Effect of guest gas on the mixed tetrahydrofuran hydrate kinetics in a quiescent system

Abstract Clathrate hydrates are ‘inclusion compounds’ that have the ability to encompass multifold volumes of guest gas molecules, thus being advantageous for gas storage and gas separation applications. CO 2 capture in the form of hydrates is an environmentally benign and cost-effective approach. In this work, we examine the kinetics of CO 2 hydrate formation at different operating conditions that result in the formation of pure sI hydrate, pure sII hydrates and/or a mixture of sI and sII hydrates. Morphology observations of different hydrates formed are presented with the associated CO 2 uptake achieved under different experimental conditions. We report strikingly contrasting morphology of mixed CO 2 and mixed CH 4 hydrates observed in presence of stoichiometric THF (5.6 mol%) under similar pressure diving force and operating conditions. Interesting results observed during mixed CO 2 hydrates using Differential Scanning Calorimetry (DSC) are documented. Based on DSC thermograms, we report interesting observations on the effect of guest gas in the mixed THF hydrate formation and dissociation. Moreover, mixed CH 4 /THF hydrates were found to be more stable in comparison to mixed CO 2 /THF hydrates. This work highlights that the choice of guest gas plays a significant role in the associated hydrate formation kinetics in presence of THF.

[1]  Hari Prakash Veluswamy,et al.  Enhanced clathrate hydrate formation kinetics at near ambient temperatures and moderate pressures: Application to natural gas storage , 2016 .

[2]  Asheesh Kumar,et al.  Experimental Investigation To Elucidate Why Tetrahydrofuran Rapidly Promotes Methane Hydrate Formation Kinetics: Applicable to Energy Storage , 2016 .

[3]  Mahmut Parlaktuna,et al.  Storage of Natural Gas as Frozen Hydrate , 1994 .

[4]  Donald B. Robinson,et al.  Hydrate formation in systems containing methane, ethane, propane, carbon dioxide or hydrogen sulfide in the presence of methanol , 1985 .

[5]  Saman Alavi,et al.  Facilitating guest transport in clathrate hydrates by tuning guest-host interactions. , 2015, The Journal of chemical physics.

[6]  Yong Tae Kang,et al.  Characteristics of CO2 hydrate formation/dissociation in H2O + THF aqueous solution and estimation of CO2 emission reduction by district cooling application , 2017 .

[7]  D. Robinson,et al.  Hydrates In the PropaneCarbon Dioxide- Water System , 1971 .

[8]  Y. Kang,et al.  Study on dissociation characteristics of CO2 hydrate with THF for cooling application , 2017 .

[9]  Hari Prakash Veluswamy,et al.  Influence of cationic and non-ionic surfactants on the kinetics of mixed hydrogen/tetrahydrofuran hydrates , 2015 .

[10]  Yasuhiko,et al.  RECENT ADVANCES IN HYDRATE-BASED TECHNOLOGIES FOR NATURAL GAS STORAGE--A REVIEW , 2003 .

[11]  J. Arons,et al.  Mixed hydrates of methane and water‐soluble hydrocarbons modeling of empirical results , 2001 .

[12]  Jyun-Yi Wu,et al.  Molecular dynamics study on the nucleation of methane + tetrahydrofuran mixed guest hydrate. , 2016, Physical chemistry chemical physics : PCCP.

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

[14]  Asheesh Kumar,et al.  Enhanced carbon dioxide hydrate formation kinetics in a fixed bed reactor filled with metallic packing , 2015 .

[15]  Chun-Gang Xu,et al.  Tetra-n-butyl ammonium bromide semi-clathrate hydrate process for post-combustion capture of carbon dioxide in the presence of dodecyl trimethyl ammonium chloride , 2010 .

[16]  R. Kumar,et al.  Carbon Dioxide Sequestration: Influence of Porous Media on Hydrate Formation Kinetics , 2015 .

[17]  J. Ripmeester,et al.  Application of the ATR-IR spectroscopic technique to the characterization of hydrates formed by CO(2), CO(2)/H(2) and CO(2)/H(2)/C(3)H(8). , 2009, The journal of physical chemistry. A.

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

[19]  Zhou Lijun,et al.  Analysis of factors influencing thermal conductivity and viscosity in different kinds of surfactant solutions , 2012 .

[20]  Dongyoung Lee,et al.  Enclathration of CO2 as a co-guest of structure H hydrates and its implications for CO2 capture and sequestration , 2016 .

[21]  B. Militzer,et al.  Hydrogen storage in molecular clathrates. , 2007, Chemical reviews.

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

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

[24]  Hari Prakash Veluswamy,et al.  An innovative approach to enhance methane hydrate formation kinetics with leucine for energy storage application , 2017 .

[25]  Anthony Delahaye,et al.  Effect of THF on Equilibrium Pressure and Dissociation Enthalpy of CO2 Hydrates Applied to Secondary Refrigeration , 2006 .

[26]  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.

[27]  Peng Zhang,et al.  Semiclathrate hydrate process for pre-combustion capture of CO2 at near ambient temperatures , 2017 .

[28]  Peter Englezos,et al.  The clathrate hydrate process for post and pre-combustion capture of carbon dioxide. , 2007, Journal of hazardous materials.

[29]  P. Jacques,et al.  Surfactant Effects on Aeration Performance of Stirred Tank Reactors , 2008 .

[30]  D. Broseta,et al.  CO2 enclathration in the presence of water-soluble hydrate promoters: Hydrate phase equilibria and kinetic studies in quiescent conditions , 2012 .

[31]  Chun-Gang Xu,et al.  Hydrate-based pre-combustion carbon dioxide capture process in the system with tetra-n-butyl ammoniu , 2011 .

[32]  Ponnivalavan Babu,et al.  Pre-combustion capture of carbon dioxide in a fixed bed reactor using the clathrate hydrate process , 2013 .

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

[34]  S. Takeya,et al.  Structure and Guest Dynamics in Binary Clathrate Hydrates of Tetrahydropyran with Carbon Dioxide/Methane , 2015 .

[35]  J. Ripmeester,et al.  A new apparatus to enhance the rate of gas hydrate formation: Application to capture of carbon dioxide , 2010 .

[36]  Guangjin Chen,et al.  Interfacial Tension of Methane + Water with Surfactant near the Hydrate Formation Conditions , 2004 .

[37]  Junshe Zhang,et al.  Enhanced Kinetics of CO2 Hydrate Formation under Static Conditions , 2009 .

[38]  Asheesh Kumar,et al.  Influence of contact medium and surfactants on carbon dioxide clathrate hydrate kinetics , 2013 .

[39]  Y. Kang,et al.  Experimental correlation for the formation rate of CO2 hydrate with THF (tetrahydrofuran) for cooling application , 2015 .

[40]  Seong-Pil Kang,et al.  Recovery of CO2 from Flue Gas Using Gas Hydrate: Thermodynamic Verification through Phase Equilibrium Measurements , 2000 .

[41]  Huen Lee,et al.  Experimental Measurements of Hydrate Phase Equilibria for Carbon Dioxide in the Presence of THF, Propylene Oxide, and 1,4-Dioxane , 2008 .

[42]  Sang Yeon Hong,et al.  A new apparatus for seawater desalination by gas hydrate process and removal characteristics of dissolved minerals (Na+, Mg2+, Ca2+, K+, B3+) , 2011 .

[43]  Ni Liu,et al.  Experimental study on a small scale of gas hydrate cold storage apparatus , 2010 .

[44]  E. D. Sloan,et al.  Properties of the clathrates of hydrogen and developments in their applicability for hydrogen storage , 2009 .

[45]  E. D. Sloan,et al.  Thermodynamic predictions of various tetrahydrofuran and hydrogen clathrate hydrates , 2009 .

[46]  Hari Prakash Veluswamy,et al.  Macroscopic kinetics of hydrate formation of mixed hydrates of hydrogen/tetrahydrofuran for hydrogen storage , 2013 .

[47]  R. Kumar,et al.  A new porous material to enhance the kinetics of clathrate process: application to precombustion carbon dioxide capture. , 2013, Environmental science & technology.

[48]  Ponnivalavan Babu,et al.  HBGS (hydrate based gas separation) process for carbon dioxide capture employing an unstirred reactor with cyclopentane , 2013 .

[49]  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 .

[50]  K. Ohgaki,et al.  Formation of CO2 Hydrate in Pure and Sea Waters , 1993 .

[51]  Peter Englezos,et al.  A review of the hydrate based gas separation (HBGS) process for carbon dioxide pre-combustion capture , 2015 .

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

[53]  A. Mohammadi,et al.  Kinetic study of carbon dioxide hydrate formation in presence of silver nanoparticles and SDS , 2014 .

[54]  Peter Englezos,et al.  Effect of temperature and pressure on the solubility of carbon dioxide in water in the presence of gas hydrate , 2001 .

[55]  R. Kumar,et al.  Role of Surfactants in Promoting Gas Hydrate Formation , 2015 .

[56]  P. Englezos,et al.  Measurement of Dissolved Methane in Water in Equilibrium with Its Hydrate , 2002 .

[57]  F. Pessoa,et al.  Storage capacity of carbon dioxide hydrates in the presence of sodium dodecyl sulfate (SDS) and tetrahydrofuran (THF) , 2013 .