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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

Rece i ved 17 February 2003; accepted JO July 2003

The environmental issues associated with residual colour in textile efnuents have posed a major challenge to environ mental scientists as well as the textile colouration processors. The requirements to remove colour from textile

public complaints about

coloured watercourses. Dyes are highly dispersible aesthetic pollutants and are difficult to treat, as most dyes are hi g hly

stable molecules mad e 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.

efnuen t on si te prior to discharge to sewe r have been progressively tightened due to increased

Keywords: Colour removal, Dye separation, Textile effluent

fPC Code: Int. Cl. 7 C08J 11/04; C02F 1/00; C02F 3/00

1 Introduction

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.

"To whom all the correspondence should be addressed . Phone: 26596623; Fax: +91-11 -26581103; E-mail : mangala

• Most dyes have complex aromatic structure 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 ETAD survey had LD50 (Lethal Dose at 50% survival) values greater than 2 x 10 3 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

metals and chlorides in them 7 9

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

of employees to dyes in the user


due to prese nce of







• Dyes have also been known to interfere with certain municipal wastewater treatment operations 7 , i.e. UV disinfection, etc.



2 Textile Dyes and Environmental Concerns

Textile dyes are classified under the categories of anionic, cationic and nonionic types. Anionic dyes mostly include the direct, acid and reactive dyes. Basic dyes are the only class of cationic dyes used in the textile industry. Nonionic dyes refer to disperse dyes, which do not ionize in an aqueous medium. It is estimated that about 15% of the total world production of colorants are lost in the synthesis and


tend to be in the best situation in this respect since high exhaustion is normal when applying anionic dyes to wool and cationic dyes to acrylics. The biggest

problem relates to the dyeing of cotton with reactive and sulphur dyes because of the low level of exhaustion and fixation 12 as shown in Table 1.


of colorant 8 . The wool and acrylic dyes







cellulose fibres with anionic reactive dyes is the requirement of large amount of inorganic salt to suppress the negative charge at the fibre surface so as to increase its exhaustion level on the fibre. However, various developments have taken place in the recent years to increase the exhaustion level of reactive dyes lJ - 23 . In 1986, the Health and Safe ty executive

issued publications concerning the possible respiratory irritant and sensitization effe cts from handling the dry powders or from aerosols containing these materials 4 .

The chromophores in ani o ni c and nonionic dy es are mostly azo group or anthraquinone types. The

reactive cleavage o f azo fo rmation o f toxic

Anthraquinone based dyes are more resistant to

linkage is responsible for the amines in the efflu e nt.

degrad atio n due to their fu sed aromatic s truc tures

and ,

the refo re, re mai n coloured for a lo nger pe ri od o f in the waste wate r.


The azo dye and pigme nt manu facturing plan ts prod uce a was te which has low pH , hig h co lou r, high organic content (high COD) and low amenabil ity to

biological degradation

as a typical dye waste 8 . Dyes have a very low rate of

removal ra tio for BOD t o C OD (B O~ /C O ~

than O.l) and not removed by typical biological treatment plants. Furthermore, dyes can be detrimental to the microbial population present in such plants and may decrease the efficiency or lead to treatment failures in such plants 24

is less

(low BOD) and can be defi ned

'The alkaline reducing systems based on Na2S in some dyeing recipe cause discharges of the effluent containing sulphur, which give foul smell and

Table 1-- Exhaustion range of various dye classes· 2

Dye class


Degree of

Loss to


fixation, %

effluent , %





Bas ic


95 -1 00






Di sperse


90-1 00

0- 10


Woo l


2- 10













contaminate sea water/river water with their toxicity and destroy marine life 9 The environmental impact of metals in wastewater effluents is also an important issue faced by the dye manufacturing and application industries today. This is an important point because a significant number of dyestuffs are metallized dyes. Commonly employed metals are chromium, cobalt, nickel and copper, all of which are designated as priority pollutants by the US Environmental Protection Agency (EPAi.

3 Dyestuff and Colour Removal from Textile Emuents

Colour removal is a pertinent problem for all categories of textile effluents due to the variety of chemicals used in dyeing and printing of fibre, yam or fabric. Colour pollution can be most efficiently controlled by good source reduction practices, administrative and engineering controls, process and product design and work practices. The search for dynamic response and improved productivity has served to focus the attention of the colouration industry on right first time (RFf) production techniques 2 4-27. A hi gh level o f RFf minimizes waste and makes a signifi cant contribution

to red uce colour loads in the effluent 28 Improving the e xhau sti o n level s o f the various dy es in the dye bath is another area which has received lot of attention from researchers as it will not only improve shade reproducibility and problem of repeat shades but also the colour effluent problems which will then reduce to a matter of controlling and handling spills and clean-up. Dyes showi ng a high level of

exhaus ti on and fixati o n o n the fi bre have been

will continue to be the prime targets of research a nd development activity. However, quantitative dye bath exhaustion is not possible with most systems and hence the remo val of colour from textile e~f1uents is a m ajor pro bl em faced by environmental scientists and engineers.















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 ie 8 . Coagulant

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

aids can be used

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 and sulphur dyes 4 . 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 th e 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 th at 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 an d flocculation is the generation of large amount of toxic sludge creating a lot of handling and di sposa l problems . The reappearance of colour in subsequent steps due to oxidation is also a critical problem fac ed 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.



3. 1. 1.1 Sy nth eti c Organic Co aglliants

These pol ymer coagulants are highly charged cationic polyelectrolytes and promote precipitation of dye residues , formin g s mall in soluble col o ur particles.

These small

solid/liquid separation process. These often completely eliminate the need for the large amounts of aluminum or iron based salts traditionally used. The mechani s m of dye removal is electro static attraction between oppositely charged soluble dye and polymer molecule (Scheme 1).

particles are removed using a su itable

3.1.2 Adsorption

Adsorption is the phenomenon by which the molecules of a gas, vapour or liquid spontan eously 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 hi g h surface area inorganic material , for removing species from a liquid stream depends on the equilibrium between the adsorbed and the free species 4 . The variou s adsorbents reported in literature for the removal of colour from textile effluent are:

3. 1.2. 1 Acti vated Carbon

Activated carbon has been evaluated extensively

fo r the treatm e nt of different classes of dyes, i. e . acid ,

d irect, bas ic , di sperse, reactive, etc and is no w the most widely used adsorbent for dyes 37 - 38 . Several pilot pl a nt and comme rci al- scale systems using activ a ted carbon adsorption columns have been developed 39 . The molecular 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

reasons for the observed poor

carbon . One of the main

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




dy e mo lec ul e








molecul e





XXX- R -

O---- -N -



















XXX- R -

(). ---- --N-R




Stro nge r and

enlarge fl oc

(Not yet residual change)




XXX-R--()' - - - - - -N-R



Weakly bo und Coprcc ipi tatc





R-N -




High r.m.m fl occ ul an t



Sche me l-Coagul ation and fl occulati o n mec hani sm

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 a nd 10- 15 % loss of adsorbent on reactivation. 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, sawdust 4 1 .42 , carbonized wool 43 , activated sludge 44 ,wood bark, rice husk"and cotton waste 45 .

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 resuIt 46 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 celluloses and ligno-celluloses extracted from cotton

waste, sawdust and corn stalks 47 .

coagulation or biodegradation , it becomes a very useful polish ing step for efficient dye removal.


mpe rature, pH , contact time and dosage must be

3.1 .2.4 Chitin

and Chitosan

Factors such as choice of activated carbon ,

Chitin, a polysaccharide, is very similar in structure to cellulose, being composed of poly 2-acetamido-2-


ken into con s ideration for optimum remo val of dyes

dioxy-D-glucose . Chitosan is a well-known derivative









of chitin produced by the deacetylation of chitin which is a natural biopolymer extracted from the shell of arthropods 4 . 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

There are several studies on the

affinity is basic dyes.

use of chitin and chitosan for the removal of dyes 48 . 51 . Knorr 48 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.


et al. did extensive work on chitin and

reported adsorption equilibrium studies 49 , batch and

, kinetic studies and mass transfer

column studies

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

A moderately

crosslinked chitosan fibre 53 .

allows the fibres to be

capacity and much easier desorption.





Hu 57 examined the adsorption of reactive dyes to Aeromonas biomass. Dye absorption kinetics was moderately fast with the equilibrium reaching within 2 h. 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 s o binds Acid Blue 25 slowly, requiring more than 3 h to reach the equilibrium.

3.1 .2. 7 Ch emically· modified Cellulo se and Lignocellulose



Chen 63 . 65





adsorbents prepared from the reaction of polyamide- epichlorohydrin resin and cellulose. This material, composed of 10-30% cellulose, has a high adsorption capacity for acid, direct and reactive dyes. Unfortunately, the rate of dye adso rption is very slow ,

requiring 3 days at 30°C 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 di valent anion) of the PAE-cellulose (25 % cellulose) material is 1.0 mollkg.

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

prepared cellulose/glycidyl methacrylate/acrylic acid cation exchange composite and could 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.

al. 68

Youssef>6 described the chemical



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. 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 verrucaria 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



Quaternary ammonium groups can be introduced into cellulose and lignocellulosic materials. The quaternary ammonium group introduces a permanent

positive charge to the substrate, making the materials very effective acidic dye adsorbents. Gangneux et

demonstrated that quatermzed cellulose has an

a .


70 ,7 1


exchange capacity of 0.6-0.7 eq/kg for acid, direct and reactive dyes. The equilibrium adsorption of the dye was achieved in < 2 h. While quaternized cellulose has most of the desired performance characteristics (high capacity, rapid kinetics, etc), it fails to retain the

most important attribute--Iow cost. Presumably, this is due to the cost of preparing pure cellulose, not because of the cost of quaternization. A low-cost adsorbent can be prepared by quaternization of lignocellulosic materials, such as corn cob 72 , saw

ust an sugarcane agasse . These matenals have the exchange capacities in the range of 0.35-0.85 eq/kg. The dye adsorption and desorption characteristics of the quaternized lignocelluloses are quite comparable to the cationic materials prepared from pure cellulose. Thus, relatively inexpensive, moderately high capacity, anionic dye adsorbents could be prepared from lignocellulose biomass. However, none of these adso rbents has any commercial importance. Table 2 summarises the main advantages and disadvantages of different bioadsorbents reported for the removal of dyes from textile wastewater.







3. 1.2.8 Inorganic AdsorbenlS

In recent years, investigations have been undertaken to evaluate inexpensive inorganic materials as potential adsorbents for dyes, which include peat?, flyash 75 , bentonite 76 , calcium metasilicate 77 , activated aluminum 78 , clay and bauxite 79 . The use of bentonite for basic dyes and anthracite charcoal for acid yellows are also known 80 . The use of inorganic adsorbents, such as high surface area silica, cinder ash and clays, has been tried for a range of dyes 81 . 84 Silica was found to be reasonably effective for treating effluents containing basic dyes . Again the process has little effect on the major inorganic charge of the effluent. The use of cinder ash appears to be a cost effective solution where a readily available supply of the ash is found locally and the effluent does not contain reactive dyes.

3. 1.2.91011 /:.xchange Resins








or cationic, they could in theory be removed

on ion

Table 2- Principle difference between reverse osmosis, nano filtration and ultra filtration 108



Cross flow



















Process tlux


Im· 2 1









exc ange reSInS " . owever, t ey have not been widely used for the treatment of dye containing effluents, mai nly due to the fact tha t 10n excharlge resins cannot accommodate a wide range of dyes i.e. not effective for disperse dyes and have to be regenerated using costly organic solvents once they are saturated. The process is feasible provided an organic solvent such as methanol is used during the regeneration step, which can be recovered later. In the early 1980s , the Institute Textile de France studied the use of cellulose based ion exchange materials for the treatment of dye house effluents 4 . Because of the synthetic nature of these materials, they could be tailored to have great chemical resistance. A combined process involving adsorption on synthetic polymer and ion exchange has been used to decolour dye wastes 85 The process has several operating and performance advantages over activated carbon adsorption.






3. 1.2.10 Macrosorb / Acrasorb



Macrosorb is synthetic inorganic clay and the crystal

structure consists of parallel layers of clay platelets, which due to their chemical composition carry a net

positive charge. Between these layered pl atelets,

is anion which balances the cationic nature of clay. They are thus engineered for optimum adsorption of the compounds found in dyehouse effluents, which have a larger negatively charged or polar molecule, i.e. dyes, organohalides, pesticides, etc. The adsorbent capacities are very high and can remove these

contaminants from process water down to extremely low levels and are then removed by gravity settlement in the form of pumpable sludge. This offers prospect of being able not only to meet any current or envisaged consent limits but also of water reuse. Acid, metal complex, direct and reactive dyes are











developed 9I ,92.




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 stream 93 . 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. 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

candidate in this respect 94 . 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 pumpkin 95 (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 product 97

Table 3 -Summary of bioadsorbenr.s 47


Adso~tion caQacit:t. mol/kg


Monovalent dye

Divalent dye





Blue 25)


Red I)



(Acid Red I)

Crosslinked chitosan


(Acid orange II)


Fungal biomass


0 . 11 (Acid Red 114)

(Acid orange II)

Bacterial biomass


(Reactive Yellow)"

Sugarcane bagasse


(Acid orange 25)


Wood shaving


(Congo Red)

Maize cob


(Acid Blue 25)


Peat moss


(Lanasyn Black)


Rice Hull


(Lanasyn Black)



CarbamoyIcell ulose


Direct Blue 86)


0.6-1.1 b



0.035-0.85 b

(Acid Blue 13)


"Trivalent anion bCaQacit:t ( eqlkg)

Major drawback

Slow kinetics

Slow kinetics

pH sensitive

Slow kinetics

Low capacity

Low capacity

Low capacity

Low capacity

Low capacity

Slow kinetics

Low capacity





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, ho wever, reject even the smallest ions and allow the passage of pure water o nly. Hence, the operatio nal pressure for reverse osmosis systems is higher in the range of 0.69-6.9 MPa whereas ultra fi ltratio n 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 reported 97 - 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 l O3 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


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 (50-80°C). 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


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 wi thstand higher mechanical forces and tolerate rough effluent conditions, such as temperature higher than 100°C and pH greater than 12. Generally, the membrane lifetime

copolymer I 14,

ketone) 113,


is longer than for organic membranes but they are

fragile and require frequent back pul sing .

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,

modules 117 . Spiral wound modules provide a relatively high

packing density «1000m 2 /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

tubular, spiral wound and hollow fibre



effluent l18 . Nowaka et al. I19 reported the suitability of capillary membrane modules (UF and NF) for decolourization of both simulated and industrial dye effluent and found 92-99 % retention coefficient for organic dyes of molecular wt -780. The main advantage of membrane processes is that concentration is achieved without any input of thermal energy or a change of state, making the process energy efficient. Calabro et at. 120 conducted energy analysis of integrated membrane processes in treatment of solutions simulating textile effluents and did an energy analysis. Another great advantage of these membrane processes is that the wastewater can be treated successfully to a level required for recycle and reuse l21 . Reuse options for the nano filtration permeates exist either as dye bath makeup stream or in the following rinsing stages, depending on specification. Reductions of fresh water use of the order of 60 % and energy savings up to 50% can be achieved by integration of membrane technology into continuous washing/rinsing processes. The removal of the dyestuffs from the spent dye bath liquor using membrane technology makes it possible the recycling of water in dye houses and the concentration and reuse of dyestuffs. Thus, it not only helps in pollution control and waste management but also helps in conservation of chemicals and water. Techno-economic viable solutions have been suggested to combat water shortages with innovative use of membranes by Yedavyasan 122 Compared to other

separation processes their space requirements are low and modular construction and design allow relatively easy expansion. The major problem faced in application of membrane technology for effluent treatment is the high cost of membrane and other membrane filtration equipment, depending on the size of plant, the operating condition and associated water treatment costs besides the problem of lower productivity with time due to the deposition of precipitated dyestuff, i.e. fouling. Membrane systems are limited in several ways as a consequence of their structure. The use of polymeric membranes is limited to the temperature of 70°C, pressure of < 6-7 MPa and a pH range of 2-12 (maximum). Another problem faced is the disposal of concentrates from the membrane processes. There have been several attempts to solve this difficulty by oxidative degradation of the membrane concentrates by Fenton's reagent l23 and ozonation of membrane concentrated secondary effluent l24

3.2 Chemical Techniques

3.2.1 Chemical Oxidation

Many dyes are effectively decolourized using chemical oxidizing agents and found to hold potential for future use in the textile industry. Many studies on usage of different oxidizing agents, i.e. chlorination, chlorine dioxide treatment, ozonation, use of hydrogen peroxide with other salts (Fenton's reagent), permanganate, etc, have been reported in literature 8l , l25 and summarized in Table 4.

Table 4 -Summary of chemical oxidati o n techniques used for decolourisation 125



Sodium hypochlorite

Effective on decolorisation, cheaper than other oxidants, and easily applicable (20-40°C, 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.


Specially useful in decolorisation of water-soluble dyes . Does not sufficiently decrease COD


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

Gamma irradiation

New technique.

UV irradiationlhydrogen peroxide

Increased rate and strength of oxidation, but the cost of producing UV irradiation does not compensate 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 .


INDIAN J. FIBRE TEXT. RES ., JUNE 2004 Chlorination

Chlorination (using chlorine gas or sodium hypochlorite, i.e. NaOCI) has been evaluated l26 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



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 tex tile dyes 129 . In situ production of hy pochlorous acid was achieved in an undivided electrolytic cell. Although, decolourization using sodium hypoc holorite 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.










ff ectlve



onne IS reporte



e more e

3.2.1. 2 Chlorille Dioxide

Chlorine dioxide is less reactive than chlorine and has been claimed to give rise to fewer side reactions 4 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 H 2 0 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 =~O Et

1 0,

EtO --Q- N= N --Q-C HO




OOHC -O-- N = ~O Et


H 2 0

Scheme 2-Ozone fading of Crysophe 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 wastewaterI30-135. Some classes of dye respond more readily to oxidation by ozone than others. According to some authors 4 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


. 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.

COD to be removed with no res idues or sludge


no tOXIC . meta

bol Ites '



zonatIOn may


10rmatIOl1 an


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



some mean s, for example ultra violet light, inorganic salts ( Fe+ 2 ) , ozone or ultrasound. Many methods of chemical decolourization vary, depending on the way in which H 2 0 2 is activated.

3.2.1 .5 H 2 0r 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

th e

co ncentrated and dilute waste

investigated 4 . 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 th e

performance depending on final floc formation and it 's set tlin g quality . In a comparative study' 38 on

oxidation of di s perse dyes by electrochemical process, ozone, hypochlorite and fenton's reagent, the best results were obtained with Fenton process which

under the optimal pH

600 and 550 mgm- 3 respectively results in a final

of 3 and H 2 0 2 and FeS doses of

colourless effluent with low residual COD (100 mg/cm\

3.2. 1.6 H 2 0 2 1UV

Decolourization of dyes using UV/H 2 0 2


investigated b y several researchers 139- 143 . This method

degrades dye molecules to CO 2 and H 2 0 by UV treatment in the prese nce 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 H 2 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 dy e 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,





Scheme 3--(:atalytic action of iron on hydroge n perox id e 94

Scheme 4--Hydroxyl radical generation through UV radiation 139











produced 139.









containing effluent-no sludge is produced and foul odors are greatly reduced.

3.2. 1. 7 H 2 0 ] - Ozone

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


biodegradable l l. 143 . Decolourization by means

of H z 0 2 /0 3 combination is app li cable for direct d yes , metal complex or blue disperse dyes, but there are


d Isperse




yes an









t h' elr mIxture .

3. 2.1 .8 H 2 0 r Peroxidase

Peroxidase can also be used as an acti vator for

H 2 0 2 for decolourization purposes. Morita et

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 2 0 2 -UV-Ultrasound

Fung et al. 145 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.

al .


3.2.2 Irradiation

Gamma radiation induced oxidation has also been reported 125.146 in decolouring refractory dyes that withstand many of the conventional textile waste treatment processes. The rate of reaction is controlled



by radi a ti o n dos e and th e availability of oxy ge n in th e so luti o n . It prove d to be an effec ti ve techniqu e fo r th e

re mova l o f dy es as we ll as to xi c o rg anic co mp o und s, i. e. be nze ne , to lu e ne a nd chl oro ph e no ls, by ox idi z in g

th e m into mo re eas ily biodeg rad abl e co mpo und s .

Bo th C OD a nd AOX we re dec reased a nd 90 % of

wastew ate r was e limin ate d. However, is th e m aj o r di sad va nt age.

(W AO) is a no th e r process by w hi c h e ffec tively di sposed 147.

the efflu e nt co uld be

co lo ur in th e

ver y hi g h cos t

W e t ai r ox id ati o n

3.2.3 Ch emical R edu ctioll

c h e mi ca l

reductio n is an effective deco lo uri sation tec hnique. Che mi ca l redu c ti on of azo dy es ca uses clea vage of azo

bo nd ,

Jm in cs th a t in theolY a re mo re a me nab le to s ubsequ e nt

aerobic b io logi cal treatme nt th a n the pare nt dye s tru c ture.

r eac ti ve

w he n based

on bisulphi te catalyzed sodium borohydride a lo ng w ith a cat io ni c age nt have bee n appli ed to wa te r- so lubl e dy es

pretreated w ith a redu c ing age nt l48 . Technologies


Tn a d d it io n , p ubli s h e d r es ult s indi cate t ha t c e rt a i n




ma n y

d yes,

p W1 i c ui a rl y

sma ll


d yes,

ge ne ratin g


ad so rbed

no nc h ro mo ph o ri c

we ll

o n


act ivated c arbo n

con taining


reduct io n of >90% was poss ibl e . Sod ium boro hydrid e is

o ne

co mm e rc ia ll y avail a bl e, w hil e bi s ulphi te is not co ns um ed

a rege ne ra bl e co reagent or cata lys t l49 . The

oth e r mos t co mmo nl y used che mi ca l reducin g age nts w·e sodium hydros ulphite, thi o urea di o xid e, tin (II ) c hl o rid e,

but acts

stronges t water-solubl e reducin g agents

co ppe r co lo ur


o r

o th er dyes 149.

redu c ibl e Us ing

gro ups

thi s

a nd

metalli zed

o f




etc. Whil e eva lu atin g th e ch e mi ca l deco lo uri sa ti o n


wastewate r us ing redu c in g age nts, it is impo l1a nt


invest iga te th e po ten ti a l rev ersa l of the reacti o n

ex pos ure to oxyge n, s ince col o ur may

di sc hw·g ing the wa stewate r to th e e nvi ronm e nt

3.3 Biological Treatment

up o n rea ppear upo n

Bi o log ica l d iges ti o n in vo lves th e aerob ic ( in prese nce

of O 2 )

o rga ni c

w ide ly researc hed a nd rev ie wed I50.151.

o r an aero bi c (in a bsen ce of O 2 ) deg rad ati o n of

sub sta nces


microo rgani s ms

a nd



3.3.1 A erobic Treatmellt

bi o log ic a l treatment us in g ac ti vate d s lud ge is most co mm o nl y used treatment me th ods fo r

was tewa te r genera ted from te xtil e d ye in g o pe ra ti o ns .

o ne


ro bic

o f

th e

o nn ally , thi s rem oves

th e biodegrada bl e co mpo nen ts of

the e ffluent, e.g. carbohydrates, waxes and th e readil y

deg rada bl e auxjliwy compounds, al thou g


surfactants re main as it is.


h more






The ineffec tive ness of ae robic bi o log ical syste m in

re mo vin g co lo ur has caused aesthetic problems in the

encouraged d ischw·gers to


ge ne rally res ista nt to oxida ti ve biodeg rad ation , s ince o ne

of the mos t imp0l1ant prope rti es built in th e comme rc ial

d yes is res ista nce to f adin g ca used by che mi cal a nd li g h t

indu ced oxi d ati o n. Th e iss ue o f tox ic ity of th e e fflu en t is

a lso

bi o log ical treatm e nt of dy e was tewater is th e diffi c ulty in


Acclima ti o n

aerob ic

in ves ti gate o th e r alte m a ti ves . Dyes th e mse lves





li s in g

co ncem . A no the r

th e


probl e m

wi th

clim atin g

microo rgani sms to th e s ubstrate .


pro bl e m


tex tiles

d ue


co nsta nt p ro du c t ch a nges a nd batch dye ing o peration s.

Shri ver


expected to un dergo bi odeg rad at io n J.t s lowe r rate than

th at fro m typ ica l do mes ti c was tewa ter. Seve ra l st ud ies on

aero bic

was tewa te r


mecha ni s m in vo lves adso rp tio n to ac ti vated s ludge.

in the ir study o n BOD tes ts

concluded th a t co lo ur in

Dague l52


tex til e

was tewa te r wo uld

I· Itt I e





tex til e

eg rac I at lon ·

prim cuy

bio logical




t h

a t th a t



111 . d · Icate

occ urs

a nd

ac tu a ll y

remova l

T h e ad so rpti o n pro pe rti es of ac ti va ted s lu dge are


im il ar


th at

of ac ti vated ca rb on in vo lv in g acid,


irec t, reactive, disperse and bas ic dyes a nd are

ma inl y depe ndent o n dye pro perties (mo lecular


tru c tur e

a nd

t y p e,

numb e r

a n d

p OS it IO n



u bs titu e nts in th e dy e mo lec ul e) . A d sor pt io n is


s ulph o ni c acid grou p sl 53 . The

facto rs inhibitin g perm ea ti o n of th e d ye thro ug h th e

m icro bial ce ll m e mbra ne (e.g . in c reased or d ecreased

wate r

red uce th e effic ie ncy of th e bi o log ica l syste m. ET AD

stud ies 155 o n

process indi cate th a t lo w ad so rpti o n on s ludge occ urs

s ludge


gro up s but d ec r ease d b y



prese nce

a nd

o f

hy dro xy,

n itro


so lu bility

in creased


molec ul a r weig ht)


aet ivated

re mova l of

with ac id a nd reacti ve dyes,

w it h

a nd

ad so rpti o n occ urs with di spe rse d yes .

hi gh adsorptio n occ urs

med iu m


direc t


a nd

h ig h


Cll e m o me tn c

a na lys is to find o ut th e le ve l o f bi oe limin a ti o n of wa te r

so lu b le dyes. T hi s an aly s is was co nd uc ted



was found th a t th e lev e l o f bi oe limin a ti o n is propol1i o na l

an d

to th e s ize/c hw·ge rati o o

d irec t dyes, bi oe limin ati o n vwi es be twee n 0% an d 95 %


es of dyes s tudi e d , whil e in case o f reac ti ve

clyes, th e l e v e l o f bio e limin a ti o n v cu·ies f rom 0 % to o nl y

25%. To max imi ze the bi oeliminatio n o f reacti ve dyes,

la rge a nd plan e r triazine based d ye s s ho ul d be used l57 .

lU rc 1 ey





156 157


cWTl . e



o u t




to co rre late

oe limin a tio n with c he mi ca l s tru c ture/fun c ti o na li ty.

r the

se ri


th e dye.

Tn case of aci d



In an activated sludge tank, water is mixed and aerated with a suspension of microorganisms. A microbial flocculation forms; oxidizing dissolved and suspended organic 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


excessive bio solids l58 . Thi s is done through the use of a

solid but porous matrix (beads) to which a tailored microbi al consol1ium of organism has been attached. Thi s 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 conditioning. Both methods aim to produce a biased microbial community, dominated by species that are

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

the waste without concomitant production of




l59 .












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

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, H 2 S 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. l64 studied the


1.162 an d

Acid yellow 36

PRIMARY _ ~-1-r--"".


- ,






3- Aminobenzane· sui phonic acid

N·Phcnyl-I ,4-diaminobenzene

Fig . I-Two-s tage PACT sys te m as used at th e Du Pont chamber wo rk s l 60

Scheme 5--Anaerobic redu ction of Acid Yellow 36 (ref. lSI )



removal of colour from textile effluent using a laboratory 'upfl ow anaerobic s ludge b lanket' reacto r. Several

com mercia l dyes were selected to stud y the effect of dye structure on colour removal. The average removal effic iency for acid dyes using thi s method was be twee n 80 % and 90 % and that o bserved fo r the direct dy e used was 8 1%. Laboratory ex periments usin g thi s anaerobic reactor with disperse dyes, such as an anthraquino ne- based dye, were un successful even a t ve lY low concentration s. However, the breakdown of azo dyes to thei r

co rrespo nding

decolo uri zat io n of wastewate r, a nd (ii ) preparation of wastewater for subseq uent biological treatme nt since the aromatic amines released by anaerobic digestion of azo dyes are effectively treated by aerobic treatment processes. Hence, the CUITent literature '65 revea ls th at an

a naerob ic - aerob ic treat me nt sequence has been found more effective method fo r tex til e wastewater treatment. Anaerobic process usually occupies less space, treats waste up to 30,000 mglL COD, has lower recurrin g cos ts and produces less sludge. If co mpl ete mineralisation occ urs , convers ion of orga ni c co ntamina nt s into me th a ne an d O 2 and then prod uction of biogas are the major attraction because of heat, power and reduced energy costs .

a min es accompli shes two goals (i)

3.3.3 Anaerobic - Aerobic Treatment

The anaerobic - aerob ic sequ ence shows sig nificantl y greater co lour reduction than aerob ic alone (88 % vs 28 %) , in add itio n to improved co lo ur red uction . TOe reduction (79-90%) a lso improves w hen compared to aero bi c treatment alone . The reducti o n in COD and BOD is greater (up to 8%) fo r anaerobic-aerobic seq uence than that fo r aerobic treatment. T able 5 compares the results fo r colour, C OD, BOD and TOe reduction from both treatme nt sche mes. A similar process, namely AB (adsorption/bio-

o xida tion) process has been devel oped in Europe l66 . The

treatment process is a modified two-s tage activated sludge desig n and uses physica l, biochemical and

biol og ical reaction mechani sms to red uce a vely wide spectrum of organic pollutants. The firs t stage is the

with anaerobic conditi ons w ith a

very hi gh food to microorgani s m (F/M) rati o fostering

bacte ri a and a sho lt retenti on ti me. The second

s tage is bi o log ical ox idation (B) with aero bic acti va ted

s lud ge syste m. The microbial ecosystems in the two s tages are ke pt di stinctly separate, enab ling job sharin g a nd better effici ency of th e process. This pate nted process reduces COD and BOD vely e ffectively , while being largely resistant to shock loads and pH fl uctu a ti o ns.

grow th of

adsorption stage (A)

3.3.4 Decolourisatioll. using Cullures of Bacteria, Fungi, A lgae and Yeast

Microbial decolourization and degradation of dyes have been fo und as cos t effective and ecofrie ndly method fo r removing them fro m textile e ffluen ts. Recent fund ame ntal wo rk has rev ea led the existence of a wide variety of microorganisms capable of decolourizing equ a lly w id e ra nge of dyes. Banat e/ al. 150 have given a detailed review of progress in biological decolou rization of dyes.

3.].4.1 Bacle rial Cullures

Nu merous bacteria capable of dye deco lOLllization have been repolted '5o . Effo rt s to isolate bacterial c ul tures

capab le of degrading azo dyes started in 1970's with report s of Bacillus SUblilis l 67 , the n Acroillonas ltydrip h i l68 followed by Bacillus cereus l69 . [solating such microbes proved to be a difficult task and ex tended periods of

adap tation under chemos tat conditi ons were needed

isolate the strain capable of decolourization . An azo

red uctase e nzyme was responsible for the in itial

degradation of th e Orange 11 d ye by th ese strai ns b ut

s ubstitutin g any of the g roups near the azo gro up in the chemical structure of the dye hindered th e degradati on.


Tab le 5-- Per ce nt red uc ti o n from laboratory sca le trea tme nt processes invo lov ing Navy 106 usin g anaerob ic-aerob ic sequ ence l5 1

Treatment process

Treatment step

Co lou r





Diluti o n


4 1


3 8






Ae rob ic





Total reduct io n



9 1


Aerob ic

D iluti o n










Total red uction








An upsurge in interest in these bacterial cult ures took place in 1990's and Haug et a l. 17o described a bacterial consOitium capable of mineralizing the sulphonated azo

dye- mordant yellow. An alterat ion from anaerobic to

aerobic conditions was req uired for comp lete 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 th rough adsorption of dye s to the ce ll ular



lomass Wit lout any





egra atlon


. Algae

Few species of algae, namely Chlorella and Oscillatorial 50 , are capable of degrading azo dyes to their aromat ic amines through an induced form of azo reductase and further metabolise the aromatic amines to simple orga nic compounds or CO 2 , These algae species

utilize azo dyes as th ei r so le source nitrogen. Such algae can be used for

ponds as they can play a role in aro matic amines


of carbo n and stabilizat ion of FUllgi

Several fun gal sys tems including the white rot fungi

(Phanerochaete chrysosporuilll), in pruticular, have been

the subject of intense reseru'ch related to the

biodegradat ion of a wide range of recalcitrant xe nobi otic


are th ose o rga ni sms 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), othe r enzymes such as gl ucose-l- oxidase , gl ucose- 2-oxidase laccase and a phenol oxidase enzyme.

lru'gest clas s o f commercial dyes, is not

co mp o un S lIlC UC lIlg azo






150 17 1 17?





Ite rot



Azo dye, the

easily degraded by microorgan ism 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 consecut ive one electron oxidation steps with intermediate cation radical. While Mn-P only attacks

phenolic substrates using Mn 2 +lMn 3 + as an inte rmediate redox couple, Li-P with a higher redox potential prefers non phe nol ic methoxy substituted lignin subunits as


173 . Laccases have very broad substrate

specifi city with respect to the electron donor. They catalyse the removal of a hydrogen atom from the hydroxyl gro up of oltho and para substit uted mono and poly phenolic substrates and from aromatic amines by

one electro n abstractio n to form free radicals capable of undergoing fLllther depolymerization, repolymerization,

. White rot fungi (P. chrysoporu im ) is also capable of


emet y atlon or qUlllone ormation







degrading dioxin s, polychlorinated biphenyl (PCBs)


other chloro -organics, thus rendering the effluents toxiC l74 .


The co lour removal ac hi eved with these enzymatic

ran ge from 40% to 99 % , depending on the


dye comp lexity, nitrogen availab le, activity of the cul ture, presence of other auxiliaries in the effl uent, concentration of dye, retention time, etc. The nature of subst ituten ts on the dyes, i.e. benzene rings, influence rhe enzyme activity . Electron donating meth yl and methoxy substituents seemed to enhance enzy matic degradation ,

wh il e electron withdrawing chloro, fluoro and nitro substituen ts inhibited oxidation by enzyme Iaccase l73. T he presence of salts and other textile dyeing auxi liaries shows a potential inhibitory effect on

enzy matic action . Higher salt

decolourization efficiency by up to 80% and even lead to partial precipitation of proteins caused by increased surface tension and hydrophobic interactions. Laccase,

co ntainin g 3 copper binding sites per protein mol ec ul e or one copper, one iron and two zi nc atoms per protein mo lecule, is inac tivated by copper and iron . Chelating agents and anionic detergents seem to

concentrations decrease the

prutially denature prote:ns

of activity is repOited. Th us, knowledge not only about the substrate specifici ty but also about the effect of auxiliru'ies is important for selecti ng suitable enzymes for

dye decolourization under industrial conditions. So me of the drawbacks of enzymatic decolourization ru'e:

(enzyme) and almost 70 % loss

• Substrate specificity of some enzy mes and hence

fo r


co ntinuously

effluent may be an ard uous task.

se lection





varyi ng

compOSIti on


• The rate of reaction, whic h can be slow unl ess cond iti o n of pH and temperat ure are optimal.

• Co mm ercial production of th ese

specific enzymes

is very diffic1.!1t.

• T he prese nce of salts and other auxiliaries in the effl uent has an inhibitory effect on enzymatic activity .



Yeasts, such as Klyveromyces of decolourizing Ramazol Bl ac k

175). Zissi et al. 176 showed that Bacillus slIbtilis could be

used to breakdow n p-amino azo benzene, a specific azo dye. Further research using mesophilic and thermo phili c microbes has al so shown them to deg rad e and decolourize dye s.

lI1arx ialllls , are capable B dyes by 78-98 % (ref.

Future Trends

• The advantages of mixed culture are apparent as some strains can collectively CatTY out complex

strai n can

biore medi atation tas k th at no indi vidual

achieve independently. Similar bacte ri a l cultures

have been reported recently 177.

• Future investi gation should fo cus o n the

immobilization of selected enzymes to form the base for industrial application of enzymatic

decoloLlIization. Ba nat

c heap

s uppOtt media for bio film deve lo pm en t for ac ti ve

tex til e dye deco lourization using grave l, calcium a lg in ate beads, PS a nd PU foam chip s, nyl on webs inett PE chips, porous volcanic rocks, etc.

et af . 178 ha ve reported

• One of the routes still to be explored is the use of thermotol e rant or therm o philic mi croorga ni s ms in decolourization systems. This would be an advantage as many textil es and other dye effluents are produced at re lativel y hi gh temperatures (50- 60°C), even after cooling or heat exchange step.

review thu s suggests a great potential for

microbial decolourizing system for achieving total colour re moval and occasionally with only hours of exposure. Such biological processes could be adopted as a pretreatme nt decolouri zation step combined with the conventional treatment system to reduce the BOD and COD as an effect ive alternative for use in tex til e dyeing industti es .

The literature

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 electroc hemical cell to ge nerate ferrous hydroxide


(Fi g.

elec trodes . The elec troch e mica l cell

body containing a








g lass

number of electrodes separated from each other by small gaps. Wastewater flows through the gaps a nd rem a in s in contact with the electrodes. A direct cun'ent (DC) power supply is connected between the two end e lectrodes of

power supply is connected between the two end e lectrodes of Emuent:contamillats adsorbed, coprecipitated within iron
power supply is connected between the two end e lectrodes of Emuent:contamillats adsorbed, coprecipitated within iron

Emuent:contamillats adsorbed, coprecipitated within iron matrix



Fig. 2 -

E lec trochemical ce ll 179




+ Anode PVTI



Cooling jacket

pHIR RIR Surge esse l

Samp ling

c : Cooling jacket pHIR RIR Surge esse l Samp ling Cooling water Fig. 3--Expe rimental

Cooling water

Fig. 3--Expe rimental la bora to ry pilot plant using e lectroc he mi ca l


indic a tor contro lle r

Rec irc ul a tin g

ce ll




Electrolytic pump , TICR

ce ll ,


= E lec tromagne ti c

va lve,


= Te mpera ture

reco rd e r, pHIR = pH indicator, a nd RIR = Redox indicator]

th e cell (Fig. 3). As CUITent flows

from one e lectrode to

anoth er throu g h th e process water,

the pos itively


sides of the electrodes (anodes) give off ferrou s

ions. At

negative sides (the cathodes), the water decomposes into

hydroge n

res ults in th e formation of hydrous iron oxide, ferrous

electrodes are

slow ly consumed as the metal hyd roxide is generated. The process water then enters a degass in g tank, pH is adjus te d at < 7 or> 11 for sa tisfac to ry Fe +2 precipit a tion.

hydrox ide a nd felnc oxyhydroxide. The

gas and hydroxyl ions. 11le overall reaction



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 th e literature. If aluminum is used, th e end products are a


Recently , the use of titanium or titanium-pl atinum-

iridium e lectrode, as anodes Electroflocc ul a tion is th e

fl occ ul a ti o n and fl o tation . Oxidation is

ac hi eved by

means of e lectrodes, dipped in the effluent to treat where

a d iffere nce of potenti al is app li ed. Tlivalent iron a nd aluminum flocculate oxidized substances because of

electrostatic inte raction

metals are present as soluble inorganic ions, co-

prec ip itatio n a nd adsorp ti on are

mechanisms. Efficiency of the process depends on

several parameters i.e. difference of potential, nature of

electrodes, pH, salt concentration of so luti o n, number of

electrodes, distance between them, stirring and CUlTent

of aluminum hydroxide or oxy hydroxid e.

has also bee n repo rted l80 . combination of an ox idati o n,

and co-precipitation . Whe n

the primary removal

. Il1tens lty .

Elec troche mi ca l technology is repOlted to remove acid, disperse and metal complex dyes effectivel/ 82 . The removal of dyes from aqueous soluti on results from adsorption ancl/or degradation of the dyestuff following the interaction wi th iron e lectrodes. If metal co mpl ex dyes are present, dye so lubili s ing and charge are the most important factors for successful removal of heavy metals. pH has to be adjusted to maximize dye in so lubili ty. Demmin and Uhrich . 183 in their studi es found that BOD

level is ge nerall y reduced by 30-35 % and CO D leve l by

50-70 %. Lin and Chen l 84 have reported that the addition of sma ll a mount of hydrogen peroxide in th e 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 gene ration of

radi cal generated (Fenton 's reagent Fe+ 2 /H 2 0 2 ) electrode is used , leadin g to rap id ox idation of

hydroxide whe n iron Fe+ 2 to Fe+ 3 .

E lec trofloccul ati o n is , thu s, a promising method for prod uc ing recyclable process water because it co mbines 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 co ntrast to conventional chemical precIpItation methods that introduce either chloride or sulphate ions both of which

18 1

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 of colour removal techniques work

either by concentrating the colour into sludge or by the partial or complete breakdown of the coloured


us ing o ne or combination of th e foll ow in g

methods: adsorption, filtration , precipitation, coag ul a tion , fl occ ulation, chemical, photo and biod eg radati o n. Coagulation/ flocculation is the most widely used method for colour removal because of economic feasib ilit y, rap id re m ova l of colour a nd sig ni ficant

reduction o f COD. With rapid changes in dy es and st ri cter consent limits, these alone d o not g ive co mpl etely satisfactory treatments es peciall y with hi gh ly so lubl e reac tive dyes . Moreover, large quantity of sludge generation contalnll1g all the toxic compo und s present in th e effluent is like ly to in creas e disposal costs substantially and thi s mu st be considered before choosing a system.

ac hi eva ble

mo lec ul e . In principle , decolouriz a tion s









attentio n for colour removal. Activated carbon is used mostly as the final po li s hin g or tertiary trea tm ent because rege nera tion cos ts are very hi g h and hi gh

volume of textile effl ue nt in vo lved with dyeing. The size and cost of plant required become

hi g h and pay back is poor. Low

cost bioadsorbents have been employed for treatment

of wastes co ntaining dyes. However the specificity to

remove certain contaminates, slow kinetics, regeneration and flow problems have limited the

co mm erci a l success of these adsorbents at th e industrial scale. Membrane systems provide a means to recover water a nd other auxiliari es fo r total treatment or stand alone process for scouring o r dye


bath liquo r separation. The major limitations are


eco nomic feasibility becau se of hi g h costs an d treatment of hi g hly concentrated streams.

th e

I n the li g ht of an integra ted a pproach to waste treatment, it is likely that destruction technologies will ga in favo ur at th e expense of techn o 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 destruction technologi es are based on chemical, bio and



elec troch emica l oxidation techniques. These lead to either part ial oxi dation of th e dye, destroying th e co nju gated bonding syste m in the chromoph o re and

thu s, re moving colour or tota l oxidatio n to

ca rbon di oxide and inorganic ion s whic h is th e mos t ideal. How ever, total oxidation using these rea ge nts is

no t eco nomicall y viab le. Th e problem associated with parti al oxidation lies in th e unkno wn nature of th e


eve n be more harmful to th e e nvironm e nt th an the initial compo nents of th e effl ue nt. Moreov er, nea rl y


th e reac tion start s and therefore co ntrol over reac ti o n may be diffi cult eve n in th e lab sys te ms and virtuall y imposs ibl e in a variable feed stoc k such as an industria l tex tile effluent. These mo stly reduc e carbon loadin g of th e effluent but can lIlcrea se th e

co nce ntration o f inorga ni c content. Enzymatic microbial deco louri za ti o n of text il e dyeing efflue nts is also a very promisin g and inn ova tivc area of investigation. It eliminate s th e need fo r in organic oxidizing agents (ozone) o r precipitating age nts (polymeric f1occul ents), which lead to hi g her tox ici ty in wastewater and ge ne rate additional so li d was te. Microbial decolourizati on using enzy mes deg rad es th e aromatic rin g structure to ca rb on

d iox id e, mol ec ul ar nitro gen

ca using less toxic ity. Howev er specific ity of e nz y mes, slow ratc of reac tion unless pH and temperature are

l chemical mechani s ms are difficult to co ntrol o nce


formed and the risk that some of th ese may

and water, thereby


ptimal and difficulty of commercial production of


nzy mes may be limit ation s whic h need to be

ove rcom e by more intens e research in th e fie ld

biotechnology. Th e probl e m of colo ur in the efflu e nt can be

reduced to an extent by adopting ri g ht first tim e approach, proper work practices a nd waste minimi zation prog ram s. The dy e manufactures ma y

a lso he lp by producing dye s (pa rti cula rl y reactiv e dyes) with a better fixation that can be achieved at

present. Alth ough ongo ing, in future

increas in g seve rity by th e reg ul ators. Hen ce is urge nt and immediate a nd the press ure

maintained to evolve more effec tive , widel y app li cable and commercially viable techniques of


development s in thi s field are standards will be e nforced with

th e need must be

co lour re mo va l from textile effluents.



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