Fuel 106 (2013) 111–117

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Biodiesel production from jatropha seeds: Solvent extraction and

in situ transesterification in a single step
I. Amalia Kartika a,⇑, M. Yani a, D. Ariono b, Ph. Evon c,d, L. Rigal c,d
a
Department of Agroindustrial Technology, FATETA-IPB, Darmaga Campus, P.O. Box 220, Bogor 16002, Indonesia
b
Department of Chemical Engineering, FTI-ITB, Ganesha 10 Road, Bandung 40132, Indonesia
c
Université de Toulouse, INP, LCA (Laboratoire de Chimie Agro-Industrielle), ENSIACET, 4 allée Émile Monso, BP 44362, Toulouse 31030 Cedex 4, France
d
INRA, LCA (Laboratoire de Chimie Agro-industrielle), Toulouse 31030, France

h i g h l i g h t s

" We investigate the biodiesel production directly from jatropha seeds.

" We examine influences of reaction conditions on biodiesel yield and its quality.
" Increasing methanol to seed ratio and alkali concentration will increase yield and quality.
" Increasing reaction temperature will increase yield.
" Temperature, time and stirring speed effects on biodiesel quality were less important.

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

Article history: The objective of this study was to investigate solvent extraction and in situ transesterification in a single
Received 31 March 2011 step to allow direct production of biodiesel from jatropha seeds. Experiments were conducted using
Received in revised form 10 October 2012 milled jatropha seeds, and n-hexane as extracting solvent. The influence of methanol to seed ratio
Accepted 9 January 2013
(2:1–6:1), amount of alkali (KOH) catalyst (0.05–0.1 mol/L in methanol), stirring speed (700–900 rpm),
Available online 31 January 2013
temperature (40–60 °C) and reaction time (3–5 h) was examined to define optimum biodiesel yield
and biodiesel quality after water washing and drying. When stirring speed, temperature and reaction
Keywords:
time were fixed at 700 rpm, 60 °C and 4 h respectively, highest biodiesel yield (80% with a fatty acid
Biodiesel
Jatropha seed
methyl ester purity of 99.9%) and optimum biodiesel quality were obtained with a methanol to seed ratio
In situ transesterification of 6:1 and 0.075 mol/L KOH in methanol. Subsequently, the influence of stirring speed, temperature and
Solvent extraction reaction time on biodiesel yield and biodiesel quality was studied, by applying the randomized factorial
experimental design with ANOVA (F-test at p = 0.05), and using the optimum values previously found for
methanol to seed ratio and KOH catalyst level. Most experimental runs conducted at 50 °C resulted to
high biodiesel yields, while stirring speed and reaction time did not give significantly effect. The highest
biodiesel yield (87% with a fatty acid methyl ester purity of 99.7%) was obtained with a methanol to seed
ratio of 6:1, KOH catalyst of 0.075 mol/L in methanol, a stirring speed of 800 rpm, a temperature of 50 °C,
and a reaction time of 5 h. The effects of stirring speed, temperature and reaction time on biodiesel qual-
ity were not significant. Most of the biodiesel quality obtained in this study conformed to the Indonesian
Biodiesel Standard.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction cause this plant can be used to reclaim land, prevent and/or control
erosion, plus it provides a new agricultural development mode
Jatropha curcas is a drought-resistant shrub or tree belonging to with no competition between food and non-food uses.
the family Euphorbiaceae, which is cultivated in Central and South The seed is the part of the jatropha plant with the highest po-
America, South–East Asia, India and Africa [1]. It is a plant with tential for utilization. It contains between 40% and 60% oil, and be-
many attributes, multiple uses and considerable potential [2–4]. tween 20% and 30% proteins. The jatropha seed is generally toxic to
In Indonesia, the land area for jatropha plantation is increasing be- humans and animals, with phorbol ester and curcin identified as
the main toxic agents [1,5].
⇑ Corresponding author. Tel.: +62 251 8621974; fax: +62 251 8625088. J. curcas oil is regarded as a potential alternative to diesel fuel,
E-mail address: [email protected] (I. Amalia Kartika). and vegetable oils have numerous advantages in this respect

0016-2361/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.fuel.2013.01.021
112 I. Amalia Kartika et al. / Fuel 106 (2013) 111–117

because they are safe to store and handle because of their high to seed ratio, amount of alkali (KOH) catalyst, stirring speed, tem-
flash points. The fact that jatropha oil cannot be used for nutri- perature and reaction time was examined to identify the optimal
tional purposes without detoxification makes its use as an energy reaction conditions and define best performance of biodiesel yield
source for fuel production, very attractive [6,7]. and quality.
In Indonesia, the availability of biofuel as a substitute for fossil
fuel is urgently needed because national oil production has been 2. Materials and methods
falling over the past 5 years due to the natural decline of oil wells.
The use of biodiesel from jatropha oil is a promising alternative be- 2.1. Materials
cause it is renewable, and environmentally friendly, and it can also
be produced locally. Cultivating jatropha plants on land where no All trials were carried out using jatropha seeds (IP2 Lampung
other crops can grow, and using its oil as an alternative energy variety) supplied by the Indonesian Spices and Industrial Crops Re-
source does not, at least in theory, reduce the availability of edible search Institute (Sukabumi, Indonesia), and shells were removed
oils in the country. manually before the study. Seed moisture content at storage was
Conventional industrial technology for the synthesis of biodie- 6.2 ± 0.5% (standard NF V 03-909) [33]. Methanol (>98% purity)
sel from vegetable oils involves isolation of the oil from the seed, and n-hexane (>98% purity) were supplied by BRATACO Chemical
refining, and then transesterification. Industrial oil extraction from Ltd. (Indonesia), and all analysis solvents and chemicals were pure
oilseeds is usually done by mechanical pressing with a hydraulic or analytical grades obtained from Sigma–Aldrich, Fluka and J.T. Ba-
single expeller press, followed by solvent extraction. The combina- ker (Indonesia and France).
tion of these operations produces oil extraction yields up to 98% in
the case of sunflower, with residual oil content in cake meal be-
2.2. Experimental
tween 0.5% and 1.5% [8]. The solvent extraction most commonly
used today is by percolation with a countercurrent flow using hex-
For all trials, moisture content determined by weight loss
ane as extracting solvent [9–13]. Currently, twin-screw extrusion
according to standard NF V 03-909 [33] and mesh size of jatropha
has been successfully carried out to extract oil from oilseeds [14–
seeds were less than 1% and 35, respectively. To obtain a moisture
19], and to conduct mechanical pressing and solvent extraction
content of less than 1%, jatropha seeds were dried at 70–90 °C for
of sunflower oil in a single step [20]. Highest oil extraction yield
24–48 h, and then milled using an electric grinder fitted with a
(98%) with best cake meal quality (residual oil content lower than
mesh size of 35.
3%) was obtained using a screw rotation speed of 185 rpm, feed
The effect of methanol to seed ratio and amount of KOH on bio-
rate of 30 kg/h, and solvent-to-solid ratio of 0.55. Industrial oil
diesel yield and biodiesel quality was studied first. 100 g of milled
refining normally includes many separate steps including degum-
jatropha seeds were mixed with methanol in which KOH had been
ming, neutralization, bleaching and deodorisation. These processes
dissolved. The methanol to seed ratio (v/w, expressed in mL/g) and
consume large amounts of energy, water and chemicals with much
the amount of KOH in methanol were 2:1–6:1 and 0.05–0.1 mol/L,
loss of neutral oil, and the production of large amounts of un-
respectively. The amount of KOH used in this study was based on
wanted by-products [21].
literature values [30]. 100 mL of n-hexane (seed to n-hexane ratio
The preparation of biodiesel from various vegetable oils using
(w/v) of 1:1) was then added to increase oil miscibility in the mix-
alkaline transesterification of triglycerides with monohydric alco-
ture, accelerate the reaction and complete it in a single phase. The
hol has been studied for several decades, and a large part of indus-
reaction was carried out in a three-necked 2000 mL round bottom
trial production has been achieved using this method [22,23],
flask equipped with a reflux system, a magnetic stirrer and a hea-
although it requires extra-steps during the extraction and refining
ter, under reaction conditions of 700 rpm stirring speed, 60 °C tem-
processes. As the cost of vegetable oil production accounts for
perature and 4 h reaction duration.
approximately 70% of biodiesel production costs [24–26], there is
At the end of the reaction period, the mixture was cooled to
a need for the development of a new biodiesel production process
room temperature, and vacuum filtered to separate the filtrate
that is simple, compact, efficient, low-cost, and that consumes less
from the cake. The filtrate was then evaporated using a rotary
energy.
evaporator to recover methanol and n-hexane, and allowed to set-
Recently, the preparation of biodiesel using in situ transesterifi-
tle and separate into two layers. The lower layer was dark brown in
cation has been successfully carried out with various oilseeds [24–
color and contained glycerol, while the upper layer (crude biodie-
32]. In situ transesterification is a biodiesel production method
sel) was yellow in color and contained the fatty acid methyl esters,
that uses the original agricultural products as the source of triglyc-
the unreacted glycerides (triglycerides, diglycerides and monogly-
erides, instead of purified oil, with direct transesterification, and
cerides), and other impurities. Methanol and n-hexane may extract
works with virtually any lipid-bearing material. It reduces the
materials other than triglycerides, such as fatty acids and phospho-
time-consuming pre-extracted oil production system, and maxi-
lipids. The crude biodiesel was then washed with water until neu-
mizes ester yield.
trality, and dried at 105 °C for 1 h. The fatty acid methyl ester,
The conversion of jatropha seed to fatty acid methyl esters
triglyceride, diglyceride, monoglyceride and fatty acid contents in
(FAME) by acid-catalyzed in situ transesterification has been suc-
crude biodiesel after washing and drying were then determined
cessfully carried out [31]. Using seed size less than 0.355 mm
by gas chromatography. The mass of crude biodiesel after washing
and n-hexane as co-solvent under reaction conditions of 60 °C tem-
and drying was measured, and the biodiesel yield was calculated
perature, for 24 h, 7.5 mL/g methanol to seed ratio, and 15 wt.% of
from the equation:
H2SO4, the FAME yield reached 99.8%. However, the conversion of
jatropha oil to FAME by in situ alkaline transesterification has Mass of crude biodiesel after washing and drying ðgÞ
Biodiesel yield ð%Þ ¼
never been reported. Thus, a systematic study should be conducted Mass of triglycerides in jatropha seeds ðgÞ
to investigate and identify optimal reaction conditions for single 100
step in situ alkaline transesterification combined with solvent
extraction of jatropha oil. with Mass of triglycerides in jatropha seeds (g) = Mass of oil con-
The objective of this study was thus to investigate solvent tained in jatropha seeds (g) Glyceride fraction content in jatropha
extraction and in situ transesterification in a single step to produce oil (%) Triglyceride content in glyceride fraction (%). The biodiesel
biodiesel directly from jatropha seeds. The influence of methanol yield is calculated on the basis of a pure biodiesel (i.e. containing
I. Amalia Kartika et al. / Fuel 106 (2013) 111–117 113

only fatty acid methyl esters). Taking into account the fact that perature was programmed from 55 °C to 360 °C at a rate of
components contained in the crude biodiesel are not only fatty acid 45 °C min1 to 80 °C, followed by 10 °C min1, and was then main-
methyl esters, such formula may lead to a potential source of error. tained at 360 °C for 16 min. Injector temperature was programmed
Each experiment was conducted twice to give an average bio- from 55 °C to 340 °C at a rate of 200 °C min1 and then maintained
diesel yield with corresponding standard deviation. After the fil- at 340 °C for 40 min, and detector temperature was set at 365 °C.
trate separation, the cake was not washed with methanol to take Heptadecane was used as the internal standard. The peaks corre-
out the esters, meaning that it still contained a part of the fatty acid sponding to the different glycerides and free fatty acids were iden-
methyl esters produced during the in situ transesterification. It was tified by comparing the retention times of each detected
directly dried overnight at room temperature, and the total volatile component in the sample with the ones of pure glyceride and fatty
matter content and the n-hexane extracted matter content (i.e. acid standard compounds. To quantify each compound family (tri-
weight loss upon n-hexane extraction) were then determined glycerides, diglycerides, monoglycerides and free fatty acids) in the
according to standards [33,34], respectively. All determinations sample, a stock solution of triolein, diolein, monoolein and oleic
were carried out in duplicate. acid added in the same proportions was prepared and then diluted
The effect of three other operating conditions (stirring speed, to different concentrations. Stock solution and diluted solutions
temperature and reaction time) on biodiesel yield and biodiesel were used to obtain standard curves relating each peak area to
quality was studied in the second stage. The corresponding exper- the actual amounts of triolein, diolein, olein and oleic acid. For each
iments were conducted using a methanol to seed ratio of 6:1 (v/w) of the four families above mentioned, the compound mass in the
and 0.075 mol/L KOH in methanol. The stirring speed, the temper- sample was obtained first by summing the peak areas from all
ature and the reaction time were 700–900 rpm, 40–60 °C and 3– same-family compounds, and then by relating area sums to stan-
5 h, respectively. Sample collection and analyses were performed dard curves. In each family, response factor of all the compounds
using the same procedure as for effect of methanol to seed ratio was considered to be the same as the one of the corresponding
and amount of KOH on biodiesel yield and biodiesel quality. Each oleic compound. The ratio between the sum of masses for triglyc-
experiment was duplicated, and biodiesel yield was taken as the erides, diglycerides, monoglycerides and free fatty acids and the
average with corresponding standard deviation. The randomized test sample mass was used to determine the glyceride fraction con-
factorial experimental design with ANOVA (F-test at p = 0.05) tent in jatropha oil. The glyceride distribution between the four
was used to study the effects of stirring speed, temperature and compound types was also calculated.
reaction time on biodiesel yield and biodiesel quality using SAS Once the biodiesel produced, its quality was analyzed. It in-
software. cludes the following parameters: (i) its acid value, expressed in
mg of KOH/g of sample (standard NF T 60-204) [35], which is an
2.3. Analytical methods indication of the free fatty acid content of the sample, (ii) its sapon-
ification value, expressed in mg of KOH/g of sample (standard NI
Seed oil content was determined according to standard NF V 03- 01-3555-1998) [36], which is the amount of alkali necessary to
908 [34]. Ground seed was placed into an extraction thimble, and saponify a certain quantity of the sample, (iii) its iodine value, ex-
the oil was extracted using Soxhlet extraction apparatus with pressed as the number of centigrams of iodine absorbed per gram
n-hexane for 6 h. The solvent was then evaporated using rotary of sample (standard AOCS-Cd 1d-92) [37], which is a measurement
vacuum evaporator, and the remaining oil was weighed. Seed oil of the unsaturations of the sample, and (iv) its viscosity, estimated
content was expressed as percent by mass of the dry matter. using the AOAC 974:07 method [38] with an Ostwald viscometer,
The fatty acid composition of oil extracted from jatropha seed measured at 40 °C.
was determined by gas chromatography (GC) using the following In addition, the biodiesel fatty acid methyl ester content was
FAME method. The sample analyzed (i.e. the oil extracted from determined by gas chromatography using the method described
jatropha seed using the Soxhlet extraction apparatus and n-hexane as follows. The sample was diluted in cyclohexane (concentration
as extracting solvent) was diluted in tert-butyl methyl ether of around 8 mg/mL). The GC (Perkin Elmer Autosystem XL) was
(TBME) (concentration of around 20 mg/mL). A 100 lL aliquot of equipped with a flame ionization detector using helium as carrier
the prepared sample was then converted to methyl esters using gas, and the injected sample was separated in a VF-5 ms (VARIAN)
50 lL of 0.5 mol/L trimethylsulphonium hydroxide (TMSH) in column (15 m 0.32 mm). GC oven temperature was programmed
methanol. The GC (VARIAN 3800) was equipped with a flame ion- from 55 °C to 360 °C at a rate of 45 °C min1 to 80 °C, followed by
ization detector using helium as carrier gas (1.2 mL/min). The sam- 10 °C min1, and was then maintained at 360 °C for 15 min. Injec-
ple injected (i.e. methyl esters) was separated in a CP Select CB tor temperature was programmed from 55 °C to 340 °C at a rate of
(VARIAN) column (50 m 0.25 mm). GC oven temperature was 200 °C min1 and then maintained at 340 °C for 35 min, and detec-
programmed at 185 °C for 40 min, then increased at a rate of tor temperature was set at 365 °C. Methyl heptadecanoate was
15 °C min1 to 250 °C, and then maintained at 250 °C for used as the internal standard. The peaks of different methyl esters
11.68 min. Injector temperature was programmed at 250 °C for were identified by comparing the retention time of each compo-
55 min, and detector temperature set at 250 °C. nent in the sample with the peaks of pure methyl ester standard
The glyceride fraction content in jatropha oil and its composi- compounds.
tion (i.e. distribution between triglycerides, diglycerides, monogly- The biodiesel produced under the optimal reaction conditions
cerides, and free fatty acids) was also determined by GC using the was completely characterized in accordance with Indonesian Bio-
following method. 1.5 mg of the sample analyzed (i.e. the oil ex- diesel Standard [39]. All determinations were carried out in
tracted from jatropha seed using the Soxhlet extraction apparatus duplicate.
and n-hexane as extracting solvent) was diluted in 1 mL of
chloroform. 20 lL of silylation reagent (a mixture of 1 mL of N-
methyl-N-trimethylsilyl-heptafluorobutyramide (MSHFBA) and 3. Results and discussion
50 lL of 1-methyl imidazole) was added to a 180 lL aliquot of
the prepared sample, and then heated at 103 °C for 3 min. The In transesterification reactions with alkaline catalysts, the pres-
GC (Perkin Elmer) was equipped with a flame ionization detector ence of water can cause ester saponification. Thus jatropha seeds
using helium as carrier gas, and the injected sample was separated with less than 1% moisture content were used in all experiments.
in a CP Sil 8CB (VARIAN) column (15 m 0.32 mm). GC oven tem- Moreover, results from previous studies showed that this seed
114 I. Amalia Kartika et al. / Fuel 106 (2013) 111–117

moisture content affected biodiesel yield [24,30,40], and that the

latter increased as moisture content of jatropha seed was de-
creased [40]. In addition, this decrease in seed moisture content in-
creased the amount of oil dissolved in methanol [30].
The oil content of the jatropha seed used in this study was
39.4 ± 1.5% relative to its dry matter content (standard NF V 03-
908), and this agrees with the 22–48% results reported by some
researchers [4,41]. The fatty acid composition of jatropha oil (FAME
method) was palmitic (14.7 ± 0.2%), palmitoleic (0.9 ± 0.0%), stearic
(7.4 ± 0.3%), oleic (39.4 ± 0.8%), linoleic (36.5 ± 0.9%), linolenic
(0.7 ± 0.0%), arachidic (0.2 ± 0.0%), and gadoleic (0.2 ± 0.0%). Thus,
the oil in this study was rich in oleic and linoleic fatty acids, like
other jatropha oils described in the literature [1–5,41,42]. Its glyc-
eride fraction content, i.e. the content of triglycerides, diglycerides, Fig. 1. Influence of methanol to seed ratio and amount of alkali (KOH) catalyst on
monoglycerides and free fatty acids in the oil, was 99.0 ± 0.5%, biodiesel yield (700 rpm stirring speed, 60 °C temperature, and 4 h reaction time).
meaning that the unsaponifiable compounds such as sterols and
tocopherols were minor compounds. It was composed of triglycer-
ides (95.8 ± 0.2%), diglycerides (2.6 ± 0.1%) and monoglycerides to seed ratio was at least 4:1. Thus, a methanol to seed ratio of only
(0.3 ± 0.0%), and it contained 1.4 ± 0.1% of free fatty acids. These 2:1 was not sufficient for complete transesterification of the tri-
are carboxylic acids released from triglycerides via lipase or oxida- glycerides released from jatropha seed. However, when the
tion. There is a high risk of oxidation of the jatropha oil inside the amount of KOH exceeded 0.075 mol/L in methanol, it had less ef-
seed due to its high unsaturated fatty acid content, especially oleic fect on the biodiesel yield, with only a slight increase when the
and linoleic, and those containing one or more of the non-conju- methanol to seed ratio was 4:1 (from 62% to 68%). For a methanol
gated pentadiene system (ACH@CHACH2ACH@CHA) are espe- to seed ratio of 6:1, increasing the amount of KOH from 0.075 to
cially sensitive [43]. In alkaline transesterification, the free fatty 0.1 mol/L in methanol even caused a drop in yield (from 80% to
acids quickly react with the catalyst to produce soaps that are dif- 74%). Thus, 0.075 mol/L KOH in methanol is the optimal concentra-
ficult to separate, and this may reduce the quantity of catalyst tion of alkali catalyst. Excess catalyst gave rise to formation of an
available for transesterification, lowering the ester production emulsion that increased the viscosity and led to the formation of
yield. Soaps produced could cause an increase in viscosity, and a gel, lowering the ester production yield [48].
the appearance of gels, and also make the separation of glycerol For the reaction conditions investigated (2:1–6:1 methanol to
difficult [30]. Low free fatty acid content in the oil (less than 3%) seed ratio, and 0.05–0.1 mol/L KOH in methanol), the best biodiesel
is therefore required for alkali-catalyzed transesterification [44]. yield (80% with a fatty acid methyl ester purity of 99.9%) was
An attractive way to control free fatty acids in the seed is by con- therefore obtained with a methanol to seed ratio of 6:1 (expressed
trolling its water activity (aw) to a level that disables any undesir- in mL/g) and 0.075 mol/L KOH in methanol. For comparison, the
able reactions or enzyme activities. This means understanding seed optimal molar ratio for conventional alkaline transesterification
characteristics and behavior in response to changes in environ- of different oils is of the order of 6:1 (expressed in mol/mol) at
mental conditions, particularly relative humidity, which has been 60 °C [4,22,23,42,48,49]. Thus, the in situ transesterification of
successfully applied to jatropha seed [45]. Thus, control of free jatropha oil from seed used about 17 times more methanol (lipid
fatty acids in the seed, can be achieved by proper handling and to methanol ratio of 1:104, expressed in mol/mol) than the conven-
storage before oil extraction and in situ transesterification. tional method (1:6). However, the excess reagents could be recov-
Simultaneous solvent extraction and in situ transesterification ered for reuse.
on biodiesel processing of jatropha seeds had a positive effect on Compared with acid-catalyzed in situ transesterification of
both biodiesel yield and biodiesel quality. The main advantage of jatropha oil from seed (over 12 h reaction time and 15 wt.%
this combined process is that it allows solvent extraction to be ap- H2SO4) [31], the alkali-catalyzed process is faster and uses less re-
plied to oilseeds and then in situ transesterification of the ex- agents (4 h reaction time and 6.4 wt.% KOH). For 4 h reaction time,
tracted oils. Methanol was not a very effective solvent for oil the yield obtained from acid-catalyzed in situ transesterification of
extraction due to its immiscibility. However, the addition of a co- jatropha oil from seed was only 40% [31] instead of 80% with the
solvent such as n-hexane into the reaction mixture can signifi- alkali-catalysed process described in this study. The greater yield
cantly improve mass transfer of oil into alcohol (methanol or eth- with alkaline catalysis is consistent with its greater effectiveness
anol) and also intensify the transesterification reaction between oil in transesterification of triglycerides, and may also indicate better
and alcohol [31,32,46,47]. n-Hexane is an efficient solvent for oil access of the transesterification reagent to the oil component of
extraction from oilseeds and, in the case of jatropha seed, its the seed, under alkaline conditions [25]. As observed in previous
non-polarity can also limit the removal of free fatty acids and studies [25,30], alkaline alcohol could destroy intracellular com-
water from the seed [47]. In this study, the ratio of n-hexane added partments in oilseeds, allowing solubilisation and subsequent
to seed was 1:1 (volume/weight, expressed in mL/g) for all transesterification of triglycerides. In the present study, maximum
experiments. ester yield (80% with a fatty acid methyl ester purity of 99.9%) was
As previously observed by some researchers [25,29,30,47], Fig. 1 achieved with a reaction time of 4 h and 6.4 wt.% KOH (compared
shows that the methanol to seed ratio and the amount of alkali to the oil contained in the jatropha seed) or 0.075 mol/L in metha-
(KOH) catalyst affected the biodiesel yield. For the three levels of nol. For comparison, the amount of catalyst (KOH) required for the
KOH tested, a systematic increase in biodiesel yield was observed conventional alkaline transesterification of different vegetable oils
when the methanol to seed ratio increased from 2:1 to 6:1. In addi- is 1% (based on oil weight) [48]. Thus, the in situ transesterification
tion, for a methanol to seed ratio of 2:1, the biodiesel yield re- of jatropha oil from seed used about 6.4 times more KOH than the
mained relatively stable (between 35% and 38%), meaning that it conventional method.
did not depend on the amount of KOH in the methanol. Conversely, The biodiesel produced by in situ transesterification of jatropha
increasing the amount of KOH from 0.05 to 0.075 mol/L in metha- oil from seed was of excellent quality using a methanol to seed ra-
nol significantly increased the biodiesel yield when the methanol tio of 6:1 (Table 1). And, for this ratio, an increase in the amount of
I. Amalia Kartika et al. / Fuel 106 (2013) 111–117 115

Table 1
Crude biodiesel quality at different methanol to seed ratios and amounts of alkali (KOH) catalyst (700 rpm stirring speed, 60 °C temperature, and 4 h reaction time).

Methanol to seed Amount of KOH (mol/L Acid value (mg Saponification value Viscosity at 40 °C Composition (wt.%)
ratio (v/w) in methanol) KOH/g) (mg KOH/g) (106 m2/s)
FAME MAG DAG TAG FA
2:1 0.05 1.48 ± 0.00 212 ± 4 24.1 ± 0.0 3.0 ± 0.1 0.2 ± 0.0 4.1 ± 0.1 91.7 ± 0.1 1.0 ± 0.1
2:1 0.075 1.48 ± 0.00 195 ± 1 21.9 ± 3.5 3.5 ± 1.5 0.1 ± 0.0 2.9 ± 0.2 91.9 ± 1.6 1.6 ± 0.3
2:1 0.1 0.81 ± 0.00 193 ± 1 21.9 ± 1.8 8.3 ± 0.8 0.1 ± 0.0 2.5 ± 0.1 88.3 ± 1.0 0.8 ± 0.0
4:1 0.05 0.27 ± 0.00 207 ± 4 21.5 ± 1.2 10.6 ± 1.0 0.3 ± 0.1 2.9 ± 0.1 85.4 ± 1.0 0.8 ± 0.0
4:1 0.075 0.27 ± 0.00 215 ± 1 8.1 ± 0.9 56.2 ± 3.5 0.2 ± 0.1 2.0 ± 0.0 40.9 ± 7.1 0.7 ± 0.1
4:1 0.1 0.27 ± 0.00 209 ± 0 3.7 ± 0.0 91.2 ± 0.8 0.1 ± 0.0 0.3 ± 0.1 8.1 ± 1.3 0.3 ± 0.1
6:1 0.05 0.27 ± 0.00 215 ± 2 3.5 ± 0.0 99.6 ± 0.1 0.1 ± 0.0 0.0 ± 0.0 0.0 ± 0.0 0.3 ± 0.1
6:1 0.075 0.27 ± 0.00 212 ± 1 3.4 ± 0.1 99.9 ± 0.1 0.0 ± 0.0 0.0 ± 0.0 0.0 ± 0.0 0.1 ± 0.0
6:1 0.1 0.27 ± 0.00 193 ± 1 3.5 ± 0.1 99.7 ± 0.5 0.0 ± 0.0 0.0 ± 0.0 0.0 ± 0.0 0.2 ± 0.1

FAME, fatty acid methyl esters; MAG, monoglycerides; DAG, diglycerides; TAG, triglycerides; FA, free fatty acids.

Table 2
Effect of operating conditions on process performance and crude biodiesel quality (6:1 methanol to seed ratio and 0.075 mol/L KOH in methanol).

Stirring Temperature Reaction Crude Acid value Saponification Viscosity at 40 °C Cake meal
speed (rpm) (°C) time (h) yield (mg KOH/g) value (mg KOH/g) (106 m2/s)
Total volatile n-Hexane extracted
(wt.%)
matter content (%) matter content (%)
700 40 3 81 ± 1 0.49 ± 0.10 198 ± 2 3.6 ± 0.0 10.2 ± 0.6 14.6 ± 2.8
800 40 3 82 ± 3 0.42 ± 0.10 190 ± 6 3.5 ± 0.0 9.8 ± 0.9 13.5 ± 0.5
900 40 3 83 ± 1 0.49 ± 0.10 201 ± 1 3.5 ± 0.0 11.3 ± 1.1 14.8 ± 0.5
700 50 3 83 ± 1 0.35 ± 0.10 197 ± 5 3.5 ± 0.0 10.7 ± 0.3 13.0 ± 0.7
800 50 3 81 ± 0 0.28 ± 0.00 200 ± 0 3.5 ± 0.0 11.3 ± 0.7 11.9 ± 1.4
900 50 3 82 ± 2 0.42 ± 0.00 200 ± 4 3.5 ± 0.0 10.0 ± 0.3 14.5 ± 2.1
700 60 3 77 ± 0 0.35 ± 0.10 205 ± 3 3.5 ± 0.1 9.8 ± 0.6 14.7 ± 1.7
800 60 3 83 ± 3 0.28 ± 0.00 199 ± 1 3.5 ± 0.0 11.1 ± 0.2 15.2 ± 3.0
900 60 3 85 ± 1 0.28 ± 0.00 200 ± 5 3.5 ± 0.0 10.1 ± 0.7 14.3 ± 1.7
700 40 4 79 ± 2 0.28 ± 0.00 197 ± 2 3.5 ± 0.0 11.2 ± 1.8 15.4 ± 0.3
800 40 4 76 ± 3 0.28 ± 0.00 203 ± 2 3.5 ± 0.0 10.4 ± 0.8 14.0 ± 0.9
900 40 4 83 ± 2 0.42 ± 0.00 201 ± 1 3.5 ± 0.0 10.9 ± 0.6 15.0 ± 0.5
700 50 4 86 ± 2 0.42 ± 0.00 194 ± 0 3.5 ± 0.0 11.8 ± 0.4 15.8 ± 2.4
800 50 4 83 ± 0 0.35 ± 0.10 194 ± 0 3.5 ± 0.0 11.5 ± 0.4 14.9 ± 0.0
900 50 4 84 ± 1 0.49 ± 0.10 202 ± 5 3.5 ± 0.0 9.7 ± 1.4 11.5 ± 2.0
700 60 4 76 ± 1 0.28 ± 0.00 200 ± 4 3.5 ± 0.0 10.6 ± 0.7 14.1 ± 0.9
800 60 4 85 ± 2 0.42 ± 0.00 196 ± 3 3.5 ± 0.0 10.7 ± 0.8 14.7 ± 0.0
900 60 4 75 ± 3 0.35 ± 0.10 200 ± 0 3.5 ± 0.1 9.1 ± 0.2 12.2 ± 2.9
700 40 5 84 ± 3 0.42 ± 0.00 196 ± 2 3.5 ± 0.0 10.0 ± 0.3 15.6 ± 0.8
800 40 5 83 ± 2 0.42 ± 0.00 198 ± 3 3.5 ± 0.0 10.6 ± 0.7 12.4 ± 0.1
900 40 5 84 ± 1 0.28 ± 0.00 201 ± 1 3.5 ± 0.1 11.9 ± 2.5 13.8 ± 1.2
700 50 5 85 ± 1 0.42 ± 0.00 200 ± 2 3.5 ± 0.0 10.0 ± 0.4 12.5 ± 1.3
800 50 5 87 ± 1 0.35 ± 0.10 199 ± 4 3.5 ± 0.0 10.5 ± 0.3 13.9 ± 1.8
900 50 5 85 ± 0 0.28 ± 0.00 198 ± 1 3.5 ± 0.0 9.4 ± 0.2 12.8 ± 1.4
700 60 5 80 ± 2 0.28 ± 0.00 206 ± 1 3.5 ± 0.0 10.8 ± 0.3 14.9 ± 0.8
800 60 5 76 ± 1 0.28 ± 0.00 203 ± 4 3.5 ± 0.1 10.2 ± 0.3 13.4 ± 3.3
900 60 5 76 ± 0 0.28 ± 0.00 200 ± 1 3.5 ± 0.0 10.5 ± 0.1 13.7 ± 0.8

KOH (from 0.05 to 0.1 mol/L in methanol) had no significant influ- proved the biodiesel quality. Acid value and viscosity decreased,
ence on the biodiesel quality which remained excellent. The acid and fatty acid methyl ester purity increased with an increase in
value and the viscosity remained stable at less than 0.3 mg of methanol to seed ratio and amount of KOH in methanol. The
KOH/g of biodiesel and less than 3.5 106 m2/s, respectively. saponification value remained stable at over 190 mg of KOH/g of
Saponification value and fatty acid methyl ester purity were high biodiesel with increasing methanol to seed ratio and amount of
(more than 190 mg of KOH/g of biodiesel and more than 99.6%, KOH in methanol.
respectively). These qualities would favor the use of such biodiesel The influence of stirring speed, temperature and reaction time
as automotive fuel. The quality of the biodiesel obtained in this on biodiesel yield was studied using randomized factorial experi-
study was equivalent to that of one produced using the conven- mental design with three variables. For this study, methanol to
tional method, and it conformed to the Indonesian Biodiesel Stan- seed ratio was 6:1, and KOH amount was 0.075 mol/L in methanol.
dard [39]. Moreover, the biodiesel quality was directly correlated The results obtained are shown in Table 2 and generally, stirring
to its yield. Indeed, best biodiesel quality was achieved with a speed, temperature and reaction time affected biodiesel yield.
methanol to seed ratio of 6:1 (Table 1) that also gave the best bio- But here, applying ANOVA to actual data (F-test at p = 0.05) shows
diesel yield (Fig. 1). that the effect of temperature on biodiesel yield was more signifi-
The quality of biodiesels produced by in situ transesterification cant than the two others. Five of the seven best yields corre-
of jatropha oil from seed with a methanol to seed ratio of less than sponded to experiments conducted at 50 °C, with different
6:1 (Table 1) was relatively poor. Acid value and viscosity were stirring speeds (700–900 rpm) and different reaction times
high, whereas fatty acid methyl ester purity was low. Increasing (4–5 h). Temperature can influence reaction rate and jatropha oil
the methanol to seed ratio and the amount of KOH in methanol im- conversion, because intrinsic rate constants are largely dependent
116 I. Amalia Kartika et al. / Fuel 106 (2013) 111–117

Table 3
Jatropha crude biodiesel quality produced under optimal reaction conditions (6:1 methanol to seed ratio, 0.075 mol/L KOH in methanol, 800 rpm stirring speed, 50 °C
temperature, and 5 h reaction time).

Parameter Unit Jatropha biodiesel Biodiesel standard [39]

Density at 40 °C g/cm3 0.885 0.850–0.890
Viscosity at 40 °C 106 m2/s 3.5 2.3–6.0
Flash point °C 107 100 min
Pour point °C 0 0 max [60]
Cloud point °C 11 18 max
Acid value mg KOH/g 0.35 0.8 max
Cetane number – 47 51 min
Water and sediment content wt.% Trace (<0.05) 0.05 max
Sulfated ash content wt.% 0 0.02 max
Iodine number g iodine/100 g 107 115 max
HHV MJ/kg 40 35 min [60]
Composition: wt.%
Fatty acid methyl esters 99.7 96.5 min [60]
Monoglyceride (MAG) 0.1 0.8 max [60]
Diglyceride (DAG) 0 0.2 max [60]
Triglyceride (TAG) 0 0.2 max [60]

on temperature [47]. A higher temperature can decrease the tively constant as the stirring speed increased from 700 to
viscosities of oils, can increase the solubility of reactants, and can 900 rpm, meaning that the lowest stirring speed of 700 rpm was
result in an increased reaction rate and a shorter reaction time sufficient to efficiently mix up the reactants before the establish-
[23]. In addition, high temperatures favor reactions with higher ment of the single phase.
activation energy, and low temperatures those with lower activa- For all the reaction conditions tested, the biodiesel quality was
tion energy [50]. However, in this study, results indicated that satisfactory (Table 2). The acid value and the viscosity remained
when reaction temperature was increased from 50 to 60 °C, biodie- stable at less than 0.5 mg of KOH/g of biodiesel and less than 3.6
sel yield mostly decreased (from 86% to 76% with 700 rpm stirring 106 m2/s, respectively. The saponification value was high (more
speed and 4 h reaction time, and from 87% to 76% with 800 rpm than 190 mg of KOH/g of biodiesel), and these qualities favor its
stirring speed and 5 h reaction time, for example). Indeed, with a use as automotive diesel, and conform to the Indonesian Biodiesel
reaction temperature close to the boiling points of methanol and Standard [39].
n-hexane, the methanol and n-hexane would partially vaporize ANOVA applied to actual acid and saponification values (F-test
and form some bubbles, which would restrain the reaction. This at p = 0.05) shows that temperature significantly affected them,
phenomenon was already observed during preparation of biodiesel while stirring speed and reaction time had no significant effect.
from J. curcas oil produced by two-phase solvent extraction [47]. A The same tendency was previously observed for biodiesel yield,
reaction temperature of 50 °C for in situ transesterification of jatro- meaning that reaction conditions had exactly the same effect on
pha oil from seed led to the best biodiesel yields, and the highest both biodiesel yield and biodiesel quality.
one (87% with a fatty acid methyl ester purity of 99.7%) was ob- ANOVA applied to actual viscosity data (F-test at p = 0.05)
tained with 800 rpm stirring speed, 50 °C temperature, and 5 h shows that stirring speed, temperature and reaction time did not
reaction time. significantly affect viscosity. Biodiesel viscosity remained rela-
Generally, reaction time is an important factor that affects alka- tively constant when stirring speed, temperature and reaction time
li-catalyzed in situ transesterification, and triglyceride conversion increased.
increases at longer reaction time [23,25,29,30,47]. Nevertheless, The residual oil and fatty acid methyl ester contents in the cake
within the 3–5 h reaction time investigated in this study, increas- meal were high (more than 11%, cf. Table 2). Although this quality
ing this parameter did not systematically increase the biodiesel was a disadvantage for direct utilization of the cake meal, it can be
yield, as previously reported by Ozgul-Yucel and Turkay [51]. In- converted into usable energy by combustion, gasification or pyro-
stead, biodiesel yield remained relatively constant as the reaction lysis [52,53], or transformed into agromaterials [54–59].
time increased from 3 to 5 h, meaning that the equilibrium compo- The analysis of the biodiesel produced by solvent extraction and
sition had already been achieved by the system after only 3 h. Nor- in situ transesterification of jatropha oil from seed under optimal
mally, biodiesel yield reaches a maximum as reaction time reaction conditions (6:1 methanol to seed ratio, 0.075 mol/L KOH
increases (e.g. at a value less than 90 min for transesterification in methanol, 800 rpm stirring speed, 50 °C temperature, and 5 h
of isolated and refined vegetable oils), and then remains relatively reaction time) indicated that the product met the standard specifi-
constant with any further increase [23]. Moreover, a reaction time cation for biodiesel fuel in most regards (Table 3). Even if its cetane
that is too long will lead to a reduction in the biodiesel yield, due to number (47) did not meet the Indonesian Biodiesel Standard spec-
reverse transesterification reactions. A previous study [29] has ification (51 min) [39], it met the specification of ASTM D 6751
shown that the alkali-catalyzed in situ transesterification reaction (47 min) [60].
from sunflower seeds is extremely fast, requiring only 20 min for
complete conversion.
In transesterification reactions, reactants initially form a two 4. Conclusion
phase liquid system [50]. The reaction is diffusion-controlled, and
poor diffusion between the two phases results in a slower rate. This study showed that a new application for simultaneous sol-
As methyl esters are formed, they act as a co-solvent for the reac- vent extraction and in situ transesterification of jatropha oil from
tants and a single phase system is formed. When the single phase is seeds has been successfully carried out, and was a promising alter-
established, the mixing effect is insignificant and reaction rate is native technology for biodiesel processing from jatropha seeds.
primarily influenced by reaction temperature. In this study, stirring Biodiesel yield was 87% under the optimal reaction conditions with
speed did not affect the biodiesel yield, and this remained rela- a FAME purity of 99.7%. Most of the quality of biodiesel produced
I. Amalia Kartika et al. / Fuel 106 (2013) 111–117 117

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