Electrocatalytic oxidation of methyl tert-butyl ether (MTBE) in aqueous solution at a nickel electrode

This study utilized the electrocatalytic characteristics of nickel electrode to perform degradation of methyl tert-butyl ether (MTBE) in aqueous solution. Lab experiments were conducted in a spiltless bath type cell equipped with a nickel electrode as working electrode, a platinum wire as counter electrode, and an Ag/AgCl electrode as reference electrode. Effects of controlled potential, supporting electrolyte, and solution pH on the efficiency of MTBE removal were examined under the control of the constant-potential conditions. Experiment results showed that the optimum electrolytic condition was operated at 0.35 V in a 1M KOH electrolyte solution, and the initial 20 mgl(-1) MTBE was reduced by 73% within 180 min under the optimum control. As using 1M Na2SO4 and 1M KCl as electrolyte, the efficiency of MTBE removal dropped to 60% and 50% under the similar controls. Comparing with various pH controls, the strong basic condition is favorable for electrocatalytic oxidation of MTBE in the Ni-electrolytic system. The efficiency of MTBE removal showed a rising trend with increasing initial pH of the solution. The formation of a redox NiOOH/Ni(OH)2 layer on the anode surface, which was observed on the SEM image, can explain that nickel plays a mediator role on improving electrocatalytic oxidation of MTBE at 0.35 V in a strong basic condition. The by-products of MTBE degradation were identified as acetone and CO(2) by GC/MS, and the distributions of carbon atoms in acetone, CO2, and MTBE were found 22%, 51%, and 27% through the optimum control of electrochemical oxidation.     

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 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.     

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。     

吸附-电化学氧化耦合处理对氯苯酚废水及动力学

以毡状活性炭纤维为阳极,不锈钢为阴极,吸附-电化学氧化耦合降解对氯苯酚废水进行了研究。考察了吸附或耦合电化学氧化过程、电流密度、支持电解质硫酸钠浓度和活性炭纤维重复使用对废水COD去除率的影响,结果表明,采用吸附-电化学氧化耦合方法,当电流密度7.6 mA/cm2支持电解质（硫酸钠）浓度为1 g/L,处理时间为180 min,4-CP废水COD去除率可达97.09%。毡状活性炭纤维对4-CP的静态吸附过程符合Langmiu吸附等温方程。建立了吸附-电化学氧化COD去除动力学模型,动力学模型参数表明,对于COD的去除,电化学氧化作用比吸附作用大。     

Decolorization and degradation of H-acid and other dyes using ferrous-hydrogen peroxide system

In this study, advanced oxidation process utilizing Fenton's reaction was investigated for the decolorization and degradation of two commercial dyes viz., Red M5B, Blue MR and H-acid, a dye intermediate used in chemical industries for the synthesis of direct, reactive and azo dyes. Effect of Fe2 +, H2O2, pH, and contact time on the degradation of the dyes was studied. Maximum color and COD removal was obtained for Red MSB, H-acid and Blue MR at 10-25 mg/l of Fe2+ dose and 400-500 mg/l of H2O2 dose at pH 3.0. The initial oxidation reaction was found to fit into first order rate kinetics and the rate of oxidation of H-acid was higher than the other dyes. Release of chloride and sulfate from the Fenton's treated Red M5B dye and sulfate from H-acid and Blue MR indicates that the dye degradation proceeds through cleavage of the substituent group.     

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。     

有毒难降解有机物高级氧化电催化电极

在电催化电极的作用下 ,电化学反应和化学催化作用结合 ,导致有机分子的电催化降解。在分析中 ,综述了电催化高级氧化电极研究现状 ,阐述与评价了过渡金属涂层电极、金属氧化物涂层电极、含掺杂半导体涂层电极、金刚石膜电极、三维电极等几个主要方面的研究成果 ,并对今后工作的重点提出了一些意见。     

Synergistic effects of liquid and gas phase discharges using pulsed high voltage for dyes degradation in the presence of oxygen

The technology of combined liquid and gas phase discharges (LGD) using pulsed high voltage for dyes degradation was developed in this study. Apparent synergistic effects for Acid orange II (AO) degradation in the presence of oxygen were observed. The enhancement of AO degradation rate was around 302%. Furthermore, higher energy efficiency was obtained comparing with individual liquid phase discharge (LD) or gas phase discharge process (GD). The AO degradation in the presence of oxygen by LGD proceeded through the direct ozone oxidation and the ozone decomposition induced by LD. Important operating parameters such as electrode distance, applied voltage, pulse repetition rate, and types of dyes were further investigated.     

The influence of FeCl3 on the photocatalytic degradation of dissolved azo dyes in aqueous TiO2 suspensions

The study concerned decolouration of solutions of azo, anionic (Acid Orange 7, Reactive Red 45, Acid Yellow 23) and cationic (Basic Blue 41 and Basic Orange 66) dyes during illumination with UV (lambdamax 366 nm) irradiation in the presence of TiO2 and FeCl3. The process of decolouration during illumination of the solutions studied containing FeCl3 underwent significant intensification in the case of anionic dyes and unfavourable inhibition in case of cationic dyes. It was also observed that FeCl3 had a diverse influence on the adsorption of the dyes studied on TiO2. The adsorption of anionic dyes and decolouration of solutions before the illumination was observed only in the presence of FeCl3. In case of cationic dyes the addition of FeCl3 caused elimination of these phenomena. An additional cause of decolouration of anionic dyes solutions before illumination was the precipitation of their poorly soluble compounds from Fe3+. The processes of degradation and mineralization of the dye that accompanied decolouration of Acid Orange 7 solutions were also observed. It was stated that similarly to the case of Acid Orange 7, the decolouration of the studied anionic dyes' solutions can depend on the concentration of FeCl3, the amount of TiO2 and the initial concentration of the dye in its solution.     

PbO2电极的改性及其在难降解有机废水电化学处理中的应用

电化学方法处理难降解有机废水是一种很有前途的技术,其应用的关键是开发出高效、稳定、低成本的电极材料.PbO2电极在工业领域具有广泛的应用基础,具有较高的析氧电势和电催化活性,被认为在电化学处理难降解有机废水方面有重要的应用前景.本文对PbO2电极制备方法与改性以及在难降解有机废水电化学处理中应用的研究成果和最新进展进行了综述,并对该研究领域今后的发展趋势进行了分析.     

PbO2电极的改性及其在难降解有机废水电化学处理中的应用

电化学方法处理难降解有机废水是一种很有前途的技术,其应用的关键是开发出高效、稳定、低成本的电极材料.PbO2电极在工业领域具有广泛的应用基础,具有较高的析氧电势和电催化活性,被认为在电化学处理难降解有机废水方面有重要的应用前景.本文对PbO2电极制备方法与改性以及在难降解有机废水电化学处理中应用的研究成果和最新进展进行了综述,并对该研究领域今后的发展趋势进行了分析.     

电催化氧化处理除草剂异噁草酮废水的效能

为有效处理含异噁草酮除草剂废水，以Sb掺杂Ti／SnO2电极为阳极，不锈钢板为阴极，采用电催化氧化技术对异噁草酮废水进行降解，研究了不同影响因素对异噁草酮去除率的影响，并分析了异噁草酮的降解效果。结果表明，当异噁草酮初始浓度为100mg／L、电流密度为20mA／cm2、电解质投加量为0．10mol／L，反应120min后，异噁草酮去除率达到94％，此时TOC去除率为57．9％，能耗为25kWh／m2，且废水的可生化性能显著提高。     

电解质种类对电催化氧化降解苯酚的影响

研究了不同电解质对有机物电催化氧化性能的影响。以高温热解法制备了Ti/SnO2+Sb2O3阳极,用SEM和XRD对电极结构进行了表征。以苯酚为目标有机物,考察了Na2SO4、NaCl和NaNO33种不同电解质对苯酚降解效果的影响。用循环伏安法研究了苯酚在不同支持电解质条件下的电化学行为。采用碘量法测定了在不同电解质溶液中氧化性物质的生成量。研究结果表明,电极的活性涂层主要由SnO2和微量的Sb2O3组成,均匀完整地覆盖住了Ti基体表面。以NaCl为支持电解质时苯酚降解效果明显优于用Na2SO4、NaNO3为支持电解质,并且苯酚的降解主要以电极表面电化学生成的HClO和ClO-的间接化学氧化为主。以Na2SO4为支持电解质时有利于降低和稳定槽电压。在3种电解质条件下,苯酚的降解均遵循一级反应动力学规律。在降解过程中NaCl溶液中生成的氧化性物质浓度最大,且随降解时间延长逐渐增大。     

Degradation of microcystins in aqueous solution with in situ electrogenerated active chlorine

A new and efficient method for the degradation of microcystins (one family of blue algal toxins) was developed and studied. Microcystins (MCs) in water were directly and effectively removed by active chlorine transformed in situ from the naturally existing Cl- in water resource using electrochemical method. Titanium coated with RuO2 and TiO2 was used as the anode. Microcystin-RR (MCRR) and Microcystin-LR (MCLR) were chosen as the model compounds of MCs. The results suggested that 20.87 mgl(-1) MCs (12.58 mgl(-1) MCRR and 8.29 mgl(-1) MCLR) in aqueous solution with 1.85 mM Cl- could be synchronously decomposed within 15 min electrolysis under the condition of the current density 8.89 mAcm(-2), 20 degrees C and pH 7.00. The qualitative analysis showed that the heptapetide ring and the Adda group of both treated MCs were changed. The results also indicated that the removal rates of both MCs increased with the increasing of chloride concentration and applied current density, but decreased with the increasing of initial concentration of MCs and initial pH of electrolyte. In the absence of Cl-, only a small fraction of both MCs were decomposed by direct anodic oxidation, while their almost complete removals could be obtained in the case of indirect electrooxidation with in situ electrogenerated active chlorine from Cl- in water.     

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。     

Degradation of tetracycline at a boron-doped diamond anode: influence of initial pH,applied current intensity and electrolyte

The anodic oxidation of tetracycline was performed in an up-flow reactor, operating in batch mode with recirculation, using as anode a boron-doped diamond electrode. The influence on the degradation rate of solution initial pH (2 to 12), applied current intensity (25 to 300 A m^?2) and type of electrolyte (sodium sulphate or sodium chloride) were investigated. For the assays run at equal current density, with sodium sulphate as electrolyte, the solution’s initial pH of 2 presented the highest absorbance and chemical oxygen demand removals. Regarding the influence of current density, for equal charge passed, the organic load removal rate decreased with the increase in applied current. When sodium sulphate was used as an electrolyte, high-performance liquid chromatography (HPLC) results have shown an almost complete removal of tetracycline after a 2-h assay. HPLC results have also shown the presence of oxamic acid as one of the intermediates of tetracycline anodic oxidation. The complete removal of tetracycline was much faster in the presence of chloride ions that promoted the complete degradation of this antibiotic in 30 min. However, in the presence of chloride ions, the tetracycline mineralization is slower, as observed by the lower organic carbon removal rate when compared to that of the tetracycline degradation in the presence of sulphate.     

电催化氧化处理除草剂异草酮废水的效能简

为有效处理含异草酮除草剂废水，以Sb掺杂Ti/SnO₂电极为阳极，不锈钢板为阴极，采用电催化氧化技术对异草酮废水进行降解，研究了不同影响因素对异草酮去除率的影响，并分析了异草酮的降解效果。结果表明，当异草酮初始浓度为100 mg/L、电流密度为20 mA/cm²、电解质投加量为0.10 mol/L，反应120 min后，异草酮去除率达到94%，此时TOC去除率为57.9%，能耗为25 kWh/m³，且废水的可生化性能显著提高。     

Degrading a mixture of three textile dyes using photo-assisted electrochemical process with BDD anode and O2–diffusion cathode

In this paper, degradation of a mixture of three azo dyes was studied by the photo-assisted electrochemical process using an O₂-diffusion cathode containing carbon nanotubes and boron-doped diamond (BDD) anode. The concentration of three textile dyes (C.I. Acid Orange 8 (AO8), C.I. Acid Orange 10 (AO10), and C.I. Acid Orange 12 (AO12)) was determined simultaneously despite the severe overlap of their spectra. For this purpose, partial least square (PLS), as a multivariate calibration method, was utilized based on recording UV–Vis spectra during the decolorization process. Moreover, the central composite design was used for the modeling of photo-assisted electrochemical decolorization of the aqueous solutions containing three dyes. The investigated parameters were the initial concentration of three dyes, applied current and reaction time. Analysis of variance (ANOVA) revealed that the obtained regression models match the experimental results well with R (Khataee et al. 2010, Clean-Soil Air Water 38 (1):96–103, 2010) of 0.972, 0.971, and 0.957 for AO8, AO10, and AO12, respectively. Three-dimensional surface and contour plots were applied to describe the relation between experimental conditions and the observed response. The results of TOC analysis confirmed good ability of proposed photo-assisted electrochemical process for degradation and mineralization of textile industry wastewater.     

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.