Materials Today: Proceedings xxx (xxxx) xxx

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Materials Today: Proceedings

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Improved yield of palm oil biodiesel through nano catalytic

transesterification
R. Saravana Sathiya Prabhahar b, V.S. Benitha a, J. Nagarajan b,⇑
a
Department of Electronics and Communication Engineering, Mepco Schlenk Engineering College (Autonomous), Sivakasi 626005, India
b
Department of Mechanical Engineering, Mepco Schlenk Engineering College (Autonomous), Sivakasi 626005, India

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

Article history: Biodiesel was found to be a perfect alternative for fossil fuels. Among various methods, transesterification
Received 2 March 2021 was found to be an effective method in biodiesel production. The yield of biodiesel plays a major role in
Received in revised form 12 March 2021 improving its market value. In the present study, palm oil biodiesel yield was increased by employing
Accepted 16 March 2021
Nanoparticles such as Titanium dioxide and Iron oxide. Titanium dioxide and Iron oxide Nanoparticles
Available online xxxx
have been synthesized by means of the Sol-Gel method and Gel combustion method respectively. The
synthesized nanoparticles were characterized by means of various techniques such as XRD, FESEM,
Keywords:
and AFM analysis. The increased biodiesel yield % was found to be 91.06 for TiO2 and 84.24 for Fe2O3
Biodiesel
Titanium dioxide
when compared to 82.14 for KOH. The percentage of biodiesel yield obtained was found to be comparable
Iron oxide with previous studies. The biodiesel synthesized was characterized through Gas Chromatography and
Transesterification Mass Spectroscopy technique. Among the Nanoparticles synthesized, the maximum yield was obtained
employing Titanium dioxide nanoparticles.
Ó 2021 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the 3rd International Con-
ference on Materials, Manufacturing and Modelling.

1. Introduction
The global energy situation of the world greatly relies on non-
renewable sources like fossil fuels. This imposed an increased
demand on energy security and if required steps are not taken it
may lead to depletion of fuel sources. This problem can be over-
come with the selection of suitable renewable sources and imple-
menting the same to a major extent. Despite various benefits such
as eco-friendly characteristics, suitability in diesel engines without
modifications, biodiesel is a perfect alternative to diesel fuel [1].
The demand for alternative sources of energy was increasing
due to the necessity to cope up with global energy consumption.
Various research works suggested that the conventional fuel
sources can be substituted with biofuels that originate from differ-
ent feedstocks [2]. The long-chain fatty acid monoalkyl esters
derived from various vegetable oil feedstock are termed biodiesel.
Biodiesel possesses numerous benefits such as reduction of PM,
decreased greenhouse gases, increased Cetane number, flash point,
biodegradability, and enhanced lubrication properties. The
selection of feedstock for biodiesel is decided based on the oil yield
obtained from the crop. Increased yield reduces the cost of biodie-
sel production [3].
Biodiesel has similar fuel properties to that of diesel fuel in both
physical and chemical forms. The benefits of biodiesel include
enhanced lubrication properties, cetane number, reduced CO and
unburned HC emissions [4]
The transesterification process required for the conversion of
vegetable oil to fatty acid methyl ester has been catalyzed by var-
ious means like the usage of acids, enzymes, and bases. Homoge-
neous and heterogeneous are the two classifications of base
catalysts of which the most used homogeneous catalysts are KOH
or NaOH. The homogeneous catalyst leads to equipment corrosive-
ness together with H2SO4 neutralization has also to be checked. A
significant quantity of energy and material usage are involved in
the utilization of sulphuric acid, separation of sulfate from the
neutralization process. Also, the issues associated with the homo-
geneous catalyst can be solved by means of heterogeneous cata-
lysts [5].

(i) Base or alkaline catalyzed transesterification is faster than

⇑ Corresponding author. acid-catalyzed one and also base catalysts are producing
E-mail address: nagarajmepcoeng@gmail.com (J. Nagarajan). reduced corrosion comparing to the acid catalyst. Alkaline

https://doi.org/10.1016/j.matpr.2021.03.473
2214-7853/Ó 2021 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the 3rd International Conference on Materials, Manufacturing and Modelling.

Please cite this article as: R. Saravana Sathiya Prabhahar, V.S. Benitha and J. Nagarajan, Improved yield of palm oil biodiesel through nano catalytic trans-
esterification, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2021.03.473
R. Saravana Sathiya Prabhahar, V.S. Benitha and J. Nagarajan
metal alkoxides, sodium and potassium carbonates, and
hydroxides come under alkaline catalysts. The mechanism
of base-catalyzed transesterification includes the following,
(ii) Production of protonated catalyst and alkoxide on the reac-
tion between base and alcohol
(iii) Despite nucleophilic attack at the carbonyl group by alkox-
ide, tetrahedral intermediate is formed from which alkyl
ester and diglyceride anion are produced.
(iv) The diglyceride anion deprotonates the catalyst thus regen-
erating the active species, which starts another catalytic
cycle by reaction with a second molecule of alcohol. The
conversion of diglycerides and monoglycerides occurs by
the same mechanism into an alkyl ester and glycerol
mixture [6].
Palm oil and jatropha were found to be a significant sources of
renewable energy possessing increased potential in the coming
days. Palm oil has various benefits such as increased yield (oil pro-
duction/hectare of the plantation) and it is a perennial crop. The
other name for palm fruit is Elais Guineensis. The mesocarp of
the palm fruit is refined by means of processes like cooking, mash-
ing, and pressing. The shell is cracked and the seeds are separated.
The kernel is processed to obtain the palm kernel oil. The crude
palm oil was thus converted to biodiesel by the transesterification
process [7].
Recently TiO2 was found to be a suitable heterogeneous catalyst
due to its high surface area. They gained increased attention due to
enhanced activity for oxidation and reduction at low temperatures
and pressures. Also, it possesses various advantages like metallic
support interactions, chemical stability, and acid-base property.
Economical synthesis modalities and increased availability make
TiO2 a heterogeneous catalyst. Homogeneous catalysts carry the
following negative effects such as increased separation costs of cat-
alysts from the reaction mixture, energy consumption increase,
and purification of raw material. The above said disadvantages
can be overcome by the usage of the heterogeneous catalyst which
can also be separated and reused [8].
In the current study, palm oil was transesterified with TiO2, Iron
oxide nano catalysts and KOH with reaction conditions of 65 °C
reaction temperature, methanol quantity of 255 ml, and 1000 ml
of oil, and a reaction time of 2 h. The biodiesel yield employing var-
ious Nanocatalysts through transesterification was determined.
2. Materials
The raw palm oil required for the current study has been pro-
cured from the nearby shops in Southern Tamilnadu, India. The
moisture content present in the raw oil was removed through
heating and further stored in an air-tight container. The chemicals
used in this study were purchased from E Merck Chemicals and
used as such without any further purification
2.1. Biodiesel production process
Experiments were performed out in a laboratory-scale appara-
tus. Transesterification was performed in a 2000 ml flask equipped
with a thermometer, reflux condenser, and magnetic stirrer. About
1000 ml of oil was preheated to 65 °C in the flask. Potassium
hydroxide of 12.75 g was dissolved in 225 ml of methanol which
was added to the previously heated oil. This was mixed for a period
of about 2 h and was transferred to a separating funnel to separate
the glycerol content. The methyl ester collected was washed using
warm water twice, with 5% acetic acid. Finally, the ester
was heated to about 100 °C in order to remove excess alcohol
and water [12].
2
Materials Today: Proceedings xxx (xxxx) xxx
2.2. Biodiesel characterization
The obtained palm oil biodiesel was analyzed using gas
chromatograph-mass spectroscopy with a flame ionization detec-
tor. The chromatographic analysis has been made using Agilent
7890B Gas chromatograph connected with 5977A MSD mass spec-
trometry. The gas chromatography unit was equipped and coupled
to an HP 5 MS 5% Phenyl Methyl Silox 325 °C column of dimension
30 m  250 mm  0.25 mm. Initially, the equipment was set to a
temperature of 50 °C. At the completion of the preparatory period,
the oven temperature was raised to 300 °C with a ramp rate of 5 °C/
min and maintained at about 9 min. The injection temperature was
250 °C and the flow rate of Helium was maintained at
1 ml/min [13].
Palm oil methyl esters are blended with diesel fuel and the
blends are characterized as an alternative fuel for diesel engines.
The results show that the fuel properties of the blends were very
close to that of diesel till 30% unless other characteristics are
within the limits [12].
3. Synthesis of oxide nanoparticles
Titanium oxide nanoparticles are synthesized by the Sol-Gel
Method. Briefly, 100 ml of isopropyl alcohol is added to 15 ml of
titanium tetraisopropoxide. It is stirred in a magnetic stirrer for
about 10 min. 10 ml of deionized water is added drop-wise and
stirred for about 24 h. After that a gel formation takes place, the
gel is collected and dried at 100 °C in a hot air oven for 3–4 h.
The dried gel powder is then calcinated at 500 °C for a period of
1 h which produces TiO2 Nanoparticle [14].
The Fe2O3 nanoparticles are synthesized by the gel-combustion
method. by employing 1:2 mixture containing iron nitrate (1 M)
and citric acid (2 M) dissolved in 60–70 ml of distilled water are
mixed and stirred at room temperature for 1 hr. Then the pH of
the solution is raised to 10 by adding ammonia solution. The
obtained solution is heated at 80 °C with continuous stirring. Then
it is evaporated and further heating leads to the combustion of the
mixture due to the presence of citric acid and the oxidizer. After
combustion, the ash is collected and ground in an agate mortar
and calcinated in a furnace at a temperature of 700 °C leads to
the formation of Fe2O3 nanoparticles [15].
3.1. XRD pattern analysis of synthesized oxide materials
Fig. 1.a. is the XRD pattern of TiO2 nanoparticles display its
characteristic peak at 2h = 24.83°, 37.54°, 47.78°, 53.98°, 54.61°,
62.89°, 68.25°, 74.84° with the miller indices of (1 0 1), (0 0 4),
(2 0 0), (1 0 5), (2 1 1), (2 0 4), (1 1 6) and (1 0 7) respectively (JCPDS.
No.89-4921) [16]. The crystallite size is evaluated as 25 nm using
the Debye-Scherer equation. The crystalline phase of the TiO2 is
found as tetragonal with body-centered cubic lattice.
Fig. 1.b. shows the X-ray diffraction pattern of Fe2O3 nanoparti-
cles synthesized by gel-combustion techniques. The diffraction
peaks found at 2h = 24.35°, 33.04°, 35.51°, 40.78°, 49.38°,
53.907°, 57.99°, 62.37°, 63.92°, 71.96°, and 75.32° are attributable
to the planes corresponding to Miller indices (0 1 2), (1 0 4), (1 1 0),
(1 1 3), (0 2 4), (1 1 6), (1 2 2), (2 1 4), (3 0 0), (1010), and (2 1 7)
respectively. As per the JCPDS standard 87-1164, the interplanar
spacing supports the formation of rhombohedral a-Fe2O3 crystal
geometry. The average size of the Fe2O3 nanoparticles is calculated
as 21 nm [15].
3.2. FESEM analysis of oxide nanomaterials
Fig. 2.a. shows the FESEM micrograph of Titanium oxide
nanoparticles. The nanoparticles are uniformly distributed without
R. Saravana Sathiya Prabhahar, V.S. Benitha and J. Nagarajan Materials Today: Proceedings xxx (xxxx) xxx

Fig. 1. XRD pattern of synthesized nanoparticles a) TiO2 b) Fe2O3.

Fig. 2. FESEM analysis of synthesized nanoparticles. Inset image shows the histogram analysis of nanoparticles using ImageJ software a) TiO2 b) Fe2O3.

Fig. 3. AFM image of a) TiO2 b) Fe2O3.

any agglomeration. The maximum size of the nanoparticle is found
to be 15 nm analyzed through ImageJ software.
The FESEM micrograph of iron oxide nanoparticles is shown in
Fig. 2.b. From the FESEM image, it is clear that the particles are in
the agglomerated state, individually the size of particles is evalu-
ated using the Image J software as 25 nm.
3.3. AFM analysis of synthesized nanoparticles
3.4. Biodiesel yield
In the present study, reaction temperature of 65 °C, 255 ml of
methanol, 1000 ml of oil, with a reaction time of 2 h yield biodiesel
of 91.06%, 84.24%, and 82.14% with Titanium oxide, Iron oxide, and
potassium hydroxide as catalyst. Thus the yield for Titanium diox-
ide is found to be maximum among the synthesized catalysts as
shown in Fig. 4.

The three-dimensional topography of TiO2 nanoparticles is

shown in Fig. 3 (a). From the figure, it is observed that TiO2
nanoparticles(NPs) are in the range of 10–20 nm. The 3D profile
analysis is shown in Fig. 3 (a & b ) wherein the horizontal line is
drawn at 6 lm and the vertical line is drawn at 6 lm. From the
analysis, it is observed that the majority of TiO2 NPs are very small
in size lying in the range of 10–20 nm Fig. 5.
The three-dimensional topography of Fe2O3 nanoparticles is
shown in Fig. 3.,b From the figure, it is observed that Fe2O3
nanoparticles are in the range of 10–20 nm. From the analysis, it
is observed that the majority of Fe2O3 NPs are very small in size
lying in the range of 20–30 nm. The results are matching with
the size range indicated in the FESEM analysis. Fig. 4. Palm oil biodiesel yield employing various synthesized nano catalysts.

3
R. Saravana Sathiya Prabhahar, V.S. Benitha and J. Nagarajan Materials Today: Proceedings xxx (xxxx) xxx

Fig. 5. GCMS of the synthesized biodiesel.

Table 1
shows the comparison of biodiesel yield from various feedstocks and nanocatalysts.

# Feedstock Nanocatalyst Reaction conditions Yield % Reference

Soybean oil Zirconia loaded with potassium bitartrate Methanol to oil; 16:1 98.03 [4]
Reaction time; 2 h
Reaction temperature; 60 °C
Catalyst quantity; 6%
Used cooking oil Titanium Methanol to oil; 9:1 97.1 [7]
Reaction time; 3 h
Reaction temperature; 75 °C
Catalyst quantity; 1.5 wt%
Castor oil Iron (II) doped zinc oxide Methanol to oil; 12:1 91 [9]
Reaction time; 50 min
Reaction temperature; 65 °C
Catalyst quantity; 14 wt%
Palm oil TiO2 – ZnO Methanol to oil; 6:1 92.2 [10]
Reaction time; 5 h
Reaction temperature; 60 °C
Catalyst quantity; 200 mg
Crude jatropha oil Calcium oxide Methanol to oil; 5.5:1 95.8 [11]
Reaction time; 133.1 min
Reaction temperature; 60 °C
Catalyst loading; 0.02:1(w/w) catalyst ratio

4
R. Saravana Sathiya Prabhahar, V.S. Benitha and J. Nagarajan
Table 2
The output of the present study.
# Feedstock Nanocatalysts Reaction conditions
Palm oil TiO2 T = 65 °C, t = 120 min., Methanol = 225 ml, Oil = 1000 ml Cat. Loading = 12.75 gm
Fe2O3
KOH
4. Conclusion
In the current study palm oil biodiesel has been produced
through transesterification process employing different synthe-
sized Nanocatalysts. Titanium oxide nanoparticles are synthesized
by the Sol-Gel Method. The Fe2O3 nanoparticles are synthesized by
the gel-combustion method. In the present study, reaction temper-
ature of 65 °C, 255 ml of methanol, 1000 ml of oil, with a reaction
time of 2 h yield biodiesel of 91.06%, 84.24%, and 82.14% with Tita-
nium oxide, Iron oxide, and potassium hydroxide respectively as
the catalyst. The synthesized biodiesel was analyzed by the GCMS
method to determine the fatty acid methyl ester compounds pre-
sent in it (Fig. 5). The biodiesel yield obtained employing various
catalysts was shown in Table 2 which has been compared with
Table 1. The yield percentage obtained was comparable to that of
the previous studies and TiO2 was found to give the maximum
yield among the selected Nanocatalysts. Thus the increase in bio-
diesel yield employing Nanoparticles promoted an increase in mar-
ket value .
Funding
The research no specific grant from any funding agency in the
public, commercial, or not for profit sectors.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgment
The authors would like to thank the management of Mepco Sch-
lenk Engineering College, Sivakasi for providing laboratory facili-
ties to perform this study.
Materials Today: Proceedings xxx (xxxx) xxx
Yield Reference
91.06 Present study
84.24
82.14
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