Journal of Environmental Chemical Engineering 1 (2013) 975–980 Contents lists available at ScienceDirect Journal of Environmental Chemical Engineering journal homepage: www.elsevier.com/locate/jece Degradation of textile dye C.I. Vat Black 27 by electrochemical method by using carbon electrodes Prakash Kariyajjanavar a,*, J. Narayana a, Y. Arthoba Nayaka b a b Department of P.G. Studies & Research in Environmental Science, Kuvempu University, Jnana Sahyadri, Shankaraghatta, 577 451 Karnataka, India Department of P.G. Studies & Research in Chemistry, Kuvempu University, Jnana Sahyadri, Shankaraghatta, 577 451 Karnataka, India A R T I C L E I N F O A B S T R A C T Article history: Received 18 April 2013 Received in revised form 2 August 2013 Accepted 4 August 2013 The electrochemical degradation of industrial wastewater has become an attractive method in recent years. In this work simulated dye wastewater containing vat dye C.I. Vat Black 27 is degraded from electrochemical method using graphite carbon electrodes. The experimental results indicated that initial pH, current density and supporting electrolytes were played an important role in the degradation of dye. Electrochemical behavior of dye has been studied with cyclic voltammetry in basic medium using glassy carbon as working electrode. The potentials selected for the dye was in the range 0.0 to 1.0 V. The UV– vis and chemical oxygen demand (COD) studies were selected to evaluate the degradation efficiency. The maximum color removal efficiency of 98% and chemical oxygen demand (COD) removal of 68% could be achieved for dye, at 25 g/L of NaCl concentration. The LC–MS and FTIR studies revealed the degradation of dye and confirmed that aromatic rings were destroyed. The results revealed the suitability of the present process for the effective degradation of dye C.I. Vat Black 27. ß 2013 Elsevier Ltd. All rights reserved. Keywords: Carbon electrodes Cyclic voltammetry Electrochemical degradation FTIR LC–MS UV–vis Introduction The discharge of textile wastewater to the environment causes aesthetic problems due to the color and also damages the quality of the receiving water [1]. Vat dyes account for about 15% of total consumption of textile dyes [2,3]. Vat dyes cause environmental concerns when released in industrial wastewaters due to their carcinogenic health effects [4]. Vat dyes are practically insoluble in water, but can be reduced in the presence of an alkali and a reducing agent to form a soluble dye known as the leuco dye [5,6], which have a certain affinity to cellulosic fibers. It needs to be reduced to its water soluble leuco-form before dying. The treatment of textile dye effluent is difficult and ineffective with conventional biological processes [7] and several physicochemical methods because many synthetic dyes are very stable to light, temperature and are non-biodegradable nature of most dyes [8]. In this context, electrochemical technique is considered to be a powerful means for the treatment of dyeing wastewater. Indeed, electrochemical method has been successfully tested and it has certain significant advantages such as simple equipment, easy operation and lower operating cost [9–12]. The process requires significantly less equipment than conventional * Corresponding author. Tel.: +91 8282256251. E-mail address: [email protected] (P. Kariyajjanavar). 2213-3437/$ – see front matter ß 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.jece.2013.08.002 biological treatment processes [13,14]. Graphite electrodes were used as anode and cathode by many researchers for the application in organic oxidation [15,16]. Hence, there is an interest in electrochemical methods to develop an efficient, costeffective and eco-friendly alternative for the degradation of dyestuffs [17]. In the past, graphite was frequently used as an anode for the electrochemical degradation of textile dye as it is relatively cheaper and gives satisfactory results [18]. The aim of this work was to test the feasibility of electrochemical method for the degradation of C.I. Vat Black 27 using graphite carbon electrodes. Experimental Materials The commercial vat dye, Indanthren Olive R Coll. (C.I. Vat Black 27, CAS No. 2379-81-9) and was obtained from textile industry Himatsingka Linens, Hassan, India. All other chemicals used for the experiments were of analytical grade reagents and obtained from s d fine chem-limited, Mumbai, India. Cylindrical carbon electrodes (chemical composition: graphite carbon + coke: 85% and ash 15%) were obtained from Power Cell Battery India Limited. A digital DC power supply (AD 302S: 30 V, 2A) was used as an electrical source. Double distilled water was used to prepare the desired concentration of dye solutions and the reagents. [(Fig._1)TD$IG] P. Kariyajjanavar et al. / Journal of Environmental Chemical Engineering 1 (2013) 975–980 976 Instrumentation 1.4 Electrochemical degradation studies Graphite carbon electrodes of 4.5 cm length and 0.8 cm diameter were used as anode and cathode for electrochemical degradation studies [19]. The effective electrode area was 11.82 cm2. The supporting electrolytes such as NaCl and Na2SO4 were added to the electrolytic solution, which increases the conductivity of the solution and reduces the electrolysis time. The solution was kept under agitation using magnetic stirrer. 1.2 Current 10-5 (A) UV–vis studies A UV–vis spectrophotometer (Systronics-119) was employed to measure the optical density of dye solution (lmax = 590) before and after electrolysis. The degradation efficiency was calculated using the relation: %E ¼ Ai A f 100 Ai 1.0 0.8 Ipc 0.6 0.4 0.2 Vat Black 27 Blank 0.0 -0.2 0.0 -0.2 -0.4 (1) -0.6 -0.8 -1.0 Potential (V) where, Ai and Af are absorbance values of dyes solutions before and after treatment with respect to their lmax, respectively or Ai and Af are initial and final COD values of the dyes solutions, respectively. Fig. 1. Cyclic voltammograms of dye C.I. Vat Black 27 on glassy carbon: scan rate. 100 mV s1; pH: 9; concentration of dye: 50 mg/L. Inset plot: DPV: scan rate 100 mV s1. pH and conductivity measurement A water analyser (Systronics, Model-371) was used to measure the pH and conductivity of the dye solution before and after electrolysis under different electrolysis conditions. was no anodic peak found, indicating the irreversible nature of the dye (Fig. 1). The cathodic peak currents observed for C.I. Vat Black 27 attributed to the reduction of ketones to alcohols. These data are very much important to assess the feasibility of the electrochemical process for the degradation of the dye C.I. Vat Black 27. Liquid chromatography–mass spectrometry studies (LC–MS) The extent of degradation of dye samples were analyzed by LC– MS studies (LCMS-2010A, Shimadzu, Japan). The LC–MS was fitted with column C18. The mobile phase was methanol:water (90:10). The flow rate was 0.2 mL min1 and the injection volume of dye was 5 mL. The dye solutions were injected into LC column before and after electrolysis. Analyses using ESI (electron spray ionization) interface were done under the same chromatographic conditions as described for the APCI (atmospheric pressure chemical ionization) analysis, except the guard column, which was not used in the ESI analysis. FTIR studies To study the structural changes of dye before and after electrolysis the dye samples were characterized by using Fourier transform Infrared Spectrometry (FTIR) spectrometer (model 3010 Jasco, Japan). The scan range of the wave number was set from 400 to 4600 cm1. The dye samples (freeze dried) were kept in the sample holder and scanned to obtain the FTIR spectra. Influence of electrolysis conditions on dye degradation Effect of supporting electrolytes From the experimental observation, it could be concluded that, the degradation efficiency of dye solutions were found to be enhanced in the presence of NaCl than that of Na2SO4. Since, may be attributed to the generation of more powerful oxidizing agents such as Cl2, HOCl and OCl [19]. The degradation in the presence of Na2SO4 is attributed to the generation of persulfate ions that can oxidize organic dyes [21]. The S2O82 ions are formed the oxidation of SO42 species: 2Na2 SO4 ! S2 O8 2 þ 2Naþ þ 2e (2) Moreover, the increased concentration of supporting electro[(Fig._2)TD$IG] lytes results in a decrease in the operating voltage at the given 6.0 The C.I. Vat Black 27 is a commercial textile dye, best known to polycyclic aromatic carbonyl dyes cover the entire color range of black [20]. Voltammetry The cyclic voltammetric measurements were carried out using CHI660D electrochemical workstation (CH Instruments Austin, USA) controlled by electrochemical software. A three electrodes system was used for the cyclic voltammetric experiments. The working electrode was highly polished, glassy carbon disk with an effective surface area of 0.06 cm2. A platinum wire and saturated calomel were used as counter and reference electrodes, respectively. The cyclic voltammagrams of C.I. Vat Black 27 (50 mg/L,) was recorded in pH 9 using glassy carbon as working electrode. The potential range selected was 0.0 to–1.0 V. The voltammetric curve of C.I. Vat Black 27 shows a cathodic peak at 0.692 V (Ipc), and there (a) 5.0 4.5 4.0 NaCl Na2SO4 3.5 Decolourisation (%) Results and discussion Voltage (V) 5.5 3.0 100 80 60 40 (b) 20 0 5 10 15 20 25 30 35 -1 Electrolyte concentration (g L) Fig. 2. Effect of supporting electrolytes on (a) voltage variation and (b) degradation efficiency. Electrolysis condition: concentration of the dye solution: 50 mg/L; electrodes: graphite carbon; current density: 170 A m2; time: 240 min. [(Fig._3)TD$IG] P. Kariyajjanavar et al. / Journal of Environmental Chemical Engineering 1 (2013) 975–980 current density (Fig. 2a). An increase in the concentration of NaCl up to 25 g/L accelerated the degradation rate, enabling the degradation efficiency of C.I. Vat Black 27 of 98% (Fig. 2b). 977 Removal of Colour & COD (%) 100 Effect of initial pH A significant difference in the extent of degradation was noted when the concentration of NaCl was at 25 g/L. The initial pH of the solution (3–11) was adjusted using 1 M H2SO4 or NaOH [22,23]. The electrolysis was carried out at the current density of 170 A m2 for 240 min with a dye concentration of 50 mg/L at room temperature. From the absorption spectral studies it was confirmed that, the larger dye molecules were degraded into simple substituted aromatic compounds [24]. However, the hypochlorite can lead to partial mineralization of dyes [21] and the degradation efficiency of C.I. Vat Black 27 was found higher in both neutral and basic pH and slightly lower in acidic pH. After electrolysis the final pH was found to be slightly basic. 90 80 70 60 Colour COD 50 40 85 170 255 340 425 2 Current Density (A/m ) Fig. 3. Effect of current densities on degradation and COD removal efficiencies of dye C.I. Vat Black 27. Electrolysis condition: concentration of the dye solution: 50 mg/L; pH: 9; NaCl: 25 g/L; current density 170 A m2; time: 240 min. Effect of current density The electrolysis of dye solution was carried out at different current densities (85, 170, 255, 340 and 425 A m2) at graphite carbon electrodes to investigate the influence of current density on the degradation efficiency of C.I. Vat Black 27 keeping NaCl concentration at 25 g/L, dye concentration at 50 mg/L, pH at 9 and temperature at 300 K. It can be found that, the degradation and COD removal efficiencies increased (Fig. 3) with increasing the applied current density [25]. This is because of the increased rate of generation of oxidants, such as chlorine/hypochlorite at higher current densities [26]. It was also reported that current density only slightly affects current efficiency or enhances chlorine/hypochlorite production when increased along with the chloride concentration [27]. Up to a current density of 170 A m2, the degradation efficiency of the dye was increased almost linearly. pH is another parameter that plays an important role in indirect electrochemical processes because it influences the form of the electrogenerated active chlorine and its oxidation potential; thus, depending on the pH, the electrogenerated molecular chlorine can disproportionate to form hypochloric acid (Eq. (3)) which is deprotonate to hypochlorite ions (Eq. (4)) Cl2 þ H2 O ! HOCl þ HCl (3) HOCl ! Hþ þ OCl (4) At higher current densities accumulation of OCl in the electrolyte causes the increase in pH after which the concentration of OCl reaches to a certain level at which point the oxidation process is initiated [28]. The degradation efficiency was attained almost constant and energy consumption was found to be more at higher current densities (>170 A m2) with a subsequent stripping of electrodes [29]. Therefore, the optimal current density for the successive electrochemical degradation was fixed at 170 A m2. Analysis of COD The electrolysis was carried out at a current density of 170 A m2. At this current density, hypochlorite (OCl) generated [(Fig._4)TD$IG] 70 70 (a) (b) 60 COD removal (%) COD removal (%) 60 50 40 50 40 30 20 30 10 20 0 2 4 6 8 pH 10 12 5 10 15 20 25 30 35 -1 NaCl (g L ) Fig. 4. Effect of pH and NaCl concentrations on COD removal efficiencies of the dye C.I. Vat Black 27. Electrolysis condition: concentration of the dye solution: 50 mg/L; electrodes: graphite carbon; current density: 170 A m2; time: 240 min. 978 P. Kariyajjanavar et al. / Journal of Environmental Chemical Engineering 1 (2013) 975–980 in the solution drives the oxidation process at basic pH. The maximum COD removal efficiency of 68% was observed at pH 8 (Fig. 4a). The percent removal of COD increased with increase in the concentration of NaCl (Fig. 4b). This confirmed that the electrogenerated chlorine/hypochlorite will play an important role in the electrochemical degradation process of the dyestuffs. Liquid chromatography–mass spectrometry studies (LC–MS). LC–MS studies were employed to monitor the diminution in mass of the fragments of C.I. Vat Black 27 dye before and after electrolysis. MS spectrum of the dye C.I. Vat Black 27 recorded before electrolysis shows more number of peaks at higher m/z values due to the presence of dye and other impurities (Fig. 5a). The MS spectrum of the filtrate solution after complete electrolysis shows the absence of majority of the peaks (Fig. 5b). This clearly indicated that almost all dye was coagulated and removed in the form of sludge. The remaining peaks at low m/z values in the mass spectra may be due to the presence of substituted simple aromatic compounds. shows a broad and intense band at 3476 cm1 could be attributed to stretching vibrations of –N–H groups. The sharp bands at 1639 cm1 could be attributed to stretching vibrations of C5 5O group. The medium band at 2934, 1587, 1514, 1456 cm1 could be attributed to stretching vibrations of 5 5C–H, –C–H, –C5 5C–, –C–C– groups respectively. The weak bands at 1342, 1265, 1024, 690 and 418 cm1 could be due to bending of frequencies of 5 5C–H, –C5 5C–, –N–H and –C–H groups. After the treatment of dye C.I Vat Black 27 the spectrum confirms that, almost stretching and bending frequencies of different groups were gradually disappeared (Fig. 6b). In addition, the broad peak around 3400 cm1, which is assigns to –OH vibration [30]. Electrical energy consumption The major operating cost is associated with the electrical energy consumption during electrochemical degradation process. The electrical energy consumption (E) is required to decompose 50 mg/ L C.I Vat Black 27 dye solution at various current densities was calculated using the relation: VIt E 103 Vs FT-IR E¼ FT-IR spectroscopic technique employed to follow up the electrochemical degradation process of C.I. Vat Black 27 during 240 min of electrochemical process. The spectrum of dye (Fig. 6a) where, E is the electrical energy consumption (kWh m3), V is the applied voltage (V), I is the applied current (A), tE is the electrolysis time (h) and Vs is the volume of dye solution (m3). As per the [(Fig._5)TD$IG] (5) Fig. 5. Mass spectrum of C.I. Vat Black 27: (a) before electrolysis and (b) clear filtrate after complete electrolysis. Electrolysis condition: concentration of the dye solution: 50 mg/L; electrodes: graphite carbon; pH: 9; current density 170 A m2; time: 240 min. [(Fig._6)TD$IG] P. Kariyajjanavar et al. / Journal of Environmental Chemical Engineering 1 (2013) 975–980 979 Fig. 6. FT-IR spectrum of C.I. Vat Black 27 (a) before electrolysis and (b) after electrolysis, Electrolysis condition: concentration of the dye solution: 50 mg/L; electrodes: graphite carbon; pH: 9; current density: 170 A m2; time: 240 min. Table 1 The electrical energy consumed during electrochemical degradation of C.I. Vat Black 27 dye solution (50 mg/L); Electrolysis time 240 min. Current (A) Current density (A m2) Energy consumption (kWh m3) Degradation (%) 0.10 0.20 0.30 0.40 0.50 085 170 255 340 425 7.40 15.20 31.20 44.00 59.00 87 99 99 99 99 results, the minimum electrical energy consumption was 15.20 kWh m3 at 170 A m2 current density. At higher current densities, the energy consumption was found to be increased and it may be attributed to the increased hydrogen and oxygen evolution reaction (Table 1). Conclusions In the present work the electrochemical degradation of C.I Vat Black 27 was carried out using graphite carbon as anode and cathode, in the optimal operating conditions (current density 170 A m2, NaCl concentration 25 g/L and at room temperature). Increasing the initial pH will lead to corresponding decrease in the degradation efficiency of C.I. Vat Black 27 dye. The effect of the hypochlorite at pH 9 can lead the degradation efficiency of the dye. Cyclic voltammograms of C.I. Vat Black 27 shows irreversible electrochemical natures. UV–vis, MS spectral studies and FT-IR studies confirmed that the proposed electrochemical degradation process is an effective method for the degradation of C.I. Vat Black 27 dye. Acknowledgements The Authors are grateful to DBT, DST and UGC, New Delhi for the financial support extended. Also grateful to Kuvempu University, Power Cell Battery India Limited, DyStar Textilfarben GmbH & Co. Deutschland KG for their support to carry out this work. References [1] D. Georgiou, C. Metallinou, A. Aivasidis, E. Voudrias, K. Gimouhopoulos, Decolorization of azo-reactive dyes and cotton-textile wastewater using anaerobic digestion and acetate-consuming bacteria, Biochem. Eng. 19 (2004) 75–79. [2] I. Chaari, M. Feki, M. Medhioub, J. Bouzid, E. Fakhfakh, F. Jamoussi, Adsorption of a textile dye indanthrene blue RS (C.I. Vat Blue 4) from aqueous solutions onto smectite-rich clayey rock, J. Hazard. Mater. 172 (2009) 1623–1628. [3] I. Chaari, F. Jamoussi, Application of activated carbon for vat dye removal from aqueous solution, J. Appl. Sci. Environ. Sanit. 6 (2011) 247–256. [4] D.S.L. Balan, R.T.R. Monteiro, Decolorization of textile Indigo dye by ligninolytic fungi, J. Biotechnol. 89 (2001) 141–145. [5] P. Santhi, J.J. Moses, Study on different reducing agents for effective vat dyeing on cotton fabric, Indian J. Fibre Text. Res. 35 (2010) 349–352. [6] P. Kariyajjanavar, J. Narayana, Y.A. Nayaka, Degradation of simulated dye wastewater by electrochemical method on carbon electrodes, Indian J. Nat. Sci. 1 (2012) 809–821. [7] G. Guven, A. Perendeci, A. Tanyolac, Electrochemical treatment of simulated beet sugar factory wastewater, Chem. Eng. J. 151 (2009) 149–159. [8] A. Anouzla, Y. Abrouki, S. Souabi, M. Safi, H. Rhbal, Colour and COD removal of disperse dye solution by a novel coagulant: application of statistical design for the optimization and regression analysis, J. Hazard. Mater. 166 (2009) 1302–1306. [9] A. Dirany, I. Sires, N. Oturan, A. Ozcan, M.A. Oturan, Electrochemical treatment of the antibiotic sulfachloropyridazine: kinetics reaction pathways and toxicity evolution, Environ. Sci. Technol. 46 (2012) 4074–4082. [10] F. Akbal, A. Kuleyin, Decolorization of levafix brilliant blue E-B by electrocoagulation method, Environ. Prog. Sustainable Energy 30 (2011) 29–36. 980 P. Kariyajjanavar et al. / Journal of Environmental Chemical Engineering 1 (2013) 975–980 [11] Y. Chu, D. Zhang, L. Liu, Y. Qian, L. Li, Electrochemical degradation of m-cresol using porous carbon-nanotube-containing cathode and Ti/SnO2–Sb2O5–IrO2 anode: kinetics, byproducts and biodegradability, J. Hazard. Mater. 252 (2013) 306–312. [12] M. Hongzu, W. Bo, L. Xiaoyan, Studies on degradation of methyl orange wastewater by combined electrochemical process, J. Hazard. Mater. 149 (2007) 492–498. [13] P. Kariyajjanavar, J. Narayana, Y.A. Nayaka, Degradation of textile wastewater by electrochemical method, Hydrol. Curr. Res. 2 (2011) 110, http://dx.doi.org/ 10.4172/2157-7587.1000110. [14] F. Li, Z. Yanwei, Y. Weishen, C. Guohua, Y. Fenglin, Electrochemical degradation of aqueous solution of Amaranth azo dye on ACF under potentiostatic model, Dyes Pigments 76 (2008) 440–446. [15] C. Cameselle, M. Pazos, M.A. Sanroman, Selection of an electrolyte to enhance the electrochemical decolourisation of indigo optimisation and scale-up, Chemosphere 60 (2005) 1080–1086. [16] M.A. Sanroman, M. Pazos, M.T. Ricart, C. Cameselle, Decolourisation of textile indigo dye by DC electric current, Eng. Geol. 77 (2005) 253–261. [17] C.A. Martinez-Huitle, E. Brillas, Decontamination of wastewaters containing synthetic organic dyes by electrochemical methods: a general review, Appl. Catal. B Environ. 87 (2009) 105–145. [18] P. Kariyajjanavar, J. Narayana, Y.A. Nayaka, Electrochemical degradation of C.I. Vat Brown1 dye on carbon electrode, Adv. Chem. Lett. 1 (2013) 32–39. [19] P. Kariyajjanavar, J. Narayana, Y.A. Nayaka, Studies on degradation of reactive textile dyes solution by electrochemical method, J. Hazard. Mater. 190 (2011) 952–961. [20] K. Hunger, Industrial Dyes, Chemistry, Properties, Applications, Wiley-VCH, Germany, 2003. [21] F. Yi, S. Chen, C. Yuan, Effect of activated carbon fiber anode structure and electrolysis conditions on electrochemical degradation of dye wastewater, J. Hazard. Mater. 157 (2008) 79–87. [22] I.M. Hasnain, L.S. Lang, F.A.H. Asaari, H.A. Aziz, N.A. Ramli, J.P.A. Dhas, Low cost removal of disperse dyes from aqueous solution using palm ash, Dyes Pigments 74 (2007) 446–453. [23] J. Basiri Parsa, M. Rezaei, A.R. Soleymani, Electrochemical oxidation of an azo dye in aqueous media investigation of operational parameters and kinetics, J. Hazard. Mater. 168 (2009) 997–1003. [24] A. Fatiha, R.G. Mouffok, M. Belhadj, A. Addou, J. Brisset, Bleaching and degradation of textile dyes by nonthermal plasma process at atmospheric pressure, Ind. Eng. Chem. Res. 45 (2006) 23–29. [25] N.M. Abu Ghalwa, L.M.S Abdel, Electro-chemical degradation of acid green dye in aqueous wastewater dyestuff solutions using a lead oxide coated titanium electrode, J. Iran. Chem. Soc. 2 (2005) 238–243. [26] H. Ma, B. Wang, X. Luo, Studies on degradation of methyl orange wastewater by combined electrochemical process, J. Hazard. Mater. 149 (2007) 492–498. [27] M. Li, Q. Xue, Z. Zhang, C. Feng, N. Chen, X. Lei, Z. Shen, N. Sugiura, Removal of geosmin (trans-1,10-dimethyl-trans-9-decalol) from aqueous solution using an indirect electrochemical method, Electrochim. Acta 55 (2010) 6979–6982. [28] J.B. Parsa, M. Rezaei, A.R. Soleymani, Electrochemical oxidation of an azo dye in aqueous media investigation of operational parameters and kinetics, J. Hazard. Mater. 168 (2009) 997–1003. [29] D. Rajkumar, B.J. Song, J.G. Kim, Electrochemical degradation of Reactive Blue 19 in chloride medium for the treatment of textile dyeing wastewater with identification of intermediate compounds, Dyes Pigments 72 (2007) 1–7. [30] Z. Seferoglu, N. Ertan, T. Hokelek, E. Sahin, The synthesis spectroscopic properties and crystal structure of novel, bis-hetarylazo disperse dyes, Dyes Pigments 77 (2008) 614–625.
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