Publication Details (including relevant citation information):
Ind. Eng. Chem. Res. 49, 7210 (2010)
Homogeneous production of hydroperoxides concentrate has been simulated via multivariate calibration of yield data, obtained during an earlier study [Naqvi S. M. D.; Khan F. Ind. Eng. Chem. Res. 2009, 48, 5642] made on the air oxidation of diluted gas oils in the presence of chemically generated redox couple Co(III)/Co(II). Principal component analysis has been applied to abstract dynamic hydroperoxides yield data that provides the basis for the simulation. A novel chemometric technique, inverse nonlinear principal component regression, has been introduced to simulate experimental yield profiles with exceptional accuracy (R2 = 0.9841). Simulated yield profiles have then been subjected to Levenberg-Marquardt method in order to estimate the rate constants for formation and decomposition of hydroperoxides. These estimations have permitted the development of two reasonably accurate multivariate global models that relate the specific rates, for formation (R2 = 0.8873) and decomposition (R2 = 0.9504) of hydroperoxides, to process and composition variables. Construction of such models allows the specific rates to be optimized so that the reactor could be operated at an oil conversion (up to ≈ 5%) that is almost proportional to the yield of hydroperoxides ensuring selectivity ≈ 88%.
Address (URL): http://pubs.acs.org/doi/abs/10.1021/ie100327m