Optimisation of decolourisation and degradation of Reactive Black 5 dye under electro-Fenton process using Fe alginate gel beads

The aim of this work was to improve the ability of the electro-Fenton process using Fe alginate gel beads for the remediation of wastewater contaminated with synthetic dyes and using a model diazo dye such as Reactive Black 5 (RB5). Batch experiments were conducted to study the effects of main parameters, such as voltage, pH and iron concentration. Dye decolourisation, reduction of chemical oxygen demand (COD) and energy consumption were studied. Central composite face-centred experimental design matrix and response surface methodology were applied to design the experiments and to evaluate the interactive effects of the three studied parameters. A total of 20 experimental runs were set, and the kinetic data were analysed using first-order and second-order models. In all cases, the experimental data were fitted to the empirical second-order model with a suitable degree for the maximum decolourisation of RB5, COD reduction and energy consumption by electro-Fenton–Fe alginate gel beads treatment. Working with the obtained empirical model, the optimisation of the process was carried out. The second-order polynomial regression model suggests that the optimum conditions for attaining maximum decolourisation, COD reduction and energy consumption are voltage, 5.69 V; pH 2.24 and iron concentration, 2.68 mM. Moreover, the fixation of iron on alginate beads suggests that the degradation process can be developed under this electro-Fenton process in repeated batches and in a continuous mode.     

间接阳极氧化处理活性黑5模拟染料废水的研究

采用Ti/IrO2电极间接阳极氧化处理活性黑5模拟废水,主要研究pH值、电压、电解时间及NaCl投加量对其降解效果的影响.结果表明,在pH值为3,电压20 V,电解时间60 min,NaCl投加量2.5 g/L的条件下,该染料的降解率及脱色率均达到100%,苯环结构的降解可达45%,COD去除率可达60%.并对该染料的...     

3种污泥对活性黑KN-B的生物吸附及降解研究

对比研究了好氧污泥、厌氧污泥和厌氧颗粒污泥对染料活性黑KN-B的吸附和降解。结果表明,这3种污泥对活性黑的吸附均符合Freundlich模型(R~2为0.9665～0.9859)和Langmuir模型(R~2为0.9460～0.9906),但3种污泥对活性黑这种染料的吸附量较小;并且厌氧污泥对活性黑的吸附能力优于好氧污泥和厌氧颗粒污泥。实验还发现,3种污泥对活性黑的脱色主要是生物降解作用,而不是吸附作用。     

CuAPO-5分子筛催化氧化水溶液中苯酚的性能

以水热晶化法合成了铜磷铝分子筛CuAPO-5,并用XRD、SEM,FT-IR,UV-Vis等对样品进行了表征,结果表明Cu²⁺进入到了AlPO₄-5分子筛骨架中。研究了以CuAPO-5为催化剂, H₂O₂为氧化剂对水溶液中苯酚的催化氧化性能。在苯酚初始浓度200 mg/L 、H₂O₂添加量1 200 mg/L、pH值5.0、处理温度80 ℃时,处理240 min时苯酚去除率达到100％,TOC去除率达81.76％,析出到溶液中Cu²⁺浓度仅为0.527 mg/L。温度从40 ℃上升到80 ℃时,苯酚的去除率及TOC去除率明显增大,表明温度对催化剂的活性影响显著,相比于均相催化剂骨架Cu催化过氧化氢分解需要更多的能量。重复性实验表明,催化剂性能稳定。     

Fe/沸石对偶氮染料活性黑5的催化降解

为了对水中偶氮染料活性黑5的去除进行研究,通过沉淀法在沸石上负载Fe2O3制备出一种具有较高催化活性的催化剂,采用X-射线衍射仪（XRD）和扫描电镜（SEM）对其结构和形貌进行了表征,并利用Fe/沸石进行非均相Fenton反应处理模拟染料废水的研究,考察不同操作条件对活性黑5降解效果的影响。实验结果表明,活性黑5的脱色率随催化剂投加量的升高而升高,但是随着染料初始浓度的升高而降低。H2O2浓度和pH的升高均使得活性黑5的脱色率先升高而后降低。在最佳pH为3,最佳H2O2浓度为200 mg·L-1的条件下,活性黑5的脱色率达到最大,为95.7%。通过对催化剂Fe/沸石稳定性研究,发现经5次连续循环使用后,活性黑5脱色率仍然可保持在94%以上,说明该催化剂具有良好的循环使用性能。     

零价铝/酸体系对活性黑染料的降解

利用铝粉研究了零价铝/酸(zero valent-aluminum acid system)体系对活性黑5染料的降解效果,并采用Design-expert 8.0 软件对单因素和因素之间的交互作用进行分析。结果表明,零价铝/酸体系对活性黑5脱色效果较好;在pH为0.87、温度为34.4℃、铝粉投加量为1.2 g/L,转速为160 r/min时,反应8 h后,活性黑去除率达到94.89%。采用响应面法和排列图分析,pH和温度是影响活性黑溶液去除率的主要因素,并通过UV-Vis光谱分析,对活性黑在零价铝/酸体系的降解规律进行了初步探讨。     

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.     

Efficient activation of peroxymonosulfate by Co-doped mesoporous CeO2 nanorods as a heterogeneous catalyst for phenol oxidation

Environmental Science and Pollution Research - Sulfate radical?based advanced oxidation processes have received considerable attentions in the remediation of organic pollutants due to their...     

Mechanism and kinetic model for the decolorization of the azo dye Reactive Black 5 by hydrogen peroxide and UV radiation

A kinetic model for the decolorization of C.I. Reactive Black 5 by the combination of hydrogen peroxide and UV radiation was developed based on experimental results and known chemical and photochemical reactions. The observed kinetic reaction coefficient was determined and correlated as a function of hydrogen peroxide concentration and UV intensity. The validity of the rate expression was tested experimentally in a parameterization study. The decolorization rate follows pseudo-first order kinetics with respect to dye concentration. The rate increases linearly with UV intensity and nonlinearly with increasing hydrogen peroxide concentration, going from a linear relationship at low H(2)O(2) concentrations to a maximum as hydrogen peroxide concentration continues to increase. The decolorization rate expression derived from the proposed reaction mechanism was reconciled with that used for correlating the experimental data.     

Catalytic oxidation of organic compounds in incineration flue gas by a commercial palladium catalyst

The object of this study is to investigate the effect of different operation conditions on the catalytic oxidation of trace organic compounds [i.e., benzene, toluene, ethylbenzene, and xylene (BTEX); and polyaromatic hydrocarbons (PAHs)] in incineration flue gas. A commercial Pd-based honeycomb catalyst, which is applied to treat flue gas with low organic concentrations and high gas velocity, is employed in this study. The investigated parameters include (1) effect of different space velocities, (2) effect of heavy metals, (3) effect of acid gas, and (4) effect of water vapor and ash particles. In this work, an effective catalyst oxidation system is constructed and expected to purify the incineration flue gas. Catalyst oxidation is a potential purification system that will meet the stricter regulations on the emissions of incineration systems. Experimental results showed that the destruction efficiency of PAHs and BTEX in Pd catalyst was generally greater than 80%. Decreasing the space velocity increased the decomposition efficiency of organic compounds. When the feedstock contained the heavy metals Pb and Cr, the oxidation of organic compounds was not inhibited. But the presence of Cd significantly decreased the oxidation efficiency. The acid gases SO2 and HCl in the flue gas could have influenced the crystal structure of PdO and subsequently deactivated/poisoned the Pd catalyst. The effect of water vapor on the catalytic destruction of PAHs and BTEX was not obvious.     

Degradation of the herbicide 2,4-DP by anodic oxidation, electro-Fenton and photoelectro-Fenton using platinum and boron-doped diamond anodes

This paper reports the degradation of 2,4-DP (2-(2,4-dichlorophenoxy)-propionic acid) solutions of pH 3.0 by environmentally friendly electrochemical methods such as anodic oxidation, electro-Fenton and photoelectro-Fenton with a Pt or boron-doped diamond (BDD) anode. In the two latter techniques an O(2)-diffusion cathode was used and 1.0mM Fe(2+) was added to the solution to give hydroxyl radical (*OH) from Fenton's reaction between Fe(2+) and H(2)O(2) generated at the cathode. All treatments with BDD are viable to decontaminate acidic wastewaters containing 2,4-DP since they give complete mineralization, with loss of chloride ion, at high current due to the great production of oxidant *OH at the BDD surface favoring the destruction of final carboxylic acids. *OH formed from Fenton's reaction destroys more rapidly aromatic products, making the electro-Fenton and photoelectro-Fenton processes much more efficient than anodic oxidation. UVA light in photoelectro-Fenton with BDD has little effect on the degradation rate of pollutants. The comparative procedures with Pt lead to slower decontamination because of the lower oxidizing power of this anode. The effect of current on the degradation rate and efficiency of all methods is studied. The 2,4-DP decay always follows a pseudo-first-order kinetics. Chlorohydroquinone, chloro-p-benzoquinone and maleic, fumaric, malic, lactic, pyruvic, acetic, formic and oxalic acids are detected as products by chromatographic techniques. A general sequence accounting for by the reaction of all these intermediates with the different oxidizing agents is proposed.     

丝瓜瓤固定化脱色菌Enterobactor sp.S8 对活性黑5的脱色

利用植物载体丝瓜瓤对肠杆菌(Enterobactor sp.S8)进行固定,并对活性黑5进行脱色研究.探讨了固定化菌体的菌龄、菌量、pH、温度对染料脱色的影响.研究了该固定化菌体的重复利用和动力学实验.结果表明,最佳脱色条件为:菌龄3d、接菌量2％、温度30℃、pH 6.0.该固定化菌体对不同初始浓度活性黑5的脱色符合二级反应动力学方程.经9次重复利用后的该固定化菌体,其脱色率仍达76.8％.在优化实验条件下,根据降解3d前后的紫外-可见光谱图分析可知,活性黑5并非完全被降解为CO2和H2O,而是生成一些小分子有机中间体.     

Cu-ZnO双反应中心类芬顿催化剂降解水中碘乙腈性能与机制

多相芬顿催化虽然克服了均相芬顿pH适用范围窄,铁泥二次污染等问题,但还面临着稳定性差,H₂O₂利用率低的问题,从而限制了其实际应用。本文利用锌和铜的电负性差异制备了一种双反应中心催化剂Cu-ZnO,通过在催化剂表面构建贫富电子中心,从而诱导H₂O₂产生·OH降解污染物。采用TEM、EDS、XRD、FTIR、XPS以及EPR对催化剂进行表征,并研究了催化剂投加量、H₂O₂投加量、pH以及共存离子对碘乙腈降解效果的影响。结果表明,在催化剂投加量为1 g·L^-1,双氧水投加量为10 mmol·L^-1时,Cu-ZnO对碘乙腈的去除率在91%。大部分共存离子对催化剂的降解效果影响较小,且在酸性条件下催化剂稳定性较好,中性和碱性条件下金属离子基本无释放。催化剂诱导产生的•OH和HO₂^•/O₂^•−是碘乙腈(IAN)降解的主要活性物种,降解产物包括CO₂,H₂O,I^－和IO₃^- 等。     

Degradation and mineralization of sulcotrione and mesotrione in aqueous medium by the electro-Fenton process: a kinetic study

Introduction

The degradation and mineralization of two triketone (TRK) herbicides, including sulcotrione and mesotrione, by the electro-Fenton process (electro-Fenton using Pt anode (EF-Pt), electro-Fenton with BDD anode (EF-BDD) and anodic oxidation with BDD anode) were investigated in acidic aqueous medium.

Methods

The reactivity of both herbicides toward hydroxyl radicals was found to depend on the electron-withdrawing effect of the aromatic chlorine or nitro substituents. The degradation of sulcotrione and mesotrione obeyed apparent first-order reaction kinetics, and their absolute rate constants with hydroxyl radicals at pH?3.0 were determined by the competitive kinetics method.

Results and discussion

The hydroxylation absolute rate constant (k _abs) values of both TRK herbicides ranged from 8.20?×?10⁸ (sulcotrione) to 1.01?×?10⁹ (mesotrione) L?mol^?1?s^?1, whereas those of the TRK main cyclic or aromatic by-products, namely cyclohexane 1,3-dione , (2-chloro-4-methylsulphonyl) benzoic acid and 4-(methylsulphonyl)-2-nitrobenzoic acid, comprised between 5.90?×?10⁸ and 3.29?×?10⁹?L?mol^?1?s^?1. The efficiency of mineralization of aqueous solutions of both TRK herbicides was evaluated in terms of total organic carbon removal. Mineralization yields of about 97?C98% were reached in optimal conditions for a 6-h electro-Fenton treatment time.

Conclusions

The mineralization process steps involved the oxidative opening of the aromatic or cyclic TRK by-products, leading to the formation of short-chain carboxylic acids, and, then, of carbon dioxide and inorganic ions.     

Fe (III) supported on resin as effective catalyst for the heterogeneous oxidation of phenol in aqueous solution

FeIII supported on resin as an effective catalyst for oxidation was prepared and applied for the degradation of aqueous phenol. Phenol was selected as a model pollutant and the catalytic oxidation was carried out in a batch reactor using hydrogen peroxide as the oxidant. The influent factors on oxidation, such as catalyst dosage, H2O2 concentration, pH, and phenol concentration were examined by considering both phenol conversion and chemical oxygen demand (COD) removal. The FeIII-resin catalyst possesses a high oxidation activity for phenol degradation in aqueous solution. The experimental results of this study show that almost 100% phenol conversion and over 80% COD removal can be achieved with the FeIII-resin catalyst catalytic oxidation system. A series of prepared resin were investigated for improving the oxidation efficiency. It was found that the reaction temperature and initial pH in solution significantly affected both of phenol conversion and COD removal efficiency. The activity of the catalyst significantly decreased at high pH, which was similar to the Fenton-like reaction mechanism. Results in this study indicate that the FeIII-resin catalytic oxidation process is an efficient method for the treatment of phenolic wastewater.     

A batch kinetic study on decolorization and inhibition of Reactive Black 5 and Direct Brown 2 in an anaerobic mixed culture

Decolorization and inhibition kinetic characteristics of two azo dyes namely Reactive Black 5 (RB 5) and Direct Brown 2 (DB 2) were investigated with partially granulated anaerobic mixed culture using glucose (3000 mg l(-1) COD) as carbon source and electron donor during batch incubation. Monod, zero-, first-, and second-order reaction kinetic models were tested in order to determine the most suitable rate model of substrate and color removal kinetic. The course of the decolorization and substrate removal process approximates to first-order kinetic model under batch conditions. Decolorization, and substrate removal were achieved effectively under test conditions but ultimate removal of azo dyes and substrate were not observed at high dye concentrations. Aromatic amine and volatile fatty acid accumulation were observed proportionally at a higher azo dye concentration. A competitive kinetic model that describes the anaerobic co-metabolism of increasing RB 5 and DB 2 dye concentrations with glucose as co-substrate has been developed based on the experimental data.     

缓释铁源耦合气体扩散电极强化电芬顿降解环丙沙星

气体扩散电极(GDE)气液固三相界面可高效产生H₂O₂,但对铁离子还原能力较弱。针对这一问题,本文构建了一种基于缓释铁源的电芬顿体系(SRIS-EF),通过引入柱状铁棒与GDE电极协同作用加强体系的氧化能力。该体系旨在改进Fe²⁺投加方式,通过电场与溶液酸碱度协同作用持续生成Fe²⁺,提高羟基自由基(·OH)的生成和利用率,加速污染物的降解与矿化。以100 mg·L⁻¹环丙沙星(CIP)为目标物,通过定量分析体系内生成的主要活性氧化物质(ROS)表征其氧化能力,结果表明SRIS-EF能够持续生成更高浓度的·OH。对比了不同体系对CIP的矿化能力,发现SRIS-EF的TOC矿化率与常规EF相比提高了12.1%。此外,考察了SRIS-EF体系中柱状铁棒面积、初始pH、电流密度等因素对降解效能的影响,得出了SRIS-EF体系的最佳条件为：铁棒面积2.89 cm²,初始pH 3.00,电流密度30 mA·cm⁻²,在此条件下反应60 min即可被完全去除CIP,处理360 min后TOC去除率可达47.3%。还对体系中无机离子和小分子有机酸的生成情况进行了测定,检测出CIP内的N和F主要以NH₄⁺、NO₃⁻和F⁻形式释放,降解过程中生成了草酸、甲酸、富马酸和丙二酸等四种短链羧酸,其中甲酸浓度较高。研究证实了SRIS-EF体系在降解水中难降解有机污染物方面优异的氧化性能。     

Influence of resorcinol chemical oxidation on the removal of resulting organic carbon by activated carbon adsorption

Activated carbon adsorption and chemical oxidation followed by activated carbon adsorption of resorcinol in water has been studied. Three chemical oxidants have been used: hypochlorite, permanganate and Fenton's reagent. The influence of concentrations of resorcinol and activated carbon on adsorption removal rates has been investigated. Both isotherm and adsorption kinetics have been studied. Results are fit well by Freundlich isotherms and adsorption rates of resorcinol were found to follow a pseudo-second-order kinetic model. However, pyrogallol, an intermediate of resorcinol oxidation with permanganate and Fenton's reagent, showed an unfavourable isotherm type. At the conditions investigated, chemical oxidation allows slight reductions of TOC and intermediates formed were found to inhibit the adsorption rate of TOC in the case of permanganate and Fenton's reagent oxidation, likely due to formation of some polymer pyrogallol product. The adsorption process was found to be controlled by pore internal diffusion, which justifies the poor affinity of oxidation intermediates toward activated carbon since molecules of larger size should diffuse rapidly for the adsorption to be effective.     

Metal solubility as a function of pH in a contaminated, dredged sediment affected by oxidation

The solubility as a function of pH for metals in a reduced dredged sediment, subjected to different redox conditions, was studied in a laboratory experiment. The redox conditions imposed simulated (i) the undisturbed sediment (flooded), (ii) a dredged material stored in a confined pond (aerated once and then flooded), (iii) an upland stored dredged material (drained and dried), and (iv) an upland stored sediment subjected to tillage (drained, dried and mixed). Minor differences in the solubility as a function of pH were observed between the treatments after two weeks. After three months, the solubility of Cd, Cu, Pb and Zn increased strongly in the oxidized sediments. Leachability of Fe decreased, while Mn, Ni and Co were mostly unaffected. Both short- and long-term mobility of metals (except Fe) is expected to be lowest when a reduced sediment remains in reduced conditions. Studying the solubility as a function of pH may provide additional information on the chemical association of metals in sediments.     

Study of the toxicity of diuron and its metabolites formed in aqueous medium during application of the electrochemical advanced oxidation process "electro-Fenton"

Diuron (N'-[3,4-dichlorophenyl]-N,N-dimethylurea) is a herbicide belonging to the phenylurea family, widely used to destroy weeds on uncultivated surfaces. Because of its toxicity for aquatic organisms and suspicion of being carcinogenic for humans, diuron is the object of growing environmental concern. Therefore, we have developed the electro-Fenton method, an electrochemical advanced oxidation process (EAOP), to degrade diuron in aqueous medium, and we have studied the evolution of the toxicity of treated solution during the process. Indeed, the EAOPs catalytically generate hydroxyl radicals that oxidize the persistent organic pollutants, and can ultimately destroy and mineralize them. But, sometimes, relatively toxic organic metabolites are formed during the oxidation reaction. In this work, the evolution of toxicity of diuron aqueous solutions was studied at different initial concentrations, during treatment by the electro-Fenton method. Samples were collected at various electrolysis times and mineralization degrees during the treatment. The toxicity of the samples was measured using the bacteria Vibrio fischeri (Microtox) and the green alga Scenedesmus obliquus. Our results demonstrated that the toxicity of diuron aqueous solutions (concentrations=3.0-27.6 mg L(-1)) varied considerably with time. The formation and disappearance of several metabolites, having toxicity often stronger than that of the initial herbicide, were observed. To improve the efficiency of water decontamination, the electro-Fenton method should be applied during a time long enough (several hours) and at relatively high electrolysis current (I=250 mA) to reach a nearly complete mineralization of the herbicide in the aqueous medium.