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Abstract
Rice husk as a low-value agricultural by-product can be made into sorbent materials which are used in heavy metal
and dye removal. It has been investigated as a replacement for currently expensive methods of heavy metal removal
from solutions. CkLrrently,the study of rice husk as a low-cost sorbent for removing heavy metals has regained
attention. The heavy metals being studied are: As(V) [1], Au [2,3], Cr(IV) [4], Cu and Pb [5,6], Fe, Mn, Zn, Cu [7]
and Cd(II) [8-10]. Rice husk is also being used to treat textile dyes such as like malachite green [11,12] and acid
yellow 36 [13]. The treatment and preparation office husk activated carbon are of importance and became a subject
of study [14-16]. In this review an extensive list ofprevions and current literature on rice husk activated carbons in
removing heavy metals and dyes, their preparation or treatment and isotherms studies were complied to provide a
summary of available information on rice husk and its potential as a low-cost sorbent.
I. Introduction
contaminating groundwater and other water
Heavy metal contamination exists in aqueous resources. Heavy metals are not biodegradable
waste streams from many industries such as metal and tend to accumulate in living organisms, caus-
plating, mining, tanneries, painting, car radiator ing various diseases and disorders. For example,
manufacturing, as well as agricultural sources chromium causes serious ailments in both animal
where fertilizer and fungicidal spray are intens- and plant bodies [4]. Table 1 shows the Environ-
ively used. Cu, Zn, Cr, Cd, etc., are harmful mental Quality Act 1974, Environmental Quality
wastes produced by industry that pose a risk of (Sewage and Industrial Effluents) Regulations,
1979, in Malaysia with selected parameter limits
*Corresponding author. of effluent o f heavy metals.
0011-9164/05/$- See front matter © 2005 Elsevier B.V. All fights reserved
doi: 10.1016/j.desal.2004.10.014
306 T.G. Chuah et al. / Desalination 175 (2005) 305-316
available is far in excess of any local uses and, ous diseases and disorders. Treatment processes
thus, has posed disposal problems [ 15]. Rice husk for metal-contaminated waste streams include
accounts for about 20% of the whole rice and chemical precipitation, membrane filtration, ion
contains about 20% silica. Rice husk possesses a exchange, and carbon adsorption. Currently, the
granular structure, is insoluble in water, has maj or methods of industrial wastewater treatment
chemical stability and high mechanical strength. involve physical and/or chemical processes.
A previous study reported that rice husk has a Some examples are summarised in Table 4.
low calorific value of 3585 kcal kg-1 and high ash
content [47]. Due to its high ash content, a proper 4. Rice husk as a sorbent for heavy metal and
method of disposal and utilization of rice husk dye removal
has yet to be developed [48]. However, studies
have also shown that rice husk is suitable for Rice husk used as a sorbent in removing heavy
the production of activated carbon [16,49-51]. metals has been intensively studied and reported.
Tables 2 and 3 show the typical composition and Among the metal ions studied are: As(V), Au,
chemical compositions office husk and reported Cd, Co, Cr (III), Cr(VI), Cu, Hg, Ni, Pb and Zn.
values on their physicochemical characteristics. The maximum ofsorption capacity for each metal
ion from previous works are summarized in
Table 5.
3. Current technologies available for treatment
McKay [19,59] and his co-workers [40] first
methods of heavy metals and dyes
reported their works on colour removal using rice
Heavy metals are not biodegradable and tend husk and other low-cost sorbents. Many subse-
to accumulate in living organisms, causing vari- quent works studied basic dyes. McKay [59]
Table 4
Current treatment technologies for heavy metals and dyes removal involving physical and/or chemical processes
Table 5
Reported maximum heavy metals adsorption capacities (mg/g) for rich husk
Table 7
Reported Langmuir isotherms from previous batch studies using rice husk as adsorbent
Table 8
Reported Freundlich isotherms from previous batch studies using rice husk as adsorbent
previous studies. Most of the reported heavy a greater amount of uptake with decreasing initial
metal systems suggest the applicability Langmuir, concentration. However, sorption of As(V) was
which assumes there is monolayer coverage and very rapid, taking 20 min to achieve equilibrium
constant sorption energy on the sorbent surface. irrespective of the initial concentration. It also
Mishra et al. [58], however, reported that the data attains equilibrium faster than the adsorption such
of Zn ion adsorption are well fitted to the Freund- as fly ash and chrome waste, which attained equi-
lich isotherm rather than the Langmuir isotherm. librium after 72 min and 2 h, respectively [61,62].
This may be due to the adsorbent's heterogeneity Guo et al. [4] reported their findings in ad-
of the surface, and is further confirmed with the sorption of Cr(VI); equilibrium was achieved in
fractional value of 1/n of 0.909 (0< 1/n<l) [60]. about 2 h and it was found that the equilibrium
Malik [13] reported that both Langmuir and time was much faster than any other adsorbents
Freundlich models could be used to represent the such as cow dung carbon, coconut shell carbon
trends of adsorption on Acid yellow 36 dye. His and peach stones. The same equilibrium time was
finding indicates that Acid yellow 36 is favour- achieved and observed by them on the adsorption
ably adsorbed by the activated carbon prepared of malachite green using the same adsorbent dose
from rice husk. of 0.8 g/1 of rice husk [11]. Both experimental
It should be noted that some studies have results indicate the rapid uptake of the treated rice
shown data well fitted in the Freundlich isotherm; husk on heavy metals and dyes.
however, the values of 1/n and K were not in their Nawar and Doma [41] studied the effect of
works [ 11,12,41 ]. Guo et al. [ 11,12], however, contact time on basic dye (Sandocryl orange
emphasized that the Freundlich model in no way B-3RLE) and acid dye (Sandoz lanasyn black
is meant to imply that the model assumptions are BRL ABK). The contact time required to reach
valid for their works. Moreover, the model used equilibrium for the basic dye is short using rice
is only to provide a simple representation of the husk - - 15 min. This agreed with the findings
trends they observed. reported by Tinh et al. [63] on saturation of mate-
dais with a cellulose-type structure that was
achieved after only 15 min for low concentrations
6. Effect of contact time and effect of initial
of a basic dye. However, for acid dyes, lower
concentration
uptake is observed at equilibrium.
Tiwari et al. [57] found that the initial concen-
tration of Hg(II) has little effect on the contact
time to reach equilibrium. However, adsorption 7. Effect of pH
capacity is increased with the increment of initial It is known that the sorption of heavy metal
concentration. A similar situation was observed ions by solid substracts depends on the pH of the
for Zn(II) adsorption by rice husk [58]. Initial solution. Mishra et al. [58] suggested that the
concentration of Zn(II) has little effect on the contents of amino acids, the active functional
contact time to reach equilibrium. The adsorption groups and metal oxides in rice husk, may have
capacity is also increased with the increment of an effect on the uptake process. Adsorption of
initial concentration of Zn(II).It should be noted Zn(II) increases with the increase of pH values.
that Marshall et al. [35] and Munaf and Zein [56] Rice husk could exhibit a hydration shell at lower
did not report on the effect of contact time and pH positively charged by the hydronium ion, H+,
effect initial concentration of Zn(II) by rice husk. in the solution. This restricted the uptake of
Lee et al. [ 1] have reported that the amount of Zn(II) ions. Adsorption capacity increases with
uptake of As (V) by rice husk follows the trend of increasing pH values. At moderate to high pH
T.G. Chuah et al. /Desalination 175 (2005) 305-316 313
values, zinc ions exist as Zn 2+, Zn(OH) ÷ and dye (Sandocryl orange) and an acid dye (Sandoz
Zn(OH)2 , which are favourable species for lanasyn black).
adsorption of trace zinc ions. A similar observa- The adsorption of malachite green [11] was
tion was found in the adsorption ofCr(IV), Cu(II) increased with pH when the same rice husk was
and Cd(II) by rice husk [56]. This is further used. This may be due to the increase of negative
supported by the work of Wong et al. [5]. charges on the carbon surface; hence, the electro-
The effect of pH on Hg(II) adsorbed by rice static force, like van de Waals, between the car-
husk was studied by Tiwari et al. [57]. They bon surface and dye ion, were increased.
found that a maximum adsorption efficiency at
pH 6 seems to be related to the dominant species
of Hg(OH)2. Chloride species, such as HgC12, 8. Effect of particle size
dominate at pH <6. Disappearance of hydroxyl-
mercury group species at pH <6 caused a de- The adsorption capacity of rice husk very
crease in adsorption. Dissolution of metal oxides much depends on the surface activities-- in other
office husk may also increase the pH value of the words, specific surface area available for solute-
solution. This is further supported by the findings surface interaction, which is accessible to the
observed by Feng et al. [64]. By using solutions solute. It is expected that adsorption capacity will
with an initial pH of 5.60-5.80, they obtained the be increased with a larger surface area. In other
highest absorption capacity values on Hg. words, smaller particle size increases the adsorp-
Guo et al. [4] observed the maximum adsorp- tion capacity. Munaf and Zein [56] reported that
tion of Cr(VI) was found in the range below 5, when the size of rice husk particles increases,
and the adsorbed amount was found to be negli- metal ions decrease. Similar trends have been
gible in the pH value over 8. These findings are reported by Wong et al. [5]. Adsorption being a
further supported by the work of Sumathi et al. surface phenomenon, the smaller adsorption sizes
[65]. They found that the solution pH had a will offer comparatively larger surface areas and
marked influence on Cr(VI) adsorption. Gene- higher adsorption will occur at equilibrium.
rally, adsorption of Cr(VI) was higher at lower Tiwafi et al. [57] found that the adsorption
pH and decreased with increasing pH. This could capacity of Hg(II) on rice husk decreased with
be due to the redox reaction between the sorbent increasing particle size. Higher sorption for
surface groups and sorbate. Higher H + ion con- smaller particle size seems due to larger surface
centration could strengthen the redox reaction and area per unit mass of rice husk. His findings also
enable the carbon to adsorb more Cr(VI). Vasan- indicated that, in the initial stage of adsorption,
thy and Lakshmanaperumalsamy [66] also sug- Hg(II) adsorption was dominated by diffusional
gested that the high adsorption of Cr(VI) at low transport.
pH was due to the fact at low pH a large number
of hydrogen ions can neutralize the oppositely
charged surface and thus enhance the electrostatic 9. Effect of agitation rate
attraction between the adsorbent and adsorbate Wong et al. [5] show that the uptakes of Pb
overcoming electrostatic repulsion between them. and Cu increased with increasing agitation rates.
The effect of different pH values on dye An increasing agitation rate may reduce the film
adsorption capacity of rice husk was studied by boundary layer surrounding the sorbent particles,
Nawar and Doma [41 ]. They observed that there thus increasing the external film diffusion rate
is a general trend for the adsorption capacity to be and the uptake rate. However, Lee et al. [1]
constant at pH values between 3and 9 for a basic showed that varying the agitation rate does not
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