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Enhanced biodiesel production from Jatropha oil using calcined waste animal
bones as catalyst

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 Renewable Energy 101 (2017) 111e119

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

Enhanced biodiesel production from Jatropha oil using calcined waste

animal bones as catalyst
Jan Nisar a, *, Rameez Razaq a, Muhammad Farooq a, Munawar Iqbal a, b, Rafaqat Ali Khan c,
Murtaza Sayed c, Afzal Shah d, Inayat ur Rahman e
a
National Centre of Excellence in Physical Chemistry, University of Peshawar, Peshawar, 25120, Pakistan
b
Department of Chemistry, The University of Lahore, Lahore, Pakistan
c
Department of Chemistry, COMSATS Institute of Information Technology, Abbottabad, 22060, Pakistan
d
Department of Chemistry, Quaid-i-Azam University, Islamabad, 45320, Pakistan
e
PCSIR Labs Complex Peshawar, Pakistan

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

Article history: This study is focused on the investigation of animal bones modified with potassium hydroxide (KOH) as
Received 6 April 2016 heterogeneous solid base catalyst for transesterification of non-edible Jatropha oil. The prepared catalyst
Received in revised form was characterized by energy dispersive X-ray (EDX) spectroscopy, powder X-ray diffraction (XRD),
9 August 2016
scanning electron microscopy (SEM) and thermo-gravimetric analysis (TGA). The prepared catalyst had a
Accepted 24 August 2016
high catalytic activity for transesterification. In addition, the catalyst had excellent stability, there by
having potential use as a heterogeneous catalyst for biodiesel production from Jatropha oil with a high
free fatty acid (FFA) yield. The experimental results revealed the optimal parametric conditions viz.
Keywords:
Animal bone
methanol/oil molar ratio, 9:1, calcination temperature, 900
C and catalyst concentration, 6.0 wt % of oil
Heterogeneous catalyst corresponding to a maximum fatty acid methyl esters (FAME) yield of 96.1% at temperature of 70 ± 3
C
Hydroxyapatite in reaction time of 3 h. Reusability results of the prepared catalyst confirmed that it could be reutilized
Jatropha oil up to 4 times without losing much activity, thus giving birth to a potentially applicable possibility in
Transesterification biodiesel production.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction biodegradable, nontoxic, carbon neutral, low pollutant,

Energy resources are considered to be the back bone and most
vital instrument for socio-economic development of any country.
Based on current energy scenario, the world is going towards a
global energy crisis in the near future. Energy consumption and
energy crisis are increasing day by day due to ever-increasing world
population and high speed of economic development. As a result,
petroleum reserves are being depleted that result into unstable
petroleum prices. Moreover, petroleum being a potential source of
carbon dioxide in the environment, leads to global warming and
climate change. Therefore, it is essential to search for an energy
source which should be renewable and eco-friendly in nature [1].
Among different renewable energy sources, biodiesel is a
promising candidate that would probably reduce the dependency
on and preserving petroleum. Biodiesel is a renewable, clean,
* Corresponding author.
E-mail address: pashkalawati@gmail.com (J. Nisar).
environment-friendly and carries efficient combustion due to
higher oxygen content and higher flash point [2]. Chemically, bio-
diesel consists of long chain fatty acid methyl esters (FAME), pro-
duced as a result of transesterification reaction from renewable
feedstocks like oils and animal fats.
Different feedstock, such as vegetable oils (edible and non-
edible oils), animal's fat and waste cooking oils are commonly
used for biodiesel production [2,3]. Presently, biodiesel is mainly
produced from edible oil by transesterification reaction. More than
95% of biodiesel feedstock comes from edible oil. However, the use
of edible oil for fuel purpose may create the problems of food in
developing countries [4]. Therefore, it is essential to search a po-
tential feedstock for biodiesel production. In this context, non-
edible oil such as Jatropha oil may be a good choice for biodiesel
production because it is non-edible and provides commercially
viable alternative to edible oil [5].
Jatropha seed contains 35e40% oil content and 50e60% in the
kernel. The oil comprises of about 79% unsaturated fatty acids and
21% saturated fatty acids [6]. Seed of Jatropha plant contains some

http://dx.doi.org/10.1016/j.renene.2016.08.048
0960-1481/© 2016 Elsevier Ltd. All rights reserved.
112 J. Nisar et al. / Renewable Energy 101 (2017) 111e119
chemical elements which possess poisonous and purgative prop-
erties that make the oil non-edible and also a good source for
biodiesel [7]. The oil from the seeds is potentially the most valuable
end product, with properties like: low acidity, good oxidation sta-
bility as compared to soybean oil, low viscosity as compared to
castor oil and better cold properties as compared to palm oil. In
addition, viscosity, free fatty acids and density of the oil and the
biodiesel are stable within the period of storage. Jatropha oil is plant
based oil that is commonly employed as a raw material for biodiesel
production [8]. Jatropha curcas is a member of Euphorbiaceous
family which is cultivated in Central and South America, South-East
Asia, India, and Africa. As drought resistant plant, it can be culti-
vated almost everywhere and may also be used for soil erosion
control [9].
Homogeneous catalysts are commonly used for biodiesel pro-
duction from vegetable oils [10]. Homogeneous catalysts are very
effective because of their fast reaction rate at mild conditions, low
price and high activity [11]. However, they bear several process
problems such as soap formation, separation during purification
and generate a large amount of waste water during washing [11].
Heterogeneous catalysts are being employed to overcome the
problems encountered with homogeneous biodiesel technology. In
contrast, heterogeneous catalysts have several process advantages
such as easy separation, environment-friendly, lack of toxicity,
ability to withstand at high temperature and ease of recycling [12].
However, in case of heterogeneous transesterification the rate of
reaction is lesser as compared to homogeneous system due to the
diffusion limitations in three phases. In order to minimize mass
transfer limitation and to maximize the surface area of catalyst,
structure promoters or catalyst supports are to be used which can
provide pores for active species and more surface area for trans-
esterification reaction. Different types of supports have been used
in heterogeneous transesterification. It has been stated that
aluminium oxide [13], zinc oxide [14] and palm shell activated
carbon [15] showed favourable support properties for alkali cata-
lysts in biodiesel production.
Different researchers synthesized and used different kinds of
solid wastes based catalysts (such as mollusk shells, eggshells,
calcined fish scale, sheep bone, etc.) in order to produce cost-
effective catalysts and biodiesel [16e19]. Among these solid
wastes, animal bone is one of the best solid wastes that are easily
and abundantly available all over the world. Although, the waste
bone derived catalysts have shown a reasonable performance and
constancy in the reaction, however these catalysts are required in
high amount, high methanol/oil molar ratio with longer time for
the reaction to occur. All these disadvantages make waste bone
derived catalysts practically and economically unsuitable. To over-
come these difficulties, it would be imperative to impregnate
calcined waste animal bones in an aqueous solution of KOH to make
waste animal bone derived catalyst more active and to boost the
surface chemical properties of waste animal bones. Calcined animal
bones have proved to be highly effective as a catalyst support. The
properties of calcined bone make it advantageous for use as catalyst
support in transesterification reaction. Calcined bone contains hy-
droxyapatite [Ca10(PO4)6(OH)2], that is highly porous and also has a
large surface area which allows catalyst to disperse over it largely
and effectively. Calcined bones can also be used in high pressure
and temperature reaction conditions. For solid catalyst among the
different bases, KOH has shown high catalytic activity in trans-
esterification reaction and could be supported on bentonite and
palm shell activated carbon as solid base catalysts [15,20]. It is
obvious from the above literature review that there is no report
wherein pure biodiesel of ASTM specifications has been prepared
from jatropha curcas oil, using potassium hydroxide catalyst sup-
ported on calcined waste animal bones. It is therefore an objective
of the instant invention to prepare biodiesel from non-edible oil
(Jatropha curcas oil) by using potassium hydroxide catalyst sup-
ported on calcined bones to produce methyl esters from Jatropha oil
and to develop cheap technology process for efficient biodiesel
production for sustainable energy production. Once loaded with
KOH on the ox bones, the acquired potassium hydroxide supported
calcined animal bones catalyst displayed higher catalytic activity.
Experiments under different reaction conditions, such as methanol/
oil molar ratio, catalyst loading, reaction temperature and reaction
time were performed in order to optimize biodiesel yield.
2. Materials and methodology
2.1. Materials
The waste animal bones were obtained from butcher shop.
Jatropha oil was purchased from a local market. Methanol (99.8%),
n-hexane and n-heptane (GC grade), anhydrous Na2SO4 (99%) were
procured from Sigma-Aldrich. Pure potassium hydroxide (98.9%)
was used as a catalyst and was purchased from Sigma-Aldrich.
Sulphuric acid (98% pure) was procured from Acros Organics.
Methyl ester reference standards including methyl oleate, methyl
palmitate, methyl linoleate, and methyl stearate of 99% purity were
supplied by Supelco. Derivatization agent, N-Methyl-N-(trime-
thylsilyl) trifluoroacetamide (MSTFA) (98.5% GC grade) was pur-
chased from the same company.
2.2. Catalyst preparation
Waste animal bones were washed with boiled water for almost
4 h to remove the dust, meat and cartilages and then dried in an
oven at 110
C for about 5 h. After cooling them at room temper-
ature the bones were crushed in the form of powder using a
grinder. Later the powder bones were calcined at variable tem-
perature range (500e1100
C) in a furnace [18]. After calcination
the bone powder was soaked with potassium hydroxide solutions
of different concentration, in order to boost its surface chemical
properties. This process involves forming a slurry mixture of animal
bones with KOH aqueous solution. Animal bones soaked in a so-
lution of potassium hydroxide were then gradually heated in a
shaker at 200 rpm until water contents evaporated completely. As a
result of heating, a hard cake was formed that was crushed and
dried at 120
C for 12 h.
2.3. Characterization of catalyst
The physico-chemical characteristics of the produced catalysts
were determined by various techniques i.e. TG/DTG (Perkin Elmer
Pyris 1), N2 adsorption desorption (Micromeritics, ASAP 2020), X-
ray diffraction (Bruker D8 X-ray diffractometer equipped with a Cu
anode), scanning electron micrographs (JSM-5910, JEOL), energy
dispersive X-rays (JSM-7610F) and fourier transform infrared
spectroscopy (Shimadzu, IR Prestigue-21).
2.4. Transesterification of Jatropha curcas oil
Jatropha oil has a FFA content over 2.5 wt %, a pre-treatment step
is necessary before the transesterification process. Prior to the start
of transesterification reaction, the oil was filtered and heated at
105
C for 1 h to remove the impurities and water contents. For
esterification reaction a mixture of methanol and oil in 12:1 M ratio
was put into a three necked round bottom flask having a ther-
mometer and magnetic stirrer attached with a water-cooled
condenser and stirred at low stirring rate for 90 min at 50
C fol-
lowed by addition of 0.8% (v/v) sulphuric acid. The reaction mixture
 J. Nisar et al. / Renewable Energy 101 (2017) 111e119 113

was then transferred into a separating funnel and shaken well to

remove the excess alcohol, sulphuric acid and impurities.
For transesterification reaction, the same experimental set up
was used as employed for acid esterification. A mixture of methanol
and catalyst in designated amount was agitated and heated at 60
C
with constant stirring (600 rpm) for 40 min so that activation of
catalyst prior to the transesterification reaction took place. The
transesterification reaction was carried out using excess alcohol,
different molar ratios of methanol to oil for 3 h at 70± oC with
constant stirring (600 rpm). After completion of reaction, the
mixture was cooled down to room temperature and then filtered. In
order to separate the ester phase from glycerol phase, the filtrate
was centrifuged at about 3000 rpm for 15 min. Biodiesel was ob-
tained as the top layer while glycerol at the bottom. The biodiesel
phase was then purified by distillation in order to recover unreac-
ted methanol in a batch vacuum distillation flask. The traces of
alcohol were removed by washing with hot distilled water followed
by drying with anhydrous Na2SO4 [18,19].

2.5. Yield, purity and fuel properties of synthesized biodiesel

The yield of biodiesel production obtained through trans-

Fig. 1. The TGA profile of animal bones.
esterification of Jatropha oil was calculated based on the fatty acid
methyl esters (FAME), using the relation shown in Eq. (1).
  stability of the calcined animal bones at or above 900
C. On the
Weight of biodiesel producedTotal wt: % of FAME
Yieldð%Þ¼ other hand, animal bones calcined beyond 1000
C enhanced the
Weight of oil
sintering effect that ultimately reduced the surface area and
100 resultantly the activity of the catalyst by decreasing the surface area
(1) [21,22].

Gas Chromatogram (GC-2010 Plus, Shimadzu) fitted with a

flame ionization detector (FID) and automated split injector (AOC-
20i), employed with a capillary column, TRB-1 (30 m  0.25
mm  0.1 mm) was used to check the fatty acid profile of biodiesel.
Nitrogen with a flow rate of 21 mL/min was employed as a carrier
gas. At first the oven temperature was fixed at 84
C for 5 min, and
then it was increased to 280
C at 5
C min1 and then held it for
5 min. The temperatures of detector and injector were held at
250
C. FAME mix standards were employed as an external stan-
dard to analyse the methyl ester. The fuel properties of the syn-
thesized biodiesel were tested and compared with ASTM standard
methods.
3. Results and discussion
3.1. Characterization of catalyst
3.1.1. Thermogravimetric analysis
To study the influence of calcination temperature on weight
loss, the animal bones powder were subjected to thermal analysis
(250e1050
C) at heating rate of 10
C/min in N2 atmosphere. The
thermogram in Fig. 1 shows a preliminary loss in weight at tem-
perature range of 50e170
C. This indicates the loss of water in the
form of evaporation of adsorbed water. The next step indicates the
loss in weight in the temperature range of 200e510
C, which is due
to the decomposition of macromolecules and removal of organic
portion. An additional very small and steady weight loss is also
observed in the temperature range 600
Ce900
C. This may be
attributed to the formation of gaseous fraction as a result of
transformation of bone to hydroxyapatite (HAP). Around 900
C
more loss in weight takes place that could be assigned to the
transformation of HAP (hydroxyapatite) into b-Ca3 (PO4)2 [17]. Fig. 1
also shows that the bones calcined at 900
C or above, did not
indicate any further loss in weight. It confirms the high thermal
3.1.2 Scanning electron micrograph
The scanning electron micrographs of the uncalcined, calcined
and potassium hydroxide supported bones samples are presented
in Fig. 2. The morphology of the uncalcined bone looks like mass of
aggregates that have less surface area as compared to the bone,
calcined at 900
C, which shows some alteration in its morphology.
In calcined bone particle size reduction was maximum, exhibiting
higher surface area, an important characteristic of a heterogeneous
catalyst. The SEM photograph of potassium hydroxide supported
bones shows good scattering of potassium hydroxide on the surface
of bones. The results indicate that after loading of potassium hy-
droxide on calcined bone, its particle size reduces and exhibits
higher surface area. Moreover, the potassium species were also
found highly scattered upon the surface of the calcined bones
uniformly.
3.1.3. X-ray diffraction analysis
The XRD-patterns of uncalcined and calcined animal bones are
illustrated in Fig. 3. Indexing of the diffraction peaks was completed
using a standard JCPDS (Joint Committee on Powder Diffraction
Standards) file.
The diffractogram of uncalcined bones confirms the existence of
two different phases of CaCO3, known as aragonite and calcite.
Calcination at 900
C for 5 h has promoted the conversion of the
aragonite (CaCO3) phase to calcium oxide CaO [16,23]. The occur-
rence of calcite (CaCO3) on the surface of a calcined bone along with
Ca(OH)2 is caused by carbonation and hydroxylation reactions that
takes place due to direct exposure to atmospheric air [24]. XRD-
diffractogram from Fig. 3, also confirms the existence of calcium
phosphate oxide that was formed through the calcination process
of hydroxyapatite. The peaks of calcined bones were compared
with the Joint Committee on Powder Diffraction Standards (JCPDS).
The peaks at 21.438
, 25.80
, 39.84
, 45.25
, 49.73
, 51.43
, 56.57
,
60.12
, 62.94
and 65.12
are attributed to the presence of
114 J. Nisar et al. / Renewable Energy 101 (2017) 111e119
Fig. 2. (A) SEM image of uncalcined animal bones (B) SEM image of calcined bones and
(C) SEM image of KOH/calcined animal bones.
Fig. 3. (a) XRD pattern of un-calcined animal bones and (b) XRD pattern of calcined
animal bones at 900
C for 5 h.
hydroxyapatite [12,25]. The peaks at 28.76
, 30.45
and 31.74
are
attributed to b-Ca3(PO4)2 phase, thus confirm the transformation of
hydroxyapatite into b-Ca3(PO4)2 that could act as a base catalyst for
transesterification reaction [18]. The peaks at 18.60
and 34.02
are
attributed to the Ca(OH)2 phase. The peak at 53.23
is the charac-
teristics of CaO phase in the catalysts [19].
Similarly, XRD-diffractograms of the KOH/calcined bones cata-
lysts are assembled in Fig. 4.
The observed diffraction peaks of calcined bones based catalysts
show that a weak KOH- support interaction occurred at low KOH
contents 10 wt%. This is due to high Ca:P molar ratios. On the
other hand, increased KOH content beyond >10 wt% also promoted
the formation of a hydroxyapatite PHA phase, which was a sup-
plementary growth as Ca:P decreased at higher KOH. Animal bones
when loaded with KOH, clearly shows a new phase of KCaPO4 at
30.37
, however no other peaks of KOH was detected in the syn-
thesized catalyst and that might be due to the interaction of KOH
with calcined animal bones and the formation of KCaPO4 [26]. Fig. 4
also shows the effect of calcination temperature on the crystallinity
of catalyst. When the calcination temperature was increased from
500 to 900
C the crystallinity of the catalyst increased and hence
the peak of KCaPO4 was clearly seen in the diffractograms when the
calcination temperature was increased from 500 to 900
C. The
diffractograms of Fig. 4 also propose the formation of CaO phase at
34.02
that is formed due to ion exchange of calcium ions of bones
with potassium ions of KOH at high temperature [27].
3.1.4. Energy dispersive X-ray analysis
The elemental analysis of pure calcined bones and KOH/calcined
bones are illustrated in Fig. 5 and Table 1(a) and (b). The inorganic
composition (C/O/Mg/P/Ca) of the different catalysts were deter-
mined by OXFORD INCA EDS. EDX analyses revealed that the
inorganic phases of bones were mainly composed of calcium and
phosphorus with some minor components such as C, Na, and Mg.
The results in Table 2 also indicate that the calcium, oxygen and
phosphorous contents increase as the temperature is increased and
reach a maximum at 900
C, confirming the formation of hy-
droxyapatite [19]. The EDX analysis of animal bones modified with
potassium hydroxide show that K active sites increase from 0.0% to
11.29% as KOH loading to animal bones structure increases.
3.2. Catalyst reusability
Reusability of catalyst was examined by carrying out trans-
esterification reaction several times. The used catalyst in 1st time
Fig. 4. XRD patterns of all catalyst samples at different KOH loading percent.
 J. Nisar et al. / Renewable Energy 101 (2017) 111e119 115

3.3. Biodiesel characterization

Physiochemical properties of produced biodiesel from Jatropha

oil using KOH/AB as a catalyst were considered and compared with
ASTM standard methods. The outcomes of this characterization are
listed in Table 3, which meet with standards of ASTM. The relative
composition and identity of different fatty acid methyl esters were
analyzed by Gas Chromatography (GC-2010 Plus) and FTIR.

3.3.1. Gas chromatography analysis

To detect the different fatty acids methyl esters existing in the
biodiesel, GC-FID analysis was used by developing a method. The
composition of methyl ester in the synthesized biodiesel is pre-
sented in the gas chromatogram (Fig. 6). Different peaks appeared
in the chromatogram were identified by comparing them with the
standards and reported data that agree well with the methyl esters
found in the synthesized biodiesel. The chromatogram also con-
firms the successful conversion of Jatropha oil into biodiesel.

3.3.2. Fourier-transform infrared spectroscopy analysis

FT-IR spectra of the Jatropha oil and the biodiesel produced from
this oil are illustrated in Fig. 7. The Jatropha oil indicates a peak at
3410 cm1 conforming the stretching and bending vibration of O-H
bonds due to the presence of water molecules. The antisymmetric
Fig. 5. (a) EDX spectra of calcined bones and (b) EDX spectra of KOH/calcined bones.
and symmetric stretching vibrations of C-H in CH2 and CH3 groups
can be confirmed by the presence of peaks at 2924 cm1 and
Table 1 2853 cm1 respectively. The strong peak present at 1743 cm1 is
(a) EDX analysis of calcined bones and (b) EDX analysis of KOH/calcined bones. attributed to the presence of C¼O stretching vibration of carbonyl
a b groups that is present in the triglycerides. The peaks at 1400-
1200 cm1 region confirmed the bending vibrations of CH2 and CH3
Elements Weight% Atomic Elements Weight Atomic
aliphatic groups. Similarly bending of HCH takes place at 1373 cm1
(%) (%) (%) (%) and CH2 and scissoring at 1466 cm1 respectively. The peaks
CK 12.18 10.58 CK 8.93 14.73
OK 45.26 59.28 OK 45.26 59.28
Mg K 0.44 0.87 Mg K 0.51 0.44 Table 3
PK 15.21 15.57 PK 11.14 7.54 Physical and chemical properties of biodiesel and its comparison with diesel fuel
Ca K 26.95 13.7 KK 11.21 6.01 characteristics.
e e Ca K 22.95 12
e Properties Method Biodiesel Diesel
Total 100 Total 100 Kinematics viscosity (mm2/s) ASTM D445 2.45 2.5
Density (kg/m3) ASTM D4052 869 853
Acid number (mg KOH/g oil) ASTM D664 0.629 e
Moisture content (%) ASTM D2709 0.003 0.02
Table 2
Iodine value (g iodine/100 g) PORIM 98 93
EDX analysis of calcined bones at different temperatures (
C).
Calorific value (MJ/kg) ASTM D240 39.72 42
Elements 700
C 800
C 900
C Flash point (
C) ASTM D93 73 68

Weight Atomic Weight Atomic Weight Atomic

(%)

CK 15.67 25.31 17.51 28.49 14.48 24.50

OK 43.40 52.63 39.30 48.01 39.00 49.56
Mg K 0.79 0.63 0.91 0.73 0.64 0.54
PK 14.07 8.82 13.60 8.85 14.26 9.36
Ca K 26.07 12.62 28.69 14.18 31.62 16.04

Total 100 100 100

transesterification reaction was taken out from the reaction vessel

and fully dried for reutilization. It was found that the activity of
catalyst was still 86% of the 1st time used catalyst, when it was used
for fourth time. This is due to the high basicity of KOH/AB (potas-
sium hydroxide/animal bone) catalyst that stopped the further
decomposition of b-Ca3(PO4)2 in the reaction mixture. The
decomposition of catalyst was attributed to the hydration and
leaching of active sites into the reaction mixture. Leaching of active
sites are due to the breakage of bond with the creation of CH3O
and Kþ ions which is very much negligible in this loss. Fig. 6. Gas chromatogram of the synthesized biodiesel.
116 J. Nisar et al. / Renewable Energy 101 (2017) 111e119
Fig. 7. FT-IR spectrum of (a) Jatropha oil (b) synthesized biodiesel.
present in the region of 1120e1090 cm1 presented the stretching
vibration of C-O ester. The peak obtained at 721 cm1 confirmed the
rocking vibration of (CH2)n overlapping [28,29]. Moreover, the peak
at1742 cm1 confirmed the stretching vibration of C¼O present in
the esters and peaks present in the range of 1300e1000 cm1
conforming to that of the C-O stretching vibrations [30,31]. The
stretching vibrations of CH3, CH2, and CH groups can be seen at
2980e2950, 2950e2850 and 3050e3000 cm1, while the bending
vibrations of CH3, CH2, and CH groups appeared at 1475e1350,
1350e1150 and 722 cm1 respectively [31,32]. The FT-IR spectra of
the Jatropha oil and biodiesel produced from it are comparable to
each other because of the presence of triglycerides and esters.
However, very small differences were observed where the peaks
appeared at 1743, 1373, 1155, 1038 and 876 cm1 in the Jatropha oil
were shifted to 1742, 1365, 1172, 1018 and 884 cm1 in the biodiesel
respectively. So, the disappearance of the peaks from the spectrum
of the Jatropha oil at 1443, 1096 and 965 cm1 and formation of new
peaks at 1430 cm1 and 1194 cm1 in the produced biodiesel
sample evidently confirm the conversion of Jatropha oil into bio-
diesel. Moreover, the absence of a broad peak in the region of
3100e3500 cm1 proposes that the biodiesel synthesized from
Jatropha oil contains low water contents.
3.4. Optimization of transesterification over KOH/CAB catalysts
3.4.1. Effect of calcination temperature
To observe the effect of the calcination temperature on the
catalyst activity, potassium hydroxide impregnated animal bones
were calcined at different temperature ranging from 200 to
1000
C. Calcination beyond 600
C did not show any significant
change in the activity of catalyst. However, calcination at 900
C
increased the crystallinity and optimal active sites of the catalyst
that increased the yield of biodiesel up to 96% at 70 ± 3
C within
3 h (Fig. 8). When the calcination temperature was further
increased to 1000
C, it resulted in the suppression of catalytic
activity due to the high sintering rate of the catalyst and high
 J. Nisar et al. / Renewable Energy 101 (2017) 111e119 117

the formation of new phases that were less active [19,34,35]. Hence,
the best catalytic performance of the catalyst was obtained at a
calcination temperature of 900
C. Sintering rate of catalyst not only
reduced the BET surface but also reduced basicity of the catalyst.
Thus, the experimental results showed that calcination at 900
C is
considered to be the most perfect, appropriate and optimum
temperature for the calcination of this particular catalyst.

3.4.2. Effect of KOH loading

Fig. 8. Effect of calcination temperature on biodiesel yield.
energy consumption, which was confirmed by decrease in biodiesel
production by successive experiments [18,33]. This showed that at
higher temperatures, excessive structure collapse and formation of
new inactive phases seriously affected the activity of the catalyst.
Earlier studies have also found that calcination at 900
C resulted in
To determine the effect of catalyst loading on FAME conversion a
series of KOH/CAB catalysts were synthesized by changing the
concentration of KOH from 1 to 14 wt %. When the calcined bones
were loaded and activated with KOH at higher temperature, they
showed higher catalytic activity than the virgin calcined bones
(Fig. 9a). By increasing the amount of KOH loading, biodiesel pro-
duction increased. When the loaded KOH was less than 10 wt %, it
did not provide enough catalytic activity because of formation of
least basic active site for FAME conversion. However, when the
amount of KOH was increased from 10 wt % onward, the catalyst
still provided weak catalytic activity due to agglomeration of
extreme active sites. These excessive active sites also caused poor
scattering of K on the surface of calcined bones and made some
active sites unreachable to the substrate [36,37]. Thus, the KOH
loading of 10 wt % could be designated as the best value for solid
catalyst.

Fig. 9. (a): Effects of KOH loading on the yield of biodiesel (The reaction parameters: catalyst calcination temperature 900
C, 9:1 M ratio of methanol to oil, 70 ± 3
C for 3 h), (b):
Effects of catalyst dosage on the yield of biodiesel (The reaction parameters: catalyst calcination temperature 900
C, 9:1 M ratio of methanol to oil, 70 ± 3
C for 3 h), (c) Effects of
methanol to oil molar ratio on the yield of biodiesel (The reaction parameters: catalyst calcination temperature 900
C, 6.0 wt % catalyst dosage, 70 ± 3
C for 3 h) and (d): Effects of
reaction time on the yield of biodiesel (The reaction parameters: catalyst calcination temperature 900
C, 9:1 M ratio of methanol to oil, 6.0 wt % catalyst dosage, 70 ± 3 s
C).
118 J. Nisar et al. / Renewable Energy 101 (2017) 111e119
3.4.3. Effect of catalyst loading
To investigate the effect of catalyst loading on FAME conversion,
different wt. % of catalyst were loaded (Fig. 9b). Initially when the
small amount of catalyst was used, no remarkable conversion
occurred. However, when the amount of catalyst was increased
from 2 to 6 wt % then the biodiesel yield was increased from 65 to
96.1 and the maximum of 96.1% was achieved by loading 6 wt % of
catalyst. But, when the amount of catalyst was increased from 6 wt
% onward, the yield dropped to a significant level and led to the
formation of viscous slurries to enable adequate stirring [38]. Thus
it is indicative of the fact that the optimum catalyst loading is 6 wt %
in this study.
3.4.4. Effect of methanol to oil molar ratio
In order to drive the reaction to forward side, it is necessary to
use excessive methanol because the transesterification reaction is a
reversible reaction. When the methanol/oil molar ratio was
increased from 3:1 to 13:1, the biodiesel yield increased gradually
and significantly. However, the optimum molar ratio of methanol to
oil was found to be 9:1 that was due to the formation of methoxy
species formed on the surface of catalyst and caused a shift in the
equilibrium in the forward direction. While further increasing the
molar ratio from 9:1 onward, a decrease in the biodiesel yield was
observed as shown in Fig. 9c, and this reduction was attributed to
the deactivation of catalyst and difficulty in the separation of bio-
diesel from glycerol was faced due to high amount of methanol.
Hence excessive use of methanol decreased the conversion by
shifting the equilibrium in the reverse direction.
3.4.5. Effect of reaction temperature
The effect of reaction temperature on biodiesel yield over KOH/
CAB catalyst was examined at different temperatures. Increasing
the reaction temperature from 60 to 70
C, an increase in the
conversion of oil into biodiesel was noted and maximum conver-
sion of 96.1% was achieved at 70 ± 3
C. Increasing the reaction
temperature above 70
C, a reduction in the yield of FAME was
observed. This is due to the fact that, when methanol is heated
above its boiling point it bubbles out and as a result of this bubbling
mass transfer on the interface of the phases inhibits. Hence, the
optimum reaction temperature for the transesterification of Jatro-
pha oil in the presence of KOH/CAB was found out to be 70 ± 3
C in
the present study.
3.4.6. Effect of reaction time
Among others parameters, reaction time is one of the important
parameter that has a profound effect on the FAME yield in this
transesterification reaction. The catalytic performance of KOH/CAB
was examined by varying the reaction time from 0.5 h to 4 h.
Fig. 9d, shows that FAME content increased on increasing the re-
action time from 0.5 h to 4 h. However, the maximum yield of
96.10% was attained after 3 h and on further increasing the reaction
time, the yield of biodiesel started to decline. The lower yield at
lesser reaction time is due to the absence of calcium methoxide,
which is the main driving force for the transesterification reaction.
The optimum reaction time was found out to be 3 h over the
catalyst in the present study. Therefore, transesterification using
animal bones modified with KOH as heterogeneous solid base
catalyst is viable method for the conversion of Jatropha oil into
biodiesel, which is a green method to avoid environmental issue
related to conventional fuels [39,40].
4. Conclusion
The present study reveals the effective application of potassium
hydroxide catalyst supported on calcined animal bones as a
heterogeneous catalyst for biodiesel production from Jatropha oil.
Potassium hydroxide impregnated on calcined animal bone effec-
tively catalyzed the transesterification of refined Jatropha oil to
produce biodiesel. Furthermore, the prepared catalyst, showed
promising reusability, high specific surface area and higher bio-
diesel yield that could be achieved at moderate methanol to oil
molar ratio and lower catalyst amount. Among the different
transesterification parameters, catalyst loading and reaction tem-
perature were found to be the most important parameters on
production yield. The optimum condition of transesterification
using potassium hydroxide catalyst supported on calcined animal
bones was 70 ± 3
C reaction temperature, 6.0 wt % of oil catalyst
loading and 9:1 methanol to oil molar ratio. Under these optimum
conditions 96.01% production yield was obtained. The produced
biodiesel under these reaction parameters was characterized and
its physiochemical properties were compared with the ASTM
standard. As the waste bone catalyst shows high catalytic activity
and is simple, economical, ecologically friendly, therefore, it could
be utilized as potential catalyst for biodiesel production on indus-
trial scale.
Acknowledgement
The financial/facility support provided by Higher Education of
Pakistan through project No. 20-1491 is gratefully acknowledged.
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