JECET; June – August-2013; Vol.2.No.3, 610-618.
Journal of Environmental Science, Computer Science and Engineering & Technology
An International Peer Review E-3 Journal of Sciences and Technology
Available online at www.jecet.org Environmental Science
Review Article
JECET; June – August 2013; Vol.2.No.3, 610-618. 610
A Review on Electrochemical Decolorization of Dye Effluent
T. Marimuthu1*, S.Rajendran2, 3, M. Manivannan4,
1Research and Development Centre, Bharathiar University, Coimbatore, Tamil Nadu, India.
2Corrosion Research Centre, PG and Research Department of Chemistry, GTN Arts College, Dindigul, Tamil Nadu, India.
3Department of Chemistry, RVS School of Engineering and Technology, Dindigul, Tamil Nadu, India.
4Department of Chemistry, Chettinad College of Engineering and Technology, Karur, Tamil Nadu, India.
Received: 18 June 2013; Revised: 10 July 2013; Accepted: 18 July 2013
Abstract: The textile effluent treatment industry uses the electrochemical techniques in both textile processes & wastewaters treatments (color removal). Electrochemical reduction reactions are mostly used in sulfur and vat dyeing, but in some cases, they are applied to dye effluents decolorization. However, the main use of electrochemical treatments in the textile industries based on oxidation reactions. Most of electrochemical oxidation processes involve indirect reactions, which imply the generation of hypochlorite or when sodium chloride solution is electrolysed, positive chloride ion (Cl+) is produced. It is highly reactive. It decolourises the coloured material into colourless product. or hydroxyl radical in situ. These elctrogenerated species are able to bleach indigo-dyed denim fabrics and to degrade dyes in wastewater in order to achieve the effluent color removal. The aim of this paper is to review the electrochemical techniques applied to textile industry. In particular, they are an efficient method to remove color of textile effluents.
Key words: electrochemical decolorization,dye effluent,effluent treatment
JECET; June – August 2013; Vol.2.No.3, 610-618. 611 INTRODUCTION
Traditionally, the electrochemical techniques have been used for the synthesis of compounds or for metal recovery treatments. But more recently, a wide range of other applications have been proposed. Some of them are proposed to solve several technical problems of the textile industry. This is the case of a recent application to produce smart textiles1–15 by obtaining functionalized fabrics. These textiles with specific properties are prepared by using the electrochemistry in the synthesis of conductive polymers, especially conductive fibers. Another interesting use of the electrochemical techniques is the bleaching of cotton fibers and the bleaching of finished denim fabric16–21. In order to achieve the visual effect in jeans, the generation in situ of hypochlorite by electrochemical reaction has been proposed, instead of its addition.
REVIEW OF LITERATURE
The objective of this paper is to review the main applications of electrochemical techniques in textile industry (production processes and wastewater treatments). Nowadays, there are only few applications at industrial scale as most of electrochemical treatments are still being studied at laboratory scale.
Colours in water bodies reduce light penetration, alter the pH, increase the Biochemical Oxygen Demand (BOD) and Chemical Oxygen Demand (COD) and thereby make aquatic life difficult22. Dye house effluents are therefore of serious environmental concern.
Although, biotreatment offers a cheaper and environmentally friendlier alternative for colour removal in textile effluents, it has its own demerits. Anaerobic decolourisation of azo dyes produces aromatic amines which are toxic to aquatic life23, mutagenic to humans and cannot be degraded further under anaerobic conditions24,25. It has been reported that the only safe biodegradation method for azo dyes is combined aerobic treatment 26, 27.However ,there are very few reports of aerobic bacteria that can grow with azo compounds28-32.
Several treatments of textile effluents to achieve decolourisation have been reported. These include physiochemical methods such as filtration, specific coagulation, use of activated carbon and chemical flocculation .Some of these methods are effective but quite expensive 33.
Using the Pt/Ti electrodes better results for dye decolourisation were obtained under milder conditions than those used for pure Pt. For the Pt electrode, colour removal of 93 % (λ = 493 nm) was obtained after 60 min, at 2.2 V vs. RHE, using 0.017 mol L-1 NaCl + 0.5 mol L-1 H2SO4 solution. For the Pt/Ti electrode there was better colour removal, 98%, than for the Pt electrode. Moreover, we used 0.017 mol L-1 NaCl solution and the applied potential was 1.8 V. Under this condition after 15 min of electrolysis, more than 80% of colour was removed. The rate reaction constant, assuming a first order reaction34, was 0.024 min -1 and 0.06
Several treatments of textile effluents to achieve decolourisation have been reported. These include physiochemical methods such as filtration, specific coagulation, use of activated carbon and chemical flocculation .Some of these methods are effective but quite expensive35,36
Using the Pt/Ti electrodes, better results for dye decolourisation were obtained under milder conditions than those used for pure Pt. For the Pt electrode, colour removal of 93 % (λ = 493 nm) was obtained after 60 min, at 2.2 V vs. RHE, using 0.017 mol L-1 NaCl + 0.5 mol L-1 H2SO4 solution. For the Pt/Ti electrode there was better colour removal, 98%, than for the Pt electrode. Moreover, we used 0.017 mol L-1 NaCl solution and the applied potential was 1.8 V. Under this condition after 15 min of electrolysis, more than 80% of colour was removed. The rate reaction constant, assuming a first order reaction25, was 0.024 min -1 and 0.06 .
JECET; June – August 2013; Vol.2.No.3, 610-618. 612 Recently electrochemical methods25-32 and chemical methods have been used to decolourize various dye solutions29
Azo dye CNWB was performed with cyclic voltammetry in sulphuric acid medium using glassy carbon as working electrode. The potential range selected for the dye was in the range +700 mV to -450 mV.
The voltammetric curve of CNWB shows cathodic peaks at +50 mV, -155 mV and -317 mV and anodic peaks at +382 mV and +547 mV, respectively. The decolourisation efficiency was assessed through UV- Visible studies. The LC- Electrochemical methods can also be used to decolourise dyes. Methyl orange fluorescein Eriochrome Black -T have been decolourised by electrochemical method 33-42.
The removal of pollutants from effluents by electrochemical degradation29 has become an attractive method in recent years. This paper deals with the removal of reactive textile dye Cibacron Navy W-B (CNWB) from an aqueous medium by the electrochemical method using graphite carbon electrodes.
Electrochemical behavior of reactive MS of the dye were analyzed before and after electrochemical treatment and confirmed that the azo groups and aromatic rings were destroyed. The effect of pH and nature of supporting electrolytes on the electrochemical degradation of dye was also studied. The maximum Chemical Oxygen Demand (COD) removal efficiency was ~100% for the dye solutions at 5 gL-1 of NaCl concentration. The results revealed the suitability of the present process for the effective degradation of dye effluents
The electrochemical oxidation of a synthetic wastewater containing Acid Yellow 1 on boron-doped diamond was investigated. The influence of applied current (0.5-3 A), dye concentration (1-3 g L-1), temperature (25-40 °C) and flow-rate (75-300 L h-1) on colour removal and current efficiency was evaluated. It was demonstrated that the complete decolourization and COD removal were achieved in any experimental conditions indicating that the electrochemical oxidation on BDD electrodes is a suitable method for treatment of wastewaters polluted with synthetic dyes. .Electrochemical decolourisation of Reactive Orange 16 was carried out in an electrochemical flow-cell, using as working electrodes a Pt thin film deposited on a Ti substrate (Pt/Ti) prepared by the Pechini method and a pure platinum (Pt) foil.
Rajkumar et al.43studied the electrochemical degradation ofReactive Blue 19 over a titanium-based dimensionally stableanode regarding the effect of operating conditions (currentdensity, salinity, reaction temperature and initial dye concen-tration) on treatment performance, while they also identifiedmajor reaction intermediates. The effect of various operatingconditions on Acid Blue and Basic Brown degradation over alead/lead oxide anode and on Acid Orange 7 degradation overa boron-doped diamond anode was studied by Awad and AboGalwa[40]and Fernandes et al.44, respectively. Basic Yellow28 and Reactive Black 5 were used as test substances to comparethe efficiency of a diamond electrode to that of conventionalmetallic electrodes (iron, aluminium and copper)45, whilean activated carbon fiber electrode was used to assess theelectrochemical degradability of 29 different textile dyes43.In further studies44, several advanced oxidation processesnamely wet oxidation, TiO2 photocatalysis, electro-Fenton andUV- assisted electro-Fenton were compared concerning theirefficiency in treating Reactive Black 5.
Lin and Peng45developed a continuousprocess comprising coagulation, electrochemical oxidation andactivated sludge to treat textile effluents. Th effect of changingoperating conditions such as coagulant concentration, solution pH, current density, number of electrodes, residence times inelectrochemical and biological reactors on treatment efficiencywas thoroughly investigated and optimal conditions were estab-lished. In further studies, Vlyssides et al.46 investigated the electrooxidation of textile effluents over a Ti–Pt electrode atdifferent chloride concentrations and reported that electrochem-ical treatment improved the biotreatability (as assessed by theBOD/COD ratio) of the original effluent. Naumczyk et al.47compared the decolorization and mineralization rates of textileeffluent electrochemical degradation
JECET; June – August 2013; Vol.2.No.3, 610-618. 613 over three Ti-based elec-trodes coated with different metals and they also attempted toidentify major reaction by-products. In a recent work, Sakalis etal.48 demonstrated a continuous, pilot-scale cascade electro-chemical reactor capable of achieving 90% decolorization of atextile effluent at a residence time of 40 min.
The electrochemical oxidation49 of textile effluents over a titanium–tantalum–platinum–iridium anode was investigated. Batch experiments were conducted in a flow-through electrolytic cell with internal recirculation at current intensities of 5, 10, 14 and 20 A, NaCl concentrations of 0.5, 1,2 and 4% and recirculation rates of 0.81 and 0.65 L/s using a highly colored, synthetic effluent containing 16 textile dyes at a total concentrationof 361 mg/L and chemical oxygen demand (COD) of 281 mg/L. Moreover, an actual dyehouse effluent containing residual dyes as well as various inorganic and organic compounds with a COD of 404 mg/L was tested. In most cases, quantitative effluent decolorization was achieved after10–15 min of treatment and this required low energy consumption; conversely, the extent of mineralization varied between 30 and 90% after180 min depending on the operating conditions and the type of effluent. In general, treatment performance improved with increasing current intensity and salinity and decreasing solution pH. However, the use of electrolytes not containing chloride (e.g.
FeSO4; Na2SO4) suppressed degradation.
Electrochemical oxidation of reactive textile dyes using platinum anode and Na2SO4 was realized.
Electrochemical degradation was done with sodium sulfate already present in textile effluents, so additional chemical usage was not required and process is more cost effective. After 60 minutes of electrolysis complete degradation of dyes was reached (CO Dvalue below 30 mg/L O2) except Reactive Black 5 which has reached degradation degree of 57.95% with membrane and 35.28% without membrane. Electrochemical oxidation is capable of destroying the chromophore groups, and full decolorization of dyes found in textile effluents can be done at short treatment times. Indirect electrochemical oxidation via hydroxyl radicals is a convenient way for the degradation and mineralization of reactive dyes and offers approach to developing new technology for removal of reactive dyes in real textile industry effluents with low energy consumption50
Over the past 10 years, the electro chemical techniques have been found of special interest for wastewater remediation51. Electrochemical techniques used for dye removal can be classified as electrocoagulation, electrochemical reduction, electrochemical oxidation, indirect electro-oxidation with strong oxidants (electro-oxidation with active chlorine, electro-Fenton), and photo-assisted electrochemical methods (photoelectro-Fenton, Photoelectrocatalysis)52 hesetechniques are compatible with the environment because the main reagent, the electron, is a clean one53. They have advantages such as simple equipment, easy operation, lower operating temperature, etc. 54 It is interestingto notice the high yields of removal of polluting substances with maximum energy resourcemanagement51. The electric current induces redox reactions upon the electrodes surface resulting in the transformation and destruction of the organic compound, and almost complete oxidation55 to CO2and H2O.
Electrochemical oxidation (EO) of dyes can be done in electrochemical cell by:
(1) Direct anodic oxidation (direct electron transfer to the anode), which yields very poor decontamination ,(2) chemical reaction with electrogenerated species from water discharge at the anode, such as physically adsorbed ‘‘active oxygen’’ (physisorbed hydroxyl radical (*OH)) or chemisorbed
‘‘active oxygen’’ (oxygen in the lattice of a metal oxide (MO) anode). Brillaset al., 2003) *OH radical is the second strongest oxidant known after fluorine, with a high standard potential (E0= 2.80 V vs. SHE) The existence of oxidation with different electrogenerated species formed from water ischarge has allowed the proposal of two main approaches for the wastewaters treatment by EO.the aim to solve two
JECET; June – August 2013; Vol.2.No.3, 610-618. 614 major problems that occur in textile waste water, intense color and high COD values, electrochemical oxidation is used for decolorization and
(i) The electrochemical conversion method, with chemisorbed ‘‘active oxygen’’ in which
refractory organics are selectively transformed into biodegradable compounds, usually carboxylic acids, (ii) The electrochemical combustion (or electrochemical incineration) method, with physisorbed *OH where organics are completely oxidized to CO2and inorganic ions56.
Fisher platinum57 electrodes were employed as anode and cathode. Applied voltage during electrolysis of 6, 12, and 24 V, with and without membrane and influence of pH on decolorization was examined for model dye (Reactive Blue 52, 200mg/L). Highest degradation degree was achieved at 12 V for model dye, so electrolysis of other dyes was done on this voltage Decolorization was monitored Spectrofotometrically and electrochemical degradation was monitored with cyclic voltammetry, by COD values and LC.
Textile dye wastewater is well known to contain strong colour, high pH, temperature, Chemical Oxygen Demand (COD) and biodegradable materials. The electrochemical treatment of wastewater is considered as one of the advanced oxidation processes, potentially a powerful method of pollution control, offering high removal efficiencies the removal of colour of methyl red azo dye is a challenge in textile industry.
The following methods have been adopted for the treatment of real textile wastewater: 1) Electro- oxidation (EO) and 2) Bio-treatment (BT). In EO process, reduction of COD and removal of colour were 70% and 81% re-spectively. The effluent was further treated by BT. BT showed a final reduction of 92%
of COD and removal of colour by 95%. Both the combined processes were highly competitive and showed a very good reduction of COD and colour removal. Electrochemical processes generally have lower temperature requirement than those of other equivalent non-electrochemical treatments and there is no need for additional chemicals. These treatment methods may also be employed successfully to treat other industrial effluent58.
Industrial effluents59 usually contain large quantities of synthetic organic compounds. Effluents fromsuch type of industries cause considerable pollutions and poses serious threat to nvironment.Conventional wastewater treatments cannot degrade the majority of these pollutants. In this paper degradation of synthetic organic dyes in wastewater were studied using electrochemical process.For electro-oxidation, electrodes were fabricated in laboratory using aluminum, iron, titanium andstainless steel as substrate.
Metals were coated using different metal oxides RuO2, Sb2O5 and SnO2 by thermal decomposition method. Effects of fabricated electrodes Al/ Sb2O5, Fe/ Sb2O5-SnO2, Ti/RuO2-Sb2O5-SnO2 and SS/RuO2-Sb2O5-SnO2 were studied on synthetic organic dyes Reactive Black-5, Reactive Yellow-245 and Acid Red-97 for degradation and decolourization. Experiments wereconducted at pH 2, current density at 50 and distance between electrodes at 8mm for 50 and 100 ppmof dye solution with constant ionic strength. Colour and COD reduction were observed using UVspectrophotometer and COD reactor.
Maximum colour and COD reduction was respectively 99% and85% in Reactive yellow-145 employing Ti/ RuO2-Sb2O5-SnO2 electrode.
As an innovative alternative, the electrochemical processes60 for treating wastewater containing dyes have been recently proposed. In this work, the treatment of synthetic wastewaters containing Methylene Blue (MB), as model dye, by anodic oxidation using Ti/Pt anodes was investigated. Galvanostatic electrolyses of MB synthetic wastewaters have led to the complete decolorization removal at different operating conditions (current density, agitation rate and temperature). According to the experimental results obtained, the electrochemical oxidation process is suitable for removing COD and decolorizing wastewaters containing MB dye, due to the electrocatalytic properties of Ti/Pt anode.
JECET; June – August 2013; Vol.2.No.3, 610-618. 615 COCLUSION
The electrochemical techniques have been proved to be efficient in different oxidation or reduction steps of the textile processes. Taking into account the considerable amount of salt contained in the reactive dyes residual dye bath, the best method for the treatment of these effluents is the indirect oxidation with chlorine, because of the following:
(i) The degradation takes place in the same bath.
(ii) The addition of chemical reagents is not required (the residual salts act as electrolyte).
(iii) The modification of the pH is not necessary.
(iv) No solid waste is generated.
(v) The reuse of the treated effluent for new dyeing is possible, which implies a saving of 70% water and 60% salt.
(vi) it takes less time than any other methods of decolorization of dye and dye effluent when compared with other methods.
The bases of electrochemistry are simple but, as showed in this review, it is possible to find the application of these techniques in a wide range of textile processes.
ACKNOWLEDGMENT
The authors thank the management and UGC for completing this work.
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*Corresponding Author: T. Marimuthu;Research and Development Centre, Bharathiar University, Coimbatore, Tamil Nadu, India.
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