Reactor modeling in heterogeneous photocatalysis: toxicity and biodegradability assessment.

Photocatalysis employing titanium dioxide is a useful method to degrade a wide variety of organic and inorganic pollutants from water and air. However, the application of this advanced oxidation process at industrial scale requires the development of mathematical models to design and scale-up photocatalytic reactors. In the present work, intrinsic kinetic expressions previously obtained in a laboratory reactor are employed to predict the performance of a bench scale reactor of different configuration and operating conditions. 4-Chlorophenol was chosen as the model pollutant. The toxicity and biodegradability of the irradiated mixture in the bench photoreactor was also assessed. Good agreement was found between simulation and experimental data. The root mean square error of the estimations was 9.9%. The photocatalytic process clearly enhances the biodegradability of the reacting mixture, and the initial toxicity of the pollutant was significantly reduced by the treatment.

Degradation of a mixture of pollutants in water using the UV/H2O2 process.

The degradation reaction of a simple mixture of pollutants (dichloroacetic acid + formic acid) employing H2O2 and UVC radiation (253.7 nm) has been studied in a well-mixed reactor which operates inside a recycling system. The aim of this work is to develop a systematic methodology for treating degradation of mixtures of pollutants, starting from a rather manageable system to more complex aggregates. In this contribution, the effects of different variables such as hydrogen peroxide/pollutant mixture initial concentration ratio, pH and incident radiation at the reactor wall were studied. The results show that the best degrading conditions are: pH = 3.5 and hydrogen peroxide concentrations from 3.9 to 11.8 mM (134-400 mg/L), for initial concentrations of 1.10 and 0.39 mM for formic acid and dichoroacetic acid respectively (50 mg/L for both pollutants). The influence of the incident radiation at the reactor wall on the degradation rates of the mixture is significant. In addition to this, it has been shown that in the employed aqueous solution no stable reaction intermediates are formed. On this basis, a complete reaction scheme for the mixture is proposed that is suitable for a reaction kinetics mathematical modeling of the mixture and further studies of increasing complexity.

Quantum efficiencies in a multi-annular photocatalytic reactor.

Radiative energy efficiencies of a multi-annular photocatalytic reactor were evaluated and analysed. The total quantum efficiency, defined as the ratio of the number of molecules of the pollutant reacted to the number of photons emitted by the lamp, is expressed as the product of three factors: (i) the reactor radiation incidence efficiency, (ii) the catalyst radiation absorption efficiency, and (iii) the overall reaction quantum efficiency. By means of a detailed mathematical model, the numerical values of each one were 83, 92, and 0-2.5%, respectively. The dependence of the overall reaction quantum efficiency upon operating variables was also studied.

Modelling the kinetics of UV/H2O2 oxidation of dichloroacetic acid.

The intrinsic reaction kinetics of the decomposition of dichloroacetic acid (DCA) using UV/H2O2 was studied. A complete mathematical model, including the effect of the absorbed radiation intensities and H2O2 concentration was developed. The results of the kinetic measurements were analysed using a complete mathematical model of the experimental device that was used for the laboratory operation (a differential reactor inside a recycle). In this way it was expected to obtain intrinsic kinetic parameters. Experimental data agree well with theoretical predictions esmploying just two kinetic parameters derived from the proposed reaction mechanism.

Water decolorization using UV radiation and hydrogen peroxide: a kinetic study.

Sometimes, provision of water for domiciliary consumption faces the problem of natural contamination originated by the presence of organic substances such as humic or fulvic acids. Very often, after conventional sanitary treatments this water exhibits a persistent yellowish coloration that affects its use. Moreover, these substances may act as precursors of tri-halomethanes formation during pre-disinfection with chlorine. This paper presents, with a simplified mechanistic approach, the intrinsic reaction kinetics of natural water decolorization employing UV radiation and hydrogen peroxide. The main variables for the model are: contaminant concentration expressed as TOC, hydrogen peroxide concentration and the photon absorption rate.

Reactor scale-up in AOPs: from laboratory to commercial scale.

A procedure to scale-up photoreactors employed in AOPs using laboratory information has been developed. Operating with a model compound the proposed procedure was applied to the decomposition of formic acid in water solution using hydrogen peroxide and UV radiation. With laboratory experiments the parameters of the kinetic equation were obtained in a small batch reactor operated within a recycling apparatus. The whole system was modeled employing radiation and mass balances. These balances were used together with a non-linear parameter estimator to derive the model kinetic constants. Then, these results were used in the modeling of the large-scale reactor to predict exit conversions in an isothermal, continuous, tubular flow reactor that is 2 m long and has a volume of 12 I. Once more, radiation and mass balances were used to predict formic acid output concentrations. Experimental data in the large-scale apparatus are in good agreement with theoretical predictions.

Glyphosate degradation in water employing the H2O2/UVC process.

Glyphosate is the organophosphate herbicide most widely used in the world. Any form of spill or discharge, even if unintentional, can be transferred to the water due to its high solubility. The combination of hydrogen peroxide and UV radiation could be a suitable option to decrease glyphosate concentration to acceptable limits. In this work, the effects of initial pH, hydrogen peroxide initial concentration, and incident radiation in glyphosate degradation were studied. The experimental device was a cylinder irradiated with two tubular, germicidal lamps. Conversion of glyphosate increases significantly from pH = 3-7. From this value on, the increase becomes much less noticeable. The reaction rate depends on the initial herbicide concentration and has an optimum plateau of a hydrogen peroxide to glyphosate molar concentration ratio between 7 and 19. The expected non linear dependence on the irradiation rate was observed. The identification of critical reaction intermediaries, and the quantification of the main end products were possible and it led to propose a plausible degradation path. The achieved quantification of the mineralization extent is a positive indicator for the possible application of a rather simple technology for an in situ solution for some of the problems derived from the intensive use of glyphosate.

Comparison of H2O2/UV and heterogeneous photocatalytic processes for the degradation of dichloroacetic acid in water.

A comparative study between two advanced oxidation technologies for pollutant degradation has been made. With the use of dichloroacetic acid (DCA) as the model pollutant, the reactions with hydrogen peroxide and UV radiation (H2O2/UV, 253.7 nm) and photocatalysis with titanium dioxide (TiO2/UV, 300-400 nm) are analyzed. Three criteria have been selected to compare the performances of both processes: (i) the percentage conversion of DCA and TOC (total organic carbon) at a fixed reaction time; (ii) the quantum efficiency, employing the true radiation absorption rates for both activated species (H2O2 and TiO2); (iii) the specific energy consumption to degrade 50% of the initial TOC. The optimal molar concentration ratio of H2O2/DCA and the optimal catalyst concentration have been employed in the experiments. The results indicate that, under the optimal operating conditions, the H2O2/UV process exhibits, by a large difference, the best performance taking into account the above-mentioned criteria. Nevertheless, both systems show similar values of specific energy consumption when a thinner reactor is employed. These results cannot be safely extrapolated to other contexts if (i) other compounds of different structure are degraded and (ii) a different catalyst is used. Moreover, they were obtained under optimized conditions, and typical, real-life situations may render quite different results due to the robustness of the titanium dioxide operation. They should serve as an indication that, under the studied conditions, a much-improved catalyst performance must be achieved to parallel, with a heterogeneous process, a yield similar to the one obtained with the homogeneous system.