Degradation of nitrogen-heterocyclic compounds by anodic oxidation and electro-Fenton methods.

This study describes the degradation of nitrogen-heterocyclic compounds (NHCs) by anodic oxidation and electro-Fenton. Using indole as a model nitrogen-heterocyclic compound, the removal of indole reached 68% and 97% by anodic oxidation and electro-Fenton, respectively, while the decay of TOC was 15% and 38% correspondingly. By the analysis of ultraviolet-visible spectra and liquid chromatography/mass spectrum, the degradation mechanism of indole by electro-Fenton was proposed as hydroxyl oxidation and anodic oxidation. The degradation of other NHCs including quinoline, isoquinoline and pyridine by anodic oxidation and electro-Fenton revealed the same sequence: quinoline approximately equal isoquinoline > indole > pyridine. A significant correlation between ln k (natural logarithm of rate constants) and E(LUMO) (the energy of the lowest unoccupied molecular orbit) was obtained by quantitative structure-activity relationship analysis. Degradation of coking plant wastewater showed the removal of COD and TOC were 42% and 22% respectively after 180 min treatment by electro-Fenton.     

Optimisation of decolourisation and degradation of Reactive Black 5 dye under electro-Fenton process using Fe alginate gel beads

The aim of this work was to improve the ability of the electro-Fenton process using Fe alginate gel beads for the remediation of wastewater contaminated with synthetic dyes and using a model diazo dye such as Reactive Black 5 (RB5). Batch experiments were conducted to study the effects of main parameters, such as voltage, pH and iron concentration. Dye decolourisation, reduction of chemical oxygen demand (COD) and energy consumption were studied. Central composite face-centred experimental design matrix and response surface methodology were applied to design the experiments and to evaluate the interactive effects of the three studied parameters. A total of 20 experimental runs were set, and the kinetic data were analysed using first-order and second-order models. In all cases, the experimental data were fitted to the empirical second-order model with a suitable degree for the maximum decolourisation of RB5, COD reduction and energy consumption by electro-Fenton–Fe alginate gel beads treatment. Working with the obtained empirical model, the optimisation of the process was carried out. The second-order polynomial regression model suggests that the optimum conditions for attaining maximum decolourisation, COD reduction and energy consumption are voltage, 5.69 V; pH 2.24 and iron concentration, 2.68 mM. Moreover, the fixation of iron on alginate beads suggests that the degradation process can be developed under this electro-Fenton process in repeated batches and in a continuous mode.     

Electro-Fenton pretreatment for the improvement of tylosin biodegradability

The feasibility of an electro-Fenton process to treat tylosin (TYL), a non-biodegradable antibiotic, was examined in a discontinuous electrochemical cell with divided cathodic and anodic compartments. Only 15 min electrolysis was needed for total tylosin degradation using a carbon felt cathode and a platinum anode; while 6 h electrolysis was needed to achieve high oxidation and mineralization yields, 96 and 88 % respectively. Biodegradability improvement was shown since BOD₅/COD increased from 0 initially to 0.6 after 6 h electrolysis (for 100 mg L^?1 initial TYL). With the aim of combining electro-Fenton with a biological treatment, an oxidation time in the range 2 to 4 h has been however considered. Results of AOS (average oxidation state) and COD/TOC suggested that the pretreatment could be stopped after 2 h rather than 4 h; while in the same time, the increase of biodegradability between 2 and 4 h suggested that this latter duration seemed more appropriate. In order to conclude, biological cultures have been therefore carried out for various electrolysis times. TYL solutions electrolyzed during 2 and 4 h were then treated with activated sludge during 25 days, showing 57 and 67 % total organic carbon (TOC) removal, respectively, namely 77 and 88 % overall TOC removal if both processes were considered. Activated sludge cultures appeared, therefore, in agreement with the assessment made from the analysis of physico-chemical parameters (AOS and COD/TOC), since the gain in terms of mineralization expected from increasing electrolysis duration appeared too low to balance the additional energy consumption.     

Transformation characteristics of refractory pollutants in plugboard wastewater by an optimal electrocoagulation and electro-Fenton process

The treatment of the plugboard wastewater was performed by an optimal electrocoagulation and electro-Fenton. The organic components with suspended fractions accounting for 30% COD were preferably removed via electrocoagulation at initial 5 min. In contrast, the removal efficiency was increased to 76% with the addition of H(2)O(2). The electrogenerated Fe(2+) reacts with H(2)O(2) and leads to the generation of (·)OH, which is responsible for the higher COD removal. However, overdosage H(2)O(2) will consume (·)OH generated in the electro-Fenton process and lead to the low COD removal. The COD removal efficiency decreased with the increased pH. The concentration of Fe(2+) ions was dependent on the solution pH, H(2)O(2) dosage and current density. The changes of organic characteristics in coagulation and oxidation process were differenced and evaluated using gel permeation chromatography, fluorescence excitation-emission scans and Fourier transform infrared spectroscopy. The fraction of the wastewater with aromatic structure and large molecular weight was decomposed into aliphatic structure and small molecular weight fraction in the electro-Fenton process.     

阳极氧化联合电-Fenton氧化深度处理垃圾渗滤液

采用多孔碳素阴极、Ti/SnO2-Sb2O5-IrO2阳极构建电化学氧化系统用于渗滤液的深度处理。研究结果表明,所构建的电化学氧化系统通过阳极氧化和电-Fenton氧化2种机制降解有机污染物;处理过程中阴极表面形成的沉淀物对TOC和COD的衰减也产生了影响。在阴极电位为-1.0 V、Fe2+ 初始浓度为0.5 mmol/L的条件下,电化学处理120 min获得了58% 的TOC去除;处理480 min COD去除率为55%,NH3-N去除率为99%,TN去除率为60%,色度几乎被完全去除。GC-MS分析结果表明,渗滤液中以腐殖质类物质为主的有机化合物被降解为分子量相对较小的有机物,直至完全矿化。联合阳极氧化和电-Fenton氧化机制的电化学处理方法为垃圾渗滤液深度处理提供了新的选择。     

光电芬顿氧化法深度处理垃圾渗滤液研究

采用光电芬顿氧化法对北京市某垃圾填埋场已经生化处理后的垃圾渗滤液进行深度处理,分别考察了电流强度和铁的不同价态等因素对渗滤液总有机碳（TOC）、化学需氧量（COD）以及色度去除效果的影响,并对阳极氧化、电芬顿和光电芬顿不同反应过程进行了对比。通过分析渗滤液UV-Vis光谱(200～500 nm)变化和渗滤液中有机污染物的分子量变化,发现光电芬顿反应可以明显改善渗滤液生化性。深入研究了反应过程中铁价态的变化规律。试验结果发现,以高比表面积的活性炭纤维(ACF)为阴极的光电芬顿反应可以有效降解垃圾渗滤液,在pH为3,Fe²⁺ 浓度为1 mmol/L,电流为0.5 A,O₂通入量为250 mL/min条件下降解360 min,垃圾渗滤液TOC和COD去除率分别达到78.9%和62.8%,色度完全去除。     

新型电芬顿反应器处理酸性矿山废水中的Sb(Ⅲ)

为了高效地去除酸性矿山废水中的Sb(Ⅲ),采用一种基于电芬顿反应的新型反应器进行处理。探讨了新型反应器各项性能(去除率、能耗、·OH产量)的优势;分别考察了电流强度、pH、板间距、曝气速率、电解质浓度对Sb(Ⅲ)去除效果的影响;使用水杨酸和苯醌对电芬顿体系中Sb(Ⅲ)的去除机理进行了分析;并探究新型电芬顿反应器对实际废水中的Sb(Ⅲ)处理效果。结果表明：与吸附、电氧化、传统电芬顿法相比,新型反应器在Sb(Ⅲ)的处理中更加高效,并且能耗更低,通过阴极旋转能够提高·OH的产量,增强电芬顿反应氧化能力;在电流强度为120 mA,pH为3,板间距为2 cm,曝气速率为90 mL·min⁻¹,电解质浓度为100 mg·L⁻¹的最佳反应条件下,Sb(Ⅲ)废水去除率接近100%;在电芬顿反应体系中,·OH和HO₂·能够共同促进Sb(Ⅲ)的去除;通过该反应器处理实际废水,Sb(Ⅲ)去除率能够达到89%。以上结果可为新型电芬顿反应器高效处理含Sb(Ⅲ)的酸性矿山废水提供参考。     

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.     

Recent updates on electrochemical degradation of bio-refractory organic pollutants using BDD anode: a mini review

Boron-doped diamond (BDD) is playing an important role in environmental electrochemistry and has been successfully applied to the degradation of various bio-refractory organic pollutants. However, the review concerning recent progress in this research area is still very limited. This mini-review updated recent advances on the removal of three kinds of bio-refractory wastewaters including pharmaceuticals, pesticides, and dyes using BDD electrode. It summarized the important parameters in three electrochemical oxidation processes, i.e., anodic oxidation (AO), electro-Fenton (EF), and photoelectro-Fenton (PEF) and compared their different degradation mechanisms and behaviors. As an attractive improvement of PEF, solar photoelectro-Fenton using sunlight as UV/vis source presented cost-effectiveness, in which the energy consumption for enrofloxacin removal was 0.246 kWh/(g TOC), which was much lower than that of 0.743 and 0.467 kWh/(g TOC) by AO and EF under similar conditions. Finally the existing problems and future prospects in research were suggested.     

三维粒子电极处理染料废水的效能及机制

以自制的负载Sb掺杂SnO2的陶瓷颗粒为粒子电极,构建三维电极体系,对其处理活性艳红X-3B废水的效能进行研究,并借助于循环伏安曲线、羟基自由基的荧光光谱检测技术对三维粒子电极体系的电催化氧化机制进行研究。结果表明,优化槽电压为13 V,处理时间为60 min时,三维电极体系对活性艳红X-3B废水的COD去除率和相应能耗分别为85.6%与16.8 kW·h/(kg COD),与二维电极体系相比COD去除率提高了32.9%,能耗降低了33.3%。UV-Vis吸收光谱分析表明电催化氧化技术可以破坏活性艳红X-3B分子中的偶氮键、苯环和萘环,将大分子降解为小分子。电催化氧化机制研究表明,在本实验条件下三维电极主要通过间接氧化而不是直接氧化提高电催化氧化效能,即在三维粒子电极体系中羟基自由基的产生量多于二维电极体系,从而实现高效低耗处理活性艳红X-3B废水。     

模拟太阳光协同三维电极/电Fenton降解甲基橙

以TiO2纳米管为阳极、石墨电极为阴极、泡沫镍颗粒为粒子电极组成新型的模拟太阳光协同三维电极/电Fenton(3D/SPEF)体系降解甲基橙。研究了该体系的协同处理效果,以及该体系降解甲基橙的影响因素和反应动力学。结果表明:模拟太阳光与3D/EF体系光电催化联合处理表现出良好的协同效应,其处理能耗仅为3D/EF的9/16;协同体系降解甲基橙过程的表观反应动力学总级数为0.97;通过单因素实验确定协同体系最优反应条件为:电压为15 V、初始pH为7、甲基橙初始浓度为50 mg/L、Fe2+投加量为1 mmol/L,甲基橙的去除率达到93.77%,3D/SPEF体系在中性条件更有利于甲基橙的降解,克服了常规三维电极/电Fenton一般只能在酸性条件下进行的不足。     

Fenton降解涂装废水的因素影响及动力学分析

以江苏某电动自行车制造企业的涂装废水为研究对象,采用单因素和响应面优化Fenton氧化处理的反应条件,分析了其动力学过程。结果表明：在pH=3.21、n(H₂O₂/Fe²⁺)=8∶1、m(H₂O₂/COD)=4.17∶1、氧化反应时间为120 min的条件下,COD和TP的去除率均达到最高,分别为81.32%和98%,其降解过程符合一级反应动力学,室温下降解速率常数k为0.014 2 min⁻¹,活化能为4.76 kJ·mol⁻¹。在pH=3.21、n(H₂O₂/Fe²⁺)=8∶1、m(H₂O₂/COD)=0.78∶1、反应时间120 min的条件下,Fenton半氧化体系对COD去除率可达42.5%左右,处理后废水的B/C比由0.12提高至0.35。综合经济因素,认为Fenton半氧化与生物处理工艺耦合处理实际涂装废水更佳。     

Degradation of Acid Orange 7 by electrochemically generated (*)OH radicals in acidic aqueous medium using a boron-doped diamond or platinum anode: a mechanistic study

A comparative study of the degradation of Acid Orange 7 (AO 7) aqueous solutions in acidic medium of pH 3.0 by electro-Fenton process using Pt or boron-doped diamond (BDD) anode was reported. The oxidative degradation of AO 7 by electrochemically generated hydroxyl radicals follows a pseudo-first order kinetic with a similar rate constant with BDD or Pt anode. The absolute rate constant of the AO 7 hydroxylation reaction was determined as (1.10+/-0.04)x10(10)M(-1)s(-1) by using the competition kinetic method. The comparative study of TOC measurements during electro-Fenton treatment showed a higher mineralization rate with BDD than Pt anode at the first hours of electrolysis because of the higher oxidizing power of this anode. The electro-Fenton degradation of AO 7 was followed by monitoring the formation and evolution of aromatic intermediates which are oxidized to aliphatic carboxylic acids before mineralization (transformation to CO(2) and inorganic ions, i.e. sulphate, nitrate and ammonium). The follow-up of the solution toxicity evolution shows the formation of intermediates more toxic than AO 7 and the connection between toxicity and aromaticity. A mineralization reaction pathway of AO 7 by electro-Fenton degradation involving all the intermediates identified was proposed.     

Electrooxidation of industrial wastewater containing 1,4-dioxane in the presence of different salts

The treatment of 1,4-dioxane solution by electrochemical oxidation on boron-doped diamond was studied using a central composite design and the response surface methodology to investigate the use of SO₄ ^2? and HCO₃ ^? as supporting electrolytes considering the applied electric current, initial chemical oxygen demand (COD) value, and treatment time. Two industrial effluents containing bicarbonate alkalinity, one just carrying 1,4-dioxane (S1), and another one including 1,4-dioxane and 2-methyl-1,3-dioxolane (S2), were treated under optimized conditions and subsequently subjected to biodegradability assays with a Pseudomonas putida culture. Electrooxidation was compared with ozone oxidation (O₃) and its combination with hydrogen peroxide (O₃/H₂O₂). Regarding the experimental design, the optimal compromise for maximum COD removal at minimum energy consumption was shown at the maximum tested concentrations of SO₄ ^2? and HCO₃ ^? (41.6 and 32.8 mEq L^?1, respectively) and the maximum selected initial COD (750 mg L^?1), applying a current density of 11.9 mA cm^?2 for 3.8 h. Up to 98 % of the COD was removed in the electrooxidation treatment of S1 effluent using 114 kWh per kg of removed COD and about 91 % of the COD from S2 wastewater applying 49 kWh per kg of removed COD. The optimal biodegradability enhancement was achieved after 1 h of electrooxidation treatment. In comparison with O₃ and O₃/H₂O₂ alternatives, electrochemical oxidation achieved the fastest degradation rate per oxidant consumption unit, and it also resulted to be the most economical treatment in terms of energy consumption and price per unit of removed COD.     

Efficient removal of triphenylmethane dyes from aqueous medium by in situ electrogenerated Fenton's reagent at carbon-felt cathode

Fenton's reagent (Fe2+ +H2O2) has been electrogenerated in situ in an undivided electrolytic cell from the effective reduction of Fe3+ and O2 at carbon-felt cathode for the treatment of aqueous solutions of four triphenylmethane dyes (TPMs), namely malachite green (MG), crystal violet (CV), methyl green (MeG) and fast green FCF (FCF), at pH 3.0 and room temperature. MG has been used as a model among them to study the influence of some experimental parameters on the decay kinetics, COD removal and current efficiency. The results in such electro-Fenton system are explained in terms of the many parasitic reactions involving .OH. Higher efficiency values are obtained with rising organic content and decreasing applied current. The first stage of the mineralization process, involving aromatic by-products, leads to fast decoloration as well as quick initial COD removal that fit well to a pseudo-first-order kinetics. At prolonged electrolysis time, the mineralization rate and efficiency decrease due to the formation of hardly oxidizable compounds and the enhancement of wasting reactions. Solutions of all four TPMs are quickly degraded following a pseudo-first-order decay kinetics. The absolute rate constant (kTPM) for their reaction with .OH increases in the order MeG相似文献   

CQDs-rGO/GF阴极电芬顿体系中过氧化氢的生成和对硝基苯酚的降解

对二维材料石墨烯进行表面修饰以提高其催化性能为目前较为重要的研究方向。利用水热法合成了直径5 nm的零维材料碳量子点(carbon quantum dots, CQDs),将其与还原石墨烯(reduced graphene oxide,rGO)进行结合,并载于石墨片(graphite flake,GF)表面制备了CQDs-rGO/GF复合电极。将该电极作为电芬顿体系的阴极,考察了CQDs对氧的二电子电化学还原生成过氧化氢的阴极反应的影响;以对硝基苯酚(p-nitrophenol,PNP)为目标污染物,考察了在Fe²⁺存在时该电芬顿体系对PNP的降解性能。结果表明：CQDs显著提高了阴极的活性,CQDs-rGO/GF阴极体系中过氧化氢的生成量是rGO/GF电极的1.9倍,是GF电极的2.4倍;在Fe²⁺存在时,该电芬顿体系对PNP的降解率达到90.6%,COD去除率为64.3%;羟基自由基是使PNP降解的主要活性物种。降解过程中PNP的UV-Vis谱图和COD去除率的变化均显示绝大部分PNP已被矿化,少量转化为小分子羧酸。以上研究结果表明,零维CQDs可用于提高二维材料rGO电极的催化性能。     

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。     

电解催化氧化法废水处理机制研究

采用电解催化氧化法（electrochemical enhanced catalytic oxidation reaction）处理某高浓度有机废水（COD约10 000 mg·L-1）,该工艺主要包括电解反应、催化氧化反应以及催化氧化反应后废水内循环进行电解反应等过程。开展了不同因素对废水COD降解效率影响的研究,并对反应降解机制和反应动力学进行了探讨。结果显示,内循环设计结合H2O2溶液投加量逐步增加的方式,使得体系在420 min反应时间内均保持着不断削减COD的能力。当FeSO4·7H2O初始投加量为0.6 g·L-1、回流比R为0.5时,COD减少量可达9 340 mg·L-1。反应过程中工作电流I及氧化还原电势ORP监测值的不断波动表明反应体系中有机物不断被降解,氧化还原环境不断地变化。该工艺耦合电解氧化和Fenton技术,协同因子约为1.48,且可极大提高废水混凝性能,反应60 min后经废水混凝处理可使COD去除率由4.27%提高至26.21%。     

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 ⁺.     

Fe (III) supported on resin as effective catalyst for the heterogeneous oxidation of phenol in aqueous solution

FeIII supported on resin as an effective catalyst for oxidation was prepared and applied for the degradation of aqueous phenol. Phenol was selected as a model pollutant and the catalytic oxidation was carried out in a batch reactor using hydrogen peroxide as the oxidant. The influent factors on oxidation, such as catalyst dosage, H2O2 concentration, pH, and phenol concentration were examined by considering both phenol conversion and chemical oxygen demand (COD) removal. The FeIII-resin catalyst possesses a high oxidation activity for phenol degradation in aqueous solution. The experimental results of this study show that almost 100% phenol conversion and over 80% COD removal can be achieved with the FeIII-resin catalyst catalytic oxidation system. A series of prepared resin were investigated for improving the oxidation efficiency. It was found that the reaction temperature and initial pH in solution significantly affected both of phenol conversion and COD removal efficiency. The activity of the catalyst significantly decreased at high pH, which was similar to the Fenton-like reaction mechanism. Results in this study indicate that the FeIII-resin catalytic oxidation process is an efficient method for the treatment of phenolic wastewater.