The Role of Lewis Acid Sites in γ-Al2O3 Oligomerization

Breckner, Christian J.; Pham, Hien N.; Dempsey, Michael G.; Perez‐Ahuatl, Michelle A.; Kohl, Alyssa C.; Lytle, Corryn N.; Datye, Abhaya K.; Miller, Jeffrey T.

doi:10.1002/cphc.202300244

The Role of Lewis Acid Sites in γ-Al₂O₃ Oligomerization

Journal Article · Fri Jun 09 00:00:00 EDT 2023 · ChemPhysChem

DOI:https://doi.org/10.1002/cphc.202300244· OSTI ID:2423699

Breckner, Christian J. ^[1]; Pham, Hien N. ^[2]; Dempsey, Michael G. ^[1]; Perez‐Ahuatl, Michelle A. ^[1]; Kohl, Alyssa C. ^[1]; Lytle, Corryn N. ^[1]; ^[2]; ^[1]

Purdue Univ., West Lafayette, IN (United States)
Univ. of New Mexico, Albuquerque, NM (United States)

Olefin oligomerization by γ-Al₂O₃ has recently been reported, and it was suggested that Lewis acid sites are catalytic. The goal of this study is to determine the number of active sites per gram of alumina to confirm that Lewis acid sites are indeed catalytic. Addition of an inorganic Sr oxide base resulted in a linear decrease in the propylene oligomerization conversion at loadings up to 0.3 wt %; while, there is a >95 % loss in conversion above 1 wt % Sr. Additionally, there was a linear decrease in the intensity of the Lewis acid peaks of absorbed pyridine in the IR spectra with an increase in Sr loading, which correlates with the loss in propylene conversion, suggesting that Lewis acid sites are catalytic. Characterization of the Sr structure by XAS and STEM indicates that single Sr²⁺ ions are bound to the γ-Al₂O₃ surface and poison one catalytic site per Sr ion. The maximum loading needed to poison all catalytic sites, assuming uniform surface coverage, was ~0.4 wt % Sr, giving an acid site density of ~0.2 sites per nm2 of γ-Al₂O₃, or approximately 3 % of the alumina surface.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

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

Grant/Contract Number:: AC02-06CH11357; SC0012704

OSTI ID:: 2423699

Journal Information:: ChemPhysChem, Journal Name: ChemPhysChem Journal Issue: 14 Vol. 24; ISSN 1439-4235

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

References (34)

Polymerisation der Äthylen‐Kohlenwasserstoffe bei hohen Temperaturen und Drucken Ipatiew, W. Berichte der deutschen chemischen Gesellschaft, Vol. 44, Issue 3 https://doi.org/10.1002/cber.191104403146	journal	July 1911
Kinetics of the formation of cyclobutane from ethylene Quick, L. M.; Knecht, D. A.; Back, M. H. International Journal of Chemical Kinetics, Vol. 4, Issue 1 https://doi.org/10.1002/kin.550040105	journal	January 1972
Ene reactions of olefins. I. The addition of ethylene to 2-butene and the decomposition of 3-methylpentene-1 Richard, C.; Scacchi, G.; Back, M. H. International Journal of Chemical Kinetics, Vol. 10, Issue 3 https://doi.org/10.1002/kin.550100307	journal	March 1978
Kinetics of the bimolecular initiation process in the thermal reactions of ethylene Ayranci, G.; Back, M. H. International Journal of Chemical Kinetics, Vol. 13, Issue 9 https://doi.org/10.1002/kin.550130913	journal	September 1981
An infrared study of pyridine adsorbed on acidic solids. Characterization of surface acidity Parry, E. Journal of Catalysis, Vol. 2, Issue 5 https://doi.org/10.1016/0021-9517(63)90102-7	journal	October 1963
In situ FTIR spectra of pyridine adsorbed on SiO2–Al2O3, TiO2, ZrO2 and CeO2: general considerations for the identification of acid sites on surfaces of finely divided metal oxides Zaki, Mohamed I.; Hasan, Muhammad A.; Al-Sagheer, Fakhryia A. Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 190, Issue 3 https://doi.org/10.1016/S0927-7757(01)00690-2	journal	October 2001
Pd/BEA hydrocarbon traps: Effect of hydrothermal aging on trapping properties and Pd speciation Zelinsky, Ryan P.; Dean, David P.; Breckner, Christian J. Applied Catalysis B: Environmental, Vol. 320 https://doi.org/10.1016/j.apcatb.2022.121938	journal	January 2023
Pyridine adsorption on NiSn/MgO–Al2O3: An FTIR spectroscopic study of surface acidity Penkova, Anna; Bobadilla, Luis F.; Romero-Sarria, Francisca Applied Surface Science, Vol. 317 https://doi.org/10.1016/j.apsusc.2014.08.093	journal	October 2014
Probing the acid sites of zeolites with pyridine: Quantitative AGIR measurements of the molar absorption coefficients Zholobenko, Vladimir; Freitas, Cátia; Jendrlin, Martin Journal of Catalysis, Vol. 385, p. 52-60 https://doi.org/10.1016/j.jcat.2020.03.003	journal	May 2020
High-Temperature Conversion of Olefins to Liquid Hydrocarbons on γ-Al₂O₃ Conrad, Matthew A.; DeLine, Jaiden E.; Miller, Jeffrey T. Industrial & Engineering Chemistry Research, Vol. 62, Issue 12 https://doi.org/10.1021/acs.iecr.2c02759	journal	March 2023
Insights into the Nature of Selective Nickel Sites on Ni/Al₂O₃ Catalysts for Propane Dehydrogenation Ma, Rui; Gao, Junxian; Kou, Jiajing ACS Catalysis, Vol. 12, Issue 20 https://doi.org/10.1021/acscatal.2c03240	journal	October 2022
Olefin Disproportionation. A New Catalytic Process Banks, R. L.; Bailey, G. C. I&EC Product Research and Development, Vol. 3, Issue 3 https://doi.org/10.1021/i360011a002	journal	September 1964
Chemistry of olefin oligomerization over ZSM-5 catalyst Quann, Richard J.; Green, Larry A.; Tabak, Samuel A. Industrial & Engineering Chemistry Research, Vol. 27, Issue 4 https://doi.org/10.1021/ie00076a006	journal	April 1988
Thermal Reactions of Gaseous Hydrocarbons Egloff, Gustav; Wilson, Edith Industrial & Engineering Chemistry, Vol. 27, Issue 8 https://doi.org/10.1021/ie50308a017	journal	August 1935
Symposium on the Chemistry of Gaseous Hydrocarbons Cracking and Polymerization of Low Molecular Weight Hydrocarbons Frolich, Per K.; Wiezevich, Peter J. Industrial & Engineering Chemistry, Vol. 27, Issue 9 https://doi.org/10.1021/ie50309a022	journal	September 1935
Pyrolysis and Polymerization of Gaseous Paraffins and Olefins Sullivan, F. W.; Ruthruff, R. F.; Kuentzel, W. E. Industrial & Engineering Chemistry, Vol. 27, Issue 9 https://doi.org/10.1021/ie50309a026	journal	September 1935
Catalytic Reactions of Ethylene Walker, H. W. The Journal of Physical Chemistry, Vol. 31, Issue 7 https://doi.org/10.1021/j150277a001	journal	July 1927
Polymerization and Decomposition of Acetylene Hydrocarbons Egloff, Gustav; Lowry, C. D.; Schaad, R. E. The Journal of Physical Chemistry, Vol. 36, Issue 5 https://doi.org/10.1021/j150335a014	journal	May 1932
Polymerization of Ethylene with Aluminum Chloride Ipatieff, V. N.; Grosse, Aristid V. Journal of the American Chemical Society, Vol. 58, Issue 6 https://doi.org/10.1021/ja01297a019	journal	June 1936
Kinetics of Ethylene Polymerization. II¹ Storch, H. H. Journal of the American Chemical Society, Vol. 57, Issue 12 https://doi.org/10.1021/ja01315a082	journal	December 1935
Kinetics of the Polymerization of Ethylene at Pressures Above one Atmosphere Pease, Robert N. Journal of the American Chemical Society, Vol. 53, Issue 2 https://doi.org/10.1021/ja01353a025	journal	February 1931
THE NON-CATALYTIC POLYMERIZATION AND HYDROGENATION OF ETHYLENE¹ Pease, Robert N. Journal of the American Chemical Society, Vol. 52, Issue 3 https://doi.org/10.1021/ja01366a052	journal	March 1930
Kinetics of the Thermal Reactions of Ethylene¹ Dahlgren, George; Douglas, John E. Journal of the American Chemical Society, Vol. 80, Issue 19 https://doi.org/10.1021/ja01552a028	journal	October 1958
A new nickel complex for the oligomerization of ethylene Peuckert, Marcell; Keim, Wilhelm Organometallics, Vol. 2, Issue 5 https://doi.org/10.1021/om00077a004	journal	May 1983
Olefin oligomerization by main group Ga3+ and Zn2+ single site catalysts on SiO2 LiBretto, Nicole J.; Xu, Yinan; Quigley, Aubrey Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-22512-6	journal	April 2021
Nickel-based solid catalysts for ethylene oligomerization – a review Finiels, Annie; Fajula, François; Hulea, Vasile Catal. Sci. Technol., Vol. 4, Issue 8 https://doi.org/10.1039/C4CY00305E	journal	January 2014
Part II.—Special. Recent progress in thermal polymerisation and condensation of gaseous hydrocarbons Dunstan, A. E. Trans. Faraday Soc., Vol. 32, Issue 0 https://doi.org/10.1039/TF9363200227	journal	January 1936
The velocity of ethylene polymerization at high pressures Laird, R. K.; Morrell, A. G.; Seed, L. Discussions of the Faraday Society, Vol. 22 https://doi.org/10.1039/df9562200126	journal	January 1956
382. The kinetics of the thermal decomposition of olefins. Part I. Propylene Ingold, K. U.; Stubbs, F. J. Journal of the Chemical Society (Resumed) https://doi.org/10.1039/jr9510001749	journal	January 1951
75. The kinetics of the thermal decomposition of olefins. Part II Molera, M. J.; Stubbs, F. J. Journal of the Chemical Society (Resumed) https://doi.org/10.1039/jr9520000381	journal	January 1952
Propane Aromatization over HZSM‐5 and Ga/HZSM‐5 Catalysts Bhan, Aditya; Nicholas Delgass, W. Catalysis Reviews, Vol. 50, Issue 1 https://doi.org/10.1080/01614940701804745	journal	February 2008
The Inner Shell Spectroscopy beamline at NSLS-II: a facility for in situ and operando X-ray absorption spectroscopy for materials research Leshchev, Denis; Rakitin, Maksim; Luvizotto, Bruno Journal of Synchrotron Radiation, Vol. 29, Issue 4 https://doi.org/10.1107/S160057752200460X	journal	May 2022
Kinetics of the thermal reactions of ethylene. Part I Boyd, M. L.; Wu, T-M.; Back, M. H. Canadian Journal of Chemistry, Vol. 46, Issue 14 https://doi.org/10.1139/v68-394	journal	July 1968
Kinetics of the thermal reactions of ethylene Simon, M.; Back, M. H. Canadian Journal of Chemistry, Vol. 47, Issue 2 https://doi.org/10.1139/v69-035	journal	January 1969

Similar Records

Silica-alumina-supported Mo oxide catalysts: Genesis and demise of Bronsted-Lewis acidity

Journal Article · Sat Dec 31 23:00:00 EST 1994 · Journal of Catalysis · OSTI ID:75806

Highly dispersed SiO_x/Al₂O₃ catalysts illuminate the reactivity of isolated silanol sites

Journal Article · Tue Sep 22 20:00:00 EDT 2015 · Angewandte Chemie (International Edition) · OSTI ID:1227425

Molecular Design of Supported MoO_x Catalysts with Surface TaO_x Promotion for Olefin Metathesis

Journal Article · Tue Feb 22 19:00:00 EST 2022 · ACS Catalysis · OSTI ID:1866116

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Lewis acid sites
acid site poisoning
alumina
propylene oligomerization
strontium single sites

The Role of Lewis Acid Sites in γ-Al2O3 Oligomerization

Citation Formats

References (34)

Similar Records

Related Subjects

The Role of Lewis Acid Sites in γ-Al₂O₃ Oligomerization