roads), as traffic paint, in
art materials, and in marine applications (such as boats and buoys).213'217
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TABLE 6-22. LEAD EMISSION FACTORS FOR BATCH-MIX HOT-MIX ASPHALT PLANTS
--J
Emission
SCC Number Source Control Device
3-05-002-01 Rotary Dryer FF
Wet Scrubber - Medium
Efficiency
Wet Scrubber - Medium
Efficiency/Single Cyclone
Single Cyclone/Baghouse
Multiple Cyclone without Fly
Ash Reinjection/Baghouse
None
Average Emission
Factor in Ib/ton
(kg/Mg)a
7.4x1 0'7
(3.7xlO-7)
S.lOxlO'6
(1.55xlO-6)
l.OSxlO'6
(5.15xlO-7)
2.00x1 0-6
(l.OOxlO-6)
2.08xlO-7
(1.04xlQ-7)
4.0
(2.0)
Emission Factor Range
in Ib/ton
(kg/Mg)a
—
<2.30xlO-6-3.9xlO-6
(<1.15xlO-6-1.95xlO-6)
6.80x1 0-7-l. 24x1 0-6
(3.40xlO-7-6.20xlO-7)
1. 08x1 0-6- 2.77x1 0-6
(5.40xlO-7-1.39xlO-6)
3.74xlO-7-4.10xlQ-6
(1.87xlO-7-2.05xlO-6)
—
Emission
Factor
Rating
D
U
U
U
U
U
Reference
212
214
215
216
92
22
a Emission factors are expressed in Ib (kg) of pollutant emitted per ton (Mg) of waste incinerated.
"—" means data are not available.
FF = Fabric Filter.
-------
TABLE 6-23. LEAD EMISSION FACTOR FOR DRUM-MIX HOT-MIX ASPHALT PLANTS
SCC Number
3-05-002-05
Emission
Source
Drum Dryer
Control
Device
FF
Average Emission
Factor in Ib/ton
(kg/Mg)a
S.SOxlO'6
(l.TOxlO'6)
Emission Factor Range
in Ib/ton
(kg/Mg)a
—
Emission
Factor
Rating
D
Source: Reference 212.
a Emission factors are expressed in Ib (kg) of pollutant emitted per ton (Mg) of hot mix asphalt produced.
"—" means data are not available.
FF = Fabric Filter.
The future trend for the paint industry is to identify substitutes for the lead
compounds currently being used. However, there is no perfect substitute that can impart all of
the properties of lead, which include color, brightness, cost effectiveness, insolubility, opacity,
nonbleeding in solvents, and durability. At present, substitutes of acceptable quality exist for only
some of these uses.217 The major current uses of lead-based paints are discussed briefly below.
6.12.1 Source Description
Automotive Industry and Automobile Refinishing
Because lead enhances the corrosion protection and durability of surface coatings,
products such as paints and primers containing lead are frequently used to coat autobody surfaces
and in automobile refinishing shops.218 White-basic lead silicochromate is used in the
electrodeposition of water-based coatings for the automotive industry. Its use in this application
has increased because of its capability to be tinted to a variety of colors.213
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Industrial Applications
Red lead is used as a rust-inhibitive pigment in paints for structural steel, such as
bridges and support beams.213 Basic lead silicochromate, which can be thinned with either solvent
or water, is also used for its excellent anti-corrosive properties in industrial and maintenance
paints.13 The use of lead as an anti-corrosive in steel primers is decreasing because of
containment costs required for application/removal. In certain applications, titanium oxide (TiO2)
is being substituted for lead.217
Machinery Finishes/Traffic Paints
Lead chromates are added to paints because they are inexpensive and provide
durability in exterior applications. Chrome orange is used in machinery finishes, such as farm
equipment and trucks. Chrome yellow is used in traffic paints—for highway stripes and markings,
as well as curb markings, guard railings, and crosswalks. The pigment constitutes 25 percent of
the total weight of the paint.213 In 1990, about 40 million pounds of lead chromate were produced
in the United States, and an additional 8 million pounds were imported.219
Artists Paints
Oil colors contain large amounts of pigment, ranging from 30 percent for toners to
as high as 80 percent with dense pigments such as white leads.213
Marine Coatings
Anti-corrosive coatings are also used for marine applications, such as ship hulls,
buoys, and offshore towers. Red lead has been used extensively for this purpose; however, zinc
dust has largely replaced red lead. Basic lead silicochromate is also being used for corrosion
protection.213
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6.12.2 Process Description
For some of the categories discussed above, paint is applied using a surface
coating operation (such as automobiles, farm machinery, buoys, boats). For other categories, the
paint is applied (either by spraying or brushing) directly on the structure or item once it has been
erected (such as bridges, beams, marine towers, curbs, roads). Because the variety of applications
is so diverse, detailed process descriptions are not included in this document.
Industrial surface coating operations use several different methods to apply
coatings to substrates. The type of surface coating operation used will depend upon the type of
product being coated, coating requirements, and the method of application. The more commonly
used techniques include electrodeposition (EDP), spraying, dipping, flow coating, and brushing.
In the automobile industry, EDP is used to apply anti-corrosion lead-based paints
to the underbody of vehicles. In EDP, a dc voltage is applied between the coating bath (or carbon
or stainless-steel electrodes in the bath) and the part to be coated. The part (acting as either the
cathode or anode) is dipped into the bath. The coating particles in the bath are attracted to the
part because they have an opposite charge. The result is a very evenly applied coating. The
coatings used in EDP are waterbased. Transfer efficiencies for this process are generally greater
than 95 percent.220
Spraying operations are normally performed in a spray booth using one of the
following spray application methods: air atomization; airless atomization; air-assisted airless;
high-volume, low pressure (HVLP); and electrostatic methods. All of these techniques are used
in automobile refinishing. Air atomization is also used to apply traffic markings.220
Dip coating involves briefly immersing the substrate in a tank containing a bath of
paint. The object is slowly removed from the tank allowing excess paint to drain back into the
tank. Flow coating is used on articles which cannot be dipped due to their buoyancy. In this
operation, the coating material is fed through overhead nozzles, distributing the paint in a steady
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stream over the article to be coated. Excess paint is allowed to drain from the coated object and
is then recycled.220
6.12.3 Emissions
Lead emissions from paint application occur as the paint is applied—during
spraying, brushing, or dipping. Lead emissions may also occur from the paint blending tank or
during the drying and curing operations. Lead would be emitted as PM. Equipment used to
control PM emissions from spray booth operations include baffle plates, filter pads, or water
curtains.220
No specific emission factors for lead were identified for any of the paint
application source categories.
6.13 SHOOTING RANGES AND EXPLOSIVE ORDNANCE DISPOSAL SITES
6.13.1 Source Description
This section presents information on two potential lead-emitting sources: shooting
ranges and explosive ordnance disposal (EOD) sites. Shooting ranges include indoor firing ranges
and gun clubs. Many shooting ranges nationwide were identified as being potential sources of
lead emissions.221'222
Various materials and explosives are regularly destroyed at ordnance disposal sites
within military facilities. These facilities use open burn/open detonation (OB/OD) treatment
processes to eliminate the hazardous properties of reactive waste munitions. As materials are
combusted or exploded during the OB/OD treatment processes, chemical byproducts of
incomplete combustion are emitted into the atmosphere.
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6.13.2 Emissions
Lead is emitted from the firing of small arms ammunition with lead projectiles
and/or lead primers, but the explosive charge does not contribute to lead emissions.
Indoor shooting ranges may expose firing personnel to lead during indoor shooting
practices and qualification exercises. OSHA regulations may apply to indoor range situations.
Ventilation systems at indoor shooting ranges should be designed with enough air flow from the
firing line toward the target area to effectively remove the airborne lead generated during firing of
conventional ammunition. New bullet traps are also available to reduce lead exposure generated
from trap impact.
Lead emissions from small arms can be reduced by using different ammunition
types and/or special leadfree primers. The Department of Defense and ammunition manufacturers
are undertaking an R&D effort to develop lead free ammunition. Zinc bismuth, tungsten, nickel
and plastic (among other items) are being considered as potential alternatives. None are currently
available for widespread use and most are being considered for practice ammunition only. No
emission factors were available for indoor shooting activities.223
In general, EOD processes generate relatively small quantities of pollutants.
Chemical emission rates from an OB/OD event depend on the quantity and type of propellant
treated and the method of treatment. Emissions originate either from the combustion or
detonation of the propellant and primer material or nonenergetic waste (i.e., containers and other
waste associated with the propellant) or vaporization of the nonenergetic waste (i.e., casings
surrounding the propellant) during combustion. The list of propellant wastes to potentially be
treated at an OB/OD facility is fairly extensive.
Table 6-24 presents lead emission factors for various categories of propellants. All
emission factors are in gram emitted per gram of material burned or detonated. Each type of
propellant represents a fairly different material. TNT represents a specific type of explosive. The
double-based and composite-based propellants are nitroglycerin- and nitrocellulose-based
6-78
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TABLE 6-24. UNCONTROLLED LEAD EMISSION FACTORS FOR EOD ACTIVITIES
--J
Uncontrolled Average Emission
Factor
Ib emitted/lb detonated
Propellant Tested (g emitted/g detonated)
TNT
Double-based Propellant
(DB)
Composite-based
Propellant (CB)
20-mm High-explosive
Incendiary Cartridges
40-mm High-explosive
Cartridges
M18A1 Claymore
Antipersonnel Mine
T45E7 Adapter-booster
PBAN- Ammonium
Perchlorate Propellant
CTPB-Ammonium
Perchlorate Propellant
PEG/PBAN
4.1xlO-4
(4.1xlO-4)
1.3xlO-2
(1.3xlO-2)
9.4xlO-5
(9.4xlO-5)
l.SxlO-3
(l.SxlO-3)
1.3xlO-3
(1.3xlO-3)
5.3xlO-7
(5.3xlO-7)
7.7xlO-4
(7.7xlO-4)
2.2xlO-6
(2.2xl(r6)
2.3xlO-6
(2.3xlO-6)
l.OxlO-6
(l.OxlO-6)
Uncontrolled Emission Factor
Range
Ib emitted/lb detonated Emission
(g emitted/g detonated) Factor Rating Reference
U
U
U
U
U
U
U
U
U
U
221
222
222
222
221
221
221
224
224
224
Note: SCC assignment is not applicable to this category.
•'—" means data are not available.
-------
PEP; the 20-mm high-explosive incendiary and 40-mm high-explosive rounds represent RDX
(2,3,5-trinitro-l,3,5-trazine) propellants with a variety of binders and additives. The M18A1
Claymore mine is primarily comprised of C4 plastic explosive with a high RDX component. The
T45E7 booster represents a tetryl-based explosive. Finally, the PBAN/CTPB/PEG propellants
represent ammonium perchlorate and nitrate propellants with different types of binders and
stabilizers.
6.14 RUBBER PRODUCTS
Lead compounds may be added to rubber products as pigments, fillers, activators,
vulcanizers, curing additives, and plasticizers. In some cases, lead metal may be included in the
rubber product, such as lead-sheathed hosing.225
Lead is used as a pigment for rubber products that require color differentiation or
for aesthetic appeal. Some uses of lead as a pigment in rubber products include white wall tires
and markings on sporting goods such as basketballs.225 Sometimes lead chromates are used as
pigments when bright yellow or orange colors are desired.226 Recent interest has developed in
eliminating the use of lead-based pigments. However, lead pigments have several desirable
qualities that are difficult to match, including heat and light stability, and low formulation and
processing costs.226
Lead compounds used as activators and vulcanizers in rubber product include
litharge (lead oxide), lead peroxide, and lead stearate. Litharge is used as a vulcanizing agent for
chloroprene and polyethylacrylate natural and synthetic rubber. As an activator, litharge
accelerates the curing rate and scorch time of rubber and is often combined with other
accelerators.227 As an activator, litharge is used primarily in natural, styrene-butadiene, and nitrile
rubbers. Red oxide and white lead are also used as activators. Table 6-25 lists some rubber
products that may contain lead.225
According to the Department of Commerce, 1,650 tons (1,500 Mg) of lead were
consumed by the rubber industry in 1990, with about 10 percent used for pigments. The majority
of this lead was consumed in manufacturing lead sheathed hosing and for making molds for the
6-80
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TABLE 6-25. END USES OF RUBBER THAT MAY CONTAIN LEAD
Tires
Inner tubes
Cable coverings
Seals
Automotive radiator and heating hosing
Footwear
Vehicle suspension and body supports
Bridge bearings
Vibration insulators
"O" rings
Sealants
Jar rings
Miscellaneous sporting goods
Tank linings
High-voltage insulators
Hose
Conveyor belts and belting
Gaskets
Flexible bellows
Piers and boat bumpers
Springs
Packaging
Rubber-coated fabric
Mats and matting
Flooring
Miscellaneous sundries
Source: Reference 225.
manufacturing process.225 Table 6-26 lists rubber product manufacturing facilities reporting lead
and lead compound emissions in the 1992 Toxic Release Inventory.
6.14.1
Process Description
An emulsion process is frequently used during the manufacture of rubber (such as
styrene-butadiene rubber). In this process, scrubbed monomer is dispersed in water, and additives
(such as litharge, which is used as an activator) are mixed during the polymerization stage. After
the polymerization reaction is complete, the polymer emulsion is blended and stored as a finished
latex for subsequent processing into end products.228
6-81
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TABLE 6-26. RUBBER PRODUCT MANUFACTURING FACILITIES IN THE
UNITED STATES REPORTING LEAD AND LEAD COMPOUND EMISSIONS IN 1992
UNDER SARA 313
Facility
Location
SIC 3069: Fabricated Rubber Products
Ashtabula Rubber Company
Elastochem Inc.
Goodyear Tire & Rubber Company
Kennedy Company, Inc.
Mach-I Compounding
Polymerics Inc.
Rhein Chemie Corporation
Ashtabula, OH
Chardon, OH
Norfolk, NE
Scottsboro, AL
Macedonia, OH
Cuyahoga Falls, OH
Trenton, NJ
SIC 3052: Rubber & Plastics Hose & Belting
Aeroquip Corporation
Boston Industrial Products
Dayco Products Inc.
Gates Rubber Company
Rhein Chemie Corporation
Uniroyal Goodrich Tire Company
Mountain Home, AR
Forest City, NC
Hohenwald, TN
Ocala, FL
Alliance, NE
Galesburg, IL
lola, KS
Trenton, NJ
Opelika, AL
Source: Reference 159.
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6.14.2 Emissions
Although no emission factors for lead from rubber manufacturing were identified
in the literature, lead emissions from this process are expected during the materials handling stage
(especially since the additives are in particulate form) and while the additives are being combined
with the monomers, catalysts, and other compounds during the polymerization step.
6-83
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SECTION 7.0
EMISSIONS OF LEAD AND LEAD COMPOUNDS FROM MOBILE SOURCES
7.1 GENERAL
Elemental lead and lead alloys are used in the manufacture and operation of
vehicles. For example, lead is used in connecting electrical components, and antimonial lead is
used in bearings. The positive plate grids in automobile batteries are made of an alloy of lead,
antimony, tin, arsenic, and copper. Lead is also an anticorrosive additive in automobile paint
primers. Combining lead and tin produces an alloy referred to as turn or turnplate, which is used
to make corrosion-resistant gas tanks.229 Lead is also an additive in automotive plastics and is
included in ceramic electrical components. Despite this widespread use of lead in vehicles, the
largest source of lead emissions from vehicles is from fuel combustion.
Lead has been used in motor gasoline since the 1920s to boost octane and provide
lubrication for intake and exhaust valves. The lead compounds function by decomposing in the
combustion cycle to form metal oxide particles. The particles interrupt the hydrocarbon chain
branching reactions that cause rapid combustion, known as "knock." Lead anti-knock
compounds foiled 1970 catalytic converter technologies developed to reduce hydrocarbon, carbon
monoxide, and nitrogen oxide emissions. This led to the development of lead-free fuel in the early
1970s.230
The 1970 Clean Air legislation permitted the regulation of fuel additives,
established a schedule for reducing lead additives, and required automobile manufacturers to
design and construct vehicles that could run on low-lead and unleaded fuel. The phase-down of
leaded gasoline in highway motor vehicles began in 1973. Section 21 l(n) of the CAA prohibits
7-1
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the manufacture of highway engines requiring leaded gasoline after 1992. In January 1992,
remaining lead additives used in fuels were banned for use in on-road vehicles in California. The
final deadline for the abolition of all lead-containing highway vehicle fuels was December 31,
1995.
The lead levels in leaded gasoline have been gradually reduced from the industrial
average of 2.5 g lead/gal (0.66 g/L) leaded gasoline in the 1970s to 0.0002 g lead/gal
(5.283xlO~5 g/L) unleaded gasoline in 1991 (see Table 7-1). Since 1982, the majority of gasoline
fuel sold for motor vehicles is lead-free. Currently, less than 1 percent of gasoline motor vehicle
fuel is leaded (see Table 7-2). As of 1995, only one gasoline refinery continues to produce
gasoline with lead additives.231 The fuel that currently has the greatest lead content is aviation
gasoline (2 to 4 g lead/gal [0.528 to 1.057 g/L]). The petroleum industry may continue to make
and market gasoline produced with lead additives for non motor vehicle uses, including use as fuel
in aircraft, racing cars, and non-road engines such as farm equipment engines and marine
engines.231 Diesel fuel is assumed to contain quantities of lead that are insignificant compared to
gasoline fuel.17'158
7.1.1 Leaded Fuels
The two most common lead anti-knock additives are tetraethyl lead (TEL) and
tetramethyl lead (TML). TEL and TML, both high in octane, lubricate intake and exhaust valves
and help reduce engine knock.230 In 1990, 93 percent of highway fuel lead additives were TEL,
and the remaining 7 percent were TML. The composition and properties of TEL and TML are
shown in Table 7-3.
The manufacture of TEL and TML compounds for use in gasoline was
discontinued in the United States in May 1991.232 The plants that manufactured alkylated lead
compounds have been dismantled.232'233'234 However, TEL is still manufactured in Canada and
Europe and imported by a few companies in the United States to produce leaded gasoline.232'235'236
7-2
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TABLE 7-1. LEAD CONTENT OF MOTOR VEHICLE FUELS
Year
1974
1975
1976
1977
1978
1979
1980
1981
1982
1983
1984
1985
1986
1987
1988
1989
1990
1991
Leaded
2.07
1.82
2.02
2.03
1.76
1.76
1.33
1.01
1.02
0.83
0.84
0.59
0.31
0.15
0.15
0.002
0.0004
0.0002
Lead Content (g/gal)
Unleaded
0.014
0.014
0.014
0.014
0.010
0.016
0.0286
0.009
0.005
0.003
0.006
0.002
0.002
0.001
0.001
0.002
0.0004
0.0003
Source: Reference 237.
7-3
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TABLE 7-2. FUEL SALES
Finished Motor Fuel (thousand barrels)
Year
1981
1982
1983
1984
1985
1986
1987
1988
1989
1990
1991
1992
Leaded
1,213,144
1,142,590
1,085,813
990,051
885,144
795,697
833,668
490,805
299,770
140,571
92,041
38,502
Unleaded
1,190,347
1,243,032
1,331,271
1,459,410
1,608,217
1,771,738
1,896,420
2,194,340
2,374,899
2,500,170
2,531,403
2,621,411
Aviation Gasoline
11,147
9,306
9,444
8,692
9,969
11,673
9,041
9,705
9,427
8,910
8,265
8,133
Source: Reference 238.
The blend of TEL and TML used in motor vehicle fuel depends upon the grade of
gasoline being produced. For regular gasolines (i.e., below about 93 RON [research octane
number for all distillate fractions of the gasoline]), TEL is usually the preferred anti-knock
additive. For premium gasolines where elevating RON is important, TEL is normally preferred
for lead concentrations below 1.514 g lead/gal (0.40 g/L). Above this level, mixtures of TEL and
TML may be more beneficial. For premium gasolines where MON (motor octane number—a
guide to the anti-knock performance of a fuel under relatively severe driving conditions) is
important, mixtures of TEL and TML are again likely to produce the best results. For premium
gasolines where R100°C (research octane number of the fraction of gasoline distilled up to
100°C) is important, TML, or mixtures of TML with TEL, are likely to be most beneficial.230
Leaded fuels also contain 1,2-dibromoethane and 1,2-dichloroethane. These
chemicals act as lead scavengers, preventing a buildup of lead compounds in the combustion
7-4
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TABLE 7-3. COMPOSITION AND PROPERTIES OF TEL AND TML
COMPOSITION, WT %
Lead Alkyl
1 ,2-dibromoethane
1 ,2-dichloroethane
Dye, diluent, inhibitor, etc.
Lead content, wt%
PROPERTIES
Specific Gravity, 20°/4°C
Vapor pressure @ 20° C mbar
Boiling point of lead alkyl, °C
TEL
61.5
17.9
18.8
1.8
39.39
1.6
67
200
(decomposes)
TML
50.8
17.9
18.8
12.5
39.39
1.58
87
110
Source: Reference 230.
chamber. These lead deposits can flake off and cause valve burning by holding valves off their
seats, thus allowing the hot combustion gases to escape past the valves. During combustion, lead
and halogenated additives combine to form lead halides that are exhausted from the engine.230
Of the different aviation fuels currently in use, only aviation gasoline contains lead
as an anti-knock compound. Jet kerosene and JP-4 do not contain lead additives. Aviation
gasoline is used in reciprocating piston-engine aircraft and is therefore more prevalent in civil
aviation and general commercial aviation. There are two grades of aviation gasoline: low-lead,
which has a lead concentration of 2 g lead/gal (0.528 g/L) aviation gasoline, and high-lead, which
has a lead concentration of 4 g lead/gal (1.057 g/L) aviation gasoline. Only TEL is used in
leaded aircraft fuel.239
Due to the economics of producing leaded gasoline, fewer refineries and blending
facilities are producing it. This has caused the Federal Aviation Administration and the General
Aviation Manufacturer's Association to begin a cooperative research program to develop an
7-5
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unleaded gasoline for aircraft. The two organizations have set a goal to develop an American
Standard for Testing and Material (ASTM) specification for unleaded gasoline for aircraft by
1995 and the goal of eliminating the use of leaded gasoline in aircraft by 1998.240
Although Section 21 l(n) of the CAA does not require a lead phase-down of
aviation fuels, the aircraft fuel industry is currently developing standards for unleaded aviation
gasoline, but continues to rely on leaded fuels.
7.1.2 Unleaded Fuels
Refiners began producing unleaded gasoline in the early 1970s for automobiles
equipped with catalytic converters. As a result of the 1990 CAA amendments, lead additives in
gasoline were replaced by high-octane hydrocarbon fractions with properties suitable for gasoline
blending. Straight-run refinery products, for example, have comparatively low-octane numbers.
On the other hand, aromatics, isoparaffins, and olefins produced from catalytic cracking and
reforming processes have much higher octane numbers. Adjusting the relative amount of these
hydrocarbon fractions results in gasolines with different octane numbers.241 Still, a trace amount
of lead remains in unleaded gasoline. This lead is picked up as it passes through refinery
processes and fuel distribution systems that had previously contained leaded gasoline. These
trace amounts may not exceed 0.05 grams of lead per gallon. At this level, catalytic control
devices are still protected.231
7.2 EVAPORATIVE EMISSIONS FROM FUEL DISTRIBUTION FOR MOBILE
SOURCES
Calculated TML evaporative profiles are two orders of magnitude greater than
TEL profiles because the vapor pressure of TML (23 mm Hg at 68 °F) is two orders of magnitude
higher than that of TEL (0.2 mm Hg at 68 °F). The difference between TML and TEL varies
relative to ambient temperatures, with lower temperatures producing the greatest differences.
7-6
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The TML weight fraction can be applied to leaded gasoline throughput to estimate
TML emissions. The TML emission factor can be adjusted for different ambient temperatures, as
noted in the following equation:
1.321 x 10
,0.60 1289.8 f 900
TML =
gas
6900 + 1.015 x 10°-60 - I '"""•" I +
,0.60 1289.8 f 900
T + 2191 I T + 233
where: TMLgas = TML vapor phase fraction (mass TML emitted/mass leaded
gasoline throughput)
T = Temperature (°C)
Similarly, the TEL weight fraction can be applied to leaded gasoline throughput to
estimate TEL emissions. To adjust TEL emission factors for different ambient temperatures, the
following equation can be used:
1.934x10-- U1789^ ' 9°°
TEL ^ + v + 195 / I T + 233
/->ir\r\ 1 f/"> 1 r\1 451 l/o9.6
6200 + 1.563 x 10
T + 195 / T + 233
where: TELgas = TEL vapor phase fraction (mass TEL emitted/mass leaded gasoline
throughput)
T = Temperature (°C)
TEL emissions from the distribution of aviation fuel can be estimated using the following
equation:
79.25 x 10
0.914 1789.6 1115.86
TFT = I, T + 195 y I, T + 228
1JZ/1"avgas /
6900 - 62.35 x 10°™ - " + 1115-86
T + 195 / T + 228
7-7
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where: TELavgas = TEL vapor phase fraction (mass TEL emitted/mass leaded
aviation gasoline throughput)
T = Temperature (°C)
In general, most TEL and TML evaporative emissions from leaded fuel distribution
are relatively small. In 1990, 5 percent of highway fuel sold in the United States was leaded.
Given that the lead concentration of leaded fuel used in the EPA study (0.85 g/gal), and the lead
concentrations in current unleaded fuels (0.0003 g/gal) are approximately three orders of
magnitude different, and given that the quantity of fuel distributed is approximately two orders of
magnitude different, total evaporative emissions from fuel distribution should be less for unleaded
than for leaded fuel. By the end of 1995, the lead content of all motor vehicle fuels will be
reduced to zero, making the highway fuel distribution category a negligible source.
7.3 COMBUSTION EMISSIONS
Vehicles designed and operated on leaded gasoline exhaust 75 percent of the lead
in the fuel. For catalytically equipped vehicles operating on unleaded gasoline, 40 percent of the
lead burned is emitted into the atmosphere. Lead is retained in the catalyst (45 percent),
crankcase oil (25 percent), combustion chamber, and the rest of the exhaust system
(30 percent).242'243
This information can be used to approximate lead emissions from mobile
combustion sources using the following equation:
Rf
Ecf = Lf x Too x Ff
where: Ecf = Emission of lead from vehicle combustion for leaded or unleaded
fuel "f' (g/year)
Lf = Lead content of fuel "f' (g/gal)
Rf = Amount of lead released for fuel type "f' (75 percent for vehicles
designed for, and using, leaded gasoline, and 40 percent for
vehicles designed for, and using, unleaded gasoline)
Ff = Fuel throughput (gal/year)
7-8
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For a more precise estimate of mobile combustion emissions, use of the EPA/ Office of Mobile
Sources (OMS) PARTS Mobile Emission Model is recommended. The reader is cautioned that
modeling results are only estimates, not actual emissions, and have the potential for being over or
under estimated.
Presently, there are no emission factors to characterize lead emissions from aircraft
fuel combustion. The equation used to characterize motor vehicle emissions may be used, but will
probably lead to an underestimation of emissions because of differences in engine design, exhaust
system configurations, and operation.
7.4 ROAD DUST
Several studies have shown that lead from atmospheric deposition can be
reintrained by vehicles as road dust.244"248 This section provides estimation procedures for this
source derived from a U.S. EPA report entitled Estimating and Controlling Fugitive Lead
Emissions from Industrial Sources?'49
7.4.1 Paved Roads
Open dust fugitive emissions from paved roads depend upon the loose surface
material and traffic characteristics of the road. These emissions have been determined to vary
directly in proportion to the surface material loading and silt content of the road. The surface
material loading is the amount of loose dust on the road surface and is measured in units of mass
of material per unit area. (Surface material loading for a specific road is typically expressed in
units of mass per unit length of road.) The silt content is the percentage of silt (i.e., particles less
than or equal to 75 microns in diameter) in the loose surface dust. Some typical values for silt
loading on industrial paved roads are presented in Table 7-4. Other factors that affect industrial
paved road fugitive emissions include the volume of traffic, number of traffic lanes, average
vehicle weight, and the degree to which vehicles travel on nearby unpaved areas (thereby allowing
more dust to be deposited on the paved road). This last factor is known as the industrial
7-9
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TABLE 7-4. INDUSTRIAL PAVED ROAD SILT LOADINGS
Industry
Copper smelting
Iron and steel
production
Asphalt batching
Concrete batching
Sand and gravel
processing
No. of
sites3
1
6
1
1
1
No. of
samples3
3
20
3
3
3
Silt, percent w/w
Range
15.4-21.7
1.1-35.7
2.6-4.6
5.2-6.0
6.4-7.9
Mean
19.0
12.5
3.3
5.5
7.1
No. of
travel
lanes
2
2
1
2
1
Silt loading, g/m2
Range
188-400
0.09 - 79
76 - 193
11-12
53-95
Mean
292
12
120
12
70
Source: Reference 249.
a The data presented in this table are based on an EPA-sponsored sampling and analysis program, for which the number
of samples specified in the table were collected at the specified number of sites.
augmentation factor and ranges in value from 1.0 to 7.0. Higher values indicate greater fugitive
dust emissions. Typical values for this factor are found in Table 7-5.
The magnitude of fugitive lead emissions (or emissions of any other substance)
may be estimated by direct proportion with the percent by weight of lead (or substance of
concern) in the silt fraction. Because of variations from location to location, site-specific data
should be used for all of the above-mentioned factors whenever possible.
The fugitive lead emission factor for industrial paved roads in units of kilograms
per vehicle kilometer traveled (kg/VKT), or pounds per vehicle mile traveled (Ib/VMT), can be
determined by the following modified equation for total suspended particulate emissions:
E = 0.22 I
C
100,
£'
n,
s
To",
L '
280,
W
2.7.
0.7
(kg/VKT)
E = 0.22 I
C
100,
4.
n;
s
To",
L
1,000,
0.7
W
— (Ib/VMT)
7-10
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TABLE 7-5. TYPICAL VALUES FOR PAVED ROAD INDUSTRIAL AUGMENTATION
FACTOR (I)
_P Conditions
1.0 Travel on paved roads only
3.5 Travel on paved roads with unpaved shoulders—20 percent of vehicles travel with one
set of wheels on shoulder
7.0 Traffic enters from unpaved roads
Source: Reference 249.
a Values are dimensionless.
where: E = emission factor, kg/VKT (Ib/VMT)
I = industrial augmentation factor (dimensionless)
C = average percent by weight of lead in the silt fraction
n = number of traffic lanes
s = average surface material silt content, percent
L = average surface dust loading, kg/km (Ib/mile)
W = average vehicle weight, Mg (ton)
To estimate lead emissions from paved road dust, the developed emission factors should be
applied to local VMT data.
7.4.2 Unpaved Roads
Fugitive dust emissions from unpaved roads, like paved road fugitive emissions,
are directly proportional to the silt content of the surface material. In addition, fugitive lead
emissions can be estimated by direct proportion with the lead content in the silt fraction. Unpaved
road fugitive dust emissions are also proportional to the mean vehicle speed, mean vehicle weight,
and mean number of wheels. Fugitive emissions from unpaved roads are also affected by the
rainfall frequency. For particles under 30 microns in diameter, a particle size multiplier must also
be included in the computation of emissions. However, for total suspended particulate emissions,
which is the concern here, the value of this factor is assumed to be unity, and it may be dropped
from the equation.
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The fugitive lead emission factor for unpaved roads per unit of vehicle distance
traveled can be estimated by the following modified equation for total suspended particulates:
1.7 / \ 0.5 /o/:c \
w (365 - p) KT
( 4) 365
E = (5.9) -£_ A Z- -' 065 - P) (lb/VMT)
100 / 121 30 / 3 I 4 I 365
where: E = emission factor, kg/VKT (Ib/VMT)
C = percent by weight of lead in the silt fraction
s = average silt content of road surface material, percent
S = average vehicle speed, km/h (mil/h)
W = average vehicle weight, Mg (ton)
w = average number of wheels (dimensionless)
p = number of days with > 0.254 mm (0.01 in) of precipitation per year
Measured silt values for a number of industries are given in Table 7-6. The number
of wet days per year, p, for the geographical area of interest should be determined from local
climatic data. As with paved road fugitive dust emission factors, the use of site-specific data is
strongly encouraged.
To estimate lead emissions from unpaved road dust, the developed emission
factors should be applied to local VMT data.
7-12
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TABLE 7-6. TYPICAL SILT CONTENT VALUES OF SURFACE MATERIAL ON
INDUSTRIAL AND RURAL UNPAVED ROADS
--J
Industry
Copper smelting
Iron and steel production
Sand and gravel processing
Stone quarrying and processing
Taconite mining and processing
Western surface coal mining
Rural roads
Road Use or Surface Material
Plant road
Plant road
Plant road
Plant road
Haul road
Service road
Access road
Haul road
Scraper road
Haul road (freshly graded)
Gravel
Dirt
Crushed limestone
Plant
Sites3
1
9
1
1
1
1
2
3
3
2
1
2
2
TpQt —
Samples3
3
20
3
5
12
8
2
21
10
5
1
5
8
Silt, percent
Range
15.9-19.1
4.0-16.0
4.1-6.0
10.5-15.6
3.7-9.7
2.4-7.1
4.9-5.3
2.8-18
7.2 - 25
18-29
N/A
5.8-68
7.7- 13
by weight
Mean
17.0
8.0
4.8
14.1
5.8
4.3
5.1
8.4
17
24
5.0
28.5
9.6
Source: Reference 249.
a The data presented in this table are based on an EPA-sponsored sampling and analysis program, for which the number of samples specified in this table were
collected at the specified number of sites.
N/A = Not applicable.
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SECTION 8.0
SOURCE TEST PROCEDURES
The EPA has published reference methods for measuring lead in ambient air and
lead contained in stack gas emissions. EPA Reference Method for the Determination of Lead in
Suspended Paniculate Matter Collected from Ambient Air was first published in the Federal
Register on October 5, 1978, and was last revised on July 1, 1987.25° The EPA has also
published Method 12 and draft Method 29 for measuring lead in stack gases. Method 12 was
first published in the Federal Register on January 14, 1980 and last revised on
November 14, 1990 and is used to sample for only total inorganic lead in stack gases.251 Draft
Method 29 was first published in the Federal Register on July 17, 1991 as part of the boiler and
industrial furnace regulations and is used to sample for total inorganic and organic lead and other
metals in stack gases. EPA Method 29 was finalized on April 25, 1996 and is included in
Appendix A of 40 CFR Part 60.
Sections 8.1 and 8.2 of this report summarize the field sampling procedures for
measuring lead in ambient air and stack gases, respectively. Section 8.3 describes the different
analytical techniques used to analyze and measure the amount of lead collected in ambient air
and stack gas samples.
8.1 AMBIENT AIR SAMPLING METHODS
Ambient air concentrations of lead in suspended PM can be measured using EPA
Reference Method for the Determination of Lead in Suspended Paniculate Matter Collected
from Ambient Air™ Figure 8-1 shows a simplified diagram of the components of the
high-volume ambient air sampling equipment for lead. The equipment is mounted in an enclosed
8-1
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Glass Fiber Filter
Filter Holder
Sampling Head
Flow Transducer
Figure 8-1. Components of a High-Volume Ambient Air Sampler for Lead
Source: Reference 253.
8-2
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shelter equipped with a roof. Ambient air is drawn under the roof of the shelter through a
pre-weighed glass-fiber filter. Figure 8-2 shows a simplified diagram of the air flow through a
high-volume sampler located in a shelter.253 The high-volume sampler should be operated for
24 hours at an average flow rate of 1.7 cubic meters per minute (m3/min). The primary and
secondary national ambient air quality standards for lead are 1.5 micrograms per cubic meter
(|ig/m3) averaged over a calendar quarter. For determining compliance with the primary and
secondary national ambient air quality standards for lead, at least one 24-hour sample must be
collected every six days except during periods or seasons exempted by the Regional EPA
Administrator.254
After sampling, the filter is removed and sent to a laboratory for analysis. The
filter is weighed several times until a constant weight is measured and then the filter is digested
in an acid solution and analyzed for total lead content either by atomic absorption
spectrophotometry (AAS) or inductively coupled plasma emission spectroscopy (ICP). The
typical range in the amount of lead collected by use of this method is 0.07 to 7.5 |ig/m3 assuming
an upper linear range of analysis of 15 micrograms per milliliter (|ig/mL) and an air volume of
2,400 cubic meters (m3).
The major advantage to the high-volume lead sampling method is the low
detection limit that can be achieved (i.e., 0.07 to 7.5 jig lead/m3). Another advantage is that the
ambient air sample is collected over a 24-hour period, which encompasses all types of weather
conditions, particularly temperature changes, and the range of emission source activities that
occur throughout a 24-hour period.
One disadvantage of the high-volume sampling method is that it was designed for
sampling only total inorganic lead compounds in suspended PM. Inorganic lead cannot be
speciated and most organic lead compounds cannot be detected. A second disadvantage is that
the high-volume method is very dependent on meteorological conditions. Any change in wind
speed or direction and any amount of precipitation can influence the sample results. To interpret
the effects of weather conditions on the sample results, meteorological data must be recorded
during the sampling period.
8-3
-------
Shelter Roof
Shelter
Figure 8-2. Air Flow through a High-Volume Sampler in a Shelter
Source: Reference 253.
8-4
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8.2 STATIONARY SOURCE SAMPLING METHODS
Two methods are available for sampling stack gas concentrations of lead: EPA
Method 12 and EPA Method 29.251'252 Method 12 is used to sample for only total inorganic lead.
EPA Method 29 is used to sample for total inorganic and organic lead and other metals in a
stack. These two methods are described on the following pages.
8.2.1 EPA Method 12 - Methodology for the Determination of Metals Emissions in
Exhaust Gases from Hazardous Waste Incineration and Similar Combustion
Sources
Method 12 (also called a multi-metals train) can be used to sample PM and total
inorganic lead (i.e., elemental lead and inorganic lead compounds) isokinetically from stack
gases. A diagram of the Method 12 sampling train is shown in Figure 8-3. Particulate lead is
collected through a glass nozzle and probe onto a glass-fiber filter and in a dilute nitric acid
solution in the impingers. The nozzle and probe are washed with dilute nitric acid and the wash,
filter, and impinger solution are sent to a laboratory, where they are digested in an acid solution
and analyzed for total lead content by AAS or ICP.
The exact run time and volume samples vary from source to source depending on
the required detection limit. Typically, Method 12 sampling is conducted for 2 hours to sample
approximately 2.55 m3 of stack gas. The lower range of detection for this method is 25 jig of
total lead. The upper range can be extended considerably by diluting the sample prior to analysis.
The major advantage to Method 12 is that the method was designed to sample for
inorganic lead compounds from a wide variety of industrial processes, and the method has been
validated. The stack gas stream is sampled isokinetically, which provides an accurate emission
rate. Method 12 is also extremely flexible. The length of sample runs and the sample volume
collected can be adjusted depending on the expected concentration of the stack gas stream. The
disadvantage is that Method 12 cannot be used to speciate inorganic lead compounds or to
sample for organic lead compounds.
8-5
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Temperature
Sensor
. Probe
Type S Temperature
Pilot Tube Sensor Stack
Temperature
Sensor
Temperature
Sensor
Type S Pilot Tube
Figure 8-3. Method 12 Sampling Train
S ource: Reference 251.
-------
8.2.2 EPA Method 29 - Determination of Metals Emissions from Stationary Sources
EPA Method 29 can be used to sample PM and total inorganic and organic lead
compounds isokinetically from stack gases. The Method 29 sampling train is a modified EPA
reference Method 5 sampling train and is shown in Figure 8-4.
Particulate lead with a particle size diameter greater than or equal to
0.3 micrometers is collected through a glass nozzle and probe onto a pre-weighed glass-fiber
filter. Particulate lead with a particle size diameter less than 0.3 micrometers and lead
compounds in the vapor phase pass through the filter and are collected in a dilute nitric
acid/hydrogen peroxide solution in the impingers. The nozzle and probe are washed with dilute
nitric acid and the wash, filter, and impinger solution are sent to a laboratory, where they are
digested in an acid solution and analyzed for lead content either by AAS or ICP. The samples
collected on the filter and in the impinger solution can be analyzed separately to differentiate
between the amount of paniculate lead and lead in the gas phase.
The exact run time and volume sampled varies from source to source depending
on the required detection limit. Typically, the Method 29 train is run for 2 hours and samples
approximately 2.55 m3 of stack gas. The lower range of detection for this method is 25 jig of
total lead. The upper range can be extended considerably by diluting the sample prior to analysis.
This method is applicable to the determination of antimony (sb), arsenic (As),
barium (Ba), beryllium (Be), cadmium (Cd), chromium (Cr), cobalt (Co), copper (Cu), lead (Pb),
manganese (Mn), Mercury (Hg), nickel (Ni), phosphorous (P), selenum (Se), silver (Ag),
thallium (Ti), and zinc (Zn). Although it is the preferred method for sampling stack gas streams
and can measure several metals at one time, the method cannot be used to speciate inorganic or
organic lead compounds.
8-7
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Thermometer
Glass Filter Holder
Glass Probe Liner
Thermometer
0
Pilot Manometer
Empty (Optional)
5% HN03/10% H202
Silica Gel
4% KMn04/10% H2S04
Orifice
Vacuum Gauge
Air-tight
Dry Gas Pump
Meter
Figure 8-4. Method 29 Sampling Train
Source: Reference 252.
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8.3 ANALYTICAL TECHNIQUES FOR THE MEASUREMENT OF LEAD
The most common technique for measuring total lead in air samples is
spectroscopy. The two spectroscopic techniques used most by environmental laboratories are
AAS and ICP. AAS is the most common method used to measure total lead. The advantages to
AAS are that the method is simple, rapid, and applicable to a large number of metals. Samples
other than drinking water must be acid-digested prior to analysis. Two types of AAS methods
for measuring total lead are direct aspiration (flame) and graphite furnace.
The second most common technique for measuring total lead in air samples is
ICP, which allows simultaneous, or sequential, determination of several metals in a sample
during a single analytical measurement. Air samples must be acid-digested prior to analysis.
8.3.1 Direct Aspiration (Flamed Atomic Absorption Spectroscopy
Method 7420 specifies the procedure for analyzing air samples for total lead using
direct-aspiration (flame) AAS.256 In direct-aspiration (flame) AAS, a sample is aspirated and
atomized in an air/acetylene flame. A light beam from a hollow cathode lamp whose cathode is
made of the element being measured is directed through the flame into a monochromator, and
onto a detector that measures the amount of light absorbed. Absorption depends upon the
presence of free, unexcited ground-state atoms in the flame. Because the wavelength of the light
beam is characteristic of only the element being measured, the light energy absorbed by the flame
is a measure of the concentration of that element in the sample. The detection limit for lead is
100 micrograms per liter (|ig/L). The optimum concentration ranges are from 1,000 to 20,000 jig
per sample. If direct-aspiration (flame) AAS techniques do not provide adequate sensitivity,
graphite furnace techniques can be used.
8-9
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8.3.2 Graphite Furnace Atomic Absorption Spectroscopy
Method 7421 specifies the procedure for analyzing air samples for total lead using
graphite furnace AAS.257 The principle of graphite furnace AAS is essentially the same as for
direct-aspiration (flame) AAS, except a furnace rather than a flame is used to atomize the sample.
In graphite furnace AAS, a representative aliquot of a sample is placed in a graphite tube in the
furnace, evaporated to dryness, charred, and atomized. The radiation from a given excited
element is passed through the vapor containing ground-state atoms of that element. The intensity
of the transmitted radiation decreases in proportion to the amount of the ground-state element in
the vapor. The metal's atoms to be measured are placed in the beam of radiation by increasing
the temperature of the furnace, thereby causing the injected specimen to be volatized. A
monochromator isolates the characteristic radiation from the hollow cathode lamp or
electrodeless discharge lamp, and a photosensitive device measures the attenuated transmitted
radiation. The detection limit for lead is 1.0 |ig/L. The optimum concentration ranges are from
5 to 100 jig per sample.
The major advantage of this technique is that it affords extremely low detection
limits. It is the easiest technique to perform on relatively clean samples. Because this technique
is so sensitive, however, interferences can be a problem; finding the optimum combination of
digestion, heating times, temperatures, and matrix modifiers can be difficult for complex
matrices.
8.3.3 Inductively Coupled Plasma Atomic Emission Spectroscopy
Method 6010A specifies the procedures for analyzing air samples for total lead
using ICP.258 The ICP method measures element-emitted light by optical spectrometry. The
sample is nebulized and the resulting aerosol is transported to the plasma torch, where excitation
occurs. Characteristic atomic-line emission spectra are produced by radio-frequency inductively
coupled plasma. The spectra are dispersed by a grating spectrometer, and the intensities of the
lines are monitored by photomultiplier tubes. The photocurrents from the photomultiplier tubes
8-10
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are processed and controlled by a computer. The detection limit for lead is 42 |ig/L. The
optimum concentration range varies with the make and model of the instrument used.
The primary advantage of TCP is that it allows simultaneous or rapid sequential
determination of many elements in a short time. The primary disadvantage is background
radiation from other elements and the plasma gases. Although all TCP instruments utilize
high-resolution optics and background correction to minimize these interferences, analysis for
traces of metals in the presence of a large excess of a single metal is difficult.
8-11
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SECTION 9.0
REFERENCES
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Research Triangle Park, North Carolina: U.S. Environmental Protection Agency,
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2. Shiroma, Genevieve A., CARB, Letter to Dennis Beauregard, EPA. Comments on
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3. U.S. EPA Source Test Information Retrieval System (STIRS). U.S. Environmental
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4. U.S. EPA Factor Information Retrieval System Version 3.0 (FIRE 3.0). Research
Triangle Park, North Carolina: U.S. Environmental Protection Agency, Office of Air
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5. U.S. EPA. Procedures for Preparing Emission Factor Documents.
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12. U.S. EPA. Compilation of Air Pollutant Emission Factors, 5th ed. (AP-42), Vol. I:
Stationary Point and Area Sources, Section 12.16: Lead Oxide and Pigment
Production. Research Triangle Park, North Carolina: U.S. Environmental Protection
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15. Sax, N. Dangerous Properties of Industrial Materials, 1993.
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Planning and Standards, 1985.
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(August 15, 1996).
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25. Hall, R.M. and J.L. Gittleman. Control Technology for Metal Reclamation
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U.S. Department of Health and Human Services, Engineering Control Technology
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July 1995.
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Stationary Point and Area Sources, Section. Section 12.11: Secondary Lead
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Research Triangle Park, North Carolina: U.S. Environmental Protection Agency,
Office of Air Quality Planning and Standards, 1994.
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Research Triangle Park, North Carolina: Pacific Environmental Services, Inc,
March 15, 1994.
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Appendix B. EPA-450/2-77-012. Research Triangle Park, North Carolina:
U.S. Environmental Protection Agency, Office of Air Quality Planning and
Standards, Emission Standards Division, 1977.
32. U.S. EPA. Compilation of Air Pollutant Emission Factors, 5th ed. (AP-42), Vol. I:
Stationary Point and Area Sources, Section. Section 12.3: Primary Copper Smelting.
Research Triangle Park, North Carolina: U.S. Environmental Protection Agency,
Office of Air Quality Planning and Standards, 1995.
33. Jolly, J. (Bureau of Mines, U.S. Department of the Interior, Washington, D.C.).
Facsimile concerning capacities of U.S. copper smelters. January 23, 1993.
34. U.S. EPA. Compilation of Air Pollutant Emission Factors, 5th ed. (AP-42), Vol. I:
Stationary Point and Area Sources, Section. Section 12.9: Secondary Copper
Smelting and Alloying. Research Triangle Park, North Carolina: U.S.
Environmental Protection Agency, Office of Air Quality Planning and Standards,
1995.
9-3
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9-14
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164. U.S. EPA. 1993 Toxic Chemical Release Inventory (SARA Title 313) Database.
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9-15
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177. U.S. EPA. Compilation of Air Pollutant Emission Factors, 5th ed. (AP-42), Vol. I:
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9-16
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9-17
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206. Polyvinyl Chloride. Chemical Products Synopsis. Asbury Park, New Jersey:
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9-18
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224. UTC. Emissions Monitoring. United Technologies Corporation, Chemical Systems
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225. Franklin Associates. Characterization of Products Containing Lead and Cadmium
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January 1989. pp. 115-120.
226. Gordon, S. Colorants. Modern Plastics Mid-October Encyclopedia Issue. New
York, New York: McGraw Hill, October 1990. 67(11): 167-170.
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228. U.S. EPA. Locating and Estimating Air Emissions from Sources of 1,3-Butadiene,
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229. Brady, G.S. and H.R. Clauser. Materials Handbook. New York, New York:
McGraw Hill, Inc., 1991.
230. Owen, K., and T. Coley. Automotive Fuels Handbook. Warrendale, Pennsylvania:
Society of Automotive Engineers, Inc., 1990.
9-19
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231. Prohibition on Gasoline Containing Lead or Lead Additives for Highway Use, Draft
Final Rule, 61 FR 3832-3838, February 2, 1996.
232. Vitas, J. (Alliance Technologies Corporation) and A. Pagano (E.I. DuPont de
Nemours). Telecon concerning plants that manufacture alkylated lead compound in
the United States and alkylated lead compounds imported into the United States.
March 26, 1992.
233. Vitas, J. (Alliance Technologies Corporation) and E. Williams (Texas Air Control
Board). Telecon concerning plants that manufacture alkylated lead compound in the
United States. March 26, 1992.
234. Billings, R. (Radian) and J. Selsinger (E.I. DuPont De Nemours, Inc.). Telecon
concerning plants that manufacture alkylated lead compounds in the United States
and alkylated lead compounds imported into the United States. May 2, 1995.
235. Vitas, J. (Alliance Technologies Corporation) and K. Darmer (Shell Oil). Telecon
concerning alkylated lead compounds imported into the United States and the
transportation and blending of alkylated lead compounds with gasoline.
March 31, 1992.
236. Vitas, J. (Alliance Technologies Corporation) and J. Caldwell (U.S. Environmental
Protection Agency, Office of Mobile Sources). Telecon concerning alkylated lead
compounds imported into the United States. March 31, 1992.
237. U.S. EPA. Part 5 MOBILE Model. Ann Arbor, Michigan: U.S. Environmental
Protection Agency, Office of Mobile Sources, 1993.
238. U.S. Department of Energy. Petroleum Supply Annual. Washington D.C.: U.S.
Department of Energy, Energy Information Administration, 1981 to 1993.
239. TRC Environmental Corporation. Estimation of Alkylated Lead Emissions., Final
Report. Prepared for the U.S. Environmental Protection Agency, Office of Air
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240. Vitas J. (Alliance Technologies Corporation) and S. Green (Dunaway & Cross).
Telecon concerning the status of unleaded gasoline used by aircraft. May 11, 1992.
241. U.S. Department of Energy. The Motor Gasoline Industry: Past, Present, and
Future. Washington D.C.: U.S. Department of Energy, Energy Information
Administration, 1991.
242. Energy and Environmental Analysis, Inc. Supplementary Guidelines for Lead
Implementation Plans, Updated Projections for Motor Vehicles Lead Emissions.
EPA-460/3-85-006. Ann Arbor, Michigan: U.S. Environmental Protection Agency,
1985.
243. Carey, P.N. Supplementary Guidelines for Lead Implementation Plans, Updated
Projections for Motor Vehicles Lead Emissions. EPA-450/2-83-002. Ann Arbor,
Michigan: U.S. Environmental Protection Agency, 1983.
9-20
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244. Chamberlain, A.C. Fallout of Lead and Uptake by Crops. Atmospheric
Environment. 17(4): 15, 1983.
245. Deroanne-Bauvin, J., J. Delcarte, and R. Impens. Monitoring of Lead Deposition
Near Highways: A Ten Year Study. The Science of the Total Environment.
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246. Harrison, R., W.R. Johnson, J.C. Ralph, and SJ. Wilson. The Budget of Lead,
Copper and Cadmium for a Major Highway. The Science of the Total Environment.
46(1985):137-145.
247. Rice, P. Lead Emission Rates from Gasoline Engines — A Legislative and In-use
Emission Rate Study of U.K. and U.S. to 1990. Transportation Planning and
Technology. 9:37-45, 1984.
248. Tjell, J.C., M.F. Hovmand, and H. Mosbaek. Atmospheric Lead Pollution of Grass
Grown in a Background Area in Denmark. Nature, 280(2):425-426, August 1979.
249. Marinshaw, R. and D. Wallace (MRI). Estimating and Controlling Fugitive Lead
Emissions from Industrial Sources. Research Triangle Park, North Carolina:
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250. U.S. Code of Federal Regulations. Title 40, Protection of the Environment, Part 50,
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Particulate Matter Collected from Ambient Air. Washington D.C.: U. S. Government
Printing Office, 1987. p. 770.
251. U. S. EPA. Methodology for the Determination of Metals Emissions in Exhaust
Gases from Hazardous Waste Incineration and Similar Combustion Sources, 3rd ed.,
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Environmental Protection Agency, September 1988.
252. U.S. Code of Federal Regulations. Title 40, Protection of the Environment,
Part 60~Standards of Performance for New Stationary Sources, Appendix A:
Determination of Metals Emissions from Stationary Sources, Method 29.
Washington, D.C.: U.S. Government Printing Office.
253. U.S. EPA. APT1Course 435 Atmospheric Sampling, Student Manual. EPA
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Protection Agency, September 1980. pp. 4-38 and 4-51.
254. U.S. Code of Federal Regulations. Title 40, Protection of the Environment, Part 58,
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255. Tomey M. (Radian Corporation). Validation of Draft Method 29 at a Municipal
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9-21
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256. U.S. EPA. Test Methods for Evaluating Solid Waste, 3rd ed., Volume 1 A:
Laboratory Manual, Physical/Chemical Methods, Method 7420. SW-846.
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257. U.S. EPA. Test Methods for Evaluating Solid Waste, 3rd ed., Volume 1 A:
Laboratory Manual, Physical/Chemical Methods, Method 7421. SW-846.
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and Emergency Response, November 1986. pp. 7421-1 to 7421-5.
258. U.S. EPA. Test Methods for Evaluating Solid Waste, 3rd ed., Volume 1 A:
Laboratory Manual, Physical/Chemical Methods, Method 6010A. SW-846.
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259. U.S. EPA. ICCR Inventory Database Version 3.0. Office of Air Quality Planning
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March 12, 1998.
9-22
-------
APPENDIX A
EMISSION FACTOR SUMMARY TABLE
-------
TABLE A-l. SUMMARY OF EMISSION FACTORS BY SOURCE CLASSIFICATION CODES
SCC/AMS
Code Description Emission Source
3-03-010-02 Primary Lead Smelting Blast Furnace
3-03-010-04 Primary Lead Smelting Ore Crushing
3-03-010-25 Primary Lead Smelting Sinter Machine Leakage
3-03-010-28 Primary Lead Smelting Tetrahedrite Drier
3-03-010-29 Primary Lead Smelting Sinter Machine (weak gas)
3-03-010-32 Primary Lead Smelting Ore Screening
3-04-004-03 Secondary Lead Smelting Blast Furnace (Cupola)
3-04-004-04 Secondary Lead Smelting Rotary Sweating Furnace
Control
Device
None
Baghouse
Spray Tower/FF
None
Baghouse
ESP/Scrubber
Baghouse
ESP/Scrubber
Baghouse
None
Wet Scrubber/FF/
Cyclone/Settling
Chamber/Demister
None
Baghouse
Emission Factor
English
(Metric)
LOxlO'4 Ib/ton
(5.0xlO-5 kg/Mg)
6.7xlO-2 Ib/ton
(3.4xlQ-2kg/Mg)
1.7xlQ-2 Ib/ton
(8.5xlO-3 kg/Mg)
3.0x10-' Ib/ton
(1.5x10-' kg/Mg)
2.0xlO-3 Ib/ton
(l.OxlO-3 kg/Mg)
3. 2xlO'2 Ib/ton
(1.6xlO-2 kg/Mg)
6.0xlQ-4 Ib/ton
(3.0xlQ-4kg/Mg)
1.9xlQ-2 Ib/ton
(9.5xlQ-3 kg/Mg)
2.0xlO-3 Ib/ton
(l.OxlO-3 kg/Mg)
1.04xl02 Ib/ton
(5.2x10' kg/Mg)
2.9x10-'
(1.5x10-')
—
2.8xlO-2 Ib/ton
(1.4xlO-2 kg/Mg)
Factor
Rating
U
E
U
U
E
E
E
E
E
C
C
E
D
-------
TABLE A-l. SUMMARY OF EMISSION FACTORS BY SOURCE CLASSIFICATION CODES (CONTINUED)
to
SCC/AMS
Code
3-04-004-04
3-04-004-13
3-04-004-02
3-04-004-26
3-04-004-14
3-04-004-09
3-04-004-25
3-03-005-03
3-04-002-42
3-04-002-43
3-04-002-44
3-04-002-xx
Description
Secondary Lead Smelting
(continued)
Secondary Lead Smelting
Secondary Lead Smelting
Secondary Lead Smelting
Secondary Lead Smelting
Secondary Lead Smelting
Secondary Lead Smelting
Primary Copper
Smelting Facilities
Secondary Copper
Smelting Facilities
Secondary Copper
Smelting Facilities
Secondary Copper
Smelting Facilities
Secondary Copper
Smelting Facilities
Emission Source
Smelting Furnace Fugitives
Reverberatory Furnace
Kettle Refining
Kettle Refining Fugitives
Casting
Casting Fugitives
Converter
Reverberatory Furnace [charge
with other alloy (7%)]
Reverberatory Furnace [charge
with high lead (58%)]
Reverberatory Furnace (charge
with red/yellow brass)
Secondary Copper - smelting
Control
Device
Baghouse/scrubber
None
Baghouse
None
None
None
Afterburner/FF/
Venturi Scrubber/
Demister
None
None
None
None
None
None
Baghouse
Emission Factor
English
(Metric)
1.9xlO'2 Ib/ton
(9.5xlO'3 kg/Mg)
—
1.2xlO'2 Ib/ton
(6.0xlO-3 kg/Mg)
6.5x10' Ib/ton
(3. 3x10-' kg/Mg)
l.OxlO'2 Ib/ton
(6.0xlO-3 kg/Mg)
6.00xlO-4 Ib/ton
(3.00xlO-4kg/Mg)
2.4 Ib/ton
(1.2 kg/Mg)
l.OxlO'2 Ib/ton
(5.0xlO'3 kg/Mg)
7.0xlO-4 Ib/ton
(3.5xlO-4kg/Mg)
2.70x10-' Ib/ton
(0.135 kg/Mg)
5.0 Ib/ton
(2.5 kg/Mg)
5.0x10' Ib/ton
(2.5x10' kg/Mg)
1.32x10' Ib/ton
(6.6 kg/Mg)
l.OOxlO'3 Ib/ton
(5.00xlO-4 kg/Mg)
Factor
Rating
D
E
U
C
C
E
C
E
C
B
B
B
B
-------
TABLE A-l. SUMMARY OF EMISSION FACTORS BY SOURCE CLASSIFICATION CODES (CONTINUED)
OJ
SCC/AMS
Code
3-04-001-09
3-04-001-14
3-04-003-01
3-04-003-02
3-04-003-03
3-04-003-20
3-03-031-01
3-03-031-02
3-03-031-03
3-03-031-04
Description
Secondary Aluminum
Production
Secondary Aluminum
Production
Iron and Steel
Foundries
Iron and Steel
Foundries
Iron and Steel
Foundries
Iron and Steel
Foundries
Leadbearing Ore
Crushing & Grinding
Leadbearing Ore
Crushing & Grinding
Leadbearing Ore
Crushing & Grinding
Leadbearing Ore
Crushing & Grinding
Emission Source
Burning/Drying
Reverberatory Furnace
Iron Foundry - Cupola
Iron Foundry - Reverberatory
Furnace
Iron Foundry - Electric
Induction Furnace
Iron Foundry - Casting
Lead Ore (5.1% Pb content)
Zinc Ore (0.2% Pb content)
Copper Ore (0.2% Pb content)
Lead-Zinc Ore (2.0% Pb
content)
Control
Device
Venturi Scrubber
Baghouse
Multiple Cyclones
Baghouse
None
Afterburner/
Venturi Scrubber
Baghouse
None
None
Afterburner/
Venturi Scrubber
None
None
None
None
Emission Factor
English
(Metric)
4.36xlQ-3 Ib/ton
(2.18xlO-3kg/Mg)
1.04xlO-5 Ib/ton
(5.18xlO-6kg/Mg)
2. 16xlO-2 Ib/ton
(l.OSxlQ-2 kg/Mg)
1.4xlO-3 Ib/ton
(7.0xlQ-4 kg/Mg)
—
1.56xlO-3 Ib/ton
(7.80xlO-4 kg/Mg)
2.67xlQ-3 Ib/ton
(1.34xlO-3 kg/Mg)
—
—
4.80xlO-3 Ib/ton
(2.40xlO-3 kg/Mg)
3.00x10-' Ib/ton
(1.50x10-' kg/Mg)
1.20xlO-2 Ib/ton
(6.00xlQ-3 kg/Mg)
1.20xlO-2 Ib/ton
(6.00xlO-3 kg/Mg)
1.20x10-' Ib/ton
(6.00xlO-2 kg/Mg)
Factor
Rating
U
U
U
D
B
U
U
B
B
U
B
B
B
B
-------
TABLE A-l. SUMMARY OF EMISSION FACTORS BY SOURCE CLASSIFICATION CODES (CONTINUED)
SCC/AMS
Code
3-03-031-05
3-03-031-06
3-03-031-07
A21-04-
002-000
A21-04-
001-000
A21-04-
004-000
1-01-009-01
1-01-009-02
Description
Leadbearing Ore
Crashing & Grinding
Leadbearing Ore
Crashing & Grinding
Leadbearing Ore
Crashing & Grinding
Residential Coal
Combustion
Residential Coal
Combustion
Residential Distillate
Oil-fired Furnaces
Wood Waste-fired Utility
Boilers
Wood Waste-fired Utility
Boilers
Emission Source
Copper-Lead Ore (2.0% Pb
content)
Copper-Zinc Ore (0.2% Pb
content)
Copper-Lead-Zinc Ore
(2.0% Pb content)
Bituminous/ Subbituminous
Coal - All Combustor Types
Anthracite Coal - All
Combustor Types
Distillate (No. 2 oil)
Oil-fired Furnaces
Wood Waste-fired Boiler
(Bark-fired)
Wood Waste-fired Boiler
(Wood/Bark-fired)
Control
Device
None
None
None
None
None
None
None
ESP
Scrubber
Multiple Cyclone
with/without Fly ash
Emission Factor
English
(Metric)
1.20x10-' Ib/ton
(6.00xlO-2 kg/Mg)
1.20xlO-2 Ib/ton
(6.00xlO-3 kg/Mg)
1.20x10-' Ib/ton
(6.00xlQ-2 kg/Mg)
2.00xlO-2 Ib/ton
(l.OOxlQ-2 kg/Mg)
1.60xlO-2 Ib/ton
(S.OOxlO-3 kg/Mg)
2.2xlO-4 Ib/MMBtu
(9.5xlQ-14 kg/Joule)
2.90xlQ-3 Ib/ton
(1.45xlO-3 kg/Mg)
1.60xlQ-5 Ib/ton
(S.OOxlO-6 kg/Mg)
3. SOxlO'4 Ib/ton
(1.75xlO-4 kg/Mg)
3. 20xlO-4 Ib/ton
(1.60xlO-4 kg/Mg)
Factor
Rating
B
B
B
U
U
U
D
D
D
D
Reinjection
1-01-009-03
Wood Waste-fired Utility
Boilers
Wood Waste-fired Boiler
(Wood-fired)
ESP
Multiple Cyclone without
Fly ash Reinjection
None
LlOxlO'3 Ib/ton
(5.50xlQ-4 kg/Mg)
3. lOxlO'4 Ib/ton
(1.55xlO-4 kg/Mg)
2.9xlO'3 Ib/ton
(1.45xlQ-3 kg/Mg)
D
D
U
-------
TABLE A-l. SUMMARY OF EMISSION FACTORS BY SOURCE CLASSIFICATION CODES (CONTINUED)
SCC/AMS
Code
1-01-009-03
Description Emission Source
Wood Waste-fired Utility
Control
Device
Limestone Injection,
Emission Factor
English
(Metric)
4.49X10'6 lb/MMBtub
Factor
Rating
U
1-02-009-01
1-02-009-02
Boilers (continued)
Wood Waste-fired
Industrial Boilers
Wood Waste-fired
Industrial Boilers
>
1-02-009-03
Wood Waste-fired
Industrial Boilers
Wood Waste-fired Boiler
(Bark-fired, >50,000 Ib steam)
Wood Waste-fired Boiler
(Wood/Bark-fired, >50,000 Ib
steam)
Wood Waste-fired Boiler
(Wood-fired, >50,000 Ib
steam)
Thermal de-NOxwith
Ammonia Injection, Water
Treatment, Multi-Cyclone,
Fabric Collector
ESP - Medium Efficiency
None
Multiple Cyclone with
Flyash Reinjection
ESP
Scrubber
Multiple Cyclone without
Flyash Reinjection
Wet Scrubber - Medium
Efficiency
Multiple Cyclone without
Flyash Reinjection/Wet
Scrubber - Medium
Efficiency
Multiple Cyclone without
Flyash Reinjection
ESP
(1.93xlO-15 kg/Joule)
LSOxlO'6 Ib/MMBtu
(6.46xlO-16 kg/Joule)
2.90xlO'3 Ib/ton
(1.45xlQ-3kg/Mg)
3.20xlO-4lb/ton
(1.60xlO-4kg/Mg)
1.60xlO-5lb/ton
(S.OOxlO'6 kg/Mg)
3.50xlO-4lb/ton
(1.75xlO-4 kg/Mg)
3.20xlO-4lb/ton
(1.60xlO-4 kg/Mg)
1.60xlO'5 Ib/MMBtu
(6.89xlO-15 kg/Joule)
4.00xlO'5 Ib/MMBtu
(1.72xlO-14 kg/Joule)
3.10xlO-4lb/ton
(1.55xlO-4 kg/Mg)
1.10xlO-3lb/ton
(5.50xlQ-4kg/Mg)
U
D
D
D
D
D
U
U
D
D
-------
TABLE A-l. SUMMARY OF EMISSION FACTORS BY SOURCE CLASSIFICATION CODES (CONTINUED)
>
SCC/AMS
Code
1-02-009-03
(continued)
1-02-009-04
1-02-009-05
1-02-009-06
1-03-009-01
1-01-006-04
1-01-006-04
1-03-009-02
Description
Wood Waste-fired
Industrial Boilers
Wood Waste-fired
Industrial Boilers
Wood Waste-fired
Industrial Boilers
Wood Waste-fired
Industrial Boilers
Wood Waste-fired
Comm/Instit. Boilers
Natural Gas Utility Boiler
Gas-fired Utility Boiler
Wood Waste-fired
Emission Source
Wood Waste-fired Boiler
(Wood-fired, >50,000 Ib
steam)
Wood Waste-fired Boiler
(Bark-fired, <50,000 Ib steam)
Wood Waste-fired Boiler
(Wood/Bark-fired, <50,000 Ib
steam)
Wood Waste-fired Boiler
(Wood-fired, <50,000 Ib
steam)
Wood/Bark-fired Boiler (Bark-
fired)
Natural Gas Boilers
Gas Fired Boiler
Wood/Bark-fired Boiler
Control
Device
Multiple Cyclone without
Flyash Reinjection/ESP -
Medium Efficiency
None
Multiple Cyclone with
Flyash Reinjection
ESP
Scrubber
Multiple Cyclone without
Flash Reinjection
Multiple Cyclone without
Flyash Reinjection
ESP
Scrubber
None
Overfire Air and Flue Gas
Recirculation
None
Multiple Cyclone with
Emission Factor
English
(Metric)
2.25xlO-6 Ib/MMBtu
(9.70xlO'16 kg/Joule)
2.90xlO-3 Ib/ton
(1.45xlO-3 kg/Mg)
3. 20xlO-4 Ib/ton
(1.60xlQ-4 kg/Mg)
1.60xlO'5 Ib/ton
(S.OOxlO'6 kg/Mg)
3. 50xlO'4 Ib/ton
(1.75xlO-4 kg/Mg)
3. 20xlO-4 Ib/ton
(1.60xlO-4 kg/Mg)
3. lOxlO'4 Ib/ton
(1.55xlO'4 kg/Mg)
LlOxlO'3 Ib/ton
(5.50xlO'4kg/Mg)
1.14xlO-5lb/MMBtu
(4.91xlO-15 kg/Joule)
2.90xlO-3 Ib/ton
(1.45xlO-3 kg/Mg)
2.7 IxlO'4 Ib/ton
.371b/trillionBTU
3. 20xlO-4 Ib/ton
Factor
Rating
U
D
D
D
D
D
D
D
U
D
E
U
D
Comm/Instit. Boilers
(Wood/Bark-fired)
Flyash Reinjection
(1.60xlO-4 kg/Mg)
-------
TABLE A-l. SUMMARY OF EMISSION FACTORS BY SOURCE CLASSIFICATION CODES (CONTINUED)
>
SCC/AMS
Code
1-03-009-02
1-03-009-03
1-01-001-02
1-01-002-01
1-01-002-02
1-01-002-03
1-01-002-04
1-01-002-05
Description
Wood Waste-fired
Comm/Instit. Boilers
(continued)
Wood Waste-fired
Comm/Instit. Boilers
Coal-fired Utility Boilers
Coal-fired Utility Boilers
Coal-fired Utility Boilers
Coal-fired Utility Boilers
Coal-fired Utility Boilers
Coal-fired Utility Boilers
Emission Source
Wood/Bark-fired Boiler
(Wood-fired)
Anthracite Coal Travelling
Grate Overfeed Stoker
Bituminous Coal: Pulverized:
Wet Bottom
Bituminous Coal: Pulverized:
Dry Bottom
Bituminous Coal: Cyclone
Furnace
Bituminous Coal: Spreader
Stoker
Bituminous Coal: Travelling
Grate (Overfeed) Stoker
Control
Device
Scrubber
ESP
Multiple Cyclone without
Fly ash Reinjection
Multiple Cyclone without
Flyash Reinjection
ESP
None
None
None
ESP,FF or venturi scrubber
None
ESP,FF or venturi scrubber
None
None
Emission Factor
English
(Metric)
3.50xlO-4lb/ton
(1.75xlQ-4 kg/Mg)
1.60xlO-5lb/ton
(S.OOxlO'6 kg/Mg)
3.20xlO-4lb/ton
(1.60xlQ-4 kg/Mg)
3.10xlO-4lb/ton
(1.55xlQ-4 kg/Mg)
1.10xlO-3lb/ton
(5.50xlO-4kg/Mg)
8.90xlO-3 Ib/ton
(4.45xlO'3 kg/Mg)
5.07xlQ-4 Ib/MMBtu
(2. 18x10-° kg/Joule)
5.07xlQ-4 Ib/MMBtu
(2. 18x10-° kg/Joule)
4.20xlO-4(lb/ton)
2.10xlO-4kg/Mg)
5.07xlO-4 Ib/MMBtu
(2. 18x10'° kg/Joule)
4.20xlO-4(lb/ton)
2.10xlQ-4kg/Mg)
5.07xlO-4 Ib/MMBtu
(2. 18x10'° kg/Joule)
5.07xlO-4 Ib/MMBtu
(2. 18x10'° kg/Joule)
Factor
Rating
D
D
D
D
D
E
E
E
A
E
A
E
E
-------
TABLE A-l. SUMMARY OF EMISSION FACTORS BY SOURCE CLASSIFICATION CODES (CONTINUED)
>
oo
SCC/AMS
Code
1-01-002-21
1-01-002-22
1-01-002-23
1-01-002-24
1-01-002-25
1-02-001-04
1-02-002-01
1-02-002-02
1-02-002-03
Description
Coal-fired Utility Boilers
Coal-fired Utility Boilers
Coal-fired Utility Boilers
Coal-fired Utility Boilers
Coal-fired Utility Boilers
Coal-fired Utility Boilers
Coal-fired Utility Boilers
Coal-fired Industrial
Boilers
Coal-fired Industrial
Boilers
Coal-fired Industrial
Boilers
Coal-fired Industrial
Boilers
Emission Source
Subbituminous Coal:
Pulverized: Wet Bottom
Subbituminous Coal:
Pulverized: Dry Bottom
Subbituminous Coal: Cyclone
Furnace
Subbituminous Coal: Spreader
Stoker
Subbituminous Coal:
Travelling Grate (Overfeed)
Stoker
Coal-fired Unit
Coal-fired Unit
Anthracite Coal Travelling
Grate (Overfeed) Stoker
Bituminous Coal Pulverized:
Wet Bottom
Bituminous Coal Pulverized
Coal: Dry Bottom
Bituminous Coal Cyclone
Furnace
Control
Device
None
None
ESP,FF or venturi scrubber
None
ESP,FF or venturi scrubber
None
None
PM
PM/SO2
None
None
None
ESP,FF or venturi scrubber
None
Emission Factor
English
(Metric)
5.07xlO'4 Ib/MMBtu
(2. ISxlO-13 kg/Joule)
5.07X10'4 Ib/MMBtu
(2. ISxlO-13 kg/Joule)
4.20xlO-4(lb/ton)
2.10xlO-4kg/Mg)
5.07xlO'4 Ib/MMBtu
(2. ISxlO-13 kg/Joule)
4.20xlO-4(lb/ton)
2.10xlO-4kg/Mg)
5.07xlO-4 Ib/MMBtu
(2. ISxlO-13 kg/Joule)
5.07xlO-4 Ib/MMBtu
(2. ISxlO-13 kg/Joule)
4.81b/trillionBTU
5.81b/trillionBTU
8.90xlO-3 Ib/ton
(4.45xlO'3 kg/Mg)
5.07xlO-4 Ib/MMBtu
(2. ISxlO-13 kg/Joule)
5.07xlO-4 Ib/MMBtu
(2. ISxlO-13 kg/Joule)
4.20xlO-4(lb/ton)
2.10xlO-4kg/Mg)
5.07X10'4 Ib/MMBtu
(2. ISxlO-13 kg/Joule)
Factor
Rating
E
E
A
E
A
E
E
U
U
E
E
E
A
E
-------
TABLE A-l. SUMMARY OF EMISSION FACTORS BY SOURCE CLASSIFICATION CODES (CONTINUED)
VO
SCC/AMS
Code
1-02-002-03
1-02-002-04
1-02-002-05
1-02-002-06
1-02-002-13
1-01-002-21
1-01-002-22
1-01-002-23
1-01-002-24
1-01-002-25
Description
Coal-fired Industrial
Boilers (continued)
Coal-fired Industrial
Boilers
Coal-fired Industrial
Boilers
Coal-fired Industrial
Boilers
Coal-fired Industrial
Boilers
Coal-fired Industrial
Boilers
Coal-fired Industrial
Boilers
Coal-fired Industrial
Boilers
Coal-fired Industrial
Boilers
Coal-fired Industrial
Boilers
Emission Source
Bituminous Coal Spreader
Stoker
Bituminous Coal Overfeed
Stoker
Bituminous Coal Underfeed
Stoker
Bituminous Coal Wet Slurry
Subbituminous Coal:
Pulverized: Wet Bottom
Subbituminous Coal:
Pulverized: Dry Bottom
Subbituminous Coal: Cyclone
Furnace
Subbituminous Coal: Spreader
Stoker
Subbituminous Coal:
Travelling Grate (Overfeed)
Control
Device
ESP,FF or venturi scrubber
None
None
None
None
None
None
ESP,FF or venturi scrubber
None
ESP,FF or venturi scrubber
None
None
Emission Factor
English
(Metric)
4.20xlQ-4(lb/ton)
2.10xlO-4kg/Mg)
5.07xlO-4 Ib/MMBtu
(2. ISxlO-'3 kg/Joule)
5.07xlQ-4 Ib/MMBtu
(2. ISxlO-'3 kg/Joule)
2.24x10-' Ib/ton
(1.12x10-' kg/Mg)
9.89xlO-3 Ib/ton
(4.95xlO-3 kg/Mg)
5.07xlO-4 Ib/MMBtu
(2. ISxlO-'3 kg/Joule)
5.07xlQ-4 Ib/MMBtu
(2. ISxlO-'3 kg/Joule)
4.20xlO-4(lb/ton)
2.10xlO-4kg/Mg)
5.07xlO-4 Ib/MMBtu
(2. ISxlO-'3 kg/Joule)
4.20xlO-4(lb/ton)
2.10xlO-4kg/Mg)
5.07xlO-4 Ib/MMBtu
(2. ISxlO-'3 kg/Joule)
5.07xlO-4 Ib/MMBtu
(2. ISxlO-'3 kg/Joule)
Factor
Rating
A
E
E
U
U
E
E
A
E
A
E
E
1-03-001-02 Coal-fired
Comm/Inst. Boilers
Stoker
Anthracite Coal Travelling
Grate (Overfeed) Stoker
None
8.90xlO-3 Ib/ton
(4.45xlO-3 kg/Mg)
-------
TABLE A-l. SUMMARY OF EMISSION FACTORS BY SOURCE CLASSIFICATION CODES (CONTINUED)
SCC/AMS
Code
1-03-002-08
1-03-002-03
1-03-002-05
1-03-002-06
1-03-002-07
1-03-002-09
1-03-002-21
1-03-002-22
1-03-002-23
1-03-002-24
Description
Coal-fired
Comm/Inst. Boilers
Coal-fired
Comm/Inst. Boilers
Coal-fired
Comm/Inst. Boilers
Coal-fired
Comm/Inst. Boilers
Coal-fired
Comm/Inst. Boilers
Coal-fired
Comm/Inst. Boilers
Coal-fired
Comm/Inst. Boilers
Coal-fired
Comm/Inst. Boilers
Coal-fired
Comm/Inst. Boilers
Coal-fired
Comm/Inst. Boilers
Emission Source
Bituminous Coal Underfeed
Stoker
Bituminous Coal Cyclone
Furnace
Bituminous Coal Pulverized:
Wet Bottom
Bituminous Coal Pulverized
Coal: Dry Bottom
Bituminous Coal Overfeed
Stoker
Bituminous Coal Spreader
Stoker
Subbituminous Coal:
Pulverized: Wet Bottom
Subbituminous Coal:
Pulverized: Dry Bottom
Subbituminous Coal: Cyclone
Furnace
Subbituminous Coal: Spreader
Stoker
Control
Device
Multiple Cyclone without
Flyash Reinjection
None
ESP,FF or venturi scrubber
None
None
ESP,FF or venturi scrubber
None
None
None
None
ESP,FF or venturi scrubber
None
ESP,FF or venturi scrubber
None
Emission Factor
English
(Metric)
1.21xlO-3lb/ton
(6.05xlO-4kg/Mg)
5.07xlO-4 Ib/MMBtu
(2. ISxlO'13 kg/Joule)
4.20xlO-4(lb/ton)
2.10xlO'4kg/Mg)
5.07xlO-4 Ib/MMBtu
(2. ISxlO'13 kg/Joule)
5.07xlO'4 Ib/MMBtu
(2. ISxlO'13 kg/Joule)
4.20xlO-4(lb/ton)
2.10xlO-4kg/Mg)
5.07xlO'4 Ib/MMBtu
(2. ISxlO'13 kg/Joule)
5.07xlO'4 Ib/MMBtu
(2. ISxlO'13 kg/Joule)
5.07xlO'4 Ib/MMBtu
(2. ISxlO'13 kg/Joule)
5.07xlO-4 Ib/MMBtu
(2. ISxlO'13 kg/Joule)
4.20xlO-4(lb/ton)
2.10xlO'4kg/Mg)
5.07xlO-4 Ib/MMBtu
(2. ISxlO'13 kg/Joule)
4.20xlO-4(lb/ton)
2.10xlO-4kg/Mg)
5.07xlO'4 Ib/MMBtu
(2. ISxlO'13 kg/Joule)
Factor
Rating
U
E
A
E
E
A
E
E
E
E
A
E
A
E
-------
TABLE A-l. SUMMARY OF EMISSION FACTORS BY SOURCE CLASSIFICATION CODES (CONTINUED)
SCC/AMS
Code
1-03-002-25
1-01-004-01
1-01-004-04
1-01-004-05
1-01-005-01
1-02-004-01
1-02-005-01
1-03-004-01
1-03-005-01
1-02-013-02
Description
Coal-fired
Comm/Inst. Boilers
Oil-fired
Utility Boilers
Oil-fired
Utility Boilers
Oil-fired
Utility Boilers
Oil-fired
Utility Boilers
Oil-fired
Utility Boilers
Oil-fired
Utility Boilers
Oil-fired
Industrial Boilers
Oil-fired
Industrial Boilers
Oil-fired
Comm/Indust Boilers
Oil-fired
Comm/Indust Boilers
Waste Oil-fired
Industrial Boilers
Emission Source
Subbituminous Coal:
Travelling Grate (Overfeed)
Stoker
Residual Oil-fired Boiler:
No. 6 Oil, Normal Firing
Residual Oil-fired Boiler:
No. 6 Oil, Tangential Firing
Residual Oil-fired Boiler:
No. 5 Oil, Normal Firing
Oil-fired Units
Oil-fired Units
Distillate Oil Grades 1 and 2
Oil
Residual Oil Grade 6 Oil
Distillate Oil Grades 1 and 2
Oil
Residual Oil Grade 6 Oil
Distillate Oil Grades 1 and 2
Oil
Waste Oil
Control
Device
None
None
Flue Gas Recirculation
None
None
PM Control
PM/SO2 Control
None
None
None
None
None
None
Emission Factor
English
(Metric)
5.07xlO'4 Ib/MMBtu
(2. ISxlO'13 kg/Joule)
1.00xlO-5lb/MMBtu
(4.33xlO-15 kg/Joule)
2.17xlO-5lb/MMBtu
(9.35xlO-15 kg/Joule)
1.00xlO-5lb/MMBtu
(4.33xlO-15 kg/Joule)
1.60xlO-5lb/MMBtu
(6.89xlO-15 kg/Joule)
2.61b/trillionBTU
9.01b/trillionBTU
8.90X10'6 Ib/MMBtu
(3. 84xlO-15 kg/Joule)
l.OOxlO-5 Ib/MMBtu
(4.33xlO-15 kg/Joule)
8.90xlO-6 Ib/MMBtu
(3. 84xlO'15 kg/Joule)
l.OOxlO-5 Ib/MMBtu
(4.33xlO'15 kg/Joule)
8.90X10'6 Ib/MMBtu
(3. 84xlO-15 kg/Joule)
1.681b/1000gal
(2.01xlO-1kg/kL)
Factor
Rating
E
E
U
E
U
U
U
E
E
E
E
E
U
-------
TABLE A-l. SUMMARY OF EMISSION FACTORS BY SOURCE CLASSIFICATION CODES (CONTINUED)
SCC/AMS
Code Description
1-05-001-13 Waste Oil-fired
Industrial Boilers
1-01-013-02 Waste Oil-fired
Comm/Inst Boilers
1-05-002-13 Waste Oil-fired
Comm/Inst Boilers
1-01-012-01 Solid Waste-fired
Utility Boilers
1-02-012-02 Miscellaneous
Industrial Boilers
5-01-001-01 Municipal Waste
7 Combustion Sources
to
5-01-001-02 Municipal Waste
Combustion Sources
5-01-001-03 Municipal Waste
Combustion Sources
Emission Source
Waste Oil Air Atomized
Burner
Waste Oil
Waste Oil Air Atomized
Burner
Solid Waste
Solid Waste Refuse-derived
Fuel
Starved-Air: Multiple-
Chamber
Mass Burn: Single-Chamber
Refuse-derived Fuel
Control
Device
None
None
None
None
ESP
Spray Dryer/Absorber/ESP
None
None
ESP
None
None
ESP
Spray Dryer/FF
Spray Dryer/ESP
Emission Factor
English
(Metric)
50x L lb/1000 gal
(6.0xLkg/kL)
1.68 lb/1000 gal
(2.01xlO-1kg/kL)
50x L lb/1000 gal
(6.0 xL'kg/kL)
2.65x10-' Ib/ton
(1.33x10-' kg/Mg)
1.24xlO-4lb/MMBtu
(5. 34xlO-'4 kg/Joule)
<2.66xlO-4 Ib/ton
(<1.33xlO-4 kg/Mg)
1.30x10-' Ib/ton
(6.50xlQ-2 kg/Mg)
1.20x10-' Ib/ton
(6.00xlQ-2 kg/Mg)
2.82xlO-3 Ib/ton
(1.41xlO-3 kg/Mg)
1.80x10-' Ib/ton
(9.00xlO-2 kg/Mg)
2.01x10-' Ib/ton
(1.00x10-' kg/Mg)
3.66xlO-3 Ib/ton
(1.83xlQ-3 kg/Mg)
1.04xlO-3 Ib/ton
(5.20xlO-4 kg/Mg)
1. 16xlO-3 Ib/ton
(5.80xlO-4kg/Mg)
Factor
Rating
D
U
D
U
c
U
U
U
c
U
c
A
D
B
'L = weight percent lead in fuel. Multiply numeric value by L to obtain emission factor.
-------
TABLE A-l. SUMMARY OF EMISSION FACTORS BY SOURCE CLASSIFICATION CODES (CONTINUED)
SCC/AMS Control
Code Description Emission Source Device
5-01-001-04 Municipal Waste Mass Burn: Refractory Wall None
Combustion Sources Combustor
Spray Dryer/FF
Spray Dryer/ESP
Dry Sorbent Injection/FF
Dry Sorbent Injection/ESP
ESP
5-01-001-05 Municipal Waste Mass Burn: Waterwall None
Combustion Sources Combustor
Spray Dryer/FF
Spray Dryer/ESP
Dry Sorbent Injection/FF
Dry Sorbent Injection/ESP
ESP
5-01-001-06 Municipal Waste Mass Burn: Rotary Waterwall None
Combustion Sources Combustor
Spray Dryer/FF
Emission Factor
English
(Metric)
2.13xlO-1lb/ton
(1.07x10-' kg/Mg)
2.61xlO-4lb/ton
(l.SlxlO-4 kg/Mg)
9.15xlO-4lb/ton
(4.58xlO-4 kg/Mg)
2.97xlO-4lb/ton
(1.49xlO-4 kg/Mg)
2.90xlO-3 Ib/ton
(1.45xlO-3 kg/Mg)
3.00xlO-3lb/ton
(1.50xlO-3 kg/Mg)
2.13xlO-1lb/ton
(1.07x10-' kg/Mg)
2.61xlO-4lb/ton
(l.SlxlQ-4 kg/Mg)
9.15xlO-4lb/ton
(4.58xlO-4 kg/Mg)
2.97xlO-4lb/ton
(1.49xlO-4 kg/Mg)
2.90xlQ-3 Ib/ton
(1.45xlO-3 kg/Mg)
3. OOxlO'3 Ib/ton
(1.50xlO-3 kg/Mg)
2. 13x10-' Ib/ton
(1.07x10-' kg/Mg)
2.6 IxlO'4 Ib/ton
(1.31xlO-4 kg/Mg)
Factor
Rating
A
A
A
C
E
A
A
A
A
C
E
A
A
A
-------
TABLE A-l. SUMMARY OF EMISSION FACTORS BY SOURCE CLASSIFICATION CODES (CONTINUED)
SCC/AMS
Code
5-01-001-06
5-01-001-07
5-01-005-15
Description
Municipal Waste
Combustion Sources
(continued)
Municipal Waste
Combustion Sources
Sewage Sludge
Incinerator Sources
Control
Emission Source Device
Spray Dryer/ESP
Dry Sorbent Injection/FF
Dry Sorbent Injection/ESP
ESP
Modular Excess Air Combustor None
Spray Dryer/FF
Spray Dryer/ESP
Dry Sorbent Injection/FF
Dry Sorbent Injection/ESP
ESP
Multiple-hearth Furnace None
Single Cyclone/Venturi
Scrubber
Single Cyclone
ESP
Emission Factor
English
(Metric)
9.15xlO-4lb/ton
(4.58xlO'4kg/Mg)
2.97xlO-4lb/ton
(1.49xlO-4kg/Mg)
2.90xlO-3 Ib/ton
(1.45xlO'3kg/Mg)
3.00xlO-3lb/ton
(1.50xlO-3kg/Mg)
2.13xlO-1lb/ton
(1. OVxlO'1 kg/Mg)
2.61xlO-4lb/ton
(1.31xlO-4kg/Mg)
9.15xlO-4lb/ton
(4.58xlO-4kg/Mg)
2.97xlO-4lb/ton
(1.49xlO'3kg/Mg)
2.90xlO'3 Ib/ton
(1.45xlO-3kg/Mg)
3. OOxlO'3 Ib/ton
(1.50xlO-3kg/Mg)
l.OOxlO-1 Ib/ton
(5.00xlQ-2kg/Mg)
6.00xlO-3 Ib/ton
(3.00xlQ-3kg/Mg)
6.00xlO'2 Ib/ton
(3.00xlO'2kg/Mg)
2.00xlO-3 Ib/ton
(1.00xlO-3kg/Mg)
Factor
Rating
A
C
E
A
A
A
A
C
E
A
B
E
E
E
-------
TABLE A-l. SUMMARY OF EMISSION FACTORS BY SOURCE CLASSIFICATION CODES (CONTINUED)
SCC/AMS
Code
Description
Control
Emission Source Device
Emission Factor
English
(Metric)
Factor
Rating
5-01-005-15
Sewage Sludge
Incinerator Sources
(continued)
>
Venturi Scrubber
Venturi Scrubber/Wet ESP
Venturi Scrubber/
Impingement-type Wet
Scrubber
Venturi Scrubber/
Impingement-type Wet
Scrubber/Afterburner
Impingement-type Wet
Scrubber
Single Cyclone/Venturi
Scrubber/Impingement
Scrubber
1.80xlO-3lb/ton
(9.00xlO-4kg/Mg)
1.80xlO-4lb/ton
(9.00xlO-5 kg/Mg)
6.00xlO-2 Ib/ton
(3.00xlO-2kg/Mg)
l.OOxlO-1 Ib/ton
(S.OOxlO'2 kg/Mg)
4.00xlO-2 Ib/ton
(2.0xlO-2 kg/Mg)
2.20xlO-2 Ib/ton
(LlOxlO'2 kg/Mg)
E
B
E
E
5-01-005-16 Sewage Sludge FludizedBed None
Incinerator Sources
FF
Impingement-type Wet
Scrubber
Venturi Scrubber
Impingement-type Wet
Scrubber
Venturi Scrubber/
Impingement-type Wet
Scrubber/ESP
5-01-005-05 Medical Waste Other Incineration None
Combustion Sources Pathological/Rotary Kiln
4.00xlO'2 Ib/ton
(2.00xlO'2 kg/Mg)
l.OOxlO-5 Ib/ton
(5.00xlO-6 kg/Mg)
6.00xlO-3 Ib/ton
(S.OOxlQ-3 kg/Mg)
1.60x10-' Ib/ton
(S.OOxlO'2 kg/Mg)
2.00xlO-6 Ib/ton
(l.OOxlO-6 kg/Mg)
1.24x10-' Ib/ton
(6.20xlQ-2 kg/Mg)
E
E
E
E
E
E
-------
TABLE A-l. SUMMARY OF EMISSION FACTORS BY SOURCE CLASSIFICATION CODES (CONTINUED)
>
SCC/AMS
Code Description
5-01-005-05 Medical Waste
Combustion Sources
5-01-005-05 Medical Waste
Combustion Sources
5-02-005-05 Medical Waste
Combustion Sources
Control
Emission Source Device
Other Incineration None
Pathological/
Controlled Air
Other Incineration Pathological Wet Scrubber - High
Efficiency
Wet Scrubber - Medium
Efficiency/FF
FF
Spray Dryer/ FF
Spray Dryer/Carbon
Injection/FF
Dry Sorbent Injection/ ESP
Dry Sorbent Injection/FF
Dry Sorbent Injection/
Carbon Injection/FF
Dry Sorbent
Inj ection/FF/Scrubber
Wet Scrubber - Low
Efficiency
Commercial - None (Rotary Kiln
Incineration - Incinerator)
Pathological . „ ,
0 Afterburner
FF
Emission Factor
English
(Metric)
7.28xlO-2 Ib/ton
(3.64xlO-2kg/Mg)
6.98xlO-2 Ib/ton
(3.49xlO'2 kg/Mg)
1.60xlO-3 Ib/ton
(S.OOxlO'4 kg/Mg)
9.92xlO-5 Ib/ton
(4.96xlO'5 kg/Mg)
1.89xlO-4 Ib/ton
(9.45xlO'5 kg/Mg)
7.38xlO-5 Ib/ton
(3.69xlO'5 kg/Mg)
4.70xlO'3 Ib/ton
(2.35xlO-3 kg/Mg)
6.25xlO'5 Ib/ton
(3. 12x10-' kg/Mg)
9.27xlO-5 Ib/ton
(4.64xlO'5 kg/Mg)
5. 17xlO-5 Ib/ton
(2.59xlO'5 kg/Mg)
7.94xlO-2 Ib/ton
(3.97xlO'2kg/Mg)
1.24x10-' Ib/ton
(6.20xlQ-2 kg/Mg)
6.50xlO-4 Ib/ton
(3.30xlO-4kg/Mg)
9.92xlO'5 Ib/ton
(4.96xlO'5 kg/Mg)
Factor
Rating
B
E
E
E
E
E
E
E
E
E
E
E
E
E
-------
TABLE A-l. SUMMARY OF EMISSION FACTORS BY SOURCE CLASSIFICATION CODES (CONTINUED)
SCC/AMS Control
Code Description Emission Source Device
5-02-005-05 Medical Waste Wet Scrubber - High
Combustion Sources Efficiency
(continued)
Wet Scrubber - Medium
Efficiency /FF
Spray Dryer/FF
Spray Dryer/Carbon
Injection/FF
Dry Sorbent Injection/ESP
Dry Sorbent
Injection/Carbon
Injection/FF
Dry Sorbent Injection/FF
None (Controlled Air
Incinerator)
Dry Sorbent Injection/
FF/Scrubber
Wet Scrubber - Low
Efficiency
3-09-025-01 Drum and Barrel Drum Reclamation: Drum None
Reclamation Sources Burning Furnace
5-03-002-03 Open Burning of Scrap Open Burning of Shredded None
Tires Automobile Tires
Burning of Chunk Automobile None
Tires
Emission Factor
English
(Metric)
6.98xlO-2 Ib/ton
(3.49xlO'2kg/Mg)
1.60xlO-3 Ib/ton
(S.OOxlQ-4 kg/Mg)
1.89xlO-4 Ib/ton
(9.45xlO'5 kg/Mg)
7.38xlO-5 Ib/ton
(3.69xlO'5 kg/Mg)
4.70xlO-3 Ib/ton
(2.35xlO-3 kg/Mg)
9.27xlO'5 Ib/ton
(4.64xlO-5 kg/Mg)
6.25xlO-5 Ib/ton
(3. 12x10' kg/Mg)
7.28xlO-2 Ib/ton
(3.64xlO'2 kg/Mg)
5. 17xlO-5 Ib/ton
(2.59xlO'5 kg/Mg)
7.94xlO'2 Ib/ton
(3.97xlO'2kg/Mg)
3.50xlO-4lb/barrel
(1.59x10-' g/barrel)
2.00xlO'4 Ib/ton
(l.OOxlO-4 kg/Mg)
6.70xlO'4 Ib/ton
(3.35xlO-4kg/Mg)
Factor
Rating
E
E
E
E
E
E
E
B
E
E
E
C
C
-------
TABLE A-l. SUMMARY OF EMISSION FACTORS BY SOURCE CLASSIFICATION CODES (CONTINUED)
oo
SCC/AMS
Code
3-15-021-01
Description
Crematories
Emission Source
Crematory Stack
Control
Device
None
Emission Factor
English
(Metric)
4.10xlO'8lb/body
Factor
Rating
U
3-07-001-04
Kraft Process Recovery
Furnaces & Smelt
Dissolving Tanks
Direct Contact Evaporator
Kraft Recovery Furnace
ESP, ESP/Wet Scrubber
3-07-001-10 Kraft Process Recovery
Furnaces & Smelt
Dissolving Tanks
3-07-001-05
Kraft Process Recovery
Furnaces & Smelt
Dissolving Tanks
Nondirect Contact Evaporator ESP, ESP/Wet Scrubber
Kraft Recovery Furnace
Smelt Dissolving Tank Demister, Venturi Scrubber
(1.86xlO-8 kg/body)
9.5x10' lb/106 ton D
(4.8x10' kg/106 Mg)
1.2xl02 lb/106 ton D
(5.9x10' kg/106 Mg)
2.3x10' lb/106 ton D
(1.2x10' kg/106 Mg)
3-07-001-06
3-07-002-22
3-05-006-06
3-05-006-13
3-05-006-17
3-05-006-22
Lime Kilns
Sulfite Process Recovery
Furnaces
Portland Cement
Manufacturing
Portland Cement
Manufacturing
Portland Cement
Manufacturing
Portland Cement
Manufacturing
Lime Kiln
Sulfite Recovery Furnace
Dry Process Kilns
Dry Process Raw Material
Grinding or Drying
Dry Process Clinker Grinding
Dry Process Preheater Kilns
None
Scrubber
None
FF
ESP
None
None
None
FF
1.09xlO-4 Ib/ton
(5.44xlO-5 kg/Mg)
1.41xl04 Ib/ton
(7.07xl03 kg/Mg)
1.70x10' lb/106 ton
(8.5 kg/106 Mg)
7.50xlO-5 Ib/ton
(3.75xlO'5kg/Mg)
7. lOxlO'4 Ib/ton
(3.55xlO-4kg/Mg)
1.20x10-' Ib/ton
(6.00xlO-2 kg/Mg)
4.00xlO'2 Ib/ton
(2.00xlO-2 kg/Mg)
4.00xlO'2 Ib/ton
(2.00xlO-2 kg/Mg)
7.50xlO'5 Ib/ton
(3.75xlO-5kg/Mg)
U
D
D
D
D
U
U
U
D
-------
TABLE A-l. SUMMARY OF EMISSION FACTORS BY SOURCE CLASSIFICATION CODES (CONTINUED)
SCC/AMS
Code
3-05-006-22
3-05-006-23
3-05-007-06
3-05-007-17
3-05-014
3-04-005-05
3-04-005-06
3-04-005-07
Description Emission Source
Portland Cement
Manufacturing (continued)
Portland Cement Dry Process Preheater/
Manufacturing Precalcinator Kiln
Portland Cement Wet Process Kilns
Manufacturing
Portland Cement Wet Process Clinker Grinding
Manufacturing
Processed and Blown Glass All Processes
Lead-acid Overall Process
Battery Production
Lead-acid Grid Casting
Battery Production
Lead-acid Paste Mixing
Battery Production
Control
Device
ESP
FF
ESP
ESP
FF
None
None
None
None
None
Rotoclone
None
Wet Scrubber - Medium
Emission Factor
English
(Metric)
7. lOxlO'4 Ib/ton
(3.55xlO-4kg/Mg)
7.50xlO-5 Ib/ton
(3.75xlO'5kg/Mg)
7. lOxlO'4 Ib/ton
(3.55xlO'4kg/Mg)
7. lOxlO'4 Ib/ton
(3.55xlO'4kg/Mg)
7.50xlO'5 Ib/ton
(3.75xlO-5kg/Mg)
l.OOxlO'1 Ib/ton
(5.00xlO-2kg/Mg)
2.00xlO'2 Ib/ton
(1.00xlO-2kg/Mg)
51b/ton(2.5kg/Mg)
—
—
6.73xlO'2 lb/1000 batteries
(3.06xlO-2 kg/1000
batteries)
—
4.00xlO-4 lb/1000 batteries
Factor
Rating
D
D
D
D
D
U
U
B
U
B
U
B
U
Efficiency
(2.00xlO-4 kg/1000
batteries)
3-04-005-08
Lead-acid
Battery Production
Lead Oxide Mill (Baghouse
Outlet)
FF
-------
TABLE A-l. SUMMARY OF EMISSION FACTORS BY SOURCE CLASSIFICATION CODES (CONTINUED)
SCC/AMS
Code
3-04-005-09
3-04-005-10
3-04-005-11
3-04-005-12
3-04-040-01
3-09-060-01
3-04-051-01
3-04-051-02
3-04-051-03
3-05-035-05
3-06-001-01
Description
Lead-acid
Battery Production
Lead-acid
Battery Production
Lead-acid
Battery Production
Lead-acid
Battery Production
Lead Cable Coating
Ceramic/Glaze Application
Miscellaneous Lead
Products
Miscellaneous Lead
Products
Miscellaneous Lead
Products
Miscellaneous Lead
Products
Miscellaneous Lead
Products
Emission Source
Three-process Operation
Lead Reclaiming Furnace
Small Parts Casting
Formation
Cable Covering
Ceramic Glaze Spraying -
Spray Booth
Ammunition
Bearing Metals
Other Metallic Lead Processes
Abrasive Grain
Processing/Washing/Drying
Type Metal Production/
Remelting
Control
Device
None
FF
None
Scrubber
None
None
None
None
None
None
None
Wet Scrubber
Industry Average
(Cyclones, FF, ESP, or
Wet Scrubber)
Emission Factor
English
(Metric)
—
3. 77x10-' lb/1000 batteries
(1.71x10-' kg/1000
batteries)
—
1.0 1x10-' lb/1000 batteries
(5.05xlO-2 kg/1000
batteries)
1.00x10-' lb/1000 batteries
(4.60xlO-2 kg/1000
batteries)
—
5.00x10-' Ib/ton
(2.50x10-' kg/Mg)
3.01b/ton
(1.5 kg/Mg)
<1.01b/ton
(<5.0xlO-' kg/Mg)
Negligible
1.5 Ib/ton
(7.5x10-' kg/Mg)
4.4xlQ-3 Ib/ton
(2.2xlO-3 kg/Mg)
2.5x10-' Ib/ton
(1.3x10-' kg/Mg)
Factor
Rating
B
U
B
U
c
c
B
C
C
C
E
C
-------
TABLE A-l. SUMMARY OF EMISSION FACTORS BY SOURCE CLASSIFICATION CODES (CONTINUED)
>
SCC/AMS Control
Code Description Emission Source Device
3-04-004-14 Miscellaneous Lead Lead Melting Pot Afterburner/ Scrubber
Products
3-05-002-01 Batch-Mix Hot-Mix Rotary Dryer FF
Asphalt Plants
Wet Scrubber - Medium
Efficiency
Wet Scrubber - Medium
Efficiency/Single Cyclone
Single Cyclone/Baghouse
Multiple Cyclone without
Fly Ash
Reinjection/Baghouse
None
3-05-002-05 Drum-mix Hot-mix Drum Dryer FF
Asphalt Plants
No EOD Activities TNT None
SCC/AMS
code
Emission Factor
English
(Metric)
4.6xlO'2 Ib/ton
(2.3xlO'2 kg/Mg)
7.4xlO-7 Ib/ton
(3.7xlO'7 kg/Mg)
3. lOxlO'6 Ib/ton
(1.55xlO-6 kg/Mg)
1.03xlO-6 Ib/ton
(5.15xlO'7kg/Mg)
2.00xlO-6 Ib/ton
(LOOxlO'6 kg/Mg)
2.08xlO'7 Ib/ton
(1.04xlO-7 kg/Mg)
4.0 Ib/ton
(2.0 kg/Mg)
3.30xlO-6lbs/ton
(l.VOxlO'6 kg/Mg)
4.1xlO-4lbemitted/lb
treated
(4.1xlO-4gemitted/g
treated)
Factor
Rating
D
D
U
U
U
U
U
D
U
EOD Activities
EOD Activities
Double-based Propellant (DB)
Composite-based Propellant
(CB)
None
None
1.3xlO-2lbemitted/lb U
treated
(1.3xlO-2gemitted/g
treated)
9.4xlO'5 Ib emitted/lb U
treated
(9.4xlO'5 g emitted/g
treated)
-------
TABLE A-l. SUMMARY OF EMISSION FACTORS BY SOURCE CLASSIFICATION CODES (CONTINUED)
SCC/AMS
Code Description
Emission Source
Control
Device
Emission Factor
English Factor
(Metric) Rating
to
to
EOD Activities
EOD Activities
EOD Activities
EOD Activities
EOD Activities
EOD Activities
EOD Activities
20-mm High-explosive
Incendiary Cartridges
40-mm High-explosive
Cartridges
M18A1 Claymore
Antipersonnel Mine
T45E7 Adapter-booster
PBAN-Ammonium Perchlorate
Propellant
CTPB-Ammonium Perchlorate
Propellant
PEG/PBAN
None
None
None
None
None
None
None
1.8xlO-3lb emitted/lb
treated
(1.8xlO-3gemitted/g
treated)
1.3xlO-3 Ibemitted/lb
treated
(1.3xlO-3gemitted/g
treated)
5.3xlO'7 Ib emitted/lb
treated
(5.3xlO"7 g emitted/g
treated)
7.7xlO-4 Ib emitted/lb
treated
(7.7xlO'4 g emitted/g
treated)
2.2xlO-6 Ib emitted/lb
treated
(2.2xlO-6 g emitted/g
treated)
2.3xlO'6 Ib emitted/lb
treated
(2.3xlO-6g emitted/g
treated)
l.OxlO'Mb emitted/lb
treated
(1. Ox 10'6g emitted/g
treated)
U
U
U
U
U
U
U
-------
TECHNICAL REPORT DATA
(PLEASE READ INSTRUCTIONS ON THE REVERSE BEFORE COMPLETING)
1. REPORT NO.
EPA-454/R"i8-G€6
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
LOCATING AND ESTIMATING AIR EMISSIONS FROM SOURCES OF
LEAD AND LEAD COMPOUNDS
5, REPORT DATE
s/1/98
6, PERFORMING ORGANIZATION CODE
a, PERFORMING ORGANIZATION REPORT NO.
t. PERFORMING ORGANIZATION NAME AND ADDRESS
EASTERN RESEARCH GROUP, INC
PO BOX 2010
WQRRISVILLE, NC 27560
10. PROGRAM ELEMENT NO,
11. CONTRACT/GRANT NO,
. SPONSORING AGENCY NAME AND ADDRESS
U. S. ENVIRONMENTAL PROTECTION AGEWCY
OFFICE OF AIR QUALITY PLANNING AND STANDARDS (MD-14)
RESEARCH TRIANGLE PARK, NC 27711
13, TYPE OF WiPORT AWO PERJOO COVERED
FINAL
14, SPONSORING AGENCY CODE
IS,
EPA WORK ASSINGMENT MANAGER: DENNIS BEAUREGARD (919) 541-5512
16. ABSTRACT
TO ASSIST GROUPS INTERESTED IN INVENTORYING AIR EMISSIONS OF VARIOUS POTENTIALLY TOXIC
SUBSTANCES, THE U.S. ENVIRONMENTAL PROTECTION AGENCY IS PREPARING A SERIES Of
DOCUMENTS, SUCH AS THIS, TO COMPILE AVAILABLE INFORMATION ON SOURCES AND EMISSIONS OF
THESE SUBSTANCES. THIS DOCUMENT DEALS SPECIFICALLY WITH LEAD AND LEAD COMPOUNDS. ITS
INTENDED AUDIENCE INCLUDES, FEDERAL, STATE, AND LOCAL MR POLLUTION PERSONNEL AND OTHERS
INTERESTED IN LOCATING POTENTIAL EMITTERS OF LEAD AND IN MAKING GROSS ESTIMATES OF AIR
EMISSIONS THEREFROM.
THIS DOCUMENT PRESENTS INFORMATION ON (1) THE TYPES OF SOURCES THAT MAY EMIT LEAD; (2!
PROCESS VARIATIONS AND RELEASE POINTS FOR THESE SOURCES; AND (3) AVAILABLE EMISSIONS
INFORMATION INDICATING THE POTENTIAL FOR LEAD RELEASES INTO THE AIR FROM EACH OPERATION.
KEYWORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
LEAD AND LEAD COMPOUNDS
AIR EMISSION SOURCES
TOXIC SUBSTANCES
EMISSION ESTIMATION
b, IDENTIFIERSIOPEN ENDED TERMS
c. CQSAfl FtELDffiROUP
18, DISTRIBUTION STATEMENT
UNLIMITED
UNCLASSIFIED
31, NO, OF PAGES
391
22. PRICE
UNCLASSIFIED
------- |