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Fuel 89 (2010) 3642

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Fuel
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Optimization of the transesterication reaction in biodiesel production


F. Ferella a,*, G. Mazziotti Di Celso b, I. De Michelis a, V. Stanisci c, F. Vegli a
a
b
c

Department of Chemistry, Chemical Engineering and Materials, University of LAquila, Monteluco di Roio, 67040 LAquila, Italy
Department of Food Science, University of Teramo, Via C.R. Lerici 1, 64023 Mosciano SantAngelo (TE), Italy
Fox Petroli S.p.A., Via Osca 74, 66054 Vasto (CH), Italy

a r t i c l e

i n f o

Article history:
Received 7 December 2008
Received in revised form 21 January 2009
Accepted 23 January 2009
Available online 14 February 2009
Keywords:
Biodiesel
Rapeseed oil
Transesterication
ANOVA

a b s t r a c t
In this paper response surface methodology (RSM) was used to study the transesterication reaction of
rapeseed oil for biodiesel production. The three main factors that drive the conversion of triglycerides
into fatty acid methyl esters (FAME) were studied according to a full factorial design at two levels. These
factors were catalyst concentration (KOH), temperature and reaction time. The range investigated for
each factor was selected taking into account the process of Fox Petroli S.p.A. Analysis of variance (ANOVA)
was used to determine the signicance of the factors and their interactions which primarily affect the
rst of the two transesterication stages. This analysis evidenced the best operating conditions of the rst
transesterication reaction performed at Foxs plant: KOH concentration 0.6% w/w, temperature 50 C
and reaction time 90 min with a CH3OH to KOH ratio equal to 60. Three empirical models were derived
to correlate the experimental results, suitable to predict the behavior of triglyceride, diglyceride and
monoglyceride concentration. These models showed a good agreement with the experimental results,
demonstrating that this methodology may be useful for industrial process optimization.
2009 Elsevier Ltd. All rights reserved.

1. Introduction
The problems that nowadays affect fossil fuels are well known:
increasing price that makes petroleum no longer economically sustainable, emission of very dangerous pollutants for human health,
emission of carbon dioxide that is the main reason of the global
warming. Moreover fossil fuels are non-renewable resources, so
they will last for a limited period of time. In this scenario vegetable
oils are more attractive, because of their renewable nature and
environmental benets. Biodiesel is said to be carbon neutral, as
biodiesel yielding plants absorb more carbon dioxide than that
added to the atmosphere when used as fuel [14]. It is highly biodegradable in fresh water as well as in soil. The best part of biodiesel (9098%) is mineralized in 2128 days under aerobic or
anaerobic conditions [57]. Furthermore, the use of biodiesel in
diesel engines reduces the emissions of hydrocarbons, carbon
monoxide, particulate matter and sulphur dioxide. Only nitrogen
oxides emission increases: this behavior is due to the oxygen content of biodiesel [814]. However, vegetable oils have some disadvantages. First of all, the direct use in internal combustion engines
is problematic. Due to their high viscosity (about 1117 times
greater than diesel fuel) and low volatility, they do not burn completely and form deposits in the fuel injectors of diesel engine
[15,16]. An improvement on viscosity can be obtained with transe-

* Corresponding author. Tel.: +39 0862 43 4265; fax: +39 0862 43 4203.
E-mail address: francesco.ferella@univaq.it (F. Ferella).
0016-2361/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2009.01.025

sterication, which seems to be the process that assures best results in terms of lowering viscosity and improving other
characteristics [3]. Besides these technical difculties, there are
some social problems to be considered, as the extensive use of vegetable oils may cause starvation in poor and developing countries.
As regards catalyst, potassium hydroxide has been successful in
producing biodiesel at industrial level [17]. Nevertheless, potassium hydroxide produces soaps by neutralizing the free fatty acid
in the oil or by triglyceride saponication. Thus, biodiesel and glycerine have to be puried by washing with hot distilled water two
or three times, resulting in a high consumption of both time and
water [3]. Unfortunately, due to their polarity, soaps dissolve in
glycerol phase during the separation stage after the reaction, but
they may be separated by means of a simple centrifugation. Formation of soaps decreases biodiesel yield obtained after the clarication and separation stages. In addition, the dissolved soaps
increase the methyl ester solubility in glycerol, an additional cause
of yield loss [4]. Several types of vegetable oils can be used for the
biodiesel production. In this paper rapeseed oil was studied, but
there are no technical restrictions to the use of other kinds of vegetable oils, although biodiesels coming from some vegetable oils
may not full quality standards [1822].
In Italy diesel fuel consumption was about 26 million tons in
2007 [23]. Considering that from every hectare of rape is possible
to obtain around 1.11.2 tons of oil [24], the possibility of total
substitution of diesel fuel with biodiesel is unlikely. However, vegetables oil can represent a small contribution, if biodiesel and die-

37

F. Ferella et al. / Fuel 89 (2010) 3642

sel were blended together. In 2007 469,707 tons of biodiesel were


produced in Italy, of which 202,035 tons were used in domestic
market [25]. Biodiesel is blended at 5% and up to 25% with diesel
in some petrol stations, while it is used unblended for heating purposes. Fox Petroli S.p.A. is one of the most important Italian companies amongst those operating in the production of biodiesel.
The plant is situated in Vasto, Central Italy, and in 2007 it produced
around 130,000 tons of biodiesel [26]. The raw rapeseed oil undergoes rst transesterication, and then a settler lets the glycerine
separate from supernatant, which reaches a reactor for the second
transesterication: the nal triglyceride conversion is 9899%. Further glycerine is separated in another settler. A heat exchanger removes part of methanol, whereas the other part is dried off by
vacuum distillation. The raw biodiesel is then washed by water
and centrifuged for removal of last traces of glycerine and soaps.
Water is dried off in an evaporator and a vacuum dryer; nally,
the biodiesel (named BIOFOX) is stored to be distributed and sold.
The glycerine is rened and sold as by-product. Several parameters
affect the transesterication: catalyst concentration, methanol
concentration, temperature, reaction time, pressure and the type
of oil because of different content of triglycerides and phospholipids. In this study three of the most important parameters which affect the yield of the rst transesterication reaction were tested,
i.e. catalyst concentration, temperature and time of reaction. Moreover, these are the easiest factors which can be carefully controlled
during the industrial production. All the tests were performed by
using rapeseed oil at atmospheric pressure, since the transesterication proceeds very fast even at low pressure: this avoids the increase of costs both in terms of equipment and energy
consumption. As alkaline metal hydroxides are easily the most active, KOH is used for the biodiesel manufacturing. The compound
which really reacts with triglycerides is methylate, hence the
amount of methanol also affects the transesterication. The
CH3OH:KOH ratio (w/w) was xed at 60 for all the tests performed
during the experimental campaign: changing the amount of KOH,
the concentration of methanol automatically changes in different
tests. The total reaction between triglycerides and methanol to
give biodiesel is a sequence of three sequential reactions:

Triglyceride CH3 OH ! Diglyceride FAME

Diglyceride CH3 OH ! Monoglyceride FAME


Monoglyceride CH3 OH ! Glycerol FAME

2
3

tests carried out by the authors demonstrated unsatisfactory conversion rates of triglycerides. Moreover at lower temperatures miscibility of methoxide and oil is scarce: this behaviour is due to the
greater polarity of the methoxide molecule with respect to the triglyceride one, which is non-polar and determines the hydrophobic
performance of the oil itself. As a matter of fact, the greater the
temperature, the greater the miscibility of that mixture. Responses
selected to test the yield of the transesterication were triglyceride, diglyceride and monoglyceride concentration (hereafter TC,
DC, MC, respectively). Experimental results were worked out using
ANOVA, which allows to evaluate whether the effect and the interaction among the investigated factors are signicant with respect
to the experimental error. Yates algorithm is a simple technique
for estimating the main effects and interactions among them. The
signicance of the main factors and their interactions was assessed
by F-test method with a condence level of 95% [29,30]. Response
surface methodology (RSM), a mathematicalstatistical tool, was
used for modelling TC, DC and MC. These responses of interest
are inuenced by the three tested factors and RSM allows the optimization of all these responses. For example, TC can be expressed
as:

TC f A; B; C e

where e represents the error observed in the response TC. A low-order model is usually employed, like a rst-order model, but if a curvature in the surface is present, a polynomial of higher order must
be used. In this study three second-order polynomials were used to
describe the response surface for TC, DC and MC; the general structure of that polynomial is the following:

Y b0

k
X
i1

bi xi

bii x2i

XX
ii<j

bij xi xj e

where Y is the yield of the reaction, bi are the regression coefcients


and xi are the coded factors. Obviously a polynomial can not
approximate all the space of the independent variables, but it usually ts the real response for a relatively small region. The model
parameters can be estimated by using proper experimental designs
while collecting data. The experimental design for tting the second-order models was orthogonal and rotatable. Orthogonality is
the optimal design property as it minimizes the variance of the
regression coefcients. Rotability is another important property
which implies that the variance of a response at a certain point is

From a stoichiometric point of view three moles of methanol


are required for each mole of triglyceride: however, in order to
maximize ester production, a greater molar ratio is employed, usually the double [27,28]. The aim of the present work is the determination of the best operating conditions for the rst reaction of the
two-stage transesterication industrial process developed by Fox
Petroli S.p.A.
2. Materials and methods
2.1. ANOVA and regression analysis
The experimental tests were carried out according to a full 23
factorial design where factors (low and high level in parentheses)
were: KOH concentration (0.2%; 0.6% w/w), temperature (50 C;
60 C) and reaction time (30 min; 90 min).
Each test was replicated twice. The above values were chosen
taking into account economic considerations: the range of KOH
concentration (percentage by weight referred to the oil weight)
and the reaction time have been selected around the typical value
used in the industrial production of the company. The higher temperature level was determined by considering the boiling point of
methanol (65 C), whereas the lower value is 50 C, since previous

Fig. 1. Central composite design for three factors at two levels.

38

F. Ferella et al. / Fuel 89 (2010) 3642

Table 1
Test conditions of the full factorial design.
Test

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17

Treatment

Coded factors

combination

(1)
a
b
ab
c
ac
bc
abc
0
0
0

1
1
1
1
1
1
1
1
0
0
0
0
0
1.68
1.68
0
0

1
1
1
1
1
1
1
1
0
0
0
1.68
1.68
0
0
0
0

only a function of the distance of the point from the design centre
and does not depend on direction [30,31]. The central composite design carried out in this study is shown in Fig. 1.
This central composite design can be rotatable by the choice of
a; its general formula is:

a nf 1=4

where nf is the number of points used in the factorial portion of the


design. In this case, considering eight points, a is equal to 1.68. Table
1 gives the conditions of all the tests developed by the full factorial
design, both in terms of coded and non-coded variables. The central
point test was replicated three times (tests 911, Table 1), in order
to have a good estimation of the experimental error. Furthermore,
six axial tests (1217, Table 1) were also carried out to better understand the shape of the response surfaces.
The regression analysis was used to build three quantitative
models, in which only the signicant factors were taken into account. These models were built in order to predict TC, DC and
MC for many operating conditions that were not directly tested.
It should be noted that the use of the models outside the investigated range is not allowed, since it would lead to wrong results.
2.2. Experimental procedure
The experimental tests were carried out using a 500 ml jacketed
stirred reactor tank. The temperature of oil was controlled by a
thermometer and regulated by an electrically heated water bath
(Colora WK16). The reactor was mechanically stirred at 600 rpm
to assure a good mixing of the reactants.

Table 2
Quality control of the rapeseed oil.

KOH (% w/w)

Temperature (C)

Time (min)

1
1
1
1
1
1
1
1
0
0
0
0
0
0
0
1.68
1.68

0.2
0.6
0.2
0.6
0.2
0.6
0.2
0.6
0.4
0.4
0.4
0.4
0.4
0.064
0.736
0.4
0.4

50
50
60
60
50
50
60
60
55
55
55
46.6
63.4
55
55
55
55

30
30
30
30
90
90
90
90
60
60
60
60
60
60
60
9.5
110.5

For each test 200 ml of rapeseed oil (quality control reported in


Table 2) were heated at the required temperature, according to the
experimental plan shown in Table 1; in the meantime, KOH (akes,
assay > 90%, SigmaAldrich) was dissolved in a certain volume of
methanol (anhydrous 99.8%, SigmaAldrich), in order to have a
xed ratio CH3OH:KOH equal to 60 (w/w). As said before, this ratio
was kept constant for all the tests. For example, in test 1, 0.37 g of
KOH were dissolved in 22.1 g of methanol, considering the oil density of 0.92 kg/m3.
Once KOH was completely dissolved, methoxide was added to
the hot solution, and the reaction took place for the required time.
After that, 10 ml of solution were withdrawn and 2 ml of citric acid
were added to stop the transtesterication. Hence, the biodiesel
was separated from glycerine by centrifugation (Thermo Scientic
IEC CL30) and the sample was then ready for analysis.
2.3. Analytical methods
TC, DC and MC were measured by capillary column gas chromatography (Thermo TRACE GC Ultra) equipped with a cold on-column injection and autosampler apparatus. Analyses were carried
out according to the EN 14105 internal standard calibration;
100 mg of each biodiesel sample were mixed with 100 ll of
1,2,4-butanetriol (1 mg/ml, standard 1) and 100 ll of 1,2,3-Tricaprinoylglycerol (8 mg/ml, standard 2). Other 100 ll of N-methyl-Ntrimethylsilyltriuoroacetamide (MTSFA, derivatization grade)
were added to convert both free and total glycerol into volatile
compounds. All reagents were supplied by SigmaAldrich. After
15 min, 8 ml of heptane were added as solvent. Final sample
(0.5 ll) were injected into the gas chromatograph analyser for
TC, DC, MC determination.

3. Results and discussion

Parameter

Unit

Value

Method

Acidity (as oleic acid)


Cloud point
Density at 20 C
Iodine number
Lecithin (as phosphorus)
Erucic acid
Sulphur content
Total contamination
Viscosity at 20 C
Water content

%
C
kg/m3
gI2/100g
ppm
%
ppm
%
mm2/s
%

<0.10
3.8
0.92
113
<10
<0.20
<2
<0.05
77.5
<0.10

NGD C10-1976
EN 23015
EN ISO 3675
ISO 5508
UNI 22038-2001
ISO 5508
EN ISO 20846
NGD C7-1976
EN ISO 3104
KARL FISHER

3.1. ANOVA
The response of the factorial design is reported in Table 3. Each
result is expressed as arithmetic mean of two replications.
Looking at Table 3, test 6 gives the best simultaneous results in
terms of triglycerides, diglycerides and monoglycerides, as their
concentrations (0.05%, 0.09% and 0.36% w/w, respectively) are the
lowest among those of the whole experimental plan. These results
were obtained by 0.6% w/w of KOH, 50 C and 90 min of reaction.
Comparing these values with the EN 14214 specications (see

39

F. Ferella et al. / Fuel 89 (2010) 3642


Table 3
Results obtained in terms of TC, DC and MC.

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17

AB

AC

Response
TC (% w/w)

DC (% w/w)

MC (% w/w)

16.42
1.45
18.50
0.43
14.10
0.05
16.34
0.01
3.32
2.47
2.95
6.65
2.50
96.71
0.01
6.84
2.74

11.28
0.87
12.48
0.33
10.58
0.09
12.44
0.09
2.07
1.46
1.80
3.63
1.51
3.23
0.04
4.58
1.63

6.74
0.72
7.17
0.80
5.57
0.36
6.73
0.84
0.93
0.90
1.09
1.26
1.02
0.07
0.60
2.72
0.83

-2
-4

Effect (%)

Test

-6
TC
DC
MC

-8
-10
-12
-14
-16
-18

Fig. 2. Effect of factors and of their combinations on TC, DC and MC (A: KOH; B:
temperature; C: reaction time).

Table 4), the biodiesel fulls the quality requirements regarding


TC, DC and MC. At the moment, the biodiesel produced by Fox Petroli after the rst transesterication has the following composition:
TC 5.26%, DC 2.48%, MC 1.21% w/w; as expected, methanol and free
glycerine content exceeds the limits indicated in the European
specications. Table 4 also shows the analysis of biodiesel produced by that plant at the end of the process, as it is put on the
market [26].
Fig. 2 shows the main effects and interactions among factors,
which mainly inuence the nal concentration of triglycerides.
Effects with a statistical signicance lower than 95% were not
reported, according to the F-test utilized. Catalyst concentration
KOH, factor A, has a strong negative effect on the TC (16%): as expected, increasing the amount of catalyst the concentration of triglycerides decreases. In this particular case, as the response
variables (TC, DC, MC) represent the reactants, a negative effect

is advisable, because of a very low TC. This means that a greater


amount of triglycerides reacts with methylate, increasing the yield
of the transesterication.
Reaction time, factor C, has a slight negative effect, so the yield
of the process increases if the reaction time is prolonged from 30 to
90 min.
The interaction AB has a slight negative effect too; if the amount
of KOH increases together with temperature, the TC reduces, while
the nal conversion to FAME grows.
Temperature, factor B, seems to have a small positive effect, even
though it is not statistically signicant with respect to the experimental error determined by replications of the central point test.
Results of ANOVA for concentration of diglycerides are shown in
Fig. 2. As for TC, catalyst concentration has an important negative
effect on DC in the range studied, whereas interaction AB between
KOH and temperature is also negative but less determinant. Time is
not signicant: this could be explained by a greater reaction rate of
the second reaction (Eq. (2)) compared to the rst one (Eq. (1)).

Table 4
Analysis of biodiesel produced at Fox Petroli and European specication for FAME used in diesel engines.
Parameter

Unit

Value

Specication EN 14214
Min

Acid value
Ash sulphated
Carbon residue
Cetane number
Cold lter plugging point
Cloud point
Methanol content
Monoglyceride content
Diglyceride content
Triglyceride content
Free glycerol
Total glycerol
Copper strip corrosion (3 h at 50 C)
Density at 15 C
Ester content
Flash point
Iodine number
Linolenic acid methyl ester
Alkali content

mgKOH/g
% m/m
% m/m
C
C
% m/m
% m/m
% m/m
% m/m
% m/m
% m/m
Rating
kg/m3
% m/m
C
gI2/100g
% m/m
mg/kg

0.27
<0.01
0.10
53
6
0
<0.05
0.69
0.08
0.1
0.006
0.20
Class 1
883.5
97.3
183
119
7.3
<2

Phosphorus content
Oxidation stability, 110 C
Sulphur content
Total contamination
Viscosity at 40 C
Water content

mg/kg
hours
mg/kg
mg/kg
mm2/s
mg/kg

1.4
7.2
<2
9
4.46
236

Method
Max
0.5
0.02
0.30

51.0
-20
0.2
0.8
0.2
0.2
0.02
0.25
Class 1
860
96.5
120

900

120
5
10
6

3.5

10
24
5
500

EN 14104
ISO3987
EN ISO 10370
EN ISO 5165
EN116
EN 23015
EN 14110
EN 14105
EN 14105
EN 14105
EN 14105
EN 14105
EN ISO 2160
EN ISO 3675
EN 14103
EN ISO 3679
EN 14111
EN 14103
EN 14108 (Na)
EN 14109 (K)
EN 14107
EN 14112
EN ISO 20846
EN 12662
EN ISO 3104
EN ISO 12937

40

F. Ferella et al. / Fuel 89 (2010) 3642

Furthermore temperature alone (factor B) has a slight positive


effect on the nal DC, nevertheless, this factor does not have the required signicance if compared to the variance of the experimental
error.
As regards monoglycerides (see Fig. 2), there are four main factors and interactions that inuence their concentration at the end
of the reaction. As usual, factor A has a signicant negative effect,
even though not so important as for triglycerides and diglycerides.
Temperature, factor B, seems to have a positive effect on the nal MC, but this means that it plays a negative role in the conversion of monoglycerides to methyl esters in the range from 50 to
60 C. Reaction time (factor C) has a negative effect, so it will be
useful to extend the time to achieve a greater yield of FAME.
The interaction AC has a very small positive effect: increasing
simultaneously both concentration of KOH and reaction time the
total conversion of monoglycerides to methyl esters lightly
decreases.
3.2. Regression analysis
Experimental results were tted by empirical models according
to RSM [30,31], in order to predict TC, DC and MC by weight under
different operating conditions. The complete models suitable to t
the experimental data are second-order models, having the following general structure:

Y a0 a1 X 1 a2 X 2 a3 X 3 a12 X 1 X 2 a13 X 1 X 3 a23 X 2 X 3


a11 X 21 a22 X 22 a33 X 23

where all the independent variables are in the coded form and all
coefcients a0, a1, a2, a3, a12, a13, a23, a11, a22, a33 were estimated
by linear regression procedures. Coded variables can be obtained
from the real ones by the following expressions:

X 1 A  0:4=0:2
X 2 B  55=5
X 3 C  60=30

were not satisfactory and the signicance of all the model parameters was rather low.
The regression analysis was repeated, removing the results obtained from tests 14 and 16. The poor agreement between experimental results and factorial design is particularly strong in case of
mono and diglyceride data tting: this behaviour is probably due
to their trend as a function of the extent of reaction, as shown in
Fig. 3.
A non satisfying data tting was obtained for triglycerides as
well, although they showed a different trend as a function of extent
of reaction.
Fig. 3 allows to dene as critical tests 14 and 16, because their
experimental data are located in the rise side of the curve. This area
is particularly difcult to t for the second-order model, which, of
course, is dened by a parabolic trend.
This problem is guessable from a chemical point of view: if the
catalyst to triglycerides molar ratio is at least equal to the stoichiometric one, triglycerides react quickly facilitating monoglycerides
formation, but this is going to decrease in case of lower catalyst
concentrations. This is the case of test 14, where monoglyceride
concentration is very low, because triglyceride species are poorly
converted. Thus, test 14 shows experimental results which are
not tted with success by the second-order model.
A similar situation happens when the reaction time is too low:
in this case triglyceride species is poorly converted with consequently scarce mono and diglyceride concentration, as they have
not had enough time to form (case of test 16). Results of the second
regression analysis for TC are given in Table 5.
According to this analysis, the following equation was then used
in order to predict TC, as a function of catalyst concentration, temperature and reaction time:

TC%w=w 4:49  8:13X 1  0:85X 3 3:58X 21

R2 0:97

11

Eq. (11) was utilized for the optimization of the rst transesterication reaction as concerns FAME production. The adequacy of
the mathematical model obtained by the regression analysis was
conrmed by a scatter diagram (Fig. 4), where experimental data
for TC were reported as a function of the calculated ones.
As it is possible to note, all points are disposed close to the
straight line, conrming a good agreement between the experimental results and those ones calculated by the model.
Eq. (11) was also employed to represent the best-tting response surface as a function of KOH concentration and reaction
time. Dependence on temperature misses, because of low signicance of the coefcients a2, a12, a23, a22.
As shown in Fig. 5, conversion of triglycerides is rather low
when KOH concentration is below 0.45%. In case of higher values,
KOH enhances the chemical reactions, reaching more satisfactory
conversion values. At the same time, keeping constant KOH con-

10

A rst regression analysis was carried out in order to obtain an


useful tool, able to calculate the nal TC, DC, MC of the rst transesterication reaction, even for different KOH concentration, temperature and time.
Three statistical models were developed as a consequence of
the rst regression analysis. However, these models did not show
a good agreement with the experimental results of the whole factorial design, because correlation coefcients of the regression

Table 5
Estimated values for parameters in Eq. (5).
Coefcient (%)
a0
a1
a2
a3
a12
a13
a23
a11
a22
a33
Fig. 3. Mono, di and triglyceride trends as a function of extent of reaction.

R2 = 0.96

s.d

Signicance

4.49
8.13

0.65
0.49

0.85

0.46

3.58

0.61

100
100
n.s.
90
n.s.
n.s.
n.s.
100
n.s.
n.s.

41

F. Ferella et al. / Fuel 89 (2010) 3642

Calculated (% w/w)

20
Tri
Di
Mono

15

10

10

15

20

Experimental (% w/w)
Fig. 4. Scatter diagram of the experimental TC, DC and MC vs those concentrations
calculated by Eqs. (11)(13).
Fig. 7. Response surface of MC vs. catalyst concentration and reaction time.

result, the mathematical model which is able to predict the DC in


the range of the investigated factors (0.2% < A < 0.6%; 50 C < B <
60 C; 30 min < C < 90 min) is a simple second-order curve, as
shown in Fig. 6.
The trend reported in Fig. 6 suggests that the minimum catalyst
concentration required to be sure that all diglycerides react with
methanol is 0.530.55% w/w.
The second-order mathematical model resulting from the
regression analysis is as follows:

MC% 1:26  3:07X 1  0:38X 3 1:82X 21 0:30X 23

R2 0:97
13

Fig. 5. Response surface of TC vs. catalyst concentration and reaction time, obtained
by Eq. (11).

centration on high values, reaction time shows a positive effect on


triglyceride conversion. A statistical model was also developed for
DC by a different regression analysis, according to the following
equation:

DC% 2:64  5:91X 1  2:98X 21

R2 0:96

12

In this equation there are only three signicant coefcients, a0,


a1, a11, as result of a strong dependence on catalyst concentration,
which mainly drives the reaction between diglycerides and methanol. The scatter diagram of the experimental DC versus those values obtained by Eq. (12) is reported in Fig. 4: a good agreement
between the two set of data can be observed, conrming that the
model interprets the experimental range studied adequately. As a

MC calculated by Eq. (13) was reported in Fig. 4 together with


MC obtained by the experimental tests. A very good R2 value justies the choice of the model above, so it can be used in a procient
way to understand the behaviour of MC for different experimental
conditions which were not directly tested.
Eq. (13) can be represented as dimensional surface and contour
plot: this surface shows the predicted MC for the experimental
range both of reaction time and initial catalyst concentration of rapeseed oil. The tri-dimensional surface reported in Fig. 7 is the
most useful approach in terms of visualization of the reaction system, because it gives the simultaneous dependence from the two
most signicant parameters (KOH concentration and time) which
affect the production of FAME. As Fig. 7 highlights, behaviour of
monoglycerides is similar to that of triglycerides: it is rather low
when KOH concentration is below 0.400.45% whilst, in case of
higher values, KOH catalyst improves the chemical reaction enabling more satisfactory reaction rates. At the same time, keeping
constant KOH concentration on high values, reaction time shows a
positive effect on monoglyceride conversion: in particular, after 60
min the conversion to esters is complete.
4. Conclusions

12

DC (% w/w)

10
8
6
4
2
0

0.2

0.4

0.6

0.8

KOH (% w/w)
Fig. 6. Response surface of the DC using Eq. (12).

In this paper a study of the optimization of the rapeseed oil


transesterication reaction parameters was carried out by means
of Response Surface Methodology (RSM). In particular KOH catalyst
effect, temperature and reaction time were investigated considering the inuence on triglyceride, diglyceride and monoglyceride
concentration. The analysis of variance (ANOVA) showed that to
obtain satisfactory triglyceride conversion, the higher catalyst concentration studied was needed, together with a reaction time of
about 90 min. Moreover, increasing both temperature and KOH
concentration higher conversion rate could be achieved. Similar re-

42

F. Ferella et al. / Fuel 89 (2010) 3642

sults were obtained for diglyceride species; time does not seem so
signicant as in previous case: this is probably due to the greater
reaction rate of diglyceride compared to the triglyceride one. As regards monoglycerides, their behaviour is very close to that of triglycerides; however, the increase of both catalyst concentration
and time leads to lower ester conversions. The same negative effect
is reached in case of higher temperature values. The statistical
models developed for predicting TC, DC and MC showed a good
agreement between experimental and calculated yields (R2 P
0.96), demonstrating the usefulness of regression analysis as a tool
for optimization purposes. In conclusion, results evidenced the
essential role of the catalyst, taking into account the methanol to
catalyst ratio that remained constant; a very good conversion of
triglycerides, diglycerides and monoglycerides into FAME was obtained by 0.6% w/w KOH, 60 methanol to KOH ratio by weight at
50C after 90 min of reaction. The nal concentrations were
0.05% triglicerides, 0.09% diglycerides and 0.36% monoglycerides.
This suggests further work which will be aimed at the optimization
of the second transesterication reaction, achieving a full optimization of the Fox Petrolis process.

Acknowledgements
Authors are very grateful to Ing. Francesca Forgione for her precious collaboration during the experimental work at Fox Petrolis
laboratories.
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