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Fuel Processing Technology


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Transesterification of tributyrin with methanol over calcium oxide catalysts prepared


from various precursors
Yung Bok Cho a, Gon Seo a,⁎, Duck Rae Chang b
a
School of Applied Chemical Engineering and the Research Institute for Catalysis, Chonnam National University, Yungbong-Dong, Buk-Gu, Gwangju 500-757, Republic of Korea
b
Korea Institute of Industrial Technology, 1110-9 Oryong-Dong Buk-Gu, Gwangju 500-480, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: Calcium oxide catalysts were prepared by calcining various precursors such as calcium acetate, carbonate,
Received 27 March 2009 hydroxide, nitrate and oxalate and their catalytic activities were examined in the transesterification of
Received in revised form 9 June 2009 tributyrin with methanol. The prepared calcium oxide catalysts were characterized using thermogravimetry
Accepted 14 June 2009
(TG), X-ray diffraction (XRD), scanning electron microscopy (SEM), N2 adsorption and temperature
Available online xxxx
programmed desorption (TPD) of CO2. The calcium oxide catalyst obtained by calcining calcium hydroxide at
Keywords:
600–800 °C showed the highest tributyrin conversion and methyl butyrate yield. The large desorption peak
Transesterification of CO2 TPD confirmed that its numerous basic sites were responsible for its high activity. The low-
Tributyrin temperature decomposition of calcium hydroxide provided many nano-sized pores with strong basic sites.
Calcium oxide Although the activity of the calcium oxide catalyst prepared from calcium hydroxide was high, its activity was
Solid base catalyst one order of magnitude less than that of sodium hydroxide catalyst. The dissolution of calcium oxide catalysts
Precursor in products and their repeated uses were also investigated to discuss their advantages as heterogeneous
catalysts in the production of biodiesel.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction also tested in the transesterification, their catalytic activities were


insufficient for the commercial production of biodiesel.
The interest in biodiesel has increased as crude oil resources are Alkali earth metal oxides with high basicity have been considered as
declining and global warming is induced by carbon dioxide emissions. promising base catalysts for biodiesel production because of their low
Biodiesel is a sustainable fuel produced from natural biomass and a solubility in oil [12]. Among alkali metal oxides, calcium oxide has
carbon neutral transportation fuel that is not a net-emitter of carbon noticeable advantages as a heterogeneous catalyst [13–15]. It can be
dioxide. Produced through the transesterification of triglyceride with produced cheaply from many precursors, despite its sufficiently strong
methanol, biodiesel is a mixture of methyl esters and can partially basicity to act as a catalyst for the transesterification. Thus, calcium oxide
replace diesel fuel without any required modification to diesel engines catalysts were used in the transesterification of rapeseed oil and soybean
[1,2]. Homogeneous bases such as sodium and potassium hydroxides oil with methanol at reflux temperature [16,17]. The activated calcium
are employed in the transesterification as catalysts due to their high oxide was also reported as a highly active catalyst in the transesterifica-
activity and convenience [3]. However, the removal of alkali remaining tion of sunflower oil [18]. The high basicity and low price of calcium
in biodiesel products requires large amounts of acids and water to oxide have resulted in its wide application as a sorbent of carbon dioxide
neutralize alkali and to wash out salts, respectively. Heterogeneous and sulfur dioxide [19,20].
catalysts, which can be readily removed merely by filtering, have been Calcium oxide catalysts can be prepared merely by calcining various
used, but their insufficient activity limits their commercial application precursors such as carbonate, hydroxide and acetate [21]. An oyster-shell
[4]. The search for highly active heterogeneous catalysts suitable for was also used for the preparation of calcium oxide catalysts as raw
biodiesel production, therefore, has been progressing steadily [5]. material [22]. Although various precursors are available in preparing
Many heterogeneous base catalysts have been used in the transes- calcium oxide catalysts, their catalytic activity differs markedly according
terification of triglyceride with methanol [6–11]. Alkali metal oxide to their precursors because of their different decomposition behaviors. A
catalysts supported on various supports showed high activity, but their systematic investigation of the decomposition and catalytic performance
partial dissolution in biodiesel products reduced the advantages of of the precursors with different chemical compositions and structures is
heterogeneous catalysts. Although hydrotalcites and basic zeolites were necessary to obtain highly active calcium oxide catalysts comparable
with homogeneous catalysts in terms of their activity and selectivity in
the transesterification.
⁎ Corresponding author. Tel: +82 62 530 1876; fax: +82 62 530 1899. In this paper, we prepared several calcium oxide catalysts from
E-mail address: gseo@chonnam.ac.kr (G. Seo). various precursors such as acetate, carbonate, hydroxide, nitrate and

0378-3820/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2009.06.007

Please cite this article as: Y.B. Cho, et al., Transesterification of tributyrin with methanol over calcium oxide catalysts prepared from various
precursors, Fuel Process. Technol. (2009), doi:10.1016/j.fuproc.2009.06.007
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SI, Nanoporosity). Samples were evacuated at 250 °C for 2 h before


exposure to nitrogen gas at 77 K. The Brunauer–Emmett–Teller (BET)
equation was employed in the calculation of their BET surface areas.
TPD of carbon dioxide was carried out using a home-made TPD
apparatus. A 0.1 g precursor (as calcium oxide) was charged in a
quartz tube of O.D. = 1/4′ and then activated in a helium flow of
40 ml/min by increasing the calcination temperature to a preset level.
After the activated catalyst sample was cooled to 200 °C, carbon
dioxide was fed into the tube in pulses until the activated catalyst
sample was fully saturated with carbon dioxide. The temperature of
the sample was increased to 850 °C at a ramping rate of 10 °C/min and
the desorbed carbon dioxide was detected using a thermal con-
ductivity detector.
The amount of calcium oxide dissolved in the products during the
transesterification of TriB with MeOH was analyzed using an ICP
spectrometer (JY-PLUS and Perkin Elmer, Optima 4300DV).
Fig. 1. TG curves of various calcium oxide precursors. CN was pretreated at 300 °C to
remove any excessive water before charging. 2.3. Transesterification of tributyrin with methanol

The TriB underwent transesterification with MeOH over various


calcium oxide catalysts in an autoclave. Four vials were installed in the
oxalate. Their activities in the transesterification of tributyrin (TriB) stirring shaft of the autoclave preheated at 60 °C. A reactant composed of
with methanol (MeOH), a model reaction of biodiesel production, 10.0 g TriB (Sigma, 98%) and 6.37 g of MeOH (Sigma, 99%) with the molar
were investigated to evaluate their catalytic performance [23–25]. ratio of 1:6 as TriB:MeOH was poured into each vial. One gram of butyl
Their catalytic activity was discussed relating to their physicochemical ether (Sigma, 99%) was added as an internal standard. The transester-
properties obtained using X-ray diffraction (XRD), scanning electron ification was induced by charging a given amount of the catalysts on
microscopy (SEM), CO2 temperature programmed desorption (TPD) each vial, after which the vials were stirred at 200 rpm. The precursors
and N2 adsorption methods. were promptly calcined prior to charging into vials containing TriB and
MeOH to prevent them from absorbing any water or carbon dioxide. The
molar ratio of TriB:MeOH was changed to 1:12 at the repeated use of the
2. Experimental
catalysts to lower the viscosity of the reactants for their easy recovery.
After a reaction time of 1 h, the reaction products were analyzed using a
2.1. Preparation of catalysts
gas chromatograph (Donam DS 6200) equipped with a capillary column
(HP-5; 0.25 μm × 0.32 mm× 30 m) and a flame ionization detector.
Various precursors of calcium oxide such as calcium acetate
Conversion of TriB was defined as the mole percent of TriB consumed in
monohydrate (99%, Sigma; CA), calcium carbonate (99%, ACS certifi-
the transesterification. The yields of methyl butyrate (MeBu), mono-
cate; CC), calcium hydroxide (above 95%, Daejung; CH), calcium nitrate
butyrin (MonoB) and dibutyrin (DiB) were calculated as percentages of
tetrahydrate (98%, Junsei; CN) and calcium oxalate monohydrate (98%,
their mole numbers to that of the supplied TriB.
Junsei; CO) were used in the preparation of calcium oxide catalysts.
The precursors were calcined for 2 h in an electric furnace in a nitrogen
3. Results and discussion
gas flow at a calcination temperature that was varied from 500 °C to
900 °C with a ramping rate of 1.5 °C/min at an interval of 100 °C. To
The precursors of calcium oxide catalysts decompose differently
prevent air contact, the calcined catalysts were promptly used for the
according to their structures and chemical compositions. Fig. 1 shows
transesterification of TriB with MeOH. The prepared catalysts were
TG curves of the precursors recorded in their decomposition to
denoted with the acronyms of the precursors and the calcination
calcium oxide. Calcium acetate underwent a two-step decomposition
temperature in Celsius degree, such as CA-800 and CH-600. Calcium
with a large weight loss: conversion to calcium carbonate at 450 °C
oxide (Junsei, 98%) was used as the reference material for the calcium
oxide catalysts and was denoted as CaO⁎.

2.2. Characterization of prepared catalysts

Thermogravimetric (TG) curves of all the precursors except CN


were recorded on a thermogravimetric analyzer (SSC 500 series,
Seiko) without further treatment in an atmospheric condition. CN was
pretreated in air at 300 °C for 1 h to remove excessive water prior to
recording its TG curve. The precursors were heated to 800 °C at a
ramping rate of 10 °C/min.
XRD patterns of the precursors and prepared calcium oxide
catalysts were recorded on a high-resolution X-ray diffractometer
(X'Pert PRO Multi Purpose X-Ray Diffractometer, PANalytical) under
the operation condition of 40 kV and 30 mA. X-ray was filtered using a
nickel filter.
The particle sizes and shapes of the prepared catalysts were
examined using SEM (JSM-7500F, Jeol).
Adsorption isotherms of nitrogen on the prepared catalysts were Fig. 2. XRD patterns of calcium oxide catalysts prepared by calcining the precursors at
obtained using an automated volumetric adsorption apparatus (Mirae 800 °C for 2 h.

Please cite this article as: Y.B. Cho, et al., Transesterification of tributyrin with methanol over calcium oxide catalysts prepared from various
precursors, Fuel Process. Technol. (2009), doi:10.1016/j.fuproc.2009.06.007
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followed by decomposition to calcium oxide at 600–720 °C [26]. precursors were completely converted to calcium oxide by calcination
Calcium carbonate underwent a one-step decomposition at around at 800 °C, despite the variations in decomposition pathways. The
700 °C. Calcium hydroxide was mainly decomposed at 420 °C, while a relatively small (200) and (220) peaks relative to the (111) peak on
small second weight loss was observed at 650 °C. The small, broad the CN-800 catalyst suggested that its crystal morphology was
peak observed at elevated temperature was due to the decomposition considerably different from that of other calcium oxide catalysts.
of contaminated calcium carbonate [27]. Due to its excessive water The particle shapes and surface states of the prepared calcium oxide
content, the TG curve of calcium nitrate tetrahydrate was recorded catalysts differed according to their precursors, as shown in the SEM
after removing the excessive water at 300 °C for 1 h. The conversion of images of Fig. 3. The CA-800 catalyst was composed of bundles of sticks
calcium nitrate to calcium oxide was observed at 600 °C [28]. Calcium with many voids, the CC-800 catalyst of small aggregated blocks, and
oxalate (CO) decomposed to calcium oxide through calcium carbonate the CH-800 catalyst of aggregated nano-scale particles. On the
via the same pathway as that of calcium acetate [29]. The XRD patterns contrary, the SEM image of the CN-800 catalyst showed a clean surface
of the calcium oxide catalysts obtained by calcining the precursors at of large particles. The small micro-scale particles of the CO-800 catalyst
800 °C were the same as those shown in Fig. 2, indicating that the had small groves on them. The reference CaO⁎ catalyst showed surface

Fig. 3. SEM images of calcium oxide catalysts prepared by calcining the precursors at 800 °C for 2 h.

Please cite this article as: Y.B. Cho, et al., Transesterification of tributyrin with methanol over calcium oxide catalysts prepared from various
precursors, Fuel Process. Technol. (2009), doi:10.1016/j.fuproc.2009.06.007
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Table 1
Transesterification of tributyrin with methanol on calcium oxide catalysts.

Catalysta Surface Conversionb Yield (%) Concentration


area (m2/g) (%) DiB MonoB MeBu of calcium (ppm)

CA-800 21 68 18 8 38 100
CC-800 11 38 14 4 19 160
CH-800 25 82 13 12 57 150
CN-800 – b1 b1 – b1 30
CO-800 15 60 19 7 32 120
CaO⁎ 10 3 1 b1 2 –
a
The catalysts were prepared by calcining their precursors at 800 °C for 2 h.
b
Reaction condition; TriB:MeOH = 1:6, reactant/catalyst = 16.4 g/0.010 g.

from acetate, carbonate, and oxalate had similar basicity, regardless of


their precursors. On the contrary, the CN-800 catalyst, composed of
large particles, had very few basic sites because of its small external
Fig. 4. TPD profiles of carbon dioxide from calcium oxide catalysts prepared by calcining
different precursors. The numbers written nearby the peaks indicate the temperatures surface area. Among the calcium oxide catalysts, the CH-800 catalyst
at the peak maxima. showed a large desorption peak of carbon dioxide at a higher
temperature than the other catalysts, thus revealing its numerous
basic sites with strong basicity. Its small particles with many edges and
unevenness. The primary particles of the CH-800 catalyst were very vertices induced numerous insufficient coordination sites, which in
small, while the CA-800 catalyst showed many pores. Although the turn induced its numerous basic sites.
morphologies of the calcium oxide catalysts differed significantly Fig. 5 shows the variations of the conversion and product yield
according to their precursors, their BET surface areas, as calculated over the CH-800 catalyst with reaction time in the transesterification
from their nitrogen adsorption isotherms, were very small at the range of TriB with MeOH. The conversion of TriB increased gradually till
of 11–25 m2/g. The BET surface area of the CN-800 catalyst composed 60 min and approached to a plateau. The MeBu yield showed a similar
of large particles could not be determined. The small particles of the trend, while the yields of DiB and MonoB showed different behaviors.
CH-800 catalyst caused a BET surface area of 25 m2/g, which was These results were nicely coincident with the reported results [23].
relatively large compared to the other calcium oxide catalysts. The BET The decrease in the DiB yield represented its further esterification to
surface area of the fused aggregates of the CC-800 catalyst was very MonoB. The other calcium oxide catalysts exhibited similar behaviors,
small, 11 m2/g due to the absence of any production of nano-sized but the approach to the plateaus was achieved relatively in a short
pores. time. Therefore, the activity of the prepared calcium oxide catalysts
The basicity of the prepared calcium oxide catalysts also differed was compared with the conversions and product yields obtained at
according to their precursors. Fig. 4 shows the TPD profiles of carbon 60 min to maximize the difference in their activities.
dioxide from the calcium oxide catalysts. The CA-800 and CO-800 Table 1 lists the conversions and yields obtained in the transesteri-
catalysts showed similar sized desorption peaks at around 660–670 °C, fication of tributyrin with methanol over various calcium oxide
whereas the CH-800 catalyst showed a considerably larger desorption catalysts obtained by calcining at 800 °C. To investigate the difference
peak with a maximum temperature of 710 °C. The CN-800 catalyst did in the activity of the calcium oxide catalysts, the reaction conditions
not show any appreciable peak. The areas and maximum temperatures were adjusted to give a high TriB to MeOH molar ratio of 1:6 and a small
of the desorption peaks of the CA-800, CC-800, and CO-800 catalysts catalyst loading compared to those reported in the literature [30].
were very similar to each other, with profiles comparable to that of the As expected from their TPD profiles of carbon dioxide, the CH-800
CaO⁎ catalyst. This indicated that the calcium oxide catalysts prepared catalyst showed the highest conversion, while that of the CN-800

Fig. 5. Variations of the conversion and product yields over the CH-800 catalyst with the
reaction time in the transesterification of tributyrin with methanol. Reaction condition: Fig. 6. Transesterification of tributyrin with methanol over CH catalysts calcined at different
TriB:MeOH = 1:6, reactant/catalyst = 16.4 g/0.010 g. temperatures. Reaction condition: TriB:MeOH= 1:6, reactant/catalyst= 8.2 g/0.005 g.

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catalyst was less than 1%. The activity increased in the following order:
CN-800 b CC-800 b CO-800 ≈ CA-800 b CH-800. The reference CaO⁎
catalyst also showed very poor activity, indicating that the calcination
step was essential to prepare active catalysts for the transesterification.
Although the MeBu yield increased with increasing conversion over all
the calcium oxide catalysts, the MeBu yield was relatively high over the
CH-800 catalyst because of its high basicity.
The activity of the CH catalysts varied according to the calcination
temperature. Fig. 6 shows the conversions and yields in the transesteri-
fication of tributyrin with methanol over the CH catalysts calcined at
different temperatures. The conversion was increased as the calcination
temperature of the CH catalysts was increased from 500 °C to 700 °C, but
was considerably decreased with further increase of the calcination
temperature up to 900 °C. Therefore, the maximum conversion was
obtained at 700 °C. The MeBu yield exhibited the same trend with
increasing calcination temperature. However, no definite trends were
evident in the yields of MonoB and DiB. The increased conversion with
Fig. 7. TPD profiles of carbon dioxide from CH catalysts calcined at different temperatures.
The numbers written nearby the peaks indicate the temperatures at the peak maxima. increasing calcination temperature suggested the formation of active

Fig. 8. Transesterification of tributyrin with methanol over (A) CA, (B) CC, (C) CN and (D) CO catalysts as a function of calcination temperature. Reaction condition: TriB:MeOH = 1:6,
reactant/catalyst = 8.2 g/0.005 g.

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sites for the transesterification during the calcination. However, the


calcination of the calcium hydroxide at excessively higher temperatures
resulted in low catalytic activities because of the loss of basic sites by
sintering.
The TPD profiles of carbon dioxide from the CH catalysts obtained
by calcining at different temperatures clearly supported this postula-
tion. As shown in Fig. 7, the CH-700 catalyst had the largest desorption
peak. However, the CH-900 catalyst calcined at 900 °C showed a very
small desorption peak due to the high-temperature sintering. Since
the CH catalysts calcined below 700 °C retained their diffraction peaks
attributed to the precursors, their TPD profiles of carbon dioxide were
not shown. The temperature at the peak maximum of the desorption
peaks strongly depended on the number of basic sites because of the
readsorption of carbon dioxide during desorption [31]. In fact, the
reduction of the loading amount of the CH-800 catalyst considerably
decreased the temperature at the peak maximum, as expected. The
maximized conversion over the CH catalysts at 700 °C was in a good
accordance with the number of basic sites formed during calcination.
The effect of the calcination temperature of the calcium oxide
catalysts on their catalytic activity varied according to the precursors, as
shown in Fig. 8. The CA catalysts showed a maximum conversion at
800 °C, while the conversion over the CC catalysts increased with
increasing calcination temperature up to 900 °C. On the contrary, the
conversion over the CN catalysts remained consistently low and the
maximum conversion was observed at 600 °C. High-temperature
calcination at around 800 °C was required to obtain high conversion
over the CO catalyst. These volcano plots of the conversion over all the
calcium oxide catalysts except the CC catalyst also support the
postulated mechanism for the CH catalysts. The calcination of the
precursors produced active sites for the transesterification, but calcina-
tion at excessively high temperature caused low activity because of the
loss of active sites due to sintering.
Although the CH-700 catalyst was the most active catalyst among the
calcium oxide catalysts prepared by calcining the precursors, its catalytic
activity needs to be comparable to that of sodium hydroxide to facilitate
its application as a catalyst for biodiesel production. Fig. 9 compares the
conversion in the transesterification over the CH-800 and NaOH catalysts Fig. 9. Transesterification of tributyrin with methanol over (A) CH-800 and (B) NaOH
as a function of their loadings. The CH-800 catalyst was used in the catalysts. Reaction condition: TriB:MeOH = 1:6, reactant/catalyst = 16.4 g/0.010 g.
comparison because of its greater stability than the CH-700 catalyst. The
increased catalyst loading significantly increased the conversion over
both the catalysts. About 30 mg (0.53 mmol) of the CH-800 catalyst was composition. Therefore, the calcium oxide catalysts prepared by
required to achieve about 95% conversion, compared to only 2 mg calcining the precursors showed different catalytic activity due to
(0.05 mmol) of the NaOH catalyst. A loading of the CH-800 catalyst about their varying particle size and surface morphology. Calcium hydro-
10 times that of the NaOH catalyst as mole per the same amount of the xide, which was converted to calcium oxide at relatively low
reactant resulted in a similar conversion. Sodium hydroxide was temperature compared to calcium acetate, carbonate and oxalate,
expected to show a higher activity than the CH-800 catalyst, because showed the highest catalytic activity in the transesterification of
only the surface of the latter can participate in the transesterification. In tributyrin with methanol when it was calcined at 600–800 °C. Its low-
the NaOH catalyst, each molecule acts as an active species. In this aspect, temperature decomposition, compared to that of the other calcium
the activity of the active sites of the CH-800 catalyst was very high, even compounds, inhibited the sintering of the calcium oxide produced, by
though its large loading was essential to achieve a similar conversion producing calcium oxide with a high surface area [27]. The strong
compared to that of NaOH catalyst. relationship between the conversion level and the basicity of the CH
However, the CH-800 catalyst had remarkable advantages as a catalysts suggested that the basic sites formed by the removal of water
heterogeneous catalyst in its separation from products and purification by calcination worked as active sites for the transesterification.
of the produced methyl butyrate. The CH-800 catalyst can be easily
removed from biodiesel products just by filtering and repeatedly used 4. Conclusions
for transesterification. The conversion level over the CH-800 catalyst in
the transesterification was maintained above 95%, even after a five- The calcium oxide catalysts obtained by calcining various calcium
time reuse of the catalyst, when TriB:MeOH = 1:12 and reactant/ compounds showed decomposition behaviors and catalytic activities in
catalyst = 16.4 g/0.050 g. The dissolution of the calcium oxide catalysts the transesterification of tributyrin with methanol that differed
was not as high as that shown in the last column of Table 1. These according to their precursors. Calcium hydroxide was converted to
concentrations were low compared to the published data in the calcium oxide with the production of pores on its surface at relatively
literature [12]. The feasibility of repeated use and the very small low temperature compared to that of acetate, carbonate and oxalate.
dissolution of the calcium oxide catalysts indicated that the CH-800 Even though calcium nitrate was decomposed to calcium oxide at low
catalyst preserved its advantages as a heterogeneous catalyst. temperature, it formed a large crystal with a smooth surface. The calcium
The decomposition behaviors of the calcium compounds differed oxide catalysts obtained by calcining calcium hydroxide at 600–800 °C
considerably according to their physical structure and chemical showed the highest activity in the transesterification among the

Please cite this article as: Y.B. Cho, et al., Transesterification of tributyrin with methanol over calcium oxide catalysts prepared from various
precursors, Fuel Process. Technol. (2009), doi:10.1016/j.fuproc.2009.06.007
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Please cite this article as: Y.B. Cho, et al., Transesterification of tributyrin with methanol over calcium oxide catalysts prepared from various
precursors, Fuel Process. Technol. (2009), doi:10.1016/j.fuproc.2009.06.007