Decolorization and biodegradation of dye wastewaters by a facultative-aerobic process

BACKGROUND: Dye wastewater is one of the main pollution sources of water bodies in China. Conventional biological processes are relatively ineffective for color removal, the development of alternative treatment methods will become important. Our subjective was that of introducing a new biotreatment technology which combined a facultative biofilm reactor (FBR) with an aerobic reactor (AR) to treat a dye wastewater. The efficiencies of color and chemical oxygen demand (COD) removal and the mechanism of dye degradation were investigated. METHODS: The anthraquinone acid dye (acid blue BRLL) concentration, organic loading rate (OLR) and hydraulic retention time (HRT) were varied in the experiments to evaluate the treatment efficiency and process stability. The biodegradation products were detected by infrared (IR) and high performance liquid chromatography and mass spectrometry (HPLC-MS). RESULTS AND DISCUSSION: The results demonstrated that the facultative biofilm process was more effective for decolorization than the anaerobic stage of an anaerobic-aerobic process. Most color removal occurred in the facultative reaction (maximum to 88.5%) and the BOD (biochemical oxygen demand): COD of the FBR effluent increased by 82.2%, thus improving the biodegradability of dyes for further aerobic treatment. The dye concentration, OLR and HRT will be the factors affecting decolorization. Color removal efficiency falls as the influent dye concentration increases, but rises with increased HRT. The infrared and HPLC-MS analyses of the effluents of FBR and AR reveal that the dye parent compound was degraded in each reactor during the process. CONCLUSION: The Facultative-aerobic (F-A) system can effectively remove both color and COD from the dye wastewater. The FBR played an essential role in the process. The average overall color and COD in the system were removed by more than 93.9% and 97.1%, respectively, at an OLR of 1.1 kg COD m(-3) d(-1) and at the HRT of 18-20 hours in the FBR and 4-5 hours in the AR. The color removal mechanism in each reactor was not only a sort of biosorption on the floc materials, but even more an effect of biodegradation, especially in the facultative process. Recommendation and Outlook. In applying the F-A system to treat a dye wastewater, the control of facultative processes and the set up of appropriate operation conditions appear to be critical factors. Also, it is suggested a moderate COD loading rate and about a 24-hour HRT will favor the F-A system.     

UASB反应器降解活性染料废水的特性

中温（35±1）℃条件下,采用上流式厌氧污泥床（upflowanaerobicsludgebed,简称UASB）反应器处理了含蒽醌类-活性艳蓝（c．I．ReactiveBlue5,简称K—GR）或偶氮类-活性艳红（C．I．ReactiveRed20,简称KD-8B;C．I．ReactiveRed2,简称X-3B）模拟染料废水,重点研究了回流比对染料脱色率和COD去除率的影响,在最佳回流比的条件下,探讨HRT（hydraulicretentiontime）对脱色的影响和不同结构染料的脱色效果,并初步分析了脱色机理。结果表明,适宜的回流比有利于提高系统的脱色率;控制回流比和HRT分别为2和24h,当模拟废水中染料的浓度为100mg／L时,COD去除率和脱色率分别为90％～96％和85％～92％;蒽醌和偶氮类染料的脱色是通过偶氮键和葸醌共轭结构的断裂来实现的。     

Wet air oxidation of a reactive dye solution using CoAlPO(4)-5 and CeO(2) catalysts

Wet air oxidation of a prepared reactive dye solution was performed to assess the efficacy of CoAlPO(4)-5 and CeO(2) as catalysts in the reaction. Via adsorption and oxidation of dye, CoAlPO(4)-5 effectively decreased American Dye Manufacturers Institute and chemical oxygen demand (COD) values in the dye solution. At a reaction temperature of 135 degrees C and an applied pressure of 1.0 MPa, color and COD removal were as high as 95% and 90%, respectively, after 2 h. Active sites on the outer surface of CoAlPO(4)-5 are responsible for adsorption and decomposition of dye while active sites in the pores dominate further destruction and oxidation of intermediate products. Since the outer surface only represents a minor part of the total surface, the color removal does not increase appreciably with loading of CoAlPO(4)-5. The CeO(2) catalyst, calcined from cerium chloride under high thermal impact (type A CeO(2)) was very effective in removing color and COD from the solution. This catalyst demonstrated near 100% color removal at temperatures above 135 degrees C and the COD removal could be above 95% at 165 degrees C. With both CoAlPO(4)-5 and CeO(2) catalysts, COD rose and then fell back during the reaction, a feature typical of a consecutive reaction. In contrast to prepared CeO(2), a commercial CeO(2) did not exhibit any catalytic ability for the removal of color and COD. The durability of both CoAlPO(4)-5 and prepared CeO(2) is considered to be fair.     

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.     

Dye house wastewater treatment through advanced oxidation process using Cu-exchanged Y zeolite: a heterogeneous catalytic approach

Catalytic wet hydrogen peroxide oxidation of an anionic dye has been explored in this study. Copper(II) complex of NN'-ethylene bis(salicylidene-aminato) (salenH2) has been encapsulated in super cages of zeolite-Y by flexible ligand method. The catalyst has been characterized by Fourier transforms infra red spectroscopy, X-ray powder diffractograms, Thermo-gravimetric and differential thermal analysis and nitrogen adsorption studies. The effects of various parameters such as pH, catalyst and hydrogen peroxide concentration on the oxidation of dye were studied. The results indicate that complete removal of color has been obtained after a period of less than 1h at 60 degrees C, 0.175M H2O2 and 0.3g l(-1) catalyst. More than 95% dye removal has been achieved using this catalyst for commercial effluent. These studies indicate that copper salen complex encapsulated in zeolite framework is a potential heterogeneous catalyst for removal of color from wastewaters.     

The efficiency of electrocoagulation in treating wastewater from a dairy industry, part I: iron electrodes

Iron electrodes were used for electrocoagulation (EC) treatment of wastewater from a dairy plant. Electrolysis time, pH, current density and distance between electrodes were considered to assess the removal efficiency of chemical oxygen demand (COD), total solids (TS) and their fractions and turbidity. Samples were collected from the effluent of a dairy plant using a sampling methodology proportional to the flow. The treatments were applied according to design factorial of half fraction with two levels of treatments and three repetitions at the central point. The optimization of parameters for treating dairy industry effluent by electrocoagulation using iron electrodes showed that electric current application for 15 minutes, an initial sample pH close to neutral (pH 7.0) and a current density of 50 A (.)(m-2) resulted in a significant reduction in COD by 58 %; removal of turbidity, suspended solids and volatile suspended solids by 95 %; and a final treated effluent pH of approximately 9.5. Negative consequences of the type of electrode used were the emergence of an undesirable color and an increase in the proportion of dissolved solids in the treated effluent.     

不同形式电极与染料溶液的反应及其能耗

本研究对分散红E-4B、还原深蓝BO和酸性红B等三种染料分别用三维电极法和平板电极法进行了电解,结果表明三维电极法比平板电极法节能可达70%以上;并且电解效果越好的染料,采用三维电极法电解节能效果越明显.并且在不同pH值条件下,对酸性红B进行电解实验,结果表明在不同pH值条件下,色度去除率基本相同,中性条件下TOC的去除效果较好.     

Decolorization of cationic red X-GRL by wet air oxidation: performance optimization and degradation mechanism

The decolorization of a strong colored azo dye solution of cationic red X-GRL was investigated by wet air oxidation under relatively mild conditions (60-180 degrees C, PO2 = 0-1.2 MPa). Mono-factor experiments were carried out to investigate the effect of the operation factors and the relatively important parameters were selected for optimization using response surface methodology to explore the interactions of these relatively important parameters. Model regeneration analysis and the check experiments showed that the data of the general linear model agreed with the experiment results well. With multistage Monte-Carlo optimization, the best region of these variables could be predicted to dye color removal. At typical operational conditions, the intermediates of dye degradation were detected and confirmed by GC/MS system. Considering the intermediates and the structure analysis with the help of Gaussian 03W (version 6.0) and the theory of dye color, a possible degradation mechanism for the wet air oxidation of cationic red X-GRL was discussed and the probable degradation pathway was deduced.     

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.     

Comparative performance evaluation of Aspergillus lentulus for dye removal through bioaccumulation and biosorption

Dyes used in various industries are discharged into the environment and pose major environmental concern. In the present study, fungal isolate Aspergillus lentulus was utilized for the treatment of various dyes, dye mixtures and dye containing effluent in dual modes, bioaccumulation (employing growing biomass) and biosorption (employing pre-cultivated biomass). The effect of dye toxicity on the growth of the fungal isolate was studied through phase contrast and scanning electron microscopy. Dye biosorption was studied using first and second-order kinetic models. Effects of factors influencing adsorption and isotherm studies were also conducted. During bioaccumulation, good removal was obtained for anionic dyes (100 mg/l), viz. Acid Navy Blue, Fast Red A and Orange-HF dye (99.4 %, 98.8 % and 98.7 %, respectively) in 48 h. Cationic dyes (10 mg/l), viz. Rhodamine B and Methylene Blue, had low removal efficiency (80.3 % [48 h] and 92.7 % [144 h], respectively) as compared to anionic dyes. In addition to this, fungal isolate showed toxicity response towards Methylene Blue by producing larger aggregates of fungal pellets. To overcome the limitations of bioaccumulation, dye removal in biosorption mode was studied. In this mode, significant removal was observed for anionic (96.7–94.3 %) and cationic (35.4–90.9 %) dyes in 24 h. The removal of three anionic dyes and Rhodamine B followed first-order kinetic model whereas removal of Methylene Blue followed second-order kinetic model. Overall, fungal isolate could remove more than 90 % dye from different dye mixtures in bioaccumulation mode and more than 70 % dye in biosorption mode. Moreover, significant color removal from handmade paper unit effluent in bioaccumulation mode (86.4 %) as well as in biosorption mode (77.1 %) was obtained within 24 h. This study validates the potential of fungal isolate, A. lentulus, to be used as the primary organism for treating dye containing 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.     

Comparative performance of flat sheet and spiral wound modules in the nanofiltration of reactive dye solution

Background and purpose

Besides the opportunities for reuse, stringent regulations and growing public awareness demand an enhanced quality of effluent from dye industries. Treatment of an aqueous solution of dye (reactive red 198) was carried out in a nanofiltration unit using both flat sheet and spiral wound modules to obtain a comparative performance evaluation in terms of permeate flux and quality.

Methods

Hydrophilized polyamide membrane with molecular weight cutoff of 150 was used for the experiments. Effects of trans-membrane pressure (TMP), feed concentration and addition of salt on permeate flux were investigated. Percent reduction of color, chemical oxygen demand (COD), total dissolved solid (TDS), and conductivity were determined to assess performance of the membrane.

Results

The maximum flux decline was 16.1% of its initial value at 490 kPa TMP with 50 ppm feed concentration in spiral wound module, whereas the same in flat sheet under same conditions was 7.2%. The effect of TMP showed a quasi-linear increase in flux with increasing pressure. Increased permeate concentration led to the reduction in observed retention of dye in the membrane. The average reduction in color, COD, and TDS were 96.88%, 97.38%, and 89.24%, respectively. The decline in permeate flux was more in case of spiral wound module compared to flat sheet. However, spiral wound module performed better in terms of color removal, COD reduction, and TDS removal.

Conclusion

Substantial removal of color was achieved in the nanofiltration experiments with a marked reduction in COD and TDS. The process allowed the production of permeate stream with great reutilization possibilities.     

Color and COD removal from wastewater containing Reactive Black 5 using Fenton's oxidation process

In this study, Reactive Black 5 (RB5) was removed from synthetic wastewater using Fenton's oxidation (FO) process. Experiments were conducted on the samples containing 100 and 200 mg l(-1) of RB5 to remove the dye toxicity. Seventy-five milligram per litre of RB5 caused 25% toxicity on 24-h born daphnids whereas 100 mg l(-1) of RB5 displayed 100% toxicity on Daphnia magna. The study was performed in a systematic approach searching optimum values of FeSO(4) and H(2)O(2) concentrations, pH and temperature. Optimum pH and temperature for 100 mg l(-1) of RB5 were observed as 3.0 and 40 degrees C, respectively, using 100 mg l(-1) of FeSO(4) and 400 mg l(-1) of H(2)O(2) resulted in 71% chemical oxygen demand (COD) and 99% color removal. For 200 mg l(-1) of RB5, 84% COD removal was obtained using 225 mg l(-1) of FeSO(4) and 1000 mg l(-1) of H(2)O(2) yielding 0.05 molar ratio at pH 3.0 and 40 degrees C. Color removal was also more than 99%. The optimum conditions determined in accordance with the literature data. The H(2)O(2) requirement seems to be related to initial COD of the sample. FeSO(4)/H(2)O(2) ratios found were not changed for both concentrations. The temperature affected the COD removal significantly at high degrees. Toxicity was completely removed for each concentration of RB5 at optimum removal conditions.     

Electrodegradation of landfill leachate in a flow electrochemical reactor

Sanitary landfills are the major method used today for the disposal and management of municipal solid waste. Decomposition of waste and rainfall generate leachate at the bottom of landfills, causing groundwater contamination. In this study, leachate from a municipal landfill site was treated by electrochemical oxidation in a pilot scale flow reactor, using oxide-coated titanium anode. The experiments were conducted under a constant flow rate of 2000 lh(-1) and the effect of current density on chemical oxygen demand, total organic carbon, color and ammonium removal was investigated. At a current density of 116.0 mA cm(-2) and 180 min of processing, the removal rates achieved were 73% for COD, 57% for TOC, 86% for color and 49% for ammonium. The process proved effective in degrading leachate, despite this effluent's usual refractoriness to treatment.     

The efficiency of electrocoagulation in treating wastewater from a dairy industry,Part I: Iron electrodes

Iron electrodes were used for electrocoagulation (EC) treatment of wastewater from a dairy plant. Electrolysis time, pH, current density and distance between electrodes were considered to assess the removal efficiency of chemical oxygen demand (COD), total solids (TS) and their fractions and turbidity. Samples were collected from the effluent of a dairy plant using a sampling methodology proportional to the flow. The treatments were applied according to design factorial of half fraction with two levels of treatments and three repetitions at the central point. The optimization of parameters for treating dairy industry effluent by electrocoagulation using iron electrodes showed that electric current application for 15 minutes, an initial sample pH close to neutral (pH 7.0) and a current density of 50 A ^{. m?2} resulted in a significant reduction in COD by 58 %; removal of turbidity, suspended solids and volatile suspended solids by 95 %; and a final treated effluent pH of approximately 9.5. Negative consequences of the type of electrode used were the emergence of an undesirable color and an increase in the proportion of dissolved solids in the treated effluent.     

Evaluation of different electrochemical methods on the oxidation and degradation of Reactive Blue 4 in aqueous solution

The oxidation of a reactive dye, Reactive Blue 4, RB4, (C.I. 61205), widely used in the textile industries to color natural fibers, was studied by electrochemical techniques. The oxidation on glassy carbon electrode and reticulated vitreous carbon electrode occurs in only one step at 2.0 < pH < 12 involving a two-electron transfer to the amine group leading to the imide derivative. Dye solution was not decolorized effectively in this electrolysis process. Nevertheless, the oxidation of this dye on Ti/SnO2/SbO(x) (3% mol)/RuO2 (1% mol) electrode showed 100% of decolorization and 60% of total organic carbon removal in Na2SO4 0.2 M at pH 2.2 and potential of +2.4V. Experiments on degradation photoelectrocatalytic were also carried out for RB4 degradation in Na2SO4 0.1 M, pH 12, using a Ti/TiO2 photoanode biased at +1.0 V and UV light. After 1h of electrolysis the results indicated total color removal and 37% of mineralization.     

Decolorization of textile wastewater by photo-fenton oxidation technology

This paper describes the use of photo-fenton process for color removal from textile wastewater stream. The wastewater sample to be treated was simulated by using colorless polyvinyl alcohol (PVA) and reactive dyestuff of R94H. As a result, the hydroxyl radical (HO*) oxidation can effectively remove color, but the chemical oxygen demand (COD) was removed in a slight degree. The color removal is markedly related with the amount of HO* formed. The optimum pH for both the OH* formation and color removal occurs at pH 3-5. Up to 96% of color can be removed within 30 min under the studied conditions. Due to the photoreduction of ferric ion into ferrous ion, color resurgence was observed after 30 min. The ferrous dosage and UV power affect the color removal in a positive way, however, the marginal benefit is less significant in the higher range of both. PVA as the major background COD of a textile wastewater stream inhibits the color removal insignificantly as its concentration increases.     

青霉菌对印染废水吸附脱色及深度处理的研究

利用青霉菌P 1(Penicilliumsp )对 2种染浴废水中的染料进行吸附去除 ,研究结果表明 ,吸附处理 3h ,黑色和红色染浴废水色度基本被去除 ,去除率分别达 98 0 %和 74 5 % ,但去色处理后废水的CODCr值仍偏高。对去除色度的废水进一步用活性污泥进行深度处理 ,黑色和红色废水的CODCr去除率分别为 75 9%和 89 7%。青霉菌菌丝通过吸附作用从废水中抽提出的染料分子在有染料降解细菌L 1和L 2的降解池中脱色降解 ,菌丝吸附脱色能力得到再生。     

Activated carbon from industrial solid waste as an adsorbent for the removal of Rhodamine-B from aqueous solution: kinetic and equilibrium studies

The activated carbon was prepared using industrial solid waste called sago waste and physico-chemical properties of carbon were carried out to explore adsorption process. The effectiveness of carbon prepared from sago waste in adsorbing Rhodamine-B from aqueous solution has been studied as a function of agitation time, adsorbent dosage, initial dye concentration, pH and desorption. Adsorption equilibrium studies were carried out in order to optimize the experimental conditions. The adsorption of Rhodamine-B onto carbon followed second order kinetic model. Adsorption data were modeled using both Langmuir and Freundlich classical adsorption isotherms. The adsorption capacity Q0 was 16.12 mg g(-1) at initial pH 5.7 for the particle size 125-250 microm. The equilibrium time was found to be 150 min for 10, 20 mg l(-1) and 210 min for 30, 40 mg l(-1) dye concentrations, respectively. A maximum removal of 91% was obtained at natural pH 5.7 for an adsorbent dose of 100mg/50 ml of 10 mg l(-1) dye concentration and 100% removal was obtained when the pH was increased to 7 for an adsorbent dose of 275 mg/50 ml of 20 mg l(-1) dye concentration. Desorption studies were carried out in water medium by varying the pH from 2 to 10. Desorption studies were performed with dilute HCl and show that ion exchange is predominant dye adsorption mechanism. This adsorbent was found to be both effective and economically viable.     

Decolorization of direct dyes by salt fractionated turnip proteins enhanced in the presence of hydrogen peroxide and redox mediators

The present paper demonstrates the effect of salt fractionated turnip (Brassica rapa) proteins on the decolorization of direct dyes, used in textile industry, in the presence of various redox mediators. The rate and extent of decolorization of dyes was significantly enhanced by the presence of different types of redox mediators. Six out of 10 investigated compounds have shown their potential in enhancing the decolorization of direct dyes. The performance was evaluated at different concentrations of mediator and enzyme. The efficiency of each natural mediator depends on the type of dye treated. The decolorization of all tested direct dyes was maximum in the presence of 0.6mM redox mediator at pH 5.5 and 30 degrees C. Complex mixtures of dyes were also maximally decolorized in the presence of 0.6mM redox mediator (1-hydroxybenzotriazole/violuric acid). In order to examine the operational stability of the enzyme preparation, the enzyme was exploited for the decolorization of mixtures of dyes for different times in a stirred batch process. There was no further change in decolorization of an individual dye or their mixtures after 60 min; the enzyme caused more than 80% decolorization of all dyes in the presence of 1-hydroxybenzotriazole/violuric acid. However, there was no desirable increase in dye decolorization of the mixtures on overnight stay. Total organic carbon analysis of treated dyes or their mixtures showed that these results were quite comparable to the loss of color from solutions. However, the treatment of such polluted water in the presence of redox mediators caused the formation of insoluble precipitate, which could be removed by the process of centrifugation. The results suggested that catalyzed oxidative coupling reactions might be important for natural transformation pathways for dyes and indicate their potential use as an efficient means for removal of dyes color from waters and wastewaters.