catalysts

Article
Biodiesel Synthesis from Refined Palm Oil Using a Calcium
Oxide Impregnated Ash-Based Catalyst: Parametric, Kinetics,
and Product Characterization Studies
Wilson Wei Sheng Ho 1 , Hoon Kiat Ng 1 and Suyin Gan 2, *

1 Department of Mechanical, Materials and Manufacturing Engineering, University of Nottingham Malaysia,

Jalan Broga, Semenyih 43500, Selangor Darul Ehsan, Malaysia; [email protected] (W.W.S.H.);
[email protected] (H.K.N.)
2 Department of Chemical and Environmental Engineering, University of Nottingham Malaysia, Jalan Broga,
Semenyih 43500, Selangor Darul Ehsan, Malaysia
* Correspondence: [email protected]; Tel.: +60-3-8924-8162

Abstract: Heterogeneous catalyzed transesterification has been proposed as a promising technology

to mitigate the limitations of homogeneous transesterification such as wastewater generation, low
free fatty acids, low water tolerance, and inability to recycle the catalyst. This work aims to evaluate
a refined palm biodiesel synthesis process through heterogeneous catalyzed transesterification. Three
major process variables were studied over a reaction duration of 3–6 h, including the reaction
temperature (45–65 ◦ C), percentage of catalyst loading (4–6 wt.%), and methanol to oil molar ratio
(6:1–12:1). The highest biodiesel yield of 88.58% was recorded under the conditions of temperature
55 ◦ C, catalyst loading 4 wt.% and methanol to oil molar ratio 9:1 at 5 h. A pseudo-first order reaction
mechanism was applied in the kinetic analysis of the fatty acid methyl esters (FAME) concentrations.
In addition, the activation energy and pre-exponential factors, as determined through the kinetic
Citation: Ho, W.W.S.; Ng, H.K.; Gan, analysis, were 31.2 kJ/mol and 680.21 min−1 , respectively. The key fuel properties of the produced
S. Biodiesel Synthesis from Refined palm biodiesel were determined to be acceptable according to the ASTM D 6751 and EN 14214
Palm Oil Using a Calcium Oxide standards. The developed catalyst could feasibly be reused for the palm biodiesel synthesis up to the
Impregnated Ash-Based Catalyst: third cycle with lower reaction performance in the fourth cycle.
Parametric, Kinetics, and Product
Characterization Studies. Catalysts Keywords: biodiesel; fuel properties; heterogeneous catalyst; kinetics
2022, 12, 706. https://doi.org/
10.3390/catal12070706

Academic Editor: Pedro

Maireles-Torres 1. Introduction

Received: 26 May 2022

Biodiesel development has been driven by increasing concerns over the depletion of
Accepted: 23 June 2022
non-renewable fossil fuels as well as the carbon emissions arising from the use of diesel fuel.
Published: 27 June 2022
Unlike diesel, biodiesel comprises of long-chain fatty acid methyl esters. Typically, this
fuel has a higher flashpoint, negligible sulfur content, enhanced lubricity, and improved
Publisher’s Note: MDPI stays neutral
degradability compared to diesel [1]. It can be considered as a carbon neutral fuel if the
with regard to jurisdictional claims in
feedstock used for biodiesel synthesis is grown in a sustainable manner. In the Malaysian
published maps and institutional affil-
context, palm oil is the feedstock used for biodiesel production since Malaysia is the second
iations.
largest palm oil producer in the world, with a contribution of 25.8% of the world’s palm oil
production in 2020 [2].
In 2009, Malaysia made a commitment to reduce its carbon emission intensity by 40%
Copyright: © 2022 by the authors.
compared to 2005 levels by 2020. By 2015, Malaysia had already achieved 33% carbon
Licensee MDPI, Basel, Switzerland. emission intensity reduction, and made a bolder pledge to increase its carbon emission
This article is an open access article intensity reduction to 45% from its 2005 baseline by 2030 to address climate change and
distributed under the terms and global warming [3]. In line with this, the National Automotive Policy 2020 [4] has outlined
conditions of the Creative Commons measures to enhance the use of palm biodiesel, including empowering technical research
Attribution (CC BY) license (https:// activities on biodiesel application in the automotive sector.
creativecommons.org/licenses/by/ Regarding biodiesel synthesis transesterification, the use of heterogeneous catalysts
4.0/). such as calcium oxide (CaO)-based catalysts has been advocated as a promising technology

Catalysts 2022, 12, 706. https://doi.org/10.3390/catal12070706 https://www.mdpi.com/journal/catalysts

Catalysts 2022, 12, 706 2 of 13

to address the limitations of conventional, homogeneous catalysts such as significant

wastewater generation, low free fatty acids, low water tolerance, and inability to recycle the
catalyst [5,6]. For instance, one study compared the efficacy of CaO and lanthanum oxide
(La2 O3 ) catalysts in the transesterification of Jatropha oil into biodiesel [7]. CaO reportedly
had the highest biodiesel yield of 96% in contrast to only a yield of 23% yield by La2 O3 at
3 wt% catalyst loading, 25:1 methanol to oil ratio, 120 ◦ C reaction temperature, and 3 h
reaction time. This was attributed to the higher total basicity of CaO at 290.42 µmol of
CO2 /g.
In another study, a CaO catalyst derived from natural quail eggshell was used in the
transesterification of sunflower oil to biodiesel [8]. The natural quail eggshell was calcined
at 900 ◦ C for 3 h. The highest biodiesel production of 99.00 ± 0.02 wt.% was recorded under
the reaction conditions of 1:10.5 sunflower oil to methanol molar ratio, 2 wt.% catalyst
loading, 2 h reaction time, 1000 rpm stirring rate, and 60 ◦ C temperature. Likewise, a
low-cost CaO/silica catalyst prepared from eggshell and peat clay wastes was tested for
biodiesel synthesis from waste cooking oil [9]. In this work, a biodiesel yield of 78% was
attained with the CaO catalyst. This improved to 91% by using silica from peat clay waste
as a support. The yield was increased at higher temperatures and 60 min was determined
as the optimum time for reaction. A mechanism was proposed, suggesting that silica
contributed towards the esterification and CaO positively impacted the transesterification
process. The proposed mechanism was confirmed via a kinetic study.
Similar positive findings were obtained with a high performance heterogeneous
CaO nano catalyst synthesized from hen eggshells waste via a calcination-hydration-
dehydration method [10] for microalgal biodiesel transesterification. A biodiesel yield of
86.41% was obtained under the optimum conditions of 1.7% (w/w) catalyst ratio, stirring
rate of 140.6 rpm, and 3.6 h reaction time. Additionally, a new CaO/copper iron oxide
(CuFe2 O4 ) nano catalyst was synthesized for biodiesel production from chicken fat [11].
A maximum biodiesel yield of 94.52% was obtained at a reaction temperature of 70 ◦ C, a
methanol to oil ratio of 15:1, a catalyst loading of 3%, and a reaction time of 4 h.
These studies highlight the potential of using CaO-based catalysts for biodiesel syn-
thesis. Previously, the authors had investigated the development of new CaO-palm oil mill
boiler ash-based catalysts [12]. The current work is an extension from the previous work
and focuses on further evaluating a heterogeneous CaO impregnated palm oil mill fly ash
for refined palm biodiesel synthesis. The scope of work here included parametric effects,
kinetics, fuel properties, and catalyst reusability, which have not been reported to date for
refined palm biodiesel. The reaction parameters studied included reaction temperature,
catalyst loading, methanol to oil molar ratio and reaction time. A pseudo-first order kinetic
study was also carried out at five different temperatures to determine the reaction rate con-
stant (k) and the activation energy (Ea ). Additionally, key fuel properties were measured to
ascertain the quality of the synthesised biodiesel, which impacts combustion and emissions
performance. Finally, catalyst reusability for the studied reaction was assessed to highlight
the benefit of this heterogeneous catalyst.

2. Results and Discussion

2.1. Catalyst Properties
Figure 1 shows the morphological characteristics of the catalyst. The catalyst had
a spongy and porous structure. The particles within the scale of 50 µm had a uniform
distribution of miniature agglomerates with irregular shapes. Meanwhile, Table 1 lists the
elemental composition and BET surface area of the catalyst. The elemental composition
showed an abundance of Ca and O in the ash matrix. The BET surface area was recorded at
3.539 m2 /g.
Catalysts 2022, 12, 706 3 of 13

Figure 1. SEM image of catalyst at 2000 × magnification.

Table 1. Catalyst properties.

Property Value Unit

Elemental composition
C 15 wt.%
O 39 wt.%
Mg 1 wt.%
Al 1 wt.%
Si 6 wt.%
Ca 38 wt.%
BET surface area 3.539 m2 /g

2.2. Influence of Reaction Temperature on Refined Palm Oil Synthesis

The effects of reaction temperature against reaction time on the biodiesel yield at a
methanol/oil molar ratio of 12:1, catalyst loading of 4 wt.%, and stirring rate of 700 rpm
is presented in Figure 2. After 3 h of reaction, the yields at 45, 55, and 65 ◦ C runs were
79.07, 81, and 58.82%, respectively. However, the biodiesel yields reached the highest
in 4 h for all three temperatures investigated. As can be seen from Figure 1, the most
efficient catalytic system took place at a temperature of 55 ◦ C, followed by 45 ◦ C. The
transesterification activity was faster with increasing reaction temperature as the reaction
rate was increased [9]. Biodiesel yield improved from 83.41% to 87.66% when the reactions
were performed at 45 and 55 ◦ C for 4 h. However, the lowest yield was achieved at
the highest temperature of 65 ◦ C. This was because at that reaction temperature, some
methanol vaporization occurred with the formation of many bubbles, which inhibited the
reaction on the three-phase interface (oil, methanol, and solid catalyst). Generally, the key
advantage of employing a higher reaction temperature is to shorten the reaction time to
reach a targeted product yield. The suitability of the temperature depends on the individual
transesterification system and the type of oil. Therefore, in this work, the optimum reaction
temperature for the transesterification of palm oil to biodiesel was determined to be 55 ◦ C.
Catalysts 2022, 12, 706 4 of 13

Figure 2. Influence of reaction temperature on the yield (methanol to oil molar ratio 12:1, catalyst
loading 4 wt.%, stirring rate 700 rpm, reaction time 3–6 h).

2.3. Influence of Catalyst Loading on Refined Palm Oil Synthesis

Figure 3 illustrates the effects of catalyst loading on the biodiesel yield from 4 to 6 wt.%
with a fixed methanol to oil molar ratio of 12:1, temperature of 55 ◦ C, and stirring rate
of 700 rpm. The results showed that only slight changes in yields were obtained with a
catalyst loading of 4 wt.%. The yields using 5 and 6 wt.% catalysts were lower compared
to that of 4 wt.% loading. The higher catalyst loadings could possibly cause emulsion
formation that increased the viscosity and soap content in the final product, which lowered
the yields. In this work, the maximum yield of 87.66% was gained at a concentration of
4 wt.% at 4 h.

Figure 3. Influence of catalyst loading on the yield (methanol to oil molar ratio 12:1, temperature
55 ◦ C, stirring rate 700 rpm, reaction time 3–6 h).

2.4. Influence of Methanol to Oil Molar Ratio on Refined Palm Oil Synthesis
Theoretically, transesterification of oil requires 3 moles of methanol per mole of triglyc-
eride (oil). As the conversion of triglycerides to FAME is reversible, the biodiesel yield
could be improved by using excess methanol to shift the equilibrium to the product’s
side. However, the cost of methanol increases with more methanol use, thus it is crucial
to select an optimum amount which produces a high yield with as low a cost as possible.
Figure 4 shows the effect of differing methanol to oil molar ratios (6:1, 9:1, and 12:1) on
Catalysts 2022, 12, 706 5 of 13

the biodiesel yield. Other experimental conditions were fixed at 4 wt.% catalyst loading,
55 ◦ C temperature, and 700 rpm stirring rate. The reaction was incomplete for a molar
ratio less than 6:1, likely due to insufficient methanol for good mixing with the oil reactant
in the reaction. The biodiesel yield increased from 52.69% to 87.99% as the molar ratio
increased from 6:1 to 9:1 at 6 h reaction time. A further increase to 12:1 yielded 87.66%
biodiesel. Nevertheless, the highest biodiesel yield of 88.58% was recorded for a methanol
to oil molar ratio of 9:1 at 5 h. Since there were negligible differences between the molar
ratio of 9:1 and 12:1 over the studied reaction time, it was deemed that a methanol to oil
molar ratio of 9:1 was sufficient for a high yield.

Figure 4. Influence of methanol to oil molar ratio on the yield (catalyst loading 4 wt.%, temperature
55 ◦ C, stirring rate 700 rpm, reaction time 3–6 h).

2.5. Transesterification Kinetics

Figure 5 presents the gas chromatography (GC) evaluation of the biodiesel produced
throughout the reaction under the optimal conditions of catalyst loading 4 wt.%, methanol
to oil molar ratio 9:1, temperature 55 ◦ C, and stirring rate 700 rpm. Under these conditions,
the total ester content (fatty acid methyl esters (FAME) conversion) was 96.75 wt.%. The
FAME comprised of two major components, which were oleic acid and palmitic acid with
the ester content of 40.05 wt.% and 34.52 wt.%, respectively. The remaining FAMEs in order
of decreasing concentrations were linoleic acid, stearic acid, myristic acid, palmitoleic acid,
and linolenic acid. Apart from the two major FAMEs (oleic and palmitic acids), the other
methyl ester conversions remained almost constant after 180 min.
The kinetics of the transesterification reaction was analyzed at temperatures of 45,
50, 55, 60, and 65 ◦ C under fixed conditions of catalyst loading of 4 wt.%, methanol to oil
molar ratio of 9:1, and stirring rate of 700 rpm, which resulted in the best yields discussed
previously. The conversion of FAME against time is depicted in Figure 6. As can be seen,
the FAME conversions were slow at the initial stage, then it increased and finally reached a
plateau indicating equilibrium at 300 min. An increasing trend in the FAME conversion
with temperature was observed since higher temperature favored the reaction. However,
the highest FAME conversion at 65 ◦ C did not correspond to the highest biodiesel yield,
likely due to the saponification reaction that occurred at a high temperature.
Catalysts 2022, 12, 706 6 of 13

Figure 5. Evaluation of FAME conversions with time (catalyst loading 4 wt.%, methanol to oil molar
ratio 9:1, temperature 55 ◦ C, stirring rate 700 rpm, reaction time 0–6 h).

Figure 6. Evaluation of FAME conversion with time at different temperatures (catalyst loading 4 wt.%,
methanol to oil molar ratio 9:1, stirring rate 700 rpm, reaction time 0–6 h).

By plotting –ln (1–X) against time (t), where X is the methyl esters conversion, as
shown in Figure 7, clear linear correlations were obtained, which supported the hypothesis
of a pseudo-first order reaction. The correlation coefficients, R2 , and the calculated rate
constants, k, for each temperature are listed in Table 2. Subsequently, the activation energy
and the pre-exponential factor were determined using the plot in Figure 8, where a good
linearity was observed between ln k and 1/T over the studied range of temperatures.
The values obtained from the slope and intercept were 31.2 kJ/mol and 680.21 min−1 ,
respectively. As such, the Arrhenius equation for this reaction can be written as:

ln k = 6.5224 − 3.7523/T (1)

Catalysts 2022, 12, 706 7 of 13

Figure 7. Plot of –ln (1 − X) versus reaction time at different temperatures.

Table 2. Reaction rate constants for the transesterification of palm oil at different temperatures.

Temperature (◦ C) Rate Constant, k (min−1 ) Correlation Coefficient, R2

45 0.0054 0.984
50 0.0061 0.970
55 0.0066 0.973
60 0.0091 0.996
65 0.0106 0.982

Figure 8. Arrhenius plot of ln k versus 1/T × 103 .

2.6. Key Fuel Properties

The key fuel properties of the synthesized palm biodiesel are summarized in Table 3,
together with the specifications outlined in the ASTM D 6751 and EN 14214 standards.
Catalysts 2022, 12, 706 8 of 13

Table 3. Key fuel properties.

Fuel Property Value ASTM D 6751 Limits EN 14214 Limits

Kinematic viscosity at 40◦C mm2 /s
5.025 mm2 /s
1.9–6.0 3.5–5.0 mm2 /s
Density at 15 ◦ C 860.1 kg/m3 NA 860–900 kg/m3
Flash point, min 168 ◦ C 93 ◦ C 110 ◦ C
Acid value, max 0.323 mg KOH/g 0.5 mg KOH/g 0.5 mg KOH/g
Cetane number, min 58.06 47 51
Ester content 96.75 wt.% NA 96.5 wt.% min
Linolenic acid methyl ester, max 0.147 wt.% NA 12 wt.%
Higher heating value 38.96 MJ/kg NA NA

Kinematic viscosity of a fuel affects injector lubrication and fuel atomization as high
viscosity gives rise to poor fuel atomization upon injection into the diesel engine combustion
chamber, and ultimately, the formation of soot and engine deposits. As shown in Table 3,
the kinematic viscosity of the palm biodiesel was 5.025 mm2 /s, which met the ASTM D
6751 limits, but was at the upper threshold of the EN 14214. Nonetheless, the viscosity can
be further reduced by blending with other oils or diesel with lower viscosity.
The fuel injection equipment operates on a volumetric metering system, hence a
higher density biodiesel results in the delivery of a slightly greater mass of fuel. The density
recorded for the synthesized biodiesel in this work was 860.1 kg/m3 , measured at 15 ◦ C.
This met the stipulated limits by the EN 14214. The refined palm oil had a measured density
of 918 kg/m3 , which was successfully reduced via transesterification.
The flash point is a measure of the tendency of a sample to form a flammable mixture
with air on application of an ignition source under specified conditions. The flash point
varies inversely with the fuel volatility. The flash point limit is set to ensure the biodiesel is
free from residual methanol since methanol poses a safety issue. Even a very small amount
of methanol will greatly reduce the flash point. The flash point of the palm biodiesel was
much higher as compared to commercial diesel, which varies from 52 to 96 ◦ C. In the
present work, the measured flash point of 168 ◦ C was well above the specified minimums
in both the standards, which makes the fuel safe in terms of storage and handling.
The acid value is the measurement of free fatty acids due to fuel degradation. The acid
value was 0.323 mg KOH/g, which met the same maximum limit of 0.5 mg KOH/g in both
the standards. The presence of free fatty acids can affect low temperature operation as they
have higher melting points. In addition, the acids can cause corrosion of metal components
within the injection line of the fuel system.
The higher heating value or gross calorific value is the amount of thermal energy
released per unit quantity of a fuel when the fuel is burned completely, and the products of
combustion are cooled to the initial temperature of the combustible mixture. The higher
heating value of the synthesised biodiesel was 38.96 MJ/kg. This meant that the biodiesel
had approximately 10% less energy as compared to typical diesel fuel with a higher heating
value of 45 MJ/kg. Although there are no specifications for this property, the value obtained
here was in line with that measured by others [13].
Cetane number is a relative measure of the ignition delay between injection and
auto-ignition of a fuel. Fuels with high cetane numbers process a short ignition delay
which is desirable for good cold start behaviour, thereby ensuring smooth running of a
diesel engine [14]. The calculated cetane number of 58.06 exceeded both the minimum
requirements specified in the ASTM D 6751 and EN 14214.
The ester content depends on the biodiesel synthesis process, since it is an indication
of the degree of conversion of oil to biodiesel. Meanwhile, the linolenic acid methyl ester
content needs to be limited, as linoleic acid methyl ester has three double bonds with a
very high oxidation instability. Hence, it can be easily oxidised or reacted, forming sludge.
The ASTM D 6751 does not stipulate limits for these two properties, unlike the EN 14214.
The measured values in this study were in accordance with the EN limits of ester content
exceeding 96.5 wt.% and 12 wt.% maximum linolenic acid methyl ester.
Catalysts 2022, 12, 706 9 of 13

2.7. Catalyst Reusability

The reusability of the heterogeneous was assessed by regenerating the spent catalyst
using methanol washing followed by recalcination at 850 ◦ C for 2 h. As shown in Table 4,
the yield dropped from 87.99% to 71.15% from the first cycle to the third one whereas the
conversion decreased marginally from 96.75% to 82.83%. Nonetheless, the values obtained
were considered acceptable, unlike the yield and conversion obtained in the fourth cycle,
which were 60.48% and 72.17%, respectively. Overall, the reusability of this heterogeneous
catalyst has been demonstrated, which highlights its benefit as a heterogeneous catalyst
over conventional, homogenous ones.

Table 4. Catalyst reusability results.

Cycle Number Yield (%) Conversion (%)

1 87.99 96.75
2 84.08 92.47
3 71.15 82.83
4 60.48 72.17

2.8. Discussion
A heterogeneous CaO impregnated palm oil mill fly ash catalyst was developed and
assessed for its efficacy in refined palm biodiesel synthesis. The elemental composition
results indicated that CaO was embedded within the ash matrix. From FESEM, the presence
of a miniature agglomerated structure within the catalyst supported the formation of metal
oxides upon heat treatment [15]. The measured surface area of 3.539 m2 /g was comparable
to that reported in the literature for CaO catalysts derived from eggshell, crab shell, and
bovine bone waste [16–18].
Through the parametric study, it was ascertained that the conditions of catalyst loading
4 wt.%, methanol to oil molar ratio 9:1, temperature 55 ◦ C, and stirring rate 700 rpm resulted
in the highest biodiesel yield of 88.58%. The transesterification conditions produce high
yields that vary with different reported studies [16–20]. This could be attributed to the
different variations in raw feedstock, catalyst origin, and synthesis methods of CaO-based
catalysts. The kinetics study demonstrated that the measured activation energy and pre-
exponential factor were 31.2 kJ/mol and 680.21 min−1 , respectively.
The synthesized biodiesel met the limits specified in ASTM D 6751 and EN 14214
standards with reference to kinematic viscosity, density, flash point, acid value, ester
content, and linolenic acid methyl ester content. Its higher heating value is acceptable
considering that this was in line with that measured by others [13].
Finally, the benefit of this heterogeneous catalyst was highlighted through the catalyst
reusability test. The catalyst could be feasibly reused up until the third cycle in contrast
to the lower performance in the fourth cycle, where yield and conversion of 60.48% and
72.17% were obtained, respectively. The number of reusability cycles agree with the data for
other waste CaO catalysts within the range of 2–4 [8,9,17,19]. The drop in yield in the fourth
cycle might be due to catalyst poisoning by glycerol and soap [21]. Additionally, it could
be possible that Ca dissolution to the alcoholic phase resulted in the poisoning of active
sites [22]. However, the superiority of the catalyst over conventional homogenous ones,
such as sodium hydroxide and potassium hydroxide in terms of post-reaction recovery and
reuse, was demonstrated.
Overall, the potential of the CaO impregnated palm oil mill fly ash catalyst has been
shown in this work through a combination of parametric and kinetic studies, biodiesel
characterization, and catalyst reusability studies. Nevertheless, assessing the efficacy of this
heterogeneous catalyst in a configuration such as continuous packed bed reactor system
which can be upscaled is recommended for future work.
Catalysts 2022, 12, 706 10 of 13

3. Materials and Methods

3.1. Materials
Refined palm oil was procured from a local supermarket. The chemicals methanol
(>99% purity) and calcium carbonate (99.95% purity) were purchased from Merck (Selan-
gor, Malaysia) and Sigma Aldrich (Selangor, Malaysia), respectively. An internal standard,
methyl heptadecanoate (analytical grade), was purchased from Sigma Aldrich, Selangor,
Malaysia. In addition, palm oil mill boiler ash was collected from Seri Ulu Langat Palm
Oil Mill Sdn. Bhd., Dengkil, Malaysia, to be used as the catalyst support. For determina-
tion of the oil acid value, the reagents employed included potassium hydroxide (KOH)
solution prepared to 0.1 M using KOH pellets (99.9% purity), isopropanol (99% purity),
phenolphthalein indicator, and distilled water.
The acid value of the oil was measured using a titration process. An acid value of
0.45 mg KOH/g was determined. A small sample of oil was also analyzed for its fatty
acid composition according to the MPOB Test Method p3.4—Part 4:2004 and MPOB Test
Method p3.5:2004 [23,24]. The fatty acid composition of palm oil was determined as follows:
0.77 wt.% myristic, 39.48 wt.% palmitic, 0.17 wt.% palmitoleic, 3.73 wt.% stearic, 45.99 wt.%
oleic, 9.7 wt.% linoleic, and 0.14 wt.% linolenic. The molecular weight of the oil (MWoil )
was calculated to be 851.32 g/mol using the following equation [25]:

MWoil = 3 Σ MWi xi + 38.0488 (2)

where xi is the mole fraction of each fatty acid component i and MWi is its corresponding
molecular weight.

3.2. Catalyst Synthesis and Characterization

The wet impregnation method was utilized to prepare the heterogeneous catalyst [12].
Briefly, palm oil mill fly ash was sieved and dried at 105 ◦ C for 24 h. CaO was derived from
CaCO3 calcined at 800 ◦ C for 90 min. 13.5 g of calcined CaCO3 was added to 200 mL of
deionized H2 O and heated in a closed system at 70 ◦ C under magnetic stirring at 700 rpm.
16.5 g of fly ash was slowly added to the solution and mixed for 4 h until a homogenous
mixture was obtained. The sample was then aged for 18 h. Removal of adhering H2 O in
the mixture was accomplished using a hot air oven at 105 ◦ C for 24 h. The dried catalyst
was calcined at 850 ◦ C in a muffle furnace for 2 h.
Field emission scanning electron microscopy (FESEM) equipped with energy dis-
persive X-ray spectroscopy (EDX) was utilized to estimate the particle size and shape of
the catalyst with an FEI Quanta 400F operating at 15 kV. The EDX elemental composi-
tion was determined using Oxford-instruments INCA 400. The Brunauer–Emmett–Teller
(BET) surface area analysis was conducted via N2 adsorption–desorption isotherms in a
Micromeritics’ ASAP 2020 analyzer to measure the specific surface area of the catalyst.

3.3. Parametric Studies

Firstly, the experiments were designed to ascertain the effects of three process variables
over varying reaction time. The three variables investigated over a reaction time of 3 to
6 h were reaction temperature, catalyst loading, and methanol to oil molar ratio, while the
response was the percentage of biodiesel yield. The times of 1 and 2 h were not considered
because the conversion of methyl esters was low and incomplete. The studied reaction
temperatures were 45, 55, and 65 ◦ C. Meanwhile, the catalyst loading was varied from
4 to 6 wt.%. Finally, the effects of methanol to oil molar ratio was tested at 6:1, 9:1, and
12:1. From this parametric study, the optimum conditions which produced the highest
biodiesel yield were determined. The optimum conditions were used to investigate the
changes in the fatty acid methyl esters conversion throughout the reaction. For this kinetic
analysis, sampling was conducted at 1 h intervals until 6 h. Furthermore, the changes in
the individual fatty acid compositions were observed up to 6 h.
Catalysts 2022, 12, 706 11 of 13

3.4. Transesterification Procedures

The transesterification experiments were carried out in a 250 mL three-neck round
bottom flask equipped with a reflux condenser, magnetic stirrer, and thermometer. Briefly,
100 mL (87 g) of refined palm oil was preheated to the required temperature in the round
bottom flask before the reaction started. Meanwhile, the CaO impregnated palm oil mill fly
ash catalyst was added into methanol and mixed for 15 min at a temperature of 40 ◦ C with
a stirring speed of 500 rpm. The methanol-catalyst mixture was then introduced into the
round bottom flask for the initiation of the experiments.
After the completion of the reaction, the product was filtered using a vacuum pump
to remove the solid catalyst. The filtered sample was then separated by centrifugation
at 4000 rpm for 15 min and the sample equilibrated into two phases. The upper phase
consisted of methyl esters with small amounts of impurities such as alcohol while the
lower phase contained of glycerol and soap. After separation of the two layers, the upper
methyl ester was purified by removing the excess methanol using a rotary evaporator. The
remaining impurities were removed by successive rinses with 0.1 M acetic acid solution.
The residual water was removed by oven drying. The final biodiesel mass was measured
for the yield calculation as shown:

Yield (%) = Mass of biodiesel (g)/Mass of oil (g) × 100 (3)

3.5. Gas Chromatography (GC) Analysis

The palm fatty acid methyl esters were quantitatively analyzed by GC. To prepare the
sample for GC, 50 mg of sample was weighed into a 2 mL vial, and 1 mL of methyl hep-
tadecanoate solution (10 mg/mL) was added using a pipette. The methyl heptadecanoate
solution was prepared by weighing 500 mg of methyl heptadecanoate in 50 mL of hexane.
The quantification of esters content in the biodiesel sample was performed according
to the EN 14103 [Fat and oil derivatives—Fatty Acid Methyl Esters (FAME)—Determination
of Ester and linolenic acid methyl esters contents]. The configuration used here was a
Perkin Elmer gas chromatograph; model Clarus 500 GC, equipped with a flame ionization
detector. The FAME analysis was carried out with a split injection coupled to an auto
sampler. 0.1 µL of sample was injected into the GC at a split ratio of 100:1. The capillary
column used was a highly polar Agilent J&W HP-88 cyanopropyl column with dimension
of 0.25 mm ID × 60 m length × 0.2 µm film thickness. The oven temperature was fixed
isothermally at 185 ◦ C for 15 min, while the injector and detector temperatures were set at
240 and 250 ◦ C, respectively. Helium was used as a carrier gas at 32 psi.

3.6. Kinetics Studies

At consistent 1 h intervals, 2 mL of sample was withdrawn from the reaction mixture
for GC analysis. Each experiment was allowed to proceed until 6 h to ensure the complete
conversion of the oil into FAMEs. The withdrawn sample was immediately quenched
with 4 mL 0.1 M aqueous acetic acid solution in a glass test tube to neutralize the reaction.
The covered test tube was shaken gently before centrifuging at 1600 rpm for 15 min. A
two-phase mixture would form—the oil phase and aqueous phase. The aqueous layer was
discarded, and the upper methyl ester layer was dried in an oven at 105 ◦ C for 24 h. The
final product was sent for GC analysis.
In terms of analyzing the kinetics, the reverse reaction could be ignored, since an
excess of methanol was used in the reaction to shift the reaction equilibrium towards the
product side. The following rate equation was developed by [26], assuming the reaction to
be a pseudo-first order reaction, and was utilized for the analysis.

ln k = −Ea /(R × T) + ln k0 (4)

where Ea (J/mol) is the activation energy, R (8.413 J/(mol K)) is the gas constant, T (K) is
the temperature, and k0 is the pre-exponential factor (min−1 ).
Catalysts 2022, 12, 706 12 of 13

3.7. Fuel Properties Characterization

The following key fuel properties were determined: (i) kinematic viscosity at 40 ◦ C
using glass capillary viscometers according to ASTM D 445; (ii) density using a hydrometer
method according to ASTM D 1298; (iii) flash point using a rapid equilibrium closed cup
method according to ASTM D 93; (iv) acid value by volumetric titration according to ASTM
D 664; and (v) higher heating value using a bomb calorimeter according to ASTM D 240.
The cetane number was calculated from the following equation [14]:

Cetane number = 33.6 + 0.539 (C18:0) + 0.303 (C18:1) + 0.0878 (C18:2) + 0.233 (C22:1) (5)

where (C18:0), (C18:1), (C18:2), (C22:1) are the mass concentrations of stearic, oleic, linoleic,
and erucic acids, respectively.

3.8. Catalyst Reusability

The reusability of the catalyst was assessed under the optimum transesterification
reaction conditions for 6 h. In each cycle, the catalyst was subjected to transesterification
and recovered through filtration. The spent catalyst was washed with methanol first and
then dried in the oven at 65 ◦ C for 3 h before recalcining at 850 ◦ C for 2 h. For each cycle,
the yield and conversion were calculated.

4. Conclusions
In this work, the parametric effects, kinetics, and product characterization of refined
palm biodiesel synthesis catalyzed by CaO impregnated palm oil mill fly ash were evaluated.
The transesterification conditions which produced the highest biodiesel yield of 88.58%
were 4 wt.% catalyst loading, 9:1 methanol to oil molar ratio, 55 ◦ C reaction temperature,
and 5 h reaction time. The activation energy and pre-exponential factor of the reaction was
determined as 31.2 kJ/mol and 680.21 min−1 , respectively, from a kinetic study. In addition,
the fuel properties of the synthesized biodiesel, including kinematic viscosity, density, flash
point, acid value, and cetane number, were in good agreement with the ASTM D 6751 and
EN 14214 standards. The heterogeneous catalyst could feasibly be reused up to the third
cycle, whereas the fourth cycle produced lower reaction performance in terms of yield and
conversion. Overall, the synthesis of a low carbon fuel using a heterogeneous catalyst has
been successfully elucidated in this work.

Author Contributions: Conceptualization, W.W.S.H., H.K.N. and S.G.; methodology, formal analysis,
visualization, W.W.S.H. and S.G.; software, investigation, resources, data curation, writing—original
draft preparation, W.W.S.H.; validation, writing—review and editing, supervision, project admin-
istration, funding acquisition, H.K.N. and S.G. All authors have read and agreed to the published
version of the manuscript.
Funding: This research received no external funding.
Data Availability Statement: Data obtained during this study are included in the main text.
Acknowledgments: The authors would also like to thank the Faculty of Engineering, The University
of Nottingham Malaysia Campus for its support towards this project. The authors are also grateful to
Seri Ulu Langat Palm Oil Mill for the supply of palm oil mill boiler ash.
Conflicts of Interest: The authors declare no conflict of interest.

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