List of Contributors ......................................... XVII
Mercury R&D Book Foreword ..................................... XXI
Preface ..................................................... XXIII
List of Abbreviations ....................................... XXVII
Part I: Mercury in the Environment: Origin, Fate, and
Regulation ...................................................... 1
1 Mercury in the Environment ................................. 3
Leonard Levin
1.1 Introduction ............................................... 3
1.2 Mercury as a Chemical Element .............................. 4
1.2.1 Physical and Chemical Properties of the Forms of
Mercury ............................................. 6
1.2.2 Associations with Minerals and Fuels ................ 6
1.3 Direct Uses of Mercury ..................................... 6
1.4 Atmospheric Transport and Deposition ....................... 7
1.5 Atmospheric Reactions and Lifetime ......................... 8
1.6 Mercury Biogeochemical Cycling ............................. 8
References ................................................ 10
2 Mercury and Halogens in Coal .............................. 13
Allan Kolker and Jeffrey C. Quick
2.1 Introduction .............................................. 13
2.1.1 Mode of Occurrence of Mercury (Hg) in Coal ......... 13
2.1.2 Effectiveness of Pre-Combustion Mercury Removal .... 14
2.1.3 Methods for Mercury Determination .................. 15
2.2 Mercury in U.S. Coals ..................................... 16
2.2.1 U.S. Coal Databases ................................ 16
2.2.1.1 USGS COALQUAL Database ......................... 16
2.2.1.2 1999 EPA ICR ................................... 19
2.2.1.3 2010 EPA ICR ................................... 19
2.2.2 Comparison of U.S. Coal Databases .................. 20
2.3 Mercury in International Coals ............................ 22
2.3.1 Review of Mercury in Coal in the Largest Coal
Producers ............................................... 22
2.3.1.1 China .......................................... 23
2.3.1.2 India .......................................... 24
2.3.1.3 Australia ...................................... 26
2.3.1.4 South Africa ................................... 26
2.3.1.5 Russian Federation ............................. 27
2.3.1.6 Indonesia ...................................... 29
2.4 Halogens in Coal .......................................... 29
2.4.1 Introduction ....................................... 29
2.4.1.1 Chlorine (CI) .................................. 30
2.4.1.2 Bromine (Br) ................................... 32
2.4.1.3 Iodine (I) ..................................... 35
2.4.1.4 Fluorine (F) ................................... 35
2.5 Summary ................................................... 36
Acknowledgments ........................................... 37
References ................................................ 37
3 Regulations ............................................... 45
Nick Hutson
3.1 U.S. Regulations .......................................... 45
3.1.1 Background ......................................... 45
3.1.2 Electric Generating Units (EGUs) ................... 46
3.1.3 Mercury and Air Toxics Standards ("MATS") -
Existing Sources ................................... 47
3.1.4 Mercury and Air Toxics Standards ("MATS") - New
Sources ............................................ 49
References ................................................ 50
4 International Legislation and Trends ...................... 51
Lesley L. Sloss
4.1 Introduction .............................................. 51
4.2 International Legislation ................................. 52
4.2.1 UNEP International Legally Binding Instrument on
Mercury ("Minamata Convention") .................... 53
4.2.2 European Union (EU) ................................ 53
4.3 Regional and National Legislation ......................... 59
4.3.1 Europe ............................................. 59
4.3.1.1 Germany......................................... 59
4.3.1.2 Netherlands .................................... 59
4.3.2 Asia ............................................... 60
4.3.2.1 China .......................................... 60
4.3.2.2 Japan .......................................... 62
4.3.2.3 Other Asian Countries .......................... 63
4.3.3 Other Countries .................................... 64
4.3.3.1 Australia ...................................... 64
4.3.3.2 Canada ......................................... 65
4.3.3.3 Russia ......................................... 65
4.3.3.4 South Africa ................................... 65
4.4 Summary ................................................... 65
References ................................................ 66
Part II: Mercury Measurement in Coal Gas ....................... 69
5 Continuous Mercury Monitors for Fossil Fuel-Fired
Utilities ................................................. 71
Dennis L. Laudal
5.1 Introduction .............................................. 71
5.2 Components of a CMM ....................................... 73
5.2.1 Mercury Analyzer ................................... 73
5.2.1.1 Cold-Vapor Atomic Absorption Spectrometry ...... 73
5.2.1.2 Cold-Vapor Atomic Fluorescence Spectrometry .... 74
5.2.1.3 Other Analytical Methods ....................... 75
5.2.2 Pretreatment/Conversion Systems and Probe .......... 75
5.2.2.1 Sampling Probe ................................. 76
5.2.2.2 Pretreatment and Mercury Conversion ............ 77
5.2.3 CMM Calibration System ............................. 79
5.3 Installation and Verification Requirements ................ 82
5.3.1 Installation ....................................... 82
5.3.2 CMM Verification ................................... 82
5.3.2.1 Measurement Error .............................. 83
5.3.2.2 Seven-Day Calibration Drift .................... 83
5.3.2.3 Relative Accuracy Test Audit ................... 83
5.4 Major CMM Tests ........................................... 84
5.5 CMM Vendors ............................................... 87
References ................................................ 88
6 Batch Methods for Mercury Monitoring ...................... 91
Constance Senior
6.1 Introduction .............................................. 91
6.2 Wet Chemistry Batch Methods ............................... 91
6.2.1 Early EPA Total Hg Methods ......................... 91
6.2.2 Development of Wet Chemistry Methods to Speciate
Hg ................................................. 93
6.2.3 Method Application and Data Quality
Considerations ..................................... 94
6.3 Dry Batch Methods ......................................... 95
6.3.1 Sorbent Trap Method History ........................ 95
6.3.2 Method Overview .................................... 97
6.3.3 Total Hg Measurements .............................. 97
6.3.3.1 PS-12B ......................................... 97
6.3.3.2 Method ЗОВ ..................................... 98
6.3.4 Speciation Measurements ............................ 98
6.3.5 Sampling Protocol .................................. 99
6.3.5.1 Procedure and Apparatus ........................ 99
6.3.6 Trap Analysis ..................................... 100
6.3.7 Relative Accuracy and Quality Assurance/Quality
Control ........................................... 100
6.4 Recommendations .......................................... 105
6.4.1 Particulate Matter ................................ 105
6.4.2 Total Versus Speciated Mercury .................... 105
6.4.3 Expected Mercury Concentration in the Flue Gas .... 105
6.4.4 Need for Real-Time Data ........................... 106
6.4.5 Complexity of Installation and Operation .......... 106
References ............................................... 106
Part III: Mercury Chemistry in Coal Utilization Systems and
Air Pollution Control Devices ................................. 109
7 Mercury Behavior in Coal Combustion Systems
Constance Senior ......................................... 111
7.1 Introduction ............................................. 111
7.2 Coal Combustion Boilers .................................. 112
7.3 Mercury Chemistry in Combustion Systems .................. 113
7.4 Air Pollution Control Devices on Utility and Industrial
Boilers .................................................. 117
7.4.1 PM Control ........................................ 118
7.4.2 NO, Control ....................................... 119
7.4.3 SO2 Control ....................................... 119
7.4.4 Boiler Populations in the United States ........... 120
7.5 Mercury Behavior in Coal-Fired Boilers ................... 121
7.5.1 Data Sources ...................................... 121
7.5.2 Mercury Behavior in APCDs ......................... 123
7.6 Summary .................................................. 129
References ............................................... 130
8 Gasification Systems ..................................... 133
Nicholas Lentz
8.1 Principles of Coal Gasification .......................... 133
8.2 Gasification Technologies Overview and Gasifier
Descriptions ............................................. 134
8.3 Gasification Applications and Downstream Gas Cleanup
and Processing ........................................... 135
8.4 Mercury Transformations and Fate ......................... 135
8.5 Hg Measurement in a Reducing Environment ................. 137
8.6 Hg Control Technologies for Gasification ................. 138
8.7 Hg and the MATS Rule for Gasifiers ....................... 139
References ............................................... 140
9 Mercury Emissions Control for the Cement Manufacturing
Industry ................................................. 141
Robert Schreiber Jr., Shameem Hasan, Carrie Yonley,
and Charles D. Kellett
9.1 Introduction ............................................. 141
9.2 Cement Manufacturing Process Description ................. 141
9.2.1 Wet Process Kiln .................................. 144
9.2.2 Dry Process Kiln .................................. 145
9.3 State of Knowledge on the Source and Behavior of
Mercury in the Cement Kiln System ........................ 147
9.4 Mercury Emissions Control Solutions in the Cement
Industry ................................................. 153
9.4.1 Activated Carbon Injection (ACI) .................. 156
9.4.2 Wet Scrubbing ..................................... 157
9.4.3 Selective Catalytic Reduction (SCR) and Wet
Scrubbing ......................................... 158
9.5 Conclusions .............................................. 159
References ............................................... 160
Part IV: Mercury Research Programs in the United States ....... 163
10 DOE's Mercury Control Technology Research, Development,
and Demonstration Program ................................ 165
Thomas J. Feeley III, Andrew P. Jones, James T. Murphy,
Ronald K. Munson, and Jared P. Ciferno
10.1 Introduction ............................................. 165
10.2 Background ............................................... 165
10.2.1 NETL's Hg Control Technology R&D .................. 166
10.2.2 Mercury Speciation ................................ 167
10.2.3 Mercury Control Technologies ...................... 168
10.2.4 Results from Field Testing Program ................ 169
10.2.5 Oxidation Enhancements ............................ 169
10.2.6 Chemical Additives ................................ 170
10.2.7 Catalysts ......................................... 170
10.2.8 Activated Carbon Injection ........................ 171
10.2.8.1 Untreated РАС ................................. 171
10.2.8.2 Chemically Treated РАС ........................ 173
10.2.8.3 Conventional РАС with Chemical Additives ...... 175
10.2.8.4 ACI Upstream of a Hot-Side ESP ................ 176
10.2.9 Remaining Technical Issues ........................ 176
10.2.9.1 Impacts on Fly Ash ............................ 176
10.2.9.2 Sulfur Trioxide Interference .................. 178
10.2.10 NETL In-House Development of Novel Control
Technologies ........................................... 179
10.2.11 Hg Control Technology Commercial Demonstrations .. 180
10.2.12 Mercury Control Cost Estimates ................... 180
10.2.12.1 Economic Analyses for ACI .................... 181
10.2.12.2 Economic Analyses for Wet FGD Enhancement .... 181
10.2.13 Coal Utilization Byproducts (CUB) R&D Program .... 182
10.2.14 Determining the Fate of Hg in FGD Byproducts ..... 183
10.2.15 Determining the Fate of Hg in Fly Ash ............ 184
10.3 Summary .................................................. 185
Disclaimer ............................................... 186
References ............................................... 186
11 U.S. EPA Research Program ................................ 191
Nick Hutson
11.1 Introduction ............................................. 191
11.2 Congressionally Mandated Studies ......................... 191
11.3 Control Technology from Work on Municipal Waste
Combustors (MWCs) ........................................ 193
11.4 Mercury Chemistry, Adsorption, and Sorbent Development ... 194
11.4.1 Halogenated Activated Carbon Sorbents ............. 196
11.4.2 Non-Carbonaceous Sorbents ......................... 197
11.4.3 Mercury Control in a Wet-FGD Scrubber ............. 198
11.4.4 Effect of SCR on Mercury Oxidation/Capture ........ 200
11.5 Coal Combustion Residues and By-Products ................. 201
11.6 EPA SBIR Program ......................................... 202
References ............................................... 202
12 The Electric Power Research Institute's Program to
Control Mercury Emissions from Coal-Fired Power Plants ... 205
Ramsay Chang
12.1 Introduction ............................................. 205
12.2 Co-Benefits of Installed Controls ........................ 205
12.2.1 Selective Catalytic Reduction/Flue Gas
Desulfurization ................................... 205
12.2.2 Unburned Carbon ................................... 206
12.3 Sorbent Injection ........................................ 207
12.3.1 Units Equipped with Electrostatic Precipitators ... 208
12.3.1.1 Western Coals ................................. 208
12.3.1.2 Eastern Bituminous Coals and High-Sulfur
Flue Gases ............................................. 208
12.3.2 Units Equipped with Fabric Filters or TOXECON ..... 209
12.3.3 Challenges and Responses .......................... 211
12.3.3.1 Preserving Fly Ash Sales ...................... 211
12.3.3.2 Optimizing Electrostatic Precipitator
Performance .......................................... 211
12.3.3.3 Optimizing Fabric Filter and TOXECON
Performance .......................................... 212
12.4 Boiler Chemical Addition ................................. 213
12.4.1 Combined Technologies ............................. 214
12.4.2 Challenges and Responses .......................... 215
12.4.2.1 Wet Flue Gas Desulfurization Chemistry and
Mercury Partitioning ................................. 216
12.4.2.2 Corrosion along Flue Gas Path and in the
wFGD ................................................. 216
12.4.2.3 Preserving Fly Ash Sales ...................... 217
12.4.2.4 Selenium Partitioning in Wet Flue Gas
Desulfurization Systems .............................. 217
12.4.2.5 Bromide Leaching from Fly Ash ................. 217
12.5 Novel Concepts for Mercury Control ....................... 218
12.5.1 TOXECON II® ....................................... 218
12.5.2 Gore® Carbon Polymer Composite Modules ............ 218
12.5.3 Sorbent Activation Process ........................ 220
12.6 Integration of Controls for Mercury with Controls for
Other Air Pollutants ..................................... 221
12.7 Summary .................................................. 222
References ............................................... 222
Part V: Mercury Control Processes ............................. 225
13 Mercury Control Using Combustion Modification ............ 227
Thomas K. Gale
13.1 Mercury Speciation in Coal-Fired Power Plants without
Added Catalysts .......................................... 227
13.1.1 Mercury is all Liberated and Isolated in the
Furnace ........................................... 227
13.1.2 Chlorine Speciation in Coal-Fired Power Plants .... 227
13.1.3 Mechanisms Governing Mercury Speciation ........... 228
13.2 Role of Unburned Carbon in Mercury Oxidation and
Adsorption ............................................... 229
13.2.1 UBC is the Only Catalyst with Enough Activity in
Coal-Fired Power Plants ........................... 229
13.2.2 UBC can Remove Hg or Oxidize Hg, Depending on
the UBC Concentration ............................. 230
13.2.3 Nature of Carbon Type Depends on Parent Coal and
Combustion Efficiency ............................. 231
13.2.4 Concentration of UBC Needed to Oxidize or Remove
Mercury from Flue Gas ............................. 232
13.3 Synergistic Relationship between UBC and Calcium in
Flyash ................................................... 233
13.3.1 Calcium Enhances the Retention of Mercury on
Carbon ............................................ 233
13.3.2 Calcium/Carbon Synergism is Limited to a Range
of Conditions ..................................... 234
13.4 Potential Combustion Modification Strategies to
Mitigate Mercury Emissions ............................... 236
13.5 Effects of Combustion Modifications on Mercury
Oxidation across SCR Catalysts ........................... 238
13.5.1 Inhibition of Mercury Oxidation can Occur in
Low-Chlorine Flue Gas ............................. 238
References ............................................... 238
14 Fuel and Flue-Gas Additives .............................. 241
John Meier, Bruce Keiser, and Brian S. Higgins
14.1 Background ............................................... 241
14.1.1 Bromine-Salt Mercury Oxidation .................... 242
14.1.2 Fuel Additive Injection Equipment ................. 242
14.1.3 Case Study Results ................................ 243
14.1.3.1 Case Studies where Halogen-containing Fuel
Additives are Advantageous .................... 244
14.1.4 Case Studies where Conditions are
Disadvantageous to Fuel Additive ....................... 248
14.1.4.1 Units Burning High Chlorine Fuel with an SCR .. 249
14.1.4.2 Subbituminous Fired Units with Flue Gas
Conditioning (S03 Injection) ......................... 249
14.1.4.3 Units without Acid Gas Scrubbing and
a Fabric Filter (FF) ................................. 250
14.2 Summary .................................................. 250
References ............................................... 250
15 Catalysts for the Oxidation of Mercury ................... 253
April Freeman Sibley
15.1 Introduction ............................................. 253
15.1.1 Process Overview .................................. 253
15.2 Hg Oxidation and Affecting Parameters .................... 254
15.2.1 Hg0 Oxidation Reaction Mechanism .................. 255
15.2.2 Homogeneous Oxidation of Mercury .................. 255
15.2.3 Heterogeneous Oxidation of Mercury over SCR
Catalysts ......................................... 255
15.2.4 SCR Operation-Hg0 Reaction Effects ................ 257
15.2.5 Hg0 Oxidation and SO2/SO3 Conversion .............. 258
15.3 Conclusions and Future Research .......................... 259
References ............................................... 260
16 Mercury Capture in Wet Flue Gas Desulfurization Systems .. 261
Gary Blythe
16.1 Introduction ............................................. 261
16.2 Fate of Net Mercury Removed by Wet FGD Systems ........... 263
16.2.1 Phase Partitioning ................................ 263
16.2.2 Mercury in FGD By-product Streams ................. 264
16.3 Mercury Reemissions ...................................... 267
16.3.1 Definition and Reporting Conventions .............. 267
16.3.2 Reemission Chemistry .............................. 269
16.3.3 Reemission Additives .............................. 271
16.4 Effects of Flue Gas Mercury Oxidation Technologies on
FGD Capture of Mercury ................................... 272
References ............................................... 274
17 Introduction to Carbon Sorbents for Pollution Control .... 277
Joe Wong
17.1 Carbon Materials ......................................... 277
17.2 Carbon Activation ........................................ 277
17.3 Carbon Particle Shapes and Forms ......................... 280
17.3.1 Powdered Activated Carbon (РАС) ................... 280
17.3.2 Granular Activated Carbon (GAC) ................... 281
17.3.3 Shaped Activated Carbon ........................... 282
17.3.4 Other Activated Carbon Forms ...................... 282
17.4 Activated Carbon Applications ............................ 282
17.5 Activated Carbon Properties in Emission Systems .......... 283
17.5.1 Activated Carbon Surface .......................... 285
17.5.2 Activated Carbon Pores ............................ 286
17.5.3 Activated Carbon Particles ........................ 289
17.6 Summary .................................................. 291
References ............................................... 291
18 Activated Carbon Injection ............................... 293
Sharon M. Sjostrom
18.1 Introduction ............................................. 293
18.2 The Activated Carbon Injection System .................... 294
18.2.1 Powdered Activated Carbon Storage ................. 294
18.2.2 Process Equipment ................................. 295
18.2.2.1 Metering ...................................... 295
18.2.2.2 Conveying ..................................... 295
18.2.3 РАС Distribution .................................. 296
18.3 Factors Influencing the Effectiveness of Activated
Carbon ................................................... 296
18.3.1 Site-Specific Factors ............................. 296
18.3.1.1 Flue Gas Characteristics: Halogens and SOs .... 297
18.3.1.2 TOXECONTM ..................................... 303
18.3.2 PAC-Specific Factors .............................. 303
18.3.3 ACI System Design-Specific Factors ................ 304
18.3.3.1 Injection Location ............................ 304
18.3.3.2 Distribution .................................. 304
18.4 Balance-of-Plant Impacts ................................. 305
18.4.1 Coal Combustion By-Products ....................... 305
18.4.1.1 Autoignition of РАС in Ash Hoppers ............ 306
18.4.1.2 Impacts on Particulate Emissions .............. 306
18.4.1.3 Corrosion Issues .............................. 307
18.5 Future Considerations .................................... 307
References ............................................... 307
19 Halogenated Carbon Sorbents .............................. 311
Robert Nebergall
19.1 Introduction ............................................. 311
19.2 Application of Activated Carbon for Mercury Control ...... 311
19.3 Development of Halogenated Activated Carbon .............. 313
19.3.1 Motivation ........................................ 313
19.3.2 Manufacture ....................................... 315
19.3.3 Performance ....................................... 316
19.3.4 Balance-of-Plant Impacts .......................... 319
References ............................................... 320
20 Concrete-Compatible Activated Carbon ..................... 323
S. Behrooz Ghorishi
20.1 Introduction ............................................. 323
20.2 Concrete-Compatibility Metrics ........................... 324
20.2.1 The New and Innovative Concrete-FriendlyTM
Metrics; the Acid Blue Index ...................... 326
20.3 Production of Concrete-Compatible Products Including
C-PACTM .................................................. 329
20.4 C-PACTM Specification .................................... 331
20.4.1 Commercial Application of С-РАСTM ................. 331
20.4.2 Full-Scale C-PACTM Trials at Midwest Generation's
Crawford Station .................................. 332
20.4.3 Full-Scale C-PAC™ Trials the PPL Montana Corette
Station ........................................... 333
20.4.4 Cement Kiln Mercury Emission Control Using
C-PACTM ........................................... 334
20.5 Concrete Compatibility Test - Field Fly Ash/C-PACTM
Mixture .................................................. 335
20.5.1 Air Content of Fresh Concrete ..................... 336
20.5.2 Unconfined Compressive Strength (UCS) ............. 336
20.5.3 Stability of Mercury in Fly Ash and Concrete ...... 337
References ............................................... 337
21 Novel Capture Technologies: Non-carbon Sorbents and
Photochemical Oxidations ................................. 339
Karen J. Uffalussy and Evan J. Granite
21.1 Introduction ............................................. 339
21.2 Non-carbon Sorbents ...................................... 340
21.2.1 Amended Silicates, Novinda ........................ 340
21.2.1.1 Background and Motivations .................... 340
21.2.1.2 How Does the Amended Silicates Sorbent Work? .. 341
21.2.1.3 Demonstrations ................................ 342
21.2.1.4 Conclusions ................................... 344
21.2.2 MinPlus CDEM Group BV ............................. 345
21.2.2.1 Background and Motivations .................... 345
21.2.2.2 How Does the MinPlus Sorbent Work? ............ 345
21.2.2.3 Demonstrations of Sorbent ..................... 347
21.2.2.4 Conclusions ................................... 348
21.2.3 Pahlman Process - Enviroscrub ..................... 348
21.2.3.1 Background and Motivations .................... 348
21.2.3.2 How Does the Process and Sorbent Work? ........ 349
21.2.3.3 Demonstrations ................................ 349
21.2.3.4 Conclusions ................................... 350
21.3 Photochemical Removal of Mercury from Flue Gas ........... 350
21.3.1 Sensitized Oxidation of Mercury: GP-254 Process ... 350
21.3.2 Photocatalytic Oxidation of Mercury ............... 552
Disclaimer ............................................... 352
References ............................................... 353
22 Sorbents for Gasification Processes ...................... 357
Henry W. Pennline and Evan J. Granite
22.1 Introduction ............................................. 357
22.2 Background ............................................... 358
22.3 Warm/Humid Gas Temperature Mercury Sorbent Capture
Techniques ............................................... 360
22.4 Cold Gas Cleanup of Mercury .............................. 366
22.4.1 Carbon-Based Materials ............................ 367
22.4.2 Other Materials ................................... 368
22.4.3 Wet Scrubbing Technique ........................... 369
22.5 Summary .................................................. 370
Disclaimer ............................................... 370
References ............................................... 371
Part VI: Modeling of Mercury Chemistry in Air Pollution
Control Devices ............................................... 375
23 Mercury-Carbon Surface Chemistry ......................... 377
Edwin S. Olson
23.1 Nature of the Bonding of Mercury to the Carbon Surface ... 377
23.2 Effects of Acid Gases on Mercury Capacities on Carbon .... 378
23.3 Kinetic HCl Effect ....................................... 382
23.4 Summary .................................................. 385
References ............................................... 386
24 Atomistic-Level Models ................................... 389
Jennifer Wilcox
24.1 Introduction ............................................. 389
24.2 Homogeneous Mercury Oxidation Kinetics ................... 390
24.2.1 Mercury - Chlorine Chemistry ...................... 390
24.2.2 Mercury - Bromine Chemistry ....................... 397
24.3 Heterogeneous Chemistry .................................. 400
24.3.1 Mercury Adsorption on Activated Carbon ............ 400
24.3.2 Mercury Adsorption on Precious Metals ............. 404
24.4 Conclusions and Future Work .............................. 407
References ............................................... 407
25 Predicting Hg Emissions Rates with Device-Level Models
and Reaction Mechanisms .................................. 413
Stephen Niksa and Balaji Krishnakumar
25.1 Introduction and Scope ................................... 413
25.2 The Reaction System ...................................... 414
25.3 Hg Transformations ....................................... 416
25.3.1 In-Furnace Transformations ........................ 416
25.3.2 In-Flight Transformations ......................... 419
25.3.3 Hg0 Oxidation across SCR Catalysts ................ 427
25.3.4 Hg Transformations within WFGDs ................... 430
25.4 Summary .................................................. 433
References .................................................... 435
Index ......................................................... 437
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