José E. F. Moraes

Photo-Fenton degradation of wastewater containing organic compounds in solar reactors

Abstract In this work, the photo-Fenton oxidation of phenol in aqueous solutions has been investigated using Fe 2+ , H 2 O 2 and UV–visible light (sunlight). Laboratory-scale experiments were carried out using solar reactors of two different configurations: (1) a concentrating parabolic trough reactor (PTR) and (2) a non-concentrating thin-film reactor. Global solar irradiance was measured during the experiments. Additional laboratory experiments were carried out in an annular photochemical reactor using an artificial light source, at the same experimental conditions. The results indicate that the photo-Fenton process using solar irradiation is an effective treatment for industrial wastewater containing phenol. At low contaminant concentration (TOC 0 =100 ppm), more than 90% of the total organic carbon content of the initial phenol solution could be converted to inorganic carbon within about 3 h of irradiation, using artificial light or sunlight (even on cloudy days), in reactors of different geometry. At moderate or higher phenol concentrations (TOC 0 =550 or 1000 ppm), the results indicate satisfactory TOC removal (45–55%) at reasonable degradation rates. Experiments under different insolation conditions suggest a direct linear dependence of the organic carbon removal on the accumulated sunlight energy reaching the system. Solar light can be used either as a complementary or alternative source of photons to the process.

A mechanistic kinetic model for phenol degradation by the Fenton process.

The objective of this paper is to develop and validate a mechanistic model for the degradation of phenol by the Fenton process. Experiments were performed in semi-batch operation, in which phenol, catechol and hydroquinone concentrations were measured. Using the methodology described in Pontes and Pinto [R.F.F. Pontes, J.M. Pinto, Analysis of integrated kinetic and flow models for anaerobic digesters, Chemical Engineering Journal 122 (1-2) (2006) 65-80], a stoichiometric model was first developed, with 53 reactions and 26 compounds, followed by the corresponding kinetic model. Sensitivity analysis was performed to determine the most influential kinetic parameters of the model that were estimated with the obtained experimental results. The adjusted model was used to analyze the impact of the initial concentration and flow rate of reactants on the efficiency of the Fenton process to degrade phenol. Moreover, the model was applied to evaluate the treatment cost of wastewater contaminated with phenol in order to meet environmental standards.

Laser flash photolysis study of the photocatalytic step of the photo-fenton reaction in saline solution.

Abstract The photo-Fenton reaction (Fe2+/Fe3+, H2O2, UV light) is strongly inhibited by high concentrations of added chloride ion. In this work, the effect of added chloride ion on the photocatalytic step that converts Fe(III) back to Fe(II) is studied by nanosecond laser flash photolysis over a wide range of pH (1.0–3.3) and concentrations of Fe(III) (0.1–1.0 mM) and chloride ion (0.05–0.75 M). An explicit mechanistic model based on the preferential formation of the less-reactive Cl2·− radical anion via two routes (competitive photolysis of the iron(III)-chloride complex to chlorine atoms instead of the desired hydroxyl radical and pH-dependent scavenging of the hydroxyl radical by chloride ion) is proposed. This model, which fits the laser flash photolysis data for the production and decay of Cl2·− over the entire range of conditions investigated, suggests that inhibition of the photocatalytic step of the photo-Fenton process in the presence of chloride ion can be circumvented by maintaining the pH of the medium at or slightly above 3.0 throughout the reaction.

Fundamental Mechanistic Studies of the Photo-Fenton Reaction for the Degradation of Organic Pollutants

Very few regions of the planet possess abundant fresh water and access to adequate fresh water resources can be expected to worsen as a result of population growth and industrial demands for water. Liquid effluents containing toxic substances are generated by a variety of chemistry-related industrial processes, as well as by a number of common household or agricultural applications. The inadequate management of these residues can cause contamination of the soil and of subterranean and surface water sources. In general, the recovery of industrial effluents containing low levels of organic substances by conventional treatments is not economically viable. Thus, for example, removal of the pollutant by adsorption onto active charcoal, while often efficient, requires subsequent recovery or incineration of the charcoal and merely transfers the pollutant from one phase to another (Matthews, 1992). Substances that are biocides or that are non-biodegradable represent a particular threat to the environment and prevent the use of conventional biological treatments. Social and legal demands for environmental safety increasingly require that effluents discharged into the environment have minimal impact on human health, natural resources and the biosphere. These demands have fueled increasing research into the development of new, more effective and economically viable methods for pollution control and prevention. When applied to the degradation of pollutants, these reactions are usually grouped together under the designations of Advanced Oxidation Processes (AOP) or Advanced Oxidation Technologies (AOT).

Photo-Fenton oxidation of phenol and organochlorides (2,4-DCP and 2,4-D) in aqueous alkaline medium with high chloride concentration

A highly concentrated aqueous saline-containing solution of phenol, 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4-dichlorophenol (2,4-DCP) was treated by the photo-Fenton process in a system composed of an annular reactor with a quartz immersion well and a medium-pressure mercury lamp (450 W). The study was conducted under special conditions to minimize the costs of acidification and neutralization, which are usual steps in this type of process. Photochemical reactions were carried out to investigate the influence of some process variables such as the initial concentration of Fe(2+) ([Fe(2+)](0)) from 1.0 up to 2.5 mM, the rate in mmol of H(2)O(2) fed into the system (FH(2)O(2);in) from 3.67 up to 7.33 mmol of H(2)O(2)/min during 120 min of reaction time, and the initial pH (pH(0)) from 3.0 up to 9.0 in the presence and absence of NaCl (60.0 g/L). Although the optimum pH for the photo-Fenton process is about 3.0, this particular system performed well in experimental conditions starting at alkaline and neutral pH. The results obtained here are promising for industrial applications, particularly in view of the high concentration of chloride, a known hydroxyl radical scavenger and the main oxidant present in photo-Fenton processes.

Photolysis of ferric ions in the presence of sulfate or chloride ions: implications for the photo-Fenton process

The photo-Fenton process (Fe(2+)/Fe(3+), H(2)O(2), UV light) is one of the most efficient and advanced oxidation processes for the mineralization of the organic pollutants of industrial effluents and wastewater. The overall rate of the photo-Fenton process is controlled by the rate of the photolytic step that converts Fe(3+) back to Fe(2+). In this paper, the effect of sulfate or chloride ions on the net yield of Fe(2+) during the photolysis of Fe(3+) has been investigated in aqueous solution at pH 3.0 and 1.0 in the absence of hydrogen peroxide. A kinetic model based on the principal reactions that occur in the system fits the data for formation of Fe(2+) satisfactorily. Both experimental data and model prediction show that the availability of Fe(2+) produced by photolysis of Fe(3+) is inhibited much more in the presence of sulfate ion than in the presence of chloride ion as a function of the irradiation time at pH 3.0.

Photo-Fenton degradation of phenol, 2,4-dichlorophenoxyacetic acid and 2,4-dichlorophenol mixture in saline solution using a falling-film solar reactor

In this work, a saline aqueous solution of phenol, 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4-dichlorophenol (2,4-DCP) was treated by the photo-Fenton process in a falling-film solar reactor. The influence of the parameters such as initial pH (5–7), initial concentration of Fe2+ (1–2.5 mM) and rate of H2O2 addition (1.87–3.74 mmol min−1) was investigated. The efficiency of photodegradation was determined from the removal of dissolved organic carbon (DOC), described by the species degradation of phenol, 2,4-D and 2,4-DCP. Response surface methodology was employed to assess the effects of the variables investigated, i.e. [Fe2+], [H2O2] and pH, in the photo-Fenton process with solar irradiation. The results reveal that the variables’ initial concentration of Fe2+ and H2O2 presents predominant effect on pollutants’ degradation in terms of DOC removal, while pH showed no influence. Under the most adequate experimental conditions, about 85% DOC removal was obtained in 180 min by using a reaction system employed here, and total removal of phenol, 2,4- and 2,4-DCP mixture in about 30 min.

Application of artificial neural network for modeling of phenol mineralization by photo-Fenton process using a multi-lamp reactor.

An artificial neural network (ANN) was implemented for modeling phenol mineralization in aqueous solution using the photo-Fenton process. The experiments were conducted in a photochemical multi-lamp reactor equipped with twelve fluorescent black light lamps (40 W each) irradiating UV light. A three-layer neural network was optimized in order to model the behavior of the process. The concentrations of ferrous ions and hydrogen peroxide, and the reaction time were introduced as inputs of the network and the efficiency of phenol mineralization was expressed in terms of dissolved organic carbon (DOC) as an output. Both concentrations of Fe(2+) and H2O2 were shown to be significant parameters on the phenol mineralization process. The ANN model provided the best result through the application of six neurons in the hidden layer, resulting in a high determination coefficient. The ANN model was shown to be efficient in the simulation of phenol mineralization through the photo-Fenton process using a multi-lamp reactor.