Vol. 132 (2017) ACTA PHYSICA POLONICA A No.

3-II

Special issue of the 3rd International Conference on Computational and Experimental Science and Engineering (ICCESEN 2016)

Preparation and Characterization of High Purity Silica

Obtained from Rice Husks
Y.E. Şımşek∗
Bilecik Şeyh Edebali University, Chemical and Process Engineering Department, Bilecik, Turkey
Although SiO2 is produced mostly from mineral sources like quartz, it has recently been obtained from
lignocellulosic natural resources, such as rice husk (hull). Several methods for extracting silica (SiO2 ) from rice
husks are available in the literature. These methods are based essentially on heat treatment and/or extraction.
This study represents a thorough account of heat treatment and acid-base extraction, to obtain silica from rice
husks with a high purity and to eliminate other inorganic impurities. Rice husks, considered to be a potential silica
source, were pretreated with various acids, base and water and then thermally degraded in a fixed bed reactor
under an inert gas atmosphere (N2 ). The materials produced in these conditions were characterized by Brauner-
Emmett-Teller analysis, for surface area and pore volume, by Fourier transform infrared spectroscopy, powder
X-ray diffraction, X-ray fluorescence, and scanning electron microscopy.
DOI: 10.12693/APhysPolA.132.1002
PACS/topics: 81.20.–n, 81.20.Ka, 81.40.–z

1. Introduction Millipore. Ultra-pure water was used in the preparation

of all solutions and in the hot water pretreatment of the
Silicon is a crystalline semi-metal. Though silicon, rice husks.
which makes up about 30% of the Earth’s crust, is so
ample and ubiquitous, it is not naturally found in its 2.2. Materials and chemical pretreatment
pure state. Silicon in nature occurs mainly in the forms The raw material used in experiments, which was col-
of dioxides and hydrates. The only stable form of silicon lected from a poultry farm at the city of Balıkesir in the
at normal conditions is silicon dioxide (silica). Silica is Northwest region of Turkey, was washed thoroughly with
consumed in large quantities in many industrial areas, distilled water to remove surfactants, dust and contami-
such as construction industry, in the production of glass, nants. The material was then dried in air oven at 105 ◦C
and optical fibers and silicon chips for telecommunication for 24 hrs. The washed rice husks were designated as
and as additive and fining agent in food industry. untreated rice husks (UP). The other designations are
Rice husks contain over 70 percent of silica by mass, given in Tables I and II. Prior to experiments, 0.1 M
with minor amounts of metallic elements, such as cal- acid and base solutions were prepared. Afterwards, 20 g
cium, potassium, sodium and magnesium and could be of dried and ground rice husks were mixed separately
a viable option for the production of silica [1–4]. Com- with 300 ml of H2 SO4 , HCl, H3 PO4 and HNO3 acids and
mercial silica is mainly produced in multi-step processes, 300 ml of (NH4 )H2 PO4 base. The mixtures were placed
involving high temperature and pressure. Many rese- in 400 ml Erlenmeyer flasks, kept at 85 ◦C for 5 hrs in
archers have been studying alternative ways to extract a laboratory-scale hot-water bath with vigorous stirring.
silica from rice husks more effectively. Silica has been The pretreated rice husks samples were washed repea-
prepared using different techniques, including vapor- tedly with ultra-pure water to a pH of about 7 and dried
phase reaction [5], sol-gel [6], thermal decomposition met- at 70 ◦C for 24 hrs in an oven and stored at room tempe-
hods [7] and acidic-basic pretreatments [8]. The aim rature.
of this study was to use a simple and effective way to
2.3. Rice husk ash production (thermal treatment)
obtain silica from rice husks at a relatively low tempe-
rature (500 ◦C), in the inert N2 atmosphere, using acid, Thermal treatments of rice husk at temperatures up to
base and hot water pretreatment. 400 ◦C under the inert N2 atmosphere are characteristi-
cally unable to completely decompose the organic com-
2. Experimental ponents i.e. cellulose, hemicellulose and lignin and yield
2.1. Chemicals black char, which contains a relatively low amount of
silica. Therefore, to maximize rice husk ash (RHA) pro-
Analytical grade hydrochloric (37%), sulphuric (90%), duction, all thermal degradation experiments, for each
nitric (90%), phosphric (85%) (acids), ammonium dihyd- pretreatment, were conducted in a fixed bed reactor at
rogen phosphate (base) were all purchased from Merck 500 ◦C with a nitrogen flow rate of 150 cm3 /min. The de-
tailed description of experimental set-up and of the fol-
lowed procedure can be found elsewhere [9].
∗ e-mail: [email protected]

(1002)
 Preparation and Characterization of High Purity Silica Obtained from Rice Husks 1003

2.4. Characterization of the produced RHAs 3.2. FTIR and crystallinity analysis
Quantitative chemical analysis of the RHAs obtai- The obtained RHAs were analyzed by FTIR, as seen in
ned by acid, base and hot water pretreatment was ac- Fig. 1. The spectra of all untreated and pretreated RHAs
complished by X-ray fluorescence (XRF, Rigaku Pri- show strong broad absorption bands at 1030 cm−1 and
mus II). Mineralogical analysis was performed by 800 cm−1 , corresponding to the stretching vibrations of
X-ray diffractometry (XRD, PANanaytical X’Pert HT- Si–O and Si–O–Si, respectively. Similarly, the absorp-
XRD), with Cu Kα radiation in the 2θ range from 5◦ tion peaks at 530 cm−1 , 725 cm−1 and 1417 cm−1 were
to 90◦ , with a step size of 0.02◦ , at a scanning speed assigned to Si–O asymmetrical bending, Si–O symme-
of 1◦ /min. The surface properties of the RHAs were trical bending and Si=O stretching vibrations, respecti-
determined by Brunauer-Emmett-Teller (BET) analy- vely. In addition, the peak at 3100 cm−1 was ascribed to
sis using Micrometrics ASAP 2020 Plus Physisorption. Si–O–H stretching vibrations, caused by absorbed sur-
Inorganic functional analysis was performed by Fourier face water [9, 10]. The crystallinity of the RHAs was
transform infrared spectroscopy (FTIR) (Perkin-Elmer calculated by comparing the ratio of intensity of the cha-
Spectrum 100). racteristic peaks at 766 cm−1 and 700 cm−1 [11].
3. Results and discussion 3.3. X-Ray diffraction and amorphous form analysis
3.1. XRF and inorganic composition X-ray powder diffraction (XRD) analysis was used to
evaluate the crystalline form of silica, which occurred
XRF was used for identifying the chemical composi- in the RHAs. Figure 2 depicts the XRD patterns of
tions and percentage of silica, produced from rice husks the RHAs produced by the nontreating and pretreating
by thermal degradation at 500 ◦C, under an inert N2 at- methods. The XRD patterns of RHAs have a typical
mosphere. Table I shows that silica (SiO2 ) is the main amorphous shape, that shows a broad peak centered at
component and the RHA contain metallic impurities in 2θ = 22.3◦ , related to amorphous silica. The lack of
varying amounts, depending on pretreatment. It is clear sharp and distinctive peaks reveals the absence of any
that acid pretreated RHAs, especially those after hyd- crystalline form. This information is in agreement with
rochloric acid pretreatment, have much higher content the results calculated from the FTIR spectra (Table I).
of silica.

TABLE I
Chemical composition of RHAs obtained from untreated and pretreated rice husks, after thermal degradation.

Production procedure
Base Water
Acid pretreatment
pretreatment pretreatment
Ammonium
Inorganic Nitric Phosphoric Sulphuric Hydrochloric Hot
a Untreated dihydrogen
content acid acid acid acid water
material phosphate
[wt.%] (HNO3 ) (H3 PO4 ) (H2 SO4 ) (HCl) (H2 O)
((NH4 )H2 PO4 )
Designation UP AP NP PP SP CP WP
SiO2 79.6 91.49 92.1 96.1 97.9 98 89.85
Al2 O3 1.59 0.40 0.39 0.20 0.50 0.44 0.28
Fe2 O3 0.48 0.24 0.16 0.31 - 0.16 0.3
CaO 3.18 1.61 1.50 0.58 0.17 0.18 1.61
MgO 0.49 0.39 0.13 - - - 0.16
Na2 O 0.47 0.86 1.39 0.14 0.11 - 0.10
K2 O 7.64 1.67 3.48 0.63 0.59 0.52 2.48
SO3 1.85 0.22 0.21 0.21 0.42 0.24 0.10
P 2 O3 1.96 0.84 - 1.58 0.10 0.24 0.11
MnO 0.54 0.42 0.38 - - - 0.28
F 0.21 0.14 - - - - 0.15
Others 1.99 1.72 0.26 0.25 0.21 0.22 4.58
Amorphicityb [%] 99.14 99.08 99.06 98.97 98.89 98.74 99.12
Crystallinityb [%] 0.86 0.92 0.94 1.03 1.11 1.26 0.88
a
expressed as oxides, b for silica.
1004 Y.E. Şımşek

pretreatment, marked and significant changes in mor-

phology can be seen. Because pretreatment hydroly-
zes the organic components, especially cellulose in rice
husks, untreated RHA yielded a rougher surface. A si-
milar trend is reported in the literature [8].

Fig. 1. FTIR spectra of RHAs.

Fig. 3. SEM images of RHAs produced from (a) untre-

ated (UP) rice husks and rice husks treated with (b)
ammonium dihydrogen phosphate (AP), (c) hot wa-
ter (WP), (d) hydrochloric acid (CP), (e) sulphric acid
(SP), (f) nitric acid (NP) and (g) phosphoric acid (PP).

3.5. Properties of the RHAs

The pore parameters of RHAs are presented in Ta-
ble II. The surface area, total pore volume and average
pore width ranged from 116.92 m2 /g to 268.05 m2 /g,
from 0.071 cm3 /g to 0.146 cm3 /g and from 21.03 Å to
23.734 Å, respectively. The pore properties of the RHAs
Fig. 2. XRD patterns of untreated and pretreated
RHAs. were markedly influenced by pretreatment, as shown in
Table II. The presence of acid, base and hot water has led
3.4. SEM analysis to a much larger surface area and total pore volume. This
increase can be ascribed to the hydrolysis of the inherent
Figure 3 depicts the SEM micrographs of the RHAs. organic components into smaller substances, which could
The morphological structure of all RHAs has predomi- facilitate the decomposition of the raw material into the
nantly a rough and undulating surface texture. After volatiles by thermal treatment.

TABLE II
Surface area and textural properties of RHAs, obtained by BET analysis.

BET surface Total pore Average pore

Designation area volume width
[m2 /g] [cm3 /g] [Å]
Production procedure
Untreated UP 119.62 0.071 23.734
Acid treatment
Phosphoric acid PP 268.05 0.146 21.731
Sulphuric acid SP 253.96 0.133 21.023
Hydrochloric acid CP 247.63 0.137 22.138
Base treatment
Ammonium dihydrogen phosphate AP 251.03 0.145 23.109
How water treatment
Hot water WP 223.42 0.131 23.542
 Preparation and Characterization of High Purity Silica Obtained from Rice Husks 1005

4. Conclusions [5] Y.K. Chung, J.H. Koo, S.A. Kim, E.O. Chi,
J.H. Hahn, C. Park, Cer. Intenational. 40, 14563
The physicochemical pretreatment using acid, base (2014).
and hot water was employed to pretreat rice husks for [6] P. Velmurugan, J. Shim, K.J. Lee, M. Cho, S.S. Lim,
the production of silica. The results of elemental compo- S.K. Seo, K.M.M. Cho, K.S. Bang, B.T. Oh, J. Ind.
sition, results of surface characteristic properties and the Eng. Chem. 29, 298 (2015).
observations of the morphological surface properties of [7] I.J. Fernandes, D. Calheiro, A.G. Kieling,
the produced RHAs confirm that sulphuric acid pretre- C.A.M. Moraes, T.L.A.C. Rocha, F.A. Berhmand
G.C.E. Modolo, Fuel 165, 351 (2016).
atment can effectively produce amorphous silica (>98%).
In addition, the pretreated RHAs are porous and have [8] R.A. Bakar, R. Yahyaa, S.N. Gana, Proc. Chem. 19,
189 (2015).
high surface areas. Thus pretreated RHAs could be good
candidates for adsorbents [12] for the removal of dyes and [9] S. Yorgun, Y.E. Şimşek, Biore. Technol. 99, 8095
(2008).
heavy metals, and adsorbents in air pollution and water
purification systems [13, 14]. [10] W. Roschat, T. Siritanon, B. Yoosuk, V. Promarak,
Energ. Conv. Mang. 119, 453 (2016).
[11] B.J. Saika, G. Parthhasarathy, N.C. Sarmah, Bull.
References Mater. Sci. 31, 775 (2008).
[12] B. Tuğrul, S. Erentürk, S. Haciyakupoğlu, N. Kara-
[1] E.G. Rochow, J.C. Bailar, H.J. Emeleus, R. Nyholm, tepe, N. Altinsoy, N. Baydoğan, F. Baytaş, B. Büyük,
Pergamon Text in Organic Chemistry, Vol. 9, Perga- E. Demir, S. Gedik, Acta Phys. Pol. A 128, B-180
mon Press, 1973. (2015).
[2] I.U. Haq, K. Akhtar, A. Malik, J. Chem. Soc. Pak. [13] B. Gurel, O. Ipek, M. Kan, Acta Phys. Pol. A 128,
36, 382 (2014). B-43 (2015).
[3] G.D.O. Okwadha, P.W. Nyingi, Int. J. Environ. Sci. [14] M. Günal, A. Kösen, Acta Phys. Pol. A 128, B-107
Technol. 13, 2731 (2016). (2015).
[4] A. Vural, Acta Phys. Pol. A 130, 191 (2014).