ELECTROCHEMICAL OXIDATION OF TEXTILE DYE WASTEWATER USING DIFFERENT ELECTRODES

Mahaveer Devoor#, Rekha H B +, U ha N M!r"h#$

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%G "!&e'", +A " %ro(e or, $%ro(e or, De)" o( C*v*+ E',,-, U.CE, Ba',a+ore U'*ver *"#, Ba',a+ore/012201, 3ar'a"aka, I'&*a+

Email:rekhahb@gmail.com

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An attempt has been made to investigate the performance of different electrodes such as mild steel, stainless steel, copper and aluminum to treat the industrial textile wastewater in a batch reactor. On the basis of their comparative performance, stainless steel was selected. irstl!, the time and interelectrode distance were optimi"ed. urther, the effect of various current densities on the decolori"ation and #O$ removal efficienc! was studied w.r.t stainless steel under optimi"ed conditions. Additionall!, the energ! consumption and #O$ removal rate were also studied. %owever, it was observed that increase in electrol!sis time and current densit! increased the removal efficienc! of color and #O$. &esults indicated, stainless steel proves to be efficient at an optimum current densit! of '( A)m* at +*, min with a removal efficienc! of -./ color and (0/ #O$ with +cm spacing of electrodes.

1e! words: Electrochemical Oxidation, 2ild steel, 3tainless steel, Aluminum, #O$, #olor.

INTRODUCTION
#onsidering both volumes discharged and effluent composition, the wastewater generated b! the textile industr! is rated as the most polluting among all industrial sectors. 4he main sources of wastewater generated b! the textile wet5processing industr! originate from the washing and bleaching of natural fibers and from the d!eing and finishing steps. 6iven great variet! of the fibers, d!es, process aids and finishing products in use, these processes generate wastewaters of great chemical complexit! and diversit! which are not ade7uatel! treated in conventional wastewater treatment plant. 2ost significant is the current popularit! of cotton fabrics and bright colors leading to greater usage of reactive and a"o d!es, respectivel! 89andevivere, +''0:. $ue to the new and)or tighter regulations coupled with increased enforcement concerning wastewater discharges have been established in man! countries. Over the recent !ears, there has been a growing interest in the development of efficient electrochemical processes for the removal of toxic organic wastewater contaminants. 3uch processes have been successfull! tested to treat various industrial wastewaters, including d!e wastewaters 8#er7ueira, *,,':.

4he electrochemical oxidation of pollutants from wastewaters has been studied using anodes made from different materials. 3everal researchers have investigated the feasibilit! of electrochemical degradation of d!es with various electrode materials for wastewater treatment such as 4i);rO* electrodes 8<ose =, *,,0 :, graphite and stainless steel 82iled, *,+,:, >t) 4i electrodes 89l!ssides, +''':, 33) 4i electrodes 8Efthalia, *,,(:, cast iron 83heng, +''?:. Applications of this method for textile wastewater have been tested on a lab scale and a good removal of organic substances at various operating conditions is obtained. Electrochemical methods offer ma! distinctive advantages such as environmental compatibilit!, versatilit!, energ! efficienc!, safet!, selectivit! and amenabilit! to automation and cost effectiveness. 82iled, *,+,:. #onse7uentl! it is imperative to stud! these factors and to find how to operate electrochemical oxidation more effectivel!. 4he primar! goal of this stud! was to derive experimental data on electrochemical degradation of #O$ and color from the textile d!e wastewater. 4he wastewater was characteri"ed for @O$, #O$, p%, total solids, suspended solids, dissolved solids, alkalinit!, chlorides, and color b! using the standard methods. 4he characteristics of the wastewater are shown in 4able +.
4able +: ;nitial #haracteristics of 4extile $!e Effluent

%ara6e"er p% Electrical #onductivit!8As: 4otal 3olids 8mg)=: 4otal $issolved 3olids 8mg) = : 4otal 3uspended 3olids 8mg)=: Alkalinit! 8mg) =: #hlorides 8mg) =: #O$ 8mg) =: #olor 8Absorbance: @O$ 8mg) =:

Ra',e o( .a+!e -.?.5-.. +**,5+B., 0.,50-( -(,50B* ??5.. +(,5+?(' +0'5*,, +'-?5*?(? ,.+(,5,.BB. *.-5B-(

I- MATERIALS AND METHODOLOGY

4he wastewater used in this stud! was collected from the d!e bath unit of the textile industr!. 4he wastewater was characteri"ed for various parameters as shown in 4able +. 4he electrochemical cell consists of an undivided reactor with two parallel electrodes. 4he electrochemical cell has a volume of +,,,ml. @oth anode and cathode were placed vertical and

parallel to each other. 4he electric power re7uired during the electrol!sis was provided b! a laborator! $ual $# power suppl! 84extronix B.$, ,5+.9, ,5+,A:. 4he electrol!tic cell was e7uipped with a magnetic stirrer in order to keep the electrol!te well mixed. 4he schematic diagram of the experimental setup is shown in igure.+ ;n this stud!, individual effects of electrode surface area and applied current on decolori"ation rate and #O$ removal were 7uantified. #ommerciall! available 2ild 3teel 823:, stainless steel 833:, aluminum 8Al: and copper 8#u: of . cm C . cm dimensions were used as anode and cathode respectivel!.
$# $ual >ower 3uppl!

+ h

#D#athode A

+ + + + +

+
-

5 % ADAnode

%D%eadplate 2D2agnetic bit

M 2agnetic 3tirrer
ig. +: 3chematic $iagram of an Electrochemical #ell

4he p% measurements were made on Elico ;on Anal!ser 8=; +*(:. 4he chemical oxidation demand of the effluent sample was determined b! closed reflux method, using #O$ digestion apparatus 2odel E4 +,0, =ovibond. 4he absorption spectra of the samples were recorded on Elico scanning mini spectrophotometer 83= +--:, recording the spectra over B?,nm to +,,,nm range. 4he characteristics of industrial effluents were determined according to the standard methods. All the reagents were prepared and anal!"ed as per standard methods for the examination of water and wastewater. 4o estimate the color removal, the disappearance of the absorbance peaks of the solution was monitored. #olor removal in percentage was calculated as follows: Abs8/:D E8Absi5Absf:)AbsiF C+,, where,

Abs8/: D Absorbance in percentage., Absi D ;nitial absorbance of the raw sample., Absf D Absorbance of the treated samples at regular intervals.

RESULTS AND DISCUSSIONS

>reliminar! studies on electrode materials, including aluminum, stainless steel, copper and mild steel were carried out. =ife c!cle stud! was done for all the metal electrodesG the stud! included the anal!sis of percentage removal of color, #O$, anode consumption, and sludge 7uantification. After three repeated runs of the same electrode, at the end of the completion of third c!cle 23 started corrosion and imparted iron content in the wastewater. Aluminium is less efficient in the removal of color and #O$ when compared to iron electrodes. #opper also used as electrode but for the first run itself it generated large 7uantit! of sludge and proved ver! poor in the removal color and #O$ when compared to other metals. 4herefore on the basis of their comparative performance, stainless steel was selected as efficient electrode.

ig. *: #omparative values of 23, 33 and Al 8#O$ and #olor removal in /, Anode consumption and 3ludge weightD g, iron mg)=:.

ig * shows the removal efficiencies of various parameters b! the electrodes i.e 23, 33 and Al. rom the results it was observed that, the removal efficienc! is in the order of 33HH23HHAl. e B+ has considerable advantages as a flocculating agent because of its innocuit! as compared to AlB+ ions, which exhibit some toxic effects 82ahesh et.al, *,,(:. Electrochemical treatment of both anionic and cationic species is possible b! using an iron plate) rod as the sacrificial electrode. urther, operating parameters like time and interelectrode distance were optimi"ed.
1. The E((e5" o( I'"ere+e5"ro&e D* "a'5e a'& E+e5"ro+# * D!ra"*o'

6reater the interelectrode distance, greater the potential applied, because the solution presents the higher resistivit! to the electrical current. According to the characteristics of the effluent, the process efficienc! can be improved b! var!ing the distance between the electrodes. 4his is an important variable with regards to operational costs. #er7ueira, et.al., *,,', reported similar findings in terms of spacing between the electrodes. ;n the present experiment, for the selected electrode i.e., stainless steel, interelectrode distance was varied from +cm to (cm. @etter removal efficienc! of '(/ #O$ and ''/ of color obtained with +cm distance at max current. 4he experiment was conducted with existing p% and the maximum of -0/ #O$ reduction achieved with a duration of +0, min at a current densit! of +?? A)m*, after that there was a slight decline in the #O$ removal which ma! be due to deposition of metals or materials on anode which might have further prevented #O$ removal 81rishna, et.al, *,+,:. 4herefore, stud! arrived with +cm of interelectrode distance and electrol!sis duration of B hrs as optimum conditions.
2. .ar*a"*o' o( Che6*5a+ O7#,e' De6a'& a'& Co+or

or the optimi"ed conditions, current was varied from ,.,( A to ,.B( A 8*? A)m * to +?? A)m*:. %igher values of removal efficienc! of contaminants with increased current densit! was due to the higher amount of ions produced on the electrodes that promote destabili"ation of the pollutant molecules and finall!, the aggregation of the induced flocs, while increasing h!drogen evolution. %owever, the increase of the current densit! causes higher consumption of the anode material. Ising iron electrode, the results of removal efficiencies of #O$ and color are shown in fig B and ? respectivel!. 9ar!ing the current from ,.,( A to ,.B( A or current densit! from *? to +?? A)m* the best removal efficiencies of #O$, color occurred at the largest value. 4he increase of the supplied current densit! from *? to +?? A)m* led to better values of #O$ and color removal, but this is not economicall! interesting due to the higher electrode and energ! consumption. ;t can be seen that the best removal efficiencies of #O$ and color are obtained in the range of ,.*? A to ,.B( A 8'( to +?? A)m*:. At an applied current of ,.*? A, there is maximum #O$ and color removal. -./. rom the fig it is clear that, compare to other current densities, with a current of ,.*? A, at +*, min there was reduction of #O$ b! (0/ and color b!

ig. B: >ercent of #O$ &emoval under 9arious Applied #urrent.

ig. ?: >ercent of #olor &emoval under 9arious Applied #urrent.

3. )H a'& Te6)era"!re

;t has been established that the influent p% is an important operating factor influencing the performance of electrochemical process 8#hen, *,,?:. 4he effluent p% would increase for acidic influent but decrease for alkaline influent. 4his is one of the advantages of this process. 4he increase of p% at acidic condition was attributed to h!drogen evolution at cathodes. @ut besides

h!drogen evolution, the formation of O%5 ions near the anode would release %+ leading to decrease of p%. ;n addition, there is also ox!gen evolution reaction leading to p% decrease. As for the p% decrease at alkaline conditions, it can be the result of formation of h!droxide precipitates with other cations.

ig. .: p% and 4emperature variations for ,.*? A.

rom the ig. . it can be observed that for an optimum current of ,.*? A, p% was decreased to -.* during (, min to ', min and there is a gradual increase from ', min. 4he variation of temperature with electrol!sis time for optimum current is also shown in ig. .. ;t was observed that the temperature rose in the range of *5BJ # from the initial values. 4his ma! be due to the electrol!tic dissociation 8Arrhenius ;onic 4heor!: or migration of ions towards the oppositel! charged electrodes which constitutes the flow of electric current in the solution. ;ncrease in temperature increases the decoloni"ation rate and #O$ removal. An increase in temperature strongl! favours the direct oxidation of pollutants to the final products. 4his explanation was substantiated b! the fact that the electrochemical reaction is highl! temperature dependent 83heng, et.al. +''0:.
4. COD Re6ova+ Ra"e a'& E'er,# Co' !6)"*o'

4he #O$ removal rate has been calculated in kgs of #O$ removed per hour ampere and per s7uare meter 8kg #O$)h)A)m*: and energ! consumption in kilo watt hour per kg of #O$ removal for a current of ,.*? A. 4he cell voltage during the electrol!sis was taken for calculating the energ! consumption. ;t was observed that application of higher current densities actuall! decreases the #O$ removal rate and increases the energ! consumed per kg of #O$ removed. 4his correlates with the results reported b! K. K. &ao, et.al. 8*,,+:. 4his ma! be due to the competing water electrol!sis reaction that becomes dominant at higher current densities. 4able * shows the results of removal rate and energ! consumption for a current of ,.*? A.
4able *: Efficienc! of 33 Electrode at a #urrent of ,.*? A.

S+ 'o + * B ? .

%ara6e"er 9oltage #O$ removal rate Energ! consumption #O$ removal / #olor removal /

.a+!e -.(' 9 +.+ kg #O$)h)A)m* B kLh)kg #O$ -* 0B

II- CONCLUSIONS
4he results showed in general that the #O$ and color removal depends on the nature of the electrode material and it dependent on the applied current or current densit! and electrol!sis time. 4hus the removal efficienc! follows the order of 33HH23HHAl. %owever, it was observed that increase in electrol!sis time and current densit! increased the removal efficienc! of color and #O$. 33 being the efficient electrode best #O$ and color removal were attained at a duration of +*, min 8(0/ and -./ respectivel!: and -*/ of #O$ and 0B/ of color at a duration of +0, min respectivel! at an applied current of ,.*? A.

REFERENCES
+. #er7ueira A, &usso #G 2ar7ues 2&#, 8*,,':, MElectroflocculation for textile wastewater treatmentN,
Brazilian J of Chemical Engineering, 9ol.*( 8?:.

*. #hen 6uohua, *,,?, MElectrochemical technologies in wastewater treatmentN, Separation and Purification
Technology, 9ol. B+.

B. Efthalia #hat"is!men, Kikolaos . Oekoukoultakis, Alberto co", Kicolas 1alogerakis, $ionissis 2nt"avinos,
*,,(, MElectrochemical treatment of textile d!es and d!ehouse effluentsN, j. haz mat @+B-, pp ''05+,,-.

?. <ose =. Kava, 2arc A Puiro", and #arlos A 2artine"5%uitle,8*,,0:, MElectrochemical treatment of

s!nthetic wastewaters containing alpha"urine a d!e: role of electrode material in the color and #O$ removalN, J. Mex. Chem. Soc., .* 8?:, pp. *?'5*...

.. 1rishna @ 2, Isha K 2, 2anoQ kumar @, =okesh 13, 8*,+,:, MElectrochemical pretreatment of distiller!
wastewater using aluminun electrodeN, J. appl electrochem, 9ol ?,, pp. ((B5(-B.

(. 2ahesh 3, >rasad @, 2all, and 2ishra, 8*,,(:, MElectrochemical degradation of >ulp and >aper 2ill
Lastewater. >art +. #O$ and #olor &emovalN, nd, Eng. Chem !e", 9ol. ?., pp *0B,5*0B'.

-. 2iled L, %aQ 3aid A and &oudesli 3, 8*,+,:,N $ecolori"ation of high polluted textile wastewater b!
indirect electrochemical oxidation processN, J. Textile and #pparel, Technology and Management, 9ol (8B:, >>. +5(.

0. &ao KK, 3omasekhar 12, 1aul 3K and 3"p!rkowic" =, 8*,,+:, MElectrochemical oxidation of tanner!
wastewaterN, j. chem. Tech, -(, pp.++*+5++B+.

'. 3heng %. =in, #hing 4 sh!u and 2eic. 3un, 8+''0:, M3aline wastewater treatment b! electrochemical
methodN, $ater !e"earch, 9ol B*, >> +,.'5+,((.

+,. 9andevivere >. #., @ianchi &., and 9erstraete L., 8+''0: M4reatment and reuse of wastewater from the
textile wet5processing industr!: review of emerging technologies,N J.Chem.Technol.Biotechnol.,89, pp.*0'5 B,*.

++. 9l!ssides A 6, =oi"idou 2, 1arlis > 1, Rorpas A A, 8+''':, MElectrochemical oxidation of a textile d!e
wastewater using a >t)4i electrodeN, J. %az Mat, @-,, pp. ?+5.*.