7-009 (O)

Proceedings of the
2nd Regional Conference on Energy Technology Towards a Clean Environment
12-14 February 2003, Phuket, Thailand

Utilization of Metal Hydroxide Sludge for Textile

Wastewater Treatment
S. Netpradit1, P. Thiravetyan2* and S. Towprayoon1
1. The Joint Graduate School of Energy and Environment, King Mongkut’s University of Technology
Thonburi, 91 Pracha-Utit Rd., Bangmod, Thungkru, Bangkok 10140, Thailand.
2. Division of Biotechnology, School of Bioresources and Technology, King Mongkut’s University of
Technology Thonburi , 91 Pracha-Utit Rd., Bangmod, Thungkru, Bangkok 10140, Thailand.

Abstract
The feasibility of the utilization of metal hydroxide sludge in the treatment of
textile wastewater was investigated. The purpose is to reuse the waste sludge
before disposal and to improve textile wastewater treatment in terms of efficiency
and investment. To alternatively replace existing chemical coagulants, metal
hydroxide sludge, obtained from an electroplating plant, was utilized as an
adsorbent for real textile wastewater in a batch system. The results showed that
approximately 1% (w/v) of metal hydroxide sludge is able to remove anionic dyes
from textile wastewater. After agitation for 30 min, 82-99% of color (SU), 64-
96% of COD, and 32-99% of SS were removed from 3 samples of textile
wastewater. The pH and amount of heavy metals (Cu2+, Cr3+, Ni2+ and Zn2+) in
the treated water were also within the standard limitations of industrial effluent.
Therefore, metal hydroxide sludge can economically and safely be utilized for
textile wastewater treatment.

Keywords
adsorbent; anionic dyes; coagulants; metal hydroxide; textile wastewater

Introduction
Textile wastewater usually contains a high concentration of colorants: dyes and
pigments, which come from the textile dyeing and printing processes. Presently,
reactive dyes (anionic dyes) are widely used because of their bright colors and
fastness. Nearly 50% of the reactive dyes may be lost to the effluent after dyeing
of cellulose fiber [1], and have therefore been identified as problematic
compounds in textile effluents. Reactive dye has limited biodegradability in an
aerobic environment, and many azo dyes, constituting the largest dye groups,
may, under anaerobic conditions in the environment, decompose into potential
carcinogenic aromatic amines [2]. Treatment by activated carbon adsorption,
oxidation, and chemical coagulation are very expensive and ineffective for
reactive dyes. Activated carbon is costly with the problems of regeneration,
oxidation by chlorine may cause toxic compounds, and coagulation is not able to
remove water-soluble dyes. Several economic adsorbents and other low cost
agricultural by-products can be used. Generally, these agricultural by-products
contain negatively charged cellulose, which repels anionic dyes such as acid dyes,
direct dyes and reactive dyes. They can be modified in low pH conditions to
reduce the coulombic repulsion but this means the higher cost of pH adjustment.
7-009 (O)
Proceedings of the
2nd Regional Conference on Energy Technology Towards a Clean Environment
12-14 February 2003, Phuket, Thailand

Metal hydroxide sludge is a waste sludge from the electroplating industry, which
is produced by precipitation of metal ions in wastewater using ferrous sulfate and
calcium hydroxide [3]. The sludge containing hydroxides of iron and other metals
has a positive charge and ability to act as either a coagulant or an adsorbent for
wastewater containing anionic colloid and solute. The possibilities of waste
Fe(III)/Cr(III) hydroxide and chrome sludge for the adsorption of anionic dyes
from aqueous solutions have been reported [4,5]. Metal hydroxide sludge also
shows a high tendency to remove reactive dyes from dye solutions [6], and may
therefore have potential in the removal of color from real textile wastewater. The
utilization of this sludge will not only be of benefit to the electroplating industry,
but also useful for the textile industry. Therefore the potential of using metal
hydroxide sludge for textile wastewater treatment was examined.

Materials and Methods

To determine the feasibility of metal hydroxide sludge in real wastewater
treatment, 3 samples of wastewater containing reactive dyes from 3 textile plants
were treated with metal hydroxide sludge in batch experiments.
- Sample A was discharged from several processes collected from an
equalization pond at a textile plant. It was dark bluish-green in color.
- Sample B was collected from a settling tank at a textile printing plant. It
still appeared dark green in color although some colloids were readily settled.
- Sample C was obtained from a tank connected to the dyeing section. It
was discharged from several batches of dyeing processes, and was separated from
other non-color wastewater. It was very dark brown in color due to a very high
concentration of reactive dyes.

For the batch adsorption system, the optimum dosage of metal hydroxide sludge
(<75 µm) was studied by varying at 1, 2, 3, 4 and 5% (w/v) in 300 ml of Sample
A using an agitation speed of 150 rpm. The effect of the contact time was also
compared among 30, 60 and 120 min. The batch adsorption was also conducted
with Samples B and C using a contact time of 60 min and a minimum dosage of
1% (w/v).

The absorbance spectrum of the effluent was analyzed before and after treatment
by the metal hydroxide sludge by scanning from 400 to 700 nm with a
spectrophotometer (DU 7500, BECKMAN). The parameters of textile
wastewater - such as color, chemical oxygen demand (COD), suspended solid
(SS), and pH, were measured before and after treatment following the standard
methods for examination of water and wastewater. The color intensity, which was
determined in the visible wavelength, is expressed as a space unit [2]. The color
in space units (SU) is calculated from the total area beneath the curve of the
absorbance spectra, as shown in Eq. (i). The colors of the effluent and the treated
water were also measured in ADMI units with a spectrophotometer (DR 4000,
Hach).

SU = ∫ (mean Abs) dλ from 400-700 nm (i)

7-009 (O)
Proceedings of the
2nd Regional Conference on Energy Technology Towards a Clean Environment
12-14 February 2003, Phuket, Thailand

For the assessment of possible impact on the environment, the treated water after
separation of metal hydroxide sludge was analyzed by ICP spectroscopy (JY 124,
JOBIN YVON) for the concentration of heavy metal ions such as Cu2+, Cr3+, Ni2+
and Zn2+. Determination of sludge disposal, the leachable heavy metals from
spent sludge, loaded with dyes, were also investigated by using leachate
extraction procedures (US EPA SW 846).

Results and Discussion

- Effect of adsorbent dosage on the treatment of textile wastewater
Figure 1 shows the effect of dosages from 1% (w/v) to 5% (w/v) of metal
hydroxide sludge using a contact time of 30 min. The spectrum in the visible
range was highly reduced, and a slight pale green color remained. The
absorbance reduction was found to be 93-99% at a wavelength of 623 nm. This
indicates that the anionic dyes were almost all removed. After treatment, the
treated water with a dosage of 1-2% (w/v) showed the same residual color, which
was slightly darker than that with the dosage of 3-5% (w/v). Although a greater
dosage slightly increased the removal of color, it causes a higher amount of waste
sludge destined for disposal in a secure landfill, which means an increased cost of
sludge treatment and landfill disposal. Therefore, the optimum dosage of metal
hydroxide sludge should be around 1-2% (w/v).

1.4
623 nm
1.2

1
Absorbance value

Textile wastewater
0.8

0.6

0.4

0.2
Treated water

0
400 450 500 550 600 650 700
Wavelength (nm)

Figure 1. Absorbance spectrum of textile wastewater (Sample A) and treated

water by metal hydroxide sludge in batch system:
( ) 1-2%; ( )3%; ( ) 4-5% (w/v).
(Contact time: 30 min; adsorbent size: <75 µm; agitation speed 150 rpm)

The color (SU and ADMI), COD, SS and pH values are reported in Table 1,
showing that the color was highly removed from the wastewater, and the qualities
of treated water are within the standard range. Thereafter, the treated water,
analyzed by ICP spectroscopy, contained small amounts of Cu2+, Cr3+, Ni2+ and
Zn2+, however, the concentrations of toxic heavy metals was within the permitted
7-009 (O)
Proceedings of the
2nd Regional Conference on Energy Technology Towards a Clean Environment
12-14 February 2003, Phuket, Thailand

range, meaning that the treated water would not be harmful when using the dosage
of 1-5% (w/v). In addition, the amount of leachable heavy metals from spent
adsorbent was very low. The ICP spectroscopy reported that the concentration of
Cu2+, Cr3+, Ni2+ and Zn2+ in the leachate was 0.12, 0.17, 0.06 and 0, respectively.
Therefore, metal hydroxide sludge can be used in the treatment process and
disposed of without an impact on the environment.
The contact time studies show that the absorbance spectrums were slightly
different between the agitation time of 30 and 60 min. The longer contact time of
120 min did not significantly show an increase in color removal. Therefore, the
optimum contact time for textile wastewater treatment by metal hydroxide sludge
is 30-60 min.

Table 1. Parameters of textile wastewater (Sample A) and treated water by

various dosage of metal hydroxide sludge in batch system.

Parameters Wastewater Treated water Standard

1% 2% 3% 4% 5% Thailand

Color (SU) 255 27.5 27.6 18.9 7.3 5.8 no issue

Color (ADMI) 3860 415 416 360 334 330 no issue
% Color removal - 89 89 93 97 98 -
Apparent color bluish-green +++ +++ ++ + + (pale)
COD (mg/l) 1098 - 340 - 283 - 400
% COD removal - - 69 - 74 - -
SS (mg/l) 0.04 0.01 0.01 0.015 0.02 0.025 50
% SS removal - 75 75 63 50 38 -
pH 7.5 8.2 7.92 7.63 7.42 7.50 5-9
Cu2+ (mg/l) - 0.58 0.51 0.38 0.34 0.36 2.00
Cr3+ (mg/l) - 0.11 0.24 0.25 0.24 0.25 0.75
Ni2+ (mg/l) - 0.23 0.16 0.17 0.15 0.16 1.00
Zn2+ (mg/l) - 0.08 0.01 0.01 0.01 0.01 5.00

- Treatment of textile printing wastewater by metal hydroxide sludge

The textile printing wastewater, Sample B, was dark green in color and the
dominant peak was at 620 nm, as shown in Figure 2. This shows that the color of
the wastewater was highly removed by the metal hydroxide sludge. The
absorbance reduction was found to be 92% at a wavelength of 620 nm.
7-009 (O)
Proceedings of the
2nd Regional Conference on Energy Technology Towards a Clean Environment
12-14 February 2003, Phuket, Thailand

0.45
0.4
0.35 (620, 0.283)
0.3

Absorbance
0.25 Wastewater
0.2
0.15
0.1
Treated water (620, 0.024)
0.05
0
400 450 500 550 600 650 700
Wavelength (nm)

Figure 2. Absorbance spectrum of textile printing wastewater (Sample B) and

treated water by metal hydroxide sludge (Dose: 1% (w/v); contact time: 60 min).

The color (SU and ADMI), COD, SS and pH values of Sample B were
significantly reduced by the treatment of metal hydroxide sludge, as shown in
Table 2. The results show that there was a correlation between the color, COD,
and alkaline removal, indicating that the dyes or other organic materials were
removed from the effluent. The final apparent color of the treated water is
acceptable (pale yellow). The leachate of toxic heavy metals in the treated water
was still lower than the standard limitations of effluents for Thailand.

Table 2. Parameters of textile printing wastewater (Sample B) and treated water

by 1% (w/v) of metal hydroxide sludge in batch system.

Parameters Wastewater Treated water % Removal Standard

Color (SU) 71.25 13.12 82 no issue

Color (ADMI) 868 282 68 no issue
Apparent color dark green pale yellow - -
COD (mg/l) 364 131 64 400
SS (mg/l) 27.9 0.1 99 50
pH 9.2 8.3 - 5-9
Cu2+ (mg/l) - 0.57 - 2.00
Cr3+ (mg/l) - 0.20 - 0.75
Ni2+ (mg/l) - 0.04 - 1.00
Zn2+ (mg/l) - 0 - 5.00

- Treatment of textile dyeing wastewater by metal hydroxide sludge

The absorbance spectrum of textile dyeing wastewater (Sample C) is shown in
Figure 3. After the adsorption with 1% (w/v) of metal sludge for 60 min, the
apparent color could not be observed. The absorbance reduction was found to be
7-009 (O)
Proceedings of the
2nd Regional Conference on Energy Technology Towards a Clean Environment
12-14 February 2003, Phuket, Thailand

99% at a wavelength of 430 nm. The color (SU and ADMI), COD, SS and pH
values of Sample C are reported in Table 3, showing that the treated water was
very clear in color and acceptable in COD, SS and pH values, and the leachate of
toxic heavy metals was also below the standard limitations of effluent.
3
Wastewater
2.5 (430, 2.306)

2
Absorbance

1.5

0.5 Treated water

(430, 0.026)
0
400 450 500 550 600 650 700
Wavelength (nm)
Figure 3. Absorbance spectrum of textile dyeing wastewater (Sample C) and
treated water by metal hydroxide sludge (Dose: 1% (w/v); contact time: 60 min).

Table 3. Parameters of textile dyeing wastewater (Sample C) and treated water

by 1% (w/v) of metal hydroxide sludge in batch system.

Parameters Wastewater Treated water % Removal Standard

Color (SU) 300.63 3.07 99 no issue

Color (ADMI) 1080 103 91 no issue
Apparent color strong brown clear -
COD (mg/l) 93 4 96 400
SS (mg/l) 22 15 32 50
pH 9.10 8.24 - 5-9
Cu2+ (mg/l) - 0.38 - 2.00
Cr3+ (mg/l) - 0.20 - 0.75
Ni2+ (mg/l) - 0.05 - 1.00
Zn2+ (mg/l) - 0 - 5.00

Conclusions
Feasibility studies show that metal hydroxide sludge could be applied as an
effective adsorbent to remove color, COD and SS from textile wastewater to
within an acceptable pH and without causing harm to the environment by toxic
heavy metals. The higher dose, 3-5% (w/v), yielded the higher adsorption
efficiency without higher leachate of heavy metals, however, the minimum dosage
of 1-2% (w/v) is suitable for use due to the smaller amount of sludge for disposal.
7-009 (O)
Proceedings of the
2nd Regional Conference on Energy Technology Towards a Clean Environment
12-14 February 2003, Phuket, Thailand

Acknowledgements
The authors would like to thank the National Metal and Materials Technology
Center, Thailand, and JGSEE, King Mongkut’s University of Technology
Thonburi, Bangkok, Thailand, for supporting this research.

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