You are on page 1of 7

Reactive Extraction of Jatropha

curcas L. Seed for Production of
Biodiesel: Process Optimization
Study
S I E W H O O N G S H U I T ,

K E A T T E O N G L E E , *
, †
A Z L I N A H A R U N K A M A R U D D I N ,

A N D
S U Z A N A Y U S U P

School of Chemical Engineering, Engineering Campus,
Universiti Sains Malaysia, Seri Ampangan,
14300 Nibong Tebal, Pulau Pinang, Malaysia, and
Department of Chemical Engineering, Universiti Teknologi
PETRONAS, 31750 Tronoh, Perak, Malaysia
Received September 8, 2009. Revised manuscript received
April 20, 2010. Accepted April 27, 2010.
Biodiesel from Jatropha curcas L. seed is conventionally
producedviaatwo-stepmethod: extractionof oil andsubsequent
esterification/transesterification to fatty acid methyl esters
(FAME), commonly known as biodiesel. Contrarily, in this study,
a single step in situ extraction, esterification and transesteri-
fication (collectively known as reactive extraction) of J. curcas
L. seed to biodiesel, was investigated and optimized. Design
of experiments (DOE) was used to study the effect of various
processparametersontheyieldof FAME. Theprocessparameters
studied include reaction temperature (30-60 °C), methanol
to seed ratio (5-20 mL/g), catalyst loading (5-30 wt %), and
reaction time (1-24 h). The optimumreaction condition was then
obtained by using response surface methodology (RSM)
coupled with central composite design (CCD). Results showed
that an optimum biodiesel yield of 98.1% can be obtained
under the following reaction conditions: reaction temperature
of 60 °C, methanol to seed ratio of 10.5 mL/g, 21.8 wt % of H
2
SO
4
,
and reaction period of 10 h.
Introduction
Owing to the worldpetroleumcrisis, productionof biodiesel
in Malaysia has increased steadily for the past three years;
from325,000 tons in2006 to400,000 tons in2007 and420,000
tons in 2008 (1). This increase is in tandem with the world’s
increasing biodiesel demand, especially in the European
region. However, the practice of using edible oils, which is
currently the most common feedstock for biodiesel produc-
tion, has raised criticism from various sectors, especially
nongovernmental organization (NGO), claiming that biodie-
sel is competing for resources with the food industry.
Therefore, production of biodiesel fromnonedible oils such
as Jatropha curcas L. seeds (2), beef tallow(3), waste cooking
oil (4), and Cerbera odollam (sea mango) (5) would be a
potential solutiontothis issue. Amongthesechoices, J. curcas
L. seed has recently been hailed as the promising feedstock
for biodiesel production because it can be cultivated in dry
and marginal lands (6), and thus it does not compete for
arable land that would have otherwise being planted with
food crops. Besides, its oil yield as shown in Table 1 is
comparable tothat of palmoil but muchhigher as compared
to other edible oil crops such as rapeseed, sunflower, and
soybean (7, 8). Therefore, even Malaysia, the world’s second
largest palm oil producer, is now diversifying its biodiesel
feedstocktowardjatropha. The total jatrophaplantationarea
in Malaysia, at the end of 2008, was estimated at 750,000
acres and is expected to increase to 1.5 million acres in 2009
and 2.5 million acres in 2010 (9).
Conventional methods for producing biodiesel from
jatropha and other types of oil seeds involve various stages:
oil extraction, purification (degumming, dewaxing, deacidi-
fication, dephosphorization, dehydration, etc.), and subse-
quent esterification or transesterification. These multiple
biodiesel processing stages constitute >70% of the total
biodiesel production cost if refined oil is used as feedstock
(10). Recently, in our previous study, it was shown that in
situ extraction and esterification/transesterification, simply
known as reactive extraction, is a feasible technology for the
production of biodiesel using a single step that can cut the
processing cost. Inthe reactive extractionprocess, extraction
of oil andesterification/transesterificationproceedinasingle
step in which the oil-bearing material contacts with alcohol
directly instead of reacting with pre-extracted oil. In other
words, alcohol acts both as an extraction solvent and as a
transesterification reagent during reactive extraction, and
therefore a higher amount of alcohol is required. However,
reactiveextractioneliminates therequirement of twoseparate
processes, the costly hexane oil extraction process and the
transesterificationreactionprocess, thus reducingprocessing
time, cost, andamount of solvent required(11). Furthermore,
onthe basis of a similar study reportedinthe literature (using
soybeans), it was demonstrated that the reactive extraction
process can be scaled up without encountering much
problem in mass and heat transfer limitations (12).
Nevertheless, in our previous study, the requirement of
a 24 hreactiontime to achieve a highfatty acidmethyl esters
(FAME) yield of 99.9% makes this process unattractive from
an industrial perspective (11). Thus, the aim of this study is
to optimize the process parameters of the acid-catalyzed
reactive extraction process for the production of FAME from
J. curcas L. seed.
Experimental Section
Materials. J. curcas L. seed was purchased from Misi Bumi
Alam Sdn Bhd, Malaysia. Methanol (99.9% purity) was
purchased from J. T. Baker, Germany. The remaining
chemicals used in this study, sulfuric acid (H
2
SO
4
, 95-97%
purity), methyl heptadecanoate(internal standard), andpure
methyl esters such as methyl palmitate, methyl stearate,
* Correspondingauthor phone: +604-5996467; fax: +604-5941013;
e-mail: chktlee@eng.usm.my.

School of Chemical Engineering, EngineeringCampus, Universiti
Sains Malaysia, Seri Ampangan, 14300 Nibong Tebal, Pulau Pinang,
Malaysia

Department of Chemical Engineering, Universiti Teknologi
PETRONAS, 31750 Tronoh, Perak, Malaysia
TABLE 1. Oil Yield of Jatropha curcas L. Seed and Other
Major Oil Crops
oil crop oil yield (tons/ha/year)
J. curcas L. seed 2.70 (7)
oil palm (mesocarp) 3.62 (8)
rapeseed 0.68 (8)
sunflower 0.46 (8)
soybean 0.40 (8)
Environ. Sci. Technol. 2010, 44, 4361–4367
10.1021/es902608v © 2010 American Chemical Society VOL. 44, NO. 11, 2010 / ENVIRONMENTAL SCIENCE & TECHNOLOGY
9
4361
Published on Web 05/10/2010
methyl oleate, and methyl linoleate, were purchased from
Fluka Chemie, Germany.
Pretreatment of J. curcas L. Seed and Oil Content.
Initially, fresh J. curcas L. seed was blended and sieved to a
size of <1 mm(11). It was thenweighedanddriedinthe oven
at 76 °C repeatedly until constant weight was achieved (13).
The dried seed was then sieved again to obtain fine particles
of e0.355 mm in size. To determine the maximum amount
of oil that can be extracted from the seed using the
conventional method, a Soxhlet extractor with excess n-
hexane as the solvent was utilized. After the extraction
process, hexane was removedusing a rotary evaporator, and
the extracted oil was measured (11). This value will be used
in the calculation of yield.
Reactive Extraction. The reactive extraction to convert
jatropha seedtobiodiesel was carriedout ina round-bottom
flask equipped with a reflux system, magnetic stirrer, and
heater. Initially, 20 g of jatropha seed was loaded into a 500
mL round-bottom flask. Methanol and concentrated H
2
SO
4
in the ranges of 5-20 mL/g and 5-30 wt %, respectively,
were then added into the round-bottomflask. After that, the
mixture was heatedtothe desiredtemperature (ranging from
30 to 60 °C) for the necessary duration (ranging from 1 to
24 h). Upon completion of the reaction period, the mixture
was cooled and then filtered. The solid residue was washed
repeatedly with methanol, and the excess methanol in the
filtrate was recovered using a rotary evaporator. After
evaporation, two layers of liquid were formed. The upper
layer was dark yellow in color containing crude biodiesel,
whereas the bottomlayer was darkbrownincolor containing
glycerol. The volume of the toplayer was thenmeasuredand
recorded (11). Then, the upper layer was washed with 20%
NaCl solution several times until the pH became neutral.
After washing, the upper layer was dried over anhydrous
sodium sulfate.
Sample Analysis. The composition and yield of fatty acid
methyl esters (FAME) or biodiesel in the upper layer of the
reactive extraction products were analyzed using gas chro-
matography(PerkinElmer, claurus 500) equippedwithaflame
ionized detector (FID) and a Nukol capillary column (15 m
×0.53 mm; 0.5 µm film). n-Hexane was used as the solvent,
whereas helium was used as the carrier gas. The oven
temperature was set at 110 °C and then increased to 220 °C
at a rate of 10 °C/min. The temperatures of the detector and
injector were set at 220 and 250 °C, respectively. Methyl
heptadecanoate was usedas the internal standard. The peaks
of different methyl esters were identified by comparing the
retention time of each component in the reaction samples
with the peak of pure methyl ester standard compounds.
The yield of FAME in the samples was calculated as (11)
Statistical Analysis and Optimization Using Design of
Experiments (DOE). The effect of reactive extractionprocess
parameters on the yield of FAME was studied using DOE.
The process parameters studied include reaction temper-
ature, methanol to seed ratio, catalyst loading, and reaction
time. The DOEselectedwas response surface method(RSM)
coupled with central composite design (CCD) using Design-
Expert version 6.0.6 (Stat-Ease, Inc.) software. Table 2
indicates the coded and actual values of the process
parameters used, whereas Table3shows thecompletedesign
matrix. Onthe basis of the statistical analysis result, the yield
of FAME was correlated to the process parameters with a
quadraticmodel usingregressionanalysis. It was thenutilized
for optimization purposes.
Results and Discussion
Development of Regression Model. Table 3 shows the yield
of FAME obtained using reactive extraction with a combina-
tion of various process parameters. The result was then
analyzed using analysis of variance (ANOVA) and is shown
inTable4. Byeliminatingtheinsignificant parameters (values
of “prob > F” of >0.05), multiple regression analysis gives the
following quadratic model equation (in coded factors) that
correlates the yield of FAME to the various process
parameters:
As shown in Table 4, the F test (Fisher) on eq 2 gives an
F value of 21.8 and a “prob > F” value of <0.0001, indicating
that thedevelopedmodel is significant. Besides that, R
2
shown
in Table 4 is very close to unity, 0.9532, indicating that the
developed model equation successfully captured the cor-
relationbetweentheprocess parameters totheyieldof FAME
for reactive extraction process of jatropha seed.
Effect of Single Process Parameter. On the basis of the
results showninTable 4, all four process parameters studied,
reactiontime (A), reactiontemperature (B), methanol toseed
ratio(C), andcatalyst loading (D), were foundtosignificantly
affect the yield of FAME because their F values are higher
than the theoretical value, F
1,15
of 4.54 at the 95%confidence
interval. THe parameter with the highest F value will have
the most significant effect. Thus, by referring to Table 4, the
parameter with the most significant effect on the yield of
FAME in descending order is catalyst (H
2
SO
4
) loading,
followed by reaction temperature, reaction time, and finally
methanol to seed ratio. Apart fromthat, the positive sign for
all four regressioncoefficients (A, B, C, andD) ineq2indicates
a positive effect on the yield of FAME. These findings can be
easily verifiedby visually inspecting the experimental results
showninTable 3. For example, by comparisonbetweenruns
2 and 7 (and other comparable runs), an increase in H
2
SO
4
loading causeda vast increase inthe yieldof FAME. Asimilar
finding can be made for the effect of reaction temperature
(e.g., runs 6 and 22). However, for reactiontime (runs 20 and
25) and methanol to seed ratio (runs 3 and 13), increases in
these parameters caused only a slight increment in the yield
of FAME.
Figure 1 shows the effect of reaction time on the yield of
FAME. As shown in Figure 1, the yield of FAME increased
with higher reaction time. In our previous study, it was
reportedthat thelimitingfactor for reactiveextractionprocess
TABLE 2. Coded and Actual Values of Process Parameters in Central Composite Design
level
variable code unit -2 (-r) -1 0 +1 +2 (+r)
reaction time A h 1 7 13 18 24
reaction temperature B °C 30 38 45 53 60
methanol to seed ratio C g/mL 5 8.75 12.5 16.25 20
H
2
SO
4
loading D wt % 5 11.25 17.5 23.75 30
yield (%) )
(Σconcn of each component) × (vol of upper layer)
total wt of oil in sample
× 100%
(1)
yield (wt %) ) 58.6 + 10.2A + 16.8B + 9.11C + 18.5D -
5.34A
2
- 4.28D
2
+ 5.63BD (2)
4362 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 44, NO. 11, 2010
is the leaching of oil from the seed itself (11). Therefore,
sufficient time will be required to leach the oil fromthe seed
and subsequently be transesterified to FAME. From Figure
2, the yield of FAME was found to increase linearly with
reaction temperature in agreement with those reported in
the literature (14, 15). This can be easily justified as higher
temperature can increase the extraction rate of oil from
the seed and, in addition, the endothermic nature of the
transesterification reaction will shift the reaction toward the
forward direction at higher reaction temperature (16). It is
noted here that in this study, the reaction temperature is
limited to 60 °C so that this process can be comparable with
the conventional base-catalyzedtransesterificationreaction.
The role of methanol in reactive extraction is not only as
anextractionsolvent but alsoas a transesterificationreagent.
Therefore, the requirement of methanol in this particular
process is higher than in other conventional transesterifi-
cation reaction. As shown in Figure 3, the yield of FAME was
foundtoincrease linearly withhigher methanol toseedratio.
This is because with a higher amount of methanol, the
concentration gradient to leach oil from the seed will be
larger. Furthermore, theexcess amount of methanol will drive
thetransesterificationreactionforwardtowardtheformation
of FAME. However, it was found that the effect of methanol
to seed ratio on the yield of FAME is least significant among
the four process parameters studied as indicated by the
TABLE 3. Experiment Matrix with Coded Factors of CCD and Response
run
A, reaction
time (h)
B, reaction
temperature (°C)
C, methanol to
seed ratio (g/mL)
D, catalyst
loading (wt %) yield (%)
1 13 45 12.50 5.00 4.23
2 7 38 16.25 11.25 19.20
3 18 53 16.25 11.25 60.76
4 13 45 5.00 17.50 30.20
5 7 53 8.75 11.25 16.82
6 13 60 12.50 17.50 99.54
7 7 38 16.25 23.75 48.58
8 7 38 8.75 23.75 29.65
9 7 38 8.75 11.25 1.75
10 7 53 16.25 23.75 86.24
11 18 53 8.75 23.75 90.93
12 18 53 16.25 23.75 94.78
13 18 53 8.75 11.25 52.27
14 18 38 8.75 23.75 40.68
15 18 38 8.75 11.25 22.22
16 1 45 12.50 17.50 15.54
17 7 53 8.75 23.75 70.15
18 13 45 20.00 17.50 93.19
19 7 53 16.25 11.25 28.75
20 24 45 12.50 17.50 68.40
21 13 45 12.50 30.00 88.17
22 13 30 12.50 17.50 28.00
23 18 38 16.25 11.25 30.65
24 18 38 16.25 23.75 48.29
repeated experiments
25 13 45 12.50 17.50 60.83
26 13 45 12.50 17.50 60.45
27 13 45 12.50 17.50 56.66
28 13 45 12.50 17.50 60.39
29 13 45 12.50 17.50 53.23
30 13 45 12.50 17.50 60.13
TABLE 4. ANOVA for Response Surface Quadratic Model for the Yield of FAME
source sum of squares DF mean square F value prob > F
model 21688.99 14 1549.21 21.84 <0.0001
a
A 2504.31 1 2504.31 35.30 <0.0001
a
B 6758.98 1 6758.98 95.27 <0.0001
a
C 1994.00 1 1994.00 28.11 <0.0001
a
D 8242.14 1 8242.14 116.18 <0.0001
a
A
2
788.11 1 788.11 11.01 0.0047
a
B
2
0.35 1 0.35 0.004984 0.9447
b
C
2
4.5 1 4.5 0.063 0.8045
b
D
2
502.2 1 502.2 7.08 0.0178
a
AB 183.06 1 183.06 2.58 0.1290
b
AC 81.09 1 81.09 1.14 0.3019
b
AD 219.93 1 219.93 3.10 0.0987
b
BC 9.09 1 9.09 0.13 0.7254
b
BD 507.6 1 507.6 7.15 0.0173
a
CD 0.002025 1 0.002025 0.00002854 0.9958
b
residual 1064.19 15 70.95
R
2
) 0.9532; adjusted R
2
) 0.9096; predicted R
2
) 0.7394; standard deviation ) 8.42; mean ) 50.69
a
Significant at 95% confident interval.
b
Not significant at 95% confident interval.
VOL. 44, NO. 11, 2010 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 4363
smallest F value shown in Table 4. This is probably because
evenat the lower range of methanol to seedratio usedinthis
study (5), there is already sufficient methanol to create the
concentration gradient required to leach oil from the seed.
As mentioned in the earlier section, catalyst (H
2
SO
4
)
loading was foundtohave the most significant positive effect
on the yield of FAME among all four reaction parameters.
FromFigure 4, it canbe seenthat a higher amount of catalyst
used will increase the yield of FAME significantly. For
instance, when the amount of H
2
SO
4
in the reaction mixture
was set at a minimum level of 5 wt % (run 1), the yield of
FAME was merely 4.23%; however, at a higher amount of
catalyst of 30 wt % (run 21) the yield increased significantly
to 88.2%. This is because H
2
SO
4
plays the role of catalyst not
only inthereactiveextractionprocess but alsoinaccelerating
the extraction of oil from jatropha seed as it was reported
that lipid or oil dissolved better in acidic solvent (17).
Therefore, by increasing the amount of H
2
SO
4
inthe reaction
mixture, more oil can be extracted more quickly and easily
and be transesterified to FAME. The acidic nature of the
product mixtureduetousageof H
2
SO
4
canbeeasilyovercome
FIGURE 1. Individual effect of reaction time on FAME yield in
reactive extraction of Jatropha seed.
FIGURE 2. Individual effect of reaction temperature on FAME
yield in reactive extraction of Jatropha seed.
FIGURE 3. Individual effect of methanol to seed ratio on FAME
yield in reactive extraction of Jatropha seed.
FIGURE 4. Individual effect of catalyst loading on FAME yield
in reactive extraction of Jatropha seed.
FIGURE 5. Interaction effect between reaction temperature and
catalyst loading on FAME yield shown as (a) a three-dimensional
plot and (b) a two-dimensional plot.
4364 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 44, NO. 11, 2010
in the industry by washing using alkaline water (NaOH
solution). Then the resulting neutral washed water can be
reused for the subsequent washing cycle. This can signifi-
cantly reduce the usage of water, making it more environ-
mentally friendly.
Interaction between Parameters. As shown in Table 4,
among all of the interaction terms, only the term BD is
significant at the 95%confidence level. This means that only
theinteractionbetweenreactiontemperature(B) andcatalyst
loading (D) affects the yieldof FAMEsignificantly. The three-
dimensional and two-dimensional plots for the interaction
betweenreactiontemperatureandcatalyst loadingareshown
in Figure 5, panels a and b, respectively. It can be seen that
when the catalyst loading is set at a lower value (11.25 wt %),
there is only a marginal increase in the yield of FAME with
higher reaction temperature. However, when the catalyst
loading is set at a higher value (23.75 wt %), the yield of
FAME increases more significantly with higher reaction
temperature. This finding further strengthens our claimthat
catalyst loading is a more prominent process parameter that
affects the yield of FAME as compared to reaction temper-
ature(higher Fvaluefor catalyst loadingcomparedtoreaction
temperature as shown in Table 4). This can be justified as
transesterification of oil to FAME is a catalyst-dependent
reaction (18), in which the transesterification reaction can
proceed well even at room temperature, provided sufficient
catalyst is available (19). The importance of the presence of
catalyst is that it canlower the activationenergy of achemical
reaction (such as the transesterification reaction) so that the
reaction can proceed at lower temperature, but without
sufficient catalyst, the transesterificationreactionrate would
be very slow even at high temperature (18).
Optimization of Process Parameters. Up to this point,
the results revealed that for the reactive extraction process,
all of the process parameters studied significantly affect the
yield of FAME. Thus, the next step is to optimize the process
parameters to obtain the highest yield of FAME. The
optimization procedure used must be able to take into
account not only the individual process parameter but also
the interaction between parameters. This was carried out
with the help of the optimization function embedded in
Design-Expert softwareusingtheregressionmodel developed
as shown in eq 2. Table 5 shows the limits for each of the
process parameters usedinthe optimizationprocedure. The
software predicted (based on the 95% confidence interval)
that an optimum FAME yield of 99.8 wt % can be obtained
withthe following process parameters; reactiontemperature
of 60 °C, methanol to seed ratio of 10.5 mL/g, 21.8 wt % of
H
2
SO
4
, and reaction period of 10 h. The predicted optimum
yield was then verified by carrying out three repeated
experimental runs using the suggested optimum condition.
The repeated experiments gave an average optimum yield
of 98.1 wt %, which is very close to the predicted value (<5%
error), indicating that the predicted optimum process condi-
tions are valid for this study. It is noted here that although
the optimum yield was slightly lower (1.44%) than the yield
obtained in run 6 (Table 3), the optimum yield can be
obtained at milder reaction conditions requiring less metha-
nol usage(20%reduction) andreactiontime(23%reduction).
Besides that, the time requirement for reactive extraction
was successfullyreducedto10from24h(whichwas obtained
inour previous study) whilemaintainingahighyieldof almost
100% (11).
Although the reaction period required for optimumyield
of FAME is 10 h, which is rather long as compared to
conventional transesterification process, it should be noted
that in reactive extraction, both extraction and transesteri-
fication occur simultaneously. In a conventional FAME or
biodiesel production process, oil is initially extracted from
the seed; for example, extraction of oil from jatropha seed
requires 8 h (20), and subsequently the oil is transesterified
to FAME, which requires an additional 5 h using two steps,
acid-base-catalyzedtransesterification(21). This brings the
total processing period to 13 h, which is still 30% more than
the time required for reactive extraction. Therefore, reactive
extractioncanactually reduce the time requiredfor biodiesel
production from various oilseeds as compared to the
conventional method, and this will eventually bring down
the cost of biodiesel production.
It was found that the optimum FAME yield obtained in
this study was higher than in other similar studies reported
in the literature (14, 22). Su et al. reported (22) the use of
reactiveextractionfor fattyacidester productionwithJ. curcas
L. seed as feedstock, but methyl acetate was used as reaction
solvent and enzyme as catalyst instead of methanol and
H
2
SO
4
, respectively (used in this study). The yield of FAME
reported was much lower than those reported in this study.
In their study, the yield obtained using 12 h of reaction time
TABLE 5. Constraints Used To Optimize FAME Yield in Reactive
Extraction
variable goal
lower
limit
upper
limit
A: reaction time (h) in range 6.75 18.25
B: reaction temperature (°C) in range 30 60
C: methanol to seed ratio (g/mL) in range 8.75 16.25
D: catalyst loading (wt %) in range 11.25 23.75
Y: FAME yield (wt %) in range 95 100
TABLE 6. Comparison of Optimum Process Conditions for Jatropha Biodiesel Production Using Various Processing Technologies
process parameter
reactive
extraction
homogeneous two-step
acid-base-catalyzed
transesterification (21)
lipase-catalyzed
transesterification (23)
supercritical
transesterification (24)
reaction temperature (°C) 60 50 °C for acid esterification
65 °C for base
transesterification
50 320 °C with pressure
of 8.4 MPa
methanol to oil ratio 10.5 mL/g
(methanol to
seed ratio)
60% w/w for acid esterification
24% w/w for base
transesterification
3 (molar ratio) 43 (molar ratio)
catalyst loading (wt %) 21.8 1% w/w H
2
SO
4
for acid
esterification
1.4% w/w NaOH for base
transesterification
100
reaction time (h) 10 3 h for acid esterification
2 h for base
transesterification
24 4 min
optimum yield (wt %) 98.1 90 22.5 100
VOL. 44, NO. 11, 2010 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 4365
was only 63.9 wt %, but in this study, 98.1 wt % FAME yield
canbe achieved inonly 10 h of reactiontime (22). Inanother
study, municipal primary and secondary sludges were used
as lipid feedstock for the production of biodiesel using acid-
catalyzedreactive extraction. The maximumreportedFAME
yields were merely 14.5 and 2.5%for primary and secondary
TABLE 7. Step-by-Step Unit Operation Comparison for Production of Biodiesel from Jatropha Using Reactive Extraction and
Conventional Process
4366 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 44, NO. 11, 2010
sludges, respectively, even at 24 h of reaction time (14). This
reveals the fact that J. curcas L. seeds are actually a very
promising feedstock for the production of biodiesel using
acid-catalyzedreactive extractionas comparedtomunicipal
sludges becausethesewastes couldcontainalot of impurities
that might affect the reactive extraction process (11).
Table 6 shows the comparison of optimum process
conditions for various biodiesel processing technologies.
Although homogeneous two-step acid-base-catalyzed trans-
esterification requires less time and catalyst, the need for a
two-step process, higher methanol usage, and lower yield
are not favorable. On the other hand, although lipase-
catalyzed transesterification requires less methanol as com-
pared to reactive extraction, this enzymatic process needs
high catalyst loading as well as reaction time and the FAME
yield obtained was significantly lower. Supercritical trans-
esterification can achieve a very high FAME yield in a short
reaction time, but the requirement of very high reaction
temperature and reaction pressure (50 times higher than
reactive extractionandother processing technologies) made
this technology unfavorable froman industrial point of view
as a large amount of energy is required. In addition, special
handling, especially from the safety aspect, is also required
for the supercritical transesterification process.
An attempt was also made to compare the step-by-step
unit operations for producing biodiesel fromjatropha using
the conventional homogeneous two-step acid-base-cata-
lyzed transesterification and reactive extraction as shown in
Table 7. It can be clearly shown that reactive extraction
reduced the overall biodiesel processing steps owing to the
exclusion of the oil extraction step and a simpler transes-
terification process. In short, acid-catalyzed reactive extrac-
tion can be a breakthrough technology for biodiesel pro-
ductionfromoilseedthat contains highFFAsuchas J. curcas
L. using a single-step method.
Acknowledgement
We acknowledge the funding given by Universiti Sains
Malaysia (ResearchUniversity Grant 1001/PJKIMIA/814062,
Short TermGrant 304/PJKIMIA/6039015, ResearchUniversity
Postgraduate Research Grant Scheme 1001/PJKIMIA/
8031017), and the Ministry of Science, Technology and
Innovation, Malaysia (National Science Fellowship), for this
project.
Literature Cited
(1) Malaysia biofuels annual report 2009; available at http://
gai n. fas. usda. gov/Recent%20GAIN%20Publ i cati ons/
General%20Report_Kuala%20Lumpur_Malaysia_6-12-2009.pdf.
(2) OmTapanes, N. C.; Gomes Aranda, D. A.; de Mesquita Carneiro,
J. W.; Ceva Antunes, O. A. Transesterificationof Jatropha curcas
oil glycerides: theoretical and experimental studies of biodiesel
reaction. Fuel 2008, 87, 2286–2295.
(3) Nelson, R. G.; Schrock, M. D. Energetic andeconomic feasibility
associated with the production, processing, and conversion of
beef tallow to a substitute diesel fuel. Biomass Bioenerg. 2006,
30, 584–591.
(4) Chhetri, A. B.; Chris Watts, K.; Rafiqul Islam, M. Waste cooking
oil as an alternate feedstock for biodiesel production. Energies
2008, 1, 3–18.
(5) Kansedo, J.; Lee, K. T.; Bhatia, S. Cerbera odollam (sea mango)
oil as apromisingnon-ediblefeedstockfor biodiesel production.
Fuel 2009, 88, 1148–1150.
(6) Prueksakorn, K.; Gheewala, S. H. Full chain energy analysis of
biodiesel from Jatropha curcas L in Thailand. Environ. Sci.
Technol. 2008, 42, 3388–3393.
(7) Jatropha shines as non-food oil for biodiesel 2008; available at
http://www.reuters.com/article/GlobalAgricultureandBiofuels08/
idUSHKG28600520080115.
(8) Lam, M. K.; Tan, K. T.; Lee, K. T.; Mohamed, A. R. Malaysian
palmoil: surviving the foodversus fuel dispute for a sustainable
future. Renew. Sust. Energ. Rev. 2009, 13, 1456–1464.
(9) Missionbiofuel primesfor biodiesel action2008; availableat http://
www.energycurrent.com/index.php?id)2&storyid)10461.
(10) Zeng, J.; Wang, X.; Zhao, B.; Sun, J.; Wang, Y. Rapid in situ
transesterification of sunflower oil. Ind. Eng. Chem. Res. 2009,
48 (2), 850–856.
(11) Shuit, S. H.; Lee, K. T.; Kamaruddin, A. H.; Yusup, S. Reactive
extraction and in situ transesterification of Jatropha curcas L.
seeds for the production of biodiesel. Fuel 2010, 89, 527–530.
(12) Haas, M. J; Scott, K. M. Moisture removal substantially improves
the efficiency of in situ biodiesel production from soybeans.
J. Am. Oil Chem. Soc. 2007, 84, 197–204.
(13) Haas, M. J.; Scott, K. M.; Foglia, T. A.; Marmer, W. N. The general
applicability of in situ transesterification for the production of
fatty acid esters from a variety of feedstocks. J. Am. Oil Chem.
Soc. 2007, 84, 963–970.
(14) Mondala, A.; Liang, K.; Toghiani, H.; Hernandez, R.; French, T.
Biodiesel production by in situ transesterification of municipal
primary and secondary sludges. Bioresour. Technol. 2008, 100,
1203–1210.
(15) Siler-Marinkovic, S.; Tomassevic, A. Transesterification of
sunflower oil in situ. Fuel 1998, 17 (12), 1389–1391.
(16) Samart, C.; Sreetongkittikul, P.; Sookman, C. Heterogeneous
catalysis of transesterification of soybean oil using Kl/meso-
porous silica. Fuel Process. Technol. 2009, 90 (7-8), 922–925.
(17) Hensarling, T. nP.; Jacks, T. J. Solvent extraction of lipids from
soybeans with acidic hexane. J. Am. Oil Chem. Soc. 1983, 80 (4),
783–784.
(18) Li, H.; Xie, W. Transesterification of soybean oil to biodiesel
with Zn/I
2
catalyst. Catal. Lett. 2006, 107 (1-2), 25–30.
(19) Haas, M. J.; Scott, K. M.; Marmer, W. N.; Foglia, T. A. In situ
alkaline transesterification: an effective method for the produc-
tion of fatty acid esters from vegetable oils. J. Am. Oil Chem.
Soc. 2004, 81 (1), 83–89.
(20) Sayyar, S.; Abidin, Z. Z.; Yunus, R.; Muhammad, A. Extraction
of oil from Jatropha seeds-optimization and kinetics. Am. J.
Appl. Sci. 2009, 6 (7), 1390–1395.
(21) Berchmans, H. J.; Hirata, S. Biodiesel production from crude
Jatropha curcas L. seed oil with a high content of free fatty
acids. Bioresour. Technol. 2008, 99, 1716–1721.
(22) Su, E.; Xu, W.; Gao, K.; Zheng, Y.; Wei, D. Lipase-catalyzed in
situ reactive extraction of oilseeds with short-chained alkyl
acetates for fatty acid ester production. J. Mol. Catal. B: Enzym.
2007, 48, 28–32.
(23) Rattanaphra, D.; Srinophakun, P. Biodiesel production from
crude sunflower oil and crude Jatropha oil using immobilized
lipase. J. Chem. Eng. Jpn. 2010, 43 (1), 104–108.
(24) Hawash, S.; Kamal, N.; Zaher, F.; Kenawi, O; Diwani, G. E.
Biodiesel fuel from Jatropha oil via non-catalytic supercritical
methanol transesterification. Fuel 2009, 88, 579–582.
ES902608V
VOL. 44, NO. 11, 2010 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 4367