| List of Contributors |
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xvii | |
| Mercury R&D Book Foreword |
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xxi | |
| Preface |
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xxiii | |
| List of Abbreviations |
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xxvii | |
| Part I: Mercury in the Environment: Origin, Fate, and Regulation |
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1 | (108) |
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1 Mercury in the Environment |
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3 | (10) |
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3 | (1) |
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1.2 Mercury as a Chemical Element |
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4 | (2) |
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1.2.1 Physical and Chemical Properties of the Forms of Mercury |
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6 | (1) |
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1.2.2 Associations with Minerals and Fuels |
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6 | (1) |
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1.3 Direct Uses of Mercury |
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6 | (1) |
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1.4 Atmospheric Transport and Deposition |
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7 | (1) |
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1.5 Atmospheric Reactions and Lifetime |
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8 | (1) |
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1.6 Mercury Biogeochemical Cycling |
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8 | (2) |
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10 | (3) |
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2 Mercury and Halogens in Coal |
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13 | (32) |
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13 | (3) |
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2.1.1 Mode of Occurrence of Mercury (Hg) in Coal |
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13 | (1) |
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2.1.2 Effectiveness of Pre-Combustion Mercury Removal |
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14 | (1) |
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2.1.3 Methods for Mercury Determination |
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15 | (1) |
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2.2 Mercury in U.S. Coals |
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16 | (6) |
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2.2.1 U.S. Coal Databases |
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16 | (1) |
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2.2.1.1 USGS COALQUAL Database |
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16 | (1) |
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19 | (1) |
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19 | (1) |
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2.2.2 Comparison of U.S. Coal Databases |
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20 | (2) |
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2.3 Mercury in International Coals |
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22 | (7) |
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2.3.1 Review of Mercury in Coal in the Largest Coal Producers |
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22 | (1) |
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23 | (1) |
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24 | (1) |
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26 | (1) |
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26 | (1) |
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2.3.1.5 Russian Federation |
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27 | (1) |
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29 | (1) |
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29 | (7) |
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29 | (1) |
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30 | (1) |
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32 | (1) |
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35 | (1) |
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35 | (1) |
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36 | (1) |
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37 | (1) |
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37 | (8) |
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45 | (6) |
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45 | (5) |
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45 | (1) |
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3.1.2 Electric Generating Units (EGUs) |
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46 | (1) |
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3.1.3 Mercury and Air Toxics Standards ("MATS") - Existing Sources |
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47 | (2) |
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3.1.4 Mercury and Air Toxics Standards ("MATS") - New Sources |
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49 | (1) |
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50 | (1) |
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4 International Legislation and Trends |
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51 | (20) |
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51 | (1) |
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4.2 International Legislation |
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52 | (7) |
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4.2.1 UNEP International Legally Binding Instrument on Mercury ("Minamata Convention") |
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53 | (1) |
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4.2.2 European Union (EU) |
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53 | (6) |
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4.3 Regional and National Legislation |
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59 | (6) |
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59 | (1) |
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59 | (1) |
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59 | (1) |
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60 | (1) |
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60 | (1) |
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62 | (1) |
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4.3.2.3 Other Asian Countries |
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63 | (1) |
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64 | (1) |
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64 | (1) |
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65 | (1) |
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65 | (1) |
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65 | (1) |
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65 | (1) |
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66 | (3) |
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Part II: Mercury Measurement in Coal Gas |
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69 | (2) |
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5 Continuous Mercury Monitors for Fossil Fuel-Fired Utilities |
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71 | (20) |
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71 | (2) |
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73 | (9) |
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73 | (1) |
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5.2.1.1 Cold-Vapor Atomic Absorption Spectrometry |
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73 | (1) |
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5.2.1.2 Cold-Vapor Atomic Fluorescence Spectrometry |
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74 | (1) |
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5.2.1.3 Other Analytical Methods |
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75 | (1) |
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5.2.2 Pretreatment/Conversion Systems and Probe |
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75 | (1) |
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76 | (1) |
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5.2.2.2 Pretreatment and Mercury Conversion |
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77 | (2) |
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5.2.3 CMM Calibration System |
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79 | (3) |
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5.3 Installation and Verification Requirements |
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82 | (2) |
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82 | (1) |
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82 | (1) |
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5.3.2.1 Measurement Error |
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83 | (1) |
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5.3.2.2 Seven-Day Calibration Drift |
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83 | (1) |
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5.3.2.3 Relative Accuracy Test Audit |
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83 | (1) |
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84 | (3) |
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87 | (1) |
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88 | (3) |
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6 Batch Methods for Mercury Monitoring |
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91 | (18) |
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91 | (1) |
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6.2 Wet Chemistry Batch Methods |
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91 | (4) |
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6.2.1 Early EPA Total Hg Methods |
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91 | (2) |
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6.2.2 Development of Wet Chemistry Methods to Speciate Hg |
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93 | (1) |
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6.2.3 Method Application and Data Quality Considerations |
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94 | (1) |
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95 | (10) |
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6.3.1 Sorbent Trap Method History |
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95 | (2) |
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97 | (1) |
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6.3.3 Total Hg Measurements |
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97 | (1) |
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97 | (1) |
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98 | (1) |
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6.3.4 Speciation Measurements |
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98 | (1) |
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99 | (1) |
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6.3.5.1 Procedure and Apparatus |
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99 | (1) |
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100 | (1) |
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6.3.7 Relative Accuracy and Quality Assurance/Quality Control |
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100 | (5) |
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105 | (1) |
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105 | (1) |
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6.4.2 Total Versus Speciated Mercury |
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105 | (1) |
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6.4.3 Expected Mercury Concentration in the Flue Gas |
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105 | (1) |
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6.4.4 Need for Real-Time Data |
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106 | (1) |
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6.4.5 Complexity of Installation and Operation |
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106 | (1) |
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106 | (3) |
| Part III: Mercury Chemistry in Coal Utilization Systems and Air Pollution Control Devices |
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109 | (54) |
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7 Mercury Behavior in Coal Combustion Systems |
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111 | (22) |
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111 | (1) |
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7.2 Coal Combustion Boilers |
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112 | (1) |
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7.3 Mercury Chemistry in Combustion Systems |
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113 | (4) |
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7.4 Air Pollution Control Devices on Utility and Industrial Boilers |
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117 | (4) |
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118 | (1) |
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119 | (1) |
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119 | (1) |
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7.4.4 Boiler Populations in the United States |
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120 | (1) |
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7.5 Mercury Behavior in Coal-Fired Boilers |
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121 | (8) |
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121 | (2) |
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7.5.2 Mercury Behavior in APCDs |
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123 | (6) |
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129 | (1) |
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130 | (3) |
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133 | (8) |
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8.1 Principles of Coal Gasification |
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133 | (1) |
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8.2 Gasification Technologies Overview and Gasifier Descriptions |
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134 | (1) |
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8.3 Gasification Applications and Downstream Gas Cleanup and Processing |
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135 | (1) |
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8.4 Mercury Transformations and Fate |
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135 | (2) |
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8.5 Hg Measurement in a Reducing Environment |
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137 | (1) |
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8.6 Hg Control Technologies for Gasification |
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138 | (1) |
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8.7 Hg and the MATS Rule for Gasifiers |
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139 | (1) |
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140 | (1) |
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9 Mercury Emissions Control for the Cement Manufacturing Industry |
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141 | (22) |
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141 | (1) |
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9.2 Cement Manufacturing Process Description |
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141 | (6) |
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144 | (1) |
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145 | (2) |
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9.3 State of Knowledge on the Source and Behavior of Mercury in the Cement Kiln System |
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147 | (6) |
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9.4 Mercury Emissions Control Solutions in the Cement Industry |
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153 | (6) |
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9.4.1 Activated Carbon Injection (ACI) |
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156 | (1) |
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157 | (1) |
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9.4.3 Selective Catalytic Reduction (SCR) and Wet Scrubbing |
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158 | (1) |
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159 | (1) |
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160 | (3) |
| Part IV: Mercury Research Programs in the United States |
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163 | (62) |
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10 DOE's Mercury Control Technology Research, Development, and Demonstration Program |
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165 | (26) |
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165 | (1) |
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165 | (20) |
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10.2.1 NETL's Hg Control Technology R& D |
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166 | (1) |
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10.2.2 Mercury Speciation |
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167 | (1) |
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10.2.3 Mercury Control Technologies |
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168 | (1) |
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10.2.4 Results from Field Testing Program |
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169 | (1) |
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10.2.5 Oxidation Enhancements |
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169 | (1) |
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10.2.6 Chemical Additives |
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170 | (1) |
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170 | (1) |
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10.2.8 Activated Carbon Injection |
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171 | (1) |
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171 | (1) |
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10.2.8.2 Chemically Treated PAC |
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173 | (1) |
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10.2.8.3 Conventional PAC with Chemical Additives |
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175 | (1) |
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10.2.8.4 ACI Upstream of a Hot-Side ESP |
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176 | (1) |
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10.2.9 Remaining Technical Issues |
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176 | (1) |
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10.2.9.1 Impacts on Fly Ash |
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176 | (1) |
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10.2.9.2 Sulfur Trioxide Interference |
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178 | (1) |
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10.2.10 NETL In-House Development of Novel Control Technologies |
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179 | (1) |
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10.2.11 Hg Control Technology Commercial Demonstrations |
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180 | (1) |
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10.2.12 Mercury Control Cost Estimates |
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180 | (1) |
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10.2.12.1 Economic Analyses for ACI |
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181 | (1) |
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10.2.12.2 Economic Analyses for Wet FGD Enhancement |
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181 | (1) |
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10.2.13 Coal Utilization Byproducts (CUB) R& D Program |
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182 | (1) |
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10.2.14 Determining the Fate of Hg in FGD Byproducts |
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183 | (1) |
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10.2.15 Determining the Fate of Hg in Fly Ash |
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184 | (1) |
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185 | (1) |
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186 | (1) |
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186 | (5) |
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11 U.S. EPA Research Program |
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191 | (14) |
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191 | (1) |
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11.2 Congressionally Mandated Studies |
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191 | (2) |
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11.3 Control Technology from Work on Municipal Waste Combustors (MWCs) |
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193 | (1) |
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11.4 Mercury Chemistry, Adsorption, and Sorbent Development |
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194 | (7) |
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11.4.1 Halogenated Activated Carbon Sorbents |
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196 | (1) |
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11.4.2 Non-Carbonaceous Sorbents |
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197 | (1) |
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11.4.3 Mercury Control in a Wet-FGD Scrubber |
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198 | (2) |
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11.4.4 Effect of SCR on Mercury Oxidation/Capture |
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200 | (1) |
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11.5 Coal Combustion Residues and By-Products |
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201 | (1) |
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202 | (1) |
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202 | (3) |
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12 The Electric Power Research Institute's Program to Control Mercury Emissions from Coal-Fired Power Plants |
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205 | (20) |
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205 | (1) |
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12.2 Co-Benefits of Installed Controls |
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205 | (2) |
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12.2.1 Selective Catalytic Reduction/Flue Gas Desulfurization |
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205 | (1) |
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206 | (1) |
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207 | (6) |
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12.3.1 Units Equipped with Electrostatic Precipitators |
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208 | (1) |
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208 | (1) |
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12.3.1.2 Eastern Bituminous Coals and High-Sulfur Flue Gases |
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208 | (1) |
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12.3.2 Units Equipped with Fabric Filters or TOXECON® |
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209 | (2) |
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12.3.3 Challenges and Responses |
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211 | (1) |
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12.3.3.1 Preserving Fly Ash Sales |
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211 | (1) |
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12.3.3.2 Optimizing Electrostatic Precipitator Performance |
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211 | (1) |
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12.3.3.3 Optimizing Fabric Filter and TOXECON Performance |
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212 | (1) |
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12.4 Boiler Chemical Addition |
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213 | (5) |
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12.4.1 Combined Technologies |
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214 | (1) |
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12.4.2 Challenges and Responses |
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215 | (1) |
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12.4.2.1 Wet Flue Gas Desulfurization Chemistry and Mercury Partitioning |
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216 | (1) |
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12.4.2.2 Corrosion along Flue Gas Path and in the wFGD |
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216 | (1) |
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12.4.2.3 Preserving Fly Ash Sales |
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217 | (1) |
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12.4.2.4 Selenium Partitioning in Wet Flue Gas Desulfurization Systems |
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217 | (1) |
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12.4.2.5 Bromide Leaching from Fly Ash |
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217 | (1) |
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12.5 Novel Concepts for Mercury Control |
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218 | (3) |
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218 | (1) |
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12.5.2 Gore® Carbon Polymer Composite Modules |
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218 | (2) |
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12.5.3 Sorbent Activation Process |
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220 | (1) |
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12.6 Integration of Controls for Mercury with Controls for Other Air Pollutants |
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221 | (1) |
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222 | (1) |
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222 | (3) |
| Part V: Mercury Control Processes |
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225 | (150) |
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13 Mercury Control Using Combustion Modification |
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227 | (14) |
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13.1 Mercury Speciation in Coal-Fired Power Plants without Added Catalysts |
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227 | (2) |
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13.1.1 Mercury is all Liberated and Isolated in the Furnace |
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227 | (1) |
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13.1.2 Chlorine Speciation in Coal-Fired Power Plants |
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227 | (1) |
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13.1.3 Mechanisms Governing Mercury Speciation |
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228 | (1) |
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13.2 Role of Unburned Carbon in Mercury Oxidation and Adsorption |
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229 | (4) |
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13.2.1 UBC is the Only Catalyst with Enough Activity in Coal-Fired Power Plants |
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229 | (1) |
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13.2.2 UBC can Remove Hg or Oxidize Hg, Depending on the UBC Concentration |
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230 | (1) |
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13.2.3 Nature of Carbon Type Depends on Parent Coal and Combustion Efficiency |
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231 | (1) |
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13.2.4 Concentration of UBC Needed to Oxidize or Remove Mercury from Flue Gas |
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232 | (1) |
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13.3 Synergistic Relationship between UBC and Calcium in Flyash |
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233 | (3) |
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13.3.1 Calcium Enhances the Retention of Mercury on Carbon |
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233 | (1) |
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13.3.2 Calcium/Carbon Synergism is Limited to a Range of Conditions |
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234 | (2) |
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13.4 Potential Combustion Modification Strategies to Mitigate Mercury Emissions |
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236 | (2) |
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13.5 Effects of Combustion Modifications on Mercury Oxidation across SCR Catalysts |
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238 | (1) |
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13.5.1 Inhibition of Mercury Oxidation can Occur in Low-Chlorine Flue Gas |
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238 | (1) |
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238 | (3) |
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14 Fuel and Flue-Gas Additives |
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241 | (12) |
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241 | (9) |
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14.1.1 Bromine-Salt Mercury Oxidation |
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242 | (1) |
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14.1.2 Fuel Additive Injection Equipment |
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242 | (1) |
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14.1.3 Case Study Results |
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243 | (1) |
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14.1.3.1 Case Studies where Halogen-containing Fuel Additives are Advantageous |
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244 | (4) |
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14.1.4 Case Studies where Conditions are Disadvantageous to Fuel Additive |
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248 | (1) |
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14.1.4.1 Units Burning High Chlorine Fuel with an SCR |
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249 | (1) |
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14.1.4.2 Subbituminous Fired Units with Flue Gas Conditioning (SO3 Injection) |
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249 | (1) |
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14.1.4.3 Units without Acid Gas Scrubbing and a Fabric Filter (FF) |
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250 | (1) |
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250 | (1) |
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250 | (3) |
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15 Catalysts for the Oxidation of Mercury |
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253 | (8) |
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253 | (1) |
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253 | (1) |
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15.2 Hg Oxidation and Affecting Parameters |
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254 | (5) |
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15.2.1 He Oxidation Reaction Mechanism |
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255 | (1) |
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15.2.2 Homogeneous Oxidation of Mercury |
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255 | (1) |
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15.2.3 Heterogeneous Oxidation of Mercury over SCR Catalysts |
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255 | (2) |
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15.2.4 SCR Operation-He Reaction Effects |
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257 | (1) |
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15.2.5 Hg° Oxidation and SO2/SO3 Conversion |
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258 | (1) |
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15.3 Conclusions and Future Research |
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259 | (1) |
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260 | (1) |
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16 Mercury Capture in Wet Flue Gas Desulfurization Systems |
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261 | (16) |
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261 | (2) |
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16.2 Fate of Net Mercury Removed by Wet FGD Systems |
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263 | (4) |
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16.2.1 Phase Partitioning |
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263 | (1) |
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16.2.2 Mercury in FGD By-product Streams |
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264 | (3) |
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267 | (5) |
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16.3.1 Definition and Reporting Conventions |
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267 | (2) |
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16.3.2 Reemission Chemistry |
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269 | (2) |
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16.3.3 Reemission Additives |
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271 | (1) |
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16.4 Effects of Flue Gas Mercury Oxidation Technologies on FGD Capture of Mercury |
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272 | (2) |
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274 | (3) |
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17 Introduction to Carbon Sorbents for Pollution Control |
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277 | (16) |
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277 | (1) |
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277 | (3) |
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17.3 Carbon Particle Shapes and Forms |
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280 | (2) |
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17.3.1 Powdered Activated Carbon (PAC) |
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280 | (1) |
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17.3.2 Granular Activated Carbon (GAC) |
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281 | (1) |
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17.3.3 Shaped Activated Carbon |
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282 | (1) |
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17.3.4 Other Activated Carbon Forms |
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282 | (1) |
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17.4 Activated Carbon Applications |
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282 | (1) |
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17.5 Activated Carbon Properties in Emission Systems |
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283 | (8) |
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17.5.1 Activated Carbon Surface |
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285 | (1) |
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17.5.2 Activated Carbon Pores |
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286 | (3) |
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17.5.3 Activated Carbon Particles |
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289 | (2) |
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291 | (1) |
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291 | (2) |
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18 Activated Carbon Injection |
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293 | (18) |
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293 | (1) |
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18.2 The Activated Carbon Injection System |
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294 | (2) |
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18.2.1 Powdered Activated Carbon Storage |
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294 | (1) |
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295 | (1) |
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295 | (1) |
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295 | (1) |
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296 | (1) |
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18.3 Factors Influencing the Effectiveness of Activated Carbon |
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296 | (9) |
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18.3.1 Site-Specific Factors |
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296 | (1) |
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18.3.1.1 Flue Gas Characteristics: Halogens and SO3 |
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297 | (1) |
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303 | (1) |
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18.3.2 PAC-Specific Factors |
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303 | (1) |
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18.3.3 ACI System Design-Specific Factors |
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304 | (1) |
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18.3.3.1 Injection Location |
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304 | (1) |
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304 | (1) |
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18.4 Balance-of-Plant Impacts |
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305 | (2) |
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18.4.1 Coal Combustion By-Products |
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305 | (1) |
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18.4.1.1 Autoignition of PAC in Ash Hoppers |
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306 | (1) |
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18.4.1.2 Impacts on Particulate Emissions |
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|
306 | (1) |
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18.4.1.3 Corrosion Issues |
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307 | (1) |
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18.5 Future Considerations |
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|
307 | (1) |
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|
307 | (4) |
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19 Halogenated Carbon Sorbents |
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311 | (12) |
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311 | (1) |
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19.2 Application of Activated Carbon for Mercury Control |
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311 | (2) |
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19.3 Development of Halogenated Activated Carbon |
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313 | (7) |
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313 | (2) |
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315 | (1) |
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316 | (3) |
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19.3.4 Balance-of-Plant Impacts |
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319 | (1) |
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320 | (3) |
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20 Concrete-Compatible Activated Carbon |
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323 | (16) |
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323 | (1) |
|
20.2 Concrete-Compatibility Metrics |
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|
324 | (5) |
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20.2.1 The New and Innovative Concrete-Friendly™ Metrics; the Acid Blue Index |
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|
326 | (3) |
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20.3 Production of Concrete-Compatible Products Including C-PAC™ |
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329 | (2) |
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20.4 C-PAC™ Specification |
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|
331 | (4) |
|
20.4.1 Commercial Application of C-PAC™ |
|
|
331 | (1) |
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20.4.2 Full-Scale C-PAC™ Trials at Midwest Generation's Crawford Station |
|
|
332 | (1) |
|
20.4.3 Full-Scale C-PAC™ Trials the PPL Montana Corette Station |
|
|
333 | (1) |
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20.4.4 Cement Kiln Mercury Emission Control Using C-PAC™ |
|
|
334 | (1) |
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20.5 Concrete Compatibility Test - Field Fly Ash/C-PAC™ Mixture |
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|
335 | (2) |
|
20.5.1 Air Content of Fresh Concrete |
|
|
336 | (1) |
|
20.5.2 Unconfined Compressive Strength (UCS) |
|
|
336 | (1) |
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20.5.3 Stability of Mercury in Fly Ash and Concrete |
|
|
337 | (1) |
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337 | (2) |
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21 Novel Capture Technologies: Non-carbon Sorbents and Photochemical Oxidations |
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339 | (18) |
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339 | (1) |
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340 | (10) |
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21.2.1 Amended Silicates, Novinda |
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|
340 | (1) |
|
21.2.1.1 Background and Motivations |
|
|
340 | (1) |
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21.2.1.2 How Does the Amended Silicates Sorbent Work? |
|
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341 | (1) |
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342 | (1) |
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344 | (1) |
|
21.2.2 MinPlus CDEM Group BV |
|
|
345 | (1) |
|
21.2.2.1 Background and Motivations |
|
|
345 | (1) |
|
21.2.2.2 How Does the MinPlus Sorbent Work? |
|
|
345 | (1) |
|
21.2.2.3 Demonstrations of Sorbent |
|
|
347 | (1) |
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348 | (1) |
|
21.2.3 Pahlman Process - Enviroscrub |
|
|
348 | (1) |
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21.2.3.1 Background and Motivations |
|
|
348 | (1) |
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21.2.3.2 How Does the Process and Sorbent Work? |
|
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349 | (1) |
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349 | (1) |
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350 | (1) |
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21.3 Photochemical Removal of Mercury from Flue Gas |
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350 | (2) |
|
21.3.1 Sensitized Oxidation of Mercury: GP-254 Process |
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350 | (2) |
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21.3.2 Photocatalytic Oxidation of Mercury |
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352 | (1) |
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352 | (1) |
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353 | (4) |
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22 Sorbents for Gasification Processes |
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357 | (18) |
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357 | (1) |
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358 | (2) |
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22.3 Warm/Humid Gas Temperature Mercury Sorbent Capture Techniques |
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|
360 | (6) |
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22.4 Cold Gas Cleanup of Mercury |
|
|
366 | (4) |
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22.4.1 Carbon-Based Materials |
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|
367 | (1) |
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|
368 | (1) |
|
22.4.3 Wet Scrubbing Technique |
|
|
369 | (1) |
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|
370 | (1) |
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|
370 | (1) |
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|
371 | (4) |
| Part VI: Modeling of Mercury Chemistry in Air Pollution Control Devices |
|
375 | (62) |
|
23 Mercury-Carbon Surface Chemistry |
|
|
377 | (12) |
|
|
|
23.1 Nature of the Bonding of Mercury to the Carbon Surface |
|
|
377 | (1) |
|
23.2 Effects of Acid Gases on Mercury Capacities on Carbon |
|
|
378 | (4) |
|
|
|
382 | (3) |
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|
|
385 | (1) |
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|
386 | (3) |
|
24 Atomistic-Level Models |
|
|
389 | (24) |
|
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|
|
389 | (1) |
|
24.2 Homogeneous Mercury Oxidation Kinetics |
|
|
390 | (10) |
|
24.2.1 Mercury - Chlorine Chemistry |
|
|
390 | (7) |
|
24.2.2 Mercury - Bromine Chemistry |
|
|
397 | (3) |
|
24.3 Heterogeneous Chemistry |
|
|
400 | (7) |
|
24.3.1 Mercury Adsorption on Activated Carbon |
|
|
400 | (4) |
|
24.3.2 Mercury Adsorption on Precious Metals |
|
|
404 | (3) |
|
24.4 Conclusions and Future Work |
|
|
407 | (1) |
|
|
|
407 | (6) |
|
25 Predicting Hg Emissions Rates with Device-Level Models and Reaction Mechanisms |
|
|
413 | (24) |
|
|
|
|
|
25.1 Introduction and Scope |
|
|
413 | (1) |
|
|
|
414 | (2) |
|
|
|
416 | (17) |
|
25.3.1 In-Furnace Transformations |
|
|
416 | (3) |
|
25.3.2 In-Flight Transformations |
|
|
419 | (8) |
|
25.3.3 Hg° Oxidation across SCR Catalysts |
|
|
427 | (3) |
|
25.3.4 Hg Transformations within WFGDs |
|
|
430 | (3) |
|
|
|
433 | (2) |
|
|
|
435 | (2) |
| Index |
|
437 | |