Understanding the Reactive Adsorption of H2S and CO2 in Sodium-Exchanged Zeolites

Fetisov, Evgenii O.; Shah, Mansi S; Knight, Christopher; Tsapatsis, Michael; Siepmann, J. Ilja

doi:10.1002/cphc.201700993

Title: Understanding the Reactive Adsorption of H₂S and CO₂ in Sodium-Exchanged Zeolites

Journal Article · 19 February 2018 · ChemPhysChem

DOI: https://doi.org/10.1002/cphc.201700993 · OSTI ID:1426239

Fetisov, Evgenii O. ^[1]; Shah, Mansi S ^[1]; Knight, Christopher ^[2]; Tsapatsis, Michael ^[3]; Siepmann, J. Ilja ^[1]

Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry and Chemical Theory Center
Argonne National Lab. (ANL), Argonne, IL (United States). Leadership Computing Facility
Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemical Engineering and Materials Science

Abstract Purifying sour natural gas streams containing hydrogen sulfide and carbon dioxide has been a long‐standing environmental and economic challenge. In the presence of cation‐exchanged zeolites, these two acid gases can react to form carbonyl sulfide and water (H ₂ S+CO ₂ ⇌H ₂ O+COS), but this reaction is rarely accounted for. In this work, we carry out reactive first‐principles Monte Carlo (RxFPMC) simulations for mixtures of H ₂ S and CO ₂ in all‐silica and Na‐exchanged forms of zeolite beta to understand the governing principles driving the enhanced conversion. The RxFPMC simulations show that the presence of Na ⁺ cations can change the equilibrium constant by several orders of magnitude compared to the gas phase or in all‐silica beta. The shift in the reaction equilibrium is caused by very strong interactions of H ₂ O with Na ⁺ that reduce the reaction enthalpy by about 20 kJ mol ⁻¹ . The simulations also demonstrate that the siting of Al atoms in the framework plays an important role. The RxFPMC method presented here is applicable to any chemical conversion in any confined environment, where strong interactions of guest molecules with the host framework and high activation energies limit the use of other computational approaches to study reaction equilibria.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1426239

Alternate ID(s):: OSTI ID: 1422250

Journal Information:: ChemPhysChem, Vol. 19; ISSN 1439-4235

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 12 works

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References (41)

H2S adsorption by Ag and Cu ion exchanged faujasites Kumar, Parveen; Sung, Chun-Yi; Muraza, Oki Microporous and Mesoporous Materials, Vol. 146, Issue 1-3 https://doi.org/10.1016/j.micromeso.2011.05.014	journal	December 2011
TraPPE-zeo: Transferable Potentials for Phase Equilibria Force Field for All-Silica Zeolites Bai, Peng; Tsapatsis, Michael; Siepmann, J. Ilja The Journal of Physical Chemistry C, Vol. 117, Issue 46 https://doi.org/10.1021/jp4074224	journal	November 2013
Influence of weakly coordinated cations and basic sites upon the reaction of H2S and CO2 on zeolites Fellmuth, P.; Lutz, W.; Bülow, M. Zeolites, Vol. 7, Issue 4 https://doi.org/10.1016/0144-2449(87)90041-8	journal	July 1987
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Gaussian basis sets for accurate calculations on molecular systems in gas and condensed phases VandeVondele, Joost; Hutter, Jürg The Journal of Chemical Physics, Vol. 127, Issue 11 https://doi.org/10.1063/1.2770708	journal	September 2007
Hybrid Monte Carlo Duane, Simon; Kennedy, A. D.; Pendleton, Brian J. Physics Letters B, Vol. 195, Issue 2 https://doi.org/10.1016/0370-2693(87)91197-X	journal	September 1987
Deep eutectic solvents for highly efficient separations in oil and gas industries Warrag, Samah E. E.; Peters, Cor J.; Kroon, Maaike C. Current Opinion in Green and Sustainable Chemistry, Vol. 5 https://doi.org/10.1016/j.cogsc.2017.03.013	journal	June 2017
Reactive Monte Carlo and grand-canonical Monte Carlo simulations of the propene metathesis reaction system Hansen, Niels; Jakobtorweihen, Sven; Keil, Frerich J. The Journal of Chemical Physics, Vol. 122, Issue 16 https://doi.org/10.1063/1.1884108	journal	April 2005
Violations of Löwenstein's rule in zeolites Fletcher, Rachel E.; Ling, Sanliang; Slater, Ben Chem. Sci., Vol. 8, Issue 11 https://doi.org/10.1039/C7SC02531A	journal	January 2017
Free energy and phase equilibria for the restricted primitive model of ionic fluids from Monte Carlo simulations Orkoulas, Gerassimos; Panagiotopoulos, Athanassios Z. The Journal of Chemical Physics, Vol. 101, Issue 2 https://doi.org/10.1063/1.467770	journal	July 1994
First-Principles Monte Carlo Simulations of Reaction Equilibria in Compressed Vapors Fetisov, Evgenii O.; Kuo, I-Feng William; Knight, Chris ACS Central Science, Vol. 2, Issue 6 https://doi.org/10.1021/acscentsci.6b00095	journal	April 2016
Liquid Water from First Principles: Investigation of Different Sampling Approaches Kuo, I-Feng W.; Mundy, Christopher J.; McGrath, Matthew J. The Journal of Physical Chemistry B, Vol. 108, Issue 34 https://doi.org/10.1021/jp047788i	journal	August 2004
The reaction ensemble method for the computer simulation of chemical and phase equilibria. I. Theory and basic examples Smith, W. R.; Triska, B. The Journal of Chemical Physics, Vol. 100, Issue 4 https://doi.org/10.1063/1.466443	journal	February 1994
Identifying Optimal Zeolitic Sorbents for Sweetening of Highly Sour Natural Gas Shah, Mansi S.; Tsapatsis, Michael; Siepmann, J. Ilja Angewandte Chemie International Edition, Vol. 55, Issue 20 https://doi.org/10.1002/anie.201600612	journal	April 2016
Hydrogen Sulfide Capture: From Absorption in Polar Liquids to Oxide, Zeolite, and Metal–Organic Framework Adsorbents and Membranes Shah, Mansi S.; Tsapatsis, Michael; Siepmann, J. Ilja Chemical Reviews, Vol. 117, Issue 14 https://doi.org/10.1021/acs.chemrev.7b00095	journal	May 2017
The reaction ensemble method for the computer simulation of chemical and phase equilibria. II. The Br2+Cl2+BrCl system Lı́sal, Martin; Nezbeda, Ivo; Smith, William R. The Journal of Chemical Physics, Vol. 110, Issue 17 https://doi.org/10.1063/1.478767	journal	May 1999
Reaction Ensemble Monte Carlo Simulation of Xylene Isomerization in Bulk Phases and under Confinement Mullen, Ryan Gotchy; Maginn, Edward J. Journal of Chemical Theory and Computation, Vol. 13, Issue 9 https://doi.org/10.1021/acs.jctc.7b00498	journal	August 2017
Adsorption of hydrogen sulphide on molecular sieves Lutz, W.; Suckow, M.; Bülow, M. Gas Separation & Purification, Vol. 4, Issue 4 https://doi.org/10.1016/0950-4214(90)80041-I	journal	December 1990
Molecular-level simulations of chemical reaction equilibrium for nitric oxide dimerization reaction in disordered nanoporous carbons Lísal, Martin; Cosoli, Paolo; Smith, William R. Fluid Phase Equilibria, Vol. 272, Issue 1-2 https://doi.org/10.1016/j.fluid.2008.07.015	journal	October 2008
Chemical reaction equilibrium in nanoporous materials: NO dimerization reaction in carbon slit nanopores Lísal, Martin; Brennan, John K.; Smith, William R. The Journal of Chemical Physics, Vol. 124, Issue 6 https://doi.org/10.1063/1.2171213	journal	February 2006
Rigorous Basis of the Frenkel‐Band Theory of Association Equilibrium Stillinger, Frank H. The Journal of Chemical Physics, Vol. 38, Issue 7 https://doi.org/10.1063/1.1776907	journal	April 1963
Simultaneous absorption of carbon dioxide and hydrogen sulfide into aqueous monoethanolamine solutions Sada, E.; Kumazawa, H.; Butt, M. A. Chemical Engineering Science, Vol. 31, Issue 9 https://doi.org/10.1016/0009-2509(76)80059-0	journal	January 1976
Gas Solubility in Ionic Liquids Lei, Zhigang; Dai, Chengna; Chen, Biaohua Chemical Reviews, Vol. 114, Issue 2 https://doi.org/10.1021/cr300497a	journal	November 2013
Simulation of chemical reaction equilibria by the reaction ensemble Monte Carlo method: a review† Heath Turner, C.; Brennan, John K.; Lísal, Martin Molecular Simulation, Vol. 34, Issue 2 https://doi.org/10.1080/08927020801986564	journal	February 2008
Determining the location and nearest neighbours of aluminium in zeolites with atom probe tomography Perea, Daniel E.; Arslan, Ilke; Liu, Jia Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8589	journal	July 2015
Molecular simulation of multicomponent reaction and phase equilibria in MTBE ternary system Lísal, Martin; Smith, William R.; Nezbeda, Ivo AIChE Journal, Vol. 46, Issue 4 https://doi.org/10.1002/aic.690460419	journal	April 2000
Utilization of Zeolites for Processes of Gas Desulphurization Bülow, Martin; Micke, André The Kluwer International Series in Engineering and Computer Science https://doi.org/10.1007/978-1-4613-1375-5_15	book	January 1996
Vapor–liquid equilibria of mixtures containing alkanes, carbon dioxide, and nitrogen Potoff, Jeffrey J.; Siepmann, J. Ilja AIChE Journal, Vol. 47, Issue 7, p. 1676-1682 https://doi.org/10.1002/aic.690470719	journal	July 2001
Effects of supercritical clustering and selective confinement on reaction equilibrium: A molecular simulation study of the esterification reaction Turner, C. Heath; Gubbins, Keith E. The Journal of Chemical Physics, Vol. 119, Issue 12 https://doi.org/10.1063/1.1602691	journal	September 2003
Development of the Transferable Potentials for Phase Equilibria Model for Hydrogen Sulfide Shah, Mansi S.; Tsapatsis, Michael; Siepmann, J. Ilja The Journal of Physical Chemistry B, Vol. 119, Issue 23 https://doi.org/10.1021/acs.jpcb.5b02536	journal	May 2015
Superior Sorbent for Natural Gas Desulfurization Crespo, Dennis; Qi, Gongshin; Wang, Yuhe Industrial & Engineering Chemistry Research, Vol. 47, Issue 4 https://doi.org/10.1021/ie071145i	journal	February 2008
Effect of confinement on chemical reaction equilibria: The reactions 2NO⇔(NO)2 and N2+3H2⇔2NH3 in carbon micropores Turner, C. Heath; Johnson, J. Karl; Gubbins, Keith E. The Journal of Chemical Physics, Vol. 114, Issue 4 https://doi.org/10.1063/1.1328756	journal	January 2001
Hydrogen Sulfide and Carbon Dioxide Removal from Dry Fuel Gas Streams Using an Ionic Liquid as a Physical Solvent ^† ^‡ Heintz, Yannick J.; Sehabiague, Laurent; Morsi, Badie I. Energy & Fuels, Vol. 23, Issue 10 https://doi.org/10.1021/ef900281v	journal	October 2009
Benchmarking DFT-GGA calculations for the structure optimisation of neutral-framework zeotypes Fischer, Michael; Evers, Felix O.; Formalik, Filip Theoretical Chemistry Accounts, Vol. 135, Issue 12 https://doi.org/10.1007/s00214-016-2014-6	journal	November 2016
Reactive canonical Monte Carlo: A new simulation technique for reacting or associating fluids Johnson, J. Karl; Panagiotopoulos, Athanassios Z.; Gubbins, Keith E. Molecular Physics, Vol. 81, Issue 3 https://doi.org/10.1080/00268979400100481	journal	February 1994
The framework topology of zeolite beta Higgins, J. B.; LaPierre, R. B.; Schlenker, J. L. Zeolites, Vol. 8, Issue 6 https://doi.org/10.1016/S0144-2449(88)80219-7	journal	November 1988
Isobaric-Isothermal Monte Carlo Simulations from First Principles: Application to Liquid Water at Ambient Conditions McGrath, Matthew J.; Siepmann, J. Ilja; Kuo, I-Feng W. ChemPhysChem, Vol. 6, Issue 9 https://doi.org/10.1002/cphc.200400580	journal	September 2005
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
Sweetening of sour natural gases by mixed-solvent absorption: Solubilities of ethane, carbon dioxide, and hydrogen sulfide in mixtures of physical and chemical solvents Rivas, O. R.; Prausnitz, J. M. AIChE Journal, Vol. 25, Issue 6 https://doi.org/10.1002/aic.690250608	journal	November 1979
Simulating Fluid-Phase Equilibria of Water from First Principles ^† McGrath, Matthew J.; Siepmann, J. Ilja; Kuo, I-Feng W. The Journal of Physical Chemistry A, Vol. 110, Issue 2 https://doi.org/10.1021/jp0535947	journal	January 2006
cp2k: atomistic simulations of condensed matter systems Hutter, Jürg; Iannuzzi, Marcella; Schiffmann, Florian Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 4, Issue 1 https://doi.org/10.1002/wcms.1159	journal	June 2013

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