掺硼金刚石电极降解模拟焦化废水中的喹啉

采用掺硼金刚石（BDD）电极电化学氧化法降解模拟焦化废水中的喹啉,并通过GC-MS技术分析了喹啉的降解机理及途径。实验结果表明：在常温、初始喹啉质量浓度为50.0 mg/L、电解质Na₂SO₄浓度为0.05 mol/L、模拟废水pH为7、电解时间为2.5 h、电流密度为30 mA/cm²、极板总面积与模拟废水体积的比为160 cm²/cm³的条件下,喹啉降解率接近100%;TOC由初始时的29.43 mg/L降至5.76 mg/L,TOC去除率达80%;COD由初始时的95.25 mg/L降至20.65 mg/L,COD去除率达78%;在降解过程中,首先在喹啉苯环的5位和8位发生羟基化反应,然后苯环发生断裂,形成带有吡啶环的中间产物及羧酸类产物,最后氮杂环开环,生成二氧化碳和水。     

单极性三维电极电解处理含钴废水

采用并联式单极性三维电极电解处理低浓度含钴废水并回收金属钴,比较了二维电极与三维电极的钴离子去除效果,探讨了填充材料、电流、填充比（填充材料与废水的质量比）、废水pH对钴离子去除效果的影响,建立了反应动力学模型,并进行了经济性分析。实验结果表明：三维电极对钴离子的去除效果远优于二维电极;在以网状Ti/RuO₂为阳极、不锈钢板为阴极并作为主电极、空心钢球为第三极、极间距5 cm、电解时间60 min、电流为0.6 A、填充比为2.5、不调节废水pH的条件下处理钴离子质量浓度为112.3 mg/L的废水,钴离子去除率可达85.6%、电流效率为68.3%;去除钴离子的电化学反应符合一级反应动力学模型;该方法具有良好的环境与经济效益。     

三维电极法处理六硝基茋生产废水

以Ti板为阴极、Ti/IrO₂-Ta₂O₅电极为阳极,采用三维电极法处理六硝基茋生产废水。通过单因素实验和正交实验确定的最佳工艺条件为：电解电压8 V,电解时间4 h,极板间距5 mm,初始废水COD=3 120 mg/L,m（玻璃珠）∶m（活性炭）=1∶3（选定活性炭的质量为5.0 g）,ρ（硫酸钠）=500 mg/L。在此最佳工艺条件下,废水COD去除率为36.5%。     

碳纳米管电极原位产生过氧化氢及其对亚甲基蓝脱色效果

将碳纳米管固定化制成多孔疏水性导电薄膜构建电化学阴极还原体系,实现过氧化氢在阴极的原位产生。电极特性研究表明,电极在较宽的电压范围内均具有较好的活性。考察了阴极电位、电极成分、氧气流量和电解质浓度对过氧化氢原位产生的影响,在优化条件下经过120min后过氧化氢达到66．17mg／L,并探讨过氧化氢原位产生的机理。在此基础上考察原位过氧化氢氧化工艺下对亚甲基蓝的脱色效果,并分析其脱色机理。     

铝铁电极联用电絮凝法处理Cu-EDTA络合废水

采用电絮凝法处理Cu-EDTA模拟废水,研究电极组合方式、初始pH值和氯化钠浓度3个因素对化学需氧量(COD)和Cu去除效果的影响。实验研究发现,当电极组合方式为2个铝阳极和2个铁阴极,起始pH值为3,氯化钠浓度为0.5 g/L,换极周期为40 min,反应时间为80 min时,COD去除率达到78.7%,Cu离子去除率达到99.9%。通过实验研究确定EDTA的去除机制主要是:酸性条件下的次氯酸氧化作用,碱性条件下的氢氧化物絮凝沉淀作用及单核态铝/铁与多核态铝/铁电荷中和作用,Cu的去除机制主要是氢氧化物的絮凝沉淀作用和铁电极的电沉积作用。     

Electrochemical oxidation of nitrogen-heterocyclic compounds at boron-doped diamond electrode

Nitrogen-heterocyclic compounds (NHCs) are toxic and bio-refractory contaminants widely spread in environment. This study investigated electrochemical degradation of NHCs at boron-doped diamond (BDD) anode with particular attention to the effect of different number and position of nitrogen atoms in molecular structure. Five classical NHCs with similar structures including indole (ID), quinoline (QL), isoquinoline (IQL), benzotriazole (BT) and benzimidazole (BM) were selected as the target compounds. Results of bulk electrolysis showed that degradation of all NHCs was fit to a pseudo first-order equation. The five compounds were degraded with the following sequence: ID > QL > IQL > BT > BM in terms of their rates of oxidation. Quantum chemical calculation was combined with experimental results to describe the degradation character of NHCs at BDD anode. A linear relationship between degradation rate and delocalization energy was observed, which demonstrated that electronic charge was redistributed through the conjugation system and accumulated at the active sites under the attack of hydroxyl radicals produced at BDD anode. Moreover, atom charge was calculated by semi empirical PM3 method and active sites of NHCs were identified respectively. Analysis of intermediates by GC-MS showed agreement with calculation results.     

电凝聚法对活性红241染料废水脱色实验的研究

通过实验研究了铁阳极电凝聚法对活性红241废水的脱色处理效果,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、染料浓度对染料脱色效率的影响,结果表明:在一定实验条件下活性红241模拟废水的脱色效率达97%;电流强度、染料浓度、电解液初始pH值、电解液温度、电解质的浓度及种类对脱色效率均有不同程度的影响;以铁为阳极的原位电凝聚处理活性红241模拟废水混凝过程中主要作用机理以吸附电性中和为主;电凝聚过程中活性红241发生了阴极还原反应.     

Mechanism of ball milled activated carbon in improving the desalination performance of flow- and fixed-electrode in capacitive deionization desalination

● BACs were used in electrode material for both fixed and flowing electrodes. ● ASAR of FCDI and MCDI was improved by 134% and 17%, respectively. ● ENRS of FCDI and MCDI was improved by 21% and 53%. ● The mechanism of improving desalination performance was analyzed in detail. Capacitive deionization (CDI) is a novel electrochemical water-treatment technology. The electrode material is an important factor in determining the ion separation efficiency. Activated carbon (AC) is extensively used as an electrode material; however, there are still many deficiencies in commercial AC. We adopted a simple processing method, ball milling, to produce ball milled AC (BAC) to improve the physical and electrochemical properties of the original AC and desalination efficiency. The BAC was characterized in detail and used for membrane capacitive deionization (MCDI) and flow-electrode capacitive deionization (FCDI) electrode materials. After ball milling, the BAC obtained excellent pore structures and favorable surfaces for ion adsorption, which reduced electron transfer resistance and ion migration resistance in the electrodes. The optimal ball-milling time was 10 h. However, the improved effects of BAC as fixed electrodes and flow electrodes are different and the related mechanisms are discussed in detail. The average salt adsorption rates (ASAR) of FCDI and MCDI were improved by 134% and 17%, respectively, and the energy-normalized removal salt (ENRS) were enhanced by 21% and 53%, respectively. We believe that simple, low-cost, and environmentally friendly BAC has great potential for practical engineering applications of FCDI and MCDI.     

实海环境下钢壳混凝土结构局部电位监测与参比电极稳定性研究

目的 确定高纯锌、钛以及铂等3种参比电极在不同工况下的稳定性差异,以及不同参比电极针对沉管的最佳使用位置。方法 以银/氯化银参比电极的监测电位数据为钢壳的实际电位基准,通过在不同区域设计安装电位传感器,持续监测沉管不同区域的钢壳电位,以及9个多月的波动情况。结果 高纯锌参比电极所监测数据的变化趋势与钢壳实际电位数据接近,且环境介质的改变对其监测电位数值的影响不大,电位数据波动小。铂和钛参比电极在钢壳底面海泥/抛石耦合的服役环境下,其监测电位数据稳定,但是二者在海水中监测电位时,对环境介质中的溶解氧浓度、金属离子等氧化性介质较为敏感,极易受到氧化性介质的影响,导致测得的电位偏移剧烈。结论 高纯锌参比电极更适合应用于沉管侧面阴极保护电位的长期监测,铂和钛参比电极更适用于钢壳底部保护电位的长期测量。     

铁和铝离子对土壤水溶性氟化物检测的干扰研究

通过离子选择电极法测定Fe3+和Al3+不同含量的土壤样品中水溶性氟化物试验,研究Fe3+和Al3+对测定的干扰与消除方法,证实了在总离子强度调节缓冲溶液共存下,Fe3+和Al3+对土壤提取液中水溶性氟化物检测结果存在不同程度的负干扰。选择6种代表性土壤样品,在水溶性氟化物提取液中加入20 mg/L的Al3+和100 mg/L的Fe3+做干扰试验,比较了分取不同体积土壤提取液对氟化物检测结果的影响,结果表明,对水溶性ρ(Fe3+)和ρ(Al3+)高的土壤样品,可选择减少提取液取样体积来消除干扰。选取的5种标准样品测试结果与标准值相符,干扰消除方法具有良好的适用性。