||Numerical Simulation of CO2 Hydrate Formation in Lab-Scale Experiment
||Department of Resources Engineering
CO2 is a byproduct of burning fossil fuels and it is a gas that is notoriously associated with global warming, a concept that has had widespread effects on both human and environmental systems. Storing CO2 in solid hydrates are promising option for the long-term storage of CO2. The injection of CO2 into a hydrate layer may also replace CH4 as a guest molecule inside of an already-formed hydrate structure. This replacement reaction results in the release CH4 and the formation of CO2 hydrate. The formation rate of a hydrate is generally dependent upon the thermodynamic conditions. To obtain the optimal formation rate, this study was conducted to investigate the CO2 hydrate formation behavior in a laboratory setting.
In this study, the STARS simulator developed by CMG Ltd. was used to build a reliable model of the CO2 hydrate reaction and predict the behavior of CO2 hydrate formation in a reservoir. This research was based on experiments used in previous research conducted by the team from the National Taiwan University of Science and Technology (NTUST). The numerical simulation was modeled identically to that of the former experiment and it used as a reference for the similarity of the results of pressure and temperature. Sensitive analysis was carried out to understand the parameters affecting the reaction. The investigated parameters included the absolute permeability, relative permeability, activation energy, enthalpy, thermal conductivity and heat capacity.
This study was successful in establishing a CO2 hydrate model based on comparison with the results of experimentation. With the establishment of such a model, the following conclusions could be made:  rock and flow properties were the fundamental parameter which control hydrate formation,  the reaction parameters were the main parameter of the CO2 hydrate phase behavior which control the molecular exchange, and  the thermal properties of the porous medium did not greatly impact the hydrate formation. A directly proportional relationship between the hydrate concentration and average temperature distribution was determined to due the exothermic reactions that occurred at the boundary between the gas and the porous medium.
TABLE OF CONTENTS III
LIST OF TABLES VI
LIST OF FIGURES VII
CHAPTER 1 INTRODUCTION 1
1.1 Research Background 1
1.2 Objective 4
CHAPTER 2 LITERATURE REVIEW 5
2.1 Global Energy Demand 6
2.2 Hydrate Resources 7
2.3 Gas Hydrate Deposit 8
2.4 Correlation to Global warming 9
2.4.1 Global Warming 9
2.4.2 CO2 as greenhouse gasses 10
2.5 Anticipating of CO2 Emission 12
2.6 Recovery techniques 14
2.7 Characteristic of gas hydrate 16
2.7.1 Structure of hydrate 16
2.7.2 Thermal properties 18
2.7.3 Stability of hydrate 19
2.8 Hydrate formation 20
2.8.1 Hydrate Nucleation 20
2.9 Kinetic model of gas hydrate 22
2.10 Simulation study of gas hydrate 24
2.11 Literature Review of CO2 Hydrate and Previous Research 25
CHAPTER 3 RESEARCH DESIGN AND METHODOLOGY 27
3.1 Experimental 27
3.1.1 Experimental Apparatus 27
3.1.2 Materials 29
3.1.3 Experimental Process 30
3.2 Numerical simulation 31
3.2.1 CMG STARS 32
3.2.2 Governing Equations 32
3.2.3 Conservation Equations 32
3.3 Numerical Model Design 37
3.3.1 Grid Discretization 37
3.3.2 Initial Saturation 39
3.3.3 Formation Parameters 39
3.3.4 Component Properties 40
3.3.5 Hydrate Reaction 41
3.3.6 Rock Fluid Properties 43
3.3.7 Initial Condition 45
3.3.8 Well and Recurrent Data 45
CHAPTER 4 RESULTS 47
4.1. Initial Simulation Result 47
4.2. Sensitivity Analysis 52
CHAPTER 5 DISCUSSION 58
5.1 Comparison of Experimental and Simulation Final Results 58
5.2 Average Pressure 59
5.3 Temperature Profile 60
5.4 Cumulative CO2 Gas Injection 62
5.5 CO2 Hydrate volume 63
5.6 Spatial Distribution 64
CHAPTER 6 CONCLUSIONS AND SUGGESTIONS 69
6.1 Conclusions 69
6.2 Suggestions 70
Birkedal, K. A., Hauge, L. P., Graue, A., & Ersland, G. (2015). Transport mechanisms for CO2-CH4 exchange and safe CO2 storage in hydrate-bearing sandstone. Energies, 8(5), 4073-4095.
Boswell, R., & Collett, T. S. (2011). Current perspectives on gas hydrate resources. Energy Environ. Sci., 4(4), 1206–1215. https://doi.org/10.1039/C0EE00203H
British Petroleum. (2017). BP Statistical Review of World Energy 2017. British Petroleum, (66), 1–52.
Bryant, E. (1997). Climate Process & Change. Cambridge: Cambridge University Press. https://doi.org/10.1017/CBO9781139166751
Carroll, J. (2014). Natural gas hydrates: a guide for engineers. Gulf Professional Publishing.
Chong, Z. R., Yang, S. H. B., Babu, P., Linga, P., & Li, X. Sen. (2016). Review of natural gas hydrates as an energy resource: Prospects and challenges. Applied Energy, 162, 1633–1652. https://doi.org/10.1016/j.apenergy.2014.12.061
Clarke, M. A., & Bishnoi, P. R. (2004). Determination of the intrinsic rate constant and activation energy of CO2 gas hydrate decomposition using in-situ particle size analysis. Chemical Engineering Science, 59(14), 2983–2993.
CMG. (2009). Gas Hydrate Simulation Using STARS. Calgary, Alberta, Canada: Computer Modelling Group Ltd.
Conti, J., Holtberg, P., Diefenderfer, J., LaRose, A., Turnure, J. T., & Westfall, L. (2016). International Energy Outlook 2016 With Projections to 2040 (Vol. 484). https://doi.org/10.2172/1296780
EIA. (2017). International Energy Outlook 2017 Overview. U.S. Energy Information Administration, IEO2017(2017), 143.
Gaddipati, M. (2008). Code Comparison of Methane Hydrate Reservoir Simulators using CMG STARS Manohar. West Virginia University.
Gaddipati, M. (2014). Reservoirs Modeling of Gas hydrate deposits in North Slope of Alaska and Gulf of Mexico. West Virginia University.
Goel, N. (2006). In situ methane hydrate dissociation with carbon dioxide sequestration: Current knowledge and issues. Journal of Petroleum Science and Engineering, 51(3–4), 169–184. https://doi.org/10.1016/j.petrol.2006.01.005
Hauge LP, Birkedal KA, Ersland G, & Graue A. (2014). Methane Production from Natural Gas Hydrates by CO2 Replacement - Review of Lab Experiments and Field Trial. SPE Conference. https://doi.org/10.2118/169198-MS
Hong, H., & Pooladi-Darvish, M. (2003). A Numerical Study on Gas Production F rom Formations Containing Gas Hydrates. In Canadian International Petroleum Conference. Petroleum Society of Canada.
IPCC. (2014). Climate Change 2014 Synthesis Report Summary Chapter for Policymakers. Ipcc, 31. https://doi.org/10.1017/CBO9781107415324
Kamath, V. A. (1984). Study of heat transfer characteristics during dissociation of gas hydrates in porous media.
Kim, H. C., Bishnoi, P. R., Heidemann, R. A., & Rizvi, S. S. H. (1987). Kinetics of methane hydrate decomposition. Chemical Engineering Science, 42(7), 1645–1653. https://doi.org/10.1016/0009-2509(87)80169-0
Ledley, T. S., Sundquist, E. T., Schwartz, S. E., Hall, D. K., Fellows, J. D., & Killeen, T. L. (1999). Climate change and greenhouse gases. Eos, Transactions American Geophysical Union, 80(39), 453–458.
Makogon, Y. F., & Holditch, S. a. (2001). OTC 13035 Hydrate Formation from CO 2 and Sea Water Liquids : Offshore Technology Conference.
McMullan, R. K., & Jeffrey, G. A. (1965). Polyhedral clathrate hydrates. IX. Structure of ethylene oxide hydrate. The Journal of Chemical Physics, 42(8), 2725–2732. https://doi.org/10.1063/1.1703228
Milkov, A. V. (2004). Global estimates of hydrate-bound gas in marine sediments: How much is really out there? Earth-Science Reviews, 66(3–4), 183–197. https://doi.org/10.1016/j.earscirev.2003.11.002
Moridis, G., Collett, T. S., Pooladi-Darvish, M., Hancock, S. H., Santamarina, C., Boswell, R., … Koh, C. (2011). Challenges, Uncertainties, and Issues Facing Gas Production From Gas-Hydrate Deposits. SPE Reservoir Evaluation & Engineering, 14(1), 76–112. https://doi.org/10.2118/131792-PA
Qorbani, K., Kvamme, B., & Kuznetsova, T. (2017). Injection of CO2 into an Intact Methane Hydrate Reservoir. SPE Bergen One Day Seminar, (April), 1–8. https://doi.org/10.2118/185896-MS
Shpakov, V. P., Tse, J. S., Tulk, C. A., Kvamme, B., & Belosludov, V. R. (1998). Elastic moduli calculation and instability in structure I methane clathrate hydrate. Chemical Physics Letters, 282(2), 107–114.
Shu, S. S., & Lee, M. J. (2016). Dynamic behavior of methane hydrates formation and decomposition with a visual high-pressure apparatus. Journal of the Taiwan Institute of Chemical Engineers, 62, 1–9. https://doi.org/10.1016/j.jtice.2016.01.015
Sloan, E. D. (1998). Clathrate Hydrates of Natural Gases, Second Edition, Revised and Expanded. Taylor & Francis. Retrieved from https://books.google.com.tw/books?id=jBaLcv6qKnsC
Sloan, E. D., & Koh, C. A. (2007). Clathrate hydrates of natural gases. Fuel.
STARS. (2015). ADVANCED PROCESSES & THERMAL RESERVOIR SIMULATOR. Calgary, Alberta, Canada: Computer Modelling Group Ltd.
Uddin, Mafiz; Coombe, Dennis Allan; Law, David Hin-Sum; Gunter, W. D. (2006). Numerical Studies of Gas-Hydrates Formation and Decomposition in a Geological Reservoir. SPE, (Sun Jan 01 00:00:00 GMT 2006). https://doi.org/10.2118/100460-MS
USGS. (2018). U.S. Geological Survey Gas Hydrates Project. Retrieved from https://www.usgs.gov/media/images/map-gas-hydrates
Waite, W. F., Santamarina, J. C., Cortes, D. D., Dugan, B., Espinoza, D., Germaine, J., … Shin, H. (2009). Physical properties of hydrate‐bearing sediments. Reviews of Geophysics, 47(4). https://doi.org/doi:10.1029/2008RG000279
Warzinski, R. P., Gamwo, I. K., Rosenbaum, E. J., Myshakin, E. M., Jiang, H., Jordan, K. D., … Shaw, D. W. (2016). Thermal Properties of Methane Hydrate by Experiment and Modeling and Impacts Upon Technology. Alternative Energy and Shale Gas Encyclopedia, 680–686. https://doi.org/10.1002/9781119066354.ch66
Wu, C. Y., & Hsieh, B. Z. (2016). Gas recovery from hydrate accumulations using depressurization: A case study of the Yuan-an Ridge site in southwestern offshore Taiwan. The Bulletin of the Chinese Institute of Mining and Metallurgical Engineers, 236, 46–61.
Yang. (2016). Numerical Simulation of Gas Hydrate Dissociation in Lab-Scale Depressurization Experiment. National Chengkung University.
Zatsepina, O. Y., & Pooladi‐Darvish, M. (2011). Storage of CO2 hydrate in shallow gas reservoirs: pre‐and post‐injection periods. Greenhouse Gases: Science and Technology, 1(3), 223–236.
Zhou, X., Fan, S., Liang, D., & Du, J. (2008). Determination of appropriate condition on replacing methane from hydrate with carbon dioxide. Energy Conversion and Management, 49(8), 2124–2129. https://doi.org/10.1016/j.enconman.2008.02.006