Advances in nuclear magnetic resonance (NMR) techniques for the investigation of clathrate hydrates

Over the years, clathrate hydrates have been investigated for its potential as an energy resource and other industrial applications. Nuclear magnetic resonance (NMR) spectroscopy and magnetic resonance imaging (MRI) are two powerful NMR technologies for both molecular level and microscopic measurement, which have been applied in gas hydrate research to provide fundamental and useful information. 1H and 13C NMR spectroscopy are the most commonly applied method to study cage occupancies of guest species and crystal structures. MRI technique, on the other hand, provides microscopic insights towards the gas hydrate formation and dissociation in porous media and the study of CH4/CO2 hydrate replacement. We also reviewed the state of the art application of NMR based technology in research on the gas-liquid multiphase flow and temperature mapping within porous media. Potential improvements in NMR technology to improve the fundamental understanding towards gas hydrates is also discussed in this review article.

[1]  Peng Zhang,et al.  Experimental Investigation of Flow and Heat Transfer Characteristics in the Generation of Clathrate Hydrate Slurry , 2014 .

[2]  D L Parker,et al.  Temperature distribution measurements in two-dimensional NMR imaging. , 1983, Medical physics.

[3]  Yu Liu,et al.  Dynamic Measurements of CO2 Flow in Water Saturated Porous Medium at Low Temperature Using MRI , 2013 .

[4]  B. Khoo,et al.  Size Effect of Porous Media on Methane Hydrate Formation and Dissociation in an Excess Gas Environment , 2016 .

[5]  Yu Liu,et al.  Magnetic Resonance Imaging of CO2/Water Two Phase Flow in Porous Media , 2013 .

[6]  D. Klug,et al.  Synthesis and characterization of a new structure of gas hydrate , 2009, Proceedings of the National Academy of Sciences.

[7]  E. D. Sloan,et al.  Microsecond Simulations of Spontaneous Methane Hydrate Nucleation and Growth , 2009, Science.

[8]  L. Gladden,et al.  MRI: Operando measurements of temperature, hydrodynamics and local reaction rate in a heterogeneous catalytic reactor , 2010 .

[9]  Sapna Sarupria,et al.  Molecular dynamics study of carbon dioxide hydrate dissociation. , 2011, The journal of physical chemistry. A.

[10]  B. Buffett,et al.  Formation of gas hydrate from dissolved gas in natural porous media , 2000 .

[11]  Peter Englezos,et al.  Recovery of Methane from a Variable-Volume Bed of Silica Sand/Hydrate by Depressurization , 2010 .

[12]  Xiao-Sen Li,et al.  Experimental Investigation of Production Behavior of Methane Hydrate under Ethylene Glycol Injection in Unconsolidated Sediment , 2007 .

[13]  J. Ripmeester,et al.  129Xe nuclear magnetic resonance in the clathrate hydrate of xenon , 1981 .

[14]  Kun-Hong Lee,et al.  Gas-Hydrate Phase Equilibrium for Mixtures of Sulfur Hexafluoride and Hydrogen , 2012 .

[15]  Yunju Kim,et al.  CH4 recovery and CO2 sequestration using flue gas in natural gas hydrates as revealed by a micro-differential scanning calorimeter , 2015 .

[16]  Michael Dennis,et al.  Clathrate hydrate technology for cold storage in air conditioning systems , 2014 .

[17]  Huen Lee,et al.  Structure Transition from Semi- to True Clathrate Hydrates Induced by CH4 Enclathration , 2012 .

[18]  C. Mcdowell,et al.  Molecular Motion of Enclathrated Compounds as studied by Nuclear Magnetic Resonance , 1959, Nature.

[19]  Carolyn A. Koh,et al.  MACROSCOPIC INVESTIGATION OF HYDRATE FILM GROWTH AT THE HYDROCARBON/WATER INTERFACE , 2007 .

[20]  P. Englezos,et al.  Morphology of methane and carbon dioxide hydrates formed from water droplets , 2003 .

[21]  E. D. Sloan,et al.  NMR studies on CH4+CO2 binary gas hydrates dissociation behavior , 2008 .

[22]  Ponnivalavan Babu,et al.  Medium pressure hydrate based gas separation (HBGS) process for pre-combustion capture of carbon dioxide employing a novel fixed bed reactor , 2013 .

[23]  Juan G. Beltran,et al.  Morphological Investigations of Methane−Hydrate Films Formed on a Glass Surface , 2010 .

[24]  Weiguo Liu,et al.  Dynamic measurements of hydrate based gas separation in cooled silica gel , 2014 .

[25]  F. Varaminian,et al.  Kinetic study on the process of CHClF2 (R22) hydrate formation in the presence of SDS surfactant based on chemical affinity , 2014 .

[26]  J. Ripmeester,et al.  Spectroscopic observation of critical guest concentration appearing in tert-butyl alcohol clathrate hydrate. , 2008, The journal of physical chemistry. B.

[27]  R. Kumar,et al.  Kinetic inhibitor effects on methane/propane clathrate hydrate-crystal growth at the gas/water and water/n-heptane interfaces , 2008 .

[28]  Kazushige Nagashima,et al.  Pattern Variety of Tetrahydrofuran Clathrate Hydrates Formed in Porous Media , 2012 .

[29]  Jiafei Zhao,et al.  Heat Transfer Analysis of Methane Hydrate Sediment Dissociation in a Closed Reactor by a Thermal Method , 2012 .

[30]  J. G. Dash,et al.  Premelting of ice in porous silica glass , 1996 .

[31]  L. Gladden,et al.  Spatially and chemically resolved measurement of intra― and inter-particle molecular diffusion in a fixed-bed reactor , 2011 .

[32]  B. Tohidi,et al.  Clathrate formation and dissociation in vapor/water/ice/hydrate systems in SBA-15, sol-gel and CPG porous media, as probed by NMR relaxation, novel protocol NMR cryoporometry, neutron scattering and ab initio quantum-mechanical molecular dynamics simulation. , 2007, Magnetic resonance imaging.

[33]  T. Ebinuma,et al.  Microscopic observations of formation processes of clathrate-hydrate films at an interface between water and carbon dioxide , 1999 .

[34]  E. D. Sloan,et al.  Structural Transition Studies in Methane + Ethane Hydrates Using Raman and NMR , 2000 .

[35]  Lynn F. Gladden,et al.  Structure-flow correlations in packed beds , 1998 .

[36]  Timothy J. Kneafsey,et al.  Methane hydrate induced permeability modification for multiphase flow in unsaturated porous media , 2011 .

[37]  J. Ripmeester,et al.  Critical guest concentration and complete tuning pattern appearing in the binary clathrate hydrates. , 2006, Journal of the American Chemical Society.

[38]  K. Ogawa,et al.  High-pressure magnetic resonance imaging up to 40 MPa. , 2000, Magnetic resonance imaging.

[39]  Mehran Pooladi-Darvish,et al.  Effect of Conductive and Convective Heat Flow on Gas Production from Natural Hydrates by Depressurization , 2004 .

[40]  Barry Freifeld,et al.  Investigating Methane Hydrate in Sediments using X-Ray Computed Tomography , 2004 .

[41]  A. Bensely,et al.  Experimental Investigation on Pressure Drop and Heat Transfer Characteristics of Copper Metal Foam Heat Sink , 2010 .

[42]  B. Kvamme,et al.  Simulations of long term methane hydrate dissociation by pressure reduction using an extended RetrasoCodeBright simulator , 2013 .

[43]  Y. Seo,et al.  Inhibition of natural gas hydrates in the presence of liquid hydrocarbons forming structure H. , 2010, The journal of physical chemistry. B.

[44]  P. Zhang,et al.  Pressure drop and heat transfer characteristics of tetra-n-butyl ammonium bromide clathrate hydrate slurry during flow melting and generating in a double-tube heat exchanger , 2013 .

[45]  Andrew J Sederman,et al.  Recent advances in flow MRI. , 2013, Journal of magnetic resonance.

[46]  Saman Alavi,et al.  Molecular-dynamics study of structure II hydrogen clathrates. , 2005, The Journal of chemical physics.

[47]  J. Ripmeester,et al.  Phase behavior and structural characterization of coexisting pure and mixed clathrate hydrates. , 2003, Chemphyschem : a European journal of chemical physics and physical chemistry.

[48]  K. Ogawa,et al.  MRI Measurement of Hydrate Growth and an Application to Advanced CO2 Sequestration Technology , 2000 .

[49]  Qing Yuan,et al.  Experimental Study on Gas Production from Methane Hydrate-Bearing Sand by Hot-Water Cyclic Injection , 2010 .

[50]  Wooyong Um,et al.  Imaging wellbore cement degradation by carbon dioxide under geologic sequestration conditions using X-ray computed microtomography. , 2013, Environmental science & technology.

[51]  Hari Prakash Veluswamy,et al.  Crystal Growth of Hydrogen/Tetra-n-butylammonium Bromide Semiclathrates Based on Morphology Study , 2014 .

[52]  Seungmin Lee,et al.  Structural transformation of isopropylamine semiclathrate hydrates in the presence of methane as a coguest. , 2012, The journal of physical chemistry. B.

[53]  Jiafei Zhao,et al.  Effects of additive mixtures (THF/SDS) on carbon dioxide hydrate formation and dissociation in porous media , 2013 .

[54]  Jeffery B. Klauda,et al.  Global Distribution of Methane Hydrate in Ocean Sediment , 2005 .

[55]  R. Larsen,et al.  NMR Imaging Study of Hydrates in Sediments , 2000 .

[56]  Lynn F. Gladden,et al.  Magnetic Resonance Imaging of fluidized beds , 2008 .

[57]  S. Meiboom,et al.  Modified Spin‐Echo Method for Measuring Nuclear Relaxation Times , 1958 .

[58]  K. Schmidt-Rohr,et al.  Quantitative Characterization of Humic Substances by Solid-State Carbon-13 Nuclear Magnetic Resonance , 2000 .

[59]  S. Alavi,et al.  Determination of NMR lineshape anisotropy of guest molecules within inclusion complexes from molecular dynamics simulations. , 2008, Chemphyschem : a European journal of chemical physics and physical chemistry.

[60]  Youngjun Lee,et al.  Guest gas enclathration in semiclathrates of tetra-n-butylammonium bromide: stability condition and spectroscopic analysis. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[61]  Franklin M. Orr,et al.  Gas Hydrate Formation in the Deep Sea: In Situ Experiments with Controlled Release of Methane, Natural Gas, and Carbon Dioxide , 1998 .

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

[63]  R M Henkelman,et al.  Ex vivo tissue‐type independence in proton‐resonance frequency shift MR thermometry , 1998, Magnetic resonance in medicine.

[64]  J. Tse,et al.  Thermal conductivity of Xe clathrate hydrate at low temperatures , 2006 .

[65]  E. Purcell,et al.  Relaxation Effects in Nuclear Magnetic Resonance Absorption , 1948 .

[66]  Yoshimasa Kanawaku,et al.  Measurement of temperature changes in cooling dead rats using magnetic resonance thermometry. , 2011, Legal medicine.

[67]  C. Ratcliffe,et al.  NMR Studies of Guest Dynamics in Clathrate Hydrates: Spherical Tops SF6, SeF6 and CH4 in Structure II Hydrate , 2004 .

[68]  Lynn F. Gladden,et al.  Dynamic Mr Imaging of Single- and Two-Phase Flows , 2006 .

[69]  Yongchen Song,et al.  Hydrate-based technology for CO2 capture from fossil fuel power plants , 2014 .

[70]  D. Gembris,et al.  Three-dimensional imaging of pore water diffusion and motion in porous media by nuclear magnetic resonance imaging , 2002 .

[71]  B. A. Baldwin,et al.  Monitoring hydrate formation and dissociation in sandstone and bulk with magnetic resonance imaging. , 2003, Magnetic resonance imaging.

[72]  R. Kleinberg.  9. Nuclear Magnetic Resonance , 1999 .

[73]  Yongchen Song,et al.  Visualization and Measurement of CO2 Flooding in Porous Media Using MRI , 2011 .

[74]  A. Pines,et al.  Time-of-flight flow imaging using NMR remote detection. , 2005, Physical review letters.

[75]  E. Stejskal,et al.  Carbon-13 nuclear magnetic resonance of polymers spinning at the magic angle , 1976 .

[76]  L. G. Tang,et al.  Experimental Investigation of Production Behavior of Gas Hydrate under Thermal Stimulation in Unconsolidated Sediment , 2005 .

[77]  Y. Mori,et al.  Behavior of clathrate hydrate formation at the boundary of liquid water and a fluorocarbon in liquid or vapor state , 1996 .

[78]  Weiguo Liu,et al.  The effects of porous medium and temperature on exothermic tetrahydrofuran hydrate formation , 2014 .

[79]  P. Schultheiss,et al.  Comparison of methane mass balance and X-ray computed tomographic methods for calculation of gas hydrate content of pressure cores , 2014 .

[80]  D. Naylor,et al.  DIRECT TEMPERATURE GRADIENT MEASUREMENT USING INTERFEROMETRY , 1999 .

[81]  Huen Lee,et al.  Spectroscopic identification of the mixed hydrogen and carbon dioxide clathrate hydrate. , 2005, Journal of the American Chemical Society.

[82]  R. Ohmura,et al.  Formation, growth and dissociation of clathrate hydrate crystals in liquid water in contact with a hydrophobic hydrate-forming liquid , 1999 .

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

[84]  Visualisation of structure and flow in packed beds. , 1998, Magnetic resonance imaging.

[85]  M. Johns,et al.  Determining NMR flow propagator moments in porous rocks without the influence of relaxation. , 2008, Journal of magnetic resonance.

[86]  Gye-Chun Cho,et al.  Evolution of Compressional Wave Velocity during CO2 Hydrate Formation in Sediments , 2009 .

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

[88]  R. Kumar,et al.  Morphology of Carbon Dioxide–Hydrogen–Cyclopentane Hydrates with or without Sodium Dodecyl Sulfate , 2013 .

[89]  Jiafei Zhao,et al.  Measurement of fluid flow in pipe and porous media by high-resolution magnetic resonance imaging , 2012 .

[90]  Yu Liu,et al.  MRI measurements of CO2 hydrate dissociation rate in a porous medium. , 2011, Magnetic resonance imaging.

[91]  Andrew Palmer,et al.  Morphology of Methane Hydrate Formation in Porous Media , 2013 .

[92]  L. Tomutsa,et al.  Multinuclear NMR microscopy of two-phase fluid systems in porous rock. , 1996, Magnetic resonance imaging.

[93]  P. Kusalik,et al.  Explorations of gas hydrate crystal growth by molecular simulations , 2010 .

[94]  Walter G Chapman,et al.  NMR/MRI study of clathrate hydrate mechanisms. , 2005, The journal of physical chemistry. B.

[95]  Seungmin Lee,et al.  Stability conditions and guest distribution of the methane + ethane + propane hydrates or semiclathrates in the presence of tetrahydrofuran or quaternary ammonium salts , 2013 .

[96]  Jong-Won Lee,et al.  13C NMR spectroscopies and formation kinetics of gas hydrates in the presence of monoethylene glycol as an inhibitor , 2013 .

[97]  Emmanuel C. Nsofor,et al.  FORCED-CONVECTION GAS-TO-WALL HEAT TRANSFER IN A PACKED BED FOR HIGH-TEMPERATURE ENERGY STORAGE , 2003 .

[98]  K. Hynynen,et al.  Optimization of spoiled gradient‐echo phase imaging for in vivo localization of a focused ultrasound beam , 1996, Magnetic resonance in medicine.

[99]  P. Englezos,et al.  Unusual kinetic inhibitor effects on gas hydrate formation , 2006 .

[100]  A. Gupta,et al.  Modeling pure methane hydrate dissociation using a numerical simulator from a novel combination of X-ray computed tomography and macroscopic data , 2009 .

[101]  C. Ratcliffe,et al.  Low-temperature cross-polarization/magic angle spinning carbon-13 NMR of solid methane hydrates: structure, cage occupancy, and hydration number , 1988 .

[102]  T. Kahn,et al.  Magnetic Resonance Imaging of Microwave Induced Tissue Heating , 1995, Magnetic resonance in medicine.

[103]  E. Purcell,et al.  Effects of Diffusion on Free Precession in Nuclear Magnetic Resonance Experiments , 1954 .

[104]  Bjørn Kvamme,et al.  Kinetics of solid hydrate formation by carbon dioxide: Phase field theory of hydrate nucleation and magnetic resonance imagingPresented at the 3rd International Workshop on Global Phase Diagrams, Odessa, Ukraine, September 14?19, 2003. , 2004 .

[105]  D. Davidson,et al.  Proton Resonance Spectra of Some Gas Hydrates , 1967 .

[106]  Peter Englezos,et al.  Magnetic Resonance Imaging of Gas Hydrate Formation in a Bed of Silica Sand Particles , 2011 .

[107]  Ponnivalavan Babu,et al.  Rapid methane hydrate formation to develop a cost effective large scale energy storage system , 2016 .

[108]  Stapf,et al.  NMR characterization of the pore structure and anisotropic self-diffusion in salt water Ice , 2000, Journal of magnetic resonance.

[109]  Ponnivalavan Babu,et al.  Unusual behavior of propane as a co-guest during hydrate formation in silica sand: Potential application to seawater desalination and carbon dioxide capture , 2014 .

[110]  Michael C. Kolios,et al.  Magnetic resonance imaging of temperature changes during interstitial microwave heating: a phantom study. , 1997, Medical physics.

[111]  N. Kalogerakis,et al.  EQUILIBRIUM CONDITIONS FOR METHANE HYDRATE FORMATION IN AQUEOUS MIXED ELECTROLYTE SOLUTIONS , 1991 .

[112]  E. R. Andrew,et al.  Nuclear Magnetic Resonance Spectra from a Crystal rotated at High Speed , 1958, Nature.

[113]  P. Servio,et al.  Morphology Study of Structure I Methane Hydrate Formation and Decomposition of Water Droplets in the Presence of Biological and Polymeric Kinetic Inhibitors , 2009 .

[114]  Seungmin Lee,et al.  Phase behavior and 13C NMR spectroscopic analysis of the mixed methane + ethane + propane hydrates in mesoporous silica gels. , 2010, Journal of Physical Chemistry B.

[115]  J. Krason.  Messoyakh Gas Field (W. Siberia): A Model for Development of the Methane Hydrate Deposits of Mackenzie Delta , 2000 .

[116]  Seong-Pil Kang,et al.  Kinetic behaviors of CO2 hydrates in porous media and effect of kinetic promoter on the formation kinetics , 2010 .

[117]  H. Hertz.  Chapter 5 Microdynamic behaviour of liquids as studied by NMR relaxation times , 1967 .

[118]  A. Manakov,et al.  Self-Preservation Behaviour of Methane Hydrate Particles in Oil Suspensions , 2012 .

[119]  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 .

[120]  M. Kelland,et al.  Novel Benchtop Wheel Loop for Low Dosage Gas Hydrate Inhibitor Screening: Comparison to Rocking Cells for a Series of Antiagglomerants , 2015 .

[121]  Gang-woo Lee,et al.  Thermodynamic stability, spectroscopic identification, and gas storage capacity of CO2-CH4-N2 mixture gas hydrates: implications for landfill gas hydrates. , 2012, Environmental science & technology.

[122]  William F. Waite,et al.  Simultaneous determination of thermal conductivity, thermal diffusivity and specific heat in sI methane hydrate , 2007 .

[123]  Jan Hundseid,et al.  Hydrate Management in Practice , 2015 .

[124]  Gunnar Brix,et al.  Magnetic resonance imaging of paramagnetic tracers in porous media: Quantification of flow and transport parameters , 1997 .

[125]  E. Hammerschmidt.  Formation of Gas Hydrates in Natural Gas Transmission Lines , 1934 .

[126]  K. Schmidt-Rohr,et al.  Quantitative solid-state 13C NMR with signal enhancement by multiple cross polarization. , 2014, Journal of magnetic resonance.

[127]  William F. Waite,et al.  Methane gas hydrate effect on sediment acoustic and strength properties , 2007 .

[128]  E. D. Sloan,et al.  Measurement of Clathrate Hydrates via Raman Spectroscopy , 1997 .

[129]  J. Ripmeester,et al.  Effect of clathrate hydrate formation and decomposition on NMR parameters in THF-D2O solution. , 2012, The journal of physical chemistry. B.

[130]  Y Zhang,et al.  On the accuracy of noninvasive thermometry using molecular diffusion magnetic resonance imaging. , 1992, International journal of hyperthermia : the official journal of European Society for Hyperthermic Oncology, North American Hyperthermia Group.

[131]  J. Hindman,et al.  Proton Resonance Shift of Water in the Gas and Liquid States , 1966 .

[132]  Koichi Oshio,et al.  Feasibility of internally referenced brain temperature imaging with a metabolite signal. , 2003, Magnetic resonance in medical sciences : MRMS : an official journal of Japan Society of Magnetic Resonance in Medicine.

[133]  E. D. Sloan,et al.  Dissociation studies of CH4-C2H6 and CH4-CO2 binary gas hydrates , 2007 .

[134]  Partha P. Mitra,et al.  Mechanism of NMR Relaxation of Fluids in Rock , 1994 .

[135]  Paweł Siuda,et al.  Calculations of NMR properties for sI and sII clathrate hydrates of carbon dioxide , 2014 .

[136]  Yongchen Song,et al.  MRI measurements of CO2–CH4 hydrate formation and dissociation in porous media , 2015 .

[137]  Peter Englezos,et al.  Methane–ethane and methane–propane hydrate formation and decomposition on water droplets , 2005 .

[138]  A. T. Watson,et al.  10. NMR Imaging of Fluids and Flow in Porous Media , 1999 .

[139]  J. Ripmeester,et al.  Hydrogen-gas migration through clathrate hydrate cages. , 2007, Angewandte Chemie.

[140]  Timothy J. Kneafsey,et al.  X-ray computed-tomography observations of water flow through anisotropic methane hydrate-bearing sand , 2009 .

[141]  George J. Moridis,et al.  Methane hydrate formation and dissociation in a partially saturated core-scale sand sample , 2005 .

[142]  Lynn F. Gladden,et al.  Single- and two-phase flow in fixed-bed reactors: MRI flow visualisation and lattice-Boltzmann simulations , 2001 .

[143]  B. Kvamme,et al.  Effects of salinity on hydrate stability and implications for storage of CO2 in natural gas hydrate reservoirs , 2009 .

[144]  Walter G Chapman,et al.  Application of low field NMR T2 measurements to clathrate hydrates. , 2009, Journal of magnetic resonance.

[145]  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.

[146]  Y. Mori.  Estimating the thickness of hydrate films from their lateral growth rates: application of a simplified heat transfer model , 2001 .

[147]  Shuichiro Hirai,et al.  MRI velocity measurements of water flow in porous media containing a stagnant immiscible liquid , 2001 .

[148]  K. Ogawa,et al.  Three-dimensional velocity measurement of complex interstitial flows through water-saturated porous media by the tagging method in the MRI technique , 2001 .

[149]  Particle size distribution of TBPB hydrates by focused beam reflectance measurement (FBRM) for secondary refrigeration application , 2015 .

[150]  E Moser,et al.  Temperature- and pH-dependence of proton relaxation rates in rat liver tissue. , 1995, Magnetic resonance imaging.

[151]  Masaki Ota,et al.  Review of CO2–CH4 clathrate hydrate replacement reaction laboratory studies – Properties and kinetics , 2013 .

[152]  Y. Mori,et al.  Clathrate-hydrate film growth along water/hydrate-former phase boundaries—numerical heat-transfer study , 2006 .

[153]  Huen Lee,et al.  Phase Equilibria and Spectroscopic Identification of (2-Methylpropane-2-peroxol + Gaseous Guests) Hydrates , 2012 .

[154]  Peter Englezos,et al.  Structure and composition of CO2/H2 and CO2/H2/C3H8 hydrate in relation to simultaneous CO2 capture and H2 production , 2009 .

[155]  E. D. Sloan,et al.  NMR Investigation of Methane Hydrate Dissociation , 2007 .

[156]  P. Englezos,et al.  Prediction of gas hydrate formation conditions in aqueous electrolyte solutions , 1988 .

[157]  A J Sederman,et al.  Magnetic resonance velocity imaging of liquid and gas two-phase flow in packed beds. , 2009, Journal of magnetic resonance.

[158]  Lynn F. Gladden,et al.  Magnetic resonance imaging of liquid flow and pore structure within packed beds , 1997 .

[159]  Seungmin Lee,et al.  Influences of large molecular alcohols on gas hydrates and their potential role in gas storage and CO2 sequestration , 2015 .

[160]  A. Pines,et al.  Visualization of gas flow and diffusion in porous media. , 2000, Proceedings of the National Academy of Sciences of the United States of America.

[161]  M. Gadala,et al.  Investigation of Error Sources in Temperature Measurement Using Thermocouples in Water Impingement Cooling , 2005 .

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

[163]  Syed S. H. Rizvi,et al.  Kinetics of methane hydrate decomposition , 1987 .

[164]  Sapna Sarupria,et al.  Homogeneous Nucleation of Methane Hydrate in Microsecond Molecular Dynamics Simulations. , 2012, The journal of physical chemistry letters.

[165]  K. Shin,et al.  Catastrophic growth of gas hydrates in the presence of kinetic hydrate inhibitors. , 2013, The journal of physical chemistry. A.

[166]  Yutaek Seo,et al.  Enhancing CO2 separation for pre-combustion capture with hydrate formation in silica gel pore structure , 2010 .

[167]  Jong-Won Lee,et al.  Hydrate-Phase Equilibria and 13C NMR Studies of Binary (CH4 + C2H4) and (C2H6 + C2H4) Hydrates , 2013 .

[168]  George J. Moridis,et al.  Toward Production From Gas Hydrates: Current Status, Assessment of Resources, and Simulation-Based Evaluation of Technology and Potential , 2008 .

[169]  S. O. Smith,et al.  Towards quantitative CP-MAS NMR. , 1996, Solid state nuclear magnetic resonance.

[170]  C. Ratcliffe,et al.  Xenon-129 NMR studies of clathrate hydrates: new guests for structure II and structure H , 1990 .

[171]  John De Poorter,et al.  Noninvasive MRI thermometry with the proton resonance frequency method: Study of susceptibility effects , 1995 .

[172]  Weiguo Liu,et al.  Effects of operating mode and pressure on hydrate-based desalination and CO2 capture in porous media , 2014 .

[173]  E. D. Sloan,et al.  Hydrate Plug Dissociation via Nitrogen Purge: Experiments and Modeling , 2011 .

[174]  Huen Lee,et al.  Optical Properties of Tetrahydrofuran Clathrate Hydrates with Polyvinylpyrrolidone (THF + H2O + PVP) Revealed by Terahertz (THz) Time-Domain Spectroscopy , 2015 .

[175]  B. Kvamme,et al.  Transport and storage of CO2 in natural gas hydrate reservoirs , 2009 .

[176]  J. Ripmeester,et al.  Methane and carbon dioxide hydrate formation in water droplets: Spatially resolved measurements from magnetic resonance microimaging , 2004 .

[177]  Seungmin Lee,et al.  1-Propanol as a co-guest of gas hydrates and its potential role in gas storage and CO2 sequestration , 2014 .

[178]  P. Englezos,et al.  Morphology Study of Structure H Hydrate Formation from Water Droplets , 2003 .

[179]  Yu Liu,et al.  CO2 hydrate formation and dissociation in cooled porous media: a potential technology for CO2 capture and storage. , 2013, Environmental science & technology.

[180]  J. Poorter,et al.  Noninvasive MRI Thermometry with the Proton Resonance Frequency (PRF) Method: In Vivo Results in Human Muscle , 1995, Magnetic resonance in medicine.

[181]  Yutaek Seo,et al.  Kinetics of methane hydrate replacement with carbon dioxide and nitrogen gas mixture using in situ NMR spectroscopy. , 2015, Environmental science & technology.

[182]  C. Ratcliffe,et al.  Proton and carbon-13 NMR studies on carbon dioxide hydrate , 1986 .

[183]  J. Ripmeester,et al.  Nucleation and Growth of Hydrates on Ice Surfaces: New Insights from 129Xe NMR Experiments with Hyperpolarized Xenon , 2001 .

[184]  Lounes Tadrist,et al.  Experimental analysis of heat transfer with phase change in porous media crossed by a fluid flow , 1992 .

[185]  Carolyn A. Koh,et al.  Investigation of the Hydrate Plugging and Non-Plugging Properties of Oils , 2010 .

[186]  E. Hahn,et al.  Nuclear Double Resonance in the Rotating Frame , 1962 .

[187]  Yongchen Song,et al.  CO2 Hydrate Formation Characteristics in a Water/Brine-Saturated Silica Gel , 2014 .

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

[189]  E. Dendy Sloan,et al.  A changing hydrate paradigm—from apprehension to avoidance to risk management , 2005 .

[190]  Bernhard Blümich,et al.  NMR velocimetry of flow in model fixed-bed reactors of low aspect ratio , 2005 .

[191]  T. Buanes,et al.  Storage of CO2 in natural gas hydrate reservoirs and the effect of hydrate as an extra sealing in cold aquifers , 2007 .

[192]  Seungmin Lee,et al.  Thermodynamic and spectroscopic identification of guest gas enclathration in the double tetra-n-butylammonium fluoride semiclathrates. , 2012, The journal of physical chemistry. B.

[193]  Liam C Jacobson,et al.  Amorphous precursors in the nucleation of clathrate hydrates. , 2010, Journal of the American Chemical Society.

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

[195]  C. Ruppel,et al.  Permeability evolution during the formation of gas hydrates in marine sediments , 2003 .

[196]  S. Obi,et al.  Microscopic observations of clathrate-hydrate films formed at liquid/liquid interfaces. II. Film thickness in steady-water flow , 2003 .

[197]  Kuethe.  Measuring distributions of diffusivity in turbulent fluids with magnetic-resonance imaging. , 1989, Physical review. A, General physics.

[198]  Paweł Siuda,et al.  Nuclear magnetic resonance parameters for methane molecule trapped in clathrate hydrates. , 2011, The journal of physical chemistry. A.

[199]  Timothy J. Kneafsey,et al.  Permeability of Laboratory-Formed Methane-Hydrate-Bearing Sand: Measurements and Observations Using X-Ray Computed Tomography , 2011 .

[200]  L. Gladden,et al.  MRI strategies for characterising two-phase flow in parallel channel ceramic monoliths , 2007 .

[201]  J. Vatamanu,et al.  Molecular insights into the heterogeneous crystal growth of si methane hydrate. , 2006, The journal of physical chemistry. B.

[202]  M. D. Mantle,et al.  Dynamic MRI in chemical process and reaction engineering , 2003 .

[203]  O. Zabotina,et al.  Structure and dynamics of Brachypodium primary cell wall polysaccharides from two-dimensional (13)C solid-state nuclear magnetic resonance spectroscopy. , 2014, Biochemistry.

[204]  P. Englezos,et al.  Dynamics of Methane−Propane Clathrate Hydrate Crystal Growth from Liquid Water with or without the Presence of n-Heptane , 2006 .

[205]  Migration of CO2 in Porous Media Filled with water. , 2006 .

[206]  Praveen Linga,et al.  Hydrogen storage in clathrate hydrates: Current state of the art and future directions , 2014 .

[207]  A. Sum,et al.  Mechanism of Cohesive Forces of Cyclopentane Hydrates with and without Thermodynamic Inhibitors , 2014 .

[208]  K. J. Packer,et al.  The characterization of multiphase fluid transport in a porous solid by pulsed gradient stimulated echo nuclear magnetic resonance , 1998 .

[209]  M. Biot.  THEORY OF ELASTICITY AND CONSOLIDATION FOR A POROUS ANISOTROPIC SOLID , 1955 .

[210]  Yu Liu,et al.  An experimental study on CO2/water displacement in porous media using high-resolution Magnetic Resonance Imaging , 2012 .

[211]  L. Gladden,et al.  Magnetic resonance visualisation of single- and two-phase flow in porous media. , 2001, Magnetic resonance imaging.

[212]  C. Karcher,et al.  Determination of Interior Surface Temperature Using Luminance Measurement of Thermochromic Liquid Crystals , 2008 .

[213]  Trygve Helgaker,et al.  Ab Initio Methods for the Calculation of NMR Shielding and Indirect Spin-Spin Coupling Constants , 1999 .

[214]  Eiichi Fukushima,et al.  Nuclear magnetic resonance as a tool to study flow , 1999 .

[215]  Douglas M. Smith,et al.  Effective diffusivity measurement in porous media via NMR radial imaging , 1991 .

[216]  Fundamentals of NMR , 2009 .

[217]  Jong-Won Lee,et al.  Spectroscopic identification on cage occupancies of binary gas hydrates in the presence of ethanol. , 2012, The journal of physical chemistry. B.

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

[219]  A. Milkov.  Global estimates of hydrate-bound gas in marine sediments: how much is really out there? , 2004 .

[220]  Rapid imaging of fluid flow patterns in a narrow packed bed using MRI. , 2005, Magnetic resonance imaging.

[221]  P. Englezos,et al.  Enhanced growth of methane-propane clathrate hydrate crystals with sodium dodecyl sulfate, sodium tetradecyl sulfate, and sodium hexadecyl sulfate surfactants , 2010 .

[222]  T. Carpenter,et al.  Study of flow and hydrodynamic dispersion in a porous medium using pulsed–field–gradient magnetic resonance , 1997, Proceedings of the Royal Society of London. Series A: Mathematical, Physical and Engineering Sciences.

[223]  Yu Liu,et al.  Behaviour of hydrate-based technology for H2/CO2 separation in glass beads , 2015 .

[224]  Sung Chan Nam,et al.  Recovery of Methane from Hydrate Formed in a Variable Volume Bed of Silica Sand Particles , 2009 .

[225]  Hoon Kiang Tan,et al.  Review of gas hydrate dissociation kinetic models for energy recovery , 2016 .

[226]  T. Ebinuma,et al.  CO2 hydrate film formation at the boundary between CO2 and water: effects of temperature, pressure and additives on the formation rate , 2002 .

[227]  Lynn F. Gladden,et al.  Measuring adsorption, diffusion and flow in chemical engineering: applications of magnetic resonance to porous media , 2011 .

[228]  C. Ratcliffe,et al.  Hydrate Layers on Ice Particles and Superheated Ice: a 1H NMR Microimaging Study† , 1999 .

[229]  Shigehiro Morikawa,et al.  An easy-to-use microwave hyperthermia system combined with spatially resolved MR temperature maps: phantom and animal studies. , 2006, The Journal of surgical research.

[230]  H. Daigle,et al.  Nuclear magnetic resonance characterization of shallow marine sediments from the Nankai Trough, Integrated Ocean Drilling Program Expedition 333 , 2014 .

[231]  Carola-Bibiane Schönlieb,et al.  Phase reconstruction from velocity-encoded MRI measurements--a survey of sparsity-promoting variational approaches. , 2014, Journal of magnetic resonance.

[232]  A. Pines,et al.  Dispersion measurements using time-of-flight remote detection MRI. , 2007, Magnetic resonance imaging.

[233]  R. Ohmura,et al.  Effects of kinetic inhibitors on the formation and growth of hydrate crystals at a liquid–liquid interface , 2003 .

[234]  Lynn F. Gladden,et al.  Magnetic resonance imaging as a quantitative probe of gas–liquid distribution and wetting efficiency in trickle-bed reactors , 2001 .

[235]  Josef Granwehr,et al.  Multiphase imaging of gas flow in a nanoporous material using remote-detection NMR , 2005, Nature materials.

[236]  Christopher J. Elkins,et al.  Magnetic resonance velocimetry: applications of magnetic resonance imaging in the measurement of fluid motion , 2007 .

[237]  Steven F. Dec,et al.  Evidence of structure II hydrate formation from methane+ethane mixtures , 2000 .

[238]  L. Gladden,et al.  8. Nuclear Magnetic Resonance Spectroscopy , 2012 .

[239]  T. Ebinuma,et al.  Clathrate hydrate crystal growth in liquid water saturated with a hydrate-forming substance: variations in crystal morphology , 2004 .

[240]  R. Behbahani,et al.  Investigation of kinetics of methane hydrate formation during isobaric and isochoric processes in an agitated reactor , 2012 .

[241]  E. Peltzer,et al.  Deep sea NMR: Methane hydrate growth habit in porous media and its relationship to hydraulic permeability, deposit accumulation, and submarine slope stability , 2003 .

[242]  L. Anadón,et al.  Rationalising MRI, conductance and pressure drop measurements of the trickle-to-pulse transition in trickle beds , 2008 .

[243]  Mingjun Yang,et al.  Methane hydrate formation in excess water simulating marine locations and the impact of thermal stimulation on energy recovery , 2016 .

[244]  J. Ripmeester,et al.  Structure and Kinetics of Gas Hydrates from Methane/Ethane/Propane Mixtures Relevant to the Design of Natural Gas Hydrate Storage and Transport Facilities , 2008 .

[245]  Y. Mori,et al.  Clathrate‐hydrate film growth along water/methane phase boundaries—an observational study , 2013 .

[246]  Young Seok Kim,et al.  Gas hydrate formation process for pre-combustion capture of carbon dioxide , 2010 .

[247]  Huen Lee,et al.  Spectroscopy Identification and Thermodynamic Stability of tert-Butyl Nitrite and Methane Clathrate Hydrate , 2010 .

[248]  George J. Moridis,et al.  X-Ray computed tomography examination and comparison of gas hydrate dissociation in NGHP-01 expedition (India) and Mount Elbert (Alaska) sediment cores: Experimental observations and numerical modeling , 2014 .

[249]  R. Niessner,et al.  Direct 3-D measurement of the flow velocity in porous media using magnetic resonance tomography. , 2000 .

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

[251]  Diffusion and flow in a porous structure by the gradient spin echo spectral analysis , 2001 .

[252]  S. Okuda,et al.  Temperature mapping using the water proton chemical shift: Self‐referenced method with echo‐planar spectroscopic imaging , 2000, Magnetic resonance in medicine.

[253]  T. Ishida,et al.  Possible application of non-invasive thermometry for hyperthermia using NMR. , 1981, Nihon Igaku Hoshasen Gakkai zasshi. Nippon acta radiologica.

[254]  H. Narita,et al.  Characterization of sand sediment by pore size distribution and permeability using proton nuclear magnetic resonance measurement , 2008 .

[255]  Carolyn A. Koh,et al.  State of the art: Natural gas hydrates as a natural resource , 2012 .

[256]  Toshihiro Kawaguchi,et al.  MRI measurement of granular flows and fluid-particle flows , 2007 .

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

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

[259]  Praveen Linga,et al.  Review of natural gas hydrates as an energy resource: Prospects and challenges ☆ , 2016 .

[260]  J. Ripmeester,et al.  Assessing the performance of commercial and biological gas hydrate inhibitors using nuclear magnetic resonance microscopy and a stirred autoclave , 2013 .