Characteristics and Composition of Jatropha Gossypiifolia and Jatropha Curcas L. Oils and Application For Biodiesel Production

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biomass and bioenergy 33 (2009) 449453

Available at www.sciencedirect.com

http://www.elsevier.com/locate/biombioe

Characteristics and composition of Jatropha gossypiifolia


and Jatropha curcas L. oils and application for biodiesel
production
Jefferson S. de Oliveiraa, Polyanna M. Leitea, Lincoln B. de Souzaa, Vincius M. Melloa,
Eid C. Silvab, Joel C. Rubima, Simoni M.P. Meneghettib, Paulo A.Z. Suareza,*
a

Laboratorio de Materiais e Combustveis, Instituto de Qumica, Universidade de Braslia, C.P. 4478, 70919-970 Braslia, DF, Brazil
Instituto de Qumica e Biotecnologia, Universidade Federal de Alagoas, Av. Lourival de Melo Mota, s/n, Cidade Universitaria,
57072-970 Maceio-AL, Brazil

article info

abstract

Article history:

In this work two genus of the Jatropha family: the Jatropha gossypiifolia (JG) and Jatropha

Received 10 May 2007

curcas L. (JC) were studied in order to delimitate their potential as raw material for biodiesel

Received in revised form

production. The oil content in wild seeds and some physicalchemical properties of the oils

23 August 2008

and the biodiesel obtained from them were evaluated. The studied physicalchemical

Accepted 29 August 2008

properties of the JC and JG biodiesel are in acceptable range for use as biodiesel in diesel

Published online 19 October 2008

engines, showing a promising economic exploitation of these raw materials in semi-arid


regions. However, further agronomic studies are needed in order to improve the seed

Keywords:

production and the crude oil properties.


2008 Elsevier Ltd. All rights reserved.

Biodiesel
Jatropha gossypiifolia
Jatropha curcas L.
Transesterification
Methanol

1.

Introduction

Brazilian Government has started an ambitious program to


introduce biodiesel in the internal market [1,2]. Different from
other countries, the Brazilian policy is based on regional
production of biodiesel, using the more appropriate technology and raw material for each region. For instance, in the
semi-arid northeast states castor seed oil was the alternative
of choice, since this culture appears to be excellent adaptable
to the semi-arid lands and suitable to promote a sustainable
agriculture in the poorest Brazilians region, where underdevelopment is critical. For this reason, 100% of reduction on
the federal tributes is given in the case of the use of castor

seeds (Ricinus sp.) produced in the semi-arid northeast by


familiar agriculture [1].
However, castor oil, obtained from Ricinus communis seeds,
is composed almost entirely (ca. 90%) of triglycerides containing the unusual fatty acid ricinoleic acid (12-hydroxy-cisoctadec-9-enoic acid) [3]. Due to the hydroxyl group at C12,
castor oil possesses several unique chemical and physical
properties that are exploited in various industrial applications
including the production of coatings, plastics and cosmetics
[4]. Thus, castor oil and its derivatives, such as methyl or ethyl
ricinoleic esters, are completely soluble in alcohols and
present viscosities and densities several times higher than
those of other vegetable oils and their derivatives, which will

* Corresponding author. Tel.: 55 61 33072162; fax: 55 61 32734149.


E-mail address: psuarez@unb.br (P.A.Z. Suarez).
0961-9534/$ see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biombioe.2008.08.006

450

biomass and bioenergy 33 (2009) 449453

certainly limit the use of biodiesel/diesel blends with high


content in the biofuel because they will not attend the Brazilian, US or European specifications [58]. Besides, the presence of the hydroxyl group leads also to several technological
problems during the transesterification, such as (i) using
alkaline catalysis, the hydroxyl group at C12 of ricinoleic acid
can be converted into an alkoxide derivative, which is inactive
as catalysts but compromises the generation of active methoxide or ethoxide species, and, thus, compromising the
conversion reaction; (ii) the compatibility of the ricinoleic acid
derivatives with alcohols leads, at the end of the reaction, to
stable emulsions and/or solutions, making difficult the separation of biodiesel from the reaction mixture [5,6].
It becomes clear from the technological problems previously
discussed that the use of castor oil as raw material is limited.
Thus, the investigation of other sources of triacylglycerides
from species adapted for semi-arid lands of Brazil or other
countries would make possible to produce biodiesel with
competitive prices, allowing the sustainable production of biofuels in these areas using local raw materials [9].
From the family Euphorbiaceae, sub-family Platilobeae, the
genus Jatropha possesses more than 70 shrub species, such as
Jatropha pohliana, Jatropha gossypiifolia and Jatropha curcas,
which produce seeds with high oil contents [10]. Although
these species are native from the south-American tropics,
especially Brazil, they are commonly found and utilized
throughout most of the tropical and subtropical regions of the
world [11]. Several properties of the plant, including its hardness, rapid growth, easy propagation and wide ranging
usefulness have resulted in its spread far beyond its original
distribution [11]. Thus, it is reasonable to think that these
species could be highlighted as potential vegetable cultures to
produce oil to feed biodiesel and other industrial uses.
Several authors have studied J. curcas oil and the biodiesel
obtained after this oil and some papers are available in the
literature [1217]. It is worth to mention that some countries
have already proposed the use of this raw material in their
biodiesel programs [18,19]. In this work it is evaluated the
potential of other genus from the Jatropha family, the J. gossypiifolia (JG), being evaluated the oil content in wild seeds and
some physicalchemical properties of the oils and the biodiesel obtained from them. For comparison reasons, it was
also studied wild seeds of J. curcas (J.C.) from Brazil, being
established a comparison between the two Jatropha genus.

2.

Materials and methods

2.1.

Materials

Analytical grade n-hexane, H3PO4, H2SO4, KOH, NaCl, MgSO4,


NaHCO3 and methanol were obtained from commercial
source (VETEC) and used as received.

2.2.

Oil extraction

The seeds of J. gossypiifolia and J. curcas L. were collected from


wild species, respectively, in the north-eastern (Sao Miguel
dos Campos, Alagoas) and central-west of Brazil (Luziania,
Goias). The seeds were dried in a stove at 70  C for 12 h, milled

and dried for other 12 h. Thus, the oil was extracted using
n-hexane in a Soxhlet apparatus. The resulting micelle was
dried over MgSO4, filtered and finally the solvent was removed
under vacuum until the weight was constant.

2.3.

Biodiesel preparation

The J. curcas L. methyl esters were synthesized in a glass batch


reactor equipped with mechanic stirrer. Potassium hydroxide
was completely dissolved in CH3OH under stirring. Then, the
vegetable oil was added into the reactor under stirring at
5000 rpm. The mixture was maintained under the stirring
condition for 2 h at room temperature (23  1  C). After 2 h of
reaction completion the mixture was allowed to stand and the
two phases (the unreacted oil plus methyl ester and glycerin)
were separated. The excess of methanol in the methyl ester
phase was removed by rotary evaporator (Buchi, Rotavapor
RE120, 70  C). Then the methyl ester was washed with phosphoric acid (5% v/v) and 3 times with brine. The reaction was
repeated 3 times until purity of more than 99 mass% in methyl
esters was detected by high performance liquid chromatography (HPLC), using the method described in Section 2.4. It is
worth mentioning that for the consecutive reactions a similar
procedure was followed, using the reaction product instead of
vegetable oil as reagent and the same amounts of methanol
and KOH. The reaction yield was finally determined by
comparing the initial oil mass and the recovered biodiesel
with more than 99 mass% purity. The methyl esters were
finally stored in amber flasks in a refrigerator at 6  C.
The J. gossypiifolia methyl esters were synthesized in a glass
batch reactor equipped with mechanic stirrer in two steps. At
first, the vegetable oil, methanol and sulfuric acid were kept
under gentle reflux for 2 h. Then, the reaction mixture was
washed 3 times with 5% (w/v) sodium bicarbonate solution.
Thus, the biodiesel/oil phase was dissolved in hexane, kept
over magnesium sulphate for 2 h, filtered and, finally, the
volatiles were removed under vacuum. In the second step, the
biodiesel/oil phase obtained after step one was mixed with
a solution of potassium hydroxide in CH3OH, and the mixture
was maintained under the stirring condition for 2 h at room
temperature (23  1  C). After 2 h of reaction completion the
mixture was allowed to stand and the two phases were separated. The excess of methanol in the methyl ester phase was
removed by rotary evaporator (Buchi, Rotavapor RE120, 70  C).
Then the methyl ester was washed with phosphoric acid (5% v/v)
and 3 times with brine. The second step was repeated 3 times
until purity of more than 99 mass% in methyl esters was
detected by HPLC, using the method described in Section 2.4. It
is worth mentioning that for the consecutive reactions
a similar procedure was followed, using the reaction product
instead of vegetable oil as reagent and the same amounts of
methanol and KOH. The reaction yield was finally determined
by comparing the initial oil mass and the recovered biodiesel
with more than 99 mass% purity. The methyl esters were
finally stored in amber flasks in a refrigerator at 6  C.

2.4.

Oil and biodiesel characterization

The extracted seed meals were thoroughly air dried to remove


traces of solvent. The extracted seed oils were analysed for

451

biomass and bioenergy 33 (2009) 449453

some physicochemical properties (iodine value, saponification value, acid value, refractive index, specific gravity,
hydroxyl value, acetyl value, viscosity) by methods described
by the Association of Official Analytical Chemists (AOAC,
reapproved 1997). The calorific value was evaluated in a calorimeter bomb Parr 1241 using oxygen at a pressure of 3.0 Mega
Pascal (MPa), as according to the standard method of the
American Society for Testing and Materials (ASTM) D240.
Fatty acid composition of the oils was determined by high
performance liquid chromatography (HPLC) on a Shimadzu
CTO-20A chromatograph with UVvis detector at l 205 nm,
equipped with Shim-Pack VP-ODS column (C18, 250 mm,
4.6 mm i.d.). The solvents were filtered through a 0.45-mm
Millipore filter prior use. The injection volumes of 10 mL and
the flow-rate of 1 mL/min were used in all experiments. The
column temperature was held constant at 40  C. All samples
were dissolved in 2-propanol-hexane (5:4, v/v). A 35-min
ternary gradient with two linear gradient steps was employed:
30% water and 70% acetonitrile in 0 min, 100% acetonitrile in
10 min, 50% acetonitrile and 50% 2-propanol-hexane (4:5 v:v)
in 20 min, followed by isocratic elution with 50% acetonitrile
and 50% 2-propanol-hexane (4:5 v:v) for the last 15 min.

3.

Table 2 Fatty acid composition (%) of the Jatropha curcas


L. (JC) and Jatropha gossypiifolia (JG) oils.
Fatty acid
Lauric (C12:0)
Miristic (C14:0)
Palmitic (C16:0)
Stearic (C18:0)
Oleic (C18:1)
Linoleic (C18:2)
Others

Jatropha
gossypiifolia (JG)

Jatropha
curcas L. (JC)

9.8
4.3
26.8
10.4
22.4
19.2
7.1

5.9
2.7
13.5
6.1
21.8
47.4
2.7

composition of JC determined in this work (Table 2) and those


published elsewhere presented variations in fatty acid contents,
probably due to variations in the farmer conditions, such as
wheatear, soil and seed variety. The JG and JC oils exhibit
conventional fatty acid composition (absence of functional
groups in the alkyl chain, alkyl chain length between C12 and
C18, and unsaturation degree from 40% to 70%), comparable
with those reported for some conventional oilseeds like soybean
and palm-tree oils [20]. The studied physicalchemical
properties of JG and JC showed in Table 1 are in the range
expected for oils showing these conventional compositions.

Results and discussion


3.2.
Transesterification of J. curcas L. (JC) and
J. gossiypiifolia (JG) oils

3.1.
Characteristics of J. curcas L. (JC) and
J. gossypiifolia (JG) oils
The J. curcas L. (JC) and J. gossypiifolia (JG) seeds oil contents and
physicalchemical properties of the oils are summarized in
Table 1. As can be seen, the oil content of JC (32 mass%) and JG
(24 mass%) are higher than those usually reported for soybean,
cottonseed and other commercial oil sources, implying that
processing the seeds to obtain oil would be economic. High acid
value was observed for both JC (8.45 mg KOH/g) and JG (17.34 mg
KOH/g), which can be related with the wild origin (different
maturation degrees) and seeds store conditions. It is important
to highlight that the oil content and acid value can be improved
by plant breeding and developing a proper farm system.
The fatty acid composition of JG and JC are presented in
Table 2. As far as our knowledge, there are some reports in the
literature for JC [12,18] and no references for JG vegetable oil. The

Table 1 Jatropha curcas L. (JC) and Jatropha gossiypiifolia


(JG) seeds oil contents and properties of the oils.
Jatropha
Jatropha
gossypiifolia (JG) curcas L. (JC)
Oil content (w/w %)
23.9
Calorific value (MJ/kg)
39.88
Acid value (mg KOH/g)
17.32
Water content (w/w %)
0.089
Ash content (w/w %)
Not detected
0.9236
Density at 15  C (g/cm3)
24.529
Kinematic viscosity at 40  C (cSt)
Conradson carbon
0.2541
residue (w/w %)
Pour point ( C)
8
Copper strip corrosion
1a

31.6
40.31
8.45
0.052
Not detected
0.9215
30.686
0.5396
2
1a

It is well established in the literature that transesterification of


triglycerides can be conducted using basic or acid catalysts. It
is also well established that basic catalysts are widely
preferred because of their lower corrosivity and higher efficiency [21]. However, when triglycerides containing high
amounts of free fatty acid are used, consumption of the
alkaline catalyst occurs, leading to soap formations and, thus,
generating emulsions. Thus, in the case of soap and emulsion,
the final purification step of the process is compromised and
lower reaction yield is achieved [2124].
As already discussed in Section 3.1, vegetable oils from
both species presented high acid value (JG: 17.32 mg KOH/g
and JC: 8.45 mg KOH/g). In a first attempt to produce biodiesel
from JG and JC, sodium hydroxide was employed. In the case
of JC, three following reactions were needed to obtain biodiesel with more than 99% of fatty acid methyl esters. In this
case, the final reaction yield achieved was 68%. It is important
to highlight that in all steps of this process occurred the
formation of stable emulsions, making difficult to recover the
biodiesel. To break this emulsions and recover biodiesel,
several washings with acid solutions and brine were needed,
which is the possible reason for the mild reaction yield and
high acid value in the final product (5.04 mg KOH/g).
On the other hand, because of its higher acid value, it was
impossible to use the same synthetic protocol for JG oil. It was
already proposed the use of two steps in order to obtain methyl
esters from triglycerides containing high free fatty acid: (i) acid
catalyzed esterification, followed by (ii) basic catalyzed transesterification [21]. Thus, first it was carried out an esterification
step for this raw material using sulfuric acid as catalyst. In
sequence, three transesterification steps using potassium
hydroxide were done. As a result, a biodiesel containing fatty

452

biomass and bioenergy 33 (2009) 449453

Table 3 Reaction yields and biodiesel properties of


Jatropha curcas L. (JC) and Jatropha gossypiifolia (JG).
Property

Jatropha
Jatropha
gossypiifolia (JG) curcas L. (JC)

Density at 15  C (g/cm3)
0.8874
3.889
Kinematic viscosity at 40  C (cSt)
Water content (w/w %)
0.020
Conradson carbon
0.3666
residue (w/w %)
6
Pour point ( C)
133
Flash point ( C)
Cupper strip corrosion
1a
Ash content (w/w %)
Not detected
Calorific value (MJ/kg)
40.32

0.8826
4.016
0.003
0.0223
5
117
1a
Not detected
41.72

acid methyl esters with purity higher than 99% was obtained.
This procedure leaded to mild reaction yield (73%) and high
acid value in the final product (6.64 mg KOH/g).

3.3.
Fuel properties of biodiesel from J. curcas L. (JC) and
J. gossiypiifolia (JG) oils
Table 3 summarized the physicochemical properties of biodiesel from JC and JG. The physicochemical properties of JC are
comparable to those obtained elsewhere [18] and the differences can be attributed to the different fatty acid compositions
(see Section 3.1). As can be seen, the studied properties of both
biofuels are close to those values usually obtained for biodiesel
from raw material with conventional fatty acid compositions,
such as canola, linseed and sunflower [25].

4.

Conclusions

The high acid values of the crude vegetable oils lead to difficulties in the biodiesel preparation, occurring the formations
of soaps and stable emulsions. In the case of JG, this was an
obstacle to use only basic catalyst, being imperative the use of
a previous acid esterification step.
The studied physicochemical properties of the JC and JG
biodiesel are in acceptable range for use as biodiesel in diesel
engines, showing a promising economic exploitation of these
raw materials in semi-arid regions. Indeed, these values
match the international specifications. However, further
agronomic studies are needed in order to improve the seed
production and the crude oil properties.

Acknowledgements
Financial support from Brazilian research founding agencies,
such as Research and Projects Financing (FINEP), National
Counsel of Technological and Scientific Development (CNPq),
Brazilian Federal Agency for Support and Evaluation of Graduate Education (CAPES), Banco do Brasil Foundation (FBB) and
Federal District Research Support Foundation (FAPDF) are
gratefully acknowledged. LBS, VMM and ECS express their
appreciation for fellowships granted from CNPq. JCR, SMPM
and PAZS thank CNPq for research fellowships. The authors

are indebt with Carlos R. Wolf for CG analysis to confirm the


fatty acid characterization.

references

[1] Pousa GPAG, Santos ALF, Suarez PAZ. History and policy of
biodiesel in Brazil. Energy Policy 2007;35:53938.
[2] Suarez PAZ, Meneghetti SMP, Ferreira VF. Biodiesel and
politics of Brazilian C&T. Qum Nova 2006;29:1157.
[3] Lima DG, Soares VCD, Ribeiro EB, Carvalho DA, Cardoso ECV,
Rassi FC, et al. Diesel-like fuel obtained by pyrolysis of
vegetable oils. J Anal Appl Pyrolysis 2004;71:98796.
[4] Suarez PAZ, Meneghetti SMP, Meneghetti MRM, Wolf CR.
Transformation of triglycerides into fuels, polymers and
chemicals: some applications of catalysis in oleochemistry.
Quim Nova 2007;30:66776.
[5] Meneghetti SMP, Meneghetti MR, Wolf CR, Silva EC,
Lima GES, Coimbra MA, et al. Ethanolysis of castor and
cottonseed oil: a systematic study using classical catalysts.
J Am Oil Chem Soc 2006;83:81922.
[6] Meneghetti SMP, Meneghetti MR, Wolf CR, Silva EC,
Lima GES, Silva LL, et al. Biodiesel from castor oil:
a comparison of ethanolysis versus methanolysis. Energy
Fuels 2006;20:22625.
[7] Conceicao MM, Candeia RA, Dantas HJ, Soledade LEB,
Fernandes VJ, Souza AG. Rheological behavior of castor oil
biodiesel. Energy Fuels 2005;19:21858.
[8] Cvengros J, Paligova J, Cvengrosova Z. Properties of alkyl esters
based on castor oil. Eur J Lipid Sci Technol 2006;108:62935.
[9] Santos ICF, Carvalho SHV, Soletti JI, Ferreira de la Salles W,
Teixeira da Silva de la Salles K, Meneghetti SMP. Studies of
Terminalia catappa L. oil: characterization and biodiesel
production. Bioresour Technol 2008;99:65459.
[10] Shah S, Sharma A, Gupta MN. Extraction of oil from Jatropha
curcas L. seed kernels by enzyme assisted three phase
partitioning. Ind Crops Prod 2005;20:2759.
[11] Openshaw K. A review of Jatropha curcas: an oil plant of
unfulfilled promise. Biomass Bioenergy 2000;19:115.
[12] Modi MK, Reddy JRC, Rao BVSK, Prasad RBN. Lipase-mediated
conversion of vegetable oils into biodiesel using ethyl acetate
as acyl acceptor. Bioresour Technol 2007;98:12604.
[13] Zhu HP, Wu ZB, Chen YX, Zhang P, Duan SJ, Liu XH, et al.
Preparation of biodiesel catalyzed by solid super base of calcium
oxide and its refining process. Chin J Catal 2006;27:3916.
[14] Zhou H, Lu HF, Liang B. Solubility of multicomponent systems
in the biodiesel production by transesterification of Jatropha
curcas L. oil with methanol. J Chem Eng Data 2006;51:11305.
[15] Kumar N, Sharma PB. Jatropha curcas a sustainable source
for production of biodiesel. J Sci Ind Res 2005;64:8839.
[16] Vasudevan P, Sharma S, Kumar A. Liquid fuel from biomass:
an overview. J Sci Ind Res 2005;64:82231.
[17] Azam MM, Waris A, Nahar NM. Prospects and potential of
fatty acid methyl esters of some non-traditional seed oils for
use as biodiesel in India. Biomass Bioenergy 2005;29:293302.
[18] Foidl N, Foidl G, Sanchez M, Mittelbach M, Hackel S. Jatropha
curcas L. as a source for the production of biofuel in
Nicaragua. Bioresour Technol 1996;58:7782.
[19] Subramanian KA, Singal SK, Saxena M, Singhal S. Utilization
of liquid biofuels in automotive diesel engines: an Indian
perspective. Biomass Bioenergy 2005;29:6572.
[20] Abreu FR, Alves MB, Macedo CCS, Zara LF, Suarez PAZ. New
multi-phase catalytic systems based on tin compounds
active for vegetable oil transesterificaton reaction. J Mol Catal
A Chem 2005;227:2637.
[21] Keim GI. Fat acid alkyl esters from low-grade oils and fats. US
Patent 2,383-601. Chem Abstr 1945;40:4617 [1946].

biomass and bioenergy 33 (2009) 449453

[22] Macedo CCS, Abreu FR, Tavares AP, Alves MB, Zara LF,
Rubim JC, et al. New heterogeneous metal-oxides based
catalyst for vegetable oil transesterification. J Braz Chem Soc
2006;17:12916.
[23] Mittelbach M, Tritthart P. Diesel fuel derived from vegetable
oils 3. Emission tests using methyl-esters of used frying oil.
J Am Oil Chem Soc 1988;65:11857.

453

[24] DaSilveira Neto BA, Alves MB, Lapis AAM, Nachtigall FM,
Eberlin MN, Dupont J, et al. 1-n-Butyl-3-methylimidazolium
tetrachloro-indate (BMI$InCl4) as a media for the synthesis of
biodiesel from vegetable oils. J Catal 2007;249:15461.
[25] Lang X, Dalai AK, Bakhshi NN, Reaney MJ, Hertz PB.
Preparation and characterization of bio-diesels from various
bio-oils. Bioresour Technol 2001;80:5362.

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