Removal of metsulfuron methyl by Fenton reagent

The removal of metsulfuron methyl (MeS)—a sulfonyl urea herbicide from contaminated water was investigated by advanced oxidation process (AOP) using Fenton method. The optimum dose of Fenton reagent (Fe²⁺/H₂O₂) was 10 mg/L Fe²⁺ and 60 mg/L H₂O₂ for an initial MeS concentration ([MeS]₀) range of 0–80 mg/L. The Fenton process was effective under pH 3. The degradation efficiency of MeS decreased by more than 70% at pH > 3 (pH 4.5 and 7). The initial Fe²⁺ concentration ([Fe²⁺]₀) in the Fenton reagent affected the degradation efficiency, rate and kinetics. The degradation of MeS at optimum dose of Fenton reagent was more than 95% for [MeS] ₀ of 0–40 mg/L and the degradation time was less than 30 min. The determination of residual MeS concentration after Fenton oxidation by UV spectrophotometry was affected by the interferences from Fenton reagent. The estimation of residual MeS concentration after Fenton oxidation by high pressure/performance liquid chromatograph (HPLC) was interference free and represented the actual concentration of MeS and does not include the by-products of Fenton oxidation. The degradation kinetics of MeS was modelled by second order reactions involving 8 rate constants. The two reaction constants directly involving MeS were fitted using the experimental data and the remaining constants were selected from previously reported values. The model fit for MeS and the subsequent prediction of H₂O₂ were found to be within experimental error tolerances.     

Degradation of 2,4-dichlorophenol in aqueous solution by sono-Fenton method

This study presents the results of the Sono-Fenton process for the degradation of 2,4-dichlorophenol (DCP). The influential parameters such as H₂O₂, Fe²⁺ and pH for the Sono-Fenton process were investigated. Sono-Fenton method was found to be the best one for degradation efficiency of DCP when compared with that of the Fenton process. The optimum concentrations for the degradation of DCP using conventional Fenton’s method were found to be 20 mg/L of Fe²⁺ and 580 mg/L of H₂O₂ at pH 2.5. In the case of Sono-Fenton, the optimal concentrations were found to be 10 mg/L of Fe²⁺ and 400 mg/L of H₂O₂ at pH 2.5. Sono-Fenton method resulted in the reduction of required Fe²⁺ concentration (50%) and H₂O₂ concentration (31%). In addition, this method could be applicable even at pH 5.0 and a degradation efficiency of DCP was 77.6%. Kinetic studies for the degradation of DCP proved that the degradation of DCP tends to follow pseudo first order reaction and the rate constant was found to be 7 × 10⁻⁴ min⁻¹.     

Comparison of granular activated carbon bio-sorption and advanced oxidation processes in the treatment of leachate effluent

Landfill leachate is a toxic effluent of a decomposing landfill that is produced when rainwater percolates through the landfill leaching out contaminants and pollutants. Untreated leachate is a potential source for the contamination of soil, surface and ground water. In this study, the treatment processes such as granular activated carbon (GAC) adsorption/bio-sorption (batch), and advanced oxidation processes (AOP) viz. photocatalysis and Fenton’s process were evaluated and compared by using synthetic landfill leachate (SLL) as a contaminant. TiO₂ was used as a catalyst in photocatalysis, and Fenton’s reagent (H₂O₂/Fe⁺²) was used in Fenton’s process. The degradation of SLL effluent by the three above-mentioned processes was characterized by the % TOC removal. The % TOC removed by photocatalysis, Fenton oxidation and bio-sorption (which includes adsorption and biodegradation) was 30, 60 and 85%, respectively. The bio-sorption increased with the increasing GAC dose. The optimum dose of Fenton’s reagent in advanced oxidation was 15 and 400 milli moles of Fe⁺² and H₂O₂, respectively. The Fenton’s process showed faster degradation kinetics compared to biodegradation and photocatalysis.     

Studies in mineralization of aqueous aniline using Fenton and wet oxidation (FENTWO) as a hybrid process

A hybrid process for mineralization of aqueous aniline using Fenton and wet oxidation (FENTWO) is studied. It is important to have maximum conversion of ‘N’ atoms from the waste to N₂. The conversion of input ‘N’ atoms in aniline to N₂ was 15% during wet oxidation without the Fenton process and was improved to 50% with the Fenton process. Therefore, a hybrid process of Fenton followed by wet oxidation was studied for mineralization of the aqueous aniline stream. The parameters for the Fenton process were optimized (pH, catalyst, H₂O₂ to catalyst (FeSO₄) ratio, quantity of H₂O₂). The waste obtained after the Fenton process was then treated by wet oxidation for mineralization by having homogeneous CuSO₄ as the catalyst by keeping FeSO₄ therein. This combined catalyst was found to be more effective for the degradation of the intermediates formed in the Fenton process. Wet oxidation (WO) was studied in the temperature range 473–513 K and the oxygen partial pressure range 0.345–1.38 MPa at pH 6.5. The kinetic data was modeled using a power law rate expression in terms of chemical oxygen demand (COD). The optimum temperature for formation of more N₂ gas was found to be 493 K. The treated waste stream was found to contain oxalic acid using HPLC, and NH₄⁺, NO₃^? and NO₂^? ions using ion chromatography analysis. Copyright © 2007 Society of Chemical Industry     

The sonochemical decolorisation of textile azo dye CI Reactive Orange 127

In the present study, Fenton and sono‐Fenton processes were applied to the oxidative decolorisation of synthetic textile wastewater including CI Reactive Orange 127 and polyvinyl alcohol. Process optimisation [pH, ferrous ion (Fe²⁺) and hydrogen peroxide (H₂O₂)], kinetic studies and their comparison were carried out for both of the processes. The sono‐Fenton process was performed by indirect sonication in an ultrasonic water bath, which was operated at a fixed 35‐kHz frequency and 80 W power. The optimum conditions were determined as [Fe²⁺] = 20 mg l^?1, [H₂O₂] = 15 mg l^?1 and pH = 3 for the Fenton process and [Fe²⁺] = 25 mg l^?1, [H₂O₂] = 5 mg l^?1 and pH = 3 for the sono‐Fenton process. The colour removals were 89.9% and 91.8% by the Fenton and sono‐Fenton processes, respectively. The highest decolorisation was achieved by the sono‐Fenton process because of the production of some oxidising agents as a result of sonication. Consequently, ultrasonic irradiation in the sono‐Fenton process slightly increased the colour removal to 91.8%, while decreasing the hydrogen peroxide dosage to one‐third of that of the Fenton process.     

Solar photoassisted anodic oxidation of carboxylic acids in presence of Fe using a boron-doped diamond electrode

This paper reports a comparative study on the anodic oxidation of 2.5 l of 50 mg l⁻¹ TOC of formic, oxalic, acetic, pyruvic or maleic acid in 0.1 M Na₂SO₄ solutions of pH 3.0 with and without 1.0 mM Fe³⁺ as catalyst in the dark or under solar irradiation. Experiments have been performed with a batch recirculation flow plant containing a one-compartment filter-press electrolytic reactor equipped with a 20 cm² boron-doped diamond (BDD) anode and a 20 cm² stainless steel cathode, and coupled to a solar photoreactor. This system gradually accumulates H₂O₂ from dimerization of hydroxyl radical (OH) formed at the anode surface from water oxidation. Carboxylic acids in direct anodic oxidation are mainly oxidized by direct charge transfer and/or OH produced on BDD, while their Fe(III) complexes formed in presence of Fe³⁺ can also react with OH produced from Fenton reaction between regenerated Fe²⁺ with electrosynthesized H₂O₂ and/or photo-Fenton reaction. Fast photolysis of Fe(III)-oxalate and Fe(III)-pyruvate complexes under the action of sunlight also takes place. Chemical and photochemical trials of the same solutions have been made to better clarify the role of the different catalysts. Solar photoassisted anodic oxidation in presence of Fe³⁺ strongly accelerates the removal of all carboxylic acids in comparison with direct anodic oxidation, except for acetic acid that is removed at similar rate in both cases. This novel electrochemical advanced oxidation process allows more rapid mineralization of formic, oxalic and maleic acids, without any significant effect on the conversion of acetic acid into CO₂. The synergistic action of Fe³⁺ and sunlight in anodic oxidation can then be useful for wastewater remediation when oxalic and formic acids are formed as ultimate carboxylic acids of organic pollutants, but its performance is expected to strongly decay in the case of generation of persistent acetic acid during the degradation process.     

The feasibility of using combined Fenton-SBR for antibiotic wastewater treatment

The first part of this study examined the effect of operating conditions on Fenton pretreatment of an antibiotic wastewater containing amoxicillin and cloxacillin. The optimum H₂O₂/COD and H₂O₂/Fe²⁺ molar ratios were 2.5 and 20, respectively. Under the optimum operating conditions, complete degradation of the antibiotics occurred in 1 min. In the second part of this study, a bench-scale SBR was operated for 239 days and fed with Fenton-treated wastewater under different operating conditions. BOD₅/COD ratio below 0.40 of the Fenton-treated wastewater had negative effect on the SBR performance. Hydraulic retention time (HRT) of 12 h was found suitable for the SBR and increasing HRT to 24 and 48 h did not significantly improve the SBR efficiency. Statistical analysis (two-way ANOVA) was made on the results to optimize the H₂O₂/Fe²⁺ molar ratio and Fenton reaction time and it was found possible to reduce the Fe²⁺ dose and increase the Fenton reaction time. Under the best operating conditions (H₂O₂/COD molar ratio 2.5, H₂O₂/Fe²⁺ molar ratio 150, Fenton reaction time 120 min and HRT 12 h), the combined Fenton-SBR process efficiency was 89% for sCOD removal and the SBR effluent met the discharge standards. Combined Fenton-SBR is a feasible process for antibiotic wastewater treatment.     

Fe/AC催化过氧化氢降解双酚A

传统Fenton反应存在对液相pH要求较高、Fe³⁺回收困难以及难以重复使用等问题。基于"活性离子固载化,酸性环境局部化"的设计思路,通过对活性炭(AC)表面酸化改性,制备得到载铁活性炭(Fe/AC)催化剂。研究了Fe/AC制备工艺与其性能之间的关系,结果表明,在载Fe³⁺量44.05 mg·g^-1、煅烧温度200℃的制备工艺下可得到催化活性较高、稳定性好的Fe/AC催化剂。用性能优良的Fe/AC催化H₂O₂降解双酚A(BPA),其较佳催化反应条件为:反应时间60 min、反应温度20℃、溶液pH值为4.0≤pH≤8.0、Fe³⁺/H₂O₂摩尔比为0.007～0.012、30% H₂O₂用量为0.04 ml H₂O₂·(mg BPA)^-1。本工作制备得到的Fe/AC催化剂具有较好的重复使用性能,在实际废水处理领域具有较大的应用前景。     

Textile wastewater treatment efficiency by Fenton oxidation with integration of membrane separation system

This work investigates the performance of an integrated Fenton-Ultrafiltration treatment scheme to treat textile wastewater. The treated effluent is particle-free at a quality higher than that obtained by any novel membrane based process or Fenton oxidation in singularity. The study is divided into three parts: part one, Fenton process was optimized for COD: H₂O₂ (wt/wt), H₂O₂: Fe⁺² (wt/wt) and pH to attain highest degradation removal and lowest sludge generation. The process efficiency was analyzed by considering COD, TOC and color removal as key parameters. Part two, the process was scaled up to 5?L and efficiency of integrated system was investigated under optimized conditions by using two different types of membranes at different operating pressures. Part three, the performance of membrane process was studied in terms of flux behavior and its recovery. The treated effluent has COD, TOC and color removal values of 48.0?mg/L, 1.2?mg/L and >99% respectively. These values are compliant to typical discharge environmental standards.     

Mercury removal from coal combustion by Fenton reactions – Part A: Bench-scale tests

This series of papers describes the development of technology to convert Hg(0) to Hg(II) in coal-derived flue gas based on the well-known Fenton reactions so that a Hg control strategy can be implemented in a wet scrubber. This effort consists of both bench-scale and pilot-scale work. This first paper reports on the bench-scale tests. The bench-scale results showed that Hg(0) oxidation can be achieved by the Fenton reactions and the oxidation rate is quantitatively dependent on the residence time of the Hg stream in the solution. An average of 75% oxidation of Hg(0) was achieved. Iron-based Fenton-type additives gave much more promising results compared to Cu-based Fenton-like additives for Hg(0) oxidation. The pH value of the sorbent solution also had a significant effect on the oxidation of Hg(0) and a suitable pH window was found to lie between 1.0 and 3.0 for this application. This may be attributed to the chain reaction mechanisms of Fe³⁺/H₂O₂ for Fenton reactions, i.e., the decomposition of H₂O₂ for the production of OOH radicals in the Fe³⁺/H₂O₂ system which is kinetically favoured under a wide range of conditions at pH values of 3 or less. At higher pH values, H₂O₂ is converted to H₂O instead of OOH radicals in the presence of Fe³⁺.     

亚甲基蓝光度法研究基于CaO2的Fenton反应条件

CaO₂作为原位Fenton 氧化修复中H₂O₂持续供源的作用逐渐受到关注。利用亚甲基蓝分光光度法评价了基于CaO₂的Fenton反应中催化剂种类、初始pH值、CaO₂用量、催化剂和CaO₂比例、磷酸缓冲溶液浓度对羟基自由基（HO·）产率的影响。结果表明,采用Fe²⁺作为催化剂,在pH值为4、CaO₂相似文献   

Treatment of PAH‐contaminated soil by combination of Fenton's reaction and biodegradation

A combination of modified Fenton and biological treatment was used to remove polycyclic aromatic hydrocarbons (PAHs) from creosote oil‐contaminated soil. After modified Fenton reaction the toxicity of column leachate and soil to Vibrio fischeri increased. The number of intact bacterial cells and utilisation of PAHs in PAH utilisation microplate assay decreased after modified Fenton reaction. However, bacteria in chemically treated soil utilised PAHs without addition of other carbon sources. The activity of extracellular esterases increased during incubation of modified Fenton‐treated soil. PAH removal in combined chemical oxidation and incubation (43–59%) was higher than in incubation alone (22–30%). Residual H₂O₂ in soil allowed chemical oxidation of PAHs during incubation. Copyright © 2006 Society of Chemical Industry     

Influence of nature/concentration of halide promoters and oxidation state on the direct oxidation of H2 to H2O2 over Pd/ZrO2 catalysts in aqueous acidic medium

The nature/concentration of halide promoters and influence of the Pd oxidation state on the promoted reaction system has been investigated on the direct H₂O₂ process over a 2.5 wt.% Pd/ZrO₂ catalyst in an aqueous acidic reaction medium. The oxidation state of Pd had a profound influence on the H₂O₂ synthesis process. Interestingly, the nature of the halide determined the magnitude/type of influence the Pd oxidation state exerted on the overall process. While the effect of the oxidation state on the H₂O₂ yields was large for the reaction systems containing F⁻ or no halide, the effect was significantly smaller for the reaction systems containing Br⁻ and Cl⁻. The nature of the halide also strongly influenced the H₂O₂ synthesis process. Br⁻ strongly enhanced the H₂O₂ yields, while F⁻ had a negative influence on the H₂O₂ yields. The ability of the halides to enhance the H₂O₂ process was found to strongly depend on its propensity to suppress the secondary H₂O₂ decomposition reaction. The influence of Br⁻ and Cl⁻concentration studies revealed that the optimum halide concentration for the direct H₂O₂ synthesis process was dependent on the nature of the halide. While the maximum in H₂O₂ yields for the Br⁻ containing reaction medium corresponded to a concentration of ∼0.9 mmol/dm³ (KBr) the maximum for the Cl⁻ containing solution was obtained at ∼1.5 mmol/dm³ (KCl). Such knowledge is crucial from the viewpoint of optimization (catalyst/reaction system screening studies) of the direct H₂O₂ process. The qualitative trends (H₂O₂ selectivity/yield) observed in case of the incorporated halide catalysts were similar to those observed with halides in reaction medium over the Pd/ZrO₂ catalyst.     

Stabilization and dewatering of wastewater treatment plant sludge using combined bio/Fenton-like oxidation process

Wastewater sludge usually contains large amounts of water and organic materials; therefore, its stabilization and dewatering are of particular importance. The present study aimed to investigate the possibility of sludge stabilization and dewatering from wastewater sludge by bioleaching (Thiobacillus ferrooxidans), Fenton/bioleaching, and bioleaching/Fenton-like processes. To evaluate sludge stabilization and dewatering, specific resistance to filtration (SRF), volatile suspended solids (VSS), total suspended solids (TSS), and soluble chemical oxygen demand (SCOD) were measured. In biological treatment with T. ferrooxidans with Fe²⁺ (2?g?L^?1), 99.75, 33, 37, and 72% reduction were observed in SRF, VSS, TSS, SCOD, respectively, after 2 days. In the combined treatment of Fenton before bioleaching (including Fe²⁺ 2?g?L^?1 and H₂O₂ 1?g?L^?1 with Fenton oxidation for 30?min followed by biological treatment with T. ferrooxidans for 2 days), the reduction rates in TSS, VSS, SCOD, and SRF were 40.18, 40.88, 60.95, and 75.43%, respectively. In treatment with the combined method of bioleaching before Fenton-like oxidation, the removal rates of the aforementioned parameters were 52.5, 54.4, 88, and 99.82%, respectively. In comparison to Fenton oxidation and bioleaching alone, combined biological method of bioleaching/Fenton-like oxidation using a lower dose of H₂O₂ and Fe²⁺ significantly improved sludge dewatering and stabilization.     

Ecotoxicological evaluation of a fish farming effluent treated by Fenton oxidation and coagulation process

ABSTRACT

This study has evaluated the efficiency of Fenton process followed by coagulation to treat real effluent from fish farm. Fenton obtained Chemical Oxygen Demand and turbidity removal of 48% at (0.5 mg L^?1 Fe²⁺ and 10 mmol H₂O₂). Fenton followed by coagulation reduced COD and turbidity by almost 100%. The process also decreased the concentrations of suspended solids, phosphate, nitrate, Biological Oxygen Demand, and nitrite. Ecotoxicology test indicated that the effluent treated with 0.5 mmol L^?1 Fe²⁺ in 10 mmol L^?1 H₂O₂ displayed the lowest toxicity. These findings can indicate an environmental friendly alternative to treat fish farm effluent.     

Fenton oxidation process control using oxidation-reduction potential measurement for pigment wastewater treatment

The Fenton oxidation process was applied as a pretreatment process to degrade non-biodegradable organic matters in pigment wastewater. It was necessary to continuously measure the fluctuating concentration of organics in the pigment wastewater and to determine the amount of Fenton’s reagent required to oxidize the organics. Batch and continuous flow tests were used to evaluate the relationship between the concentration of organics (COD_Cr) and the amount of Fenton’s reagent required to achieve a sufficient oxidation of the organics. On-line measurements of the oxidation-reduction potential (ORP) value in the batch and continuous flow tests showed that the maximum ORP values were highly related to the organic concentrations (expressed as COD_Cr) and the Fenton’s reagent dosage (expressed as H₂O₂ concentration). The empirical equation was [COD_Cr]=8808+0.494[H₂O₂]-14.6ORP. A control program of Fenton’s reagent dosage based on the empirical equation was applied to control of a pilot scale Fenton oxidation process using ORP measurement. The concentration of organics predicted with the control program well agreed with the observed concentration of organics in the pigment wastewater. The variation of the effluent organics concentration of the controlled Fenton oxidation process was significantly reduced compared to that of a process without the control system. These results suggested that the control system of Fenton’s reagent dosage using ORP measurement would be applicable to the Fenton oxidation process for efficient pretreatment of pigment wastewater.     

The Fenton Chemistry and Its Combination with Coagulation for Treatment of Dye Solutions

Abstract

Aqueous solutions of Acid Blue 74, Acid Orange 10, and Acid Violet 19 were subjected to Fenton/Fenton‐like oxidation and its combination with lime coagulation. The analysis indicated no dependence of chemical oxidation efficacy on dye concentration in the range of 0.1–1 g L^?1. Complete or nearly complete (higher than 95%) color removal of all treated samples was observed. Dye:H₂O₂ weight ratio of 1∶2 proved optimal for treatment of all dye solutions by means of Fenton/Fenton‐like oxidation. Moderate doses of hydrogen peroxide led to the improvement of biodegradability of dye solutions. No formation of any toxic intermediates during the oxidation of Acid Orange 10 and Acid Violet 19 was detected. Only a slight toxicity increase was observed after Acid Blue 74 degradation by Fenton chemistry. H₂O₂/Fe³⁺ system with pH adjusted to 3 proved the most effective oxidation process. The combination of Fenton chemistry and subsequent lime coagulation was the most feasible treatment method of removing COD and UV₂₅₄ and UV_max absorbance of dye solutions. Combined oxidation and coagulation was more effective for Acid Blue 74 and Acid Orange 10 elimination than for Acid Violet 19.     

Advanced oxidation of cork‐processing wastewater using Fenton's reagent: kinetics and stoichiometry

This work evaluates Fenton oxidation for the removal of organic matter (COD) from cork‐processing wastewater. The experimental variables studied were the dosages of iron salts and hydrogen peroxide. The COD removal ranged from 17% to 79%, depending on the reagent dose, and the stoichiometric reaction coefficient varied from 0.08 to 0.43 g COD (g H₂O₂)^?1 (which implies an efficiency in the use of hydrogen peroxide varying from 17% to 92%). In a study of the process kinetics, based on the initial rates method, the COD elimination rate was maximum when the molar ratio [H₂O₂]_o:[Fe²⁺]_o was equal to 10. Under these experimental conditions, the initial oxidation rate was 50.5 mg COD dm^?3 s^?1 with a rate of consumption of hydrogen peroxide of 140 mg H₂O₂ dm^?3 s^?1, implying an efficiency in the use of the hydrogen peroxide at the initial time of 77%. The total amount of organic matter removed by Fenton oxidation was increased by spreading the H₂O₂ and ferrous salt reagent over several fractions by 15% for two‐fractions and by 21% for three‐fractions. Copyright © 2004 Society of Chemical Industry     

Optimization of the operating parameters using RSM for the Fenton oxidation process and adsorption on vegetal carbon of MO solutions

This study focused on the application of RSM on the Fenton process and the adsorption of vegetal carbon (VC) to obtain the optimal conditions for the minimization of the colored synthetic wastewater. Methyl orange (MO) with an azo dye was used as the model organic compound. Fenton processes were investigated to establish the optimal conditions. The Fe²⁺/H₂O₂ ratio was studied to establish the major MO degradation when 100 and 200 mg/L of MO were treated. For the adsorption process, to determine the optimal conditions, the principal variables studied were the vegetal carbon mass dosage, degradation time and dye concentration.     

The mechanism and application of the electro‐Fenton process for azo dye Acid Red 14 degradation using an activated carbon fibre felt cathode

BACKGROUND: The discharge of azo dyes into the environment poses concerns due to their limited biodegradability. The electro‐Fenton process (EF) is a good method to effectively degrade these dyes. The aim of this work was to study the mechanism and the feasibility of the EF reaction using an activated carbon fibre (ACF) cathode. In this study, two methods were used to measure the reactive species generated in anodic oxidation (AO), anodic oxidation with electrogenerated H₂O₂ (AO‐H₂O₂) and the EF process. Acid Red 14 (AR14) was chosen as a model pollutant. The effects of the operational parameters, pH and initial concentrations were investigated. A short‐term biodegradability test was also carried out to evaluate the EF process from a biological point of view. RESULTS: After 2 h EF reaction 118.7 µmol L^?1?OH were produced, which was much higher than that of the AO‐H₂O₂ (63.2 µmol L^?1) process. H₂O₂ is largely generated and Fe³⁺ efficiently reduced on the high surface area of the ACF cathode. The EF process provides more effective degradation of AR14 than the conventional Fenton process, and its current efficiency is significantly affected by the initial pH and the initial AR14 concentration. Following EF treatment, the biodegradability of AR14 is significantly increased. CONCLUSION: The higher formation of ^?OH in the EF process suggests it is an effective method for pollutant removal. This process also leads to increased biodegradability, which is expected to facilitate subsequent biological treatment. Copyright © 2010 Society of Chemical Industry