Epoxidation of 1-octene under harsh tail-end conditions in a flow reactor I: a comparative study of crystalline vs. amorphous catalystsElectronic supplementary information (ESI) available. See DOI: 10.1039/c7re00076f
Amorphous silica versus crystalline delaminated-zeolite catalysts consisting of grafted Ti( iv ) Lewis-acid active sites were investigated from the perspective of 1-octene olefin epoxidation with ethylbenzene hydroperoxide (EBHP) as oxidant. Reactions were performed at conditions of temperature and...
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Format | Journal Article |
Language | English |
Published |
29.11.2017
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Abstract | Amorphous silica
versus
crystalline delaminated-zeolite catalysts consisting of grafted Ti(
iv
) Lewis-acid active sites were investigated from the perspective of 1-octene olefin epoxidation with ethylbenzene hydroperoxide (EBHP) as oxidant. Reactions were performed at conditions of temperature and concentrations of organic hydroperoxide and inhibitors (epoxide product and alcohol co-product) that mimic the harsh conditions found at the tail-end of the flow reactor for industrial propylene-oxide (PO) synthesis, where there is a current need to improve activity and selectivity, because of deactivation. Catalyst synthesis was performed by grafting a Ti-alkoxide precursor onto framework vacancies ("silanol nests") of the delaminated zeolite UCB-4, as well as onto amorphous SiO
2
. Both catalysts were characterized by powder X-ray diffraction (PXRD), nitrogen physisorption at 77 K, and UV-visible spectroscopy before and after catalysis. Experiments at different conversions were performed, and show that crystalline Ti-UCB-4 exhibits a ∼9% higher average selectivity (73%
versus
64%) and greater conversion, stability, and robustness upon increasing time on stream relative to amorphous Ti-SiO
2
. UV-vis spectra are discussed for fresh, spent, and spent/calcined materials and demonstrate that Ti sites in Ti-UCB-4 exist as isolated grafted complexes with four-fold coordination to the zeolite framework, whereas Ti-SiO
2
consists of grafted Ti-sites on the silica surface, some of which are isolated but a dominant proportion of which are TiO
2
oligomers. The observed increased stability of the crystalline catalyst under tail-end reactor conditions is attributed to the surface pockets of the crystalline material, in which Ti is grafted.
The crystalline Ti-UCB-4 epoxidation catalyst is more active, selective, and stable than the amorphous Ti-SiO
2
. |
---|---|
AbstractList | Amorphous silica
versus
crystalline delaminated-zeolite catalysts consisting of grafted Ti(
iv
) Lewis-acid active sites were investigated from the perspective of 1-octene olefin epoxidation with ethylbenzene hydroperoxide (EBHP) as oxidant. Reactions were performed at conditions of temperature and concentrations of organic hydroperoxide and inhibitors (epoxide product and alcohol co-product) that mimic the harsh conditions found at the tail-end of the flow reactor for industrial propylene-oxide (PO) synthesis, where there is a current need to improve activity and selectivity, because of deactivation. Catalyst synthesis was performed by grafting a Ti-alkoxide precursor onto framework vacancies ("silanol nests") of the delaminated zeolite UCB-4, as well as onto amorphous SiO
2
. Both catalysts were characterized by powder X-ray diffraction (PXRD), nitrogen physisorption at 77 K, and UV-visible spectroscopy before and after catalysis. Experiments at different conversions were performed, and show that crystalline Ti-UCB-4 exhibits a ∼9% higher average selectivity (73%
versus
64%) and greater conversion, stability, and robustness upon increasing time on stream relative to amorphous Ti-SiO
2
. UV-vis spectra are discussed for fresh, spent, and spent/calcined materials and demonstrate that Ti sites in Ti-UCB-4 exist as isolated grafted complexes with four-fold coordination to the zeolite framework, whereas Ti-SiO
2
consists of grafted Ti-sites on the silica surface, some of which are isolated but a dominant proportion of which are TiO
2
oligomers. The observed increased stability of the crystalline catalyst under tail-end reactor conditions is attributed to the surface pockets of the crystalline material, in which Ti is grafted.
The crystalline Ti-UCB-4 epoxidation catalyst is more active, selective, and stable than the amorphous Ti-SiO
2
. |
Author | Aigner, Martina Zones, Stacey Okrut, Alexander Grosso-Giordano, Nicolás Andrés Katz, Alexander |
AuthorAffiliation | Chevron Energy Technology Company University of California at Berkeley Department of Chemical and Biomolecular Engineering |
AuthorAffiliation_xml | – name: Department of Chemical and Biomolecular Engineering – name: University of California at Berkeley – name: Chevron Energy Technology Company |
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References_xml | – issn: 2007 publication-title: Titanium catalyst, its preparation and its use in epoxidation reactions doi: Buijink Van – issn: 2017 publication-title: Highly active, selective, accessible, and robust zeolitic Sn-baeyer-villiger oxidation catalyst doi: Ouyang Zones Katz – issn: 2011 publication-title: Ullmann's Encyclopedia of Industrial Chemistry doi: Kahlich Wiechern Lindner – issn: 2006 publication-title: Molecular sieve SSZ-70 composition of matter and synthesis thereof doi: Zones Burton – issn: 2012 publication-title: Ullmann's Encyclopedia of Industrial Chemistry doi: Baer Bergamo Forlin Pottenger Lindner – issn: 2008 publication-title: Propylene epoxidation via Shell's SMPO process: 30 years of research and operation doi: Buijink Lange Bos Horton Niele – issn: 2000 publication-title: Kirk-Othmer Encyclopedia of Chemical Technology doi: Trent |
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versus
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iv
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Title | Epoxidation of 1-octene under harsh tail-end conditions in a flow reactor I: a comparative study of crystalline vs. amorphous catalystsElectronic supplementary information (ESI) available. See DOI: 10.1039/c7re00076f |
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