Almost all dyestuffs used for textile processing impose heavy colors on effluents such that they can¡¦t meet effluent regulations. Sodium hypochlorite (NaOCl) has long been used for effluent decoloration by most textile plants. However, despite by the operators¡¦ experience, there is still no scientific method for controlling the dosing rate of sodium hypochlorite. An insufficient dosage may result in an aesthetically and legally unacceptable effluent. Whereas an excessive one may lead to the formation of chlorine-containing organic compounds which are harmful to the aquatic life and may limit the water utilization. It is necessary to develop a control technique for chlorination decoloration of textile wastewaters. In this study, secondary effluent samples from a textile wastewater plant and synthetic wastewater samples prepared by two azo-type dyestuffs were used for chlorination decoloration tests in a batch reactor with a residual chlorine indicator. Experimental results indicate that the most economic and effective reaction conditions for decoloration of the test wastewaters were pH = 4 and residual chlorine = 14 mg/L. In the conditions, wastewaters with true color intensity = 1,200 ADMI could be reduced to values less than 400 ADMI within 60 min. Results also confirm that on-line monitoring of residual chlorine concentration in the reacting liquid can be used to achieve a better control of chlorine addition. Experimental data also indicate that the color removal rate (-dC/dt) was linearly proportional to the color intensity (C) and free hypochlorous acid (HOCl) concentration.

Este trabalho apresenta o estudo da degradação eletroquímica e eletroquímica foto-assistida de efluentes têxteis industriais usando ânodos dimensionalmente estáveis (ADE). As amostras analisadas foram coletadas diretamente do tanque de equalização (efluente bruto) e do tanque final (efluente biologicamente tratado) cedidas pela empresa Toalhas São Carlos, de São Carlos, São Paulo. As degradações foram realizadas em uma célula de fluxo do tipo filtro prensa com eletrodo ADE comercial (composição nominal Ti/Ti0,7Ru0,3O2) sob recirculação constante. A fim de avaliar os melhores parâmetros de degradação, foram estudadas as influências do tipo de eletrólito suporte (NaCl e Na2SO4), concentrações de NaCl (0,05 a 0,30 mol L-1), densidade de corrente (10 a 120 mA cm-2) e pH (4, 7, 8, 9 e 12). Após definição dos melhores parâmetros, novas amostras do tanque de equalização foram coletadas, em dias alternados para avaliar a influência da composição do efluente. Ensaios eletroquímicos foto-assistidos foram realizados nas mesmas condições que os ensaios eletroquímicos visando a comparação dos métodos. Caracterizações do ADE foram realizadas por voltametria cíclica na ausência e presença de efluente e de luz. Durante as eletrólises de 2 horas, amostras foram coletadas e analisadas por espectroscopia UV vis, carbono orgânico total (COT) e demanda química de oxigênio (DQO). Análises da formação de subprodutos foram realizadas pelos métodos de fitotoxicidade e organoclorados que mostraram uma maior toxicidade após 10 horas de eletrolise. Avaliação do residual de cloro e cloreto complementaram os estudos. Observou-se que a degradação é mais efetiva pelo método eletroquímico foto-assistido em relação ao método eletroquímico. Também, a adição de NaCl favorece a degradação pela formação de agentes oxidantes, ao contrário do Na2SO4. Nas maiores concentrações de NaCl e densidades de corrente implicam em maior remoção de cor e DQO. Contudo no estudo com diferentes valores de pH, os melhores resultados foram em pH mais baixo. Considerando todos os resultados, os melhores parâmetros para degradação de efluentes têxteis industriais foram densidade de corrente de 40 mA cm-2, pH 8, 0,15 mol L-1 de NaCl utilizado como eletrólito suporte e degradação com o método eletroquímico foto-assistido em efluente do tanque de equalização (efluente sem tratamento biológico). / This study presents the electrochemical and photo-assisted electrochemical degradation of real textile industrial effluent at Dimensionally Stable Anodes (DSA). The effluent samples were collected directly from the mixing tank and from the final effluent discharge after biological treatment. The effluent samples were provided by the company Toalhas São Carlos situated in the city of São Carlos, São Paulo state. The degradation assays were performed in a filter-press cell with a commercial DSA electrode (nominal composition Ti/Ti0,7Ru0,3O2) under constant recirculation. In order to assess the best degradation parameters the influences of the type of electrolyte (NaCl and Na2SO4) was studied. NaCl concentrations (0.05 to 0.30 mol L-1), current density (10 a 120 mA cm-2) and pH (4, 7, 8, 9 and 12) were investigated. After defining the best parameters, new effluent samples were collected on alternate days to assess the influence of the effluent composition. Photo-assisted electrochemical tests were performed under the same conditions as the electrochemical tests in order to compare the two methods. Characterizations of the DSA materials were performed by cyclic voltammetry in the absence and presence of wastewater and light. During the 2 h electrolyses, samples were collected and analyzed by UV-vis spectroscopy, total organic carbon (TOC), chemical oxygen demand (COD) and conductivity. Analyses of the formation of degradation products were performed by phytotoxicity tests and AOX analysis. Greater toxicity was observed after 10 hours of electrolysis. Evaluation of residual chlorine and chloride complemented the studies. It was observed that degradation is more effective for the photo-assisted electrochemical method than electrochemical method. Also the addition of NaCl promotes degradation by in-situ generated oxidizing agents. Higher concentrations of NaCl and current densities increased color removal and COD. However in tests with different pH values, the best results were observed at lower pH. Considering all the results, the best parameters for degradation of real textile effluent were current density at 40 mA cm-2, pH 8 and 0.15 mol L-1 NaCl used as supporting electrolyte and degradation using the photo-assisted electrochemical method.

<p>Decolorization of Azo dyes in synthetic wastewater composition which is similar to real textile wastewater was carried out by microbial process. Experiments were performed in two continuous systems. Experiments were performed under anaerobic conditions in order to break the nitrogen bond of the azo group (-N=N-). A synthetic dye solution which contained 200 mg/L Reactive Black 5, 200 mg/L Procion Red MX-5B and 1 g/L yeast extract was prepared. In this study, living microorganisms were used to degrade the dyes in wastewater. Rice husks which contain bacteria and fungi were used in the reactors of continuous systems. The parameters tested on continuous system were wastewater composition, the number of reactors, the amount of yeast extract in wastewater composition, the wastewater flowrate, washing the system with wood chips solution, addition of yeast extract solution.  Results have shown that increasing the number of reactors, the retention time, the amount of yeast extract and washing the system with wood chips solution had positive effects for degradation of the dyes from wastewater. When the flowrate was increased the retention time has decreased so degradation of dyes has decreased but although the flowrate increased twice, % degradation hasn’t decreased as the same ratio. Therefore this result showed that this process can be worked for faster flowrates. Microbial process is a promising technology which might be used to treat wastewater containing azo dyes with good performance.</p><p> </p>

Este trabalho apresenta o estudo da degradação eletroquímica e eletroquímica foto-assistida de efluentes têxteis industriais usando ânodos dimensionalmente estáveis (ADE). As amostras analisadas foram coletadas diretamente do tanque de equalização (efluente bruto) e do tanque final (efluente biologicamente tratado) cedidas pela empresa Toalhas São Carlos, de São Carlos, São Paulo. As degradações foram realizadas em uma célula de fluxo do tipo filtro prensa com eletrodo ADE comercial (composição nominal Ti/Ti0,7Ru0,3O2) sob recirculação constante. A fim de avaliar os melhores parâmetros de degradação, foram estudadas as influências do tipo de eletrólito suporte (NaCl e Na2SO4), concentrações de NaCl (0,05 a 0,30 mol L-1), densidade de corrente (10 a 120 mA cm-2) e pH (4, 7, 8, 9 e 12). Após definição dos melhores parâmetros, novas amostras do tanque de equalização foram coletadas, em dias alternados para avaliar a influência da composição do efluente. Ensaios eletroquímicos foto-assistidos foram realizados nas mesmas condições que os ensaios eletroquímicos visando a comparação dos métodos. Caracterizações do ADE foram realizadas por voltametria cíclica na ausência e presença de efluente e de luz. Durante as eletrólises de 2 horas, amostras foram coletadas e analisadas por espectroscopia UV vis, carbono orgânico total (COT) e demanda química de oxigênio (DQO). Análises da formação de subprodutos foram realizadas pelos métodos de fitotoxicidade e organoclorados que mostraram uma maior toxicidade após 10 horas de eletrolise. Avaliação do residual de cloro e cloreto complementaram os estudos. Observou-se que a degradação é mais efetiva pelo método eletroquímico foto-assistido em relação ao método eletroquímico. Também, a adição de NaCl favorece a degradação pela formação de agentes oxidantes, ao contrário do Na2SO4. Nas maiores concentrações de NaCl e densidades de corrente implicam em maior remoção de cor e DQO. Contudo no estudo com diferentes valores de pH, os melhores resultados foram em pH mais baixo. Considerando todos os resultados, os melhores parâmetros para degradação de efluentes têxteis industriais foram densidade de corrente de 40 mA cm-2, pH 8, 0,15 mol L-1 de NaCl utilizado como eletrólito suporte e degradação com o método eletroquímico foto-assistido em efluente do tanque de equalização (efluente sem tratamento biológico). / This study presents the electrochemical and photo-assisted electrochemical degradation of real textile industrial effluent at Dimensionally Stable Anodes (DSA). The effluent samples were collected directly from the mixing tank and from the final effluent discharge after biological treatment. The effluent samples were provided by the company Toalhas São Carlos situated in the city of São Carlos, São Paulo state. The degradation assays were performed in a filter-press cell with a commercial DSA electrode (nominal composition Ti/Ti0,7Ru0,3O2) under constant recirculation. In order to assess the best degradation parameters the influences of the type of electrolyte (NaCl and Na2SO4) was studied. NaCl concentrations (0.05 to 0.30 mol L-1), current density (10 a 120 mA cm-2) and pH (4, 7, 8, 9 and 12) were investigated. After defining the best parameters, new effluent samples were collected on alternate days to assess the influence of the effluent composition. Photo-assisted electrochemical tests were performed under the same conditions as the electrochemical tests in order to compare the two methods. Characterizations of the DSA materials were performed by cyclic voltammetry in the absence and presence of wastewater and light. During the 2 h electrolyses, samples were collected and analyzed by UV-vis spectroscopy, total organic carbon (TOC), chemical oxygen demand (COD) and conductivity. Analyses of the formation of degradation products were performed by phytotoxicity tests and AOX analysis. Greater toxicity was observed after 10 hours of electrolysis. Evaluation of residual chlorine and chloride complemented the studies. It was observed that degradation is more effective for the photo-assisted electrochemical method than electrochemical method. Also the addition of NaCl promotes degradation by in-situ generated oxidizing agents. Higher concentrations of NaCl and current densities increased color removal and COD. However in tests with different pH values, the best results were observed at lower pH. Considering all the results, the best parameters for degradation of real textile effluent were current density at 40 mA cm-2, pH 8 and 0.15 mol L-1 NaCl used as supporting electrolyte and degradation using the photo-assisted electrochemical method.

Decolorization of Azo dyes in synthetic wastewater composition which is similar to real textile wastewater was carried out by microbial process. Experiments were performed in two continuous systems. Experiments were performed under anaerobic conditions in order to break the nitrogen bond of the azo group (-N=N-). A synthetic dye solution which contained 200 mg/L Reactive Black 5, 200 mg/L Procion Red MX-5B and 1 g/L yeast extract was prepared. In this study, living microorganisms were used to degrade the dyes in wastewater. Rice husks which contain bacteria and fungi were used in the reactors of continuous systems. The parameters tested on continuous system were wastewater composition, the number of reactors, the amount of yeast extract in wastewater composition, the wastewater flowrate, washing the system with wood chips solution, addition of yeast extract solution.  Results have shown that increasing the number of reactors, the retention time, the amount of yeast extract and washing the system with wood chips solution had positive effects for degradation of the dyes from wastewater. When the flowrate was increased the retention time has decreased so degradation of dyes has decreased but although the flowrate increased twice, % degradation hasn’t decreased as the same ratio. Therefore this result showed that this process can be worked for faster flowrates. Microbial process is a promising technology which might be used to treat wastewater containing azo dyes with good performance.

The goal of this case study was to investigate the behavior of real textile wastewater in DCMD (Direct Contact Membrane Distillation) treatment and subsequently to develop a simple and effective pretreatment for it. To this moment, this work is one of the only studies to make an in-depth analysis of the treatment while considering the complexity of this effluent, which is inherently composed of Volatile Organic Compounds (VOCs) and surfactants. After the application of pretreatment, it became clear that the main concern with textile wastewater treatment using MD is wetting, not fouling. Sedimentation and filtration alone were effective in removing suspended solids, but insufficient in stopping wetting. However, neutralization before sedimentation and filtration was proven to be a fundamental step in reducing wetting rates. This improved performance happens due to the change in pH of the wastewater sample, which increases the rejection rates by the membrane. The best experiments, neutralized to pHs 7.40 and 9.06, achieved up to 99.89% rejection by the membrane, with up to 97% conductivity decrease when compared to an experiment without neutralization, 97% removal of COD, and 98% TOC. Overall, the permeate obtained in this work after pretreatment demonstrated excellent quality, and the recovered effluent can possibly be reused in the textile industry, aiming for Zero Liquid Discharge (ZLD) processes. Thus, scaling up this technology for real industrial use is still necessary, tailoring the treatment to the effluent's characteristics to obtain the best results.

No description available.

Philosophiae Doctor - PhD / Persistent organic pollutants (POPs) are very tenacious wastewater contaminants with negative impact on the ecosystem. The two major sources of POPs are wastewater from textile industries and pharmaceutical industries. They are known for their recalcitrance and circumvention of nearly all the known wastewater treatment procedures. However, the wastewater treatment methods which applied advanced oxidation processes (AOPs) are documented for their successful remediation of POPs. AOPs are a group of water treatment technologies which is centered on the generation of OH radicals for the purpose of oxidizing recalcitrant organic contaminants content of wastewater to their inert end products. Circumvention of the reported demerits of AOPs such as low degradation efficiency, generation of toxic intermediates, massive sludge production, high energy expenditure and operational cost can be done through the application of the combined AOPs in the wastewater treatment procedure. The resultant mineralisation of the POPs content of wastewater is due to the synergistic effect of the OH radicals produced in the combined AOPs. Hydrodynamic cavitation is the application of the pressure variation in a liquid flowing through the venturi or orifice plates. This results in generation, growth, implosion and subsequent production of OH radicals in the liquid matrix. The generated OH radical in the jet loop hydrodynamic cavitation was applied as a form of advanced oxidation process in combination with hydrogen peroxide, iron (II) oxides or the synthesized green nano zero valent iron (gnZVI) for the treatment of simulated textile and pharmaceutical wastewater.

Denim production is one of the leading sub-sectors of textile industry which basically generates highly colored indigo dyeing effluents. In the present study, ozonation was applied to the indigo-dyeing effluent(COD=820 mg/L / color=5500 Pt-Co), and to the whole effluent from a denim-producing plant before(COD=2750 mg/L / color=3950 Pt-Co) and after(COD=800 mg/L,color=3700 Pt-Co) biological treatment for degradation/detoxification purposes. Ozonation was also tried in the wastewater of the plant(COD=3100 mg/L / color=4500 Pt-Co) that would be produced after some foreseen cleaner production measures / caustic recovery and reusing of dyeing process wastewater. When applied to indigo-dyeing wastewater / ozonation provided 95% color and 61% COD removals at 1320 mg/h ozone dose within 60 minutes The optimum pH was evaluated as 4 when indigo-dyeing wastewater exposed to ozonation at different pHs(1.6-12.3). On the other side, ozonation applied as pre-treatment to the plant effluent provided 86% color and 46% COD removals with 3240 mg/h ozone dose in 70 minutes. Less satisfactory results were obtained when ozonation was tried in the wastewater after measures, with 86% color and 31% COD removals at 3960 mg/h ozone dose in 80 minutes. When applied to the biologically-treated effluent / at 420 mg/h ozone dose and within 40 minutes, ozonation removed 47% of influent COD and 96% of influent color indicating better performance of ozonation in postoxidation. In order to assess possible improvements on ozonation with the addition of H2O2, different concentrations were tried, but no significant improvement was obtained. The improvement in BOD5/COD index was also determined for the ozonetreated plant effluent to measure the effects of ozonation on biodegradability and found out that BOD5/COD ratio has improved to 0.39 from 0.22.

Textile wastewaters are highly colored and non-biodegradable having variable compositions of colored dyes, surfactants and toxic chemicals. Recently, ozonation is considered as an effective method that can be used in the treatment of industrial wastewaters / catalytic ozonation being one of the advanced oxidation processes (AOPs), is applied in order to reduce the ozone consumption and to increase the chemical oxygen demand (COD) and total organic carbon (TOC) removals. In this study, catalytic ozonation of industrial textile wastewater (ITWW) obtained from AKSA A.S. (Yalova, Istanbul) textile plant has been examined in a three phase fluidized bed reactor at different conditions. The effects of inlet chemical oxygen demand concentration (CODin), pH, different catalyst types [perflorooctyl alumina (PFOA) and alumina] and catalyst dosage on ozonation process were determined. Moreover, the changes in the organic removal efficiencies with gas to liquid flow rate ratio were investigated. The dispersion coefficients (DL) and volumetric ozone-water mass transfer coefficients (kLa) were estimated at various gas and liquid flow rates in order to observe the effect of liquid mixing in the reactor on ozonation process. It was observed that increasing both gas and liquid flow rates by keeping their ratio constant provided higher organic removal efficiencies due to the higher mixing in the liquid phase. The dyes present in ITWW sample were known to be Basic Blue 41 (BB 41), Basic Red 18.1 (BR 18.1) and Basic Yellow 28 (BY 28). The &ldquo / absorbance vs. concentration&rdquo / calibration correlations were developed to estimate the amounts of these colored dyes in the ITWW sample. This provided the opportunity to examine the degradation of each dye in this wastewater separately. While PFOA catalyst was found to increase the removal efficiency of BY 28 at an acidic pH of 4, alumina yielded highest color removals for BB 41 and BR 18.1 at a pH of 12. The highest TOC and COD reductions being 24.4% and 29.5%, respectively, were achieved in the catalytic ozonation of the ITWW using alumina as the catalyst at a pH of 12 and at a gas to liquid flow rate ratio of 1.36 (QG = 340 L/h, QL = 250 L/h). At the same conditions, also the highest overall color removal in terms of Pt-Co color unit, namely 86.49%, were obtained due to the lower BY 28 concentration in the WW sample than those of the BB 41 and BR 18.1. In addition, the oxidation of BB 41, BR 18.1 and BY 28 dyes were investigated in a semi-batch reactor by sole and catalytic ozonations with alumina and PFOA catalyst particles. The sole and catalytic ozonation reactions followed a pseudo-first order kinetics with respect to dye concentration. The highest TOC and COD removals being 58.3% and 62.9%, respectively, were obtained at pH of 10 for BB 41 and 55.2% and 58.8%, respectively, for BR 18.1 with alumina catalyst. On the other hand, for BY 28 PFOA catalyst yielded highest TOC and COD reductions being 61.3% and 66.9%, respectively, at pH of 4.