Evaluating the catalytic effect of Fe@Fe2O3-modified granulated cork as an innovative heterogeneous catalyst in electro-fenton degradation of benzoquinone in different aqueous matrices.

This study investigated the potential of a novel biomass-derived cork as a suitable catalyst after its modification with Fe@Fe2O3 for in-situ application in heterogeneous electro-Fenton (HEF) process for benzoquinone (BQ) elimination from water. No attempts on the application of modified granulated cork (GC) as a suspended heterogeneous catalyst in the HEF process for water treatment have been published yet. GC was modified by sonification approach in a FeCl3 + NaBH4 solution to reduce the ferric ions to metallic iron in order to obtain Fe@Fe2O3-modified GC (Fe@Fe2O3/GC). Results clearly demonstrated that this catalyst exhibited excellent electrocatalytic properties, such as a high conductivity as well as relatively high redox current and possessed several active sites for water depollution applications. Using Fe@Fe2O3/GC as catalyst in HEF, 100% of BQ removal was achieved in synthetic solutions by applying 33.3 mA cm-2 after 120 min. Different experimental conditions were tested to determine that best possible conditions can be as follow: 50 mmol L-1 Na2SO4 and 10 mg L-1 of Fe@Fe2O3/GC catalyst using Pt/carbon-PTFE air diffusion cell by applying 33.3 mA cm-2. Nevertheless, when Fe@Fe2O3/GC was used in the HEF approach to depollute real water matrices, no complete BQ concentration was removal achieved after 300 min of treatment, achieving between 80 and 95% of effectiveness.

Electrochemical Production of Hydrogen Peroxide in Perchloric Acid Supporting Electrolytes for the Synthesis of Chlorine Dioxide.

This work focuses on the electrochemical production of hydrogen peroxide in supporting electrolytes containing perchlorate ions for being used as a reagent in the reduction of chlorates to produce chlorine dioxide, as a first step in the manufacture of portable ClO2 production devices. This study evaluates the effect of the current density, pressure, and temperature on the production of hydrogen peroxide, and concentrations over 400 mg L-1 are reached. The average rate for the formation of hydrogen peroxide is 9.85 mg h-1, and the effect of increasing electrolyte concentration (3.0 and 30.0 g L-1 perchloric acid), intensity, and pressure results in values of, respectively, -2.99, -4.49, and +7.73 mg h-1. During the manufacturing process, hydrogen peroxide is decomposed through two mechanisms. The average destruction rate is 1.93 mg h-1, and the effects of the three factors results in values of, respectively, +0.07, +0.11, and -0.12 mg h-1. Solutions of this hydrogen peroxide produced electrochemically in a perchloric acid aqueous electrolyte were used to reduce chlorates in strongly acidic media and produce chlorine dioxide. Conversions of around 100% were obtained, demonstrating that this electrochemical product can be used efficiently to reduce chlorates to chlorine dioxide.

Cathodic hydrogen production by simultaneous oxidation of methyl red and 2,4-dichlorophenoxyacetate in aqueous solutions using PbO2, Sb-doped SnO2 and Si/BDD anodes. Part 2: hydrogen production.

In this work, results concerning hydrogen gas production during the oxidation of methyl red (MR) and sodium 2,4-dichlorophenoxyacetate (2,4-DNa), is presented, emphasizing not only the amount of hydrogen gas that was produced but also the kinetic and efficiency parameters involved in this process. For this purpose, a two-compartment electrochemical cell was used with a Nafion® membrane as separator in order to collect H2 without other chemical species (only with traces of water vapor). Under these experimental conditions, it was possible to guarantee the purity of the H2 collected. The electrochemical oxidation of MR and 2,4-DNa solutions was carried out by applying 30 mA cm-2 at 298 K, using different non-active anodes (Si/BDD, Pb/PbO2, or Sb-doped SnO2) and different cathodes (Pt mesh, 316-type stainless-steel, or Pt-10%Rh) in order to investigate the effect of the electrocatalytic materials and experimental conditions. Thus, the H2 produced was measured as a function of the electrolysis time and compared with the values estimated by Faraday's law. The results showed that the hydrogen production rate r(H2) is independent of the nature of the anodic material, although an important effect on the oxygen production was observed on the BDD anode by using sulfuric acid as supporting electrolyte. The effect was discussed through the formation of sulphate-oxidizing species (SO4 -˙ and S2O8 2-) which interfere in the oxygen production step on BDD anodes. The use of different cathodes showed small changes in the hydrogen production rate r(H2), which were basically associated with the differences in hydrogen adsorption energy prior to its evolution. The results were discussed in light of the existing literature.

Cathodic hydrogen production by simultaneous oxidation of methyl red and 2,4-dichlorophenoxyacetate aqueous solutions using Pb/PbO2, Ti/Sb-doped SnO2 and Si/BDD anodes. Part 1: electrochemical oxidation.

In this work, the electrochemical oxidation of the Methyl Red (MR) dye and the herbicide sodium 2,4-dichlorophenoxyacetate (2,4-DNa) was investigated on Si/BDD, Pb/PbO2 and Ti/Sb-doped SnO2 anodes in aqueous acidic medium by applying 30 mA cm-2 at 298 K. The electrochemical experiments were carried out in a two-compartment electrochemical cell separated through a Nafion® membrane (417 type) in order to use two types of supporting electrolyte to measure the elimination of the organic compound, the hydrogen production and the amount of oxygen produced during the oxidation of the pollutants. Although the main goal of this study is to understand the relationship between both processes, the evaluation of the current efficiencies (η) is a key parameter to determine the anodic oxidative capacity to degrade the proposed pollutants. The results clearly showed that MR and 2,4-DNa can be oxidized on Si/BDD, Pb/PbO2 and Ti/Sb-doped SnO2 anodes; however, significant variations in the oxidation level and η are achieved. Thus, although the MR solutions were completely discolored in all cases, only on the Si/BDD anode was MR oxidized to carboxylic acids in less than 15 min of electrolysis time. On Pb/PbO2 and Ti/Sb-doped SnO2 electrodes, the discoloration was slower and the oxidation was quasi-completed, leaving in solution some organic by-products, such as 2-aminobenzoic acid and/or N,N'-dimethyl-p-phenylenediamine, in the fixed electrolysis time. The behavior observed during the elimination of 2,4-DNa is due to its difficulty in degrading the chlorine groups in its aromatic ring which makes 2,4-DNa a more stable molecule. In the first oxidation stage, 2,4-dichlorophenol (2,4-DP) is produced in all cases, but on Si/BDD, this intermediate is quickly consumed. From the polarization curves and Tafel analysis, a reaction scheme for the formation and consumption of 2,4-DP was proposed.

Removal of oxyfluorfen from ex-situ soil washing fluids using electrolysis with diamond anodes.

In this research, firstly, the treatment of soil spiked with oxyfluorfen was studied using a surfactant-aided soil-washing (SASW) process. After that, the electrochemical treatment of the washing liquid using boron doped diamond (BDD) anodes was performed. Results clearly demonstrate that SASW is a very efficient approach in the treatment of soil, removing the pesticide completely by using dosages below 5 g of sodium dodecyl sulfate (SDS) per Kg of soil. After that, complete mineralization of organic matter (oxyflourfen, SDS and by-products) was attained (100% of total organic carbon and chemical oxygen demand removals) when the washing liquids were electrolyzed using BDD anodes, but the removal rate depends on the size of the particles in solution. Electrolysis of soil washing fluids occurs via the reduction in size of micelles until their complete depletion. Lower concentrations of intermediates are produced (sulfate, chlorine, 4-(trifluoromethyl)-phenol and ortho-nitrophenol) during BDD-electrolyzes. Finally, it is important to indicate that, sulfate (coming from SDS) and chlorine (coming from oxyfluorfen) ions play an important role during the electrochemical organic matter removal.

Combined soil washing and CDEO for the removal of atrazine from soils.

In this work, it is studied the removal of atrazine from spiked soils by soil washing using surfactant fluids, followed by the treatment of the resulting washing waste by electrolysis with boron doped diamond (BDD) anode. Results confirm that combination of both technologies is efficient for the removal and total mineralization of atrazine. Ratio surfactant/soil is a key parameter for the removal of atrazine from soil and influences significantly in the characteristic of the wastewater produced, affecting not only to the total organic load but also to the mean size of micelles. The higher the ratio surfactant soil, the lower is the size of the particles. Electrolyses of this type of waste attain the complete mineralization. TOC and COD are removed from the start of the treatment but the key of the treatment is the reduction in size of the micelles, which lead to a higher negative charge in the surface and to the faster depletion of the surfactant as compared with the pesticide.

Scale-up of electrochemical oxidation system for treatment of produced water generated by Brazilian petrochemical industry.

Scale-up of anodic oxidation system is critical to the practical application of electrochemical treatment in bio-refractory organic wastewater treatment. In this study, the scale-up of electrochemical flow system was investigated by treating petrochemical wastewater using platinized titanium (Ti/Pt) and boron-doped diamond (BDD) anodes. It was demonstrated that flow cell was successfully scaled-up because when it was compared with batch mode (Rocha et al. 2012b), higher performances on organic matter removal were achieved. Under the suitable operating conditions and better anode material, the chemical oxygen demand (COD) of petrochemical wastewater was reduced from 2,746 to 200 mg L(-1) within 5 h with an energy consumption of only 56.2 kWh m(-3) in the scaled-up BDD anode system. These results demonstrate that anode flow system is very promising in practical bio-refractory organic wastewater treatment.

Decontamination of produced water containing petroleum hydrocarbons by electrochemical methods: a minireview.

Produced water (PW) is the largest waste stream generated in oil and gas industries. The drilling and extraction operations that are aimed to maximize the production of oil may be counterbalanced by the huge production of contaminated water (called PW) with pollutants, such as heavy metals, dissolved/suspended solids, and organic compounds. PW is conventionally treated through different physical, chemical, and biological methods. In offshore platforms, because of space constraints, compact physical and chemical systems are used. However, major research efforts are being developed with innovative technologies for treating PW in order to comply with reuse and discharge limits. Among them, electrochemical technologies have been proposed as a promising alternative for the treatment of this kind of wastewaters. Then, this paper presents a minireview of efficient electrochemical technologies used until now for treating PW generated by petrochemical industry.