In this study, flat-type photocatalytic reaction system is applied to reduce toxic hexavalent chromium (Cr(VI)) to trivalent chromium (Cr(III)) in aqueous solution under UV irradiation. To overcome the limitation of conventional photocatalysis, a novel approach toward photocatalytic system for reduction of hexavalent chromium including nanotubular TiO2 (NTT) on two kinds of titanium substrates (foil and mesh) were established. In addition, modified Ti substrates were prepared by bending treatment to increase reaction efficiency of Cr(VI) in the flat-type photocatalytic reactor. For the fabrication of NTT on Ti substrates, Ti foil and mesh was anodized with mixed electrolytes (NH4F-H2O-C2H6O2) and then annealed in ambient oxygen. The prepared NTT arrays were uniformly grown on two Ti substrates and surface property measurements were performed through SEM and XRD. Hydraulic retention time(HRT) and substrate type were significantly affected the Cr(VI) reduction. Hence, the photocatalytic Cr(VI) reduction was observed to be highest up to 95% at bended(modified) Ti mesh and lowest HRT. Especially, Ti mesh was more effective as NTT substrate in this research.

A carbonaceous sorbent was prepared from rice husk via sulphuric acid treatment. After preparation and washing, the wet carbon with moisture content 85% was used in its wet status in this study due to its higher reactivity towards Cr(VI) than the dry carbon. The interaction of Cr(VI) and the carbon was studied and two processes were investigated in terms of kinetics and equilibrium namely Cr(VI) removal and chromium sorption. Cr(VI) removal and chromium sorption were studied at various initial pH (1.6-7), for initial Cr(VI) concentration (100 mg/l). At equilibrium, maximum Cr(VI) removal occurred at low initial pH (1.6-2) where, Cr(III) was the only available chromium species in solution. Cr(VI) removal, at such low pH, was related to the reduction to Cr(III). Maximum chromium sorption (60.5 mg/g) occurred at initial pH 2.8 and a rise in the final pH was recorded for all initial pH studied. For the kinetic experiments, approximate equilibrium was reached in 60-100 hr. Cr(VI) removal data, at initial pH 1.6-2.4, fit well pseudo first order model but did not fit pseudo second order model. At initial pH 2.6-7, Cr(VI) removal data did not fit, anymore, pseudo first order model, but fit well pseudo second order model instead. The change in the order of Cr(VI) removal process takes place in the pH range 2.4-2.6 under the experimental conditions. Other two models were tested for the kinetics of chromium sorption with the data fitting well pseudo second order model in the whole range of pH. An increase in cation exchange capacity, sorbent acidity and base neutralization capacity was recorded for the carbon sorbent after the interaction with acidified Cr(VI) indicating the oxidation processes on the carbon surface accompanying Cr(VI) reduction.

The effect of temperature on the removal process of Cr(VI) ion contained in wastewater by a precipitation method has been investigated for the improvement of its design and operation. The distribution diagram of chromium ion was constructed by employing the MINTEQ program and the quantitative feature of Cr(VI) depending on pH was investigated. As the temperature increases, the relative amount of H2CrO4 was examined to be raised and the pH range in which H2CrO4 exists as a stable form was also investigated to be extended according to the temperature. Cr(VI) ion was shown to be changed from HCrO4 − to Cr2O7 2− as the concentration of Cr(VI) ion is increased in the neutral pH condition and the concentration of Cr(VI) ion which is necessary for the ionic transformation was observed to rise in the acidic and alkaline conditions. The major reactant which involved in the reduction reaction for the removal of Cr(VI) ion was examined to be HCrO4 − and the reduction of Cr(VI) ion to Cr(III) ion was investigated to be influenced much by the temperature change at higher pH conditions. The reduction reaction of Cr(VI) ion for its removal as a precipitate was examined to be promoted as the temperature decreases and pH is lowered. In addition, the stable region of Cr(OH)3 was shown to be enlarged with temperature based on the thermodynamic estimation and it was thought to be necessary to design and control the precipitating process of Cr(VI) ion by considering the thermal characteristics of reduction and precipitation stage.