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研究生(外文):Pei-Wen Tsai
論文名稱(外文):The Effect of tert-Butanol on the Growth Mechanism of Gas Hydrates via Molecular Dynamics Simulations
指導教授(外文):Shiang-Tai Lin
口試委員(外文):Li-Jen ChenJer-Lai KuoYen-Tien, Tung
外文關鍵詞:gas hydratethermodynamic promoterkinetic inhibitortert-butanol
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Conventional approach for transport and storage of natural gas by pressurization is energy costly and also potentially risky. Gas hydrates are an alternative form of handling natural gas at lowered pressures. The addition of a suitable promoter can further stabilize the hydrate structure and shift the hydrate formation condition to an even lower pressure. It has been reported that tert-butaonol (TBA) is a thermodynamic promoter of methane hydrates. In this work we use molecular dynamics simulations to elucidate how tert-Butanol effects the growth of gas hydrate, and compare the similarity and difference between the growth of gas hydrates with and without tert-Butanol. Three-phase models comprising liquid, gas and solid hydrate phases are used. Both thermodynamic and kinetic properties are studied, it is found that a tert-Butanol molecule can stabilize the large cage in structure II (sII) hydrate (51264), while its size is too large to be enclosed by a large cage in structure I (sI) hydrate (51262). The encapsulation of TBA in to the large cage of sII hydrate is found to be a two-step process: first, a TBA molecule is adsorbed into an incomplete-cage; second, the TBA stabilizes the cage and attracts surrounding water molecules to form an entire cage. The similar geometry of sI and sII often leads to adsorption of tert-Butanol to the incorrect position at the hydrate-liquid interface, which hinders the growth of hydrate. As a consequence, while TBA is a thermodynamic promoter, it is a kinetic inhibitor.

摘要 iii
Abstract iv
Outline v
Figures vii
Tables xiii
Chapter 1. Introduction 1
1.1 Clathrate Hydrates 1
1.2 Structures of Clathrate hydrate 2
1.3 Application of Clathrate hydrate 6
1.4 Additives - Promoters & Inhibitors 7
1.5 Computational Molecular Simulation 10
1.6 Motivation 10
Chapter 2. Theory 12
2.1 Molecular Dynamics Simulations 12
2.2 Integration of Equation of Motion 13
2.3 Force Field 14
2.3.1 Non-Bond Terms 15
2.3.2 Valence Terms 18
2.4 System Controls 19
2.4.1 Temperature Thermostat 20
2.4.2 Pressure Barostat 21
Chapter 3. Computational Details 22
3.1 Simulation Models & Settings 22
3.1.1 Pure Methane Hydrate 23
3.1.2 Methane Hydrate with TBA 25
3.1.3 Force Field 27
3.2 Angular Order Parameter 29
3.3 Hydrogen Bond Identification 30
3.4 Definition of “Right Position” in sII gas Hydrates 31
3.5 Determination of Cage Types 36
Chapter 4. Results & Discussion 38
4.1 Thermodynamic Properties 38
4.1.1 Melting Point 38
4.1.2 Stability of Clathrate hydrates 44
4.2 Kinetic Properties 46
4.2.1 Growth Rate 46
4.2.2 Interactions between Water Molecules and tert-Butanol Molecules 51
4.2.3 Occupancy 61
4.2.4 Growth Mechanism 62
Chapter 5. Conclusions 77
References 79
Appendix Cycle Detection 87

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