THE USE OF MODIFIED BENTONITES IN THE TREATMENT

OF TEXTILE WASTEWATER
Nguyen Thi Hanh, Nguyen Van Noi, Ha Minh Ngoc, Duong Thi Hanh
Laboratory of Environmental Chemistry,
Faculty of Chemistry, Hanoi University of Science

ABSTRACT

In this study, hexadecyltrimethylammonium (HDTMA) bentonite was synthesized by placing

alkylammonium cation onto bentonite. Adsorption of some textile dyes such as direct dye,
acid dye and reactive dye on Na-bentonite and HDTMA-bentonites s was investigated. While
the Na-bentonite had very weak affinity for the direct dye, the HDTMA-bentonites showed
significant adsorption from direct dye aqueous solution. The Langmuir and Freundlich
isotherm equations were applied to the data, and values of parameters of these isotherm
equations were evaluated. The sorption capacity of the HDTMA-bentonites attained 247.18
mg/g for direct dye, and the sorption capacity of the bentonite was only 1.28 mg /g. There is
not significant difference of affinity of Na-bentonite and HDTMA-bentonites for acid dye
and reactive dye. The organoclay was also successfully applied in the treatment of wastewater
from Duong Noi textile handicraft village in Ha Dong town, Ha Tay province.

Keywords: Organoclays, Textile dyes, HDTMA-bentonites, Na-bentonite, Langmuir

isotherm, Freundlich isotherm, Sorption capacity.

INTRODUCTION

The fact that synthetic dyes are largely used in many industries presents certain hazards and
environmental problems. Today there are more than 10,000 dyes with different chemical
structures available commercially [1]. Color in water body is not only aesthetically unpleasant
but also interferes light penetration and reduces photosynthetic action. Many dyes or their
metabolites have toxic as well as carcinogenic, mutagenic and teratogenic effects on aquatic
life and humans [2,3].

In order to minimize the possible damage to people and the environment arising from the
production and application of dyes, several studies have been conducted around the world.
The development of sorbents of different types is carried out by many research and
commercial institutions. Active carbon, for example, is known as an effective sorbent of toxic
materials from water solution. Its sorbent characteristics are regenerable by thermal
desorption; however, a significant part of the sorbent is lost in each desorption cycle. This is
the main reason for low economical efficiency in its application. Therefore, the interest in the
development of sorbents of specific surface, e.g., organoclays, has significantly increased in
recent years. A number of researchers have used various organoclays for the removal of
textile dyes from aqueous solutions.

The aluminosilicate sheets of common clay minerals possess a net negative electrical charge
compensated for by inorganic exchangable cations (e.g., Na+ and Ca2+), which are strongly
hydrated in the presence of water. Surface properties of natural clays can be modified by
simple ion exchange with organic cations. Bentonite and kaolinite clays are easily modified
by exchanging their inorganic cations with quaternary ammonium cations. This may result in
an increase in the inter-lamellar spacing and exposure of new sorption sites of the clays. More
importantly, the substituted organic cations are weakly hydrated. As the inorganic cations are
progressively replaced by the organic cations, the surface properties of a clay may change
considerably from highly hydrophilic to increasingly organophilic (hydrophobic).

The mechanisms controlling the sorption of compounds on organoclays are dependent on the
type of organic cations forming organoclays. The clays are often modified by quaternary
ammonium cations of the general form [(CH3)3NR]+, where R is an aromatic or alkyl
hydrocarbon group, to replace inorganic cations on clays.

This study examines a method for removing some textile dyes such as direct dye, acid dye and
reactive dye from dye contaminated water by HDTMA-bentonites.

MATERIALS AND METHODS

The bentonite clay used in this study was obtained from Di Linh – Lam Dong. Chemical
composition and cation exchange capacity (CEC) of the bentonite were given in a previous
study [13]. Coarse-fraction impurities such as iron oxides and silica were removed by
subjecting the bentonite dispersions to repeated sedimentation. The layer at the bottom was
removed and the upper portions were exposed to sedimentation until no gritty layer remained.
After drying at 60oC, the sample was pulverized to pass through a 0.15mm sieve. The
<0.15mm clay fractions were saturated with Na+ cations by using NaHCO3, with the
NaHCO3/bentonite ratio of 3/100 (by weight). Water was added into the mixture of bentonite
and NaHCO3, subsequently it was agitated on a magnetic stirrer at room temperature for 12h.
Na-bentonite was washed with water to neutral pH and dried.

Distilled water was added shaking flask containing 30g Na-bentonite, and the mixture was
stirred using a magnetic stirrer, The temperature of the mixture was raised to 60 – 700C,
further stirred, and solution of hexadecyltrimethylammonium (HDTMA)-bromide in an
amount equivalent with the ratios respectively 75%, 100% and 125% of CEC were added
dropwise while stirring. Mixture was further stirred at 60 – 700C for 2h. The mixture was
agitated overnight on a magnetic stirrer at room temperature. The HDTMA-bentonites
suspension was then washed with distilled water repeatedly until free of bromide ions as
indicated by AgNO3. The organoclay was dried at room temperature and stored in bottles for
experimental use.

The X-ray diffractions of samples were recorded using X-Ray diffractometer Bruker D8
Advance. The IR spectra were obtained using Fourier Transform Infrared Spectrometer FT-IR
8101M Shimadzu.

The dye stock solutions were prepared by dissolving accurately weighted dyes in distilled
water to the concentration of 1000 mg/l. The experimental solutions were obtained by diluting
the dye stock solutions in accurate proportions to different initial concentrations.

Sorption experiments were carried out in a rotary shaker at 150 rpm and at room temperature
using 250ml shaking flasks containing 100 ml different concentrations and initial pH values
of dye solution. Different doses of sorbent were added to each flask. After shaking the flasks
for predetermined time intervals, the samples were withdrawn from the flasks and the dye
solutions were separated from the sorbent by sedimentation/centrifugation. Dye
concentrations in the supernatant solutions were estimated by measuring absorbance at
maximum wavelengths of dyes by spectrophotometry using UV-VIS spectrophotometer 1601
PC Shimadzu at ambient temperature and computing from the calibration curves. The
experiments were conducted in duplicate and the negative controls (with no sorbent) were
simultaneously carried out to ensure that sorption was by sorbent and not by the container.

RESULTS AND DISCUSSION

The X-ray diffraction spectra of Na-bentonite and modified bentonites were showed in Fig.1.
The intercalation of the HDTMA cation increased the interlamellar distances from 15.227Ao
(Na-bentonite) to 19.042Ao , 19.643Ao , 20.519Ao with respectively VL1, VL2, VL3
(HDTMA-bentonites ). The larger basal spacing (d001) of HDTMA-bentonites corresponds to
the formation of bilayers, in which the long-chained surfactant cations are in direct contact
with each other, leading to the formation of organic phases consisting mostly of the C16
hydrocarbon groups into which solutes are partitioned.

90 0
Na-Bentonite VL1

d=19.043
300
80 0

70 0
d=15.227

Lin (Counts)
60 0
Lin (Counts)

d=34.299
50 0 200
d=3.340

40 0

d=3.349
d=4.471

d=4.247

30 0

d=4.477
d=2.558
d=2.886

d=2.570
d=7.130
d=7.167

20 0
100

10 0

5 10 20 30 40

2 - T h e t a - S c a le
F ile : D u c K 4 9 B - m a u b e n t t in h c h e . ra w - S t a r t : 5 . 0 0 0 ° - E n d : 4 4 .9 9 0 ° - S t e p : 0 . 0 3 0 ° - S te p t i m e : 1 . s - 2 - T h e t a : 5 . 0 0 0 ° - T h e t a : 2 .5 0 0 ° - A n o d e : C u - W L 1 : 1 . 5 4 0 6 - C re a t io n : 3 / 2 3 / 2 0 0 7
0 0 -0 0 3 -0 0 1 4 ( D ) - M o n t m o r i llo n i te - M g O · A l2 O 3 · 5 S iO 2 ·x H 2 O - W L : 1 . 5 4 0 6 - 0
0 0 -0 3 3 -1 1 6 1 ( D ) - Q u a r t z , s y n - S iO 2 - W L : 1 . 5 4 0 6 - H e x a g o n a l - a 4 . 9 1 3 4 0 - b 4 .9 1 3 4 0 - c 5 . 4 0 5 3 0 - a lp h a 9 0 .0 0 0 - b e t a 9 0 . 0 0 0 - g a m m a 1 2 0 . 0 0 0 - P r im it iv e
2 10 20 30 4

22 0
VL2 VL3
21 0

20 0

19 0

18 0
d=19.642

Lin (Counts)

17 0
d=20.519

16 0

15 0 200
Lin (Counts)

14 0
d=35.156

d=3.350

13 0
d=4.486

12 0
d=3.352
d=4.254

11 0
d=4.482

d=4.259
d=2.566

10 0
d=2.894

d=36.015

90

d=2.569
80
100
70

60

50

40

30

20

10
0
0
2 10 20 30 4
2 10 20 30 4

Fig.1. Powder X-ray diffraction spectra of Na-bentonite, VL1, VL2, and VL3

The IR spectra were showed in Fig. 2. The appearance of absorption peaks at 2852.33cm-1
and 2924.06cm-1 in the spectra of modified bentonites that are inherent for vibration of –CH3
and –CH2– groups. In addition, the absorption peak at 1472.49cm-1 showed the presence of
quaternary ammonium cations in organoclays.

Na-Bentonite VL1
 VL2 VL3

Fig.2. The IR spectra of Na-bentonite, VL1, VL2, and VL3

To observe the uptake of the textile dyes, the clays were placed in aqueous solutions of the
textile dyes and allowed to equilibrate for one day. The experimental results showed that Na-
bentonite had very low affinity for the dyes. In HDTMA-bentonites -dye system it is clear that
adsorption may be enhanced by the hydrophobic interaction between the adsorbed dye
molecule and HDTMA-bentonites. Thus, the degree of sorption of dyes depends on the
amount of the surfactant ions in the bentonite interlayer sites.
The amount of dye adsorbed per unit weight of an adsorbent, q, was calculated using the
following formula:
( C 0 − C) V
q=
m
where Co is the initial concentration of dye (mg/l), C is the equilibrium concentration of dye
in solution (mg/l), m is the mass of the clay (g) and V is the volume of solution (l). The values
of qmax and correlation coefficients r are reported in tables 1 – 3. The isothermal data could be
well described by the Langmuir and Freundlich isotherm equations. Many experimental
isotherms conforming to a Langmuir isotherm involve monolayer coverage. The value of
monolayer coverages of HDTMA-bentonites by direct dye increased in the order VL3 > VL2
> VL1 > Na-Bentonite. The modified bentonites also showed very good sorption capacity to
acid and reactive dyes.

Table 1. Langmuir and Freundlich isotherms constants for the adsorption of direct dye

Langmuir isotherm Freundlich isotherm

Sorbent

qmax (mg/g) R2 K 1/n R2

Na-Bentonite 1.28 0.906 0.332 0.246 0.852

VL1 161.13 0.906 69.96 0.131 0.976

VL2 224.55 0.878 106.30 0.138 0.970

VL3 247.18 0.793 148.71 0.096 0.977

Table 2. Langmuir and Freundlich isotherms constants for the adsorption of reactive dye

Langmuir isotherm Freundlich isotherm

Sorbent
2
qmax (mg/g) R K 1/n R2
VL1 548.93 0.97 121.15 0.327 0.98

VL2 586.85 0.98 276.15 0.269 0.94

VL3 623.52 0.99 307.20 0.123 0.87

Table 3. Langmuir and Freundlich isotherms constants for the adsorption of acid dye

Langmuir isotherm Frendlich isotherm

Sorbent
qmax (mg/g) R2 K 1/n R2
VL1 242.489 0.953 62.124 0.230 0.951

VL2 234.999 0.964 53.760 0.245 0.952

VL3 229.897 0.949 37.751 0.290 0.972

The organoclay (VL1) was also successfully applied in the treatment of wastewater from
Duong Noi textile handicraft village. The result of the treatment was showed that the COD of
wastewater was decreased from 350 mg/l to 52 mg/l with the use of 1g of organoclay for 1l of
wastewater.

CONCLUSION

The sorption of textile dyes such as direct dye, acid dye and reactive dye on bentonites with
and without quaternary ammonium salt (HDTMA) was investigated. The bentonite was
modified with HDTMA, rendering it organophilic. Whilst very low sorption of textile dyes
occurred on Na-bentonite, they were strongly sorbed on HDTMA-bentonites. This could be
explained by adsorption interaction between the adsorbed dye molecules and hydrophobic
alkyl group on HDTMA-bentonites, which should enhance the adsorptive capacity of the
bentonite.
There was a good fit of the sorption experimental data for HDTMA-bentonites with the
Langmuir and Freundlich models. It can be said that HDTMA-bentonites may be used as
adsorbents for adsorption and decolorization of some textile dyes from wastewater. The
usability of HDTMA-bentonites in industrial waste water requires further investigations.

ACKNOWLEDGEMENTS

We acknowledge the financial support provided by Vietnam National University, Hanoi

through the project QG-06-10.
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