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 · Mon Feb 19 00:00:00 EST 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: 10 works

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

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