Natural Gas Hydrates: A Guide for Engineers

John J. Carroll Published by Gulf Professional Publishers http://members.shaw.ca/hydrate/

Table of Contents
Preface Acknowledgements Chapter 1 Introduction Natural Gas Sales Gas Hydrates Water Molecule Normal Boiling Point of Water Enthalpy of Vaporization Expansion Upon Freezing Shape of the Water Molecule and the Hydrogen Bond Hydrates Water and Natural Gas Free-Water Heavy Water Additional Reading Units References Bibliography Chapter 1 Appendix: Periodic Table of the Elements Hydrate Types and Formers Type I Hydrates Type I Formers Type II Hydrates Type II Formers Size of the Guest Molecule n-Butane Other Hydrocarbons Cyclopropane 2-Butene Hydrogen and Helium Chemical Properties of Potential Guests Liquid Hydrate Formers Type H Hydrates Type H Formers Hydrate Forming Conditions xv xvii 1 2 2 2 3 3 5 6 7 9 11 12 13 13 14 14 15 16 17 17 19 20 20 20 22 22 23 23 24 24 24 25 25 25

Chapter 2

Natural Gas Hydrates: A Guide for Engineers Table of Contents John J. Carroll, Gulf Professional Publishing, Amsterdam, The Netherlands, (2003) 1

Pressure-Temperature Composition Caution Nitrogen Quadruple Points Cyclopropane Other Hydrate Formers Freons Halogens Noble Gases Air Others Mixtures Mixtures of the Same Type Type I Plus Type II Azeotropy Mixtures with Nonformers Examples Example 2-1 Example 2-2 Example 2-3 Example 2-4 Example 2-5 Example 2-6 References Chapter 2 Appendix: Water Content of the Fluid in Equilibrium with Hydrate for Pure Components Chapter 3 Hand Calculation Methods Gas Gravity Method K-Factor Method Calculation Algorithms Flash Incipient Solid Formation Liquid Hydrocarbons Computerization Comments on the Accuracy of the K-Factor Method Baillie-Wichert Method Comments on These Methods Water Non-formers Isobutane vs. n-Butane Quick Comparison Mei et al. (1998) Fan and Guo (1999) Ng and Robinson (1976)

26 28 31 31 32 35 35 35 36 36 36 36 37 37 37 38 39 39 39 40 40 40 41 41 42 43 50 51 53 54 54 55 55 57 58 60 65 66 66 67 68 68 70 71

Natural Gas Hydrates: A Guide for Engineers Table of Contents John J. Carroll, Gulf Professional Publishing, Amsterdam, The Netherlands, (2003) 2

Examples Example 3-1 Example 3-2 Example 3-3 Example 3-4 Example 3-5 Example 3-6 References Chapter 3 Appendix: Katz K-factor Charts Chapter 4 Computer Methods Phase Equilibrium Van der Waals and Platteeuw Parrish and Prausnitz Ng and Robinson Calculations Compositions Commercial Software Packages Accuracy of These Programs Pure Components Methane Ethane Carbon Dioxide Hydrogen Sulfide Mixtures Mei et al. (1998) Fan and Guo (1999) Ng and Robinson (1976) Dehydration Margin of Error Examples Example 4-1 Example 4-2 References Inhibiting Hydrate Formation With Chemicals Freezing Point Depression Hammerschmidt Equation Nielsen-Bucklin Equation New Method A Chart Accuracy of the New Method Brine Solutions Comment on the Simple Methods Advanced Calculation Methods Word of Caution

73 73 74 74 75 75 76 77 79 91 91 93 93 95 95 96 97 98 98 99 100 101 101 103 103 104 106 107 109 109 109 110 110 111 113 115 118 119 120 120 123 125 127 129

Chapter 5

Natural Gas Hydrates: A Guide for Engineers Table of Contents John J. Carroll, Gulf Professional Publishing, Amsterdam, The Netherlands, (2003) 3

Acetone Inhibitor Vaporization Comment On Injection Rates Kinetic Inhibitors Price for Inhibitor Chemicals Examples Example 5-1 Example 5-2 Example 5-3 Example 5-4 Example 5-5 Example 5-6 Example 5-7 Example 5-8 Example 5-9 References Chapter 6 Dehydration of Natural Gas Water Content Specification Glycol Dehydration Liquid Desiccants Glycols Process Description Inlet Separator Contactor Flash Tank Lean-Rich Exchanger Regenerator Glycol Pump Short Cut Design Method BTEX Software Approximate Capital Cost Mole Sieves Process Description Simplified Modeling Refrigeration Process Description Glycol Injection Examples Example 6-1 Example 6-2 Example 6-3 References Combating Hydrates Using Heat and Pressure

129 130 133 135 135 135 135 137 137 137 137 139 139 140 140 141 143 143 144 144 145 145 146 147 147 148 148 149 149 150 152 152 152 153 154 158 159 160 162 162 162 162 164 165

Chapter 7

Natural Gas Hydrates: A Guide for Engineers Table of Contents John J. Carroll, Gulf Professional Publishing, Amsterdam, The Netherlands, (2003) 4

Use of Heat Heat Loss from a Buried Pipeline Fluid Contribution Pipe Contribution Soil Contribution Overall Heat Transferred Additional Comments Line Heater Deign Bath Tube Bundle Fire Tube Other Considerations Heat Transfer Two-Phase Heater Transfer Depressurization Melting a Plug with Heat Buildings Capital Costs Examples Example 7-1 Example 7-2 Example 7-3 References Chapter 7 Appendix: Output from Pipe Heat Loss Program for the Examples in the Text Chapter 8 Physical Properties of Hydrates Molar Mass Density Enthalpy of Fusion Heat Capacity Thermal Conductivity Mechanical Properties Volume of Gas In Hydrate Ice versus Hydrate Examples Example 8-1 Example 8-2 Example 8-3 Example 8-4 Example 8-5 References Phase Diagrams Phase Rule

165 166 167 168 168 169 169 170 170 172 173 173 174 174 174 175 177 179 179 179 179 182 183 183 184 198 198 200 201 203 203 203 204 205 205 205 206 206 207 208 209 210 210

Chapter 9

Natural Gas Hydrates: A Guide for Engineers Table of Contents John J. Carroll, Gulf Professional Publishing, Amsterdam, The Netherlands, (2003) 5

Comments About Phases Single Component Systems Water Binary Systems Constructing T-x and P-x Diagrams Methane + Water Free-Water Carbon Dioxide + Water Hydrogen Sulfide + Water Propane + Water Phase Behavior Below 0C Methane + Water Multicomponent Systems An Acid Gas Mixture A Typical Natural Gas Examples Example 9-1 Example 9-2 Example 9-3 Example 9-4 Example 9-5 Example 9-6 Example 9-7 References Chapter 10 Water Content of Natural Gas Equilibrium with Liquid Water Ideal Model McKetta-Wehe Chart Sharma-Campbell Method Bukacek Ning et al. Maddox Correction Robinson et al. Charts Wichert Correction AQUAlibrium Equilibrium with Solids Ice Hydrate Methane Gas Gravity Examples Example 10-1 Example 10-2 Example 10-3 Example 10-4

211 212 213 214 217 218 221 221 222 224 224 224 225 226 227 228 228 229 229 229 230 230 231 231 232 232 233 234 237 238 239 241 243 244 246 247 247 249 249 251 253 253 253 254 255

Natural Gas Hydrates: A Guide for Engineers Table of Contents John J. Carroll, Gulf Professional Publishing, Amsterdam, The Netherlands, (2003) 6

Example 10-5 Example 10-6 References Appendix: Programs on the Companion Website Index

255 256 257 258 267

Natural Gas Hydrates: A Guide for Engineers Table of Contents John J. Carroll, Gulf Professional Publishing, Amsterdam, The Netherlands, (2003) 7