Calcium Ethoxide as a Solid Base Catalyst for the

Transesterication of Soybean Oil to Biodiesel

Xuejun Liu, Xianglan Piao, Yujun Wang,* and Shenlin Zhu
State Key Laboratory of Chemical Engineering, Tsinghua UniVersity, Beijing 100084, China
ReceiVed August 29, 2007. ReVised Manuscript ReceiVed NoVember 20, 2007
In this work, calcium ethoxide is proposed as a catalyst for the transesterication of soybean oil to biodiesel
with methanol and ethanol. First, calcium ethoxide was synthesized through a calcium reaction with ethanol.
Then, its physical and chemical characteristics were determined using instrumental methods such as
Brunauer-Emmett-Teller surface area measurements, scanning electron micrographs, and particle size
distribution measurements. The effects of the mass ratio of catalyst to oil, the molar ratio of methanol to oil,
and the reaction temperature were studied to optimize the reaction conditions. The experimental results showed
that the optimum conditions are a 12:1 molar ratio of methanol to oil, the addition of 3% Ca(OCH
2
CH
3
)
2
catalyst, and a 65 C reaction temperature. A 95.0% biodiesel yield was obtained within 1.5 h in these conditions,
and the activation energy was 54 149 J/mol. It also indicated that the catalysis performance of calcium ethoxide
is better than that of CaO. Besides, a 91.8% biodiesel yield was obtained when it catalyzed soybean oil to
biodiesel with ethanol.
1. Introduction
Fatty acid methyl esters are known as the sources of biodiesel,
which is synthesized by the direct transesterication of vegetable
oils with a short-chain alcohol in the presence of a catalyst.
The transesterication reaction can be carried out using both
homogeneous (acid or base) and heterogeneous (acid, base, or
enzymatic) catalysts.
1,2
Homogeneous base catalysts provide
much faster reaction rates than heterogeneous catalysts, but it
is considerably more costly to separate homogeneous catalysts
from the reaction mixture.
3,4
Heterogeneous catalysis has many advantages, such as being
noncorrosive, being environmentally benign, and presenting
fewer disposal problems. These catalysts are also much easier
to separate from liquid products, and they can be designed to
give a higher activity and selectivity and to have longer catalyst
lifetimes. Many types of heterogeneous catalysts, such as
alkaline earth metal oxides, anion exchange resins, and various
alkali metal compounds supported on alumina or zeolite, can
catalyze many types of chemical reactions, such as isomeriza-
tion, aldol condensation, Knoevenagel condensation, Michael
condensation, oxidation, and transesterication.
58
In transes-
terication of vegetable oils to biodiesel, most supported alkali
catalysts and anion exchange resins exhibit a short catalyst
lifetime because the active ingredients are easily corroded by
methanol.
9,10
Some researchers found that alkaline-earth oxide
compounds, such as CaO and SrO, have a slight solubility in
methanol and have good catalytic activity and a long catalyst
lifetime.
11,12
Gryglewicz studied the alkaline-earth metal alkoxides as
catalysts for alcoholysis reactions in terms of the synthesis of
di(2-ethylhexyl) adipate and an oligomeric ester of neopentyl
glycol and found that magnesium methoxide and calcium
alkoxides appear to be active catalysts for the transesterica-
tion.
13
Gryglewicz
12
and Liu et al.
14
studied calcium methoxide
as a solid base catalyst to catalyze the transesterication of
soybean oil to biodiesel and found that it has excellent catalytic
activity and a long catalyst lifetime. In this research, we studied
calcium ethoxide as one of the alkaline-earth metal alkoxide
catalysts for the transesterication of soybean oil to biodiesel.
* To whom correspondence should be addressed. Telephone: +8610-
62773017. Fax: +8610-62770304. E-mail: wangyujun@
mail.tsinghua.edu.cn.
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factorial design of experiments and response surface methodology to
optimize biodiesel production. Ind. Crops Prod. 1998, 8, 2935.
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yields of fatty esters from transesteried vegetable oils. J. Am. Oil Chem.
Soc. 1984, 61, 16381643.
(3) Ma, F.; Hanna, M. A. Biodiesel production: a review. Biotechnol.
Tech. 1999, 70, 115.
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J. S.; Lee, K. Y. Tranesterication of vegetable oil to biodiesel using
heterogeneous base catalyst. Catal. Today 2004, 93, 315320.
(5) Schachter, Y.; Herman, P. Calcium-oxide-catalyzed reactions of
hydrocarbons and of alcohols. J. Catal. 1968, 11, 147158.
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catalyzed by potassium loaded on alumina as a solid-base catalyst. Appl.
Catal., A 2006, 300, 6774.
(7) Suppes, G. J.; Dasari, M. A.; Doskocil, E. J.; Mankidy, P. J.; Goff,
M. J. Transesterication of soybean oil with zeolite and metal catalysts.
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to 3-buten-2-one over solid base catalysts. Appl. Catal., A 2001, 214, 121
124.
(9) Ebiura, T.; Echizen, T.; Ishikawa, A.; Murai, K.; Baba, T. Selective
transesterication of triolein with methanol to methyl oleate and glycerol
using alumina loaded with alkail metal salt as a soid-base catalyst. Appl.
Catal., A 2005, 283, 111116.
(10) Veldurthy, B.; Clacens, J. M.; Figueras, F. Correlation between
the basicity of solid bases and their catalytic activity towards the synthesis
of unsymmetrical organic carbonates. J. Catal. 2005, 229, 237242.
(11) Liu, X. J.; He, H. Y.; Wang, Y. J.; Zhu, S. L. Transesterication
of soybean oil to biodiesel using SrO as a solid base catalyst. Catal.
Commun. 2007, 8, 11071111.
(12) Gryglewicz, S. Rapeseed oil methyl esters preparation using
heterogeneous catalysts. Bioresour. Technol. 1999, 70, 249253.
(13) Gryglewicz, S. Alkaline-earth metal compounds as alcoholysis
catalysts for ester oils synthesis. Appl. Catal., A 2000, 192, 2328.
(14) Liu, X. J.; He, H. Y.; Wang, Y. J.; Zhu, S. L. Calcium methoxide
as a solid base catalyst for the transesterication of soybean oil to biodiesel
with methanol. Fuel 2007, in press, available online 19 July 2007.
Energy & Fuels 2008, 22, 13131317 1313
10.1021/ef700518h CCC: $40.75 2008 American Chemical Society
Published on Web 01/31/2008
The physical and chemical characterizations of calcium ethoxide
were analyzed with some instrumental methods. Then, the
effects of various reaction conditions on the biodiesel yields
were investigated.
2. Experimental Section
2.1. Materials and Catalyst Preparation. Ca(OCH
2
CH
3
)
2
was
synthesized in a 100 mL glass reactor with a condenser. The
magnetic stirring rate was 800 rpm. The reaction procedure was as
follows: First, calcium was dispersed in ethanol under magnetic
stirring. Then, it was heated to 65 C by water circulation. The
reaction can be expressed by eq 1. After 8 h of reaction, ethanol
was rst distilled off under vacuum. Then, the catalyst was dried
in an oven at 105 C for 1 h.
Ca +2CH
3
CH
2
OH )
65 C
Ca
(
OCH
2
CH
3
)
2
+H
2
v (1)
Rened soybean oil was purchased from Tianjin Jiali Oil Plant.
The fatty acid composition consisted of 12.5% palmitic acid, 5.2%
stearic acid, 23.5% oleic acid, 47.8% linoleic acid, 10% linolenic
acid, and traces of other acids. Methanol was analytical reagent
grade and was purchased from Beihua Fine Chemical Co., Beijing.
Analytical reagents (e.g., standards for high performance liquid
chromatography (HPLC)) were of high grade and were obtained
from Sigma Chemical Co. All other chemicals were analytical
reagents and were purchased from Beihua Fine Chemical Co.,
Beijing.
2.2. Apparatus and Procedure. The Brunauer-Emmett-Teller
(BET) surface area, total pore volume, and pore size distribution
of Ca(OCH
2
CH
3
)
2
were measured with a Quantachrome Autosorb-
1-C chemisorption-physisorption analyzer. A weighed sample of
the catalyst was prepared by outgassing for 1.5 h at 423 K on the
degas port. Adsorption isotherms were generated by dosing nitrogen
onto the catalyst in a bath of liquid nitrogen at approximately 77
K. The BET surface area was calculated from the adsorption
branches in the relative pressure range of 0.050.25 bar, and the
total pore volume was evaluated at a relative pressure of about 0.99
bar. The pore size distribution was calculated from the desorption
branches using the BarrettJoynerHalenda (BJH) method. The
particle size distribution was measured using a Malvern Mastersizer
MICRO-PLUS laser particle size analyzer and evaluated by a
volume concentration. An FTIR-8201 (PC) infrared spectropho-
tometer was used to identify the surface group of the catalyst.
Scanning electron microscopy (SEM) observations were performed
on a Hitachi JEOL JSM 7401F microscope operating at 1.0 kV.
Thermogravimetry (TG) was performed with a Netzsch TA-449C
TG analyzer from 25 to 1000 C at a heating rate of 10 C/min
under air atmosphere. The solubility of the catalyst in methanol
and ethanol was determined by measuring the calcium concentration
with a HITACHI Z-5000 polarized zeeman atomic absorption
spectrophotometer.
2.3. Reaction Procedures. The transesterication reactions (eq
2) were carried out in a 100 mL glass reactor with a condenser.
The magnetic stirring rate was 800 rpm. The reaction procedure
was as follows: First, the catalyst was dispersed in methanol under
magnetic stirring. Then, the soybean oil was added into the mixture
and heated by water circulation. The amount of soybean oil was 28
mL every time. After the reaction, the excess methanol was distilled
off under vacuum and the Ca(OCH
2
CH
3
)
2
catalyst was separated
by centrifugation. After removal of the glycerol layer, the biodiesel
was collected for chromatographic analysis.
2.4. Analysis. The biodiesel samples were analyzed in an HP
5890 gas chromatograph equipped with a ame ionization detector
and a capillary column HP-INNOWAX (30 m 0.15 mm 0.25
m). Four microliters of the upper oil layer were dissolved in 300
L of n-hexane and 100 L of the internal standard solutions
(heptadecanoic acid methyl ester-n-hexane solution) for gas
chromatography (GC) analysis. Samples (1 L) were injected by a
sampler at an oven temperature of 220 C. After an isothermal
period of 4 min, the GC oven was heated at 10 C/min to 230 C
and held for 7.5 min. Nitrogen was used as the carrier gas at a
ow rate of 2 mL/min measured at 20 C and as the detector make
up gas at a ow rate of 30 mL/min. The inlet pressure was 96.4
kPa. The split ratio was 10:1. The injector temperature and detector
temperatures were 300 and 320 C, respectively.
The biodiesel yield in each experiment was calculated by the
following expression:
yield )
m
actual
m
theoretical
100%
C
esters
n V
esters
m
oil
100%
C
esters
n V
oil
m
oil
100%
C
esters
n
F
oil
100%
where both m
actual
[g] and m
theoretical
[g] are the masses of methyl
ester; m
oil
[g] is the mass of the vegetable oil that was used in the
reaction; C
ester
[g/mL] is the mass concentration of methyl ester
which was acquired by GC; n is the diluted multiple of methyl
ester; F
oil
[g/mL] is the density of the vegetable oil; and V
esters
[mL]
and V
oil
[mL] are the volumes of crude ester layer and vegetable
oil, respectively.
3. Results and Discussion
3.1. Characterizations of the Ca(OCH
2
CH
3
)
2
Solid Base
Catalyst. The analyzed results indicate that calcium ethoxide
possesses a surface area of 15.02 m
2
/g and a total pore volume
of 0.100 cm
3
/g. It is favorable for use in a slurry reactor. Fig-
ure 1 shows the SEM image of the Ca(OCH
2
CH
3
)
2
catalyst. It
shows that the surfaces comprise a large number of small pores.
Figure 2 shows the pore size distribution. It can be seen that a
Figure 1. SEM image of Ca(OCH
2
CH
3
)
2
.
(2)
1314 Energy & Fuels, Vol. 22, No. 2, 2008 Liu et al.
large part of the surface area is occupied by pores of relatively
large size between 30 and 100 nm.
Figure 3 shows the particle size distribution of the
Ca(OCH
2
CH
3
)
2
catalyst. It indicates that it has a broad particle
size distribution and that a large number of the catalyst particles
are within the size range of 1300 m; the remainder are within
the range of 0.61 m. Particle size distribution can markedly
affect the settling and ltering characteristics in a slurry reactor,
and a size range of 5200 m is favorable.
Figure 4 shows the IR spectra of Ca(OCH
2
CH
3
)
2
. It can be
seen that the important features appear in the C-H stretching
(28003000 cm
-1
), -C-H (alkane) bending (1460 cm
-1
), and
-C-O (primary alcohol) stretching (10501085 cm
-1
). The IR
peak between 2000 and 1500 cm
-1
is characteristic of CdO
because of the catalyst surface adsorbed CO
2
. Figure 5 shows
the TG and differential thermal analysis (DTA) thermogram of
the Ca(OCH
2
CH
3
)
2
catalyst. It can be seen that Ca(OCH
2
CH
3
)
2
begins to decompose at about 350 C, and a clear exothermic
peak appears between 330 and 400 C. The IR spectrum of
Ca(OCH
2
CH
3
)
2
, which was calcined under air at 350 C for
1 h, is identical to the spectrum of CaCO
3
. It indicates that the
decomposition of Ca(OCH
2
CH
3
)
2
has formed calcium carbonate.
Then, the calcium carbonate began to decompose, and this
appears in Figure 5 as a steep slope between 550 and 700 C.
The results of the TG analysis indicates that the Ca(OCH
2
CH
3
)
2
catalyst is stable under 300 C.
The solubility of a catalyst in reactants is an important
characteristic of a solid catalyst. The reaction will be homoge-
neous if the catalyst is soluble in reactants. Table 1 shows the
solubility of calcium ethoxide in methanol and ethanol at
different temperatures. The results indicate that the Ca
2+
concentration increases with increasing temperature, and the
solubility in methanol is much lower than that of the calcium
methoxide heterogeneous catalyst, which is about 0.04 wt %.
14
Therefore, calcium ethoxide mostly acted as a heterogeneous
catalyst in the transesterication of vegetable oils to biodiesel
with methanol or ethanol. The experimental results also indicate
that the biodiesel yield is proportional to the amount of catalyst.
3.2. Reaction Results. 3.2.1. Effect of Mass Ratio of Cata-
lyst to Oil on Biodiesel Yield. The mass ratio of Ca(OCH
2
CH
3
)
2
to soybean oil was varied within the range of 0.25-4.0%. The
biodiesel yield increased with increasing Ca(OCH
2
CH
3
)
2
, and
a 95.0% biodiesel yield was obtained by adding 4.0%
Ca(OCH
2
CH
3
)
2
(Figure 6). Therefore, with the addition of more
catalyst, there was also the faster rate at which the reaction
Figure 2. Pore size distribution of Ca(OCH
2
CH
3
)
2
.
Figure 3. Particle size distribution of Ca(OCH
2
CH
3
)
2
.
Figure 4. IR pattern of Ca(OCH
2
CH
3
)
2
.
Figure 5. TG/DTA thermogram of Ca(OCH
2
CH
3
)
2
.
Table 1. Ca
2+
Concentration (ppm) in Methanol and Ethanol at
Different Temperatures
temperature
solvent 20 C 30 C 40 C 50 C 60 C 65 C
methanol 1 2 9 12 14 36
ethanol 2 3 5 9 12 38
Transesterication of Soybean Oil to Biodiesel Energy & Fuels, Vol. 22, No. 2, 2008 1315
equilibrium was reached because of the increase in the total
number of available active catalytic sites for the reaction.
However, when the catalyst amount exceeded 3.0%, there was
little impact on the biodiesel yield by increasing Ca(OCH
2
CH
3
)
2
.
The biodiesel yield is determined by the surface reaction and
the mass transfer. In this reaction, the optimum addition of
catalyst is 3.0% by weight of oil. Gryglewicz obtained a 93.0%
biodiesel yield at 2.5 h using CaO powder as a solid base
catalyst. Therefore, the catalytic activity of calcium ethoxide is
better than that of CaO.
3.2.2. Effect of the Molar Ratio of Methanol to Oil on
Biodiesel Yield. The stoichiometry of this reaction requires 3
M methanol/1 M triglyceride. Excess methanol was used in this
study to obtain a higher biodiesel yield. The results are shown
in Figure 7. It indicates that the fast reaction rate was obtained
at a high molar ratio. The biodiesel yield was only 70.0% at
3 h of reaction when the molar ratio of methanol to oil was
3:1. However, the biodiesel yields all exceeded 93.0% when
the molar ratios were higher than 6:1. Considering both the
biodiesel yield and the saving methanol amount, the optimum
molar ratio of methanol to oil is 12:1.
3.2.3. Effect of Reaction Temperature on Biodiesel Yield.
Reaction temperature can inuence the reaction rate and the
biodiesel yield because the intrinsic rate constants are strong
functions of temperature. Figure 8 shows the effect of the
reaction temperature on the biodiesel yield. It indicates that the
reaction rate was higher at high temperature than at low
temperature. The biodiesel yield was only 29.9% at 30 C after
3 h of reaction, and it reached to 93.2% at 65 C after 1.5 h.
Therefore, the optimum reaction temperature for the transes-
terication of soybean oil to biodiesel is 65 C.
In excess of methanol, the transesterication is a pseudo-rst-
order reaction. The overall rate equation (k) can be given as eq 3.
k )-ln(1 -)/t (3)
where is the biodiesel yield. The average overall reaction rate
constant at different temperatures can be calculated according
to the above experimental data. Besides, the overall reaction
rate constant has a relationship with temperature as follows:
ln k )-
E
a
RT
+C (4)
where E
a
is the activation energy, R is the gas constant (J mol
-1
K
-1
), T is the absolute temperature, and C is a constant. Figure
9 gives the plot of ln k versus 1/T for the transesterication
reaction. Linear regression analysis of these data gives a slope
of -6513.855 with a correlation coefcient of -0.996 93. From
Figure 6. Effect of the mass ratio of Ca(OCH
2
CH
3
)
2
to oil on biodiesel
yield. Methanol/oil molar ratio, 12:1; reaction temperature, 65 C.
Figure 7. Effect of the molar ratio of methanol to oil on biodiesel
yield. Ca(OCH
2
CH
3
)
2
/oil mass ratio, 3.0%; reaction temperature, 65
C.
Figure8. Effect of reactiontemperatureonbiodiesel yield. Ca(OCH
2
CH
3
)
2
/
oil mass ratio, 3.0%; methanol/oil molar ratio, 12:1.
Figure 9. Plot of ln k vs 1/T for the transesterication reaction.
Table 2. Transesterication of Soybean Oil to Biodiesel with
Ethanol at Different Temperatures
a
biodiesel yield (%)
temperature 0.5 h 1 h 1.5 h 2 h 2.5 h 3 h
75 C 27.5 40.0 52.3 64.2 81.1 91.8
70 C 3.5 13.3 17.5 21.2 27.6 32.9
65 C 0.1 1.1 1.9 2.9 5.7 8.5
a
Catalyst/oil weight ratio, 3%; ethanol/oil molar ratio, 12:1.
1316 Energy & Fuels, Vol. 22, No. 2, 2008 Liu et al.
the plot of ln k versus 1/T, the slope is equal to (-E
a
/R). Thus,
a value for E
a
of 54 149 J/mol (12 954 cal/mol) was calculated
for the reaction. It indicates that the experimental value of the
activation energy in this study is consistent with that reported
in the literature for this transesterication using homogeneous
catalysts, such as NaOH, KOH, NaOCH
3
, NaOBu, H
2
SO
4
, and
so on.
1517
Noureddini reported activation energies for the
reaction involved in the transesterication of soybean oil to be
in the range of 6400-20 000 cal/mol, and Bernard and
co-workers reported these in the range of 800020 000 cal/mol.
3.2.4. Transesterication of Soybean Oil to Biodiesel with
Ethanol. Biodiesel can be produced by the transesterication
of soybean oil with ethanol. The experimental results are shown
in Table 2. It indicates that the reaction rate was slow at low
temperature. It cost 3 h to reach a 91.8% biodiesel yield at 75
C. Therefore, calcium ethoxide can also catalyze the transes-
terication soybean oil to biodiesel with ethanol. It has strong
basicity and can catalyze many transesterication reactions.
Some researchers have proposed some possible mechanisms in
chemical reactions over solid base catalysts.
5,1113,18,19
When
calcium ethoxide is used as a solid base catalyst, the catalysis
mechanism could be assumed to be one where that the catalytic
reactions take place on the surface of calcium ethoxide. The
proposed mechanism of the transesterication reaction by
calcium methoxide with ethanol is given in Figure 10. Alcohol
and triglyceride are adsorbed on two neighboring free catalytic
sites (O
-
and Ca
+
). The surface O
-
extracts an H
+
, and Ca
+
adsorbs CH
3
CH
2
O
-
from alcohol. The adsorbed triglyceride
forms a surface intermediate with the catalyst. The two
neighboring adsorbed species react to result in the formation
of a fatty acid methyl and a diglyceride. The diglyceride reacts
with alcohol along similar processes on the surface of the
catalyst to form glycerol and biodiesel.
4. Conclusions
From the experimental results, it can be seen that
Ca(OCH
2
CH
3
)
2
has excellent catalytic abilities as a solid base
catalyst. It has a moderate surface area, a relatively broader
particle size distribution, and a better low solubility in methanol
and ethanol. When it catalyzes the transesterication of soybean
oil to biodiesel with methanol, the optimal conditions are a 12:1
molar ratio of methanol to oil, the addition of 3.0%
Ca(OCH
2
CH
3
)
2
catalyst, a 65 C reaction temperature, and about
1.5 h of reaction time. The reactions are completed under mild
temperature and pressure conditions. This catalyst can also be
applied in other chemical reactions as a solid base catalyst.
Acknowledgment. The authors would like to thank Professor
Yigui Li for his kind help. This work was supported by the National
Basic Research Program (973 Plan, No. 2007CB714302).
EF700518H
(15) Darnoko, D.; Cheryan, M. Kinetics of palm oil transesterication
in a batch reactor. J. Am. Oil Chem. Soc. 2000, 77, 12631267.
(16) Noureddini, H.; Zhu, D. Kinetics of Transesterication of soybean
oil. J. Am. Oil Chem. Soc. 1997, 74, 14571463.
(17) Bernard, F.; Royden, O. B.; Evereff, H. P. Transesterication
kinetics of soybean oil. J. Am. Oil Chem. Soc. 1986, 63, 13751380.
(18) Dossin, T. F.; Reyniers, M. F.; Marin, G. B. Kinetics of hetero-
geneously MgO-catalyzed transesterication. Appl. Catal., B 2006, 61, 35
45.
(19) Hideto, T.; Fuyuki, Y.; Hideshi, H.; Hideaki, K. Self-condensation
of n-butyraldehyde over solid base catalysts. J. Catal. 1994, 148, 759
770.
Figure 10. Reaction mechanism for the transesterication of triglyceride with ethanol over the Ca(O CH
2
CH
3
)
2
catalyst, where R
1
, R
2
, and R
3
represent the long chain alkyl group.
Transesterication of Soybean Oil to Biodiesel Energy & Fuels, Vol. 22, No. 2, 2008 1317