High Ethylene-Yield Oxidative Dehydrogenation of Ethane Using Sulfur Vapor as a “Soft” Oxidant

Shanfu Liu; Allison M. Arinaga; Tracy L. Lohr; Tobin J. Marks

doi:10.1002/cctc.202000858

High Ethylene-Yield Oxidative Dehydrogenation of Ethane Using Sulfur Vapor as a “Soft” Oxidant

Shanfu Liu, Allison M. Arinaga, Tracy L. Lohr, Tobin J. Marks^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

3 Scopus citations

Abstract

Ethylene remains one of the most valuable chemical feedstocks. Currently the industrial conversion of ethane to ethylene is achieved largely by steam cracking. The catalytic, highly exothermic oxidative dehydrogenation (ODH) of ethane with O₂ is a challenging alternative that has been extensively studied on the laboratory scale. Here we investigate the possibility of using disulfur (S₂) vapor as a thermodynamically “soft” oxidant for catalytically converting ethane to ethylene (“SODH”). Investigating a series of four catalysts we report a maximum ethylene yield of 76 % over an earth-abundant FeS_x-based catalyst (maximum 90.2 % C₂H₄ selectivity at 820 °C). Yield and selectivity are stable for 50 hours on stream. The SODH rate law is 1^st order in ethane and (Formula presented.) order in S₂, supporting a proposed Mars van Krevelen-like mechanism at temperatures '700 °C. Furthermore, conversion and selectivity become insensitive to catalyst identity at temperatures '860 °C, suggesting the intrusion of radical pathways.

Original language	English (US)
Pages (from-to)	4538-4542
Number of pages	5
Journal	ChemCatChem
Volume	12
Issue number	18
DOIs	https://doi.org/10.1002/cctc.202000858
State	Published - Sep 17 2020

Keywords

Ethane
Ethylene
Heterogeneous Catalysis
Oxidative Dehydrogenation
Sulfur

ASJC Scopus subject areas

Catalysis
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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10.1002/cctc.202000858

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title = "High Ethylene-Yield Oxidative Dehydrogenation of Ethane Using Sulfur Vapor as a “Soft” Oxidant",

abstract = "Ethylene remains one of the most valuable chemical feedstocks. Currently the industrial conversion of ethane to ethylene is achieved largely by steam cracking. The catalytic, highly exothermic oxidative dehydrogenation (ODH) of ethane with O2 is a challenging alternative that has been extensively studied on the laboratory scale. Here we investigate the possibility of using disulfur (S2) vapor as a thermodynamically “soft” oxidant for catalytically converting ethane to ethylene (“SODH”). Investigating a series of four catalysts we report a maximum ethylene yield of 76 % over an earth-abundant FeSx-based catalyst (maximum 90.2 % C2H4 selectivity at 820 °C). Yield and selectivity are stable for 50 hours on stream. The SODH rate law is 1st order in ethane and (Formula presented.) order in S2, supporting a proposed Mars van Krevelen-like mechanism at temperatures '700 °C. Furthermore, conversion and selectivity become insensitive to catalyst identity at temperatures '860 °C, suggesting the intrusion of radical pathways.",

keywords = "Ethane, Ethylene, Heterogeneous Catalysis, Oxidative Dehydrogenation, Sulfur",

author = "Shanfu Liu and Arinaga, {Allison M.} and Lohr, {Tracy L.} and Marks, {Tobin J.}",

note = "Funding Information: We thank the Center for Innovative and Strategic Transformation of Alkane Resources (CISTAR, NSF award number: 1647722) for funding this project. We thank Professor Fabio H. Ribeiro of Purdue U., Dr. Matthias Peter of BASF as well as Professor Justin M. Notestein and Dr. Neil Schweitzer of Northwestern U. for helpful suggestions. Funding Information: We thank the Center for Innovative and Strategic Transformation of Alkane Resources (CISTAR, NSF award number: 1647722) for funding this project. We thank Professor Fabio H. Ribeiro of Purdue U., Dr. Matthias Peter of BASF as well as Professor Justin M. Notestein and Dr. Neil Schweitzer of Northwestern U. for helpful suggestions. Publisher Copyright: {\textcopyright} 2020 Wiley-VCH GmbH",

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AU - Liu, Shanfu

AU - Arinaga, Allison M.

AU - Lohr, Tracy L.

AU - Marks, Tobin J.

N1 - Funding Information: We thank the Center for Innovative and Strategic Transformation of Alkane Resources (CISTAR, NSF award number: 1647722) for funding this project. We thank Professor Fabio H. Ribeiro of Purdue U., Dr. Matthias Peter of BASF as well as Professor Justin M. Notestein and Dr. Neil Schweitzer of Northwestern U. for helpful suggestions. Funding Information: We thank the Center for Innovative and Strategic Transformation of Alkane Resources (CISTAR, NSF award number: 1647722) for funding this project. We thank Professor Fabio H. Ribeiro of Purdue U., Dr. Matthias Peter of BASF as well as Professor Justin M. Notestein and Dr. Neil Schweitzer of Northwestern U. for helpful suggestions. Publisher Copyright: © 2020 Wiley-VCH GmbH

PY - 2020/9/17

Y1 - 2020/9/17

N2 - Ethylene remains one of the most valuable chemical feedstocks. Currently the industrial conversion of ethane to ethylene is achieved largely by steam cracking. The catalytic, highly exothermic oxidative dehydrogenation (ODH) of ethane with O2 is a challenging alternative that has been extensively studied on the laboratory scale. Here we investigate the possibility of using disulfur (S2) vapor as a thermodynamically “soft” oxidant for catalytically converting ethane to ethylene (“SODH”). Investigating a series of four catalysts we report a maximum ethylene yield of 76 % over an earth-abundant FeSx-based catalyst (maximum 90.2 % C2H4 selectivity at 820 °C). Yield and selectivity are stable for 50 hours on stream. The SODH rate law is 1st order in ethane and (Formula presented.) order in S2, supporting a proposed Mars van Krevelen-like mechanism at temperatures '700 °C. Furthermore, conversion and selectivity become insensitive to catalyst identity at temperatures '860 °C, suggesting the intrusion of radical pathways.

AB - Ethylene remains one of the most valuable chemical feedstocks. Currently the industrial conversion of ethane to ethylene is achieved largely by steam cracking. The catalytic, highly exothermic oxidative dehydrogenation (ODH) of ethane with O2 is a challenging alternative that has been extensively studied on the laboratory scale. Here we investigate the possibility of using disulfur (S2) vapor as a thermodynamically “soft” oxidant for catalytically converting ethane to ethylene (“SODH”). Investigating a series of four catalysts we report a maximum ethylene yield of 76 % over an earth-abundant FeSx-based catalyst (maximum 90.2 % C2H4 selectivity at 820 °C). Yield and selectivity are stable for 50 hours on stream. The SODH rate law is 1st order in ethane and (Formula presented.) order in S2, supporting a proposed Mars van Krevelen-like mechanism at temperatures '700 °C. Furthermore, conversion and selectivity become insensitive to catalyst identity at temperatures '860 °C, suggesting the intrusion of radical pathways.

KW - Ethane

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KW - Heterogeneous Catalysis

KW - Oxidative Dehydrogenation

KW - Sulfur

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JF - ChemCatChem

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ER -

High Ethylene-Yield Oxidative Dehydrogenation of Ethane Using Sulfur Vapor as a “Soft” Oxidant

Abstract

Keywords

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