DECOLORISATION OF DYE WASTE WATER USING ORGANIC/INORGANIC

HYBRIDIZATION WITH GROWING CALCIUMCARBONATE

Saurabh Meshram*, Dr. Mrs. A.B.Soni**

*Lecturer, IES-IPS Academy, Indore
saurabhmeshram38@yahoo.in
**Reader, Department of Chemical Engineering
National Institute of Technology, Raipur (C.G.)

Abstract

Inorganic/organic hybridization is often employed to synthesize functional materials but seldom

considered in industrial wastewater treatment. Dye conjugate hybridization was proposed by
immobilizing the anionic (e.g. Congo red)–cationic (e.g. Methylene blue) dye complex with growing
calcium carbonate. Applied to treatment of concentrated organic wastewaters, the simple single-step
hybridization performed adsorption, flocculation and ionic complexation and exhibited a high level of
removal of organic substances. This work provides a convenient, cost-effective and environment
friendly wastewater treatment by ‘‘using waste to treat waste’’.

Introduction significant amount of sludge or cause

Now-a-days, over 10,000 dyes are
commercially available and more than 700,000
tonnes are produced annually. The colored
effluents discharged from textile processing
and dye manufacturing industries contain a
significant amount of un-reacted dye. During
dyeing processes, up to 15% of the dyestuff
doesn’t bind to the fibers and is therefore
released into the environment. Azo dyes, being
the largest group of synthetic dyes, constitute
up to 70% of all the known commercial dyes
produced. Their chemical structures are often
characterized by highly substituted aromatic
rings joined by one or more Azo groups (–
N=N–). They lead to acute toxic effects on the
flora and fauna of the ecosystem when
released into the environment. Moreover,
many Azo dyes and their metabolites are
mutagenic and carcinogenic. The majority of
color removal techniques are based on
coagulation/adsorption of dyes by physical
methods or the complete destruction of dye
molecules by chemical methods such as
electrolysis, ozonation, etc. Treatment of
textile wastewater in India mostly occurs in
conventional municipal wastewater treatment
systems. However, the conventional treatments
have inherent drawbacks as they generate a
secondary pollution due to formation of
hazardous by-products. Though the
combination of physical and biological
treatments achieves a satisfactory removal of
organic contaminants, the complicated
procedure and long period brought out a high
running cost and secondary pollution. Thus,
highly concentrated wastewater treatment must
focus on innovative methods together with the
recycling of waste.
The objective of this work is to establish a new
type of wastewater treatment method by
immobilizing waste anionic (e.g. Congo Red,
CR)–cationic (e.g. Methylene Blue, MB) dyes
by conjugation onto a harmless inorganic
skeleton (e.g. CaCO3). Also, based on the dye
wastewater characteristics, the feasibility of
reuse of the dye-immobilized CaCO3 sludge
was investigated (e.g. reuse as more efficient
dye) in order to avoid secondary pollution.
Experimental Procedure
An anionic dye e.g. CR (100µM) and cationic
dye e.g. MB (100µM) solutions were prepared
and considered as dye waste water. CR
solution was mixed with MB solution and
sodium carbonate (10mM) was added. After
mixed thoroughly, calcium chloride (40mM)
was added slowly under stirring. After 30
minute, the suspending substance was settled
down and removed to obtain the clear water.
The conjugated sludge was dried for 3hours at
60-700C to remove moisture. The dried sludge
was ground to obtain fine powder and reused
as dye and to manufacture paint.
Results and Discussion
Effect of calcium carbonate concentration
It was observed that concentrations of CO32-
and Ca2+ affect the sedimentation rate of the
conjugate hybrid. The presence of calcium
carbonate accelerated the sedimentation rate of
conjugate especially within 20 minute as it
provides the excess surface for adsorption
(fig.1). The increase of CO32- and Ca2+
concentrations were favorable for the
sedimentation of the conjugate, as it works as
flocculants to accelerate the sedimentation. It
was also observed from the result that the
molar concentration of CaCO3 to CR should be
10:1 for the removal of dye.
Effect of pH
Sedimentation rate was very rapid in alkaline
medium and same was very slow at low pH
value as the dissolution of calcium chloride
was increased with decrease in pH value.
Sedimentation height was reduced to 2cm in
first five minute for the alkaline solution
having pH value 11.8 and the same was 8cm
for the pH value 8.4. Thus, the presence of
concentrated electrolyte was favorable for the
salting-out of the CR-MB-CaCO3 conjugate
(fig.2).
COD Removal
The best result for the COD removal by the
treatment was about 75% for the 100µM of
both the solution of CR and MB, when treated
with 20mM of Na2CO3 and 40mM of CaCl2.
This result may vary for the dye waste water
from industries, because of the presence of the
various contaminants other than dye effluents.
Effect of Temperature
Effect of temperature was observed by varying
the temperature of the CR-MB mixture from
300C to 700C by using heating chamber and
then treated with sodium carbonate and
calcium chloride. It was observed from fig.3,
that temperature has no effect on the
hybridization and on the removal of dye.
Color Removal
Nearly colorless solution was obtained after
the treatment of 100µM of CR and MB, when
treated with 20mM of Na2CO3 and 40mM of
CaCl2. It was observed that CR and MB
powder gives red and dark blue color when
dissolved in distilled water, and the mixed
solution of CR and MB gives dark brown
color. Colorless solution was obtained after the
treatment (fig.4).
It was observed from the fig.5, that color
removal increases with the increase of CaCO3
concentration, as high concentration of CaCO3
enhances the removal of dye effluent, so as to
color removal. The color removal obtained by
the treatment of dye waste water is about 95%.
COMPARISON OF PAINTS PREPARED
Dried powder obtained after treatment was
used as dye and compared with the solution of
CR-MB. The two solutions was applied on the
cloth and dried for 24 hours at room
temperature. It was observed that the dye
(dried powder) shows the resistance to color
release, while the dye (CR-MB mix) releases
the color (fig.7). One can easily understand
that, resistance to release of color substance of
paint1 was due to the presence of CaCO3.
Beyond all doubt, using the dye–CaCO3 hybrid
sludge raised the fastness of color substance.
As is well known, calcium carbonate is often
employed as the additive or reinforcing filler
during the production of paint, rubber, paper
and plastic.
COMPARISON OF ADSORPTION
CAPACITY
When a cationic dye was mixed with CR
according to ion-pair equilibrium, a dye
conjugate was formed and then precipitated
rapidly together with CaCO3. Different from a
conventional adsorbent, the in situ
immobilization of the CR–MB conjugate in
growing CaCO3 has no direct correlation with
the surface area of material. From the above
experimental results, the adsorption capability
of growing CaCO3 was calculated to be 232mg
CR and 213mg MB per gram of CaCO3 and
also their adsorptions occurred simultaneously.
From Table1, the CR-sorbing capacity of the
adsorbents e.g. activated carbon, fly ash and so
on is between 3.0 and 66.23 mg/g and the MB-
sorbing capacity between 4.92 and 27.78
mg/g.11 Therefore, the dye conjugate
hybridization resulted in a much more dye
removal than those by using the conventional
adsorbents.
 Table1-Adsorption capacity of various adsorbents for removals of MB and CR.

Adsorbents Dye Adsorption capacity (mg/g)

Growing CaCO3 MB/CR 213/232

Saw dust-pitch pine MB 27.78

Coconut coir MB 15.59
Class fly ash MB 4.92
Fly ash-HNO3 MB 7.74
Activated carbon MB/CR 17.63/3.0
FA-C CR 31.14
Baggase fly ash CR 11.84
Orange peel CR 22.40
Palm kemel seed coat CR 66.23

Conclusions the preparation of paint, which can be

Single step hybridization process was found to
be very efficient and environment friendly
method for the treatment of dye waste water by
using waste to treat waste. On the basis of
results following conclusions have been
drawn:-
1. Sedimentation rate of conjugate dye is
very high especially within 20min of
the treatment and it reaches to
equilibrium after 30min.
2. Concentration of Na2CO3 and CaCl2 in
the molar ratio of 1:2 is found
favorable for the treatment of dye
waste water, and also the concentration
of CaCO3 to CR in the molar ratio of
10:1 is found suitable for the treatment.
3. Sedimentation rate is very fast in the
alkaline medium. Maximum dye
removal is obtained at the pH value of
11.8.
4. 75% of the COD is reduced by
hybridization within the 30min of the
treatment of dye waste water.
5. Color removal of about 95% is
obtained by the treatment.
6. Adsorption of dye effluents on growing
CaCO3 satisfies the second order
kinetics with the rate constant of
3.11gm/(gm-min).
7. Conjugate dye obtained as a residue
after the treatment has been utilized for
reused on cotton, plastics etc.
References
1. Abdul Latif Ahmad, Wan Azlina Harris,
Syafiie & Ooi Boon Sen, Journal
Technology, Jun 2002: 31–44.
2. C. T. M. J. Frijters, R. H. Vos, G.
Scheffer and R. Mulder, Water Res.,
2006, 40, 1249–1257.
3. Dan-Hua Zhao, Ya-Lei Zhang, Yan-Ping
Wei and Hong-Wen Gao, Facile eco-
friendly treatment of a dye wastewater
mixture by in situ hybridization with
growing calcium carbonate, Journal of
Materials Chemistry, 24th August 2009.
4. Eltaief Khelifia, Hassib Bouallaguia,
Youssef Touhamia, Jean-Jacques
Godonb, Moktar Hamdia, Enhancement
of textile wastewater decolourization and
biodegradation by isolated bacterial and
fungal strains, Desalination and Water
Treatment, 2 (2009) 310–316
5. Jyoti Sharma a and Beena Janveja, A
study on removal of congo red dye from
the effluents of textile industry using rice
husk carbon activated by steam, Rasayan
J. Chem. Vol.1, No.4 (2008), 936-942.
6. M. K. Purkait, A. Maiti, S. Das Gupta
and S. J. De, J. Hazard. Mater, 2007,
145, 287-295.
7. M.Sujatha, A.Geetha, P.Sivakumar and
P.N.Palanisamy, orthophosphoric acid
 activated babul seed carbon as an
adsorbent for the removal of methylene
blue, Journal of Chemistry, Vol. 5, No.4, 14.
pp. 742-753, October 2008.
8. M. S. Khehra, H. S. Saini, D. K. Sharma,
B. S. Chadha and S. S. Chimni, Water 15.
Res., 2005, 39, 5135–5141.
9. Macro. S. Lucas, A. A. Dias, A.
Sampaio, C. Amaral and J. A. Peresa,
Water Res., 2007, 41, 1103–1109. 16.
10. Rosa María Melgoza–Alemán, Fernanda
Morales-Guzmán, Effect of activated
carbon on the biodegradability of direct 17.
azo dyes in a sequential batch reactor
under anaerobic/aerobic environments,
Australian Journal of Basic and Applied
Sciences, 3(4): 3677-3683, 2009.
11. S. Wang, Y. Boyjoo, A. Chouei and Z.
H. Zhu, Water Res., 2005, 39, 129–138.
12. Separation Process Principles (second
edition)-J. D. Seader and Ernst J. Henley.
13. Thirachitra Tapalad, Arthit
Neramittagapong, Sutasinee
Neramittagapong and Mallika Boonmee,
Degradation of congo red dye by
ozonation, J. Sci. 2008; 35(1): 63-68.
Unit Operations of Chemical
Engineering (seventh edition)- Warren L.
McCabe, Julian C. Smith, Peter Harriot.
Wayne Boyles-The Science of
CHEMICAL OXYGEN DEMAND
Technical Information Series, Booklet
No. 9.
Yogesh C. Sharma, Uma and Siddh, N.
Upadhyay Energy Fuels, 2009, 23 (6), pp
2983–2988.
Y.C. Sharma, Uma S.N. Upadhyay and
F. Gode, Adsorptive removal of a basic
dye from water and wastewater by
activated carbon, journal of applied
sciences in environmental sanitation,
Volume 4, Number 1: 21-28, January-
April, 2009.