Polieletrolito Natural (5) LEEER

Journal of Environmental Management 93 (2012) 154e168
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Journal of Environmental Management

journal homepage: www.elsevier.com/locate/jenvman
Review
A review on chemical coagulation/occulation technologies for removal of colour

from textile wastewaters
Akshaya Kumar Verma, Rajesh Roshan Dash, Puspendu Bhunia*
Department of Civil Engineering, School of Infrastructure, Indian Institute of Technology Bhubaneswar, Orissa 751 013, India
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 13 April 2011
Received in revised form
26 August 2011
Accepted 15 September 2011
Available online 5 October 2011
Textile industry is one of the most chemically intensive industries on the earth and the major polluter of
potable water. It generates huge quantities of complex chemical substances as a part of unused materials
including dyes in the form of wastewater during various stages of textile processing. The direct discharge
of this wastewater into environment affects its ecological status by causing various undesirable changes.
As environmental protection becomes a global concern, industries are nding novel solutions for
developing technologies that can diminish the environmental damage. However, colour removal from
textile wastewater by means of cheaper and environmental friendly technologies is still a major challenge. In this manuscript, several options of decolourisation of textile wastewater by chemical means
have been reviewed. Based on the present review, some novel pre-hydrolysed coagulants such as Polyaluminium chloride (PACl), Polyaluminium ferric chloride (PAFCl), Polyferrous sulphate (PFS) and Polyferric chloride (PFCl) have been found to be more effective and suggested for decolourisation of the
textile wastewater. Moreover, use of natural coagulants for textile wastewater treatment has also been
emphasised and encouraged as the viable alternative because of their eco-friendly nature.
2011 Elsevier Ltd. All rights reserved.
Keywords:
Dye
Decolourisation
Coagulation
Flocculation
Textile wastewater
1. Introduction
Textile industries are one of the biggest users of water and
complex chemicals during textile processing at various processing
stages. The unused materials from the processes are discharged as
wastewater that is high in colour, biochemical oxygen demand
(BOD), chemical oxygen demand (COD), pH, temperature, turbidity
and toxic chemicals. The direct discharge of this wastewater into
the water bodies like lakes, rivers etc. pollutes the water and affects
the ora and fauna. Efuent from textile industries contains
different types of dyes, which because of high molecular weight
and complex structures, shows very low biodegradability (Hsu and
Chiang, 1997; Pala and Tokat, 2002; Kim et al., 2004; Gao et al.,
2007). Also, the direct discharge of this industrial efuent into
sewage networks produces disturbances in biological treatment
Abbreviations: BOD, biochemical oxygen demand; COD, chemical oxygen

demand; TDS, total dissolved solid; AOX, absorbable organic halides; SS, suspended
solid; TSS, total suspended solid; DS, dissolved solid; NTU, nephelometric turbidity
unit; DO, dissolved oxygen; UV, ultraviolet; nm, nanometer; AOP, advanced
oxidation process; PACl, polyaluminium chloride; PFCl, polyferric chloride; PFS,
polyferric sulphate; PAFCl, polyaluminium ferric chloride.
* Corresponding author. Tel.: 91 674 2300 714; fax: 91 674 2301 983.
E-mail addresses: akshaya@iitbbs.ac.in (A.K. Verma), rrdash@iitbbs.ac.in
(R.R. Dash), pbhunia@iitbbs.ac.in (P. Bhunia).
0301-4797/$ e see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jenvman.2011.09.012
processes. These efuents produce high concentrations of inorganic

salts, acids and bases in biological reactors leading to the increase of
treatment costs (Gholami et al., 2001; Babu et al., 2007). Moreover,
traditionally produced fabric industries generate residuals of
chemicals that evaporate into the air that we breathe or are
absorbed through our skin. Some of the chemicals such as heavy
metals either in free form in efuents or adsorbed in the suspended
solids are either carcinogenic (Tamburlini et al., 2002; Bayramoglu
and Arica, 2007) or may cause harm to children even before birth,
while others may trigger allergic reactions in some people.
Industrial emissions and the waste efuents generated from the
factories are associated with heavy disease burden (WHO, 2000,
2002) and this could be one of the reasons for short life expectancy of 64 years in India compared to developed countries such as
Japan, where life expectancy is 83 years (UNICEF, 2008). Although
the industrial sector only accounts for 3% of the annual water
withdrawals in India, its contribution to water pollution, particularly in urban areas, is considerable. Wastewater generation from
this sector has been estimated as 55 106 m3 per day, of which
68.5 103 m3 are dumped directly into local rivers and streams
without prior treatment (MOWR, 2000). The developing countries
contribute the largest amount of textile wastewater. For an
example, developing countries of South Asia contributed around
35% textile wastewater out of total industrial wastewater generated
by South Asian countries in 2001 (World Bank, 2005). Out of seven
A.K. Verma et al. / Journal of Environmental Management 93 (2012) 154e168
core countries of South Asia (Bangladesh, Bhutan, India, Maldives,

Nepal, Pakistan, and Sri Lanka), India is the major manufacturer of
textiles which constitute 83 composite mills and 2241 semi
composite processing units (COINDS, 2000). Hence, it can be said
that India may be the major contributor of textile wastewater in
South Asia. The textile industries in India are mainly located in
Mumbai, Surat, Ahmedabad, Coimbatore, Ludhiyana and Kanpur.
1.1. Characteristic and composition of textile wastewater
On the basis of waste and wastewater (or efuent) generation,
the textile mills can be classied into two main groups namely dry
processing mills and wet processing mills (ISPCH, 1995). In the dry
processing mills, mainly solid waste is generated due to the rejects
of cotton. In the other group, desizing, scouring, bleaching, mercerising, dyeing, printing, and nishing are the main processing
stages. The wastewater generated by textile industry includes
cleaning wastewater, process wastewater, noncontact cooling
wastewater, and storm water. The amount of water used varies
widely in this industry, depending on the specic processes operated at the mill, the equipment used, and the prevailing philosophy
of water use. The components of major pollutants involved at
various stages during wet processing of cotton-based textile
industry are shown in Fig. 1. On account of the involved complexity
of different processes at different stages, textile wastewater typically contains a complex mixture of chemicals. Apart from this,
large numbers of associated hazards have also been reported by the
Constituents
Yarn waste, unused
starch-based sizes
Process
Sizing
Enzymes, starch,
waxes, ammonia
Desizing
Disinfectants and
insecticides
residues, NaOH,
surfactants, soaps,
Scouring
H2O2, AOX,
NaOCl, organics
Bleaching
NaOH
Mercerisation
Colour, metals,
sulphide, salts,
acidity/alkalinity,
formaldehyde
Dyeing
Urea, solvents,
colour, metals
Printing
Chlorinated
compounds, resins,
spent solvents,
softeners, waxes,
acetate
Finishing
155
various chemicals used in different stages of textile processing (Lee

et al., 2006; Jadhav et al., 2007; Shi et al., 2007; Anouzla et al.,
2009).
Wet processing operations (including preparation, dyeing, and
nishing) generate the majority of textile wastewater having very
high COD, BOD, TDS and very deep colour as shown in the Table 1.
Large numbers of chemical constituents such as alkali, acids,
bleaching chemicals, enzymes, starch, dyes, resins, solvents, waxes,
oils etc. are used in the various steps during textile processing and
nally comes out in the efuent after its consumption. Desizing, or
the process of removing size chemicals from textiles, is one of the
industrys largest sources of wastewater pollutants (Bisschops and
Spanjers, 2003; Dos Santos et al., 2007). In this process, large
amount of size chemicals used in weaving processes are discarded.
Dyeing operation generates a large portion of the industrys total
wastewater. The primary source of wastewater in dyeing operations
is spent dye bath and wash water. Such wastewater typically
contains by-products, residual dyes, and auxiliary chemicals.
Additional pollutants include cleaning solvents, such as oxalic acid
(USPEA, 1997). Of the 700,000 tons of dyes produced annually
worldwide (Papic et al., 2004; Lee et al., 2006; Riera-Torres et al.,
2010), about 10e15 percent of the dyes are disposed off in efuent
from dyeing operations (Snowden-Swan, 1995; Husain, 2006; Hai
et al., 2007; Gupta and Suhas, 2009).
Dyes in wastewater may be chemically bound to fabric bers
(ATMI, 1997). Dyeing and rinsing processes for disperse dyeing
generate about 91e129 m3 of wastewater per ton of product
Wastewater characteristics
High BOD, medium COD
BOD (34-50% of total), high

COD, temp. (70-80 C)
Oily fats, BOD (30% of

total), high pH, temp. (7080 C), dark colour
High pH, TDS
High BOD, high pH

suspended solids
High toxicity, BOD (6% of
total), high dissolved solids,
high pH,
High toxicity, high COD, high
BOD, high dissolved solids,
high pH, strong colour
Low alkalinity, low BOD, high
toxicity
Fig. 1. The component of major pollutants involved at various stages of a textile manufacturing industry (SEAM Project, 1999; Yusuff and Sonibare, 2004; Joseph, 2007; Paul, 2008;
Charoenlarp and Choyphan, 2009).
156
Table 1
Major characteristics of real textile wastewater studied by various researchers.
pH
COD (mg/L)
BOD5 (mg/L)
TSS (mg/L)
TDS (mg/L)
Colour
Turbidity (NTU)
References
8.8e9.4
11.2
5e10
6.5e8.5
2.7
13.56
12e14
10
9
2e10
8.32e9.50
8.7 0.2
9.30
7.8
13 1
6.95
7.86
7.5 0.3
595 131
2276
1100e4600
550e1000
7000
2968
1500e2000
1150
750
50e5000
278e736
17900 100
3900
810 50.4
2300 400
3422
340
131 18
379 110
660a
110e180
e
e
e
e
170
160
200e300
137
5500 100
e
188 15.2
e
276 76
e
e
100e400
440
e
e
150
e
50e500
85e354
23900 50
e
64 8.5
300 100
1112
300
75 13
e
47.9
50
e
930
e
e
e
e
e
1715e6106
1200 50
e
e
e
e
e
1885 80
e
e
1450e1475(ADMI)
7.50e25.50b
e
e
e
15e200
2140
120
e
e
e
e
e
e
240
e
e
5700
130
e
El-Gohary and Tawk, 2009

Golob et al., 2005
Dos Santos et al., 2007
Ciabatti et al., 2010
Al-Malack et al., 1999
Joo et al., 2007
Gozalvez-Zafrilla et al., 2008
Selcuk, 2005
Schrank et al., 2007
Lau and Ismail, 2009
Phalakornkule et al., 2010
Rodrguez et al., 2008
Paschoal et al., 2009
Haroun and Idris, 2009
Debik et al., 2010
Bayramoglu et al., 2004
Merzouk, 2010
Ustun et al., 2007
a
b
210
e
3586 (C.U)
Dark blue
1.24436nm
e
>300 (C. U)
e
e
e
0.15669nm
e
e
>200 (Pt-Co)
e
BOD7 and efuent is from reactive dye bath.

Integral of the absorbance curve in the whole visible range (400e800 nm), ADMI : American dye manufacturer institute, C.U: Colour Unit.
(Snowden-Swan, 1995). Similar processes for reactive and direct

dyeing generate even more wastewater, about 113e151 m3 per ton
of product (Snowden-Swan, 1995; Karcher et al., 2002; Riera-Torres
et al., 2010). This can be attributed by the fact that disperse dyes
show higher percentage of xation to the ber as compared to acid
and reactive dyes. Finishing processes typically generate wastewater containing natural and synthetic polymers and a range of
other potentially toxic substances (Snowden-Swan, 1995). Textile
industries typically generate 200e350 m3 of wastewater per ton of
nished product (Ranganathan et al., 2007; Gozlvez-Zafrilla et al.,
2008) resulting in an average pollution of 100 kg COD per ton of
fabric (Jekel, 1997).
Raw textile wastewater can be characterised by measurement of
BOD, COD, colour, suspended solids (SS), dissolved solids (DS) and
heavy metals etc. Typical characteristics of textile industry wastewater generally include a wide range of pH, COD, dissolved solids
and strong colour (El-Gohary and Tawk, 2009; Lau and Ismail,
2009; Ciabatti et al., 2010; Debik et al., 2010; Phalakornkule et al.,
2010), which may be comparable to moderate municipal wastewater (Rott and Minke, 1999). However, the main challenge is to
eliminate the colour of wastewater, which is due to the remaining
dyes. The major characteristics of real textile wastewater have been
described in the Table 1. It has been observed from the Table 1, that
the textile wastewaters exhibit wide range of pH from 2 to 14, COD
from 50 mg/L to approximately 18,000 mg/L, TDS from 50 mg/L to
over 6000 mg/L and very strong colour. This wide variation in the
characteristics of textile wastewater is due to complexity of materials used in the textile industry during the processing of textiles.
1.2. Effects of textile wastewater
Textile wastewaters generated from different stages of textile
processing contains huge amount of pollutants that are very
harmful to the environment if released without proper treatment.
Harmful direct and indirect effects of textile wastewater have been
summarized in Fig. 2. The release of textile wastewater to the
environment causes aesthetic problems as the changed colour of
the water bodies such as lakes and rivers, after releasing of
wastewater from the industry, cannot be tolerated by the local
people. Also, the accumulation of colour hinders sunlight penetration, disturbs the ecosystem of receiving water (Georgiou et al.,
2003; Merzouk et al., 2010). Ground water systems are also get
affected by these pollutants due to leaching through the soil
(Namasivayam and Sumithra, 2005; Khaled et al., 2009). Apart from

this, several dyes and their decomposition derivatives have proved
toxic to aquatic life (aquatic plants, microorganisms, sh and
mammals) (Georgiou et al., 2002; Kim et al., 2004; Ustun et al.,
2007). Additionally, fairly intensive studies has inferred that such
coloured allergens may undergo chemical and biological assimilations, cause eutrophication, consume dissolved oxygen, prevent reoxygenation in receiving streams and have a tendency to sequester
metal ions accelerating genotoxicity and microtoxicity (Walsh et al.,
1980; Foo and Hameed, 2010). In a wider sense, sporadic and
excessive exposure to coloured efuents is susceptible to a broad
spectrum of immune suppression, respiratory, circulatory, central
nervous and neurobehavioral disorders presage as allergy, autoimmune diseases, multiple myeloma, leukemia, vomiting, hyperventilation, insomnia, profuse diarrhea, salivation, cyanosis,
jaundice, quadriplegia, tissue necrosis, eye (or skin) infections,
irritation to even lung edema (Anliker, 1986; Foo and Hameed,
2010).
1.3. Present practices for treatment of textile wastewater
The available literature shows a large number of well established conventional decolourisation methods involving physicochemical, chemical and biological processes, as well as some of
new emerging techniques like sonochemical or advanced oxidation
processes. However, there is no single economically and technically
viable method to solve this problem and usually two or three
methods have to be combined in order to achieve adequate level of
colour removal (Kang and Chen, 1997; Robinson et al., 2001).
Researches on chemical coagulation/occulation, is observed as
one of the most practised technology. Regardless of the generation
of considerable amount of sludge, it is still used in developed and in
developing countries. Because the mechanism of coagulant applied
to decolourise wastewater is still not absolutely clear, colour
removal by coagulation is found in some cases very effective, in
some cases however, has been failed completely.
Hence, the objectives of this review are the analysis of various
chemical technologies developed for decolourisation of textile
wastewater, giving more stress upon chemical coagulation/occulation technology, short description and critical appraisal of
decolourisation methods, comparison of their relative advantages
and disadvantages and propose for the effective and cheaper
alternatives.
157
Fig. 2. Schematic representation of the effect of textile wastewater into the environment.
2. Chemical composition and structure of colour causing dyes

in textile processing
A dye is used to impart colour to a material, of which it becomes
an integral part. An aromatic ring associated with a side chain usually
required for resonance and thus to impart colour. Characterisation of
dyes is based on their chemical structure and application. They are
composed of the atoms responsible for the dye colour called chromophores as well as an electron withdrawing or donating substituent that causes or intensies the colour of chromophores, called
auxochrome (Christie, 2001). Usual chromophores are eC]Ce
(ethenyl), eC]O (carbonyl), eC]Ne (imino), eCH]S (thiocarbonyl), eN]Ne (azo), eN]O (nitroso), eNO2 (nitro) and usual
auxochromes are eNH2 (amino), eCOOH (carboxylic), eSO3H (sulphonyl) and eOH (hydroxyl) (Van der Zee, 2002). The intensity of
colour depends upon the number of such groups. Compounds of
benzene containing chromophore radicals are called chromogens.
Such compounds, though coloured, are not dyes, since they do not
have the afnity or the ability to unite with tissue. To be a dye,
a compound must contain not only the chromophore groups, but also
the additional group(s) called Auxochrome(s). These auxiliary groups
are responsible for imparting the property of electrolytic dissociation
i.e., the separation of the dye molecule into its components or atoms
and to form salts with either acid or alkali. They can also belong to the
classes of reactive, acid, basic, direct, mordant, disperse, pigment, vat,
anionic, sulphur and disperse dye (Welham, 2000). Anthraquinone
dyes possess wide range of colours in the whole visible spectrum and
constitute the second most important class of textile dyes after azo
dyes, which are used to give blue, green and violet colours (Christie,
2001; Fontenot et al., 2003). The characteristics of different dyes that
are used widely in the textile industry have been summarised in
Table 2. It has been observed from the Table 2 that reactive dyes are
widely used to colour the cotton which contribute as half of the
worldwide textile-ber market. The reactive dyes that are used for
cotton, show poorest rate of xation due to which textile efuent
possesses strong colour. The chemical structure of different azo dye,
vat dye and anthraquinone dye molecules comprising of auxochrome
and chromophore has been illustrated in Fig. 3.
3. Physico-chemical methods for removal of colour from
textile wastewaters
Plenty of Physico-chemical methods in the form of pretreatment, post treatment or main treatment have been investigated by
158
Table 2
Characterisation of different class of dyes mainly used in textile industry and its method of application (Easton, 1995; Akbari et al., 2002; Hees et al., 2002; Lau and Ismail,
2009).
Class
Characteristics
Substrate (bre)
Dye-bre interaction
Method of application
Acid
Basic
Direct
Anionic, water soluble

Cationic, water soluble
Nylon, wool, silk

Modied nylon, polyester
Cotton, rayon, leather, nylon
Electrostatic, Hydrogen bonding

Electrostatic attraction
Intermolecular forces
Disperse
Very low water solubility
Polyester, poly-amide, acetate,

plastic, acrylic
Hydrophobic- Solid state

mechanism
Reactive
Cotton, nylon, silk, wool
Covalent bonding
Sulfur
Colloidal, insoluble
Cotton, rayon
Covalent bonding
Vat
Colloidal, insoluble
Cotton, rayon
Impregnation and oxidation
Applied from neutral to acidic dyebaths

Applied from acidic dyebaths
Applied from neutral or slightly
alkaline baths containing
additional electrolytes
Fine aqueous dispersions often
applied by high temperature
pressure or lower temperature
carrier methods
Reactive site on dye reacts with
functional group on bre to bind
dye covalently under inuence of
heat and pH(alkaline)
Aromatic substrate vatted with s
odium sulde and re-oxidised to
insoluble sulfur-containing
products on bre
Water insoluble dyes solubilised
by reducing with sodium hydrosulte,
then exhausted on bre and re-oxidised
various researchers throughout the World. A brief discussion on

these methods along with a comprehensive discussion particularly,
on the chemical coagulation and occulation technology for colour
removal has been presented in this section.
One of the most commonly known methods is the ltration
technology. Filtration methods such as ultraltration, nanoltration and reverse osmosis have been used for water reuse and
the chemical recovery (Marcucci et al., 2001; Fersi and Dhahbi,
2008). In the textile industry, these ltration methods can be
used for both ltering and recycling of not only pigment rich
wastewaters, but also mercerising and bleaching wastewaters. The
specic temperature and chemical composition of the wastewaters
determines the type and porosity of the lter to be applied. Further,
the utilisation of membrane technology for dye removal from
textile wastewater is very effective as reported by various
researchers (Ledakowicz et al., 2001; Ahmad et al., 2002). However,
the main drawbacks of membrane technology are the high cost,
frequent membrane fouling, requirement of different pretreatments depending upon the type of inuent wastewaters, and
production of concentrated dyebath which further needs proper
treatment before its safe disposal to the environment (Robinson
et al., 2001; Akbari et al., 2006). For membrane ltration, proper
pretreatment units for removing SS of the wastewaters are almost
mandatory to increase the life time of the membranes. These make
the process more expensive and thereby limit the application of
this expensive technology for wastewater treatment.
Another most popular method is adsorption technology. Adsorption method for colour removal is based on the afnity of various dyes
for adsorbents. It is inuenced by physical and chemical factors such as
dyeeadsorbent interactions, surface area of adsorbent, particle size,
temperature, pH and contact time (Anjaneyulu et al., 2005; Patel and
Vashi, 2010). The main criteria for selection of adsorbents are based on
the characteristics like high afnity, capacity of target compound and
possibility of adsorbent regeneration (Karcher et al., 2002). Activated
carbon is most commonly used adsorbent and can be very effective for
many dyes (Walker and Weatherly, 1997; Pala and Tokat, 2002).
However, efciency is directly dependent upon the type of carbon
material used and wastewater characteristics (Robinson et al., 2001).
The limitations of this technology are the eco-friendly disposal of
spent adsorbents, excessive maintenance costs, and pretreatment of
wastewater to reduce the SS under acceptable range before it is fed
into the adsorption column. Because of these reasons, eld scale
application of adsorption technology is limited not only for colour

removal of textile wastewaters but also for other water and wastewater treatment.
Chemical methods mainly involve use of oxidising agents such
as ozone (O3), hydrogen peroxide (H2O2) and permanganate
(MnO4) to change the chemical composition of compound or group
of compounds, e.g. dyes (Metcalf and Eddy, 2003). Among these
oxidants, ozone is widely used because of its high reactivity with
dyes and good removal efciencies (Alaton et al., 2002). However, it
is also been reported that ozone is not efcient in decolourising
nonsoluble disperse and vat dyes which react slowly and take
longer reaction time (Marmagne and Coste, 1996; Rajeswari, 2000).
The decoulorisation efciency also depends upon the pH. As the pH
decreases, ozonation of hydrolysed dyes (Reactive Yellow 84)
decreases (Rein, 2001; Konsowa, 2003). It has also been reported
that the O3/UV as the more effective method for decolourising of
dyes compared to oxidation by UV or ozonation alone. However,
Perkowski and Kos, (2003) have reported no signicant differences
between ozonation and O3/UV in terms of colour removal. This may
be due to the fact that production of hydroxyl radical (HO) during
photodecomposition of ozone may improve the degradation of
organics. However, most of the UV light gets absorbed by the dyes
and hence very small amount of hydroxyl free radical can be
produced to decompose the dyes. Therefore, approximately same
colour removal efciencies using O3 and O3/UV could be expected.
In H2O2/UV process, HO radicals are formed when water containing H2O2 is exposed to UV light, normally in the range of
200e280 nm (Metcalf and Eddy, 2003). The H2O2 photolysis occurs
as per the reaction shown in Equation (1).
H2 O2 UV l 200 280 nm/HO$ HO$
(1)
This process is most widely used in Advanced Oxidation Process

(AOP) technology for the decomposition of chromophores present
in the dyes (Ferroro, 2000; Kurbus et al., 2002) and consequently
relies complete decolourisation. Fenton reaction is also an example
of AOP in which hydrogen peroxide is added in an acid solution (pH
2e3) containing Fe2 ions (Equation (2)).
Fe2 H2 O2 /Fe3 HO$ HO
(2)
As compare to ozonation, this method is relatively cheap and

also presents high COD reduction and decolourisation efciencies
159
Fig. 3. Structure of various azo dyes showing chromophore and auxochrome (Van der Zee, 2002; Yang and McGarrahan, 2005; Dos Santos et al., 2007; Riera-Torres et al., 2010),
Anthraquinone dye (Kim et al., 2004) and vat dye (Silvia et al., 2007).
(Van der Zee, 2002). The main drawback is high sludge generation
due to the occulation of reagents and dye molecules (Robinson
et al., 2001; Azbar et al., 2004). Most of the AOP for textile wastewaters are highly expensive and its effectiveness varies widely with
the type of constituents present in the textile wastewaters. Also,
from the several reports it is observed that the in some cases, at
certain conditions, these technologies give very attractive results,
however, in some other cases, their application has been reported
not worthy considering the cost and complexity involved in these
technologies.
Chemical coagulation and occulation in wastewater treatment
involves the addition of chemicals to alter the physical state of
dissolved and suspended solids and facilitate their removal by
sedimentation. In some cases the alteration is slight, and removal is
affected by entrapment within a voluminous coagulate consisting
mostly the coagulant itself. Another result of chemical addition is
a net increase in the dissolved constituents in the wastewater.
Coagulation is used for removal of the waste materials in suspended or colloidal form that do not settle out on standing or may
settle by taking a very long time. In water treatment, coagulation as
pretreatment is regarded as the most successful pretreatment
(Huang et al., 2009; Leiknes, 2009).
Coagulation of dye-containing wastewater has been used for
many years as main treatment or pretreatment due to its low
capital cost (Anjaneyulu et al., 2005; Golob et al., 2005). However,
the major limitation of this process is the generation of sludge and
ineffective decolourisation of some soluble dyes (Anjaneyulu
et al., 2005; Hai et al., 2007). Further, the sludge production can
be minimised if only a small volume of highly coloured efuent
treated directly after the dyeing bath (Golob et al., 2005). The
reasons could be the non-availability of other chemical additives
except hydrolysing and xing agents in the efuent coming from
dyeing bath. The chemical additives that are normally present in
the textile wastewaters provide hindrance to the colour removal.
If interfering chemical additives are absent in the textile wastewater except colour causing dyes, then less coagulant dosage
might be required which in turns will reduce the sludge
production.
On account of this, coagulation of water soluble dyes is
challenging due to their high solubility. Further, due to development of synthesis technology, large number of innovative
dyes with complex structures have been synthesised and still in
process of synthesis, which provides difculties for the selection
of appropriate coagulant (Yu et al., 2002). In general colour
removal decreases with increase in dye concentration and dye
solubility (Bouyakoub et al., 2009; Zahrim et al., 2010). Therefore, re-evaluation of optimum conditions for coagulation of
different types of dyes is necessary. Moreover, the effectiveness
of the coagulation can be improved by appropriate selection of
coagulant, occulant aids, optimization of process parameters
such as pH, dosage of coagulant/occulant aids, mixing time,
settling time, etc. The relative advantages and disadvantages of
different physico-chemical methods have been summarised
in Table 3.
160
Table 3
Advantages and limitations of various methods of dye removal from textile efuents.
Physical/chemical
methods
Method description
Ozonation
Oxidation using ozone gas
Advantages
Application in gaseous state,

no alteration of volume
Effective decolourisation
Fenton reagents
Oxidation using H2O2-Fe(II)
of both soluble and
insoluble dyes
Photochemical
Oxidation using mainly H2O2-UV No sludge production
Sonolysis
Destruction of chemical bond by No Extra sludge production
producing free radical
using ultrasound
Adsorption
Dye removal based
Excellent removal of
on solid support
wide variety of dyes
Membrane ltration Physical separation
Removal of all types of dye
Ion exchange
Ion exchange resin
Easy regeneration
Electro-coagulation
Treatment based on
anode and cathode
Treatment based on i
onizing radiation
Treatment based on
microbiological degradation
Good removal of dye
Irradiation
Biological Process
Chemical coagulation Addition of coagulants

and occulation
and occulants
Disadvantages
References
Short half-life (20 min),

High cost
Sludge generation and
its handling
Hao et al., 2000; Ince and Tezcanli, 2001;

Robinson et al., 2001; Gogate and Pandi., 2004
Hao et al., 2000; Arslan and Balcioglu, 2001;
Meric et al., 2004
Formation of by-products
Requires a lot of dissolved
oxygen, High cost
Konstantinou and Albanis, 2004; Hai et al., 2007

Adewuyi, 2001; Arslan-Alaton, 2003
Regeneration difculties,
costly disposal of adsorbent
Production of concentrated
sludge, High cost
Not effective for all dyes
Hao et al., 2000; Fu and Viraraghavan, 2001;

Hai et al., 2007
Marcucci et al., 2001;
Barredo-Damas et al., 2006
Slokar and Marechal, 1998;
Robinson et al., 2001; Hai et al., 2007
Chen et al., 2005; Merzouk et al., 2010;
Phalakornkule et al., 2010
Robinson et al., 2001; Hai et al., 2007
High cost, less electrode

reliability
Effective oxidation at lab scale Not effective for all dyes,
High cost
Environmental friendly
Slow Process, need of adequate Lin and Peng, 1996; Sandhya and
nutrients, narrow operating
Swaminathan, 2006; Togo et al., 2008
temperature range
Economically feasible,
Sludge production
Hao et al., 2000; Fu and Viraraghavan,
excellent colour removal
2001; Aboulhassan et al., 2006;
Gao et al., 2007; Ciabatti et al., 2010
Operating cost and time required for the desired degree of

treatment may be the major criteria for the selection of suitable
method. It can be observed from the Table 3 that each and every
method is associated with some type of limitations such as ozanation gives good colour removal but not signicant COD reduction,
also the expensive method. Good colour removal and COD reduction can be achieved by using Fentons reagent but comparatively
longer treatment time and handling of iron contaminated sludge is
the major problem. Oxidation using H2O2-UV is not very effective
since colour and COD reduction is not very signicant, moreover it
is not applicable to all types of dyes, produces large number of byproducts and also suffers from UV light penetration limitation.
Sonolysis gives good colour removal by the destruction of chemical
bond present in the dye structure with the help of free radical
production, however it requires enormous amount of dissolve
oxygen and involves high electricity cost. Good removal of wide
variety of dyes can be achieved by adsorption but regeneration is
expensive and it also necessitates costly disposal. Removal of all
types of dyes may be achieved by selecting appropriate membrane
but production of concentrated sludge and high cost of the
membrane are again major limitations. Easy regeneration and
efcient recovery of dyes may be possible in the ion exchange
method but cost of regeneration is high and the method is not
applicable to all types of dyes since, ion exchange resins are dye
specic.
Apart from these, various researchers have also proposed the
enzymatic degradation of synthetic dyes. In this direction Bhunia
et al. (2001) investigated the application of novel enzymes horseradish peroxidase for decomposition and precipitation of azo dyes.
The degradation rate was dependent on the pH of the wastewater.
In another study, Bumpus et al. (1991) revealed that the enzyme
from white rot fungus degraded Crystal Violet via N-demethylation
in a considerable amount. Hence, after standardisation and facilitation of accurate dosage, effective dye degradation performance
can be achieved. Simplicity in application and rapid modication
according to the character of dye to be removed makes it attractive
choice for decolourisation of textile wastewater. However, the
major limitation may be the denaturation of enzyme due the effect
of temperature since wastewater coming out from the textile

industry is generally having high temperature.
Both soluble and insoluble dyes can be effectively removed by
electro-coagulation process but high cost of electricity and generation of secondary pollutants from chlorinated organics, heavy
metals are the major limitations. Complete decolourisation may not
be achieved by the treatment with the help of irradiation for all
types of dyes. Though, there is no sludge production in this technology, but high cost of electricity may be the limitation. Cost
effectiveness of biological treatment process makes it attractive
which can efciently remove most of the dyes used in the textile
industry because dyes generally possess high level of adsorption on
to the activated sludge. However, longer duration of treatment,
toxicity of dyes and its low biodegradability are the major limitations. Excellent colour removal may be achieved by coagulationocculation which can remove most of the dyes used in the
textile industry. Though the sludge production is the major limitation in this process, cost effectiveness of the treatment as
compared to other methods makes it one of the attractive options
for treatment of textile wastewaters.
Addition of some chemicals (polyelectrolyte) enhances coagulation by promoting the growth of large, rapid settling of ocs.
Polyelectrolytes are high-molecular-weight polymers, which
contain absorbable groups and when small dosages of polyelectrolyte (1 mg/L to 5 mg/L) are added in conjunction with
coagulant, these are also referred as coagulant aids. The polyelectrolyte is substantially unaffected by pH variations and serve as
a coagulant itself by reducing the effective charge on colloids. It
produces a large amount of ions in water and shows properties of
both polymers and electrolytes. The most practical benet of
polyelectrolyte is the formation of massive ocs. These massive
ocs speed up the oc settling velocity, reduce the expense of
decolourisation and also decrease the settled sludge volume
(Bidhendi et al., 2007).
Since Coagulation occulation is cost effective technology and
gives excellent colour removal for wide variety of dyes, it becomes
promising technology for decolourisation of textile wastewater.
Sludge production can also be minimised by optimising process
parameters and suitable selection of coagulant and occulant. Due

to scarcity of landll sites, the disposal of sludge becomes more
problematic and expensive. Therefore, recycle of sludge becomes
the only viable option. In this regard, the use of sludge as a building
material (Balasubramanian et al., 2006), a soil conditioner (Pearson
et al., 2004; Rosa et al., 2007; Islam et al., 2009) or as a fuel (Van der
Bruggen et al., 2005) has been studied by several researchers.
Coagulation by means of biopolymers is very effective method
for treatment of industrial wastewater. Chitosan as a bioocculant
can be successfully applied for the removal of both particulate and
dissolved substances (Renault et al., 2009). The main reasons for
the success of this biopolymer in wastewater treatment using
coagulation/occulation are, chitosan has the advantage of being
a non-toxic material, non corrosive and safe to handle (non
hazardous product, not irritating for skin and eyes) (Bolto and
Gregory, 2007; Bratby, 2007). Moreover, chitosan is also efcient
in cold water and at much lower concentration than metal salts.
The lower concentration of polymers reduces the volume of sludge
production compared to sludge obtained with alum. In addition, as
biopolymers are biodegradable, hence, the sludge can be efciently
degraded by microorganisms. Various studies have been reported
that the sludge produced from the treatment of milk processing
plant wastewater (Chi and Cheng, 2006) and kaolinite suspensions
(Divakaran and Pillai, 2001) was non-toxic and could be used to
stimulate growth in plants.
4. Chemical coagulation technologies
Chemical coagulation is a complex phenomenon involving
various inter-related parameters, hence it is very critical to dene
that how well coagulant will function under given conditions. On
the basis of effectiveness to decolourise the textile wastewater,
chemical coagulants can be categorised in the three parts as
described in the following Fig. 4.
It has been reported that pre-hydrolysed metallic salts are often
found to be more effective than the hydrolysing metallic salts such
as aluminium sulphate (alum), ferric chloride and ferric sulphate
those are readily soluble in water (Jiang and Graham, 1998). Prehydrolysed coagulants such as Polyaluminium chloride (PACl),
Polyaluminium ferric chloride (PAFCl), Polyferrous sulphate (PFS)
and Polyferric chloride (PFCl) seem to give better colour removal
even at low temperature and may also produce lower volume of
sludge. In this connection, Gregory and Rossi (2001) have studied
the effectiveness of various pre-hydrolysing coagulants for the
treatment of wastewater, and reported that PACl products give
more rapid occulation and strong ocs than that of alum at

equivalent dosage. This can be attributed by the fact that these
coagulants are pre-neutralised, have smaller effect on the pH of
water and so reduce the need of pH correction. Most of the dyes
used in textile industries are of negatively charged and hence
cationic polymer is preferred over anionic and nonionic polymers
due to the better dye removal performance. However, the mechanisms of these products are not well established yet. Further, to
conduct and evaluate the work, it is necessary to consider only the
most critical controlling parameters. Various authors have suggested the most important parameters to be consider in coagulation are pH and concentration of applied metal ions (coagulant)
such as alum (El-Gohary and Tawk, 2009), FeCl3 (Kim et al., 2003;
Bidhendi et al., 2007), MgCl2 (Tan et al., 2000; Semerjian and
Ayoub, 2003; Gao et al., 2007), polyaluminium chloride (PACl)
(Sanghi and Bhattacharya, 2005; Choo et al., 2007), lime (Mishra
et al., 2002; Georgiou et al., 2003) and ferrous sulphate and
organic polymeric coagulants (Mishra et al., 2002; Bidhendi et al.,
2007).
Apart from these, mixing speed and time (Gurses et al., 2003),
temperature and retention time (Ong et al., 2005; Naimabadi et al.,
2009) also inuence the colour removal efciency. Hence, the
optimisation of these factors may signicantly increase the process
efciency. Different coagulants affect different degrees of destabilisation. The higher the valence of the counter ion, the more is its
destabilising effect and the less is the dose needed for coagulation.
If pH is below the isoelectric point of metal hydroxide while
precipitation of colloids by different coagulants supported by
suitable polymer, then the positively charged polymers will prevail
and adsorption of these positively polymers can destabilise negatively charged colloids by charge neutralisation. Above the
isoelectric point, anionic polymers will predominate where particle
destabilization may take place through adsorption and bridge
formation. At high dose of metal ions (coagulant), a sufcient
degree of oversaturation occurs to produce a rapid precipitation of
a large quantity of metal hydroxide, enmeshing the colloidal
particles which are termed as sweep oc (Peavy et al., 1985). For
example, when Fe(III) salts are used as coagulants, monomeric and
polymeric ferric species are formed, the formation of which is
highly pH dependent (Abo-Farha, 2010). Some of the reported
chemical coagulation technology and their performance have been
summarised in Table 4.
The studies made by various researchers as described in the
Table 4 show that the natural pH of ferric chloride solution is acidic.
However, the effective colour removal can be achieved when the
Chemical coagulants
Hydrolysing
metallic salts
161
Pre- hydrolysing
metallic salts
Synthetic cationic
polymers
Ferric chloride
Polyaluminium chloride (PACl)
Aminomethyl polyacrylamide
Ferric sulphate
Polyferric chloride (PFCl)
Polyalkylene
Magnesium chloride
Polyferrous sulphate (PFS)
Polyamine
Alum
Polyaluminium ferric chloride
Polyethylenimine
(PAFCl)
Polyaluminium sulphate (PAS)
Polydiallyldimethyl ammonium
chloride (poly-DADMAC)
Fig. 4. Categorisation of chemical coagulants according to their effectiveness.
162
pH is maintained near to neutral, but it again depends upon the

type of dyes to be removed (Kim et al., 2004; Guendy, 2010;
Moghaddam et al., 2010). Hence, the addition of base to maintain
the pH becomes prime requirement. Lime or NaOH can be used for
this purpose. However, addition of lime may produce extra sludge.
Whereas, addition of polyelectrolyte as a coagulant aid generally
improves the performance of coagulant. It can be seen from the
Table 4 that optimum pH for alum is near to neutral and hence
higher colour removal efciency can be obtained at this pH.
Moreover, addition of polyelectrolyte generally improves the colour
removal performance. However, generation of large amount of
sludge associated with this process makes it unattractive.
PACl products are aluminium-based coagulants. They are similar
to alum, with several important differences:
of basic efuent after treatment, may not be considered as the good

coagulants. Though, both the ferric chloride and alum give roughly
high efciency, at low concentration, colour removal efciency is
reported less for ferric chloride (Kim et al., 2004; Golob et al., 2005;
Bidhendi et al., 2007). However, signicant improvement in the
colour removal has been reported if ferric chloride used with small
amount of cationic polymer (Suksaroj et al., 2005). Very limited
information is available based on the coagulant studies using PFS.
PFS makes it attractive coagulant because it is practically soluble in
water, and forms large amount of polynucleic complex ions like
(Fe2(OH)3)3, (Fe2(OH)2)2, (Fe8(OH)20)4, which are prone to
render occulation. It is advantageous as regards the following
points:
-
Partially pre-neutralised (Higher basicity than alum)

Contains Cl instead of SO2
4
Contains up to three times the aluminium content
Rapid aggregation velocity, bigger and heavier ocs
Moreover, PACl shows better colour removal efciency in

a wider pH range of 7e10. The optimum pH for FeSO4 is alkaline in
the range 7e9 and gives higher colour removal at this pH range.
Various researchers have also revealed that the addition of polyelectrolyte generally increases turbidity and volume of settled
sludge. This undesired effect may be eliminated if the used
concentration of polyelectrolyte is less than 2 mg/L (Bidhendi et al.,
2007).
The optimum pH for magnesium chloride varies between 9 and
12 (Gao et al., 2007; El-Gohary and Tawk, 2009). It gives very good
colour removal performance if used with lime. However, it generates large amount of sludge which may cause sludge disposal
problem and also involves extra cost. Alum and magnesium chloride, because of large amount of sludge generation and production
Fast settling of ocs

Broad pH compatibility
Low iron contamination
High heavy metal removal rate
Easy dehydration of sludge etc.
The principle mechanism for coagulation is similar to the PACl

i.e. adsorption and charge neutralisation. At high turbidity, the
coagulation may follow Sweep coagulation (Peavy et al., 1985).
Gao et al. (2001) have investigated the application of PAFCl for
the decolourisation of petrochemical wastewater and reported that
PAFCl gives better turbidity removal in 7.0e8.4 pH range and good
colour removal for suspension dyes over the other selected coagulant such as PFS and PACl. In addition to the performance of better
coagulation efciency for colour removal, it also reects the ability
to quick formation of the ocs. The ability of quick formation of the
ocs and superior colour removal efciency may be due to the
reason that PAFCl combines the coagulatory advantages of both
aluminium and iron salts and hence able to form ocs rapidly with
more bulky and rapid sedimentation. This novel coagulant is not
Table 4
Effectiveness of different chemical coagulants studied by different researchers for colour removal of textile wastewater.
Name of coagulant
Optimised
dose (mg/L)
Coagulant aids (if any)
Steel industry wastewater

Potassium ferrate
Polyaluminium Chloride (PACl)
Poly-epichlorohydrin-diamine
Alum
100
10
20
200
Polyamine based polymer
Alum
Alum
5000
20
Alum
Ferrous Sulphate
Ferric chloride
Ferric chloride
7 104
200
400
293
Ferric chloride
Magnesium chloride
Magnesium chloride
Magnesium chloride
56
400
120
800
Cationic polymer
Polyelectrolyte (Koaret PA 3230)
Lime
Hydrated lime
0.1
Poly acrylamide-seed gum
800
Ferrous sulphate
Ferrous sulphate
400
1000
Anionic polyacrlamide,
Exeroc 204
Lime and Cationic polymer
Anionic
polyelectrolyte (Henkel23500)
Ferrous sulphate
Ferric sulphate
7 104
7 104
Polyacrylamide
based polymer (Cytec)
Copper sulphate as catalyst
Commercial cationic
occulant (Coloc-RDeCiba)
Polyelectrolyte
Experiments were carried out at original pH of raw wastewater.
Type of dyes
present
Optimum
pH
Disperse
4.25
6.5e8.5
7.2
7
5.3
99
95
99.9
95
78.9
Anouzla et al., 2009

Ciabatti et al., 2010
Choo et al., 2007
Kang et al., 2007
4
Near to
neutral
5.7e6.5a
9.4
8.3
6
74
98
Kumar et al., 2008

Golob et al., 2005
74
90
100
71
Patel and Vashi, 2010

Bidhendi et al., 2007
Bidhendi et al., 2007
Kim et al., 2004
4
11
11
12
92
85
100
98
Suksaroj et al., 2005

Tan et al., 2000
Gao et al., 2007
8.5
80
Sanghi et al., 2006
7.5
75
Tun et al., 2007
12.5
9.5
90
60
Georgiou et al., 2003

Selcuk, 2005
5.7e6.5a
5.7e6.5a
85
58

Reactive
and acid
Sulfur
Sulfur
Reactive and
disperse
Reactive
Reactive and
disperse
Reactive,
acid and direct
Reactive
% Colour
removal
Reference
163
Natural coagulants
Animal based
Plant based
Chitosan
Guar gum
Micro-organism based
Xanthan gum
Gum Arabic
Seed extract from
Strychnos potatorum,
Moringa Oilifeira etc.
Cactus latifaria extract
Potato starch
Fig. 5. Categorisation of natural coagulants with their examples.
widely studied for textile wastewater treatment hence very limited

information is available. The principle mechanism of PAFCl is
charge neutralisation and bridging (Chen et al., 2010). Recently,
Ciabatti et al. (2010) have studied the use of potassium ferrate in
combination of polyamine based polymer for treatment of dyeing
efuents and found excellent colour removal as well as COD
reduction. Since ferrate (VI) ion is a strong oxidant in entire the pH
range, hence after reduction to Fe(III) ion or ferric hydroxide during
oxidation process, it possesses the ability to act as coagulant. Hence
potassium ferrate represents a unique dual function (Oxidant and
coagulant) chemical reagent that can be an effective alternative to
current approaches for water and wastewater treatment.
5. Coagulation with the help of natural coagulants
Chemical coagulation with the help of above discussed coagulants may be the method of choice for decolourisation of textile
wastewater before being fed to the biological treatment, if
necessary. However, it has also some drawbacks as the efciency
of the treatment strongly depends on pH. Moreover, the coagulation process is not always efcient enough because at different
environmental conditions such as at extreme pH and at very low
or very high temperature, it may produce very sensitive, fragile
ocs, which result in poor sedimentation. These ocs may rupture
under any type of physical forces. To improve the efciency of
coagulation process, number of high molecular weight
compounds such as polymers from synthetic or natural origin
may be recommended. These polymers can function as coagulant
itself or in the form of coagulant aids/bioocculants, depending
upon the wastewater and polymer characteristics. These polymers
are normally macro-molecular structure with variety of functional
groups which can either work as coagulants by destabilising the
charged stable particles mainly through the process of adsorption
and neutralisation or can work as coagulant aids by attaching the
destabilised particles with the functional groups by interparticle
bridging. Here organic polymeric compounds are advantageous
over inorganic materials, which posses several novel characteristics such as their ability to produce large, dense, compact ocs
that are stronger and have good settling characteristics (Renault
et al., 2009). In contrast to some traditionally used coagulant
such as alum, organic polymers are benecial because of the
lower coagulant dosage requirement, efciency at low temperature and produce small volume of sludge whereas inorganic
polymers and chemical coagulants generally involve higher cost,
less biodegradability and toxicity. For example, acrylamide is very
much toxic and gives severe neurotoxic effects (Bratby, 2007).
Toxicity effect due to cationic polymers to the plants has been
established long back (Gao et al., 2001). In this connection, Bolto
and Gregory (2007) also reported that anionic and nonionic
polymers are generally less toxic as compared to cationic polymers especially to aquatic organisms. The major advantage of
natural polymer is its non-toxicity to the environment and
biodegradability. Therefore, the efuent after natural polymer
treatment can be treated by biological means, if required. This
efuent will not pose any harm to the biological organisms, as is
offered, if it is treated by means of synthetic coagulants. Not only
this, the sludge generated by the natural polymers can further be
treated biologically or can be disposed off safely as soil conditioners because of their non-toxicity. Hence, there is an urgent
need to establish the use of natural low cost polymers for textile
wastewater treatment.
In the view of this, many researchers have studied the effectiveness of various natural coagulants (Joshi and Nanoti, 1999)
extracted from plants or animals (Christman, 1967) for the treatment of textile wastewater. These natural coagulants may also
prove their effectiveness if used as coagulant aids along with the
chemical coagulants. Most of the natural coagulants fall under the
category of polysaccharides, hence also termed as polymeric
coagulants. On the basis of the origin of production, natural coagulant can be divided in to three categories as shown in Fig. 5. Unlike
synthetic coagulants, natural coagulants generally exhibit two
types of mechanism namely i) adsorption and charge neutralisation, and ii) adsorption and interparticle bridging. As their molecular weight is high and contain long chained structure, therefore
offers a large number of available adsorption sites. Adsorption and
charge neutralisation refers to the sorption of two oppositely
charged ions, while interparticle bridging occurs when polysaccharide chain of coagulant sorbs the particulates (Miller et al.,
2008). The existence of adsorption and interparticle bridging
between dye molecules and polysaccharides is due to the interaction of p- electron system of dyes and OH group of polysaccharides (Fig. 6), which was rst suggested by Yoshida et al.
164
Fig. 6. Schematic representation of intermolecular interaction between p- electron

from dye molecule and hydroxyl group of polysaccharide (Yoshida et al., 1964).
(1964) and then reviewed by Blackburn and Burkinshaw (2002)

and Yin (2010).
5.1. Plant based polymers as coagulants

Various plant extracted polymers such as starch, guar gam, gum
arabic, nirmali seeds, tannin, Moringa oleifera and cactus etc. are
generally well known as coagulants within the scientic community. These polymers have large number of industrial application as
these are polysaccharides and possess various commercial applications such as in paper industry, as food additives etc. By virtue of
the effectiveness of natural polymer as coagulant, Sanghi et al.
(2006) have investigated the use of Ipomeoa dasysperma seed
gum and guar gum as coagulant aids along with PACl and found 86%
and 87% removal of acid dye at the PACl dosage of 1 mg/L and
I. dasysperma seed gum and guar gum dosage of 5 mg/L each, at
optimum pH of 9.5. Signicant removals of the order 73% and 80%
were also been reported for direct dye at the same dosage of
coagulant and coagulant aid and at the same pH of 9.5.
Adinol et al. (1994) have reported that polysaccharide extracted from Strychnos potatorum (Nirmali) seeds can effectively reduce
upto 80% turbidity of kaolin solution. M. oleifera, known as drumstick tree is widely found throughout India, Asia, some parts of
Africa and America. The trees bark, root, fruit, owers, leaves seeds
and gum are also used as medicines. The seed of these trees is also
used as coagulant and/or occulants in the water and wastewater
treatment. Beltrn-Heredia et al. (2009) have investigated the use
of M. oleifera seed extract for the removal of anthraquinone dye and
reported 95% dye removal at the coagulant dose of 100 mg/L and at
pH 7. Further, Lea (2010) has investigated the effectiveness of M.
oleifera seed extract for the treatment of turbid water and found
99.5% turbidity removal at the dosage of 400 mg/L. Typically,
increased dosage of seed extract does not enhance the dye removal
after maximum adsorption is reached. It might be due to the fact
that no more new sites for adsorption remain available at the
surface of seed extract. M. oleifera seeds are also considered as an
excellent biofuel source for making biodiesel.
Gum Arabic, also known as Gum Acacia is highly branched with
beta-Galactose backbone having high molecular weight of
250,000e750,000 Da, water and fat soluble polysaccharide. The
coagulation studies with this novel natural coagulant are yet to be
established. Although the mechanism of coagulation with natural
coagulants has not been extensively investigated but the presence
of hydroxyl groups along the polysaccharide chain provides a large
number of available adsorption sites that might lead to the interparticle bridging between polysaccharide and dye molecule as
shown in Fig. 7.
Paulino et al. (2006) studied the removal of methylene blue with
the help of hydrogel formed by modied Gum Arabic, polyacrylate
and polyacrylamide and reported that 98% of dye removal can be
achieved at pH 8 with maximum adsorption capacity of 48 mg of
the dye per gram of hydrogel. However, use of gum arabic and guar
gum for colour removal due to the widely used dyes in the textile
industries are yet to be established. In connection with application
of natural coagulants, various researchers (Kumar, 2000; No and
Fig. 7. Schematic representation of the interaction of dye molecule with (a) Guar Gum
and (b) Gum Arabic.
Meyers, 2000; Kurita, 2006; Renault et al., 2009) have studied the
effectiveness of animal extracted polymer as coagulants for
industrial wastewater treatment.
5.2. Animal based polymers as coagulants
Chitosan is a linear copolymer of D-glucosamine (deacetylated
unit) and N-acetyl-D-glucosamine (acetylated unit) produced by
the deacetylation of chitin, a natural polymer of major importance
(Roberts, 1992; Kurita, 2006). The degree of deacetylation can be
determined by NMR spectroscopy. Chitin is the structural element
in the exoskeleton of crustaceans (crabs, shrimps etc.) and in the
endoskeleton of other invertebrate.
Chitosan possesses several intrinsic properties such as nontoxicity, its biodegradability and its outstanding chelation
behavior that make it an effective coagulant and/or occulant for
removal of contaminant in the dissolved state. Various studies for
treatment of industrial wastewater using chitosan have been
carried out during late 70s by Bough and coworkers (Bough, 1975,
1976; Bough et al., 1978). They have investigated the effectiveness
of chitosan for coagulation and recovery of suspended solids (SS) in
processing of waste from variety of food processing industries and
found that this novel coagulant is very much effective for efcient
reduction of COD as well as removal of SS and turbidity. Numerous
works claim that chitosan involved in a dual mechanism including
coagulation by charge neutralisation and occulation by bridging
mechanism (No and Meyers, 2000; Guibal and Roussy, 2007). The
possible interactions between dye molecules and chitosan have
been shown in Fig. 8. Zhang et al. (1995) have used carboxymethyl
chitosan for printing and dyeing wastewater treatment. The
experimental results showed that, carboxymethyl chitosan in
wastewater decolourisation and COD reduction, are superior over
other commonly used polymer occulants. Szygula et al. (2009)
reported approximately 99% colour removal from the simulated
textile wastewater containing Acid Blue 92 at an optimum chitosan
dosage of 100 mg/L maintaining optimum pH of 9. In continuation
of this, Mahmoodi et al. (2011) investigated the effectiveness of
chitosan for removal of Acid Green 25 and Direct Red 23 and reported approximately 75% and 95% dye removal respectively in
10 min at optimum pH 2 maintaining the stirring speed of 200 rpm.
5.3. Microorganism based polymer as coagulant
Xanthan gum is a polysaccharide, derived from the bacterial
coat of Xanthomonas campestris, used as food additive and rheology
modier (Davidson, 1980). It is produced by the fermentation of
glucose by the X. campestris bacterium. After fermentation, the
polysaccharide is separated from the growth medium with the help
165
Fig. 8. Schematic representation of the formation of chitosan from chitin polysaccharide and its interaction with dye molecules.
of solvent separation technique, dried and ground into a ne

powder (Cohan, 2010). The use of xanthan gum for the treatment of
textile wastewater is not been reported in the literature yet. Due to
complex structure and higher molecular weight of xanthan gum
(250,000e750,000 Da), as compared to guar gum (about
220,000e250,000 Da), it may also be considered as one of the
promising coagulant and/or coagulant aids for the treatment of
textile wastewater. Hence, extensive study is required to be conducted to establish the various facts about effectiveness of xanthan
gum for the treatment of textile wastewater. The possible mechanism of coagulation by interparticle bridging as observed for guar
gum can also be observed for xanthan gum (Fig. 9).
It can be summarised from the above discussions that plant
extracted coagulant may be encouraged over animal extracted
coagulant for the treatment of textile wastewater due to the fact
that non plant sources possess limited potential for the mass
production as compared to the plant sources. Extra involvement of
cost in the processing of microorganism based coagulant may not

be an attractive option. Application of plant based coagulants will
become more attractive if the coagulants producing plants are
indigenous.
The main advantage of coagulation and occulation is decolourisation of the waste stream due to the removal of dye molecules
from the dyebath efuents, and not due to a partial decomposition
of dyes, which can lead to an even more potentially harmful and
toxic aromatic compound. The major disadvantage of coagulation/
occulation processes is the production of sludge. However, the
sludge amount could be minimised if only a low volume of the
highly coloured dyebath could be eliminated by chemical treatment directly after the dyeing process (Golob et al., 2005).
6. Future scope of research
Very limited work has been carried out on the decolourisation of
textile wastewater containing multiple dyes of different classes
along with the various chemical additives which are used during
textile processing. Also the effectiveness of most of the prehydrolysed coagulants for decolourisation of textile wastewater
containing multiple dyes is yet to be established. Considering the
industries dependencies on the cost effective chemical coagulation
and occulation technologies for their coloured wastewater treatment, it is required to conduct more and more future research to
come up with best coagulants or combinations of coagulants along
with coagulant aids which can produce very promising results even
at a wider variations of pH and other interfering agents of the
textile wastewaters. Investigation of the effectiveness of more
number of natural coagulants is also need to be assessed. This
assessment may be carried out using natural polymers as coagulant
aids as well as coagulant itself. Effectiveness of natural coagulants
also required to be carried out against simulated as well as raw
textile wastewater.
7. Conclusion
Fig. 9. Schematic representation of possible interaction between xanthan gum and dye
molecule.
All decolourisation methods described in this review have some

advantages as well as some drawbacks, and their selection will
mostly governed by the textile wastewater characteristics like class
and concentration of dyes, pH, organic contents, heavy metals, etc.
Among different physical, chemical, biological, and advanced
166
chemical oxidation technologies, chemical coagulation and occulation is still a cost-comparative alternative for the treatment of
industrial textile wastewaters and is widely practiced by the small
to large scale industries. Among chemical coagulation and occulation technologies, comparatively, pre-hydrolysed coagulants such
as PACl, PFCl, PFS and PAFCl may be considered as the better
coagulants because of their superior colour removal even at small
dosage and affectivity at wider pH range of wastewater. Ferrous
sulfate may also be considered as a better coagulant over other
hydrolysing metallic salts. Additionally, due to some novel properties of natural coagulants such as non-toxic, biodegradability,
environment friendly, ability to encapsulate etc., these may also be
considered as the promising coagulants as well as coagulant aids
for textile wastewater treatment specially at rst stage, which will
not hinder the biological treatment (if required) because the
residual coagulant may act as nutrient for the microorganisms.
However, till date the applicability of these natural coagulants for
the textile wastewater is very limited. More and more studies
required to evaluate their application for colour removal of textile
wastewaters particularly, their behaviour at high pH of textile
wastewaters.
Acknowledgement
The authors wish to thank all the reviewers for their valuable
suggestions for improving the quality of the manuscript and
Department of Civil Engineering, School of Infrastructure, Indian
Institute of Technology Bhubaneswar, India, for providing facilities
for carrying out research work in the related area.
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Journal of Environmental Management 93 (2012) 154e168

Contents lists available at SciVerse ScienceDirect

Journal of Environmental Management

A review on chemical coagulation/occulation technologies for removal of colour

Abbreviations: BOD, biochemical oxygen demand; COD, chemical oxygen

processes. These efuents produce high concentrations of inorganic

A.K. Verma et al. / Journal of Environmental Management 93 (2012) 154e168

core countries of South Asia (Bangladesh, Bhutan, India, Maldives,

various chemicals used in different stages of textile processing (Lee

BOD (34-50% of total), high

Oily fats, BOD (30% of

High BOD, high pH

A.K. Verma et al. / Journal of Environmental Management 93 (2012) 154e168

El-Gohary and Tawk, 2009

BOD7 and efuent is from reactive dye bath.

(Snowden-Swan, 1995). Similar processes for reactive and direct

(Namasivayam and Sumithra, 2005; Khaled et al., 2009). Apart from

A.K. Verma et al. / Journal of Environmental Management 93 (2012) 154e168

2. Chemical composition and structure of colour causing dyes

A.K. Verma et al. / Journal of Environmental Management 93 (2012) 154e168

Anionic, water soluble

Nylon, wool, silk

Electrostatic, Hydrogen bonding

Very low water solubility

Polyester, poly-amide, acetate,

Hydrophobic- Solid state

Anionic, water soluble

Cotton, nylon, silk, wool

Impregnation and oxidation

Applied from neutral to acidic dyebaths

various researchers throughout the World. A brief discussion on

application of adsorption technology is limited not only for colour

H2 O2 UV l 200  280 nm/HO$ HO$

This process is most widely used in Advanced Oxidation Process

Fe2 H2 O2 /Fe3 HO$ HO

As compare to ozonation, this method is relatively cheap and

A.K. Verma et al. / Journal of Environmental Management 93 (2012) 154e168

A.K. Verma et al. / Journal of Environmental Management 93 (2012) 154e168

Oxidation using ozone gas

Application in gaseous state,

Ion exchange resin

Good removal of dye

Chemical coagulation Addition of coagulants

Short half-life (20 min),

Hao et al., 2000; Ince and Tezcanli, 2001;

Konstantinou and Albanis, 2004; Hai et al., 2007

Hao et al., 2000; Fu and Viraraghavan, 2001;

High cost, less electrode

Operating cost and time required for the desired degree of

of temperature since wastewater coming out from the textile

A.K. Verma et al. / Journal of Environmental Management 93 (2012) 154e168

parameters and suitable selection of coagulant and occulant. Due

more rapid occulation and strong ocs than that of alum at

Polyaluminium chloride (PACl)

Polyferric chloride (PFCl)

Polyferrous sulphate (PFS)

Polyaluminium ferric chloride

Fig. 4. Categorisation of chemical coagulants according to their effectiveness.

A.K. Verma et al. / Journal of Environmental Management 93 (2012) 154e168

pH is maintained near to neutral, but it again depends upon the

of basic efuent after treatment, may not be considered as the good

Partially pre-neutralised (Higher basicity than alum)

Moreover, PACl shows better colour removal efciency in

H2 O2 UV l 200 280 nm/HO$ HO$

Fe2 H2 O2 /Fe3 HO$ HO