Journal of Cleaner Production 42 (2013) 198e203

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Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

Biodiesel production from vegetable oil by using modified CaO as solid basic
catalysts
Ying Tang a, *, Jingfang Xu a, Jie Zhang a, Yong Lu b
a
College of Chemistry and Chemical Engineering, Xi’an Shiyou university, Second Dianzi Road No. 18, Xi’an, Shaanxi 710065, China
b
Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Department of Chemistry, East China Normal University, Shanghai 200062, China

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

Article history: A high efficient production of fatty acid methyl ester (FAME) from soybean oil and rapeseed oil was
Received 14 August 2011 carried out using modified CaO as solid basic catalyst by connecting bromooctane to the surface of CaO
Received in revised form chemically in a simple way. It was found that 99.5% yield of the FAME over modified CaO was obtained
27 October 2012
from soybean oil using 15:1 molar ratio of methanol to oil after 3 h at reaction temperature of 65
C,
Accepted 1 November 2012
Available online 26 November 2012
which is much higher than the yield of 35.4% over commercial CaO at the same reaction conditions. For
the transesterification between rapeseed oil and methanol, the reaction time to its highest yield, 99.8%,
was shortened to 2.5 h. The physical and chemical properties of catalysts were characterized by using
Keywords:
Biodiesel
techniques of X-ray diffraction (XRD), scanning electron microscope (SEM), BET surface area measure-
Basic catalyst ment (BET), Fourier transform-infrared (FT-IR) spectroscopy and thermogravimeter (TG). The results
CaO indicated that well dispersed CaO with relatively small particle sizes and high surface areas were
Modification obtained after modification. Furthermore, the thermal stability of modified CaO is improved and the
amount of Ca(OH)2 formed during the modifying process is very little. Influence of the amount of
modifier and various reaction conditions, such as mass ratio of catalyst to oil, reaction temperature and
molar ratio of methanol to oil, were investigated in detail. Furthermore, water-tolerance of the modified
CaO was tested by adding water in the reaction system.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction catalysts offer several process disadvantages including the waste

water produced during the product cleaning and no opportunity to
Insufficient fossil storage makes urgent search for alternate operate a continuous process. Therefore many types of solid bases,
fuels, which have the same properties as diesel, to supply or replace such as alkali earth oxides and hydroxides, have been reported
fossil fuel (Ma and Hanna, 1999; Srivastava and Prasad, 2000; in the preparation of biodiesel to develop an eco-friendly and
Upham et al., 2009). Biodiesel, fatty acid methyl esters of seed efficiently biodiesel produce (Kawashima et al., 2008; Cantrell et al.,
oils and fats, has already been found suitable for using as an 2005; Dorado et al., 2004; Ngamcharussrivichai et al., 2008).
alternative fuel in diesel engine (Lynd, 1996). Besides, in the view of Among these heterogeneous basic catalysts, calcium oxide (CaO) is
environmental protection, biodiesel is a cleaner burning fuel for its a potential one for its low cost, high basic strength (H_ ¼ 26.5) and
essentially free of sulfur. The conventional method for biodiesel low methanol solubility (Nair et al., 2012). While the relatively low
production is transesterification of vegetable oils or animal fats reaction rate of CaO baffles its wide application. Many works have
with short-chain alcohols (generally methanol) in the presence of been devoted to enhance the reaction rate of CaO catalyst. Zhu et al.
catalysts (Marchetti et al., 2007; Meher et al., 2006a). (2006) obtained a 93% conversion of jatropha curcas oil using
Normally, both strong base and strong acid can be used as ammonium carbonate solution treated CaO. Watkins et al. (2004)
catalysts for transesterification between triglycerides and short promoted the basicity of CaO by doping CaO with lithium. Reddy
alcohol in a homogeneous system. Liquid base is preferred to liquid et al. tested nanocrystalline CaO in biodiesel productiond under
acid catalysis like sulfuric or sulphonic acids for its low corrosion to room temperature (Reddy et al., 2006), and the results showed that
equipment and high reaction activity. However, homogeneous base the first three cycles provided >99% conversions, but the conver-
sion decreased in the fourth and fifth cycles obviously. However,
the preparations of these catalysts are quite expensive or compli-
* Corresponding author. cated because the avoidance the rapid hydration and carbonation
E-mail address: tangying78@xsyu.edu.cn (Y. Tang). of CaO during the process of contacting with moisture air or in

0959-6526/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jclepro.2012.11.001
 Y. Tang et al. / Journal of Cleaner Production 42 (2013) 198e203 199

reaction system is very difficult. So the deactivation and stability of temperature range from 25
C to 800
C with a ramping rate
CaO catalyst are still the unsolved problems for biodiesel produc- of 10
C min1. X-ray diffraction patterns were recorded on
tion. Recently, the research of accelerating catalytic activity of CaO a D/Max-3C X-ray powder diffractometer (Rigalcu Co., Japan) using
for biodiesel production was aimed at the activation of CaO by a Cu-Ka source fitted with an Inel CPS 120 hemispherical detector.
pretreatment with methanol (Kawashima et al., 2009; Liu et al., An FT-IR infrared spectrophotometer (Nicolet 6700, USA) was used
2008a) or under supercritical condition (Kiwjaroun et al., 2009), to identify the surface group of the CaO. SEM photographs were
while the activation mechanism was still controversial. taken by Quanta 200 scanning electron microscope equipped
The interesting of our research group is to develop a new CaO with an energy dispersive spectrometer (Philips-FEI Co., the
derivate catalyst for the transesterification between vegetable oil and Netherlands). The nitrogen adsorptionedesorption isotherms at
methanol with excellent performance and good stability in water- 77 K of the solid catalysts were measured by the static method in an
contained reaction system. Both the CaO activation condition and automatic volumetric Micrometritics ASAP 2010 adsorption
various reaction conditions for transesterification were investigated. analyzer. The leaching of the catalyst into the reaction medium was
determined using inductively coupled plasma mass spectrometry
2. Experimental (ICP-MS, Thermo Jarrell Asch IRIS Advange 1000) technique.

2.1. Materials 3. Results and discussion

Soybean oil and rapeseed oil were purchased from Oil and Fats 3.1. Characterization of the catalyst
Company of Xi’an (Shaanxi, China). The oil was refined by
neutralization with Na2CO3 (105 g/kg, Na2CO3/oil) as described (Liu The IR spectra of the commercial CaO and modified CaO with
et al., 2008b). Calcium oxide (CaO) was purchased form Keou Fine 5 mg/g bromoocatane are shown in Fig. 1. The bottom spectrum
Chemical Co., Tianjing. Methanol (99.8% purity), bromooctane and represents the modified CaO. The spectra bands at 867 cm1 and
heptadecanoic acid methyl ester were obtained from Sigma 1477 cm1 are detected over two catalysts that can be assigned to
Chemcial Co. the vibration modes of mono and bidentate carbonates. Besides, the
characteristic absorption of C]O between 2000 and 1500 cm1
2.2. Modification of CaO indicates the presence of calcium carbonate over these two cata-
lysts. Apparently, the intensity increased after modifying, sug-
The commercial CaO was modified as follows: 2.1 g of gesting the modified CaO still has strong basic property which
commercial CaO particles without elimination of its hydroxide and causes the adsorption of CO2 at room temperature. The bands at
carbonates were added into 30 ml bromooctane/hexane solution 1621 and 3460 cm1 are associated with eOH mode of water
with bromooctane concentration (weight to CaO) ranged from physisorbed on the surface of the CaO. The important feature
5 mg/g to 105 mg/g under stirring at room temperature for acti- stretching of alkane at the range from 2800 to 3000 cm1 and the
vation. After 24 h, the particles were separated and washed with bending alkane at 1440 cm1 is observed over modified CaO
hexane; then, the modified CaO was obtained after a vacuum (Granados et al., 2007). Furthermore, the characteristic stretching
drying process. of eCeO appeared at the band from 1050 cm1 to 1085 cm1
indicates the modifier connects CaO surface chemically.
2.3. The procedure for the synthesis of biodiesel Fig. 2 shows the XRD pattern of the CaO before and after
modifying with 5 mg/g bromoocatane. A series of reflections at 32.1,
The catalytic activities for the transesterification of soybean oil 37.3 and 53.9 is consistent with X-ray diffractograms of CaO. Minor
with methanol were measured using typical procedure as follows: reflections at 17.9, 28.6, 34.1, 46.9 and 50.7 of commercial CaO are
a given amount of modified CaO and methanol were placed in attributed to Ca(OH)2 phases, indicating the hydration of
a three necked flask equipped with a reflux condenser and a ther- commercial CaO (Ngamcharussrivichai et al., 2007). The peaks at
mometer. Then, the soybean oil was added into the mixture and 29.2 and 38.9 are assigned to the reflection of CaCO3 due to the
heated to set temperature. Samples (about 0.05 g) were withdrawn exposure of fresh CaO in air during modification process.
at various intervals, and then the solid catalyst was separated by
filtration and excess methanol was distilled off under vacuum. The
products were analyzed by the GC (HP-6890) using inner standard
method as described by Granados et al. (2007). The yield was
defined as a ratio of the weight of fatty acid methyl esters to the
weight of fatty acid methyl esters in theory.
Transmission [%]

2.4. Reusability

The reusability of modified CaO was investigated at same react

condition by repeating the transesterification reaction several
times with used catalysts. Catalysts were separated from the
previous reaction mixture by centrifugation, washed with hexane,
and then dried at 60
C. The sample was collected and was sub-
jected to GC analysis for the fatty acid methyl ester determination
as described earlier.

2.5. Catalyst characterization 4000 3500 3000 2500 2000 1500 1000 500
-1
Frequence [cm ]
TGA experiments were carried out using Q600 SDT thermal
analysis machine (TA Instruments, USA) under a flow of air in the Fig. 1. IR pattern of commercial CaO and modified CaO.
200 Y. Tang et al. / Journal of Cleaner Production 42 (2013) 198e203

CaO Table 1
Ca(OH)2 BET surface area, total pore volume and average pore diameter of commercial CaO
CaCO3 and modified CaO.

Catalyst Commercial CaO Modified CaO

BET area (m2/g) 21.1 68.6
Modified CaO Total pore volume (cm3/g) 0.012 0.033
Intensity(a.u.)

Average pore diameter (nm) 1.96 1.93

temperature range from 400
C to 700
C due to the loss of H2O and
CO2 from hydrated and carbonated CaO. Furthermore, the DSC
curve of the modified CaO presents two broad peaks at 450
C and
Commercial CaO
700
C corresponding to the decomposition of Ca(OH)2 and CaCO3
formed by the hydration and carbonation of CaO in the storage
and preparation (Yang et al., 2009), which are lower than those
reported (Vujicic et al., 2010) due to the deposition of organic
15 20 25 30 35 40 45 50 55 60 65 70 75 80
modifier over CaO surface (Ngamcharussrivichai et al., 2008).
o
However, decomposition temperatures of Ca(OH)2 and CaCO3 over
2 Theta [ ] modified CaO are still higher than those of commercial CaO (339
C
and 614
C), suggesting that the thermal stability of modified CaO is
Fig. 2. XRD pattern of commercial CaO and modified CaO.
enhanced. Furthermore, from the percentage of weight loss corre-
sponding to the decomposition of Ca(OH)2 in the two samples,
Comparing the main peak area, it can be seen that the diffraction 2.305% for commercial CaO and 2.414% for modified CaO, it can be
peaks corresponding to the CaO phases of commercial CaO particles concluded that the amount of Ca(OH)2 formed during modifying
are slightly less intense than that of the modified CaO. The high procedure is relatively less.
intensity observed in the XRD pattern of modified CaO points to the
larger dimensions of the modified crystallite. 3.2. Catalytic activities test
Scanning microscopy was extensively been used for examina-
tion of the morphology of catalyst surfaces. The SEM micrographs 3.2.1. Transesterification reaction
of commercial CaO particles and modified CaO with 5 mg/g bro- The transesterification process conducted by GC at the catalysis
moocatane are shown in Fig. 3. Great difference can be found of modified CaO with 5 mg/g bromoocatane were introduced and
between these two samples. It can be seen that the surface of discussed. Fig. 5 gives the compositions of produced biodiesel,
commercial CaO particle is built in aggregates, while the modified wherein soybean oil was successively converted into diglyceride
CaO presents a more exfoliated morphology, which can be regarded and monoglyceride, and finally into glycerin and FAMEs as same as
as one aspect to its higher catalytic activities. reported results (Xie and Li, 2006; Barakos et al., 2008). It can be
The BET surface area, total pore volume and pore diameter of seen that the obtained biodiesel consisted of six FAMEs: palmitic
commercial CaO and modified CaO with 5 mg/g bromoocatane acid (C16:0), palmitoleic acid (C16:1), stearic acid (C18:0), oleic acid
were measured and summarized in Table 1. From the result, it can (C18:1), linoleic acid (C18:2), and linolenic acid (C18:3).
be seen that the modified CaO processes a higher surface area
(68.6 m2/g) as a result of surface exfoliation. On the other hand, 3.2.2. Influence of amount of modification reagent
large pores (0.03 cm3/g) on modified CaO indicate that there are The amount of modifier is a key factor to the catalytic activity
few pores located between the exfoliated sheets, which is favorable of modified CaO. In this work, the influence of modifier amount on
to be used in the liquidesolid heterogeneous phase reactions due to the catalytic activity was investigated by using the commercial
the enough large reaction area in stirred reactor. CaO particles treated with different amount of bromooctane
Fig. 4 shows the TG/DSC thermogram of modified CaO with from 105 mg/g to 5 mg/g (the mass ratio of modifier to CaO).
5 mg/g bromoocatane. There are two steps in the TG curve in the The transesterification activity results are summarized in Fig. 6.

Fig. 3. SEM photographs of commercial CaO (A) and modified CaO (B).
 Y. Tang et al. / Journal of Cleaner Production 42 (2013) 198e203 201

20 9 100

DSC(mV/mg) 90
10

80
8
0

Weight loss [mg]

70

FAME yield [%]

-10
DSC [mV]

60
7
TG(%) 50
-20

40
-30 5 mg/g
6
30 1 mg/g
-40
0.1 mg/g
-3
20 10 mg/g
-5
-50 5 10 mg/g
10
100 200 300 400 500 600 700 800
o
Temperaure [ C] 1 2 3 4 5
Reaction time [h]
Fig. 4. TG/DSC thermogram of modified CaO.
Fig. 6. Effect of amount of modifier on the FAME yield from soybean oil. Reaction
conditions: temperature 65
C, concentration of modified CaO 5 wt%, methanol/oil
These results show that after 1 h the catalyst that treated with molar ratio 30:1.
1 mg/g gives FAME yield of 27.12% while after 5 h the conversion of
triglycerides into FAME increases to an optimal value of 99.5%.
Further modifier incensement leads to lower yield of FAME because methanol to oil from 5 to 15, and further increase of methanol
of the occupation of active sites on CaO surface by excessive amount effect on the yield of FAME slightly, which is due to the
modifier. dilution effect by too much alcohol, and moreover high alcohol
amount slows down the separation of the glycerin phase and the
3.2.3. Influence of catalyst concentration methyl ester phase (Kawashima et al., 2009). Therefore, the
The effect of modified CaO concentration on the trans- optimum ratio of methanol/oil is 15:1.
esterification was investigated with the concentration varying from
1 wt% to 15 wt% (weight to oil) at 65
C with methanol/oil molar ratio 3.2.5. The comparison of modified CaO and commercial CaO
of 30:1. From the results (Fig. 7), it can be found that low concen- The comparison on the catalytic activities of the modified CaO
tration of catalyst is insufficient to catalyze the reaction for and commercial CaO was carried out under the optimum reaction
completion (Eevera et al., 2009), initially increasing the amount of condition obtained from above study: 65
C, 5 wt% catalyst of
catalyst results in enhancement of the yield. No further enhance- catalyst (weight to oil) and 15:1 molar ratios of methanol/oil. It can
ment of FAME yield is gained as excessive catalyst is employed. The be noticed that the difference in FAME yield for these two pro-
reason for this decreasing trend is due to the saponification in cessed is obvious. Fig. 9 shows that the yield of FAME over the
presence of high amount of catalysts, which increases the viscosity modified catalyst was enhanced near to 99.2% in the presence of the
of the reactants and lowers the yield of FAME as suggested by Yang modified CaO, while 35.4% for commercial CaO at the same reaction
et al. (2007). Therefore the 5 wt% modified CaO is the optimal time when soybean oil was used as resource. Only larger surface
catalyst amount in this reaction. area and pores of modified CaO cannot cause the great enhance of

3.2.4. Influence of methanol/oil ratio

An excessive alcohol is used in biodiesel production to ensure 100
the oils completely converting to methyl esters in a short time. In
our work, the investigation of methanol/oil ratio on the FAME yield 90
(Fig. 8) showed that the yield of FAME increases with the ratio of
80
FAME yield [%]

70

60

50
1%
3%
40
5%
10%
30 15%

1 2 3 4 5
Reaction time [h]

Fig. 7. Effect of modified CaO concentration on the FAME yield from soybean oil.
Reaction conditions: temperature 65
C, amount of modifier 1 mg/g, methanol/oil
Fig. 5. GC graph for biodiesel. molar ratio 30:1.
202 Y. Tang et al. / Journal of Cleaner Production 42 (2013) 198e203

100 Table 2
Water content test for biodiesel production over modified CaO.

90 Water content (%) Biodiesel yield (%)

0.5 98.8
80 1.0 99.3
2.0 99.1
5.0 91.4
FAME yield [%]

70
6.0 70.8

60

occur (Reddy et al., 2006). In our work, the effect of water content
50
on FAME yield over the modified CaO was carried out. From Table 2,
5.0:1
it can be seen that the reaction maintains 91.4% yield of biodiesel
40 10.0:1
even 5% water contained in the reaction system, which is much
15.0:1
30.0:1 higher than the reported water tolerance limit, 3.2%. The possible
30
reason may be attributed to the hydrophobicity of alkyl groups of
1 2 3 4 5
modifier, which protect the water molecular away from CaO surface
and keep its stability.
Reaction time [h]

Fig. 8. Effect of molar ratio of methanol to oil on the FAME yield from soybean oil. 3.2.7. Repeated experiments and properties of biodiesel
Reaction conditions: temperature 65
C, amount of modifier 1 mg/g, catalyst In general, the tests of reusability are important factors to
concentration 5%. heterogeneous catalysts for industry application. Therefore, unless
the stability of catalysts can be improved significantly, none will be
suitable for industrial use. The reusable property of commercial
FAME yield but the hydrophobic alkyls of modifier greatly promote
CaO and modified CaO was investigated under the optimum reac-
the diffusion of oil to CaO surface and then enhance the internal
tion condition (Fig. 10). The results showed that, in the commercial
diffusion. Therefore, the heterogeneity of the three-phase reaction
CaO catalyzed reactions, the yield maintains on a low level, no more
system is weakened. In order to investigate the activity of modified
than 56%, and the deactivation occurs after reused in 4 cycle. The
CaO to other kind of oil, rapeseed oil was used for comparison. As
FAME yield reaches to 95% over modified CaO and maintains sus-
same as the activity results for transesterification between soybean
tained activity even after being used for 15 cycles with slight
oil and methanol, modified CaO has shown promising results in the
decrease which is higher than previous report (Granados et al.,
case of rapeseed oil. The FAME yield from rapeseed oil is little
2009) and provides the opportunity to operate a continuous
higher than that when using soybean oil during the total reaction
process in industrial application. The filtrates of the reaction
time. This should be contributed to the different composition of the
mixture were measured by ICPeAES to evaluate the leaching of
two oils.
calcium. Less calcium of 26 ppm and 10 ppm was detected after first
and second cycles indicating that the dissolve amount of calcium
3.2.6. Water tolerance of modified CaO
oxide into the reaction medium is insignificant.
Previous study for the transesterification between methanol
Furthermore, some properties of prepared biodiesel produced
and oil showed that trace water increases the reaction rates for the
by modified CaO including viscosity, density, flash point and ester
generation of more methoxide anions (Meher et al., 2006b).
content are listed in Table 3. Obtained values over commercial CaO
However, too much water leads to saponification of FAME and
and modified CaO are similar and coherent with EN14214 and the
greatly reduces the hydroxyl groups since the hydration of CaO will
literature values (Demirbas, 2003). However, the time required to

100
100

80 80
FAME yield [%]

60
FAME yield %

60

modified CaO
40 40 commercial CaO

modified CaO+soybean oil

20 20
commercial CaO+soybean oil
modified CaO+rapeseed oil
commercial CaO+rapeseed oil
0 0
1 2 3 4 5 0 2 4 6 8 10 12 14 16
Reaction Time [h] Number of repetitions

Fig. 9. Comparison the catalytic activity over commercial CaO and modified CaO. Fig. 10. Effect of repeated use on FAME yield over commercial CaO and modified CaO
Temperature: 65
C concentration of modified CaO: 5 wt% molar ratio of methanol to from soybean oil: 65
C temperature, 15:1 molar ratios of methanol to oil, 5 h and 5 wt
oil: 15:1 Amount of modifier: 1 mg/g. % catalyst amount.
 Y. Tang et al. / Journal of Cleaner Production 42 (2013) 198e203 203

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