Advanced Powder Technology 20 (2009) 468472

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Advanced Powder Technology

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Original research paper

A facile method for production of high-purity silica xerogels from bagasse ash
Samsudin Affandi a, Heru Setyawan a,*, Sugeng Winardi a, Agus Purwanto b, Ratna Balgis a
a
b

Department of Chemical Engineering, Faculty of Industrial Technology, Sepuluh Nopember Institute of Technology, Kampus ITS Sukolilo, Surabaya, East Java 60111, Indonesia
Department of Chemical Engineering, Faculty of Engineering, Sebelas Maret University, Jl. Ir. Sutami 36 A, Surakarta, Central Java 57126, Indonesia

a r t i c l e

i n f o

Article history:
Received 29 January 2009
Received in revised form 17 March 2009
Accepted 23 March 2009

Keywords:
Bagasse ash
Caustic extraction
Silica xerogels
Purication
Adsorption capacity

a b s t r a c t
In this paper, we systematically report the synthesis of mesoporous silica xerogels in high purity from
bagasse ash. The bagasse ash was chosen as the raw material due to its availability and low-price, and
environmental considerations also were important. Silica was extracted as sodium silicate from bagasse
ash using NaOH solution. The sodium silicate was then reacted with HCl to produce silica gel. To produce
high-purity silica xerogels, three different purication methods were investigated, i.e., acid treatment, ion
exchange treatment, and washing with de-mineralized water. We were able to produce high-purity silica
(>99 wt.%) by washing the produced gels with either de-mineralized water or with ion exchange resin.
The specic surface area of the prepared silica xerogels ranged from 69 to 152 m2 g1 and the pore volume ranged from 0.059 to 0.137 cm3 g1. The pore radii were 3.23.4 nm, which indicated that the silica
xerogels was mesoporous. From the adsorption characterization, it was obvious that adsorptive capacity
was better for high-purity silica xerogels compared with low-purity. The maximum adsorption capacity
by high-purity silica xerogel was 0.18 g-H2O/g-SiO2. Finally, we demonstrate the potential of bagasse ash
for mesoporous silica production with its excellent adsorptive capacity that makes it benecial as an
environmental solution.
2009 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder
Technology Japan. All rights reserved.

1. Introduction
In the sugar cane industry, bagasse is the main waste from the
milling process. Bagasse is often used as fuel for the boilers to generate steam in during sugar processing. Burning of bagasse in the
boiler produces bagasse ash as a combustion product. Depending
on their collection source, bagasse ash is classied as either y
ash or bottom ash. Bagasse y ash (BFA) is a waste that is collected
from the particulate in the upstream of boilers, while waste collected from boiler burners is called bagasse bottom ash (BBA) [1].
Bagasse ash is used mainly for land-ll and as ller for building
materials [2,3]. Reportedly, BFA can be utilized as low-cost adsorbent for the removal of phenolic compounds [1,4,5], pyridine [6],
dyes [7], and heavy-metal ions [8].
On the other hand, bagasse ash is rich in silica that is an economically viable raw material for silica gel and powder production.
Silica gel has many potential applications, such as reinforced ller,
an adsorbent, a catalyst host, for chromatograph packing columns,
in cosmetics, in pharmaceuticals, in paint and coating, etc. [911].
Silica gel is a rigid three-dimensional network of colloidal silica
that can be classied into three different types depending on the
preparation process. The types of silica gel are aquagel (water lled
* Corresponding author. Tel.: +62 31 5995273; fax: +62 31 5995273.
E-mail address: sheru@chem-eng.its.ac.id (H. Setyawan).

pores), xerogel (the aqueous phase in the pores is removed by

evaporation), and aerogel (supercritical process to remove aqueous
phase) [10]. Generally, silica gel is produced from acidication of
sodium silicate. The fabrication of sodium silicate is done commercially by reacting material containing silica, e.g., quartz sand, with
soda ash in a furnace at a temperature of more than 1300 C [12]. It
is obvious that this technique consumes a large amount of energy,
which may discourage the sugar industries from converting bagasse ash into silica gel. Therefore, it would be advantageous to develop a simple, cheap, and low-energy method for the production
silica gel from bagasse ash, thereby utilizing waste for an economically value-added product.
An alkali extraction method reportedly can be used to recover
silica from rice hull ash using a low-temperature reaction
[10,11]. This method was developed based on the unique solubility
properties of an amorphous silica. The high solubility of amorphous silica under basic conditions enables silica to be extracted
from amorphous silica-containing materials [11]. The extraction
of silica from rice hull ash yields a high concentration (91 wt.%)
of silica xerogels [10]. The structure, density and mechanical
strength of silica xerogels is greatly affected by gelation pH and
by silica concentration [13]. For further application, sodium silicate
extracted from rice hull ash has been used for exible lm fabrication [11]. Overall, the utilization of silica-containing ash using
low-temperature extraction is promising for xerogels production.

0921-8831/$ - see front matter 2009 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.
doi:10.1016/j.apt.2009.03.008

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S. Affandi et al. / Advanced Powder Technology 20 (2009) 468472

However, research has focused mainly on the utilization of rice

husk ash as a silica source. In this investigation, we use bagasse
ash as raw material for silica xerogels fabrication.
The preparation of mesoporous silica xerogels from BBA was
conducted from a sodium silicate route followed by gelation using
acid. In addition, to minimize the impurities that can inuence the
surface adsorption properties of the silica xerogels, a method using
a purication process was proposed. Later, we show that the purication of dried silica gel using de-mineralized water, and passing
a sodium silicate solution through an ion exchange resin H+ prior
to neutralization, were effective in improving the purity of silica
by as much as 99 wt.%. In addition, the prepared mesoporous silica
xerogels have been evaluated using a water vapor absorption test.
2. Experimental

2.2. Characterization
The silica content and other components in bagasse ash and
product were determined using an X-ray uorescent (XRF) method
(HORIBA MESA-500 MODEL, Japan). The pore volume of silica gel
was determined by oil absorption method. The oil (glycol) absorption test was used for indirect measurement of the porosity of asprepared silica xerogels. Quantitatively, the surface area, pore volume and pore diameter were determined using the Brunauer, Emmett and Teller (BET) method (Quantachrome Nova 2000,
Quantachrome Instruments, Boynton Beach, Florida). The total
pore volume was calculated from the volume of nitrogen adsorbed
at a relative pressure, P/P0, approached one. The total pore volume
was then calculated as

Vp

2.1. Silica xerogel production

The ow diagram of silica xerogels production is shown in
Fig. 1. Silica xerogels were prepared using three different methods.
These methods were (1) pretreatment of BBA using acid washing,
(2) treatment of as-prepared sodium silicate using cation exchange
resin, and (3) washing of dried gels using de-mineralized water.
Silica was extracted from 10 g BBA (PG. Candi, Ltd., Sidoarjo, Indonesia) using 60 ml of 2 M NaOH (Merck, Germany) producing sodium silicate. In method 1, prior silica extraction, BBA was
washed using acid treatment. During silica extraction, the mixture
of bagasse ash and NaOH solution was boiled for 1 h with constant
stirring. The solution was then ltered through an ashless lter
Whatman No. 41 (Whatman Plc, Kent, England) to remove the carbon residue. The pore size of Whatman No. 41 lter paper is 2025
micrometer (particle retention). The ltrate solution was sodium
silicate, which subsequently was cooled to room temperature. In
method 2, after ltration process, silicate was inputted to ion exchange resin. In the gelation process, the sodium silicate solution
was titrated with 1 N HCl under constant stirring. The pH of the
solution was monitored and the titration was stopped at a pH of
7, 8, 9 and 10 to produce silica gels. The soft gel was aged for 10,
18, 28, 38 and 48 h. After aging, the gel was gently broken by adding 100 ml of de-ionized water to make a slurry. In method 3, the
slurry was ltered and washed three times with de-ionized water.
The powder was dried in a vacuum oven at 80 C for 12 h.
Synthesis
Bagasse ash (10 g)

Purification
Method 1: Pretreatment acid
washing (100 mL HCl 1 M)

Extract with 2 M NaOH (60 ml)

Filtration
Method 2: Cation exchange resin
treatment
Gelation (Titrated with 1 M HCl
until designated pH )

where Wa is the weight of nitrogen adsorbed at P/P0 approached one

and qliq is the density of liquid nitrogen at its boiling point (0.807 g/
cm3). In addition, the mean radius of pore was calculated using

rp

2V p
SBET

X-ray diffraction (XRD) (RINT 2200V, Rigaku-Denki Corp., Tokyo, Japan) analysis was used to obtain information on the crystallographic structure of silica xerogels. In addition, the morphology of
silica xerogels was examined using Scanning Electron Microscopy
(SEM) (S-5000, Hitachi Ltd., Tokyo, Japan). Furthermore, the adsorption characteristic of as-prepared silica xerogels was evaluated
using humid air. The adsorptive capacity of water vapor on the silica
surface was analyzed using a gravimetric method. All adsorption
characterizations (glycol adsorption and BET test) were conducted
under room temperature and atmospheric pressure condition
(30 C and 1 atm.).
3. Results and discussion
Prior to its use as a raw material, the components of bagasse ash
were characterized using XRF, as shown in Table 1. The silica content of the bagasse was 50.36 wt.% and the main impurities were
K2O, Fe2O3, and CaO (19.34 wt.%, 18.78 wt.%, and 8.81 wt.%, respectively). It is well known that to enhance the adsorption capacity of
silica xerogels, high-purity silica is required. In this investigation,
the silica xerogels were puried using three different methods, as
shown in Fig. 1. These methods were (1) pretreatment of BBA using
acid washing, (2) treatment of as-prepared sodium silicate using
cation exchange resin, and (3) washing of dried gels using de-mineralized water. For this experiment, silica xerogels was prepared
using gelation pH 7 with an aging time of 18 h. The chemicals composition of the as-prepared silica xerogel was characterized using
XRF, and the complete compositional analysis can be found in
Table 1
The compositional analysis of bottom bagasse ash (BBA) and silica xerogels puried
by three different methods

Aging (10 to 48 h)

Component

Slurry formation

Washing

Drying

Wa

qliq

Method 3: Post treatment washing

(using demineralized water)

Fig. 1. Flow diagram of the procedure used to produce silica xerogels from bagasse
ash.

SiO2
K2O
CaO
TiO2
V2O5
MnO
Fe2O3
CuO
ZnO

Weight, % (dry basis)

Bagasse

Method 1

Method 2

Method 3

50.36
19.34
8.81
0.26
0.51
0.68
18.78
0.15
0.15

91.58
6.25
0.49
0.19
0.23
0.00
1.26
0.00
0.00

99.37
0.00
0.00
0.18
0.18
0.00
0.36
0.01
0.00

99.16
0.00
0.00
0.06
0.00
0.00
0.69
0.00
0.09

S. Affandi et al. / Advanced Powder Technology 20 (2009) 468472

10
18
28
38
48

0.8

0.4

h
h
h
h
h

Volume of N2 adsorbed (cm /g)

40
20
Adsorption
Desorption

10

pH (-)
(-)
pH
Fig. 2. Glycol adsorption capacity as a function of gelation pH.

11

0.4

0.6

0.8

1.0

Fig. 3. Typical nitrogen adsorptiondesorption isotherms of silica xerogels produced from bagasse ash at pH 7 and an aging time of 18 h.

gels corresponds to H4 type which associated with the narrow slitlike pores.
The effect of gelation pH on the specic surface area of silica
xerogels prepared at an aging time 18 hrs is shown in Fig. 4a.

(a) 200

0.15
Pore volume
Surface area

150

0.10

100

0.05

50

10

10

0.00

pH (-)

3.6

3.4

3.2

3.0
6

0.2

P/P0

Pore diameter (nm)

Gycol
absorbed
(cm(cm
/g) 3/g)
Glycol
adsorbed

1.2

60

1.6

80

0
0.0

(b)

2.0

0.0

100

Pore volume (cm /g)

Table 1. It is shown that method 1, method 2, and method 3 produced silica xerogels with a purity of 91.58, 99.37, and
99.16 wt.%, respectively. Moreover, It is also shown that the weight
fraction of Fe2O3 in silica xerogels prepared from method 2 and 3
was 0.36 and 0.69 wt.%, respectively. Silica xerogel prepared from
method 2 contained lower Fe2O3 due to the better extraction of
Fe compound under ion exchange treatment using acid resin. In
addition, among those methods, ion exchange treatment (method
2) and water purication (method 3) showed great promise for
high-purity silica xerogels production. Since the control of pH solution was difcult in method 2, method 3 was employed for the successive investigation.
In the preparation of silica xerogels, gelation pH is a critical
parameter in determining quality [13]. Since the silica xerogels will
be applied for the adsorbent, the characterization focused on the
adsorption capacity. The oil adsorption test is a common method
to determine the adsorption characteristics of pore materials
[12]. Thus, we used an oil (glycol) adsorption test to evaluate the
effects of gelation pH on the pore distribution of as-prepared silica
xerogels. The effects of gelation pH and aging time on the adsorptive capacity of glycol are shown in Fig. 2. Gelation pH was varied
from 7 to 10 due to low purity of silica xerogels (<90 wt.%) when a
gelation pH < 7 was used. Fig. 2 shows that the adsorption capacity
of glycol generally was reduced when the gelation pH increased.
The optimal adsorptive capacity of glycol was observed for silica
xerogel prepared at gelation pH 7. The glycol adsorptive capacity
is an indirect method to predict the surface area of as-prepared
gel. Thus, it can be concluded that surface area of silica gels are
smaller when prepared in high gelation pH. In addition, it was also
found that aging time for 18 h was optimal for the production of
silica xerogels with a high adsorptive capacity (1.68 mL g1).
To quantitatively examine the effect of pH gelation on the specic surface area, pore volume, and pore diameter, BET analysis
was carried out. Fig. 3 shows the typical nitrogen adsorption
desorption isotherms of silica xerogel produced under pH gelation
7 with an aging time 18 h. The adsorption isotherms curve was
similar to type II which typical for nonporous or mesoporous solids
[14]. These can be characterized by a fairly rapid initial rise in the
amount of gas adsorbed with increasing gas pressure followed by a
return to rising slowly. This inection point corresponds to both
completion of the monolayer coverage and mesoporous lling by
capillary condensation. The rest of the curve corresponds to normal
multilayer formation. Moreover, the hysteresis loop is usually
associated with the capillary condensation in the mesoporous
structures. The type of hysteresis loop of the prepared silica xero-

Surface area (m /g)

470

8
pH (-)

Fig. 4. (a) Dependence of surface area and pore volume on pH for the gels aged for
18 h; (b) their corresponding pore radius (nm).

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S. Affandi et al. / Advanced Powder Technology 20 (2009) 468472

Fig. 5. The scanning electron micrograph (SEM) image of silica xerogels from bagasse ash.

Adsorption capacity (g H O / g SiO )

0.20

0.15

Intensity (a.u)

Silica xerogels

Bagasse ash

10

20

30

40

50

60

70

80

2 (degree)
Fig. 6. X-ray diffraction (XRD) pattern of silica xerogels produced from bagasse ash.

The surface area and pore volume decreased with an increase in

gelation pH. This trend was in agreement with the glycol test, as
explained above. The surface areas of as-prepared silica xerogels
were 152.4, 160.2, 84.59, and 69.00 m2 g1 prepared under a pH
gelation of 7, 8, 9, and 10, respectively. In addition, the calculated
pore diameters were 3.37, 3.42, 3.28, and 3.41 nm for silica xerogels prepared under pH gelations of 7, 8, 9, and 10, respectively
(Fig. 4b). According to the IUPAC classication, the prepared silica
xerogels can be classied as mesoporous materials, for which pore
size is in the range of 250 nm. Furthermore, the gelation pH was
found to affect the surface area far more than the pore size.
To explain the above ndings, the general theory of silica polymerization must be addressed. Silica polymerization is inuenced
by many factors, but gelation pH and the presence of metal cations
are the primary ones [12]. In the preparation of silica xerogels, two
reactions took place simultaneously, i.e., condensation and sodium

0.10

0.05

0.00

Low-purity SiO2 xerogels

High-purity SiO2 xerogels
40

60
80
Relative humidity (%)

100

Fig. 7. Effect of relative humidity on adsorptive capacity of low-purity and highpurity SiO2 xerogels.

silicate acidication. The condensation reaction, which is the formation of a siloxane linkage between surface silanol groups, can
be written as:

SiOH4 HOSiOH3 ! OH3 SiOSiOH3 H2 O

And the reaction of the sodium silicate solution with hydrochloric

acid during acidication process can be written as:

Na2 O  xSiO2 2HCl ! xSiO2 # 2NaCl H2 O

In the acidication reaction (Eq. (4)), silica starts to precipitate

when the pH decreases to less than 10. At pH > 7 in the absence
of salts, electrostatic interaction between charged particles limits
the aggregation process to form a three-dimensional, porous silica
network. Therefore, primary particles increase in size and decrease
in number as a result of the Oswald ripening process. As a result, the

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S. Affandi et al. / Advanced Powder Technology 20 (2009) 468472

primary size of silica is larger when produced at a high gelation pH.

In addition, the presence of a Na+ ion as the reaction proceeds
would speed up the condensation reaction (Eq. (3)). This ion interacts with a negatively charged silicate species and screens the surface charge of particles that favors their aggregation (coagulation).
This makes it possible to form a gel in addition to a sol. Both processes, the formation of gel and sol, take place simultaneously. From
the above results, it seems that the rate of aggregation would become faster with a decrease in gelation pH due to the increase in
salt concentration. Therefore, in low gelation pH, both reactions
produce silica xerogels that are composed of smaller primary particles with larger surface areas. In addition, it is found that pore diameter was relatively same under variation of gelation pH. The pore
size may be more affected by the degree of compaction rather than
primary particles diameter.
To further characterize the physical properties of the prepared
silica xerogels, scanning electron micrograph (SEM) and XRD analysis were conducted. Fig. 5 shows the SEM image of silica xerogels
prepared using gelation pH 7 and an aging time of 18 h. The silica
xerogels were irregular in shape with a size that varied from the
nano to the micron order. In addition, X-ray diffraction (XRD) analysis indicated that the silica xerogels were amorphous, which was
conrmed by the absence of any ordered crystalline structure
(Fig. 6). The formation of amorphous silica xerogels were also reported when rice husk ash was used as a raw material [10]. For
comparison, the XRD pattern of raw materials (BBA) shows many
diffraction peaks, which indicates the presence of a crystalline
structure from K2O, Fe2O3, and CaO. Moreover, the XRD pattern
shows the effectiveness of our proposed method for the production
of high-purity silica xerogels. Overall, we found that high-purity
silica xerogels with high adsorption capacity can be produced from
BBA using a gelation pH of 78 with an aging time of 18 h continuing with purication treatment using method 3.
After high-purity silica xerogels were processed, their adsorptive characteristics were tested using water vapor in a plug-ow
column. The water vapor adsorption of silica xerogels prepared
using two different purication methods as a function of relative
humidity are shown in Fig. 7. Low silica content was prepared by
method 1, while high Si content was prepared using method 3.
Generally, the adsorptive capacity of silica xerogels increases as
relative humidity (Rh) is increased. When Rh < 70%, the adsorptive
capacity of both materials is almost identical. However, when
Rh > 70%, the adsorptive capacity of high-purity SiO2 is higher. This
result showed that high-purity silica xerogels have better adsorptive capacity compared to low-purity silica xerogels. Moreover,

Adsorption capacity (g H O / g SiO )

0.20

0.15

Rh= 40 %
Rh= 60 %
Rh= 80 %
Rh= 100 %

0.10

0.05

0.00
20

40

60

80

100

120

Time (min)
Fig. 8. Effect of contact time on adsorptive capacity at various Rhs.

the effect of contact time on adsorptive capacity of the high-purity

silica xerogels at various relative humidities (Rh) is shown in Fig. 8.
In general, the adsorptive rate of prepared silica xerogels is highly
dependent on the Rh of water vapor. For low Rh, the rate of adsorption is low and it increases with an increase in Rh. Moreover, it is
also shown that high Rh condition need longer time to reach equilibrium condition. Thus, high-purity silica xerogels prepared from
our proposed method using BBA as a raw material is a promising
material for adsorbent application. In addition, these results will
also provide a sensible solution for the recycling of BBA as a raw
material for a new value-added product in the sugar cane industry.
4. Conclusions
High-purity silica xerogels was prepared from bagasse ash via a
sodium silicate process with subsequent acidic treatment for gelation. From three different methods of purication, washing treatment using de-mineralized water was found to be effective for
improving the purity to as high as 99 wt.%. As characterized by
BET analysis, the surface area of as-prepared mesoporous silica
xerogels was 69152 m2 g1 (pH 107). In addition, the pore volume was 0.0590.137 cm3 g1 with the pore diameter from 32 to
34 (3.23.4 nm), which is indicative for mesoporous silica. Further characterization using XRD analysis indicated that the as-prepared silica xerogels were amorphous in phase. The adsorptive
capacity of the silica gel was tested using water vapor and it was
found that high-purity silica xerogels exhibited better adsorption
compared to low-purity silica xerogels.
Acknowledgements
The authors would like to acknowledge nancial support from
the Ministry of National Education, Republic of Indonesia through
the Hibah Bersaing Project (H.S, S.W.) and doctoral scholarships
(S.A). We also thank the Laboratory of Pertamina, Surabaya for
helping with the XRF analysis of our samples and D. Kusumaningrum and D. Handriyani for assisting with the experiments.
References
[1] V.C. Srivastava, B. Prasad, I.M. Mishra, I.D. Mall, M.M. Swamy, Prediction of
breakthrough curves for sorptive removal of phenol by bagasse y ash packed
bed, Ind. Eng. Chem. Res. 47 (2008) 16031613.
[2] K. Ganesan, K. Rajagopal, K. Thangavel, Evaluation of bagasse ash as
supplementary cementitious material, Cem. Concr. Compos. 29 (2007) 515
524.
[3] G.C. Cordeiro, R.D. Toledo, L.M. Tavares, E.M.R. Fairbairn, Pozzolanic activity
and ller effect of sugar cane bagasse ash in Portland cement and lime mortars,
Cem. Concr. Compos. 30 (2008) 410418.
[4] S. Mukherjee, S. Kumar, A.K. Misra, M.H. Fan, Removal of phenols from water
environment by activated carbon, bagasse ash and wood charcoal, Chem. Eng.
J. 129 (2007) 133142.
[5] M. Ahmaruzzaman, Adsorption of phenolic compounds on low-cost
adsorbents: a review, Adv. Colloid Interf. Sci. 143 (2008) 4867.
[6] D.H. Lataye, I.M. Mishra, I.D. Mall, Removal of pyridine from aqueous solution
by adsorption on bagasse y ash, Ind. Eng. Chem. Res. 45 (2006) 39343943.
[7] I.D. Mall, V.C. Srivastava, N.K. Agarwal, I.M. Mishra, Removal of congo red from
aqueous solution by bagasse y ash and activated carbon: kinetic study and
equilibrium isotherm analyses, Chemosphere 61 (2005) 492501.
[8] V.K. Gupta, I. Ali, Removal of lead and chromium from wastewater using
bagasse y ash a sugar industry waste, J. Colloid Interf. Sci. 271 (2004) 321
328.
[9] S.R. Kamath, A. Proctor, Silica gel from rice hull ash: preparation and
characterization, Cereal Chem. 75 (1998) 484487.
[10] U. Kalapathy, A. Proctor, J. Shultz, A simple method for production of pure
silica from rice hull ash, Bioresour. Technol. 73 (2000) 257262.
[11] U. Kalapathy, A. Proctor, J. Shultz, Production and properties of exible sodium
silicate lms from rice hull ash silica, Bioresour. Technol. 72 (2000) 99106.
[12] R.K. Iler, The Chemistry of Silica, John Wiley & Sons, New York, 1979.
[13] U. Kalapathy, A. Proctor, J. Shultz, Silica xerogels from rice hull ash: structure,
density and mechanical strength as affected by gelation pH and silica
concentration, J. Chem. Technol. Biotechnol. 75 (2000) 464468.
[14] E.P. Ng, S. Mintova, Nanoporous materials with enhanced hydrophilicity and
high water sorption capacity, Micropor. Mesopor. Mater. 114 (2008) 126.