Mechanistic Interpretations and Insights for the Oxidative Dehydrogenation of Propane via CO2 over Cr2O3/Al2O3 Catalysts

Karakaya, Canan; Kidder, Michelle; Wolden, Colin; Kee, Robert J.; Deutschmann, Olaf

doi:10.1021/acs.iecr.2c02298

Title: Mechanistic Interpretations and Insights for the Oxidative Dehydrogenation of Propane via CO₂ over Cr₂O₃/Al₂O₃ Catalysts

Journal Article · Thu Sep 22 00:00:00 EDT 2022 · Industrial and Engineering Chemistry Research

DOI:https://doi.org/10.1021/acs.iecr.2c02298· OSTI ID:1892407

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^[2]; Kee, Robert J. ^[2];

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Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Colorado School of Mines, Golden, CO (United States)
Karlsruhe Inst. of Technology (KIT) (Germany)

Oxidative dehydrogenation (ODH) of alkanes using carbon dioxide as a soft oxidant has recently emerged as a potentially attractive alternative to steam cracking for the production of light olefins. To elucidate reaction pathways and their dependence on the operating conditions, CO₂-assisted propane dehydrogenation over a redox-active Cr₂O₃/Al₂O₃ catalyst was examined in a packed bed reactor as a function of temperature, Cr₂O₃/CO₂ feed ratio, and residence time. Previous ODH studies have largely focused on CO₂-rich conditions with the aim of preventing coke formation. However, at T = 600 °C the present study finds that the use of propane-rich conditions (1 ≤ C₃H₈/CO₂ ≤ 2.5) maximizes propylene production and selectivity while maintaining catalyst stability. In this work, it is postulated that the selective Mars van Krevelen dehydrogenation process is optimized at these ratios. Excess CO₂ apparently promotes nonselective dehydrogenation and dry reforming pathways that generate additional CO, adversely impacting catalyst stability via the Bouduard reaction. This hypothesis is supported by complementary investigations of the reverse water gas shift reaction and thermodynamic analysis. The findings and methodology presented here are likely applicable to related ODH processes with other alkanes and redox-active catalysts.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Fossil Energy (FE); Colorado School of Mines Foundation

Grant/Contract Number:: AC05-00OR22725; FWP-FEAA421

OSTI ID:: 1892407

Journal Information:: Industrial and Engineering Chemistry Research, Vol. 61, Issue 39; ISSN 0888-5885

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
CO2 utilization
alkane dehydrogenation
olefin formation
metal-oxide catalyst
Cr2O3/Al2/O3

Title: Mechanistic Interpretations and Insights for the Oxidative Dehydrogenation of Propane via CO2 over Cr2O3/Al2O3 Catalysts

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Title: Mechanistic Interpretations and Insights for the Oxidative Dehydrogenation of Propane via CO₂ over Cr₂O₃/Al₂O₃ Catalysts