Chen 2013

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JTICE-571; No. of Pages 8
Journal of the Taiwan Institute of Chemical Engineers xxx (2013) xxx–xxx
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Journal of the Taiwan Institute of Chemical Engineers

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Rice husk ash as a catalyst precursor for biodiesel production

Kung-Tung Chen b, Jian-Xun Wang a, Yong-Ming Dai a, Po-Hsiang Wang a,
Cyong-Ying Liou c, Chia-Wei Nien a, Jhong-Syuan Wu a, Chiing-Chang Chen a,*
a
Department of Science Application and Dissemination, National Taichung University of Education, Taichung 40306, Taiwan
b
The Teaching Center of Natural Science, Minghsin University of Science and Technology, Hsinchu 30401, Taiwan
c
Department of Applied Chemistry, Chung Shan Medical University, Taichung 40227, Taiwan
A R T I C L E I N F O A B S T R A C T
Article history: The transesterification of soybean oil with methanol was carried out in the presence of Li-modified rice
Received 23 August 2012 husk ash catalyst at atmospheric pressure. The catalyst was prepared using a simple solid-state reaction,
Received in revised form 1 January 2013 mixing, and well grinding 1.00 g RHA with 1.23 g Li2CO3 calcined at 900 8C in air for 4 h. The catalysts
Accepted 6 January 2013
were characterized using XRD, SEM, FTIR, TGA-DTA, and the Hammett indicator. The XRD peaks were
Available online xxx
mainly consistent with Li2SiO3. The catalyst was highly active because its basic strength (H_) exceeded
15.0. The catalyst was also air-insensitive, as only a few CO32 anions formed on the surface of catalyst
Keywords:
after exposure to air for 72 h, and no obvious LiOH formed on the catalyst surface. Under the optimal
Biodiesel
Rice husk ash
reaction conditions of a methanol/oil molar ratio of 24:1, a 4% catalyst amount, and a reaction
Heterogeneous catalyst temperature of 65 8C for 3 h, this approach achieved 99.5% conversion to biodiesel.
Transesterification ß 2013 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Soybean oil
1. Introduction could be a good solid fuel for burning in a boiler to produce steam
in various industries [17], and thus conserving both energy and
Biodiesel has recently attracted attention as a renewable resources. The burning of rice husk in air always produces rice husk
biofuel with fewer pollutant emissions than mineral diesel upon ash (RHA), which is typically viewed as agricultural waste [18].
combustion [1–3]. Heterogeneous catalysts have the advantage Each ton of rice produces 200 kg of rice-husks, which upon
that they can be easily removed from the reaction mixture by complete combustion produce 40 kg of RHA. No other crop by-
filtration and recycled [4]. One way to reduce the cost of the product generates a greater quantity of ash when it is burnt [19].
catalysts is to use agricultural wastes as catalytic materials. In RHA is largely composed of silica (87–99%) with small amounts of
addition to reducing the cost of procuring and synthesizing the inorganic salts [20,21]. About 70 million tons of RHA is produced
catalytic material, this approach creates additional revenue annually worldwide and adequate alternative dispositions must be
opportunities for farmers. Using waste materials as catalysts planned to avoid negative environmental effects. RHA has been
(instead of discarding them) also reduces the cost of waste widely used as a construction material in concrete [15,22], or as an
handling and disposal. The waste materials used as heterogeneous adsorbent to adsorb organic dye, such as malachite green [23], and
catalysts studied so far include waste oyster shell [5,6], Turbonilla inorganic metal such as Pd2+and Cu2+ metal ions [24,25]. Because
striatula shell [7], cockle shell [8], mussel shell [9], mollusk shell of its high silica content, RHA can be an economically viable raw
[10], egg shell [11], mud crab shell [12], Meretrix shell [13], and material for producing silicates and silica in recent years [26,27].
snail shell [14]. Some researchers have used RHA to synthesize ZSM-5 zeolite [25]
Rice covers 1% of the earth’s surface and is a primary source of or NaY [28].
food for billions of people [15]. Rice husk is the outer cover of the Waste shells can be used as a catalyst and source of CaO, which
rice, and accounts for approximately 20% of paddy production, adds value to the generated waste. Calcium oxide (CaO) is a
based on weight. The main characteristics of rice husk include a promising basic heterogeneous catalyst for synthesizing biodiesel
16.3 MJ/kg heating value, a content of 74.0% volatile matter, and at mild temperatures (below the boiling point of methanol) and at
12.8% ash [16]. These characteristics indicate that the rice husk atmospheric pressure [29], but it is rapidly hydrated and
carbonated upon contact with room temperature air. A few
minutes are adequate for CaO to chemisorb a substantial amount of
* Corresponding author.
H2O and CO2 in atmospheric air [30]. The experiments in this study
E-mail address: [email protected] (C.-C. Chen). used RHA as a low-cost material to prepare solid base catalyst
1876-1070/$ – see front matter ß 2013 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jtice.2013.01.006
Please cite this article in press as: Chen, K.-T., et al., Rice husk ash as a catalyst precursor for biodiesel production. J. Taiwan Inst. Chem.
Eng. (2013), http://dx.doi.org/10.1016/j.jtice.2013.01.006
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2 K.-T. Chen et al. / Journal of the Taiwan Institute of Chemical Engineers xxx (2013) xxx–xxx
using Li2CO3 as an activating agent through a solid state reaction. electron microscope (SEM, JEOL JSM-7401F, Tokyo, Japan). For FTIR
To the best of our knowledge, this is the first attempt to use silica spectroscopy, samples were analyzed using a Spectrometer
from RHA as a raw material for biodiesel production. The catalyst NICOLET 380 operating in attenuated total reflection mode (Pike
was air-insensitive and can be directly used for biodiesel Technologies, GladiATR for FTIR with diamond crystal) at a spectral
production without further drying or thermal pretreatment. This range of 4000–400 cm1. The infrared spectra were collected and
approach avoids the usual activation of solid catalysts at high analyzed using a data acquisition computer and OMNIC 4.1b
temperature. software (Nicolet Corp.). The background and spectral measure-
ments were averaged against 32 scans with a resolution of 4 cm1.
2. Materials and methods Thermogravimetric analyses were carried out with a Seiko SSC
5000 instrument. The samples (13.8 mg) were heated from room
2.1. Catalyst preparation temperature up to 1000 8C, with a scan rate of 5 8C/min, and under
an air atmosphere stream (air flow = 80 ml/min) to ensure water
Soybean cooking oil (Great Wall Enterprise Co., Taiwan), desorption. The samples were analyzed as received (i.e. without
methanol (ACS grade, ECHO Chemical Co., Miaoli, Taiwan) and any vacuum pre-treatment or special heat conditioning).
reagent grade Li2CO3 (Shimakyu’s Pure Chemicals, Osaka, Japan)
were used as received. Rice husk was obtained from a rice farm in 2.4. Analytical methods
Yunlin, Middle Taiwan.
Dry raw rice husks (RHs) were sieved to eliminate residual rice FAME concentrations, expressed as the biodiesel purity of the
and clay particles. After thorough washing with deionized water, product, were determined using a gas chromatography system
the RHs were filtered and air-dried at room temperature. A sample (Thermo trace GC ultra, Thermo Co., Austin, TX, USA), equipped
of rice husk was converted into rice husk ash by heat-treating rice with a flame ionization detector, a capillary column (Tr-biodiesel
husk at 900 8C for 4 h. After washing with deionized water and (F), Thermo Co., 30 m in length with 0.25 mm i.d. and 0.25 mm film
filtration, the RHA was dried at 120 8C for 16 h. Results show that thickness), the programmed column oven, and a programmed
highly active solid catalyst can be obtained by mixing and well temperature injector. The oven temperature program consisted of:
grinding 1.00 g RHS with 1.23 g Li2CO3 calcined at 900 8C in air for start at 120 8C (hold 1 min), increase at a rate of 30 8C/min to 220 8C
4 h. (hold 1 min), then increase at a rate of 10 8C/min to 250 8C (hold
1 min). The temperature of the programmed temperature injector
2.2. Reaction procedures was 90 8C for 0.05 min, programmed to 260 8C, at a rate of 10 8C/
min. Nitrogen was used as a carrier gas with a flow-rate of 2 ml/
The conversion of soybean oil to biodiesel was performed in a min. Fig. 1(a) shows characterization data of internal standard.
250 ml flat-bottomed flask, equipped with a reflux condenser and a Amounts of FAME were calculated using the internal standard
magnetic stirrer. The reactor was initially filled with 12.5 g of (methyl heptadecanoate) method, according to method EN 14103.
soybean oil, which was heated to 65 8C for 3 h while stirring at Fig. 1(b) shows the Chromatogram obtained from GC-FID analysis
300 rpm. The reactant was stirred evenly to avoid splashing in the of biodiesel. The peaks were C16:0, C17:0, C18:0, C18:1, C18:2 and
flask at the stirring speed. The timing of the reaction was initiated C18:3, respectively. These six peaks were the most common peaks
as soon as the mixture of methanol and the catalyst was added into in analyzing methyl esters from gas chromatograph.
the reactor. The effects of molar ratio of methanol to oil (3:1–24:1), For quantitative evaluation of the leaching of solid base catalyst
and catalyst/oil weight ratio (1–5 wt.%), on the conversion of under the reaction conditions, some of the samples taken from the
triglycerides to biodiesel were investigated. All of the experiments reactor were filtered, and then the residual methanol was
were performed at atmospheric pressure. After the transester- evaporated in a rotary evaporator so that the FAME and glycerol
ification reaction, DI water was added into the reaction mixture to were left as separate phases. After evaporation, the dry fraction
stop the reaction. The biodiesel and glycerol layers were easily was treated with 0.1 N hydrochloric acid [32,33]. The resulting
separated due to differing densities, of 0.86 and 1.126 g/cm3, solution was analyzed using inductively coupled plasma optical
respectively. A supernatant was filtered through a common filter emission spectroscopy (ICP-OES, SPECTRO GENESIS, Kleve,
paper, and then excess methanol and water were evaporated prior Germany) to determine the Li concentration.
to fatty acid methyl ester (FAME) analysis.
3. Results and discussion
2.3. Catalyst characterization
3.1. Catalyst characterization
The base strength of as-prepared catalysts (H_) was determined
using Hammett indicators [31]. Approximately 50 mg of the Fig. 2(a) shows the XRD results of RHA, Li2CO3 (JCPDS 87-0728),
sample was shaken with 1 ml methanol solution of the Hammett and as-prepared catalyst (Li2CO3/RHA weight ratio of 1.23). The
indicator. 2 h were allowed to elapse for the reaching of parent material RHA is crystalline and consists of a-cristobalite
equilibrium after which no additional change of color took place. (JCPDS 89-3434) and tridymite (JCPDS 73-0469). The crystalline
The basic strength was defined as being stronger than the weakest phase of the RHA was transformed to the Li2SiO3 (JCPDS 74-2145)
indicator which exhibited a color change, and weaker than the and a few Li4SiO4 (JCPDS 37-1472) phase after solid state synthesis
strongest indicator which produced no color change. Bromthymol with Li2CO3.
blue (H_ = 7.2), phenolphthalein (H_ = 9.8), 2,4-dinitroaniline Fig. 2(b) shows the XRD patterns of the as-prepared sample,
(H_ = 15.0), and 4-nitroaniline (H_ = 18.4) were obtained from samples exposed to air for 24–72 h and after used. The XRD peaks
Sigma–Aldrich (St. Louis, MO, USA) and used as Hammett were mainly consistent with Li2SiO3 (JCPDS 74-2145). Similar to
indicators at a concentration of 0.02 mol/L. The characterization Na2SiO3 at ambient pressure and temperature, Li2SiO3 has an
of as-prepared catalysts was performed using a powder X-ray orthorhombic structure whose space group was C-center Cmc21
diffractometer (XRD, MAC MXP18, Tokyo, Japan), with Cu Ka space group (no. 36), and lattice parameters were a = 9.380 Å,
radiation, over a 2u range from 10 to 808 with a step size of 0.048, b = 5.400 Å and c = 4.680 Å.
and at a scanning speed of 38 min1. The microstructures of as- The intensity of Li4SiO4 peaks in the diffractogram was very
prepared catalysts were observed using a field emission scanning weak, indicating a low Li4SiO4 content in the product. To remove
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K.-T. Chen et al. / Journal of the Taiwan Institute of Chemical Engineers xxx (2013) xxx–xxx 3
RT: 1.51 - 7.76

(a) C14:0 C17:0
3.99
C18:0 NL:
1.41E8
7500000
Channel 1
7000000
C16:0 C18:1 Analog
8ester-test-
6500000 C12:0 02
6000000 4.82 C18:2

5.33
5500000 3.27
5000000
5.88 C18:3
6.70
6.02
4500000
6.30
Counts 4000000
3500000
3000000
2500000
2000000
1500000
1000000 7.40
500000 5.82
3.92 4.45
3.21
0
2 3 4 5 6 7
Time (min)
(b) C17:0 C18:0

C18:2
RT: 2.97 - 11.26
C16:0 6.33
NL:
1.11E8
110000000
Channel 1
Analog
100000000 biodiesel-02
C18:1
90000000 5.35
80000000
C14:0
70000000
Counts
6.04
60000000
C18:3
50000000
4.84
40000000
30000000
20000000 6.70
10000000
4.00 6.78 7.11 8.49 8.94 9.54 10.41
0
3 4 5 6 7 8 9 10 11
Time (min)
Fig. 1. Chromatogram obtained from GC-FID analysis of (a) internal standard (b) biodiesel.
adsorbed species from the catalyst surface, the reused catalysts Table 1 shows the basic strength of the as-prepared catalyst,
were washed with anhydrous methanol and dried at 95 8C (water CaO, and Li2CO3 after different exposure times to ambient air
bath) for 1 h under a vacuum (water-pump suction) prior to XRD (temperature 25 2 8C, relative humidity: 50 5%). This study
and SEM. The crystalline phase of the catalyst stabilized upon investigates the effects of exposure to air on the catalytic activity of
exposure to air. It is uncommon for CaO to chemisorb a substantial the transesterification reaction. The as-prepared catalyst and CaO
amount of H2O quickly in the air and be converted into Ca(OH)2 appear to have the same initial basic strength. However, the basic
following a loss of catalytic activity. strength of CaO decreased significantly following the exposure of the
Fig. 3(a) shows the FTIR spectra of the as-prepared catalyst catalysts to air (7.2 < H_ < 9.8), thus influencing the conversion to
synthesized using a solid-state reaction. The bands located at 611, FAME. This deactivation was likely the result of hydration, followed
733, 981, and 1057 cm1 correspond to Si–O–Si bonds [34]. Bands by carbonation on the surface, even after a 3 min exposure to air,
at 1450 and 1483 cm1 were attributed to Li2CO3 vibrations [35]. when the CaO was appreciably deactivated [36]. This severely limits
The CO32 anions probably formed on the surface of the samples by the practical application of CaO because of its need for an inert
absorbing CO2 molecules from the air after calcination. The atmosphere during handling, storage, reactor loading, and use.
absorption bands originating from the Si–O– and Li–O– groups The basic strength (H) of catalyst decreased to 9.8–15.0 after
were located at 410 and 490 cm1 [34]. The CO32 anions formed exposure to air for 24–72 h. Therefore, slight differences in the
on the surface of the samples probably by absorbing CO2 molecules soybean oil conversion appeared between the air-exposed catalyst
from the air after calcining. The catalyst exposed to air for 72 h and (94.6–87.2%) and the fresh catalyst (97.0%). These results verify that
unexposed catalysts had similar FTIR spectra (Fig. 3(b)). the catalytic sites of as-prepared catalyst were more air-insensitive
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Fig. 3. FTIR spectra of the (a) fresh catalyst and (b) catalyst exposure to air for 72 h.
Gibbs free energy changes (DG) for the reaction becomes zero. This
is likely because Li2SiO3 can absorb CO2 at temperatures of less
than 250 8C, but the absorption rate is very slow in this
temperature range from the viewpoint of kinetics [37,38].
Lithium orthosilicate (Li4SiO4) has been widely studied as a
promising carbon dioxide (CO2) absorbent [35]. The process of CO2
capture, using Li4SiO4 as a solid absorbent, occurs according to the
following reaction [37]:
Li4 SiO4ðsÞ þ CO2ðgÞ $ Li2 CO3ðsÞ þ Li2 SiO3ðsÞ DE ¼ 56 KJ=mol (2)
Kato and Nakagawa [37] used a thermogravimetric analyzer to

determine the CO2 absorption of Li4SiO4 in dry pure CO2 gas with a
flow rate of 300 ml/min. A clear weight increase was observed at
approximately 720 8C. This weight change was approximately 35
mass%, which represents the amount of CO2 absorption. In contrast
with Li4SiO4, Li2SiO3 is non-sensitive to CO2 capture in atmospheric
Fig. 2. The XRD patterns of (a) RHA, Li2CO3 and as-prepared catalyst (Li2CO3/RHA air [39] and was a candidate air-exposure tolerant catalyst. Kato
weight ratio of 1.23). (1-tridymite, 2-a-cristobalite), (b) fresh catalyst, catalysts and Nakagawa [37] tested Li2SiO3 for the dry pure CO2 capture, and
exposed to air for 24–72 h and used catalyst (Li2CO3/RHA weight ratio of 1.23).
(*Li4SiO4).
observed no weight increase at temperatures up to 900 8C.
Li2CO3 species appeared in the FTIR spectrum of the catalyst
(Fig. 3), indicating a favorable dispersion of a small amount of
than CaO. The as-prepared catalyst was a solid base catalyst with the Li2CO3 on the catalyst surface. An interesting aspect from the FTIR
advantage of tolerance to air-exposure, which facilitated the results is that band vibrations of the Li2CO3 type bonds increased in
operation of the catalytic reaction. intensity as the air-exposed time increased. This indicates an
A reversible reaction between Li2SiO3 and CO2 takes place at increase in the number of species over the catalyst surface. These
temperatures lower than 250 8C [34]. results suggest the reaction of atmospheric CO2 with catalyst. After
exposure to air for 24–72 h, Li2SiO3 reacted with CO2 in the air to
Li2 SiO3 þ CO2 $ Li2 CO3 þ SiO2 DE ¼ 115 KJ=mol (1) form Li2CO3 over the catalyst surface. The basic strength (H_) of
Li2CO3 stayed in the range of 9.8–15.0 even after exposure to air for
The equilibrium temperature of Li2SiO3 was calculated to be 250 8C 72 h. Therefore, only slight differences appeared in the soybean oil
[37], at which the reaction of CO2 absorption apparently stops, was conversion between the air-exposed catalyst (24–72 h) (94.6–
calculated from thermodynamics. This is the temperature at which 87.2%) and the fresh catalyst (97.0%). This implies that the catalytic
Table 1
Base strengths (H_) of as-prepared catalyst, CaO after exposing to air.
Exposure time (h) Catalyst Conversiona CaO Conversionb
0 15.0 < H_ < 18.4 97 0.2 15.0 < H_ < 18.4 95

24 9.8 < H_ < 15.0 94.6 0.6 7.2 < H_ < 9.8 3
48 9.8 < H_ < 15.0 93 0.5 7.2 < H_ < 9.8 2
72 9.8 < H_ < 15.0 87 1.2 7.2 < H_ < 9.8 1
Reused 9.8 < H_ < 15.0 82 2.3 N < H_ < A N/A
a
Reaction conditions: methanol to oil molar ratio = 12:1; catalyst amount = 4 wt.%; reaction temperature = 65 8C; reaction time = 3 h.
b
Reaction conditions: methanol to oil molar ratio = 12:1; catalyst amount = 3 wt.%; reaction temperature = 65 8C; reaction time = 2 h.
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Fig. 4. (a) SEM morphology and EDS elemental analysis of RHA; SEM micrograph of (b) as-prepared catalyst, (c) catalyst exposure to air for 72 h, (d) fresh Li2CO3 and (e) Li2CO3
exposure to air for 72 h.
activity of the as-prepared catalyst was not seriously deactivated catalyst without taking special action to prevent contact with the
than CaO by carbonation in air on the catalyst surface. The XRD ambient air.
patterns (Fig. 2(b)) agree with this view, because the catalyst did Guo et al. used Na2SiO3 as an efficient solid base catalyst in the
not decompose to Li2CO3 and SiO2 by absorbing CO2 in the air at transesterification of soybean oil with methanol [40]. Na2SiO3 was
room temperature. hygroscopic and easy to deliquesce in the air [41]. In contrast to
Fig. 4(a) presents SEM images of the RHA sample and the Na2SiO3, the Li2SiO3 catalyst in this study was a more anti-
chemical composition of the ash determined by EDS. SEM deliquescent catalyst in the air. The SEM patterns in Fig. 4
micrographs of the rice husk ash indicated that the surface was correspond with this view, because no further particle adhesion
spherical and impermeable porous in nature. Elemental composi- was apparent. This indicates that the as-prepared catalyst was not
tion with EDS showed that the SiO2 was the main detected easily deliquesced in air for at least 72 h. Moreover, there were no
component, with a relatively low K content. Fig. 4(b) and (c) shows obvious particles cohered on the surface of Li2CO3 after exposure to
typical SEM images of the as-prepared catalyst and catalyst air for 72 h, implying that the deliquescent reaction in the air of the
exposed to air for 72 h. All catalysts particles have an average Li2CO3 on the surface of catalyst was also slight.
grain size of approximately 50–100 mm. Many of the small Ortiz et al. [35] used a TGA method to examine the hydration
particles with polyhedral crystals and flake cohered on the surface process of Li4SiO4 to elucidate water absorbed by Li4SiO4 particles.
of catalyst. Fig. 4(d) and (e) also shows typical SEM images of the They reported that only approximately 0.045% (wt./wt. Li4SiO4)
fresh Li2CO3 and Li2CO3 exposure to air for 72 h. Most Li2CO3 water adsorption on the Li4SiO4 surface was observed at 26 8C and
catalysts were in the form of irregular-shaped particles, with an 60% RH. In contrast with Li4SiO4, Li2SiO3 was non-sensitive to H2O
average diameter of approximately 0.1–10 mm, and had imper- chemisorption in atmospheric air. Thermodynamic data show that
meable porous surfaces. Results demonstrated that Li2CO3 the following reaction (3) do not occur spontaneously:
catalytically tolerated exposure to air. This has important benefits
when considering the industrial application of Li2CO3 as a solid Li2 SiO3ðsÞ þ H2 OðgÞ $ 2LiOHðsÞ þ SiO2ðsÞ ; DG ¼ 62:84 KJ=mol (3)
catalyst, and the possibility of storing and handling the activated
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1 Catalyst amount (wt%)

100
0 1 2 3 4 5
weight loss (%)1
-1
100
Conversion (%)
-2
Δt
95 80
-3
60 MeOH/oil
-4
90 -5 40 catalyst amount
0 200 400 600 800 1000
20
Temperature ° C
3 6 9 12 15 24
Fig. 5. TG-DTA curves for the catalyst exposure to air for 72 h.
Molar ratio of methanol/ oil (mol/mol)
Fig. 6. Influence of catalyst amount (reaction conditions: 12.5 g soybean oil,
methanol/oil molar ratio 12:1, reaction time 3 h, reaction temperature 65 8C) and
This claim is supported by experimental results because the reaction methanol/oil molar ratio on the conversion (reaction conditions: 12.5 g soybean oil,
was not observed (Figs. 2b and 3). Hashizume et al. (1997) examined catalyst amount 4 wt.%, reaction time 3 h, reaction temperature 65 8C).
the XRD patterns of Na-montmorillonite and NaCl at a relative
humidity of 0–95%. They concluded that the crystal lattice of Na-
montmorillonite and NaCl collapsed because of deliquescence. amount increased from 1 to 4%. The conversion reached a plateau
Fig. 1(b) shows that the crystal lattice of the as-prepared catalyst did value at the catalyst weight percentage between 4 and 5%.
not collapse after exposure to air for 24–72 h, indicating that there Additional catalysts increased the contact opportunity of the
was no obvious deliquescent reaction on the catalyst surface. catalyst and the reactant, directly influencing the reaction speed
Absorbed water produces superficial hydroxylated species such as and the conversion. Mass transfer and reactant adsorption on the
Si–OH and Li–OH between the Li4SiO4 and water vapor [35]. The FTIR catalyst are crucial in heterogeneous catalysis [47–49]. Therefore, a
spectrum of the as-prepared catalyst exposed to air (Fig. 3(b)) did not molar ratio higher than the stoichiometric molar ratio of methanol
show OH stretching vibration (3562 cm1) and OH stretching is required to shift the equilibrium for the reaction. As Fig. 6 shows,
vibrations of hydrogen-bonded (3530–2800) cm1 [42], indicating conversion increased considerably with an increase in the
that it was difficult for the as-prepared catalyst to chemisorb H2O methanol-loading amount. The maximal conversion ratio was
and transform to LiOH in the air. 99.5% at the methanol/oil molar ratio of 24:1. Fig. 7 displays the
The TGA curve for the as-prepared catalyst exposure to air for effects of reaction time and reaction temperature on conversion.
72 h (Fig. 5) produced by the solid state method, showed that the More than 93.0% of the conversion can occur within 1 h reaction
initial reduction of weight occurred between room temperature time, and thereafter remained nearly constant as a result of a
and 100 8C. This weight loss was attributed to an evaporation nearly equilibrium conversion. Four different temperatures were
process for H2O physisorption. A second weight loss of 4.7% used for the transesterification of refined soybean oil with
between 450 and 750 8C, which is due to a decarbonation process, methanol (12:1) using 4 wt.% catalyst. After 3 h, conversions were
appears between 450 and 650 8C [43]. It might also be the result of 97.0, 86.7, 51.5, and 19.9% for 65, 50, 40, and 30 8C, respectively.
complicated reactions between the lithium compounds and silicon Temperature clearly influenced the reaction rate and the biodiesel
compounds [44], which might be divided into two steps [45]: purity.
After the transesterification was completed, the samples were
recovered using simple decantation. The remaining catalyst in the
515565 C : Li2 CO3 þ SiO2 ! Li2 SiO3 þ CO2 reactor was used to catalyze the next batch of transesterification. A
565730 C : Li2 CO3 þ SiO2 ! Li2 SiO3 þ CO2 biodiesel purity of 86.7% could be obtained even after recycling the
and then
Reaction time (h)
Li2 SiO3 þ Li2 CO3 ! Li4 SiO4 þ CO2 (4)
1 2 3 4 5
XRD analyses did not show the presence of impurities (Li2CO3 and 110
SiO2), which might form after the experiment from a decomposi- 100
Conversion (%)1
tion reaction of Li4SiO4 with moisture and CO2 in the air. However, 90
thermal analyses demonstrated that both materials contained 80
some minor impurities. Note that the lower detection limit of the 70
XRD technique depends on the scattering properties of the 60
components of the materials. Silicates are typically detected when 50 Reaction temperature
the concentration is higher than 3% and the crystal is bigger than
40
3 nm [43]. After the second change, the weight kept decreasing Reaction time
30
slowly with an endothermic signal, showing the vaporization of
20
Li2O(s) can easily occur [46].
30 40 50 65
3.2. Transesterification reaction condition optimization Reaction temprature (ºC)
Fig. 7. Influence of reaction time (reaction conditions: 12.5 g soybean oil, methanol/
This study also investigates the effects of catalyst amount on oil molar ratio 12:1, catalyst amount 4 wt.%, reaction temperature 65 8C) and
conversion. The catalyst amount varied from 1 to 5% (catalyst/oil reaction temperature on the conversion (reaction conditions: 12.5 g soybean oil,
weight ratio). As Fig. 6, the conversion increased as the catalyst methanol/oil molar ratio 12:1, catalyst amount 4 wt.%, reaction time 3 h).
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extremely small quantities (free Li+ concentration of less than

1 ppm) in the biodiesel. These results indicate that the as-prepared
catalyst was suitable for use in biodiesel production from soybean
oil. The main advantage of the solid base catalyst is that it can be
used repeatedly. Fig. 9 shows that RHA reprocessing as a silica
source to synthesize a Li2SiO3 catalyst exhibiters a fairly good
operational stability, i.e., 94% of the conversion for the first reaction
and 86% of the conversion is retained for the fifth reaction. It clearly
indicates the advantage of solid base catalyst for reaction stability
and the possible feasibility can be enhanced in industrial
production.
4. Conclusions
This study revealed RHA reprocessing as a silica source to

synthesize a Li2SiO3 catalyst for possible applications in biodiesel
production. Experimental results show that as-prepared catalyst
Fig. 8. The Li leaching of reaction time (reaction conditions: 12.5 g soybean oil, demonstrated excellent catalytic activity because of its basic
methanol/oil molar ratio 12:1, catalyst amount 4 wt.%, reaction temperature 65 8C). strength (H_), above 15.0. In many base-catalyzed reactions, solid
base catalysts are easily poisoned by carbon dioxide and water. The
as-prepared catalyst is tolerant to water and carbon dioxide and
the catalytic activity of transesterification reactions were not
catalyst 5 times. Because the amount of catalyst used in the next
significantly lower because no obvious LiOH formed on the catalyst
run was lower than the initial run, which might partly be
surface and Li2CO3 was yet an efficient solid base catalyst
responsible to the reduced biodiesel purity during the subsequent
(H_ > 9.8). It clearly indicates the advantage of solid base catalyst
run. Glycerol covering the surface of catalyst was another possible
for reaction stability and the possible feasibility can be enhanced in
reason for activity loss. Among the alkali and alkali earth oxides,
industrial production.
CaO is one of the solids that have displayed higher transesterifica-
tion activity (Granados et al., 2007). The glycerol released during
the transesterification reaction reacts with CaO to form Ca Acknowledgment
glyceroxides [29]. In the present study, the crystalline phase of
the catalyst remained unchanged (Fig. 1(b)) after catalyst The authors thank NSC Taiwan for financially supporting this
regeneration. This indicates that the catalyst has greater stability study under grant NSC100–2622-M-42–001-CC1.
than CaO in the transesterification reaction, but its lifetime in an
industrial setting must be significantly prolonged to be practical. References
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JTICE-571; No. of Pages 8

Journal of the Taiwan Institute of Chemical Engineers xxx (2013) xxx–xxx

Contents lists available at SciVerse ScienceDirect

Journal of the Taiwan Institute of Chemical Engineers

Rice husk ash as a catalyst precursor for biodiesel production

RT: 1.51 - 7.76

6000000 4.82 C18:2

(b) C17:0 C18:0

Li4 SiO4ðsÞ þ CO2ðgÞ $ Li2 CO3ðsÞ þ Li2 SiO3ðsÞ DE ¼ 56 KJ=mol (2)

Kato and Nakagawa [37] used a thermogravimetric analyzer to

Exposure time (h) Catalyst Conversiona CaO Conversionb

0 15.0 < H_ < 18.4 97 0.2 15.0 < H_ < 18.4 95

1 Catalyst amount (wt%)

extremely small quantities (free Li+ concentration of less than

This study revealed RHA reprocessing as a silica source to

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