Fuel 97 (2012) 848–855

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Fuel
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Optimization of reactive extraction of castor seed to produce biodiesel using

response surface methodology
Subhalaxmi Pradhan a,c, C.S. Madankar a,d, Pravakar Mohanty b,d, S.N. Naik a,⇑
a
Centre for Rural Development and Technology, Indian Institute of Technology, Delhi, Hauz Khas, New Delhi 110 016, India
b
Department of Chemical Engineering, Indian Institute of Technology, Delhi, Hauz Khas, New Delhi 110 016, India
c
Department of Food and Bioproduct Sciences, College of Agriculture & Bioresources, University of Saskatchewan, Saskatoon, Saskatchewan, Canada S7N 5A9
d
Catalysis and Chemical Reaction Engineering Laboratories, Department of Chemical Engineering, University of Saskatchewan, Saskatoon, Saskatchewan, Canada S7N 5A9

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

Article history: Biodiesel was produced by reactive extraction (RE) of castor seed to reduce the cost and time associated
Received 13 January 2012 with conventional method. The objective of this study is to determine the relationship between various
Received in revised form 20 February 2012 important parameters of the RE process to obtain a high yield of FAME. Response surface methodology
Accepted 21 February 2012
(RSM) was used to statistically analyze and optimize the operating parameters of the process. A central
Available online 11 March 2012
composite design (CCD) was adopted to study effects of catalyst concentration, methanol to oil molar
ratio, reaction temperature and mixing intensity on yield of FAME. The results of RSM analysis indicate
Keywords:
that catalyst concentration and methanol to oil molar ratio have most significant effect on the yield of
Castor seed
Extraction
FAME, with R2 = 0.998 shows fitness of a second-order model. The interaction terms of catalyst concen-
Reactive extraction tration with both methanol to oil molar ratio and reaction temperature exhibited a positive effect deliv-
Biodiesel ering (P < 0.0001). Based on second-order model, optimum condition for this reaction is found to be
Response surface methodology (RSM) methanol to oil molar ratio of 225:1, catalyst concentration 1.0 wt.% of oil, reaction temperature 55 °C
and mixing intensity of 350 rpm. The mathematical model (a quadratic polynomial equation) has devel-
oped adequately describing ranges of the experimental parameters studied and provides a statistically
accurate prediction of the optimum yield of FAME.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction weight [10]. The oil consists of approximately 80–90% ricinoleic

The ever increasing oil demands, depleting oil reserves and
environmental pollution problem caused due to the extra-
dependency on fossil fuels have created a renewed interest in
alternative fuels of biological origin [1–3]. One of such alternatives
is biodiesel which is biodegradable, renewable, non-toxic and
derived from transesterification of vegetable oils and animal fat
[4–7]. Annual consumption of edible oil of India is about 10 million
tonnes, half of which is fetched by imports. Due to the ‘‘food verses
fuel’’ problem, use of edible oil as a fuel source for transportation/
industry may not be viable, so the non-edible oils such as Jatropha
(Jatropha curcas), Karanja (Pongamia pinnata) and Castor (Ricinus
communis) can be used for biodiesel production [8].
Castor, R. communis L. (Euphorbiaceae) is an oleaginous species
cultivated in almost all of the tropical and subtropical zones. India
occupies the second position among castor seed producing coun-
tries in the word following Brazil and average yield of castor seed
over India is 200–290 kg/ha [9]. There are different varieties of cas-
tor seeds but on the average, they contain about 46–55% oil by
⇑ Corresponding author. Tel.: +91 11 26591162; fax: +91 11 26591121.
E-mail addresses: naiksn@gmail.com, sn_naik@hotmail.com (S.N. Naik).
acid, 3–6% linoleic acid, 2–4% oleic acid, and 1–5% saturated fatty
acids [11]. The presence of ricinoleic acid, containing both a double
bond and a hydroxyl group, impart increased lubricity to the castor
oil and its derivatives as compared to other vegetable oils, which
can be used as fuel additive [12–14]. The use of castor oil in inter-
nal combustion engines is complicated due to its extremely high
viscosity and high water content but transesterified oil (biodiesel)
is better adapted as fuel.
The conventional method for producing biodiesel involves oil
extraction, purification (degumming, deacidification, dewaxing,
dehydration, etc.) and transesterification [2,3,15,16]. This multiple
processing stages constitute over 70% of the total production costs
of biodiesel when refined oil is used as a feed stock [17]. However
in RE (Simultaneous extraction and transesterification reaction), oil
extraction and transesterification proceed in one single step, in
which alcohol acting both as an extraction solvent and transesteri-
fication reagent. RE differs from conventional method of biodiesel
production by using oil bearing material directly in alcohol instead
of reacting pre-extracted oil [18]. Therefore RE eliminates the
costly oil extraction process and transesterification reaction, thus
reducing cost of biodiesel, processing time and amount of solvent
required [19]. Although there have been different studies reported

0016-2361/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2012.02.052
 S. Pradhan et al. / Fuel 97 (2012) 848–855
on production of biodiesel from castor oil [20,21], however RE of
castor seed is rarely studied. Optimization of the reaction parame-
ters is very important during RE. In conventional experiments,
optimization is usually carried out by varying a single factor while
keeping all the other factors fixed at a specific set of conditions.
This method requires a large number of experiments and time con-
suming. Statistical experimental design can be used for optimiza-
tion of reaction parameters in order to avoid the limitations of
the classical method [22,23]. Response surface methodology
(RSM) is an effective statistical technique for designing such exper-
iments, building models and investigating complex processes for
optimization of target value or yield [24,25].
The present study focused on the development of a mathemat-
ical model for RE to describe the effects and the relationships be-
tween the process variables to give the maximum yield of FAME
from castor seed. An RSM method comprising a central composite
design (CCD) was used to evaluate the interactive effect and opti-
mize the reaction conditions of reactive extraction of castor seed
to produce FAME.
2. Materials and methods
2.1. Reagents and materials
Castor seeds were collected from Gujarat, western part of India
to focus the study. Reagents like analytical grade methanol
(P99%), KOH (P85%) was procured from Merck and was used
without purification. Pure methyl esters such as methyl ricinoleate,
methyl stearate, methyl oleate and methyl linoleate, methyl linol-
enate, methyl myristate were purchased from Sigma Aldrich (USA).
2.2. Oil content of castor seeds and physicochemical characterization
The seeds were decorticated to separate kernel and husk. The oil
was extracted from the grinded seed and kernel separately by
Soxhlet apparatus using methanol as solvent. The extract was con-
centrated in rotary evaporator; the residual oil was cooled and
weighed. The physico-chemical properties (density, viscosity, acid
value, iodine value, saponification value and unsaponifiable mat-
ter) of the oil were determined.
The oil was converted to fatty acid methyl esters by using trans-
methylating agent as described by Hammond [26]. The fatty acid
composition of the oil was determined by gas chromatograph (Nu-
con 5765) equipped with a flame ionization detector (Nucon Engi-
neers, Delhi, India), with fused silica capillary column BPX-70,
60 m  0.25 mm  0.25 lm (SGE, India). The column temperature
was programmed to increase from 180 °C to 240 °C at 4 °C/min
ramp rate. The detector and injector temperature was set at
240 °C and 230 °C respectively. The carrier gas used was Nitrogen
(40 psi) at a flow rate of 45.0 mL/min, air and hydrogen flow rates
were 30 mL/min and 300 mL/min respectively. The sample injec-
tion volume was 1.0 ll with a split flow of 60 mL/min. The stan-
dard fatty acid methyl esters, purchased from Sigma Aldrich
(USA) were injected to gas chromatograph and identification of
individual fatty acids were done by comparing the retention times
of fatty acid methyl ester of the samples with that of reference
methyl esters. The percentage fatty acid compositions were calcu-
lated from their peak areas.
2.3. Experimental design
RSM was employed to evaluate the influence of various param-
eters on the yield of (Fatty acid methyl ester/biodiesel) FAME dur-
ing RE of castor seed. The factorial level was preferred taking
different process parameters into account with its properties for
849
the reaction. The experimental design for this reaction was carried
out utilizing a central composite design (CCD). A 24 full-factorial
CCD for four independent variables was employed giving a total
number of experiments of 30 (= 2n + 2n + 6) where n is the number
of independent variables. Eight axial and 16 factorial experimental
runs were carried out with six extra replications at the center point
to evaluate the pure error. The four independent variables were
catalyst concentration (A), methanol to oil molar ratio (B), mixing
intensity (C) and reaction temperature (D). The reaction was car-
ried out at varied alcohol to oil molar ratio (100:1–350:1), catalytic
concentration (0.5–1.5%), different rotations (100–600 rpm) and
temperature (45–65 °C). The value of a (alpha) was limited at level
2. All variables at zero level constitute the center points, therefore
the lowest and the highest levels are assigned to be 2 and +2
respectively.
2.4. Experimental procedure
Reactive extraction (RE) was carried out taking kernel (without
husk) using methanol both as an extraction solvent and transeste-
rification reagent. The kernels (20 g) were macerated and trans-
ferred into a 250 mL three necked round bottom flask equipped
with reflux condensor. The round bottom flask was merged in
water bath placed on the plate of magnetic stirrer set at 600 rpm.
The potassium hydroxide–alcohol solution was prepared freshly
in order to maintain the catalytic activity and to prevent moisture
absorbance. The reaction flask with macerated sample was heated
to a reaction temperature and freshly prepared potassium hydrox-
ide–alcohol solution was added under mechanical stirring. Then
hexane was used as co-solvent (15 v/v% of methanol) in reaction
mixture to improve the rate of extraction significantly which plays
the role of both extraction solvent and reaction promoter in the
process and accelerates the in situ transesterification [17]. The
reaction was carried out for 3 h at desired temperature with stir-
ring. After 3 h of reaction time the reaction mixture was cooled
and centrifuged at 4000 rpm. The solvent was recovered from the
supernatant by vacuum distillation. The product was transferred
into the separating funnel and allowed to separate gravitationally.
The upper biodiesel layer was purified by washing with hot dis-
tilled water. The moisture was removed from biodiesel by drying
at 80 °C under vacuum rotary evaporator and passing the ester
layer over anhydrous sodium sulfate.
2.5. Statistical analysis
The experimental data obtained by CCD procedures were ana-
lyzed by RSM using the following second-order polynomial equa-
tion, developed to describe the relationship between the
predicted response variable (FAME yield) and the independent var-
iable of the RE process.
P
n P
n P
n P
n
0
Y ¼ bo þ bi  X i þ bii  X 2i þ bij  X i X j ð1Þ
i¼1 i¼1 i¼1j>1
where Y is the response (Yield of FAME), bo, bi, bii, bij are intercept,
linear, quadratic and interaction constant coefficients, respectively;
n is the number of factors studied and optimized in the experiment;
Xi, Xj are the encoded independent variables. The Design Expert ver-
sion 8.0.6 (STAT-EASE Inc.) software was used for regression and
graphical analysis of the experimental data. The quality of the mod-
el fit was evaluated using the coefficients of determination (R2) and
analysis of variance (ANOVA). Response surfaces and contour plots
were developed using the fitted quadratic polynomial equation ob-
tained from regression analysis, holding two of the independent
variables at a constant value corresponding to the stationary point
and changing the other two variables.
850 S. Pradhan et al. / Fuel 97 (2012) 848–855
2.6. Analytical procedure
The amount of methyl esters in the product of RE of castor seed
were analyzed using high performance liquid chromatography
(Waters 600 HPLC system) equipped with refractive index detector
(Waters 2414). A reverse phase C18 column (Waters Spherisorb,
5 lm, 250 mm  4 mm i.d.) at temperature 40 °C was used for sep-
aration with 1 mL/min flow rate of methanol as a carrier solvent.
The sample injection was 20 ll and each constituent was quanti-
fied by comparing the peak areas with their respective standards.
The viscosity and acid value of the FAME produced after RE was
measured.
3. Results and discussion
3.1. Characterization of oil and biodiesel
The oil content of the seed is 48.25% but that of in kernel is 66%.
As the husk has no oil, so oil content in the kernel is more as com-
pared to seed. Extraction with methanol gives the maximum oil
yield as compared to hexane (solvent for other oil seeds) because
castor oil has 85–90% ricinoleic acid which is soluble in alcohols.
The physicochemical characteristics of the oil are listed in Table
1. The oil has FFA (Free fatty acid) level of 0.45%. Low FFA of the
oil suggests that the oil is suitable for biodiesel production in single
step alkali catalyzed transesterification. The oil content of seed and
acid value of the oil are important parameters to carry out in-situ
transesterification. The physicochemical properties obtained for
the oil is comparable with the results obtained by other research-
ers [11,27]. The fatty acid composition of the oil is represented in
Table 1. Fig. 1 represents gas chromatogram of fatty acid methyl
esters of castor oil. The oil mainly consists of ricinoleic acid
(87%), 5% of linoleic acid and 3.4% of oleic acid. Palmitic acid
(1.3%), stearic acid (1.5%) and linolenic acid (0.6%) are present in
small amount. The data obtained is comparable with results of
other researchers [28–30]. The acid value of the biodiesel obtained
after reactive extraction is 0.52 mg KOH/g oil. The viscosity of cas-
tor oil is 241 cp, whereas that for FAME produced after reactive
extraction is 14.3 cp at 40 °C. HPLC chromatogram of castor oil
FAME is shown in Fig. 2 and the FAME mainly consists of ricinoleic
acid, linoleic acid, oleic acid, palmitic acid and stearic acid methyl
esters.
3.2. Optimization of reaction conditions by response surface
methodology
3.2.1. Model fitting and ANOVA
To optimize the reaction parameters of RE a CCD with a
five-level-four-factor design that addressed catalyst concentration
(A), methanol to oil molar ratio (B), mixing intensity (C) and reac-
tion temperature (D) was selected. ANN (artificial neutral network)
or other multivariate techniques can be explored for this kind of
Table 1
Characteristics and fatty acid composition of castor oil.
Properties Castor Fatty acid
oil
Specific gravity at 20 °C (g/cm3) 0.961 Ricinoleic acid
(C18:1OH)
Acid value (mg KOH/g oil) 0.91 Linoleic acid (C18:2)
Iodine value (g I2/100 g oil) 89 Oleic acid (C18:1)
Saponification value (mg KOH/g 185 Palmitic acid (C16:0)
oil)
Unsaponifiable matter (%, w/w) 0.94 Stearic acid (C18:0)
Viscosity (cp) at 40 °C 241 Linolenic acid (C18:3)
optimization process [31,32]. The experimental parameters, ranges
and levels of the independent variables investigated in this study
and the results on the basis of the CCD experimental design are
shown in Table 2. All of the 30 designed experiments were con-
ducted and the results analyzed by multiple regression. A qua-
dratic polynomial equation was obtained from the design
experimental data and the following equation was generated to
predict the yield of FAME, as shown below (in terms of the code
factors):
Yield of FAME ¼ 88:2 þ 2:083A þ 14:225B þ 2:375C
þ 2:8167D  3:3375AB þ 0:4125AC
 0:425AD þ 0:4875BC þ 3:4BD þ 0:3CD
 6:15A2  4:5875B2  3:8125C 2
 2:5125D2 ð2Þ
Here A–D are actual variables of the predictors namely catalyst con-
centration (%), methanol to oil molar ratio, mixing intensity (rpm)
and temperature (°C) respectively. To evaluate the analysis of vari-
ance (ANOVA) and check the adequacy of the empirical model, sta-
tistical analysis of the model was performed. The results of ANOVA
for fitting the second order response surface model by a mean
square method are summarized in Table 3. The coefficients of the
response surface model as provided by Eq. (2) were also evaluated.
The significance of each of the coefficients are checked from P-val-
ues (probability of error value), which also indicate the interaction
strength of each parameter. According to Table 3, the P-value of the
model is less than 0.0001 demonstrating high significance in pre-
dicting the response values and the suitability of the deduced mod-
el. The high F value (F model = 636.62) with very low probability
value (P < 0.0001) indicates the high significance of the fitted mod-
el. The significance of all coefficients was established by P-values
shown in Table 3.
The smaller the P value for a parameter the more significant is
the parameter, hence reflecting the relative importance of the term
attached to that parameter [33]. Furthermore, all first order inter-
action effects of the four factors were statistically significant, with
the greatest significance for the interaction of catalyst concentra-
tion  molar ratio (P-value < 0.0001), molar ratio  temperature
(P-value < 0.0001). At the same time, the low value of the coeffi-
cient of variation (CV = 1.21%) indicates that results of the fitted
model are reliable. The quality of the model fit was evaluated by
the coefficient of determination (R2), this value being calculated
to be 0.9983 for the response. This implies that 99% of the experi-
mental data confirm compatibility with the data predicted by the
model. The R2 value is always between 0 and 1, and its magnitude
indicates the aptness of the model. For a good statistical model, the
R2 value should be close to 1.0. The adjusted coefficient of determi-
nation (R2 Adj.) value reconstructs the expression with all the sig-
nificant terms included. The value of the adjusted coefficient of
determination (R2 Adj. = 0.9967) is also very high, supporting the
significance of the model. A high value of predicted R2 (0.9903) is
also an indication of reasonable precision of the model fitted.
Fig. 3 shows that the values of the response predicted from the
empirical model are in agreement with the observed values over
the selected range of the operating variables with a reasonable
Amount
high value of coefficient of determination (R2 = 0.9983). As the fit-
(%)
ted model Eq. (2) provides a good approximation to the experi-
87.0
mental condition, the model was employed to find the values of
5.0 the process variables for maximum yield of biodiesel.
3.4
1.3 3.2.2. Influence of the parameters on the yield of biodiesel
The response surface plots which are the graphical representa-
1.5
0.6 tion of the regression Eq. (2) were obtained using design
expert software. The plots representing the effects between the
 S. Pradhan et al. / Fuel 97 (2012) 848–855
Fig. 1. Gas chromatogram of fatty acid methyl esters of castor oil.
700.00
600.00
500.00
400.00
MV
300.00
200.00
100.00
0.00
2.00 4.00 6.00
Fig. 2. HPLC Chromatogram of castor oil methyl esters.
independent and dependent variables for different fixed parame-
ters were shown in Figs. 4–7. The effect of varying methanol to
oil molar ratio and catalyst concentration on RE of castor seed to
produce FAME at 350 rpm and a reaction temperature of 55 °C is
shown in Fig. 4. At a lower methanol to oil molar ratio, the yield
of biodiesel increased with increase in catalyst concentration. A
similar pattern was followed when increasing the methanol to oil
molar ratio and catalyst loading simultaneously. Therefore, a com-
bined increase in methanol to oil molar ratio and catalyst concen-
tration improved the yield of biodiesel, indicates that the methanol
to oil molar ratio and catalyst concentration are individually signif-
icant parameters. When the catalyst concentration increases from
0.75% to 1.0%, the yield of FAME increases gradually, afterwards
while moving towards 1.25% loading there is very less effect on
FAME yield. A substantial change in the contour plot signifies high-
er molar ratio always suits the RE process but for economic viabil-
ity one can choose the methanol to oil molar ratio of 225:1 for
maximum FAME yield.
Fig. 5 shows the effect of catalyst concentration and mixing
intensity and their combined interaction on the yield of FAME dur-
ing RE at methanol to oil molar ratio of 225:1 and reaction temper-
ature of 55 °C. From this figure it can be seen that the yield of FAME
851
8.00 10.00 12.00 14.00 16.00 18.00 20.00
Minutes
increases with increase in catalyst concentration towards 1%, up to
a certain mixing intensity, 350 rpm and after that there is no sub-
stantial increase in yield with increasing mixing intensity. In pres-
ence of excess amount of catalyst during RE, the yield of methyl
esters decreases due to soap formation, this increases the viscosity
of the reaction products. The formation of soap occurs due to
saponification reaction at higher catalytic concentration above 1%
loading. F. Kasim and Harvey reported that higher catalytic concen-
tration decreases the yield of methyl esters during RE of Jatropha
seed [34].
The effect of catalyst concentration, reaction temperature and
their combined interaction at constant molar ratio (methanol to
oil) of 225:1 and 350 rpm is depicted in Fig. 6. At low temperature
the yield of methyl ester almost has negligible changes with in-
crease in catalyst concentration. Generally maximum FAME yield
is depicted at higher catalytic concentration towards 1% and high
temperature towards 55 °C as catalyst has positive influence on
FAME yield. Continuous increase in the yield of FAME was achieved
with the increase in catalyst concentration in the range (0.95–
1.05%) considered but the rate of improvement decreased towards
the upper value above 1.05%. It is evident that the yield of biodiesel
is improved by increasing the reaction temperature. The response
852 S. Pradhan et al. / Fuel 97 (2012) 848–855

Table 2
Experimental design matrix and results.

Std Catalyst concentration (%); A Methanol to oil molar ratio; B Mixing Intensity (rpm);C Temperature (°C); D Coded level of factors Yield – FAME (%)
A B C D
1 0.75 287.5 225 50 0 0 0 2 78.2
2 1 225 350 65 1 1 1 1 83.4
3 1.25 162.5 225 50 0 0 0 0 61
4 1 225 350 55 1 1 1 1 88.3
5 1.25 287.5 225 60 0 2 0 0 86
6 1 350 350 55 0 0 2 0 98.6
7 1.25 287.5 225 50 0 0 0 0 75.5
8 0.75 162.5 225 60 2 0 0 0 49.5
9 1.25 162.5 225 60 0 0 0 0 60
10 1.25 287.5 475 60 1 1 1 1 93
11 1 225 350 55 0 2 0 0 88.2
12 1 225 350 45 0 0 0 0 71.8
13 0.75 287.5 225 60 1 1 1 1 90.2
14 0.75 162.5 475 60 1 1 1 1 53.2
15 0.5 225 350 55 2 0 0 0 58.9
16 1 225 350 55 0 0 2 0 88.4
17 1.5 225 350 55 1 1 1 1 67.2
18 0.75 287.5 475 60 1 1 1 1 97.2
19 0.75 287.5 475 50 0 0 0 0 81.1
20 1.25 162.5 475 60 0 0 0 2 64.4
21 1.25 162.5 475 50 1 1 1 1 65.9
22 1 225 600 55 1 1 1 1 76.8
23 1 225 350 55 1 1 1 1 88.2
24 0.75 162.5 225 50 1 1 1 1 51.2
25 0.75 162.5 475 50 1 1 1 1 54
26 1 225 100 55 1 1 1 1 68
27 1 225 350 55 0 0 0 0 88.4
28 1 100 350 55 1 1 1 1 40
29 1 225 350 55 1 1 1 1 88.2
30 1.25 287.5 475 50 1 1 1 1 82.2

Table 3
Analysis of variance (ANOVA) for response surface quadratic model.

Source of variation Sum of squares Degrees of freedom (df) Mean squares F value P value
Model 7279.68 14 519.98 636.62 <0.0001 Significant
A-catalyst 104.16 1 104.16 127.53 <0.0001
B-molar ratio 4856.41 1 4856.41 5945.82 <0.0001
C-RPM 135.375 1 135.37 165.74 <0.0001
D-temperature 190.40 1 190.41 233.12 <0.0001
AB 178.22 1 178.22 218.20 <0.0001
AC 2.72 1 2.72 3.33 0.0879
AD 2.89 1 2.89 3.54 0.0795
BC 3.80 1 3.80 4.65 0.0476
BD 184.96 1 184.96 226.45 <0.0001
CD 1.44 1 1.44 1.76 0.2041
A2 1037.41 1 1037.41 1270.13 <0.0001
B2 577.24 1 577.24 706.72 <0.0001
C2 398.68 1 398.68 488.11 <0.0001
D2 173.15 1 173.15 211.99 <0.0001
Residual 12.25 15 0.82
Lack of fit 12.25 10 1.22
Pure error 0 5 0
Cor total 7291.93 29
CV = 1.21% R2 = 0.9983 Adj R2 = 0.9967 Predicted R2 = 0.99033

values (yield) reached the highest level and most efficient near the
boiling point (bp) of the alcohol used (methanol bp 65 °C). The
temperature above boiling point of alcohol is avoided because
extraction will be difficult to complete due to evaporation of meth-
anol. Kasim and Harvey and this research group investigated that
before completion of alcoholysis, saponification of triglycerides
facilitated at faster rate at high reaction temperature by the effects
of alkali catalyst [34,35].
The effect of both methanol to oil molar ratio and mixing inten-
sity and their combined interaction on RE at 1% catalyst concentra-
tion and reaction temperature of 55 °C was studied. The yield of RE
process increases with increase in methanol to oil molar ratio up to
a certain mixing intensity and after that there is no substantial in-
crease in yield of FAME. The reaction was incomplete with lower
mixing intensity because the rate of mixing was insignificant for
extraction of oil and transesterification with further reaction prop-
agation. At lower mixing speed, distributions of seeds are not much
uniform as that of at higher mixing speeds.
The effect of the methanol to oil molar ratio, reaction tempera-
ture and their combined interaction on RE process at constant cat-
alyst concentration of 1 wt.% and at 350 rpm is represented by 2D
contour plot in Fig. 7. From this figure, it can be depicted that the
 S. Pradhan et al. / Fuel 97 (2012) 848–855 853

Predicted vs. Actual

100.00 100

90

90.00 80
6

Yield - FAME
70
80.00
60
Predicted

50
70.00

40

60.00

150.00
1.25 240.00
50.00 1.15 330.00
1.05
420.00
0.95
0.85 510.00 C: RPM
40.00 A: Catalyst
0.75 600.00

40.00 50.00 60.00 70.00 80.00 90.00 100.00 Fig. 5. Combined effect of catalyst loading and RPM on the yield of FAME during
Actual reactive extraction of castor seed at constant temperature of 55 °C and methanol to
oil molar ratio of 225:1.
Fig. 3. Graphical comparison between actual and predicted yield of FAME during
reactive extraction of castor seed.

90
100
80
90
70
80
Yield - FAME

60
Yield - FAME

70
50
60
40
50
30
40

65.00 1.25
300.00 1.25
61.00 1.15
260.00 1.15
57.00 1.05
220.00 1.05
53.00 0.95
180.00 0.95
0.85
A: Catalyst D: Temp 49.00 0.85 A: Catalyst
B: Molar ratio 140.00 45.00 0.75
100.00 0.75

Fig. 6. Combined effect of catalyst loading and temperature on the yield of FAME
Fig. 4. Combined effect of molar ratio and catalyst loading on the yield of FAME
during reactive extraction of castor seed at constant mixing speed of 350 rpm and
during reactive extraction of castor seed at constant temperature of 55 °C and
225:1 methanol to oil molar ratio.
mixing intensity of 350 rpm.

yield of biodiesel increased with increase in both temperature and

molar ratio. Methanol to oil molar ratio and temperature has sig-
nificant interaction between each other but the rate of RE will de-
crease above the boiling point of alcohol.
The combined effect of both temperature and mixing intensity
on RE of biodiesel from castor seed at constant methanol to oil mo-
lar ratio (225:1) and catalyst concentration of 1 wt.% was studied.
The yield of FAME increases with increase in reaction temperature
(65 °C) up to a certain mixing intensity (350 rpm) and thereafter,
no substantial increase in the yield with increase in both temper-
ature and mixing intensity.
3.2.3. Process optimization
The optimal values of the selected variables were obtained
by solving the regression equation (Eq. (2)) using the software
design expert 8.0.6. This model was employed to find the value
of the process variables that gives maximum yield FAME. The
predicted optimal value, that obtained from the model equation
for RE of castor seed to produce FAME are methanol to oil mo-
lar ratio 225:1, catalyst concentration 1.0 wt.% of oil, reaction
temperature 55 °C and mixing intensity of 350 rpm (Table 4).
The model predicts that the maximum yield that can be ob-
tained under these optimum conditions of the variables is
88.4%. To verify the model predictions, the optimum response
variables were tested under the following conditions; methanol
to oil molar ratio 225:1, catalyst concentration 1.0 wt.% of oil,
reaction temperature 55 °C and mixing intensity of 350 rpm.
The yield of biodiesel from the experiment is 88.2% at the opti-
mized set of conditions, which is very close to the model pre-
diction (Table 4).
854 S. Pradhan et al. / Fuel 97 (2012) 848–855

Yield - FAME Department of Chemical Engineering, University of

65.00 Saskatchewan, Canada for his valuable advice and support to
prepare this manuscript.

41.9065

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