Syed Naqvi - Selective Homogeneous Oxidation System for Producing Hydroperoxides Concentrate: Kinetics of Catalytic Oxidation of Gas Oils

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      Ind. Eng. Chem. Res. 48, 5642 (2009)


      A selective and mild (55oC and 50 psig) homogeneous   oxidation system has been described to produce hydroperoxides   from a narrow cut made from typical gas oil. During this process   oil, dissolved in wet acetic acid, is treated with air in the   presence of the redox couple Co(III)/Co(II) (Partially Oxidized   Catalyst, POC). A straightforward route to POC consists of   oxidizing Co(II) in wet acetic acid with calculated aqueous   potassium chlorate. Initiation is the manifestation of the potent   oxidizing ability of Co(III) towards generating alkyl radicals   from hydrocarbons in the oil. Classical propagation then leads to   assorted hydroperoxides, simultaneously decomposed by POC.   Kinetics of the simultaneous formation and decomposition of   hydroperoxides, under varying sets of process and composition   variables, was studied in an isothermal, mechanically-agitated,   semi-batch reactor, operating in the pure kinetic regime. A   unique kinetic model, based on a rare irreversible consecutive   reaction network (pseudo first order formation of hydroperoxides   followed by their second order decomposition), has been found to   reasonably describe the kinetic data (R2=0.9214). This   kinetic model allowed the evaluation of the formation and   decomposition rate constants that permitted the estimation of   conversion of oil and selectivity to hydroperoxides.  On   average 15.12±3.23% conversion was achieved in 9.3±4.0 minutes   with 99.86±0.23, 92.88±7.95 and 28.77±11.67% selectivities for   0.10, 1.00, and 10.0% conversions respectively.

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