| Preface |
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xix | |
| Authors |
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xxv | |
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Overview and Historical Perspective |
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1 | (44) |
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Hydrates as a Laboratory Curiosity |
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1 | (8) |
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Hydrates of Hydrocarbons Distinguished from Inorganic Hydrates and Ice |
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5 | (1) |
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Methods to Determine the Hydrate Composition |
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5 | (1) |
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Phase Diagrams Provide Hydrate Classification |
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6 | (3) |
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Hydrates in the Natural Gas Industry |
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9 | (13) |
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Initial Experiments on Natural Gas Hydrates |
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9 | (2) |
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Initial Correlation of Hydrate Phase Equilibria |
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11 | (1) |
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Hydrate Crystal Structures and Hydrate Type Definitions |
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11 | (3) |
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Basis for Current Thermodynamic Models |
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14 | (2) |
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Time-Dependent Studies of Hydrates |
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16 | (3) |
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Work to Enable Gas Production, Transport, and Processing |
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19 | (1) |
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Hydrates in Mass and Energy Storage and Separation |
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20 | (2) |
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Hydrates as an Energy Resource |
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22 | (5) |
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23 | (3) |
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Investigations Related to Hydrate Exploration and Recovery |
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26 | (1) |
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Environmental Aspects of Hydrates |
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27 | (1) |
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Safety Aspects of Hydrates |
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27 | (1) |
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Relationship of This
Chapter to Those That Follow |
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28 | (17) |
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29 | (16) |
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Molecular Structures and Similarities to Ice |
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45 | (68) |
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Crystal Structures of Ice Ih and Natural Gas Hydrates |
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46 | (46) |
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Ice, Water, Hydrogen Bonds, and Clusters |
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46 | (1) |
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46 | (3) |
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49 | (1) |
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49 | (1) |
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Hydrogen bonds cause unusual water, ice, and hydrate properties |
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50 | (2) |
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52 | (1) |
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Hydrate Crystalline Cavities and Structures |
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53 | (1) |
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53 | (6) |
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Hydrate crystal cells---structures I, II, and H |
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59 | (13) |
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Characteristics of Guest Molecules |
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72 | (1) |
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Chemical nature of guest molecules |
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72 | (1) |
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Geometry of the guest molecules |
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73 | (12) |
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Filling the hydrate cages |
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85 | (6) |
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Summary Statements for Hydrate Structure |
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91 | (1) |
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Comparison of Properties of Hydrates and Ice |
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92 | (10) |
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Spectroscopic Implications |
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93 | (2) |
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95 | (1) |
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95 | (1) |
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96 | (1) |
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97 | (1) |
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Thermal conductivity of hydrates |
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97 | (4) |
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Thermal expansion of hydrates and ice |
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101 | (1) |
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The What and the How of Hydrate Structures |
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102 | (11) |
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102 | (11) |
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Hydrate Formation and Dissociation Processes |
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113 | (76) |
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116 | (34) |
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Knowledge Base for Hydrate Nucleation |
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117 | (1) |
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Key properties of supercooled water |
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117 | (2) |
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Solubility of natural gases in water |
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119 | (2) |
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Nucleation theory for ice and hydrates |
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121 | (8) |
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Site of hydrate nucleation |
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129 | (1) |
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Conceptual Picture of Hydrate Nucleation at the Molecular Level |
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130 | (1) |
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Labile cluster nucleation hypothesis |
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131 | (3) |
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Nucleation at the interface hypothesis |
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134 | (1) |
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Local structuring nucleation hypothesis |
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135 | (3) |
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Stochastic Nature of Heterogeneous Nucleation |
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138 | (4) |
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Correlations of the Nucleation Process |
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142 | (1) |
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Driving force of nucleation |
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143 | (4) |
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The ``Memory Effect'' Phenomenon |
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147 | (2) |
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State-of-the-Art for Hydrate Nucleation |
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149 | (1) |
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150 | (26) |
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Conceptual Picture of Growth at the Molecular Level |
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150 | (1) |
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Crystal growth molecular concepts |
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150 | (2) |
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152 | (3) |
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Hydrate Crystal Growth Processes |
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155 | (1) |
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155 | (1) |
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Hydrate film/shell growth at the water-hydrocarbon interface |
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156 | (10) |
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Crystal growth with interfacial agitation |
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166 | (1) |
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Growth of metastable phases |
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167 | (1) |
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Correlations of the Growth Process |
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168 | (1) |
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Growth kinetics---the Englezos---Bishnoi model |
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169 | (2) |
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Mass transfer---the Skovborg---Rasmussen model |
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171 | (1) |
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172 | (4) |
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State-of-the-Art for Hydrate Growth |
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176 | (1) |
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176 | (4) |
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Conceptual Picture of Hydrate Dissociation |
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176 | (1) |
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Correlations of Hydrate Dissociation |
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177 | (2) |
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Anomalous Self-Preservation |
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179 | (1) |
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State-of-the-Art for Hydrate Dissociation |
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180 | (1) |
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180 | (9) |
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181 | (8) |
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Estimation Techniques for Phase Equilibria of Natural Gas Hydrates |
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189 | (68) |
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189 | (7) |
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Hydrate Phase Diagrams for Water + Hydrocarbon Systems |
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196 | (12) |
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Pressure---Temperature Diagrams of the CH4 + H2O (or N2 + H2O) System |
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197 | (3) |
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Systems (e.g., H2O + C2H6, C3H8, or i-C4H10) with Upper Quadruple Points |
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200 | (1) |
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Pressure---Temperature Diagrams for Multicomponent Natural Gas Systems |
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201 | (1) |
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Pressure---Temperature Diagrams for Systems with Inhibitors |
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202 | (1) |
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Temperature---Composition Diagrams for Methane + Water |
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202 | (3) |
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Solubility of Gases Near Hydrate Formation Conditions |
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205 | (1) |
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Pressure---Temperature Diagrams for Structure H Systems |
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205 | (3) |
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Three-Phase (LW-H-V) Equilibrium Calculations |
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208 | (18) |
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209 | (3) |
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Hydrate limits to gas expansion through a valve |
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212 | (3) |
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The Distribution Coefficient (Kvsi-Value) Method |
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215 | (11) |
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Quadruple Points and Equilibrium of Three Condensed Phases (LW-H-LHC) |
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226 | (3) |
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The Location of the Quadruple Points |
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226 | (1) |
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Condensed Three-Phase Equilibrium |
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227 | (2) |
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Effect of Thermodynamic Inhibitors on Hydrate Formation |
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229 | (7) |
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Hydrate Inhibition via Alcohols and Glycols |
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231 | (3) |
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Hydrate Inhibition Using Salts |
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234 | (2) |
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Two-Phase Equilibrium: Hydrates with One Other Phase |
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236 | (4) |
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Water Content of Vapor in Equilibrium with Hydrate |
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237 | (2) |
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Water Content of Liquid Hydrocarbon in Equilibrium with Hydrates |
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239 | (1) |
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Methane Content of Water in Equilibrium with Hydrates |
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240 | (1) |
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Hydrate Enthalpy and Hydration Number from Phase Equilibrium |
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240 | (12) |
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The Clausius-Clapeyron Equation and Hydrate Equilibrium |
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241 | (2) |
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Enthalpy of dissociation and cavity occupation |
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243 | (3) |
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Determination of the Hydration Number |
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246 | (1) |
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Using the Clapeyron equation to obtain hydration number |
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247 | (3) |
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Hydration numbers by the Miller and Strong method |
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250 | (2) |
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Summary and Relationship to
Chapters Which Follow |
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252 | (5) |
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252 | (5) |
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A Statistical Thermodynamic Approach to Hydrate Phase Equilibria |
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257 | (62) |
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Introduction and Overview |
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257 | (1) |
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Statistical Thermodynamics of Hydrate Equilibria |
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258 | (38) |
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Grand Canonical Partition Function for Water |
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259 | (4) |
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The Chemical Potential of Water in Hydrates |
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263 | (7) |
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The Langmuir Adsorption Analogy |
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270 | (2) |
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Relating the Langmuir Constant to Cell Potential Parameters |
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272 | (5) |
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Activity Coefficient for Water in the Hydrate |
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277 | (4) |
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Defining the Hydrate Fugacity and Reference Parameters |
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281 | (4) |
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The Gibbs Free Energy Method |
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285 | (6) |
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Accuracy of CSMGem Compared to Commercial Hydrate Frograms |
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291 | (2) |
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Ab Initio Methods and the van der Waals and Platteeuw Method |
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293 | (3) |
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Application of the Method to Analyze Systems of Methane + Ethane + Propane |
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296 | (11) |
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Pure Hydrate Phase Equilibria |
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296 | (3) |
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Binary Hydrate Phase Equilibria |
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299 | (1) |
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Methane + propane hydrates |
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299 | (1) |
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Methane + ethane hydrates |
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299 | (3) |
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Ethane + propane hydrates |
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302 | (3) |
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Ternary hydrate phase equilibria and industrial application |
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305 | (2) |
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Computer Simulation: Another Microscopic---Macroscopic Bridge |
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307 | (6) |
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Basic Techniques of Monte Carlo and Molecular Dynamics Simulation |
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308 | (1) |
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309 | (1) |
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310 | (1) |
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What Has Been Learned from Molecular Simulation? |
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311 | (2) |
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Chapter Summary and Relationship to Following
Chapters |
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313 | (6) |
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314 | (5) |
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Experimental Methods and Measurements of Hydrate Properties |
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319 | (218) |
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Experimental Apparatuses and Methods for Macroscopic Measurements |
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320 | (22) |
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Measurement Methods for Hydrate Phase Equilibria and Kinetics |
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320 | (7) |
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Principles of equilibrium apparatus development |
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327 | (1) |
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Apparatuses for use above the ice point |
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328 | (6) |
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Apparatus for use below the ice point |
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334 | (1) |
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Apparatuses for two-phase equilibria |
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335 | (1) |
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Flow loops for hydrate formation kinetics |
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335 | (2) |
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Methods for Measurement of Thermal Properties |
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337 | (1) |
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Heat capacity and heat of dissociation methods |
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338 | (3) |
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Methods for thermal conductivity measurements |
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341 | (1) |
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Measurements of the Hydrate Phase |
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342 | (16) |
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Mesoscopic Measurements of the Hydrate Phase |
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342 | (4) |
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Molecular-Level Measurements of the Hydrate Phase |
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346 | (3) |
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349 | (1) |
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350 | (8) |
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Data for Natural Gas Hydrate Phase Equilibria and Thermal Properties |
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358 | (165) |
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358 | (1) |
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Equilibria of simple natural gas components |
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358 | (34) |
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Equilibria of binary guest mixtures |
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392 | (48) |
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Equilibria of ternary guest mixtures |
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440 | (8) |
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Equilibria of multicomponent guest mixtures |
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448 | (13) |
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Equilibria with inhibitors |
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461 | (58) |
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519 | (1) |
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Heat capacity and heat of dissociation |
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519 | (4) |
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Summary and Relationship to
Chapters that Follow |
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523 | (14) |
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523 | (14) |
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537 | (106) |
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Introduction and Overview |
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537 | (2) |
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The Paradigm Is Changing from Assessment of Amount to Production of Gas |
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539 | (11) |
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Extent of the Occurrence of In Situ Gas Hydrates |
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539 | (11) |
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Sediments with Hydrates Typically Have Low Contents of Biogenic Methane |
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550 | (16) |
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Generation of Gases for Hydrate Formation |
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551 | (4) |
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The SMI, the Hydrate Upper Boundary, and the SMI Rule-of-Ten |
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555 | (2) |
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Mechanisms for Generation of Hydrates |
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557 | (1) |
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Hydrate formation in the two-phase region |
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558 | (2) |
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Models for in situ hydrate formation |
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560 | (6) |
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Sediment Lithology and Fluid Flow Are Major Controls on Hydrate Deposition |
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566 | (1) |
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Remote Methods Enable an Estimation of the Extent of a Hydrated Reservoir |
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566 | (10) |
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The Hydrate Pressure-Temperature Stability Envelope |
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567 | (4) |
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Seismic Velocity Techniques and Bottom Simulating Reflections |
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571 | (4) |
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Methane Solubility Further Limits the Hydrate Occurrence |
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575 | (1) |
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Drilling Logs and/Coring Provide Improved Assessments of Hydrated Gas Amounts |
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576 | (7) |
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577 | (1) |
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Evidence of Hydrates in Cores |
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578 | (4) |
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Combining Laboratory and Field Experiments |
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582 | (1) |
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Hydrate Reservoir Models Indicate Key Variables for Methane Production |
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583 | (4) |
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Future Hydrated Gas Production Trends Are from the Permafrost to the Ocean |
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587 | (2) |
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Hydrates Play a Part in Climate Change and Geohazards |
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589 | (39) |
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Case Study 1: Leg 164 in the Blake-Bahama Ridge (Hydrate Assessment) |
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592 | (2) |
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594 | (3) |
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597 | (1) |
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598 | (1) |
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598 | (1) |
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Case Study 2: Hydrate Ridge (Hydrate Assessment) |
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599 | (2) |
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Near surface hydrates: the chemosynthetic community and chemoherms |
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601 | (3) |
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Deeper hydrates at Southern Hydrate Ridge: characterization and assessment |
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604 | (1) |
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605 | (2) |
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Coring and direct evidence |
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607 | (1) |
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The lessons of Hydrate Ridge |
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608 | (1) |
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Case Study 3: Messoyakha (Hydrate Production in Permafrost) |
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609 | (7) |
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Case Study 4: Mallik 2002 (Hydrate Production in Permafrost) |
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616 | (1) |
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Background of the Mallik 2002 well |
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617 | (1) |
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Overview of the Mallik 2002 well |
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618 | (2) |
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620 | (1) |
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Pressure stimulation tests in the 5L-38 well |
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620 | (1) |
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The Thermal stimulation test in Mallik 5L-38 |
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621 | (4) |
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Modeling gas production from hydrates |
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625 | (3) |
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628 | (15) |
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629 | (14) |
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Hydrates in Production, Processing, and Transportation |
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643 | (42) |
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644 | (1) |
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How Do Hydrate Plugs Form in Industrial Equipment? |
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644 | (12) |
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Case Study 1: Hydrate Prevention in a Deepwater Gas Pipeline |
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645 | (2) |
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Case Study 2: Hydrates Prevention via Combination of Methods |
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647 | (1) |
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648 | (1) |
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Line burial with wellhead heat addition |
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649 | (1) |
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Burial, heat addition, and insulation |
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649 | (1) |
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Methanol addition alternative |
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650 | (1) |
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Case Study 3: Hydrate Formation via Expansion through Valves or Restrictions |
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651 | (2) |
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Conceptual Overview: Hydrate Plug Formation in Oil-Dominated Systems |
|
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653 | (1) |
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Conceptual Overview: Hydrate Formation in Gas-Dominated Systems |
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654 | (2) |
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How Are Hydrate Plug Formations Prevented? |
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656 | (13) |
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Case Study 4: Thermodynamic Inhibition Canyon Express and Ormen Lange Flowlines |
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656 | (2) |
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Case Study 5: Under-Inhibition by Methanol in a Gas Line |
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658 | (1) |
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Kinetic Hydrate Inhibition |
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659 | (3) |
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Antiagglomerant means of preventing hydrate plugs |
|
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662 | (6) |
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Case Study 6: AAs are a Major Hydrate Plug Prevention Tool |
|
|
668 | (1) |
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How Is a Hydrate Plug Dissociated? |
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669 | (7) |
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Case Study 7: Gulf of Mexico Plug Removal in Gas Export Line |
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675 | (1) |
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Safety and Hydrate Plug Removal |
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676 | (2) |
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Case Study 8: Hydrate Plug Incident Resulting in Loss of Life |
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|
677 | (1) |
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Applications to Gas Transport and Storage |
|
|
678 | (1) |
|
Summary of Hydrates in Flow Assurance and Transportation |
|
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679 | (6) |
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679 | (6) |
|
Appendix A CSMGem Example Problems |
|
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685 | (8) |
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685 | (1) |
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686 | (1) |
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Setting up the Natural Gas Example |
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686 | (1) |
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Incipient Hydrate Formation Conditions |
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686 | (2) |
|
Plotting a 2-Phase VLE Curve |
|
|
688 | (1) |
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688 | (2) |
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Adding Hydrate Inhibitor Solutions |
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690 | (1) |
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690 | (1) |
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Expansion Across a Valve Solutions |
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691 | (1) |
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691 | (2) |
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Appendix B CSMPlug Example Problems |
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693 | (10) |
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693 | (1) |
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Example Problem for One-Sided Dissociation |
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693 | (1) |
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694 | (1) |
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Example Problem for Two-Sided Dissociation |
|
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695 | (2) |
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697 | (1) |
|
Example Problem for Safety Simulator |
|
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697 | (1) |
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Safety Simulator Solutions |
|
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698 | (1) |
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Example Problem for Electrical Heating |
|
|
699 | (1) |
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Electrical Heating Solutions |
|
|
699 | (4) |
| Index |
|
703 | |
