Energy Conversion and Management 112 (2016) 199–207

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Energy Conversion and Management

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

Biodiesel production from soybean oil deodorizer distillate usingcalcined

duck eggshell as catalyst
Xiulian Yin a,b,c, Xiuli Duan a, Qinghong You c,d,⇑, Chunhua Dai e, Zhongbiao Tan a, Xiaoyan Zhu a
a
Huaiyin Institute of Technology, School of Life Science and Food Engineering, Huaian, Jiangsu 223003, China
b
Jiangsu Key Lab of Biomass-based Green Fuels and Chemicals, Nanjin Forestry University, Nanjing, Jiangsu 210037, China
c
Jiangsu Provincial Engineering Laboratory for Biomass Conversion and Process Integration, Huaiyin Institute of Technology, Huaian 223003, China
d
Huaiyin Institute of Technology, School of Chemical Engineering, Huaian 223003, Jiangsu, China
e
School of Food and Biological Engineering, Jiangsu University, 301 Xuefu Road, Zhenjiang 212013, Jiangsu, China

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

Article history: Biodiesel production from soybean oil deodorizer distillate (SODD) using calcined duck eggshell (DES) as
Received 25 November 2015 catalyst was studied. An inexpensive and environment-friendly catalyst was prepared from waste DES
Accepted 11 January 2016 which is a source of calcium carbonate. The calcium carbonate could be changed to calcium oxide
Available online 23 January 2016
(CaO) under high temperatures. The obtained CaO was characterized by X-ray diffraction (XRD),
Fourier Transmission Infrared Spectra (FT-IR), Scanning Electron Microscopy (SEM). XRF was used to
Keywords: determine the elemental composition of the catalyst. BET analysis was performed to determine specific
Duck eggshells
surface area, pore volume and particle size of the catalysts. Results showed that at 800 °C and 900 °C the
Biodiesel
Soybean oil deodorizer distillate
calcium carbonate in DES was changed to CaO. The pre-esterification of SODD was conducted under the
Transesterification following conditions: H2SO4 concentration (v/w, based on oil weight) 1.5%, methanol to oil molar ratio
12:1, reaction time 120 min and reaction temperature 60 °C. Thephytosterols were removed by cooling
down step by stepand temperature steps were 15 °C, 5 °C,
5 °C. The process of biodiesel production from
pre-esterified SODD using the obtained CaO as catalyst was studied and the optimal conditions were: cal-
cination temperature of 900 °C, catalyst amount of 10 wt.%, methanol to oil ratio of 10:1, reaction tem-
perature of 60 °C and reaction time of 80 min and the biodiesel yield was 94.6% at these conditions.
The reusability of the DES-derived catalyst was tested and the results showed that the biodiesel yield
was above 80% after five times usage and was lower than 60% after 8 times usage.
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction
Due to the energy crisis and enhanced environmental pollution,
there is growing interest to develop green energy to replace the
fossil fuels. Biodiesel or fatty acid methyl ester (FAME), is of
increasing research and commercial interest for that it is
renewable, bio-degradable, non-toxic, and free from sulfur [1–4].
However, the cost of biodiesel production is high. The cost of bio-
diesel is approximately 1.5–2 times higher than that of fossil fuel.
Biodiesel is usually produced by transesterification of triglycerides
such as vegetable oils or animal fats with methanol catalyzed by
catalyst. Usually basic catalysts, such as NaOH, KOH or NaOCH3
are applied in the transesterification due to the fast reaction rate
they induce [5]. The cost of feedstock is about 75–80% of the total
⇑ Corresponding author at: Huaiyin Institute of Technology, School of Chemical
Engineering, Jiangsu, China. Tel.: +86 517 83591044.
E-mail address: youqhong@163.com (Q. You).
biodiesel cost. The application of waste oils and non-edible oils
could reduce biodiesel price [6–8]. On the other hand, the biodiesel
yield depends tightly on the choice of the catalyst [9].
Both homogeneous and heterogeneous catalysts could cat-
alyze transesterification. Homogeneous base catalysts such as
NaOH and KOH have high catalytic activity but it is difficult
to separate and reuse them after the reaction [10]. In order
to solve this problem, heterogeneous catalysts is receiving con-
siderable attention. Heterogeneous catalysts are non-corrosive,
recyclable and effective and could simplify the separation and
purification steps.
Many heterogeneous catalysts for the transesterification of oils
had been studied. Alkaline earth metal oxides with high basicity
are suitable for biodiesel production and among which calcium
oxide (CaO) is one of the most promising one [2]. Mollusk shells,
eggshells, and mussel shells could be calcined to obtain calcium
oxide that could be used as heterogeneous catalyst in biodiesel
production [11,12]. Rezaei [13] used waste mussel shells as a

http://dx.doi.org/10.1016/j.enconman.2016.01.026
0196-8904/Ó 2016 Elsevier Ltd. All rights reserved.
200 X. Yin et al. / Energy Conversion and Management 112 (2016) 199–207
resource of calcium carbonate which changed to calcium oxide in
calcinations temperatures higher than 950 °C. Transesterification
reaction was done in the presence of soybean oil, methanol and
mussel shell catalyst in a temperature of 60 °C. Nakatani et al.
[14] used combusted oyster shell as catalysts for transesterifica-
tionreaction of soybean oil.
One of the most common CaO natural resource is eggshells. Egg-
shells are mostly made up of calcium carbonate (85–95%) [15,16].
Duck eggs are consumed worldwide for its multi nutrition. Due to
the huge consumption of duck eggs, the waste duck eggshells (DES)
are generated and posed a solid waste disposal problem, particu-
larly in over populated countries such as China and India. The
waste eggshells could create disposal problems and add to envi-
ronmental pollution. Joshi [17] studied the transesterification of
jatropha and karanja oils by using waste eggshell derived calcium
based mixed metal oxides as catalyst. High surface areas of the cat-
alysts were observed when they were calcined at 900 °C and there-
fore showed high catalytic activity. Niju [18] revealed that the
calcinations-hydration-dehydration treatment was a sufficient
method to increase the catalytic activity of waste shells. Though
there’re some studies on CaO production from waste eggshells,
there’re few studies on duck eggshells. There are some differences
between duck eggshells and other eggshells in the eggshell shaping
process, structure, physical characters, chemical composition and
quality index of eggshell. These differences may cause difference
in the characteristics of catalyst got from the eggshells. Therefore,
it is necessary to study the production and activity of the calcined
duck eggshell catalyst.
Feedstocks play an important role in biodiesel production. Edi-
ble oils such as sunflower, soybean, palm oil are the main resources
for biodiesel production in the present. However, the use of these
oils to produce biodiesel is not feasible for that there’s a big gap
in the demand and supply of such oils as food, on the other side,
they are far expensive to be used. Usingnon-edible oils such as ani-
mal fats, fish oil and waste frying oilas feedstock is an effective way
to reduce biodiesel production cost [19,20]. Soybean oil deodorizer
distillate (SODD) is a byproduct in the refining of soybean oil. It
contains free fatty acids (FFAs) (from 3 wt.% to 50 wt.%), triglyc-
erides (45–55%), tocopherols (3–12%), sterols (7–8%), hydrocar-
bons and other unsaponifiables in trace amounts [21]. The actual
composition of SODD depends on the source and process condi-
tions employed for the refining process of the soybean oil. The high
content of FFAs and triglycerides makes it a potential cheap feed-
stock for biodiesel production. Most of the FFAs and triglycerides
in SODD are wasted. There are few studies on biodiesel production
using SODD as feedstock. If there’s a process that could change the
FFAs and triglycerides in SODD to biodiesel, that means we could
change the waste to treasure.
High FFAs content in the feedstocks could prevent the effec-
tive use of alkaline catalyst. Therefore, biodiesel production
from high FFAs feedstocks is better performed in the presence
of acid catalysts as they can promote FFAs esterifcation [22]
in the first step. Then the alkaline catalyzed transesterification
was performed when the content of FFAs was not exceed
0.5 wt.% [22].
The aim of this study was to prepare a heterogeneous catalyst
from waste duck eggshells, then the catalytic activity for biodiesel
production from soybean oil deodorizer distillate was investigated.
The calcination conditions and the transesterification conditions
were optimized. The obtained CaO was characterized by X-ray
diffraction (XRD), Fourier Transmission Infrared Spectra (FT-IR),
Scanning Electron Microscopy (SEM). Furthermore, the reusability
of the catalyst was also investigated. It is expected that DES could
be used as an alternative and cheap catalyst for the biodiesel
production.
2. Materials and methods
2.1. Materials and chemicals
Waste duck eggshells were collected from local market. Metha-
nol, H2SO4, anhydrous sodium sulfate and phosphoric acid were of
analytical grade and were purchased from Sinopharm Chemical
Reagent Co., Ltd.
The SODD used for the study was supplied by Zhenjiang branch
of China Grain Reserves Corporation. The chemical and physical
properties of the SODD are shown in Table 1. Chemical standards
of Hexadecanoic acid methyl ester, Octadecanoic acid methyl ester,
13-Octadecenoic acid methyl ester, 9,12-Octadecadienoic acid
methyl ester, 9,12,15-Octadecatrienoic acid methyl esterwere
obtained from NU-CHEK PREP, INC.
2.2. Catalyst preparation
Duck eggshells were washed to remove the unwanted material
that adhered on the surface thoroughly in tap water. The washed
eggshells were again rinsed twice with distilled water. Then the
washed eggshells were dried in hot air oven at 105 °C. The dried egg-
shells were ground with a grinder, and sieved through a 60 mesh
sieve. Then the eggshell powder was calcined in a muffle furnace
at different temperatures (500 °C, 600 °C, 700 °C, 800 °C, 900 °C)
for different time to transform the calcium species into CaO particle,
then the calcined eggshell powder was stored in a desiccators.
2.3. Catalyst characterizations
X-ray diffraction (XRD) patterns were determined by a high-
resolution X-ray diffractometer (D8ADVANCE, Bruker Corporation,
Germany) coupled with Cu-ka radiation source (k = 1.1542 Å). The
data that shows intensity is plotted in a chart based on 2-Theta in a
range of 5–90° with a step of 0.02° [13]. The diffraction peakswere
assigned after consulting the Joint Committee on Powder Diffrac-
tion Standards (JCPDS) powder diffraction files.
Fourier Transmission Infrared Spectra (FTIR) analysis was
applied to investigate the functional groups of the catalyst with a
FT-IR spectrometer (Nicolet 5700, ThermoFisher Scientific). The
FT-IR spectra were recorded in the wavelength region of 4000–
400 cm
1 in KBr (0.3% w/w) disks.
Scanning Electron Microscopy (SEM) analysis was performed to
confirm the morphology of the catalyst by S-3000N scanning elec-
tron microscope (Hitachi Limited, Japan). The working sample was
analyzed at three different locations to ensure reproducibility.
X-ray fluorescence spectrometer (XRF, S4 PIONEER, BRUKER)
was used to determine the elemental composition of the DES
derived catalyst.
2.4. Pre-esterification of SODD
The reactor was a 1000 mL 3-neck-boiling flask with a water-
cooling reflux condenser and a mechanic stirrer. After preliminary
Table 1
Chemical and physical properties of SODD (n = 3).
Properties Units Average ± SD
Water content wt.% 0.32 ± 0.013
Acid value mg KOH/g oil 107.64 ± 2.28
Saponification value mg KOH/g oil 154.87 ± 2.62
Free fatty acid wt.% 53.8 ± 1.07
Triglycerides wt.% 28.53 ± 0.57
Vitamin E content wt.% 9.56 ± 0.21
Phytosterols content wt.% 10.32 ± 0.35
 X. Yin et al. / Energy Conversion and Management 112 (2016) 199–207
and optimization experiments, the optimal pre-esterification con-
ditions for SODD were H2SO4 concentration (v/w, based on oil
weight) 1.5%, methanol to oil molar ratio 12:1, reaction time
120 min and reaction temperature 60 °C.
2.5. Transesterificationof pre-esterified SODD
The pre-esterified SODD was put into a separating funnel after
pre-esterification and was washed with deionized water to remove
the excess methanol, catalyst. Then the pre-esterified SODD was
put into a beaker and the phytosterols were removed by cooling
down step by step, and after each step, the solution was cen-
trifuged to remove the phytosterols. The temperature steps were
15 °C, 5 °C,
5 °C and the cooling time was 2 h for each step.
The pre-esterified SODD was dehydrated by adding 25% anhy-
drous sodium sulfate, thereafter, it was introduced into the reactor
where the transesterification reaction was carried out. The chemi-
cal and physical properties of pre-esterified SODD are shown in our
previous published study [21]. After pre-esterification, the acid
value, free fatty acid content, FAME content, phytosterols content,
water content was about 1.94 mg KOH/g oil, 1.06 wt.%, 58.73 wt.%,
1.16 wt.%, 0.26 wt.%, respectively.
Different methanol/oil molar ratios (6:1; 8:1; 10:1, 12:1, 14:1),
catalyst loading amounts (2, 4, 6, 8 and 10 wt% based on the oil
weight), temperature (45, 50, 55, 60, 65, and 70 °C) and reaction
times (20, 40, 60, 80, 100 and 120 min) were studied. The product
was centrifuged at 6000 rpm for 15 min after the reaction. The
upper ester layer was washed with deionized water and cen-
trifuged again. This procedure was repeated for several times until
pH value in the aqueous phase reached 7.0.
Biodiesel yield obtained in transesterification reaction was cal-
culated by Eq. (1):
weight of FAME obtained in transesterification reaction
Biodiesel yieldð%Þ ¼
theoretically obtained weight of FAME in transesterification reaction
2.6. Analysis of biodiesel samples
During the reaction, 1 mL sample was taken from the reaction
tank and then it was neutralized to stop the reaction immediately
by adding 1 mL 5% phosphoric acid aqueous solution. The sample
phase was put into a separating funneland was separated. The
FAME primarily in the upper layer was washed with deionized
water, and then dehydrated by anhydrous sodium sulfate. The
samples were diluted in n-hexane and filtered by microporous
membrane before analyzed by gas chromatography. Chemical
standards were dissolved in chromatographically pure n-hexane
(Sigma Aldrich). The GC–MS spectrum of FAME produced from
SODD is shown in Fig. 1.
2.7. Reusability and leaching analysis
The reusability determines the life spent activity of heteroge-
neous catalysts and gives additional value to the catalysts. Thus,
the reusability of DES derived catalyst was investigated for transes-
terification of SODD. The reaction conditions for reusability test
were chosen based on optimum conditions which were calcination
temperature of 900 °C, catalyst amount of 10 wt.%, methanol to oil
ratio of 10:1, reaction temperature of 60 °C and reaction time of
201
80 min. When the reaction completed, the mixture was centrifuged
to separate solid catalyst and liquid layer. Then, the excess metha-
nol was discarded without removing the catalyst, and additional
amount of pre-esterification SODD and methanol were added to
the reaction with the same weight as the first reaction. The reac-
tion was repeated and carried out under the same optimum
conditions.
The leaching analysis was performed by measuring the calcium
content in the FAME and the glycerol phase by Atomic Absorption
Spectrometer (TAS-990, Persee Instrument Co. Ltd, China).
3. Results and discussion
3.1. Catalyst characterizations
The TGA profile for DES was showed in Fig. 2. From the figure,
we can see that the weight loss of DES was slight (weight loss
was about 4.356%) when the temperature was lower than 600
and this weight loss was caused by the loss of water and some
organism in the egg. The major degradation peak with total weight
loss was about 38% when the temperature was from 690 °C to
850 °C. This corresponded with the decomposition of CaCO3 to
CaO. Then the weight loss kept zero with the temperature increas-
ing which means that the composition of the eggshell was mainly
CaO when the calcination temperature was higher than 850 °C.
The XRD patterns of the DES before and after the calcination at
600–900 °C were shown in Fig. 3. The data that shows intensity is
plotted in a chart based on 2-Theta in a range of 5–90° with a step
of 0.02°.
The results showed that when the temperature was lower than
800 °C the composition of the DES was dominantly CaCO3. These
low intensity diffraction peaks of CaCO3 could be observed at
 100% ð1Þ
2h = 23.12°, 26.31°, 36.36°, 39.49°, 43.29°, 47.58°, 48.58°. When
the temperature was higher than 800 °C, the peaks of CaO
appeared at 2h = 34.12°, 37.48°, 53.98°, 64.46°, 67.49°. These
results confirmed that the crystalline of activated CaO phase
formed at the calcination temperature of 800 °C and 900 °C.
The FTIR spectra of DES at different calcination temperatures
were showed in Fig. 4. The spectra of natural eggshells and calcina-
tion temperatures lower than 800 °C showed major peaks at 1418,
866 and 714 cm
1, but these peaks disappeared when calcinations
temperatures were 800 and 900 °C. These peaks are attributed to
asymmetric stretch, out-of plane bend and in-plane bend vibration
of CO2

3 molecules [23].
The morphology of natural and calcined DES was detected by
SEM (4000 magnification) and results were showed in Fig. 5. From
the figure, we can see that the morphology of natural DES and cal-
cined temperature lower than 800 °C (Fig. 4a–d) displayed a typical
layered architecture with macro-pores and irregular shapes of par-
ticles of various sizes. When the calcined temperature was 800 °C
as showed in Fig. 4e, the morphology of calcium oxide could be
observed. When the calcined temperature was 800 °C and 900 °C
as showed in Fig. 4e and f, the particle shapes become more regu-
lar. The SEM images of CaO showed a cluster ofwell-developed
cubic crystal with obvious edges.
202 X. Yin et al. / Energy Conversion and Management 112 (2016) 199–207

Fig. 1. GC–MS spectrum of FAME produced from SODD. (a) TIC of FAME, (b) mass spectrum of Hexadecanoic acid methyl ester, (c) mass spectrum of Octadecanoic acid methyl
ester, (d) mass spectrum of 13-Octadecenoic acid methyl ester, (e) mass spectrum of 9,12-Octadecadienoic acid methyl ester, (f) mass spectrum of 9,12,15-Octadecatrienoic
acid methyl ester.

Fig. 2. The TGA profile for DES. Fig. 3. XRD patterns of DES at different temperatures.
 X. Yin et al. / Energy Conversion and Management 112 (2016) 199–207 203

particle size of DES-900 were higher than those of the DES-800.

The surface area of the DES derived catalyst was closely related
to the calcination temperature. High calcination temperature leads
to high surface area, pore volume and particle size.
The elemental composition of DES-900 was determined and the
results were shown in Table 3. The results indicated the presence
of Ca, Mg, S, Fe and P in the catalyst, 98.16% of the chemical com-
ponent was attributed to Ca.

3.2. Transesterification

3.2.1. Effect of calcined temperature on the activity

Fig. 4. FTIR spectra of DES at different calcination temperatures.
Brunauer–Emmer–Teller (BET, Micromeritics Instrument
Corporation) analysis was performed on DES 800 °C and 900 °C
(DES-800 and DES-900) to determine the specific surface area, pore
volume and particle size of the catalysts and the results are shown
in Table 2. Results showed that surface area, pore volume and
The effect of calcined temperature on the catalyst activity was
studied. The activities of the two catalysts DES-800 and DES-900
were studied by catalyzing the biodiesel production. The condi-
tions were as follows: methanol to triglyceride molar ratio 8:1,
temperature 65 °C, catalyst content 8 wt.%, reaction time 90 min.
The results were shown in Fig. 6. From the figure, one can see that
the biodiesel yield increased with time prolonged. The biodiesel
yield and reaction speed catalyzed by DES-900 was higher than
that of catalyzed by DES-800. The biodiesel yield reached 94% for
DES-900 while it is about 86% for DES-800 at the time of 80 min.
From the BET test results, we can see that the surface area, pore
volume and particle size of DES-900 were all bigger than those of

Fig. 5. Typical SEM images of DES at different calcination temperatures (a) natural eggshells, (b) calcination temperature 500 °C, (c) calcination temperature 600 °C, (d)
calcination temperature 700 °C, (e) calcination temperature 800 °C, (f) calcination temperature 900 °C.
204 X. Yin et al. / Energy Conversion and Management 112 (2016) 199–207

Table 2 results were shown in Fig. 7. As the reaction is reversible, excessive

Surface area, pore volume and particle size of the catalysts. alcohol is used to shift the equilibrium to the product side. One can
Catalyst Suface area Proe volume Average particle size see from the figure that when methanol to triglyceride molar ratio
(m2/g) (cm3/g) (nm) rise from 6:1 to 10:1 the biodiesel yield increased from 58% to 95%.
DES-800 1.4133 0.01370 27.9290 When the methanol to triglyceride molar ratio was higher than
DES-900 2.2290 0.01638 44.2700 10:1, the biodiesel conversion decreased slightly. Vegetable oils
are esters of glycerol with saturated and unsaturated long-chain
fatty acids, and the theoretical methanol to oil molar ratio is three
as taken from stoichiometric transesterification. But excess
amount of methanol is needed in order to drive the reaction to
Table 3
the forward direction because the reaction is reversible [17]. High
Elemental composition of DES-900.
methanol concentration can shift the reaction equilibrium forward
Species Ca wt.% Mg wt.% S wt.% Fe wt.% P wt.% Others wt.% to get high biodiesel yields. However, when the methanol concen-
DES-900 98.16 0.41 0.22 0.30 0.24 0.67 tration kept increase, the contents of catalyst and reactants were
diluted by methanol, which may initiate reverse reaction and lead
to the biodiesel conversion reduce [24,25]. So 10:1 was the optimal
100 methanol to triglyceride molar ratio.

90 3.2.3. Effect of catalyst content

The catalyst amount is an important parameter. When the FFAs
80 content is high in the feedstock, base catalyst can react with FFAs
Biodiesel yield / %

DES-800
to form saponification. This may complicate the product separation
70 and purification process and thus reducing the FAME yield. The
DES-900
effect of DES catalyst amount on biodiesel yield was studied with
60 the other conditions set as follows: temperature 65 °C, methanol
to triglyceride molar ratio 10:1, time 90 min. The results of the
50 experiment are shown in Fig. 8. The figure showed that the biodie-
sel yield increased with the increase of catalyst amount, when the
40 catalyst amount reached 8%, the biodiesel yield was higher than
90%, when the catalyst amount was 10%, the biodiesel yield was
30 about 94%, when the catalyst amount increased any more, the bio-
20 40 60 80 100 diesel yield did not increased accordingly. This tendency is similar
Time/min with references that also reported that biodiesel yield increased as
catalyst loading is increased until reached optimum catalyst load-
Fig. 6. Effect of calcined temperature on the activity.
ing. Excess catalyst may disturb the mixing of methanol, oil and
catalyst and led to phase separation [2,10]. Therefore, in this study,
10 wt.% catalysts loading were was the optimal catalyst content.
100

90 3.2.4. Effect of the temperature

The effect of temperature on the biodiesel yield was studied
80 with the other conditions were: DES-900 amount 10%, methanol
Biodiesel yield / %

to triglyceride molar ratio 10:1, time 90 min. The results were

70 shown in Fig. 9. From the results, it can be seen that when temper-
ature was lower than 60 °C, the FAME yield increased with the
60 increase of the temperature, and achieved the highest value at

50

40

30
6 8 10 12 14
Molar ratio of methanol / oil

Fig. 7. Effect of methanol to triglyceride molar ratio on the biodiesel yield.

the DES-800. The increase in the surface area leads to better

catalytic activity. So we choose DES-900 as the catalyst in the
following experiments.

3.2.2. Effect of methanol to triglyceride molar ratio

The effect of methanol to triglyceride molar ratio on biodiesel
yield was studied when the other conditions were as follows: tem-
perature 65 °C, DES-900 content 8 wt.%, reaction time 90 min. The Fig. 8. Effect of catalyst amount on the biodiesel yield.
 X. Yin et al. / Energy Conversion and Management 112 (2016) 199–207 205

soap formation [3]. Reaction time of 80 min was chosen as the

100 optimal time for DES catalized transesterification reaction.

3.3. Reusability and leaching test of the DES catalyst

Biodiesel yield / %

80 The reusability is one of the most important characters of

60
40
40 45 50 55 60
o
Temperature / C
Fig. 9. Effect of temperature on the biodiesel yield.
60 °C. Then, the biodiesel yield decreased slightly with the increase
of the temperature. Many references assumed the reaction to be
athermic [26,27] but there are references assumed it slightly
exothermic [28,29]. The molecular movement increased with the
increase of temperature which result the increase of reaction rate.
But in this reaction, when the temperature keep increasing up to
65 °C which is the boiling temperature of methanol, the methanol
will be evaporated and lost from the reaction mixture. Thus
the biodiesel yield decreased. So the optimal temperature was
60 °C.
3.2.5. Effect of reaction time
The effect of reaction time on biodiesel yield was shown in
Fig. 10. The other conditions were: DES-900 amount 10%, methanol
to triglyceride molar ratio 10:1, temperature 60 °C. The biodiesel
yield increased with the time prolonging and got the highest value
of 94.6% at 80 min, and then the biodiesel yield decreased slightly
when the time prolonged. The reason for this result may be that
when reaction time was 80 min, the reaction had already achieved
equilibrium. Excess reaction time could decrease biodiesel yield in
that the transesterification reaction will shift to the left and lead to
heterogeneous catalyst. The reusability is the most important
advantages of heterogeneous catalyst over homogeneous catalyst.
The reusability of the DES-derived catalyst was tested under the
optimal conditions that were calcination temperature of 900 °C,
catalyst amount of 10 wt.%, methanol to oil ratio of 10:1, reaction
temperature of 60 °C and reaction time of 80 min. The catalyst
appearance was changed from grayish white to dark brown after
being separated from the reaction mixture.
The catalysts were recovered by centrifugation between each
reaction, and then the recovered catalyst was washed with hot
65 70 75 methanol and then being activated at 120 °C for an hour. The
reusability tests results were shown in Fig. 11. As is shown in the
figure, the yield of biodiesel declined after each cycle. The biodiesel
yield was above 80% after five times usage and after 8 times usage
the biodiesel yield was lower than 60%. The reason for this activity
loss may be lies that some catalyst lost during filtration and metha-
nol wash or due to the pore blockage of the catalyst with reactant
and production [30].
The used catalysts (after 5 cycles) were characterized by SEM
(Quanta FEG 250) and XRD. The results were shown in Figs. 12
and 13. From Fig. 12, compared with Fig. 4(e) and (f), we can see
that after 5 times usage, the cluster of well-developed cubic crystal
with obvious edges were disappeared, and the pores in the used
catalyst were nearly destroyed. This reduced the surface area of
the catalyst.
The XRD pattern of the recycled catalyst (after 5 cycles) showed
notable shifting of the peaks, the peaks of CaO and CaCO3 disap-
peared. This may be due to that the used catalysts were covered
by intermediates or products such as glycerol, biodiesel. This
reduced the contacts between the catalyst and the reactant mix-
tures, consequently catalytic activity was decreased.
AAS analysis was performed to confirm the possibility of the
leaching of catalysts. The results showed that the concentration
of Ca in the biodiesel and glycerol were 2.21 mg/kg and 3.04 mg/
kg, respectively. The leaching value was in the range of the Amer-
ican and European quality standard for biodiesel, where maximum
limit is 5 mg/kg [2]. The leaching of Ca may be a reason for the
deactivation of the catalyst.

100
100

90
80
Biodiesel yield / %

Biodiesel yield/%

80
60

70
40

60
20

50
0
20 40 60 80 100 120 1 2 3 4 5 6 7 8
Reaction time / min Run times

Fig. 10. Effect of reaction time on biodiesel yield. Fig. 11. Reusability of the DES catalyst.
206 X. Yin et al. / Energy Conversion and Management 112 (2016) 199–207
Fig. 12. Typical SEM images of used DES catalyst. (a) Used DES-800, (b) used DES-900.
Fig. 13. XRD patterns of DES catalyst. (a) Natural eggshell, (b) used DES-800, (c)
used DES-900, (d) DES-800, (e) DES-900.
4. Conclusions
In this study, an inexpensive and environment-friendly catalyst
was prepared from waste duck eggshell (DES). The DES is a source
of calcium carbonate which could be changed to calcium oxide
under high temperatures. The obtained CaO was characterized by
X-ray diffraction (XRD), Fourier Transmission Infrared Spectra
(FT-IR), Scanning Electron Microscopy (SEM). XRF was used to
determine the elemental composition of the catalyst. BET analysis
was performed to determine specific surface area, pore volume and
particle size of the catalysts. Results showed that at 800 °C and
900 °C the calcium carbonate in DES could be changed to CaO.
The transesterification reaction was done in the presence of soy-
bean oil deodorizer distillate (SODD), methanol and DES derived
catalyst. The process of biodiesel production using the obtained
CaO as catalyst was studied and the optimal conditions were:
calcination temperature of 900 °C, catalyst amount of 10 wt.%,
methanol to oil ratio of 10:1, reaction temperature of 60 °C and
reaction time of 80 min, andthe biodiesel yield was 94.6% at these
conditions. The reusability of the DES-derived catalyst was tested
and the results showed that the biodiesel yield was above 80% after
five times usage and was lower than 60% after 8 times usage. The
used catalysts (after 5 cycles) were characterized by SEM and XRD
and also the leaching of catalysts was test. Results implied that the
reason for the deactivation of the catalyst may be reduced the sur-
face area and the leaching of Ca. The results of this study indicated
that catalyst prepared by duck eggshell is suitable for catalyzing
biodiesel production.
Acknowledgements
This work was supported by Jiangsu Key Lab of Biomass-based
Green Fuels and Chemicals (No: JSBGFC13003), Six Talent Peaks
Project of Jiangsu Province (No: XNY-012), Open project of Key
Laboratory for Palygorskite Science and Applied Technology of
Jiangsu Province (No: HPK201305), Independent Innovation Fund
of Agricultural Science and Technology of Jiangsu Province (No:
CX(15)1009 and CX(13)3068), Huaian Key Research and Develop-
ment Project (Modern Agriculture) (No: HAN2015003), Colleges
and universities in Jiangsu Province Natural Science Fund (No:
13KJD550001), Jiangsu Provincial Science and Technology Depart-
ment, Production and Research Projects (No: BY2015051-03).
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