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Treatment of rice mill wastewater using modified adsorbent

prepared from rice husk ash


Bratin Senguptaa, Anuj Kumar a, Dalia Dasgupta b, Tamal Mandal a* ,T. Kumar a

Department of Chemical Engineering, National Institute of Technology, Durgapur,


Mahatma Gandhi Avenue, Durgapur-713209, West Bengal, India

Department of Biotechnology, National Institute of Technology, Durgapur, Mahatma


Gandhi Avenue, Durgapur-713209, West Bengal ,India

Abstract
The aim of this study is to treat of rice mill wastewater by batch adsorption process onto
modified rice husk ash, which is a waste generated from the same industry. By means of
chemical modification, silica was removed from the rice husk ash and the carbonaceous part
was used effectively as an adsorbent. The adsorptive treatment process of rice mill
wastewater was carried out as a function of initial pH of wastewater, adsorbent dose, initial
COD of wastewater, temperature and contact time. The output variable was considered as
removal of Chemical Oxygen Demand (COD). Maximum adsorption was achieved at an
adsorbent dose of 10 g/L, pH 5 and a contact time of 120 min. Kinetics studies and
equilibrium studies were performed and it was observed that the recorded data fits best onto
pseudo second order kinetics equation and the Freundlich isotherm model best suitable the
equilibrium adsorption data. Thermodynamic study of this process reveals the values of
change in Gibbs free energy to be negative, which refers to the feasibility and spontaneity of
the adsorption process. The enthalpy and entropy change for the adsorption of rice mill
wastewater onto modified activated carbon prepared from rice husk ash the results were 161
J/(mol.K) and 213 J/(mol.K) respectively.

Keywords: Rice mill waste water; Rice husk ash; Adsorption; COD removal; Silica.

1. Introduction:
Being one of the staple foods for billions of people, Rice is grown worldwide.
Processing of rice is the oldest and the largest agro based industry. It will be prolific to
enhance its productivity in reference to increase in the population which use rice as principle
food. Presently major portion of rice production is carried out in modern rice mills. Parboiled
rice production in rice mills generally require large amount of water mainly for pre cleaning
and soaking of paddy. Hence, it generates a huge amount of wastewater (1.01.2 L/kg of
paddy fed), which contains very high concentration of organic and inorganic pollutants
(Rajesh et al., 1999). Improperly untreated rice mill waste water may cause water pollution as
it can be toxic to aquatic life over and above can cause severe damage to human beings also.
The rice husk obtained from the rice milling process as a waste product is generally used as
fuel in paddy milling process to save energy and to make the process resource-efficient as it
has a heating value of 13.6 MJ/kg (Armestoa et al., 2002). While combusting the rice husk at
high temperature (around 300C), the loose wet structure is destroyed and the burnt rice husk
generates rice husk ash (RHA), which is usually considered as a waste. The light weighted
RHA particles are usually carried by air and these airborne particles can cause respiratory
disease in humans whereas its disposal at landfill site leading to air and water pollution
(Mansaray et al., 1999). In modern rice mills, a, large amount of harmful solid and liquid
wastes are being generated, mainly in form of wastewater (15 L/kg of rice produced) and rice
husk ash (0.22 kg/kg of rice produced).
The proper disposal of rice mill wastewater is a very challenging issue for an industry
considering the cost, complexity and limited efficiency of the conventional processes
involved in removal of contaminants from the water. Wastewater is generally treated by
different physico-chemical processes like coagulation, oxidation, and biological treatment
methods (Mehata, 1999). The other processes being either time consuming or non
economical, adsorption is the most preferred of the well known treatment process for
wastewater.
The objective of the present study is to prepare modified adsorbent from rice husk ash
from which silica has been extracted out. Adsorbent was prepared by chemical activation and
impregnation with a very effective activating agent like o-H3PO4, followed by carbonization
to obtain two different adsorbents with increased pore volume. Thus by preparing such a
adsorbent an attempt has been made to make a treatment process which uses the waste
product from one industry to treat another waste generated from the same industry.

2. Materials and Methods:


2.1 Wastewater
Rice mill wastewater for the study was collected from Laxmi Shree rice mill of
Burdwan, West Bengal. It was stored at 4C in laboratory and immediately analyzed to avoid

discrepancies in its measured characteristics values. The initial characteristics of rice mill
wastewater were: pH = 5.5; COD = 3388 mg/L; Color = yellowish; Odor = obnoxious;
Lignin = 284 mg/L; Phenol = 32 mg/L.
2.2 Preparation of Adsorbent
For preparing the adsorbent, acid washed RHA was dispersed in 1N NaOH solution
and stirred for 120 min at a temperature of 95C. It was then cooled and filtered through
Whatmann 41 filter paper. Filtrate Na2SiO3 was stored and the solid residue obtained was
used for preparation of another adsorbent. It was washed with distilled water and dried to get
carbonaceous RHA, which was then grinded to prepare finer particles (-90 m). Afterward
adsorbent was prepared by activation with o-H3PO4 in 1:1 ratio followed by carbonization at
350C for 120 min. Subsequent washing steps were done for obtaining final adsorbent.
2.3 Characterization
For the purpose of characterization of exterior surface, structure and morphology of
treated and untreated adsorbents SEM images were recorded using a Scanning Electron
Microscope (Model: Hitachi 3000).
Fourier Transform Infrared spectrograph (FTIR) analysis was done for the study of surface
chemistry and identifying the functional groups present of the adsorbent; both treated and
untreated, using Model Perkin Elmer FTIR- 2000, US. The spectra were measured form/from
4000cm-1 to 400cm-1.
2.4 Experiment methodology
Experiments were carried out in batch mode in 250mL Erlenmeyer asks containing
100mL of rice mill wastewater and the amount of adsorbent varied from 2g/L to 20g/L. The
flasks were agitated at 140 rpm in an incubator shaker with temperature at 303K for a contact
time of 120 min. After finishing the experiment the reaction media was filtered with
Whatmann filter paper number 1 to eradicate the adsorbent and the filtrate was then analyzed
to measure the residual contaminant. The process controlling parameters - pH, amount of
adsorbent, initial concentration of rice mill wastewater, temperature were varied in a
prescribed one variable manner.
The adsorbent dose was varied from 2g/L to 20g/L at a constant temperature of 303K,
at initial pH 5.5 with a contact time of 120 min and initial COD concentration of 3388mg/L.
The pH was varied within a range of 2 to 10, with the adsorbent amount being constant at
10g/L, at 303K and a contact period of 120 min, while the initial COD was at 3388g/L. The
initial effect of COD was studied for both the adsorbent with constant adsorbent weight of
10g/L, at 303K and pH of 5.5 for a contact time of 120 min.
The effect of contact time was observed in the kinetic study and it was observed that
120 min was sufficient for COD removal. The COD removal of the samples was determined
by

% = 100

( )

(1)

Amount of adsorbed contaminants (qt, mg/g) of adsorbents added was calculated according to
the formula
= ( )

(2)

The equilibrium uptake for adsorption, qe was determined by the formula


=

( )

(3)

Where COD0 is the initial COD value, CODt is the final COD value after each experiment,
CODe is the COD value at equilibrium, V is the volume of rice mill waste water added and w
is the weight of adsorbent added.

3. Results and Discussions:


3.1 Characterization of adsorbents
The SEM photographs of the treated and untreated adsorbents and are shown in Fig.
1. It shows that the adsorbents have uneven, porous and small crystalline structure. The
heterogeneous sized pores and cavities on the adsorbent surface provide large surface area to
trap and contain contaminant particles present in rice mill wastewater. From the SEM images
it is also noticed that the pores in the treated adsorbent [Fig. 1 (a)] are significantly reduced
compared to its untreated counterpart [Fig. 1 (b)] due to the adsorption of contaminant
particles.
Fourier Transform Infrared Spectroscopy (FTIR) study in the 4000-400 cm-1 range
was carried out for identification of the functional groups present in the adsorbents. All
spectra shows sharp peak around 1660 cm-1 and 1400 cm-1 which indicate the -C=O- group
stretching from aldehydes and ketones. This might also and may be due to the carboxyl
carbonate structures (Srivastava et al., 2006). The fluctuation around 3000 cm-1 indicates C-H
bond stretch in alkanes and this stretching is due to the presence of silanol groups (SiOH) on
the surface (Hun et al., 2006).

Fig. 1. SEM photographs of (a) Untreated (b) Treated adsorbent.

3.2 Effect of different parameters on adsorption


3.2.1 Effect of adsorbent dose
The results illustrated in Fig. 2 shows that with an increase in adsorbent dose, there is a
subsequent increase of the COD removal percentage for the adsorbent. This is because of the
increment of surface area and availability of more active adsorption sites (Sharma et al.,
2010).

Fig. 2. Effect of adsorbent dose on COD removal; (COD0 = 3388 mg/L, temperature = 303 K,

pH = 5.5 and contact time = 120 min)

3.2.2 Effect of initial pH


The adsorption capacity of the adsorbents was observed by using the adsorbents in rice mill
wastewater at different pH. Fig. 3 shows the percentage COD removal from wastewater by
the adsorbent. The graph shows that at pH 5, the percentage of COD removal is maximum for
the modified adsorbent.

Fig. 3. Effect of pH on adsorption (at condition: adsorbent weight = 10g/L, temperature =


303 K, contact time = 120 min, CODo = 3388 mg/L).

3.3.3 Effect of initial COD


It was observed that, for the adsorbent, as the initial COD increases, the percentage
COD removal values have fluctuated but COD adsorbing capacities, qe have increased.
Theoretically, greater the initial COD of wastewater, greater the adsorption capacity because
it offers a bigger driving force (concentration gradient) to overcome the mass transfer
resistance between the wastewater and solid adsorbent (Sharma et al., 2010).
3.3.4 Equilibrium study
Adsorption of contaminants from rice mill wastewater using ADS and ADC was
carried out in different temperatures ranging from 293 K to 313 K. The adsorptive capacity
increases with the increase in temperature. With the gradual increase in temperature the
activity of adsorbate increases and hindering forces acting on the diffusing particles decrease.
The process is influenced by both chemical adsorption and intra particle pore diffusion.
Chemical adsorption is generally an endothermic process but diffusion is an exothermic
process (Sekara et al., 2004). So the variations of temperature influence equilibrium
adsorption capacity as these two mechanisms are simultaneously controlling the process. As
the temperature increases, the mobility of the contaminant particles in rice mill wastewater
increase and the rate of diffusion of adsorbate particles through the external boundary layer
and within the internal pores of the adsorbent particles become vigorous. The temperature
decreases the adsorption capacity as the adsorption mechanism is an exothermic process in

nature (Larous et al., 2012). This phenomenon indirectly indicates that the reaction
mechanism is both chemical kinetics and diffusion controlled.
The correlation coefficient (R2) values indicate that the Freundlich isotherm fits the
data best, as the values of R2 are closer to unity. The values of Freundlich constant 1/n is
low indicating higher affinity for adsorption. These values being close to 1, inferring
relatively homogeneous surfaced (Pelekania et al., 2010).
3.3.5 Kinetic Study
The determination of the batch adsorption kinetic parameters is essential for the design of
adsorption columns in pilot plants and for further scale up. . A comprehensive kinetic study
has been carried out by varying the initial COD of rice mill wastewater within the range 847
and 3388 mg/L. The kinetic parameters along with correlation coefficient (R2) for fitting the
experimental data are tabulated in Table 1. It is observed that the R2 values are nearly one in
case of pseudo second order model and the qe,cal and qe,exp values are also very near.
Table 1: Kinetic parameters for adsorption. (conditions: weight of adsorbent = 10g/L,
temperature = 303 K, Contact time = 120 min, CODo = 3388 mg/L).
CODo

qe [exp]

qe [cal]

Ks

h = ks*qe2

R2

mg/L

mg/g

mg/g

g/(mg.min)

mg/(g.min)

3388

163.24

164.6

0.015

399.709464

0.936

2541

146.66

138.9

0.008

172.073245

0.958

1694

91.36

85.1

0.0031

25.8746138

0.986

847

47.69

41.8

0.0072

16.3752199

0.855

It is observed that pseudo second order kinetic parameters, qe and h (initial adsorption rate),
value increases with the increase in CODo values. In adsorptive removal of wastewater, the
wastewater components may be transported from the bulk into the adsorbent surface through
intra-particle diffusion. So the intra particle diffusion is another kinetic model which was
used for the study adsorption process. There is a possibility that intra particle diffusion may
be the rate controlling step for the adsorption process. This is because the intra particle
diffusion controls the adsorption process in system which has better mixing, large adsorbent
particle size and high concentration of the adsorbate (Aravindhan et al., 2007).

3.3.6 Thermodynamic study


Negative G0 indicates that the rice mill wastewater adsorption process is feasible and
spontaneous. The increase in G0 value with increase of temperature also indicates that the
affinity of containment particle of the wastewater rises as the temperature increases. The H0
value of both the adsorbents indicates that the process is overall endothermic. The adsorption
process is clearly chemo-adsorption process as the H0 value is 32.88 KJ/mole which is
greater than 30 KJ/mol. In this case a chemical bond is formed between molecule and the
surface; the adsorption energy is comparable to the energy of a chemical bond. The positive
value of S0 indicates that arbitrariness takes place at the adsorbent-wastewater interface and
the affinity of adsorbent towards the rice mill wastewater component is high. Positive S0
value also indicates an increase in the degree of freedom of the adsorbed particles (Penga et
al., 2003).
4. Conclusion
The optimum conditions for both the adsorbents were determined to be at initial pH 5,
contact time 120 min, adsorbent dose = 10 g/L, reaction temperature 308 K. The kinetics
of adsorption follows a pseudo second order model and it proceeds via a complex mechanism
including both intra particle transport and surface adsorption. The treatment method not only
uses a waste material from one industry to treat the wastewater generated from the same
industry but also generates silica simultaneously, which is of great economic value.

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* Corresponding author:
Prof. Tamal Mandal,
Department of Chemical Engineering, National Institute of Technology, Durgapur,
Mahatma Gandhi Avenue, Durgapur-713209, West Bengal, India
E-mail: prof.tamalmandal@gmail.com, tamal_mandal@yahoo.com
Mob: +91-9434788078, Fax+91-343-2547375