J. Chem. T echnol. Biotechnol.

1998, 72, 289302

Review
Treatment and Reuse of Wastewater from the
Textile Wet-Processing Industry: Review of
Emerging Technologies
Philippe C. Vandevivere,1 Roberto Bianchi2 & Willy Verstraete1*
1 Laboratory of Microbial Ecology, Coupure L 653, University of Gent, 9000 Gent, Belgium
2 Centro Imprese Depurazione Acque s.r.1. (CIDA), Via Laghetto 1, 22073 Fino Mornasco (Co), Italy
(Received 28 July 1997 ; revised version received 10 December 1997 ; accepted 6 April 1998)
Abstract : New ecolabels for textile products and tighter restrictions on wastewater discharges are forcing textile wet processors to reuse process water and
chemicals. This challenge has prompted intensive research in new advanced
treatment technologies, some of which currently making their way to full-scale
installations. These comprise polishing treatments such as ltration, chemical
oxidation and specialized occulation techniques and pre-treatment steps including anaerobic digestion, xed-lm bioreactors, Fentons reagent oxidation, electrolysis, or foam otation. Though several of these new technologies are
promising in terms of cost and performance, they all suer limitations which
require further research and/or need broader validation. A segment of the
research deals with the separate handling of specic sub-streams such as dyebath
effluents to which membrane ltration is sometimes applied. The main limitation
of this approach is the treatment of the concentrate stream. The spectrum of
available technologies may, in the future, be further broadened to include
fungi/H O -driven oxidation, specialized bio-sorptive processes, solvent extrac2
tion, or 2photocatalysis.
( 1998 SCI
J. Chem. T echnol. Biotechnol. 72, 289302 (1998)
Key words : textile ; wastewater ; dyes ; azo ; full-scale ; activated sludge ; ltration ;
coagulation ; ozonation

NOTATION
AOX
BOD
B
v
COD
HRT
IC
x
LC
x
MLVSS
NF
NPE

RO
SRT
SS
TS
TSS
UASB
UF
WWTP

Adsorbable organic halogens

Biological oxygen demand
Volumetric loading rate
Chemical oxygen demand
Hydraulic retention time
Concentration causing x% inhibition
Concentration causing x% lethality
Mixed liquor volatile SS
Nanoltration
Nonyl phenol ethoxylate

Reverse osmosis
Sludge retention time
Suspended solids
Total solids
Total suspended solids
Upow anaerobic sludge blanket
Ultraltration
Wastewater treatment plant
1 INTRODUCTION

Considering both volume discharged and effluent composition, the wastewater generated by the textile
industry is rated as the most polluting among all industrial sectors.1 In Flanders in 1994, four textile wet processors were among the six factories ranked with the

* To whom correspondence should be addressed.

E-mail address : Willy.Verstraete=rug.ac.be
Contract/grant sponsor : European Commission ; Contract/
grant number : ENV4-CT95-0064.

289
( 1998 SCI.

J. Chem. T echnol. Biotechnol. 0268-2575/98/$17.50.

Printed in Great Britain

290
largest annual BOD discharges.2 During the last few
years, new and/or tighter regulations coupled with
increased enforcement concerning wastewater discharges have been established in many countries. This
new legislation, in conjunction with international trade
pressures such as increasing competition and the introduction of ecolabels for textile products on the European and US markets, is threatening the very survival
of the textile industry in many industrialized countries.3
The textile industry swiftly responded to these new constraints with a broad range of drastic changes and innovations in the generation, treatment, and reuse of textile
wastewaters (Fig. 1). This review article is an attempt to
summarize and compare the diverse innovative treatment technologies which have been used to treat and
reuse textile effluents. The focus is placed on full-scale
plants in order to be able to assess the new technologies
in real situations.
2 THE NATURE OF TEXTILE EFFLUENTS
The main sources of wastewater generated by the textile
wet-processing industry originate from the washing (or
scouring) and bleaching of natural bers and from the
dyeing and nishing steps. Given the great variety of
bers, dyes, process aids and nishing products in use,
these processes generate wastewaters of great chemical
complexity and diversity which are not adequately

P. C. V andevivere, R. Bianchi, W . V erstraete

treated in conventional WWTP. The chemical composition of textile mill effluents is also changing rapidly as a
result of shifting consumers preferences. Most signicant is the current popularity of cotton fabrics and
bright colors leading to greater usage of reactive and
azo dyes,4 respectively. An even more important cause
of shifting wastewater composition are the new and
tighter restrictions on discharged effluents and consumer goods5 as, for example, the 1996 German ban on
consumer goods containing those azo dyes which cleave
to yield any one of 20 specied carcinogenic aromatic
amines.1,6 Another example is the emergence of US and
European ecolabels which might include considerations
of emissions to the environment and chemicals used
during the manufacture of textile products.7 In response
to these new restrictions, dye manufacturers are
developing new lines of dyeing auxiliaries in order to
comply with these ecologically-advanced labels, e.g.
emulsiers not derived from alkyl phenols, pigments not
containing halogeno substituents or heavy metals,
chlorine-free bleaching agents, and synthetic thickening
agents which reduce the amount of dye wasted.8h10
The nature of textile wastewaters has already been
reviewed in terms of process chemicals used and in
terms of the classical parameters (BOD, COD, TSS, TS)
and contents of N, P, and heavy metals.11h13 This
section will therefore focus on those pollutants which
often pose problems in conventional WWTP (as illus-

Fig. 1. Compilation of possible process technologies, both commercial and experimental, for the treatment and reuse of nal
effluents of textile mills. 1 : Alto Lura WWTP managed by CIDA Srl in the Como area (Italy) and treating 22 000 m3 day~1 of a
mixture consisting of 17% domestic wastewater, 32% rain water and 51% equalized effluents from textile nishing factories
(cellulose, wool, silk, and synthetic ber). 2 : Levis Strauss WWTP, Wervik (Belgium).

T reatment and reuse of wastewater

291

trated in the following section), i.e. dyes, recalcitrant

organics, toxicants, AOX, and surfactants.

2.1 Color
Dye molecules consist of a chromagen, i.e. an aromatic
structure absorbing visible light and which anchors the
dye into or within the bers. There are about 12 classes
of chromogenic groups, the most common being the azo
type which makes up to 6070% of all textile dyestus
produced,14 followed by the anthraquinone type.13 A
second classication of dyes is based on their mode of
application to textiles and distinguishes acid, reactive,
metal-complex, disperse, vat, mordant, direct, basic and
sulfur dyes. Research on textile effluent decolorization
has often focused on reactive dyes for three reasons.
First, reactive dyes represent an increasing market
share, currently about 2030% of the total market for
dyes, because they are used to dye cotton which makes
up about half of the worlds ber consumption.5,15
Second, a large fraction, typically around 30%, of the
applied reactive dyes is wasted because of dye hydrolysis in the alkaline dyebath. As a result, dyehouse effluents typically contain 0608 g dye dm~3.8,16,17 Third,
conventional wastewater treatment plants, which rely
on sorption and aerobic biodegradation, have a low
removal efficiency for reactive and other anionic soluble
dyes, which leads to colored waterways, and public
complaints. As a result, new restrictions have been
established for the discharge of colored effluents, e.g. in
Germany8 and in the UK,5 often forcing dyehouses to
decolorize their effluents on-site.
Since dyes are intentionally designed to resist degradation, it is no surprise that little dye degradation
occurs in activated sludge systems.18h20 Among more
than 100 azo dyes tested, only a very few were degraded
aerobically.21 The degree of stability of azo dyes under
aerobic conditions is proportional to the structural
complexity of the molecule.22 While C.I. Acid Orange 7
(Fig. 2) is aerobically biodegradable, the 2@-methyl
derivative (C.I. Acid Orange 8) is less biodegradable, a
related disulfonate dye (Acid Orange 10) is nonbiodegradable. Under anoxic conditions, however, azo
dyes are readily cleaved to aromatic amines since the
azo bond can serve as electron acceptor in the electron
transport chain provided a carbon source is available
and nitrates absent.14,23h26 The by-products of the azo
bond cleavage, aromatic amines, are not further metabolized under anaerobic conditions but are readily biodegraded in an aerobic environment.21 It is important
to note that most types of dyes are partially degraded
under anaerobic conditions, though less readily than
azo dyes.25,27,28 The rate of degradation may be
lowered by the dyes structural complexity, as cell
uptake was shown to be inversely proportional to the
number of sulfonate groups,14,25 and moreover is sub-

Fig. 2. Chemical structures of 1-phenylazo-2-naphthol dyes.

C. I. Acid Orange 7 is one of the rare dyes which is aerobically
biodegradable.

jected to inhibition in the presence of 15100 mg dm~3

of certain acid azo dyes.14,29
2.2 Persistent organics
Due to a shift in process chemicals used, the biodegradability of textile wastewaters has been increasing steadily during recent years. In Flanders, for example, the
BOD /COD ratio for the total wastewater discharged
5
from textile wet processors increased from 018 in 1991
to 029 in 1994.30 The latter value, which is representative for the sector in other countries,31 points toward a
moderately biodegradable organic load. The persistent
molecules present in textile effluents belong to very
diverse chemical classes, each used in relatively small
amounts. Aside from dye molecules (see above), these
include dyeing auxiliaries such as polyacrylates, phosphonates, sequestering agents (e.g. EDTA), deocculation agents (lignin or naphthalenesulfonates), antistatic
agents for synthetic bers, carriers in disperse dyeing of
polyester, xing agents in direct dyeing of cotton, preservatives (substituted phenol), and a large number of
nishing auxiliaries used for re-, moth-, and waterproong.4,11,32 EDTA may amount of 1 g dm~3 in
reactive dyebath effluent.33 A particular case of persistence is the wash (scour) effluent of raw wool, consisting
of a stable emulsion of detergents (08 g dm~3 nonyl
phenol ethoxylate), animal grease (15 g dm~3 lanolin)
and suint salts (animal secretions) together with the

292
liposoluble pesticides sprayed on the sheep for parasite
control. Scouring of cotton also releases a great variety
of persistent pesticides used in the growing of cotton.
Finally, carpet factory effluents may contain latex which
appears moderately biodegradable.

P. C. V andevivere, R. Bianchi, W . V erstraete

life.41,42 Data at chronic-level exposure are lacking for
most of the commercial dyes and their derivatives17,43
and the potential toxicity of degradation intermediates
remains therefore undocumented. Numerous dyes,
together with the aromatic amines formed by reductive
cleavage of azo bonds, are mutagenic.44

2.3 Toxicants
2.4 Surfactants
Textile effluents tend to inhibit only slightly, or not at
all, the heterotrophic activity within activated sludges.
This was illustrated by on-line toxicity measurements of
the equalized effluent of a carpet factory in Flanders
using the Rodtox sensor.34 During the 2-month-long
data acquisition period, as part of the project nancing
this paper, the highest inhibition of the heterotrophic
respiration within sludge samples reached 1020%. A
1020% decrease of the COD removal capacity was
also detected upon addition of various acid azo dyes to
laboratory-scale activated sludge reactors35 or biolm
reactors.22 Less biolm accumulation was also observed
in the presence of the dyes.
Unlike heterotrophs, chemoautotrophic nitrifying
bacteria are often substantially inhibited in activated
sludges fed with textile effluents. Bohm36 measured
oxygen uptake rate by nitriers in a xed-bed reactor
upon feeding with wastewater from two textile plants.
The IC values were 11 and 27% (v/v). Vandevivere
25
and Verstraete (unpublished), using a short-term nitrication inhibition test, determined IC values in the
50
range of 1040% (v/v) for the equalized effluents from
two Flemish carpet factories. The inhibition was attributed mainly to copper chelators because addition of
copper to the wastewater eliminated the inhibition.
Gruttner et al.37 singled out a textile dyeing factory as
the most important source of nitrication inhibitors in
an industrial catchment area in Denmark.
Numerous large-scale studies have been conducted to
assess the toxicity of textile effluents toward aquatic life.
Typical LC (96 h) values amount to 56% (v/v) with
50
bleaching, dyeing, or mixed textile effluents, using a
freshwater sh as test organism.38 Costan et al.39 found
that a textile effluent ranked second in toxicity, among
eight industrial sectors represented, by using a series of
bioassays assessing the acute, sublethal and chronic toxicity at various trophic levels. Using the Microtox assay,
Unden40 ranked textile industries as heavy polluters
among 49 Swedish industries tested. The actual process
chemicals causing such harm remain unidentied.
Unlawful discharge of organic solvents used in printing
processes has at times been linked to effluent toxicity
toward activated sludge (Bianchi, unpublished) or
aquatic life.3 Extensive work has been dedicated to the
potential toxicity of commercial dyes toward aquatic
life. Since the exposure level in rivers is always much
lower than the LC values of the vast majority of dyes,
50
these are not thought to cause acute toxicity to aquatic

Most textile wet processes, such as sizing, spinning,

weaving, desizing, dyeing, scouring and washing
consume large amounts of surfactants. Wool scour effluents may contain up to 800 mg dm~3 NPE.45 Combined municipal and textile effluents in the Como area
contain peak concentrations of 11 and 67 mg dm~3
anionic and non-ionic surfactants respectively (Bianchi,
unpublished) and the effluent of a silk and Lycra dyeing
factory contained typically 3040 mg dm~3 anionic surfactants.46 A large fraction of the non-ionic surfactants
used in textile processes are alkyl phenol ethoxylates as
the textile industry is the largest consumer of these surfactants.47 The issue is rather controversial in view of
the fact that the discharge of alkyl phenol surfactants to
sewers is often restricted, e.g. 05 mg dm~3 of phenol
equivalents in Portugal, or even banned, e.g. in
Germany.8 These restrictions were established because
alkyl phenol polyethoxylate surfactants are biodegraded
to alkyl phenols which tend to sorb onto and accumulate in sewage sludge wherein average concentrations up
to 1000 ppm have been recorded.48,49 Alkyl phenols
are, however, much more toxic than the ethoxylated
forms, with maximum accepted concentration in the
low ppb range.47 The discharge limit for other surfactants (in natural waters) is typically set at
2 mg dm~3 (Italy, Portugal).

2.5 AOX and heavy metals

Traditionally, sodium hypochlorite was usually preferred to H O for the bleaching of cotton and linen
2 2
because of superior whiteness, lower cost and possible
ber damage by radicals arising from H O decomposi2 2
tion.50 Hypochlorite bleaching effluents contain up to
100 mg dm~3 AOX including considerable amounts of
carcinogenic chloroform.9 Hypochlorite is being superseded by alkaline peroxide bleaching. Spent liquors
from shrinkproong with chlorine and mothproong of
wool may also contain AOX, up to 39 and
12 mg dm~3, respectively.50 Finally, certain reactive
dyes are AOX. Given their carcinogenic nature, the discharge of AOX is restricted in a number of countries
including Belgium, Sweden, and Germany, with a discharge limit of 05 mg dm~3 in the latter country.9,50
Gruttner et al.37 measured an average of 075 mg dm~3
AOX in the effluent of a textile dyeing factory.

T reatment and reuse of wastewater

293

Heavy metals concentrations in dyebath effluents,

typically in the 110 mg dm~3 range, were reviewed by
Correia et al.11 The use and discharge of heavy metals
in the textile wet processing industry has decreased by
an average of 50% in Flanders during the period 1991
1994.30 In 1994, textile wastewaters in Flanders still
typically contained about 015 mg dm~3 of Cr and Cu
(used as metal-complex dyes) and 08 mg Zn dm~3.30
Carpet factory effluents have higher concentrations of
Cr and Ni (0609 mg dm~3) and Zn (19 mg dm~3).

3 PERFORMANCE OF FULL-SCALE
TREATMENT PLANTS
3.1 Full-scale plants relying solely on conventional
activated sludge systems
The performance of activated sludge treatment is summarized in Table 1, together with other treatment technologies. In 1994, 27% of the wastewater generated by
the textile mills located in Flanders was treated on-site
and most of it subsequently discharged to surface
waters.30 Average effluent COD and BOD were 163
and 19 mg dm~3, respectively, while total N and P
amounted to 22 and 1 mg dm~3, respectively. Such
values exceed the tighter discharge norms established

recently in many countries, with maximum permitted

levels of COD and total N typically around 80 and
10 mg dm~3, respectively. Because the above performance data apply to both conventional and
advanced treatment, they probably overestimate the
performance of conventional activated sludge systems.
Other reports mention a 6080% COD reduction in
activated sludge plants31,51 or laboratory-scale reactors.52 Considering a typical COD content of
700 mg dm~3 for textile effluents, these values correspond to c. 200 mg COD dm~3 effluent. The performance of an activated sludge plant treating the
effluent of a carpet factory in Flanders was followed for
4 months. Average effluent COD usually fell in the
range 150220 mg dm~3 but peak values above
250 mg dm~3 were frequently observed (Fig. 3 ; P. Van
Meenen and B. Vanderhaegen, private communication).
Conventional activated sludge systems are clearly
ineective in decolorizing textile effluents even in cases
where these are mixed and treated together with sewage.
At the Pixton works (UK), the discharged effluent has
an absorbance three times higher than the new discharge consent (though it should be noted that some of
the new discharge consents in the UK specify extremely
small absorbance values).53 This leads to colored watercourses at the points of discharge and public complaints.3,5,54 Primary settling removes relatively high

TABLE 1
Evaluation of Various Technologies for the Treatment of Textile Effluents
Process

Stage

Status

Performance

L imitations

Fenton
oxidation

Pre-treatment

Several full-scale
plants in S. Africa

Full decolorization ; low

capital and running costs

Electro
lysis

Pre-treatment

Pilot-scale

Full decolorization ; cheap

Foam
otation

Pre-treatment

Laboratory-scale

Removes 90% color and

40% COD ; cheap, compact

Filtration

Main- or
post-treatment

Extensive use in
S. Africa

High performance ; reuse of

water, salts, and heat

Handling and disposal

of concentrate stream

Main treatment

Widely used

Removes bulk COD, N

Main treatment

Very few reports

Main treatment

Some pilot trials in

China
Laboratory-scale

Better removal of COD,

color, and toxicants
Better removal of COD,
color
Full-decolorization

High residual COD, N,

color, surfactants.
High residual color
and COD

Biodegradation
Activated
sludge
Sequential anaerobic
aerobic
Fixed-bed

Foaming and electrode

lifespan

Fungi/H O
2 2
Coagulation
occulation

Main treatment
Pre-, main or
post-treatment

Extensive use

Full decolorization ; water

reuse

Not always eective ;

sludge disposal

O
3

Post-treatment

Full-scale

Full decolorization ; water

reuse

Expensive ; aldehydes
formed

Sorption
(carbon,
clay, biomas)

Pre- or posttreatment

Laboratory or full-scale,
depending on
sorbent type

New sorbents are eective

and cheap ; water reuse

High disposal or
regeneration costs

Photocatalysis

Post-treatment

Pilot-scale

Near-complete color
removal ; detoxication

Only as nal polishing

step

294

P. C. V andevivere, R. Bianchi, W . V erstraete

near-complete degradation since it was estimated that
6065% of all NPE entering sewage works are in fact
removed with the excess sludge.

3.2 Full-scale plants using sequential anaerobic/aerobic

reactors or xed lm reactors

Fig. 3. Time courses of the COD and ammonium concentrations (daily averages) in the nal effluent of a conventional
activated sludge plant treating the wastewater of a carpet
factory in Flanders, Belgium.

proportions of insoluble disperse and vat dyes, while

activated sludge removes medium to high proportions
of soluble basic and direct dyes, principally by adsorption. On the other hand, the widely-used reactive and
acid dyes are poorly removed.4,18,19,20,54,55
Aside from COD and color removal, nitrication is
occasionally impaired in sewage works receiving
untreated textile effluents.37,40 At the Alto Lura WWTP
(Italy), which treats a mixture of domestic and textile
mills wastewaters, the NH`-N content in the nal efflu4
ent exceeded the discharge limit (118 mg dm~3) on 47
days out of the 217 days monitored (Bianchi,
unpublished). Similar problems were noted in a WWTP
treating carpet effluents in Flanders, with NH`-N level
4
amounting to 92 ^ 97 mg dm~3 in the treated effluent
(Fig. 3). Bortone et al.52 found that long SRT (up to
3040 days) were necessary to overcome the nitrication inhibitory eect in bench-scale reactors treating a
mixture of municipal and textile effluents. With respect
to heavy metals, conventional WWTP designs do not
achieve the discharge limits for surface waters, as Cr
and Ni still amount to about 01 mg dm~3 and Zn to
07 mg dm~3 in the nal effluent of the industrial treatment plants in Flanders.30
Another problem with a seemingly high incidence in
WWTP treating textile wastes are Nocardia foaming
and lamentous bulking.47,51,55h57 While these are
complex and poorly-understood phenomena, their frequent occurrence in WWTP receiving textile effluents
may possibly be linked to high levels of starch and surfactants. NPE, a class of surfactants extensively used in
the textile industry, together with their degradation
intermediate nonyl phenol, are readily removed in activated sludge systems, with a removal efficiency lying
between 925 and 998%.47 In a survey encompassing a
large number of sewage works, treated effluents contained up to 261 ppb NPE and up to 94 ppb nonyl
phenol.47,58 These low values do not necessarily reect

Several laboratory-scale investigations have illustrated

the potential of sequential anaerobic/aerobic biotreatment steps for textile wastewaters. Anaerobic pretreatment oers several potential advantages such as
better removal of color, AOX, and heavy metals.
Improved heavy metal removal may follow sulde production,46 while the improvement of the color and
AOX removal stems from the rapid reduction and
cleavage under anaerobic conditions of the azo groups
in arylazo pollutants and of electron-withdrawing
chloro or nitro substituents.21,59 Jianrong et al.60
achieved 90% COD reduction and 96% color reduction
in a laboratory-scale UASB reactor (HRT \ 8 h) followed by an activated sludge reactor (HRT \ 6 h) fed
with a deeply-colored high-strength effluent of a dye
manufacturing plant. The greatest fraction of the color
and COD reduction occurred in the UASB reactor.
Other studies have shown, however, that methanogenesis, and hence COD removal, is easily inhibited
by textile effluents.61 The inhibition of methanogenesis
can be avoided by inserting granular activated carbon
in UASB reactors treating textile effluents. This was
demonstrated with a bench-scale set-up that achieved
full decolorization and effluent COD level below
100 mg dm~3 when fed with deeply-colored carpet
factory effluents (Verstraete, not published). In cases
where the inhibition of methanogenesis cannot be circumvented, anaerobic pre-treatment may remain useful
as, for example, a decolorizing step, which seems to
proceed optimally around a redox potential of
[250 mV,62 or as a bioocculation step. The latter
may achieve high removal rates of poorly degradable
organics such as the grease and detergents present in
the very high-strength wool scouring effluents.45,56,63
The effluent from a silk and Lycra printing factory in
Como (250 m3 day~1) is being treated in a full-scale
denitrication/nitrication
single-sludge
system.46
Operating conditions included the dosing of
22 mg dm~3 sodium sulde to remove Zn, the addition
of 330 mg dm~3 pharmaceutical waste in the denitrication reactor as a source of reducing equivalents, and
the addition of 1 mg dm~3 lyophilized bacteria to the
nitrication plant. A tertiary treatment, consisting of
quartz bed ltration and UV sterilization, has allowed
3040% water reuse without deleterious eects on
garment quality during 10 months of full-scale operation. Effluent COD (less than 120 mg dm~3), color,
and NH`-N (less than 10 mg dm~3) all met Italian dis4
charge standards. The nitrication rate (003005 g N

T reatment and reuse of wastewater

g~1 MLVSS, day~1) was much lower than that which
can be obtained with the municipal sewage. This low
rate was attributed to inhibition caused by the presence
of 3040 mg dm~3 anionic surfactants in the wastewater. Both the Seveso and Alto Lura WWTP, located
in Como (Italy), treat sewage containing 80% textile
effluent. The Seveso plant, in which two-thirds of the
inuent passes through an anaerobic selector (2 g
COD g~1 MLVSS day~1 with an HRT of 45 min) performs better than the Alto Lura plant, which does not
include such a selector.57 Increased performance was
reected in the elimination of the foaming and bulking
problems, better P removal, and low effluent TSS
(average of 20 mg dm~3 instead of more than 100 in
Alto Lura).
Despite the numerous laboratory-scale trials showing
the potential of anaerobic treatment for color removal,
large-scale installations equipped with an anaerobic
pre-treatment do not generally achieve full decolorization. Zaoyan et al.64 operated a large pilot plant (24 m3
day~1) for 9 months at a textile dyeing mill which used
reactive and other dye classes on polyester/cotton
fabric. The plant consisted of two multi-stage rotating
biological contactors, a rst anaerobic one (HRT \ 7 h ;
B \ 2 g COD day~1 dm~3) followed by a second
v
aerobic one (HRT \ 5 h ; B \ 23 g COD day~1
v
dm~3). The sequential anaerobic/aerobic system
achieved a higher color removal (72%) than the aerobic
system alone (\60%) but the nal effluent was still
deeply colored. Both systems achieved 78% COD
removal (155 mg dm~3), 95% BOD
removal
5
(13 mg dm~3) and 70% anionic surfactants removal
(07 mg dm~3). Another pilot two-stage anaerobic/
aerobic plant achieved [70% color removal from
dyeing wastewater.65 The Hammarsdale (South Africa)
sewage works consists of a conventional ve-stage bardenpho nutrient removal process treating deeply-colored
textile effluents.62 Though the overall system achieves
95% decolorization, of which 60% takes place in the
rst anaerobic state (HRT of 1 h and redox potential of
[135 mV), the nal effluent is still excessively colored.
Since decolorization is fastest at [250 mV (24 h), the
color removal at the Hammarsdale works may be
improved by increasing the HRT in the anaerobic
stage.62
Several experiments have been carried out in South
Africa to investigate the possibility of feeding dyebath
effluents directly to the anaerobic digesters treating
primary sludge from sewage works. Carliell et al.33
mixed spent reactive dyebath effluent with the primary
sludge (6% v/v) entering the digester at Umbilo sewage
works. Color was completely eliminated as shown by
comparison with a control digester. Laboratory-scale
side trials indicated, however, that methanogens may
become inhibited after a few days operation at a higher
loading (18%) due to the build up of sulde originating
from the 42 g dm~3 sulfate in the dyebath effluent. Pro-

295
posed measures to overcome the inhibition were the
substitution of NaCl for sodium sulfate, the addition of
heavy metals (e.g. from electroplating effluents) to precipitate the suldes, or molybdate to block sulfate
reduction. Similar full-scale trials were carried out by
Gravelet-Blondin et al.3 for a period of 5 months. No
color was present in the overow of the digester but
transport costs were considered prohibitive.
The combined activity of anaerobic/aerobic bacteria
can also be obtained in a single step if the bacteria are
immobilized in biolms since O penetration seldom
2
exceeds several hundred micrometers.21 In addition to
providing anaerobic/aerobic zones, xed lm reactors
oer the advantages of higher SRT necessary to prevent
washout of adapted microorganisms, protection against
toxicants such as azo dye Acid Orange 7 (Fig. 2), and
low sludge production.35 Laboratory-scale studies have
demonstrated that acid azo dyes which are not
degraded in activated sludge were removed up to 60%
in xed lm reactors provided the dissolved O concen2
tration is kept below 1 mg dm~3 and the loading rate is
high.22,35 Jian et al.66 could treat the effluent from a
dye manufacturing plant very eectively using multistage percolation columns with immobilized decolorizing bacteria. The pilot scale installation, which
treated 20 m3 day~1, removed consistently 97% of both
color and COD during a 7-month trial.

3.3 Full-scale plants using a combination of activated

sludge and coagulation/occulation
Chemical coagulation is applied as either a pre-, postor main process for the treatment of dyeing mill effluents (Fig. 1) and is, according to Gahr et al.,8 the treatment most widely used in Germany for these effluents.
This author reports, however, the drawback associated
with the large amounts of toxic sludge requiring combustion. Many French textile manufacturers likewise
rely on a physico-chemical post-treatment, following
activated sludge, to treat their colored effluents.31 Marmagne and Coste31 contend that the nal effluent
usually contains from 150 to 300 mg dm~3 COD (85%
removal) and color levels above the maximum discharge
standard of 100 mg Pt.Co dm~3 which is expected to be
enforced in France in the near future. Insufficient color
removal is a result of the poor occulation of certain
types of dyes, e.g. reactive or certain acid dyes.31 For
example, a mere 20% color removal was achieved in
pilot experiments in which polyaluminum chloride
(10 mg Al dm~3) was dosed in the effluent of an activated sludge treating a mixture of municipal and textile
wastewaters.67
New occulants have, however, been developed with
a high affinity for reactive dyes.68,69 Several reports
detail, for example, the successful use of cationic polymers allowing a few major UK textile processors to

296
meet their color consent for direct discharge to
rivers.17,54 Dissolved air otation can eectively
separate the occulated dyes with little sludge produced. At Livescia WWTP (Como, Italy) treating a mixture
of municipal and textile wastewaters, a 35% color
removal was obtained by dosing 20 mg dm~3 of
cationic polymers in the effluent of the biological oxidation treatment (Bianchi, unpublished). Adequate color
removal may be achieved by dosing cationic polymers
directly to the activated sludge. The Wanlip sewage
works (UK), receiving 11% of its dry weather ow from
textile mills, could meet the discharge consent following
the addition of 5 ppm Magnaoc 368 directly to the
activated sludge tank and a concomitant halving of the
effluent absorbance.53 In cases where higher polymer
concentrations were necessary, however, severe problems with inhibition of nitrication were observed.17
The toxicity of polymers toward nitriers is highly variable, with IC values ranging from 8 to [100 ppm.
50
Heathcoat & Co. Ltd (UK) discharges 2000 m3
day~1 from reactive dyeing and nishing operations.
They achieve their direct discharge consent with a
chemical pre-treatment using lime (pH 113), FeSO
4
and polyelectrolyte followed by percolation through
beds of expanded porous shales against a ow of
air.70 Together with color, the physico-chemical
pre-treatment removes anionic surfactants (but not
the non-ionic ones). Many process chemicals, including
several non-ionic surfactants and one complete range
of dyestus, had to be replaced by more biocompatible
ones.
Coagulation/occulation, alone or in combination
with biological processes, can sometimes allow water
reuse. A production plant of Courtaulds Textile, the
largest UK manufacturer of socks, has been using, since
1995, a full-scale purely physico-chemical process to
treat the mixed effluent from their dyeing, printing and
nishing units. The process consists of dye adsorption
onto synthetic organic clays which are separated following the addition of alkali and a coagulant with high
relative molecular mass. Even though cotton is the main
ber being processed, and thus reactive dyes the main
dye class used ; 50% water reuse is possible in the
dyeing units.71 This new technology is being applied at
several locations. Similarly, a leading denim conditioning and washing mill in Yorkshire recently built a fullscale occulation plant. The effluent quality is
consistently within the consent limit and half of it is
reused.72 Finally, a textile processing plant located in
Cyprus recycles its effluent (200 m3 day~1) on irrigated
land.51 Equalized wastewater is rst treated with lime,
FeSO and polyelectrolyte before entering the activated
4
sludge tank which is equipped with an oxic selector in
order to eliminate bulking. Tertiary treatment consists
of disinfection with Cl , occulation with alum and
2
polyelectrolyte, and nally ltration on anthracite,
quartz sand and barytes. The nal colorless effluent

P. C. V andevivere, R. Bianchi, W . V erstraete

(518 nephelometric turbidity units) had a BOD and
5
COD of 10 and 100310 mg dm~3, respectively. Total
operating costs amount to 02 US$ m~3.
While most coagulation/occulation systems rely on
lime, one laboratory study reported efficient color
removal (90%) from spent reactive dyebath with
50 ppm Fe3` or Al3` under acid conditions.73 Final
clarication allowed reuse of water and salt with no loss
of fastness to light or washing.

3.4 Full-scale plants using ozonation

Ozone decolorizes all dyes, except non-soluble disperse
and vat dyes which react slowly.31,74h77 Because O is
3
less efficient with high-strength raw textile wastewater,
it is advisable to use O only as a nal treatment or at
3
least following chemical coagulation.74,78,79 Aside from
color, ozonation also removes a large proportion of
AOX8,80 and surfactants.46,81 Typical ozonation products are dicarboxylic acids and aldehydes, which
explains the little reduction of COD (020%) but substantial increase of BOD during ozonation.8,81
Ozonation is becoming increasingly popular as a nal
treatment to eliminate color and other persistent substances. The sewage works at Leek receives 60% of its
total load (76 000 inhabitant equivalents) from seven
dyehouses. Considerable extensions to the works were
required following tighter discharge consent since
1992.5 Following pilot-scale investigations showing that
required color removal could be achieved with 95 ppm
O with an HRT of 20 min, a tertiary treatment involv3
ing lagoons, sand lters and an ozonation plant was
built at a capital cost of 5 million. In about 1 year,
only four samples out of 39 analyzed have failed the
color consent. It is considered that O may be used on
3
treated sewage effluent where the proportion of colored
dyewaste to domestic sewage is high enough to justify
the capital cost. In one case, the installation of an ozonator at a sewage works doubled the discharge levies
billed to the textile companies, from 04 to 08 m~3.54
The Alto Lura WWTP (Como, Italy) treats a mixture of
75% textile and 25% municipal wastewater with a
sequence of pre-denitrication, activated sludge, sand
ltration and ozonation. The ozonator was built in
1992 in order to reduce surfactants and color in the
nal effluent. These goals are being achieved with 20 mg
O dm~3 but unwanted by-products are formed, espe3
cially aldehydes in the range 052 mg HCHO dm~3
(Bianchi, unpublished). Plans are made to reduce aldehyde formation by adding a tertiary occulation unit
before the sand lters (Fig. 1).
Numerous textile wet-processors also use ozonation
in order to reuse the water. Capital costs are, however,
high. A dyeing mill, producing 100 m3 h~1 wastewater,
was recently built in Italy at a total cost of 13 million
US$, of which 20% was allocated to the wastewater

T reatment and reuse of wastewater

treatment plant (clarication, equalization, activated
sludge, decanter, ltration, and ozonation).80 In the case
of the above-mentioned silk and Lycra printing factory
in Como, laboratory trials have demonstrated that up
to 65% reuse, in washing and printing units, will be
possible by integrating an ozonation reactor
(20 mg dm~3 O ) which eliminates the residual color
3
and non-ionic surfactants.46 The Levi Strauss nishing
plant at Wervik, Belgium, was recently facing limitations in groundwater pumping and stringent discharge standards. Use of tap or river water was
inadequate. Reuse trials in pilot plants with
coagulation/occulation or ultraltration showed deterioration of garment quality.82 Activated carbon ltration yielded a better COD and color removal and
garment quality but sulde formation in the lter
yielded odor problems. Finally, a solution was found by
treating the mixed stream with a sequence of
coagulation/occulation, activated sludge, and a 10-min
nal ozonation step (Fig. 1). Three years of pilot testing
demonstrated the feasibility of 70% water reuse without
deterioration of garment quality.
Numerous laboratory-scale experiments have documented the feasibility of ozonating dyebaths effluents
separately and reusing the decolorized effluent several
times with excellent color reproducibility.75h77,83,84 For
example, spent reactive dyebath can be renovated and
reused by coarse ltration followed by ozonation. Cost
savings associated with the reuse of salts (80 g dm~3 in
reactive dyebaths) are up to 30 times larger than the
savings associated with the reuse of water.75 Even
though considerable amounts of O (up to 1 g dm~3)
3
may be required to achieve nearly complete color
removal due to high dye concentration (several
hundreds ppm) and interference by dyeing auxiliaries,
theoretical payback periods as short as 13 years are
claimed.75 Reports on full-scale application of a reuse
strategy involving separate ozonation of dyebath effluents are, however, apparently lacking. The reason could
be the sometimes considerably lower decolorization
rate, up to 20 times,76,77 in the presence of dyebath
additives such as EDTA, silicone defoamers, ethoxylated alcohol surfactants, leveling agents, butyl benzoate carriers, guar gum and salts.5,8,74 As a
consequence, the amount of O necessary for near com3
plete decolorization may become prohibitively expensive.

3.5 Full-scale plants using ltration processes

Ultraltration, nanoltration and reverse osmosis have
been used for the full-scale treatment and reuse of water
and chemicals by South African textile wet processors
for nearly two decades. Specic lter congurations
have been developed for the reuse of wool scour and
bleaching effluents, spent sizing and desizing liquors,

297
and spent dyebaths.84h86 The high cost of ltration
techniques may be outweighed by the signicant costs
savings achieved through the reuse of permeate, salts
and sizes (i.e. polymers applied to warp yarns to facilitate weaving). While careful choice of the membrane
system, use of pre-lters and regular cleaning eliminate
membrane fouling problems, economic viability of concentrated waste treatment and disposal remains uncertain. In South Africa, where ltration techniques are
widely used in order to reuse water, the concentrates are
often dumped in the ocean or disposed to a sewer.3,13
Desizing effluents typically contain 2550% of the
total organic load in 510% of total effluent volume. As
early as 1978, UF was used commercially to recover
polyvinyl alcohol sizes from desizing effluents.87 Both
the retained sizes and the permeate are reused.84,87,88
Polyacrylate sizes were also successfully recovered and
reused from desizing effluents using high temperature
UF pilot plants. Hot permeate reuse yields savings in
heat and water.87,89
Wool scouring liquors can also be treated by ltration techniques.86 Norways largest yarn factory generates hot wool scouring liquors containing high pH
detergents and up to 100 g COD dm~3. A full-scale
ultraltration treatment plant has been operating since
1989 with [ 80% removal of COD, fats and suspended
solids.90 The permeate is disposed to a sewer and the
concentrate (10% v/v) must be trucked to lagoons at
high cost. Membrane lifetime is 1 year with an average
ow of 60 dm3 m~2 h~1. AOX, of which 50% are in
solid form in wool effluent, are also signicantly
reduced by ltration techniques.50 Wool scouring
liquors are also being reused in full-scale plants using
dynamic UF membranes.91 The latter oer the advantage of not requiring membrane replacement since it is
formed in situ by deposition of a colloidal suspension of
hydrated zirconium oxide on a porous support. The
membranes, which are reformed every other month,
achieve up to 90% TS rejection and allow 85% water
recovery.
Dyehouse effluents are also being reused successfully
following reverse osmosis.85,89 In this case, only water
reuse is possible. Coagulation and microltration are
necessary to prevent membrane fouling. Trery-Goatley
et al.92 reported the successful treatment and reuse of
dyehouse effluents in a pilot plant (50 m3 day~1) integrating the sequence of alum coagulation, microltration and reverse osmosis. Concentrate volume was
only 510% and RO membrane lifespan 2 years. Similarly, Buckley13 reports on a alum coagulation
microltrationRO sequence treating 40 m3 day~1 of
cotton/polyester dyehouse effluent. A UF plant
equipped with dynamic membranes has been achieving,
since 1985, 85% water recovery with 80% ionic rejection and 95% color rejection at a textile mill dyeing
polyester/viscose bers.13,91 The application of ltration technologies remains, however, severely limited

298
by the problem of disposal of the concentrate stream
since the currently-used schemes, such as evaporation
or ocean discharge,3 are either economically or environmentally unacceptable.
Because dyebath salts may have a 10-fold greater
value than water, it may be preferable to treat and reuse
dyebath and rinse effluents separately with membranes
that let pass the salts but retain the dyes. Such a reuse
strategy is described by Erswell et al.93 for a South
African cotton dyehouse. In this case, a charged UF
membrane was used for dyebath effluents that allowed
90% reuse of salt and water, while a 10% (v/v) concentrate was disposed of. The volume of the concentrate
stream was reduced to only 2% in an elegant reuse
scheme described by Woerner et al.94 in the case of a
cotton mill (160 tons per month). The rinse liquors are
reused following a sequence of UF and RO. The concentrate is mixed with the dyebath effluent which is subjected to the sequence UF and NF enabling both water
and electrolytes reuse. Buckley13 reports on an NF
plant treating reactive dye liquors from a cotton dyehouse (200 tons per month). Reuse of permeate with
electrolytes yielded a payback period of less than 3
years. Even microltration has been used in the case of
polyester dyebaths using insoluble disperse dyes.13 The
slight residual color in the permeate did not prejudice
its reuse in dyeing or rinsing units.

P. C. V andevivere, R. Bianchi, W . V erstraete

4 EMERGING TECHNOLOGIES AWAITING
FULL-SCALE TRIALS
4.1 Electrolysis
Through Fe(OH) production with sacricial iron elec2
trodes, electrolysis can be used to remove acid dyes very
eectively via sorption onto the precipitated iron and
via Fe(II)-driven reduction of azo dyes to arylamines.99
Solutions containing 50 mg dm~3 dyes were 100%
decolorized with 100150 mg Fe dm~3. Greater than
80% decolorization of a real textile effluent was
achieved in laboratory-scale trials by applying 2 kWh/
m~3.100 The process was used very successfully by
Lin and Peng101 in a pilot scale installation treating the
raw effluent from a cotton/polyester dyeing and nishing mill in Taiwan. The effluent, which contained 15 different dyes and 8001600 mg COD dm~3, was fully
decolorized in an electrolyte cell (HRT \ 18 min) with a
concomitant 50% COD reduction. The total process,
consisting of coagulationelectrolysisactivated sludge,
was cheaper (running costs, not including sludge disposal, was 03 US$ m~3) and more eective (COD in
nal effluent \ 80 mg dm~3) than the conventional
treatment. Other pilot-scale trials have proven equally
successful.65

4.2 Photocatalysis
3.6 Full-scale plants using the Fentons reagent
(H O + ferrous iron)
2 2
Several full-scale Fentons reagent plants were built
recently in South Africa to treat textile mill effluents.3
This technology is eective in decolorizing a wide range
of dyes.95,96 According to Lin and Peng,97 the Fentons
reagent works by oxidizing ferrous to ferric iron with
simultaneous splitting of H O into hydroxide ion and
2 2
hydroxyl radical. The latter oxidizes the dye while the
former precipitates with ferric iron together with
organics. The reagent is used preferably at pH values
around 34.96h98 Ferric seems as eective as ferrous
iron, and only a few ppm are required if high temperatures are used.95 For example, 1 g dm~3 of a direct
dye was completely decolorized in 30 min with
15 g dm~3 of H O in the presence of 2 mg dm~3 Fe
2 2
at 98C. At normal temperatures, 50100 mg Fe2`
dm~3 are required. Lin and Peng97 obtained very good
performance in a pilot scale installation treating actual
textile wastewaters with the sequence of chemical precipitation, Fentons reagent and activated sludge. Complete decolorization was obtained after the Fentons
reagent stage and nal COD, after activated sludge, was
only 80 mg dm~3. Estimated total running costs, not
including sludge disposal, was 04 US $ m~3 which was
cheaper than that of the conventional treatment.

UV light has been tested in combination with H O or

2 2
solid catalysts such as TiO for the decolorization of
2
dye solutions. While the UV/H O process appeared
2 2
too slow, costly and little eective for potential full-scale
application,102,103 the combination UV/TiO seems
2
more promising.104h106 Because UV penetration in dye
solutions is an inherent limitation, Huang et al.107
found the best use of UV technology as a posttreatment after ozonation. Not only was the residual
color completely removed, close to 90% of residual
total organic carbon was also removed from the effluents of two textile mills. The German rm Wedeco is
using such a combination of O /UV/H O in a mobile
3
2 2
pilot plant.80

4.3 Sorption
Despite the fact that eective decolorization has often
been shown to be feasible via sorption onto activated
carbon as a nal step,5,31,54,82,108 full-scale use of this
technology has apparently not been reported yet, a
likely consequence of high capital and regeneration
costs and possible foul odors.82 CIDA Srl is currently
testing full-scale GAC lters at the Alto Lura WWTP
(Fig. 1) as part of the research project supporting this

T reatment and reuse of wastewater

paper. The nal effluent seems suitable for reuse in silk
desizing units but not in silk dyeing units. Full-scale
biologically-activated GAC lters are also under investigation at the site. Though certain microbial species
may sorb impressive quantities of dyes (up to 3 g sulfur
dye and 045 g reactive dye per g biomass),109 estimated
treatment costs remain prohibitive (26 US$ m~3).
Sorptive capacity is almost two-fold higher with particles of polyamideepichlorohydrincellulose but the
reaction rate seems too low.110 Several authors tested
the use of industrial or agricultural wastes as a low-cost
alternative for developing countries. Results obtained
with corn cobs, chrome sludge from the electroplating
industry, yash or biogas residual slurry were disappointing.111h114 Lazlo115 reviewed the eectiveness of
all biological adsorbents for removing anionic dyes. The
highest affinity adsorbent was cross-linked chitosan at a
pH of 34. The best choice was quaternized lignocellulosic biomass which oers the advantages of high sorption capacity, low cost, rapid kinetics and possible
regeneration.

4.4 Flotation and others

Lin and Lo116 demonstrated the potential of foam otation as an eective and simple technology for the
decolorization of dyehouse effluents. Mixing the wastewater with 70 mg dm~3 of a surfactant and compressed
air yielded, after a few minutes, 90% color removal and
40% COD removal. Color and COD were recovered in
a highly concentrated stream after the foam, leaving the
contact chamber at the top, had passed through a foam
breaker. Solvent extraction can also be applied for dye
recovery from dyebath effluents. For example, sulfonated dyes can be rendered hydrophobic with long
chain amines at pH 25 and concentrated up to 1000fold in a solvent phase.16 Dyes, solvent and surfactants
are reused.
Phanerochate chrysosporium and other fungal species
can mineralize all types of dyes at a very rapid pace via
a peroxidation pathway.43,117,118 Van der Waarde et
al.119 developed a decolorization technique based on
the combined use of fungal degradation and in situ electrochemical H O production, an essential substrate for
2 2
fungal activity. They achieved complete decolorization
of several spent dye liquids (reactive and disperse dyes)
in an air lift continuous reactor.
At 150250C and partial O pressures of 035
2
14 MPa, concentrated solutions of dyes are fully
decolorized and almost completely mineralized in 1
4 h.120 Because no external energy is required when the
COD exceeds 20 g dm~3, wet air oxidation may oer a
solution for the problematic disposal of the concentrate
streams produced by ltration or foam otation technologies.

299
5 CONCLUSIONS
Conventional WWTP relying on activated sludge
systems are not adequate for the treatment of textile
mill effluents, neither on site nor after dilution with
domestic wastewater at the sewage works. Activated
sludge and other types of bioreactor fail to remove sufficient color, COD, N, surfactants and other micropollutants present in the textile effluents. Tertiary
coagulation/occulation is often used with variable
results but at times near-complete decolorization and
water reuse is possible ; sludge disposal remains,
however, a problem. Ozone is increasingly used as a
nal step but cost and aldehyde formation prevent its
wider acceptance. Membrane ltration of process substreams may yield substantial cost savings by allowing
water, chemicals and heat reuse. Handling and disposal
of the concentrate stream remains, however, a severe
limitation to ltration processes. In view of the need for
a technically- and economically-satisfying treatment
technology, a urry of emerging technologies are being
proposed and tested at dierent stages of commercialization. Promising among these are biologicallyactivated GAC ltration, foam otation, electrolysis,
photocatalysis, (bio)sorption and Fenton oxidation.
Broader validation of these new technologies and integration in the current treatment schemes will, most
likely in the near future, render these both efficient and
economically viable.

ACKNOWLEDGEMENTS
The writing of this paper is part of the project Integrated water reuse and emission abatement in the textile
industry, supported by a grant from the Environment
and Climate program of the European Commission
(ENV4-CT95-0064).

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