Recovery of methane from gas hydrates intercalated within natural sediments using CO(2) and a CO(2)/N(2) gas mixture.

The direct recovery of methane from massive methane hydrates (MHs), artificial MH-bearing clays, and natural MH-bearing sediments is demonstrated, using either CO(2) or a CO(2)/N(2) gas mixture (20 mol % of CO(2) and 80 mol % of N(2), reproducing flue gas from a power plant) for methane replacement in complex marine systems. Natural gas hydrates (NGHs) can be converted into CO(2) hydrate by a swapping mechanism. The overall process serves a dual purpose: it is a means of sustainable energy-source exploitation and greenhouse-gas sequestration. In particular, scant attention has been paid to the natural sediment clay portion in deep-sea gas hydrates, which is capable of storing a tremendous amount of NGH. The clay interlayer provides a unique chemical-physical environment for gas hydrates. Herein, for the first time, we pull out methane from intercalated methane hydrates in a clay interlayer using CO(2) and a CO(2)/N(2) gas mixture. The results of this study are expected to provide an essential physicochemical background required for large-scale NGH production under the seabed.

[1]  G. Barone,et al.  Hydrates of natural gases and small molecules: structures, properties, and exploitation perspectives. , 2009, ChemSusChem.

[2]  Pierre Henry,et al.  Formation of natural gas hydrates in marine sediments: 2. Thermodynamic calculations of stability conditions in porous sediments , 1999 .

[3]  R. Cygan,et al.  Molecular Models for the Intercalation of Methane Hydrate Complexes in Montmorillonite Clay , 2004 .

[4]  Sun-Hwa Yeon,et al.  Abnormal methane occupancy of natural gas hydrates in deep sea floor sediments , 2011 .

[5]  Youngjune Park,et al.  Effect of interlayer ions on methane hydrate formation in clay sediments. , 2009, The journal of physical chemistry. B.

[6]  Keun-Pil Park,et al.  Swapping Phenomena Occurring in Deep-Sea Gas Hydrates , 2008 .

[7]  Chul-Soo Lee,et al.  Hydrate phase equilibria of the guest mixtures containing CO2, N2 and tetrahydrofuran , 2001 .

[8]  K. Kvenvolden,et al.  Potential effects of gas hydrate on human welfare. , 1999, Proceedings of the National Academy of Sciences of the United States of America.

[9]  Hans J. Rath,et al.  Particle−Surface Capillary Forces , 1999 .

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

[11]  T. Collett Energy resource potential of natural gas hydrates , 2002 .

[12]  E. Russell,et al.  Soil Physics , 1941, Nature.

[13]  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.

[14]  Yongwon Seo,et al.  Recovering methane from solid methane hydrate with carbon dioxide. , 2003, Angewandte Chemie.

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

[16]  Ross Anderson,et al.  Thermodynamic prediction of clathrate hydrate dissociation conditions in mesoporous media , 2004 .

[17]  G. Artioli,et al.  Quantitative Phase Analysis of Natural Raw Materials Containing Montmorillonite , 2001 .

[18]  S. Guggenheim,et al.  New gas-hydrate phase: Synthesis and stability of clay–methane hydrate intercalate , 2003 .

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

[20]  Sun-Hwa Yeon,et al.  Structural, Mineralogical, and Rheological Properties of Methane Hydrates in Smectite Clays , 2009 .

[21]  N. Ross Chapman,et al.  Complex gas hydrate from the Cascadia margin , 2007, Nature.

[22]  Ross Anderson,et al.  Experimental measurement of methane and carbon dioxide clathrate hydrate equilibria in mesoporous silica , 2003 .

[23]  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 .

[24]  Huen Lee,et al.  Efficient recovery of CO2 from flue gas by clathrate hydrate formation in porous silica gels. , 2005, Environmental science & technology.

[25]  Huen Lee,et al.  Structure and guest distribution of the mixed carbon dioxide and nitrogen hydrates as revealed by X-ray diffraction and 13C NMR spectroscopy , 2004 .

[26]  J. Tse,et al.  Laboratory analysis of a naturally occurring gas hydrate from sediment of the Gulf of Mexico , 1986 .

[27]  Ian R. MacDonald,et al.  Evidence of structure-H hydrate, Gulf of Mexico Continental slope , 1994 .

[28]  M. Lee,et al.  Identification of Marine Hydrates In Situ and Their Distribution off the Atlantic Coast of the United States a , 1994 .

[29]  Jae W. Lee,et al.  Investigation of macroscopic interfacial dynamics between clathrate hydrates and surfactant solutions. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[30]  S. Guggenheim,et al.  Montmorillonite under high H2O pressures: Stability of hydrate phases, rehydration hysteresis, and the effect of interlayer cations , 1997 .