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 · 11 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. ^[5]

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

View Accepted Manuscript (DOE)

Cite

Export

Save

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

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

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

OSTI ID:: 2004905

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

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (33)

The Effect of Transition Alumina (γ‐, η‐, χ‐Al₂O₃) on the Activity and Stability of Chromia/Alumina Catalysts. Part II: Industrial‐Like Catalysts and Real Plant Aging Conditions Nazimov, Daniil A.; Klimov, Oleg V.; Shaverina, Anastasiya V. Energy Technology, Vol. 7, Issue 4 https://doi.org/10.1002/ente.201800736	journal	April 2019
Chemical and Physical Characterization of Alumina-Supported Chromia-Based Catalysts and Their Activity in Dehydrogenation of Isobutane Cavani, F.; Koutyrev, M.; Trifirò, F. Journal of Catalysis, Vol. 158, Issue 1 https://doi.org/10.1006/jcat.1996.0023	journal	January 1996
The dehydrogenation of ethane over chromium catalysts Lugo, H. Journal of Catalysis, Vol. 91, Issue 1 https://doi.org/10.1016/0021-9517(85)90297-0	journal	January 1985
Reduction and aromatization activity of chromia-alumina catalysts II. An XPS investigation of chromia-alumina catalysts Grunert, W. Journal of Catalysis, Vol. 100, Issue 1 https://doi.org/10.1016/0021-9517(86)90079-5	journal	July 1986
Differential redox and sorption of Cr (III/VI) on natural silicate and oxide minerals: EXAFS and XANES results Peterson, Maria L.; Brown, Gordon E.; Parks, George A. Geochimica et Cosmochimica Acta, Vol. 61, Issue 16 https://doi.org/10.1016/S0016-7037(97)00165-8	journal	August 1997
Recent progress in diffuse reflectance spectroscopy of supported metal oxide catalysts Weckhuysen, Bert M.; Schoonheydt, Robert A. Catalysis Today, Vol. 49, Issue 4 https://doi.org/10.1016/S0920-5861(98)00458-1	journal	March 1999
Dehydrogenation of i-butane on CrOx/Al2O3 catalysts prepared by ALE and impregnation techniques Hakuli, A.; Kytökivi, A.; Krause, A. O. I. Applied Catalysis A: General, Vol. 190, Issue 1-2 https://doi.org/10.1016/S0926-860X(99)00310-5	journal	January 2000
Pathways of light compounds formation during propane and isobutane dehydrogenation on Al-Cr catalysts Fridman, V. Z. Applied Catalysis A: General, Vol. 382, Issue 2 https://doi.org/10.1016/j.apcata.2010.04.026	journal	July 2010
Investigating the CrOx/Al2O3 dehydrogenation catalyst model: I. identification and stability evaluation of the Cr species on the fresh and equilibrated catalysts Fridman, Vladimir Z.; Xing, Rong; Severance, Michael Applied Catalysis A: General, Vol. 523 https://doi.org/10.1016/j.apcata.2016.05.008	journal	August 2016
Investigating the CrO x /Al 2 O 3 dehydrogenation catalyst model: II. Relative activity of the chromium species on the catalyst surface Fridman, Vladimir Z.; Xing, Rong Applied Catalysis A: General, Vol. 530 https://doi.org/10.1016/j.apcata.2016.11.024	journal	January 2017
An XPS study of CrOx on a thin alumina film and in alumina supported catalysts Sainio, J.; Aronniemi, M.; Pakarinen, O. Applied Surface Science, Vol. 252, Issue 4 https://doi.org/10.1016/j.apsusc.2005.02.029	journal	November 2005
Effect of the K loading on effective activation energy of isobutane dehydrogenation over chromia/alumina catalysts Nazimov, D. A.; Klimov, O. V.; Saiko, A. V. Catalysis Today, Vol. 375 https://doi.org/10.1016/j.cattod.2020.03.005	journal	September 2021
Initial catalytic behavior of chromium oxide during induction period of fluidized dehydrogenation of propane Song, Changyeol; Park, Hawon; Choi, Won Choon Chemical Engineering Journal, Vol. 440 https://doi.org/10.1016/j.cej.2022.135860	journal	July 2022
Effect of Cu modifier on the performance of CrOx/Al2O3 catalysts for isobutane dehydrogenation Salaeva, A. A.; Salaev, M. A.; Mamontov, G. V. Chemical Engineering Science, Vol. 215 https://doi.org/10.1016/j.ces.2019.115462	journal	April 2020
In situ, Cr K-edge XAS study on the Phillips catalyst: activation and ethylene polymerization Groppo, E.; Prestipino, C.; Cesano, F. Journal of Catalysis, Vol. 230, Issue 1 https://doi.org/10.1016/j.jcat.2004.11.017	journal	February 2005
The nature of active chromium species in Cr-catalysts for dehydrogenation of propane: New insights by a comprehensive spectroscopic study Santhoshkumar, M.; Hammer, N.; Ronning, M. Journal of Catalysis, Vol. 261, Issue 1 https://doi.org/10.1016/j.jcat.2008.11.014	journal	January 2009
Deactivation Studies of the CrOx/Al₂O₃ Dehydrogenation Catalysts under Cyclic Redox Conditions Fridman, Vladimir Z.; Xing, Rong Industrial & Engineering Chemistry Research, Vol. 56, Issue 28 https://doi.org/10.1021/acs.iecr.7b01638	journal	July 2017
Stable Cr-MFI Catalysts for the Nonoxidative Dehydrogenation of Ethane: Catalytic Performance and Nature of the Active Sites De, Sudipta; Ould-Chikh, Samy; Aguilar, Antonio ACS Catalysis, Vol. 11, Issue 7 https://doi.org/10.1021/acscatal.0c05170	journal	March 2021
Catalytic Dehydrogenation of Light Alkanes on Metals and Metal Oxides Sattler, Jesper J. H. B.; Ruiz-Martinez, Javier; Santillan-Jimenez, Eduardo Chemical Reviews, Vol. 114, Issue 20 https://doi.org/10.1021/cr5002436	journal	August 2014
Acidic properties of alumina-supported metal oxide catalysts: an infrared spectroscopy study Turek, Andrzej M.; Wachs, Israel E.; DeCanio, Elaine The Journal of Physical Chemistry, Vol. 96, Issue 12 https://doi.org/10.1021/j100191a050	journal	June 1992
Reactions between Hydrocarbons and Deuterium on Chromium Oxide Gel. I. General¹ Burwell, Robert L.; Littlewood, A. B.; Cardew, M. Journal of the American Chemical Society, Vol. 82, Issue 24 https://doi.org/10.1021/ja01509a019	journal	December 1960
Rapid Excited-State Structural Reorganization Captured by Pulsed X-rays Chen, Lin X.; Jennings, Guy; Liu, Tao Journal of the American Chemical Society, Vol. 124, Issue 36 https://doi.org/10.1021/ja017214g	journal	September 2002
MLCT State Structure and Dynamics of a Copper(I) Diimine Complex Characterized by Pump−Probe X-ray and Laser Spectroscopies and DFT Calculations Chen, Lin X.; Shaw, George B.; Novozhilova, Irina Journal of the American Chemical Society, Vol. 125, Issue 23 https://doi.org/10.1021/ja0294663	journal	June 2003
Dynamic Surface Reconstruction Unifies the Electrocatalytic Oxygen Evolution Performance of Nonstoichiometric Mixed Metal Oxides Samira, Samji; Hong, Jiyun; Camayang, John Carl A. JACS Au, Vol. 1, Issue 12 https://doi.org/10.1021/jacsau.1c00359	journal	November 2021
Dynamic restructuring of supported metal nanoparticles and its implications for structure insensitive catalysis Vogt, Charlotte; Meirer, Florian; Monai, Matteo Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-27474-3	journal	December 2021
Insights into Cr/SiO ₂ catalysts during dehydrogenation of propane: an operando XAS investigation Botavina, M.; Barzan, C.; Piovano, A. Catalysis Science & Technology, Vol. 7, Issue 8 https://doi.org/10.1039/C7CY00142H	journal	January 2017
Active phases in chromia–alumina dehydrogenation catalysts. Electron spin resonance and kinetic studies Ashmawy, Fathy M.; McAuliffe, Charles A. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 80, Issue 7 https://doi.org/10.1039/f19848001985	journal	January 1984
Commentary: The Materials Project: A materials genome approach to accelerating materials innovation Jain, Anubhav; Ong, Shyue Ping; Hautier, Geoffroy APL Materials, Vol. 1, Issue 1 https://doi.org/10.1063/1.4812323	journal	July 2013
In-situXAFS study for calcination process of Cr catalyst supported on γ-Al₂O₃and SiO₂ Watanabe, T.; Ikeda, K.; Katayama, M. Journal of Physics: Conference Series, Vol. 712 https://doi.org/10.1088/1742-6596/712/1/012073	journal	May 2016
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
EXAFS and XANES analysis of oxides at the nanoscale Kuzmin, Alexei; Chaboy, Jesús IUCrJ, Vol. 1, Issue 6 https://doi.org/10.1107/S2052252514021101	journal	October 2014
Effect of Steam–Air Treatment of Alumina–Chromia Dehydrogenation Catalysts on Their Physicochemical and Catalytic Characteristics Nazimov, D. A.; Klimov, O. V.; Saiko, A. V. Russian Journal of Applied Chemistry, Vol. 94, Issue 9 https://doi.org/10.1134/S1070427221090111	journal	September 2021
X-Ray Photoelectron Spectroscopic Studies of Catalysts—Chromia–Alumina Catalysts— Okamoto, Yasuaki; Fujii, Masaki; Imanaka, Toshinobu Bulletin of the Chemical Society of Japan, Vol. 49, Issue 4 https://doi.org/10.1246/bcsj.49.859	journal	April 1976

Similar Records

Lanthanide doped V{sub 2}O{sub 5}/Al{sub 2}O{sub 3} catalysts: Structure-activity relationship in the SCR of NO{sub x}

Journal Article · 2000 · Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical · OSTI ID:20034446

Centeno, M A; Malet, P; Carrizosa, I; +1 more

Nature of cobalt species during the in situ sulfurization of Co(Ni)Mo/Al₂O₃ hydrodesulfurization catalysts

Journal Article · 2019 · Journal of Synchrotron Radiation (Online) · OSTI ID:1528874

al Samarai, Mustafa; van Oversteeg, Christa H. M.; Delgado-Jaime, Mario Ulises; +8 more

Effect of Cr{sub 2}O{sub 3} on solubility and thermo-physical properties of BaO-CaO-Al{sub 2}O{sub 3}-B{sub 2}O{sub 3}-SiO{sub 2} g

Journal Article · 2012 · AIP Conference Proceedings · OSTI ID:22004124

Goswami, M; Kumar, Rakesh; Patil, A S; +2 more

Related Subjects

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

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

Citation Formats

References (33)

Similar Records

Related Subjects

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