Electro-Fenton decolourisation of dyes in an airlift continuous reactor using iron alginate beads

In this study, electro-Fenton dye degradation was performed in an airlift continuous reactor configuration by harnessing the catalytic activity of Fe alginate gel beads. Electro-Fenton experiments were carried out in an airlift reactor with a working volume of 1.5 L, air flow of 1.5 L/min and 115 g of Fe alginate gel beads. An electric field was applied by two graphite bars connected to a direct current power supply with a constant potential drop. In this study, Lissamine Green B and Reactive Black 5 were selected as model dyes. Fe alginate gel beads can be used as an effective heterogeneous catalyst for the degradation of organic dyes in the electro-Fenton process, as they are more efficient than the conventional electrochemical techniques. At optimal working conditions (3 V and pH 2), the continuous process was performed. For both dyes, the degree of decolourisation increases when the residence time augments. Taking into account hydrodynamic and kinetic behaviour, a model to describe the reactor profile was obtained, and the standard deviation between experimental and theoretical data was lower than 6 %. The results indicate the suitability of the electro-Fenton technique to oxidise polluted effluents in the presence of Fe alginate gel beads. Moreover, the operation is possible in a continuous airlift reactor, due to the entrapment of iron in the alginate matrix.     

Oxidative and energetic efficiency of different electrochemical oxidation processes for chloroanilines abatement in aqueous medium

The oxidative efficiency and energy consumption, in the degradation of chloroanilines by anodic oxidation, indirect oxidation with electrogenerated hydrogen peroxide and electro-Fenton have been compared, using a laboratory system driven by a LabVIEW virtual controller. Solutions were oxidized in an undivided cell, where H(2)O(2) was generated electrochemically by reduction of atmospheric oxygen bubbled at a carbon cloth cathode. The electro-Fenton process showed the best degradation power, in terms of efficiency of removal and energy consumption. This process was applied to the purification of a solution obtained by washing a polluted soil. Under laboratory conditions, electro-Fenton removed 75% COD of this wastewater with a specific energy consumption of 0.3kWh per gram of COD, corresponding to 41.8kWhm(-3).     

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.     

Application of central composite face-centered design and response surface methodology for the optimization of electro-Fenton decolorization of Azure B dye

Purpose

The aim of this work was to improve the ability of electro-Fenton technique for the remediation of wastewater contaminated with synthetic dyes using a model azo dye such as Azure B.

Methods

Batch experiments were conducted to study the effects of main parameters, such as dye concentration, electrode surface area, treatment time, and voltage. In this study, central composite face-centered experimental design matrix and response surface methodology were applied to design the experiments and evaluate the interactive effects of the four studied parameters. A total of 30 experimental runs were set, and the kinetic data were analyzed using first- and second-order models.

Results

The experimental data fitted to the empirical second-order model of a suitable degree for the maximum decolorization of Azure B by electro-Fenton treatment. ANOVA analysis showed high coefficient of determination value (R ²?=?0.9835) and reasonable second-order regression prediction. Pareto analysis suggests that the variables, time, and voltage produce the largest effect on the decolorization rate.

Conclusion

Optimum conditions suggested by the second-order polynomial regression model for attaining maximum decolorization were dye concentration 4.83?mg/L, electrode surface area 15?cm², voltage 14.19?V, and treatment time of 34.58?min.     

Photocatalytic degradation of dyes in aqueous solution operating in a fluidised bed reactor.

This work reports a preliminary design of a new photochemical reactor and its application to photochemical degradation of two dyes, Crystal Violet and Azure B, operating in both batch and continuous processes. A novel kind of photocatalyst, consisting of ZnO immobilised in alginate gel beads, which is able to photodegrade organic dyes effectively, has been employed in the present study. When this photocatalyst, at a concentration of 1 g of ZnO per litre of alginate gel at 3%, was employed in batch process, almost total decolourisation of Crystal Violet in reaction times lower than 120 min was observed. Operating in continuous process at different residence times, it was possible to achieve a total decolourisation of both Crystal Violet and Azure B. Moreover, the total organic carbon content (TOC) was reduced to 90% in the former and to 52% in the latter. These results indicated that the photoreactor developed in the present work was able to degrade effectively dyes of different structures, revealing the non-specificity of the system.     

Biosorption of reactive black 5 by Corynebacterium glutamicum biomass immobilized in alginate and polysulfone matrices

Corynebacterium glutamicum, a lysine fermentation industry waste, showed promise for the removal of Reactive black 5 (RB5). Due to practical difficulties in solid-liquid separation, the free biomass was immobilized in two polymer matrices: calcium alginate and polysulfone. Initially, the optimization of biomass loading in polymeric beads and bead dosage were examined. Of the different combinations examined, 4% (with bead dosage of 2 g per 40 ml) and 14% (with bead dosage of 1 g per 40 ml) in the case of alginate and polysulfone beads, respectively, were identified as the optimal conditions. According to the Langmuir model, at pH 1, the maximum RB5 uptakes of 352, 282 and 291 mg g(-1) were observed for free, alginate and polysulfone-immobilized biomass, respectively. According to the Weber-Morris model, intraparticle diffusion was found to be the potential rate limiting step for the immobilized beads. Regeneration experiments, with 0.01 M NaOH and Na(2)CO(3) as eluents, revealed that polysulfone beads exhibited invariable RB5 uptake capacity and very high mechanical stability even at the end of twentieth cycle, confirming the technical feasibility of the biosorption process for industrial applications.     

Electro-Fenton pretreatment for the improvement of tylosin biodegradability

The feasibility of an electro-Fenton process to treat tylosin (TYL), a non-biodegradable antibiotic, was examined in a discontinuous electrochemical cell with divided cathodic and anodic compartments. Only 15 min electrolysis was needed for total tylosin degradation using a carbon felt cathode and a platinum anode; while 6 h electrolysis was needed to achieve high oxidation and mineralization yields, 96 and 88 % respectively. Biodegradability improvement was shown since BOD₅/COD increased from 0 initially to 0.6 after 6 h electrolysis (for 100 mg L^?1 initial TYL). With the aim of combining electro-Fenton with a biological treatment, an oxidation time in the range 2 to 4 h has been however considered. Results of AOS (average oxidation state) and COD/TOC suggested that the pretreatment could be stopped after 2 h rather than 4 h; while in the same time, the increase of biodegradability between 2 and 4 h suggested that this latter duration seemed more appropriate. In order to conclude, biological cultures have been therefore carried out for various electrolysis times. TYL solutions electrolyzed during 2 and 4 h were then treated with activated sludge during 25 days, showing 57 and 67 % total organic carbon (TOC) removal, respectively, namely 77 and 88 % overall TOC removal if both processes were considered. Activated sludge cultures appeared, therefore, in agreement with the assessment made from the analysis of physico-chemical parameters (AOS and COD/TOC), since the gain in terms of mineralization expected from increasing electrolysis duration appeared too low to balance the additional energy consumption.     

Treatment of Basic Red 29 dye solution using iron-aluminum electrode pairs by electrocoagulation and electro-Fenton methods

The aim of this study is the treatment of Basic Red 29 (BR29) dye solution using hybrid iron-aluminum electrodes by electrocoagulation and electro-Fenton methods. The effect of current density, initial pH, supporting electrolyte, H₂O₂, and initial dye concentration on dye removal efficiency was investigated, and the best experimental conditions were obtained. Time-coarse variation of UV-Vis spectra and toxicity and chemical oxygen demand (COD) removal were also examined at the best experimental conditions. Both systems were found very successful for the removal of BR29 dye. The removal efficiency of >95 % for BR29 dye solution was reached easily in a short time. At the best experimental conditions, for the initial BR29 concentration of 100 mg/L, >95 % BR29 dye and 71.43 % COD removal were obtained after 20 and 40 min of electrolysis, respectively. Additionally, toxicity results for electro-Fenton treatment of 100 mg/L BR29 were also very promising. According to the results obtained, although electro-Fenton is more effective, both systems can be used successfully to treat textile wastewater including dyes.     

Using iron-loaded sepiolite obtained by adsorption as a catalyst in the electro-Fenton oxidation of Reactive Black 5

This study explores the possibility of using iron-loaded sepiolite, obtained by recovering iron from polluted water, as a catalyst in the electro-Fenton oxidation of organic pollutants in textile effluents. The removal of iron ions from aqueous solution by adsorption on sepiolite was studied in batch tests at iron concentrations between 100 and 1,000 ppm. Electro-Fenton experiments were carried out in an electrochemical cell with a working volume of 0.15 L, an air flow of 1 L/min, and 3 g of iron-loaded sepiolite. An electric field was applied using a boron-doped diamond anode and a graphite sheet cathode connected to a direct current power supply with a constant potential drop. Reactive Black 5 (100 mg/L) was selected as the model dye. The adsorption isotherms proved the ability of the used adsorbent. The removal of the iron ion by adsorption on sepiolite was in the range of 80–100 % for the studied concentration range. The Langmuir and Freundlich isotherms were found to be applicable in terms of the relatively high regression values. Iron-loaded sepiolite could be used as an effective heterogeneous catalyst for the degradation of organic dyes in the electro-Fenton process. Successive batch processes were performed at optimal working conditions (5 V and pH 2). The results indicate the suitability of the proposed combined process, adsorption to iron remediation followed by the application of the obtained iron-loaded sepiolite to the electro-Fenton technique, to oxidize polluted effluents.     

Competitive adsorption of dye metanil yellow and RB15 in acid solutions on chemically cross-linked chitosan beads

One kind of adsorbent with a high adsorption capacity for anionic dyes was prepared using ionically and chemically cross-linked chitosan beads. A batch system was applied to study the adsorption behavior of one acid dye (MY, metanil yellow) and one reactive dye (RB15, reactive blue 15) in aqueous solutions by the cross-linked chitosan beads. The adsorption capacities was 3.56 mmol g(-1) (1334 mg g(-1)) for dye MY and 0.56 mmol g(-1) (722 mg g(-1)) for dye RB15 at pH4, 30 degrees C. The Langmuir model agreed very well with the experimental data (R(2)>0.996). The kinetics of adsorption for a single dye and the kinetics of removal of ADMI color value in mixture solutions at different initial dye concentrations were evaluated by the nonlinear first-order and second-order models. The first-order kinetic model fits well with the dynamical adsorption behavior of a single dye for lower initial dye concentrations, while the second-order kinetic model fits well for higher initial dye concentrations. The competitive adsorption favored the dye RB15 in the mixture solution (initial conc. (mM): MY=1.34; RB15=1.36); while it favored the dye MY in the mixture solution (initial conc. (mM): MY=3.00; RB15=1.34) and the adsorption kinetics for dye RB15 has the tendency to shift to a slower first order model.     

Adsorption of Cu and Mn on covalently cross-linked alginate gel beads

The covalently cross-linked alginate gel beads were prepared by the reactions of Ca(2+)-doped alginate gel beads, which were formed by spraying a viscous alginate solution into a calcium chloride solution, with cyanogen bromide and following 1,6-diaminohexane. The cross-linking of alginate matrix decreased the mean bead diameter by about 30% and made the beads durable in some extent under alkaline conditions. The adsorption of metal ions on the covalently cross-linked alginate gel beads was rapid and reached at equilibrium within 30 min at 25 degrees C. Adsorption isotherms of Cu(II), Mn(II), and Ca2+ on the beads possessed a stepwise shape, which was firstly determined by Rorrer et al. [Ind. Eng. Chem. Res. 32 (1993) 2170] for cross-linked chitosan gel beads and explained by a pore-blockage mechanism. Higher selectivity was determined against Cu(II) over Mn(II) and Ca2+, especially at a low concentration region. These metal adsorption profiles for the covalently cross-linked alginate gel beads was almost the same as those for the un-cross-linked beads, indicating that the cross-linking reactions were performed without interfering the adsorption characteristics of alginate gel beads.     

Fe3+(NTA)还原菌的固定化小球制备及还原特性

采用海藻酸钠包埋驯化得到的优势铁还原菌,用于还原络合吸收法脱除NOx过程中形成的中间副产物Fe³⁺(NTA)。结果表明,最佳包埋条件为海藻酸钠质量浓度4%,菌体质量浓度0.2%,CaCl₂质量浓度3%,此条件下制备的小球还原性能好,在微生物用量为20 g（湿重）/L时还原10 mmol/L Fe³⁺(NTA),经12 h反应后还原率达到96.1％,而相同条件下游离微生物的还原率仅为11.8％,但反应16 h后游离微生物与固定化小球的还原率相近,均为97％左右。但此法制备的小球机械强度不高,溶胀、破裂现象严重。通过添加聚乙烯醇和硅藻土改良固定化小球,可强化小球的机械强度、降低小球的溶胀及破裂现象,对Fe³⁺(NTA)的还原效果也较改良前的小球有所提高,两者最佳添加量均为20 g/L。改良后的小球与游离微生物相比,耐酸性增强,在pH=5的条件下,仍具有79.8％的还原效率,远高于相同条件下游离微生物的39.5％,但对温度的适应范围两者基本一致。     

卡拉胶、膨润土改性PVA包埋小球

对PVA+卡拉胶包埋小球和PVA+海藻酸钠包埋小球的性能进行比较,并首次使用PVA+卡拉胶+膨润土混合包埋材料制作包埋小球.结果表明,PVA+海藻酸钠包埋小球在制作过程中有一定的拖尾现象,红墨水到达小球中心的时间为80 min,6d可去除50％的COD;PVA+卡拉胶包埋小球更容易成球,而且红墨水到达小球中心的时间为50 min,6d可去除56％的COD.此外,在PVA+卡拉胶包埋材料中添加适量的膨润土可以将红墨水到达小球中心的时间由50 min缩短到30 min.因此,使用PVA+卡拉胶+膨润土的混合材料制作包埋小球是可行的.最后,通过包埋小球处理抗生素废水的正交实验,得出包埋材料中各组分的最佳配比:PVA浓度11％、卡拉胶浓度0.5％、膨润土浓度2.5％.在这种配比下,包埋小球对抗生素废水中COD的去除率可以达到65％左右.     

Efficient removal of triphenylmethane dyes from aqueous medium by in situ electrogenerated Fenton's reagent at carbon-felt cathode

Fenton's reagent (Fe2+ +H2O2) has been electrogenerated in situ in an undivided electrolytic cell from the effective reduction of Fe3+ and O2 at carbon-felt cathode for the treatment of aqueous solutions of four triphenylmethane dyes (TPMs), namely malachite green (MG), crystal violet (CV), methyl green (MeG) and fast green FCF (FCF), at pH 3.0 and room temperature. MG has been used as a model among them to study the influence of some experimental parameters on the decay kinetics, COD removal and current efficiency. The results in such electro-Fenton system are explained in terms of the many parasitic reactions involving .OH. Higher efficiency values are obtained with rising organic content and decreasing applied current. The first stage of the mineralization process, involving aromatic by-products, leads to fast decoloration as well as quick initial COD removal that fit well to a pseudo-first-order kinetics. At prolonged electrolysis time, the mineralization rate and efficiency decrease due to the formation of hardly oxidizable compounds and the enhancement of wasting reactions. Solutions of all four TPMs are quickly degraded following a pseudo-first-order decay kinetics. The absolute rate constant (kTPM) for their reaction with .OH increases in the order MeG相似文献   

海藻酸钠-刺槐豆胶复合凝胶珠吸附孔雀绿

以刺槐豆胶、海藻酸钠为材料制备复合凝胶珠,利用红外光谱、热重分析对其进行表征,探讨孔雀绿浓度、吸附时间及pH对复合凝胶珠吸附孔雀绿的影响。红外光谱和热重分析表明,复合凝胶珠制备成功且热稳定性介于刺槐豆胶和海藻酸钠之间。复合凝胶珠对孔雀绿的吸附在5h后达到平衡,pH=6为最佳吸附pH,相同条件下复合凝胶珠对孔雀绿的吸附作用优于活性炭,其对孔雀绿的吸附行为符合Freundlich吸附等温方程和颗粒内扩散模型。海藻酸钠一刺槐豆胶复合凝胶珠有望成为新的处理印染废水的吸附剂。     

Treatment of phenol-containing wastewater by photoelectro-Fenton method using supported nanoscale zero-valent iron

This study presents the degradation of phenol by the photoelectro-Fenton method using nano zero-valent iron (nZVI) immobilized in polyvinyl alcohol–alginate beads. The effect of nZVI loading, H₂O₂ concentration, pH, and initial phenol concentration on phenol degradation and chemical oxygen demand reduction was studied. The scanning electron microscope images of the nZVI beads were used to analyze their morphology, and their diameters were in the range of 500–600 μm. The concentration of nZVI in the beads was varied from 0.1 to 0.6 g/L. Fe²⁺ leakage of 1 and 3 % was observed with 0.5 and 0.6 g/L of nZVI, respectively, and the observed beads' fracture frequency was 2 %, which confirmed the stability of the beads. The optimum operating conditions that arrived for better degradation were 0.5 g/L of nZVI, pH 6.2, and 400 mg H₂O₂/L. The treatment of effluent by this method increased the biodegradability index of the effluent, and the degradation data were found to follow pseudo first-order kinetics.     

光电芬顿氧化法深度处理垃圾渗滤液研究

采用光电芬顿氧化法对北京市某垃圾填埋场已经生化处理后的垃圾渗滤液进行深度处理,分别考察了电流强度和铁的不同价态等因素对渗滤液总有机碳（TOC）、化学需氧量（COD）以及色度去除效果的影响,并对阳极氧化、电芬顿和光电芬顿不同反应过程进行了对比。通过分析渗滤液UV-Vis光谱(200～500 nm)变化和渗滤液中有机污染物的分子量变化,发现光电芬顿反应可以明显改善渗滤液生化性。深入研究了反应过程中铁价态的变化规律。试验结果发现,以高比表面积的活性炭纤维(ACF)为阴极的光电芬顿反应可以有效降解垃圾渗滤液,在pH为3,Fe²⁺ 浓度为1 mmol/L,电流为0.5 A,O₂通入量为250 mL/min条件下降解360 min,垃圾渗滤液TOC和COD去除率分别达到78.9%和62.8%,色度完全去除。     

海藻酸钠-刺槐豆胶复合凝胶珠吸附孔雀绿简

以刺槐豆胶、海藻酸钠为材料制备复合凝胶珠,利用红外光谱、热重分析对其进行表征,探讨孔雀绿浓度、吸附时间及pH对复合凝胶珠吸附孔雀绿的影响。红外光谱和热重分析表明,复合凝胶珠制备成功且热稳定性介于刺槐豆胶和海藻酸钠之间。复合凝胶珠对孔雀绿的吸附在5 h后达到平衡,pH=6为最佳吸附pH,相同条件下复合凝胶珠对孔雀绿的吸附作用优于活性炭,其对孔雀绿的吸附行为符合Freundlich吸附等温方程和颗粒内扩散模型。海藻酸钠-刺槐豆胶复合凝胶珠有望成为新的处理印染废水的吸附剂。     

Degradation of nitrogen-heterocyclic compounds by anodic oxidation and electro-Fenton methods.

This study describes the degradation of nitrogen-heterocyclic compounds (NHCs) by anodic oxidation and electro-Fenton. Using indole as a model nitrogen-heterocyclic compound, the removal of indole reached 68% and 97% by anodic oxidation and electro-Fenton, respectively, while the decay of TOC was 15% and 38% correspondingly. By the analysis of ultraviolet-visible spectra and liquid chromatography/mass spectrum, the degradation mechanism of indole by electro-Fenton was proposed as hydroxyl oxidation and anodic oxidation. The degradation of other NHCs including quinoline, isoquinoline and pyridine by anodic oxidation and electro-Fenton revealed the same sequence: quinoline approximately equal isoquinoline > indole > pyridine. A significant correlation between ln k (natural logarithm of rate constants) and E(LUMO) (the energy of the lowest unoccupied molecular orbit) was obtained by quantitative structure-activity relationship analysis. Degradation of coking plant wastewater showed the removal of COD and TOC were 42% and 22% respectively after 180 min treatment by electro-Fenton.     

Selection of an electrolyte to enhance the electrochemical decolourisation of indigo. Optimisation and scale-up

The investigation presented here focussed on the electrochemical decolourisation of a commercial, textile indigo dye, in an undivided electrochemical cell using graphite electrodes. The decolourisation values obtained employing halide salts--sodium chloride, potassium bromide and potassium iodide--and a reductive agent--sodium meta-bisulphite--as electrolytes are higher than those attained when no electrolyte was used. The highest decolourisation value at a low level of electric power consumption was obtained with sodium chloride. Besides, this electrolyte is usually found in the coloured wastewaters of textile industry. Thus, a detailed study was carried out to determine the influence of electrolyte--sodium chloride--and dye concentration on the efficiency of the process expressed in terms of energy consumption and extension of the decolourisation reaction. The scale-up of the treatment with sodium chloride was satisfactorily tested in a 20 l cell.