Elucidation of puzzling questions regarding the CrOx/Al2O3 catalyst I. X-ray absorption spectroscopy aided identification of the nature of the chromium oxide species in the CrOx/Al2O3 dehydrogenation catalyst system

Hoffman, Adam S.; Greaney, Matthew; Finzel, Jordan; Xing, Rong; Covelli, Danielle; Fridman, Vladimir Z.; Lugmair, Claus; Bare, Simon R.

doi:10.1016/j.apcata.2023.119187

Title: Elucidation of puzzling questions regarding the CrO_x/Al₂O₃ catalyst I. X-ray absorption spectroscopy aided identification of the nature of the chromium oxide species in the CrO_x/Al₂O₃ dehydrogenation catalyst system

Journal Article · 12 April 2023 · Applied Catalysis. A, General

DOI: https://doi.org/10.1016/j.apcata.2023.119187 · OSTI ID:2004905

Hoffman, Adam S. ^[1]; Greaney, Matthew ^[2]; Finzel, Jordan ^[3]; Xing, Rong ^[4]; Covelli, Danielle ^[4]; Fridman, Vladimir Z. ^[4]; Lugmair, Claus ^[2]; Bare, Simon R. ^[1]

SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Clariant Corporation, Palo Alto, CA (United States)
Univ. of California, Santa Barbara, CA (United States)
Clariant Corporation, Louisville, KY (United States)

The CATOFIN© process produces propylene from propane using a CrO_x /Al₂O₃ catalyst. Despite its use, there are still uncertainties surrounding the nature of Cr species formed during synthesis, regeneration, and aging. It has been observed that ppm levels of Cr₂O₃ can be oxidized to Cr(VI) in air; however, when Cr₂O₃ is in direct contact with Al₂O₃, Cr(VI) formation increased more than 100-fold. Here, to confirm physical contact between Cr₂O₃ and Al₂O₃ results in increased Cr(VI) formation, Cr₂O₃ and Cr₂O₃/Al₂O₃ samples were synthesized, calcined, and characterized. Catalytic activity measurements confirm propylene selectivity inversely tracks with Cr(VI). Wet chemical titration and X-ray absorption spectroscopy (XAS) quantified and determined the structure of the Cr(VI) species. FEFF X-ray absorption near edge structure simulations determined the potential sensitivity of the XAS to the presence of Al³⁺/Cr³⁺ neighboring atoms. XAS correlated to FEFF simulations suggested that Al³⁺_xCr³⁺_2–xCr⁶⁺₃O₁₂ comprises a significant fraction of the Cr(VI) species formed.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Office of Workforce Development for Teachers & Scientists (WDTS); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC02-76SF00515; AC02-05CH11231; SC0014664

OSTI ID:: 2004905

Journal Information:: Applied Catalysis. A, General, Vol. 660; ISSN 0926-860X

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
dehydrogenation
CrOx/Al2O3 catalyst
XAS
XANES
chromium oxide

Title: Elucidation of puzzling questions regarding the CrOx/Al2O3 catalyst I. X-ray absorption spectroscopy aided identification of the nature of the chromium oxide species in the CrOx/Al2O3 dehydrogenation catalyst system

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Title: Elucidation of puzzling questions regarding the CrO_x/Al₂O₃ catalyst I. X-ray absorption spectroscopy aided identification of the nature of the chromium oxide species in the CrO_x/Al₂O₃ dehydrogenation catalyst system