19447450, 2015, 1, Downloaded from https://aiche.onlinelibrary.wiley.com/doi/10.1002/ep.11939 by UFCG - Universidade Federal de Campina Grande, Wiley Online Library on [19/12/2022].

See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Preparation of Biodiesel from Waste Frying Oil
Using a Green and Renewable Solid Catalyst
Derived from Egg Shell
Subramaniapillai Niju, Kader Mohamed Meera Sheriffa Begum, and Narayanan Anantharaman
Department of Chemical Engineering, National Institute of Technology, Tiruchirappalli 620015, Tamil Nadu, India; meerasherif-
fa@gmail.com (for correspondence)
Published online 15 January 2014 in Wiley Online Library (wileyonlinelibrary.com). DOI 10.1002/ep.11939

Biodiesel was produced from waste frying oil using cal-
cium oxide derived from the calcination of egg shell as a het-
erogeneous base catalyst. The catalyst was characterized by
X-ray diffraction, Fourier transform infrared (FTIR) spectros-
copy, Brunauer–Emmett–Teller analysis, scanning electron
microscopy, and energy-dispersive atomic X-ray spectrometry.
The effects of reaction variables such as methanol/oil molar
ratio, amount of catalyst, reaction temperature, and reaction
time on biodiesel yield were investigated. The activity of the
egg shell-derived CaO was compared with the commercial
CaO. A high biodiesel yield of 95.05% and conversion of
96.11% were obtained at 3 wt % catalyst (based on oil
weight), methanol/oil molar ratio of 9:1, reaction tempera-
ture of 65 C, and reaction time of 3 h. The structure of bio-
diesel was characterized by FTIR, and the biodiesel
conversion was determined by 1H nuclear magnetic reso-
nance spectroscopy. V C 2014 American Institute of Chemical
Engineers Environ Prog, 34: 248–254, 2015
Keywords: egg shells, calcium oxide, waste frying oil, bio-
diesel, transesterification
INTRODUCTION
The search for alternative energy resources to supplement
or replace fossil fuels has been increased in the recent years
because of the increased environmental concern, energy secu-
rity, and fast depletion of fossil fuel resources. Biodiesel has
become more attractive as it is nontoxic, environmental
friendly, and made from renewable resources [1,2]. The most
commonly used vegetable oils for biodiesel production are
soybean, sunflower, palm, rapeseed, and canola oil. The major
drawback with biodiesel is the high cost of feedstock, which
leads to the high price of biodiesel [3]. Hence, the use of edible
oils for biodiesel production is not feasible. One possible way
to reduce the production cost of biodiesel is to use nonedible
oils [4,5], waste frying oil (WFO) [6,7], and poultry fats [8] as
raw materials. The price of WFO is 2–3 times cheaper than vir-
gin vegetable oil [9], and it is a potential feedstock for biodiesel
production that does not compete directly with the food crops
as in the case of edible oils. Huge quantity of WFO is available
abundantly that could be generated locally wherever food is
cooked or fried in oil. Some of the WFOs are used for soap
preparation and as additive oil for fodder making; however, a
C 2014 American Institute of Chemical Engineers
V near to the institution. WFO was procured from the canteen
major amount of WFO is illegally dumped into landfills and
rivers [6]. The usage of WFO as a reactant for biodiesel synthe-
sis not only helps the disposal problem but also reduces the
production cost of biodiesel. Transesterification is the most
preferred method for the production of biodiesel using acidic
or alkali catalysts. It is the reaction between triglycerides and
alcohol in the presence of catalyst to form esters and glycerol
[2]. The most commonly used homogeneous alkali catalysts for
biodiesel production includes sodium hydroxide, potassium
hydroxide, and sodium methoxide. Transesterification process
using homogeneous alkali catalyst provides high yield of bio-
diesel at mild temperature, atmospheric pressure, and shorter
reaction time; however, some technical problems arise such as
separation of the catalyst after reaction, generation of excess
wastewater, emulsification, and consumption of energy [10].
The problems posed by the homogeneous catalysts can be
overcome by using heterogeneous catalysts [11]. Moreover,
using heterogeneous catalyst in biodiesel production can sig-
nificantly decrease the purification steps and production cost
[12,13]. Different heterogeneous catalysts such as hydrotalcites
[14], zeolites and metal catalysts [15], metal oxides [12,16], and
supported catalysts [17] have been synthesized and used for
biodiesel production. CaO is one among the most promising
heterogeneous catalysts [16,18]. Recently, researchers have
derived CaO from white bivalve clam shell [19], capiz shell
[20], mussel shell [21], and Turbonilla striatula shell [22] and
used as a heterogeneous catalyst for biodiesel production. In
the current investigation, CaO derived from egg shell was used
as a solid base catalyst for the transesterification of WFO. The
effects of process parameters such as methanol/oil molar ratio,
amount of catalyst, reaction temperature, and time were stud-
ied to obtain the maximum yield of biodiesel. The egg shell-
based CaO was characterized by X-ray diffraction (XRD), Fou-
rier transform infrared (FTIR) spectroscopy, Brunauer–
Emmett–Teller (BET) analysis, scanning electron microscopy
(SEM), and energy-dispersive atomic X-ray (EDAX) spectrome-
try. The structure of biodiesel was characterized by FTIR, and
the biodiesel conversion was determined by 1H nuclear mag-
netic resonance spectroscopy (1H NMR).
MATERIALS AND METHODS
Materials
Waste chicken egg shells were collected from a bakery

248 January 2015 Environmental Progress & Sustainable Energy (Vol.34, No.1) DOI 10.1002/ep

at the National Institute of Technology (Tiruchirappalli, Tamil
Nadu, India), and it was pretreated with activated carbon for
the reduction of free fatty acids [23]. The physiochemical
properties of the WFO were measured, and these properties
are presented in Table 1. Anhydrous methanol and commer-
cial CaO of analytical grade, purchased from Merck Limited,
Mumbai, India, were used in the transesterification reaction.
Preparation of Catalyst
The egg shells were washed thoroughly in tap water to
remove any unwanted material adhered on its surface and
rinsed twice with distilled water. The washed shells were
dried in a hot air oven at 105 C for 24 h. The dried shells
were crushed to small pieces and then calcined in a muffle
furnace under static air conditions at 900 C for 2.5 h. Alkali
earth metal oxides have very reactive surface with CO2 and
water [11]. Therefore, the calcined shells were ground to fine
powder in an agate mortar and stored in a closed vessel to
Table 1. Physicochemical properties of waste frying oil used
in this study
Properties Measured values
Density at 25 C (kg/m3) 914
Kinematic viscosity at 40 C (mm2/s) 28.93
Acid value (mg of KOH/g of oil) 2.14
Water content (g) 0.068 wt %
Solid content Nil
Figure 1. Experimental setup for transesterification process. [Color figure can be viewed in the online issue, which is available
at wileyonlinelibrary.com.]
Environmental Progress & Sustainable Energy (Vol.34, No.1) DOI 10.1002/ep
19447450, 2015, 1, Downloaded from https://aiche.onlinelibrary.wiley.com/doi/10.1002/ep.11939 by UFCG - Universidade Federal de Campina Grande, Wiley Online Library on [19/12/2022]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
avoid the reaction with CO2 and moisture in the air before
used.
Characterization of Catalyst
The CaO formation on calcination of the egg shell was
confirmed by powder XRD using a Rigaku (Model: DMAX
2200/Ultima1) diffractometer equipped with Cu Ka radia-
tion. FTIR spectroscopy was performed to study the presence
of functional groups using Perkin–Elmer system (Model:
Spectrum RXI). SEM and EDAX analyses were performed to
confirm the morphology and composition of the catalyst
using high-resolution SEM (Model: FEI Quanta FEG 200)
equipped with EDAX spectrometry. The surface area of the
commercial CaO and the egg shell-based CaO were deter-
mined by BET analysis using a ASAP 2020 surface area and
porosity analyzer (Micromeritics).
Transesterification Process
The experimental setup for transesterification process is
shown in Figure 1, and the reaction was carried out in a
three-necked 1000 mL round-bottomed flask. The middle
neck is used to insert a mechanical stirrer, one of the side
necks is fitted with a water-cooled condenser, and the other
neck is fitted with a temperature indicator. The reaction was
performed to obtain the maximum yield of biodiesel by vary-
ing the operating variables such as the methanol/oil molar
ratio, catalyst wt %, reaction temperature, and time. The
transesterification products along with the catalyst were fil-
tered through a Whatman No. 41 filter paper of 125 mm
diameter and a pore size of 20 lm into a separatory funnel.
January 2015 249

Figure 2. XRD of the calcined egg shell.
Figure 3. FTIR of the calcined egg shell.
The catalyst was separated, and the transesterification prod-
ucts were allowed to settle overnight for the clear separation
of fatty acid methyl esters (FAMEs) and glycerol. The upper
layer, FAME, formed by the conversion of fatty acids to their
respective esters is termed as biodiesel, and the lower dense
layer is termed as glycerol. The conversion of oil to FAME
was analyzed by 1H NMR using Bruker Avance III 500 MHz
(AV 500) spectrometer. CDCl3 was used as a solvent.
RESULTS AND DISCUSSION
Characterization of the Calcined Egg Shell
XRD Analysis
Figure 2 depicts the XRD pattern of the calcined egg
shells. The peaks obtained were compared with the standard
peaks in the Joint Committee on Powder Diffraction Stand-
ards file, and it was found that the peaks for the calcined cat-
alyst that appeared at 2h 5 32.36 , 37.50 , 54.00 , 64.30 ,
and 67.48 were the characteristics of calcium oxide [24,25],
and the peaks that appeared at 2h 518.16 and 34.34 were
the characteristics of calcium hydroxide [12].
Rivera et al. [25] obtained similar peaks for calcium oxide
derived from egg shell, and Verziu et al. [24] obtained similar
peaks for commercial calcium oxide. The appearance of
Ca(OH)2 may be due to the exposure of CaO to atmospheric
air [11].
FTIR Analysis
The FTIR analysis of the calcined egg shell was per-
formed, and the spectrum is shown in Figure 3. It was
250 January 2015 Environmental Progress & Sustainable Energy (Vol.34, No.1) DOI 10.1002/ep
19447450, 2015, 1, Downloaded from https://aiche.onlinelibrary.wiley.com/doi/10.1002/ep.11939 by UFCG - Universidade Federal de Campina Grande, Wiley Online Library on [19/12/2022]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Figure 4. SEM image of the egg shell calcined at 900 C for
2.5 h.
Table 2. EDAX analysis of egg shell calcined at 900 C for
2.5 h
Calcination Weight Atomic
temperature Element (%) (%)
900 C O 45.42 67.59
Ca 54.58 32.41
observed that on calcination at 900 C, egg shells started to
lose the carbonate ions, and the absorption band of CO22 3
molecules were shifted to higher energy (1455.04 and
21
1079.17 cm ). This is due to the decrease of the reduced
mass of the functional group attached to the CO22
3 ions [26].
In addition, a sharp OH2 stretching band is observed at
3645.37 cm21, which clearly indicates the presence of cal-
cium hydroxide [24,26]. These results are in accordance with
the findings of Engin et al. [26].
SEM and EDAX Analyses
Figure 4 shows the SEM image of the calcined egg shell.
It expressed the regular micromorphology of rod-like par-
ticles with size ranges from 1.29 to 2.0 mm of width. The ele-
mental composition of the egg shells performed by EDAX
fluorescence spectrometer reported in Table 2 indicates the
presence of oxygen (45.42%, w/w) and calcium (54.58%, w/
w) at 900 C.
BET Analysis
BET analysis was performed on commercial CaO and egg
shell-derived CaO to determine the surface area. The surface
area of a solid catalyst has direct impact on its catalytic activ-
ity, and hence the higher surface area catalyst is expected for
higher catalytic activity [27].
The surface area of the CaO obtained from the calcination
of egg shell at 900 C for 2.5 h was found to be 3.7262 m2/g.
The measured surface area of the commercial CaO used in
this study was found to be 3.0022 m2/g. However, the sur-
face area of the commercial CaO reported in the literature
was 1.0 [8], 2 [24], and 4.3 m2/g [28], respectively. Therefore,

Figure 5. Effect of methanol/oil molar ratio on yield (cata-
lyst 5 3 wt %, time 5 3 h, temperature 5 65 C, and stirring
speed 5 600 rpm).
Figure 6. Effect of catalyst wt % on yield (methanol/oil
molar ratio 5 9:1, time 5 3 h, temperature 5 65 C, and stir-
ring speed 5 600 rpm).
the surface area of the egg shell-derived CaO was compara-
ble with the commercial CaO.
Effect of Process Parameters
Effect of Methanol/Oil Molar Ratio
Figure 5 depicts the effect of methanol/oil molar ratio on
biodiesel yield over egg shell-based CaO catalyst. The yield
increased from 67.65 to 95.05% when the molar ratio was
increased from 3:1 to 9:1. This is due to the formation of
methoxy species on the catalyst surface that favors the reac-
tion and shifts it toward the forward direction [17,29]. How-
ever, after a certain extent, that is, 9:1 methanol/oil ratio, the
yield becomes more or less constant as the reaction achieved
equilibrium for the fixed values of the other variables such
as catalyst wt %, reaction temperature, reaction time, and
stirring speed.
Effect of Amount of Catalyst
The effect of catalyst loading on the yield of biodiesel
over egg shell-based CaO catalyst is shown in Figure 6. The
yield increased significantly with increased amount of cata-
lyst. As more the amount of catalyst, more the number of
basic active sites led to an increase in the biodiesel yield
[30]. The yield increased from 54.21 to 95.05% when the
amount of catalyst was increased from 1 to 3 wt % (based on
oil weight). However, after a certain extent of 3 wt % cata-
lyst, the yield becomes more or less constant as the reaction
achieved equilibrium for the fixed values for the other varia-
Environmental Progress & Sustainable Energy (Vol.34, No.1) DOI 10.1002/ep
19447450, 2015, 1, Downloaded from https://aiche.onlinelibrary.wiley.com/doi/10.1002/ep.11939 by UFCG - Universidade Federal de Campina Grande, Wiley Online Library on [19/12/2022]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Figure 7. Effect of reaction temperature on yield (methanol/
oil molar ratio 5 9:1, time 5 3 h, temperature 5 65 C, and
stirring speed 5 600 rpm).
bles such as methanol/oil molar ratio, reaction temperature,
reaction time, and stirring speed.
Effect of Reaction Temperature
Figure 7 depicts the effect of temperature on the yield of
biodiesel over egg shell-based CaO catalyst. The yield
increased significantly from 80.69 to 95.05% as the reaction
temperature was increased from 50 to 65 C; however,
beyond this temperature range, a sudden fall in the yield
was observed, which may be due to the serious volatilization
of methanol. The boiling point of methanol being 64.5 C led
most of the methanol to the vapor state, which lowered the
interaction between methanol and oil molecules [17,30].
Effect of Reaction Time
Figure 8 represents the effect of reaction time on the yield
of biodiesel over egg shell-based CaO catalyst. Longer reac-
tion time increased the contact period between methanol
and oil molecules on basic sites of catalyst and brought more
chances for the reaction [30]. The yield increased progres-
sively from 43.85 to 95.05% as the reaction time increased
from 30 to 180 min. For the operation beyond 3 h, the yield
decreased slightly, which may be due to the longer reaction
time that resulted in the hydrolysis of esters and caused
more fatty acids to form soap [31].
Thus from the influence of the parameters on transesterifi-
cation, it was found that 3 wt % catalyst (based on oil
weight), 9:1 methanol/oil molar ratio, 65 C reaction tempera-
ture, and 3 h of reaction time are required to produce a high
biodiesel yield of 95.05%. The speed of the agitator was
maintained constant at 600 rpm for all the experimental
investigations.
Characterization of Biodiesel
FTIR Analysis
The FTIR spectrum of biodiesel is shown in Figure 9. A
sharp absorption band at 1743 cm21 is the characteristic of
the axial deformation of the aliphatic ester AC@O bond. The
absorption bands at 2924 and 2855 cm21 correspond to the
axial deformation of ACH2 bond. The absorption bands at
3008 correspond to the axial deformation of @CAH bond. A
weak absorption band at 3447 cm21 is due to the AOH
stretching vibration. The absorption bands at 1459 and 1361
cm21 indicates the ACH2 shear-type vibration and ACH3
bending vibration. The absorption bands at 1245, 1196, 1171,
and 1018 cm21 are expected for CAOA C stretching vibra-
tions. The observation of an absorption band at 723 cm21
may be due to the ACH2 rocking vibration. Therefore, the
January 2015 251
 19447450, 2015, 1, Downloaded from https://aiche.onlinelibrary.wiley.com/doi/10.1002/ep.11939 by UFCG - Universidade Federal de Campina Grande, Wiley Online Library on [19/12/2022]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Table 3. Comparison of properties of the synthesized biodie-
sel with the ASTM standards of biodiesel.

Values
Standard values obtained
of biodiesel for
(as per ASTM synthesized
Properties D-6751) biodiesel
Density (g/cm3) 0.86–0.9 0.8814
at 25 C
Kinematic 1.9–6.0 4.84
viscosity
at 40 C (mm2/s)
Figure 8. Effect of reaction time on yield (catalyst 5 3 wt %, Flash point ( C) 100–170 157
methanol/oil molar ratio 5 9:1, temperature 5 65 C, and Cloud point ( C) 23 to 15 4.0
stirring speed 5 600 rpm). Calorific – 37.92
value (MJ/kg)

Figure 9. FTIR spectrum of biodiesel.

synthesized biodiesel from WFO possessed all the necessary

functional groups, and the structure was in compliance with
the findings of Qiu et al. [32].
Figure 10. 1H NMR spectrum of biodiesel.

Determination of the Properties of Synthesized Biodiesel

The properties such as density, kinematic viscosity, flash
point, cloud point, and calorific value of the synthesized bio-
diesel were measured and compared with the ASTM stand-
ards of biodiesel, and the results are presented in Table 3.
Yield and Conversion of Biodiesel
Yield
The yield of the reaction can be estimated by using Eq. 1
given by Leung and Guo [7].
Weight of the biodiesel
Yield ð%Þ5 3100;
Weight of the raw oil
Yield ð%Þ595:05%:
Conversion
The conversion of triglycerides to FAMEs was determined
by 1H NMR, and the 1H NMR spectrum of the biodiesel is
shown in Figure 10. The relevant signals chosen for integra-
tion were those of methoxy group in the methyl esters at 3.6
ppm and the protons on the carbon next to the glyceryl moi-
ety (a-CH2) at 2.3 ppm. Equation 2 given by Knothe [33] has
been used to find the conversion.
2AME
C51003 ; (2)
3Aa2CH2
where C is the percentage conversion of triglycerides to
methyl esters, AME is the integration value of the methoxy
protons of the methyl esters, and Aa2CH2 is the integration
value of the a-methylene protons.
The characteristic peaks of methoxy protons as a singlet
at 3.664 ppm and a-methylene protons as a triplet at 2.288
ppm were observed. These two peaks are the distinct peaks
for the confirmation of methyl esters [33]. The other peaks
(1) observed were at 0.87 ppm due to terminal methyl protons,
a strong signal at 1.30 ppm arises from the methylene proton
of carbon chain, a multiplet at 1.6 ppm related to b-carbonyl
methylene protons, and a signal at 5.34 ppm due to olefinic
hydrogen [34]. The percentage conversion of triglycerides to
methyl esters using Eq. 2 was found to be 96.11%.
Reusability of the Egg Shell-Based CaO
One of the most important features of a solid catalyst is
the ability to be recycled. From Figure 11, it was observed
that a high biodiesel yield of above 90% was obtained for all

252 January 2015 Environmental Progress & Sustainable Energy (Vol.34, No.1) DOI 10.1002/ep

the 11 tested runs conducted with 3 wt % catalyst, methanol/
oil ratio of 9:1, 65 C reaction temperature, and 3 h of reac-
tion time. At the end of each run, CaO was separated from
the reaction mixture by filtration and washed with methanol
to remove the adsorbed stains and then calcined in a muffle
furnace at 900 C for 2.5 h for further reuse.
Comparison of Egg Shell-Derived CaO
with the Commercial CaO
In this work, the activity of the CaO derived from egg
shell was compared with the commercial CaO and also with
the state of the art in the literature. The results are presented
in Table 4.
To maintain uniformity, WFO possessing similar physio-
chemical properties was tested with the egg shell-based CaO
and the commercial CaO. The parameters such as methanol/
oil ratio, catalyst wt % (based on oil weight), reaction tem-
perature, and reaction time were varied to obtain the maxi-
mum yield of biodiesel. In the case of egg shell-based CaO it
was found that the maximum biodiesel yield of 95.05% was
obtained at methanol/oil molar ratio of 9:1, 3 wt % catalyst
(based on oil weight), 65 C reaction temperature, and 3 h of
reaction time. However, the commercial CaO was able to
produce a high biodiesel yield of 95.66% using methanol/oil
molar ratio of 12:1, 5 wt % catalyst (based on oil weight),
65 C reaction temperature, and 3 h of reaction time. Liu
et al. [16] reported a maximum biodiesel yield of 95% for the
commercial CaO using methanol/oil molar ratio of 12:1, 8 wt
% catalyst (based on oil weight), 65 C reaction temperature,
and 3 h of reaction time for transesterification of soybean oil.
Hence, the waste egg shells can effectively be used as a solid
catalyst for transesterification of WFO, and its activity is com-
parable and better than the commercial CaO.
CONCLUSION
This study has revealed that CaO derived from egg shells
is an effective heterogeneous base catalyst for transesterifica-
Figure 11. Reusability of the egg shell-based CaO.
Table 4. Comparison of transesterification reaction condition for different catalysts
Optimum transesterification reaction conditions
Methanol/
Catalyst used Feedstock used oil molar ratio
CaO derived from Waste frying oil 9:1
the egg shell (This study)
Commercial CaO Waste frying oil 12:1
(This study)
Commercial CaO Soybean oil [16] 12:1
Environmental Progress & Sustainable Energy (Vol.34, No.1) DOI 10.1002/ep
19447450, 2015, 1, Downloaded from https://aiche.onlinelibrary.wiley.com/doi/10.1002/ep.11939 by UFCG - Universidade Federal de Campina Grande, Wiley Online Library on [19/12/2022]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
tion of WFO with methanol. A high biodiesel yield of 95.05%
and conversion of 96.11% were obtained at 3 wt % catalyst
(based on oil weight), methanol/oil molar ratio of 9:1, reac-
tion temperature of 65 C, and reaction time of 3 h. The activ-
ity of the egg shell-derived CaO was comparable and
effective than the commercial CaO for transesterification of
WFO. The synthesized biodiesel was compared with the
ASTM standards of biodiesel, and the physiochemical proper-
ties confirmed to the ASTM D-6751 specifications.
ACKNOWLEDGMENTS
The authors gratefully acknowledge the financial assis-
tance from the Council of Scientific and Industrial Research
(CSIR), New Delhi, India, in the form of Senior Research Fel-
lowship to S. Niju. The authors are thankful to the Depart-
ment of Chemical Engineering, National Institute of
Technology (Tiruchirappalli, Tamil Nadu) and Sophisticated
Analytical Instruments Facility (SAIF, IIT Madras) for 1H
NMR, SEM, and EDAX studies.
LITERATURE CITED
1. Meher, L.C., Sagar, D.V., & Naik, S.N. (2006). Technical
aspect of biodiesel production by transesterification—A
review, Renewable and Sustainable Energy Review, 10,
248–268.
2. Vyas, A.P., Verma, J.L., & Subrahmanyam, N. (2010). A
review on FAME production processes, Fuel, 89, 1–9.
3. Issariyakul, T., Kulkarni, M.G., Meher, L.C., Dalai, A.K., &
Bakhshi, N.N. (2008). Biodiesel production from mixtures
of canola oil and used cooking oil, Chemical Engineering
Journal, 140, 77–85.
4. Mohamedmusthafa, M., Sivapirakasam, S.P., Udayakumar,
M., & Balasubramanian, K.R. (2012). Effects of Al2O3
coating on diesel engine performance, combustion, and
emission characteristics fueled by Pongamia methyl ester
and its blends with diesel, Environmental Progress and
Sustainable Energy, 31, 147–156.
5. Koberg, M., & Gedanken, A. (2012). Direct transesterifica-
tion of castor and jatropha seeds for FAME production by
microwave and ultrasound radiation using a SrO catalyst,
Bioenergy Research, 5, 958–968.
6. Math, M.C., PremKumar, S., & Chetty, S.V. (2010). Tech-
nologies for biodiesel production from used cooking
oil—A review, Energy for Sustainable Development, 14,
339–345.
7. Leung, D.Y.C., & Guo, Y. (2006). Transesterification of
neat and used frying oil: Optimization for biodiesel pro-
duction, Fuel Processing Technology, 8, 883–890.
8. Reddy, C.R.V., Oshel, R., & Verkade, J.G. (2006). Room-
temperature conversion of soybean oil and poultry fat to
biodiesel catalyzed by nanocrystalline calcium oxides,
Energy Fuels, 20, 1310–1314.
9. Tanawannapong,Y., Kaewchada, A., & Jaree, A. (2013).
Biodiesel production from waste cooking oil in a
Catalyst Temperature Time
wt % ( C) (min) Yield (%)
3 65 180 95.05
5 65 180 95.66
8 65 180 95
January 2015 253

microtube reactor, Journal of Industrial and Engineering
Chemistry, 19, 37–41.
10. Helwani, Z., Othman, M.R., Aziz, N., Kim, J., & Fernando,
W.J.N. (2009) Solid heterogeneous catalysts for transester-
ification of triglycerides with methanol: A review, Applied
Catalysis A, 363, 1–10.
11. Endalew, A.K., Kiros, Y., & Zanzi, R. (2011). Inorganic
heterogeneous catalysts for biodiesel production from
vegetable oils, Biomass and Bioenergy, 35, 3787–3809.
12. Kawashima, A., Matsubara, K., & Honda, K. (2009).
Acceleration of catalytic activity of calcium oxide for bio-
diesel production, Bioresource Technology, 100, 696–700.
13. Feng, Y., Zhang, A., Li, J., & He, B. (2011). A continuous
process for biodiesel production in a fixed bed reactor
packed with cation-exchange resin as heterogeneous cat-
alyst, Bioresource Technology, 102, 3607–3609.
14. Xie, W., Peng, H., & Chen, L. (2006). Calcined Mg–Al
hydrotalcites as solid base catalysts for methanolysis of
soybean oil, Journal of Molecular Catalysis A, 246, 24–32.
15. Suppes, G.J., Dasari, M.A., Doskocil, E.J., Mankidy, P.J., &
Goff, M.J. (2004). Transesterification of soybean oil with
zeolite and metal catalysts, Applied Catalysis A, 257, 213–
223.
16. Liu, X., He, H., Wang, Y., Zhu, S., & Piao, X. (2008).
Transesterification of soybean oil to biodiesel using CaO
as a solid base catalyst, Fuel, 87, 216–221.
17. Yan, S., Lu, H., & Liang, B. (2008). Supported CaO cata-
lysts used in the transesterification of rapeseed oil for the
purpose of biodiesel production, Energy and Fuel, 22,
646–651.
18. Boey, P.-L., Maniam, G.P., & Hamid, S.A. (2011). Perform-
ance of calcium oxide as a heterogeneous catalyst in bio-
diesel production: A review, Chemical Engineering
Journal, 168, 15–22.
19. Girish, N., Niju, S., Meera S. Begum, K.M., &
Anantharaman, N. (2013). Utilization of a cost effective
solid catalyst derived from natural white bivalve clam
shell for transesterification of waste frying oil, Fuel, 111,
653–658.
20. Suryaputra, W., Winata, I., Indraswati, N., & Ismadji, S.
(2013). Waste capiz (Amusium cristatum) shell as a new
heterogeneous catalyst for biodiesel production, Renew-
able Energy, 50, 795–799.
21. Rezaei, R., Mohadesi, M., & Moradi, G.R. (2013). Optimi-
zation of biodiesel production using waste mussel shell
catalyst, Fuel, 109, 534–541.
22. Boro, J., Thakur, A.J., & Deka, D. (2011). Solid oxide
derived from waste shells of Turbonilla striatula as a
254 January 2015 Environmental Progress & Sustainable Energy (Vol.34, No.1) DOI 10.1002/ep
19447450, 2015, 1, Downloaded from https://aiche.onlinelibrary.wiley.com/doi/10.1002/ep.11939 by UFCG - Universidade Federal de Campina Grande, Wiley Online Library on [19/12/2022]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
renewable catalyst for biodiesel production, Fuel Process-
ing Technology, 92, 2061–2067.
23. Kheang, L.S., Subari, F., & Kadir, S.A.S.A. (2011). Pre-
treatment of palm olein-derived used frying oil as a feed-
stock for non-food applications, Journal of Oil Palm
Research, 23, 1185–1192.
24. Verziu, M., Coman, S.M., Richards, R., & Parvulescu, V.I.
(2011). Transesterification of vegetable oils over CaO cat-
alysts, Catalysis Today, 167, 64–70.
25. Rivera, E.M., Araiza, M., Brostow, W., Castano, V.M.,
Dias-Estrada, J.R., Hernandez, R., & Rodriguez, J.R.
(1999). Synthesis of hydroxyapatite from eggshells, Mate-
rials Letters, 41, 128–134.
26. Engin, B., Demirtas, H., & Eken, M. (2006). Temperature
effects on egg shells investigated by XRD, IR and ESR
techniques, Radiation Physics and Chemistry, 75, 268–
277.
27. Kumar, D., & Ali, A. (2012). Nanocrystalline K–CaO for
the transesterification of a variety of feedstocks: Structure,
kinetics and catalytic properties, Biomass and Bioenergy,
46, 459–468.
28. Vujicic, D.J., Comic, D., Zarubica, A., Micic, R., &
Boskovic, G. (2010). Kinetics of biodiesel synthesis from
sunflower oil over CaO heterogeneous catalyst, Fuel, 89,
2054–2061.
29. Liu, X., Xiong, X., Liu, C., Liu, D., Wu, A., Hu, Q., & Liu,
C. (2010). Preparation of biodiesel by transesterification
of rapeseed oil with methanol using solid base catalyst
calcined K2CO3/Al2O3, Journal of the American Oil
Chemists Society, 87, 817–823.
30. Teng, G., Gao, L., Xiao, G., Liu, H., & Lv, J. (2010). Bio-
diesel preparation from Jatropha curcas oil catalysed by
hydrotalcite loaded with K2CO3, Applied Biochemistry
and Biotechnology, 10, 8953–8959.
31. Tang, Y., Meng, M., Zhang, J., & Lu, Y. (2011). Efficient
preparation of biodiesel from rapeseed oil over modified
CaO, Applied Energy, 88, 2735–2739.
32. Qiu, F., Li, Y., Yang, D., Li, X., & Sun, P. (2011). Biodiesel
production from mixed soybean oil and rapeseed oil,
Applied Energy, 88, 2050–2055.
33. Knothe, G. (2001). Determining the blend level of mix-
tures of biodiesel with conventional diesel fuel by fiber
optic NIR spectroscopy and 1H NMR spectroscopy, Jour-
nal of the American Oil Chemists Society, 78, 1025–1028.
34. Monteiro, M.R., Ambrozin, A.R.P., Liao, L.M., & Ferreira,
A.G. (2009). Determination of biodiesel blend levels in
different diesel samples by 1H NMR, Fuel, 88, 691–696.