Se Treatment of Dye Effluent
Se Treatment of Dye Effluent
Se Treatment of Dye Effluent
Abstract
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 fol-
lowing 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 effluents.
Keywords: Textile Wastewater, COD, Colour Removal, Electro Oxidation, Biological Process, FTIR
and 0 - 30 V. Stirring was done with a magnetic stirrer. Table 3. Effect of current density on the treatment of efflu-
Electrolysis was carried out under batch mode. During ent by electro-oxidation process.
these processes samples were collected at different time Final COD (mg/l) (5 hours)
intervals and the COD was measured. Standard methods
Initial COD
for examination of wastewater [29] were used for the Current density (A/dm2)
(mg/l)
estimation of COD and colour. 1 1.5 2 2.5
The textile sample was serially diluted using 9 ml dis- Table 4. Treatment of textile effluent by Biological Treat-
tilled water blanks. The total viable counts were enumer- ment method.
ated using nutrient agar medium by pour plate method Biological Treatment
[30]. Duplicate samples were tested along with control. COD (mg/l) % Reduction
Name of the % Reduction
of colour
Total viable counts were made based on the following Organism Final of COD
removal
Initial
formulae: (5 days)
Pseudomonas
Average number of colony 10 ml 2430 215 91.15 95.23
CFU/cm 2 putida
Dilution factor volume of sample added Phanerochaete
2430 350 85.59 93.02
chrysosporium
Bacillus
2.3. Analytical Measurements cereus
2430 455 81.27 90.27
Tricoderma
FTIR and UV techniques were adopted for analysis of virdae
2430 540 77.77 85.16
treated and untreated dye effluent by EO and BT.
radical (OH) as shown in Equation (1) It may be speculated in this case that physisorbed ac-
tive oxygen predominantly oxidized the organics and
RuO 2 H 2 O RuO 2 OH H
e (1) chemisorbed oxygen RuO2(•O) decides the fate of the
intermediate product.
Later, the (•OH) radical, gets adsorbed on to the RuO2
forming a complex of the type (RuO2(•OH)) which inturn
3.3. Biological Process
gets converted to (RuO2(•O)) of higher oxidation state.
RuO 2 OH RuO 2 O H
*
e (2) More than 20 microbes were isolated from the textile
wastewater. Four microbes namely Pseudomonas, phan-
Thus both physisorbed (RuO2(•OH)) active oxygen and erochaete, Bacillus and tricoderma were used in this
study. The microbes culture were cultivated in a fer- concluded that by the action of hydrolysis microbes, azo
menter containing sterilized media, nutrient broth, and in raw waste water produced organic amine and NH3 and
utilized to inoculate into wastewater. The COD reduction these product solutions were alkaline, the quantities of
by the biological treatment was carried out. Table 3 organic amine and NH3 augmented gradually.
shows COD removal efficiency. At the end of 5th day,
Pseudomonas putida gives the maximum reduction of 3.5. Mechanism of Azo Dye Reduction
COD as 92% and colour removal as 95% respectively.
The very first step in the bacterial degradation of azo
3.4. Mechanism of Pseudomonas Putida in dyes, in both the anaerobic or aerobic conditions, is the
Treatment reduction of the –NN– bond. This reduction might be
involving different mechanisms. For example the reac-
Among the microbes, the addition of Pseudomonas tions of the enzymes, low molecular weight redox me-
putida into the RTWW gave the best performance in the diators, chemical reduction by biogenic reductants like
reduction of COD. Aromatic compounds are susceptible sulfide or a combination which is shown in the Figure 3.
to biological degradation in both aerobic and anaerobic Additionally, the location of the reactions can be either
conditions. Diazo bond in azo dyes could be parted by intracellular or extracellular depending on the availabil-
azo reductive enzyme produced by Pseudomonas putida ity of the active microbial species.
in anoxic or anaerobic condition, and then an azo dye Microorganisms, bacteria, with their enzyme systems
molecule was made of two amine molecules holding degrade the aromatic structure under aerobic and anoxic
–NH2 [31]. conditions [33-34]. However, in both the conditions,
microbes metabolize aromatic compounds in both the
R1 N N R 2 4e 4H R1 NH 2 R 2 NH 2
peripheral and central path-ways of the cell [35]. Periph-
(7) eral pathways convert a wide variety of compounds into
where R1 and R2 were various phenol and naphthol resi- a few intermediate products or fragments. In aerobic
dues. Then after, amine could be decomposed by ammo- metabolism, the initial reactions involve the replacement
nia by an action of hydrogenation enzyme and hydrolysis of other functional groups attached to the aromatic ring
enzyme in anoxic condition [32]. From the study it is with hydroxyl groups, followed by cleavage by involving
Figure 3. Schematic representation of different mechanisms of anaerobic azo dye reduction. RM = Redox mediator; ED =
electron donor; b = bacteria(enzymes).
two oxygen atoms. These reactions are catalysed by before treatment and after EO treatment and BT treat-
enxymes like hydroxylases and oxygenases. Under an- ment and are shown in Figure 5. The intensity of peaks
oxic conditions ring reduction and other unique reactions was reduced by EO and is shown in Figure 5(b) and
such as carboxylation, reductive dehydroxylation, addi- followed by BT method Figure 5(c). The dye UV spec-
tion reactions etc are predominant which are absent in trum before treatment exhibited absorption bands at 545
the aerobic metabolism [35]. nm. The characteristic band at 485 to 570 nm could be
The trend of the microorganism in removal of COD assigned to the n-* transition of –N=N– group [37]. The
and colour is as follows: weak band below 350 nm could be attributed to the -*
Pseudomonas > phanerochaete > Bacillus > Tri- transition related to the aromatic ring attached to the
coderma. –N=N– group in the dye molecule. It is apparent that the
intensity of characteristic band (545 nm) of dye solution
3.6. FTIR Analysis of the Sample was found to diminish gradually during the experiment
and disappeared totally after EO and BT. The disappear-
The sample was given for FTIR spectrum analysis before ance of the bands indicates the effective destruction of
and after treatment. Figure 4 shows the FTIR spectra of the azo. The intensity of the absorption spectra was re-
untreated and treated by electrooxidation and biological duced further by BT as it is evident from Figure 5(b)
method dye effluent. Major peaks were obtained for un- when compared with EO treatment shown in Figure 5(c).
treated sample at 3302.08, 2107.55, 1636.47 and 709.29 It could be concluded that the dye molecule undergoes
cm−1 shown in Figure 4(a). The absorbance of peaks at degradation in the presence of microorganisms. This
3302.03 cm−1 and 1636.47 cm−1 were due to the structural clearly indicates that the intensity of the absorption spec-
vibration of hydrogen in bound with OH groups of phenol
or OH of carboxyl groups COOH and the hydrogen vi-
bration of amide N-H functions. It shows that the sample
contain high content of water molecule and considerable
amount of alkanes (C−H). After decolourization showed
absence of peak at 1600 cm−1 indicates breakdown of azo
bond, might be due to action of azo reductase. Absence of
peaks at 688 cm−1, 726 cm−1, 765 cm−1 and 827 cm−1 in-
dicates loss of aromatic or benzene ring.
The absorbance of peaks at 2107.99 cm−1 was due to
the vibration of C=O and intense absorbance of the bands
at 1620 - 1640 and 1510 - 1540 cm−1 was also observed,
indicating enrichment in amide and aromatic. The ap-
pearance of peak at 1636.47 cm−1 indicates the pressure
of C=C conjugated diene groups. This is due to the func-
tional group of aromatic carbons. The absorbance of Figure 4. FTIR spectra of untreated dye effluent (a), elec-
peaks at 709.23 cm−1 (out-of plane bending modes of tro-oxidation (b) and biologically treated (c).
aromatic C−H bonds) was found to be due to the vibra-
tion of aromatic compounds and benzene ring. Figure
4(b) shows the FTIR spectra of treated sample by Elec-
tro-Oxidation. After the EO method, decolourization
showed absence of peak at 1636.47 cm−1 indicates
breakdown of aromatic rings. Peak at 1615 cm−1 indi-
cates synthesis of aliphatic secondary amines and di-
methyl groups it seems that azo reductase catalyses the
reductive cleavage of the azo bond of methyl red [36].
Figure 4(c) shows the FTIR spectra of biologically
treated sample. Out of the four organisms used Pseudo-
monas putida showed the best performance which de-
grades to facilitate by oxidative enzymes.
3.7. UV
Figure 5. UV–vis spectra of untreated dye effluent (a), elec-
The samples were given for UV–Vis spectra analysis tro oxidation (b) and biologically treated (c).
tra was reduced drastically after the combined effect of chemistry, Vol. 31, No. 5, 1995, pp. 435-442.
both the treatments. doi:10.1016/0032-9592(95)00085-2
[9] I. Kapdan, F. Kargi, G. McMullan and R. Marchant,
4. Conclusions “Comparison of White-Rot Fungi Cultures for Decolori-
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22, No. 4, 2000, pp. 347-351.
The following conclusions were drawn: doi:10.1007/s004490050742
1) COD and colour were reduced significantly by elec-
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