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Characteristics and composition of Jatropha gossypiifoliaand Jatropha curcas L. oils and application for biodieselproduction

Jefferson S. de Oliveiraa, Polyanna M. Leitea, Lincoln B. de Souzaa, Vinıcius M. Melloa,Eid C. Silvab, Joel C. Rubima, Simoni M.P. Meneghettib, Paulo A.Z. Suareza,*aLaboratorio de Materiais e Combustıveis, Instituto de Quımica, Universidade de Brasılia, C.P. 4478, 70919-970 Brasılia, DF, BrazilbInstituto de Quımica e Biotecnologia, Universidade Federal de Alagoas, Av. Lourival de Melo Mota, s/n, Cidade Universitaria,

57072-970 Maceio-AL, Brazil

a r t i c l e i n f o

Article history:

Received 10 May 2007

Received in revised form

23 August 2008

Accepted 29 August 2008

Published online 19 October 2008

Keywords:

Biodiesel

Jatropha gossypiifolia

Jatropha curcas L.

Transesterification

Methanol

* Corresponding author. Tel.: þ55 61 3307216E-mail address: psuarez@unb.br (P.A.Z. S

0961-9534/$ – see front matter ª 2008 Elsevidoi:10.1016/j.biombioe.2008.08.006

a b s t r a c t

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

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

production. The oil content in wild seeds and some physical–chemical properties of the oils

and the biodiesel obtained from them were evaluated. The studied physical–chemical

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

production and the crude oil properties.

ª 2008 Elsevier Ltd. All rights reserved.

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

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 tech-

nology 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 Brazilian’s region, where under-

development is critical. For this reason, 100% of reduction on

the federal tributes is given in the case of the use of castor

2; fax: þ55 61 32734149.uarez).er Ltd. All rights reserved

familiar agriculture [1].

However, castor oil, obtained from Ricinus communis seeds,

is composed almost entirely (ca. 90%) of triglycerides con-

taining the unusual fatty acid ricinoleic acid (12-hydroxy-cis-

octadec-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

.

b i o m a s s a n d b i o e n e r g y 3 3 ( 2 0 0 9 ) 4 4 9 – 4 5 3450

certainly limit the use of biodiesel/diesel blends with high

content in the biofuel because they will not attend the Bra-

zilian, US or European specifications [5–8]. Besides, the pres-

ence 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 meth-

oxide 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 sepa-

ration 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 bio-

fuels 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 hard-

ness, 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 [12–17]. 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. gos-

sypiifolia (JG), being evaluated the oil content in wild seeds and

some physical–chemical properties of the oils and the bio-

diesel 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 phos-

phoric 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 chromatog-

raphy (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 sepa-

rated. The excess of methanol in the methyl ester phase was

removed by rotary evaporator (Buchi, Rotavapor RE120, 70 �C).

Then the methyl esterwas washedwith 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

Table 2 – Fatty acid composition (%) of the Jatropha curcasL. (JC) and Jatropha gossypiifolia (JG) oils.

Fatty acid Jatrophagossypiifolia (JG)

Jatrophacurcas L. (JC)

Lauric (C12:0) 9.8 5.9

Miristic (C14:0) 4.3 2.7

Palmitic (C16:0) 26.8 13.5

Stearic (C18:0) 10.4 6.1

Oleic (C18:1) 22.4 21.8

Linoleic (C18:2) 19.2 47.4

Others 7.1 2.7

b i o m a s s a n d b i o e n e r g y 3 3 ( 2 0 0 9 ) 4 4 9 – 4 5 3 451

some physicochemical properties (iodine value, saponifica-

tion 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 calo-

rimeter 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 UV–vis detector at l¼ 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. Results and discussion

3.1. Characteristics of J. curcas L. (JC) andJ. gossypiifolia (JG) oils

The J. curcas L. (JC) and J. gossypiifolia (JG) seeds’ oil contents and

physical–chemical 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.

Jatrophagossypiifolia (JG)

Jatrophacurcas L. (JC)

Oil content (w/w %) 23.9 31.6

Calorific value (MJ/kg) 39.88 40.31

Acid value (mg KOH/g) 17.32 8.45

Water content (w/w %) 0.089 0.052

Ash content (w/w %) Not detected Not detected

Density at 15 �C (g/cm3) 0.9236 0.9215

Kinematic viscosity at 40 �C (cSt) 24.529 30.686

Conradson carbon

residue (w/w %)

0.2541 0.5396

Pour point (�C) �8 �2

Copper strip corrosion 1a 1a

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 reportedfor someconventional oilseeds like soybean

and palm-tree oils [20]. The studied physical–chemical

properties of JG and JC showed in Table 1 are in the range

expected for oils showing these conventional compositions.

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

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 effi-

ciency [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 [21–24].

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 bio-

diesel 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 trans-

esterification [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

Table 3 – Reaction yields and biodiesel properties ofJatropha curcas L. (JC) and Jatropha gossypiifolia (JG).

Property Jatrophagossypiifolia (JG)

Jatrophacurcas L. (JC)

Density at 15 �C (g/cm3) 0.8874 0.8826

Kinematic viscosity at 40 �C (cSt) 3.889 4.016

Water content (w/w %) 0.020 0.003

Conradson carbon

residue (w/w %)

0.3666 0.0223

Pour point (�C) �6 �5

Flash point (�C) 133 117

Cupper strip corrosion 1a 1a

Ash content (w/w %) Not detected Not detected

Calorific value (MJ/kg) 40.32 41.72

b i o m a s s a n d b i o e n e r g y 3 3 ( 2 0 0 9 ) 4 4 9 – 4 5 3452

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) andJ. gossiypiifolia (JG) oils

Table 3 summarized the physicochemical properties of bio-

diesel from JC and JG. The physicochemical properties of JC are

comparable to those obtained elsewhere [18] and the differ-

ences 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 diffi-

culties 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 Grad-

uate 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.

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