零价铁复合有机膨润土处理染料废水的研究

针对目前印染废水处理现状及膨润土在水处理中回收困难等问题，提出将零价铁复合到有机膨润土中制成零价铁复合有机膨润土(ZVI-OB)，以达到高效吸附并降解污染物的目的。以染料废水(Orange II) 作为研究对象，考察了废水中染料的初始浓度、pH以及吸附时间对ZVI-OB去除染料效率的影响，并研究了吸附后降解过程中时间和pH对污染物降解的影响以及降解前后膨润土层结构的变化。研究结果表明，ZVI-OB相对于CTMAB改性的有机膨润土而言，其吸附量有所降低，但ZVI-OB在吸附污染物之后能有效降解有机物。ZVI-OB在饱和吸附Orange II后经催化氧化，总有机碳含量降低为原来的19%，可以重复利用。     

Hydroxyl radical concentration profile in photo-Fenton oxidation process: generation and consumption of hydroxyl radicals during the discoloration of azo-dye Orange II

Dynamic behaviors of hydroxyl (OH) radical generation and consumption in photo-Fenton oxidation process were investigated by measuring OH radical concentration during the discoloration of azo-dye Orange II. The effects of operating parameters for photo-Fenton discoloration, i.e. dosages of H₂O₂ and Fe, initial dye concentration, solution pH and UV irradiation, on the generation and consumption of OH radicals playing the main role in advanced oxidation processes were extensively studied. The scavenger probe or trapping technique in which coumarin is scavenger of OH radical was applied to estimate OH radical concentration in the photoreactor during the photo-Fenton discoloration process. The OH radical generation was enhanced with increasing the dosages of Fenton regents, H₂O₂ and Fe. At the initial stage of photo-Fenton discoloration of Orange II, the OH radical concentration rapidly increased (Phase-I) and the OH radical concentration decreased after reaching of OH radical concentration at maximum value (Phase-II). The decrease in OH radical concentration started when the complete discoloration of Orange II was nearly achieved and the H₂O₂ concentration became rather low. The dynamic behavior of OH radical concentration during the discoloration of Orange II was found to be strongly linked with the change in H₂O₂ concentration. The generation of OH radical was maximum at solution pH of 3.0 and decreased with an increase of solution pH. The OH radical generation rate in the Fenton Process was rather slower than that in the photo-Fenton process.     

Degradation of Acid Orange 7 in aqueous solution by dioxygen activation in a pyrite/H2O/O2 system

Increasing attention has been paid to pyrite due to its ability to generate hydroxyl radicals in air-saturated solutions. In this study, the mineral pyrite was studied as a catalyst to activate molecular oxygen to degrade Acid Orange 7 (AO7) in aqueous solution. A complete set of control experiments were conducted to optimize the reaction conditions, including the dosage of pyrite, the AO7 concentration, as well as the initial pH value. The role of reactive oxygen species (ROS) generated by pyrite in the process was elucidated by free radical quenching reactions. Furthermore, the concentrations of Fe(II) and total Fe formed were also measured. The mechanism for the production of ROS in the pyrite/H₂O/O₂ system was that H₂O₂ was formed by hydrogen ion and superoxide anion (O₂ ^·?) which was produced by the reaction of pyrite activating O₂ and then reacted with Fe(II) dissolved from pyrite to produce ^·OH through Fenton reaction. The findings suggest that pyrite/H₂O/O₂ system is potentially practical in pollution treatment. Moreover, the results provide a new insight into the understanding of the mechanism for degradation of organic pollutants by pyrite.     

Effects of operating parameters on advanced oxidation of diuron by the Fenton's reagent: a statistical design approach

Advanced oxidation of diuron in aqueous solution by Fenton's reagent using FeSO(4) as source of Fe(II) was investigated in the absence of light. Effects of operating parameters namely the concentrations of pesticide (diuron), H(2)O(2) and Fe(II) on oxidation of diuron was investigated by using Box-Behnken statistical experiment design and the surface response analysis. Diuron oxidation by the Fenton reagent was evaluated by determining the total organic carbon (TOC), diuron, and adsorbable organic halogen (AOX) removals. Concentration ranges of the reagents resulting in the highest level of diuron oxidation were determined. Diuron removal increased with increasing H(2)O(2) and Fe(II) concentrations up to a certain level. Diuron concentration had a more profound effect than H(2)O(2) and Fe(II) in removal of diuron, TOC and AOX from the aqueous solution. Nearly complete (98.5%) disappearance of diuron was achieved after 15min reaction period. However, only 58% of diuron was mineralized after 240min under optimal operating conditions indicating formation of some intermediate products. Optimal H(2)O(2)/Fe(II)/diuron ratio resulting in the maximum diuron removal (98.5%) was found to be 302/38/20 (mgl(-1)).     

Catalytic activity of Ru/Al2O3 for ozonation of dimethyl phthalate in aqueous solution

With dimethyl phthalate as the model pollutant and Ru/Al(2)O(3) as catalyst, this paper systemically investigates the removal of total organic carbon (TOC) of system. Our results have confirmed that Ru/Al(2)O(3) can significantly increase the effect of ozonation. TOC removal in 120 min can reach 72% while only 24% with ozone alone. The optimal catalyst preparing condition was 0.1 wt% Ru content, 600 degrees C calcination temperature, 0.5-1.0mm particle diameter, which is characterized by a high surface area and a large population of surface active sites. The contrasting experiments of ozone alone, catalyst adsorption after ozonation, and catalytic ozonation confirmed that catalytic reaction was the most important process to TOC removal in system with Ru/Al(2)O(3) as catalyst.     

NaNO(2)/FeCl(3) catalyzed wet oxidation of the azo dye Acid Orange 7

A combination of ferric chloride and sodium nitrite significantly improved the wet oxidation of the azo dye Acid Orange 7 (AO7) in acid aqueous media (pH 2.6) under moderate conditions (T=150 degrees C; oxygen pressure=0.5 MPa). To evaluate the catalytic system, wet oxidation of AO7 was carried out at temperatures between 90 and 150 degrees C and oxygen pressures ranging from 0.1 to 0.5 MPa. The effect of initial solution pH from 2.6 to 11.4 and the amount of catalyst on the degradation of AO7 were also investigated. AO7 initial concentration was kept 200 mg L(-1). The degradation process was monitored by UV-visible spectroscopy, HPLC, IC (ion chromatography), GC-MS and TOC analysis. At 150 degrees C and 0.5 MPa oxygen pressure, 56% TOC was removed after 4h of treatment, while no obvious TOC removal were achieved without catalyst at the same experimental condition. The main degradation products were some small organic acids: formic acid, acetic acid, pyruvic acid, oxalic acid, succinic acid (identified and quantified by IC) and phthalic acid (identified by GC-MS).     

Cu-SBA-15催化湿式过氧化氢氧化水溶液中罗丹明B

采用水热晶化法合成了不同含铜量的Cu—SBA-15介孔分子筛，并且用XRD、N2吸附、TEM以及uV—vis对所合成的样品进行表征。以Cu—SBA-15为催化剂，H2O2为氧化剂，催化湿式过氧化水溶液中的罗丹明B，主要考察H2O2浓度、催化剂用量、处理温度、初始pH等因素对罗丹明B氧化效果的影响。结果表明，在同样的处理条件下罗丹明的脱色率明显高于TOC去除率，处理温度、初始pH对罗丹明B的脱色与氧化有重要影响。在罗丹明B初始浓度100mg／L，H2O2初始浓度1．8g／L，催化剂量0．3g／L，温度60℃，pH为7．0，处理时间100min时，罗丹明B的脱色率为98．6％，TOC去除率为62．8％。     

Factors influencing the preparation of supported iron oxide in fluidized-bed crystallization

Our previous work applied a novel supported iron oxyhydroxide (FeOOH) catalyst to effectively treat benzoic acid by hydrogen peroxide. The FeOOH catalyst was prepared via the oxidation of Fe2+ by H2O2 in the acidic condition using a fluidized-bed crystallization reactor. The major components coated on the surface were identified as amorphous FeOOH and gamma-FeOOH. In terms of the crystallization conditions of FeOOH, some parameters including the operational pH, superficial velocity, specific iron loading, and influent H2O2 concentration were investigated to quantify their effects on the crystallization efficiency. All these parameters were found to significantly influence the crystallization efficiency. Two types of FeOOH catalysts were synthesized: FeOOH I was prepared at pH 3.5, and FeOOH II was formed by aging FeOOH I at pH 13. The percentages of surface amorphous FeOOH reduced from 70% to 30% after aging. The FeOOH II catalyst presented a higher reactivity toward H2O2 but lower stoichiometric efficiency in oxidizing benzoic acid than FeOOH I, similar to the result of the commercial goethite. Therefore, it is concluded that the crystalline property significantly affects the performance of catalytic oxidation.     

Sonolysis of alkylphenols in aqueous solution with Fe(II) and Fe(III)

The sonolytic degradation of alkylphenols (APs), such as butylphenol, pentylphenol, octylphenol, and nonylphenol (NP), in water was investigated at a sound frequency of 200 kHz with an acoustic intensity of 6 W cm(-2) under argon, oxygen, and air atmospheres. The sonolytic degradation rate of the APs under the conditions of the present study depended upon their alkyl chain length. The decrease in the degradation rate by the radical scavenging effect was in the range of about 48-82% for APs in the presence of 3 mM 2-methyl-2-propanol. The free radicals play a significant role in the sonolytic degradation process of the APs. In the presence of Fe(II) and Fe(III), the pseudo-first-order rate constants for the sonolytic degradation of 30 microM NP as a function of the concentration of Fe(II) and Fe(III) were estimated under argon and oxygen. The maximum rate constants were observed at 50 microM Fe(II) (0.139 +/- 0.008 min(-1)) and 100 microM Fe(III) (0.103 +/- 0.001 min(-1)) under oxygen. The total organic carbon concentration (TOC) was investigated under same conditions. TOC decreased in the range of about 50-70% during the sonication in the presence of Fe(II) and Fe(III) under argon and oxygen. The sonochemical effects by the addition of Fe(II) and Fe(III) as catalyst during the sonication under the proper atmosphere result in a remarkable enhancement of degradation and mineralization.     

Photodegradation of alachlor with the TiO(2) film immobilised on the glass tube in aqueous solution

Alachlor photodegradation was performed using TiO(2), which was synthesized by a modified sol-gel method. The thickness of a TiO(2) film immobilised by a 5-time dip-coating was 174 nm and the average diameter of TiO(2) particles was about 10-15 nm in SEM images. The crystal structure of a TiO(2) film calcinated at 300 degrees C for 1 h was observed as a typical anatase type. The stability of a TiO(2) film by a modified sol-gel method was 4% better than TiO(2) by a typical sol-gel method.The removal rate of alachlor with both Fe(3+) and UV radiation in the absence of TiO(2) was 0.28 mg/l/h in 10 h and the removal rate of alachlor with Fe(3+)/UV in the presence of TiO(2) was 0.32 g/l/h, which was higher by 14% than that with Fe(3+)/UV system. TOC concentration during the alachlor degradation with both TiO(2) and UV radiation in the absence of added Fe(3+) decreased from 100%, through 81% and 51%, to 44% with time elapses of 4, 8, and 10 h, respectively, while TOC concentration with both added Fe(3+) and UV radiation in the absence of TiO(2) decreased from 100% to 70% in 10 h.     

Photo-oxidation of cork manufacturing wastewater

Several photo-activated processes have been investigated for oxidation of a cork manufacturing wastewater. A comparative activity study is made between different homogeneous (H2O2/UV-Vis and H2O2/Fe2+/UV-Vis) and heterogeneous (TiO2/UV-Vis and TiO2/H2O2/UV-Vis) systems, with degradation performances being evaluated in terms of total organic carbon (TOC) removal. Results obtained in a batch photo-reactor show that photo-catalysis with TiO2 is not suitable for this kind of wastewater while the H2O2/UV-Vis oxidation process, for which the effect of some operating conditions was investigated, allows to remove 39% of TOC after 4 h of operation (for C(H2O2)=0.59 M, pH=10 and T=35 degrees C). The combined photo-activated process, i.e., using both TiO2 and H2O2, yields an overall TOC decrease of 46% (for C(TiO2)=1.0 gl(-1)). The photo-Fenton process proved to be the most efficient, proceeds at a much higher oxidation rate and allows to achieve 66% mineralization in just 10 min of reaction time (for C(H2O2)=0.31 M, T=30 degrees C, Fe2+:H2O2=0.12 (mol) and pH=3.2).     

Fe(II)EDTA/H_2O_2电催化降解甲基橙模拟废水的研究

在无隔膜电解槽中,采用SPR(Ru-Ir-TiO_2)为阳极,石墨为阴极,考察了Fe(II)EDTA/H_2O_2电催化降解甲基橙(methyl orange)模拟废水的影响,发现EDTA很大程度上促进了类电Fenton试剂对甲基橙模拟废水的降解.实验研究表明,在外加电压为5.0v,EDTA:Fe~(2+) =2:1(摩尔比,Fe~(2+) =40 mmol/L),H_2O_2=48 mmol/L,电解质Na_2SO_4=40 mmol/L,废水pH值为(6.5±0.1)的条件下,降解260 mg/L的甲基橙模拟废水90 min,EDTA的加入可以使甲基橙模拟废水的脱色率由29.5%上升到78.4%,COD由571.429 mg/L降至80 mg/L,COD的降解率为86%,EDTA在此过程中既是催化剂又是反应物,可有效避免EDTA带来二次环境污染的可能性.     

Decolorization of synthetic dyes using a copper complex with glucaric acid

Selected azo, acridine, triphenyl methane, anthraquinone and thiazine-based dyes were decolorized using a catalytic system consisting of Cu(II)/glucaric acid/H(2)O(2). More than 90% decolorization was obtained with 100 ppm Acridine Orange, Azure B, Chicago Sky Blue, Crystal Violet, Methyl Orange, Poly B-411, Reactive Black 5, Reactive Blue 2, and Remazol Brilliant Blue R within 24 h. Seventy to eighty percent decolorization was achieved within the first 6 h. The decolorizaton was not affected by pH. The involvement of hydroxyl radicals produced in the system in the decolorization of the dye molecules was confirmed by electron spin resonance study.     

Experimental in situ chemical peroxidation of atrazine in contaminated soil

Lab-scale experiments of in situ chemical oxidation (ISCO), were performed on soil contaminated with 100 mg kg(-1) of atrazine (CIET). The oxidant used was hydrogen peroxide catalysed by naturally occurring minerals or by soluble Fe(II) sulphate, added in aqueous solution. The oxidation conditions were: CIET:H2O2=1:1100, 2 PV or 3 PV reaction volume, Fe(II):H2O2=0, 1:22, 1:11. Stabilized (with KH2PO4 at a concentration of 16 g l(-1)) or non-stabilized hydrogen peroxide was used. The pH of the reagents was adjusted to pH=1 with sulphuric acid, or was not altered. Results showed that the addition of soluble Fe(II) increased the temperature of the soil slurry and the use of stabilized hydrogen peroxide resulted in a lower heat generation. The treatment reduced the COD of the soil of about 40%, pH was lowered and natural organic matter became less hydrophobic. The highest atrazine conversion (89%) was obtained in the conditions: 3 PV, Fe(II):H2O2=1:11 with stabilized hydrogen peroxide added in two steps. The stabilizer only increased H2O2 life-time significantly when soluble Fe(II) was added. Results indicate as preferential degradation pathway of atrazine in soil dechlorination instead of dealkylation.     

Mineralization of Reactive Black 5 in aqueous solution by basic oxygen furnace slag in the presence of hydrogen peroxide

Basic oxygen furnace slag (BOF slag) is a solid waste arisen from the steel making process. FeO is one of the major components of BOF slag. The FeO-containing property of BOF slag makes it possible to catalyze the Fenton reaction. Reactive Black 5 (RB5) dye is chosen as the target compound in this study. This study has investigated the catalytic performance of BOF slag on the Fenton reaction to decompose RB5 in aqueous solution. A first-order kinetic model with respect to TOC was adopted to explain the mineralization of RB5 by the H(2)O(2)/BOF slag process. The experimental results in this study suggested that dosage with 1.49 x 10(-4)M min(-1) H(2)O(2) and 12.5 g l(-1) BOF slag in the solution at pH 2 provided the optimal operation conditions for the mineralization of RB5 yielding a 51.2% treatment efficiency at 100 min reaction time, and complete decoloration can be achieved within 30 min reaction time. The H(2)O(2)/Fe(2+) ratio was then determined to be 6.06:1.     

铁酸锌纳米晶的合成及其催化脱色性能研究

采用改进的共沉淀法与溶剂热法相结合制备了ZnFe2O4纳米晶,利用X射线衍射(XRD)、透射电镜(TEM)对ZnFe2O4的晶型和形貌进行了表征,讨论了其表面的光伏效应,以酸性橙Ⅱ的光催化脱色性能作为探针反应,详细地考察了催化剂的用量、底物浓度及溶液pH等因素对其脱色效果的影响.结果表明,制备的ZnFe2O4为正尖晶石型结构,平均粒径为7 nm左右,样品具有一定的捕获电子能力,在外加电场下光伏响应变化明显,在正电场下有最佳响应值,而当负电场达到一定值时,外电场的光伏响应占据主导地位.在酸性橙Ⅱ为20 mg/L、催化剂用量为1.0 g/L的中性条件下,其脱色效率达95%左右,而且经过4次重复使用后催化剂仍然具有一定的脱色性能.     

Photocatalytic discoloration of Methyl Orange by anatase/schorl composite: optimization using response surface method

The anatase/schorl composites were prepared and employed for the photocatalytic discoloration of an azo dye, Methyl Orange (MO). X-ray diffraction results indicated that TiO₂ existed in the form of anatase phase and no diffraction peaks of schorl could be observed for all the composite samples. Scanning electron micrographs showed that the particles of anatase were well deposited and dispersed on the surface of schorl. Photocatalytic experiments revealed that the anatase/schorl composites exhibited higher photocatalytic activity for MO discoloration than pure TiO₂ and more than 90 % discoloration ratio could be obtained within 60 min UV irradiation when the sample containing 3 wt.% of schorl as TiO₂ support was used. Then, the central composite design (CCD) under the response surface methodology (RSM) was employed for the experiment design and process optimization. The significance of a second-order polynomial model for predicting the optimal values of MO discoloration was evaluated by the analysis of variance (ANOVA) and 3D response surface plots for the interactions between two variables were constructed. Based on the model prediction, the optimum conditions for the photocatalytic discoloration of MO by TiO₂/schorl composite were determined to be 15?×?10^?3 mM MO initial concentration, 2.7 g/l photocatalyst dosage, solution pH 6.6 and 43 min reaction time, with a maximum MO discoloration ratio of 98.6 %. Finally, a discoloration ratio of 94.3 % was achieved for the real sample under the optimum conditions, which was very close to the predicted value, implying that RSM is a powerful and satisfactory strategy for the process optimization.     

臭氧辅助UV/Fenton法处理电镀添加剂生产废水

采用臭氧辅助光芬顿法处理电镀添加剂生产废水，考察双氧水、FeSO₄·7H₂O、pH和反应时间等因素对废水COD和UV₂₅₄去除的影响。实验结果表明，pH=4，臭氧通入量为0.25 g，双氧水的投加量93.3 mL/L，FeSO₄·7H₂O投加量为5.3 g/L，最佳反应时间为30 min，COD和UV₂₅₄去除率分别达到92.64%和87.95%。这表明，臭氧辅助光芬顿法对电镀添加剂生产废水处理效果显著，处理时间大大减少。     

Transformation characteristics of refractory pollutants in plugboard wastewater by an optimal electrocoagulation and electro-Fenton process

The treatment of the plugboard wastewater was performed by an optimal electrocoagulation and electro-Fenton. The organic components with suspended fractions accounting for 30% COD were preferably removed via electrocoagulation at initial 5 min. In contrast, the removal efficiency was increased to 76% with the addition of H(2)O(2). The electrogenerated Fe(2+) reacts with H(2)O(2) and leads to the generation of (·)OH, which is responsible for the higher COD removal. However, overdosage H(2)O(2) will consume (·)OH generated in the electro-Fenton process and lead to the low COD removal. The COD removal efficiency decreased with the increased pH. The concentration of Fe(2+) ions was dependent on the solution pH, H(2)O(2) dosage and current density. The changes of organic characteristics in coagulation and oxidation process were differenced and evaluated using gel permeation chromatography, fluorescence excitation-emission scans and Fourier transform infrared spectroscopy. The fraction of the wastewater with aromatic structure and large molecular weight was decomposed into aliphatic structure and small molecular weight fraction in the electro-Fenton process.