Journal of Chemical Technology and Biotechnology J Chem Technol Biotechnol 77:437443 (online: 2002)

DOI: 10.1002/jctb.537

Treatment of wastewater containing dyes used

in the Syrian textile industry
Saleh El-Kadri, Ousama Dabbit* and Hassan Kakhia
Chemistry Department, Science Faculty, Aleppo University, Aleppo, Syria

Abstract: Three types of wastewater, from commercial dyeings containing reactive, disperse and
direct dyes were treated using an organic coagulant at pH 5.5 as a rst step, with stirring for 5 min. The
second step was oxidation by Fenton's reagent (hydrogen peroxide and iron(II) sulfate) at pH 2.53 for
30 min. The pH of the solution was then raised to 7.58 where coagulation by iron hydroxide took place
over 20 min. Finally, sand ltration was performed. The percentage of color removal from treated
wastewater was more than 99.00% and the percentage decrease in COD was more than 96.00%.
# 2002 Society of Chemical Industry

Keywords: environment; pollution; wastewater; dyes; coagulant; COD

INTRODUCTION dyes.5 Organic polymers have therefore been devel-

The principal route by which dyes enter the environ-
ment is via wastewater from batch processes in both
the dye-manufacturing and the dye-consuming indus-
tries. In 1978 it was estimated that of the 450 000
tonnes of dye produced worldwide, some 9000 tonnes
(2%) were discharged in aqueous efuents from
manufacturing operations and 40 000 tonnes (9%)
from the coloration.2
Dyes are required to show a high degree of chemical
and photolytic stability in order to full the fastness
requirements of both retailers and consumers. One
consequence of this stability is that they are not readily
degraded under the aerobic conditions prevailing in
the biological treatment plant at a sewage treatment
works. So unless color is removed by physical or
chemical means, either at the dyehouse or in tertiary
treatment, it may well pass to the receiving water.1,3
Dye wastewater forms a serious problem in Aleppo,
because about 250 dyehouses discharge to the
environment at least 4 000 000 m3 of wastewater per
year, which may contain more than 5 tonnes of
dyes.
Many techniques have been used for treatment of
dye wastewater, such as adsorption, biological treat-
ment, oxidation, coagulation and/or occulation, of
which coagulation is one of the most commonly used
techniques. Inorganic coagulants such as lime and
salts of iron, magnesium and aluminum have been
used over many years, but with changes in dyes and
with the dye consents proposed by water authorities,
these no longer give completely satisfactory treat-
ments.6 Not all dyes are effectively removed by in-
organic coagulants; thus alum is unsatisfactory for the
removal of soluble dyes such as reactive and direct
oped for color-removal treatments and, in general,
they offer the same advantages with the production of
less sludge and signicantly improved color removal.6
For the removal of color from dyehouse efuent, no
such effective and simple inorganic option exists for
many soluble dyes.10
The treatment procedure described depends on an
organic coagulant marketed as Setax-wws (Setash),
which is also used as a xative for the direct dyeings.
Any xing agent not absorbed by the ber enters the
dyehouse efuent.
EXPERIMENTAL
Three samples of real dye wastewater from com-
mercial dyeings in Aleppo were treated. Each type of
wastewater contained pairs of reactive, disperse or
direct dyes (see below).
Materials
Hydropon-ERN (Sabo)
This is a leveling and dispersing agent, which has the
following chemical and physical properties:
Chemical constitution: synergistic blend of anionic
and non-ionic agents
Appearance at 20 C: dark brownish liquid
Ionic type: anionic
Solubility: easily soluble in hot or cold water
pH of 5% aqueous solution: about 7
Stability: stable to hard water, alkaline and acidic
conditions and electrolytes in the amounts normally
used in dyeing

* Correspondence to: Ousama Dabbit, Chemistry Department, Science Faculty, Aleppo University, Aleppo, Syria
(Received 27 September 2000; revised version received 8 September 2001; accepted 5 October 2001)

# 2002 Society of Chemical Industry. J Chem Technol Biotechnol 02682575/2002/$30.00 437

S El-Kadri, O Dabbit, H Kakhia

Dye name l max (nm) Constitution Number in CI Supplier

Reactive Yellow 81 (RY 81) 344 Youhoaw
Reactive Blue 21 (RB 21) 668 Setash
Disperse Yellow 82 (Dis Y 82) 460 Spectrom
Disperse Blue 60 (Dis B 60) 750 61104 Basf
Direct Yellow 11 (Dir Y 11) 412 40000 Goint-Stock
Disperse Yellow 56 (Dis Y 56) 328 Spectrom
Table 1. Commercial dyes used in this study

Setalan-BNH (Setash) Analysis

This is a detergent for washing-off reactive dyes, which
has the following chemical and physical properties:
Chemical composition: condensation product of
etoksile
Ionic character: non-ionic
Appearance: viscous yellow liquid
pH value: 6.08.0 (10% solution)
Solubility: soluble in water in all proportions
Setafix-wws (Setash)
This is a xing agent for direct dyeings, and has the
following chemical and physical properties:
Chemical composition: diciandiamide and formal-
dehyde condensation polymer
Ionic character: cationic
Appearance: colorless clear liquid
pH value: 4.56 (concentrated)
Solubility: soluble in water in all proportions
Commercial dyes
The commercial dyes shown in Table 1 have the
following chemical structures.4
Reactive Yellow 81 is a bifunctional monochloro-
triazine dye of the azo class.
Reactive Blue 21 is a venylsulfone dye of the
phthalocyanine class.
Disperse Yellow 82 is an azo dye.
Disperse Blue 60 has the structure shown in
Scheme 1.
Direct Yellow 11 is an azostilbene dye made by self
condensation of 4-netrotoluene-2-sulfonic acid (see
Scheme 2).
Disperse Yellow 56 has the structure shown in
Scheme 3.
The concentrations of all dye wastewaters were
obtained by measuring the absorbency with a Shi-
madzu Co type UV-240 spectrophotometer.
The COD of all samples were determined by the
dichromate reux method.13 Quantitative analysis for
the ions studied was carried out using an HACH DR/3
spectrophotometer.
Collection and composition of dye wastewater
All dye wastewaters were sampled as follows: a quan-
tity of the dye wastewater was taken from the dyeing
machine after the end of the dyeing process, and the
same quantity was taken from the washing-off water.
The reactive dye wastewater resulted from the dye-
ing of 120 kg of cotton (on mass of ber) with 3.7%
Reactive Blue 21 and 0.6% Reactive Yellow 81 in
1200 dm3 deionized water. Auxiliaries present were
1.04 g dm 3 Hydropon-ERN, 104 g dm 3 sodium sul-
fate and 20.8 g dm 3 sodium carbonate. The rst
washing-off solution contained 3 g dm 3 Setalan-
BNH.
The disperse dye wastewater resulted from the
dyeing of 120 kg of polyester with 0.75% Disperse
Blue 60 and 0.02% Disperse Yellow 82 in 1200 dm3
water.
Scheme 2

Scheme 1 Scheme 3

438 J Chem Technol Biotechnol 77:437443 (online: 2002)

 Treatment of wastewater containing dyes

The disperse/direct dye wastewater resulted from

the dyeing of 120 kg of polyester/cotton with 0.06%
Disperse Yellow 56 and 0.06% Direct Yellow 11 in
1200 dm3 water.
We have used Disperse Yellow 56 with Direct
Yellow 11 because it is not common in Aleppo to use
direct dyes alone but generally they are used jointly
with disperse dyes for fabrics made of cotton and
Scheme 4
polyester.

Treatment procedure
The treatment was performed in two steps, viz co- anions and positive groups in the polymer result in co-
agulation followed by oxidation and inorganic coagu- precipitation, as shown in Scheme 5.6
lation.

Coagulation RESULTS AND DISCUSSION

The procedure for coagulation is carried out as
follows:
adjust the wastewater to pH 55.5
add the coagulant Setax-wws to 100 cm3 of the
pH-adjusted sample
stir for 5 min then let the sample stand for 1 min
nally, lter through a sand lter
Oxidation and inorganic coagulation
Hydrogen peroxide and ferrous ions are usually more
stable in a strong acid. But if hydrogen peroxide is
added to an aqueous system containing an organic
substrate and excess ferrous ions in a strong acid, a
complex redox reaction will occur. This reaction will
generate the vigorous hydroxyl radicals and ferric ions.
The hydroxyl radicals may be used to decolorize the
dye wastes.15 Ferric ions may form ferric hydroxo
complexes with hydroxide ions. These complexes have
a pronounced tendency to polymerize at pH 3.57.14
Thus coagulation would probably occur. The remain-
ing decolorized dye molecules in wastewater can be
coagulated and precipitated.8
The oxidation and inorganic coagulation has been
performed as follows:
reduce the pH of water from the rst step of treat-
ment to less than pH 3
add the desired amounts of hydrogen peroxide and
iron(II) sulfate (Fenton's Reagent)
stir for 30 min
increase the pH to 8, and stir for a further 20 min
stop the stirring and allow the sample to stand for
2 min
nally, lter through a sand lter
Determination of effective amount of coagulant
Figures 1, 2 and 3 show the effect of coagulant dosage
on the percentage of COD reduction and color
removal for reactive, disperse and the mixture of direct
and disperse dyes, respectively. Table 2 illustrates the
percentage of COD reduction and color removal due
to the effective amount of coagulant for the dye waste-
waters studied. These results indicate that a signicant
amount of dye can be removed in the rst step of
treatment and the removal of dye increases with
increases in the coagulant dose. The percentage
reduction of COD increases as the coagulant dose
increases up to the effective amount, where the COD
has a minimum value. When more than this amount is
used, the percentage reduction of COD reduces as
residual coagulant remains in the treated water.
Since the decolorization mechanism, in the rst step
of treatment, depends on the electrostatic attraction
between the oppositely charged soluble dye and
polymer molecules, so the coagulant dose depends
on the chemical structure of the dye molecule,
especially on the negative groups. The coagulant dose
depends also on the presence of other compounds
such as Hydropon-ERN which is present in the
reactive dye wastewater. It is evident from the results
(Table 2) that this dye wastewater required the highest
dose of coagulant (700 mg dm 3). This is because of
the competitive reaction between the coagulant and
Hydropon-ERN molecules with dye molecules. This
explanation will be reinforced if we remember that the
Hydropon-ERN is a leveling and dispersing agent
which is frequently used as an auxiliary in the dyeing
processes to prevent the accumulation of dye mol-
ecules. Thus it will oppose the coagulant role which
brings the dye molecules together. But the percentages

Mechanism of decolorization
The mechanism by which synthetic organic polymer
coagulants remove dissolved dyes depends on electro-
static attraction between the oppositely charged
soluble dye and polymer molecules.6 The coagulant
we used (setax-wws) has the structure shown in
Scheme 4.
Interaction between negative reactive or direct dye Scheme 5

J Chem Technol Biotechnol 77:437443 (online: 2002) 439

S El-Kadri, O Dabbit, H Kakhia

taining a mixture of disperse and direct dyes required

the lowest dose of coagulant (50 mg dm 3). This is for
two reasons; rstly this wastewater did not contain any
auxiliaries to interfere with the reaction of the coagu-
lant and dye molecules. Secondly it contained Direct
Yellow 11 which is strongly negatively charged (con-
tains 11 negative groups, as is clear from its chemical
structure), and this will result in easier electrostatic
attraction between the polymer molecules and the
Direct Yellow 11 molecules.

Determination of effective amount of ferrous sulfate

and hydrogen peroxide
The most effective amounts of FeSO4 and H2O2 were
determined for each sample of wastewater. Figures 4,
5 and 6 show the effects of varying the FeSO4 dosage at
a xed concentration of hydrogen peroxide on the
percentage of COD reduction. Table 3 illustrates the
percentage of COD reduction and color removal due
to the effective amounts of FeSO4 and H2O2 for the
dye wastewaters studied.
It is clear from these results that the percentage of
COD reduction increases as the FeSO4 dose increases,

Figure 1. Effect of coagulant dosage on the percentage of (a) COD

reduction and (b) color removal.

of dye removal were 93 and 95% for Reactive Yellow

81 and Reactive Blue 21, respectively. These high
values mean that the removal of dyes was not
signicantly affected in the presence of the leveling
and dispersing agent Hydropon-ERN. The low value
of the percentage of COD removal (56%, Table 2)
may be attributed to the non-ionic fraction of the
Hydropon-ERN (return to the Hydropon-ERN
chemical composition) because it most likely will not
be removed by the cationic polymer.
Electrostatic attraction also takes place between the
insoluble disperse dye, which is partially negatively
charged, and the positively charged coagulant mol-
ecules. Despite the fact that the disperse dye molecules
are not strongly charged, they do not require large
amounts of coagulant. The percentages of Disperse
Yellow 82 and Disperse Blue 60 remained were 99 and
97% (Table 2) respectively. It seems that this coagu-
lant is effective in removing the insoluble dyes (small
particles) in addition to its efciency in removing the
soluble dyes, as has been observed before. Figure 2. Effect of coagulant dosage on the percentage of (a) COD
It is clear from Table 2 that the wastewater con- reduction and (b) color removal.

440 J Chem Technol Biotechnol 77:437443 (online: 2002)

 Treatment of wastewater containing dyes

Figure 4. Effect of FeSO4 dosage on the percentage of COD reduction in

the treatment of reactive dyes.

Figure 5. Effect of FeSO4 dosage on the percentage of COD reduction in

the treatment of disperse dyes.

Figure 3. Effect of coagulant dosage on the percentage of (a) COD Figure 6. Effect of FeSO4 dosage on the percentage of COD reduction in
reduction, and (b) and (c) color removal. the treatment of direct and disperse dyes.

Table 2. The percentage of COD reduction and color removal due to the effective amount of coagulant for the dye wastewaters studied

Reactive dyes Disperse dyes Direct and disperse dyes

3
Effective amount of coagulant (mg dm ) 700 200 50
COD removal (%) 56 92 85
Name of dye RY 81 RB 21 Dis Y 82 Dis B 60 Dir Y 11 Dis Y 56
Color removal (%) 93 95 99 97 94 99

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S El-Kadri, O Dabbit, H Kakhia

Table 3. The percentage of COD reduction and color removal due to the effective amounts of FeSO4 and H2O2 for the dye wastewaters
studied

Reactive dyes Disperse dyes Direct and disperse dyes

Effective amount of H2O2 (mg dm 3) 500 350 600
Effective amount of FeSO4 (mg dm 3) 1900 950 4000
COD removal (%) 97 98.5 94
Name of dye RY 81 RB 21 Dis Y 82 Dis B 60 Dir Y 11 Dis Y 56
Color removal (%) >99% >99% >99% >99% >99% >99%

treated sample will react with potassium dichromate

during the COD measurement, leading to a high value
of the COD of the sample. It is evident from Fig 7
that when large doses of FeSO4 (2000, 2700 and
3200 mg dm 3) are added, the percentage of COD
reduction will increase again to the value obtained
when the effective amount of hydrogen peroxide was
added (about 97%). This increase resulted from the
consumption of the excess hydrogen peroxide by
iron(II) being oxidized to iron (III). This may be
taken as evidence for the previous explanation.

Measurement of some physical and chemical

Figure 7. Effect of FeSO4 dosage on the percentage of COD reduction in
the treatment of reactive dyes using 800mg dm 3 H2O2.
up to an optimum amount where the COD has the
minimum value. On the other hand, when more than
the effective amount of FeSO4 is added, the percent-
age of COD reduction will not increase signicantly.
This might it be attributed to the existence of
chemicals that either resist the oxidation by Fenton's
Reagent and/or they are oxidized to products that are
not capable of removal by coagulation with the iron
complexes which are formed in the second step of
treatment.
It was found that when more than the effective
amount of hydrogen peroxide is added (Fig 7), the
percentage of COD reduction was less than 97%
(obtained when the effective amount of hydrogen
peroxide was added, Table 3). This result is similar to
the conclusions of Kou8 and Perkins et al. 9 The reason
is that the residual hydrogen peroxide remaining in the
parameters of wastewater before and after treatment
Some analyses were performed on the reactive and
disperse dye wastewater, before and after treatment, to
compare the quality of the treated wastewater with
some specications for treated wastewater (Table 4)
which is acceptable for release to the environment, as
determined by the Directory of Prevention of Public
Water Pollution of the Syrian irrigation ministry.11
Table 5 shows analytical data for reactive and disperse
dye wastewaters before and after treatment.
The important result that can be noted from Table 5
is that the organic coagulant used in the treatment has
a high ability for removing iron ions, Total Dissolved
Solids (TDS) and Total Suspended Solids (TSS). It is
clear from Table 5 that the decrease in the amount of
iron ions is about 95% when dyeing wastewater
resulting from reactive dyes is treaded. The decreases
in the amounts of TDS are about 78 and 82% when
reactive and disperse dye wastewaters respectively are
treated and the decreases in the amounts TSS are
about 92 and 97% when dyeing wastewaters resulting
from reactive and disperse dyes respectively are
treated.

Table 4. Specifications of treated wastewater acceptable for release to the environment, as determined by the Directory of Prevention of Public Water Pollution of
the irrigation ministry11

Parameter
2
HPO4 CN S2 H2S NO3 TSS TDS
3
Draining place pH T ( C) mg dm COD%
Rivers, streams, lakes 69.5 35 40 0.1 1 10 80 2000 100150
Sewage 6.59.5 40
Agricultural lands 1 80 150

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 Treatment of wastewater containing dyes

Reactive wastewater Disperse wastewater

Parameter Before treatment After treatment Before treatment After treatment
3
COD (mgO2 dm ) 805.9 24.3 1788.2 25.2
TDS (mg dm 3) 10 800 2600 8300 1770
TSS (mg dm 3) 125 10 325 10.7
NO3 (mg dm 3)
H2S (mg dm 3)
S2 (mg dm 3)
CN (mg dm 3)
HPO42 (mg dm 3)
Total Fe (mg dm 3) 6.6 0.1 0.4 0
Table 5. Analytical data for reactive and T ( C) 40 23 40 23
disperse dye wastewater before and after pH 7.74 7.72
treatment

CONCLUSION
The main point we want to make in this paper is the
possibility of using some organic pollutants present in
the wastewater of the nishing process as coagulants
instead of inorganic coagulants to be used before
advanced treatment of dye wastewater. It was ob-
served that, acceptable when compared with inorganic
coagulants such as aluminum salts results could be
obtained in some cases (disperse wastewater and the
mixture of direct and disperse dye wastewaters) by
using one of these organic pollutants (Setax-wws). It
is clear from Table 2 that the COD reduction could
reach about 92%. Sheng12 obtained a COD reduction
of about 72% by treating the dye wastewater using
aluminum salts while Hung et al 7 obtained a COD
reduction of about 80% by treating the dye wastewater
using 700800 mg dm 3 aluminum sulfate with a
mixture of polyacrylamide, acrylic acid and ethelen-
diamine at a pH of 78 for 5 h.
We have tested some more organics (without deter-
mining the effective amounts) used in the nishing
process, such as the cationic xing agents Arix 40
(DANNA), which is an amino-amide condensate and
Alcox FD (Allied Colloids), and cationic softeners
such as Garipan soft (Dr Th. Bohme) which is a fatty
acid amide derivative, Sabonina S3 (Sabo) which is a
synergic blend of amide derivatives and waxes, and
Alcolube XJS (Allied Colloids). It was found that all
compounds in both groups could coagulate the three
types of dye wastewaters studied. More investigations
are needed to detect the effective amounts. The
anphotric, non-ionic and ionic xing agents and
softeners did not result in any coagulation.
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