Fenton氧化法对磺胺类抗生素的降解动力学

采用Fenton氧化法同时降解水溶液中磺胺吡啶(SPY)、磺胺二甲基嘧啶(SMZ)和磺胺甲噁唑(SMX)。系统考查了初始H2O2浓度、Fe2+浓度、pH对3种磺胺类抗生素降解性能的影响。结果表明,3种磺胺抗生素被完全降解的最佳Fenton氧化条件是:H2O2浓度为2.0 mmol/L,Fe2+浓度为0.10 mmol/L,pH为3.0~3.5,反应时间为20 min。Fenton试剂对3种磺胺类抗生素的降解符合一级反应动力学,速度常数为0.0318~0.2002 min-1。     

Efficient use of Fe metal as an electron transfer agent in a heterogeneous Fenton system based on Fe0/Fe3O4 composites

In this work a novel heterogeneous Fenton system based on Fe(0)/Fe3O4 composites is described. The composites with several Fe(0)/Fe3O4 ratios were prepared by two different methods, i.e. mechanical alloying of Fe(0) and Fe3O4 powders and controlled reduction of Fe3O4 with H2. Reaction studies and detailed Conversion Electron M?ssbauer surface characterization of the composites Fe(0)/Fe3O4, Fe(0), Fe3O4, alpha-Fe2O3 and gamma-Fe2O3 suggested that Fe2+surf species are essential to produce an active Fenton system. Kinetic studies for the oxidation of the dye methylene blue, used as an organic model molecule, and for the peroxide decomposition suggest that the reactions proceed via HO* radicals generated from Fe2+surf species and H2O2 in a Fenton like mechanism. The increase in activity caused by the addition of Fe(0) is discussed in terms of a creation of Fe2+surf species during the preparation of the composite and by an electron transfer mechanism from Fe(0) to Fe3+surf during the Fenton reaction to regenerate the Fe2+surf active species.     

Fenton试剂氧化对硝基酚中氧化还原电位的变化规律

考察了Fenton试剂氧化对硝基苯酚(PNP)过程中氧化还原电位(ORP)的变化规律.结果表明:(1)当pH为3、H2O2投加量为3 mmol/L、Fe2+投加量为0.3 mmol/L时,废水中PNP在5.0 min时降到5 mg/L左右,去除率达95%;废水可生化性得到有效改善(BOD5/COD由最初的0.073升至...     

Parathion degradation and its intermediate formation by Fenton process in neutral environment

The purpose of this study is to investigate parathion degradation by Fenton process in neutral environment. The initial parathion concentration for all the degradation experiments was 20 ppm. For hydrogen ion effect on Fenton degradation, the pH varied from 2 to 8 at the [H₂O₂] to [Fe²⁺] ratio of 2-2 mM, and the result showed pH 3 as the most effective environment for parathion degradation by Fenton process. Apparent degradation was also observed at pH 7. The subsequent analysis for parathion degradation was conducted at pH 7 because most environmental parathion exists in the neutral environment. Comparing the parathion degradation results at various Fenton dosages revealed that at Fe²⁺ concentrations of 0.5, 1.0 and 1.5 mM, the Fenton reagent ratio ([H₂O₂]/[Fe²⁺]) for best-removing performance were found as 4, 3, and 2, resulting in the removal efficiencies of 19%, 48% and 36%, respectively. Further increase in Fe²⁺ concentration did not cause any increase of the optimum Fenton reagent ratio for the best parathion removal. The result from LC-MS also indicated that hydroxyl radicals might attack the PS double bond, the single bonds connecting nitro-group, nitrophenol, or the single bond within ethyl groups of parathion molecules forming paraoxons, nitrophenols, nitrate/nitrite, thiophosphates, and other smaller molecules. Lastly, the parathion degradation by Fenton process at the presence of humic acids was investigated, and the results showed that the presence of 10 mg L⁻¹ of humic acids in the aqueous solution enhanced the parathion removal by Fenton process twice as much as that without the presence of humic acids.     

Photogeneration of hydroxyl radical in Fe(III)-citrate-oxalate system for the degradation of fluconazole: mechanism and products

Environmental Science and Pollution Research - The photochemical role of Fe(III)-citrate complex is significant in natural waters due to its ubiquitous existence and excellent photoreactivity at...     

MIL-88B(Fe)非均相芬顿催化降解磺胺甲恶唑

采用溶剂热法合成了铁基金属有机骨架材料MIL-88B(Fe),将其作为类芬顿催化剂用于催化降解水中磺胺甲恶唑(SMX)。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、傅立叶变换红外光谱(FTIR)和X射线光电子能谱(XPS)等对催化剂的结构和性能进行表征,并研究了H₂O₂浓度、催化剂投加量、溶液初始pH和污染物初始浓度等对SMX降解效果的影响。结果表明,在H₂O₂摩尔浓度为6.0mmol/L、催化剂投加量为0.2g/L、pH为4、SMX为5mg/L的优化反应条件下,MIL-88B(Fe)对SMX的降解率可达99%。在较宽的pH(4～6)范围内,MIL-88B(Fe)仍保持较好的催化活性,且5次循环使用后对SMX去除率仍可达95%以上。表明合成的MIL-88B(Fe)具有较高的催化活性和重复性能,是一种优良的非均相类芬顿催化剂。     

有机配体对铁电絮凝体系中羟基自由基氧化降解苯胺的影响

铁电絮凝(Fe-EC)是一种高效的水处理方法,但其中有机污染物的去除机制尚不明晰。为研究有机废水中常见的有机配体对铁电絮凝过程中羟基自由基(·OH)产生以及有机污染物降解的影响,采用了对照实验、淬灭实验和电子自旋共振（ESR）等测试方法。结果表明：草酸(H₂C₂O₄)和乙二胺四乙酸(EDTA)能有效促进铁电絮凝对苯胺(AN)的氧化降解,而·OH是起主要作用的活性氧化物;草酸和EDTA体系中主要存在的Fe(Ⅱ)络合物浓度与羟基自由基产率成正相关关系,1 mol的Fe(Ⅱ)-EDTA²⁻会产生235 mmol的·OH,是草酸的9倍;EDTA会与污染物竞争羟基自由基。进一步分析可知,在铁电絮凝体系中,EDTA的浓度为0.05 mmol·L⁻¹时,对苯胺氧化降解的促进效果最佳。以上研究结果可为认识铁电絮凝中污染物的去除机制提供参考。     

磁性还原氧化石墨烯负载Fe0对罗丹明B的类芬顿降解

合成了磁性还原氧化石墨烯负载零价纳米铁材料（Fe0-MF-RGO）,并在双氧水（H2O2）的作用下构成类芬顿试剂用于对罗丹明B（RhB）的吸附-催化降解。通过正交实验研究了pH值、Fe0-MF-RGO用量、RhB初始浓度、温度和H2O2浓度5个影响因素。在15 ℃、pH值为7.0、Fe0-MF-RGO投加量1.0 g·L-1、RhB初始浓度为50 mg·L-1以及H2O2浓度为0.8 mmol·L-1的条件下,150 min后模拟废水中RhB的去除率达到98.17%,经5次循环使用后去除率为72.97%。     

Oxidative degradation of dimethylsulfoxide by locally concentrated hydroxyl radicals in streamer corona discharge process

This study systematically investigates the characteristic degradation behaviors of dimethylsulfoxide (DMSO) by the streamer corona discharge process (SCDP) in water. The analysis of the oxidized intermediates of DMSO shows that hydroxyl radical (*OH) is the main oxidant responsible for the degradation of DMSO in the SCDP. The various experiments on the degradation and mineralization of DMSO, and the effect of the *OH scavenger suggest that the SCDP produces locally concentrated *OHs in and around the plasma channel. This explanation was also supported by the formation of H(2)O(2) and the effect of the *OH scavenger on the H(2)O(2) production rate in the SCDP. Based on the kinetic data for the degradation of DMSO and the production of H(2)O(2) in the SCDP, the volume of the active region in which the *OHs are concentrated, and the effective concentration of *OH in that region were estimated to be 0.21 microl and 5.0 x 10(-3)M, respectively. This level of *OH concentration in the SCDP is approximately 10(7)-10(9) times higher than that generated in ordinary advanced oxidation processes using *OH. The ramifications of the results obtained in this study on successful water treatment using the SCDP are also discussed.     

Factors affecting degradation of dimethyl sulfoxide (DMSO) by fluidized-bed Fenton process

In this study, the target compound is dimethyl sulfoxide (DMSO), which is used as a photoresist stripping solvent in the semiconductor and thin-film transistor liquid crystal display (TFT-LCD) manufacturing processes. The effects of the operating parameters (pH, Fe²⁺ and H₂O₂ concentrations) on the degradation of DMSO in the fluidized-bed Fenton process were examined. This study used the Box-Behnken design (BBD) to investigate the optimum conditions of DMSO degradation. The highest DMSO removal was 98 % for pH 3, when the H₂O₂ to Fe²⁺ molar ratio was 12. At pH 2 and 4, the highest DMSO removal was 82 %, when the H₂O₂ to Fe²⁺ molar ratio was 6.5. The correlation of DMSO removal showed that the effect of the parameters on DMSO removal followed the order Fe²⁺?>?H₂O₂?>?pH. From the BBD prediction, the optimum conditions were pH 3, 5 mM of Fe²⁺, and 60 mM of H₂O₂. The difference between the experimental value (98 %) and the predicted value (96 %) was not significant. The removal efficiencies of DMSO, chemical oxygen demand (COD), total organic carbon (TOC), and iron in the fluidized-bed Fenton process were higher than those in the traditional Fenton process.     

电解液条件对苯酚降解及羟自由基生成的影响

以钛基PbO2电极为活性阳极,通过电化学氧化法降解处理苯酚模拟废水,系统考察了羟自由基（·OH）抑制剂、支持电解质、酸碱性等电解液条件对苯酚水溶液COD去除率的影响。同时,以水杨酸（SA）为·OH捕捉剂,通过高效液相色谱分析技术对不同电解液条件下·OH的生成量进行间接检测。结果发现,PbO2电极上苯酚水溶液的COD去除符合一级反应动力学规律,其表观反应速率常数在分别加入·OH抑制剂NaHCO3、Na2CO3和叔丁醇时显著下降,表明苯酚的电化学氧化降解遵循·OH反应机理;支持电解质对电解液体系中·OH生成量的影响不明显,主要通过在阳极氧化生成的氧化剂参与苯酚的降解,以NaCl为支持电解质时降解效率最高,其次是Na2SO4,最后为NaNO3;随电解液pH值的增加,苯酚水溶液的COD去除速率不断提高,而·OH的生成量在碱性条件下亦显著增加。     

Kinetics of acetaminophen degradation by Fenton oxidation in a fluidized-bed reactor

Acetaminophen (ACT), an analgesic and antipyretic substance, is one of the most commonly detected pharmaceutical compound in surface waters and wastewaters. In this study, fluidized-bed Fenton (FB-Fenton) was used to decompose ACT into its final degradation products. The 1.45-L cylindrical glass reactor had inlet, outlet and recirculating sections. SiO₂ carrier particles were supported by glass beads with 2–4 mm in diameter. ACT concentration was determined by high performance liquid chromatography (HPLC). During the first 40 min of reaction, a fast initial ACT removal was observed and the “two-stage” ACT degradation conformed to a pseudo reaction kinetics. The effects of ferrous ion dosage and [Fe²⁺]/[H₂O₂] (FH ratio) were integrated into the derived pseudo second-order kinetic model. A reaction pathway was proposed based on the intermediates detected through SPME/GC–MS. The aromatic intermediates identified were hydroquinone, benzaldehydes and benzoic acids while the non-aromatic substances include alcohols, ketones, aldehydes and carboxylic acids. Rapid initial ACT degradation rate can be accomplished by high initial ferrous ion concentration and/or low FH ratio.     

Heterogeneous Fenton degradation of bisphenol A catalyzed by efficient adsorptive Fe3O4/GO nanocomposites

A new method for the degradation of bisphenol A (BPA) in aqueous solution was developed. The oxidative degradation characteristics of BPA in a heterogeneous Fenton reaction catalyzed by Fe₃O₄/graphite oxide (GO) were studied. Transmission electron microscopic images showed that the Fe₃O₄ nanoparticles were evenly distributed and were ～6 nm in diameter. Experimental results suggested that BPA conversion was affected by several factors, such as the loading amount of Fe₃O₄/GO, pH, and initial H₂O₂ concentration. In the system with 1.0 g L^?1 of Fe₃O₄/GO and 20 mmol L^?1 of H₂O₂, almost 90 % of BPA (20 mg L^?1) was degraded within 6 h at pH 6.0. Based on the degradation products identified by GC–MS, the degradation pathways of BPA were proposed. In addition, the reused catalyst Fe₃O₄/GO still retained its catalytic activity after three cycles, indicating that Fe₃O₄/GO had good stability and reusability. These results demonstrated that the heterogeneous Fenton reaction catalyzed by Fe₃O₄/GO is a promising advanced oxidation technology for the treatment of wastewater containing BPA.     

旋转填充床中Fenton+O_3氧化降解模拟阿莫西林废水

以旋转填充床(RPB)作为反应装置,研究了Fenton工艺与Fenton+O3工艺处理模拟阿莫西林废水的效果,考察了FeSO4·7H2O的投加量、温度、旋转床转速、液体流量及pH对COD去除率的影响。实验表明,Fenton+O3工艺的COD脱除率及BOD5/COD相对于Fenton工艺分别提升26.7%和140%。该工艺在pH为3、温度为25℃、液体流量30 L/h、气体流量2.5 L/h、转速800 r/min、H2O2的投加量为1 mmol/L及Fe2+投加量为0.4 mmol/L的条件下,100 mg/L的模拟阿莫西林废水中COD的去除率达到57.9%,BOD5/COD从0增加到0.36,满足后续生化处理要求。     

Leaching of bisphenol A (BPA) from polycarbonate plastic to water containing amino acids and its degradation by radical oxygen species

In this study, (1) the change in the concentration of bisphenol A (BPA) leached from polycarbonate plastic (PCP) tube to water samples containing phosphate, sodium barbital, glycine, methionine or albumin at 37 degrees C as a function of time, and (2) the degradation rate of BPA leached from PCP tube to amino acid solutions in the presence of radical oxygen species (ROS) were investigated. The BPA leaching velocity (BPA-LV) from PCP tube to 50 mM glycine at pH 6 or 7 was twice that to control water, and the leaching was enhanced above pH 8. At pH 11, BPA-LV was significantly higher in 50 mM glycine and methionine solutions than in 50 mM NaOH. These results indicate that basic pH and amino acids contained in water could accelerate BPA leaching. The BPA-LV in phosphate buffer was different from the BPA-LVs in other buffers (barbital and glycine) at the same pH. BPA leached to the glycine or methionine solutions at pH 11 was degraded time dependently in a similar manner as the control water in the presence of ROS. The degradation of leached BPA was inhibited in the glycine solution, but was accelerated in the methionine solution. However, degradation of BPA added to freshly prepared methionine was inhibited in a similar manner to BPA in glycine. BPA degradation could be influenced by some kinds of amino acids, but glycine and methionine might be involved in BPA degradation in different ways.     

US-UV-Fenton降解硝基苯

采用超声波(US)、紫外光(UV)和Fenton联合降解硝基苯,初步探讨了其作用规律。研究结果表明, UV可以促进双氧水转化自由基的效率,而US同时具有强化传质作用和超声氧化作用,两者均能够强化Fenton氧化硝基苯的降解过程。正交实验结果表明,H2O2初始浓度是硝基苯降解和矿化的最显著影响因素,反应时间和超声功率是矿化的显著影响因素。最佳反应条件为:H2O2 500 mg/L、Fe2+10 mg/L、反应时间60 min、超声波功率100 W,此时,硝基苯完全降解,TOC去除率达到73.0%。Fenton、UV/Fenton和US/UV/Fenton降解硝基苯过程均符合伪一级反应动力学模式,反应速率常数分别为3.37×10-2、3.81×10-2和5.10×10-2min-1。     

Photochemical generation rates of hydroxyl radical in aqueous solutions containing Fe(III)-hydroxy complex

The rates of photochemical generation of hydroxyl radical at 313 nm in aqueous solutions containing ferric ion at acidic pH were measured by the competitive kinetic method using 2-chlorophenol as a test compound and 1-octanol as a radical scavenger. The quantum yield of hydroxyl radical generation calculated from the rates was about 0.02. From the results, it was suggested that this system could be used as a method of wastewater treatment.     

Remediation of a biodiesel blend-contaminated soil by using a modified Fenton process

A soil contaminated with a B20 biodiesel blend (20 % biodiesel, 80 % diesel) has been treated by modified Fenton process with or without chelant addition. All experiments were conducted without pH adjustment. The reagents used were as follows: hydrogen peroxide as oxidant (400–4,000 mmol L^?1), ferric ion as catalyst (5–20 mmol L^?1), and trisodium citrate (50 mmol L^?1) as chelating agent. Soil was spiked at two different pollutant concentrations (1,000–10,000 mg diesel kg^?1 soil). Higher total petroleum hydrocarbon (TPH) removal efficiencies were obtained (up to 75 %) after the treatment in the absence of the chelant due to the low pH obtained in this case. In the presence of chelant, the TPH conversion obtained was lower because both higher pH is obtained and chelant competes with diesel for the oxidant. On the other hand, at neutral pH, the lifetime of the oxidant was increased. Fatty acid methyl esters (FAMEs) are easier to remove than diesel aliphatic hydrocarbons from the blend. An important decrease of the aqueous phase toxicity was observed after the modified Fenton reaction, supporting that nontoxic by-products were released to the aqueous phase during the treatment.     

Degradation of rhodamine B by Fe(0)-based Fenton process with H2O2

Degradation of rhodamine B by Fe(0)-based Fenton process with H₂O₂ was investigated. The effects of H₂O₂ dose, Fe(0) dose, initial concentration of rhodamine B and initial pH value on the degradation of rhodamine B were examined. The results showed that the degradation and mineralization of rhodamine B occurred with low dose of H₂O₂ and Fe(0). The intermediates of rhodamine B were analyzed with UV-Vis spectrophotometry and ion chromatography and the mechanism of oxidative degradation of rhodamine B was also discussed. The reactive oxygen species (·OH) produced in Fe(0)-based Fenton process with H₂O₂ is the key to the degradation of rhodamine B by ways of N-de-ethylation, chromophore cleavage, ring-opening and mineralization.