Evaluation of different electrochemical methods on the oxidation and degradation of Reactive Blue 4 in aqueous solution

The oxidation of a reactive dye, Reactive Blue 4, RB4, (C.I. 61205), widely used in the textile industries to color natural fibers, was studied by electrochemical techniques. The oxidation on glassy carbon electrode and reticulated vitreous carbon electrode occurs in only one step at 2.0 < pH < 12 involving a two-electron transfer to the amine group leading to the imide derivative. Dye solution was not decolorized effectively in this electrolysis process. Nevertheless, the oxidation of this dye on Ti/SnO2/SbO(x) (3% mol)/RuO2 (1% mol) electrode showed 100% of decolorization and 60% of total organic carbon removal in Na2SO4 0.2 M at pH 2.2 and potential of +2.4V. Experiments on degradation photoelectrocatalytic were also carried out for RB4 degradation in Na2SO4 0.1 M, pH 12, using a Ti/TiO2 photoanode biased at +1.0 V and UV light. After 1h of electrolysis the results indicated total color removal and 37% of mineralization.     

Aniline degradation by Electro-Fenton and peroxi-coagulation processes using a flow reactor for wastewater treatment

The degradation of 10-30 l of a 1000 ppm aniline solution in 0.050 M Na2SO4 + H2SO4 at pH 3.0 and 40 degrees C by Electro-Fenton and peroxi-coagulation processes at constant current until 20 A has been studied using a pilot flow reactor in recirculation mode with a filter-press cell containing an anode and an oxygen diffusion cathode, both of 100 cm2 area. H2O2 is produced by the two-electron reduction of O2 at the cathode, being accumulated with a current efficiency between 60% and 80% at the first stages of electrolyses performed with a Ti/Pt anode. In the presence of 1 mM Fe2+, less H2O2 is accumulated, but it is not detected using an Fe anode. The Electro-Fenton process with 1 mM Fe2+ and a Ti/Pt or DSA anode yields an insoluble violet polymer, while the soluble total organic carbon (TOC) is gradually removed, reaching 61% degradation after 2 h at 20 A. In this treatment, pollutants are preferentially oxidized by hydroxyl radicals formed in solution from reaction of Fe2+ with H2O2. The peroxi-coagulation process with an Fe anode has higher degradation power, allowing to remove more than 95% of pollutants at 20 A, since some intermediates coagulate with the Fe(OH)3 precipitate formed. Both advanced electrochemical oxidation processes (AEOPs) show moderate energy costs, which increase with increasing electrolysis time and applied current.     

三维电极法深度处理维生素生产废水

采用三维电极法对维生素废水进行深度处理,分别以钛涂钌铱板、铁板和不锈钢板作为电极阳极,石墨板作为电极阴极,柱状活性炭作为粒子电极,结果表明,当以钛涂钌铱板作为阳极,以粒径为1 mm的柱状活性炭作为粒子电极时电解效果最好,COD和色度去除率最高。实验选择电解电压、电极板间距、电解时间和初始pH值作为主要影响因素进行正交实验,实验研究证明,各因素的影响大小为电解电压>电极板间距>电解时间>初始pH值,得到的最佳参数组合分别为:电解电压为10 V,电极板间距为8 cm,电解时间为20 min,初始pH值为4,得到COD和色度最大去除率分别为59.5%和93.57%。     

基于Ti/SnO_2阳极氧化法的典型染料废水电化学氧化规律

采用Ti/SnO2电极间接阳极氧化法处理直接深棕M和活性艳蓝KNR模拟染料废水,研究电解质种类、pH、电压、NaCl投加量及电解时间对其降解效果的影响;在最佳组合条件下,通过分析UV-Vis光谱以及降解过程中氮元素的存在形式,研究上述2种染料的降解规律。结果表明,在pH为3,电压20 V,NaCl投加量为2.5 g/L的条件下,电解30 min后,直接深棕M和活性艳蓝KNR的脱色率分别达到80%和95%,60 min后直接深棕M的COD去除率可达75%,活性艳蓝KNR的COD去除率达到90%;电解60 min后,直接深棕M的偶氮双键完全破坏,萘环和苯环结构被逐步降解,活性艳蓝KNR溶液电解2 min,其分子结构中的蒽醌共轭体系被破坏,随反应的进行,蒽醌结构逐渐被破坏,染料逐步降解。     

Electrochemical treatment of domestic wastewater using boron-doped diamond and nanostructured amorphous carbon electrodes

The performance of the electrochemical oxidation process for efficient treatment of domestic wastewater loaded with organic matter was studied. The process was firstly evaluated in terms of its capability of producing an oxidant agent (H₂O₂) using amorphous carbon (or carbon felt) as cathode, whereas Ti/BDD electrode was used as anode. Relatively high concentrations of H₂O₂ (0.064 mM) was produced after 90 min of electrolysis time, at 4.0 A of current intensity and using amorphous carbon at the cathode. Factorial design and central composite design methodologies were successively used to define the optimal operating conditions to reach maximum removal of chemical oxygen demand (COD) and color. Current intensity and electrolysis time were found to influence the removal of COD and color. The contribution of current intensity on the removal of COD and color was around 59.1 and 58.8 %, respectively, whereas the contribution of treatment time on the removal of COD and color was around 23.2 and 22.9 %, respectively. The electrochemical treatment applied under 3.0 A of current intensity, during 120 min of electrolysis time and using Ti/BDD as anode, was found to be the optimal operating condition in terms of cost/effectiveness. Under these optimal conditions, the average removal rates of COD and color were 78.9?±?2 and 85.5?±?2 %, whereas 70 % of total organic carbon removal was achieved.     

钛基氧化物涂层电极在污水处理方面的实验研究

用涂刷热分解氧化法研究制作了3种钛基金属氧化物涂层电极：SnO₂-Sb₂O₃-CeO₂/SnO₂-Sb₂O₃/Ti、SnO₂-Sb₂O₃-CoO₂/SnO₂-Sb₂O₃/Ti和SnO₂-Sb₂O₃-CoO₂/IrO₂/Ti，用于处理生活污水，筛选出了处理效果最好的电极：SnO₂-Sb₂O₃-CeO₂/SnO₂-Sb₂O₃/Ti电极。通过SnO₂-Sb₂O₃-CeO₂/SnO₂-Sb₂O₃/Ti电极处理生活污水的静态实验，研究了电解时间、电流密度等因素对电解效果的影响，得出该电极较佳的运行参数是：极板间距1 cm、电流密度10 mA/cm²、电解时间2 h，此时，COD、NH₃-N、总磷、总氮、SS和大肠菌群的去除率分别为94.0％、99.8％、51.8％、70.8%、100％和100％；并用该参数进行了动态实验，连续运行60 d，得到了稳定的出水水质数据。     

Sequential electrochemical treatment of dairy wastewater using aluminum and DSA-type anodes

Dairy wastewater is characterized by a high content of hardly biodegradable dissolved, colloidal, and suspended organic matter. This work firstly investigates the performance of two individual electrochemical treatments, namely electrocoagulation (EC) and electro-oxidation (EO), in order to finally assess the mineralization ability of a sequential EC/EO process. EC with an Al anode was employed as a primary pretreatment for the conditioning of 800 mL of wastewater. A complete reduction of turbidity, as well as 90 and 81 % of chemical oxygen demand (COD) and total organic carbon (TOC) removal, respectively, were achieved after 120 min of EC at 9.09 mA cm^?2. For EO, two kinds of dimensionally stable anodes (DSA) electrodes (Ti/IrO₂-Ta₂O₅ and Ti/IrO₂-SnO₂–Sb₂O₅) were prepared by the Pechini method, obtaining homogeneous coatings with uniform composition and high roughness. The ^·OH formed at the DSA surface from H₂O oxidation were not detected by electron spin resonance. However, their indirect determination by means of H₂O₂ measurements revealed that Ti/IrO₂-SnO₂–Sb₂O₅ is able to produce partially physisorbed radicals. Since the characterization of the wastewater revealed the presence of indole derivatives, preliminary bulk electrolyses were done in ultrapure water containing 1 mM indole in sulfate and/or chloride media. The performance of EO with the Ti/IrO₂-Ta₂O₅ anode was evaluated from the TOC removal and the UV/Vis absorbance decay. The mineralization was very poor in 0.05 M Na₂SO₄, whereas it increased considerably at a greater Cl^? content, meaning that the oxidation mediated by electrogenerated species such as Cl₂, HClO, and/or ClO^? competes and even predominates over the ^·OH-mediated oxidation. The EO treatment of EC-pretreated dairy wastewater allowed obtaining a global 98 % TOC removal, decreasing from 1,062 to <30 mg L^?1.     

基于Ti/SnO2阳极氧化法的典型染料废水电化学氧化规律

采用Ti／SnO2电极间接阳极氧化法处理直接深棕M和活性艳蓝KNR模拟染料废水，研究电解质种类、pH、电压、NaCl投加量及电解时间对其降解效果的影响；在最佳组合条件下，通过分析uV—Vis光谱以及降解过程中氮元素的存在形式，研究上述2种染料的降解规律。结果表明，在pH为3，电压20V，NaCl投加量为2．5g／L的条件下，电解30min后，直接深棕M和活性艳蓝KNR的脱色率分别达到80％和95％，60min后直接深棕M的COD去除率可达75％，活性艳蓝KNR的COD去除率达到90％；电解60min后，直接深棕M的偶氮双键完全破坏，萘环和苯环结构被逐步降解，活性艳蓝KNR溶液电解2min，其分子结构中的蒽醌共轭体系被破坏，随反应的进行，蒽醌结构逐渐被破坏，染料逐步降解。     

Electrochemical oxidation of two organophosphoric obsolete pesticide stocks

Organophosphoric pesticides are widely used for crop and fruit tree treatment, but their disposal causes serious environmental problems. Two commercial organophosphoric pesticides (Monocrotophos and Phosphamidon) were treated by an electrolysis system using Ti/Pt as anode and stainless steel 304 as cathode. A number of experiments were run in a laboratory scale pilot plant and the results are presented. For Monocrotophos, the achieved reduction was over 28%, while for Phosphamidon it was nearly 26%. Phosphamidon had a higher energy demand than Monocrotophos. The COD/BOD5 ratio was improved considerably after electrolysis for both pesticides examined. Therefore, electrochemical oxidation could be used as a pretreatment method for their detoxification.     

Electrochemical degradation of Acid Blue and Basic Brown dyes on Pb/PbO2 electrode in the presence of different conductive electrolyte and effect of various operating factors

Electrocatalytic degradation of Acid Blue and Basic Brown dyes from simulated wastewater on lead dioxide anode was investigated in different conductive electrolytes. It was shown that complete degradation of these dyes is dependent primarily on type and concentration of the conductive electrolyte. The highest electrocatalytic activity was achieved in the presence of NaCl (2g/l) and could be attributed to indirect oxidation of the investigated dyes by the electrogenerated hypochlorite ions formed from the chloride oxidation. In addition, contribution from direct oxidation could also be possible via reaction of these organic compounds with the electrogenerated hydroxyl radicals adsorbed on the lead dioxide surface. In the presence of NaOH, the electrocatalytic activity of the employed anode was not comparable to that in NaCl due primarily to the absence of chloride. This indicates that dyes degradation in NaOH occurs exclusively via direct electrochemical process. However, in H2SO4, the electrode performance was poor due partially to the absence of chloride from the conductive solution. The possibility of electrode poisoning as a result of growth of adherent film on the anode surface or production of stable intermediates not easily further oxidized by direct electrolysis in H2SO4 might also be accountable for the poor performance observed in this conductive electrolyte. Optimizing the conditions that ensure effective electrochemical degradation of Acid Blue and Basic Brown dyes on lead dioxide electrode necessitates the control of all the operating factors.     

石墨电极-低压脉冲电解含油废水影响因素研究

采用石墨电极-低压脉冲电解方法,对含油废水去油影响因素进行了单因子实验研究。结果表明:该方法对浓度为95 mg/L的含油废水中油的去除率超过75%。油去除率随电解时间、电压增加而增大,达到一定值后受油分子扩散浓度影响而增加缓慢;适宜占空比、脉冲频率即可发挥脉冲作用,消除钝化效果,又可增强电解效果;体系pH值对电解影响较大,酸性和中性电解效果好于碱性条件;适当调整电极直径、电极间距可改善电解效果。     

电化学方法用于酸性红B模拟废水脱色试验研究

本文研究了两种电极材料 (SnO2 Ti和RuO2 Ti)对酸性红B模拟废水的脱色效果 ,考察了不同 pH、电流密度(j)及外加电解质 (Na2 SO4/NaCl)对处理过程的影响。结果表明 ,两种电极材料都能对酸性红B染料废水进行有效脱色 ,主要是Cl-在电解过程中的间接氧化作用 ,同时也包括电极表面的直接氧化作用。     

Evaluation of the efficiency of monopolar and bipolar BDD electrodes for electrochemical oxidation of anthraquinone textile synthetic effluent for reuse

The efficiency of the electrochemical degradation of synthetic wastewater containing an anthraquinone dye has been comparatively studied in two electrolytic cells with a synthetic boron-doped diamond (Si/BDD) as an anode. The first is an individual cell (Cell 1) with monopolar electrode BDD and the second (Cell 2) has two bipolar electrodes BDD self-polarized. The bulk electrolysis was performed at the same initial operating conditions in order to quantify the influence of the initial pH and current density on dye discoloration and global mineralization removal. The current efficiency and the consumption energy were also evaluated. When the same solutions have been comparatively treated with the two cells, a quite good mineralization is found in Cell 2. This result supposed more fraction of the applied current is used for the electrocombustion reaction on Cell 2 if compared to Cell 1 and small amount rest for the side reaction of oxygen evolution. The HPLC analyses confirmed this hypothesis and showed that the concentration trend of intermediates (sulfanilic acid, phthalate acid and salicylic acid) with electrolysis time was different on two cells. Phototoxicity tests show that the electrochemical oxidation with BDD electrodes could be useful as a pretreatment technique for reducing hazardous wastewater toxicity.     

Electrochemical detoxification of four phosphorothioate obsolete pesticides stocks

The phosphorothioate pesticides are widely used for crop production and fruit tree treatment, but their disposal causes serious environmental problems. Four commercial phosphorothioate pesticides (Demeton-S-methyl, Metamidophos, Fenthion and Diazinon) were treated by an electrolysis system using Ti/Pt as anode and stainless steel 304 as cathode. A number of experiments were run in a laboratory scale pilot plant and the results are presented. For Fenthion the achieved reduction was over 60%, while for Demeton-S-methyl, Metamidophos and Diazinon was more than 50%. Diazinon had the lowest energy demand. The COD/BOD5 ratio was improved considerably after electrolysis for all four pesticides examined. As a conclusion, electrochemical oxidation could be used as a pretreatment method of the pesticides detoxification.     

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%。     

Detoxification of tannery waste liquors with an electrolysis system

This paper describes an electrochemical treatment and detoxification of tannery waste liquors (TWL). In this technique, TWL was passed through an electrolytic cell using a Ti/Pt anode and a stainless steel 304 cathode. Owing to the strong oxidizing potential of the chemicals produced (chlorine, oxygen, hydroxyl radicals and other oxidants) the organic and inorganic pollutants (ammonia, sulfides and chromium) were wet oxidized to carbon dioxide, nitrogen oxides and sulfur dioxide. In addition, chromium was precipitated as Cr(2)(SO(4))(3). Experiments were run in a batch, laboratory-scale, pilot-plant, and the results are reported herein. After 30 min and 3 h of electrolysis at 0.26 A cm(-2), 45 degrees C and pH 9, total chemical oxygen demand (COD) was reduced by 52 and 83% and biochemical oxygen demand (BOD(5)) was reduced by 35 and 66%, respectively. Additionally, total suspended solids (TSS) were reduced by 8.6 and 26%, total phenolic compounds were reduced by 95.6 and 99.4%. Ammonia, sulfides and soluble chromium were reduced by 100% in both cases, while the mean anode efficiency was 81 g h(-1) A(-1) m(-2) and 1.9 g h(-1) A(-1) m(-2). Also, the mean energy consumption was 4.8 kwh kg(-1) of COD reduced and 200 kwh kg(-1) of COD reduced for 0.5 and 3 h, respectively. These results strongly indicate that this electrolytic method of total oxidation of TWL cannot be cost effective for wide use. However, it can be used as an effective pretreatment stage for detoxification of the wastewater, owing to great efficiency especially with respect to COD and toxicity (phenolics) reduction.     

含中间层的DSA电极电催化氧化硝基苯废水的研究

为了提高难降解有机废水的可生化性，以及更高效地去除废水中的特征污染物，同时避免二次污染，利用自制的含锡锑中间层的钌钯氧化物涂层电极对有机废水中的硝基苯进行处理，并利用SEM、XRD等方法对电极中间层、表层进行微观表征。微观测试表明，基体、中间层、表层之间结合力较强，有利于增强电极寿命；水处理实验表明，电催化氧化反应体系适合高浓度有机废水的处理，由于该反应体系需要外加电解质加强传质，这在实际运用中为废水中盐度的处理提供了一种新的途径，当电流密度为20 mA/cm²、电解质浓度为10 g/L、pH=5、极板间距=2 cm时，电催化氧化体系对硝基苯具有较高的去除效率。     

处理苯胺废水的电化学研究

采用电化学法处理苯胺废水 ,系统的氧化电极以恒电位法聚合制成高导电聚苯胺并压制成颗粒填料分多级填充在塔中形成固定床式电极。实验研究了不同的电位扫描速度、苯胺浓度及温度对电化学氧化还原反应的影响。实验表明 ,采用导电聚苯胺作为处理苯胺废水的氧化电极 ,可以有效地降低电化学反应的电解电位 ,提高氧化电流和反应速度 ,它是采用铂电极处理苯胺废水消耗电能的 1/ 2 .78。     

Degradation of azo dye Acid Red 14 in aqueous solution by electrokinetic and electrooxidation process

A new wastewater treatment technology--electrokinetic-electrooxidation process (EK-EO process) is developed in this paper. The EK-EO process can take advantage of both electrooxidation on the anode surface and the electrokinetic process of anionic impurities under an electric field, which can enhance the TOC removal in electrolysis process. The degradation of an anionic azo dye Acid Red 14 (AR14) was experimentally investigated. It was found that under an electric field AR14 could be migrated into anode compartment and be efficiently mineralized. After 360 min electrolysis of 100 mgl(-1) AR14 solutions at 4.5 mAcm(-2), complete discoloration was observed in both cathode and anode compartment. About 60% TOC was electromigrated from cathode compartment to anode compartment, and more than 25 mgl(-1) TOC was abated in anode compartment. A possible degradation mechanism of AR14 by EK-EO process was proposed. Additionally, the effect of current density, recycling flux, and electrolyte concentration on the EK-EO degradation of AR14 was also investigated.     

Application of response surface methodology to the removal of the antibiotic tetracycline by electrochemical process using carbon-felt cathode and DSA (Ti/RuO2-IrO2) anode

The removal of antibiotic tetracycline (TC) from water by electrochemical advanced oxidation process (EAOP) was performed using a carbon-felt cathode and a DSA (Ti/RuO(2)-IrO(2)) anode. The influence of applied current, initial pH and initial TC concentration on TC removal efficiency was investigated. Response surface methodology (RSM) based on Box-Behnken statistical experiment design (BBD) was applied to analyze the experimental variables. The positive and negative effects of variables and the interaction between variables on TC removal efficiency were determined. The applied current showed positive effect, while the initial pH value and initial tetracycline concentration gave negative effect on TC removal. The interaction between applied current and initial pH value was significant, while the interactions of initial TC concentration with applied current or initial pH were not pronounced. The results of adequacy check confirmed that the proposed models were accurate and reliable to analyze the variables of EAOP. The reaction intermediates were identified by high-performance liquid chromatography-mass spectrometry (LC-MS) technique and a plausible degradation pathway for tetracycline degradation was proposed. The acute toxicity experiments illustrated that the Daphnia magna immobilization rate reached the maximum after 240 min of electrolysis and then decreased with the progress of the reaction.