Fuel Processing Technology, Vol.86, No.1, 49-59, 2004
Oxidation of dibenzothiophene by laccase or hydrogen peroxide and deep desulfurization of diesel fuel by the later
Enzymatic oxidation of dibenzothiophene (DBT) catalyzed by laccase in the presence of 2,2'-azino-bis-(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) was compared with the chemical oxidation with hydrogen peroxide catalyzed by phosphotungstic acid. Enzymatic oxidation with laccase (2.4 U/ml) of 25 muM DBT with 1.5 mM ABTS required a molar ratio [O-2]/[ABTS] = 140 and 72 h at 40 degreesC in a water-acetonitrile reaction mixture, showing a rate constant of k(1) = -6.3 x 10(-4) min(-1). Whereas peroxide oxidation of 10 mM DBT with 39 muM phosphotungstic acid required only a molar ratio [H2O2]/[DBT] = 2, showing a rate constant of k(2) = -6.1 X 10(-2) min(-1) in a hexane-ethanol system. A sample of diesel fuel, containing 342 ppm of sulfur, was chemically oxidized by an excess of hydrogen peroxide and 119 muM phosphotungstic acid dissolved in ethanol, in less than 3 h at 60 degreesC and atmospheric pressure. No sulfur could be detected in these samples after an additional extraction with an equal volume of ethanol. (C) 2004 Elsevier B.V. All rights reserved.