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

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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

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3
3
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7
9
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Chapter 2

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

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Natural Gas Hydrates: A Guide for Engineers

Table of Contents
John J. Carroll, Gulf Professional Publishing, Amsterdam, The Netherlands, (2003)
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Chapter 3

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

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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)

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Natural Gas Hydrates: A Guide for Engineers

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John J. Carroll, Gulf Professional Publishing, Amsterdam, The Netherlands, (2003)
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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

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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

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Chapter 5

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

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Natural Gas Hydrates: A Guide for Engineers

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John J. Carroll, Gulf Professional Publishing, Amsterdam, The Netherlands, (2003)
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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

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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

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Chapter 7

Combating Hydrates Using Heat and Pressure

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Natural Gas Hydrates: A Guide for Engineers

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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

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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

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Chapter 9

Phase Diagrams
Phase Rule

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Natural Gas Hydrates: A Guide for Engineers

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John J. Carroll, Gulf Professional Publishing, Amsterdam, The Netherlands, (2003)
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Chapter 10

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

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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

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Natural Gas Hydrates: A Guide for Engineers

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John J. Carroll, Gulf Professional Publishing, Amsterdam, The Netherlands, (2003)
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Example 10-5
Example 10-6
References
Appendix: Programs on the Companion Website
Index

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Natural Gas Hydrates: A Guide for Engineers

Table of Contents
John J. Carroll, Gulf Professional Publishing, Amsterdam, The Netherlands, (2003)
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