CO2/CH4, CH4/H-2 and CO2/CH4/H-2 separations at high pressures using Mg-2(dobdc)

Abstract High-pressure separations of binary and ternary mixtures of CO2, CH4, and H2 are relevant to carbon dioxide capture as well as hydrogen and natural gas purification. Metal–organic frameworks represent a class of porous materials that could be used to accomplish these separations, and Mg2(dobdc) (dobdc4− = 1,4-dioxido-2,5-benzenedicarboxylate), also sometimes referred to as Mg–MOF-74 or CPO-27–Mg, is an especially lightweight metal–organic framework with a high concentration of coordinatively-unsaturated metal sites decorating its interior surfaces. High pressure CH4 adsorption isotherms presented here, together with CO2 and H2 adsorption behavior, are analyzed using the Ideal Adsorbed Solution Theory to model CO2/CH4, CH4/H2, and CO2/CH4/H2 mixture separations using Mg2(dobdc). The selectivities, working capacities and breakthrough performances for these three mixtures are reported, and Mg2(dobdc) is shown to outperform zeolite 13X in each scenario.

[1]  Chongli Zhong,et al.  Exceptional CO2 Capture Capability and Molecular-Level Segregation in a Li-Modified Metal−Organic Framework , 2010 .

[2]  B. Smit,et al.  Enhanced adsorption selectivity of hydrogen/methane mixtures in metal-organic frameworks with interpenetration: A molecular simulation study , 2008 .

[3]  Jianwen Jiang.  Charged soc Metal-Organic Framework for High-Efficacy H2 Adsorption and Syngas Purification: Atomistic Simulation Study , 2009 .

[4]  Steven Chu,et al.  Carbon Capture and Sequestration , 2016 .

[5]  Alírio E. Rodrigues,et al.  Adsorption Equilibrium of Methane, Carbon Dioxide, and Nitrogen on Zeolite 13X at High Pressures , 2004 .

[6]  Jianguo Mi,et al.  Li-modified metal–organic frameworks for CO2/CH4 separation: a route to achieving high adsorption selectivity , 2010 .

[7]  Shamsuzzaman Farooq,et al.  Hydrogen purification from refinery fuel gas by pressure swing adsorption , 1998 .

[8]  S. Sandler,et al.  Storage and separation of CO2 and CH4 in silicalite, C168 schwarzite, and IRMOF-1: a comparative study from Monte Carlo simulation. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[9]  Sukumar Devotta,et al.  CO2 emission and its mitigation by adsorption on zeolites and activated carbon , 2007 .

[10]  Alírio E. Rodrigues,et al.  A parametric study of layered bed PSA for hydrogen purification , 2008 .

[11]  R. Krishna,et al.  In silico screening of metal-organic frameworks in separation applications. , 2011, Physical chemistry chemical physics : PCCP.

[12]  J. Johnson,et al.  Prediction of CH4/H2 Mixture Selectivity in Zn(tbip) from Computer Simulations , 2009 .

[13]  Hong-Cai Zhou,et al.  Selective gas adsorption and separation in metal-organic frameworks. , 2009, Chemical Society reviews.

[14]  Jianwen Jiang,et al.  A bio-metal-organic framework for highly selective CO(2) capture: A molecular simulation study. , 2010, ChemSusChem.

[15]  Ulrich Müller,et al.  Industrial applications of metal-organic frameworks. , 2009, Chemical Society reviews.

[16]  Jianwen Jiang,et al.  Cation Characterization and CO2 Capture in Li+-Exchanged Metal−Organic Frameworks: From First-Principles Modeling to Molecular Simulation† , 2011 .

[17]  M. Eddaoudi,et al.  Highly porous ionic rht metal-organic framework for H2 and CO2 storage and separation: a molecular simulation study. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[18]  Orhan Talu,et al.  Needs, status, techniques and problems with binary gas adsorption experiments , 1998 .

[19]  D. Sholl,et al.  Testing the accuracy of correlations for multicomponent mass transport of adsorbed gases in metal-organic frameworks: diffusion of H2/CH4 mixtures in CuBTC. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[20]  S. Sandler,et al.  Molecular simulations for adsorptive separation of CO2/CH4 mixture in metal-exposed, catenated, and charged metal-organic frameworks. , 2009, Langmuir : the ACS journal of surfaces and colloids.

[21]  Seda Keskin.  Atomistic Simulations for Adsorption, Diffusion, and Separation of Gas Mixtures in Zeolite Imidazolate Frameworks , 2011 .

[23]  José A.C. Silva,et al.  A Microporous Metal−Organic Framework for Separation of CO2/N2 and CO2/CH4 by Fixed-Bed Adsorption , 2008 .

[24]  Timothy Christopher Golden,et al.  Purification of Hydrogen by Pressure Swing Adsorption , 2000 .

[25]  Krista S. Walton,et al.  A novel metal-organic coordination polymer for selective adsorption of CO2 over CH4. , 2009, Chemical communications.

[26]  Seda Keskin.  Comparing Performance of CPO and IRMOF Membranes for Gas Separations Using Atomistic Models , 2010 .

[27]  Seda Keskin.  High CO2 Selectivity of A Microporous Metal–Imidazolate Framework: A Molecular Simulation Study , 2011 .

[28]  David S. Sholl,et al.  Progress, Opportunities, and Challenges for Applying Atomically Detailed Modeling to Molecular Adsorption and Transport in Metal−Organic Framework Materials , 2009 .

[29]  C. Serre,et al.  High uptakes of CO2 and CH4 in mesoporous metal-organic frameworks MIL-100 and MIL-101. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[30]  Shivaji Sircar,et al.  Nanoporous carbon membranes for separation of gas mixtures by selective surface flow , 1993 .

[31]  Chongli Zhong,et al.  Molecular simulation of carbon dioxide/methane/hydrogen mixture adsorption in metal-organic frameworks. , 2006, The journal of physical chemistry. B.

[32]  Ravi Kumar,et al.  Pressure Swing Adsorption Process: Performance Optimum and Adsorbent Selection , 1994 .

[33]  R. Krishna,et al.  Investigating the potential of MgMOF-74 membranes for CO2 capture , 2011 .

[34]  Jie‐Peng Zhang,et al.  An ionic porous coordination framework exhibiting high CO2 affinity and CO2/CH4 selectivity. , 2011, Chemical communications.

[35]  Alexander M. Spokoyny,et al.  Carborane-based metal-organic frameworks as highly selective sorbents for CO(2) over methane. , 2008, Chemical communications.

[36]  Jianwen Jiang,et al.  Unprecedentedly high selective adsorption of gas mixtures in rho zeolite-like metal-organic framework: a molecular simulation study. , 2009, Journal of the American Chemical Society.

[37]  Alexander M. Spokoyny,et al.  Separation of gas mixtures using Co(II) carborane-based porous coordination polymers. , 2010, Chemical communications.

[38]  S. Poulopoulos,et al.  4 – Adsorption and Ion Exchange , 2006 .

[39]  Rajamani Krishna,et al.  Metal-organic frameworks as adsorbents for hydrogen purification and precombustion carbon dioxide capture. , 2011, Journal of the American Chemical Society.

[40]  Kenji Sumida,et al.  Evaluating metal–organic frameworks for post-combustion carbon dioxide capture via temperature swing adsorption , 2011 .

[41]  Chi Tien,et al.  Adsorption calculations and modeling , 1994 .

[42]  Bo Wang,et al.  Highly efficient separation of carbon dioxide by a metal-organic framework replete with open metal sites , 2009, Proceedings of the National Academy of Sciences.

[43]  Seda Keskin,et al.  Separation of CO2 Mixtures Using Zn(bdc)(ted)0.5 Membranes and Composites: A Molecular Simulation Study , 2011 .

[44]  Richard Blom,et al.  Application of metal–organic frameworks with coordinatively unsaturated metal sites in storage and separation of methane and carbon dioxide , 2009 .

[45]  T. Stocker,et al.  Orbital and millennial-scale features of atmospheric CH4 over the past 800,000 years , 2008, Nature.

[46]  R. T. Yang,et al.  Adsorbents: Fundamentals and Applications , 2003 .

[47]  Carl-Jochen Winter,et al.  Into the hydrogen energy economy—milestones , 2005 .

[48]  Patrick Ryan,et al.  Separation of CO2 from CH4 using mixed-ligand metal-organic frameworks. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[49]  J. Hupp,et al.  Synthesis and gas sorption properties of a metal-azolium framework (MAF) material. , 2009, Inorganic chemistry.

[50]  Alan L. Myers,et al.  Thermodynamics of mixed‐gas adsorption , 1965 .

[51]  Rajamani Krishna,et al.  Screening metal–organic frameworks by analysis of transient breakthrough of gas mixtures in a fixed bed adsorber , 2011 .

[52]  Chongli Zhong,et al.  Molecular Simulation of CO2/H2 Mixture Separation in Metal-organic Frameworks: Effect of Catenation and Electrostatic Interactions , 2009 .

[53]  J. Hupp,et al.  Enhancement of CO2/CH4 selectivity in metal-organic frameworks containing lithium cations , 2011 .

[54]  R. T. Yang,et al.  Gas Separation by Adsorption Processes , 1987 .

[55]  C. Serre,et al.  Different adsorption behaviors of methane and carbon dioxide in the isotypic nanoporous metal terephthalates MIL-53 and MIL-47. , 2005, Journal of the American Chemical Society.

[56]  Michael O'Keeffe,et al.  Systematic Design of Pore Size and Functionality in Isoreticular MOFs and Their Application in Methane Storage , 2002, Science.

[57]  Guangjin Chen,et al.  Molecular simulation studies of separation of CH4/H2 mixture in metal-organic frameworks with interpenetration and mixed-ligand , 2011 .

[58]  G. Pirngruber,et al.  A complete experimental approach for synthesis gas separation studies using static gravimetric and column breakthrough experiments , 2007 .

[59]  Chongli Zhong,et al.  Comparative Study of Separation Performance of COFs and MOFs for CH4/CO2/H2 Mixtures , 2010 .

[60]  M. Carreon,et al.  Amino-functionalized SAPO-34 membranes for CO2/CH4 and CO2/N2 separation. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[61]  Berend Smit,et al.  Molecular Simulation Studies of Separation of CO2/N2, CO2/CH4, and CH4/N2 by ZIFs , 2010 .

[62]  Guodong Qian,et al.  Metal-organic frameworks with functional pores for recognition of small molecules. , 2010, Accounts of chemical research.

[63]  M. Kharoune,et al.  Advances in principal factors influencing carbon dioxide adsorption on zeolites , 2008, Science and technology of advanced materials.

[64]  A. Kidnay,et al.  Overview of the Natural Gas Industry , 2011, Fundamentals of Natural Gas Processing.

[65]  D. Sholl,et al.  Assessment of a Metal−Organic Framework Membrane for Gas Separations Using Atomically Detailed Calculations: CO2, CH4, N2, H2 Mixtures in MOF-5 , 2009 .

[66]  A. Myers,et al.  Mixed-Gas Adsorption , 2001 .

[67]  Liang Yu,et al.  Kinetic separation of carbon dioxide and methane on a copper metal-organic framework. , 2011, Journal of colloid and interface science.

[68]  Christian Voss,et al.  Applications of Pressure Swing Adsorption Technology , 2005 .

[69]  Marco Gallo,et al.  Fuel Gas Storage and Separations by Metal−Organic Frameworks: Simulated Adsorption Isotherms for H2 and CH4 and Their Equimolar Mixture , 2009 .