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30320130402003

  1. 1. International Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976 – 6995(Print), ISSN 0976 – 7002(Online) Volume 4, Issue 2, May - August (2013), © IAEME 21 MEMBRANE ASSISTED ELECTRO CHEMICAL DEGRADATION FOR QUINOLINE YELLOW, EOSIN B AND ROSE BENGAL DYES DEGRADATION B. Chirsabesan and M.Vijay* Department of Chemical Engineering, Annamalai University, Annamalai Nagar, Chidambaram -608002, India ABSTRACT Industrial waste often contains a mixture of organic and inorganic compounds, in addition to solid or soluble material, and because of this diverse feature no universal strategy of remediation is feasible. In the present study, Quinoline Yellow, Eosin B and Rose Bengal model dye were chosen and its characterization was done by measuring pH, EC, TDS, COD, and Color etc. Degradation studies of Quinoline Yellow, Eosin B and Rose Bengal model dye was carried out with Membrane assisted electro chemical degradation cell in specially designed reaction vessel in the electro membrane reactor equipped with poly electrolyte membranes. Experiments were performed in four poly electrolyte membranes (PEM) such SPES, SPSf, SPEEK and Nafion at optimized condition. The SPES, SPSf, SPEEK were prepared with different ion exchange capacity. The dyes degradation were compared with commercial Nafion commercial PEM membranes. Key words: Quinoline Yellow, Eosin B, Rose Bengal Quinoline Yellow, Membrane assisted electro chemical degradation, decolourization of dye. 1. INTRODUCTION Industrial waste often contains a mixture of organic and inorganic compounds, in addition to solid or soluble material, and because of this diverse feature no universal strategy of remediation is feasible. As to the treatment of effluents polluted with organic compounds, biological oxidation is the cheapest process, but the presence of toxic or bio- refractory molecules may hinder this approach. It is important to design (or select) an electrochemical reactor for a specific process, and it is clear that reactors for energy conversion and electrochemical synthesis will have different drivers to those used in the INTERNATIONAL JOURNAL OF DESIGN AND MANUFACTURING TECHNOLOGY (IJDMT) ISSN 0976 – 6995 (Print) ISSN 0976 – 7002 (Online) Volume 4, Issue 2, May - August (2013), pp. 21-41 © IAEME: http://www.iaeme.com/IJDMT.asp Journal Impact Factor (2013): 4.2823 (Calculated by GISI) www.jifactor.com IJDMT © I A E M E
  2. 2. International Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976 – 6995(Print), ISSN 0976 – 7002(Online) Volume 4, Issue 2, May - August (2013), © IAEME 22 destruction of electrolyte-based contaminants. Adequate attention must be paid to the form of the electrode, its geometry and motion, together with the need for cell division or a thin electrolyte gap. However, some limitations are there in electrochemical technology such as relatively few “showcases” for the technology, shortage of experienced electrochemical engineers, Chemical reactions, corrosion, adsorption, etc., at electrode surfaces can cause complications, Damage to electrodes via, e.g., corrosion and fouling, can restrict performance and longevity. Ion-exchange membranes can play a critical role in electrochemical reactors, it provides high surface area electrodes, acceptable cost, lifetime, and practicality of electrodes and membranes, low potential drop over electrodes and membranes, membranes that are selective to a particular ion and low solvent transport rate through membranes. Textile Printing and dyeing processes include pretreatment, dyeing / printing, finishing and other technologies. Pre-treatment includes desizing, scouring, washing, and other processes. Dyeing mainly aims at dissolving the dye in water, which will be transferred to the fabric to produce colored fabric under certain conditions. Printing is a branch of dyeing which generally is defined as ‘localized dyeing’ i.e. dyeing that is confirmed to a certain portion of the fabric that constitutes the design. Table 1 The scope for electrochemical technology in environmental treatment Avoidance of pollution clean electro synthesis Recycling of valuable materials precious metal deposition Remediation of polluted sites soil remediation by electrodialysis Monitoring and sensors in the gas and liquid phase Efficient energy conversion fuel cells and redox flow cells Avoidance of corrosion choice of materials/protective coatings Removal of contaminants metal ion, organics, and inorganics removal from water and process liquors Disinfection of water chlorination, peroxy species, or ozone Effluent from textile mills also contains chromium, which has a cumulative effect, andhigher possibilities for entering into the food chain. The scope of electrochemical technology in environmental treatment is shown in Table 1. Due to usage of dyes and chemicals,effluents are dark in color, which increases the turbidity of water body (Joseph and Egli, 2007). Adsorption techniques have recently gained a considerable importance due to their efficiency in the removal of pollutants too stable for conventional methods (Robinson et al. 2001, Aksu 2005). Most adsorbents are not equally effective towards different types of dyes (van der Zee 2002). Membrane technology has emerged as a feasible alternative to conventional treatment processes of dye wastewater and has proven to save operation costs and water consumptions by water recycling. Usually this technique is applied as a
  3. 3. International Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976 – 6995(Print), ISSN 0976 – 7002(Online) Volume 4, Issue 2, May - August (2013), © IAEME 23 tertiary/final treatment after biological and/or physical-chemical treatments (Ciardelliet al. 2000, Marcucciet al. 2002). Electro oxidation of organic compounds in aqueous solution can be obtained without electrode fouling by performing electrolysis at high anodic potentials in the region of water discharge due to the participation of intermediates of oxygen evolution. This process results in partly conversion or full mineralization of the organics, does not need to add oxidation catalysts to the solution and does in principle not produce any by-products. The decontaminated solutions showed no mutagenicity towards Salmonella typhimurium(Lunn and Sansone, 1991). In literature, it is reported that AOP using Fenton’s reagent can reduce the eosin concentration of 678 mg/l by 20% in 1hwhen treated with 278 mg/l FeSO4·7H2O and 3400 mg/l hydrogen peroxide. The results showed that anionic surfactants performed significantly better than a cationic one during the desorption of anionic dyes Eosin (Purkait et al).Quinoline yellow (QY) is also another food colorant. Different techniques such as adsorption, oxidation, reduction, electrochemical and membrane filtration are applied to remove these pollutants from the industrial effluents. Oxidation processes are widely used both in industrial preparations and in environmental treatments. Karacakaya and colleagues (2009) investigated the removal capabilities of Synechocystis sp. And Phormidium sp. The pseudo-second order kinetic model (PSOM) is widely used because of the simplicity of applying its linear form and the general applicability to adsorption kinetic data (Ho and McKay 1999). However, the models with simple expressions are more favored (Levenspiel 2002; Gonzo and Gonzo 2005). Among all the models used in adsorption kinetic studies, pseudo-first order model (PFOM) and PSOM were frequently applied (Ho and McKay 1999). However, as yet, there has not been a method employing the electrochemical oxidation process combined with the membrane filtration process for the treatment and reuse of textile dyehouse wastewater. The goal of this research is to study the performance of the arc-shaped transfer-flow membrane module, at the same time, to demonstrate these processes and to develop a potential dye wastewater treatment system for reuse. 2. MATERIALS AND METHODS Textile dye Quinoline Yellow, obtained from pollution control division, Central Electrochemical research Institute, Karaikudi, Tamilnadu.PES (3500) was received from Udel. Eosin B dye (4´,5´-Dibromo- 2´,7´dinitrofluorescein di sodium salt, colour index: 45400), chloroform, chlorosulfonic acid,methanol, and dimethylformamide (AR grade) were obtained from S.D fine Chemicals, India, and were used without any further purification. The Characteristics of organic dyes are shown Table 2. Fungal strain Corialusversicalor ((MTCC- 138)wasobtained from microbiology laboratory, Bharathidasan University, Trichy and used for the study. 2.1. Dye Effluent Preparation Dye concentration selected for experiments was 200 mg/L. This value is included in the range of real dye concentration found in textile effluents. Synthetic Quinoline Yellowand Eosin B dye bath effluent used in the present study was prepared according to the composition commonly used in cotton dyeing. In order to dye 0.1kg of fabric, 0.004 kg of dye is used. It is dissolved in 1 L of double distilled water along with the auxiliary chemicals such as 0.003 kg Na2CO3, 1 mL of NaOH 38°Bé (441×10-3 kgm-3 NaOH solution)and0.01kg of NaCl.
  4. 4. International Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976 – 6995(Print), ISSN 0976 – 7002(Online) Volume 4, Issue 2, May - August (2013), © IAEME 24 2.2 Electrochemical process The electric current induces redox reactions resulting in the transformation and destruction of the organic compounds and almost complete oxidation to CO2 and H2O. Table 2: Characteristics of organic dyes The oxidation of pollutants in an electrolytic cell can occur through the following processes: Anodic oxidation: This refers to processes in which an electron transfer reaction of the desired pollutant occurs at the surface of the anode. The electrode reactions involving the degradation of organic compounds are given by Equations 2.1 and 2.2. The potential required for the oxidation of organic compounds is usually high and collateral reactions such as water electrolysis are inevitable. M + H2O→M (HO• ) + H+ + e− (2.1) M (HO• ) + R→M + CO2 + H2O + H+ + e− (2.2) where M is the electrode and R is the organic compound. Cathodic reduction: Electro reduction of textile wastewater with azo dyes was also reported. The reductive cleavage of the azochromogene leads to a decrease in the specific absorbance of the dye without the addition of chemicals or formation of sludge. Indirect oxidation: This process relies on the electrolytic generation of strong oxidising agents. The action of these oxidizing species leads to total or partial decontamination, respectively. When NaCl is used, the electrode reactions to indirect degradation of organic compound proceeds as follows: 2Cl− −→Cl2 + 2e− (2.3) Cl2 + H2O→H+ + Cl− + HOCl (2.4) HOCl→H+ + OCl− (2.5) R + OCl− −→CO2 + H2O + Cl− (2.6) where: R is the organic compound. Name of Dyes Class of dye (ionic type) Mwt gm/gmol Chemical structure ߣߣߣߣmax (nm) Quinoline Yellow Colour Index No.: 47005 Quinoline (anionic) 375.3 C19H11N1Na2O8S2 411 Eosin B (disodium salt) CI Number: 45400 Xanthene (anionic) 580.09 C20H6N2Na2O9Br2 514
  5. 5. International Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976 – 6995(Print), ISSN 0976 – 7002(Online) Volume 4, Issue 2, May - August (2013), © IAEME 25 The main advantages of using these electrochemical methods include that they do not consume a significant amount of chemicals, nor do they produce sludge. Additionally, the processes are commonly performed at room temperature and atmospheric pressure, thus avoiding the undesirable volatilization and discharge of untreated residues. By means of electrochemical oxidation, pollutants in wastewater can be completely mineralised by electrolysis using high oxygen over-voltage anodes such as PbO2 and boron- doped diamond. Polcaro et al. (1999) studied the performance of the Ti/PbO2 anode during electrolysis of 2-cholorophenol in terms of faradic yield and fraction of toxic intermediates removed. 2.3. Membrane Separation Process Membrane-wet oxidation, an integrated process, has been demonstrated by Dhale and Mahajani (2000) to treat the disperse dye bath waste. On the other hand, these techniques do not eliminate definitively the dyes but only separate and concentrate them. The destruction of the concentrated pollutants requires an additional operation as incineration. However, electrochemical processes that use hydroxyl radicals, a very strong oxidant to destroy compound that cannot be oxidized by conventional oxidant. An advanced oxidation method is a result of their high potential. The chain mechanism of oxidation, which involves hydroxyl and hydroperoxide radicals guarantees efficiency and quick rate of the process. The high reactivity and low selectivity of the reaction enable the method to be applied to a large number of organic compounds present in the wastewater. Further advantages include a lack of by-products, which can produce secondary pollution of the environment and thus risk over dosage of the oxidizing agents 2.4. Membrane assisted electrochemical oxidation techniques for degradation of dye effluents Electrochemical oxidation has a high COD removal efficiency (89.8%) of the textile wastewater while membrane filtration can almost totally remove TSS (nearly 100% reduction) and turbidity (98.3% elimination) in it. The traditional single-chamber electrochemical method used in the wastewater treatment mainly focuses on anodic oxidation, but hydrogen is produced on the cathode, which also consumes much energy, is often ignored. The simultaneous production of evolved hydrogen at a cathode as a byproduct, along with high power requirements is the main disadvantage for electro- oxidation of organics. In this work, an innovative two-chamber electrolytic cell, connected with an anion exchange membrane, was developed. In this new reactor, indirect oxidation at anode, indirect oxidation by hydrogen peroxide and UV/H2O2 at cathode can occur simultaneously. Therefore “dual electrodes oxidation” in one electrochemical reactor was achieved successfully. Compared to a traditional one cell reactor, this reactor considerably reduces the energy cost by 25–40%, and thus the present work becomes significant in wastewater treatment for dye effluents. Electrochemical oxidation of dye solution was carried out in electrochemical cell. Anode and cathode were Fisher platinum electrodes. The volume of solution to be treated was 400 mL and the effective electrode area was 25 cm2 . The homogeneous nature of the medium during the electrolysis was maintained using magnetic stirring. The electrolysis cell used in the present study consists of a glass beaker of 500 ml capacity closed with a PVC lid having provision to fit a cathode and an anode (surface area of the electrode19.5 cm2 ). Anode was ruthenium coated on titanium metal (RuOx–TiOx) (expanded mesh type) and cathode
  6. 6. International Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976 6995(Print), ISSN 0976 – 7002(Online) Volume 4, Issue 2, May was stainless steelplate. The current was supplied by multi source (with ammeter and voltmeter). Figure 1: Schematic diagram of electrochemical reactor employed for dye degradation Schematic diagram of electrochemical reactor in Figure 1. Electrochemical reactor was made of PTFE and divided into an anode compartment (AC) and cathode compartment (CC) by PEM (8.0×10 pumps were used to move each stream, while an adjustable dc power supply (model L 1285, Aplab, Mumbai, India) was used to apply constant potential gradient. NaOH concentration in the CC was also monitored regularly. In all cases, equal v study the feasibility of the separation process. Build determined by acid-base titration using phenolphathalein indicator. were analyzed by UV-Vis spectrometry at m calibration curve (Figure1) and dyes removal was obtained following equation Dyes removal (%) = 1- 2.5. Preparation of Polymer Electrolyte Membrane 2.5.1. Preparation of sulfonated poly Polyethersulfone (Gadone TM 3400 was sulfonated as per the procedure developed by Chen et al., (1996). Poly ether sulfone 40g was dissolved in 1,2 the solution at a temperature of 85 and 5 ml of chlorosulfonic acid was added drop wise to the solution for about 15 minutes. This reaction mixture was maintained at 4 sulfone obtained was precipitated dried in vacuum for 1-2 h at 40°C. al Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976 7002(Online) Volume 4, Issue 2, May - August (2013), © IAEME 26 inless steelplate. The current was supplied by multi-output 2 A and 30 V, DC power source (with ammeter and voltmeter). Schematic diagram of electrochemical reactor employed for dye degradation Schematic diagram of electrochemical reactor employed for dye degradation is depicted in Figure 1. Electrochemical reactor was made of PTFE and divided into an anode compartment (AC) and cathode compartment (CC) by PEM (8.0×10-3 m2 ). Two peristaltic pumps were used to move each stream, while an adjustable dc power supply (model L 1285, Aplab, Mumbai, India) was used to apply constant potential gradient. NaOH concentration in the CC was also monitored regularly. In all cases, equal volumes of AC and CC were taken to study the feasibility of the separation process. Build-up of NaOH concentration in CC was base titration using phenolphathalein indicator. The dye concentrations Vis spectrometry at maximum wavelength (λmax = 517 nm) using calibration curve (Figure1) and dyes removal was obtained following equation (C1/C0) × 100 Preparation of Polymer Electrolyte Membrane Preparation of sulfonated poly (ether sulfone) Polyethersulfone (Gadone TM 3400 was sulfonated as per the procedure developed by Chen et al., (1996). Poly ether sulfone 40g was dissolved in 1,2-dichloroethane by heating the solution at a temperature of 85°C ± 5°C, for 2-3 h. The solution was then cooled to 4 and 5 ml of chlorosulfonic acid was added drop wise to the solution for about 15 minutes. This reaction mixture was maintained at 4°C for 2 h. The solid sodium salt of sulfonated poly ether sulfone obtained was precipitated in ice cold water followed by treatment with methanol and C. al Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976 – August (2013), © IAEME output 2 A and 30 V, DC power Schematic diagram of electrochemical reactor employed for dye degradation employed for dye degradation is depicted in Figure 1. Electrochemical reactor was made of PTFE and divided into an anode ). Two peristaltic pumps were used to move each stream, while an adjustable dc power supply (model L 1285, Aplab, Mumbai, India) was used to apply constant potential gradient. NaOH concentration in olumes of AC and CC were taken to up of NaOH concentration in CC was The dye concentrations max = 517 nm) using (4.1) Polyethersulfone (Gadone TM 3400 was sulfonated as per the procedure developed dichloroethane by heating solution was then cooled to 4°C and 5 ml of chlorosulfonic acid was added drop wise to the solution for about 15 minutes. This C for 2 h. The solid sodium salt of sulfonated poly ether in ice cold water followed by treatment with methanol and
  7. 7. International Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976 – 6995(Print), ISSN 0976 – 7002(Online) Volume 4, Issue 2, May - August (2013), © IAEME 27 Figure 2: Sulfonation process sequence 2.6. Membrane Formulations The polymers of SPSf, SPES and SPEEK were prepared by individually at 17.5 wt% in presence polar solvent, DMF (82.5 wt%), under constant mechanical stirring in a round bottom flask for 3 h at 40°C. The homogeneous solution was allowed to stand for 1 h in airtight condition to get rid off the air bubbles. The compositions and casting conditions of PEM membranes is displayed in Table 3. 2.6.1.Preparation of Membranes All membranes were prepared by the “diffusion induced phase separation” method, namely, casting a thin film of the polymeric solution on a glass plate and, after allowing the solvent to evaporate for a predetermined period at the desired humidity and temperature conditions, immersing it into a bath of non-solvent (water, solvent, surfactant) for final precipitation. Prior to membrane casting, a gelation bath of 2L of distilled water (non-solvent), containing 2% DMF (Solvent) and 0.2% SLS (Surfactant) was prepared and cooled to 10°C. Table 3: Compositions and casting conditions of PEM membranes Name of Polymer Polymer composition (%) Solvent, DMF (%) SPSf 17.5 82.5 SPEEK 17.5 82.5 SPES 17.5 82.5 Nafion® 117 - - Total weight percentage of polymer = 17.5 wt %. Casting solution temperature = 85 ± 2°C, Casting temperature = 34 ± 2°C Casting relative humidity = 20 ± 2 %, Solvent evaporation time = 30 s. Poly Sulfone +Chloroform (PSU) Dissolved + Sulfonating agent PSU (TMSCS) Sulfonating Polysulfone (PSU) Silylsulfonate PSU + Sodium methoxide [A] [C] [B] [A] = reaction at ambient temperature [B] = continuous stirring for 24 h [C] = stir for 1 hour, then added drop wise into methanol bath (TMSCS) = trimethylsilylchlorosulfonate Note: The solution were contiuously stirred under N2 atmosphere during the
  8. 8. International Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976 – 6995(Print), ISSN 0976 – 7002(Online) Volume 4, Issue 2, May - August (2013), © IAEME 28 Figure 3. PEM membranes 2.6.2. Membrane properties and stability The sulfonated sample was characterized for functional group determination by FT-IR Spectroscopy. FT-IR spectra were recorded on a Perkin-Elmer, model-Spectrum RX1 Fourier transform spectrometer either with powder samples inside a diamond cell or by using KBr pellets composed of 50 mg of IR spectroscopic grade KBr and 1mg polymer sample. 2.7. Estimation of water content, ion-exchange capacity (IEC) and counter-ion transport number Membrane thickness was measured by a digital micrometer with 0.1 µm accuracy. The membrane water content was determined by weight of membrane in wet and dry conditions. Membrane was dried in vacuum oven at 60 °C for 24 h and recorded its weight. Further the dry membrane was kept in distilled water for same period of time and their wet weight was recorded. The water content was finally calculated using the following equation: (4.2) Where Ww and Wdare the weight of the wet and dry membrane, respectively. For the estimation of ion exchange capacity (IEC), desired pieces of ion-exchange membranes were conditioned in 1.0 M HCl solution for 12 h to convert them into H+ form. The excess HCl was removed by washing with distilled water. The membranes were then equilibrated in 50 ml of 0.5 M NaCl solution. The amount of H+ ions liberated from SPS membrane was determined by acid–base titration. Nafion® 117 SPSf SPEEKSPES
  9. 9. International Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976 – 6995(Print), ISSN 0976 – 7002(Online) Volume 4, Issue 2, May - August (2013), © IAEME 29 Counter-ion transport number across the membranes was estimated by membrane potential measurement in 0.01 and 0.10 M NaCl solutions, according to equation 4.3 reported previously using TMS (Teorell, Meyer, and Sievers) approach. ‫ܧ‬௠ ൌ ሺ2‫ݐ‬௜ ௠ െ 1ሻ ோ் ி ݈݊ ௔భ ௔మ (4.3) Where a1 and a2 are the activities of electrolyte solutions contacting two surfaces of the membrane, R is the gas constant, T is the absolute temperature, and F is the Faraday constant. 2.8. Membrane conductivity The membrane conductivities were recorded in equilibrium with eosin and NaCl solution of different concentrations. The specific membrane conductivity (κm ) was estimated by: ‫ܭ‬௠ ൌ ∆௫ ஺ோ೘ (4.4) Where ∆x is the thickness of equilibrated membrane, A is the membrane area. 2.9. Analytical methods 2.9.1. Chemical Oxygen Demand(COD) In order to determine the extent of degradation of the effluent Chemical Oxygen Demand (COD) was measured. The COD as the name implies is the oxygen requirement of a sample for oxidation of organic and inorganic matter. COD is generally considered as the oxygen equivalent of the amount of organic matter oxidizable by potassium dichromate. The organic matter of the sample is oxidized with a known excess of potassium dichromate in a 50% sulfuric acid solution. The excess dichromate is titrated with a standard solution of ferrous ammonium sulfate. COD of all samples were determined by the dichromate closed reflux method using thermo reactor TR620-Merck.In COD measurement, 3 samples are subjected to analysis for one COD data. From that, any two same values or the average of any two nearer values is considered as the measured data. 2.9.2. Spectral analysis using UV-visible spectrophotometer For UV-Visible spectral analysis, 5 mL of treated and untreated samples were taken and centrifuged at 12,000 rpm for 10 min. The supernatant of untreated and treated samples were analyzed by monitoring the changes in its absorption spectrum using UV–visible spectrophotometer with a cell having 1 cm optical path length. 3. RESULTS AND DISCUSSION 3.1. Characterization of sulfonated poly (ether sulfone) FTIR spectra were also used to confirm the pendant SO3H group on the polymer chain. Figure 4 shows the spectra of SPES. The presence of the sulfonic group can be visualized by the presence of the absorption bands. On the spectra of SPES, the new absorbance at 1020 cm-1 and 1250 cm-1 are contributed separately by symmetric and asymmetric O=S=O vibration. The peak at the peak at 1770 cm-1 to the ester cardo group of sulfonated poly (ether sulfone).It has been known that the asymmetrical stretching vibrations
  10. 10. International Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976 6995(Print), ISSN 0976 – 7002(Online) Volume 4, Issue 2, May of sulfonic acid groups appear at overlapping absorbance. However, it still can getconclusion that the sulfonic acid groups has been introduced into the polymer chains Figure Table 4: Physicochemical and electrochemical properties Property Thickness (µm) Water content (%) Ion-exchange capacity (mequiv./g of dry membrane) Counter ion transport number Membrane conductivityb (mScm a (tm) was estimated from membrane potential measurements in solutions of 0.1M and 0.01M concentrations. b Membrane conductivity was measured in equilibration with 1.0MNaCl solution al Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976 7002(Online) Volume 4, Issue 2, May - August (2013), © IAEME 30 of sulfonic acid groups appear at ∼1180 cm−1 , but we could not readily observe it due to near overlapping absorbance. However, it still can getconclusion that the sulfonic acid groups has ntroduced into the polymer chains Figure 4. The spectra of SPES Physicochemical and electrochemical properties of the cation exchange membrane SPSf SPES Nafion® 117 150 150 150 12 23 38 (mequiv./g of dry membrane) 1.40 0.80 0.90 Counter ion transport numbera (tm) 0.94 0.99 1.05 (mScm−1 ) 20.2 41.4 94.6 (tm) was estimated from membrane potential measurements in equilibrium with NaCl solutions of 0.1M and 0.01M concentrations. Membrane conductivity was measured in equilibration with 1.0MNaCl solution al Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976 – August (2013), © IAEME , but we could not readily observe it due to near overlapping absorbance. However, it still can getconclusion that the sulfonic acid groups has of the cation exchange membrane SPEEK 150 35 1.10 0.98 99.5 equilibrium with NaCl Membrane conductivity was measured in equilibration with 1.0MNaCl solution
  11. 11. International Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976 – 6995(Print), ISSN 0976 – 7002(Online) Volume 4, Issue 2, May - August (2013), © IAEME 31 For EMR, knowledge on membrane conductivity in equilibration with actual operating conditions is an essential parameter. Membrane conductivity data (km) for SPS membrane inequilibration with eosin B and NaCl solutions of different concentrations (10- 100 ppm) is presented in Figure 5. km values depended on ionic strength of equilibrating solution, and increased initially with concentration (eosin B and NaCl) before attending limiting value (beyond 30 ppm). This observation may be attributed to comparatively low dissociation and ionic strength of eosin B solution. However, comparable membrane conductivities under both operating conditions (eosin B or NaCl) revealed the membrane suitability for an EMR. Figure 5. Membrane potential measurements in equilibrium 3.2. Membrane Morphology The top face shows non-uniformaggregates that might have formed due to solvent removal fromthe top as mentioned earlier and the bottom face appears smooth. Dense membranes with reproducible thickness could beobtained by using a sufficient quantity of polymer solution.The pore structure of the PEM membranes were sensitively changed for SPSf, SPES, SPEEK and Nafion membranes (Figure 6). The average pore size of SPES membrane clearly increased with respective IEC. In this comparison of morphology, dyes mass transport driving forcesknown for flows of dye molecules through microporous, diffusion driven by activity gradients, migrationof protons in the electric field, pressure- driven convective flow, and electro-osmotic flow of uncharged species, dueto forces exerted on them by the migrating protons. Therefore it is necessary to analyse morphology of membranes for dyes transport mechanisms 0 1 2 3 4 5 6 Nacl Eosin B Rose bengal Km(mScm-1)
  12. 12. International Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976 6995(Print), ISSN 0976 – 7002(Online) Volume 4, Issue 2, May SPSf Membrane SPEEK Membrane Figure 6. 3.3. Chlorine tolerant of SPS, SPES and SPEEK and Nafion® 117 membranes The chlorine tolerant nature of prepared SPS, SPES and SPEEK membrane was assessed in comparison with Nafion® 117 membrane in terms of percentage in weight loss and IEC loss for definite time intervals. Formation of oxy radicals during electrochemical water splitting in the presence of halide ion occurred AC, which may attack on hydrogen containing bonds of PEM. Thus, developed PEM should be highly chlorine tolerant in nature. Resultant image are presented in Figure It is obvious that prepared membranes after 24 h treatment when compared with Nafion® 117 membrane. Progressively, loss in IEC and weight attained limiting values. Furthermore, for SPEEK membrane, weight loss was slightly higher than Nafion® 117 membra loss. al Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976 7002(Online) Volume 4, Issue 2, May - August (2013), © IAEME 32 SPSf Membrane SPES Membrane SPEEK Membrane Nafion Membrane 6. SEM image of all PEM membranes hlorine tolerant of SPS, SPES and SPEEK and Nafion® 117 membranes The chlorine tolerant nature of prepared SPS, SPES and SPEEK membrane was assessed in comparison with Nafion® 117 membrane in terms of percentage in weight loss and IEC loss for definite time intervals. Formation of oxy radicals during electrochemical r splitting in the presence of halide ion occurred AC, which may attack on hydrogen containing bonds of PEM. Thus, developed PEM should be highly chlorine tolerant in nature. Resultant image are presented in Figure 7. It is obvious that prepared membranes (SPS, SPES and SPEEK) lost about 5 after 24 h treatment when compared with Nafion® 117 membrane. Progressively, loss in IEC and weight attained limiting values. Furthermore, for SPEEK membrane, weight loss was slightly higher than Nafion® 117 membrane, while latter showed comparatively high IEC al Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976 – August (2013), © IAEME hlorine tolerant of SPS, SPES and SPEEK and Nafion® 117 membranes The chlorine tolerant nature of prepared SPS, SPES and SPEEK membrane was assessed in comparison with Nafion® 117 membrane in terms of percentage in weight loss and IEC loss for definite time intervals. Formation of oxy radicals during electrochemical r splitting in the presence of halide ion occurred AC, which may attack on hydrogen containing bonds of PEM. Thus, developed PEM should be highly chlorine tolerant in nature. (SPS, SPES and SPEEK) lost about 5-6% IEC after 24 h treatment when compared with Nafion® 117 membrane. Progressively, loss in IEC and weight attained limiting values. Furthermore, for SPEEK membrane, weight loss was ne, while latter showed comparatively high IEC
  13. 13. International Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976 – 6995(Print), ISSN 0976 – 7002(Online) Volume 4, Issue 2, May - August (2013), © IAEME 33 Figure 7. Comparison of percentage loss in weight for SPS, SPES and SPEEK and Nafion® 117 membranes The membrane degradation occurred chemically as a result of oxy-chloride free radical (•OCl) attack on the polymer chain in the vicinity of hydrophilic domains. IEC is measure of functional group concentration in the membrane matrix, and high for SPS membrane (1.40 mequiv./g) in comparison with membrane Table 4. Thus, because of more hydrophilic nature of SPS membrane than other three membranes, IEC loss was comparatively high under chlorine stability test (Figure 8). Moreover, chlorine tolerant nature for all (SPS, SPES and SPEEK and Nafion® 117) was same and these membranes showed their potential applications under chlorine environment. Figure 8. Comparison of IEC for SPS, SPES and SPEEK and Nafion® 117 membranes 0 1 2 3 4 5 6 7 8 9 0 10 20 30 40 50 60 70 80 90 100 110 %Weightloss Time allowed for NaoCl treatment (h) SPSf SPES Nafion SPEEK 0 1 2 3 4 5 6 7 8 0 10 20 30 40 50 60 70 80 90 100 110 %IECloss Time allowed for NaoCl treatment (h) SPSf SPES Nafion SPEEK
  14. 14. International Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976 6995(Print), ISSN 0976 – 7002(Online) Volume 4, Issue 2, May This result means that SPEEK membrane is highly chlorine other PEM membranes. In addition, there is no degradation moiety in this polymerbackbone which is composed ketone and ether linkage,unlike poly(ether sulfone) backbone structu which consists of thebenzene ring, ether and sulfone linkage (Figure theall membranes under5% aq. NaOClsolution, time requirement with the weight loss increased, whichmeans that the potassium ion was exchanged with sodium ionun solution. Figure 9. Comparison of percentage loss in weight for SPS, SPES and SPEEK and However, for SPEEK membranes the overall values reduced after the chlorine treatment. On the contrary, commercial Nafionmembrane 5% aq. NaOCl solution at 80◦ C for different time intervalswas lesser when compared with SPES and SPSf respectively, after exposure to NaOCl solution. The IEC loss of membraneswas main factor to measure hydrophilicity on t of membranes. The increase of the IEC loss with time of NaoCl treatment shown in Figure .The increase of hydrophilicity may correspondto % of IEC loss of membranes, which indicates that theNafionmembrane is unstable under the chlorine condition at solution at 80◦ Cas reported in other literatures.However, the % of IEC loss of SPS membranes exhibit change after the treatment under wild acidic condition. From Figure data give quite reliable informationon the hydrophobic/hydrophilic separation in the amorphouspart of the ionomer. The typical dye separation and distributionis read from % of IEC loss of membranes andits dependenton the water volume fraction 3.4.Investigations on membrane electrochemical properties 3.4.1 Electro-membrane reactor with PEM for separation dye solution The physicochemical and electrochemical investigation arepresented in Table exchange capacity, and counter specific membraneconductivity. Furthermore, comparable with the best-known ion al Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976 7002(Online) Volume 4, Issue 2, May - August (2013), © IAEME 34 This result means that SPEEK membrane is highly chlorine-resistant membrane than other PEM membranes. In addition, there is no degradation moiety in this polymerbackbone which is composed ketone and ether linkage,unlike poly(ether sulfone) backbone structu which consists of thebenzene ring, ether and sulfone linkage (Figure 9).After the treatment of theall membranes under5% aq. NaOClsolution, time requirement with the weight loss increased, whichmeans that the potassium ion was exchanged with sodium ionun Comparison of percentage loss in weight for SPS, SPES and SPEEK and Nafion® 117 membranes However, for SPEEK membranes the overall values reduced after the chlorine treatment. On the contrary, commercial Nafionmembrane displays the chlorine resistant at C for different time intervalswas lesser when compared with SPES and SPSf respectively, after exposure to NaOCl solution. The IEC loss of membraneswas main factor to measure hydrophilicity on t of membranes. The increase of the IEC loss with time of NaoCl treatment shown in Figure .The increase of hydrophilicity may correspondto % of IEC loss of membranes, which indicates that theNafionmembrane is unstable under the chlorine condition at 5% aq. NaOCl as reported in other literatures.However, the % of IEC loss of SPS membranes exhibit change after the treatment under wild acidic condition. From Figure data give quite reliable informationon the hydrophobic/hydrophilic separation in the amorphouspart of the ionomer. The typical dye separation and distributionis read from % of IEC loss of membranes andits dependenton the water volume fraction Investigations on membrane electrochemical properties membrane reactor with PEM for separation dye solution The physicochemical and electrochemical properties of PEM prepared and used in the Table 4. All membranes exhibited good watercontent, ion exchange capacity, and counter-ion transportnumbers in the membrane phase and high specific membraneconductivity. Furthermore, all properties of these membranesare known ion-exchange membranein the world.The chemical (chlorine al Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976 – August (2013), © IAEME resistant membrane than other PEM membranes. In addition, there is no degradation moiety in this polymerbackbone which is composed ketone and ether linkage,unlike poly(ether sulfone) backbone structure ).After the treatment of theall membranes under5% aq. NaOClsolution, time requirement with the weight loss increased, whichmeans that the potassium ion was exchanged with sodium ionunder NaOCl Comparison of percentage loss in weight for SPS, SPES and SPEEK and However, for SPEEK membranes the overall values reduced after the chlorine displays the chlorine resistant at C for different time intervalswas lesser when compared with The IEC loss of membraneswas main factor to measure hydrophilicity on the surface of membranes. The increase of the IEC loss with time of NaoCl treatment shown in Figure 9 .The increase of hydrophilicity may correspondto % of IEC loss of membranes, which 5% aq. NaOCl as reported in other literatures.However, the % of IEC loss of SPSf membranes exhibit change after the treatment under wild acidic condition. From Figure 9, data give quite reliable informationon the hydrophobic/hydrophilic separation in the amorphouspart of the ionomer. The typical dye separation and distributionis readily obtained from % of IEC loss of membranes andits dependenton the water volume fraction properties of PEM prepared and used in the . All membranes exhibited good watercontent, ion- ion transportnumbers in the membrane phase and high all properties of these membranesare exchange membranein the world.The chemical (chlorine
  15. 15. International Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976 – 6995(Print), ISSN 0976 – 7002(Online) Volume 4, Issue 2, May - August (2013), © IAEME 35 resistance) stabilities of these membranes are attractive features for theirapplicability in the electro-membrane processes. For developingelectrochemical membrane reactor, knowledge on membraneconductivity in equilibration with actual operating conditionsis an essential parameter. Most dye contains NaCl as the major constituent, thus electrochemicaldegradation is easy in absence of supporting electrolytes. Principle of EMR used for dye degradation wasbased on electro-membrane electrodialysis as presented in Figure 10.Generally, dye molecule is electrochemically inactive andanode changes occurred because oxidation of water/Cl− to O2/Cl2.Chlorine gas is robust oxidizing agent and dissolves in water (HOCl),which is instable in acidic solution (pKa = 7.4). HOClimmediatelydissociates and formation of OCl− is responsible for dye degradation.Thus, basic or neural pH conditions are more favorable for dyedegradation. Figure 10. Cyclic voltammetric responses of 0.1M NaCl: Scan rate in all cases was 50mVs−1 The above diagram describes the basic electrochemical principles by which Electrosep's cell works. As the stream to be treated passes through the anolyte chamber, sodium (Na+) ions are transferred through the membrane to the catholyte chamber to combine with available hydroxyl (OH-) ions and produce caustic (sodium hydroxide). Organics are oxidized or acidified at the anode, allowing them to be removed from the treated stream. Hydrogen gas (H2) is liberated at the cathode, and may be recovered for fuel.pH of the solution was monitored by using a digit al desktop,pH Meter (CP901) from Century Instrument Company and pH was adjusted with the help of 0.1MNaOH and 0.1M HCl batch mode. Constant stirring of the solution was ensured using magnetic stirrers. In AC, eosin B degraded in AC by chloride/hypochlorite mediatedoxidation. Degradation was effected by O2/OCl− generationat anode, and migration H+ /Na+ from AC through SPS membrane(CEM) towards cathode. This leads formation of NaOH in CC usingOH− formed due to reductive water splitting Moreover,eosin B degradation process depends on the initial eosin B dyeconcentration and oxidizing strength of anode (active species concentration).Electro- active species produced at electrodes exhibited peaktyperesponses in cyclic voltammetry because exchange of electronduring anodic- and cathodic-potential scans. -20 -17.5 -15 -12.5 -10 -7.5 -5 -2.5 0 2.5 5 7.5 10 12.5 15 -1.5 -1 -0.5 0 0.5 1 1.5 I/A E/V vs SCE with addition of dye solution Without dye solution
  16. 16. International Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976 – 6995(Print), ISSN 0976 – 7002(Online) Volume 4, Issue 2, May - August (2013), © IAEME 36 40 50 60 70 80 90 100 20 40 60 80 100 120 140 160 180 QuinolineYellowdyeremoval (%) Time (min) 100 ppm 50 ppm 30 ppm 10 ppm 3.5. Effect of operating conditions on Quinoline Yellowdegradation in EMR Rate of dye degradation was affected applied potential, dye concentration and feed of flow rate. Variation of Quinoline Yellow removal under different applied potential are presented in Figure 11 for 50 ppm Quinoline Yellow in feed at 40 ml/min. Quinoline Yellowconcentration was monitored by absorbance spectra before and after degradation at 411 nm band. With time and applied potential, dye removal was enhanced during electrolysis. About 95% Quinoline Yellowdegradation was achieved for it 50 ppm concentration in AC (40 ml/min flow rate) after 180 min electrochemical treatment at 12.0V applied potential. Figure 11. Variation of Quinoline Yellow removal under different applied potentials Figure12. Rate of change of dye concentration was relatively fast at high concentration under similar experimental conditions 70 75 80 85 90 95 100 25 45 65 85 105 125 145 165 185 QuinolineYellowdyeremoval(%) Time (min) 12V 10V 8V
  17. 17. International Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976 – 6995(Print), ISSN 0976 – 7002(Online) Volume 4, Issue 2, May - August (2013), © IAEME 37 40 50 60 70 80 90 100 20 40 60 80 100 120 140 160 180 QuinolineYellowdyedyeremoval(%) Time (min) 100 ppm 50 ppm 30 ppm 10 ppm Rate ofchange of dye concentration was relatively fast at high concentrationunder similar experimental conditions. It revealed about95% degradation of eosin B (40 ml/min flow rate) after 180 min at12.0 V. From Figure12, It is observed for the minimum dye concentration (100 ppm) when reduced color in EMR using SPEEK membrane for the maximum time of 180 min. When the highest dye concentration (100 ppm) was observed SPEEK membrane for time 30 min, only 66.5% of Quinoline Yellowdye removal in the dye concentration was detected in the samples. The effects of reaction time and dye concentration were significant at the 180 min. The interaction between the dye concentration and reaction time was significant in the removal ofQuinoline Yellowdye (Figure 13).These results also showed that removal efficiency SPEEK membrane at all the concentration levels. Similarly, all the times were also significantly different from each other at the different concentration.Figure 14 showed influence of time on concentration of Quinoline Yellowduring oxidative degradation of eosin. These data revealedthat high applied potential, dye concentration and low feed flowrate are required for fast and efficient degradation process. Figure 13. The interaction between the dye concentration and reaction time was significant in the removal ofQuinoline Yellowdye Further,these parameters also depended on EMR flow pattern andmembrane as well as electrode area. Thus complete optimizationof these parameters is essential for an efficient process.
  18. 18. International Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976 – 6995(Print), ISSN 0976 – 7002(Online) Volume 4, Issue 2, May - August (2013), © IAEME 38 Figure 14. Influence of feed flow rate or turbulence (AC) during oxidative degradation of eosin Under optimumconditions about 95–98% degradation was observed during180 min, which can be further enhanced with increase in appliedpotential or membrane area.The dye removal percentages when the dye was treated with 25 ml/min was higher than that observed when 50 ml/min and 75 ml/minusing SPEEK membrane. A maximum dye removal efficiency of 97% was obtained after 180 min of time. Figure 15. Effect of operating conditions on Eosin B degradation in EMR 70 75 80 85 90 95 100 25 45 65 85 105 125 145 165 185 QuinolineYellowdyeremoval(%) Time (min) 25 ml/min 50 ml/min 75 ml/min 65 70 75 80 85 90 95 100 25 45 65 85 105 125 145 165 185 EosinBdyeremoval(%) Time (min) 12V 10V 8V
  19. 19. International Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976 – 6995(Print), ISSN 0976 – 7002(Online) Volume 4, Issue 2, May - August (2013), © IAEME 39 3.6. Effect of operating conditions on Eosin B degradation in EMR The result of the Eosin Bdye color removal on time for electro membrane oxidation is shown in Figure 15. The final color removal ratio at 10V isabout 88 % which is higher than that at 8V. If the potential was up to 12V, the color was increased 95%,which was about 2 times of that at 8 V.Furtherincrease in the potential leads to increase in the color removalto95%. The result is consistent with the quasi-steadystatecurves on EMR for the Eosin B dye solution. It was supposed thatthe functional group on SO3-H underwent some reactionswhen polarized at a certain potential and could enhance the degradation for electro membrane. Figure 16. The influence of concentration of the Eosin Bdye solution The pollutant concentration is very important parameter in wastewater treatment. The influence of concentration of the Eosin Bdyesolution has been investigated on the electro membrane degradation with SPEEK membrane after the optimization of pH. In order to optimize the % removal the initial dye concentrations was varied during the EMR treatment from 10 to 100 ppm, at constant pH of 4.0. It has been observed from the graph Figure 16 that increasing concentration of dye solution from 10 to 100 ppm decreases the percentage Eosin Bdyeremoval and it was found that at 10 ppm dye concentration, % removal was 43% and at 100 ppm dye concentration, percentage removal was increased to 76%. The reason behind this behavior may be due to the increase in the extent of pore size, permeation and mass transfer through membranes at necessary dye concentration which increases the migration of dye. The increases in the dye concentration also increase the transfer ions form dye solution in to respective poles. 40 50 60 70 80 90 100 20 40 60 80 100 120 140 160 180 EosinBdyeremoval(%) Time (min) 100 ppm 50 ppm 30 ppm 10 ppm
  20. 20. International Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976 – 6995(Print), ISSN 0976 – 7002(Online) Volume 4, Issue 2, May - August (2013), © IAEME 40 Figure17. Effect of timefor various concentrations of eosin dye Experiment carried out at different contact times for various concentrations of eosin dye showed that the percentage removal increases rapidly with increasing contact time for the first 60 min (Figure17). With increase in reaction time, the external mass transfer coefficient increases, resulting in movement of eosin dye molecules through membrane. However, the membrane morphology was affecting the transfer of eosin dye molecules. At 75ml/min, the highest % removal of eosin dye was observed, hence an indication of the influence of molecular weight of eosin dye. The percentage of eosin dye removal influenced the chemistry of both the eosin dye molecule and dipoles in aqueous solutions. Eosin is a dipolar molecule and chemical structure at low pH, as shown in Figure 17. PEM contains oxygen donor sites on its surface, e.g. hydroxyl groups and sulfonic groups. CONCLUSION Membrane assisted electro chemical degradation (MAEO) process showed 97% degradation of eosin B against 92% CEand 4.97 kWh/kg of eosin B removed energy consumption, with SPES, SPSf, SPEEK membranes. While for Nafion® 117showed 76.6% CE and 3.94 kWh/kgof eosin B removed energy consumption for same extent of eosin B degradation (97%) under optimum operating conditions. Depending on polymer stabilities and properties, SPEEK membrane also can be tailored for specific separation purposes by electro dialysis, because of its high chlorine tolerance, stabilities, conductivity and counter- ion transport number. The studies presented using MAEO exhibit that the removal of Rose Bengal from its aqueous solutions can be efficiently achieved through SPES, SPSf, SPEEK. It was also found that increase in reaction time, the external mass transfer coefficient increases, resulting in movement of Rose Bengal dye molecules through membrane. However, the membrane morphology was affecting the transfer of Rose Bengal dye molecules. The percentage of Rose Bengal dye removal influenced the chemistry of both the Rose Bengal dye molecule and dipoles in aqueous solutions. 70 75 80 85 90 95 100 25 45 65 85 105 125 145 165 185 EosinBdyeremoval(%) Time (min) 25 ml/min 50 ml/min 75 ml/min
  21. 21. International Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976 – 6995(Print), ISSN 0976 – 7002(Online) Volume 4, Issue 2, May - August (2013), © IAEME 41 REFERENCES 1. Joseph Egli Italia srl (2007). Wastewater treatment in the textile industry. Dyeing Printing Finishing 10(2007) 60-66. 2. Robinson T, McMullan G, Marchant R, and Nigam P. 2001. Remediation of dyes in textile effluent: a critical review on current treatment technologies with a proposed alternative. Bioresour Technol77: 247-55 3. Aksu Z. 2005. Application of biosorption for the removal of organic pollutants: a review. Process Biochemistry 40: 997-1026. 4. Van der Zee FP. 2002. Anaerobic azo dye reduction: Wageningen University. 5. Ciardelli G, Corsi L, and Marcucci M. 2000. Membrane separation for wastewater reuse in the textile industry. Resources, Conservation and Recycling 31: 189-197. 6. Marcucci M., G. Ciardelli, A. Mateucci, L. Ranieri, M. Russo, Experimental campaigns on textile wastewater for reuse by means of different membranes processes, Desalination 149 (2002) 137–143. 7. Sharma S., R. Ameta, R. K. Malkani, S. C. Ameta, Maced. J. Chem. Chem. Eng. 30 (2011) 229 8. Lunn G, Sansone EB. Decontamination of aqueous solutions of biological stains. Biotech Histochem 1991;66:307– 15 9. Purkait M.K., S.D. Gupta, S. De, Adsorption of eosin dye on activated carbon and its surfactant based desorption, J. Environ. Manage. 76 (2005) 135–142. 10. Karacakaya, P.; Kilic, N.K.; Duygua, E.; Donmez, G. Stimulation of reactive dye removal by cyanobacteria in media containing triacontanol hormone. J. Hazard. Mater. 2009, 172, 1635-1639. 11. Ho YS, McKay G (1999) Pseudo-second order model for sorption processes. Process Biochem 34:451–465. 12. Levenspiel O (2002) Modeling in chemical engineering. ChemEngSci 57:4691–4696, 13. Gonzo EE, Gonzo LE (2005) Kinetics of phenol removal from aqueous solution by adsorption onto peanut shell acid-activated carbon. AdsorptSciTechnol 23:289–301 14. POLCARO AM, PALMAS S, RENOLDI F and MASCIA M (1999) On the performance of Ti/SnO sub(2) and Ti/PbO sub(2) anodes in electrochemical degradation of 2- chlorophenol for wastewater treatment. J. Appl. Electrochem. 29 (2) 147-151. 15. Dhale AD and Mahajani VV (2000) Studies in treatment of disperse dye waste: membrane-wet oxidation process. Waste Manage. 20. 16. V.C.Padmanaban, Soumya.S.Prakash, Sherildas P, John Paul Jacob and Kishore Nelliparambil, “Biodegradation of Anthraquinone Based Compounds: Review”, International Journal of Advanced Research in Engineering & Technology (IJARET), Volume 4, Issue 4, 2013, pp. 74 - 83, ISSN Print: 0976-6480, ISSN Online: 0976-6499. 17. Syed Abdul Moiz and Ahmed M. Nahhas, “Temperature Dependent Electrical Response of Orange-Dye Complex Based Schottky Diode”, International Journal of Electronics and Communication Engineering & Technology (IJECET), Volume 4, Issue 2, 2013, pp. 269 - 279, ISSN Print: 0976- 6464, ISSN Online: 0976 –6472. 18. Kh. EL-Nagar and Mamdouh Halawa, “Effect of Mordant Types on Electrical Measurements of Cotton Fabric Dyed with Onion Scale Natural Dye”, International Journal of Electrical Engineering & Technology (IJEET), Volume 3, Issue 2, 2012, pp. 192 - 203, ISSN Print : 0976-6545, ISSN Online: 0976-6553. 19. B. J. Agarwal, “Eco-Friendly Dyeing of Viscose Fabric with Reactive Dyes”, International Journal of Advanced Research in Engineering & Technology (IJARET), Volume 1, Issue 1, 2010, pp. 25 - 37, ISSN Print: 0976-6480, ISSN Online: 0976-6499.

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