Energy Conversion and Management 144 (2017) 10–17

Contents lists available at ScienceDirect

Energy Conversion and Management

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

Investigation of carbon-based solid acid catalyst from Jatropha curcas

biomass in biodiesel production
H. Haziratul Mardhiah a, Hwai Chyuan Ong a,⇑, H.H. Masjuki a, Steven Lim b, Yean Ling Pang b
a
Department of Mechanical Engineering, Faculty of Engineering, University of Malaya, Kuala Lumpur, Malaysia
b
Department of Chemical Engineering, Lee Kong Chian Faculty of Engineering and Science, Universiti Tunku Abdul Rahman, Kajang, Selangor, Malaysia

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

Article history: In this study, a carbon-based solid acid catalyst was prepared using the de-oiled Jatropha curcas (JC) seed
Received 9 February 2017 cake waste. The catalyst was consequently used to esterify the JC oil in order to lower the high free fatty
Received in revised form 28 March 2017 acid content (FFA) to an acceptable level (<4 mg KOH g
1) for biodiesel production. The chemical and
Accepted 10 April 2017
physical properties of the catalyst were characterized using a variety of techniques. The conversion of
Available online 19 April 2017
FFA reached 99.13% under optimum conditions of 12:1 methanol/oil molar ratio, 7.5 wt% catalyst loading,
60 min reaction time and 60 °C reaction temperature at 350 rpm. The catalyst was also determined to
Keywords:
outperform the conventionally used sulfuric acid catalyst in terms of reaction time needed to achieve
Biodiesel
Jatropha curcas
the highest conversion yield. The high catalytic ability of the catalyst was associated with the high acid
Carbon-based acid catalyst site density formed in the catalyst which was due to the high porosity and large pore size of the carbon
Free fatty acid framework of the catalyst. The hydrophobic nature of the catalyst also contributed to the stability of the
Alternative fuel catalyst in which it can be re-used up until the 4th cycle. The recyclability of the catalyst and its cheap
Reusability feedstock makes the overall process much simpler, cost-efficient and environment-friendly.
Ó 2017 Elsevier Ltd. All rights reserved.

1. Introduction
Over the years, instabilities in fuel prices, depleting fuel
reserves and increase in environmental concerns brought upon
by usage of fossil based fuel has increased the urgency of finding
a new energy source that is not only more sustainable, but also
safer for the environment [1]. In response, biodiesel has been rec-
ommended as the best replacement for diesel fuel. Biodiesel is a
mixture of long-chain alkyl esters produced from organic materials
(edible, non-edible, waste frying oil, animal fats and algae biomass)
via transesterification reaction in the presence of a catalyst (acidic,
basic or enzymatic) [2]. Biodiesel has a cleaner production process,
sustainable, biodegradable and can be readily utilized in engines
without any alterations. Exhaust fumes from biodiesel is also less
toxic and thus results in less pollutants released into the environ-
ment [3,4].
Besides several other factors affecting the sustainability of the
biodiesel production process, choice of feedstock and catalyst used
play the most prominent role to the whole process. Currently,
more than 95% of feedstock used for biodiesel production is from
edible agricultural crops that lead to increased production cost
⇑ Corresponding author.
E-mail addresses: onghc@um.edu.my, ong1983@yahoo.com (H.C. Ong).
and negatively affect the food supply market [5]. With that, a
non-agricultural, inedible and sustainable feedstock such as Jat-
ropha curcas (JC) seed oil was proposed in order to curb this prob-
lem. The JC plant is drought resistant and can be grown under
harsh conditions. It has high seed productivity that is toxic for
human consumption and the seeds has high oil content that is
deemed highly suitable as feedstock for biodiesel production
[6,7]. The oil content used to produce biodiesel generally makes
up 40 wt% of the JC seeds [8], and given the high volume of JC crude
oil extracted for biodiesel production process, a substantial amount
of seed cake waste is generated. Hence, an effective use of the JC
seed cake is due in order to expand the value of JC in biodiesel pro-
duction [9], also to reduce biomass waste and to facilitate energy
security by renewable resources [10]. Therefore in this study, the
JC seed cake is projected to be converted into a carbon-based acid
catalyst used in the esterification of JC oil.
For the case of JC oil that has a high free fatty acid content (FFA)
that exceeds the acceptable value (<4 mg KOH g
1) for direct trans-
esterification into biodiesel, a carbon-based acid catalyst can aid in
the esterification of the oil prior to transesterification into biodiesel
[11].
Compared to the usage of conventional acid catalyst such as sul-
furic acid and hydrochloric acid, the carbon-based acid catalyst
does not incur formation of emulsions or saponification [12] that

http://dx.doi.org/10.1016/j.enconman.2017.04.038
0196-8904/Ó 2017 Elsevier Ltd. All rights reserved.
 H.H. Mardhiah et al. / Energy Conversion and Management 144 (2017) 10–17
subsequently lead to a complicated, costly and energy consuming
product separation and purification process that also produces
high chemical waste that is detrimental to the environment [13].
All of these complications can be overcome by the usage of a solid
carbon-based acid catalyst instead that requires no extensive
washing step, simplifying the overall process and reduces the
chemical waste production while maintaining the production of
high quality biodiesel. Cost of production is further reduced as
the catalyst can be reused for multiple cycles [14,15]. Although
there had been other heterogeneous acid catalysts developed to
overcome these problems, most of them had centred around costly,
metal-based catalysts such as sulphated zirconia, zeolites, ion-
exchange resins and mixed oxides that require more intensive
reaction conditions [16], showed poor reusability and were non-
decomposable, all of which resulted in a more complicated and
higher cost of biodiesel production [17,18].
Hence, the carbon-based catalyst is gaining attention owing to
its low material cost, high sustainability, high surface area, high
porosity and thermal stability, all of which attributes to an effec-
tive heterogeneous catalyst [19]. With the increased recognition
of JC oil as a feasible biodiesel feedstock, a research into the utiliza-
tion of the resulting seed cake as a carbon-based acid catalyst can
be beneficial as it makes the whole process more ‘‘green”,
addresses the waste discarding concerns [4] and allows for maxi-
mum utilization of the JC feedstock potential, indirectly increasing
the sustainability of JC as biodiesel feedstock itself.
In this study, a carbon-based acid catalyst was prepared from
the de-oiled seed cake waste of JC to be used as catalyst in the ester-
ification of crude Jatropha curcas oil in order to lower the high FFA
content (25.4 mg KOH g
1) to acceptable levels (<4 mg KOH g
1)
for biodiesel production. The main objective of this study is to
determine the characteristics of the prepared catalyst and to
evaluate its effectiveness and stability as a catalyst in the
esterification process.
2. Experimental
2.1. Materials
Jaropha curcas (JC) seeds were purchased from Indonesia. JC oil
was extracted using soxhlet extraction method with hexane
(500 mL) as solvent. The JC cake was then dried overnight. Other
chemicals and solvents including hexane, sulfuric acid and metha-
nol were of analytical grade and purchased from Merck Sdn. Bhd., a
local supplier in Malaysia.
2.2. Catalyst preparation
De-oiled JC seeds were collected and dried for 24 h to remove
all traces of moisture before being crushed into powder form.
Weight changes of the carbon precursor was determined by
Thermo Gravimetric Differential Thermal Analyzer (TGA/
SDTA851e), heated from 30 to 630 °C at a rate of 10 °C/min under
a flow of N2 (flow rate 40 mL/min) to determine the suitable
carbonization temperature. The powdered JC seed cake was then
carbonized at the designated temperature for 4 h. The product car-
bon powder was then characterized and analyzed.
10 g of the carbon produced was then sulphated with concen-
trated sulfuric acid (H2SO4) (80 mL, 99%), heated at 90 °C for 5 h
under constant stirring [20]. The sulphated mixture was then fil-
tered and washed with 2 L distilled water and 200 mL of hexane.
The catalyst was then dried overnight to allow excess chemical
to evaporate before being dried in the furnace again at 110 °C for
3 h to remove any remaining moisture.
11
2.3. Catalyst characterization
In order to investigate the physical and chemical properties of
the catalyst, the carbon precursor and the prepared catalyst were
characterized using a number of varying methods. The structure
of the carbon precursor and the prepared carbon-based solid acid
catalyst were evaluated and characterized by Surface Area Analysis
(BET) via the nitrogen adsorption-desorption instrument, Micro-
metrics Tristar II 3020 instrument. Prior to analysis, the samples
were desorbed in vacuum at 150 °C until static pressure remained
less 6.6  10 Pa before carrying out the N2 adsorption at
196 °C.
Then, surface area, average pore diameter and pore volume were
calculated by Brunauer-Emmet-Teller (BET) equation and Barrett-
Joyner-Halenda (BJH) model respectively [21]. The Field Emission
Scanning Electron Microscopy (FESEM) was conducted simultane-
ously with the Energy-Dispersive X-ray Spectrometry (EDX) testing
to determine the components of the catalyst using FESEM/EDS sys-
tem PEGASUS APEX 4 (Ametek/EDAX), Electron Optrics.
The presence and types of acid sites in the catalyst was deter-
mined by observing the catalyst framework vibration through
Fourier Transform Infrared Spectroscopy (FTIR) with spectrum of
400–3900 cm
1 with resolution of 4 cm
1 and 16 scans per spec-
trum and Temperature Programmed Desorption (TPD-NH3) respec-
tively using Quantachrome equipment (Model ChemBET 3000,
Quantachrome Corporation). The sample was activated at 400 °C
in H2 flow for 2 h (heating rate 10 °C/min). The sample was then
cooled to 100 °C in He flow. At this point, 0.1% NH3 in N2 was
passed through the sample for 1 h followed by cooling to room
temperature in He flow. TPD was carried out from room tempera-
ture to 500 °C at a heating rate of 10 °C min
1 with He flow rate of
35 mL min
1.
Total acidity of the catalyst was determined using the titration
method [22], whereby 0.1 g of sample was added to 20 mL of
sodium bicarbonate solution (0.05 M) and stirred for 24 h at room
temperature. Subsequently the mixture was filtered and each 5 mL
of the filtrate was titrated using hydrochloric acid (0.1 M).
2.4. Reaction study
Esterification of JC oil was conducted using a 500 mL three-
necked round bottomed flask with attached refluxing condenser,
thermometer and a magnetic stirrer. The flask was immersed in
an oil bath heated to a stable temperature. The esterification pro-
cess used 2.5–10 wt% catalyst loading while the methanol to oil
molar ratio was varied from 6:1 to 18:1. The reaction time was also
monitored from 30 to 120 min and the reaction was carried out at
varying temperature from 45 to 70 °C. After each reaction, the sam-
ples were filtered using a vacuum pump to separate the catalyst,
methanol evaporated and the product analyzed for acid value (A.
V.) [23]. The conversion rate was calculated using the following
formula:
Conversion rate ð%Þ : ðInitial A:V:
Final A:V:Þ=Initial A:V:
 100% ð1Þ
2.5. Leaching and reusability study
After esterification, the catalyst was collected and thoroughly
washed with hot distilled water (80 °C) and hexane before being
dried at 110 °C for 3 h. The catalyst was then re-used to catalyze
the esterification process on multiple cycles under the optimum
parameters obtained from the study (12:1 methanol/oil ratio,
7.5 wt% catalyst, 60 °C, 60 min, 350 rpm). After each cycle, the
esterified oil was tested for acid value and ester conversion yield
was calculated to determine the catalyst effectiveness. The filtered
12 H.H. Mardhiah et al. / Energy Conversion and Management 144 (2017) 10–17

methanol was tested for presence of sulphates using barium chlo-

ride to determine the presence of leached sulphate (ASO3) groups
[19] that might compromise the acid value of the esterified oil. The
catalyst was also tested for any changes in the acid capacity after
each cycle by the titration method [22].

2.6. Characterization and analysis of esterified oil

The biodiesel properties were determined according to the

ASTM 6751 or EN 14214 standards (i.e. kinematic viscosity at
40 °C, density at 15 °C, calorific value, acid value, oxidation stabil-
ity at 110 °C) and compared with the physicochemical properties
of its parent crude oil to observe the changes occurred.

3. Results and discussion

3.1. Characterization of the catalyst

The TGA spectra for de-oiled Jatropha curcas seed cake is shown
in Fig. 1. Apart from the loss of weight occurred at 50–150 °C which
indicated the loss of adsorbed water in the form of evaporation, the
JC seed cake showed dissociation zone at temperature points from
350 to 450 °C thus the carbonization temperature during catalyst
preparation was selected at 350 °C as the aim is to only partially
carbonize the seed cake, while carbonization at higher temperature
might lead to excessive breakdown of the macromolecules and
removal of organic portions [24]. The carbon precursor prepared
by the selected temperature was then treated with H2SO4 at
90 °C to produce the carbon-based acid catalyst.
The morphology of the carbon precursor and the prepared cat-
alyst is shown in Fig. 2 using the scanning electron microscope
[21]. The images show that the catalyst has an irregular surface
with well-developed porous structure. The number and size of
pores became larger after the carbon precursor was sulfonated.
The external surface of the carbon precursor and the catalyst also
had crevices and cracks with grains of various sizes in the pores.
Similar morphological features were observed in a carbon-based
catalyst prepared from vegetable asphalt [25]. Pores exhibited
were abundant and of different sizes and shape allowing more sul- Fig. 2. SEM images of carbonized Jatropha curcas seed cake (a) carbon precursor and
furic acid to enter the carbon bulk, which in turn resulted in high (b) catalyst.

Fig. 1. Thermogravimetric analysis spectra of de-oiled Jatropha curcas seed cake.

 H.H. Mardhiah et al. / Energy Conversion and Management 144 (2017) 10–17
covalent binding of carbon with sulfonic acid (ASO3H) group [26].
High number of ASO3H group increases the hydrophilicity of the
catalyst. This allows more hydrophilic methanol molecules to enter
the carbon bulk, leading to reaction with hydrophobic reactants
(FFA and triglyceride) to occur on the interior of the catalyst as well
as on the surface. The reaction was also encouraged by the large
pore size of the catalyst as it allowed for formation of larger reac-
tion intermediates inside the catalyst. A catalyst with a smaller
sized pore (<2 nm) would be limited by the internal mass transfer
thus decreasing the catalytic activity [13].
Pore structure is the primary requirement for ideal esterifica-
tion reaction in the presence of solid catalysts. Table 1 shows the
microstructure of the carbon precursor and the prepared catalyst
by BET analysis. The total surface area of the carbon precursor
slightly decreased from 2.37 to 1.92 m2 g
1 in the catalyst after sul-
fonation indicating structural changes had occurred to the carbon
texture upon sulfonation including collapse and degradation of
the carbon. The pore volume and pore diameter were also reduced
due to the occupation of the pores by functional groups [27]. Even
after the impregnation of the acid groups, the catalyst still had a
feasible pore diameter that can accommodate flow of the reactant
intermediate molecules (5.8 nm at the largest for triglyceride)
through the catalyst during reaction [28].
According to the titration method, total acid site density of the
catalyst was 2.24 mmol g
1 which was considered high given the
low surface area. This might be a result of large pore size and high
pore volume of the catalyst which allowed for high accessibility of
sulfuric acid into the catalyst carbon bulk, leading to more ASO3H
groups forming covalent bonds with the carbon surface. A higher
concentration of such covalent bonds and acid sites was expected
to provide the catalyst with higher acid capacity thus better cat-
alytic ability in the production of biodiesel process [25]. The EDX
result in Table 2 shows that sulfur content of 23.61% was present
in the catalyst indicating sulfonic groups had successfully linked
to the carbon layer as a result of sulfonation. Attachment of the sul-
fonic groups are what gives the catalyst its acidic nature [29].
FTIR spectra of the catalyst before and after sulfonation are
shown in Fig. 3. Presence of sulfonic group in the catalyst was pro-
ven by characteristic peak of stretching mode of ASO3H groups at
1037 (ASO2 symmetrical stretching mode), 1161 (ASO2 asymmet-
rical stretching mode) [22] in the catalyst spectra which was
absent in the carbon precursor spectra. The absorption bands
observed at 1772 cm
1 is attributed to the (C@O) stretching mode
of the COOH group [30]. The bands at 1616 and 1541 cm
1 con-
firmed the presence of poly aromatic hydrocarbon in the catalyst
[25]. These bonds that were determined confirmed the incorpora-
tion of the SO3H functional groups in the carbon framework of the
catalyst [25,31].
Table 1
Properties of carbon precursor and prepared catalyst.
Sample Surface area (m2 g
1) Pore diameter (nm)
Carbon 2.37 6.77
Catalyst 1.92 6.67
Table 2
Elemental analysis of carbon precursor and prepared catalyst.
Element Carbon
Mean Standard deviation
%C 69.01 3.84
%N 19.49 3.52
%O 11.50 0.84
%S – –
13
The NH3-TPD plot of catalyst in Fig. 4 shows that the catalyst
had two distinctive peaks from 140 to 150 °C and at 504 °C. The
low and high temperature peaks refer to weak and strong acid site
respectively. Both of these two peaks were categorized as BrÖnsted
acid sites (AOH). The form of both strong and weak acid site may
be attributed to the difference in pore size of catalyst and distribu-
tion of acid site [32]. Generally, the strong acid site is due to the
presence of ASO3H groups while the weak acid site is due to other
AOH groups attached to the surface of the catalyst [20].
3.2. Reaction studies
3.2.1. Effect of catalyst loading
Since the presence of catalyst in a reaction quickens the
reaction rate by reducing the activation energy for the reaction
to progress, an increase in amount of catalyst used is likely to push
the reaction towards the products side at a faster rate [20].
Therefore, the carbon-based acid catalyst was used in different
loading amounts (2.5, 5, 7.5 and 10 wt%). The other parameters
(12:1 methanol/oil molarity, 60 °C, 60 min) were fixed.
The effect of catalyst loading used on conversion efficiency is
shown in Fig. 5. The conversion rate of FFA increased as the catalyst
loading was increased up until 7.5 wt%. Increment in catalyst load-
ing to 10 wt% showed no substantial increase in conversion yield.
This pattern indicated that the rate of FFA conversion was directly
proportional to the amount of catalyst loading, until the reaction
equilibrium limit was reached at 7.5 wt% according to the reaction
studied. Higher amount of catalyst loading would lead to a
decreased conversion rate which could be attributed to the poor
mass transfer between the catalyst and the FFA content in the reac-
tion and exceeding of the reaction equilibrium limit [34]. It was
determined that the optimum catalyst loading for esterification
of JC oil using the carbon-based acid catalyst was 7.5 wt%.
3.2.2. Effect of methanol/oil molar ratio
Effect of methanol/oil ratio on the conversion yield of FFA was
studied by applying different molar ratios (6:1, 9:1, 12:1, 15:1
and 18:1) to a fixed process parameter (7.5 wt% catalyst loading,
60 °C, 350 rpm).
As observed in Fig. 6, the conversion yield of FFA in JC oil
increased from 69.90% to a maximum 99.13% at 12:1 methanol/
oil molar ratio. The conversion yield decreased when higher than
12:1 M ratio was applied. This can be explained by the over excess
methanol content over-flooding the active site of the catalyst,
inhibiting the catalytic activity to take place efficiently [25]. Excess
methanol in the reaction mixture may also hamper by-product
separation later in the process [35]. Therefore, 12:1 was
Pore volume (mm3 g
1) Acid strength (mmol g
1)
3.60 –
3.20 2.24
Catalyst
Mean Standard deviation
58.38 5.78
13.51 9.26
15.00 7.98
23.61 4.77
14 H.H. Mardhiah et al. / Energy Conversion and Management 144 (2017) 10–17

100%
(a)
100%

99%

99%
Transmitance

98%

98%

97%

97%

96%
3900 3400 2900 2400 1900 1400 900 400
Wave length (cm-1)

(b)

Fig. 3. FTIR spectra of (a) carbon precursor and (b) catalyst.

Fig. 4. NH3-TPD plot of catalyst.

 H.H. Mardhiah et al. / Energy Conversion and Management 144 (2017) 10–17 15

105 110
Conversion yield (%)

100
95 100
90

Conversion yield (%)

90
85
80 80
75
70 70
65
2.5 5 7.5 10 60
Catalyst loading (wt%) 50

Fig. 5. Effect of catalyst loading (wt%) on conversion yield (%) of FFA. 40

45 50 55 60 65 70
Temperature (°C)
110
Fig. 8. Effect of reaction temperature (°C) on conversion yield (%) of FFA.
100
Conversion yield (%)

90 tion of water by-product over the duration of the reaction would

deactivate the catalyst [37]. Despite the hydrophobic carbon sur-
80
face of the catalyst, water content exceeding the minimum
70 (>0.3 wt%) would still deactivate the catalyst [34].
The optimum reaction time of 60 min was considered shorter
60 compared to other esterification reaction using similar catalysts
studied by other researchers that required up to 180 and
50
6 9 12 15 18 270 min of reaction time to achieve maximum conversion yield
Methanol/oil molar ratio [25,33].

Fig. 6. Effect of methanol/oil molar ratio on conversion yield (%) of FFA.
determined as the optimum methanol/oil molar ratio for esterifica-
tion of JC oil using the carbon-based acid catalyst.
Considering the usage of solid catalyst and oil feedstock con-
taining high FFA in this study, the methanol/oil molar ratio
required to push the reaction towards the products’ side was
expected to be very high such as displayed in other similar studies
conducted which required very high methanol/oil molar ratio of
15:1 and 45:1 [33,36]. Thus, this shows the superiority of the cat-
alyst prepared over other similar solid acid catalysts studied
previously.
3.2.3. Effect of reaction time
The reaction time played an important role in the conversion of
FFA in JC oil as shown in Fig. 7. Under fixed reaction parameters
(7.5 wt%, 12:1 methanol/oil molar ratio, 60 °C, 350 rpm) the con-
version rate greatly increased to a maximum 99.13% conversion
yield from 30 to 60 min reaction time. Further increment in reac-
tion time resulted in a rapid decrease of conversion yield instead.
This may be explained as the reaction progressed over time, the
FFA concentration dropped considerably reducing the conversion
yield that had already reached its maximum point. The accumula-
101
99
Conversion yield (%)
3.2.4. Effect of temperature
Reaction temperature affects the rate of the reaction and cost of
production. Therefore, varying temperatures (45, 50, 55, 60, 65 and
70 °C) were tested for the esterification process. The study was
conducted using methanol/oil molar ratio of 12:1, 7.5% catalyst,
for 60 min at 350 rpm. It was observed in Fig. 8 that increment
of temperature up to 60 °C increased the conversion rate to a max-
imum of 99.13%. Further increment of temperature above 60 °C
showed a decrease in conversion yield. Therefore, it can be
deduced that the optimum temperature for esterification using
the carbon-based acid catalyst was at 60 °C. This showed that tem-
perature highly influenced the conversion of FFA as esterification is
a reversible reaction and reaction temperature higher than the
optimum point will result in a backward reaction [34]. Excessively
high reaction temperature would also intensify evaporation rate of
methanol into the gas phase resulting in unavailability of required
amount of methanol for sufficient contact with reactant FFA hence
reducing the conversion rate [38].
It was also found that the optimum temperature for this study
was lower than other studies using similar types of catalyst on high
FFA oils. Dawodu et al. [36] found 180 °C as the optimum temper-
ature to give maximum conversion of C. inophyllum oil using solid
acid catalyst and Konwar et al. [39] determined 80 °C as the opti-
mum temperature using solid catalyst prepared from oil cake
waste.
3.2.5. Comparison of non-catalytic and catalytic process

97 Sulfuric acid (H2SO4) is one of the most commonly used and

95 effective acid catalyst for esterification. In order to investigate
93 the catalytic capability of the carbon-based acid catalyst prepared,
91
an esterification reaction was conducted using two different cata-
lysts: the carbon-based acid catalyst and the conventional homo-
89
geneous H2SO4 catalyst. Under standardized parameters of 12:1
87
methanol/oil molar ratio, 60 °C and 350 rpm, the reaction was car-
85 ried out at various durations (30, 60, 90 and 120 min) in order to
30 60 90 120
Time (min) obtain the optimum FFA conversion yield. The optimum conver-
sion yield of 98.97% was achieved using 1 wt% H2SO4 at 120 min
Fig. 7. Effect of reaction time (min) on conversion yield (%) of FFA. reaction time. The carbon-based acid catalyst (7.5 wt%) achieved
16 H.H. Mardhiah et al. / Energy Conversion and Management 144 (2017) 10–17

105 optimum parameters obtained from the study (12:1 methanol/oil

ratio, 7.5 wt% catalyst, 60 °C, 60 min, 350 rpm). After each cycle,
100
Conversion yield (%)

the catalyst was washed using methanol and hexane to remove

95 impurities attached to the catalyst surface such as FFAs, trace bio-
90 diesel, glycerol and oil molecules, followed by drying at 110 °C to
eliminate any residual moisture. Fig. 10 showed sustainable activ-
85 sulfuric acid catalyst
ity of catalyst up until the 4th cycle. A gradual decrease in conver-
carbon acid catalyst
80 sion yield was observed with the highest decrement of 10%
occurring by the 4th cycle.
75
Reduction in catalytic activity is a result of decreased acid
70 capacity of the catalyst after each cycle due to sulphate leaching
30 60 90 120 from the catalyst during the esterification process as indicated
Reaction time (min.) from the reduction of acid capacity in the catalyst in Table 3. The
Fig. 9. Comparison of the two processes (catalyzed by H2SO4 and the prepared
barium chloride testing of the filtered methanol showed a negative
carbon-based acid catalyst) on the conversion yield of FFA. result indicating that the leached ASO3 group was not present in
the reaction mixture in the form of sulfuric acid, hence eliminating
the possibility of the leached sulphates to mislead the acid value
100
determination of esterified oil to obtain the conversion yield
[19]. Although other similar carbon-based catalysts showed a
95 higher reusability of catalyst, up to 10 cycles, there were recom-
Conversion yield (%)

mendations on the possibility of catalyst regeneration by H2SO4

90 [22,40].
85
3.4. Properties of esterified oil
80
Several properties of the crude oil and esterified oil were eval-
75
uated in accordance to the ASTM standards as listed in Table 4. It
70 can be observed that acid value of the parent oil was greatly
1 2 3 4 reduced from its original 25.4 to 0.22 mg KOH g
1 which was
No. of cycle below the maximum acceptable value of 4 mg KOH g
1 as a result
of esterification using the catalyst, which showed the catalyst
Fig. 10. Reusability of catalyst. effectiveness during esterification process. Other properties
including the viscosity, density and oxidation stability of the JC
oil also showed improvements. Compared to the properties of
Table 3
Effect of reusability on acid capacity of catalyst.
esterified oil from another study using similar type of catalyst to
esterify Silybum marianum oil (SM) [33], it can be inferred that both
Cycle Conversion yield (%) Acid capacity (mmol g
1)
catalysts derived from waste material achieved almost similar
1 99.13 2.24 improvements in the physiochemical properties of the oil feed-
2 96.80 2.20 stock, making it suitable to be consequently transesterified into
3 90.14 2.00
4 81.03 1.60
biodiesel.

4. Conclusions
a higher conversion yield of 99.13% at 60 min reaction time.
According to Fig. 9 it can be inferred that the carbon-based acid A carbon-based solid acid catalyst was prepared from the
catalyst achieved a higher conversion rate of FFA than H2SO4 at half de-oiled seed cake of Jatropha curcas (JC) feedstock. The solid acid
the reaction time needed. The high activity of the catalyst could be catalyst was successfully used to esterify the crude JC oil at an opti-
ascribed to the presence of various hydrophilic surface functional mum reaction parameter of 12:1 methanol/oil ratio, 7.5 wt% cata-
groups (such as ACOOH, AOH and ASO3H) acting as anchoring lyst loading, 60 min reaction time and 60 °C reaction temperature,
sites for attachment of polar substrates such as FFAs and methanol achieving a 99.13% conversion yield. The catalyst showed promis-
[33]. ing catalytic efficiency and stability in esterifying high FFA oil (JC
oil) under mild reaction conditions with 4 times reusability, out-
3.3. Reusability performing the conventional sulfuric acid catalyst. Attributes of
the prepared catalyst included the large pore size, high porosity,
A series of 60 min esterification cycles were conducted to eval- hydrophobic nature of the carbon base and the covalently bonded
uate the reusability of the carbon-based acid catalyst using the ASO3H groups which contributed to the high catalytic ability of the

Table 4
Changes in physiochemical properties of oil after esterification using carbon-based acid catalyst.

Property Test procedure Crude JC oil Esterified JC oil Crude SM oil Esterified SM oil [29]
Acid value (mg KOH g
1 ASTM D667 25.40 0.22 20.00 1.12
Kinematic viscosity @ 40 °C (mm2 s
1) ASTM D445 35.7 28.8 45.2 35.6
Density @ 15.6 °C (g cm
3) ASTM D127 0.91 0.89 0.92 0.91
Calorific value (MJ kg
1) ASTM D240 40.21 40.05 – –
Oxidation value @ 100 °C (h) EN 14112 4.09 6.74 – –
 H.H. Mardhiah et al. / Energy Conversion and Management 144 (2017) 10–17
catalyst. The usage of the catalyst, procured from recycled feed-
stock waste allowed for easy separation after reaction and elimi-
nates the washing process, making the overall esterification
process more cost-efficient and environment-friendly. Therefore,
utilization of carbon-based solid acid catalyst produced from JC
seed cake as catalyst is a promising approach in accelerating the
development of industrial production of biodiesel from feedstocks
with high FFA content.
Acknowledgments
The authors would like to acknowledge the Ministry of Higher
Education of Malaysia and The University of Malaya, Kuala Lum-
pur, Malaysia for the financial support under Fundamental
Research Grant Scheme (FRGS: FP009-2014A), SATU Joint Research
Scheme (RU018 J-2016), Universiti Tunku Abdul Rahman (UTAR)
Research Fund (UTARRF/2016-C1/P01) and Postgraduate Research
Grant (PPP: PG112-2015A).
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