Fate and transformation of naphthylaminesulfonic azo dye Reactive Black 5 during wastewater treatment process

Certain aromatic amines generated by the decolorization of some azo dyes are not removed substantially by conventional anaerobic–aerobic biotreatment. These aromatic amines are potentially toxic and often released in the wastewater of industrial plants. In this study, the fate and transformation of the naphthylaminesulfonic azo dye Reactive Black 5 (RB5) during different phases of a sequencing batch reactor were investigated. The major products of RB5 decolorization during the anaerobic phase include 2-[(4-aminophenyl)sulfonyl]ethyl hydrogen sulfate (APSEHS) and 1-2-7-triamino-8-hydroxy-3-6-naphthalinedisulfate (TAHNDS). During the aerobic phase, APSEHS was hydrolyzed and produced 4-aminobenzenesulfonic acid, which was further degraded via dearomatization. TAHNDS was transformed rapidly via auto-oxidation into TAHNDS_DP-1 and TAHNDS_DP-2, which were not further removed by the activated sludge during the entire 30-day aerobic phase. In contrast, different behaviors of TAHNDS were observed during the anoxic phase. The transformation of TAHNDS was initiated either by deamination or desulfonation reaction. TAHNDS was then converted into 3,5-diamino-4-hydroxynaphthalene-2-sulfonic acid, which was subsequently removed via ring cleavage reaction under aerobic condition. In conclusion, complete degradation of TAHNDS by activated sludge occurs only during anoxic/aerobic processes instead of the conventional anaerobic/aerobic processes.     

Biological decolorization of reactive anthraquinone and phthalocyanine dyes under various oxidation-reduction conditions.

The decolorization of two anthraquinone dyes (Reactive Blue 4 [RB4] and Reactive Blue 19 [RB19]) and two phthalocyanine dyes (Reactive Blue 7 [RB7] and Reactive Blue 21 [RB21]) was investigated at an initial dye concentration of 300 mg/L using an unacclimated, enrichment culture. The culture was fed a mixture of organic compounds and maintained initially under aerobic conditions, and then progressively developed anoxic/ anaerobic conditions. Biotransformation-related decolorization of the dyes did not take place under aerobic conditions, but use of the feed organic mixture and biomass production by the enrichment culture were not affected. Complete ammonia removal occurred in the control and all dye-amended cultures. The development and extent of nitrification were much lower in the latter cultures, in which ammonia removal via air stripping was the dominant mechanism. Prolonged incubation of the culture under anoxic/anaerobic conditions with multiple carbon source additions resulted in a high decolorization extent of anthraquinone dyes (over 84%) and only partial decolorization of phthalocyanine dyes (49 to 66%). Development of significant methanogenic activity took place in the control and, to a lesser extent, in the two phthalocyanine dye-amended cultures, but the anthraquinone dyes severely inhibited the development of methanogenic activity. The RB4 and RB19 decolorization was attributed to nonreversible, microbially mediated dye transformation(s), demonstrated by the accumulation of decolorization products with absorbance maxima in the 420- to 460-nm region. The decolorization of RB4 and RB19 followed Michaelis-Menten kinetics. At an initial dye concentration of 300 mg/L, the observed maximum decolorization rate per unit biomass was 9.1 and 37.5 mg dye/mg volatile suspended solids x day for the RB4 and RB19, respectively. Thus, partial decolorization of reactive phthalocyanine dyes and extensive biological decolorization of reactive anthraquinone dyes is feasible only under anoxic/anaerobic conditions.     

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.     

沼泽红假单胞菌W12对活性黑5的厌氧脱色和降解作用

从处理印染废水的厌氧移动床生物膜反应器（moving bed biofilm reactor, MBBR）中分离到一株具有高效脱色活性的沼泽红假单胞菌W12。经实验确定W12对活性黑5（reactive black 5,RB5）脱色的适宜条件为：pH＜10;有光照;谷氨酸盐或乳酸盐作为碳源,当乳酸钠为碳源时浓度应＞500 mg/L;盐度不超过5％;RB5浓度不大于700 mg/L。紫外可见光谱扫描结果表明,RB5的脱色和降解过程生成芳香胺类化合物,这些中间产物可进一步降解。此外发现,RB5诱导生成的胞外代谢物能提高W12的脱色活性。     

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.     

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。     

Biological treatment of dye wastewaters using an anaerobic-oxic system

Three dye solutions, namely, C.I. Acid Yellow 17, C.I. Basic Blue 3, and C.I. Basic Red 2, were treated in an upflow anaerobic sludge blanket (UASB) reactor followed by a semi-continuous aerobic activated sludge tank. When hydraulic retention time was about 12 hours, no significant color removal was observed in the aerobic stage. In the anaerobic stage, Acid Yellow 17, Basic Blue 3, and Basic Red 2 were removed by 20%, 72%, and 78%, respectively. To treat wastewater from a dye manufacturing factory with COD concentration of 1200 mg/l and Color of 500 degree (dilution factor), an UASB reactor (4.5 liters) and an activated sludge tank (5 liters, adjustable), COD and color were removed by more than 83% and 90% at a COD loading rate of 5.3 kg COD/m³-day in the anaerobic stage, and at the hydraulic retention time of 6-10 hours for the anaerobic stage and 6.5 for the aerobic stage. The anaerobic stage of the A/O system removes both color and COD. In addition, it also improves biodegradability of dyes for further aerobic treatment.     

Photocatalytic degradation of azo dyes by nitrogen-doped TiO2 nanocatalysts

This study examined the photocatalytic degradation of three azo dyes, acid orange 7 (AO7), procion red MX-5B (MX-5B) and reactive black 5 (RB5) using a new type of nitrogen-doped TiO2 nanocrystals. These newly developed doped titania nanocatalysts demonstrated high reactivity under visible light (lambda>390 nm), allowing more efficient usage of solar light. The doped titania were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Experiments were conducted to compare the photocatalytic activities of nitrogen-doped TiO2 nanocatalysts and commercially available Degussa P25 powder using both UV illumination and solar light. It is shown that nitrogen-doped TiO2 after calcination had the highest photocatalytic activity among all three catalysts tested, with 95% of AO7 decolorized in 1 h under UV illumination. The doped TiO2 also exhibited substantial photocatalytic activity under direct sunlight irradiation, with 70% of the dye color removed in 1h and complete decolorization within 3 h. Degussa P25 did not cause detectable dye decolorization under identical experimental conditions using solar light. The decrease of total organic carbon (TOC) and evolution of inorganic sulfate (SO4(2-)) ions in dye solutions were measured to monitor the dye mineralization process.     

Degradation of reactive dyes I. A comparative study of ozonation, enzymatic and photochemical processes

The environmental problems associated with textile activities are represented mainly by the extensive use of organic dyes. A great number of these compounds are recalcitrant and shown carcinogenic or mutagenic character. In this work three processes were studied for degradation of an anthraquinone dye (C.I. reactive blue-19). The ozonation process leads to complete decolorization with a very short reaction time; however, effective mineralization of the dye was not observed. The enzymatic process promotes quick decolorization of the dye; nevertheless, maximum decolorization degrees of about 30% are insignificant in relation to the decolorization degree achieved by the other processes. The best results were found for the photocatalytical process. The use of ZnO or TiO2 as photocatalysts, permits total decolorization and mineralization of the dye with reaction times of about 60 min.     

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.     

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   

硫酸盐在偶氮染料厌氧生物脱色中的作用

以沼泽红假单胞菌W1为研究对象,考察了厌氧条件下硫酸盐还原对活性黑5(Reactive Black 5,RB5)和直接黄11(Direct Yellow 11,DY11)生物脱色的影响。结果表明,硫酸盐本身对2种染料脱色无明显影响,而硫酸盐的还原产物———硫化物能通过氧化还原介体使2种染料化学脱色,其脱色过程能在3 min内迅速完成。在无介体加入的情况下,硫化物能够通过RB5自身产生的介体加速RB5的脱色;而对于不能产生氧化还原介体的DY11,硫化物对其脱色无明显影响。硫化物经染料氧化后形成的硫单质能够被菌株W1重新转化为硫化物,继续还原染料。     

Biodecolorization of the azo dye Reactive Red 2 by a halotolerant enrichment culture.

The decolorization of the azo dye Reactive Red 2 (RR2) under anoxic conditions was investigated using a mesophilic (35 degrees C) halotolerant enrichment culture capable of growth at 100 g/L sodium chloride (NaCl). Batch decolorization assays were conducted with the unacclimated halotolerant culture, and dye decolorization kinetics were determined as a function of the initial dye, biomass, carbon source, and an externally added oxidation-reduction mediator (anthraquinone-2,6-disulphonic acid) concentrations. The maximum biomass-normalized RR2 decolorization rate by the halotolerant enrichment culture under batch, anoxic incubation conditions was 26.8 mg dye/mg VSSxd. Although RR2 decolorization was inhibited at RR2 concentrations equal to and higher than 300 mg/L, the halotolerant culture achieved a 156-fold higher RR2 decolorization rate compared with a previously reported, biomass-normalized RR2 decolorization rate by a mixed mesophilic (35 degrees C) methanogenic culture in the absence of NaCl. Decolorization kinetics at inhibitory RR2 levels were described based on the Haldane model (Haldane, 1965). Five repetitive dyeing/decolorization cycles performed using the halotolerant culture and the same RR2 dyebath solution demonstrated the feasibility of biological renovation and reuse of commercial-strength spent reactive azo dyebaths.     

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.     

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.     

Effect of particle size of titanium dioxide nanoparticle aggregates on the degradation of one azo dye

Introduction

Titanium dioxide (TiO₂) nanoparticle powders have been extensively studied to quickly photodegrade some organic pollutants; however, the effect of the particle size of TiO₂ nanoparticle aggregates on degradation remains unclear because microscale aggregates form once the nanoparticle powders enter into water.

Methods

The degradation of azo dye by different particle sizes of TiO₂ nanoparticle aggregates controlled by NaCl concentrations was investigated to evaluate the particle size effect. Removal reactions of reactive black 5 (RB5) with TiO₂ nanoparticles followed pseudo-first-order kinetics.

Results

The increase of TiO₂ dosage from 40 to 70?mg/L enhanced the degradation. At doses around 100?mg/L TiO₂, degradation rates decreased which could be the result of poor UV light transmittance at high-particle concentrations. At average particle sizes of TiO₂ nanopowders less than around 500?nm, the degradation rates increased with decreasing particle size. As the average particle size exceeded 500?nm, the degradation rates were not significantly changed.

Conclusions

For the complete degradation experiments, the mineralization rates of total organic carbon disappearance are generally following the RB5 decolorization kinetic trend. These findings can facilitate the application of TiO₂ nanoparticles to the design of photodegradation treatments for wastewater.     

Enzymatic treatment of sulfonated aromatic amines generated from reductive degradation of reactive azo dyes.

Anaerobic degradation, an effective treatment process of textile industry effluent, generates sulfonated aromatic amines, which are carcinogenic, mutagenic, and resistant to microbial degradation. These aromatic amines can be effectively removed by oxidative polymerization catalyzed by peroxidase enzyme. The amines, generated in this study from the anaerobic reduction by zero-valent iron of two reactive azo dyes (Reactive Red 2 [RR2] and Reactive Black 5 [RB5]), were successfully removed (90%) by Arthromyces ramosus peroxidase (ARP). For better understanding of the process, enzymatic treatment of two model compounds, diphenylamine (DPA) and 2-amino-8-naphthol-3,6-disulfonic acid (ANDSA), were also studied. Diphenylamine has a similar diarylamine bond as RR2. The ANDSA has a similar structure as the dye reduction products. The secondary amine bond in DPA and RR2 were oxidized by ARP. Enzymatic reaction of sulfonated aromatic amines generated soluble colored compounds, which were removed by coagulant. Optimum reaction parameters were also determined.     

Decolorization and detoxification of two textile industry effluents by the laccase/1-hydroxybenzotriazole system

The aim of this work was to determine the optimal conditions for the decolorization and the detoxification of two effluents from a textile industry—effluent A (the reactive dye bath Bezactive) and effluent B (the direct dye bath Tubantin)—using a laccase mediator system. Response surface methodology (RSM) was applied to optimize textile effluents decolorization. A Box–Behnken design using RSM with the four variables pH, effluent concentration, 1-hydroxybenzotriazole (HBT) concentration, and enzyme (laccase) concentration was used to determine correlations between the effects of these variables on the decolorization of the two effluents. The optimum conditions for pH and concentrations of HBT, effluent and laccase were 5, 1 mM, 50 % and 0.6 U/ml, respectively, for maximum decolorization of effluent A (68 %). For effluent B, optima were 4, 1 mM, 75 %, and 0.6 U/ml, respectively, for maximum decolorization of approximately 88 %. Both effluents were treated at 30 °C for 20 h. A quadratic model was obtained for each decolorization through this design. The experimental and predicted values were in good agreement and both models were highly significant. In addition, the toxicity of the two effluents was determined before and after laccase treatment using Saccharomyces cerevisiae, Bacillus cereus, and germination of tomato seeds.     

含铜酞菁染料废水及树脂废水的处理工艺研究及应用

采用逆流洗涤方式有效减轻酸污染。含铜酞菁废水采用铁炭微电解预处理技术 ,树脂废水采用物化预处理技术 ,再通过厌氧水解———SBR好氧生化处理技术的工艺流程 ,成功地治理了该有机化工废水 ,出水达到国家排放标准     

Semiconductor-assisted photodegradation of lignin, dye, and kraft effluent by Ag-doped ZnO

This work reports a preliminary study of semiconductor-assisted photochemical degradation of lignin, Remazol Brilliant Blue R and Kraft E1 paper effluent by using ZnO and Ag-doped ZnO photocatalysts. The doped semiconductor was prepared in the reaction media by photoreduction of silver nitrate. With the use of 100 mg of ZnO and 15 mg of Ag-ZnO, almost total decolorization of the dye and lignin samples in reaction times lower than 60 min were observed. Extending the photochemical reaction up to 120 min, the total organic carbon content (TOC) was reduced in 90%. For the paper effluent, a fast decolorization was obtained for relatively short reaction times. However, de TOC reduction was negligible (near of 10%) up to high reaction times (300 min). By using the Ag-ZnO photocatalyst, the toxicity of lignin and Kraft E1 effluent toward E. Coli was completely removed. For the dye, the formation of transient toxic species was observed.