Energy Conversion and Management 95 (2015) 242–247

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Energy Conversion and Management

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

Biodiesel production from waste cooking oil using calcined scallop shell
as catalyst
Suchada Sirisomboonchai a,b, Maidinamu Abuduwayiti a,c, Guoqing Guan a,⇑, Chanatip Samart b,
Shawket Abliz c, Xiaogang Hao d, Katsuki Kusakabe e, Abuliti Abudula a,⇑
a
North Japan Research Institute of Sustainable Energy (NJRISE), Hirosaki University, 2-1-3, Matsubara, Aomori 030-0813, Japan
b
Department of Chemistry, Faculty of Science and Technology, Thammasat University, Pathumthani 12120, Thailand
c
College of Chemistry and Chemical Engineering, Xinjiang University, 14 Shengli Road, Urumqi 830046, PR China
d
Department of Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, PR China
e
Department of Nanoscience, Sojo University, 4-22-1 Ikeda, Kumamoto 860-0082, Japan

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

Article history: Transesterification of waste cooking oil (WCO) and methanol by using calcined scallop shell (CSS) as cat-
Received 14 December 2014 alyst was carried out in a closed system for biodiesel fuel (BDF) production. It is found that the optimum
Accepted 12 February 2015 calcination temperature for the preparation of CSS was 1000 °C. The effects of transesterification tem-
perature, reaction time, methanol/oil molar ratio and catalyst loading amount on the BDF yield were
investigated. Compared with the commercial CaO, CSS showed higher catalytic activity and the BDF yield
Keywords: reached 86% at 65 °C with a catalyst loading amount of 5 wt% (WCO basis) and a reaction time of 2 h. The
Biodiesel
catalyst was reused for 5 cycles whilst the BDF yield decreased 23%. It is found that CaO in CSS was trans-
Transesterification
CaO
ferred to calcium glyceroxide after the transesterification reaction, and calcium glyceroxide also showed
Calcined scallop shell good catalytic activity and reusability. Furthermore, Water content in WCO had negative effect on BDF
Waste cooking oil yield. It is found that BDF yield reduced 15% due to the occurring of saponification when the water con-
Stability tent was increased from 0.64% to 2.48%. It is expected that CCS can be used as an alternative and cheap
catalyst for the biodiesel production.
Ó 2015 Elsevier Ltd. All rights reserved.

1. Introduction Catalyst is generally used for the transesterification reaction

The energy crisis and the impact of greenhouse gases to the
earth arouse researchers to develop alternative energy for the
replacement of fossil fuels. Biodiesel fuel (BDF) is an alternative
fuel with eco-friendly because it is produced from natural
resources. BDF is generally produced by the transesterification of
vegetable oil or animal fat with alcohol such as methanol or etha-
nol in the presence acid or alkali catalyst [1–8]. The use of edible
oils as sources of BDF will compete with the food and resulting
in some social problems [7]. A source of BDF should have low cost
and can be obtained easily around us because the major fraction of
the BDF production cost is from the raw materials. In an area like
Japan without enough natural resources, use of waste cooking oils
(WCO) instead of original oils for the BDF production is an effective
way to reduce the cost.
⇑ Corresponding authors. Tel.: +81 17 762 7756; fax: +81 17 735 5411.
E-mail addresses: guan@hirosaki-u.ac.jp (G. Guan), abuliti@hirosaki-u.ac.jp
(A. Abudula).
operated at ambient atmosphere. Various catalysts such as acid
catalysts, base catalysts and enzyme catalysts are developed. How-
ever, acid catalyst presents low catalytic activity so that longer
reaction time and higher reaction temperature are required [4–6].
Homogeneous alkali catalysts such as NaOH and KOH have good
catalytic activity but they are difficult to be separated and reused
after the reaction [7]. To solve this problem, heterogeneous alkali
catalysts is used because they are non-corrosive, recyclable and
effective. To date, various heterogeneous alkali catalysts have been
developed for BDF production [8]. Among them, CaO is one of
widely-used catalysts due to its abundant availability in nature,
low cost and high activity [9–17]. CaO catalyst can be prepared
from different source materials. For instances, it can be easily
derived from lime stones and its derivatives, and waste shells such
as waste egg shell [18,19], oyster shell [20], and scallop shell
[21–23], which can not only save sources and decrease cost, but
also solve environmental problems. However, these natural
resources always come from some special regions. If they can be
used properly for a regional sustainable development, it will
be the most cost-effective way and good for the local society. In

http://dx.doi.org/10.1016/j.enconman.2015.02.044
0196-8904/Ó 2015 Elsevier Ltd. All rights reserved.
 S. Sirisomboonchai et al. / Energy Conversion and Management 95 (2015) 242–247 243

the North Japan area, a large amount of scallop shells (Patinopecten
yessoensis) are produced every year, and the waste scallop shells
are usually stacked on the road side, resulting in the air around it
stink to high heaven. In order to use the waste scallop shell
effectively and solve the regional environmental problem, in our
previous studies [21–23], it was applied as a catalyst for the tar
reforming in the biomass gasification process. It is found that
calcined scallop shell (CSS) presents alkali property and contains
special porous structure, and shows excellent catalytic activity
for the tar reforming. To expand the utilization field of CCS as
catalyst, in this study, CCS was used as a catalyst for the production
of BDF from waste cooking oil (WCO). To increase the BDF yield,
the calcination conditions and the transesterification conditions
were optimized. Furthermore, the reusability of CSS and the effect
of water content in WCO on the activity of CSS were also
investigated. It is expected that CCS can be used as an alternative
and cheap catalyst for the biodiesel production.
[3,5]. The column temperature was remained at 40 °C. Two peaks
attributed to the unreacted glycerides (sum of mono-, di- and
tri-glycerides) and the sum of FAMEs appeared in the liquid
chromatogram [25]. Thus, the FAME yield in the product can be
calculated using the following equation:
FAME yield ¼ ðC FAME =3C oil Þ  100% ð1Þ
where CFAME and Coil are the concentrations of FAME in the product
and triglycerides in the WCO, respectively.
To investigate the effect of water content in WCO on the FAME
yield, calculated amount of water was added in the WCO and
mixed them homogeneously at first, and then they were used as
WCO sources with different water contents (0.62, 1.24, and
2.48 wt% based on dewatered WCO). For the reusability test, the
used catalyst was washed by acetone for 2 times and dried in
vacuum, and then used again.

2.3. Catalyst characterizations

2. Experimental
Morphologies of various CSSs obtained at different tem-
2.1. Materials peratures were characterized using a scanning electron microscope
(SEM, SU6600, Hitachi). X-ray powder diffraction (XRD) analysis
In this study, WCO was provided by a local restaurant in Aomori for the catalysts before and after the reaction was conducted using
City, Japan. This WCO contains 0.62 wt% of water with an acid val- RIGAKU Smartlab X-ray diffractometer with Cu Ka radiation
ue of 1.23 mgKOH/g and a saponification value of 212.2 mgKOH/g. (k = 0.154 nm) generated at 45 kV and 200 mA. Catalyst surface
Its density at 25 °C is 0.92 g/cm3. Methanol (99.5%), acetone, areas were measured using BET sorption isotherm method (Quan-
n-hexane and 2-propanol were purchased from WAKO, Japan. tachrome NOVA 4200e, USA)
Waste scallop shell (WSS) was provided by Aomori City, Japan.
Its main compositions are 98 wt% CaCO3, 0.79 wt% MgCO3 and
3. Results and discussion
0.15 wt% SrCO3. Various CSSs were prepared by crushing of WSS
to powder and calcination of it at different temperatures of 600,
3.1. Optimization of reaction conditions
800, 1000, 1100, 1200, and 1400 °C for 2 h in air in order to
understand the effect of calcination temperature on the catalytic
Fig. 1 shows XRD patterns of CSS obtained at different calcina-
activity. Since calcium glyceroxide is always generated during
tion temperatures. One can see that all calcite in the original scal-
the transesterification reaction, herein, calcium glyceroxide was
lop shell converted to CaO completely at a calcination temperature
synthesized by heating the mixture of CSS, glycerol (WAKO, Japan)
of over 1000 °C. Thus, in this study, CSS obtained at 1000 °C calci-
and methanol at 60 °C under mechanical agitation for 3 h [24]. For
nation temperature was used at first for the optimization of reac-
comparison, a commercial CaO (WAKO, Japan), which was calcined
tion conditions. During the experiments, it is found that a
at 1000 °C for 2 h in air before use , was also used at the same
reaction temperature of 65 °C, which is near the boiling point of
reaction condition.
methanol (64.7 °C at 1 atm), was the optimum temperature to
obtain the highest FAME yield in all cases. In this study, a closed
2.2. Transesterification reaction reactor was used, the pressure in the reactor should be higher than
1 atm, thus, most of methanol could remain in the liquid phase and
As methanol is much more easily evaporated than triglycerides increase the contact between oil and methanol. Therefore, all of the
in the WCO, to make sure more methanol remained in the liquid following data were obtained at the reaction temperature of 65 °C.
phase to contact with triglycerides during the reaction, in this
study, a closed reactor (50 cm3) was used instead of the reflux
reactor. Prior to transesterification reaction, CSS and methanol
were mixed in a closed reactor at 40 °C with a stirring speed of
500 rpm for 60 min. Thereafter, WCO was introduced into the reac-
tor and transesterification reaction was carried out. Different
methanol/oil molar ratios (3:1; 6:1; 12:1), catalyst loading
amounts (1, 2, 5 and 10 wt% based on the oil weight), and reaction
times (30, 60, 120 and 180 min.) were selected for the transesterifi-
cation reaction. After the reaction, the product was centrifuged at
6000 rpm for 15 min. The upper ester layer was washed with
deionized water and centrifuged again. This procedure was repeat-
ed for several times until pH value in the aqueous phase reached
7.0. Then, 0.1 mL of the product was mixed with 3 mL of n-hexane
for the analysis. The concentrations of glycerides remained in the
product and the produced fatty acid methyl ester (FAME) were
analyzed using a high performance liquid chromatography (HPLC,
Shimadzu, Japan) equipped with a silica-gel column (Shimpack
CLC-SIL, Shimadzu, Japan) and a refractive index detector. The
mobile phase was n-hexane/2-propanol at a ratio of 99.5/0.5 (v/v) Fig. 1. XRD patterns of CSS obtained at different temperature.
244 S. Sirisomboonchai et al. / Energy Conversion and Management 95 (2015) 242–247
For transesterification reaction, the theoretical methanol/oil
ratio is 3:1. However, methanol is not soluble in triglycerides,
and the existence of two phases in the initial reaction period will
restrict the contact between reagents. Moreover, transesterifica-
tion is a reversible reaction. Thus, an excess of methanol is benefit
not only to promote the contact with triglycerides but also
improve the reaction towards the formation of FAME. In this study,
as shown in Fig. 2(a), when the reaction temperature and reaction
time were fixed at 65 °C and 120 min, respectively, as the metha-
nol/oil molar ratio increased from 3:1 to 6:1, FAME yield increased
to a great extent in any catalyst loading amount. However, after the
methanol/oil molar ratio was increased to 12:1, FAME yield
decreased to some extent. It is due to that more methanol will
reduce the concentration of catalyst in the total reaction system,
decreasing the possibility of reagents contacting with the catalyst
surface simultaneously. Other researchers also found the similar
trend, and suggested that an optimum methanol/oil molar ratio
should be determined for any transesterification reaction system
in order to reduce the cost for the separation of the excess metha-
nol from the final product [6,26–28]. Therefore, the optimum
methanol/oil molar ratio of 6:1 was considered for a closed reac-
tion system in this study.
During the transesterification reaction, the conversion speed is
generally slow at the beginning due to the slow dispersion of
triglycerides into the methanol phase. With the progress of the
reaction, the generated FAME will serve as a cosolvent to enhance
the miscibility of methanol and triglycerides. As a result, after a
while, the conversion speed will become very fast until the
Fig. 2. (a) FAME yields vs. catalyst loading amount and methanol/oil molar ratio
(reaction temperature: 65 °C; CSS calcination temperature: 1000 °C); (b) FAME
yield vs. catalyst loading amounts and reaction time (MeOH/oil molar ratio = 6:1;
reaction temperature: 65 °C; reaction time: 120 min; CSS calcination temperature:
1000 °C).
reaction reaches the equilibrium. As shown in Fig. 2(b), FAME
yields were not so high in a reaction period of 30 min in any cata-
lyst loading amounts. Then, the FAME yield increased fast after
30 min reaction until the highest yield reached. One can see that
FAME yields remained almost constant when the reaction time
was over 120 min, indicating that the reaction reached the equilib-
rium state. It is reported that excess reaction time will reduce the
FAME yield due to the backward reaction of transesterification and
increase more soap formation [26,29,30]. Therefore, in this study,
the optimum reaction time of 120 min was chosen for the transes-
terification reaction.
Furthermore, as shown in Fig. 2(a) and (b), FAME yield
increased with the increase in the catalyst loading amount. How-
ever, it should be noted that the FAME yield increased only a little
as the catalyst loading amount was increased from 5 to 10 wt%.
Other researchers reported that the excessive alkali catalyst itself
could react with triglycerides to form soap [26,30]. More alkaline
catalyst loading could result in more soap formation in the reaction
system, reducing the BDF yield, especially in a longer reaction time.
In this study, the similar trend was also observed. Therefore, the
optimum catalyst loading amount of 5 wt% was chosen here.
Fig. 3 shows FAME yields when using various CSSs obtained at
different calcination temperatures. Herein, all reactions were per-
formed at 65 °C for 120 min with a catalyst loading amount of
5 wt% and a methanol/oil molar ratio of 6:1. One can see that the
optimum calcination temperature for the preparation of CSS cata-
lyst is approximately 1000 °C. As shown in Fig. 3, when the calcina-
tion temperature was over 1000 °C, with the increase in the
calcination temperature for the preparation of CSS, the catalytic
activity of the obtained CSS decreased sharply. Fig. 4 shows the
morphologies of CSS catalysts prepared at the high calcination
temperatures over 1000 °C. The particles were obviously sintered
and became larger and smoother with the increase in the calcina-
tion temperature, indicating that the surface area of the catalyst
decreased markedly. It is reported that the catalytic activity of
CaO was maximized at the calcination temperature ranging from
900 to 1100 °C for CaO catalyst prepared from other kinds of CaO
catalyst sources [31]. In this study, the optimum calcination tem-
perature for scallop shell was also in this range.
Fig. 5 compares catalytic activities of CSS and commercial CaO
product at the same reaction conditions. One can see that the cat-
alytic activity of CSS had much higher catalytic activity when the
reaction time less than 120 min, indicating that CSS can initiate
Fig. 3. Effect of calcination temperature for the preparation of CSS catalyst on the
catalytic activity (MeOH/oil molar ratio = 6:1; reaction temperature: 65 °C; reaction
time: 120 min).
 S. Sirisomboonchai et al. / Energy Conversion and Management 95 (2015) 242–247 245

Fig. 4. Morphologies of CSS catalysts obtained at high temperatures.

catalyst loading amount of 5 wt%, a methanol/oil molar ration of

6:1 and a reaction temperature of 65 °C. As shown in Fig. 6, in
the presence of small amount of water (<0.62%), the FAME yield
reached 86% after 120 min reaction. However, this value decreased
to 73% when water content was increased from 0.62% to 2.48%. It is
found that more soap was formed in the case of high water content
in WCO, similar to others‘ reports [32]. Some researchers found
that the presence of little amount of water in the reaction system
enhanced the catalytic activity of CaO and increase BDF yield
[33]. In this study, WCO was used. Free fatty acids (FFAs) contained
in it could react with CSS, resulting in the formation of soap and
water, which will have negative effect on the catalytic activity of
CSS and decrease FAME yield.

Fig. 5. Comparison of catalytic activities of CSS (h) and commercial CaO (})
(MeOH/oil molar ratio = 6:1; reaction temperature: 65 °C; catalysts calcination
temperature: 1000 °C).

transesterification reaction more easily than the commercial CaO.

In our previous study [21], a special porous structure was found
for the CCS. BET measurements showed that CCS and commercial
CaO calcined at 1000 °C had surface areas of 7.33 and 2.16 m2/g,
respectively. Although both surface areas are not high, CCS could
provide more active sites for this reaction. Furthermore, as indicat-
ed in the experimental section, other elements such as Mg and Sr
were included in CCS, which could also promote the catalytic activ-
ity of CaO [8,13,16]. However, it should be noted that BDF yields
tend to the same after the reaction time over 120 min.

3.2. Effect of water content in WCO

Fig. 6. Effect of water content in WCO for FAME yield. (h: 0.62 wt%; 4: 1.24 wt%;
The effect of water content in the WCO on FAME yield was car- s: 2.48 wt%. MeOH/oil molar ratio = 6:1; reaction temperature: 65 °C; CSS calcina-
ried out under the optimum transesterification condition, i.e., a tion temperature: 1000 °C).
246 S. Sirisomboonchai et al. / Energy Conversion and Management 95 (2015) 242–247

3.3. Reusability of CSS catalyst

Fig. 7 shows the reusability of CSS catalyst in the optimal con-

ditions (calcination temperature: 1000 °C; catalyst loading
amount: 5 wt%; methanol/oil molar ratio: 6:1; reaction tem-
perature: 65 °C; reaction time: 120 min). One can see that CSS cat-
alyst can be reused for several times although FAME yield reduced
from 86% to 66% after the 4th cycle. As shown in Fig. 8, it is obvious
that XRD pattern of the used CSS was different from the fresh one
and after the reaction a new phase called calcium glyceroxide (Ca-
glyceroxide, Ca(C3H7O3)2) was formed by the reaction of CaO with
the generated glycerol. In order to test the catalytic activity of Ca-
glyceroxide, it was also synthesized directly using CSS and the
commercial glycerol following the method indicated in the lit-
erature [24]. The XRD pattern of the as-synthesized Ca-glyceroxide
is also shown in Fig. 8, which is similar to that of the used CSS. The
synthesized Ca-glyceroxide was also applied for the BDF produc-
tion using the same reaction conditions as those in Fig. 7. Fig. 9
shows its reusability. One can see that Ca-glyceroxide itself also
Fig. 8. XRD patterns of used CSS-1000 °C and synthesized Ca-glyceroxide.
had high catalytic activity for the transesterification reaction.
FAME yield reached 82% for the fresh one, and decreased to 62%
after 4 cycles. Especially, after 3rd cycle use, its catalytic activity
seemed to be stable, suggesting that Ca-glyceroxide had relatively
stable catalytic activity. Furthermore, as shown in Fig. 9, the used
catalyst was also reused directly after the filtration without wash-
ing by acetone. In this case, higher catalytic activity was found.
Herein, in the washing case, some structures of Ca-glyceroxide
could be broken by the washing since the structure of this com-
pound is formed by tetramers (Ca4(C3H7O3)8) held together by a
complex hydrogen-bond network [33]. Hence, the catalytic activity
was lower. Anyway, although the catalytic activity of Ca-glycerox-
ide is lower than that of CaO, its formation on the surface of CaO
could protect CaO from reaction with CO2 and/or H2O in the air
[24].
Fig. 9. Reusability of Ca-glyceroxide with (h) and without (j) washing. (MeOH/oil
molar ratio = 6:1; reaction temperature: 65 °C; reaction time: 120 min).
3.4. Transesterification reaction mechanism over CSS catalyst

As stated above, the main composition of CCS is CaO. Comparing
with the commercial CaO, it has higher BET surface area and con-
tains minor amounts of other elements such as Mg and Sr. Solid
base catalytic property of CaO itself originates in its surface oxygen
anion [35]. It is found that the strength of basic sites of alkaline-
earth metal oxides is in the order of MgO < CaO < SrO while the cat-
alytic activity for the transesterification of soybean oil is also in
this order [11]. Therefore, the existence of Mg and Sr in CCS could
enhance the catalytic activity for the transesterification reaction,
Fig. 7. Reusability of CSS catalyst (MeOH/oil molar ratio = 6:1; reaction tem-
perature: 65 °C; reaction time: 120 min; CSS calcination temperature: 1000 °C).
resulting that the total catalytic activity of CCS is higher than that
of the commercial CaO.
Basic sites generally abstract proton from organic species which
initiate the base-catalyzed reaction. In the transesterification reac-
tion, at the beginning in the first run, methanol could react with
CaO and transform into nucleophile which can attack carbonyl car-
bon in glycerides [11]. With the progress of reaction, glycerol is
formed with FAME, and the generated glycerol will also react with
the CaO so that the surface is gradually covered with Ca-glycerox-
ide. As shown in Fig. 8, after the first run, CaO seems to be com-
pletely transformed to Ca-glyceroxide, which shows a slightly
weaker basic property and less catalytic activity for the transes-
terification reaction than CaO [9,11,34,36–39]. It is suggested that
glyceroxyl OH groups on the surface of Ca-glyceroxide could
attract methanol to produce a compound as CH3O–Ca–O(OH)2C3-
H5, which leads triglycerides more easily access to the structural
methoxide anion functioning as the basic site [39]. On the other
hand, it should be noted that leaching of species from the solid will
occur during the transesterification reaction, which will result in
the losing of catalyst weight. This phenomenon has been found
by many researchers [1]. However, for batch reactor, it is found
that the leaching of solid base catalyst is generally rather serious
only for the first run in the case without moisture in the feedstock
due to the water formation by transformation of CaO into Ca-glyc-
eroxide as glycerol is generated: CaO + 2C3H8O3 = Ca(C3H7O)2 + H2O
[38]. Water can bring about hydrolysis of Ca-glyceroxide and
transform CaO to Ca(OH)2, which is more dissolvable in methanol.
Since the surface of CaO particle has been transformed into
 S. Sirisomboonchai et al. / Energy Conversion and Management 95 (2015) 242–247
Ca-glyceroxide, in the second run and successive runs, no more
water will be generated by the above reaction. If no water in the
feedstock, the catalytic activity should be remained stable. Howev-
er, in this study, as shown in Figs. 7 and 9, since WCO with a little
amount of water is used, the leaching of solids could happen in
every run and result the FAME yield decreased gradually.
4. Conclusions
Transesterification of WCO and methanol in the presence of CSS
catalyst was studied and an optimal reaction condition (calcination
temperature for catalyst: 1000 °C; catalyst loading amount: 5 wt%;
methanol/oil molar ratio: 6:1; reaction temperature: 65 °C; reac-
tion time: 120 min) was obtained. FAME yield over 86% was
obtained in the presence of small amount of water while the
increase of water content to 2.48% decreased FAME yield to 73%
due to the occurring of saponification. The CSS catalyst was used
for 4 cycles whilst FAME yield decreased 20% due to the formation
of Ca-glyceroxide on its surface. It is expected that CSS will be an
alternative low-cost catalyst for the production of biodiesel from
WCO.
Acknowledgement
This work is supported by Aomori City Government, Japan.
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