Journal of Purity, Utility Reaction and Environment Vol.1 No.

6, August 2012, 308-334

An overview of rice husk applications Article Info

and modification techniques in
Received:15th July 2012
wastewater treatment Accepted: 25th July 2012
Published online: 1st August 2012

Sadon, F. N., Ahmmed Saadi Ibrahem*, Kamariah

Nor Ismail

Chemical Engineering Faculty, Universiti Teknologi MARA,

40450 Shah Alam, Selangor, Malaysia.

[email protected]

ISSN: 2232-1179 © 2012 Design for Scientific Renaissance All rights reserved

ABSTRACT
Activated carbon is one of the most common adsorbent used for adsorption and absorption processes for
removing various types of organic and inorganic materials. Thus, it has been revealed that, rice husk
which is a low price agricultural product that can be used as adsorbent to adsorb water pollutants mainly
heavy metals and textile dyes from wastewater. Heavy metals that being deliberated were Fe, Mn, Cd, Pb,
Zn, Cu, and Cr(VI). Many types of textile dyes have been studied such as Direct F. Scarlet, Everdirect
Orange – 3GL, Direct Blue – 67, Direct Red – 31, Direct Orange – 26, and Crystal Violet. Moreover,
other removal studies include removal of surfactants, phenol, and parquet. In this work, previous and
current studies of using rice husk as adsorbent including modification techniques have been listed to
provide information on rice husk as potential adsorbents in wastewater treatment.

Keywords: Rice husk, Adsorption, Heavy metals, Dyes, Adsorbents

1. Introduction

Industrialization activities for nation development contribute to global environmental

deterioration as these activities caused depletion and degradation of natural resources and
biodiversity. In addition, these industrial activities indirectly overload water body with thousands
of water pollutant and subsequently polluting the environment. Major water pollutants are heavy
metals, textile dyes as well as other organic and inorganic compounds. Heavy metals such as Iron
(Fe), Manganese (Mn), Zinc (Zn), etc, have some common characteristics which are analysis to
 Journal of Purity, Utility Reaction and Environment Vol.1 No.6, August 2012, 308-334

biological degradation, do not degrade into harmless end products, make a sensitivity and stones
inside the urea system, toxic to many life forms, and accumulate in living of tissues cells which
then to be appropriate concentrated throughout the food chain. On the other hand, significant
errors occurred through the manufacture and processing of coloured dyes also contribute to
serious water pollution problems as these lost chemicals are illegally discharged to water body
such as rivers. This is because; some dyes and their degradation products are caused highly
carcinogenic and toxic in nature (Mohamed, 2004). For instance, Abdel Wahab et al. (2005),
pointed out that, Direct Red 23 (DR-23) doses will not allow sunlight to pass through and just
like that affects the photosynthesis of aquatic process. Water contaminations by dyes are usually
reported from industrial effluents such as textile, tannery, paper, soap, cosmetics, polishes, as
well as wax. Anionic and non – ionic surfactants in sewage, chemical plants effluents as well as
raw domestic wastewater poses the same environmental problems as heavy metal and textile dyes
did. Accordingly, it has been mentioned by Adachi et al. (2001), that the toxicity of linear
sodium alkyl benzene sulfonate (LABS) to aquatic organisms is of concern when concentrations
exceed 0.1 mg/L. Besides that, recent evidence also proved that, alkyl phenol ethoxylates (APE)
breakdown products which are weakly estrogenic has intensified concern over environmental and
human health effects. It also has been noted that, surfactants are already used in high volumes in
detergents, household cleaning products and other uses. Besides that, surfactants are also utilized
by oil, textile, food and mining industries. The characteristics of other identified water pollutants
such as phenol and paraquat also similar with previously described water pollutant, in which they
are toxic due to their carcinogenicity. It has been revealed that, phenol is considered as notorious
contaminant in water environment as it is designated as main important of pollutant by the US
Environmental Protection Agency (USEPA) (Nayak and Singh, 2007). According to Busca et
al., (2008), the most important sources of phenol pollution are the wastewater from the iron –
steel, coke, etc. On the other hand, paraquat is extensively useful as herbicide, primarily for
wood and grass. It has been identified that, even a small amount of paraquat can cause severe
physiological damage. This hazardous compound is found in agricultural wastewater and the
blood of human bodies.
Accordingly, examples of the critical issues in history caused by wastewater problem
particularly heavy metal contamination were Itai – Itai and Minamata diseases. In relation to
Malaysia scenario, most of rivers and seas are contaminated with wastewater from agro-based
and manufacturing industries, as reported by Department of Environment Malaysia (2011). In
Malaysia, some regulations have been promulgated under the Environmental Quality Act (EQA)
(1974) for environmental control of effluent discharge. The most important regulation is known
as Environmental Quality (Industrial Effluents) Regulations (2009), amendment on EQA 1974
which was gazetted on 12 October 2009 by the Minister of Natural Resources. The
previous Environmental Quality (Industrial Effluent) Regulations (1979) are annulled. It is
therefore an objective to remove such water pollutants from wastewater in order to comply with
environmental regulations as well as for the sake of environmental preservation and human
health and safety as well. Thus, various treatment techniques have been employed to achieve
such objective such as ion exchange, filtration, membrane separation, flocculation, chemical
precipitation, activated sludge, trickling filter and adsorption (Tarley and Arruda, 2003).
Methods that used for removing phenol from wastewater include adsorption on activated carbon,
microbial degradation, incineration, chemical oxidation, deep – well injection, solvent extraction

309
 Journal of Purity, Utility Reaction and Environment Vol.1 No.6, August 2012, 308-334

and irradiation. Among such treatment methods, adsorption is determined to be the most
desirable and promising treatment as well as highly effective technology to remove water
pollutants from wastewater due to its simple design and produce sludge free environment. In
terms of economical aspects, it consumes low initial investment and requires small installation
space. Activated carbon is the most common adsorbent used for removing various types of heavy
metals. Its extended surface area and micro - porous structure which increases the percentage of
adsorption capacity area that have been made activated carbon is the most active adsorbent in this
system. However, it has been identified that, activated carbon suffers from major drawbacks
which are not practical in small and medium industries as well as expensive materials.
Manufacturing cost of the process will be grown. Other than that, it has been identified that, 10 –
15% loss occurred during regeneration of activated carbon adsorbent (Hashem, 2007). In view of
that situation, it is a need to seek for other low – cost and natural materials which have strong
capability to adsorb heavy metals in wastewater streams as mentioned by Tengerdy and Szakacs
(2007). Their sorption characteristics are derived from their constituent polymers which are
cellulose, hemicelluloses, as well as lignin. An adsorbent can be termed as a low - cost adsorbent
if it requires little processing, is provide in nature, or is a by-product of waste material.
Generally, cellulosic surface of plant biomass be partially negative charged in water, and
therefore possess columbic interaction with cationic species (i.e. heavy metals) in water (McKay
et al., 1987). The high binding abilities of cationic species on the adsorbents are mainly the
results of columbic interactions (Weixing et al., 1998). Thus, due to their strong properties and
characteristics of sorption, a range of agricultural products are used as adsorbent for removal of
various organic and inorganic compounds. The removal of water pollutants by agricultural waste
and by products of chemical plants have been extensively reviewed by Khan et al. (2004), Kumar
(2006), as well as Mtui (2009). For instance, Gong et al. (2009) indicated that, esterified wheat
straw (EWS) can be used to adsorb crystal violet (CV) as well as methylene blue (MB). They
have characterized that, the maximum sorption capacity of EWS for MB and CV were 129.87
and 112.36 mg/g, respectively. The equilibriums of dye sorption were respectively reached about
13 and 18 h for MB and CV. An adsorption study on coconut husk to remove Cu (II), Fe (III) and
Pb (II) ions from mono-component simulated waste effluent was also done by Abdulrasaq and
Basiru (2010). They have been revealed that, the adsorption of Pb (II) was calculated to be
maximum (94%±3.2) at pH 5, metal ion concentration of 30 ppm, temperature of 100 °C and
contact time of 30 min. The adsorption of Cu (II) and Fe (III) were maximum (92%±2.8 and
94%±1.4) at pH range of 5 - 7, metal ion concentration of 50 ppm, temperature of 50°C but at
different times of 30 and 90 min respectively. Compared to conventional adsorbent, this type of
natural adsorbents pose a lot of advantages such as inexpensive, effective, readily and local
available, technical feasibility, as well as engineering applicability. On top of that, since they are
low – cost adsorbents, the utilization of agricultural residues can simultaneously improve
profitability of particular industry, and consequently conserve natural environment. Moreover,
the usage of natural adsorbents can also contribute to the worldwide sustainable development.
Accordingly, one of the most possible waste materials in the world as reported in the literature is
rice husk, due to its high availability (Chuah et al., 2005). It has been revealed that, rice is
represented the second largest product cereal in the world. Asia is representing the biggest rice
production reaches about 90% of the world's production and consumption of rice. On the other
hand, rice is also a strategically important industry in Malaysia, due to the suitability of

310
 Journal of Purity, Utility Reaction and Environment Vol.1 No.6, August 2012, 308-334

temperature regime and rainfall distribution in the country. From the statistical data of the
Malaysia Ministry of Agriculture and Agro-Based Industries (2011), annual production of rice in
Malaysia was observed to be increased significantly between 2.35 to 2.51 x 10 6 Mt/year from
2008 to 2009. The rice production in Malaysia was then reported to be increased year by year
from 2009 to 2011. According to Mansaray and Ghaly (1998), rice husk is responsible for
approximately 20 - 25% of the total grain weight depending on the variety. Therefore, it can be
approximated that, 5.33 x 105 and 5.09 x 106 Mt of rice husks were produced in 2011 for
Malaysia and 2009 for all over the world, respectively. Therefore, the potential of rice husk
application for wastewater treatment should be highlighted due to its special and exceptional
features as adsorbent. Specifically, rice husk has granular structure as well as insoluble in water.
Moreover, it also has remarkable chemical stability and high mechanical strength. The most
significant characteristics of rice husk is regarding to its local availability at almost no cost (El -
Azab, 1992). Hence, there is no need to regenerated spent rice husk due to its low production
costs. Moreover, rice husk is also tough and woody in nature, as well as poses abrasive inherent
resistance behaviour. Other than that, rice husk also rich of silica – cellulose structural
arrangement, which make it as a good adsorbent, compared to other agricultural wastes. This
review will focus on nature of adsorption studies for heavy metals, dyes, surfactants, and organic
compounds removal using rice husk. It also includes the knowledge facts on modification
techniques of rice husk that are commonly employed by previous researchers.

Table 1 Chemical Properties of Rice Husk (Rahman et al., 1997)

COMPOSITION PERCENT (%)
Cellulose 32.24
Hemicellulose 21.34
Lignin 21.44
Extractives 1.82
Water 8.11
Mineral ash 15.05

2. Anatomy and propertied of rice husk

Rice husk has 8 – 10 mm long, 2.0 – 2.5 mm wide, and 0.1 – 0.15 mm thick (Daifullah et al.,
2002). Furthermore, chemical properties of rice husk are more explained by Rahman et al.
(1997) and it is tabulated in Table 1. Moreover, Table 2 shows the reported values of rice husk
physical properties.

311
 Journal of Purity, Utility Reaction and Environment Vol.1 No.6, August 2012, 308-334

Table 2 Physical Properties of Rice Husk (Malik, 2003).

CHARACTERISTICS VALUES
Bulk density (g/ml) 0.73
Solid density (g/ml) 1.5
Moisture content (%) 6.62
Ash Content (%) 45.97
Particle size (mesh) 200 – 16
Surface area (m2/g) 272.5
Surface acidity (meq/gm) 0.1
Surface basicity (meq/gm) 0.45

3. Rice husk as adsorbent for heavy metal removal

Rice husk used as adsorbent in removing heavy metals like Fe, Mn, Zn, Cu, Cd, and Pb.
Removal efficiencies for each metal ion are summarized in Table 3.

Table 3 Reported Heavy Metals Removal Efficiencies by Rice Husk

HEAVY METAL RESEARCHERS REMOVAL

EFFECIENCY (%)
Fe Daifullah et al., 2002 100
Chockalingam and Subramaniam, 2005 99 (Fe ), 98 (Fe2+)
3+

Mn Daifullah et al., 2002 100

Zn Daifullah et al., 2002 100
Chockalingam and Subramaniam, 2005 98
Cu Daifullah et al., 2002 100
Chockalingam and Subramaniam, 2005 95
Cd Daifullah et al., 2002 100
Pb Daifullah et al., 2002 100
Aluyor et al., 2009
Cr(VI) Wongjunda and Saueprasearsit, 2010 59.12 (Rice husk ash),
81.39 (Modified rice
husk ash)

4. Rice husk as adsorbent for textile dyes removal

Rice husk used as adsorbent in removing variety types of dyes such as Direct F. Scarlet,
Indigo Carmine, Congo Red, Everdirect Orange – 3GL, Direct Blue – 67, Direct Red – 31, Direct
Orange – 26 as well as Crystal Violet dyes. The maximum of sorption capacity of dyes from the
selected previous works are summarized in Table 4.

312
 Journal of Purity, Utility Reaction and Environment Vol.1 No.6, August 2012, 308-334

Table 4 Reported Dyes Adsorption Capacities for Rice Husk

TYPE OF DYE RESEARCHERS CAPACITIES (mg/g)

Direct F. Scarlet Abdel Wahab et al., 2005 13.00
Everdirect Orange – 3GL Safa and Bhatti, 2011 29.98
Direct Blue – 67 Safa and Bhatti, 2011 37.92
Direct Red – 31 Safa and Bhatti, 2011 57.88
Direct Orange – 26 Safa and Bhatti, 2011 36.14
Crystal Violet Chakraborty et al., 2011 43.00

5. Rice husk as adsorbent for other water pollutants removal

Apart from removal of heavy metals and dyes of rice husk capability to adsorb other types of
water pollutants have also been proved by previous researches. For instance, Mahvi et al. (2004),
have investigated the removal of phenol in aqueous systems by using rice husk. Moreover,
Hosseinnia et al., (2007) have studied the adsorption of anionic surfactants (Linear sodium alkyl
benzene sulfonate – LABS 50% and Alkyl ether sulphate – AES 70%) as well as non – ionic
surfactants (Nonyl phenol ethoxylate – NPE). The studies were continued by Hsu and Pan
(2007), where they carried out experiment to adsorb paraquat by using also rice husk as derived
material for the adsorbents. Furthermore, a study was also done by Daffalla et al., (2010) on the
description of adsorbent improved from rice husk by investigating the effect of surface functional
group on phenol adsorption. The maximum of sorption capacity of different types of water
pollutants from the selected previous works are summarized in Table 5.

Table 5 Reported Other Water Pollutants Adsorption Capacities for Rice Husk.

WATER POLLUTANTS RESEARCHERS CAPACITIES (mg/g)

Surfactants: Hosseinnia et al., 2007
(a) LABS 50% 93*
(b) AES 70% 90*
(c) NPE 70*
Phenol Mahvi et al., 2004 0.886
Daffalla et al., 2010
Paraquat Hsu and Pan,2007 317.7 (modified rice
husk)
*Values correspond to removal efficiency in %.

6. Experimental modes of previous studies

Accordingly, one of the most important factor that distinguish the studies of rice husk as
adsorbent for wastewater treatment among researchers is the mode of the studies, whether in
batch or continuous mode.

313
 Journal of Purity, Utility Reaction and Environment Vol.1 No.6, August 2012, 308-334

6.1 Batch studies using rice husk as adsorbent

In their studies were focusing on adsorption and desorption processes, in which kinetics,
mechanisms, isotherms and thermodynamics are comprehensively investigated. Apart from that,
some of the studies also emphasizing on the effects of operating parameters towards adsorption
efficiency of rice husk such as adsorbent amount, contact time, initial pH as well as initial water
pollutant concentration.

6.2 Adsorption kinetics

Theoretically, the analysis of adsorption kinetics can be modelled by various kinetic models
principally first order, pseudo second order and Elovich kinetic models. For instance, Lakshmi et
al. (2008) have been investigated that, the sorption can be more suitable by the pseudo – second
– order kinetic model than the first – order kinetic model for the adsorption of Indigo Carmine
(IC) dye onto rice husk ash. Otherwise, the studies made by Ong et al., (2009) also spotted that,
the experimental data of Congo Red dye removal by ethylenediamine – modified rice hulls
showed a better subjugation with the pseudo second order model than the pseudo- first order
model, suggesting that the rate limiting step may be chemical sorption or chemisorption
involving valency forces through sharing or exchange of electron between sorbent and sorbate.
Recently, the same results also observed by Safa and Bhatti (2011). They successfully identified
that, both pseudo second order reaction and Elovich kinetic model produced suitable fitness to all
types of biomasses showing chemisorptions nature of biosorptions for removing Everdirect
Orange – 3GL and Direct Blue – 67 dyes. Moreover, Chakraborty et al., (2011) revealed that, the
study of Crystal Violet adsorption from aqueous solution onto NaOH – modified rice husk
followed the pseudo second order kinetic model. It has been noted that, pseudo – second – order
is worked well for textile dyes removal from wastewater. In the case of other removal studies,
Mahvi et al., (2004) pointed out that, first order rate expression showed a better compliance for
adsorption of phenol using raw rice husk ash. These results are in conformity with the study
made by Abdel Wahab et al., (2005), where the best model to express the adsorption activity of
citric acid – modified rice husk is first order rate expression. The significance of adsorption
kinetic study is such determining step of the adsorption systems to be determined, whether
chemisorptions (Ong et al. (2009), Safa and Bhatti (2011)) or particle diffusions (Abdel Wahab
et al., 2005).

6.3 Adsorption isotherms

The equilibrium between the concentration of a wastewater and its concentration on the rice
husk adsorbent resembles somewhat the equilibrium solubility of a gas in a liquid. These data are
plotted as adsorption isotherms. The concentration of pollutant in the rice husk adsorbent is
expressed as q (kg adsorbate (solute)/ kg adsorbent (solid)), and in the concentration of pollutant
in fluid as c (kg adsorbate /m3 fluid). The Freundlich isotherm equation, which is empirical, often
approximates data for many physical adsorption systems and is particular useful liquids:

q  Kc n ........................................(1)

314
 Journal of Purity, Utility Reaction and Environment Vol.1 No.6, August 2012, 308-334

where K and n are constants and must be determined experimentally. If a log – log plot is made
for q versus c, the slope is dimensionless exponent n. The dimensions of K depend on the value
of n.

The Langmuir isotherm on the other hand, has a theoretical basis and is given by the
following, where qo and K are empirical constants:

q0 c
q
K c .........................(2)

Where qo is kg adsorbate /kg solid and c is kg/m3. The equation was derived by assuming that
there are only a fixed number of active sites obtainable for adsorption, that only a monolayer is
formed, and the adsorption is reversible and reaches an equilibrium condition. Therefore, it has
been noted that, adsorption isotherms are of essential importance for the attributive of how
molecules of pollutant interact with the rice husk surface. Accordingly, Table 6 and 7 shows the
reported Langmuir and Freundlich isotherms parameters from previous studies of using rice husk
as adsorbent for wastewater treatment. It has been revealed that, the Langmuir model fitted most
of the experimental results more neatly compare to Freundlich model. Accordance with the
results obtained by Hsu and Pan (2007), where they identified that, the Langmuir model fitted the
experimental results more painstakingly than Freundlich model. The same outcome also reported
by Aluyor et al., (2009) and Wongjunda and Saueprasearsit (2010).

315
 Journal of Purity, Utility Reaction and Environment Vol.1 No.6, August 2012, 308-334

Table 6 Reported Langmuir Isotherms from Previous Batch Studies Using Rice Husk as
Adsorbent

WATER TYPES OF RICE MAXIMUM CONSTANT R - VALUE RESEARCHERS

POLLUTANTS HUSK (RH) SORPTION (L/mg)
CAPACITY AT
EQUILIBRIUM
(mg/g)
Direct F. Scarlet Unmodified 2.415 0.17 0.99 Abdel Wahab et
al., 2005
Citric acid – 4.35 0.14 0.97
modified RH
Paraquat methacrylic acid – 317.7 - - Hsu and Pan, 2007
modified RH
Pb hydrogen peroxide 11.88 -4.07 0.979 Aluyor et al., 2009
- modified RH
Congo Red dye Unmodified 13.26 0.0187 0.9663 Ong et al., 2009
ethylenediamine – 26.39 0.4427 0.9980
modified RH

Cr (VI) rice husk ash 0.49 12.09 0.9962 Wongjunda and

Saueprasearsit,
2010
sodium hydroxide - 0.84 2.55 0.9947
modified rice husk
ash
Everdirect Unmodified 28.41 0.061 0.986 Safa and Bhatti,
Orange – 3GL 2011
dye
CMC Immobilized 21.74 0.0333 0.975
PVA-alginate 8.77 0.036 0.997
immobilized
HCl – modified 30.96 0.201 0.999
Direct Blue – 67 Unmodified 52.63 0.016 0.989 Safa and Bhatti,
dye 2011
CMC Immobilized 23.42 0.029 0.990
PVA-alginate 3.022 0.039 0.992
immobilized
HCl – modified 71.43 0.075 0.989
.

316
 Journal of Purity, Utility Reaction and Environment Vol.1 No.6, August 2012, 308-334

Table 7 Reported Freundlich Isotherms from Previous Batch Studies Using Rice Husk as
Adsorbent

WATER TYPES OF ADSORPTION ADSORPTION RESEARCHERS

POLLUTANTS RICE HUSK INTENSITY, 1/n CAPACITY, K
(RH) (mol/g)
Phenol Unmodified 0.195 0.00092 Mahvi et al., 2004
RHA 0.57 0.00092
Indigo Carmine RHA 0.4453 1.6018 Lakshmi et al.,
(IC) dye 2008
Crystal Violet NaOH – 0.1554 - Chakraborty et al.,
modified rice 2011
husk

One utility of the Langmuir equation in its linear form is that the maximum adsorption can be
estimated from the regression. This parameter and the equilibrium water pollutant concentrations
are useful in describing the adsorbent capacity. According to Abdel Wahab et al., (2005), the
high fitness of the Langmuir model for the adsorption process of rice husk indicates the
monolayer concealment of water pollutant on the outer surface of rice husk, in which the
adsorption occurs uniformly on the active part of the surface. This is represented by the value of
maximum sorption capacity at equilibrium. Other than that, Langmuir isotherm also provide
information on adsorption energy by the value of Langmuir constants, K. Besides that, modified
rice husk is also observed to have higher adsorption capacity compare to the unmodified rice
husk in the removal of water pollutant from wastewater. Reported was done by Ong et al.,
(2009), where the maximum adsorption capacity for Congo Red dye was enhanced by 2-fold as
compared to unmodified rice husk. On the other hand, for Freundlich isotherms, the higher value
of the Freundlich constant (K) showed easy uptake of water pollutant from wastewater.
Furthermore, higher the value of 1/n, the higher will be the affinity between the water pollutant,
rice husk, and the heterogeneity of the adsorbent sites. The 1/n value indicates the proportional
distribution of energy sites and depends on the nature and strength of the adsorption process; for
example, 1/n = 0.90 refers to the fact that 90% of the active adsorption sites have equal energy
level (Lakshmi et al., 2008).

6.4 Adsorption thermodynamics

Thermodynamic behaviour of adsorption of water pollutant from wastewater on rice husk
surface was evaluated by the thermodynamic parameters – Gibbs free energy change ( G ),
enthalpy ( H  ) and entropy ( S  ). These parameters can be evaluated using the following
equations (Anirudhan and Radhakrishnan, 2008):

G   RT ln KC ........................................(3)
Ca
KC  ....................................... (4)
Ce
G  H   TS  ........................................ (5)

317
 Journal of Purity, Utility Reaction and Environment Vol.1 No.6, August 2012, 308-334

Where Ca is an equilibrium solute concentration on the adsorbent (mg/ L), Ce is an

equilibrium solute concentration in wastewater (mg/ L), R is the gas constant (8.314 J/molK)
and T is the absolute temperature (K). A plot of G versus T will be linear with the slope and
intercept giving the values of H  and S  .In sight of that situation, it can be concluded that, the
negative values of ΔG° indicate the feasibility and spontaneity of the adsorption system, as
reported by Lakshmi et al. (2008), Chakraborty et al. (2011) and Safa and Bhatti (2011).
According to Chakraborty et al., (2011), increase in value of ΔG° with increase in temperature
suggests that lower temperature makes the adsorption easier. Moreover, Safa and Bhatti (2011)
identified that, adsorption of direct dyes onto rice husk were spontaneous at high temperature.
However, at lower temperature, the adsorption processes were observed to be not spontaneous
due to positive ΔG° values. Besides that, Lakshmi et al., (2008) also revealed that, the adsorption
process in the solid liquid system is a combination of two processes: (a) the desorption of the
molecules of solvent (water) previously adsorbed, and (b) the adsorption of adsorbate species.
The Indigo Carmine (IC) dye molecules have to displace more than one water molecule for their
adsorption and this result in the endothermicity of the adsorption process. Same results were
obtained by Safa and Bhatti (2011), where they concluded that, the positive value of ΔH°
indicated that the biosorption of Ever direct Orange-3GL and Direct Blue-67 on the rice husk
was endothermic in nature. In contrast, Chakraborty (2011) found that, the adsorption
phenomenon is exothermic in nature due to negative value of ΔH°. Moreover, the positive value
of ΔS° as studied by Lakshmi et al., (2008) and Safa and Bhatti (2011) showed the increase in
randomness at the solid/liquid interface and consider some structural changes in the adsorbate
and adsorbent as well as a good affinity of biomass towards water pollutant in wastewater. Also,
positive ΔS° value corresponds to an increase in the degree of freedom of the adsorbed species.

6.5 Effect of adsorbent amount

The investigation of the effect of adsorbent amount on adsorption capacity of rice husk is also
part of batch studies, as was done by Mahvi et al., (2004). They indicated that, the removal
efficiency of phenol by rice husk and rice husk ash increased up to best dosage beyond which the
removal efficiency is negligible. Besides that, Abdel Wahab et al., (2005) also identified that, the
increase in the citric acid – modified rice husk concentration resulted in an increase of Direct F.
Scarlet dye removal capacity, which then may be attributed to the increase of biomass
of rice husk which gives more surface area for a d sorption of the dye molecule on the
surface. Lakshmi et al., (2008) have been investigated that, the Indigo Carmine (IC) dye removal
onto rice husk ash increases up to a certain limit and then it stills almost constant. Optimum
adsorbent dosage was found to be 10g/L. The results obtained by Wongjunda and Saueprasearsit
(2010) also demonstrated similar observation. They have reported that, increase the adsorbent
dose (rice husk ash and sodium hydroxide - modified rice husk ash) resulted in the increase
amount of adsorbed Cr (VI). Recently, the results obtained by Chakraborty et al., (2011) also in
accordance with previous studies. They observed that, the adsorption efficiency of crystal
violet by sodium hydroxide – modified rice husk increased from 96.78% to 98.17%
as the adsorbent dose increased from 0.5 to 1 g. Safa and Bhatti (2011) noted that,
adsorption efficiency of Direct Red – 31 and Direct Orange – 26 textile dyes removal from
aqueous solution by rice husk decreases with increase in the adsorbent dose. The increase in the

318
 Journal of Purity, Utility Reaction and Environment Vol.1 No.6, August 2012, 308-334

adsorbent dose resulted increase in the amount of adsorbed pollutant, due to the increase in the
number of available adsorption sites. On the other side, the adsorption density amount adsorbed
per unit mass may be decreased when adsorbent dose increased due to unsaturation of adsorption
sites through the adsorption process. Another reason is because of the particle interaction, such as
aggregation, resulting from high adsorbent dose. Such aggregation would lead to decrease in total
surface area of the adsorbent and an increase in diffusion path length.

6.6 Effect of contact time

The effect of contact time on the adsorption efficiency of rice husk is also comprehensively
investigated by researchers. This is because; the contact time is the most crucial parameter in
batch studies. Thus, Hosseinnia et al., (2007) noted that, there was no great difference in the
adsorption values of Nonyl phenol ethoxylate (NPE) with the time changes. However, desorption
was observed after 5 hours. On top of that, Ong et al., (2009) pointed out that, initial adsorption
of Congo Red dye by ethylenediamine – modified rice hulls was rapid in the first 60 min
followed by a slower process. The same observation was then demonstrated by Wongjunda and
Saueprasearsit (2010). They identified that, the rate of Cr(VI) adsorption was found to be
gradually increase in the period time of 0-180 min and thereafter, the removal of Cr(VI) ions is
almost constant. Through the studies made by them, it has been revealed that, during the initial
stage of adsorption, a large number of vacant surface sites were available for adsorption. After an
error of some time, the remaining vacant surface sites have difficulty in becoming occupied
because of repulsive forces between the adsorbate molecules on the solid surface and in the bulk
phase. Besides that, another good reason is such that, the rice husk surface is already saturated
with water pollutant solute during the initial stage of adsorption. On the other hand, in parallel to
determination of optimum contact time, this study can also provide information on the
equilibrium time of the adsorption processes. Theoretically, equilibrium time is the time when
the equilibrium occurred between the water pollutant in solution of wastewater and in the
adsorbed state. Table 8 shows the reported equilibrium time from previous batch researches using
rice husk as adsorbent. Accordingly, it is identified that, modified rice husk surface would
require less equilibrium compared to rice husk without modification treatment.
It is known that, the adsorption process is dependent on the pH of the solution. Mahvi et al.,
(2004) revealed that, the adsorbed amount of phenol by rice husk and rice husk ash decreases
with increasing the pH value. This is because, phenol which is a weak acid (pKa=10), will be
adsorbed to a lesser range at higher pH values due to the repulsive force prevailing at higher pH
value. Besides that, Hosseinnia et al., (2007) also indicates that, a d s o r p t i o n values increase
in lower pH. This is true as the results revealed that, 93% a t pH 2 of a 100-mL solution
containing 1 mg of LABS (R-C6H4-SO3H) and 2 g of husks. On the other hand, the
adsorption value was less than 11% at pH 6 in the same condition. This is due to the
weak basicity of LABS; its acidic form (R-C6H4-SO3H) is predominant in acidic solutions (i.e. in
the presence of H3O+) and better adsorbed by rice husk. On the other hand, pH changes were of
no great importance in the adsorption amounts for NPE removal because of the nonionic nature
of NPE. Lakshmi et al., (2008) identified that, the Indigo Carmine dye removal by rice husk ash
is maximum and constant for pH greater than or equal to 4.0. The same results also obtained by
Wongjunda and Saueprasearsit (2010). They reported that the chromium (VI) adsorption by rice
husk ash and sodium hydroxide - modified rice husk ash decreased with an increase of pH. The

319
 Journal of Purity, Utility Reaction and Environment Vol.1 No.6, August 2012, 308-334

maximum value of chromium (VI) retention occurred approximately at pH 2. At lower pH, the
adsorbent is positively charged due to protonation and dichromate ion exists as anion leading to
an electrostatic attraction between them. As pH is increases, deprotonation starts and thereby
results in decrease of adsorption capacity. Safa and Bhatti (2011) also identified the maximum
adsorption was recorded at lower pH values (less than 3). However, Chakraborty et al., (2011)
observed that, the percentage removal of Crystal Violet (CV) by sodium hydroxide – treated rice
husk increases with the increase in pH of the dye solution, appreciably up to pH 7.0. Increase in
pH from 7.0 to 10.0, the percentage CV removal increases but the difference in the percentage
increase is not very significant. In terms of the effect of initial water pollutants concentration, the
adsorption value trend varied among studies. Abdel Wahab et al., (2005) reported that, the
amount of adsorbed dye increased with increase in concentration and remained about constant
after equilibrium time. Besides that, Hosseinnia et al., (2007) studied that the adsorption values
trends varied to the initial concentration of surfactants. The adsorption value was considerably
increased in 10 mg/L while decreased in 100 mg/L for acrylic esters (AES) solution. On the other
hand, the adsorption value was considerably decreased with an increase in the concentration and
no adsorption was observed in the 80 mg/L solution of normal polyethylene (NPE). However,
Ong et al., (2009) identified that, the percentage uptake of Congo Red dye by ethylenediamine –
modified rice hulls decrease with the increase in Congo Red dye initial concentration. Then,
Wongjunda and Saueprasearsit (2010) have been reported that, the suitable initial Cr (VI)
concentration is 10mg/L for removal by rice husk ash and sodium hydroxide - modified rice husk
ash. At higher concentrations, the available sites of adsorption become decreased and hence the
percentage adsorption of Cr (VI) decreases.

320
 Journal of Purity, Utility Reaction and Environment Vol.1 No.6, August 2012, 308-334

Table 8 Reported Equilibrium Time from Previous Batch Studies Using Rice Husk as Adsorbent

WATER TYPES OF RICE EQUILIBRIUM RESEARCHERS

POLLUTANTS HUSK TIME (hr)
Phenol Unmodified 6 Mahvi et al., 2004
Rice husk ash 3
Direct F. Scarlet Unmodified 2 Abdel Wahab et al., 2005
dye
Citric acid – modified 1.5
rice husk
LABS Unmodified 3 Hosseinnia et al., 2007
NPE Unmodified 5 Hosseinnia et al., 2007
Indigo Carmine dye Rice husk ash 8 Lakshmi et al., 2008
Congo Red dye Ethylenediamine – 4 Ong et al., 2009
modified rice hulls
Cr(VI) Rice husk ash and 3 Wongjunda and
sodium hydroxide - Saueprasearsit, 2010
modified rice husk ash
Everdirect Orange – Unmodified and 3 Safa and Bhatti, 2011
3GL Hydrochloric acid –
modified rice husk
CMC immobilized rice 5
husk
PVA – alginate 6
immobilized rice husk
Direct Blue – 67 Unmodified 4 Safa and Bhatti, 2011
CMC immobilized rice 6
husk and PVA – alginate
immobilized rice husk

Hydrochloric acid – 3
modified rice husk
Crystal Violet Sodium hydroxide - 1.5 Chakraborty et al., 2011
modified rice husk

7. Continuous studies using Rice Husk as adsorbent

It has been identified that, only a few studies have been represented under the continuous
flow (column) conditions, compared to batch conditions. Accordingly, studies that have been
carried out under continuous mode only reported by Kumar and Bandyopadhyay (2005),
Hosseinnia et al. (2007) and Ong et al. (2009). Major themes that are usually studied under
continuous system are adsorption column behaviour and design, column regeneration and reuse
as well as Bed – Depth – Service – Time (BDST) model.

321
 Journal of Purity, Utility Reaction and Environment Vol.1 No.6, August 2012, 308-334

7.1 Adsorption column behavior

Adsorption column behavior is investigated by plotting breakthrough curve of S-shaped. The
breakthrough curves for Cd(II) at bed depth of 10, 20 and 30 cm have been plotted by Kumar and
Bandyopadhyay (2005) to observe the adsorption behaviour by Sodium carbonate treated rice
husk. It was observed that, time to achieve breakthrough was increased with the increase of bed
depths. It has been noted that, similar result was reported by Ong et al., (2009) for the adsorption
of Congo Red dye by Ethylenediamine – modified rice hulls at the bed depth of 7, 10 and 15 cm.
This was belonged to the increase in binding sites on the adsorbent. In addition to that, Ong and
his colleagues also studied the effect of influent concentrations (15 to 25 mg/L) on the adsorption
characteristics of Congo Red dye. Thus, they have identified that, the percentage removal of dye
decreased with increasing dye concentrations whereby a sharper breakthrough curve was
obtained at a higher dye concentration.

7.2 Bed – Depth – Service – Time (BDST) model

Data collected to design of full-scale adsorption columns. Different mathematical models
have been developed for the use in adsorption column design. Among various design approach,
bed depth service time (BDST) approach based on Bohrat and Adams equation is widely used.
The equation of Bohrat and Adams (1920), which is based on surface reaction rate theory, can be
represented as follows:

C 
 
.
ln  0  1  ln e KN0  X / V   1  KC0t ......(6)
 CB 

With the assumption of e KN0 ( X /V ) is much greater than unity, above equation can be
rearranged for t:

N0 1 C 
t X ln  0  1 .........................(7)
C0V C0 K  CB 

Where C0 is the initial concentration of solute (mg/L), C B is the desired concentration of

solute at breakthrough (mg/L), K is the adsorption rate constant (L/mg h), N 0 is the adsorption
capacity (mg/L), X is the bed depth of column (cm), V is the linear flow velocity of feed to bed
(cm/h), t is the service time of column under above conditions (h).
Besides that, Hutchins (1973) presented a modification of Bohart–Adams equation, which
requires only three fixed bed tests to collect the necessary data instead of nine columns. This is
called the bed depth service time (BDST) approach. The Bohart–Adams Equation can be
expressed as:

t  aX  b ...................................... ..(8)

where

322
 Journal of Purity, Utility Reaction and Environment Vol.1 No.6, August 2012, 308-334

N0
a = slope = ........ ...(9)
C0V

and

1 C 
b = intercept =  ln  0  1 .....(10)
KC0  CB 

A BDST correlation can be plotted by recording the operating time to reach a certain removal
at each bed depth. The slope of the BDST line is equal to the reciprocal velocity of the adsorption
zone and the intercept on abscissa is the critical depth defined as the minimum bed depth
required obtaining the desired effluent quality at time zero. If the adsorption zone is arbitrarily
defined as the adsorbent layer through which the effluent concentration varies from 90 to 10% of
the feed concentration, then this zone is defined as the horizontal distance between these two
lines in the BDST plot.
Accordingly, a plot of BDST at 10% breakthrough have been developed by Kumar and
Bandyopadhyay (2005), and the depth of adsorption zone which also define as mass transfer zone
(MTZ) was evaluted to be 12 cm. The values of K , N 0 and X were found to be 823.85 cm3/mg
h, 0.889 mg/ cm3 and 0.544 cm, respectively. The value of K and N 0 indicated that, the sodium
carbonate treated rice husk is highly efficient for removal of Cd(II) from water environment. On
the other hand, Ong et al., (2009) developed a plot of BDST at 50% breakthrough for their
adsorption system. The plot of t against H at 50% breakthrough for Congo Red -
Ethylenediamine – modified rice hulls systems is a straight line that, however, does not pass
through the origin. The nonconformity of the BDST model may be due to the presence of more
than one rate limiting step in the adsorption system and the complex adsorption mechanism as
suggested and observed in their batch study.

7.3 Adsorption Column Design

The column design parameters as obtained from the BDST model could then be used for the
design of adsorption column in practical use. According to BDST, if the value of a is determined
from one flow rate, values for other flow rates can be computed by multiplying the original slope
by the ratio of the original and new flow rates, and the change of b value is insignificant with
respect to the changing flow rates (Hutchins, 1973). It is also proposed that, data collected at one
influent solute concentration can be adjusted by BDST technique and used to design processes
for treating other influent solute concentrations. Purposely, the studies of adsorption column
design were done for different flow rate, initial concentration, and numbers of stages and its bed
depth. These studies have been conducted by Kumar and Bandyopadhyay (2005). For example,
they indicated that, the breakthrough times (corresponding to 0.1 mg/L effluent concentration)
were found to be 27.1 and 8.7 h for 5 and 15 mL/min flow rates, respectively. The revised values
of a were calculated from flow rate ratio and the values were found to be 0.931 and 0.310 for 5
and 15 ml/min flow rate, respectively. The value of intercept was 0.2667. From these values of a
and b , the service times for 30 cm column were calculated and these are 27.67 and 9.03 h for 5
and 15 ml/min, respectively.

323
 Journal of Purity, Utility Reaction and Environment Vol.1 No.6, August 2012, 308-334

7.4 Column Regeneration and Reuse

By using data from adsorption breakthrough curve, the studies on column regeneration and
reuse can also be done as reported by also Kumar and Bandyopadhyay (2005). It was noted that,
at about 13 h the column was gruelling. Desorption was carried out by 0.01 mol/l HCl solution
through the bed in the downward direction at a flow rate of 8.5 mL/min. The application of
counter - current operation generally reduces regeneration costs and regenerate volume as well as
increases effluent quality. It has been determined that, the flow rate of eluting solution must be
slightly less than the adsorption flow rate so that volume of regenerate is less which helps in easy
handling and high in concentration so that economical solute recovery is possible.
It is therefore in theoretical aspect suggested that, the studies under continuous flow conditions
are more useful compared to batch conditions, due to its suitability to be applied in large scale
wastewater treatment. On top of that, continuous flow studies can also provide useful
information on the adsorption process before extending it to commercial systems. Therefore, it
can be concluded that, the studies under continuous system is much more practical and easily
adopted in real industrial environment. Figure 1 portrayed a summary of works reported in terms
of themes and nature of studies.

Figure 1 A summary of works reported in terms of themes and nature of studies

324
 Journal of Purity, Utility Reaction and Environment Vol.1 No.5, July 2012, 206-221

8. Modification techniques of rice husk

Although rice husk is recognized to be an effective adsorbent for a wide range of solutes
particularly water pollutants, they actually suffer from at least two major drawbacks, which
are low exchange or sorption capacity as well as poor physical stability (i.e. partial solubility)
(Laszlo and Dintzis, 1994). This is due to the inert nature of polymer inside cellulose
structure of rice husk. The polymer is relatively inert as the three hydroxyl groups of each
cellulose unit responsible for most of the interactions with organic and inorganic substances
are involved in extensive inter- and intramolecular hydrogen bonding (Mulinari et al., 2010).
In addition, both lignin and silica constitutes a major obstacle in using rice husk as an
adsorbent material. This is mainly because lignin acts as a cementing matrix between
cellulose fibrils and hemicelluloses molecules, while silica is present on the outer surface of
rice husks in the form of silicon – cellulose membrane (Ndazi et al., 2007). Lignin and silica
can reduce the binding between accessible functional groups on rice husks’ surfaces and
adsorbate ions / molecules. Over and above, the inner surface of rice husk is smooth and
contains wax and natural fats that provide good shelter for the grain but the presence of these
impurities also affects the adsorption properties of rice husk chemically and physically
(Chowdhury et al., 2011). Therefore, in order to overcome the associated problems, it is
necessary for rice husk to be modified by several treatments to remove structural and
compositional impediments to analysis and subsequent degradation processes in order to
enhance digestibility, improve the rate of enzyme analysis, and increase yields of intended
products (Hendriks and Zeeman, 2009). Moreover, Wan Ngah and Hanafiah (2008) reported
that, the treatments of rice husk can increase the cellulose content of the solid fraction by
virtue of lignin removal and hemicelluloses solubilization. On top of that, rice husk
modification can also reduce cellulose crystallinity as well as increase adsorbent porosity
nature. Thus, due to the advantages of rice husk modification in terms of adsorption
efficiency, many researchers began to explore this particular area of study. For example, Hsu
and Pan in 2007 found that, the adsorption capacity of methacrylic acid - modified rice husk
was 14 times higher than that of the unmodified rice husk and more than three times higher
than those of traditional adsorption of paraquat, by Fuller’s earth, activated carbon, cationic
exchange resin and bentonites. This is in accordance with the results identified by Safa and
Bhatti (2011). They pointed out that, the hydrochloric acid treatment of the rice husk biomass
enhanced the adsorption capacity of Everdirect Orange-3GL and Direct Blue-67 dyes, when
compared with free biomass. It is therefore revealed that, modification of rice husk can
increase adsorption capacity of water pollutant from wastewater. Accordingly, it has been
determined that, the modification of rice husk can be done via three different routes of
techniques, which are mechanical, physical and chemical treatment.

8.1 Mechanical Treatment

According to de Sousa et al., (2004), the best mechanical performance is when the
reduction of biomass below 20-mesh sieves. The purposes of mechanical treatment of rice
husk are mainly for size reduction, as well as increasing digestibility of cellulose and
hemicelluloses. In addition, mechanical treatment of rice husk can also increase specific
surface area for solute – surface interaction. This is due to the fact that, larger surface area

310
 Journal of Purity, Utility Reaction and Environment Vol.1 No.5, July 2012, 206-221

will increase adsorption capacity at equilibrium. The use of mechanical chopping (de Sousa
et al., 2004); hammer milling (Iñiguez- Covarrubias et al., 2001; Mani et al., 2004); grind
milling (Mtui and Nakamura, 2005); roll milling (Qi et al., 2005); vibratory milling
(Guerra et al., 2006) and ball milling (Inoue et al., 2008) have proved success as a low
cost treatment strategy. Table 9 shows types of mechanical treatment used in order to modify
rice husk surface prior to using it as adsorbent.

Table 9 Rice Husk Surface Modification by Mechanical Treatment.

TYPE OF MECHANICAL MESH SIEVER RESEARCHERS

TREATMENT
Crushing 30 Mahvi et al., 2004
Grinding 20 – 30 Aluyor et al., 2009.
Milling 500 – 250* Daffalla et al., 2010
Grinding (food processor) - Safa and Bhatti, 2011
Grinding (food processor) - Safa and Bhatti, 2011
*Unit is in µm.

8.2 Physical Treatment

The techniques of modification by physical treatment have been investigated intensively
by previous researchers. It has been revealed that, elevated temperatures (i.e pyrolysis,
combustion, burning) are the most successful physical treatments in rice husk applications as
adsorbent (Mtui, 2009). The physical treatment enables moisture loss as well as lignin
decomposition of rice husk (Lapuerta et al., 2004). On top of that, the treatment of rice husk
by physical treatment also reduced the content of hemicellulose, lignin and cellulose
crystallinity which leads to increase the specific surface area compared to raw rice husk
(Daffalla et al., 2010). For example, Nakbanpote et al., (2007) reported that, heating rice
husk at 300 °C resulted in a loss of C - H stretching bands (2910 cm−1), C - C and C - H
(1021 cm−1), C - O and C – O – C (1060 cm−1 and 1115 cm−1), and C – O – H (899 cm−1).
These were replaced by the primary functional groups of C=O (1715 cm−1), C=O and/or
aromatic ring (1611 cm−1) and dominated the silica functional groups of Si – O – Si (1096
cm−1), Si – H (801, 469 cm−1) and – OH and Si – OH (3000–3700 cm−1). Besides that,
Daffalla et al., (2010) employed the thermal treatments of rice husk by burning at the
temperatures of 300, 400 and 600°C for optimum burning temperature determination. They
pointed out that, at 300°C, considerable amount of carbon produced. On the other hand, at
400°C, amounts of carbon are decreased and considerably substituted by an increase amount
of silica. Apart from that, high amorphous silica produced is formed at 600°C. In addition,
based on surface morphology analysis by Field emission scanning electron microscope
(FSEM) and Scanning electron microscope (SEM), the pores of different sizes and shapes
could be determined compared to the raw rice husk. The pores were developed from the
decomposition of the raw rice husk structure by heat and convert it to small particles with
large surface area. Nevertheless, the micrograph corresponding to calcinations at high
temperature (600°C) shows the loss of micropore volume, possibly attributed to pores
collapses. Table 10 shows types of physical treatment used in order to modify rice husk prior
to using it as adsorbent.

326
 Journal of Purity, Utility Reaction and Environment Vol.1 No.5, July 2012, 206-221

Table 10 Rice Husk Surface Modification by Physical Treatment.

TYPE OF PHYSICAL TREATMENT RESEARCHERS

Heating up to:
(a) 100°C Safa and Bhatti, 2011
(b) 120°C Abdel Wahab et al., 2005
(c) 300°C Nakbanpote et al., 2007
Daffalla et al., 2010
(d) 350°C Daifullah et al., 2002
(e) 400°C Daffalla et al., 2010
(f) 500°C Nakbanpote et al., 2007
(g) 600°C Daffalla et al., 2010
(h) 750°C Hosseinnia et al., 2007
Burning at:
(a) 650°C (pyrolysis) Daifullah et al., 2002
(b) 400°C Mahvi et al., 2004
Boiling:
(a) 30 minutes Safa and Bhatti, 2011
(b) 30 minutes + KOH Daifullah et al., 2002

8.3 Chemical Treatment

Chemical treatments of rice husk are able to reduce the content of hemicelluloses, lignin
and cellulose crystallinity. The reduction in crystallinity leads to an increase the specific
surface area for treated rice husk compared to raw rice husk (Daffalla et al., 2010). Table 11
shows types of chemical treatment used in order to modify rice husk prior to using it as
adsorbent.
Modification of rice husk by using powerful oxidizing agents such as ozone and hydrogen
peroxide can effectively remove lignin; does not produce toxic residues; and the reactions are
carried out at a room temperature and pressure (Sun and Cheng, 2002). On the other hand,
treatment with acid is basically suited for hydrolysis of rice husk. Moreover, the acid is not
only able to hydrolyze cellulose and hemicelluloses, but also capable in separating lignin and
other organic components from rice husk (Rahmanet et al., 2007). Daffalla et al., (2010)
reported that, the porosity of sulphuric acid (H2SO4) treated rice husk increased compared to
the raw rice husk, as consequences from the removal of the inorganic compounds such as
carbonate and silica from the surface of adsorbent. Moreover, purposely for dye removal, the
enhancement of adsorption capacity of acid treated rice husk might also because of
protonation of the adsorbent surface. The surface became positively charged and electrostatic
attraction developed between positively charged surface and negatively charged dye molecule
which can further increased the amount of dye adsorbed. Common acids uses for the purpose
of chemical treatment of rice husk are hydrochloric acid (HCl), sulphuric acid (H2SO4) and
nitric acid (HNO3). As a conclusion, treatment with acids generally create higher specific
surface area and micropores area of rice husk adsorbent compared to non – activated
adsorbent.

327
 Journal of Purity, Utility Reaction and Environment Vol.1 No.5, July 2012, 206-221

Apart from that, alkali (base) treatment is also viewed as one of the widely employed
chemical treatment techniques for modification of rice husk for the purpose of improving its
adsorption properties. For example, treatment of rice husk with aqueous sodium hydroxide
(NaOH) solutions breaks the covalent association between lignocelluloses components,
hydrolyzing hemicelluloses and de – polymerizing lignin. Other than that, NaOH improves
mechanical and chemical properties of cellulose such as structural durability, reactivity and
natural ion – exchange capacity (Ndazi et al., 2007). Besides that, particularly for heavy
metals removal, the applications of base treatment enable removal of surface impurities and
then subsequently increase the available binding sites exposure for adsorption process. Notice
that, the theories reported by Ndazi and his co - workers are relatively consistent with the
results reported by Daffalla et al., (2010). After the treatment of raw rice husk with 0.5 M
NaOH for phenol removal, the silica reacts with NaOH to form sodium silicate (Na2SiO3).
The Na2SiO3 is soluble in water and is removed by adequate water – washing. As a result,
some large holes remain on the husks outer epidermis. In contrast, alkali treatments such as
NaOH and Ammonium hydroxide (NH4OH) decreased the adsorption capability of rice husk
for textile dyes removal due to deprotonation of functional groups on the adsorbent surface
creating a negative. This might be attributed to electrostatic repulsion between negatively
charged dye and rice husk surface (Safa and Bhatti, 2011).
On the other hand, modification of rice husk with certain salts such as sodium chloride
(NaCl), calcium chloride (CaCl2) and magnesium sulphate (MgSO4) increased the amount of
dye adsorbed (Safa and Bhatti, 2011). This might be due to activation of interior adsorbent
surface and production of more binding sites for dyes (Batzias and Sidiras, 2007). Other than
that, cationic surfactant (CTAB) able to increase the adsorbent capacity due to impregnation
of positive charge on the rice husk surface and produced an electrostatic attraction with
negative dye molecules (Baskaralingam et al., 2006). However, non – ionic surfactants
showed no effect on the adsorbent capacity of rice husk. Accordingly, it can be concluded
that, chemical modification is not necessarily improving adsorption capacity, but at some
cases it can reduce the capacity of adsorbent to adsorb water pollutant. It is dependent upon
the types of chemical used and its interaction between solute and rice husk surface.

328
 Journal of Purity, Utility Reaction and Environment Vol.1 No.5, July 2012, 206-221

Table 11 Rice Husk Surface Modification by Chemical Treatment.

TYPE OF CHEMICAL TREATMENT RESEARCHERS

Acid:
(a) Citric acid Abdel Wahab et al., 2005
(b) Methacrylic acid Hsu and Pan, 2007
(c) Sulphuric acid Daffalla et al., 2010
Safa and Bhatti, 2011
(d) Nitric acid Safa and Bhatti, 2011
(e) Hydrochloric acid Safa and Bhatti, 2011
Alkali/Base:
(a) Potassium hydroxide Daifullah et al., 2002
(b) Sodium hydroxide Daffalla et al., 2010
Safa and Bhatti, 2011
Chakraborty et al., 2011
(c) Ammonium hydroxide Safa and Bhatti, 2011
Salts:
(a) Sodium carbonate Kumar and Bandyopadhyay, 2005.
(b) Calcium chloride Safa and Bhatti, 2011
(c) Sodium chloride Safa and Bhatti, 2011
(d) Magnesium sulphate Safa and Bhatti, 2011
Oxidizing agents:
(a) Hydrogen peroxide Aluyor et al., 2009
Organics:
(a) Ethylenediamine Ong et al., 2009
(b) Formaldehyde Daffalla et al., 2010
Surfactants:
(a) Cetyl trimethyl ammonium bromide Safa and Bhatti, 2011
(b) Triton – X100 Safa and Bhatti, 2011

9. Conclusions

Rice husk is low cost adsorbent material used in wastewater treatment in wide area of
applications such as heavy metals, textile dyes, surfactants, phenol, and paraquat removals.
Generally, two modes of experiments were carried out by previous studies, either by batch or
continuous studies. This work summarizes recent studies that have been carried out by some
researchers on the adsorption of pollutants from wastewater. It was found that, techniques
used by researchers were diverged based on types of rice husk used either, raw and
unmodified rice husk or modified rice husk. The modification of rice husk can be done via
mechanical, physical, and chemical treatments. It also has been revealed that, the treatment
(i.e. activation) of raw rice husk significantly affect the surface area development, pore
structure evolution, and changes in surface functional groups. Apart from that, some new
treatment methods such as by physicochemical (combination of physical and chemical) as
well as biological systems are also valuable and interesting to investigate in near future for
rice husk applications in wastewater treatment. Figure 2 illustrated a summary of works
reported in literature showing authors and area of studies.

329
 Journal of Purity, Utility Reaction and Environment Vol.1 No.5, July 2012, 206-221

Figure 2 A Summary of Works Reported in Literature Showing Authors and Area of Studies.

References

Abdel Wahab, O., Nemr, A. E., Sikaily, A. E., and Khaled, A. (2005) ‘Use of rice husk for
adsorption of direct dyes from aqueous Direct F. Scarlet’, Egyptian Journal of Aquatic
Research, vol. 31, no.1, pp. 1110 – 0354.
Adachi A., Takagi S., and Okano T. (2001) ‘Studies on Removal Efficiency of Rice Bran for
Pesticides’, Journal of Health Science, vol. 47, no. 2, pp. 94 - 98.
Aluyor, E. O., Oboh, I. O., and Obahiagbon, K. O. (2009) ‘Equilibrium sorption isotherm for
lead (Pb) ions on hydrogen peroxide modified rice hulls’, International Journal of

330
 Journal of Purity, Utility Reaction and Environment Vol.1 No.5, July 2012, 206-221

Physical Sciences, vol. 4, no. 8, pp. 423 - 427.

Anirudhan, T. S., and Radhakrishnan, P. G. (2008) ‘Thermodynamics and kinetics of
adsorption of Cu (II) from aqueous solution onto a new cation exchanger derived from
tamarind fruit shell’, Journal of Chemical Thermodynamics, vol. 40, pp. 702–709.
Baskaralingam, P., Pulikesi, M., Ramamurthi, V., and Sivanesan, S. (2006) ‘Equilibrium
study for the adsorption of acid dye onto modified hectorite’, J. Hazard. Mater., vol.
136, pp. 989 - 992.
Batzias, F. A., and Sidiras, D. K. (2007) ‘Simulation of methylene blue adsorption by salt-
treated beech sawdust in batch and fixed bed system’, J. Hazard. Mater., vol. 149, pp. 8
- 17.
Bohart, G. S., and Adams, E. Q. (1920) ‘Some aspects of the behaviour of charcoal with
respect to chlorine’, J. Am. Chem. Soc., vol. 42, pp. 523 – 544.
Busca, G., Berardinelli, S., Resini, C., and Arrighib, L. (2008) ‘Technologies for the removal
of phenol from fluid streams: A short review of recent developments’, J. Hazard.
Mater., vol. 160, pp. 265 - 288.
Chakraborty, S., Chowdhury, S., and Saha, P. D. (2011) ‘Adsorption of Crystal
Violet from aqueous solution onto NaOH-modified rice husk’, Carbohydrate
Polymers, vol. 86, pp. 1533 – 1541.
Chang C., Page A. L. and Bingham F. T. (1982) ‘Heavy metals adsorption by winter wheat
following termination of cropland sludge applications’, Journal of Environ. Quality,
vol. 11, no. 4, pp. 750 - 758.
Chockalingam, E., and Subramanian, S. (2005) ‘Studies on removal of metal
i ons and sulphate reduction using rice husk and Desulfotomaculum nigrificans
with reference to remediation of acid mine drainage’, Chemosphere, vol. 62,
pp. 699 – 708.
Chowdhury, S., Mishra, R., Saha, P., and Kushwaha, P. (2011) ‘Adsorption
thermodynamics, kinetics and isosteric heat of adsorption of malachite green onto
chemically modified rice husk’, Desalination, vol. 265, pp. 159 – 168.
Chuah, T. G., Jumasiah, A., Azni, I., Katayon, S., and Choong, S. Y. T. (2005) ‘Rice husk as a
potentially low – cost biosorbent for heavy metal and dye removal: an overview’,
Desalination, vol. 175, October, pp. 305 – 316.
Daffalla, S. B., Mukhtar, H., and Shaharun, M. S. (2010) ‘Characterization of adsorbent
developed from rice husk: Effect of surface functional group on phenol adsorption’,
Journal of Applied Sciences, vol. 10, no. 12, pp. 1060 – 1067.
Daifullah, A. A. M., Girgis, B. S., and Gad, H. M. H. (2002) ‘Utilization of agro-residues
(rice husk) in small waste water treatment plans’, Materials Letters, vol. 57 pp. 1723 –
1731.
Department of Environment Malaysia (2011).
De Sousa, M.V., Monteiro, S.N., and d’Almeida, J.R.M. (2004) ‘Evaluation of pretreatment,
size and molding pressure on flexural mechanical behaviour of chopped bagasse –
polyester composites’, Poly. Testing, vol. 23, pp. 253 – 258.
El – Azab, A. M. M.. (1992) PhD thesis, Cairo University,
Gong, R., Zhu, S., Zhang, D., Chen, J., Ni, S., and Guan, R. (2009) ‘Adsorption behaviour of cationic

331
 Journal of Purity, Utility Reaction and Environment Vol.1 No.5, July 2012, 206-221

dyes on citric acid esterifying wheat straw: Kinetic and thermodynamic profile’, Desalination,
vol. 230, pp. 220 – 228.
Guerra, A., Filpponen, I., Lucia, L. A., Saquing, C., Baumberger, S. and Argyropoulos, D. S.
(2006) ‘Toward a better understanding of the lignin isolation process from wood’,
Journal of Agricultural Food Chemistry, vol. 54, pp. 5939 – 5947.
Hashem, M. A. (2007) ‘Adsorption of lead ions from aqueous solution by okra wastes’,
International Journal of Physical Sciences, vol. 2, pp. 178 – 184.
Hendriks, A. T. W. M., and Zeeman, G. (2009) ‘Pre treatments to enhance the digestibility of
lignocelluloses biomass’, Bioresources Technology, vol. 100, pp. 10 – 18.
Hosseinnia, A., Hashtroudi, M. S., and Banifatemi, M. (2007) ‘The use of rice husks to
remove wastewater surfactants’, Materials and Energy Research Center, Tehran,
Iran.
Hsu, S., and Pan, T. (2007) ‘Adsorption of paraquat using methacrylic acid-
modified rice husk’, Bioresource Technology, vol. 98, pp. 3617 – 3621.
Hutchin, R. A. (1973) ‘New simplified design of activated carbon systems’, Am. J. Chem.
Eng., vol. 80, pp. 133 – 138.
Ińiguez-Covarrubias, G., Lange, S. E., and Rowell, R. M. (2001) ‘Utilization of byproducts
from the tequila industry: Part 1: Agave bagasse as a raw material for animal feeding
and fibreboard production’, Bioresource Technology, vol. 77, pp. 25 -32.
Inoue, H. Yano, S., Endo, T., Sasaki, T., and Sawayama, S. (2008) ‘Combining hot
compressed water and ball milling pretreatments to improve the efficiency of the
enzymatic hydrolysis of eucalyptus’, Biotechnology Biofuels, vol. 1, pp. 1 – 9.
Jianlong, W. (2002) ‘Biosorption of copper (II) by chemically modified biomass of
Saccharomyces cerevisiae’, Process Biochem., vol. 37, pp. 847 - 850.
Khan, N. A., Ibrahim, S., and Subramaniam, P. (2004) ‘Elimination of heavy metals from
wastewater using agricultural wastes as adsorbents’, Malaysian Journal of Science, vol.
23, pp. 43 – 51.
Kumar, U. (2006) ‘Agricultural products and by – products as a low cost adsorbent for heavy
metal removal from water and wastewater: A review’, Scientific Research and Essay,
vol. 1, no. 2, November, pp. 033 – 037.
Kumar, U., and Bandyopadhy, M. (2005) ‘Fixed bed column study for Cd(II) removal from
wastewater using treated rice husk’, Indian Institute of Technology.
Lakshmi, U. R., Srivastava, V. C., Mall, I. D., and Lataye, D. H. (2008) ‘Rice husk ash as an
effective adsorbent: Evaluation of adsorptive characteristics for Indigo Carmine dye’,
Journal of Environmental Management, vol. 90, pp. 710 – 720.
Lapuerta, M., Hernández, J. J., and Rodríguez, J. (2004) ‘Kinetics of devolatilization of
forestry wastes from thermogravimetric analysis’, Biomass Bioenergy, vol. 27, no. 4,
pp. 385 – 391.
Laszlo, J. A., and Dintzis, F. R. (1994) ‘Crop residues as ion – exchange materials: Treatment
of soybean hull and sugarbeat fiber (pulp) with epichlorohydrin to improve cation -
exchange capacity and physical stability’, Journal of Applied Polymer Science, vol. 52,
pp. 531 – 538.

332
 Journal of Purity, Utility Reaction and Environment Vol.1 No.5, July 2012, 206-221

Mahvi, A. H., Maleki, A., and Eslami, A. (2004) ‘Potential of rice husk and rice husk ash for
phenol removal in aqueous systems’, American Journal of Applied Sciences.
Malik, P. K. (2003) ‘Use of activated carbons prepared from sawdust and rice-husk for
adsorption of acid dyes: a case study of acid yellow 36. Dyes and Pigments 56’, Dyes
Pigments, vol. 56, pp. 239 – 249.
Mani, S., Tabil, L.G., and Sokhansaj, S. (2004) ‘Grinding performance and physical
properties of wheat and barley straws, corn stover and switchgrass’, Biomass
Bioenergy, vol. 27, pp. 339 – 352.
Mansaray, K.G., and Ghaly, A.E. (1998) ‘Thermogravimetric analysis of rice husks in an air
atmosphere’, Energy Sources, vol. 20, pp. 653 – 663.
McKay, G., El Geundi, M., and Nassar, M. M. (1987) ‘Equilibrium studies during the
removal of dyestuffs from aqueous solutions using Bagasse pith’, Water Res., vol. 21,
pp. 1513 – 1520.
Mohamed, M. M. (2004) ‘Acid dye removal: Comparison of surfactant-modified mesoporous
FSM-16 with activated carbon derived from rice husk’, J. Colloid and Interface
Science, vol. 272, pp. 28 - 34.
Mohammadi, M., Man, H. C., Hassan, M. A., and Yee, P. L. (2010) ‘Treatment of
wastewater from rubber industry in Malaysia’, J. Biotechnology, vol. 9, pp. 6233 –
6243.
Mtui, G. Y. S. (2009) ‘Recent advances in pretreatment of lignocellulosic wastes and
production of value added products,’ African Journal of Biotechnology, vol. 8, no. 8,
April, pp. 1398 – 1415.
Mulinari, D. R., Cruz, T. G., Cioffi, M. O. H., Voorwald, H. J. C., Da Silva, M. L. C. P., and
Rocha, G. J. M. (2010) ‘Image analysis of modified cellulose fibers from sugarcane
bagasse by zirconium oxychloride’, Carbohydrate Research, vol. 345, pp. 1865 –
1871.
Nakbanpote, W., Goodman, B. A., and Thiravetyan, P. (2007) ‘Copper adsorption on rice husk
derived materials studied by EPR and FTIR’, Colloids and Surfaces A: Physicochem.
Eng. Aspects, v o l . 304, pp. 7 – 13.
Nayak, P. S., and Singh, B. K. (2007) ‘Removal of phenol from aqueous solutions by
sorption on low cost clay’, Desalination, vol. 207, pp. 71 – 79.
Ndazi, B., Tesha, J. V., and Bisanda, T. N. (2007) ‘Some opportunities and challenges of
producing bio – composites from non – wood residues’, J. Mater. Sci., vol. 41, no. 21,
pp. 6984 – 6990.
Ong, S. O., Tay, E. H., Ha, S., Lee, W., and Keng, P. (2009) ‘Equilibrium and continuous
flow studies on the sorption of Congo Red using ethylenediamine modified rice hulls’,
International Journal of Physical Sciences, vol. 4, no.11, pp. 683 – 690.
Qi, B. C., Aldrich, C., Lorenzen, L., and Wolfaardt, G. W. (2005) ‘Acidogenic fermentation
of lignocellulosic substrate with activated sludge’, Chemical Engineering
Communications, vol. 192, pp. 1221 – 1242.
Rahman, I. A., Ismail, J., and Osman, H. (1997) ‘Effect of nitric acid digestion on organic
materials and silica in rice husk’, J. Mater. Chem., vol. 7, pp. 1505 – 1509.

333
 Journal of Purity, Utility Reaction and Environment Vol.1 No.5, July 2012, 206-221

Safa, Y., and Bhatti, H. N. (2011) ‘Adsorptive removal of direct dyes by low cost rice husk:
Effect of treatments and modifications’, African Journal of Biotechnology, vol. 10,
no.16, pp. 3128 – 3142.
Safa, Y., and Bhatti, H. N. (2011) ‘Biosorption of Direct Red-31 and Direct Orange-26 dyes
by rice husk: Application of factorial design analysis’, Chemical Engineering Research
and Design, Doi:10.1016/j.cherd.2011.06.003.
Sun, Y., and Cheng, J. (2002) ‘Hydrolysis of lignocellulosic materials for ethanol production:
A review’, Bioresources Technology, vol. 83, pp. 1 – 11.
Tarley, C. R. T. and M. A. Z. Arruda. (2003) ‘Biosorption of heavy metals using rice milling
by-products: Characterization and application for removal of metals from aqueous
effluents’, Chemosphere, vol. 54, pp. 987 - 995.
Tengerdy, R. P., and Szakacs, G. (2003) ‘Bioconversion of lignocelluloses in solid substrate
fermentation’, Biochemical Engineering, vol. 13, pp. 169 – 179.
Wan Ngah, W. S., and Hanafiah, M. A. K. M. (2008) ‘Removal of heavy metal ions from
wastewater by chemically modified plant wastes as adsorbents: A review’, Biosour.
Technol., vol. 99, pp. 3935 – 3948.
Weixing, S., Xiangjing, X., and Gang, S. (1998) ‘Chemically modified sunflower stalks as
adsorbent for colour removal from textile wastewater’, J. of Appl. Poly. Sci., vol. 71,
pp. 1841 – 1850.
Wongjunda, J., and Saueprasearsit, P. (2010) ‘Biosorption of chromium (VI) using rice husk
ash and modified rice husk ash’, Environmental Research Journal, vol. 4, no. 3, pp. 244
– 250.
Yazici, H., Kilic, M., and Solak, M. (2008) ‘Biosorption of copper (II) by Marrubium
globosum subsp. Globosum leaves powder: Effect of chemical pretreatment,’ J.
Hazard. Mater., vol. 151, pp. 669 – 675.
Zhou, D., Zhang, L., and Guo, S. (2005) ‘Mechanism of lead biosorption on cellulose/chitin
beads’, Water. Res., vol. 39, pp. 3755 - 3762.

334