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Fuel 87 (2008) 27982806

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Calcium oxide as a solid base catalyst for transesterication

of soybean oil and its application to biodiesel production
Masato Kouzu a,*, Takekazu Kasuno b, Masahiko Tajika b, Yoshikazu Sugimoto c,
Shinya Yamanaka d, Jusuke Hidaka d
a

JST-KFPT Core Research Center, Keihanna Interaction Plaza Inc., Laboratory Wing 4F, Keihanna Plaza, 1-7, Hikaridai, Seika, Kyoto 6190237, Japan
b
Shiraishi Kogyo Kaisha Ltd., 4-78, Motohama, Amagasaki, Hyogo 6600085, Japan
c
Energy Technology Research Institute, National Institute for Advanced Industrial Science and Technology, Tsukuba Central 5, 1-1-1, Higashi, Tsukuba,
Ibaraki 3058565, Japan
d
Department of Chemical Engineering and Material Science, Doshisha University, 1-3, Tataramiyakodani, Kyotanabe, Kyoto 6100321, Japan
Received 6 March 2007; received in revised form 18 October 2007; accepted 19 October 2007
Available online 20 November 2007

Abstract
In order to study solid base catalyst for biodiesel production with environmental benignity, transesterication of edible soybean oil
with reuxing methanol was carried out in the presence of calcium oxide (CaO), -hydroxide (Ca(OH)2), or -carbonate (CaCO3). At 1 h of
reaction time, yield of FAME was 93% for CaO, 12% for Ca(OH)2, and 0% for CaCO3. Under the same reacting condition, sodium
hydroxide with the homogeneous catalysis brought about the complete conversion into FAME. Also, CaO was used for the further tests
transesterifying waste cooking oil (WCO) with acid value of 5.1 mg-KOH/g. The yield of FAME was above 99% at 2 h of reaction time,
but a portion of catalyst changed into calcium soap by reacting with free fatty acids included in WCO at initial stage of the transesterication. Owing to the neutralizing reaction of the catalyst, concentration of calcium in FAME increased from 187 ppm to 3065 ppm.
By processing WCO at reux of methanol in the presence of cation-exchange resin, only the free fatty acids could be converted into
FAME. The transesterication of the processed WCO with acid value of 0.3 mg-KOH/g resulted in the production of FAME including
calcium of 565 ppm.
2007 Elsevier Ltd. All rights reserved.
Keywords: Biodiesel; Calcium oxide; Solid base catalyst; Free fatty acid; Cation-exchange resin

1. Introduction
Much attention has been taken in vegetable oil as a
renewable energy resource which is benecial to easing
down greenhouse gas emission. Although vegetable oil
can be turned into fuel oil by pyrolysis, dilution with liquid
hydrocarbon, and emulsication, the most practical technique is transesterication with methanol [1]. The transesterication converts vegetable oil into fatty acid methyl
esters (FAME) with the appropriate properties for diesel

Corresponding author. Tel.: +81 774 98 2210; fax: +81 774 98 2214.
E-mail address: mkouzu@kcoe.jp (M. Kouzu).

0016-2361/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2007.10.019

fuel oil. These were the reason why the transesteried vegetable oil is extensively popularized as Biodiesel.
For a current process of biodiesel production, methanol
solution of alkali hydroxide was used as the catalyst.
Freedman et al. reported that transesterication of vegetable oil was completed for 1 h of reaction time by using the
solution of NaOH [2]. Although sulfuric acid can catalyze
the transesterication, the acid-catalyzed transesterication
is seriously slow as compared to the base-catalyzed one
[3,4].
However, it should be noted that the current process
includes some problems resulting from the homogeneous
catalysis of alkali-hydroxide. Massive wastewater was
discharged from the process to wash the dissolved
alkali-hydroxide o the produced biodiesel. Further,

M. Kouzu et al. / Fuel 87 (2008) 27982806

alkali-hydroxide invites the soap formation causing considerable loss of the transesteried product. Since the production cost runs up by reason of these problems, many
researchers have studied to develop noble process producing biodiesel without using alkali-hydroxide.
As one of the noble processes, catalyst-free transesterication utilizing supercritical methanol was studied by Saka
and Kusdiana [5,6]. By their process, rapeseed oil was converted into biodiesel for only 4 min at 350 C under
30 MPa with a molar ratio of oil to methanol of 1:42.
Lipase can lead to the enzymatic transesterication, which
has the advantage over the transesterication using alkalihydroxide: easy product recovery and the mildest reaction
condition [7]. However, the reaction rate seriously
decreases in the absence of organic solvent such as hexane
because of inactivation of lipase [8].
The transesterication catalyzed by solid base is a bright
technology for the noble process featuring the fast reaction
rate under the mild reacting condition. Xie et al. carried
out an experimental transesterication of soybean oil at
reux of methanol in the presence of alumina supported
potassium [9]. Shibasaki-Kitagawa et al. reported that
anion-exchange resin with porous texture can be utilized
as the solid base catalyst in their process including regeneration step of the catalyst with aqueous solution of alkalihydroxide [10].
Our interests were focused on calcium oxide for the purpose of studying the noble process using the solid base catalyst from the viewpoint of their economical advantage,
because we found that calcium oxide was quite active in
transesterication of soybean oil with reuxing methanol
[11]. In this paper, the catalytic activity of calcium oxide
was compared with those of other solid bases: magnesium
oxide, strontium oxide, calcium hydroxide and -carbonate.
In order to utilize calcium oxide for the noble process, we
must understand the transesterication of waste cooking
oil deeply. Indeed waste cooking oil is an economical feedstock, but it includes a considerable amount of free fatty
acids inhibiting the base-catalyzed transesterication [12].
We indicated in our previous report that calcium oxide
was converted into the inert compound by reacting with
free fatty acids [13]. In order to protect the solid base catalyst from the poisoning, we also studied the multi-step
transesterication combining with a pretreatment for
removal of the free fatty acids from waste cooking oil.
Additionally, we paid attention to the inuences of moisture and polar fraction on the catalytic activity for characterizing the transesterication of waste cooking oil.
2. Experimental
2.1. Catalyst preparation

For these calcium compounds, basic properties were determined by the indicator method. After the catalyst was dispersed in a toluene solution of the indicator, color change
of the indicator was observed. Strength of the basic site was
expressed by an acidity function (H_) dened by Eq. (1),
where [BH] and [B] are the concentration of the indicator
and its conjugated base, respectively, and pKBH is the logarithm of the dissociation constant of the indicator used
[14]:
H pK BH logB =BH

The used indicators were as follows: bromothymol blue

(pKBH = 7.2), phenolphthalein (pKBH = 9.3), 2,4-dinitroaniline (pKBH = 15.0), and 4-nitroaniline (pKBH = 18.4).
Amount of the basic sites was measured through the titration using phenolphthalein. The particle size was observed
on a scanning electron microscope (SEM). The surface area
was calculated by BET method using data on nitrogen
adsorption at 77 K. Table 1 summarizes properties of calcium compounds used as the catalyst.
Additionally, magnesium oxide (MgO) and strontium
oxide (SrO) were put use to as the reference samples of
CaO. Their carbonates were calcined at the prescribed temperature: 500 C for MgO, and 1050 C for SrO.
H-Y zeolite, sulfated titanium oxide (SO4/TiO2), and
cation-exchange resin were employed as solid acid catalyst
for esterication of free fatty acids included in waste cooking oil. H-Y zeolite with Si/Al ratio of 5.5 was purchased
from Wako chemicals. Activation of the sample was conducted at 500 C for 3 h in air [15]. SO4/TiO2 was prepared
by the method outlined by Arata [16]. After hydrolysis of
titanium (IV) isopropoxide, the collected precipitation
was immersed in a 1 M aqueous solution of ammonium
sulfate. Following lteration and drying, the sample was
calcined at 525 C for 3 h in air to activate. The employed
cation-exchange resin was sulfonated styrene-divinylbenzene copolymer bead: Amberlyst-15 manufactured by
Rohm and Haas. Since it was in the acid form, only the
immersion with methanol was carried out as the
pretreatment.

Table 1
Properties of calcium compounds used as solid base catalyst for
transesterication of soybean oil with reuxing methanol
Basic sites

CaO
Ca(OH)2
CaCO3
CaOAird
a

Calcium oxide (CaO) was obtained after calcination of

pulverized lime stone (CaCO3) at 900 C for 1.5 h in a
helium gas ow. Calcium hydroxide (Ca(OH)2) was prepared by hydration of CaO in a gas ow of moist helium.

2799

Surface areaa (m2/g)

Strengthb (H_)

Amountc (mmol/g)

13
16
10
13

15.0 < H_ < 18.4 0.12

9.3 < H_ < 15.0
0.10
7.2 < H_ < 9.3
0e
9.3 < H_ < 15.0
0.03

Calculated by BET method using data from nitrogen adsorption at 77

K.
b
c
d
e

Determined by color change of indicator.

Measured through titration using phenolphthalein.
Calcium oxide obtained after the atmospheric calcination.
All the basic sites did not color phenolphthalein.

M. Kouzu et al. / Fuel 87 (2008) 27982806

2.2. Transesterication of vegetable oil using calcium

compounds
Such calcium compounds as mentioned above were
employed as solid base catalyst for transesterication of
vegetable oil with methanol. The transesterication was
carried out at reux of methanol in a nitrogen gas ow,
using a 500 ml capacity four-neck glass ask which
equipped with a stirrer, condenser, thermometer, and nozzle to insert nitrogen gas. 100 ml vegetable oil and 50 ml
methanol were put in the glass batch reactor. Molar ratio
of methanol to vegetable oil was close to twelve, which corresponded to four times of the stoichiometry. On stirring,
14 mmol of the catalyst was added into mixture of the reactant. For CaO, 0.78 g of the sample was weighted to
employ as the catalyst. Reux of methanol was kept for
24 h with the glass batch reactor mounted on a mantle
heater. At the interval of 0.52 h, some content of the glass
batch reactor was withdrawn for analysis to measure the
yield of FAME. The analysis was conducted using a gas
chromatography with a ame ionization detector and a
stainless capillary column.
After the reacting operation, all the content was
decanted to separate FAME from the product. FAME
was obtained from the upper layer, in order to measure
its concentration of calcium by using atomic emission spectroscopy with inductivity coupled plasma atomization
(ICP-AES). The lower layer was formed out of glycerol,
in which the catalyst was settled. The sedimentation was
collected after ltration followed by vacuum drying.
In the present experiment, soybean oil (SBO) and waste
cooking oil (WCO) were transesteried. Since SBO was the
reagent of edible grade, any purication was not conducted
prior to the transesterication. The acid value and moisture
content were below 0.1 mg-KOH/g and 0.01 wt%, respectively. WCO, which had its origin in commercially available soybean oil, was tendered by a restaurant. Properties
of WCO were as follows: acid value of 5.1 mg-KOH/g,
moisture content of 0.05 wt%, and polar fraction of
18.7 wt%. The suspended solid matter deriving from the
fried food was eliminated from WCO by ltration ion in
advance of the transesterication. Measurement of the
properties was based on the standard method for the analysis of fats, oil, and related materials, edited by Japan Oil
Chemists Society.
2.3. Pretreatment of waste cooking oil

In anticipation of processing WCO, the esterication in

the presence of the edible soybean oil was put to trial.
Composition of the reactant mixture was as follows: 5 ml
of oleic acid, 20 ml of methanol, and 125 ml of SBO. The
conversion into methyl oleate was determined by decreasing ratio of the acid value.
The promising catalyst was employed to process WCO
at reux of methanol for esterifying the free fatty acids.
For the processing, 200 ml of WCO was poured into the
glass batch reactor with 40 ml of methanol and 25 g of
the catalyst. The processed WCO was obtained after lteration followed by evaporation of methanol, and then it was
transesteried using CaO in order to verify an eectiveness
of the pretreatment.
3. Results and discussion
3.1. Catalytic activities of calcium compounds
SBO was transesteried at reux of methanol using
some calcium compounds for investigating their catalytic
activities. Fig. 1 indicated that the catalytic activity was
in the sequence of CaO > Ca(OH)2  CaCO3 [11]. The
yield of FAME reached 93% at 1 h of reaction time for
CaO, but Ca(OH)2 took the longer time close upon 3.5 h
to gain the same FAME yield. CaCO3 seemed to be useless
in catalyzing the transesterication, because FAME was
not yielded at all. Sequence of the catalytic activity corresponded to that of the basic properties, as shown in Table
1. Data from the reaction experiment using CaOAir,
which obtained after the atmospheric calcination, provided
an important indication on the deactivation by exposing to
air. In the presence of CaOAir, the yield of FAME was
below 10% even at 4 h of reaction time. From Table 1, it
was evident that the basic properties were seriously deteri100

80

Yield of FAME [%]

2800

60

40

20

Primarily, esterication of oleic acid with reuxing

methanol was conducted using H-Y zeolite, SO4/TiO2, or
cation-exchange resin, in order to select the promising catalyst for pretreatment to remove free fatty acids. 5 ml of
oleic acid was merged into 125 ml of methanol in the glass
batch reactor, and then 2.5 g of the solid acid was added to
the reactant mixture. Conversion of oleinic acid into
methyl oleate was measured on the gas chromatograph
with a silica capillary column for analysis of fatty acids.

0
0

Time on stream [h]

Fig. 1. Yield of FAME for transesterifying edible soybean oil at reux of
methanol in the presence of calcium compounds as solid base catalyst: (s)
CaO; (h) Ca(OH)2; (4) CaCO3; () NaOH; (d) CaOAir. Reprinted
from [11] with permission of the Japan Institute of Energy.

M. Kouzu et al. / Fuel 87 (2008) 27982806

orated by exposing to air. It was certain that the basic sites

adsorbed CO2 or moisture included in the atmosphere.
Possibly, the strong adsorption of CO2 was responsible
for the deactivation. If moisture was the major poison for
the basic sites, CaOAir yielded FAME as much as
Ca(OH)2 did.
Additionally, kinetics on the catalyzed transesterication was illustrated by drawing a line through the points
plotted in Fig. 1. From the line for CaO, it was clear that
the reaction rate was a function of concentration of soybean oil in the reactant mixture. There was a possibility
that order of reaction changed with progress of the transesterication, because the increase in FAME promoted to
merge these reactants together. It was reported that vegetable oil was completely merged into methanol after the yield
of FAME reached 70% [17]. In the homogeneous phase, no
wonder the soybean oil was transesteried under the rst
order kinetics. Since the soybean oil and methanol separated out at the beginning of the reaction, the catalyzed
transesterication would probably be under the zeroth
order kinetics in the heterogeneous phase. With increase
in the yield of FAME, the reaction kinetics possibly varied
from the zeroth order to the rst. Such the interpretation as
mentioned above was consistent with the line for Ca(OH)2.
Through the plotted points in Fig. 1, the curved line with Sshape could be drawn. Under the zeroth order kinetics at
the beginning of the reaction, it was considered that combination of the scanty solubility of the soybean oil into
methanol and the low catalytic activity might bring about
the slow rate constant. This was the reason why the reac-

2801

tion rate was seriously slow till the rst bend of the line.
It seemed as if the catalyzed transesterication included
the induction period. Afterwards, the reaction rate
increased steeply as the soybean oil started to merge into
methanol by producing FAME.
It was essential for us to compare the catalytic activity of
CaO with that of NaOH, because eventual objective of our
research is to develop the noble process featuring the fast
reaction rate under the mild reacting condition. Assuming
the catalyzed transesterication to be under the rst order
kinetics, the reaction rate constant was 0.044 min1 for
CaO and 0.077 min1 for NaOH. It was evident that
NaOH was more active than CaO. To the transesterication, the homogeneous catalysis was advantageous with
reason. However, there was no report referring to the solid
base catalyst superior to CaO. For alumina supported
potassium, the converting ratio of soybean oil reached
87.4% at 7 h of reaction time in reuxing methanol [9],
which indicating that the reaction rate constant was
0.005 min1. In the presence of molecular sieves supported
sodium oxide as the catalyst, 24 h were taken to obtain the
converting ratio of 95% [18]. Possibly, the noble process
using calcium oxide causes as the good productivity as
the current process do, by taking advantages of the easy
product recovery and the environmental benignity.
Concerning transesterication with methanol using solid
base catalyst, abstraction of proton from methanol by the
basic sites to form methoxide anion is the rst step of the
reaction. The methoxide anion attacks carbonyl carbon
in a molecule of the triglyceride, which leading to forma-

< Step 1>

R-OH

R-O-

H+

Ca

R1-C-O-R
=

< Step 2>

O-R
CH2-O-C-R1

CH2-O-C-R1

O
H+
O

CH-O-C-R1

CH-O-C-R1

O
CH2-O-C-R1

O
CH2-O-C-R1
=

Ca

O
CH2-O-C-R1

CH-O-C-R1

R-O-

CH2-O

< Step 3>

CH2-O

CH2-O-H
H+

CH-O-C-R1
O
CH2-O-C-R1
=

Ca

Ca

CH-O-C-R1
O
CH2-O-C-R1

Fig. 2. Reaction route of transesterication of triglyceride with methanol using CaO.

M. Kouzu et al. / Fuel 87 (2008) 27982806

tion of the alkoxycarbonyl intermediate. Then, the alkoxycarbonyl intermediate divides into two molecules: FAME
and anion of diglyceride. Fig. 2 illustrates a mechanism
on the catalyzed transesterication using calcium oxide as
the solid base. From no appreciable dierence in the surface area among the employed calcium compounds, it
was probable that the nucleophilic reaction was accelerated
by an enhancement of the basic properties.
Fig. 3 shows the yields of FAME for the transesterication using alkaline-earth metal oxides, and it indicated that
the catalytic activity was in the sequence of
MgO  CaO < SrO. This was in the sequence reverse to
what was shown with the surface areas: SrO (2 m2/
g) < CaO (13 m2/g)  MgO (200 m2/g). As data from
CO2-TPD veried that the basic strength was in the
sequence of MgO < CaO < SrO [14], the basic properties
seemed to be determinant for the catalytic activity among
all the sample employed in the present work. For alkaline-earth metal oxide, it was considered that strength of
the basic site was related to electronegativity of the conjugated metal cation. Since the large electronegativity intensies the electron attractive force for the conjugated
metal cation, the basic characteristics of the oxygen anion
was deteriorated. SrO was so active as to complete the conversion into FAME for 0.5 h, but any sediment was not
observed after the reacting operation. Following the evaporation of methanol, the product mixed with the catalyst
looked like an organosol coloring in white. It goes without
saying that FAME was easily separated from the product
obtained by the transesterication using CaO. Naturally,
a considerable amount of the sediment was obvious at
the bottom of the reactor.
The collected catalyst was reused for the transesterication, in order to appreciate that CaO was the durable catalyst. Reuse of the catalyst was repeated two times. The
yields of FAME measured for the each run reusing the catalyst are drawn in Fig. 4. Although the yields of FAME
decreased gradually with number of the cycle, the catalyst
could be reused without the serious deactivation for the
transesterication. The gradual decrease of FAME was
possibly due to loss of the catalyst in the middle of the col-

Yield of FAME [%]

100
80
60
40
20
0

MgO

CaO

SrO

Fig. 3. Yield of FAME for transesterication of edible soybean oil at

reux of methanol in the presence of alkaline-earth metal oxides: (h) at
0.5 h of reaction time; (j) at 1 h of reaction time.

100

Yield of FAME [%]

2802

80
60
40
20
0

0.5

1.5

Time on stream [h]

Fig. 4. Deactivation of CaO by reusing for transesterication of edible
soybean oil at reux of methanol: (s) Fresh; (h) 1st reuse; (4) 2nd reuse.

lecting operation. Additionally, the yield of FAME was

above 90% at 2 h of reaction time for the every run. From
the high catalytic activity with the durability and the easy
separation of the product, we concluded that CaO was
the best catalyst for the transesterication among the
employed samples.
3.2. Transesterication of waste cooking oil using calcium
oxide
From viewpoint of economical biodiesel production, it
is worth employing waste cooking oil as the feedstock.
However, it is to be feared that free fatty acids included
in waste cooking oil cause damage to calcium oxide used
as the solid base catalyst. No wonder the basic site is poisoned by strong adsorption of the free fatty acids. The catalyst may change into calcium soap by reacting with the
free fatty acids adsorbed. Further, it is possible that waste
cooking oil include another poison. Moisture is a potential
neutralizer for solid base, and more important, calcium
oxide is easily hydrated under a moist condition. In addition to moisture, we should be take care of polar fraction
that is the major impurity containing non-volatile alcohols,
aldehydes, and ketones [19].
In the present work, the transesterication of WCO
using CaO was characterized on taking notice of not only
free fatty acids but also moisture and polar fraction. Therefore, some oils were prepared as the feedstock by blending
SBO with the noticed components in accordance to the
composition of WCO. Among the noticed components,
free fatty acids and polar fraction were separated from
WCO. Free fatty acids were obtained after neutralization
of them with sodium hydroxide followed by decomposition
of the neutralized product using phosphoric acid. Polar
fraction was extracted by means of silica-gel column chromatography technique.
Table 2 shows the yields of FAME for the transesterication of the oils prepared, with their composition. SBO-F,
-M, and -P were the oil blending SBO with free fatty acids,
distillated water, and polar fraction, respectively. For all

M. Kouzu et al. / Fuel 87 (2008) 27982806

Table 2
Inuences of free fatty acids, moisture, and polar fraction on transesterication of WCO using CaO
Composition (wt%)
b

WCO
SBO-Fd
SBO-Me
SBO-Pf
SBO
a
b
c
d
e
f

Yield of FAME

(%)

FFA

Moisture

Polars

0.5 (h)

1.0 (h)

2.0 (h)

2.6
2.5
<0.1
<0.1
<0.1

0.05
<0.01
0.05
<0.01
<0.01

18.7
<0.1
<0.1
15.0
<0.1

0
0
49
54
62

66
76
95
97
93

>99
>99
>99
>99
>99

By transesterifying at reux of methanol.

Free fatty acids.
Waste cooking oil with acid value of 5.1 mg-KOH/g.
Edible soybean oil blended with free fatty acids extracted from WCO.
Edible soybean oil with a dosage of distillated water.
Edible soybean oil blended with polar fraction extracted from WCO.

the oils the yield of FAME was above 99% at 2 h of reaction time, while the appreciable dierence in the data at
0.5 h was observed. Although the yield of FAME was
around 50% for SBO-M and -P, -F was not transesteried
the same as WCO. The induction period turned up in the
presence of free fatty acids for the catalyst. It was certain
that free fatty acids react with the catalyst at the initial
stage of the transesterication [12]. If free fatty acids were
merely adsorbed over the catalyst, the conversion into
FAME would not be completed for 2 h. Concerning the
transesterication of SBO using Ca(OH)2, in which the
induction period turned up, the yields of FAME did not
reach 40% at 2 h of reaction time. After the neutralizing
reaction of the catalyst, as shown in Fig. 5, the produced
calcium soap was considered to have been scraped from
the catalyst. Possibly, the scraped particles were formed
into the organosol with reactant mixture, because calcium
soap is so oleophilic that it can be utilized as the surfactant
for fats and oils. After the scrape, surface of the catalyst
was so clean as to regenerate the much more basic sites.
If Fig. 5 is a correct illustration on the inuence of free
fatty acids, considerable amount of calcium soap must be
included in the produced FAME. As a result, weight of
the catalyst collected after the transesterication obviously
decreases. Both concentration of calcium in the produced

3000

80

2500
60

2000
1500

40

1000
20
500
0

0
WCO

SBO-F

SBO-M

SBO-P

FAME and weight ratio of the collected catalyst to fresh

one were measured for the each run shown in Table 2.
Fig. 6 indicated that a portion of calcium oxide changed
into calcium soap by reacting with free fatty acids, as illustrated in Fig. 5. The concentration of calcium was higher
for SBO-F (2300 ppm) than for SBO-M (428 ppm) and P (465 ppm). The transesterication of WCO produced
FAME including 3065 ppm calcium, which reected not
only the inuence of free fatty acids but also those of moisture and polar fraction. Weight ratio of the collected catalyst to the fresh one, termed as Catalyst recovery in
Fig. 6, was in the sequence reverse to what was shown with
the concentration of calcium. It should be noted that the
production of calcium soap brought about deterioration
in the quality of the produced biodiesel, because the concentration of mineral matter is limited below 20000 ppm
on the basis of the standard for guarding the engine. For
the produced biodiesel, an amount of calcium soap is likely
to have a great eect on the concentration of mineral matter. Further, the neutralizing reaction is the cause of cutting
a lifetime of the catalyst short. The feedstock should be
processed for removing the free fatty acids in advance of
the transesterication catalyzed by calcium oxide.
Inuence of moisture on the catalytic activity was negligible in contrast with that of free fatty acids. Between SBO
and SBO-M, marked dierence in the yields of FAME was
not observed except for the data at 0.5 h. Only at 0.5 h the
yield of FAME was rather higher for SBO, which indicating that surface of the catalyst was hydrated under the
moist condition adding 0.05 wt% water. However, it was
considered that not all the surface was hydrated, since
the catalyst under the moist condition was more active than
Ca(OH)2 under the normal one. For Ca(OH)2, the yield of
FAME did not reach 10% at 0.5 h. It was probable that the
catalyst was hydrated with the rather slow rate during the
transesterication. Further, it was reported that the basic
sites on calcium oxide could adsorb the reactant in the
presence of moisture for methanolysis of ethyl acetate
[20]. There was a possibility that the competitive adsorption inhibited the hydration of the catalyst. The same as
moisture, polar fraction was interpreted as the minor poison for the catalyst.
3.3. Multi-step transesterication using calcium oxide

3500

Ca in FAME [ppm]

Catalyst recovery [wt%]

100

2803

SBO

Fig. 5. Catalyst recovery and concentration of calcium in FAME.

For biodiesel production from waste cooking oil using

calcium oxide, it was anticipated that the serious damage
was caused to the catalyst by reacting with free fatty acids.
For solving this problem, free fatty acids should be
removed from the feedstock prior to the transesterication.
The removal of free fatty acids has been studied for the
transesterication using alkali- hydroxide. The most common way is to convert free fatty acids into FAME by esterication using sulfuric acids, p-toluenesulfonic acids, or
alkyl benzene sulfonic acids [21]. However, the pretreated
feedstock must be washed with water in advance of the following transesterication to eliminate the homogeneous

2804

M. Kouzu et al. / Fuel 87 (2008) 27982806

CaO,

FFA,

<Step1>
Neutralization of CaO
with free fatty acids

Ca-soap

<Step2>
Formation of Ca-soap
on surface of the catalyst

<Step3>
Disperison of Ca-soap
in colloidal particle

<Step4>
Regeneration of catalytic
surface

Fig. 6. Mechanism on inuence of free fatty acids on calcium oxide used as a catalyst for transesterication of waste cooking oil.

catalyst employed. Since it is essential for us to process the

feedstock without any euent, we studied the pretreatment
utilizing heterogeneous catalysis for the esterication by
testing some solid acids for the catalytic activity. The catalytic activity was determined from converting ratio of oleic
acid by the esterication with reuxing methanol.
Table 3 shows the converting ratio of oleic acid for H-Y
zeolite, cation-exchange resin, and SO4/TiO2. In the
absence of vegetable oil, most of oleic acid was esteried
by using SO4/TiO2 or cation-exchange resin, while H-Y
zeolite could not catalyze the esterication at all. These
results were consistent with a research paper discussing
on esterication of lauric acid with 2-ethylhexanol using
various solid acids [22]. The research paper concluded that
the esterication was not catalyzed by H-Y zeolite owing to
limited diusion of the reactant into the narrow pores.
Also, acidic sites over H-Y zeolite might strongly adsorbed
moisture included in the methanol because of hydrophilic
characteristics of the surface.
For cation-exchange resin and SO4/TiO2, the catalytic
activity in the presence of the soybean oil was examined.
The catalytic activity was rather higher for cation-exchange
resin than for SO4/TiO2. SO4/TiO2 is commonly interpreted as a solid super-acid, and it was formed into particle
of micro-porous texture. Cation-exchange resin was
molded into bead with macro-porous texture, and the
Table 3
Catalytic activities of solid acids for esterication of oleic acid in reuxing
methanol
Converting ratio (%)

H-Y zeolite
Cation-exchange resinc
SO4/TiO2d
a
b
c
d

Oleic acid/
methanola

Oleic acid/methanol/
soybean oilb

0.5 (h)

1.0 (h)

1.0 (h)

0
71
93

0
84
98

(No measurement)
28
55
7
11

Measured using GC analysis.

Calculated from decreasing ratio of acid value.
Sulfonic groups were anchored on the surface.
Sulfated titanium oxide.

3.0 (h)

acidic property was rather weaker than for SO4/TiO2. With

respect to solid acid catalysts employed, accessibility of the
reactant was likely to have an inuence on activity for the
esterication in the presence of soybean oil. For SO4/TiO2,
the oleic acid merged into soybean oil might be dicult to
penetrate into the particle because of the micro-porous texture. Concerning cation-exchange resin, it was considered
that the reactants easily get access to the acidic site by reason of a combination of the macro-porous texture and the
hydrophobic surface.
Accordingly, cation-exchange resin was singled out as a
solid acid catalyst to esterify free fatty acid included in
WCO. Using this catalyst, WCO was processed at reux
of methanol for converting the free fatty acids into FAME.
Table 4 indicated that the esterication of free fatty acids
was catalyzed by cation-exchange resin even in waste cooking oil. By processing WCO for 4 h, the acid value
decreased from 5.1 mg-KOH/g to 0.5 mg-KOH/g. Neither
moisture nor polar fraction included in WCO interfered
with the catalyzed esterication. Further, the catalyst could
be reused for the processing without any deactivation. No
dierence in the acid values among the each run reusing the
catalyst was observed. Although the acid value could not
be reduced below 0.3 mg-KOH/g, it was thought that the
conversion of free fatty acids was completed at the acid
value. For SBO including polar fraction of 15 wt% (SBOP), the acid value reached 0.3 mg-KOH/g. The processed
WCO with acid value of 0.3 mg-KOH/g included 14 wt%
of polar fraction. Additionally, composition of the processed WCO was examined by using gas-chromatography
for proving that the catalyst was active in only esterifying

Table 4
Decrease in acid value of WCO by processing at reux of methanol in the
presence of cation-exchange resin
Acid value (mg-KOH/g)

Virgin use
1st recycle use
2nd recycle use

Polars (wt%)

0 (h)

2 (h)

4 (h)

5 (h)

5 (h)

5.1
5.1
5.1

1.1
1.0
1.1

0.5
0.4
0.6

0.3
0.3
0.4

13.9

M. Kouzu et al. / Fuel 87 (2008) 27982806

2805

Table 5
Data on transesterication of the processed WCO using CaO
Properties of feedstock

Processed WCO-1
Processed WCO-2b
As-received WCO
SBO
a
b
c

Acid value
(mg-KOH/g)

Moisture
(wt%)

Yield of FAME (%)

0.5 (h)

1.0 (h)

2.0 (h)

0.3
0.3
5.1
<0.1

0.01
0.17c
0.05
<0.01

68
44
0
62

91
95
66
93

>99
>99
>99
>99

Catalyst
recovery (wt%)

Calcium in
FAME (ppm)

75
51
22
81

565
1485
3065
187

Esterication of free fatty acids combined with elimination of the by-produced moisture.
By-passing removal of the by-produced moisture.
Calculated value on the basis of content of the free fatty acids.

free fatty acids. Besides high-volatile components such as

triglycerides or diglycerides, only FAME was detected for
the processed WCO with acid value of 0.3 mg-KOH/g.
The concentration of FAME was estimated at 2.5%, which
was close to that of the free fatty acids included in WCO
as-received.
The processed WCO with acid value of 0.3 mg-KOH/g
was transesteried using CaO in order to verify eectiveness of the pretreatment. Table 5 lists data on the transesterication of the processed WCO. It was evident that the
pretreatment was eective in easing the damage of the catalyst. Here, it should be noted that moisture by-produced
through the esterication ought to be eliminated for gaining the maximum ecacy. By combining the esterication
with elimination of the by-produced moisture, concentration of calcium in FAME produced by the following
transesterication decreased from 3065 ppm to 565 ppm.
However, the decrease in the concentration of calcium
was conned to 1485 ppm without eliminating the by-produced moisture after the esterication. We found that SBO
including 0.2 wt% moisture was converted into FAME
including 1435 ppm calcium by the transesterication.
Assuming that the esterication of the free fatty acids is
completed, the amount of the by-produced moisture is
close to 0.2 wt% on WCO.
In conclusion, the present work revealed that biodiesel
can be produced from waste cooking oil by multi-step
transesterication using calcium oxide as the solid base catalyst. As the pretreatment, esterication of free fatty acids
using cation-exchange resin combined with elimination of
the by-produced moisture was the appropriate processing.
For the practical use, we should take care of the inuence
of polar fraction as the minor poison because the catalyzed
transesterication will process the much more feedstock.
Further, calcium oxide seemed to be deteriorated even in
the transesteication of edible soybean oil, because the
obtained FAME was including 187 ppm calcium. By identifying the calcium compound included in the produced
FAME, this problem will approach solution. If it is not calcium soap in the organosol, supporting calcium oxide on
an appropriate support is likely to reduce the concentration
of calcium.

4. Conclusion
In order to study solid base catalyst for biodiesel production with environmental benignity, transesterication
of edible soybean oil with reuxing methanol was carried
out in the presence of CaO, Ca(OH)2, CaCO3. At 1 h of
reaction time, yield of FAME was 93% for CaO, 12%
for Ca(OH)2, and 0% for CaCO3. Additionally, MgO
was far from active in the transesterication. Although
NaOH caused the complete conversion into FAME under
the same reacting condition, CaO will probably brought
about as the good productivity as NaOH do, by taking
advantage of the easy product recovery and environmental benign. Therefore, CaO was for the further tests
transesterifying waste cooking oil (WCO) with acid value
of 5.1 mg-KOH/g. The yield of FAME was above 99% at
2 h of reaction time, but a portion of catalyst changed
into calcium soap by reacting with free fatty acids
included in WCO at initial stage of the transesterication.
Owing to the neutralizing reaction of the catalyst, concentration of calcium in the produced FAME increased from
187 ppm to 3065 ppm. And what is more important, it
seemed that calcium soap was formed into organosol with
FAME. As quality of biodiesel and lifetime of the catalyst
were taken into consideration, the catalyst should be
guarded from the neutralizing reaction with free fatty
acids. By processing WCO at reux of methanol in the
presence of cation-exchange resin, only the free fatty acids
could be converted into FAME. The transesterication of
the processed WCO with acid value of 0.3 mg-KOH/g
resulted in the production of FAME including 565 ppm
calcium.
Acknowledgement
The authors gratefully acknowledge support for this
research by Kyoto Prefecture Collaboration of Regional
Entities for the Advancement of Technological Excellence, Japan Science and Technology Agency. Further,
we are thankful to the Japan Institute of Energy for
his permission to use a drawing material inserted in his
publications.

2806

M. Kouzu et al. / Fuel 87 (2008) 27982806

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