亚铁羟基络合物还原转化水溶性偶氮染料

偶氮染料是印染工艺中应用最广泛的一类染料,目前染料废水脱色是污水处理难题。亚铁混凝处理染料废水过程中可能存在亚铁的还原作用,本实验制备了比溶解态亚铁更具还原反应活性的亚铁羟基络合物(ferrous hydroxycomplex,FHC),以5种不同类型的水溶性偶氮染料为目标污染物,研究FHC还原水溶性偶氮染料的脱色性能。实验结果表明,FHC对活性艳红X-3B、酸性大红GR和阳离子红X-GRL有较好的还原脱色效果,仅投加含铁89.6 mg/L的FHC,染料脱色率达到90%以上,继续增大FHC投加量可以完全脱色;中性枣红GRL的FHC还原脱色效果较差,需加入313.6 mg/L的FHC才能达到90%以上脱色率;134.4 mg/L的FHC能够将直接耐酸大红4BS完全脱色,但其脱色主要以混凝沉淀为主;溶液pH对FHC的还原性能产生重要影响,FHC还原染料脱色的适宜的pH值范围为4～10。该研究为亲水性染料脱色提供了一种新的技术,也为FHC运用于印染废水脱色提供了理论基础。     

Enhanced biodegradation of azo dyes using an integrated elemental iron-activated sludge system: I. Evaluation of system performance.

The objective of this research is to evaluate an integrated system coupling zero-valent iron (Fe(0)) and aerobic biological oxidation for the treatment of azo dye wastewater. Zero-valent (elemental) iron can reduce the azo bond, cleaving dye molecules into products that are more amenable to aerobic biological treatment processes. Azo dye reduction products, including aniline and sulfanilic acid, were shown to be readily biodegradable at concentrations up to approximately 25 mg/L. Batch reduction and biodegradation data support the proposed integrated iron pretreatment and activated sludge process for the degradation of the azo dyes orange G and orange I. The integrated system was able to decolorize dye solutions and yield effluents with lower total organic carbon concentrations than control systems without iron pretreatment. The success of the bench-scale integrated system suggests that iron pretreatment may be a feasible approach to treat azo dye containing wastewaters.     

Decolorization of mono-azo dyes in wastewater by advanced oxidation process: A case study of acid red 1 and acid yellow 23

Advanced Oxidation Processes (AOPs) have been used as emerging wastewater treatment technologies which can effectively handle various hazardous organics in wastewater and groundwater. The photooxidation of two non-biodegradable azo dyes, acid red 1 and acid yellow 23, were studied in an UV/hydrogen peroxide photochemical reactor with a 5 kW low pressure mercury lamp. It was observed that the decomposition of both azo dyes were pseudo-first order reactions with respect to the azo dye concentrations. Simultaneously, the effects of hydrogen peroxide dosage, pH, initial concentration of the azo dyes and intensity of UV light were also studied. Moreover, the time required for the 50% removal of azo dyes and observed pseudo-first order rate constants were used as parameters to show the efficiency of azo dye treatment.     

Biological decolourisation of simulated azo dye in aqueous phase by algae Spirogyra species

Biological decolourisation of two azo dye effluents (direct and reactive dye) were investigated using a commonly available green algae Spirogyra sp. in viable form. Batch studies revealed the potential of algal species in removing the dye colour and dye removal was dependant on initial algal inoculum, concentration and application class of the dye. Maximum dye uptake was noticed on the third day for both the dyes. Higher dye uptake was observed in the case of direct red 28 compared to reactive red 2. Dye colour removal by the algal species may be attributed to biosorption of the dye molecules onto the surface of algal cell and subsequent diffusion and participation in metabolism (bioconversion). The remaining dye molecules could be further removed from the aqueous phase by adsorption and/or chelation reaction of the exopolymers released by the algae (biocoagulation). The results of the present study reveal the potential nature of algae in treating azo dyes which in turn can be extended to oxidation pond system of wastewater treatment.     

Photocatalytic and combined anaerobic-photocatalytic treatment of textile dyes

A photocatalytic process based on immobilized titanium dioxide was used to treat crude solutions of azo, anthraquinone and phthalocyanine textile dyes. In addition, the process was applied to the treat autoxidized chemically reduced azo dyes, i.e. representatives of recalcitrant dye residues after biological sequential anaerobic-aerobic treatment. Photocatalysis was able to remove more than 90% color from crude as well as autoxidized chemically reduced dye solutions. UV-absorbance and COD were also removed but to a lower extent (50% in average). The end products of photocatalytic treatment were not toxic toward methanogenic bacteria. The results demonstrate that photocatalysis can be used as a pre- or post-treatment method to biological anaerobic treatment of dye-containing textile wastewater.     

Degradation of azo dyes using low iron concentration of Fenton and Fenton-like system

This study investigated Fenton and Fenton-like reactions at low iron concentration (相似文献   

Azo dye decolourisation by anaerobic granular sludge

The decolourisation of 20 selected azo dyes by granular sludge from an upward-flow anaerobic sludge bed (UASB) reactor was assayed. Complete reduction was found for all azo dyes tested, generally yielding colourless products. The reactions followed first-order kinetics and reaction rates varied greatly between dyes: half-life times ranged from 1 to about 100 h. The slowest reaction rates were found for reactive dyes with a triazine reactive group. There was no correlation between a dye's half-life time and its molecular weight, indicating that cell penetration was probably not an important factor. Since granular sludge contains sulphide, eight dyes were also monitored for direct chemical decolourisation by sulphide. All these dyes were reduced chemically albeit at slower rates than in the presence of sludge at comparable sulphide levels. Increasing sulphide concentrations, even when present in huge excess, stimulated the azo reduction rate. The results indicate that granular sludge can decolourise a broad spectrum of azo dye structures due to non-specific extracellular reactions. Reducing agents (e.g., sulphide) in sludge play an important role. The presence of anaerobic biomass is probably beneficial for maintaining the pools of these reduced compounds.     

缺氧-好氧生物滤池中高效菌对活性红KN-3B的降解特性

为了研究高效脱色菌在缺氧好氧生物滤池（A/O biofilter）中对偶氮染料的降解特性,以活性红KN-3B（C.I. reactive red 180）为降解对象,缺氧生物滤池以火山碎石为填料,接种高效脱色菌CK3柯氏柠檬酸杆菌启动,好氧生物滤池以牡蛎壳为填料,接种污水处理厂活性污泥启动。试验考察了不同工况下缺氧-好氧生物滤池对色度和COD的去除效果,结果表明：生物滤池中微生物对偶氮染料活性红KN-3B的脱色和对COD降解的最适pH条件为弱酸性;缺氧滤池中高效菌对色度的去除需要外加碳源,且增加外加碳源有助于脱色率的提高;该高效菌为耐盐菌,当进水NaCl浓度达30 g/L时,色度去除率仍可达93%以上;当染料负荷达500 mg/L时,脱色率仍可达95%。通过紫外-可见扫描图谱分析初步推断CK-3柯氏柠檬酸杆菌对偶氮染料活性红KN-3B的脱色主要是生物降解作用。     

Decolorization and biodegradability of photocatalytic treated azo dyes and wool textile wastewater

The photodegradation and biodegradability have been investigated for four non-biodegradable commercial azo dyes, Reactive YellowKD-3G, Reactive Red 15, Reactive Red 24, Cationic Blue X-GRL, an indicator. Methyl Orange, and one industrial wool textile wastewater, using TiO2 suspensions irradiated with a medium pressure mercury lamp. The color removal of dyes solution and dyeing wastewater reached to above 90% within 20-30 min. of photocatalytic treatment. Biochemical oxygen demand (BOD) was found to increase, while chemical oxygen demand (COD), total organic carbon (TOC) decreased, so that the ratio of BOD5/COD of the wastewater increased from original zero up to 0.75. The result implies that photocatalytic oxidation enhanced the biodegradability of the dye-containing wastewater and therefore relationship between decolorization and biodegradability exists. When the color disappeared completely, the wastewater biodegraded normally and could be discharged for further treatment. The experimental results demonstrate that it is possible to combine photocatalysis with conventional biological treatment for the remedy of wastewater containing generally non-biodegradable azo dyes.     

Degradation mechanism of azo dye C. I. reactive red 2 by iron powder reduction and photooxidation in aqueous solutions

We have made a comparison of the UV-VIS spectra of three azo dyes, C. I. reactive red 2, orange II and C. I. reactive black 8, in aqueous solutions during treatment with iron powder reduction and photooxidation. From this, we propose their mechanisms for reduction photooxidation. GC/MS analyses of the degradation products of the dye C. I. reactive red 2 demonstrated some important steps producing hydrogenated azo structure, substituted benzene and substituted naphthalene.     

Decolorization and degradation of H-acid and other dyes using ferrous-hydrogen peroxide system

In this study, advanced oxidation process utilizing Fenton's reaction was investigated for the decolorization and degradation of two commercial dyes viz., Red M5B, Blue MR and H-acid, a dye intermediate used in chemical industries for the synthesis of direct, reactive and azo dyes. Effect of Fe2 +, H2O2, pH, and contact time on the degradation of the dyes was studied. Maximum color and COD removal was obtained for Red MSB, H-acid and Blue MR at 10-25 mg/l of Fe2+ dose and 400-500 mg/l of H2O2 dose at pH 3.0. The initial oxidation reaction was found to fit into first order rate kinetics and the rate of oxidation of H-acid was higher than the other dyes. Release of chloride and sulfate from the Fenton's treated Red M5B dye and sulfate from H-acid and Blue MR indicates that the dye degradation proceeds through cleavage of the substituent group.     

蒸发壁式超临界水氧化反应器处理分散红和活性红染料废水的比较

采用蒸发壁式超临界水氧化反应器对染料分散红C.I.60和活性艳红M-2B配制的模拟废水进行降解实验.实验结果表明,2种染料的COD和TN去除率随着反应温度、氧化剂过量比(r)的升高而上升.COD去除率活性红要高于分散红,而TN去除率则相反.根据GC-MS分析和陶瓷膜SEM图像,分析测得2种染料主要反应中间产物均含有苯酚和苯甲酸,2种染料的反应对陶瓷膜均有轻微的腐蚀.     

Effect of different redox mediators during thermophilic azo dye reduction by anaerobic granular sludge and comparative study between mesophilic (30 degrees C) and thermophilic (55 degrees C) treatments for decolourisation of textile wastewaters

The impact of different redox mediators on colour removal of azo dye model compounds and textile wastewater by thermophilic anaerobic granular sludge (55 degrees C) was investigated in batch assays. Additionally, a comparative study between mesophilic (30 degrees C) and thermophilic (55 degrees C) colour removal was performed with textile wastewater, either in the presence or absence of a redox mediator. The present work clearly evidences the advantage of colour removal at 55 degrees C compared with 30 degrees C when dealing with azo coloured wastewaters. The impact of the redox mediators anthraquinone-2,6-disulfonate (AQDS), anthraquinone-2-sulfonate (AQS) and riboflavin was evident with all dyes, increasing decolourisation rates up to 8-fold compared with the mediator-free incubations. The generation of the hydroquinone form AH2QDS, i.e. the reduced form of AQDS, was extremely accelerated at 55 degrees C compared with 30 degrees C. Furthermore, no lag-phase was observed at 55 degrees C. Based on the present results we postulate that the production/transfer of reducing equivalents was the process rate-limiting step, which was accelerated by the temperature increase. It is conclusively stated that 55 degrees C is a more effective temperature for azo dye reduction than 30 degrees C, which on the one hand can be attributed to the faster production/transfer of reducing equivalents, but also to the decrease in activation energy requirements.     

Decolorization of mixtures of different reactive textile dyes by the white-rot basidiomycete Phanerochaete sordida and inhibitory effect of polyvinyl alcohol

We tried to decolorize mixtures of four reactive textile dyes, including azo and anthraquinone dyes, by a white-rot basidiomycete Phanerochaete sordida. P. sordida decolorized dye mixtures (200 mg l-1 each) by 90% within 48 h in nitrogen-limited glucose-ammonium media. Decolorization of dye mixtures needed Mn2+ and Tween 80 in the media. Manganese peroxidase (MnP) played a major role in dye decolorization by P. sordida. Decolorization of dye mixtures by P. sordida was partially inhibited by polyvinyl alcohol (PVA) that wastewaters from textile industries often contain. This was caused by an inhibitory effect of PVA on the decolorization of Reactive Red 120 (RR120) with MnP reaction system. Second addition of Tween 80 to the reaction mixtures in the presence of PVA improved the decolorization of RR120. These results suggest that PVA could interfere with lipid peroxidation or subsequent attack to the dye.     

真菌和细菌对染料吸附脱色的高效共培养体系研究

在含有真菌G 1培养液中加入染料厂污水排放口的污泥样品 ,从发生快速脱色降解染料的混合培养液中分离出 2株染料脱色细菌L_1和L_2 ,经API鉴定系统鉴定 ,确定菌株L_1为Enterobactersp .,菌株L_2为Peudomonassp .。研究比较了单一和不同组合混合的真菌G_1菌株 (Penicilliumsp .)、细菌L_1菌株 (Enterobactersp .)和L_2菌株 (Pseu domonassp .)对偶氮染料红M - 3BE(C .I .ReactiveRed 2 41)和蒽醌染料艳蓝KN -R(C .1.ReactiveBlue 19)的去除情况 ,发现G - 1真菌和 2种细菌组合的共培养体系对 5 0mg/L红M - 3BE和艳蓝KN -R处理 5h去除率达 10 0 %和 97.9% ,并且是以脱色降解作用为主 ,建立了染料脱色降解菌的最佳组合 ;进一步测定了此最佳共培养体系对另外 13种不同结构染料的脱色降解 ,结果表明 ,除对蒽醌染料R - 478脱色降解较差外 ,对其他染料均可在lh— 3d被完全脱色降解 ,表现出脱色降解染料的广谱性 ;向培养 4d的共培养体系中依次加入 8种染料 ,菌体可对染料连续脱色 ,维持脱色能力达 8d左右     

Formation of shaped barium sulfate-dye hybrids: waste dye utilization for eco-friendly treatment of wastewater

Purpose

Owing to the present complexity and difficulty of concentrated dye wastewater treatment, this work aimed to synthesize a reproducible waste-sorbing material for the treatment of wastewater by forming the dye-conjugating complex hybrid.

Methods

The inorganic/organic hybridization was applied to prepare the objective material by immobilizing waster dye-Mordant blue 9 (MB) with barium sulfate (BaSO₄). The composition and pattern of the formed material were determined by spectrometry and characterized by SEM and XRD, and their formation process was clarified. The adsorption of cationic dye-basic blue BO (BB) and copper ion was investigated..

Results

The hybrid of MB alone into growing BaSO₄ formed the pineapple-like particles while that of the MB/BB-conjugating complex was the rhombus material. The adsorption of BB on the MB–BaSO₄ hybrid was probably attributed to ion-pair equilibrium and that of Cu²⁺ may result from the complexation. The treatment of dye and heavy metal wastewaters indicated that the MB hybrid material removed 99.8% BB and 97% Cu²⁺ and the dye-conjugating hybrid with growing BaSO₄ 100% MB, 99.5% BB, and 44% Cu²⁺.

Conclusion

The waste MB–BaSO₄ hybrid material is efficient to treat cationic dye and Cu²⁺ wastewater. The dye-conjugating hybridization method is the first to be advanced for in situ wastewater treatment, and it showed a combined effect for the removal of both organic dyes and heavy metals.     

Comparative studies of fungal degradation of single or mixed bioaccessible reactive azo dyes

A screening using several fungi (Phanerochaete chrysosporium, Pleurotus ostreatus, Trametes versicolor and Aureobasidium pullulans) was performed on the degradation of syringol derivatives of azo dyes possessing either carboxylic or sulphonic groups, under optimized conditions previously established by us. T. versicolor showed the best biodegradation performance and its potential was confirmed by the degradation of differently substituted fungal bioaccessible dyes. Enzymatic assays (lignin peroxidase, manganese peroxidase, laccase, proteases and glyoxal oxidase) and GC-MS analysis were performed upon the assay obtained using the most degraded dye. The identification of hydroxylated metabolites allowed us to propose a possible metabolic pathway. Biodegradation assays using mixtures of these bioaccessible dyes were performed to evaluate the possibility of a fungal wastewater treatment for textile industries.     

Kinetics of chemical decolorization of the azo dye C.I. Reactive Orange 96 by sulfide

The mechanism of decolorization of azo dyes based on the extracellular chemical reduction with sulfide (H2S, HS-, S2-) was postulated for sulfate reducing environments. To design technical decolorization processes of textile wastewater treatment with sulfide produced by sulfate reducing bacteria (SRB), kinetics is of great significance. Batch experiments were made in order to investigate the kinetics of abiotic decolorization of the reactive mono-azo dye C.I. Reactive Orange 96 (RO 96) with sulfide, with varying pH. The decolorization of RO 96 by sulfide under the exclusion of O2 corresponded to first-order kinetics with respect to both dye and sulfide concentration. The decolorization of RO 96 with sulfide at neutral pH (7.1) was advantageous compared with that at pH for 4.1, 6.3, and 6.5. This is attributed to an increase in the fraction of HS- of total sulfide species at neutral pH. The rate constants k for the decolorization at 37 degrees C were obtained as 0.01 for pH = 4.1, 0.06 for pH = 6.3, 0.08 for pH = 6.5, and 0.09 for pH = 7.1 in mM(-1) min(-1). The high rate constants for sulfide at pH 6.5-7.1 support that the decolorization through SRB (i.e. by bio-sulfide) can be effective in anaerobic bacterial systems with sulfate.     

Ozonation of azo dye in a semi-batch reactor: a determination of the molecular and radical contributions

Azo dye ozonation was carried in a semi-batch reactor to evaluate both the molecular and radical contributions of ozone on the dye decay. From two mass balance equations, the simultaneous determination of mass transfer, self-decomposition and solubility parameters of ozone were determinated; thus establishing the steady state conditions in the experimental system. The results of kinetic studies showed that the decay of azo dye was a pseudo-first-order reaction with respect to dye concentration and the overall rate constant increased with an increase in the pH, however declined with an increase in the dye concentration. Furthermore, from the overall rate constants obtained at various pH values a mathematical analysis of dye decay was performed, which provides a practical new method to quantify the radical and molecular contributions in the ozonation of azo dyes.     

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.