CH4 recovery and CO2 sequestration using flue gas in natural gas hydrates as revealed by a micro-differential scanning calorimeter

The CH4–flue gas replacement in naturally occurring gas hydrates has attracted significant attention due to its potential as a method of exploitation of clean energy and sequestration of CO2. In the replacement process, the thermodynamic and structural properties of the mixed gas hydrates are critical factors to predict the heat flow in the hydrate-bearing sediments and the heat required for hydrate dissociation, and to evaluate the CO2 storage capacity of hydrate reservoirs. In this study, the 13C NMR and gas composition analyses confirmed that the preferential enclathration of N2 molecules in small 512 cages of structure I hydrates improved the extent of the CH4 recovery. A high pressure micro-differential scanning calorimeter (HP μ-DSC) provided reliable hydrate stability conditions and heat of dissociation values in the porous silica gels after the replacement, which confirmed that CH4 in the hydrates was successfully replaced with flue gas. A heat flow change associated with the dissociation and formation of hydrates was not noticeable during the CH4–flue gas replacement. Therefore, this study reveals that CH4–flue gas swapping occurs without structural transitions and significant hydrate dissociations.

[1]  Seungmin Lee,et al.  Experimental verification of methane-carbon dioxide replacement in natural gas hydrates using a differential scanning calorimeter. , 2013, Environmental science & technology.

[2]  Seungmin Lee,et al.  Thermodynamic and 13C NMR spectroscopic verification of methane–carbon dioxide replacement in natural gas hydrates , 2013 .

[3]  W. Kuhs,et al.  Calibration of Raman Quantification Factors of Guest Molecules in Gas Hydrates and Their Application to Gas Exchange Processes Involving N2 , 2015 .

[4]  Zhi-Ming Xia,et al.  Precombustion Capture of Carbon Dioxide and Hydrogen with a One-Stage Hydrate/Membrane Process in the Presence of Tetra-n- butylammonium Bromide (TBAB) , 2011 .

[5]  Wenchuan Wang,et al.  Replacement mechanism of methane hydrate with carbon dioxide from microsecond molecular dynamics simulations , 2012 .

[6]  A. Sum,et al.  Quantitative measurement and mechanisms for CH4 production from hydrates with the injection of liquid CO2. , 2014, Physical chemistry chemical physics : PCCP.

[7]  Tsutomu Uchida,et al.  Effects of Pore Sizes on Dissociation Temperatures and Pressures of Methane, Carbon Dioxide, and Propane Hydrates in Porous Media , 2002 .

[8]  C. Ratcliffe,et al.  On the contributions of NMR spectroscopy to clathrate science , 1999 .

[9]  Masaki Ota,et al.  Replacement of CH4 in the hydrate by use of liquid CO2 , 2005 .

[10]  Pierre Henry,et al.  Formation of natural gas hydrates in marine sediments 1. Conceptual model of gas hydrate growth conditioned by host sediment properties , 1999 .

[11]  K. Hester,et al.  Gas Hydrates: Immense Energy Potential and Environmental Challenges , 2011 .

[12]  B. A. Baldwin,et al.  Measuring gas hydrate formation and exchange with CO2 in Bentheim sandstone using MRI tomography , 2010 .

[13]  Jarle Husebø,et al.  Using magnetic resonance imaging to monitor CH4 hydrate formation and spontaneous conversion of CH4 hydrate to CO2 hydrate in porous media. , 2009, Magnetic resonance imaging.

[14]  Peter Englezos,et al.  Medium-pressure clathrate hydrate/membrane hybrid process for postcombustion capture of carbon dioxide. , 2008, Environmental science & technology.

[15]  Carolyn A. Koh,et al.  Clathrate hydrates of natural gases , 1990 .

[16]  Huen Lee,et al.  Phase Behavior and Structure Identification of the Mixed Chlorinated Hydrocarbon Clathrate Hydrates , 2002 .

[17]  M. Haeckel,et al.  Estimation of the global inventory of methane hydrates in marine sediments using transfer functions , 2012 .

[18]  Mike Priegnitz,et al.  A Counter-Current Heat-Exchange Reactor for the Thermal Stimulation of Hydrate-Bearing Sediments , 2013 .

[19]  Youngjun Lee,et al.  Hydrate-based pre-combustion capture of carbon dioxide in the presence of a thermodynamic promoter and porous silica gels , 2013 .

[20]  Tsutomu Uchida,et al.  Methane and Carbon Dioxide Hydrate Phase Behavior in Small Porous Silica Gels: Three-Phase Equilibrium Determination and Thermodynamic Modeling , 2002 .

[21]  R. J. Frank,et al.  Hydrates of carbon dioxide and methane mixtures , 1991 .

[22]  Yongwon Seo,et al.  Structure identification and dissociation enthalpy measurements of the CO2 + N2 hydrates for their application to CO2 capture and storage , 2014 .

[23]  Bei Liu,et al.  Evaluation of Different CH 4 -CO 2 Replacement Processes in Hydrate-Bearing Sediments by Measuring P-Wave Velocity , 2013 .

[24]  Minjun Cha,et al.  Recovery of methane from gas hydrates intercalated within natural sediments using CO(2) and a CO(2)/N(2) gas mixture. , 2012, ChemSusChem.

[25]  Carolyn A. Koh,et al.  Gas hydrates: Unlocking the energy from icy cages , 2009 .

[26]  E. D. Sloan,et al.  Fundamental principles and applications of natural gas hydrates , 2003, Nature.

[27]  Shigeru Watanabe,et al.  A DEMONSTRATION PROJECT OF NGH LAND TRANSPORTATION SYSTEM , 2008 .

[28]  E. Dendy Sloan,et al.  Natural gas hydrates in flow assurance , 2011 .

[29]  Bei Liu,et al.  Recovery of methane from hydrate reservoir with gaseous carbon dioxide using a three-dimensional middle-size reactor , 2012 .

[30]  Modeling the Injection of Carbon Dioxide and Nitrogen into a Methane Hydrate Reservoir and the Subsequent Production of Methane Gas on the North Slope of Alaska , 2013 .

[31]  Ho-Jung Ryu,et al.  Phase behavior of methane and carbon dioxide hydrates in meso- and macro-sized porous media , 2008 .

[32]  Jong-Ho Cha,et al.  Increasing Gas Hydrate Formation Temperature for Desalination of High Salinity Produced Water with Secondary Guests , 2013 .

[33]  Yousef Tamsilian,et al.  Formation and Economic Study on Hydrate Technology with NGH Pellets , 2013 .

[34]  Keun-Pil Park,et al.  Sequestering carbon dioxide into complex structures of naturally occurring gas hydrates , 2006, Proceedings of the National Academy of Sciences.

[35]  W. Kuhs,et al.  Kinetics of CO2-Hydrate Formation from Ice Powders: Data Summary and Modeling Extended to Low Temperatures , 2013 .

[36]  J. Schicks,et al.  The Driving Forces of Guest Substitution in Gas Hydrates—A Laser Raman Study on CH 4 -CO 2 Exchange in the Presence of Impurities , 2012 .

[37]  Gang Li,et al.  Experimental investigation into methane hydrate production during three-dimensional thermal stimulation with five-spot well system , 2013 .

[38]  Seungmin Lee,et al.  CO2 capture from simulated fuel gas mixtures using semiclathrate hydrates formed by quaternary ammonium salts. , 2013, Environmental science & technology.

[39]  Goodarz Ahmadi,et al.  Natural gas production from hydrate decomposition by depressurization , 2001 .

[40]  J. Schicks,et al.  The conversion process of hydrocarbon hydrates into CO2 hydrates and vice versa: thermodynamic considerations. , 2011, The journal of physical chemistry. A.

[41]  G. Hakvoort.  DSC calibration below 0°C , 1994 .

[42]  Rainer Hamann,et al.  Methane Hydrate Pellet Transport Using the Self-Preservation Effect: A Techno-Economic Analysis , 2012 .

[43]  Nils E. R. Zimmermann,et al.  Path sampling calculation of methane diffusivity in natural gas hydrates from a water-vacancy assisted mechanism. , 2008, Journal of the American Chemical Society.

[44]  Amir H. Mohammadi,et al.  Application of gas hydrate formation in separation processes: A review of experimental studies , 2012 .

[45]  Yongwon Seo,et al.  Experimental measurement and thermodynamic modeling of the mixed CH4 + C3H8 clathrate hydrate equilibria in silica gel pores: effects of pore size and salinity. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[46]  Bo Li,et al.  Depressurization induced gas production from hydrate deposits with low gas saturation in a pilot-scale hydrate simulator , 2014 .

[47]  E. D. Sloan,et al.  Measurements of methane hydrate heat of dissociation using high pressure differential scanning calorimetry , 2008 .