Chromic acid silica support

The Phillips Cr/silica catalyst is prepared by impregnating a chromium compound (commonly chromic acid) onto a support material, most commonly a wide-pore silica, and then calcining in oxygen at 923 K. In the industrial process, the formation of the propagation centers takes place by reductive interaction of Cr(VI) with the monomer (ethylene) at about 423 K [4]. This feature makes the Phillips catalyst unique among all the olefin polymerization catalysts, but also the most controversial one [17]. 

The Cr/Si02 catalyst is made by spin-coat impregnation of the flat silica support with a solution of chromic acid in water. Figure 9.25 shows the Cr XPS spectrum of the catalyst after drying. Chromium is present as a hydrated Cr(VI) oxide, with a Cr 2p binding energy characteristic of chromate species, as the reference spectra in the lower half of the figure show. An essential step in the... 

Chromic acid is a very strong oxidizing agent, but its reactivity may be tempered by adsorption onto a support. Chromic acid on alumina was found to be inactive,but on silica it gives instantaneous oxidation, in diethyl ether at room temperature, of primary and secondary alcohols to aldehydes and ketones in good to excellent yield. This reagent can also be conveniently used in the form of a column. 

Several references have appeared on the use of solid-phase oxidants. Solid potassium permanganate-copper sulphate mixtures oxidize secondary alcohols to ketones in high yield, and pyridinium chromate or chromic acid on silica gel are described as convenient off-the-shelf reagents for oxidation of both primary and secondary alcohols. Anhydrous chromium trioxide-celite effects similar transformations only when ether is present as co-solvent. An excellent review, with over 400 references, on supported oxidants covers the use of silver carbonate-celite, chromium trioxide-pyridine-celite, ozone-silica, chromyl chloride-silica, chromium trioxide-graphite, manganese dioxide-carbon, and potassium permanganate-molecular sieve. 

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