Indian Journal of Fibre & Textile Research

Vol. 29, June 2004, pp. 239-259

Review Article

Colour removal from textile effluents

M Joshi', R Bansal & R Purwar
Department of Textile Technology, Indian Institute of Technology, New Delhi 110 016, India
Received 17 February 2003; accepted JO July 2003

The environmental issues associated with residual colour in textile efnuents have posed a major challenge to
environmental scientists as well as the textile colouration processors. The requirements to remove colour from textile
efnuent on si te prior to discharge to sewer have been progressively tightened due to increased public complaints about
coloured watercourses. Dyes are highly dispersible aesthetic pollutants and are difficult to treat, as most dyes are highly
stable molecules made to resist degradation by light, chemical, biological and other treatment or exposure. There has been a
lot of research going in the past few decades to develop efficient and cost effective technologies to remove colour from
textile efnuent. This paper presents a critical review of the current literature available on various textile wastewater
decolourisation techniques being applied and researched to remove colour from textile wastewater.
Keywords: Colour removal, Dye separation, Textile effluent
fPC Code: Int. Cl. 7 C08J 11/04; C02F 1/00; C02F 3/00

1 Introduction Most dyes have complex aromatic structure

Wet processing operations during textile chemical
processing, i.e. desizing, scouring, bleaching, dyeing,
printing and finishing, are the major causes of water
pollution. A major contribution to colour in textile
wastewater is usually the dyeing and the washing
operation after dyeing during which as much as 50%
of the dye might be released into the effluent. During
dyeing, most of the dye is exhausted on the fibre, but
the unfixed dye goes into wastewater causing deep
colour. The wa<;tewater is extremely variable in
composition due to large number of dyes and other
chemicals used in processing. The problem is further
made complex by the thousands of dyestuff
commercially available. The use of different dyes
depends upon the characteristics of the fibre, the
specific colour to be applied and the desired finish
required on the fibre. Although dyes constitute a small
portion of the total volume of waste discharged in
textile processing, colour removal from effluent is a
major problem for textile industry because of several
reasons:
The presence of even a small fraction of dyes in
water is highly visible due to high tinctorial value of
dyes and affects the aesthetic merit of streams and
other water resources.
resistant to light, biological activity, ozone and
other degradative environments and hence not
readily removed by typical waste treatment
processes.
The possible long-term effects of a few dyes and
dye degradation products are becoming of
increasing concern. The possible mutagenic,
carcinogenic and/or allergenic effects of dyes
have been established'6. Over 90% of some 4000
dyes tested in an ET AD survey had LD50 (Lethal
Dose at 50% survival) values greater than 2 x 103
mg/kg. The highest rates of toxicity were found
amongst basic and diazo dyes 6.
Unless and otherwise properly treated, dyes can
significantly affect photosynthetic activity in
aquatic life due to reduced light penetration and
may also be toxic to certain forms of aquatic iife
due to presence of metals and chlorides in them 79
There is little evidence that the dyes found in
watercourses are toxic to fish and other wild life
at the concentrations likely to be present'o. Most
of the studies on toxicity of dyes and pigments are
concerned with the hazards due to occupational
exposure of employees to dyes in the user
. d II
In ustry .

Dyes have also been known to interfere with

"To whom all the correspondence should be addressed.
Phone: 26596623; Fax: +91-11 -26581103; certain municipal wastewater treatment
E-mail : man gala @textile.iitd.ernet.in operations 7 , i.e. UV disinfection, etc.
240 INDIAN J. FrBRE TEXT. RES., JUNE 2004

2 Textile Dyes and Environmental Concerns Table 1-- Exhaustion range of various dye classes 2
Textile dyes are classified under the categories of
Dye class Fibre Degree of Loss to
anionic, cationic and nonionic types. Anionic dyes fixation, % effluent , %
mostly include the direct, acid and reactive dyes.
Basic dyes are the only class of cationic dyes used in Acid Polyamide 80-95 5-20
the textile industry. Nonionic dyes refer to disperse Basic Acrylic 95-1 00 0-5
Direct Cellulose 70-95 5-30
dyes, which do not ionize in an aqueous medium. Disperse Polyester 90-1 00 0- 10
It is estimated that about 15% of the total world MetaI-comp\ex Wool 90-98 2- 10
production of colorants are lost in the synthesis and Reactive Cellulose 50-90 10-50
processing of colorant8 . The wool and acrylic dyes Sulphur Cellulose 60-90 10-40
Vat Cellulose 80-95 5-20
tend to be in the best situation in this respect since
high exhaustion is normal when applying anionic dyes contaminate sea water/river water with their toxicity
to wool and cationic dyes to acrylics. The biggest and destroy marine life 9
problem relates to the dyeing of cotton with reactive The environmental impact of metals in wastewater
and sulphur dyes because of the low leve l of effluents is also an important issue faced by the dye
exhaustion and fixation 12 as shown in Table 1. manufacturing and application industries today. This
Another important problem in the dyeing of is an important point because a significant number of
cellulose fibres with anionic reactive dyes is the dyestuffs are metallized dyes. Commonly employed
requirement of large amount of inorganic salt to metals are chromium, cobalt, nickel and copper, all of
suppress the negative charge at the fibre surface so as which are designated as priority pollutants by the US
to increase its exhaustion level on the fibre. However, Environmental Protection Agency (EPAi.
various developments have taken place in the recent
3 Dyestuff and Colour Removal from Textile
years to increase the exhaustion level of reactive
Emuents
dyes lJ-23 . In 1986, the Health and Safety executive
Colour removal is a pertinent problem for all
issued publications concerning the possible
categories of textile effluents due to the variety of
respiratory irritant and sensitization effects from
chemicals used in dyeing and printing of fibre, yam or
handling the dry powders or from aerosols containing
fabric.
these materials4 .
Colour pollution can be most efficiently controlled
The chromophores in anio nic and nonionic dyes are by good source reduction practices, administrative
mostly azo group or anthraquino ne types. The and engineering controls, process and product design
reactive cleavage of azo linkage is responsible for the and work practices. The search for dynamic response
formation o f toxic amines in the effluent. and improved productivity has served to focus the
Anthraquinone based dyes are more resistant to attention of the colouration industry on right first time
degradatio n due to their fused aromatic structures and, (RFf) production techniques 24-27. A hi gh level of RFf
therefore, remai n coloured for a lo nger period o f time minimizes waste and makes a significant contribution
in the wastewater. to reduce colour loads in the effluent28 Improving the
The azo dye and pigment manu facturing plants exhaustion levels of the various dyes in the dye bath
produce a waste which has low pH, high colour, high is another area which has received lot of attention
organic content (high COD) and low amenabil ity to from researchers as it will not only improve shade
biological degradation (low BOD) and can be defi ned reproducibility and problem of repeat shades but also
as a typical dye waste 8 . Dyes have a very low rate of s. live the colour effluent problems which will then
removal ratio for BOD to COD (B O~/CO ~ is less reduce to a matter of controlling and handling spills
than O.l) and not removed by typical biological and clean-up. Dyes showi ng a high level of
treatment plants. Furthermore, dyes can be exhaustion and fixati on o n the fi bre have been and
detrimental to the microbial population present in will continue to be the prime targets of research and
such plants and may decrease the efficiency or lead to development activity.
treatment failures in such plants24 However, quantitative dye bath exhaustion is not
'The alkaline reducing systems based on Na2S in possible with most systems and hence the removal of
some dyeing recipe cause discharges of the effluent colour from textile e~f1uents is a major problem faced
containing sulphur, which give foul smell and by environmental scientists and engineers.
 JOSHI et al.: COLOUR REMOVAL FROM TEXTILE EFFLUENTS
Most current practices for wastewater
decolourization treatment fall into following four
main classes:
-Physical or physico-chemical techniques, I.e.
precIpitation, coagulation/flocculation, ion
exchange, adsorption, and membrane separation.
These remove or separate the colour physically and
result in need for solid waste disposal,
--Chemical techniques, i.e. ozonolysis, chemical
oxidation / reduction, etc. These technologies
remove the colour from the effluent by breaking
down the dye into simpler fragments and destroy
the chromopore responsible for colour,
-Biological techniques, i.e. aerobic and anaerobic
digestion, whereby decolourization takes place
either by adsorption of dyes on activated sludge or
by biological degradation of dye molecules, and
-Electrochemical techniques, i.e. electrodialysis /
ion oxidation. It combines the oxidation of the dye
and the other polluting contaminants by means of
the electrolytic process with the physico-chemical
precipitation of the sludge.
Each technique has a specific application and
distinct advantages and disadvantages. As a result,
each method has to be evaluated according to cost,
application and performance relative to desired goal.
Although no treatment technology has universal
application, combination of one or two is generally
employed depending on wastewater characteristics.
3.1 Physical or Physico-chemical Techniques
3.1.1 Coagulation / Flocculation
Over the years, coagulation has been the only
economically feasible method for colour removal. The
primary treatment in a conventional wastewater
treatment scheme consists of coagulation and
flocculation, which removes the colloidal particles of
colour, turbidity and bacteria.
Coagulants such as Fe (III) or AI (III) salts when
added in a sufficiently high concentration, rapid
precipitation in form of hydroxides takes place. The
colloidal particles become enmeshed in the precipitate
and settle along with ie8 . Coagulant aids can be used
to produce more compact floc and lead to improve
settling. Coagulant dosing required depends on
concentration of colloidal impurities present in the
water. Synthetic organic polymers also work as
coagulant by effecting interparticle bridges due to
presence of groups, which can get adsorbed onto the
colloidal particle. Iron was found to be superior to
241
aluminum for colour removaf9. Several studies have
been reported on the use of different coagulants for
textile wastewater treatment 30. 36 . It has been found
that a particular flocculent is suitable for only certain
dyes; for example, alum is unsatisfactory for the
removal of colour generated from azoic, reactive, acid
and basic dyes, but is good for treating disperse, vat
4
and sulphur dyes . Combinations of various chemicals
have been used to improve colour removal from
effluent containing the more common dye types.
The characteristics of the molecules themselves
have an influence on their removal by coagulation .
Molecules having acidic functional groups, which are
able to coordinate with iron to form relatively
hydrophobic complexes can be removed by
coagulation. Hence, coagulation cannot treat all kinds
of dye 32 . Cationic dyes do not coagulate at all, making
their removal by this technique impossible. Acid,
direct, vat, mordant and reactive dyes usually
coagulate, but the resulting floc is of poor quality and
does not settle well even after introduction of a
flocculent. Sulphur and disperse dyes coagulate well
and settle easily . The coagulant dose required to
achieve this colour removal depends on the type of
effluent in terms of class and concentration of dye and
other processing aids used and is an important
consideration in evaluating its strength as well as
economics of the treatment and recycle. In the
presence of surfactants, the dosing of chemicals has to
be significantly increased to achieve satisfactory
colour removal. The other process parameter, viz
mlxmg intensity, duration of mlxmg and
configuration of flocculation tanks, also influence the
coagulation/flocculation process. Kang et al. 33 did a
comparative study on coagulation of textile secondary
effluents using the ferrous coagulation (pH 8.0-10.0)
vs. Fenton's coagulation (pH 3.0-5.0) and found that
with the same ferrous dosage, the ratio of COD
removal ranges from 1.4 to 2.3 and colour removal
ranges from 1.1 to l.9 respectively .
Major disadvantage of using coagulation and
flocculation is the generation of large amount of toxic
sludge creating a lot of handling and di sposal
problems. The reappearance of colour in subsequent
steps due to oxidation is also a critical problem faced
in these plants. The other major drawback is that th is
scheme is not able to reduce the total dissolved solids
(TDS) rather the TDS levels are enhanced during
treatment and hence poses lots of problems in water
recycle and reuse.
242 INDIA N J. FIBRE T EXT. RES., JUNE 2004

3. 1.1.1 Synthetic Organic Coaglliants R R

These pol ymer coagulants are highly charged ,I - 1
XXX-R-O- + N-R XXX-R--()' - - - - - -N-R
cationic polyelectrolytes and promote precipitation of 1
R R
1

Dissolved
dye residues , formin g small insoluble colour particles. dye molecule
Coagulant
Weakly bound Coprccipitatc
molecule
These small particles are removed using a su itable
R
solid/liquid separation process. These often - ,I
R

completely eliminate the need for the large amounts

of aluminum or iron based salts traditionally used.
XXX- R - O---- -N - R
1
R R
0 ,I

'~
The mechani sm of dye removal is electrostatic R-N - R
t
R
attraction between oppositely charged soluble dye and
polymer molecule (Scheme 1).
R- N - R High r.m.m flocculant
, R molecule
3.1.2 Adsorption : -
XXX- R - (). ---- --N-R
1

Adsorption is the phenomenon by which the 1

molecules of a gas, vapour or liquid spontaneously
concentrate at contacting sUlface without undergoing any
reaction. It is an effective method for lowering the
concentration of dissolved organics in an effluent. The
use of any adsorbent, whether ion-exchanger, acti vated
carbon or high surface area inorganic material , for
removing species from a liquid stream depends on the
equilibrium between the adsorbed and the free species 4 .
The various adsorbents reported in literature for the
removal of colour from textile effluent are:
3. 1.2. 1 Activated Carbon
Activated carbon has been evaluated extensively
fo r the treatment of different classes of dyes, i.e. acid,
direct, basic, di sperse, reactive, etc and is now the
most widely used adsorbent for dyes 37 -38 . Several pilot
plant and commerci al-scale systems using activated
carbon adsorption columns have been developed 39 .
T he molecul ar structure of a dye has a significant
effect on the extent to which it will be adsorbed with
decreasing solubility and polarity of the dye favouring
absorbability on carbon. Disperse dyes, vat dyes and
pigments have such low solubility in water that their
rate of adsorption on carbon is prohibitively slow at
room temperature. On the other hand, water-soluble
dyes such as acid, basic, direct, metallised mordant
and reactive dyes are also not readily adsorbed on
carbon . One of the main reasons for the observed poor
adsorption is the polar nature of these dyes vs. the
non-polar nature of carbon. Hence, the carbon
adsorption of dyes is neither efficient nor economical
when used alone, However, when used in
combination with polymer flocculation, chemical
coagulation or biodegradation, it becomes a very
useful polishing step for efficient dye removal.
Factors such as choice of activated carbon ,
te mperature, pH, contact time and dosage must be
taken into consideration for optimum removal of dyes
R
Stronger and enlarge floc
(Not yet residual change)
Scheme l-Coagulation and fl occulation mechanism4
from wastewater. Activated carbon although
reasonably effective at removing dyes from aqueous
streams needs either regeneration or disposal once it
is fully loaded. The other limitations are the high cost
and 10- 15% loss of adsorbent on reactivation.
3.1.2.2 Bioadsorbents
In recent years, investigations have been
undertaken to evaluate inexpensive alternate materials
of biological origin as potential adsorbents for dyes ,
which include chitin, chitosan 4 .40, sawdust4 1.42,
carbonized wool 43 , activated sludge44 ,wood bark, rice
husk"and cotton waste45 .
3.1 .2.3 Biomass
Because of its low cost and wide spread
avai lability, biomass has been extensively
investigated to remove colour and has shown some
promising resuIt46 Biomass here refers to dead plant
and animal matters, such as agriculture, forest,
fermentation and shellfish byproducts or wastes.
Biomass decolourizes textile wastewater by
adsorption and ion exchange mechanisms.
Unfortunately, without prior chemical modification
these materials uniformly have very low adsorption
capacities for anionic dyes. There have been several
studies reported on chemical modification of
cell uloses and ligno-celluloses extracted from cotton
waste, sawdust and corn stalks47 .
3.1 .2.4 Chitin and Chitosan
Chitin, a polysaccharide, is very similar in structure
to cellulose, being composed of poly 2-acetamido-2-
dioxy-D-glucose. Chitosan is a well-known derivative
 JOSHI et al.: COLOUR REMOVAL FROM TEXTILE EFFLUENTS
of chitin produced by the deacetylation of chitin
which is a natural biopolymer extracted from the shell
4 57
of arthropods . Due to its unique molecular structure,
chitosan has an extremely high affinity for many
classes of dyes, including disperse, direct, reactive,
acid, vat, sulphur and naphthol. The rate of the
diffusion of dyes in chitosan is similar to that in
cellulose. The only class for which chitosan has a low
affinity is basic dyes. There are several studies on the
use of chitin and chitosan for the removal of dyes 48.51 .
Knorr48 was the first one to examine the dye binding
properties of chitin and chitosan and found that
chitosan had better dye uptake property than chitin.
Mckay et al. did extensive work on chitin and
reported adsorption equilibrium studies 49 , batch and
column studies 5o , kinetic studies and mass transfer
models 51 for the adsorption of various dyestuffs on
chitin.
More recently, Quin 52 investigated the possibility
of using chitosan fibre, which has amino groups and
therefore shows the advantage of more adsorption
capacity and much easier desorption. A moderately
crosslinked chitosan fibre 53 .54 allows the fibres to be
used at low pH which improves the dye binding
capacity without solubilising the chitosan and was
found to have an Acid Orange II (a monovalent anion)
having the binding capacity of about 4.5 mollkg at
pH 3-4.
3.1.2.5 Microbial Biomass
The uptake or accumulation of chemicals by
microbial biomass is termed as biosorption. Dead
bacteria, yeast and fungi have all been used for the
purpose of decolourizing dye containing effluents 55 .56.
Depending on the dye and the species of
microorganisms used, different binding rates and
capacities were found. The use of biomass has its
advantages, especially if the dye containing effluent is
very toxic.
Biomass adsorption is effective when conditions
are not favorable for the growth of microbial
population. Adsorption by biomass occurs by IOn
exchange.
Many industrially useful fungi contain chitin and
chitosan in their cell walls. Hence, the fungal biomass
byproducts of industrial fermentation processes can
serve as dye adsorbent. The cell wall of Myrothecium
verruca ria was shown to bind azo dyes, including
Acid Orange IT and Acid Red 114 (a divalent anion).
The dye binding to the fungal material was
243
moderately slow, requiring 4-6 h to reach the
equilibrium.
Hu examined the adsorption of reactive dyes
to Aeromonas biomass. Dye absorption kinetics was
moderately fast with the equilibrium reaching
within 2 h.
3.1.2.6 Vnlllodified Lignocellulose Biomass
Mckay et a1. 43 .45 examined wood bark, rice husk,
and cotton waste for their ability to bind Congo Red
(a divalent anion) and observed negligible amounts of
adsorption. Poots et al. 58.59 showed that the wood
could adsorb acid dyes successfully but long contact
period is required to reach equilibrium. Similarly ,
Mckay et a1. 60,6 1 reported wood shavings to have a
capacity for Congo Red of 0.001 mol/kg. The binding
of Acid Blue 25 to sugarcane bagasse is slow and the
capacity is only 0.05 mol/kg. Maize (corn)62 al so
binds Acid Blue 25 slowly, requiring more than 3 h to
reach the equilibrium.
3.1.2.7 Ch emicallymodified Cellulose and Lignocellulose
Hwang and Chen 63 .65 reported a series of
adsorbents prepared from the reaction of polyamide-
epichlorohydrin resin and cellulose. This materi al,
composed of 10-30% cellulose, has a high adsorption
capacity for acid, direct and reactive dyes.
Unfortunately, the rate of dye adsorption is very slow,
requiring 3 days at 30C to reach the equilibrium. The
apparent adsorption capacity of PAE-cellulose is pH
dependent (similar to chitosan). The adsorption
capacity for Direct Blue 86 (a divalent anion) of the
PAE-cellulose (25 % cellulose) material is 1.0 mollkg.
Youssef>6 described the chemical modification of
cellulose (cotton) with the N-methylol derivatives of
tris- and bis -(2-carbamoylethyl) ethylamine to
enhance acid dye adsorption . The dye Acid Bluel3
was bound to the 30% bis derivative to the extent of
0.013 mollkg.The equilibrium with the dye was
reached within 30 min, indicating excellent kinetics.
Phosphorylated cellulose as cationic dye adsorbents
has been reported by Kammel 67. Abo-Shosha et al.68
prepared cellulose/glycidyl methacrylate/acrylic acid
cation exchange composite and co uld remove some
basic dyes from textile effluents. The cellulose
derived from sugarcane bagasse was derivatized to its
carbamoyl derivative and used as direct dye
adsorbent 69 . But, it was observed that the dye binding
capacity of the untreated cellulose was higher than its
deri vati ve.
244 INDIAN 1. FIBRE TEXT. RES., JUNE 2004

Quaternary ammonium groups can be introduced Table 2 - Principle difference between reverse osmosis, nano
into cellulose and lignocellulosic materials. The filtration and ultra filtration 108
quaternary ammonium group introduces a permanent
System Pressure Cross flow Process Retention
positive charge to the substrate, making the materials Mpa rate tlux
very effective acidic dye adsorbents. Gangneux et IllS
1
Im2 h 1
a l .70,7 1 demonstrated that quatermzed
.
cellulose has an Reverse
2-3 5-40 >90%NaCl
3-6
exchange capacity of 0.6-0.7 eq/kg for acid, direct and osmosis
reactive dyes. The equilibrium adsorption of the dye Nano >90%Lactose
2-4 2-3 20-80
was achieved in < 2 h. While quaternized cellulose filtration <.SO%NaCl
has most of the desired performance characteristics
Ultra 4-200xlcY
(high capacity, rapid kinetics, etc), it fails to retain the 0.5-2.5 3-4 5-200
filtration MWCO
most important attribute--Iow cost. Presumably, this
. 4885-90
exchange reSInS " . However, th ey have not been
is due to the cost of preparing pure cellulose, not
because of the cost of quaternization. A low-cost widely used for the treatment of dye containing effluents,
adsorbent can be prepared by quaternization of mainly due to the fact that 10n excharlge resins cannot
lignocellulosic materials, such as corn cob72 , saw accommodate a wide range of dyes i.e. not effective for
d ust73 an d sugarcane b agasse 74 . These matenals.
have disperse dyes and have to be regenerated using costly
the exchange capacities in the range of 0.35-0.85 organic solvents once they are saturated. The process is
eq/kg. The dye adsorption and desorption feasible provided an organic solvent such as methanol is
characteristics of the quaternized lignocelluloses are used during the regeneration step, which can be
quite comparable to the cationic materials prepared recovered later.
from pure cellulose. In the early 1980s , the Institute Textile de France
Thus, relatively inexpensive, moderately high studied the use of cellulose based ion exchange
4
capacity, anionic dye adsorbents could be prepared materials for the treatment of dye house effluents .
from lignocellulose biomass. However, none of these Because of the synthetic nature of these materials,
adsorbents has any commercial importance. Table 2 they could be tailored to have great chemical
summarises the main advantages and disadvantages of resistance. A combined process involving adsorption
different bioadsorbents reported for the removal of on synthetic polymer and ion exchange has been used
dyes from textile wastewater. to decolour dye wastes 85 The process has several
operating and performance advantages over activated
3.1.2.8 Inorganic AdsorbenlS carbon adsorption.
In recent years, investigations have been
undertaken to evaluate inexpensive inorganic 3. 1.2.10 Macrosorb / Acrasorb
materials as potential adsorbents for dyes, which Macrosorb is the trade name for a range of
include peat?, flyash 75 , bentonite76 , calcium inorganic particulate adsorbents developed 9 I,92.
metasilicate , activated aluminum 78 , clay and
77 Macrosorb is synthetic inorganic clay and the crystal
bauxite79 . The use of bentonite for basic dyes and structure consists of parallel layers of clay platelets,
anthracite charcoal for acid yellows are also known 80 . which due to their chemical composition carry a net
The use of inorganic adsorbents, such as high positive charge. Between these layered platelets, there
surface area silica, cinder ash and clays, has been tried is anion which balances the cationic nature of clay.
for a range of dyes 8 1. 84 Silica was found to be They are thus engineered for optimum adsorption of
reasonably effective for treating effluents containing the compounds found in dyehouse effluents, which
basic dyes . Again the process has little effect on the have a larger negatively charged or polar molecule,
major inorganic charge of the effluent. The use of i.e. dyes, organohalides, pesticides, etc. The adsorbent
cinder ash appears to be a cost effective solution capacities are very high and can remove these
where a readily available supply of the ash is found contaminants from process water down to extremely
locally and the effluent does not contain reactive dyes. low levels and are then removed by gravity settlement
in the form of pumpable sludge. This offers prospect
3. 1.2.91011 /:.xchange Resins of being able not only to meet any current or
Since most dyes are chemically either anionic envisaged consent limits but also of water reuse.
or cationic, they could in theory be removed on ion Acid, metal complex, direct and reactive dyes are
 JOSHI et al.: COLOUR REMOVAL FROM TEXTILE EFFLUENTS 245

easily adsorbed by Macrosorb. Disperse dyes are only
slightly soluble in water but a combination of
adsorption and gravity settlement in the overall
system gives good removal. In the unchromed state,
chrome dyes are adsorbed by Macrosorb. In the
chromed state such colouring matters are not in
solution but are removed by the accelerated gravity
settlement of the treatment.
Similarly Arcasorb D is a proprietary biological
adsorbent from Archaeus Technology Group which
removes soluble dyes (in particular reactive dyes) and
other contaminants from textile waste stream93 .
The main mechanisms involved in the removal of
colour and other contaminants from effluent streams
by Macrosorb and Arcasorb D are believed to be
physical adsorption and anion exchange.
3.1.2.11 Polymer Waste
Polymers are also capable of adsorbing the residual
dyestuff from textile effluent. Polyamide, which can
be dyed with most of the common dyestuff classes
and has reactive groups available, is a primary
Table 3 -Summary of bioadsorbenr.s
candidate in this respect94 . The waste polyamjde
fibres or plastics can be used as dye cleaners by
suitably degrading the polyamide to bifunctional low
molecular fragments with termjnal reactive amino and
carboxyl groups important for dye uptake.
3.1.3 Compleximeteric Technique
Cucurbiturial is a cyclic polymer of glycoluril and
formaldehyde, so named because its structure is
shaped like a pumpkin95 (a member of the plant
family cucurbitaceae). Cucurbitile showed
extraordinary good sorption capacity for various types
of textile dyes 96 It is known to form host guest
complexes with aromatic compounds and this may be
the mechanism for reactive dye adsorption. To be
industrially feasible, it needs to be incorporated into
fixed bed sorption filters. High cost is a disadvantage.
3.1.4 Membrane Separation
Membrane filtration technology is extensively applied
in process industries to concentrate, purify and improve
the final product97
47

Biomass Adso~tion caQacit:t. mol/kg Major drawback

Monovalent dye Divalent dye

Chitin 0.45 0.13 Slow kinetics

(Acid Blue 25) (Acid Red I)
Chitosan 0.45 Slow kinetics
(Acid Red I)
Crosslinked chitosan 4.5 pH sensitive
(Acid orange II)
Fungal biomass 0.05 0. 11 Slow kinetics
(Acid orange II) (Acid Red 114)
Bacterial biomass 0.08
(Reactive Yellow)"
Sugarcane bagasse 0.05 Low capacity
(Acid orange 25)
Wood shaving 0.001 Low capacity
(Congo Red)
Maize cob 0. 1 Low capacity
(Acid Blue 25)
Peat moss 0.13 Low capacity
(Lanasyn Black)
Rice Hull 0.14 Low capacity
(Lanasyn Black)
PAE-cellulose Slow kinetics

Carbamoy Icell ulose 1.0 Low capacity

Direct Blue 86)
Quaternized-cellulose 0.6-1.1 b 0.013 Expensive
(Acid Blue 13)
Quaternized- 0.035-0.85 b None
lignocellulose
"Trivalent anion
bCaQacit:t ( eqlkg)
246 INDIAN 1. FIBRE TEXT. RES., JUNE 2004
It can be sutxlivided into four categories, namely
reverse osmosis, nano filtration, ultra filtration, and micro
filtration. The principal difference between reverse
osmosis, nano filtration and ultra filtration are
summarized in Table 3. Ultra filtration is used to separate
solutes of molecular sizes between O.(X)1/Lm and O.I/Lm.
Below Mw - 1000, the osmotic pressure begins to
increase significantly and reverse osmosis or nano
filtration starts. Nano filtration retains small organic
molecules having a molecular weight >300 and even
polyvalent ions while allowing smaller ions to pass
through the membrane. True reverse osmosis
membranes, however, reject even the smallest ions and
allow the passage of pure water only. Hence, the
operational pressure for reverse osmosis systems is
higher in the range of 0.69-6.9 MPa whereas ultra
fi ltration systems operate at pressures usually in the range
of 0.069-0.69 Mpa (ref. 98).
In textile industry, membrane separation processes
have found several applications such as improvement in
the quality of finished product, increased yield, saving in
raw material or recovery of product from waste and
increased dryer capacity. The use of membrane
technology to treat liquid effluents from textile uni ts has
already been reported97- 1\0 with great interest.
Reverse osmosis and ultra filtration are very effective
for the removal of colour from dye house effluent
regardless of the type of dyestuff used. Decolourisation
by these procedures is in the range of 95-100%. The
various dyes were studied to observe if removal is
possible by micro filtration, ultra ftItration or nano
filtration modules. A large proportion of disperse and vat
dyes are removed by a 0.45 ~m pore micro filtration
membrane. The proportion of other classes of dyes
removed on these membranes is small or nil. Porter and
Gomes lO3 reported that a polypropylene micro ftItration
membrane rejects both salt and Direct Red 2 from
aqueous solution when the conductivity of the solution is
below 500 m~ siemens. Ultra filtration achieves
complete colour removal for all classes of dyes except
reactive dyes. But, care is needed to avoid membrane
clogging, which appears to occur rapidly. Nano filtration
membranes allow complete colour removal but with less
membrane fouling. Separation of reactive dyes from
effluents containing reactive dyes and salts using
commercial nano filtration membranes has recently been
reported III . An experimental investigation on electric
fieJd enhanced nano filtration is reported for a direct dye
solution. A 100% dye rejection was obtained for the
membranes tested. An electric field was found to be
efficient in reducing fouling for both membranes
studieAl 109.
3. 1.4.1 Membrane Materials
Textile effluents have a very wide range of
composition in terms of pH, acidity/alkalinity, type of
dyes and other contaminants and may be quite hot
(50-80C). Hence, the membrane to be used for such
an application should have good chemical as well as
thermal resistance. Reverse Osmosis and ultra
filtration membranes made out of a variety of
polymers, e.g. polyamides ll2 , poly (phthalazine ether
sulfone ketone) 113, styrene copolymer I 14,
polyacrylonitrile, polysulfones l15 , polycarbonate, and
fluorocarbon based polymers have been used for
textile applications I 16. These membranes have
excellent thermal, chemical and mechanical stability,
allow the system to be operated at high flux rates and
are resistant to wide range of pH, temperature and
solvents. These membranes are therefore found to be
suitable for separation of organic dyes from textile
effluents. Ceramic membranes withstand higher
mechanical forces and tolerate rough effluent
conditions, such as temperature higher than 100C and
pH greater than 12. Generally, the membrane lifetime
is longer than for organic membranes but they are
fragile and require frequent back pulsing.
3. 1.4.2 Membrane Configuration
Membranes are packaged in modules that control
the pressure, feed stream velocity and turbulence to
reduce concentration polarization (fouling) effects.
There are four basic kinds of modules, namely plate
and frame, tubular, spiral wound and hollow fibre
modules 117 .
Spiral wound modules provide a relatively high
packing density 1000m2/m 3) and allow for a
compact design, but they are intolerant of particulates.
A prefiitration step to remove fibres, grease, etc in
early process effluents may be necessary to avoid
clogging of the flow channels.
Tubular modules are relatively insensitive to
clogging and more effectively cleaned during
backwash procedures. However, packing densities are
very low C<100m2/m3) and feed flow rates per unit
membrane are high. Tubular Membranes have been
extensively used for desalting of product dyes (reactive
dyes) and it is possible to use the technique to recover
sodium chloride solution from dye bath containing
reactive dyes for reuse. Tubular membranes also find
application for organic dye removal from textile
 JOSHI et at.: COLOUR REMOVAL FROM TEXTILE EFFLUENTS 247

l18
effluent . Nowaka et al. I19 reported the suitability of separation processes their space requirements are low
capillary membrane modules (UF and NF) for and modular construction and design allow relatively
decolourization of both simulated and industrial dye easy expansion.
effluent and found 92-99 % retention coefficient for The major problem faced in application of
organic dyes of molecular wt -780. membrane technology for effluent treatment is the
The main advantage of membrane processes is that high cost of membrane and other membrane filtration
concentration is achieved without any input of equipment, depending on the size of plant, the
thermal energy or a change of state, making the operating condition and associated water treatment
process energy efficient. Calabro et at. 120 conducted costs besides the problem of lower productivity with
energy analysis of integrated membrane processes in time due to the deposition of precipitated dyestuff, i.e.
treatment of solutions simulating textile effluents and fouling. Membrane systems are limited in several
did an energy analysis. ways as a consequence of their structure. The use of
Another great advantage of these membrane polymeric membranes is limited to the temperature of
processes is that the wastewater can be treated 70C, pressure of < 6-7 MPa and a pH range of 2-12
successfully to a level required for recycle and reuse l21 . (maximum). Another problem faced is the disposal of
Reuse options for the nano filtration permeates exist concentrates from the membrane processes. There
either as dye bath makeup stream or in the following have been several attempts to solve this difficulty by
rinsing stages, depending on specification. Reductions oxidative degradation of the membrane concentrates
of fresh water use of the order of 60 % and energy by Fenton's reagent l23 and ozonation of membrane
savings up to 50% can be achieved by integration of concentrated secondary effluent l24
membrane technology into continuous washing/rinsing 3.2 Chemical Techniques
processes. The removal of the dyestuffs from the spent 3.2.1 Chemical Oxidation
dye bath liquor using membrane technology makes it Many dyes are effectively decolourized using
possible the recycling of water in dye houses and the chemical oxidizing agents and found to hold potential for
concentration and reuse of dyestuffs. Thus, it not only future use in the textile industry. Many studies on usage
helps in pollution control and waste management but of different oxidizing agents, i.e. chlorination, chlorine
also helps in conservation of chemicals and water. dioxide treatment, ozonation, use of hydrogen peroxide
Techno-economic viable solutions have been suggested with other salts (Fenton's reagent), permanganate, etc,
to combat water shortages with innovative use of have been reported in literature8l , l25 and summarized in
membranes by Yedavyasan 122 Compared to other Table 4.
Table 4 -Summary of chemical oxidation techniques used for decolourisation 125
Method Comments
Sodium hypochlorite Effective on decolorisation, cheaper than other oxidants, and easily applicable (20-40C, 5-30 min).
Risk of halogenated hydrocarbon (AOX) increase and bacterial toxicity. Can only be used with small
amounts of wastewater.
Hydrogen peroxide Environment-friendly application. Not effective on all dyes as oxidation potential is not very high.
Fenton's reagent More effective than hydrogen peroxide on different classes of dyes. Wastewater may be reused
following this treatment and removes heavy metals. Causes severe sludge problems.
Ozone Specially useful in decolorisation of water-soluble dyes. Does not sufficiently decrease COD and
turbidity. Acids, aldehydes and ketones are reaction products. Recommended that coagulation and
ozone can be used prior to biological treatment.
UV irradiation Photocatalytic reactions of some organic species in aqueous solutions are feasible. Removes heavy
metals. Sludge and harmful UV scattering problems. .
Gamma irradiation New technique.
UV irradiationlhydrogen Increased rate and strength of oxidation, but the cost of producing UV irradiation does not compensate
peroxide for the increase. Environment-friendly application, apart from some UV scattering.
UV irradiation/ozone Increased rate and strength of oxidation, but the cost incurred by the UV irradiation does not
compensate for this increase. Environment-friendly, apart from UV and ozone scattering. Wastewater
may be reused since reaction products could be carbon dioxide, water, nitrogen, etc.
248 INDIAN J. FIBRE TEXT. RES ., JUNE 2004
3.2.1.1 Chlorination
Chlorination (using chlorine gas or sodium
l26
hypochlorite, i.e. NaOCI) has been evaluated for its
effectiveness in colour removal. At a chlorine level of
150 mg/L, colour was reduced by 77 % but 110 mg/L
of total chlorine remained in wastewater. In 1980,
Auburn University reported the results of laboratory
scale studies concerning the TSI chlorination
' . ChI onne
system 127128 . .IS reporte d to be more e ffectlve
' H20
for dye decolourization at pH 3.5 than at pH 7.0 or
10.0. Chlorine rapidly decolourized acid and reactive
dyes but even large doses of chlorine failed to
completely decolourize direct and disperse dyes,
rather persistent yellow decomposition products were
formed. Recently, an electrolytic process based on
chlorine generation was adapted to the wastewater
containing textile dyes 129 . In situ production of
hypochlorous acid was achieved in an undivided
electrolytic cell.
Although, decolourization using sodium
hypocholorite is inexpensive and effective but
dechlorination of wastewater is necessary in order to
prevent toxic effects in the ensuing biological
processes. Moreover, chlorine is viewed with
increasing disfavor because it has potential for
generating toxic chlorinated compounds i.e. AOX
(absorbable organohalides) that are harmful to
humans and environment.
3.2.1. 2 Chlorille Dioxide
Chlorine dioxide is less reactive than chlorine and has
been claimed to give rise to fewer side reactions4 The
experimental study shows, however, that it does not
decoloUIize dye waste efficiently to consent conditions,
as it has no effect on some dye classes, such as vat dyes.
Nevertheless, chlorine dioxide is highly effective against
reactive, direct, disperse and anionic premetallised dyes.
It could be used as a polishing treatment.
3.2. 1.3 Ozonation
Ozone is a more powerful oxidant than chlorine and
other oxidizing agents, i.e. 0 3, Ch and H20 2 with
oxidation potential of 2.07, 1.36 and 1.78 respectively
and offers a mechanism for oxidizing dye wastewater
without producing harmful chlorinated organics. Ozone
reacts with dye molecules in two ways: (i) below pH 5-6,
ozone is present mostly as 0 3 and reacts selectively with
double bonds in dye molecules, and (ii) at higher pH
(above 8), ozone rapidly decomposes forming hydroxyl-
free radicals that react non-selectively with organic
compounds. Ozone fading of dyes occurs by the
oxidative cleavage of the conjugated system of the
Et0-Q-N= N-Q-CH=CHV'N=~OEt
NaO,S
1 0,
OOHC-O--N=~OEt
j
EtO - - Q - N= N- - Q - CHO +
'"0.'
Scheme 2-Ozone fading of Cry sop he nine G (ref. (35)
molecule (Scheme 2). Ozone is useful for removing
many toxic chemicals from wastewater, as it is capable to
decompose detergents, chlorinated hydrocarbons,
phenols, pesticides and aromatic hydrocarbons.
Ozone treatment has been successfully used to remove
colour from dyeing wastewater I30-135. Some classes of
dye respond more readily to oxidation by ozone than
others. According to some authors4 reactive dyes are
degraded to greatest extent and ozonation is moderately
successful in treating wastewater-containing sulphur,
azoic and basic dyes. However, disperse dyes have poor
response to ozonation. The dosage applied to the dye
containing effluent is dependent on total colour and
residual COD to be removed with no residues or sludge
10rmatIOl1
C
an d no tOXIC ' 136 . 0 zonatIOn
. metabol Ites . may
decrease COD and increase the bio degradability of
waste stream but produce little reduction in TOC. Cost
and efficiency are barriers associated with ozonation.
Another major drawback is its short life (half-life, 20
min), requiring continuous ozonation. Improvement in
ozone diffusion by means of membrane contractor
(higher gas / liquid contact surface) in order to further
reduce operating costs has been recently reported by
Ciardelli et at. 137 in their ozonation pilot plant study.
Additionally, since ozone is hazardous, it will require
an ozone destruction unit to prevent ozone from escaping
and damaging the environment.
3.2. 1.4 Hydrogen Peroxide
Hydrogen peroxide is the main oxidizing agent
used for decolourization by chemical means and
removes the dye from the dye containing effluent by
oxidation resulting in aromatic ring cleavage of the
dye molecules. This agent needs to be activated by
 JOSHI et al.: COLOUR REMOVAL FROM TEXTILE EFFLUENTS
some mean s, for example ultra violet light, inorganic
2
salts ( Fe+ ) , ozone or ultrasound. Many methods of
chemical decolourization vary, depending on the way
in which H 20 2 is activated.
3.2.1 .5 H20r Fe (1/) Salts (Fenton's Reagel/t)
Fenton's reagent is a suitable chemical means of
treating wastewater which is resistant to biological
treatment or is poisonous to live biomass. In acid
solution, iron (II) as a catalyst, peroxide vigorously
forms hydroxide radicals (Scheme 3), which are used
to decolourize dye wastes 94 .
It is capable of treating soluble dyes, such as
reactive, as well as insoluble dyes, such as vat and
di sperse, and does achieve consent conditions for both
4 3.2. 1. 7 H20 ] - Ozon e
the concentrated and dilute waste investigated . The
vigorous oxidation also reduces the COD of th e
effl uent. Ne utralization of the effluent after treatment
causes precipitation of the iron oxide and hydroxide,
which removes any remaining insoluble dyes from the
effl uent by adsorption and / or flocculation. One of
the major disadvantages of this method is sludge
generation through flocculation of the reagent and dye
molec ule. The sludge, which contains the
concentrated impurities, still requires disposal and the
performance depending on final floc formation and
it's settling quality . In a comparative study' 38 on
oxidation of di sperse dyes by electrochemical process,
ozone, hypochlorite and fenton's reagent, the best
results were obtained with Fenton process which
under the optimal pH of 3 and H 20 2 and FeS doses of
600 and 550 mgm-3 respectively results in a final
colourless effluent with low residual COD (100
mg/cm\
3.2.1.6 H20 2 1UV
Decolourization of dyes using UV/H 20 2
photochemical oxidation has already been
investigated by several researchers 139- 143. This method
degrades dye molecules to CO 2 and H 2 0 by UV
treatment in the presence of HzO z (refs 139,140) . The
degradation is caused by the production of high
concentration of hydroxide radicals. UV light
activates the destruction of H2 0 2 into two hydroxyl
radicals (Scheme 4), which causes chemical oxidation
of organic material.
The rate of dye removal is influenced by th e
intensity of UV radiation, pH, dye structure and the
dye bath composition 141. This may be set up in a bath
or continuous column unit l42. Depending Oil the initi al
material, additional by products, such as halides,
249
Scheme 3--(:atalytic action of iron on hydrogen perox ide94
Scheme 4--Hydroxyl radical generation through UV radiation 139
metals, inorganic acids, organic aldehydes and
organic acids, may be produced 139. There are
advantages of photochemical treatment of dye
containing effluent-no sludge is produced and foul
odors are greatly reduced.
Advanced techniques using combination of ozone
and hydrogen peroxide make it possible to remove
odor, colour, COD, TOe and absorbable organo
halogens (AOX). The resultant products are often
143
easily biodegradable l l. . Decolourization by means
of Hz0 2/0 3 combination is appli cable for direct dyes ,
metal complex or blue disperse dyes, but there are
some problems with decolouration of acid, red
d Isperse d yes an d th' .
elr mIxture 141 .
3. 2.1 .8 H 20 r Peroxidase
Peroxidase can also be used as an acti vator for
144
H 20 2 for decolourization purposes. Morita et al .
studied decolourization of acid dye using three types
of peroxidases as peroxide activators . The
decolouration rate increases with increasi ng
peroxidase concentration and temperature of the
medium and was the greatest at pH 9.5.
3.2. 1.9 H 20 2 -UV-Ultrasound
145
Fung et al. studied the decolourization and
degradation kinetics of reactive dye wastewater by a
UV/ultrasonic/peroxide system. It was found that the
degradation of the reactive dye follows a pseudo first-
order kinetic model at different pH and H 2 0 z
concentrations. It was observed that the ultrasound in
combination with UV dramatically improves the
initial reaction rate and the overall dye removal
efficiency. Ultrasound may increase the oxygen
uptake and transfer rates which enhance the oxidation
processes due to the hydroxyl radicals.
3.2.2 Irradiation
Gamma radiation induced oxidation has also been
reported 125.146 in decolouring refractory dyes that
withstand many of the conventional textil e waste
treatment processes. The rate of reaction is controlled
250 INDI AN J. FIB RE T EXT. RES., JU NE 2004
by radi ati o n dose and the availability of oxygen in th e
soluti o n. It proved to be an effecti ve techniqu e fo r th e
re mova l o f dyes as we ll as toxi c o rganic co mpo und s,
i. e. be nze ne , to lu ene and chl orophe no ls, by ox idi zing
the m into mo re eas ily biodegrad abl e co mpo unds .
Bo th C OD and AOX were dec reased and 90% of
co lo ur in the wastewater was e limin ated. However,
very hi gh cos t is the maj o r di sad vantage.
Wet ai r ox idati on (W AO) is another process by whi ch
the efflu ent could be e ffectively di sposed 147.
3.2.3 Chemical Reductioll
For many dyes, pW1icui arly azo dyes, chemi cal
reduction is an effective decolouri sation technique.
Chemica l reduction of azo dyes causes cleavage of azo
bond, generating small nonchromophoric aromatic
Jm incs that in theolY are more amenable to subsequent
aerobic bio logical treatment than the parent dye structure.
Tn add ition, publi shed results indi cate that certain reacti ve
dyes are adsorbed well on to activated carbo n when
l48
pretreated with a reducing agent . Techno logies based
on bisulphi te catalyzed sodium borohydride a lo ng with a
catio ni c agent have been appli ed to water-so luble dyes
con taining azo or other reducible groups and copper
based metalli zed dyes 149. Using thi s process, co lo ur
reductio n of >90% was poss ible. Sod ium borohydride is
o ne of the strongest water-solubl e reducing agents
commerciall y avail able, while bisulphi te is not consumed
l49
but acts as a regenerable coreagent or catalyst . The
other most commonly used chemi cal reducing agents we
sodium hydrosulphite, thio urea dioxide, tin (II) chl oride,
etc. While evaluating the chemical decolouri sati on of
wastewater using reducing agents, it is impol1ant to
investigate the potenti al reversal of the reaction upon
ex posure to oxygen, since colour may reappear upon
di schwging the wastewater to the envi ronment
3.3 Biological Treatment
Bio logical d igestion involves the aerobic (in presence
of O 2) or anaerobi c (in absence of O 2) degradation of
organic substances by microorgani sms and has been
widely researched and rev iewed I50.15 1.
3.3.1 Aerobic Treatmellt
Aerobic biological treatment using acti vated sludge is
one of the most co mmonly used treatment methods fo r
wastewater generated from textile dyeing operatio ns.
onnally , thi s removes the biodegradable compo nents of
the e ffluent, e.g. carbohydrates, waxes and the readily
degradabl e auxjliwy compounds, al though more
complex xenobiotic compounds such as dyes and
surfactants remain as it is.
The ineffectiveness of aerobic bio logical system in
removing co lo ur has caused aesthetic problems in the
recelvll1g waters and encouraged d ischwgers to
in vestigate other altem ati ves. Dyes themselves cue
generally res istant to oxidati ve biodegradation , since one
of the most imp0l1ant properti es built in the commercial
dyes is res istance to fading caused by chemical and light
induced oxidati o n. The issue of toxicity of the efflu ent is
also a li sing concem . Another probl em wi th aerobic
bi o logical treatment of dye wastewater is the diffi culty in
acclimating the microorgani sms to the substrate.
Acclimati o n presents a probl em in tex tiles due to
constant product changes and batch dyeing operations.
l52
Shri ver and Dague in their study on BOD tests
concluded that colour in textile wastewater would be
expected to undergo bi odegradation J.t slower rate than
that fro m typ ical domesti c wastewater. Several stud ies on
aerobic bio logical treatment of textile dye
wastewater 151.. 154 111
. dIcate th at IItt Ie b10 d egracIatlon
0 f
dyes actually occurs and that the primcuy removal
mechani sm in volves adsorption to acti vated sludge.
T he adsorpti o n pro pe rti es of acti vated sludge are
s imil ar to th at of acti vated carbon in vo lving acid,
d irec t, reactive, d isperse and bas ic dyes a nd are
ma inl y depe ndent o n dye pro perties (mo lecular
struc ture a nd ty pe, number and pOS itIO n of
subs titue nts in the dy e mo lecul e) . Adsorptio n is
in creased in presence of hydroxy, nitro and azo
groups but decreased by s ulpho ni c acid grou psl 53 . The
facto rs inhibitin g permeati o n of the dye thro ug h the
m icrobial ce ll me mbrane (e.g . in creased or decreased
water so lu bility and in creased molecul ar weig ht)
red uce the effic ie ncy of the bi o log ica l system. ET AD
stud ies 155 o n re mova l of dyes by aet ivated s ludge
process indi cate th at lo w adsorpti o n on s ludge occurs
with ac id a nd reacti ve dyes, hi gh adsorptio n occ urs
w ith basic and direct dyes and h ig h to med iu m
adsorpti o n occurs with di spe rse dyes .
CIlU rc I1Iey et a I.. 156157 cWTle
. d out a Cllemo
L
metn. c
analys is to find out the level of bioeliminati on of water
soluble dyes. Thi s analysis was conducted to corre late
bioelimination with che mi cal structure/functionali ty. It
was found that the level of bioelimination is propol1ional
to the size/chwge ratio of the dye. Tn case of aci d and
d irect dyes, bioeliminatio n vwi es between 0% and 95%
fo r the series of dyes studied, while in case of reacti ve
clyes, the level of bioelimin ati on vcuies from 0% to only
25%. To max imize the bioeliminatio n of reacti ve dyes,
l57
large and planer triazine based dyes sho uld be used .
 JOSH! et al.: COLOUR REMOVAL FROM TEXTILE EFFLUENTS
In an activated sludge tank, water is mixed and aerated
with a suspension of microorganisms. A microbial
flocculation forms; oxidizing dissolved and suspended
organ ic matter. Activated sludge systems lack tme
contact time between the bacteria of the system and the
suspended and dissolved waste present. Large bacterial
population creates a secondary waste treatment concern
in the form of bio solids or bactelia. These bacteria, often
called sludge, must be disposed of and this increases
overall waste treatment costs.
Immobilized microbe reactors (fMBRs) address the
need of increased contact between microbial population
and the waste without concomitant production of
excessive bio solids l58. This is done through the use of a
solid but porous matrix (beads) to which a tailored
microbi al consol1ium of organism has been attached.
This allows for a greater number of organisms to be
available for waste degradation without the need for a
suspended population and protection from shocks for
bacterial population in the interiors of porous beads.
Although aerobic digestion of textile effluent removes
60-70% of organic waste, the toxicity level was hardly
reduced due to the presence of organic matter that could
not be degraded, requiring tertiary treatments to remove
the toxicity . Efforts have also been reported to tailor the
activated sludge to accommodate the textile effluents
more effectively by sludoe seedino and sludoe
b b b
conditioning. Both methods aim to produce a biased
microbial community, dominated by species that are
l59
more suited for digesting a specific waste type .
The PACT system patented by Du Pont is a combined
powdered activated carbon-activated sludge systeml(,(I. It
consists of adding powdered activated carbon to an
activated sludge system. The carbon dosage depends on
the wastewater characteristics and varies from lOppm to
5000 ppm and can be added at any stage to the waste
V IRGIN
VIRGIN POLYELECTROLYTE
POLYELECTROLYTE CARBON
CARBON STORAGE
STORAGE STORAGE
STORAGE
PRIMARY _~-1-r--"". -,
EFFlUENr
- S.l UOGE RECYCLING
TO REGENERATION
OR DISPOSAL
Fig . I-Two-stage PACT syste m as used at the Du Pont chamber
wo rks l 60
251
stream i.e. before treatment, to the recycled sludge or to
aeration tank itself (Fig.!). It can effectively treat
effluents with COD in the range of 50-50,000 mg/L.
Some of the other advantages of the PACT system are
improved organics removal, control of odors, colour
removal and metals removal. It is also resistant to shock
loads.
3.3.2 Anaerobic Treatment
Anaerobic biological reduction of azo dyes has been
investigated from many perspectives, i.e. chemical
degradation (treatment) and colour removal. Anaerobic
reducing conditions found in the environment include
sediments at the bottom of steams of cel1ain sections of
landfills where there is no oxygen. Anaerobic
bioremediation of azo and other soluble dyes to be
decolourized by breaking them into corresponding
amines (Scheme 5) has been widely studied l6 1.162 and
contemplated with great reluctance. The intentional
generation of amines that are more toxic than dye itself
are not appealing from environmental perspective. The
decolourization occurs due to azo reduction but the
complete mineralization does not occur.
Azo dyes acts as an oxidizing agent for reduced fla vin
nucleotides of microbial electron chain and are reduced
and decolourized concun'ently with reoxidation of the
reduced flavin nuchotides. In order for this to occur,
additional carbon is required for decolourization to
proceed at a viable rate and later convel1 to methane, H2S
and CO 2. This additional carbon source may be a limiting
factor commercially.
In many conditions, decolourization of reactive azo
dyes under anaerobic conditions is due to the action of
azo reductase enzyme l63 . Gonclaves et al. studied the
l64
Acid yellow 36
EFFLUENT
+
3- Aminobenzane
NPhcnyl-I ,4-diaminobenzene
sui phonic acid
Scheme 5--Anaerobic redu ction of Acid Yellow 36 (ref. lSI )
252 INDIAN J. FIBRE T EXT. RES., JUNE 2004
removal of colour from textile effluent using a laboratory
'upfl ow anaerobic sludge blanket' reactor. Several
com mercial dyes were selected to study the effect of dye
structure on colour removal. The average removal
effic iency for acid dyes using thi s method was between
80 % and 90% and that observed for the direct dye used
was 8 1%. Laboratory ex periments usin g thi s anaerobic
reactor with disperse dyes, such as an anthraquinone-
based dye, were unsuccessful even at velY low
concentrations.
However, the breakdown of azo dyes to thei r
corresponding amines accompli shes two goals (i)
decolourization of wastewater, and (ii ) preparation of
wastewater for subsequent biological treatment since the
aromatic amines released by anaerobic digestion of azo
dyes are effectively treated by aerobic treatment
processes. Hence, the CUITent literature '65 reveals that an
anaerobic - aerobic treatment sequence has been found
more effective method fo r textil e wastewater treatment.
Anaerobic process usually occupies less space, treats
waste up to 30,000 mglL COD, has lower recurring costs
and produces less sludge. If complete mineralisation
occurs, convers ion of organic contaminants into methane
and O 2 and then prod uction of biogas are the major
attraction because of heat, power and reduced energy
costs.
3.3.3 Anaerobic - Aerobic Treatment
The anaerobic - aerobic sequence shows significantly
greater co lour reduction than aerobic alone (88 % vs
28%), in addition to improved colour reduction. TOe
reduction (79-90%) also improves when compared to
aerobic treatment alone. The reduction in COD and BOD
is greater (up to 8%) fo r anaerobic-aerobic seq uence than
that fo r aerobic treatment. Table 5 compares the results
fo r colour, COD, BOD and TOe reduction from both
treatment schemes.
A similar process, namely AB (adsorption/bio-
oxidation) process has been developed in Europe l66 . The
Table 5-- Per cent reducti on from laboratory scale treatment processes involoving Navy 106 using
anaerobic-aerobic sequence l5 1
Treatment process Treatment step Colou r
Anaerobic-aerobic Dilution 40
Anaerobic SO
Aerobic -2
Total reduct ion 88
Aerob ic Diluti on 28
Aerobic I 36
Total red uction 29
treatment process is a modified two-stage activated
sludge design and uses physical, biochemical and
biological reaction mechanisms to red uce a vely wide
spectrum of organic pollutants. The firs t stage is the
adsorption stage (A) with anaerobic conditi ons w ith a
very hi gh food to microorgani sm (F/M) ratio fostering
growth of bacteria and a sholt retention ti me. The second
stage is biological oxidation (B) with aerobic activated
sludge system. The microbial ecosystems in the two
stages are kept di stinctly separate, enabling job sharing
and better effici ency of the process. This patented
process reduces COD and BOD vely effectively , while
being largely resistant to shock loads and pH
fl uctuations.
3.3.4 Decolourisatioll. using Cullures of Bacteria, Fungi, Algae and
Yeast
Microbial decolourization and degradation of dyes
have been fo und as cost effective and ecofriendly method
fo r removing them fro m textile effluen ts. Recent
fundamental work has revealed the existence of a wide
variety of microorganisms capable of decolourizing
equally wide range of dyes. Banat e/ al. 150 have given a
detailed review of progress in biological decolou rization
of dyes .
3.].4.1 Baclerial Cullures
Nu merous bacteria capable of dye decolOLllization
have been repolted '5o. Efforts to isolate bacterial cultures
capable of degrading azo dyes started in 1970's with
l 67
report s of Bacillus SUblilis , then Acroillonas ltydriphi l68
followed by Bacillus cereus l69 . [solating such microbes
proved to be a difficult task and ex tended periods of
adaptation under chemos tat conditions were needed to
isolate the strain capable of decolourization. An azo
reductase enzyme was responsible for the in itial
degradation of the Orange 11 dye by these strains but
substituting any of the groups near the azo group in the
chemical structure of the dye hindered the degradation.
TOC BOD COD
41 13 38
3 -2 I
38 80 38
82 91 77
38 IS 39
75 30
74 90 69
 JOSHI el al.: COLOUR REMOV AL FROM TEXTILE EFFLUENTS
An upsurge in interest in these bacterial cultures took
place in 1990's and Haug et al. 17o described a bacterial
consOitium capable of mineralizing the sulphonated azo
dye- mordant yellow. An alteration from anaerobic to
aerobic conditions was required for complete degradation
in such mixed bacterial cultures. Several other strains
have been repolted which can decololllize Cu- based azo
dyes and reactive dyes including anthraquinone and
phthaJocyanine through adsorption of dyes to the cell ular
blomass Wit. Ilout any degrad'
atlon 17 1.
3.3.4.2 Algae
Few species of algae, namely Chlorella and
Oscillatorial 50 , are capable of degrading azo dyes to their
aromatic amines through an induced form of azo
reductase and further metabolise the aromatic amines to
simple organic compounds or CO2 , These algae species
utilize azo dyes as thei r sole source of carbon and
nitrogen. Such algae can be used for stabilization of
ponds as they can play a role in aromatic amines
removal.
3.3.4.3 FUllgi
Several fungal systems including the white rot fungi
(Phanerochaete chrysosporuilll), in pruticular, have been
the subject of intense reseru'ch related to the
biodegradation of a wide range of recalcitrant xenobi otic
. IUCI'lIlg azo dyes 150.17 1.17?-. WhOIte rot f '
compoun dS lIlC ungl
are those organisms that are capable of degrading lignin,
the structural component found in woody plants. They
have been found to degrade dyes using enzymes, such as
lignin peroxidase (Li-P), manganese dependent
peroxidases (MnP), other enzymes such as gl ucose-l-
oxidase, gl ucose-2-oxidase laccase and a phenol oxidase
enzyme.
Azo dye, the lru'gest class of commercial dyes, is not
easily degraded by microorganism but can be degraded
by these enzymes. Commercial azo, triruylmethane,
anthraquinone and indigoid textile dyes ru'e efficiently
decolourized with enzyme prepru'ations from Pleurotus
OSlreatus, Schizophyllul1l comm.ence, Neurospora crassa,
Polyporus, SclerotiulIl rolfsii, Trametes villosa and
Myceliophtora thermoplzila l73.
Mn- peroxidase (Mn-P) ruld Iigninase (Li-P) belong to
the class of peroxidases that oxidize their substrates by
two consecutive one electron oxidation steps with
intermediate cation radical. While Mn-P only attacks
phenolic substrates using Mn 2+lMn 3+ as an intermediate
redox couple, Li-P with a higher redox potential prefers
non phenol ic methoxy substituted lignin subunits as
substrate 173 . Laccases have very broad substrate
,',\
253
specificity with respect to the electron donor. They
catalyse the removal of a hydrogen atom from the
hydroxyl group of oltho and para substituted mono and
poly phenolic substrates and from aromatic amines by
one electron abstraction to form free radicals capable of
undergoing fLllther depolymerization, repolymerization,
. or qUlllone
demet hyIatlon . tormation
. 173.
White rot fungi (P. chrysoporuim ) is also capable of
degrading dioxins, polychlorinated biphenyl (PCBs) and
other chloro-organics, thus rendering the effluents less
toxiC l74 .
The colour removal achieved with these enzymatic
treatments range from 40% to 99% , depending on the
dye complexity, nitrogen available, activity of the
cul ture, presence of other auxiliaries in the effl uent,
concentration of dye, retention time, etc. The nature of
substitutents on the dyes, i.e. benzene rings, influence rhe
enzyme activity. Electron donating methyl and methoxy
substituents seemed to enhance enzymatic degradation,
wh ile electron withdrawing chloro, fluoro and nitro
substituen ts inhibited oxidation by enzyme Iaccase l73.
The presence of salts and other textile dyeing
auxi liaries shows a potential inhibitory effect on
enzy matic action. Higher salt concentrations decrease the
decolourization efficiency by up to 80% and even lead to
partial precipitation of proteins caused by increased
surface tension and hydrophobic interactions. Laccase,
containing 3 copper binding sites per protein molecule or
one copper, one iron and two zi nc atoms per protein
molecule, is inactivated by copper and iron.
Chelating agents and anionic detergents seem to
prutially denature prote:ns (enzyme) and almost 70% loss
of activity is repOited. Thus, knowledge not only about
the substrate specificity but also about the effect of
auxiliru'ies is important for selecti ng suitable enzymes for
dye decolourization under industrial conditions.
Some of the drawbacks of enzymatic decolourization
ru'e:
Substrate specificity of some enzy mes and hence
the selection of appropriate enzymes fo r
co ntinuously varyi ng compOSItion of textile
effluent may be an ard uous task.
The rate of reaction, which can be slow unl ess
condition of pH and temperature are optimal.
Commercial production of these specific enzymes
is very diffic1.!1t.
The presence of salts and other auxiliaries in the
effl uent has an inhibitory effect on enzymatic
activity .
254 INDIAN J. FfBRE TEXT. RES. , J UNE 2004

3.3.4.4 Yeast
Yeasts, such as Klyveromyces lI1arx ialllls , are capable
of decolourizing Ramazol Black B dyes by 78-98% (ref.
176
175). Zissi et al. showed that Bacillus slIbtilis could be
used to breakdown p-amino azo benzene, a specific azo
dye. Further research using mesophilic and thermophilic
microbes has also shown them to degrade and
decolourize dyes.

Future Trends
The advantages of mixed culture are apparent as
some strains can collectively CatTY out complex Emuent:contamillats
bioremediatation task that no indi vidual strai n can adsorbed,
achieve independently. Similar bacteri al cultures coprecipitated within
have been reported recently 177. iron matrix
Future investigation should focus on the
immobilization of selected enzymes to form the base
for industrial application of enzymatic ;.
decoloLlIization. Banat et af. 178 have reported cheap Influent
suppOtt media for bio film development for acti ve
tex tile dye decolourization using gravel, calcium Fig. 2 - Elec trochemical cell 179
alginate beads, PS and PU foam chips, nylon webs
inett PE chips, porous volcanic rocks, etc.
One of the routes still to be explored is the use of
thermotolerant or thermophilic mi croorgani sms in + Anode PVTI

decolourization systems. This would be an pHIR

advantage as many textil es and other dye effluents RIR

Cathode
are produced at relatively high temperatures (50- SS304

60C), even after cooling or heat exchange step. Cooling jacket

The literature review thu s suggests a great potential for

microbial decolourizing system for achieving total colour
re moval and occasionally with only hours of exposure. c :
E
Such biological processes could be adopted as a
pretreatment decolourization step combined with the
Surge ....essel
conventional treatment system to reduce the BOD and Cooling water
Sampling

COD as an effective alternative for use in textil e dyeing

industties.
3.4 Electrochemical Decolourization
Elecrochemical ion generation is a proven technology
for removing colour, BOD, COD, TOC, solid (suspended
and dissolved) and heavy metal s such as chromium,
copper and zinc from textile mill wastewater l79 .
The system most commonly utilizes an
electrochemical cell to generate ferrous hydroxide
directly by steel electrodes. The electrochemical cell
(Fig. 2) consists of a fibre glass body containing a
number of electrodes separated from each other by small
gaps. Wastewater flows through the gaps and remain s in
contact with the electrodes. A direct cun'ent (DC) power
supply is connected between the two end electrodes of
Fig. 3--Experimental laboratory pilot plant using e lectrochemi cal
cell l80 [C = Electrolytic cell , E = Elec tromagneti c va lve, P =
Rec ircul atin g pump, TICR = Te mperature indicator controller
reco rder, pHIR = pH indicator, and RIR = Redox indicator]
the cell (Fig. 3). As CUITent flows from one electrode to
another through the process water, the positively charged
sides of the electrodes (anodes) give off ferrou s ions. At
negative sides (the cathodes), the water decomposes into
hydrogen gas and hydroxyl ions. 11le overall reaction
results in the formation of hydrous iron oxide, ferrous
hydrox ide and felnc oxyhydroxide. The electrodes are
slowly consumed as the metal hydroxide is generated.
The process water then enters a degassing tank, pH is
adjusted at < 7 or> 11 for satisfactory Fe+2 precipitation.
 JOSHI el al.: COLOUR REMOVAL FROM TEXTILE EFFLUENTS
The water is then pumped from the reactor tank to
clarifier where the newly forming solids settle for which
a small amount of polymeric flocculent is added to
improve flocculation and setting of precipitated solids.
The clarifier supernatant flows to a polishing filter before
leaving the system. The use of aluminum cell or
combined iron- aluminum cells is also reported in the
literature. If aluminum is used, the end products are a
combination of aluminum hydroxide or oxyhydroxide.
Recently , the use of titanium or titanium-pl atinum-
l80
iridium electrode, as anodes has also been reported .
Electrofloccul ation is the combination of an oxidation,
fl occulation and fl otation . Oxidation is achieved by
means of electrodes, dipped in the effluent to treat where
a differe nce of potenti al is applied. Tlivalent iron and
aluminum flocculate oxidized substances because of
electrostatic interaction and co-precipitation. When
metals are present as soluble inorganic ions, co-
precipitation and adsorption are the primary removal
mechanisms. Efficiency of the process depends on
several parameters i.e. difference of potential, nature of
electrodes, pH, salt concentration of solution, number of
electrodes, distance between them, stirring and CUlTent
. 18 1
Il1tenslty .
Electrochemi cal technology is repOlted to remove
82
acid, disperse and metal complex dyes effectivel/ . The
removal of dyes from aqueous soluti on results from
adsorption ancl/or degradation of the dyestuff following
the interaction wi th iron electrodes. If metal complex
dyes are present, dye solubilising and charge are the most
important factors for successful removal of heavy metals.
pH has to be adjusted to maximize dye insolubili ty.
Demmin and Uhrich. 183 in their studies found that BOD
level is generally reduced by 30-35 % and COD level by
l84
50-70%. Lin and Chen have reported that the addition
of small amount of hydrogen peroxide in the magnitude
of around 200 mgIL has been found to elevate the
effic iency of electrochemical treatment process by as
much as 100%. This is due to in situ generation of
hydroxide radical generated (Fenton 's reagent Fe+2/H 20 2)
when iron electrode is used, leading to rapid ox idation of
Fe+2 to Fe+3 .
Electrofloccul ation is, thus, a promising method for
producing recyclable process water because it combines
oxidation of the polluting content by means of
electrolytic process with physico-chemical precipitation
of sludge. There is no simultaneous addition of anions
such as sulfate or chloride. This is in contrast to
conventional chemical precIpItation methods that
introduce either chloride or sulphate ions both of which
255
increase the TDS of the effluent. Moreover, evidence of
salt content (sulphate and chloride) reduction was found ,
which makes the treatment even more interesting for
recycl ing from technical point of view.
4 Conclusions
The majority o f colour re moval techniques work
eithe r by concentrating the colour into sludge or by
the partial or complete breakdown of the coloured
mo lec ul e . In principle, decolourization s are
achi evable using one or combination of the foll ow ing
methods: adsorption, filtration , precipitation ,
coagul ation , fl occulation, chemical, photo and
biodegradati on.
Coagulation/ flocculation is the most widely used
method for colour re moval because of eco nomic
feasib ility, rap id re moval of colour and signi ficant
reduction o f COD. With rapid changes in dyes and
stri cter consent limits, these alone do not give
co mpl etely satisfactory treatments es pec iall y with
hi gh ly solubl e reactive dyes. Moreover, large quantity
of sludge generation contalnll1g all the toxic
compo unds present in the effluent is likely to increase
disposal costs substantially and thi s mu st be
considered before choos ing a system .
Adsorption processes have also got a lot of
attention for colour removal. Activated carbon is used
mostly as the final po li shing or tertiary treatment
because regeneration costs are very hi gh and hi gh
volume of textile effl ue nt in vo lved with dyeing. The
size and cost of plant required become
disproportionately hi gh and pay back is poor. Low
cost bioadsorbents have been e mployed for treatment
of wastes co ntaining dyes. However the specificity to
remove certain co ntamin ates, slow kinetics ,
regeneration and flow probl e ms have limited the
co mmerci al success of these adsorbents at the
industrial scale. Membrane systems provide a means
to recover water a nd other auxiliaries fo r total
treatment or sta nd alone process for scouring o r dye
bath liquo r separation. The major limitations are the
economic feasibility because of hi gh costs and the
treatment of hi ghly concentrated streams.
In the li ght of an integrated approach to waste
treatment, it is likely that destruction technologies
will ga in favour at the expense of techno logies that
j ust transfer th e pollutant from liquid phase to sol id
phase for disposal or form a liquid concentrate for
further treatment. The best established destructi on
technologi es are based on chemical , bio and
256 INOlAN J. FIBR E T EXT. RES., JUNE 2004

electroch emical oxidation techniques. These lead to 4 T G Southern, in Colollr in Dye HOllse Efflllent. edited by P
either partial oxidation of the dye, destroying th e
5 Freeman H S, Hinks D & Esancy 1. in Physico Chemical
co njugated bonding system in the chromophore and
thus, removing colour or total oxidation to form
carbon di oxide and inorganic ions which is the most 6 Shore J, Indiall J Fibre Text Res, 2 1 ( 1996) I
ideal. However, total oxidation using these reagents is 7 Konduru R, Ramakri shna & Viraraghavan T, Alii Dyest Rep.
not eco nomicall y viable. The problem associated with
8 Thampi J & Paul R, Colollrage, 44 ( 1997) 47.
parti al oxidation lies in the unkno wn nature of th e 9 Thakur M, Shelke V & Patil S, India I! Text J, I J ( 1998) 60.
products formed and the risk that some of th ese may 10
even be more harmful to the environment th an the
initial components of the effl uent. Moreover, nearl y II
al l chemical mechani sms are difficult to control once 12
the reaction starts and therefore control over reacti on 13
may be diffi cult even in the lab systems and virtuall y 14
impossible in a variable feed stock such as an
industria l textile effluent. These mostly reduce carbon 15
loadin g of the effluent but can lIlcrease th e 16
17
co ncentration of inorgani c content.
Enzymatic microbial decolouri zati on of textile 18
dyeing effluents is also a very promising and
innovativc area of investigation. It eliminates the need 19
fo r inorganic oxidizing agents (ozone) or precipitating 20
agents (polymeric f1occul ents), which lead to hi gher 21
tox ici ty in wastewater and ge nerate additional soli d 22
waste. Microbial decolourization using enzy mes 23
degrades the aromatic ring structure to carbon 24
diox ide, mol ecul ar nitrogen and water, thereby
causing less toxicity. However specificity of enzymes, 25
slow ratc of reaction unless pH and temperature are 26
optimal and difficulty of commercial production of 27
enzymes may be limitations whic h need to be
overcom e by more intense research in the fie ld of 28
biotechnology. 29
The problem of colo ur in the efflu ent can be
reduced to an extent by adopting ri ght first time 30
approach, proper work practices and waste 31
minimi zation program s. The dy e manufactures may
also help by producing dyes (parti cularl y reactive 32
33
dyes) with a better fixation that can be achieved at
34
present. Although developments in thi s field are 35
ongo ing, in future standards will be enforced with
increas ing severity by the regul ators. Hence the need 36
is urgent and immediate and the press ure must be 37
maintained to evolve more effective, widel y
38
app li cable and commercially viable techniques of 39
colour removal from textile effluents.
40
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