Wet Peroxide Oxidation of Chlorobenzenes Catalyzed by Goethite and Promoted by Hydroxylamine

In this work, the abatement of several chlorobenzenes commonly found as pollutants in the aqueous phase has been carried out by catalytic wet peroxide oxidation using goethite as the catalyst and hydroxylamine as the promotor. Spiked water with monochlorobenzene and different positional isomers of dichlorobenzene, trichlorobenzene, and tetrachlorobenzene, at concentrations ranging from 0.4 to 16.9 mg L-1 was treated. Runs were carried out batch-way, at room conditions, without headspace. The heterogeneous catalyst was commercial goethite, with a specific surface area (S-BET) of 10.24 m(2) g(-1) and a total iron content of 57.3 wt%. Iron acts as a catalyst of hydrogen peroxide decomposition to hydroxyl radicals. Hydroxylamine (in a range from 0 to 4.9 mM) was added to enhance the iron redox cycle from Fe (III) to Fe (II), remarkably increasing the radical production rate and therefore, the conversion of chlorobenzenes. Iron was stable (not leached to the aqueous phase) even at the lowest pH tested (pH = 1). The effect of pH (from 2 to 7), hydrogen peroxide (from 1 to 10 times the stoichiometric dosage), hydroxylamine, and catalyst concentration (from 0.25 to 1 g/L) was studied. Pollutant removal increased with hydroxylamine and hydrogen peroxide concentration. An operating conditions study demonstrated that the higher the hydroxylamine and hydrogen peroxide concentrations, the higher the removal of pollutants. The optimal pH value and catalyst concentration was 3 and 0.5 g L-1, respectively. Operating with 2.4 mM of hydroxylamine and 10 times the stoichiometric H2O2 amount, a chlorobenzenes conversion of 90% was achieved in 2.5 h. Additionally, no toxic byproducts were obtained.