Chemical oxidative degradation of methyl tert-butyl ether in aqueous solution by Fenton's reagent

Degradation of methyl tert-butyl ether (MTBE) in aqueous solution by Fenton's reagent (Fe2+ and H2O2) was investigated. Effects of reaction conditions on the oxidation efficiency of MTBE by Fenton's reagent were examined in batch experiments. Under optimum conditions, 15 mM H2O2, 2 mM Fe2+, pH 2.8 and room temperature, the initial 1 mM MTBE solution was reduced by 99% within 120 min. Results showed that MTBE was decomposed in a two-stage reaction. MTBE was first decomposed swiftly based on a Fe2+/H2O2 reaction and then decomposed somewhat less rapidly based on a Fe3+/H2O2 reaction. The detection of Fe2+ also supported the theory of the two-stage reaction for the oxidation of MTBE by Fenton's reagent. The dissolved oxygen in the solution decreased rapidly in the first stage reaction, but it showed a slow increase in the second stage with a zero-order kinetics. A reaction mechanism involving two different pathways for the decomposition of MTBE by Fenton's reagent was also proposed. Chemicals including tert-butyl formate, tert-butyl alcohol, methyl acetate and acetone were identified to be the primary intermediates and by-products of the degradation processes.     

光电催化氧化法降解藻毒素MCLR

使用DSA阳极,对光电催化氧化降解藻毒素MCLR的效能及其影响因素进行了研究。结果表明,电极表面的TiO2在光催化氧化降解MCLR的过程中发挥了明显的光催化作用。在光降解、电催化氧化、光催化氧化和光电催化氧化4个过程中,光电催化氧化对MCLR和TOC的去除率最高,分别可达100%和13%,并且光电催化氧化的去除率大于光催化氧化和电催化氧化之和,表明后两者的耦合过程产生了一定的协同作用。辐照光源和电流密度存在最佳匹配条件,分别为UVC辐照、电流密度10 mA/cm2和UVA辐照、电流密度1.0 mA/cm2,此条件下光电协同作用最显著。在光电催化氧化过程中,随极板间距增大而出现的去除率下降取决于电催化过程,而不是光催化过程;光电催化氧化MCLR的去除率随其初始浓度增加而减小。     

钯修饰碳纳米管电极电催化氧化三氯生

采用钯修饰多壁碳纳米管(MWCNTs)电极电催化氧化降解三氯生,考察了极板间距、电流密度、离子强度、pH、初始浓度和电解时间对三氯生去除效率的影响,并探讨了其反应动力学。结果表明:钯修饰多壁碳纳米管(MWCNTs)电极电催化氧化降解三氯生的最佳条件为:三氯生初始浓度为50 mg/L,电流密度约为10 mA/cm2,极板间距为1 cm,pH为11,电解质Na2SO4浓度为1 000 mg/L。此条件下,反应时间为3 h时三氯生的去除率可达到99%以上,三氯生的降解为零级反应。     

Ce-PbO_2/C电极的制备及其去除水中酸性红B

采用电沉积法制备铈修饰的PbO2/C电极,通过SEM、XRD、XPS及循环伏安对PbO2/C、Ce-PbO2/C电极进行表征,结果表明,Ce-PbO2/C电极比PbO2/C颗粒细小,表面均匀致密,电化学氧化能力较强,修饰电极中Ce以CeO2的形态存在。以Ce-PbO2/C为工作电极,电解浓度为1 000 mg/L的高盐酸性红B模拟活性染料废水,考察了电压、pH、电解质浓度、极间距对脱色率、氨氮去除率及COD去除率的影响。确定适宜工艺条件为：初始酸性红B溶液浓度为1 000 mg/L,pH值为6,电压10 V,电解时间1 h,电极间距1.5 cm,该条件下脱色率、氨氮去除率和COD去除率分别为99.98%、97.23%和90.17%。通过UV-Vis及GC-MS初步分析了降解过程可能存在的中间产物及降解途径。     

钛基IrO2-SnO2电极在烟气海水脱硫恢复系统中的应用

采用浸渍-热分解法制备了含IrOx-TiO2中间层的IrO2-SnO2电极,得到的电极具有较高的析氯电催化活性和较强的稳定性,并通过电化学氧化法对Na2SO3海水脱硫模拟液进行处理,考察了电流密度、温度、pH值和电解时间等电解工艺参数对Na2SO3去除率和化学需氧量COD的影响。结果表明,在电流密度为200 mA/cm^2,pH值为3.5,电解440 mg/L的Na2SO3海水脱硫模拟液,15 min时Na2SO3去除率可达96.5%,COD去除率可达82.6%。     

Ce-PbO2/C电极的制备及其去除水中酸性红B

采用电沉积法制备铈修饰的PbO2/C电极,通过SEM、XRD、XPS及循环伏安对PbO2/C、Ce-PbO2/C电极进行表征,结果表明,Ce-PbO2/C电极比PbO2/C颗粒细小,表面均匀致密,电化学氧化能力较强,修饰电极中Ce以CeO2的形态存在。以Ce-PbO2/C为工作电极,电解浓度为1 000 mg/L的高盐酸性红B模拟活性染料废水,考察了电压、pH、电解质浓度、极间距对脱色率、氨氮去除率及COD去除率的影响。确定适宜工艺条件为:初始酸性红B溶液浓度为1 000 mg/L,pH值为6,电压10 V,电解时间1 h,电极间距1.5 cm,该条件下脱色率、氨氮去除率和COD去除率分别为99.98%、97.23%和90.17%。通过UV-Vis及GC-MS初步分析了降解过程可能存在的中间产物及降解途径。     

Evaluation of different electrochemical methods on the oxidation and degradation of Reactive Blue 4 in aqueous solution

The oxidation of a reactive dye, Reactive Blue 4, RB4, (C.I. 61205), widely used in the textile industries to color natural fibers, was studied by electrochemical techniques. The oxidation on glassy carbon electrode and reticulated vitreous carbon electrode occurs in only one step at 2.0 < pH < 12 involving a two-electron transfer to the amine group leading to the imide derivative. Dye solution was not decolorized effectively in this electrolysis process. Nevertheless, the oxidation of this dye on Ti/SnO2/SbO(x) (3% mol)/RuO2 (1% mol) electrode showed 100% of decolorization and 60% of total organic carbon removal in Na2SO4 0.2 M at pH 2.2 and potential of +2.4V. Experiments on degradation photoelectrocatalytic were also carried out for RB4 degradation in Na2SO4 0.1 M, pH 12, using a Ti/TiO2 photoanode biased at +1.0 V and UV light. After 1h of electrolysis the results indicated total color removal and 37% of mineralization.     

电催化氧化法处理染料废水的影响因素及动力学

以钛涂膜极板为阳极、石墨极板为阴极、Fe2O3/γ-Al2O3为多相催化剂,构建电-多相催化氧化体系,研究了该体系对酸性大红模拟染料废水中COD的去除效果及其影响因素,优化了实验条件,并初步探讨了COD的降解机理。结果表明,在槽电压20 V,pH 4,曝气量0.24 m3/h,极板间距3 cm的条件下,COD的去除率最高,达到64.5%;COD的降解近似符合一级动力学方程:ln(C0/C)=0.0034t+0.719。在电-多相催化氧化体系中,废水中的有机物被直接矿化或降解为小分子有机物。     

Kinetics of heat-assisted persulfate oxidation of methyl tert-butyl ether (MTBE)

The kinetics of heat-assisted persulfate oxidation of methyl tert-butyl ether (MTBE) in aqueous solutions at various pH, temperature, oxidant concentration and ionic strength levels was studied. The MTBE degradation was found to follow a pseudo-first-order decay model. The pseudo-first-order rate constants of MTBE degradation by persulfate (31.5 mM) at pH 7.0 and ionic strength 0.11 M are approximately 0.13 x 10(-4), 0.48 x 10(-4), 2.4 x 10(-4) and 5.8 x 10(-4) S(-1) at 20, 30, 40 and 50 degrees C, respectively. Under the above reaction conditions, the reaction has an activation energy of 24.5 +/- 1.6 kcal/ mol and is influenced by temperature, oxidant concentration, pH and ionic strength. Raising the reaction temperature and persulfate concentration may significantly accelerate the MTBE degradation. However, increasing both pH (over the range of 2.5-11) and ionic strength (over the range of 0.11-0.53 M) will decrease the reaction rate. Reaction intermediates including tert-butyl formate, tert-butyl alcohol, acetone and methyl acetate were observed. These intermediate compounds were also degraded by persulfate under the experimental conditions. Additionally, MTBE degradation by persulfate in a groundwater was much slower than in phosphate-buffer solutions, most likely due to the presence of bicarbonate ions (radical scavengers) in the groundwater.     

电催化氧化技术处理制革综合废水

选择DSA电极中的钛基掺硼金钢石膜电极(Ti/BDD),用于制革综合废水的电催化氧化处理研究,考察了在不同的电流密度、电压、电解质、pH值和电解时间等因素对COD去除率和电流效率的影响。结果表明,控制电流密度为30mA/cm2,电压为8.0 V,电解质(NaCl)浓度为2.0 g/L,pH为4.0,电催化氧化处理2 h后,废水的COD和NH4+-N的去除率分别达到了83.6%和90.3%,BOD/COD为0.45,比能耗为35.34 kWh/kg COD,电流效率为37%。     

Simultaneous decontamination of hexavalent chromium and methyl tert-butyl ether by UV/TiO2 process

Hexavalent chromium and methyl tert-butyl ether (MTBE) are two important environmental pollutants. Simultaneous decontamination of Cr(VI) and MTBE was studied by UV/TiO2 process. The influences of pH and the concentrations of pollutants on the kinetics of the photocatalytic reactions were evaluated. Dark adsorption tests showed that the acidic pH favored the adsorption of Cr(VI) while neutral pH favored the adsorption of MTBE. Under UV irradiation, Cr(VI) reduction was observed in Cr(VI)/TiO2 system, and MTBE oxidation was observed in MTBE/TiO2 system. The system containing Cr(VI) and MTBE by UV/TiO2 process demonstrated the synergistic effect between oxidation of MTBE and reduction of Cr(VI). The results demonstrated that two pollutants Cr(VI) and MTBE could be eliminated simultaneously by UV/TiO2 process. tert-Butyl formate, tert-butyl alcohol and acetone were identified as primary degradation products of MTBE by gas chromatography-mass spectrometry in the degradation of MTBE by UV/TiO2 process.     

Electrocatalytic reduction of nitrate in water with a palladium-modified copper electrode.

A highly active electrocatalytic electrode for nitrate reduction was prepared by the electro-deposition of palladium onto a copper electrode. The capacity of nitrate reduction by a palladium-modified copper electrode has been studied using cyclic voltammetry (CV). The existence of a reduction peak at -0.605 V versus saturated calomel electrode in 0.1-M sodium nitrate + 0.1-M perchloric acid solution (pH = 0.86) can be found in the CV measurement. The influence of solution properties, such as pH, nitrate concentration, and other anions in solution, on nitrate reduction was determined in detail. Results showed that nitrate reduction was suppressed in alkaline solution, while it was beneficial to nitrate reduction in acid or neutral solution. At low nitrate concentrations (0.01 to 0.5 M), nitrate reduction current increased with increasing nitrate concentration, but was hindered by sulfate. At high nitrate concentrations (1 to 5 M), no significant difference on nitrate reduction was observed. Compared with other different electrodes prepared in our work (copper, titanium, and palladium-modified titanium electrodes), the palladium-modified copper electrode showed the highest electrocatalytic capacity and stability in the nitrate-reduction process.     

Speciated hydrocarbon and carbon monoxide emissions from an internal combustion engine operating on methyl tertiary butyl ether-containing fuels

In the present work, engine and tailpipe (after a three-way catalytic converter) emissions from an internal combustion engine operating on two oxygenated blend fuels [containing 2 and 11% weight/weight (w/w) methyl tertiary butyl ether (MTBE)] and on a nonoxygenated base fuel were characterized. The engine (OPEL 1.6 L) was operated under various conditions, in the range of 0-20 HP. Total unburned hydrocarbons, carbon monoxide, methane, hexane, ethylene, acetaldehyde, acetone, 2-propanol, benzene, toluene, 1,3-butadiene, acetic acid, and MTBE were measured at each engine operating condition. As concerns the total HC emissions, the use of MTBE was beneficial from 1.90 to 3.81 HP, which were by far the most polluting conditions. Moreover, CO emissions in tailpipe exhaust were decreased in the whole operation range with increasing MTBE in the fuel. The greatest advantage of MTBE addition to gasoline was the decrease in ethylene, acetaldehyde, benzene, toluene, and acetic acid emissions in engine exhaust, especially when MTBE content in the fuel was increased to 11% w/w. In tailpipe exhaust, the catalyst operation diminished the observed differences. Ethylene, methane, and acetaldehyde were the main compounds present in exhaust gases. Ethylene was easily oxidized over the catalyst, while acetaldehyde and methane were quite resistant to oxidation.     

Simultaneous removal of organic compounds and heavy metals from soils by electrokinetic remediation with a modified cyclodextrin

Thousands of sites are contaminated with both heavy metals and organic compounds and these sites pose a major threat to public health and the environment. Previous studies have shown that electrokinetic remediation has potential to remove heavy metals and organic compounds when they exist individually in low permeability soils. This paper presents the feasibility of using cyclodextrins in electrokinetic remediation for the simultaneous removal of heavy metals and polycyclic aromatic hydrocarbons (PAHs) from low permeability soils. Kaolin was selected as a model low permeability soil and it was spiked with phenanthrene as well as nickel at concentrations of 500 mg kg-1 each to simulate typical mixed field contamination. Bench-scale electrokinetic experiments were conducted using hydroxypropyl beta-cyclodextrin (HPCD) at low (1%) and high (10%) concentrations and using deionized water in control test. A periodic voltage gradient of 2VDC cm-1 (with 5 d on and 2 d off) was applied to all the tests, and 0.01 M NaOH was added during the experiments to maintain neutral pH conditions at anode. In all tests, nickel migrated as Ni2+ ions towards the cathode and most of it was precipitated as Ni(OH)2 within the soil close to the cathode due to high pH condition generated by electrolysis reaction. The solubility of phenanthrene in the flushing solution and the amount of electroosmotic flow controlled the migration and removal of phenanthrene in all the tests. Even though high flow was generated in tests using deionized water and 1% HPCD, migration and removal of phenanthrene was low due to low solubility of phenanthrene in these solutions. The test with 10% HPCD solution showed higher solubility of phenanthrene which caused it migrate towards the cathode, but further migration and removal was retarded due to reduced electric current and electroosmotic flow. Approximately one pore volume of flushing resulted in approximately 50% removal of phenanthrene from the soil near the anode. Sustained higher electroosmotic flow with higher concentration cyclodextrin and maintaining low soil pH near cathode should be investigated to increase removal efficiency of both phenanthrene and nickel.     

哌啶清洁生产工艺条件的研究

研究了有机电催化还原的方法生产哌啶的清洁生产工艺,探讨了电极种类、吡啶初始浓度、电流密度、电解质溶液浓度及添加剂的加入等条件对哌啶的收率和电流效率的影响。结果表明,采用RaneyNi板式电极,吡啶初始浓度为0．2～0．3mol／L,电流密度为20-80A／dm^2,常温下在0．5mol／L的NaOH水溶液中进行电还原反应,可获得90％以上的哌啶收率和80％以上电流效率。该清洁生产工艺具有产率高、纯度高,生产条件温和,节能高效等优点。     

Degradation of tetracycline at a boron-doped diamond anode: influence of initial pH,applied current intensity and electrolyte

The anodic oxidation of tetracycline was performed in an up-flow reactor, operating in batch mode with recirculation, using as anode a boron-doped diamond electrode. The influence on the degradation rate of solution initial pH (2 to 12), applied current intensity (25 to 300 A m^?2) and type of electrolyte (sodium sulphate or sodium chloride) were investigated. For the assays run at equal current density, with sodium sulphate as electrolyte, the solution’s initial pH of 2 presented the highest absorbance and chemical oxygen demand removals. Regarding the influence of current density, for equal charge passed, the organic load removal rate decreased with the increase in applied current. When sodium sulphate was used as an electrolyte, high-performance liquid chromatography (HPLC) results have shown an almost complete removal of tetracycline after a 2-h assay. HPLC results have also shown the presence of oxamic acid as one of the intermediates of tetracycline anodic oxidation. The complete removal of tetracycline was much faster in the presence of chloride ions that promoted the complete degradation of this antibiotic in 30 min. However, in the presence of chloride ions, the tetracycline mineralization is slower, as observed by the lower organic carbon removal rate when compared to that of the tetracycline degradation in the presence of sulphate.     

Treatment of refectory oily wastewater by electro-coagulation process

Electro-coagulation was used to treat refectory wastewater with high oil and grease contents. Different operational conditions were examined, including pH, current density, reaction time, conductivity, electrode distance and inlet concentration. The optimum current density was 10-14 A m(-2) within 30 min depending on the wastewater properties tested. Conductivity had little effect on the treatment efficiency. Although the addition of extra salts (e.g., sodium chloride) to the wastewater did not help increase the pollutant removal efficiency, it could save the power consumption significantly. The COD(Cr) and oil removal efficiency descended with increasing electrode distance. The optimal electrode distance was determined to be 10 mm for this equipment in consideration of the treatment cost and efficiency together. The pH effect on the performance of the electro-coagulation process was not very significant in the range of 3-10. The removal efficiency of oil and COD(Cr) under normal condition exceeded 95% and 75%, respectively.     

电动与渗透反应格栅联合修复镉污染地下水实验

通过实验方法研究了地下水中镉污染的电动力学修复效果，并分析其迁移变化特征。实验结果表明，电动修复中由于阴阳两极的氧化还原反应造成电极附近pH值产生明显变化，其中阳极附近的pH值由开始时的7.0逐渐变小到6.8，而阴极附近则相反，由开始时6.9逐渐增大到9.1，表明土壤的酸碱条件变化明显。Cd浓度变化反映在自然渗透条件下含水层中重金属污染物的迁移能力较弱，阳极附近地下水中Cd的去除率仅8.4%，而在电场作用下地下水中重金属的浓度发生明显变化，使得重金属污染物能在电极附近富集而被去除，当实验电场强度为0.5 V/cm时，Cd在阴极的累积使得阳极附近地下水中去除率为72.9%，说明电动修复重金属Cd污染地下水的效果明显好于自然渗透状态。     

钛基IrO2-SnO2电极在烟气海水脱硫恢复系统中的应用

采用浸渍-热分解法制备了含IrOx-TiO2中间层的IrO2-SnO2电极,得到的电极具有较高的析氯电催化活性和较强的稳定性,并通过电化学氧化法对Na2SO3海水脱硫模拟液进行处理,考察了电流密度、温度、pH值和电解时间等电解工艺参数对Na2SO3去除率和化学需氧量COD的影响.结果表明,在电流密度为200 mA/cm...     

Pressurized CO2/zero valent iron system for nitrate removal

A fluidized zero valent iron (ZVI) reactor pressurized by CO(2) gas for controlling pH was employed for nitrate reduction. The proposed CO(2) pressurized system potentially has advantages of using less CO(2) gas and reaching equilibrium pH faster than CO(2)-bubbled system. However, due to weak acid nature of carbonic acid, system pH gradually increased with increasing oxidation of ZVI and reduction of nitrate. As pH increased with progress of reaction, nitrate removal rate decreased continuously. The results indicate that nitrate removal efficiency increases with increasing initial ZVI dosage but reaches plateau at ZVI doses of higher than 8.25gl(-1), and initial nitrate concentration up to 100mg l(-1) as N has minimal impact on the removal efficiency. Unlike the fluidized system with pH control by strong acid reported in our pervious study, near 100% of nitrogen recovery was observed in the current process, indicating that nitrate reduction by ZVI with different pH controlled mechanisms will have different reaction routes.