O2+、O3同时脱硫脱硝实验

针对目前的烟气同时脱硫脱硝方法中存在的投资成本、运行费用、占地面积大等问题,研究强电离放电方法产生高浓度氧活性粒子(O2+、O3)注入烟气外排管道中,进行O2+、O3消除烟气中的NO, SO2转化成HNO3, H2SO4的等离子化学反应.描述强电离介质阻挡放电制取O2+、O3原理和烟道中O2+与H2O反应形成·OH及其氧化脱硫脱硝反应机制,分析回收酸液中的酸根离子种类及浓度.在O2+、O3与NO+SO2的物质的量比为5,烟气温度为65℃,H2O体积浓度为10%,停留时间为1s的实验条件下,脱硝脱硫率分别为97.4%,83.2%.     

A simple and sensitive method for the determination of 4-n-octylphenol based on multi-walled carbon nanotubes modified glassy carbon electrode

A simple and sensitive electroanalytical method was presented for the determination of 4-n-octylphenol (OP) based on multi-walled carbon nanotubes (MWCNTs) modified glassy carbon electrode (GCE). OP was directly oxidized on the MWCNTs/GCE, and the electrochemical oxidation mechanism was demonstrated by a one-electron and one-proton process in the reaction. The oxidation peak current of OP was significantly enhanced by the use of MWCNTs/GCE compared with those of bare glassy carbon electrode, suggesting that the modified electrode can remarkably improve the performance for OP determination. Factors influencing the detection processes were optimized. Under these optimal conditions, a linear relationship between concentration of OP and current response was obtained in the range of 5×10^-8 to 1×10^-5 mol/L with a detection limit of 1.5×10^-8 mol/L and correlation coefficient 0.9986. The modified electrode showed good selectivity, sensitivity, reproducibility and high stability.     

苯酚在金刚石膜电极上的电化学氧化降解过程

采用循环伏安法、交流阻抗法、恒电位计时电流法,并结合高效液相色谱方法,研究了苯酚在金刚石膜电极上的电化学氧化降解过程.结果表明,苯酚在电化学氧化降解中经历了苯二酚、苯醌的形成和进一步被氧化的过程,苯二酚在反应过程中的积累很少,迅速氧化为苯醌,而醌类中间产物则较难进一步氧化,在反应过程中积累的浓度较高.苯酚在金刚石膜电极上有不同的电化学氧化反应途径,在低于金刚石膜电极析氧电位下,发生单纯直接电化学氧化过程;在高于金刚石膜电极析氧电位下,间接电化学氧化和直接电化学氧化将同时发生作用.     

Pd/C气体扩散电极用于电生成H2O2降解苯酚的研究

采用自制的Pd/C气体扩散阴极和Ti/IrO2/RuO2阳极,在无隔膜电解槽中对苯酚模拟废水降解效果及机制进行了研究,采用电子自旋共振法(ESR)对电解体系中产生的羟自由基(·OH)进行了检测.结果表明,在Pd/C气体扩散体系中掺杂Pd催化剂可以促进H2 O2的生成(H2 O2的稳定浓度是7.5 mg/L),有利于·OH的产生.经电化学氧化处理120 min后,苯酚和COD的去除率分别达到97.2%和50%,表明在电催化氧化过程中苯酚被氧化生成了大量低分子量中间产物.废水的BOD5/COD值达到0.73是处理前的9.1倍,苯酚废水的可生化降解性通过电化学氧化处理后显著提高.在该电化学体系中苯酚的降解是在阳极直接、间接氧化及阴极产生的H2 O2、·OH的氧化共同作用下完成的.通过对紫外扫描光谱图的分析推断出苯酚在电解过程中有醌类物质生成;由GC-MS检测到了邻苯二酚、对苯二酚、苯醌等芳香族化合物和己二酸、顺丁烯二酸、反丁烯二酸、丁二酸、丙二酸、乙二酸等短链羧酸,据此提出了苯酚降解的可能历程.     

氮氧化物气体的产生及其对厌氧氨氧化的影响研究

硝化、反硝化生物脱氮反应,因产生N2O温室气体,开始引发一些环保工作者的关注。新开发的厌氧氨氧化工艺在生物脱氮方面具有无可比拟的优越性。在其脱氮的3种反应途径中,也可能产生NO、NO2和N2O微量气体。文章对目前厌氧氨氧化反应中,这3种微量气体的产生情况进行了综述,并总结了这3种气体对厌氧氨氧化反应的影响。提出考察厌氧氨氧化过程中温室气体的排放情况和如何减少或控制温室气体的排放将成为厌氧氨氧化工艺应用中重要的研究方向之一。     

氧化物修饰电极降解有机污染物的电催化特性

采用高温热解氧化沉积法将金属氧化物SnO₂, RuO₂, Cr₂O₃, PdO修饰到钛基体表面,制备得到4种金属氧化物修饰电极.比较4种电极氧化降解苯、苯甲酸、苯酚、苯胺、硝基苯以及甲基橙染料6种有机污染物的氧化电流效率,结果表明,电极在各种介质中的析氧电位和氧化反应传递系数(β值)是衡量电极能否有效处理有机污染物废水的两个重要指标,其中SnO₂电极的析氧电位最高,PbO电极的b值最大,SnO₂电极的β 值次之.这为研制和筛选高效催化电极提供了理论依据.     

Pt/生物炭电极反应器处理水中腐殖酸的研究

构建Pt/生物炭电极反应器,研究其对水中腐殖酸的去除效率和去除特性.结果表明,在电流密度为20 m A·cm~(-2)下反应300 min,Pt/生物炭电极反应器对水中腐殖酸的去除率为74.58%,较Pt/石墨电极反应器47.10%去除率提高58.3%.Pt/生物炭电极反应器对水中腐殖酸的去除主要通过电化学氧化和气浮作用.生物炭阴极比石墨阴极能产生更多的H_2O_2,是提高Pt/生物炭电极反应器对腐殖酸去除率的重要原因.三维荧光光谱和凝胶色谱法分析表明,Pt/生物炭电极反应器具有较强的氧化能力,可将较小分子量的腐殖酸直接矿化.研究结果显示生物炭可以作为一种新型电化学反应器的阴极材料用于对水中有机污染物处理.     

一种新型电化学体系降解苯酚的机理研究

通过使用自制的碳聚四氟乙烯(CPTFE)气体扩散电极作为阴极,TiIrO2RuO2材料为阳极,研究了隔膜电解槽中电化学降解苯酚的机理.结果表明,在阴极室,CPTFE气体扩散阴极通过外界曝气提供的O2在阴极还原产生H2O2,电解80min后H2O2的稳定浓度达到8.3mg·L-1.采用电子自旋共振法(ESR)在阴极室中检测到羟自由基(HO·)的存在.采用高效液相色谱(HPLC)在阴极室检测到羟基加合物对苯二酚,证明HO·参与了苯酚的降解过程.在该电化学体系中苯酚的降解是在阳极直接、间接氧化及阴极产生的H2O2、HO·的氧化共同作用下完成的.阴极室检测到了对苯二酚、苯醌等苯环化合物和顺丁烯二酸、反丁烯二酸、丙烯酸、丙二酸、草酸、乙酸、甲酸等短链羧酸,据此提出了苯酚降解的可能历程,并对阴、阳极室中苯酚降解途径之间的差异进行了初步比较.     

pH值对氨氮电化学氧化产物与氧化途径的影响

摘要:研究了含氨氮废水在循环流动式电解槽中的电化学氧化,讨论了pH值对氨氮电化学氧化效果、产物及其途径的影响。结果表明,在弱碱性条件下,有利于电解过程中羟基自由基和游离氯的生成,氨氮的电化学氧化速率较大。在有氯离子存在的情况下,氨氮电化学氧化过程中有氯胺生成,氯胺的组成与体系的pH值有关,当pH>9时,一氯胺占优势;当pH=7时,一氯胺和二氯胺同时存在,并且近似相等;当pH<5时,主要是二氯胺;pH值大于5时,可以避免三氯化氮的生成。在电流密度为20mA/cm2时,电解产生的羟基自由基小于5×10-15mol/L,氨氮电化学氧化的2种途径中间接氧化起主要作用。     

Coulometric determination of dissolved hydrogen with a multielectrolytic modified carbon felt electrode-based sensor

A multielectrolytic modified carbon electrode (MEMCE) was fabricated by the electrolytic-oxidation/reduction processes. First, the functional groups containing nitrogen atoms such as amino group were introduced by the electrode oxidation of carbon felt electrode in an ammonium carbamate aqueous solution, and next, this electrode was electroreduced in sulfuric acid. The redox waves between hydrogen ion and hydrogen molecule at highly positive potential range appeared in the cyclic voltammogram obtained by MEMCE. A coulometric cell using MEMCE with a catalytic activity of electrooxidation of hydrogen molecule was constructed and was used for the measurement of dissolved hydrogen. The typical current vs. time curve was obtained by the repetitive measurement of the dissolved hydrogen. These curves indicated that the measurement of dissolved hydrogen was finished completely in a very short time (ca. 10 sec). A linear relationship was obtained between the electrical charge needed for the electrooxidation process of hydrogen molecule and dissolved hydrogen concentration. This indicates that the developed coulometric method can be used for the determination of the dissolved hydrogen concentration.     

pH值对氨氮电化学氧化产物与氧化途径的影响

研究了含氨氮废水在循环流动式电解槽中的电化学氧化.讨论了pH值对氨氮电化学氧化效果、产物及其途径的影响.结果表明,在弱碱性条件下.有利于电解过程中羟基自由基和游离氯的生成.氨氮的电化学氧化速率较大.在有氯离子存在的情况下,氨氮电化学氧化过程中有氯胺生成,氯胺的组成与体系的pH值有关.当pH>9时,一氯胺占优势;当pH=7时.一氯胺和二氯胺同时存在,并且近似相等;当pH<5时,主要是二氯胺;pH值>5时,可以避免三氯化氮的生成.在电流密度为20mA/cm2时.电解产生的羟基自由基<5×10-15mol/L,氨氮电化学氧化的2种途径中间接氧化起主要作用.     

Simultaneous removing SO2 and NO by a new system containing cobalt complex

Absorption and catalytic oxidation of nitric oxide can be achieved by using cobalt（Ⅲ） ethylenediamine （Co（en）3^3＋. When simultaneous absorbing SO2 and NO, the precipitation of Co2（SO3）3 will be yielded and the NO removal will be decreased. A new catalyst system using Co（en）3^3＋ coupled with urea has been developed to simultaneous remove NO and SO2 in the flue gas. NO is absorbed and catalytically oxidized to nitrite and nitrate by Co（en）3^3＋. The dissolved oxygen in scrubbing solution from the feed stream acts as oxidant. Urea restrains the precipitation of Co2（SO3）3 by oxidizing SO3^2-to SO4^2- as COSO4 is more soluble in water. The experimental results proved that nearly all SO3^2- can be oxidized to SO4^2- and the high NO and SO2 removal could be obtained with the new system. The NO removal is influenced by gas flow rate, the concentration of Co（en）3^3＋ and urea in the absorption solution, the temperature of the scrubbing solution and the content of oxygen in the flue gas. The low gas flow rate is favorable to increase the NO removal. The experiments proved that the NO removal could be maintained at more than 95% by the system of 0.02 mol/L Co（en）3^3＋ and 1% urea at 50℃ with 10% O2 in the flue gas.     

表面酸碱2步改性对活性炭吸附Cr(Ⅵ)的影响

研究了酸碱2步改性对活性炭吸附水相中Cr(Ⅵ)的影响.将活性炭(AC₀)在HNO₃溶液中氧化(AC₁),然后在NaOH和NaCl的混合液中处理(AC₂).分别采用平衡和连续吸附试验,测试Cr(Ⅵ)的吸附特征.以Boemh滴定法定量检测活性炭表面酸性官能团数量,结合元素分析结果定量表征活性炭的表面含氧官能团变化;以低温液氮(N₂/77K)吸附法分析活性炭的比表面积和孔径结构.结果表明:活性炭经2步改性后,其Cr(Ⅵ)的吸附容量和吸附速度均显著改变.吸附容量和吸附速度大小依次为AC₂>AC₁>AC₀.改性活性炭表面积下降,表面含氧酸性官能团数量增加.HNO₃液相氧化处理可使活性炭表面生成带正电含氧酸性官能团,第2步改性后活性炭表面酸性官能团H⁺部分被Na⁺取代,使活性炭表面酸性降低.表面较多的含氧酸性官能团(与AC₀相比)、适宜的表面pH(与AC₁相比)是AC₂所表现出较高Cr(Ⅵ)吸附容量的主要原因.     

光氧化反应脱汞技术发展综述

燃煤电厂烟气中汞污染的控制技术研究是目前重要的环保课题之一。气相元素汞成为大气中汞污染的主要来源。文章分析了光氧化反应脱汞技术(包括光化学氧化反应和光催化氧化反应)的反应机理,认为光化学氧化反应技术脱汞均是在紫外光作用下,产生具有强氧化性的基态原子或自由基,将难以脱除的Hg0氧化为高价汞,再通过配套的电除尘器等设备将高价汞捕集,进而达到汞污染控制的目的。不同的是,在光化学氧化反应中,汞的氧化需要借助于电厂烟气中的O2、H2O等成分,而在光催化氧化反应中,反应需要在光催化剂(TiO2或TiO2负载复合物等)的催化作用下进行。阐述了光氧化反应汞脱除技术研究进展。光氧化反应脱汞技术的汞脱除率均可达到60%~70%,具备设备简单、无二次污染等优点。     

微电解接触氧化系统处理水源中2-氯酚研究

在微电解接触氧化系统中,研究了2-氯酚的降解特性和机理。在酸性溶液中,2-氯酚的降解效率比其在中性和碱性溶液的高。向其中加入活性炭,由于表面催化的作用使得2-氯酚更易降解。溶液中的溶解氧参与电极反应并促进2-氯酚的降解。降解产物有1,2-苯二酚、丙三醇、草酸和乙酸。通过对中间产物的分析,提出了2-氯酚可能的降解途径。     

电化学氧化法去除兰炭废水中COD和NH3-N

采用电氯化氧化法处理高浓度含有机污染物和氨氮的兰炭废水,考查了NaCl添加量、外加电压、初始pH值等对废水中化学需氧量（COD）和氨氮（NH₃-N）去除效果的影响,并对电化学氧化过程及污染物氧化机理进行深入分析.研究表明,随着NaCl添加量、外加电压及电解时间的增加,废水中COD与NH₃-N去除率逐渐增大.在NaCl添加量为60g/L、电压6V、极板间距10mm、废水初始pH值不变、电解时间3h的条件下,兰炭废水中COD和NH₃-N去除率分别为84.31%和95.77%,远高于不添加NaCl时的41.18%和34.10%.废水中COD和氨氮的降解主要归因于间接氧化,阳极反应产生的Cl₂水解生成具有强氧化性的ClO^-.电解过程中大部分NH₃-N在ClO^-的作用下转化为N₂,而小部分以含氮化合物的形式存在.兰炭废水中有机污染物主要以酚类物质为主,电化学处理后其含量大幅降低,部分会转化为醚类或者烷烃类物质.     

Bi-PbO2电极电化学氧化去除模拟废水中氨氮的研究

本实验采用钛网作为基体,利用电沉积方法制备了纯PbO2电极和Bi-PbO2电极,通过SEM、XRD、XPS对电极的表面形态进行了表征,利用循环伏安法对Bi-PbO2电极电化学特性进行了研究.同时,以氨氮模拟废水作为研究对象,考察了Bi-PbO2电极的电催化活性,探讨了氨氮电化学氧化降解机理.结果表明,Bi-PbO2电极的形态表征、电催化活性明显高于纯PbO2电极,氨氮的去除效率随电流密度的增加而提高,碱性条件下氨氮的去除效果明显好于酸性条件,适量浓度的Cl-的引入在碱性条件下提高了氨氮的去除效果.当氨氮初始浓度为50 mg·L-1、电流密度为40 mA·cm-2、pH=12、Cl-浓度为600 mg·L-1时,电解120 min后,氨氮100%去除.氨氮的降解机理为:体系中无添加氯离子,酸性条件下氨氮主要是通过间接氧化去除,碱性条件下通过直接电氧化和间接氧化共同完成;体系中添加氯离子,氨氮的去除主要是通过溶液中生成的有效氯间接氧化去除.     

Catalytic wet air oxidation of phenol with functionalized carbon materials as catalysts：Reaction mechanism and pathway

The development of highly active carbon material catalysts in catalytic wet air oxidation（CWAO）has attracted a great deal of attention. In this study different carbon material catalysts（multi-walled carbon nanotubes,carbon fibers and graphite） were developed to enhance the CWAO of phenol in aqueous solution. The functionalized carbon materials exhibited excellent catalytic activity in the CWAO of phenol. After 60 min reaction,the removal of phenol was nearly100% over the functionalized multi-walled carbon,while it was only 14% over the purified multi-walled carbon under the same reaction conditions. Carboxylic acid groups introduced on the surface of the functionalized carbon materials play an important role in the catalytic activity in CWAO. They can promote the production of free radicals,which act as strong oxidants in CWAO. Based on the analysis of the intermediates produced in the CWAO reactions,a new reaction pathway for the CWAO of phenol was proposed in this study. There are some differences between the proposed reaction pathway and that reported in the literature. First,maleic acid is transformed directly into malonic acid. Second,acetic acid is oxidized into an unknown intermediate,which is then oxidized into CO2 and H2O. Finally,formic acid and oxalic acid can mutually interconvert when conditions are favorable.     

Electrochemical disinfection using the gas diffusion electrode system

A study on the electrochemical disinfection with H_2O_2 generated at the gas diffusion electrode (GDE) from active carbon/poly-tetrafluorcethylene was performed in a non-membrane cell. The effects of Pt load and the pore-forming agent content in GDE, and operating conditions were investigated. The experimental results showed that nearly all bacterial cultures inoculated in the secondary effluent from wastewater treatment plant could be inactivated within 30 min at a current density of 10 mA/cm~2. The disinfection improved with increasing Pt load. Addition of the pore-forming agent NH_4HCO_3 improved the disinfection, while a drop in the pH value resulted in a rapid rise of germicidal efficacy and the disinfection time was shortened with increasing oxygen flow rate. Adsorption was proved to be ineffective in destroying bacteria, while germicidal efficacy increased with current density. The acceleration rate was different, it initially increased with current density. Then decreased, and finally reached a maximum at a current density of 6.7 mA/cm~2. The disinfection also improved with decreasing total bacterial count. The germicidal efficacy in the cathode compartment was approximately the same as in the anode compartment, indicating that the contribution of direct oxidation and the indirect treatment of bacterial cultures by hydroxyl radical was similar to the oxidative indirect effect of the generated H_2O_2.     

活性炭催化过氧化氢去除荧光增白剂

研究了活性炭(activated carbon,AC)吸附、改性活性炭(activated carbon modified,ACM)吸附、过氧化氢(H2O2)氧化、AC催化H2O2等方法对水体中荧光增白剂VBL的处理效果,并通过自由基俘获剂叔丁醇、催化过程气体分析等探讨了AC催化H2O2分解VBL的机制.结果表明,经硝酸铁[Fe(NO3)3]改性过的ACM对VBL的吸附去除率高于未改性的AC.活性炭催化H2O2对VBL的去除效果明显,但未改性AC催化去除率高于ACM.60 min时,AC催化氧化去除率即可达到95%以上,而ACM仅为58%.叔丁醇的加入降低了AC和ACM催化氧化对VBL的去除率,表明AC催化H2O2氧化能促进H2O2形成羟基自由基(·OH)和原子氧参与反应.AC催化H2O2分解及释放气体分析表明,AC能催化H2O2形成氧气并放热,且ACM明显快于AC.结合催化H2O2去除VBL效率的结果分析,ACM催化反应时活性中间物(自由基和原子氧等)产生速率快于AC,活性中间物自身消耗形成氧气,而不是用于分解VBL.催化反应中活性中间产物的形成速率与反应物供给速率的不匹配可能是导致ACM催化效果弱于AC的重要原因.