Ecological Engineering 84 (2015) 2937

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Ecological Engineering
journal homepage: www.elsevier.com/locate/ecoleng

Simultaneous recovery of silica and treatment of rice mill wastewater

using rice husk ash: An economic approach
Anuj Kumar a , Subhajit Singha a , Dalia Dasgupta b , Siddhartha Datta c , Tamal Mandal a,
a
Department of Chemical Engineering, National Institute of Technology, Durgapur, Mahatma Gandhi Avenue, Durgapur 713209, West Bengal, India
b
Department of Biotechnology, National Institute of Technology, Durgapur, Mahatma Gandhi Avenue, Durgapur 713209, West Bengal, India
c
Department of Chemical Engineering, Jadavpur University, Raja S.C. Mallik Road, Kolkata 32, West Bengal, India

a r t i c l e i n f o a b s t r a c t

Article history: An economical, effective and eco-friendly route for utilizing agricultural byproduct rice husk ash (RHA)
Received 12 November 2014 in the treatment of rice mill wastewater has been investigated in the present study. Precious silica was
Received in revised form 17 June 2015 extracted as value added product from RHA and characterized by using SEM, FTIR and XRD. The basic
Accepted 27 July 2015
carbonaceous RHA residual was then used for the abatement of rice mill wastewater as an adsorbent with
Available online 14 August 2015
increasing its pH. Adsorptive process exhibited the percentage reduction of color, lignin, phenol and COD
were 69.38, 73.43, 66.07 and 67.85, respectively from rice mill efuent. The batch adsorption kinetic
Keywords:
study of this basic adsorbent tted well to pseudo second order model. Additional removal of pollution
Rice mill wastewater
Silica
parameters was achieved by employing MgCl2 as coagulant. For this, MgCl2 was added in the wastewater
Rice husk ash at a dose of 12 g/L at pH 12. This enhanced the percentage removal of lignin, color, phenol and COD by
Coagulation 75.21, 75.38, 40.29 and 40.14, respectively. In further study, this coagulation process was augmented
Adsorption with the use of Ca(OH)2 along with MgCl2 . The proposed study was made more economical by recovering
MgCl2 from the coagulation sludge for repeated application. Reusability of MgCl2 was explored for up to
four recycles with the objective of improving the entire work economically viable.
2015 Elsevier B.V. All rights reserved.

1. Introduction proportion of inorganic and organic pollutants (Rajesh et al., 1999).

Cleaner and better environment is a necessity for healthy living
conditions in the present adverse environmental scenario (Pooja
and Anupam, 2012; Yusoff, 2006). For the last couple of decades,
rigorous attention has been concentrated in the various aspects of
pollution control and its subsequent treatment strategies. Genera-
tion of waste efuent is a subject of great concern, which generally
causes deleterious impact on biota owing to its mobile nature.
Without any proper treatment highly contaminated efuent are
often discharged in natural water bodies (Alderson et al., 2015;
Glvez et al., 2003). In this context, rice mill wastewater in par-
ticular is worth mentioning. The demand of rice is increasing for
a rapidly growing human population that includes rice as a major
ingredient of their staple diet. The food and agriculture organiza-
tion (FAO) statistical data suggests that the world rice production
is approximately 697.9 million tons in the year 2010 (Ayswarya
et al., 2012). Rice mill wastewater is toxic that laden with high
Corresponding author.
E-mail addresses: prof.tamalmandal@gmail.com, tamal mandal@yahoo.com
(T. Mandal).
This explains the urges to critically devise scheme toward miti-
gating the intense levels of COD and dark coloration before their
discharge into the environment (Yusoff, 2006).
Besides milling of rice, a conventional rice mill performs diverse
operations like quality control, procurement, storage, drying and
nally, it make sure that it can utilize its byproducts efciently
(Rajesh et al., 1999). Out of several activities, soaking of paddy
for parboiled rice production consumes huge amount of water. It
leads to the discharge of 1.01.2 L waste efuent per kilogram of
processed paddy (Rajesh et al., 1999). Little attention has been paid
about the use of anaerobic methods and other physico-chemical
methods like adsorption, chemical oxidation for the treatment
of rice mill wastewater (Acimovic et al., 2003; Tan et al., 2000).
The real rice mill wastewater being acidic in nature (pH 4.55.5)
requires extensive pH adjustments prior to biological treatments
(Rajesh et al., 1999; Thirugnanasambandham et al., 2013).
Rice mill wastewater is characterized by its yellowish color
and pungent irritating odor. Chemical oxygen demand (COD) con-
tributing components such as phenol, lignin and humic substances
present in the rice mill wastewater impart a potential threat
to the environment (Behera et al., 2010). Thus, there is a ris-
ing concern for rice mill wastewater treatment prior to discharge

http://dx.doi.org/10.1016/j.ecoleng.2015.07.010
0925-8574/ 2015 Elsevier B.V. All rights reserved.
30 A. Kumar et al. / Ecological Engineering 84 (2015) 2937
into the environmental sink. COD can be subdued by the con-
ventional biological treatment however, they suffer limitations
regarding color removal. Thus, there is a need to explore the
novel physico-chemical methods namely adsorption and chemi-
cally aided occulation and precipitation which can concomitantly
remove the color (Rajesh et al., 1999). Magnesium salts have illus-
trated the potential as an effective alternative over conventional
coagulants such as alum, lime, ferric and ferrous sulphate to remove
the pollutants from industrial wastewater, owing to its recoverabil-
ity and reuse in the process (Gao et al., 2007). Nevertheless during
the processing of paddy to produce rice, a large amount of solid
biomass in the form of rice husk is emerged. This usually serves no
benecial purpose (Lim et al., 2012), except in some cases where
the rice husk biomass is extensively used for heating of furnace
resulting in the generation of abundant RHA. It consists of predom-
inantly silica 52% and carbon 45% (Liu et al., 2012). Thus, it can
be concluded that RHA could be an important source of silica that
may nd wide applicability in electronics, ceramic and polymer
industries (An et al., 2010a,b; Liou, 2004; Sun and Gong, 2001).
One of the major motives of the present study is harnessing
the abundantly available RHA for not only production of silica but
also as an adsorbent for the abatement of rice mill wastewater.
Thus use of RHA, another waste byproduct from the same indus-
try, was efciently used for the rice mill wastewater treatment,
is indeed novel. To the best of our knowledge, this has not been
tried before. Moreover, the main concept behind employing MgCl2
as coagulant is primarily due to its ability of being recycled that
can be recovered from the precipitated sludge generated by the
coagulationocculation procedure (Chaudhary et al., 2002). The
occulation process was demonstrated more economical with the
efcient recycle of MgCl2 which is a major coagulating aid (Gao
et al., 2007; Liao and Randtke, 1986).
Thus salient attempts have been performed to develop a promis-
ing economical route (Fig. 1) for simultaneous treatment of rice mill
wastewater treatment while converting abundant waste byprod-
uct RHA into value added silica that was characterized by using
SEM, FTIR and XRD. Reusability of recovered MgCl2 from the coag-
ulation sludge for repeated application explored for turning the
whole process economically attractive.
2. Materials and methods
2.1. Materials and rice mill wastewater
The district of Burdwan in the state of West Bengal, India is one
of the largest producer of paddy in the state that houses many rice
mills which serves the purpose of rice processing from paddy. The
mills generate large volume of wastewater as efuent that are gen-
erally disposed off in the valuable water resources. The rice mill
wastewater and RHA were collected from Laxmishree rice mill,
Alamganj, Burdwan, West Bengal, India. Rice mill wastewater was
stored in a cooler atmosphere at 4 C before using it for experimen-
tal purpose to avoid discrepancy in its physico-chemical properties.
The initial compositions and other physico-chemical properties
of the rice mill wastewater were determined through standard
laboratory procedures. AR grade hydrochloric acid, magnesium
chloride, calcium hydroxide and sodium hydroxide purchased from
Merck, India.
2.2. Extraction of silica
The RHA was rst thoroughly washed with 1 N solution of HCl
to remove dirt and minerals. It was then heated at 90 C with 1 N
NaOH to extract silica as sodium silicate (Kalapathy et al., 2000).
The ltrate was then titrated with HCl until the pH reached to 7.
After that it was centrifuged for separating the silica gel from the
liquor. The formed gel was dried in hot air oven at 70 C for 48 h and
ground to prepare ne powdered silica. After the sodium silicate
separation, the solid leftover from RHA was directly utilized as an
adsorbent for the treatment of wastewater (Della et al., 2002).
The silica extraction follows the following reaction
SiO2 (ash) + 2NaOH Na2 SiO3 + H2 O (1)
Na2 SiO3 + HCl SiO2 + NaCl + H2 O (2)
2.2.1. Characterization of silica
The crystalline structure of silica powder was analyzed by X-ray
diffraction (XRD) (Xpert PRO diffractometer) employing Ni-ltered
Cu K radiation, at a scanning rate of 6 per min with ranging from
20 to 60 (Hamdan et al., 1997).
For the characterization of the exterior surface morphology
of prepared silica, scanning electron microscope (Model: Hitachi
3000) was conducted from central mechanical research institute
(CMERI), Durgapur, India. The sample was layered with gold coat-
ing before the test. Fourier Transform Infrared spectrograph (FTIR,
Model Perkin Elmer FTIR-2000, USA) analysis was executed to iden-
tify the functional groups present on the surface of silica. The
spectra were recorded from 4000 cm1 to 400 cm1 .
2.3. Treatment of rice mill wastewater
2.3.1. Adsorption with basic residue of RHA
The basic solid residue of RHA remained after the silica extrac-
tion was used for the treatment of rice mill wastewater by
adsorption. Experiments were executed in 250 mL Erlenmeyer
asks supplemented with 100 mL of rice mill wastewater, the ini-
tial concentrations of adsorbent were in the range of 550 g/L. The
asks were agitated at 140 rpm in an incubator shaker at 30 C for
2 h. Agitation at high speed was done to eliminate the mass trans-
fer resistance and enabling the control over process adsorption rate
(Liao and Randtke, 1986).
2.3.2. Addition of MgCl2 and NaOH/Ca(OH)2 in adsorbent
pretreated rice mill wastewater
Adsorbent treated rice mill wastewater was turned basic in
nature that can support further action of MgCl2 on addition in
removing color and contaminants from wastewater at alkaline con-
ditions. For this, batch coagulation experiments were carried out in
a jar test apparatus. The pH of the wastewater sample was further
maintained to 12 by addition of 1 N NaOH. MgCl2 dose was added
under agitation at varying concentrations of 212 g/L. Solution was
properly mixed following conventional jar test procedure with ini-
tial rapid mixing at 250 rpm for 2 min, followed by slow agitation
at 60 rpm for 20 min. At the end of agitation, the coagulated sus-
pension was allowed to settle. Subsequently, it was separated from
the wastewater by centrifugation.
Ca(OH)2 not only acts as a coagulant but also increase the pH, is
reported to work better in combination with MgCl2 (Bao-Yu et al.,
2007; Tatsi et al., 2003). This study was performed to nd out
the amplication in removal efciency of using additional Ca(OH)2
along with the MgCl2 . At the beginning of the experiment, the opti-
mum dose of MgCl2 and a dose of Ca(OH)2 varying from 2 to 10 g/L
was also added.
The applicability of the reusable characteristics of MgCl2 was
also studied by using the coagulated solid fractions remaining after
the centrifugation. The same batch coagulation experiments were
performed upto four cycles. At the start of each recycle, optimized
amount of Ca(OH)2 had to be added every time as it is not reusable.
The pH of the nal sample of the treated wastewater was adjusted
using the acidic left over obtained at the acid pretreatment step of
RHA.
 A. Kumar et al. / Ecological Engineering 84 (2015) 2937
Fig. 1. Schematic representation of silica production and simultaneous rice mill wastewater treatment procedure.
A schematic ow diagram was presented in Fig. 1 demonstrating
all the key steps involved in the process of silica production and
simultaneous treatment of rice mill wastewater.
2.4. Analysis
2.4.1. Color determination
For the estimation of color, the samples were centrifuged at
10,000 rpm 30 min for removal of all the suspended matters. The pH
of the supernatant was adjusted to 7.6 by adding 2 M NaOH solution
and the absorbance was measured at OD465 nm using UVvis spec-
trophotometer (Agilent, Model Cary 7000). Color units (CU) were
measured by the following equation (Pala and Tokat, 2002).
A2
CU (PtCo) = 500
A1
where A1 is the absorbance of 500-CU standard platinumcobalt
solution (PtCo; 0.1214) and A2 is the absorbance of the wastewater
samples.
2.4.2. Measurement of lignin
Samples were then analyzed for lignin content using Pearl and
Benson (1990). The pH of the supernatant was made 7.6 using
2 M solution of NaOH. 5 mL sample was mixed with 1 mL of 10%
CH3 COOH and 1 mL of 10% NaNO2 . After elapse of 15 min, 2 mL of
NH4 OH was added to it. The solution was then left for 5 min and
absorbance was measured at 430 nm. The absorbance value was
converted to lignin content (mg/L) using the following formula:
Absorbance
Lignin (mg/L) =
0.000247
31
2.4.3. Determination of COD and phenol content
Using Standard Method of APHA (1976), COD was measured by
reactor digestion process for a COD range of 01500 mg/L using
automatic COD analyser (LoviBond, Germany). Phenolic content
was assayed by the FolinCiocalteu colorimetric method (Lister and
Wilson, 2001). Sample was placed in dark for 1 h incubation at 37 C.
Then, absorbance was taken at 725 nm using gallic acid as standard
and results were expressed in mg/L of phenol.
2.5. Kinetic study
Batch experiments were performed to determine the kinetic
study. For this, 200 mL of rice mill wastewater in 500 mL conical
ask was supplemented with optimal dose of adsorbent and the
(3) experiment was performed at optimum conditions. The ask was
kept at constant speed of 140 rpm in an incubator shaker. After
regular time intervals, 10 mL of the solution from the ask was
withdrawn, centrifuged for removing adsorbent particles and the
resultant supernatant was further analyzed.
3. Results and discussions
3.1. Physico-chemical characterization of rice mill wastewater
The rice mill wastewater characteristics were summarized in
Table 1. The analysis revealed that major harmful constituents were
lignin, phenol and color. The amount of waste concentration was
broadly represented in terms of COD (1708 mg/L). The wastewater
was acidic in nature (pH 5.5). The initial total dissolved solids (TDS)
(4)
of the wastewater were 1578 mg/L.
32 A. Kumar et al. / Ecological Engineering 84 (2015) 2937

Table 1
Characteristics of rice mill wastewater.

Rice mill wastewater Unit Measured value

COD mg/L 1708

TDS mg/L 1578
Salinity mg/L 1.1
Conductivity mS/cm 2.49
pH 4.8
Color Yellowish
Odor Obnoxious
Lignin mg/L 182
Phenol mg/L 16.21
Color CU (PtCo) 2141.68

frequency for the silanol group. A band at 1630 cm1 is assigned to

Fig. 2. The XRD graph of silica showing a broad peak at 22 conrming amorphous
structure of silica.
3.2. Characterization of silica
The morphology of prepared silica was characterized by XRD
(Fig. 2). The XRD spectra displayed a prominent broad peak at 22
(2), typical for amorphous solids (Liu et al., 2012). The appear-
ance of broad peaks conrmed the absence of ordered crystalline
structures (Sun and Gong, 2001).
Infra-red spectrum of the extracted silica was recorded by FTIR
as shown in Fig. 3. Peaks present predominantly at 1095.75 cm1
and 798 cm1 denotes the presence of Si O Si asymmetric stretch-
ing and bending vibrations. The bands at 3437 cm1 is assigned
to the O H stretching while band at 1633 cm1 corresponded
to bending vibrations. The peaks at 1101 cm1 and 804 cm1 are
due to the Si O Si asymmetric and symmetric stretching modes,
respectively. The band centered at 469 cm1 is attributed to the
bending frequency of Si O Si. A high intensity broad band around
3429 cm1 is ascribed to the presence of the O H stretching
the bending vibration of water molecules bound to the silica matrix.
No peak was found between 2800 cm1 and 3000 cm1 . This sig-
nies the absence of original organic compounds from silica after
controlled extraction.
SEM images exhibited (Fig. 4) the presence of sphere like struc-
ture (Li et al., 2011) and also depicted porous nature of the prepared
silica.
3.3. Adsorption with basic residue of RHA
NaOH was added during the extraction of silica from RHA
brought the basic nature in RHA residue. After the successful extrac-
tion of valuable silica, the left over basic residue of RHA was utilized
for the treatment of real wastewater by adsorption. The variation
of COD, color, lignin and phenol present in the wastewater treated
at different concentrations of adsorbent was detailed in the Fig. 5.
On progressive enhancement of the adsorbent dose, surface area
for adsorption also extended that facilitated availability of more
active adsorption site. Fig. 5 reected the signicant adsorption
of wastewater contaminants on increasing the adsorbent doses

Fig. 3. The FTIR results of the extracted silica showing peaks predominantly present at 1095.75 cm1 conrming Si-O-Si symmetry stretching vibration.
 A. Kumar et al. / Ecological Engineering 84 (2015) 2937
Fig. 4. SEM images showing presence of sphere like structure (A) low resolution and (B) high resolution.
Fig. 5. The variation in removal of COD, lignin, color, phenol with different doses of
the adsorbent (initial pH 5.5, contact time = 120 min, initial COD = 1708 g/L, temper-
ature = 30 C, agitation = 140 rpm).
(Daffalla et al., 2012). After a dose of 20 g/L, no further change in
the removal percentage was observed owing to the occupancy of
pores on the surface of the adsorbent and the poor driving force for
mass transfer.
The adsorption capacity of RHA can be improved when they are
activated with activating agents (Daffalla et al., 2012). But activa-
tion process involves high capital cost and long hours duration. A
simple economic process with trouble-free adsorption efciency
was the main focus of this study for the rice mill wastewater treat-
ment. There are advantages of using this basic RHA carbon residue
adsorbent. Firstly, the process became simple, requiring no fur-
ther treatments like washing, carbonization which demands high
energy consumption (Hua et al., 2012). Besides the adsorptive treat-
ment of wastewater, the basic residue of RHA resulted in the pH
increase of the treated wastewater to a range of around 10 as
illustrated in Fig. 6. The increase in pH of the treated wastewa-
ter was attributed to the basic nature of RHA adsorbent. NaOH,
used for silica extraction as sodium silicate from RHA, dwells inside
the adsorbent pores thus responsible for enhancement of pH of
the treated wastewater and facilitating the applicability of MgCl2
as coagulant for further improvement of waste reduction and pH
change. An appreciable reduction in contaminants from wastewa-
ter was achieved by employing NaOH that was used previously
for silica extraction, thus was not wasted but utilized. MgCl2 is
an effective coagulant for contaminants and color removal that
works efciently at high pH (Semerjian and Ayoub, 2003). The raw
33
Fig. 6. The variation in nal pH of the wastewater with different doses of the
adsorbent (initial pH 5.5, contact time = 120 min, initial COD = 1708 g/L, tempera-
ture = 30 C, agitation = 140 rpm).
wastewater being at initial low pH requires high dosage of base to
increase its pH in the working range. Consequently, this adsorption
process serves three important purposes: utilization of discarded
basic residue of RHA, removal of signicant content of contami-
nants and increase in the pH.
3.4. Coagulation with MgCl2
The adsorbent (basic carbon residue of RHA) pretreated rice mill
wastewater having pH 12 was subsequently treated with coagulat-
ing agent of MgCl2 . After the treatment of rice mill wastewater by
the coagulant (MgCl2 ), the percentage reduction in different con-
taminants such as content of lignin, phenol, color and COD are
depicted in Fig. 7. From the gure it is understandable that the
removal efciency was increasing with increase in MgCl2 dose.
Fig. 8 demonstrated the percentage removal of contaminants from
adsorbent treated rice mill wastewater after adding optimal dose
of 10 g/L MgCl2 along with varying doses of Ca(OH)2 .
In combination with MgCl2 , Ca(OH)2 performs better function
of coagulation with simultaneous increase in the pH (Bao-Yu et al.,
2007; Tatsi et al., 2003). The optimum removal competence for
the wastewater is accomplished when the pH of wastewater is
nearly about 12 (Tan et al., 2000). At high pH of 12 or above almost
all the Mg2+ ions are converted into perceptible Mg(OH)2 . It was
observed that Mg(OH)2 precipitate undergoes an adsorptive coag-
ulating mechanism (Leentvaar and Rebhun, 1982).
34 A. Kumar et al. / Ecological Engineering 84 (2015) 2937
Fig. 7. The variation in removal of different components of wastewater with the
varying doses of the MgCl2 (initial COD = 623 mg/L).
Structure of Mg(OH)2 endows large surface area for adsorption
and facilitates positive electrostatic surface charge to perform an
efcient coagulant (Gao et al., 2007). Figs. 7 and 8 also revealed
that the percentage removal of color and lignin was more signif-
icant than that of COD and phenol. The possible reason for this
phenomenon is the adsorptive coagulating mechanism of MgCl2
which is efcient for removal of color. As presented in Table 1, the
initial concentration of lignin was much higher than phenol. There-
fore, higher concentration gradient permits the lignin particles to
migrate rapidly toward MgCl2 sites for having greater mass trans-
fer. This results in the signicant percentage reduction of the lignin
content. (Leentvaar and Rebhun, 1982; Tan et al., 2000)
3.5. Recycle and reusability of MgCl2
One of the most attractive features about coagulating treatment
with MgCl2 was that after wastewater treatment, MgCl2 was recov-
erable and also reusable from the sludge. From Fig. 9, it can be
deduced that MgCl2 was reusable up to two times. Again, it was
observed that from the third cycle the effectiveness of MgCl2 was
declined. The probable reason might be due to the saturation of
the active sites of MgCl2 for trapping contaminants of the rice mill
wastewater. But consistently along with MgCl2 , 2 g/L of Ca(OH)2
was also added. It also observed that the coagulation effectiveness
of MgCl2 decreases with the number of recycling, yet to perform
recycling with the interest purely vested upon economic benet.
Fig. 8. The variation in the removal of different component of wastewater with the
varying doses of the Ca(OH)2 (initial COD = 623 mg/L).
Fig. 9. The percentage removal in different components of the wastewater with
MgCl2 after subsequent reuse (initial COD = 623 mg/L).
Reuse of expensive MgCl2 , if coagulated to its maximum capacity
would certainly save operational cost thus, turning the process eco-
nomically attractive (Semerjian and Ayoub, 2003). The addition of
Ca(OH)2 fullled two crucial purposes, rstly to maintain the high
pH of around 12 and secondly to act as a coagulating aid. The high
pH creates environment for MgCl2 to convert itself into Mg(OH)2
such that it can undergo the adsorptive coagulating mechanism
(Leentvaar and Rebhun, 1982). The high pH of wastewater after
adsorption by RHA and MgCl2 is still high, which can be neutral-
ized by reusing 1 N HCl as shown in Fig. 1 before discharging into
water bodies.
3.6. Kinetic study of the basic RHA residue adsorbent
The batch adsorption kinetic parameters are an important and
mandatory input for the design of further scale up study (Chatterjee
et al., 2012). The adsorption of different rice mill wastewater com-
ponents from liquid phase (wastewater) to solid phase (surface of
basic RHA adsorbent) can be termed as a reversible progression
where equilibrium is reached after a certain time. The amount of
contaminant removed was portrayed by COD elimination from the
wastewater.
Adsorption capacity at time t,
(COD0 CODt )
qt = V (5)
W
where COD0 is the initial COD (mg/L) of rice mill wastewater, CODt
is the COD of wastewater at any time instant, V is the volume
of wastewater (L) and W is the amount of adsorbent applied (g).
Adsorption capacity qt (mg/g) is the indicator of the amount of COD
uptake per gram of the adsorbent.
When the contact time = , the amount of COD remaining in
wastewater is given by CODe (mg/L) and the adsorption capacity is
dened by qe (mg/g).
It was evident from qt vs time (t) plot (Fig. 10) that the COD
uptake by basic RHA carbon residue from rice mill wastewater
through adsorption attained equilibrium within 80 min of the reac-
tion time. So, 80 min could be considered as the optimum contact
time for the adsorptive removal of COD from rice mill wastewater.
The adsorption of contaminant molecules can be termed as a
reversible process. Therefore, pseudo rst order model, pseudo sec-
ond order model and Weber Morris intra particle diffusion model
were used to analyze and tted the kinetic data (Fig. 11).
Pseudo rst order model:
dqt
= kf (qt qe ) (6)
dt
 A. Kumar et al. / Ecological Engineering 84 (2015) 2937 35

In linear form:
t 1 t
= + (10)
qt ks qe 2 qe
where the pseudo rst order rate constant is ks (g/min mg)
Initial rate of adsorption (at t = 0) is dened as h = ks qe 2
(mg/g min)
Weber Morris intra particle diffusion model (for investigating
the possibility of intra-particle diffusion):
qt = kid t 0.5 + I (11)
where kid (mg/g min1/2 ) is the intra particle diffusion rate constant,
and value of I (mg/g) indicates the thickness of the boundary layer.
For investigating, whether surface diffusion was the rate-
controlling step for the adsorption of rice mill wastewater with
Fig. 10. qt vs t graph for the basic residue RHA adsorbent (initial pH 5.5, adsorbent the adsorbent, the kinetic data were further analyzed using Boyd
dose = 20 g/L, initial COD = 1708 g/L, temperature = 30 C, agitation = 140 rpm). kinetic expression (Boyd et al., 1947):
6
after integration and linearization: F = 1 exp (Bt) (12)
2
ln (qe qt ) = ln (qe ) kf t (7) or,

where Pseudo rst order rate constant is kf (min1 ) Bt = 0.4977 ln (1 F) (13)

Pseudo second order model: where F(t) = qt /qe is the fractional attainment of equilibrium at time
dqt t, and Bt is a function of F.
= kf (qt qe )2 (8)
dt The kinetic parameters calculated from the plots (Fig. 11) using
after integration different kinetic models were presented in Table 2a, b and c. The
value of correlation coefcient (R2 ) determines the best tted
tks (qe )2 model and assist in knowing the exact controlling mechanism of
qt = (9)
1 + tks qe the adsorption process.

Fig. 11. (a) Pseudo rst order plot for the adsorbent, (b) pseudo second order plot for adsorbent, (c) Weber Morris intra particle diffusion plot for adsorbent, (d) Boyd plot
for adsorbent (by tting qt vs t data, shown in Fig. 10).
36 A. Kumar et al. / Ecological Engineering 84 (2015) 2937
Table 2
Kinetic parameters for the adsorbent (at optimum conditions).
(a) Pseudo rst order model
qe,exp [mg/g] qe,cal [mg/g]
51.8 15.72
(b) Pseudo second order model
qe,exp [mg/g] qe,cal [mg/g)
51.8 55.56
(c) Weber Morris intra particle diffusion model
kid,1 [mg/(g min0.5 )] I1 [mg/g] R2
6.097 5.757 0.979
3.6.1. Controlling mechanism
The movement of rice mill wastewater contaminants from the
solution into the pores of the adsorbent surface may be inuenced
by one or more of the following governing steps: external or lm
diffusion, pore diffusion, surface diffusion and adsorption reac-
tion on the pore surface. Identication of the rate-controlling step
throughout the adsorption process is only possible by nding the
slowest step engaged among aforementioned steps (Srivastava and
Srivastava, 2009).
Among two kinetic models as shown in Table 2a, b (pseudo rst
order and pseudo second order model) as the R2 value of the pseudo
second order model was closer to unity, it indicates that the pseudo
second order model was the best representative of the kinetic data.
The closer values of qe,exp and qe,cal also justies the fact that the
reaction follows pseudo second order kinetics. The higher value of
initial rate of adsorption (273.37 mg/g min), implied that the effect
of external mass transfer was actually negligible accredited to the
well agitated reaction system.
Intra-particle diffusion controls the adsorption process with
proper mixing, large size of adsorbent particles and high concentra-
tion of contaminants in the wastewater (Aravindhan et al., 2007).
Hence, the intra-particle diffusion may be the slowest step during
rice mill wastewater components adsorption onto the adsorbent.
In this case, Weber Morris plot tted well with the kinetic
data but exhibits multi-linear plots (Fig. 11c). So, it indicates the
impact of two or more steps on the whole adsorption process.
From Fig. 11c it was noticeable that the rst linear portion had
greater slope than the second one. So it could be concluded that
the rst linear portion was indicating dominance of intra-particle
diffusion over the others and its ultimate advent as the rate control-
ling step. Whereas second linear portion suggested the attainment
of the nal equilibrium stage for which the intra-particle diffu-
sion slows down. It might be explained by the scanty presence
of adsorbate in the solution at the end (Crank, 1965). So accord-
ingly kid,1 value was much higher [6.097 mg/(g min0.5 )] than the
kid,2 value [0.524 mg/(g min0.5 )]. Where the I1 and I2 value showed
the increment in the thickness of boundary layer as the system
steps toward equilibrium. So it was noticeable that the adsorption
process occurred through a complex reaction mechanism including
both surface adsorption and intra-particle diffusion.
The multi-linear character of intra-particle diffusion plot ver-
ied the presence of both the pore and surface diffusion. For
predicting the slower step, the kinetic data was further ana-
lyzed using Boyd kinetic expression. The linearity of the graph
of Bt vs t was used to distinguish whether intra-particle diffu-
sion or surface transport controls the adsorption mechanism. It
was observed from the Fig. 11d that the relation between Bt and
t was non-linear (R2 = 0.78) which conrmed that surface trans-
port was not the solitary rate-determining step. So pore and surface
diffusion simultaneously appeared to be the rate-limiting steps in
kf [1/min] R2
0.013 0.780
ks [g/(mg min)] h = ks qe 2 [mg/(g min)] R2
0.103 276.373 0.999
kid,2 [mg/(g min0.5 )] I2 [mg/g] R2
0.524 43.19 0.800
this adsorption process which propagates via complicated mecha-
nism.
4. Conclusion
Modern rice mills yield RHA and rice mill wastewater as harm-
ful byproducts. In the present investigation, a process scheme has
been designed to neutralize the impact of these byproducts. A
value added product pure silica was successfully extracted from
the rice husk ash. The primary adsorptive treatment of the waste-
water was performed with the basic residue of RHA, which was left
after the silica extraction. The wastewater was further sequential
treated by the combined coagulationocculation treatment with
MgCl2 /Ca(OH)2 . The maximum COD reduction obtained wastewa-
ter was 234 mg/L (86% COD reduction) and other contaminants like
color, phenol, lignin, TDS values fall below the permissible dispos-
able limit. This treatment scheme ensures that the properties of the
nal treated wastewater were according to the Indian standards
that could be reused or discharged to the aquatic system safely.
The ndings are very promising to help rapidly growing rice mills in
the practical implementation of the proposed designed economical
approach to deal with the undesirable byproducts.
Acknowledgments
The authors are thankful to the Ministry of Human Resources
and Development (MHRD), Government of India, for nancial sup-
port.
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