Energy & R

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Sani et al., Innov Ener Res 2017, 6:2
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Innovative Energy & Research
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ISSN: 2576-1463
Research Article Open Access

Production and Characterization of Heterogeneous Catalyst (CaO) from

Snail Shell for Biodiesel Production Using Waste Cooking Oil
Sani J1,2*, Samir S2, Rikoto II1,2, Tambuwal AD2, Sanda A3, Maishanu SM1 and Ladan MM2
1
Sokoto Energy Research Center, Usmanu Danfodiyo University, Sokoto
2
Department of Pure and Applied Chemistry, Usmanu Danfodiyo University, Sokoto
3
Department of Biological Sciences, Usmanu Danfodiyo University, Sokoto

Abstract
The waste snail shell was screened to determine its efficiency as heterogeneous catalyst for biodiesel
production via trans-esterification reaction. Prior to its use, the solid oxide material (shell) was calcined at 800°C
for 4 h to convert CaCO3 to CaO. Physicochemical analysis of waste cooking oil reveals the acid value (3.47
mg KOH/gm), density (0.9 g/cm3), moisture content (0.1%) and kinematic viscosity (42.2) respectively. The
prepared solid oxide catalyst was characterized using X-ray Fluorescence (XRF) and Fourier Transform Infrared
Spectroscopy (FT-IR) methods. The catalytic activity of the catalyst was evaluated by the transesterification
reaction under the following reaction conditions: temperature (60°C), time (3 h) and methanol to oil ratio (9:1)
respectively. GC-MS analysis was used to characterize the fatty acid methyl ester composition. The research
signified successful application of waste snail shell as heterogeneous catalyst for prospective economic
preparation of heterogeneous catalyst. It also developed an unconditional avenue for using the waste snail shell
as the catalyst.

Keywords: Biodiesel; Snail shell; Heterogeneous catalyst; Calcium regeneration of the catalyst are easy and cheap [8]. Heterogeneous
oxide; Transesterification basic catalysts include alkaline earth metal oxides such as calcium oxide
(CaO), magnesium oxide (MgO) and hydrotalcites [9]. Unfortunately,
Introduction the preparation of heterogeneous catalyst is quite expensive and
complex [10]. Therefore, low cost solid wastes are looked into to serve
The 21st century is faced with many problems such as energy as solid heterogeneous catalysts. Several researches have been done
sustainability, environmental problems and rising fuel prices among on waste food materials like chicken egg shell, oyster shell, mud crab
others to mention but a few. Knowledge that is known about the usual shell, golden apple snail, meretrix venus and mollusk shell as cheap and
conventional fuels is nothing to write good about as they are known abundant resources of CaO for application as low cost heterogeneous
for polluting air by emissions of sulfur dioxides, carbon-dioxides, catalyst for biodiesel synthesis [11]. Egg shell has proved to be an
particulate matter and other gases which are detrimental to the active solid catalyst, providing yields of 96% [11] and 97%-99%
environment as it contributes to global warming problems [1] Even [10]. Further, crab shell provided 97% of conversion [6] and snail
with this, we are still charged with the responsibility of harnessing shell provided a biodiesel yield of 87.28% [7]. In this work, we have
energy from other green sources because “Energy sources are the main carried out transesterification using the snail shell as inexpensive and
driver of economic growth and social development of a country [2] and environmentally-friendly catalyst. The aim was to optimize the process
if we want to progress as a country, it is of paramount important that for biodiesel production from waste cooking oil using CaO catalyst.
we should search for a greener alternative source of energy. Naveen [3],
also noted that there is an exponential increase in the consumption of Experimental
fossil fuel both in developed and developing nations; and it is estimated
that these fuels shall be exhausted by the turn of 22nd century. This is Materials
an enough convincing reason to why research should be focused on an The used oil sample was taken from the fryer which was used for
alternative source of energy. frying potatoes and other vegetables based food in Sokoto State. The
The demand for world energy continues to rise due to two main used vegetable oil was mainly contaminated with water and solid
reasons; the continuing increase in the world population and the particles. Some analyses (Table 2) were conducted on the waste oil
growing demand by developing countries for their growth [2]. One to determine the quality of the oil and a pre-treatment process was
of the alternative fuels, developed over a century ago is biodiesel. conducted to remove the solid impurity through filtration. The snail
Biodiesel has been selected as an interesting alternative fuel as it is
renewable, biodegradable, non-toxic and environment-friendly.
Biodiesel possesses a high flash point, better lubrication and high *Corresponding author: Jamilu Sani, Sokoto Energy Research Center, Usmanu
cetane number and has a quite resemblance in regard to physical Danfodiyo University, Sokoto, Tel: +2347068294175; E-mail: [email protected]
and chemical characteristics with that of conventional diesel fuel [4].
Received November 23, 2017; Accepted December 06, 2017; Published December
Vegetable oil and animal fat are the best sources for biodiesel [5]. These 13, 2017
sources can be subjected to trans-esterification reaction to undergo
Citation: Sani J, Samir S, Rikoto II, Tambuwal AD, Sanda A, et al. (2017) Production
change in viscosity and volatility. The transesterification is carried and Characterization of Heterogeneous Catalyst (CaO) from Snail Shell for Biodiesel
out with a simple alcohol in the presence of a catalyst, which can be Production Using Waste Cooking Oil. Innov Ener Res 6: 162.
either homogeneous or heterogeneous [6]. Transesterification can be
Copyright: © 2017 Sani J, et al. This is an open-access article distributed under
catalyzed by an acid, base, or enzymes [7]. the terms of the Creative Commons Attribution License, which permits unrestricted
use, distribution, and reproduction in any medium, provided the original author and
Heterogeneous catalysts have the advantage that separation and source are credited.

Innov Ener Res, an open access journal Volume 6 • Issue 2 • 1000162

Citation: Sani J, Samir S, Rikoto II, Tambuwal AD, Sanda A, et al. (2017) Production and Characterization of Heterogeneous Catalyst (CaO) from
Snail Shell for Biodiesel Production Using Waste Cooking Oil. Innov Ener Res 6: 162.

Page 2 of 4

Column oven temperature 40°C

Injection temperature 250°C
Injection mode Split (10:1)
40°C hold 1 m in ≥ 10°C/min ≥ 300°C hold
Column temperature program
2 min
Table 1: GC-MS Configuration.

Property name Value

Acid value (mg of KOH/gm of oil) 3.47 Figure 1: Conversion of snail shell to catalyst (CaO).
Kinematic viscosity at 35.1°C (mm­ /s)2
42.2
Density (g/cm3) 0.9
Free fatty acid content (%) 1.73
Specific gravity 0.9
Moisture content (%) 0.1
Odour Mild flavor
Color Light Brown
Table 2: Physicochemical properties of waste vegetable oil.

shell was obtained from Ijabgo town of Oyun local government,

Kwara State. It was well rinsed with running water to remove dust and Figure 2: Plate 1-Biodiesel separation phase.
impurities and then dried in the sun.
Characterization of the produced biodiesel using GC-MS
Preparation and characterization of snail shell waste-derived
catalyst The Fatty Acid Methyl Esters (FAMEs) in the produced biodiesel
were characterized and identified using gas chromatography-mass
CaO catalyst was prepared by calcination method. The dried snail spectroscopy. (GC-MS-QP 2010 Ultra, Shimadzu Japan) fitted with
shell (100-200 mesh) was calcined at 800°C in air atmosphere with a 5 mm column type SLB (30 m, 0.20 µm, 0.2 µmm). The machine
heating rate of 10°C/min for 4 h. The product was obtained as a white configurations were outlined in Table 1.
powder. The calcined sample was kept in close vessel to avoid the
reaction with carbon dioxide (CO2) and humidity in the atmosphere Determination of biodiesel yield
before used. Figure 1 illustrates the preparation process of snail shell
waste-derived catalyst. The yield was calculated as follows:

The physicochemical properties of the catalyst were assessed using Weight of biodiesel
Yield (%) = × 100 (1)
the following procedures: Weight of oil
1. X-ray fluorescence (XRF): Oxford instrument gave the Results and Discussion
elemental composition of the calcined catalyst. The atoms of
the sample absorb energy from x-rays and become temporarily Physicochemical analysis of the WVO
excited and then emit secondary X-rays. By measuring the
intensity and characteristic energy of the emitted X-rays, The composition of the waste vegetable oil was analyzed, with
qualitative and quantitative analysis regarding the thickness the results obtained shown in Table 2. The amount of FFA in the oil
and composition can be obtained. was found to be 1.73%. Studies have shown that high FFA reduces
catalyst effectiveness and decreases the production yield; therefore,
2. Fourier Transform Infrared Spectroscopy (FT-IR): The sample the recommended amount of FFA in WCO should not exceed 1 wt%
was mixed with alkali halide potassium bromide (KBr) and [12]. In contrast, Ngoya et al. [13] stated that heterogeneous catalysts
compressed into a thin transparent pellet using a hydraulic have proven to catalyze oil with high FFA content (6-15%) without any
press, before being placed in the standard sample compartment pre-treatment. The physical properties, like the specific gravity, density,
of the spectrometer. free fatty acid content, moisture content, odor, color are presented in
Table 2.
Catalytic testing
The trans-esterification reaction was performed in a 2000 cm3 Catalyst characterization
4-necked round bottom flask. One of the side necks was fitted with a XRF result: The major component of the calcined snail shell at
water-cooled condenser, the middle neck was used to insert magnetic 800°C for 4 h was CaO (Figure 3.1).
stirrer, the desired amount of catalysts (CaO catalyst as much as 9%
of the mass of the oil), methanol and waste frying oil was introduced The remaining composition of the catalyst composed of different
into the round bottomed flask and the third neck was fitted with a metal oxides (MgO, SiO2, SO3, P2O5, Na2O, Al2O3, K2O, Fe2O3, SrO,
temperature indicating thermometer and the reactions were carried ZnO, Mn2O3, Cr2O3, TiO2) in trace amounts. These oxides have been
out at 60°C for 3 h. After the reaction was completed, the catalyst was reported to be active materials for transesterification (7). The basic
screened by using a filter paper (0.7 µm) and the transesterification oxides (MgO, K2O, FeO3) will enhance the catalyst’s basic strength (6),
products were allowed to settle overnight for the clear separation of however MgO is not present in the snail shell as shown in Table 3.
biodiesel and glycerol as seen in plate 1 (Figure 2). FT-IR result: The FT-IR spectra of the snail shell CaO is presented

Innov Ener Res, an open access journal Volume 6 • Issue 2 • 1000162

Citation: Sani J, Samir S, Rikoto II, Tambuwal AD, Sanda A, et al. (2017) Production and Characterization of Heterogeneous Catalyst (CaO) from
Snail Shell for Biodiesel Production Using Waste Cooking Oil. Innov Ener Res 6: 162.

Page 3 of 4

below in Figure 3.2. Traces of carbonate can be found between 1250

cm-1-1600 cm-1, which might be adsorbed during sample preparation
and afterwards trapped inside the oxide during the calcination process.
The strong band at 3640 cm-1 corresponds to the O-H bonds and this
is similar to a report made by Park et al. [14]. The absence of a sharp
absorption in the region around 724 cm-1 to 924 cm-1 indicates that
CaCO3 as the basic components of the snail shell is no longer present as
it has already been converted to CaO [15].

Biodiesel composition
The analysis of the GC-MS shows there are about sixteen main
characteristic peaks of Fatty Acids Methyl Esters (FAMEs) appearing
by the retention time and the fragmentation pattern data of the
Frequency [cm-1]
biodiesel. See Figure 3.3 below.
Figure 3.2: FT-IR spectrum of CaO from snail shell.
The chemical composition of each peaks is shown below with
9-Octadecenoic acid, methyl ester, (E), Hexadecanoic acid, methyl
ester, 9, 12-Octadecadienoic acid (Z, Z)-, methyl ester and methyl
stearate having the highest peaks.
Name of the FAMEs
Octanoic acid, methyl ester
Dodecanoic acid, methyl ester
Diethyl phthalate
Methyl tetradecanoate

Figure 3.3: GC-MS spectrum of biodiesel from snail shell CaO catalyst.

Tridecanoic acid, methyl ester

9-Hexadecenoic acid, methyl ester, (Z)-
Hexadecanoic acid, methyl ester
3, 6-Dimethoxy-2, 5-dinitrobenzaldehyde oxime
Heptadecanoic acid, methyl ester
9, 12-Octadecadienoic acid (Z, Z)-, methyl ester
9-Octadecenoic acid, methyl ester, (E)-

Figure 3.1: XRF spectrum of CaO obtained from snail shell. Methyl stearate
Oxiraneoctanoic acid, 3-octyl-, methyl ester, cis
Element Composition in snail shell
Oxiraneoctanoic acid, 3-octyl-, methyl ester
Na2O 0.000 wt%
MgO 0.000 wt% cis-11-Eicosenoic acid, methyl ester
Al2O3 0.606 wt% Methyl 18-methylnonadecanoate
SiO2 3.046 wt%
P2O5 0.379 wt%
Docosanoic acid, methyl ester
SO3 0.094 wt% Tetracosanoic acid, methyl ester.
Cl 0.095 wt%
The viscosity of the produced biodiesel methyl esters measured at
K2O 0.146 wt%
40°C was found to be 4.5 mm2/sec for the biodiesel, which was in the
CaO 95.186 wt%
range recommended by EN 14214 and ASTM D445. The EN 14214
TiO2 0.055 wt% standard for biodiesel viscosity is 3.5 mm2/sec to 5.0 mm2/sec at 40°C,
Cr2O3 0.000 wt% while the ASTM D445 standard for biodiesel viscosity is 1.9 mm2/sec
Mn2O3 0.010 wt% to 6.0 mm2/sec at 40°C.
Fe2O3 0.112 wt%
ZnO 0.006 wt%
Biodiesel yield
SrO 0.265 wt% The snail shell-CaO produced a volume biodiesel conversion of
Table 3: Elemental composition of snail shell. 84.14%.

Innov Ener Res, an open access journal Volume 6 • Issue 2 • 1000162

Citation: Sani J, Samir S, Rikoto II, Tambuwal AD, Sanda A, et al. (2017) Production and Characterization of Heterogeneous Catalyst (CaO) from
Snail Shell for Biodiesel Production Using Waste Cooking Oil. Innov Ener Res 6: 162.

Page 4 of 4

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