On the performance of Fe and Fe,F doped Ti-Pt/PbO2 electrodes in the electrooxidation of the Blue Reactive 19 dye in simulated textile wastewater

The electrochemical performance of pure Ti–Pt/β-PbO₂ electrodes, or doped with Fe and F (together or separately), in the oxidation of simulated wastewaters containing the Blue Reactive 19 dye (BR-19), using a filter-press reactor, was investigated and then compared with that of a boron-doped diamond electrode supported on a niobium substrate (Nb/BDD). The electrooxidation of the dye simulated wastewater (volume of 0.1 l, with a BR-19 initial concentration of 25 mg l⁻¹) was carried out under the following conditions: current density of 50 mA cm⁻², volume flow rate of 2.4 l h⁻¹, temperature of 25 °C and electrode area of 5 cm². The performances of the electrodes in the dye decolorization were quite similar, achieving 100% decolorization, and in some cases 90% decolorization was achieved by applying only ca. 0.3 A h l⁻¹ (8 min of electrolysis). The reduction of the simulated wastewater organic load, monitored by its total organic carbon content (TOC), was greater for the Ti–Pt/β-PbO₂–Fe,F electrode obtained from an electrodeposition bath containing 1 mM Fe³⁺ and 30 mM F⁻. In this case, after 2 h of electrolysis the obtained TOC reduction was 95%, while for the pure β-PbO₂ and the Nb/BDD electrodes the reductions were 84% and 82%, respectively.     

The mechanism and kinetics of ultrasound-enhanced electrochemical oxidation of phenol on boron-doped diamond and Pt electrodes

The research on ultrasound (US) enhanced electrochemical oxidation of Phenol (Ph) on boron-doped diamond (BDD) and Pt electrodes is studied. The enhancement by US on BDD is much greater than for Pt. With the assistance of US, the degradation rate and current efficiency on BDD are increased by 301% and 100%, respectively, while those on Pt are 51% and 49%. The difference of the enhancement on these two electrodes is caused by the fact that mass transport, adsorption amount and electrode reaction affected by US on BDD are different from those of Pt. The kinetics investigation on intermediates formed during electrochemical degradation show that the variety of intermediates produced on BDD is less than for Pt. In the presence of US, on both electrodes, no change occurred to the amounts of the intermediate species. However, time for intermediates to reach the highest concentration is cut down. This effect for degradation of Ph on BDD is more obvious than for Pt. The present research indicates that BDD is suitable for degradation of Ph by US assisted electrochemical oxidation.     

混凝辅助电化学法处理橙黄G染料废水

以石墨板为阳极，研究了电化学氧化法对橙黄G染料废水的降解效果。比较了在NaCl、Na2 SO4以及NaCl与FeSO4·7H2O组合的支持电解质体系中的处理效果，同时考察了电压、初始pH、电解质浓度、电极间距和电解时间等因素对废水中橙黄G脱色率及COD去除率的影响。研究结果表明，橙黄G的脱色主要是活性氯的氧化作用，橙黄G分子的矿化可能主要是电解过程中产生的·OH的作用，FeSO4·7H2O的加入增加了混凝作用，使得处理效果进一步提高。最佳脱色条件下橙黄G脱色率和COD的去除率分别为97．6％和56．3％，B／C（BOD／COD）由0．09提高至0．41，可生化性有较大改善，并且随着降解时间的增加，COD去除率逐渐升高。此结果表明，橙黄G废水COD的去除相对于脱色存在滞后性。     

Efficient removal of insecticide “imidacloprid” from water by electrochemical advanced oxidation processes

The oxidative degradation of imidacloprid (ICP) has been carried out by electrochemical advanced oxidation processes (EAOPs), anodic oxidation, and electro-Fenton, in which hydroxyl radicals are generated electrocatalytically. Carbon-felt cathode and platinum or boron-doped diamond (BDD) anodes were used in electrolysis cell. To determine optimum operating conditions, the effects of applied current and catalyst concentration were investigated. The decay of ICP during the oxidative degradation was well fitted to pseudo-first-order reaction kinetics and absolute rate constant of the oxidation of ICP by hydroxyl radicals was found to be k _abs(ICP)?=?1.23?×?10⁹ L mol^?1 s^?1. The results showed that both anodic oxidation and electro-Fenton process with BDD anode exhibited high mineralization efficiency reaching 91 and 94 % total organic carbon (TOC) removal at 2 h, respectively. For Pt-EF process, mineralization efficiency was also obtained as 71 %. The degradation products of ICP were identified and a plausible general oxidation mechanism was proposed. Some of the main reaction intermediates such as 6-chloronicotinic acid, 6-chloronicotinaldehyde, and 6-hydroxynicotinic acid were determined by GC-MS analysis. Before complete mineralization, formic, acetic, oxalic, and glyoxylic acids were identified as end-products. The initial chlorine and organic nitrogen present in ICP were found to be converted to inorganic anions Cl^?, NO₃ ^?, and NH₄ ⁺.     

Electrochemical incineration of indigo. A comparative study between 2D (plate) and 3D (mesh) BDD anodes fitted into a filter-press reactor

This paper compares the performance of 2D (plate) and 3D (mesh) boron-doped diamond (BDD) electrodes, fitted into a filter-press reactor, during the electrochemical incineration of indigo textile dye as a model organic compound in chloride medium. The electrolyses were carried out in the FM01-LC reactor at mean fluid velocities between 0.9?≤?u?≤?10.4 and 1.2?≤?u?≤?13.9 cm s^?1 for the 2D BDD and the 3D BDD electrodes, respectively, at current densities of 5.63 and 15 mA cm^?2. The oxidation of the organic matter was promoted, on the one hand, via the physisorbed hydroxyl radicals (BDD(^●OH)) formed from water oxidation at the BDD surface and, on the other hand, via active chlorine formed from the oxidation of chloride ions on BDD. The performance of 2D BDD and 3D BDD electrodes in terms of current efficiency, energy consumption, and charge passage during the treatments is discussed.     

Mineralization of the biocide chloroxylenol by electrochemical advanced oxidation processes

Electrochemical advanced oxidation processes (EAOPs) are environmentally friendly methods based on the destruction of organic pollutants in wastewaters with in situ electrogenerated hydroxyl radical. This species is formed in anodic oxidation (AO) from water oxidation at the anode and in indirect electro-oxidation methods like electro-Fenton (EF) and photoelectro-Fenton (PEF) also from reaction between catalytic Fe2+ and H2O2 continuously produced at the O2-diffusion cathode. The PEF method involves the irradiation of the treated solution with UVA light to enhance the photolysis of organics including Fe(III) complexes. In this work, the oxidation power of such EAOPs to decontaminate synthetic wastewaters of the biocide chloroxylenol (4-chloro-3,5-dimethylphenol) at pH 3.0 is comparatively examined with an undivided electrolytic cell containing a Pt or boron-doped diamond (BDD) anode and a stainless steel or O2-diffusion cathode. The initial chlorine is released as Cl(-) ion, which remains stable in the medium using Pt or is oxidized to Cl2 on BDD. The biocide solutions can be completely decontaminated using AO with a BDD anode, as well as PEF with a Pt or BDD anode. The PEF procedure with a BDD anode is the most powerful method leading to total mineralization in about 300 min, practically independent of current density. When current density rises, the degradation rate of processes increases, but they become less efficient due to the larger enhancement of waste reactions of oxidants. Chloroxylenol is much more rapidly removed in EF and PEF than in AO. 2,6-dimethylhydroquinone, 2,6-dimethyl-p-benzoquinone and 3,5-dimethyl-2-hydroxy-p-benzoquinone are identified as aromatic by-products, and maleic, malonic, pyruvic, acetic and oxalic acids are found as generated carboxylic acids. A general pathway for chloroxylenol mineralization by all EAOPs including the above by-products is proposed.     

铁阳极电凝聚处理活性黑KN-B染料废水

对铁阳极电凝聚处理活性黑KN-B染料废水过程进行了实验研究.考察了电流密度、染料溶液初始pH值、电介质浓度及种类、温度、染料浓度等因素对脱色效率的影响.结果表明,在一定实验条件下,活性黑KN-B模拟废水的脱色效率达93%;电流强度、染料浓度、电解液初始pH值及电解质的种类对染料溶液脱色效率影响显著,电解液温度、电解质的浓度对脱色效率的影响不明显;以铁为阳极的原位电凝聚处理活性黑KN-B模拟废水混凝过程中主要作用机理以吸附电性中和为主;电凝聚过程中活性黑KN-B在阴极上发生了还原反应.     

Electrochemical oxidation of benzene on boron-doped diamond electrodes

This work presents an electrochemical investigation of the benzene oxidation process in aqueous solution on boron-doped diamond (BDD) electrodes. Additionally, in order to determine the main products generated during the oxidation process, electrolysis and high performance liquid chromatography experiments were carried out. The complete degradation of this compound was performed aiming to a further application in waste water treatment. The cyclic voltammetry studies indicate that benzene is irreversibly oxidized in acid medium (H₂SO₄ 0.5 M) on the BDD electrode surface at 2.0 V versus Ag/AgCl in a diffusion controlled process. During the cycling, other products are generated, and a pair of peaks was observed that can be associated with the oxi-reduction of anyone of the following species: hydroquinone, benzoquinone, resorcinol or catechol. The electrolysis experiments were carried out at 2.4 and 2.5 V on the BDD electrode surface in a solution containing 1 × 10⁻² M of benzene (below the saturation concentration in aqueous solution), for 3 and 5 h, respectively. The main products measured were: hydroquinone, resorcinol, p-benzoquinone, catechol and phenol. The complete electrochemical benzene degradation was performed in the electrolysis experiments using a rotating BDD disc electrode (2.5 V for 5 h) and the main products detected were all measured at concentrations lower than 10⁻⁵ M in this condition. The boron-doped diamond electrode had proved to be a valuable tool for the electrochemical degradation of the benzene, a very stable chemical compound.     

Electrochemical combustion of herbicide mecoprop in aqueous medium using a flow reactor with a boron-doped diamond anode

The anodic oxidation of 1.8l of solutions with mecoprop (2-(4-chloro-2-methylphenoxy)-propionic acid or MCPP) up to 0.64 g l(-1) in Na2SO4 as background electrolyte within the pH range 2.0-12.0 has been studied using a flow plant containing a one-compartment filter-press electrolytic reactor with a boron-doped diamond (BDD) anode and a stainless steel cathode, both of 20-cm2 area. Electrolyses carried out in batch under steady conditions and operating at constant current density between 50 and 150 mA cm(-2) always yield complete mineralization due to the great concentration of hydroxyl radical generated at the BDD anode. The degradation rate is practically independent of pH and Na2SO4 concentration, but it becomes faster with increasing MCPP concentration, current density, temperature and liquid flow rate. The effect of these parameters on current efficiency and energy cost has also been investigated. Generated weak oxidants such as H2O2 and peroxodisulfate ion have little influence on the mineralization process. The kinetics for the herbicide decay follows a pseudo first-order reaction with a higher rate constant when current density increases. Aromatic products such as 4-chloro-o-cresol, 2-methylhydroquinone and 2-methyl-p-benzoquinone, and generated carboxylic acids such as maleic, fumaric, lactic, pyruvic, tartronic, acetic and oxalic, have been identified as intermediates by chromatographic techniques. The initial chlorine is completely released in the form of chloride ion, which is slowly oxidized to Cl2 at the BDD anode. A reaction pathway for MCPP mineralization involving all products detected is proposed.     

Degradation of anti-inflammatory drug ketoprofen by electro-oxidation: comparison of electro-Fenton and anodic oxidation processes

The electrochemical degradation of the nonsteroidal anti-inflammatory drug ketoprofen in tap water has been studied using electro-Fenton (EF) and anodic oxidation (AO) processes with platinium (Pt) and boron-doped diamond (BDD) anodes and carbon felt cathode. Fast degradation of the parent drug molecule and its degradation intermediates leading to complete mineralization was achieved by BDD/carbon felt, Pt/carbon felt, and AO with BDD anode. The obtained results showed that oxidative degradation rate of ketoprofen and mineralization of its aqueous solution increased by increasing applied current. Degradation kinetics fitted well to a pseudo-first-order reaction. Absolute rate constant of the oxidation of ketoprofen by electrochemically generated hydroxyl radicals was determined to be (2.8?±?0.1)?×?10⁹ M^?1 s^?1 by using competition kinetic method. Several reaction intermediates such as 3-hydroxybenzoic acid, pyrogallol, catechol, benzophenone, benzoic acid, and hydroquinone were identified by high-performance liquid chromatography (HPLC) analyses. The formation, identification, and evolution of short-chain aliphatic carboxylic acids like formic, acetic, oxalic, glycolic, and glyoxylic acids were monitored with ion exclusion chromatography. Based on the identified aromatic/cyclic intermediates and carboxylic acids as end products before mineralization, a plausible mineralization pathway was proposed. The evolution of the toxicity during treatments was also monitored using Microtox method, showing a faster detoxification with higher applied current values.     

Degradation of the herbicide 2,4-DP by anodic oxidation, electro-Fenton and photoelectro-Fenton using platinum and boron-doped diamond anodes

This paper reports the degradation of 2,4-DP (2-(2,4-dichlorophenoxy)-propionic acid) solutions of pH 3.0 by environmentally friendly electrochemical methods such as anodic oxidation, electro-Fenton and photoelectro-Fenton with a Pt or boron-doped diamond (BDD) anode. In the two latter techniques an O(2)-diffusion cathode was used and 1.0mM Fe(2+) was added to the solution to give hydroxyl radical (*OH) from Fenton's reaction between Fe(2+) and H(2)O(2) generated at the cathode. All treatments with BDD are viable to decontaminate acidic wastewaters containing 2,4-DP since they give complete mineralization, with loss of chloride ion, at high current due to the great production of oxidant *OH at the BDD surface favoring the destruction of final carboxylic acids. *OH formed from Fenton's reaction destroys more rapidly aromatic products, making the electro-Fenton and photoelectro-Fenton processes much more efficient than anodic oxidation. UVA light in photoelectro-Fenton with BDD has little effect on the degradation rate of pollutants. The comparative procedures with Pt lead to slower decontamination because of the lower oxidizing power of this anode. The effect of current on the degradation rate and efficiency of all methods is studied. The 2,4-DP decay always follows a pseudo-first-order kinetics. Chlorohydroquinone, chloro-p-benzoquinone and maleic, fumaric, malic, lactic, pyruvic, acetic, formic and oxalic acids are detected as products by chromatographic techniques. A general sequence accounting for by the reaction of all these intermediates with the different oxidizing agents is proposed.     

Two stage biological treatment of a diazo reactive textile dye and the fate of the dye metabolites

A two stage anaerobic/aerobic bacterial process was used to decolorize and partially mineralize a reactive vinyl sulfone diazo dye C.I. Reactive Black 5 (RB5) in a synthetic wastewater. Since the anchor group of reactive dyes reacts during the dyeing process, the effect the degree of hydrolysis of the vinyl sulfone dye had on decolorization, mineralization and toxicity in each stage was investigated. An overall color removal of approximately 65% was found for both the fully and partially hydrolyzed dye. Partial mineralization of the fully hydrolyzed RB5 was achieved in the two stage rotating disc reactors. While the anchor group metabolite p-aminobenzene-2-hydroxyethylsulfonic acid (p-ABHES) was mineralized, an oxidized form of the center metabolite (1,2-ketimino-7-amino-8-hydroxynaphthalene-3,6-disulfonic acid) remained in the aerobic stage effluent, causing the effluent to be colored although no RB5 was present. Partially hydrolyzed dye in the influent with vinyl forms of the anchor group caused cessation of biogas production and a reduction in decolorization efficiency in the anaerobic stage. No evidence for mineralization of the partially hydrolyzed dye or its metabolites was found. A method for evaluating dye mineralization using lumped parameters is presented.     

Treatment of Basic Red 29 dye solution using iron-aluminum electrode pairs by electrocoagulation and electro-Fenton methods

The aim of this study is the treatment of Basic Red 29 (BR29) dye solution using hybrid iron-aluminum electrodes by electrocoagulation and electro-Fenton methods. The effect of current density, initial pH, supporting electrolyte, H₂O₂, and initial dye concentration on dye removal efficiency was investigated, and the best experimental conditions were obtained. Time-coarse variation of UV-Vis spectra and toxicity and chemical oxygen demand (COD) removal were also examined at the best experimental conditions. Both systems were found very successful for the removal of BR29 dye. The removal efficiency of >95 % for BR29 dye solution was reached easily in a short time. At the best experimental conditions, for the initial BR29 concentration of 100 mg/L, >95 % BR29 dye and 71.43 % COD removal were obtained after 20 and 40 min of electrolysis, respectively. Additionally, toxicity results for electro-Fenton treatment of 100 mg/L BR29 were also very promising. According to the results obtained, although electro-Fenton is more effective, both systems can be used successfully to treat textile wastewater including dyes.     

High efficiencies in the electrochemical oxidation of an anthraquinonic dye with conductive-diamond anodes

Oxidation of anthraquinonic dye Acid Blue 62 by electrolysis with conductive-diamond electrodes is studied in this work. COD, TOC, and color have been selected to monitor the degradation of the molecule as a function of several operating inputs (current density, pH, temperature, and NaCl concentration). Results show that the electrochemical oxidation of this model of large molecules follows a first order kinetics in all the conditions assessed, and it does not depend on the pH and temperature. The occurrence of chloride ions in wastewaters increases the rate of color and COD removal as a consequence of the mediated oxidation promoted by the chlorinated oxidizing species. However, chloride occurrence does not have an influence on the mineralization rate. First-order kinetic-constants for color depletion (attack to chromophores groups), oxidation (COD removal), and mineralization (TOC removal) were found to depend on the current density and to increase significantly with its value. A single model was proposed to explain these changes in terms of the mediated oxidation processes. Rate of mineralization remained very close to that expected for a purely mass transfer-controlled process. This was explained assuming that mediated oxidation does not have a significant influence on the mineralization in spite it has some effect on intermediate oxidation stages. The efficiency of the oxidation was found to depend mainly on the concentration of COD being negligible the effect of the other inputs assessed except for the occurrence of chloride ions. Opposite, the efficiency of mineralization depends on concentration of TOC and current density and it did not depend on the chloride occurrence. This observation was found to have an important influence on the power required to remove a given percentage of the initial TOC or COD. To decrease COD efficiently, the occurrence of chloride in the solution is very important, while to remove TOC efficiently, it is more important to work at low current densities and chloride effect is negligible. Energy consumption could be decreased by folds using the proper conditions.     

Electrochemical degradation applied to the metabolites of Acid Orange 7 anaerobic biotreatment

The electrochemical oxidation of the biotic degradation products of the textile dye C.I. Acid Orange 7 (AO7) was achieved using a boron doped diamond electrode (BDD). Tests were performed with model solutions of the biotic degradation products, sulphanilic acid (SA) and 1-amino-2-naphthol (AN), and also with real effluents obtained in experiments carried out in an up-flow anaerobic sludge blanket (UASB) reactor, fed with a simulated textile effluent containing AO7, working in mesophilic or thermophilic conditions. Bulk electrolysis was studied using two different supporting electrolytes - NaCl and Na(2)SO(4). The influence of initial metabolite concentration and current density on the electrodegradation rates of the biotic products was investigated. For the UASB effluents, oxidation tests were carried out for different electrolytes and at different current densities. Samples were collected at pre-selected intervals and absorbance measurements, chemical oxygen demand (COD) and total organic carbon (TOC) tests and high performance liquid chromatography (HPLC) analysis were performed. Results have shown an almost complete elimination of the persistent pollutants and a COD removal higher than 70% for both AN and SA. For the UASB effluents, COD removals between 45% and 90% and TOC removals varying from 19% to 41% were obtained.     

Treatment of dilute methylene blue-containing wastewater by coupling sawdust adsorption and electrochemical regeneration

In the present work, the coupling of adsorption and electrochemical oxidation on a boron-doped diamond (BDD) electrode to treat solutions containing dyes is studied. This coupling may be convenient for the treatment of diluted pollutant that is limited by the low rate of electrooxidation due to mass-transfer limitation. A pre-concentration step by adsorption could minimize the design of the electrochemical reactor. The adsorbent chosen was mixed with softwood sawdust, and methylene blue was chosen as the model dye molecule. Isotherms of adsorption and kinetics were investigated as well as the effects of current density and regeneration time. The BDD electrochemical oxidation of methylene blue adsorbed onto sawdust led simultaneously to its degradation and sawdust regeneration for the next adsorption. It was observed that multiple adsorption and electrochemical regeneration cycles led to an enhancement of adsorption capacity of the sawdust. This study demonstrated that adsorption–electrochemical degradation coupling offers a promising approach for the efficient elimination of organic dyes from wastewater.     

电催化氧化技术处理制革综合废水

选择DSA电极中的钛基掺硼金钢石膜电极(Ti/BDD),用于制革综合废水的电催化氧化处理研究,考察了在不同的电流密度、电压、电解质、pH值和电解时间等因素对COD去除率和电流效率的影响。结果表明,控制电流密度为30mA/cm2,电压为8.0 V,电解质(NaCl)浓度为2.0 g/L,pH为4.0,电催化氧化处理2 h后,废水的COD和NH4+-N的去除率分别达到了83.6%和90.3%,BOD/COD为0.45,比能耗为35.34 kWh/kg COD,电流效率为37%。     

三维电极/电-Fenton法降解苯酚

采用电-Fenton耦合三维电极法处理苯酚模拟废水，研究了活性炭作为第三电极的三维电极体系中苯酚的去除效果，重点考察了常温下初始pH值、电流强度、Fe²⁺浓度等因素对苯酚降解的影响。结果表明：在常温下，曝气速率20 L/min，初始pH=3，电流强度为0.3 A/m²，Fe²⁺浓度为0.1 mmol/L，反应时间60 min时，废水的苯酚的氧化降解率为91%，COD去除率为64%。在此条件下，三维电极/电-Fenton表现出较强的氧化能力，具有较好的去除效果，可应用于含苯酚废水的处理。     

Electro-oxidation of the dye azure B: kinetics,mechanism, and by-products

In this work, the electrochemical degradation of the dye azure B in aqueous solutions was studied by electrochemical advanced oxidation processes (EAOPs), electro-Fenton, and anodic oxidation processes, using Pt/carbon-felt and boron-doped diamond (BDD)/carbon-felt cells with H₂O₂ electrogeneration. The higher oxidation power of the electro-Fenton (EF) process using BDD anode was demonstrated. The oxidative degradation of azure B by the electrochemically generated hydroxyl radicals (^?OH) follows a pseudo-first-order kinetics. The apparent rate constants of the oxidation of azure B by ^?OH were measured according to pseudo-first-order kinetic model. The absolute rate constant of azure B hydroxylation reaction was determined by competition kinetics method and found to be 1.19?×?10⁹ M^?1 s^?1. It was found that the electrochemical degradation of the dye leads to the formation of aromatic by-products which are then oxidized to aliphatic carboxylic acids before their almost mineralization to CO₂ and inorganic ions (sulfate, nitrate, and ammonium). The evolution of the TOC removal and time course of short-chain carboxylic acids during treatment were also investigated.     

The effect of pre-ozonation on the biocompatibility of reactive dye hydrolysates

Pre-ozonation of 14 different reactive dyestuff hydrolysates at alkaline pH was investigated to assess possible relationships between ozone transfer efficiency, first order decolourization kinetics, release of initially complexed heavy metals and relative changes in the biodegradability of the partially oxidized dye waste samples. Biocompatibility of the raw (untreated) and ozonated dye hydrolysates was comparatively tracked through specific oxygen uptake rate measurements from which the respirometric inhibition of biological activated sludge imparted by raw and ozonated reactive dye wastewater with respect to synthetic domestic wastewater was determined. It could be demonstrated that preliminary ozonation of reactive azo dyes increases their biological compatibility more significantly than formazan copper complex, copper complex azo and phythalocyanine dyes as a consequence of heavy metal release associated with the cleavage of associated chromophoric groupings right at the initial stages of pre-ozonation.