Screening metal–organic frameworks by analysis of transient breakthrough of gas mixtures in a fixed bed adsorber

Metal–organic frameworks (MOFs) offer considerable potential for separating a variety of mixtures that are important in applications such as CO2 capture and H2 purification. In view of the vast number of MOFs that have been synthesized, there is a need for a reliable procedure for comparing screening and ranking MOFs with regard to their anticipated performance in pressure swing adsorption (PSA) units. For this purpose, the most commonly used metrics are the adsorption selectivity and the working capacity. Here, we suggest an additional metric for comparing MOFs that is based on the analysis of the transient response of an adsorber to a step input of a gaseous mixture. For a chosen purity of the gaseous mixture exiting from the adsorber, a dimensionless breakthrough time τbreak can be defined and determined; this metric determines the frequency of required regeneration and influences the productivity of a PSA unit. The values of τbreak are dictated both by selectivity and by capacity metrics .By performin...

[1]  Krista S. Walton,et al.  Consistency of energy and material balances for bidisperse particles in fixed-bed adsorption and related applications , 2003 .

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

[3]  Matthew R. Hill,et al.  Synthesis and hydrogen storage properties of Be(12)(OH)(12)(1,3,5-benzenetribenzoate)(4). , 2009, Journal of the American Chemical Society.

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

[5]  Dan Zhao,et al.  Tuning the topology and functionality of metal-organic frameworks by ligand design. , 2011, Accounts of chemical research.

[6]  François-Xavier Coudert,et al.  Prediction of breathing and gate-opening transitions upon binary mixture adsorption in metal-organic frameworks. , 2009, Journal of the American Chemical Society.

[7]  Rajamani Krishna,et al.  Describing the Diffusion of Guest Molecules Inside Porous Structures , 2009 .

[8]  F. Kapteijn,et al.  Thermodynamic analysis of the breathing of amino-functionalized MIL-53(Al) upon CO2 adsorption , 2011 .

[9]  Dianne E. Wiley,et al.  Reducing the Cost of CO2 Capture from Flue Gases Using Pressure Swing Adsorption , 2008 .

[10]  Mircea Dincă,et al.  Broadly hysteretic H2 adsorption in the microporous metal-organic framework Co(1,4-benzenedipyrazolate). , 2008, Journal of the American Chemical Society.

[11]  Freek Kapteijn,et al.  An amine-functionalized MIL-53 metal-organic framework with large separation power for CO2 and CH4. , 2009, Journal of the American Chemical Society.

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

[13]  A. Matzger,et al.  Effect of humidity on the performance of microporous coordination polymers as adsorbents for CO2 capture. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[14]  Randall Q Snurr,et al.  Screening of metal-organic frameworks for carbon dioxide capture from flue gas using a combined experimental and modeling approach. , 2009, Journal of the American Chemical Society.

[15]  Bjørnar Arstad,et al.  Amine functionalised metal organic frameworks (MOFs) as adsorbents for carbon dioxide , 2008 .

[16]  François-Xavier Coudert,et al.  Double structural transition in hybrid material MIL-53 upon hydrocarbon adsorption: the thermodynamics behind the scenes. , 2009, Journal of the American Chemical Society.

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

[18]  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 .

[19]  J. Stoer,et al.  Numerical treatment of ordinary differential equations by extrapolation methods , 1966 .

[20]  R. Krishna,et al.  EXPERIMENTAL VERIFICATION OF THE MAXWELL-STEFAN THEORY FOR MICROPORE DIFFUSION , 1995 .

[21]  R. Krishna,et al.  Highlighting a variety of unusual characteristics of adsorption and diffusion in microporous materials induced by clustering of guest molecules. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[22]  C. Serre,et al.  Multistep N2 breathing in the metal-organic framework co(1,4-benzenedipyrazolate). , 2010, Journal of the American Chemical Society.

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

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

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

[26]  B. Smit,et al.  Entropy effects during sorption of alkanes in zeolites. , 2002, Chemical Society reviews.

[27]  Ross Taylor,et al.  A nonequilibrium model for dynamic simulation of tray distillation columns , 1995 .

[28]  Randall Q. Snurr,et al.  Ultrahigh Porosity in Metal-Organic Frameworks , 2010, Science.

[29]  Rajamani Krishna,et al.  Insights into diffusion of gases in zeolites gained from molecular dynamics simulations , 2008 .

[30]  Rajamani Krishna,et al.  Method for Analyzing Structural Changes of Flexible Metal-Organic Frameworks Induced by Adsorbates , 2009 .

[31]  M. Hirscher,et al.  Hydrogen adsorption in a nickel based coordination polymer with open metal sites in the cylindrical cavities of the desolvated framework. , 2006, Chemical communications.

[32]  Randall Q. Snurr,et al.  Enhanced CO2 Adsorption in Metal-Organic Frameworks via Occupation of Open-Metal Sites by Coordinated Water Molecules , 2009 .

[33]  Jihyun An,et al.  High and selective CO2 uptake in a cobalt adeninate metal-organic framework exhibiting pyrimidine- and amino-decorated pores. , 2010, Journal of the American Chemical Society.

[34]  Rajamani Krishna,et al.  Segregation effects in adsorption of CO2-containing mixtures and their consequences for separation selectivities in cage-type zeolites , 2008 .

[35]  Rajamani Krishna,et al.  Investigating cluster formation in adsorption of CO2, CH4, and Ar in zeolites and metal organic frameworks at subcritical temperatures. , 2010, Langmuir : the ACS journal of surfaces and colloids.

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

[37]  Christian J. Doonan,et al.  Multiple Functional Groups of Varying Ratios in Metal-Organic Frameworks , 2010, Science.

[38]  D. D’Alessandro,et al.  Strong CO2 binding in a water-stable, triazolate-bridged metal-organic framework functionalized with ethylenediamine. , 2009, Journal of the American Chemical Society.

[39]  Rajamani Krishna,et al.  Influence of segregated adsorption on mixture diffusion in DDR zeolite , 2007 .

[40]  Wei Zhou,et al.  Exceptionally high acetylene uptake in a microporous metal-organic framework with open metal sites. , 2009, Journal of the American Chemical Society.

[41]  Mircea Dincă,et al.  Hydrogen storage in metal-organic frameworks. , 2009, Chemical Society reviews.

[42]  Douglas M. Ruthven,et al.  Principles of Adsorption and Adsorption Processes , 1984 .

[43]  Randall Q. Snurr,et al.  Enhancement of CO2/N2 selectivity in a metal-organic framework by cavity modification , 2009 .

[44]  Krista S. Walton,et al.  Molecular Simulations and Experimental Studies of CO2, CO, and N2 Adsorption in Metal−Organic Frameworks , 2010 .

[45]  C. Serre,et al.  Why hybrid porous solids capture greenhouse gases? , 2011, Chemical Society reviews.

[46]  O. Yaghi,et al.  Metal-organic frameworks with high capacity and selectivity for harmful gases , 2008, Proceedings of the National Academy of Sciences.

[47]  Rajamani Krishna,et al.  Onsager coefficients for binary mixture diffusion in nanopores , 2008 .

[48]  M. Eddaoudi,et al.  Rod packings and metal-organic frameworks constructed from rod-shaped secondary building units. , 2005, Journal of the American Chemical Society.

[49]  Nathaniel L Rosi,et al.  Tuning MOF CO2 adsorption properties via cation exchange. , 2010, Journal of the American Chemical Society.

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

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

[52]  B. Smit,et al.  Carbon dioxide capture: prospects for new materials. , 2010, Angewandte Chemie.

[53]  G. Pirngruber,et al.  CO2 and CH4 Separation by Adsorption Using Cu-BTC Metal−Organic Framework , 2010 .

[54]  A. Torrisi,et al.  Impact of ligands on CO2 adsorption in metal-organic frameworks: first principles study of the interaction of CO2 with functionalized benzenes. I. Inductive effects on the aromatic ring. , 2009, The Journal of chemical physics.

[55]  R. Krishna,et al.  Diffusion of hydrocarbon mixtures in MFI zeolite: Influence of intersection blocking , 2008 .

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

[57]  A. Matzger,et al.  Dramatic tuning of carbon dioxide uptake via metal substitution in a coordination polymer with cylindrical pores. , 2008, Journal of the American Chemical Society.

[58]  R. Krishna,et al.  On the Langmuir-Hinshelwood formulation for zeolite catalyzed reactions , 2005 .

[59]  D. Do,et al.  Adsorption analysis : equilibria and kinetics , 1998 .

[60]  Rajamani Krishna,et al.  Modelling issues in zeolite based separation processes , 2003 .

[61]  S. Deng,et al.  Adsorption of CO2 and CH4 on a magnesium-based metal organic framework. , 2011, Journal of colloid and interface science.

[62]  K. S. Knaebel,et al.  Pressure swing adsorption , 1993 .

[63]  Michael O'Keeffe,et al.  A route to high surface area, porosity and inclusion of large molecules in crystals , 2004, Nature.

[64]  S. Sircar,et al.  Thermodynamic Consistency for Binary Gas Adsorption Equilibria , 1999 .

[65]  François-Xavier Coudert,et al.  Thermodynamics of guest-induced structural transitions in hybrid organic-inorganic frameworks. , 2008, Journal of the American Chemical Society.

[66]  A. Torrisi,et al.  Functionalized MOFs for Enhanced CO2 Capture , 2010 .

[67]  David Dubbeldam,et al.  Understanding inflections and steps in carbon dioxide adsorption isotherms in metal-organic frameworks. , 2008, Journal of the American Chemical Society.

[68]  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.

[69]  Rajamani Krishna,et al.  In silico screening of zeolite membranes for CO2 capture , 2010 .

[70]  Seda Keskin,et al.  Can metal-organic framework materials play a useful role in large-scale carbon dioxide separations? , 2010, ChemSusChem.

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

[72]  Michael L. Michelsen,et al.  An efficient general purpose method for the intergration of stiff ordinary differential equations , 1976 .

[73]  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.

[74]  G. Shimizu,et al.  An amine-functionalized metal organic framework for preferential CO(2) adsorption at low pressures. , 2009, Chemical communications.