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Fuel
journal homepage: www.elsevier.com/locate/fuel
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
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
38
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
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
Parameter
Unit
Value
Method
%
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
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
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
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:
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
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
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.
R2 0:97
13
Fig. 5. Response surface of TC vs. catalyst concentration and reaction time, obtained
by Eq. (11).
R2 0:96
12
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).
42
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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