4.2 Article

Biomass toward fine chemical products: Oxidation of a.-pinene over sieves nanostructured modified with vanadium

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JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL
卷 404, 期 -, 页码 65-73

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DOI: 10.1016/j.molcata.2015.04.009

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  1. CONICET
  2. UTN-FRC

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Vanadium-containing molecular sieves (V-M(x)) were synthetized and applied as heterogeneous catalysts for the liquid phase oxidation of a-pinene with hydrogen peroxide at 70 degrees C. It has been found that the vanadium content in V-M(x) materials affected the conversion of a-pinene and product distribution. The turnover numbers increased strongly with the decreasing of V content probably caused by a high V dispersion. The major products were verbenone, trans-sobrerol and campholenic aldehyde. The acid-base properties of V-M(x) affected the distribution of products formed via the isomerization of a-pinene oxide over Lewis acid sites to campholenic aldehyde while Bronsted acid sites brought about the formation of 1,2 pinanediol and trans-sobrerol by hydrolysis and by the opening of oxirane ring. The increase in V content in V-M(x) led to the increase in campholenic aldehyde, 1,2 pinanediol, trans- sobrerol and over oxidation products. Moreover, the effect of several solvents on the reaction oxidation was studied. The results showed that the highest a-pinene conversions are obtained in the following order: acetonitrile > ethanol > isoamyl alcohol > methyl ethyl ketone. Thus, using aprotic solvents, the catalytic activity was increased and the formation of alkyl glycol ethers as by-product was not observed. (C) 2015 Elsevier B.V. All rights reserved.

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