Electrochemical study of sulfide solution in the presence of surfactants

Voltammetric curve studies on aqueous Na2S solution in the presence of three types of surfactants are presented. Presence of anodic surfactant (HTAB) in creases anode current density and makes the corresponding anode peak potential shift to more negative. Potentials of the reduction of elemental sulfur to intermediates Sx2-shift to more negative with the increasing of HTAB concentrations. In the presence of HTAB, the anode current density at 77oC increases more than at 34oC. The electrolysis indicates that anodic product sulfur loosely adhered to the graphite electrode surface when HTAB is added to the anolyte. The total efficiency of producing sulfur is high after several times of cycle electrolysis.The results show that anode passivation is minimized in the presence of HTAB. The depassivation effect of HTAB is discussed.     

硫化钠溶液电化学分解制备硫磺和氢气的研究

报道了直接电解硫化氢碱性水溶液回收硫磺和氢气的研究。实验结果表明，控制一定电流密度，阳极电势和电解温度能有效地降低 产物硫在电极表面的沉积而引起的阳极钝化。     

有无隔膜槽中成对电解脱色活性艳蓝性能比较

分别采用有/无隔膜电解槽,以活性炭纤维(ACF)为阳极和阴极,研究了不同电流密度下蒽醌染料活性艳蓝KN-R的电化学脱色。在染料脱除量、电耗、脱除当量等方面比较了两种电解槽的脱色性能。结果表明,1.0～1.5 mA/cm2时,两种电解槽中均发生阳极电氧化和阴极电还原同时进行的成对电解脱色,无隔膜槽脱色性能优于隔膜槽。     

废旧印刷线路板电解过程中铜的分布特性

以废旧印刷线路板粉末为原材料,采用压片电解方法回收单质铜,研究了CuSO_4·5H2O浓度、H_2SO_4浓度、电流密度、电解时间和NaCl浓度对电解过程中Cu分布特性的影响。结果表明:废旧印刷线路板中的Cu以Cu2+的形式进入溶液,最终以粉末形式沉积在阴极;过高的H_2SO_4浓度、电流密度和NaCl浓度会导致析氢反应等,从而降低Cu在阴极和溶液中的分布;当CuSO_4·5H_2O浓度、H_2SO_4浓度、电流密度、电解时间、NaCl浓度分别为50 g/L、6 mol/L、80 m A/cm~2、5 h、40 g/L时,Cu在阴极、溶液、阳极泥中的分布比率分别为63.16%、34.14%和2.70%。     

电极成对电解苋菜红脱色研究

采用恒电流模式,同时以活性炭纤维(ACF)为阳极和阴极,在无隔膜电解槽中研究了不同电流密度下偶氮染料苋菜红的电化学脱色。结果表明在0.6～1.5 mA/cm2时,电解槽中发生阳极电氧化和阴极电还原同时进行的成对电解脱色。成对电解的发生,可以提高电解槽的工作处理能力。当电流密度为0.9 mA/cm2时,脱色率达到95.5%。     

钛基修饰电极催化电解去除水中硝酸盐氮的研究

利用热分解法制备CuO修饰Ti基阴极和SnO2-Sb2O5修饰Ti基阳极,组成无隔膜电解体系,以模拟废水(NO3--N 50mg/L)为对象,进行了水中NO3--N去除实验研究.结果数据表明,CuO修饰Ti基阴极对水中NO3--N的去除率随电流密度、极板间距、搅拌强度和电解时间增加而增加,在电流密度10mA/cm2、极板间距9mm、中等搅拌强度下电解150min,NO3--N催化还原去除率可达93.8%.Cl-支持电解可使NO3--N催化还原产物NH4+-N氧化为N2-N去除.在电流密度10mA/cm2、极板间距9mm、NaCl添加量600mg/L、中等搅拌强度下电解120min后,NO3--N和TN的去除率达到89.3%和86.9%,NO2--N和NH4+-N未检出.分析认为NO3--N还原机制为NOx中O被阴极表面Cu吸附固定,N—O键受氢攻击破坏,逐步还原.阳极电解Cl-生成HOCl,HOCl氧化NH4+-N成N2-N.     

电化学方法处理分散金黄HF-3R废水的研究

采用钛网作为阳极,钛网为阴极,对分散金黄HF-3R模拟染料废水进行了实验研究,探讨了电解时间、电解质种类及浓度、电流密度以及进水浓度对分散金黄HF-3R脱色效率的影响。结果表明:增加电流密度,提高电解质浓度,延长反应时间有利于分散金黄HF-3R色度的脱除,对于含有110 mg/L的分散金黄HF-3R溶液,电解质NaCl的质量浓度为20.0 g/L,电流密度为2.5 A/dm2,电解时间25 min,溶液的脱色率达到99%,COD去除率为98%。     

A strategy for enhancing anaerobic digestion of waste activated sludge: Driving anodic oxidation by adding nitrate into microbial electrolysis cell

Cathodic reduction of CO₂ and anodic oxidation of organic matters are crucial to methane-producing microbial electrolysis cell (MEC) applied in anaerobic digestion of waste activated sludge. However, cathodic CO₂ reduction is usually restrained by slow metabolism rates of H₂-utilizing methanogens and low electron-capturing capacity of CO₂, which consequently slows down the anodic oxidation that participates to sludge disintegration. Herein, a strategy with adding nitrate as electron acceptor to foster electronic transfer between the anode and cathode was proposed to improve anodic oxidation. Results showed that the average efficiency of anodic oxidation in the nitrate-added MEC increased by 55.9%. Accordingly, volatile suspended solid removal efficiency in the nitrate-added MEC was 21.9% higher than that of control MEC. Although the initial cumulative methane production in the nitrate-added MEC was lower than that of control MEC, the cumulative methane production in 24?days was 8.9% higher. Fourier transform infrared spectroscopy analysis indicated that anodic oxidation of MEC with nitrate accelerated the disintegration of sludge flocs and cell walls. Calculation on current signal further revealed that anodic oxidation driven by cathodic nitrate reduction was the main mechanism responsible for the improved sludge digestion.     

Electrochemical incineration of dimethyl phthalate by anodic oxidation with boron-doped diamond electrode

The anodic oxidation of aqueous solutions containing dimethyl phthalate (DMP) up to 125 mg/L with sodium sulfate (Na2SO4) as supporting electrolyte within the pH range 2.0–10.0 was studied using a one-compartment batch reactor employing a boron-doped diamond (BDD) as anode. Electrolyses were carried out at constant current density (1.5–4.5 mA/cm2). Complete mineralization was always achieved owing to the great concentration of hydroxyl radical (.OH) generated at the BDD surface. The e ects of pH, apparent current density and initial DMP concentration on the degradation rate of DMP, the specific charge required for its total mineralization and mineralization current e ciency were investigated systematically. The mineralization rate of DMP was found to be pH-independent and to increase with increasing applied current density. Results indicated that this electrochemical process was subjected, at least partially, to the mass transfer of organics onto the BDD surface. Kinetic analysis of the temporal change of DMP concentration during electrolysis determined by High Performance Liquid Chromatography (HPLC) revealed that DMP decay under all tested conditions followed a pseudo first-order reaction. Aromatic intermediates and generated carboxylic acids were identified by Gas Chromatography- Mass Spectrometry (GC-MS) and a general pathway for the electrochemical incineration of DMP on BDD was proposed.     

电催化氧化法处理生活污水研究

研究制作了3种金属氧化物修饰电极:Ti/SnO2-Sb2O3、Ti/RuO2-IrO2、Ti/SnO2-Sb2O3-MnO2/PbO2,用这3种电极电解葡萄糖溶液,筛选出了处理效果最好的电极——Ti/SnO2-Sb2O3-MnO2/PbO2电极。通过Ti/SnO2-Sb2O3-MnO2/PbO2电极电解葡萄糖溶液实验,研究了电解时间、电流密度、电解质浓度等因素对电解效果的影响。     

A high activity of Ti/SnO2-Sb electrode in the electrochemical degradation of 2,4-dichlorophenol in aqueous solution

Electrochemical degradation of 2,4-dichlorophenol (2,4-DCP) in aqueous solution was investigated over Ti/SnO₂-Sb anode. The factors influencing the degradation rate, such as applied current density (2-40 mA/cm²), pH (3-11) and initial concentration (5-200 mg/L) were evaluated. The degradation of 2,4-DCP followed apparent pseudo first-order kinetics. The degradation ratio on Ti/SnO₂-Sb anode attained > 99.9% after 20 min of electrolysis at initial 5-200 mg/L concentrations at a constant current density of 30 mA/cm² with a 10 mmol/L sodium sulphate (Na2SO4) supporting electrolyte solution. The results showed that 2,4-DCP (100 mg/L) degradation and total organic carbon (TOC) removal ratio achieved 99.9% and 92.8%, respectively, at the optimal conditions after 30 min electrolysis. Under this condition, the degradation rate constant (k) and the degradation half-life (t_1/2) were 0.21 min^-1 and (2.8±0.2) min, respectively. Mainly carboxylic acids (propanoic acid, maleic acid, propanedioic acid, acetic acid and oxalic acid) were detected as intermediates. The energy efficiencies for 2,4-DCP degradation (5-200 mg/L) with Ti/SnO₂-Sb anode ranged from 0.672 to 1.602 g/kWh. The Ti/SnO₂-Sb anode with a high activity to rapid organic oxidation could be employed to degrade chlorophenols, particularly 2,4-DCP in wastewater.     

Electrochemical oxidation of 1H,1H,2H,2H-perfluorooctane sulfonic acid (6：2 FTS) on DSA electrode：Operating parameters and mechanism

The 6:2 FTS was the substitute for perfluorooctane sulfonate(PFOS) in the chrome plating industry in Japan. Electrochemical oxidation of 6:2 FTS was investigated in this study. The degradabilities of PFOS and 6:2 FTS were tested on the Ti/SnO2–Sb2O5–Bi2O3anode. The effects of current density,potential,and supporting electrolyte on the degradation of 6:2 FTS were evaluated. Experimental results showed that 6:2 FTS was more easily degraded than PFOS on the Ti/SnO2–Sb2O5–Bi2O3anode. At a low current density of 1.42 mA/cm2,6:2 FTS was not degraded on Ti/SnO2–Sb2O5–Bi2O3,while the degradation ratio increased when the current density ranged from 4.25 to 6.80 mA/cm2. The degradation of 6:2 FTS at current density of 6.80 mA/cm2 followed pseudo first-order kinetics with the rate constant of 0.074 hr-1. The anodic potential played an important role in the degradation of 6:2 FTS,and the pseudo first-order rate constants increased with the potential. The surface of Ti/SnO2–Sb2O5–Bi2O3was contaminated after electrolysis at constant potential of 3 V,while the fouling phenomenon was not observed at 5 V. The fouled anode could be regenerated by incinerating at 600°C. The intermediates detected by ultra-performance liquid chromatography coupled with a triple-stage quadrupole mass spectrometer(UPLC–MS/MS) were shorter chain perfluorocarboxylic acids. The 6:2 FTS was first attacked by hydroxyl radical,and then formed perfluorinated carboxylates,which decarboxylated and removed CF2 units to yield shorter-chain perfluorocarboxylic acids.     

Pd-Fe/石墨烯多功能催化阴极降解4-氯酚机制研究

制备出Pd-Fe/石墨烯多功能催化阴极,与Ti/Ir O2/Ru O2阳极、有机涤纶滤布构成隔膜电解体系,将阴极催化加氢脱氯作用和阴阳极氧化作用耦合起来对含4-氯酚的有机废水进行降解,采用TOC仪、紫外扫描、高效液相色谱、离子色谱分析方法研究其降解效果及反应历程.结果表明,在最佳反应条件下,Pd-Fe/石墨烯催化体系阴阳极室中4-氯酚转化率分别为98.1%和95.1%,优于Pd/石墨烯催化体系阴阳极室的93.3%和91.4%.Pd-Fe/石墨烯催化体系脱氯效果高于95%,表明双金属催化剂具有更强的析氢能力.在阴阳极的协同作用下,反应120 min时4-氯酚被完全转化.通过阴极加氢脱氯作用,4-氯酚被还原成苯酚.随后苯酚在阴阳极的共同氧化作用下,被氧化生成对二苯酚、苯醌等中间产物,继而被氧化为小分子有机酸,最后被矿化为CO2和H2O,据此提出了4-氯酚降解的可能历程.     

Mn~(2+)对涂层钛阳极性能的影响

针对电解海水防污工艺中钛阳极经常遇到的Mn2+污染问题,本文首先对实际运行失效的钛阳极进行分析,再在实验室模拟钛阳极在含Mn2+的海水中的电解失效情况.通过电流效率测试,电化学交流阻抗谱测试,SEM,电子探针等测试方法详细考察了海水中的杂质Mn2+对涂层阳极性能的影响.结果表明,海水中Mn2+的存在是导致钛阳极失效的重要原因.电解过程中,Mn2+在阳极形成MnO2沉积层,增大阳极表面电阻,降低了阳极的电流效率;另一方面,MnO2的形成也会影响阳极表面的电流的均匀分布,导致阳极涂层机械破裂,加速阳极涂层失效.     

阳极材料对医院污水电化学消毒处理效果的研究

分析了三维电极法处理医院污水的影响因素，探讨了阳极材料、电流密度．水力停留时间、空气流量、极水比等因素对消毒效果的影响，确定在不加化学药剂、不影响水质和低耗能条件下电化学消毒试验的最佳使用条件。结果表明，在用涂有贵金属（钌、铂、铱）氧化物的钛板作阳极，不锈钢板作阴极，电流密度为6mA／cm^2、水力停留时间为15min、空气流量为40L／h、极水比为1．0的试验条件下，消毒后污水中总大肠菌群数〈500CFU／L。电化学法消毒处理医院污水方法简单有效、运行费用低，无二次污染．处理后的污水达到国家一级排放标准（GB8978—1996）。     

电絮凝法去除水中微量叔丁醇的研究

采用电絮凝法对水中微量的叔丁醇(TBA)进行去除,分别考察了电极材料、极板间距、电流密度、溶液初始pH值对叔丁醇去除效果的影响.结果表明,以铝为阳极、不锈钢为阴极,极板间距为1.4cm,电流密度为20mA/cm²,溶液初始pH值为8时,电解120min后叔丁醇的去除率为80.4%,此时铝阳极实际损耗量(1.93kg/m³)大于理论损耗量(1.61kg/m³).同时,叔丁醇的去除过程可用准一级反应动力学方程进行预测.絮体特性分析表明,在电絮凝去除叔丁醇的过程中除AlO(OH)、Al(OH)₃絮体吸附、絮凝作用外还存在阳极氧化过程,使得叔丁醇被氧化为醛、酮等小分子物质.     

活性炭的电解氧化再生研究

通过比较饱和吸附苯酚的活性炭的交换再生和电解再生,揭示了电解再生比交换再生有更高的再生效率。无论是单独的阳极再生还是阴极再生,其再生效率均可超过80%,但由于阳极区的氧化性,可以时苯酚在活性炭的表面聚合,从而降低了再生效率和活性炭的吸附性能。同时,在研究的体系内,200 mA认为是电解过程中最佳的电流强度,这一电流强度不但可以有效地再生活性炭,还可以有效地去除再生出来的苯酚。较小粒径的活性炭不仅有较高的吸附效率,而且也有较高的电解再生效率。     

以牺牲阳极强化的电化学联用方法修复铬污染土壤

为解决重金属污染土在电动法修复过程中存在的聚焦效应问题,提出了牺牲铁阳极的电化学联用修复技术。在传统电动修复方法基础上增加电解液净化循环装置,优化Cr（Ⅵ）还原及沉淀所需技术参数,并与传统电动修复技术进行对比,探讨其修复效果及适用性。结果表明:迁出的Cr（Ⅵ）可在Fe2+作用下被还原为Cr（Ⅲ）并沉淀,pH、电压梯度、电流密度、电极面积均会影响其反应速率,电极距离对反应速率无直接影响,主要影响电解功率。Cr（Ⅵ）还原-沉淀反应的最佳技术参数为:pH值5~6.5,电压梯度0.8 V/cm,电流密度>6.67 mA/cm2,电极面积90 cm2,电极距离15 cm;较传统电动修复技术,以牺牲阳极强化铬污染土的电化学联用修复技术中,土壤室不同点位的去除率波动范围在10%,最高点位的去除率提高近24%,达93.4%。靠近阳极附近土体中Cr（Ⅵ）去除率从0.24%提高到80.38%。以牺牲阳极强化污染土的电化学联用修复方法不仅有效解决了重金属迁移的聚焦问题,而且有助于促进土中重金属污染物的整体性迁出。     

电解催化还原-氯氧化无害化去除水中硝酸盐氮

基于对Pd-Me双金属催化还原的机理分析,提出了以NH₄+-N为目标产物,Fe催化还原NO₃--N的理论设想. 结合折点氯化技术,以Ti/Fe为阴极,以Ti/Ir-Ru为阳极,以NaCl为支持电解质组建无隔膜电解体系,开展了水中NO₃--N去除的试验研究. 结果表明,利用电解催化还原-氯氧化法可将模拟水样中NO₃--N转化为N₂去除,其反应历程为阴极催化还原NO₃--N生成NH₄+-N,阳极电解氯氧化NH₄+-N生成N₂. 在ρ(Cl-)为500 mg/L,电流密度为12 mA/cm2,极板距离为9 mm,搅拌强度为450 r/min的试验条件下电解150 min,初始ρ(NO₃--N)为50 mg/L的模拟水样出水ρ(TN)和ρ(NO₃--N)可分别降至2.9和2.8 mg/L,去除率分别达到94.1%和94.3%,NH₄+-N和NO₂--N均未检出. 分析认为,阴极对NO₃--N的催化还原机理为:Fe化学吸附氮氧化合物离子中的O形成固定的N—O键,电解产生的活性还原物质攻击N—O形成N—H新键.      

剩余污泥为底物的微生物燃料电池处理含铜废水

以剩余污泥作为阳极底物,CuSO4溶液为阴极溶液构建了双室有膜微生物燃料电池(microbial fuel cell,MFC),研究了MFC的启动,污泥的降解,Cu2+的去除和阴极还原产物的性质.结果表明,Cu2+可作MFC的阴极电子受体,在外电路电阻为1 000 Ω,Cu2+浓度为6 400 mg/L的条件下获得的稳...