Geoffroy Roger Pointer Malpass

Decolourisation of real textile waste using electrochemical techniques: Effect of electrode composition

The present paper presents the study of the decolourisation of real textile effluent by constant current electrolysis in a flow-cell using a DSA type material. The effect of using different anode materials (Ti/Ru(0.3)Ti(0.7)O(2); Ti/Ir(0.3)Ti(0.7)O(2); Ti/Ru(X)Sn(1-X)O(2), where X=0.1, 0.2 or 0.3) on the efficiency of colour removal is discussed. Attempts to perform galvanostatic oxidation (40 and 60 mA cm(-2)) on the as-received effluent demonstrate that colour removal and total organic carbon (TOC) removal are limited. In this case the greatest degree of colour removal is achieved when anode containing 90% SnO(2) is used. If the conductivity of the effluent is increased by adding NaCl (0.1 mol L(-1)) appreciable colour/TOC removal is observed. The efficiencies of colour and TOC removal are discussed in terms of the energy per order (E(EO)/kW h m(-3)order(-1)) and energy consumption (E(C)/kW h kg(-1)TOC), respectively. Finally, the extent of colour removal is compared to consent levels presented in the literature.

Avaliação dos tratamentos eletroquímico e fotoeletroquímico na degradação de corantes têxteis

This paper presents the study of the oxidation of three textile dyes (Remazol black B, Remazol Brilliant Orange 3R and Remazol Golden Yellow RNL) using electrochemical and photoelectrochemical methods. In both methods, electrolysis experiments were performed at a current density of 50 mA cm-2 in an aqueous solution of each dye (30 mg L-1), using a photoelectrochemical flow-cell. For all the dyes studied, the photoelectrochemical method was demonstrated to be more efficient than the electrochemical one. Photoelectrochemical oxidation resulted in complete decoloration after 90 min of electrolysis and total organic carbon (TOC) removal reached up to 36%. It was observed that the dyes presenting chromophores at higher wavelengths are removed the quickest, which indicates that photosensitised (photoassisted) oxidation occurs. The level of color was reduced to levels below the standards presented in the literature, which indicates the viability of the photoelectrochemical process as part of the treatment of textile effluents.

Comparing atrazine and cyanuric acid electro-oxidation on mixed oxide and boron-doped diamond electrodes

The breakdown of pesticides has been promoted by many methods for clean up of contaminated soil and wastewaters. The main goal is to decrease the toxicity of the parent compound to achieve non-toxic compounds or even, when complete mineralization occurs, carbon dioxide and water. Therefore, electrochemical degradation (potentiostatic and galvanostatic) of both the pesticide atrazine and cyanuric acid (CA) at boron-doped diamond (BDD) and Ti/Ru0.3Ti0.7O2 dimensionally stable anode (DSA®) electrodes, in different supporting electrolytes (NaCl and Na2SO4), is presented with the aim of establishing the influence of the operational parameters on the process efficiency. The results demonstrate that both the electrode material and the supporting electrolyte have a strong influence on the rate of atrazine removal. In the chloride medium, the rate of atrazine removal is always greater than in sulfate under all conditions employed. Furthermore, in the sulfate medium, atrazine degradation was significant only at the BDD electrode. The total organic carbon (TOC) load decreased by 79% and 56% at the BDD and DSA® electrodes, respectively, in the chloride medium. This trend was maintained in the sulfate medium but the TOC removal was lower (i.e. 33% and 13% at BDD and DSA® electrodes, respectively). CA, a stable atrazine degradation intermediate, was also studied and it is efficiently removed using the BDD electrode in both media, mainly when high current densities are employed. The use of the BDD electrode in the chloride medium not only degrades atrazine but also mineralized cyanuric acid leading to the higher TOC removal.

The galvanostatic oxidation of aldehydes to acids on Ti/Ru0.3Ti0.7O2 electrodes using a filter-press cell

Results for the galvanostatic oxidation of formaldehyde, acetaldehyde, propionaldehyde and n-butyraldehyde in 0.5 mol dm-3 H2SO4 at Ti/Ru0.3Ti0.7O2 DSA® type electrodes, using a filter-press cell, are presented. The observed products are the respective carboxylic acids and CO2. In the case of formaldehyde the additional presence of CO32- is detected as a product. The carbon balance is observed to decrease with electrolysis time due to the partial liberation of the aldehyde in solution as a gas. The partial liberation of aldehyde gases increases with chain length and in this way the conversion of reactants to products decreases, as does the efficiency of the electro-oxidation process.

Screening process for activity determination of conductive oxide electrodes for organic oxidation

A modified method for the calculation of the normalized faradaic charge (qfN) is proposed. The method involves the simulation of an oxidation process, by cyclic voltammetry, by employing potentials in the oxygen evolution reaction region. The method is applicable to organic species whose oxidation is not manifested by a defined oxidation peak at conductive oxide electrodes. The variation of qfN for electrodes of nominal composition Ti/RuXSn1-XO2 (x = 0.3, 0.2 and 0.1), Ti/Ir0.3Ti0.7O2 and Ti/Ru0.3Ti0.7O2 in the presence of various concentrations of formaldehyde was analyzed. It was observed that electrodes containing SnO2 are the most active for formaldehyde oxidation. Subsequently, in order to test the validity of the proposed model, galvanostatic electrolyses (40 mA cm-2) of two different formaldehyde concentrations (0.10 and 0.01 mol dm-3) were performed. The results are in agreement with the proposed model and indicate that this new method can be used to determine the relative activity of conductive oxide electrodes. In agreement with previous studies, it can be concluded that not only the nature of the electrode material, but also the organic species in solution and its concentration are important factors to be considered in the oxidation of organic compounds.

Cyclic voltammetric behaviour of dimensionally stable anodes in the presence of C1 - C3 aldehydes

This work describes the cyclic voltammetry study of three aliphatic aldehydes: formaldehyde, acetaldehyde and propionaldehyde at dimensionally stable anodes (DSA®). Electrodes of nominal composition Ti/Ru0.3M0.7O2 (where M = Ti ou Sn) were used in 0.5 mol dm-3 H2SO4 in a filter-press cell. Both electrodes exhibit behaviour typical of such materials in the presence of formaldehyde. However, with acetaldehyde and propionaldehyde non-typical behaviour is observed. This is characterised by a fall in the normalised faradaic anodic charge (qnf) and also a decrease in the current density associated with the oxygen evolution reaction (OER). A possible reaction mechanism, considering the direct oxidation of the aldehyde at the electrode surface, is suggested.

Electrochemical removal of CuII in the presence of humic acid

The removal of CuII (10 mg L-1) complexed by commercial humic acid (100 mg L-1) was studied at different current densities (30-80 mA cm-2) using a filter-press cell, Ti/Ru0.3Ti0.7O2 anode and stainless steel cathode. The electrolyses were performed with and without membrane separating the cell compartments [(homogeneous anionic (Nafion R117), heterogeneous cationic (Ionac MC-3470) and heterogeneous anionic (Ionac MA-3475)]. The influence of the membrane on the rate of CuII removal was bigger for cationic membranes. Current efficiencies up to ca. 55% (Ionac MC-3470) for CuII removal at 30 mA cm-2 were obtained. By combining oxidation and reduction, 100% CuII removal was achieved at current efficiencies of 75%. The main path for the removal is the electrostatic interaction with the anode followed by diffusion through the membrane and deposition at the cathode. Additionally, the oxidative degradation of humic acid contributes to the rate of CuII removal.

Opuntia ficus indica as a polyelectrolyte source for the treatment of tannery wastewater

AbstractThis work presents the utilization of a natural polyelectrolyte, extracted from the cactus Opuntia ficus indica, as an auxiliary coagulant. The polyelectrolyte was employed together with either aluminum sulfate or ferric chloride in the treatment of real tannery wastewater. The parameters analyzed were turbidity, chemical oxygen demand, and total chromium concentration. The removal efficiency of chemical oxygen demand increased from an average of 77% using only aluminum sulfate to 90% in the presence of the natural polyelectrolyte. For ferric chloride, the efficiency increased from 91 to 98% when the natural polyelectrolyte was also used. Under all conditions employed, the level of total Cr is reduced below that permitted by the Brazilian legislation.

Electrochemical production and use of free chlorine for pollutant removal: an experimental design approach

ABSTRACT The present paper presents the study of (1) the optimization of electrochemical-free chlorine production using an experimental design approach, and (2) the application of the optimum conditions obtained for the application in photo-assisted electrochemical degradation of simulated textile effluent. In the experimental design the influence of inter-electrode gap, pH, NaCl concentration and current was considered. It was observed that the four variables studied are significant for the process, with NaCl concentration and current being the most significant variables for free chlorine production. The maximum free chlorine production was obtained at a current of 2.33 A and NaCl concentrations in 0.96 mol dm−3. The application of the optimized conditions with simultaneous UV irradiation resulted in up to 83.1% Total Organic Carbon removal and 100% of colour removal over 180 min of electrolysis. The results indicate that a systematic (statistical) approach to the electrochemical treatment of pollutants can save time and reagents.

Experimental-design-guided approach for the removal of atrazine by sono-electrochemical-UV-chlorine techniques

ABSTRACT The aim of the present study was to investigate the electrochemical formation of free chlorine species (HOCl/ClO−) and their subsequent use for the degradation of the pesticide atrazine. Initially, the process of electrochemical-free chlorine production was investigated using a bench-scale electrochemical flow-cell. The most significant variables (electrolyte concentration ([NaCl]) and inter-electrode gap) of the process were obtained using a 23 factorial design and the optimum process conditions (1.73 mol L−1 and 0.56 cm) were determined by a central composite design. Following optimization of free chlorine production, three degradation techniques were investigated, individually and in combination, for atrazine degradation: electrochemical, photochemical and sonochemical. The method using the techniques in combination was denominated sono-photo-assisted electrochemical degradation. Constant current assays were performed and the sono-photo-assisted electrochemical process promoted more efficient removal of atrazine, achieving total organic carbon removal of ∼98% and removal of atrazine to levels below the detection limit (>99%) in under 30 min of treatment. Furthermore, the combination of three techniques displayed lower energy consumption, and phytotoxicity tests (Lactuca sativa) showed that there was no increase in toxicity.