Atomically Dispersed Tin-Modified $\gamma$-alumina for Selective Propane Dehydrogenation under H2S Co-feed

Sharma, Lohit; Jiang, Xiao; Wu, Zili; DeLaRiva, Andrew; Datye, Abhaya K.; Baltrus, John; Rangarajan, Srinivas; Baltrusaitis, Jonas

doi:10.1021/acscatal.1c02859

Title: Atomically Dispersed Tin-Modified $$\gamma$$-alumina for Selective Propane Dehydrogenation under H₂S Co-feed

Journal Article · Fri Oct 22 00:00:00 UTC 2021 · ACS Catalysis

DOI: https://doi.org/10.1021/acscatal.1c02859 · OSTI ID:1844854

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Lehigh Univ., Bethlehem, PA (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Univ. of New Mexico, Albuquerque, NM (United States)
National Energy Technology Lab. (NETL), Pittsburgh, PA (United States)

Developing an earth-abundant catalyst that is sulfur-tolerant, active, and highly selective is of great interest for valorizing natural gas streams containing sour gas. Here, a tin-modified alumina catalyst is reported that is stable and selective for propane dehydrogenation in the presence of percent quantities of H₂S in the feed. In particular, Sn/Al₂O₃–S catalysts with 1.5–5% Sn content exhibit 98% selectivity with up to 16% conversion at 560 °C during the fourth cycle. Experimental and computational characterization shows that the active sites are the defect tricoordinated Al atoms. H₂S pretreatment further modifies a portion of these sites via exchanging a neighboring oxygen atom with sulfur, thereby rendering them more active and selective. At low loadings, Sn is atomically dispersed and selectively binds to hydroxyl groups or oxygen atoms on Al₂O₃. This prevents the formation of original (unmodified) defect sites on Al₂O₃ and improves overall selectivity. The activity and selectivity of the catalyst are heavily dependent on the chemical potential of sulfur and hydrogen because they influence both the relative concentration of the two types of sites and the overall reaction mechanism. Finally, the catalyst can be regenerated fully under a pure H₂S stream, thereby precluding treatment under oxygen, which can lead to sintering.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Understanding and Control of Acid Gas-Induced Evolution of Materials for Energy (UNCAGE-ME); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)

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

Grant/Contract Number:: AC02-05CH11231; AC05-00OR22725; SC0012577

OSTI ID:: 1844854

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 21 Vol. 11; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
H2S
dehydrogenation
dispersed
propane
tin on alumina

Title: Atomically Dispersed Tin-Modified $$\gamma$$-alumina for Selective Propane Dehydrogenation under H2S Co-feed

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Title: Atomically Dispersed Tin-Modified $$\gamma$$-alumina for Selective Propane Dehydrogenation under H₂S Co-feed