Amilcar Machulek

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.

Surfactant degradation by a catechol-driven Fenton reaction

The addition of 0.5mM catechol is shown to accelerate the degradation and mineralization of the anionic surfactant DowFax 2A1 (sodium dodecyldiphenyloxide disulfonate) under conventional Fenton reaction conditions (Fe(II) plus H(2)O(2) at pH 3). The catalytic effect causes a 3-fold increase in the initial rate (up to ca. 20 min) of conversion of the surfactant to oxidation products (apparent first-order rate constants of 0.021 and 0.061 min(-1) in the absence and presence of catechol, respectively). Although this catalytic rate increase persists for a certain amount of time after complete disappearance of catechol itself (ca. 8 min), the reaction rate begins to decline slowly after the initial 20 min towards that observed in the absence of added catechol. Total organic carbon (TOC) measurements of net mineralization and cyclic voltammetric and high performance liquid chromatographic (HPLC) measurements of the initial rate of reaction of catechol and the surfactant provide insight into the role of catechol in promoting the degradation of the surfactant and of degradation products as the eventual inhibitors of the Fenton 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.

Application of Different Advanced Oxidation Processes for the Degradation of Organic Pollutants

Water is not only an economic, but also an increasingly important social commodity. Potable water is an essential resource for sustaining economic and social development in all sectors. A safe water supply and appropriate sanitation are the most essential components for a healthy and prosperous life. However, increases in human activities have led to exposure of the aqueous environment to chemical, microbial and biological pollutants as well as to micropollutants. Thus, 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.

Mechanistic implications of zinc(II) ions on the degradation of phenol by the fenton reaction

A study of the interference of Zn2+ ions on phenol degradation by Fenton reaction (Fe2+/Fe3+ + H2O2) is reported. One of the first intermediates formed in the reaction, catechol, can reduce Fe3+ to Fe2+ and, in the presence of H2O2 initiates an efficient catalytic redox cycle. In the initial stages of the reaction, this catechol-mediated cycle becomes the principal route of thermal degradation of phenol and its oxidation products. The Zn2+ ion addition enhances the persistence time of catechol, probably by stabilization of the corresponding semiquinone radical via complexation.

Interference of inorganic ions on phenol degradation by the Fenton reaction

The addition of Cu2+ ions to the classical Fenton reaction (Fe2+ plus H2O2 at pH 3) is found to accelerate the degradation of organic compounds. This synergic effect causes an approximately 15 % additional reduction of the total organic carbon (TOC), representing an overall improvement of the efficiency of the mineralization of phenol. Although Fe2+ exhibits a high initial rate of degradation, the degradation is not complete due to the formation of compounds refractory to the hydroxyl radical. The interference of copper ions on the degradation of phenol by the Fenton reaction was investigated. In the presence of Cu2+, the degradation is slower, but results in a greater reduction of TOC at the end of the reaction (t = 120 min). In the final stages of the reaction, when the Fe3+ in the solution is complexed in the form of ferrioxalate, the copper ions assume the role of the main catalyst of the degradation

Synthesis and Characterization of Mesoporous Nb2O5 and Its Application for Photocatalytic Degradation of the Herbicide Methylviologen

This article reports the characterization of mesoporous Nb2O5 synthesized by the sol-gel method for application in photocatalysis. The emerging contaminant methylviologen was employed for photocatalytic tests. Parameters inherent to the synthesis process, such as stirring rate, aging temperature, and calcination temperature, were employed for a range of values to improve the synthetic route. The powders obtained were characterized by thermogravimetric analysis, X-ray diffraction, scanning and transmission electron microscopy, specific surface area, infrared spectroscopy, energy-dispersive spectroscopy, and diffuse reflectance spectroscopy. In samples calcined at 450 °C, a mixture of amorphous and hexagonal phases was observed, with a predominance of the former, while in samples calcined at 650 °C the orthorhombic phase predominated. Samples calcined at 450 °C exhibited larger specific surface areas. Mesoporous structures were confirmed for samples T8035M450 and T8045mi450, which displayed higher photoactivity, with roughly 90% removal of methylviologen.