Dechlorination of carbon tetrachloride by the catalyzed Fe-Cu process

The electrochemical reduction characteristics of carbon tetrachloride (CT) were investigated using cyclic voltammetry in this study. In addition, the difference in reduction mechanisms of CT between Master Builders' iron and the catalyzed Fe-Cu process was discussed. The results showed that CT was reduced directly on the surface of copper rather than by atomic hydrogen produced at the cathode in the catalyzed Fe-Cu process. The reduction was realized largely by atomic hydrogen in Master Builders' iron. The entire CT in 350 ml aqueous solution with 320 mgL was reduced to trichloromethane and dichloromethane in 2.25 h when 100 g of scrap iron with FeCu ratio of 10:1 (ww) were used. Moreover, the reduction rate slowed with time. CT could be reduced at acidic, neutral and alkaline pH from solution by Fe-Cu bimetallic media, but the mechanisms were di?erent. The degradation rate was not significantly in?uenced by pH in the catalyzed Fe-Cu process; in Master Builders' iron it clearly increased with decreasing pH. The kinetics of the reductions followed pseudo-first order in both cases. Furthermore, the reductions under acidic conditions proceeded faster than that under the neutral and alkaline conditions. The catalyzed Fe-Cu process was superior to Master Builders' iron in treating CT-containing water and this advantage was particularly noticeable under alkaline conditions. The reduction was investigated in the cathode (Cu) and anode (Fe) compartments respectively, the results showed that the direct reduction pathway played an important role in the reduction by the catalyzed Fe-Cu process. The catalyzed Fe-Cu process is of practical value.     

Kinetics of aniline oxidation with chlorine dioxide

For the first time, kinetics of aniline oxidation with chlorine dioxide(ClO2) were investigated systematically by detecting concentration of aniline with HPLC at regular intervals. Results showed that the reaction was first-order both in ClO2 and in aniline, and the oxidation reaction could be described as second-order reaction. Stoichiometric factor η was experimentally determined to be 2.44. The second-order-reaction rate constant k was 0.11L/(mol.s)under condition of pH 6.86 and water temperature(Tw) 287K. Reaction activation energy was 72.31 kJ/mol, indicating that the reaction could take place under usual water treatment conditions. The reaction rate constants in acidic and alkali media were greater than that in neutral medium. Chlorite ion could slightly increase reaction rate in acidic medium. p-aminophenol and azobenzene were detected by GC-MS as intermediates.     

Effects of particle composition and environmental parameters on catalytic hydrodechlorination of trichloroethylene by nanoscale bimetallic Ni-Fe

Catalytic nickel was successfully incorporated into nanoscale iron to enhance its dechlorination efficiency for trichloroethylene （TCE）, one of the most commonly detected chlorinated organic compounds in groundwater. Ethane was the predominant product. The greatest dechlorination efficiency was achieved at 22 molar percent of nickel. This nanoscale Ni-Fe is poorly ordered and inhomogeneous; iron dissolution occurred whereas nickel was relatively stable during the 24-hr reaction. The morphological characterization provided significant new insights on the mechanism of catalytic hydrodcchlorination by bimetallic nanoparticles. TCE degradation and ethane production rates were greatly affected by environmental parameters such as solution pH, temperature and common groundwater ions. Both rate constants decreased and then increased over the pH range of 6.5 to 8.0, with the minimum value occurring at pH 7.5. TCE degradation rate constant showed an increasing trend over the temperature range of 10 to 25℃. However, ethane production rate constant increased and then decreased over the range, with the maximum value occurring at 20℃, Most salts in the solution appeared to enhance the reaction in the first half hour but overall they displayed an inhibitory effect. Combined ions showed a similar effect as individual salts.     

Photoelectrocatalytic degradation of Rose Bengal

An innovative photoelectrode, TiO2/T1 mesh electrode, was prepared by galvanostaticanodisation. The morphology and the crystalline texture of the TiO2 film on mesh electrode were examined by scanning electronic microscopy and Raman spectroscopy respectively. The examination results indicated that the structure and properties of the film depended on anodisation rate, and the anatase was the dominant component under the controlled experimental conditions. Degradation of Rose Bengal (RB) in photocatalytic (PC) and photoelectrocatalytic (PEC) reaction was investigated, the results demonstrated that electric biasing could improve the efficiency of photecatalytic reaction. The measurement results of TOC in photoelectrocatalytic degradation showed that the mineralisation of RB was complete relatively. The comparison between the degradation efficiency of RB in PEC process and that in aqueous TiO2 dispersion was conducted. The results showed that the apparent first-order rate constant of RB degradation in PEC process was larger than that in aqueous dispersion with 0.1%--0.3% TiO2 powder, but was smaller than that in aaueaus disverslon with 1.0% TiO2.     

Rapid decolorization of Acid Orange II aqueous solution by amorphous zero-valent iron

Some problems including low treatment capacity, agglomeration and clogging phenomena, and short working life, limit the application of pre-treatment methods involving zero-valent iron (ZVI). In this article, ZVI was frozen in an amorphous state through a melt-spinning technique, and the decolorization effect of amorphous ZVI on Acid Orange II solution was investigated under varied conditions of experimental variables such as reaction temperature, ribbon dosage, and initial pH. Batch experiments suggested that the decolorization rate was enhanced with the increase of reaction temperature and ribbon dosage, but decreased with increasing initial solution pH. Kinetic analyses indicated that the decolorization process followed a first order exponential kinetic model, and the surface-normalized decolorization rate could reach 2.09 L/(m². min) at room temperature, which was about ten times larger than any previously reported under similar conditions. Recycling experiments also proved that the ribbons could be reused at least four times without obvious decay of decolorization rate and efficiency. This study suggests a tremendous application potential for amorphous ZVI in remediation of groundwater or wastewater contaminated with azo dyes.     

Kinetic and products study of the gas-phase reaction of Lewisite with ozone under atmospheric conditions

The rate constant for the gas-phase reaction of O_3 and Lewisite was studied in air using the smog chamber technique. The experiments were carried out under pseudo-first-order reaction conditions with [O_3] [Lewisite]. The observed rate constant of O_3 with Lewisite was(7.83 ± 0.38) × 10~(-19)cm~3/(molecule·sec) at 298 ± 2 K. Lewisite was discussed in terms of reactivity with O_3 and its relationship with the ionization potential. Our results show that the rate constant for the gas-phase reaction of O_3 with Lewisite is in line with the trend of the rate constants of O_3 with haloalkenes.     

Reduction of nitrobenzene by the catalyzed Fe/Cu process

The polarization behavior of the couple Fe/Cu in 100 mg/L nitrobenzene aqueous solution was studied using Evans coupling diagrams.The results indicated that the iron corrosion was limited by both anodic and cathodic half-cell reactions under the neutral conditions,and cathodically controlled under the alkaline conditions.Batch experiments were performed to study the effect of solution pH,reaction duration,concentration,type of electrolyte,and dissolved oxygen(DO)on the reduction of nitrobenzene by the ca...     

Removal of phenol by activated alumina bed in pulsed high-voltage electric field

A new process for removing the pollutants in aqueous solution-activated alumina bed in pulsed high-voltage electric field was investigated for the removal of phenol under different conditions. The experimental results indicated the increase in removal rate with increasing applied voltage, increasing pH value of the solution, aeration, and adding Fe^2＋. The removal rate of phenol could reach 72.1% when air aeration flow rate was 1200 ml/min, and 88.2% when 0.05 mmol/L Fe^2＋ was added into the solution under the conditions of applied voltage 25 kV, initial phenol concentration of 5 mg/L, and initial pH value 5.5. The addition of sodium carbonate reduced the phenol removal rate. In the pulsed high-voltage electric field, local discharge occurred at the surface of activated alumina, which promoted phenol degradation in the thin water film. At the same time, the space-time distribution of gas-liquid phases was more uniform and the contact areas of the activated species generated from the discharge and the pollutant molecules were much wider due to the effect of the activated alumina bed. The synthetical effects of the pulsed high-voltage electric field and the activated alumina particles accelerated phenol degradation.     

Photolysis kinetics and influencing factors of bisphenol S in aqueous solutions

The photodegradation of bisphenol S (BPS) in aqueous solutions was studied under different conditions. Photolysis and kinetics were investigated, as were the photolysis mechanism and the influences of initial pH value, light source, and environmental substances in water. The results showed that the photolysis of BPS occurred under UV light, and the rate increased with light source intensity. The photolysis of 5.0-50.0 mg/L BPS in water followed first-order kinetics: the rate was γ= 0.0161C_BPS under a 40-W UV-lamp, and the degradation half-life was 43.1 min. Due to its absorption of light, direct photolysis of BPS was a predominant pathway for BPS but was not obviously affected by reactive oxygen species. The results confirmed that the photolysis rates of BPS in alkaline water solution were faster than those in acidic and neutral water solution because of the ionization of BPS. The photodegradation rate of BPS increased in the presence of chloride and ferric ions, while the rate was inhibited by nitrate and phosphate in aqueous solution.     

Degradation kinetics and mechanism of aniline by heat-assisted persulfate oxidation

Oxidation of aniline by persulfate in aqueous solutions was investigated and the reaction kinetic rates under different temperature, persulfate concentration and pH conditions were examined in batch experiments. The results showed that, the aniline degradation followed pseudo first-order reaction model. Aniline degradation rate increased with increasing temperature or persulfate concentration. In the pH range of 3 to 11, a low aniline degradation rate was obtained at strong acid system (pH 3), while a high degradation rate was achieved at strong alkalinity (pH 11). Maximum aniline degradation occurred at pH 7 when the solution was in a weak level of acid and alkalinity (pH 5, 7 and 9). Produced intermediates during the oxidation process were identified using liquid chromatography-mass spectrometry technology. And nitrobenzene, 4-4’-diaminodiphenyl and 1-hydroxy-1,2-diphenylhydrazine have been identified as the major intermediates of aniline oxidation by persulfate and the degradation mechanism of aniline was also tentatively proposed.     

锌粉降解地下水中的农药阿特拉津

研究了Zn⁰催化还原模拟地下水中阿特拉津.结果表明,Zn⁰比Fe⁰具有更高的反应活性,反应5d对阿特拉津的降解率为100%,在Zn⁰还原脱氯的过程中,溶液的pH值逐渐增加,反应过程中通过添加磷酸缓冲溶液调节pH值,24h降解率达到100%.阿特拉津降解产物的GC/MS鉴定表明,阿特拉津还原脱氯的产物为2-乙胺基-4-乙丙胺基-1,3,5-三嗪(DCA).     

荧光增白剂生产废水不同预处理方法的比较

采用Fenton试剂氧化、O3氧化、曝气铁炭微电解3种方法对荧光增白剂生产废水进行了处理,考察了不同影响因素对3种处理方法处理效果的影响.结果表明,在H2O2投加量为0.13 mol/L、H2O2与Fe2+的物质的量比为20、pH值为5.0、反应时间为1.0h时, Fenton试剂氧化处理效果最好,CODCr去除率达到39.9%, BOD5/CODCr提高到0.51.在反应时间为70min(O3通入量为2.51 g/L)、pH值为9.2时,O3氧化处理效果较好,CODCr去除率达到36.7%,BOD5/CODCr提高到0.47.在铁炭质量比为1、反应时间为2.0h、pH值为2.5时,曝气铁炭微电解效果最好,CODCr去除率达到57.1%,BOD5/CODCr提高到0.45.3种预处理方法均可有效降解荧光增白剂生产废水中的有机物并且提高废水的可生化性,其中曝气铁炭微电解的效果最好,处理成本最低,可以应用于荧光增白剂生产废水的处理中.     

纳米磁铁矿/生物质炭催化对Fenton氧化降解苯酚的增强机理

以生物质炭负载纳米磁铁矿(nMBC)作为催化剂,采用非均相Fenton反应体系对模拟苯酚废水进行氧化降解处理研究,确定n MBC—Fenton法处理苯酚废水的最佳工艺条件,并揭示其强化机理。实验结果表明:对于质量浓度为50 mg/L的苯酚废水,其最佳降解条件为温度为45℃,pH为3.0,H_2O_2浓度为5 mmol/L,nMBC用量为2.0 g/L。反应进行20 min后,苯酚去除率可达约100%。nMBC剂量、废水初始pH和温度等因素均对处理效果有较大影响,其中pH决定苯酚去除率,而nMBC剂量是影响降解速率的主要因素。此外,nMBC—Fenton法催化氧化降解苯酚过程符合准一级动力学反应(R~2>0.97)。     

地下水除草剂阿特拉津污染微生物治理的实验研究

采用了从农药厂阿特拉津生产车间排污口污泥中分离出的菌种AT菌,进行了农药阿特拉津的静态降解实验及其污染地下水的微生物治理模拟实验研究结果表明,AT菌在pH值为5.0～10.0时对农药污染质阿特拉津均具有降解能力,且适宜的pH值范围为6.5～8.0;在实验条件(t=10℃,pH=7.5)与野外含水层的条件基本一致情况下,难于生物降解的污染质阿特拉津的一次投菌降解率达到31.08%;同时环境因素也随着AT菌作用的变化而变化,其中,DO、pH随AT菌作用加强而其值减小.另外,设计了细菌的投放方式以模拟野外条件下的菌种投加条件.并且AT菌的作用会造成被治理含水层的渗透性能降低,实验后含水层的渗透系数下降60.54%.清水冲洗10d的渗透性恢复率为48.96%,说明清水渗透恢复的方法效果明显.     

掺氮Ta2O5诱发可见光-类Fenton体系降解阿特拉津研究

通过制备具有强可见光吸收和活性的半导体掺氮Ta2O5,利用其可见光Fe3+还原活性,实现了可见光-类Fenton体系有效地降解阿特拉津.结果表明,氨气流量0.3 L.min-1、700℃氮化时间6 h制备出的掺氮Ta2O5在可见光下还原Fe3+的能力最佳;阿特拉津降解效果与各种操作条件———光强、催化剂投加量、Fe3+、H2O2、阿特拉津初始浓度及pH值有关,并通过H2O2的分解揭示影响的原因.在pH为2.6、[atrazine]0=18 mg.L-1、[H2O2]0=2.5 mmol.L-1、[Fe3+]0=0.5 mmol.L-1、掺氮Ta2O5投加量为0.6 g.L-1、500 W氙灯照射下,反应60 min时,阿特拉津的降解率为97%.该研究为可见光-类Fenton体系降解有机污染物的实际应用提供了基础数据和理论指导.     

镍/铁二元金属对莠去津脱氯特性的影响

为了考察Ni/Fe二元金属对莠去津的催化还原特性,分别以Fe粉和Ni/Fe体系作为还原和催化剂,在酸性条件下对莠去津的脱氯特性进行比较,并讨论了pH值,Ni/Fe配比以及金属添加量等因素对莠去津脱氯效率的影响.结果表明:与Fe粉比较,Ni/Fe体系对莠去津具有很明显的催化脱氯特性.在pH=2时,1.22%(W/W)Ni/Fe体系30min对莠去津的脱氯效率大于90%,相同条件下用Fe粉还原时,90min脱氯效率仅为22.21%通过Fe粉和Ni/Fe表面形态的比较以及实验结果的分析,对Ni/Fe体系的催化还原脱氯机理进行了初步探讨.     

硫化钠沉淀法处理化学镀镍废液

采用化学沉淀法处理化学镀镍废液,以硫化钠为沉淀剂,将废液的镍离子以硫化镍的形式析出,从而达到净化废液和回收镍的目的。实验结果分析表明,在影响镍去除率效果的几个因素中硫化钠投加量的影响最大,pH值次之,反应时间影响最小。在pH为6,投加200 mL质量分数为20%的硫化钠溶液,反应时间为30 min,可以使200 mL化学镀镍废液中(镍质量浓度为5450 mg/L)的镍去除率达到99.8%,残余镍的质量浓度可以降至12 mg/L左右,对其余重金属离子的去除也有明显的效果。同时得到的沉淀致密,镍含量高(质量分数为21.6%),便于进一步回收利用。     

负载型纳米Fe与负载型纳米Fe-Ni降解甲基橙的对比研究

以阳离子交换树脂为载体,合成了负载型纳米Fe和负载型纳米Fe-Ni双金属材料,并采用扫描电子显微镜和能谱分析对该材料进行表征,考察了m(FeSO4):m(树脂)、负载纳米材料加入量、溶液pH等因素对甲基橙降解率的影响.结果表明,两种负载纳米材料对0.05 g·L-1甲基橙均有较好的降解效果,甲基橙的降解率随负载纳米材料加入量的增加而增加;纳米双金属材料中Ni含量的增加有利于甲基橙的降解.在pH =4酸性条件下降解效果最佳.在优化的降解反应条件下,对比研究了负载型纳米Fe和负载型纳米Fe-Ni对甲基橙的降解效果.结果表明,负载型纳米Fe-Ni对甲基橙的降解效果要优于负载型纳米Fe.制备的材料在多次使用后经活化,仍有良好的催化稳定性.     

光助纳米铁还原Cr(VI)的研究

采用液相还原法制备了纳米铁,并用X射线衍射仪(XRD)、扫描电镜(SEM)对其晶体结构、形貌特征进行了表征.以Cr(Ⅵ)为模拟污染物,中压汞灯作为光源,考察了不同投加量、不同pH值等条件下光照对纳米铁还原Cr(Ⅵ)的影响.结果表明:制备的纳米铁具有很高的反应活性,粒径约为7.6nm,呈球形,可在空气中自燃.在25℃、Cr(Ⅵ)浓度为20mg/L、pH=7±0.5,加入0.1g的纳米铁,光照60min后Cr(Ⅵ)的还原率达到62.3%,而无光照时Cr(Ⅵ)的还原率仅为27.6%,说明光照对Cr(Ⅵ)的还原具有明显的促进作用.当纳米铁投加量较大时,纳米铁对Cr(Ⅵ)的还原速率大于光照对其产生的影响.反应液pH值对Cr(Ⅵ)还原速率的影响较光照对其产生的影响显著.在紫外光的照射下,纳米铁中电荷可能在诱导下作受迫振荡,与吸附分子发生电荷传递是光照促进纳米铁还原Cr(Ⅵ)的主要原因.     

络合-超滤耦合工艺去除水中镍离子的研究

以聚丙烯酸钠(PAANa)和聚乙烯亚胺(PEI)作为络合剂,将其与镍离子络合后的溶液转移至超滤杯中,在0.1 MPa压力下通过聚醚砜超滤膜进行分离,研究pH值和络合剂/Ni2+装载质量比(L)对Ni2+去除率的影响,并根据朗缪尔等温模型拟合络合反应平衡常数.同时研究超滤时间对膜通量和Ni2+去除率的影响.结果表明,选用PAANa为络合剂,在pH值为8、L=5时,Ni2+的去除率达到最大值99.5%.PEI为络合剂时,Ni2+去除率在pH值为7、L为5时达到最大值93.0%.不同pH值条件下拟合得到的络合平衡常数表明,pH为7时最有利于络合反应.另外,单个络合剂单体所能结合的Ni2+个数随着pH值的升高而增大.研究结果还表明,在长达12 h的超滤时间内,PAANa为络合剂时,膜通量的衰减<10%;PEI为络合剂时,膜通量基本保持不变;Ni2+的去除率都基本保持恒定.因此,在合适条件下,络合-超滤耦合工艺能有效去除水中的镍离子.