Fuel Processing Technology 90 (2009) 1447–1451

Contents lists available at ScienceDirect

Fuel Processing Technology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / f u p r o c

Application of the factorial design of experiments to biodiesel production from lard

M. Berrios ⁎, M.C. Gutiérrez, M.A. Martín, A. Martín
Departamento de Química Inorgánica e Ingeniería Química, Universidad de Córdoba, Campus Universitario de Rabanales, Edificio Marie Curie, 14071 Córdoba, Spain

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

Article history: Synthesis of biodiesel from lard was carried out using potassium hydroxide as a catalyst. A 32 factorial design
Received 23 February 2009 of experiments was used. The effects of agitation speed and catalyst concentration were studied. A regression
Received in revised form 18 June 2009 model was obtained to predict the methyl ester concentration and adequately describe the experimental
Accepted 30 June 2009
range studied.
According to this study, the most suitable operational conditions were an agitation speed of 600 rpm, and
Keywords:
0.9 wt.% catalyst concentration. Furthermore, the product characterization was set out to meet the
Biodiesel
Lard
requirements laid down by the European Standard for biodiesel fuel (EN 14214).
Methanol © 2009 Elsevier B.V. All rights reserved.
Transesterification
Factorial design

1. Introduction
Biodiesel, which consists of long-chain fatty acid methyl esters
(FAME) obtained from renewable lipids such as those found in
vegetable oils and animal fats, can be used both as an alternative fuel
and as an additive for petroleum diesel. The prefix ‘bio’ denotes its
biological origin and renewable character; by contrast, the better
known non-renewable petroleum diesel is obtained from petroleum
distillates [1].
The transesterification with methanol is a catalyzed chemical
reaction which involves vegetable oil or animal fat and methanol to
yield FAME and glycerol as a by-product [2]. Methanol is the most
commonly used alcohol because of its low cost and its physical and
chemical advantages (polar compound and short chain alcohol). At
industrial scale, the alkaline catalyst is the most commonly used due
to its suitable operational conditions: its low cost, it is easy to install
and, above all, its high reaction rate, which provides a decrease in the
size of the equipment and in immobilized capital.
In recent years, a wide range of studies have been carried out
on biodiesel production from used frying oils [2–5], as well as the
research of new vegetable species [6–9], all with a view of overcoming
the economic barrier. However, the use of animal fats has not been
developed in depth [10–14].
Fats originating from animals, which were previously researched
as raw materials for biodiesel production, include beef tallow, lard,
and fish oil [15]. As far as their fatty acid compositions are concerned,
animal fats have certain disadvantages with regard to quality due to
the fact that the high saturated fatty acid content causes problems in
winter operations. On the other hand, the high degree of saturation
yields excellent fuel properties, specifically with regard to heating
value and cetane number [15–19].
A factorial design of experiments has been applied because it
allows the simultaneous consideration of many variables at different
levels and the interactions between those variables, using a smaller
number of observations than conventional procedures [20]. This
technique has several advantages [21] and has been used extensively
to develop different transesterification processes [15,20–30].
The aim of this study was biodiesel production from lard via an
alkali catalyst. In order to optimize some reaction conditions, a
factorial design of experiments was applied to study the effect of the
variables on the process and the interaction among those variables
[28].
2. Materials and methods
2.1. Materials
Refined lard was obtained from INTEXSUR (Spain). Table 1 shows
the most important characteristics of this lard. 99.5% pure methanol
and potassium hydroxide (85% purity) used as a catalyst, were
purchased from Alcoholes del Sur, S.A. (Spain) and Panreac (Spain),
respectively. The gas chromatography reference standard (methyl
heptadecanoate) was obtained from Fluka (Sweden).
2.2. Equipment

The experimental set-up used for the transesterification process

⁎ Corresponding author. Tel.: +34 957218586; fax: +34 957218625. was identical to that previously employed in other studies [1]; batch
E-mail address: l82becam@uco.es (M. Berrios). stirring reactor of 2 L capacity, where the heating system consisted of a

0378-3820/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2009.06.026
1448 M. Berrios et al. / Fuel Processing Technology 90 (2009) 1447–1451

Table 1 Table 2
Chemical analysis of lard. Experimental matrix and FAME concentration results after 20 min.

Tests Results ar a basis wt.% Results daf b basis wt.% Experiment Run Agitation Catalyst C Mean C ± STDa
Ash content 0.14 – number order speed (rpm) concentration (% m/m) (% m/m)
Moisture 1.23 – (wt.%)
Unsaponificable matter 1.18 1.20 1 10 400 0.6 84.30 84.40 ± 0.14
Free fatty acid 0.13 0.14 2 11 400 0.6 84.50
Monoglycerides 0.00 0.00 3 6 400 0.9 88.50 88.60 ± 0.14
Diglycerides 0.00 0.00 4 17 400 0.9 88.70
Triglycerides 97.02 98.66 5 3 400 1.2 88.90 89.05 ± 0.21
a 6 4 400 1.2 89.20
As received basis.
b 7 13 600 0.6 86.50 86.60 ± 0.14
Dry ash free basis.
8 18 600 0.6 86.70
9 1 600 0.9 89.20 89.25 ± 0.07
10 7 600 0.9 89.30
jacketed reactor through which glycerol from a thermostated system 11 5 600 1.2 90.20 90.25 ± 0.07
at the required temperature was circulated. Moreover, the system was 12 12 600 1.2 90.30
13 14 800 0.6 86.90 86.90 ± 0.00
made up of magnetic agitation, which makes it possible to control the
14 16 800 0.6 86.90
agitation speed at the desired interval. 15 8 800 0.9 89.30 89.35 ± 0.07
16 9 800 0.9 89.40
2.3. Experimental procedure 17 2 800 1.2 90.70 90.80 ± 0.14
18 15 800 1.2 90.90

The experimental procedure was similar to that employed by a

Vicente et al. [21]. The reactor was initially filled with the lard and
heated to a fixed temperature. The alkali catalyst was dissolved in the
methanol and the resulting solution (with an exact concentration)
was added to the lard. The reaction time was set at 20 min because it
was observed in a preliminary study that the FAME concentration was
approximately constant around this time. Fig. 1 explains the choice.
Samples were taken from the reactor and then kept cold, the
glycerol phase was removed and the FAME phase was washed with
deionised water to remove impurities, then centrifugated and dried
under vacuum conditions.
The FAME concentration (C, % m/m) was determined in a VARIAN
3900 GC by a method in agreement with the EN 14103 Standard [31].
The selected design of experiments (full 32 factorial design) is
explained in the following section.
2.4. Statistical analysis
A factorial design of experiments was applied to find out the
influence of the operational conditions of the transesterification
process, such as the agitation speed and the catalyst concentration, on
the FAME concentration.
The experimental design applied to this study was a full 32 factorial
design (two factors each at three levels). The response selected was
the FAME concentration (C, % m/m) at 20 min. The factors were
selected according to the background literature [1,21,32], the chem-
istry of the system and previous studies. The factors chosen were
agitation speed (revolutions per minute, rpm) and catalyst concen-
STD = standard deviation.
tration (wt.%). Factor levels were chosen by considering the opera-
tional limits of the experimental set-up and preliminary tests.
Agitation speed levels were selected according to the geometry of
the system: 400, 600 and 800 rpm. Catalyst concentration levels were
0.6%, 0.9% and 1.2% depending on the weight of the lard. In all exper-
iments, the temperature was set at 60 °C, close to the boiling point of
methanol. The methanol–lard mole ratio was selected at 6:1 in order
to duplicate the stoichiometric amount.
The experimental matrix for the factorial design and the results of
FAME concentration (C, % m/m) after 20 min are shown in Table 2.
Experiments were run at random to minimize errors due to pos-
sible systematic trends in the variables [21]. The experiments were
carried out in duplicate for experimental error estimation.
The use of analysis and factorial design of experiments allowed us
to express the FAME concentration as a polynomial model [23].
3. Results and discussion
To choose the adequate response in the factorial design, several
tests were carried out with different levels of catalyst concentration
and agitation speed. In all the experiments, atmospheric pressure and
a temperature of 60 °C were used for economic and technical reasons.
A methanol–lard mole ratio of 6:1 was selected according to the
background literature [3,33–35]. The reaction time for all the experi-
ments was 1 h in order to observe when the FAME concentration was
approximately constant. In this way, the selected response was FAME
concentration at 20 min as can be observed in Fig. 1.
The response was fitted to the factors through a general linear
model (GLM). The ANOVA for the response surface linear model is
provided in Table 3. Since the p-value for the model was lower than
0.05, there was a statistical relation between the response and the

Table 3
ANOVA for response surface linear model.

Source Sum of Degree of Mean F-value p-value

squares freedom square
Model 58.228 3 19.409 36.740 0.000
Agitation speed (x1) 1.612 1 1.612 3.050 0.103
Catalyst concentration (x2) 5.577 1 5.577 10.560 0.006
x 1 ⁎ x2 0.281 1 0.281 0.530 0.478
Residual 7.397 14 0.528
Corrected total 65.624 17
Fig. 1. FAME concentration (C, % m/m) versus time (min) to select the reaction time.
 M. Berrios et al. / Fuel Processing Technology 90 (2009) 1447–1451
Fig. 2. Residual plots of FAME concentration for the model.
selected variables at 95% confidence level. The most significant factor
was the catalyst concentration (p-value 0.006 ≪ 0.05).
In the GLM, the following expression was obtained, where y is the
FAME concentration:
y = 78:068 + 0:007 • x1 + 8:653 • x2 − 0:003 • x1 • x2 :
To test the fit of the model, the regression equation Eq. (1) and
determination coefficient (R2) were evaluated. In this case, the value
of the determination coefficient (R2 = 0.887) indicates that the
sample variation of 88.729% for FAME concentration is attributed to
the independent variables selected (x1, x2) and 11.271% of the total
variations are not explained by the model. Therefore, other variables
with the process may have influenced the FAME concentration.
Fig. 2 is a graph of the residual distribution, defined as the
difference between calculated and observed values over the observed
values for the response studied [27]. The fit is good because the
residual distribution does not follow a trend with regard to the
predicted variables. All the residuals are less than 1.2%, which indi-
cates that the model accurately represents the influence of FAME
concentration over the experimental range studied. The plot of
experimental value versus predicted value proves the same as the
residual distribution and is shown in Fig. 3.
Moreover, Fig. 4 shows the normal probability plot of the residuals,
which indicates a good validity for the approximation for the linear
regression model.
The 3D response surface graph is the most common graphical
representation of the regression equation. It can be observed in Fig. 5.
Fig. 3. Experimental values versus predicted values for the model.
1449
Fig. 4. Normal probability plot of the residuals.
To evaluate the validity of the model, two additional experiments
were performed. One of them was carried out at 1 wt.% KOH and
500 rpm. A FAME concentration of 88.50% m/m was obtained, with the
ð1Þ theoretical value at 88.70% m/m. In the second case, the conditions
were 1 wt.% KOH and 700 rpm. A FAME concentration of 88.80% m/m
was obtained, which was in agreement with the predicted value:
89.40% m/m. Therefore, it can be concluded that the model accurately
represents the methyl ester production from lard over the experi-
mental range studied.
Statistical analysis of the experimental range studied shows the
catalyst concentration as the most important factor in the response.
The agitation speed also has an influence. Both of them have a positive
influence. The interaction between them is not very significant but has
a negative influence (see Eq. (1)).
In this way, the FAME concentration increases when the values of
these variables increase. However, from 600 rpm and 0.9 wt.% KOH,
the improvement does not justify more catalyst and energy
consumption. Therefore, the most suitable conditions for the process
were: 60 °C, 6:1 methanol–lard mole ratio, 600 rpm and 0.9 wt.% KOH.
In order to find out the consumed power when the number of
revolutions of the stirrer is changed, the Reynolds number has been
calculated. For stirred tanks, the Reynolds number is calculated by the
next expression:
Ni • D2i • ρ
Rei = ð2Þ
μ
where Rei is the Reynolds number, Ni the number of revolutions of the
stirrer, Di the stirrer diameter, ρ the fluid density and µ the fluid
dynamic viscosity.
For the used system, with the diameter of the stirrer at 4 cm, the
agitation speed at 600 rpm, the fluid density at 0.913 g/cm3 and the
Fig. 5. Response surface plot of FAME concentration as a function of agitation speed and
catalyst concentration.
1450 M. Berrios et al. / Fuel Processing Technology 90 (2009) 1447–1451

Table 4
Characterization of obtained biodiesel under optimal conditions.
Experimental EN 14214
values Minimum
Acid value (mg KOH/g oil) 0.117
Density at 25 °C (g/cm3) 0.872 0.860
Kinematic viscosity at 40 °C (mm2/s) 4.85 3.50
Iodine value (g I2/100 g sample) 54.4
FAME content (% m/m) 88.70 96.50
Linolenic acid methyl ester content (% m/m) 0.5
fluid dynamic viscosity at 0.295 g/cm s, the Rei was 495. Therefore, the
flow was turbulent (Rei N 10).
For systems in turbulent mode, the consumed power is calculated
by Doran [36]:
3 5
P = NpV • ρ • Ni • Di
where N′p is a constant value of the power number in turbulent mode.
Given that the power rises with the revolutions number cube, working
with the maximum value of Ni to avoid the reaction control by the
matter transfer is justified.
3.1. Characterization of the product
The obtained product over the optimal conditions was character-
ized by means of some of the EN 14214 Standard specifications: acid
value, density at 25 °C, kinematic viscosity at 40 °C, iodine value, FAME
content and linolenic acid methyl ester content. Table 4 shows these
results, which do not fulfil the FAME content from the Standard.
4. Conclusions
The following conclusions can be obtained from this work:
A 32 factorial design of experiments has been used in the biodiesel
production from lard in order to reduce the number and the cost of
experiments and obtain more information per experiment.
A regression equation has been obtained as a result of the relation
between the FAME concentration and the operational variables
(catalyst concentration and agitation speed). The model explains
the sample variation as 88.73%.
The statistical analysis shows that, within the experimental range
studied, the two factors have a positive influence, with the catalyst
concentration being the most important. However, the interaction
has a slightly negative effect.
According to this study, the most suitable operational conditions
are 0.9 wt.% KOH and an agitation speed of 600 rpm, in operation
terms.
Acid value, density at 25 °C, kinematic viscosity at 40 °C, iodine
value, FAME content and linolenic acid methyl ester content were
analyzed in the obtained biodiesel under optimal conditions. Only
the FAME content was not fulfilled according to the EN 14214
Standard specifications.
Acknowledgements
The authors are grateful to the Ministry of Education and Science
(MEC, Spain) for the PhD grant AP2005-3537 and the firm BIDA, S.A.
for funding this work.
The authors would like to thank the lab technician Inmaculada
Bellido for her collaboration.
References
[1] M. Berrios, J. Siles, M.A. Martín, A. Martín, A kinetic study of the esterification of
FFA in sunflower oil, Fuel 86 (2007) 2383–2388.
Maximum [2] Y. Zhang, M.A. Dubé, D.D. McLean, M. Kates, Biodiesel production from waste cooking
0.500 oil: 1. Process design and technological assessment, Bioresource Technology 89
0.900 (2003) 1–16.
[3] A.V. Tomasevic, S.S. Siler-Marinkovic, Methanolysis of used frying oil, Fuel
5.00
Processing Technology 81 (1) (2003) 1–6.
120
[4] Y. Wang, S. Ou, P. Liu, Z. Zhang, Preparation of biodiesel from waste cooking oil via
two-step catalyzed process, Energy Conversion and Management 48 (1) (2007)
12.0 184–188.
[5] Y. Zhang, M.A. Dubé, D.D. McLean, M. Kates, Biodiesel production from waste
cooking oil: 2. Economic assessment and sensitivity analysis, Bioresource
Technology 90 (2003) 229–240.
[6] Y. Chisti, Biodiesel from microalgae, Biotechnology Advances 25 (3) (2007)
294–306.
[7] M.G. Kulkarni, A.K. Dalai, N.N. Bakhshi, Transesterification of canola oil in mixed
methanol/ethanol system and use of esters as lubricity additive, Bioresource
Technology 98 (10) (2007) 2027–2033.
[8] L.C. Meher, V. Dharmagadda, S.N. Naik, Optimization of alkali-catalyzed transes-
terification of Pongamia pinnata oil for production of biodiesel, Bioresource
Technology 97 (12) (2006) 1392–1397.
ð3Þ [9] A.K. Tiwari, A. Kumar, H. Raheman, Biodiesel production from jatropha oil
(Jatropha curcas) with high free fatty acids: an optimized process, Biomass and
Bioenergy 31 (8) (2007) 569–575.
[10] M. Canakci, The potential of restaurant waste lipids as biodiesel feedstocks,
Bioresource Technology 98 (2007) 183–190.
[11] T. Issariyakul, M. Kulkarni, A. Dalai, N. Bakhshi, Production of biodiesel from waste
fryer grease using mixed methanol/ethanol system, Fuel Processing Technology 88
(5) (2007) 429–436.
[12] F. Ma, L.D. Clements, M. Hanna, The effect of mixing on transesterification of beef
tallow, Bioresource Technology 69 (1999) 289–293.
[13] P. Muniyappa, S. Brammer, H. Noureddini, Improved conversion of plant oils and
animal fats into biodiesel and co-product, Bioresource Technology 56 (1996)
19–24.
[14] R. Nelson, M. Schrock, Energetic and economic feasibility associated with the
production, processing, and conversion of beef tallow to a substitute diesel fuel,
Biomass and Bioenergy 30 (2006) 584–591.
[15] G. Jeong, H. Yang, D. Park, Optimization of transesterification of animal fat
ester using response surface methodology, Bioresource Technology 100 (2009)
25–30.
[16] M. Mittelbach, C. Remschmidt, Biodiesel — The Comprehensive Handbook, First ed.
Boersedruck Ges. m. b. H., Austria, 2004.
[17] Y.M. Kang, H.S. Kim, Emulsified transesterification of soybean oil into biodiesel,
Journal of Korean Oil Chemists' Society 18 (4) (2001) 298–305.
[18] H.S. Yang, G.T. Jeong, S.H. Park, J.H. Park, D.H. Park, Reaction condition for biodiesel
production from animal fats, Korean Journal of Biotechnology and Bioengineering
22 (4) (2007) 228–233.
[19] X. Lang, A.K. Dalai, N.N. Bakhshi, M.J. Reaney, P.B. Hertz, Preparation and char-
acterization of bio-fuels from various bio-oils, Bioresource Technology 80 (2001)
53–62.
[20] N. De Lima da Silva, M.R. Wolf, C. Batistella, R. Maciel, Optimization of biodiesel
production from castor oil, Applied Biochemistry and Biotechnology 130 (2006)
405–414.
[21] G. Vicente, M. Martínez, J. Aracil, Optimisation of integrated biodiesel production.
Part I: a study of the biodiesel purity and yield, Bioresource Technology 98 (2007)
1724–1733.
[22] A. Bouaid, L. Bajo, M. Martinez, J. Aracil, Optimization of biodiesel production from
joroba oil, Transactions of the Institution of Chemical Engineers. Part B, Process
Safety and Environmental 85 (2007) 378–382.
[23] A. Bouaid, M. Martinez, J. Aracil, A comparative study of the production of ethyl
esters from vegetable oils as a biodiesel fuel optimization by factorial design,
Chemical Engineering Journal 134 (2007) 93–99.
[24] G.T. Jeong, D.H. Kim, D.H. Park, Response surface methodological approach for
optimization of free fatty acid removal in feedstock, Applied Biochemistry and
Biotechnology 137 (2007) 583–593.
[25] G.M. Tashtoush, M.I. Al-Widyan, M.M. Al-Jarrah, Experimental study on evaluation
and optimization of conversion of waste animal fat into biodiesel, Energy
Conversion and Management 45 (2004) 2697–2711.
[26] G. Vicente, A. Coteron, M. Martinez, J. Aracil, Application of the factorial design of
experiments and response surface methodology to optimize biodiesel production,
Industrial Crops and Products 8 (1998) 29–35.
[27] G. Vicente, M. Martinez, J. Aracil, Optimization of Brassica carinata oil methanolysis
for biodiesel production, JAOCS 82 (2005) 899–904.
[28] G. Vicente, M. Martinez, J. Aracil, Optimisation of integrated biodiesel produc-
tion. Part II: a study of the material balance, Bioresource Technology 98 (2007)
1754–1761.
[29] W.H. Wu, T.A. Foglia, W.N. Marmer, J.G. Phillips, Optimizing production of ethyl
esters of grease using 95% ethanol by response surface methodology, JAOCS 76
(1999) 517–521.
[30] X. Yuan, J. Liu, G. Zeng, J. Shi, J. Tong, G. Huang, Optimization of conversion of waste
rapeseed oil with high FFA to biodiesel using response surface methodology,
Renewable Energy 33 (2008) 1678–1684.
[31] EN 14103. Fat and oil derivates. Fatty acid methyl esters (FAME). Determination of
ester and linolenic methyl ester contents.
 M. Berrios et al. / Fuel Processing Technology 90 (2009) 1447–1451 1451

[32] M. Allawzi, M.I. Kandah, Parametric study of biodiesel production from used
soybean oil, European Journal of Lipid Science and Technology 110 (2008)
760–767.
[33] B. Freedman, E.H. Pryde, T.L. Mounts, Variables affecting the yields of fatty esters
from transesterified vegetable oils, JAOCS 61 (1984) 1638–1643.
[34] D. Darnoko, M. Cheryan, Kinetics of palm oil transesterification in a batch reactor,
JAOCS 77 (12) (2000) 1263–1267.
[35] G. Vicente, M. Martinez, J. Aracil, Integrated biodiesel production: a comparison of
different homogeneous catalysts systems, Bioresource Technology 92 (3) (2004)
297–305.
[36] Doran PM. Bioprocess Engineering Principles, ed. Academic Press Ltd., London
1995.