Energy & Fuels 2008, 22, 3889–3893 3889

Mixtures of Vegetable Oils and Animal Fat for Biodiesel

Production: Influence on Product Composition and Quality
Joana M. Dias, Maria C. M. Alvim-Ferraz,* and Manuel F. Almeida
LEPAE, Faculdade de Engenharia, UniVersidade do Porto,
R. Dr. Roberto Frias, Porto 4200-465, Portugal

ReceiVed July 4, 2008. ReVised Manuscript ReceiVed August 18, 2008

Studying alternative raw materials for biodiesel production is of major importance. The use of mixtures,
namely, by incorporating wastes, is an environmental friendly alternative and might reduce production costs.
The objective of the present work was (i) to study biodiesel production using vegetable oils (virgin and waste)
mixed with animal fat, (ii) to analyze the variations in biodiesel composition, aiming its prediction when
mixtures with different fat contents are used as raw materials, and (iii) to understand how mixture composition
influences biodiesel quality. Production yields varyed from 81.7 to 88.8 wt %; furthermore, the obtained products
fulfilled most of the determined quality specifications according to European biodiesel quality standard EN
14214. Minimum purity was only achieved using waste frying oil or soybean oil alone as raw material; however,
it ranged from 93.9 to 96.6 wt %, always being close to the limit (96.5 wt %). It was possible to establish a
model to be used for predicting composition and some parameters of biodiesel resulting from the mixtures,
and it could be estimated that the use of at least 12% lard in a soybean oil/lard mixture would be effective in
reducing the iodine value of biodiesel to acceptable values. Considering the use of virgin or waste vegetable
oils, it was concluded that waste frying oil might be an alternative raw material to obtain a biodiesel fulfilling
European standard at a lower cost.

Introduction
Biodiesel consists of a mixture of fatty acid alkyl esters, used
as an alternative fuel in compression-ignition engines; it is
obtained from renewable resources, such as vegetable oils and
animal fats, which makes it biodegradable and nontoxic.
Furthermore, biodiesel contributes for the reduction of CO2
emissions, because of the fact that production comprises a closed
carbon cycle.1,2 Biodiesel also presents very low sulfur content,
high cetane number, and good characteristics regarding storage
and transportation, which makes it a very attractive alternative
fuel.1,3,4 Biodiesel might be produced by transesterification,
which is a three-step reversible reaction that converts the initial
triglyceride into a mixture of alkyl esters and glycerol, in the
presence of a catalyst (Figure 1).
At an industrial scale, biodiesel production is mainly made
using virgin vegetable oils. The current great obstacle for
biodiesel production is the high price of those raw materials;
also, the use of food oils for biodiesel production is controver-
sial, which is the reason why studying alternatives is of major
importance. There are many studies reporting the transesteri-
fication of different types of vegetable oils; on the contrary,
few studies can be encountered regarding the conversion of
* To whom correspondence should be addressed. Telephone: +351-22-
5081688. Fax: +351-22-5081449. E-mail: aferraz@fe.up.pt.
(1) Bozbas, K. Biodiesel as an alternative motor fuel: Production and
policies in the European Union. Renewable Sustainable Energy ReV. 2008,
12 (2), 542–552.
(2) Van Gerpen, J. Biodiesel processing and production. Fuel Process.
Technol. 2005, 86 (10), 1097–1107.
(3) Meher, L. C.; Vidya Sagar, D.; Naik, S. N. Technical aspects of
biodiesel production by transesterificationsA review. Renewable Sustainable
Energy ReV. 2006, 10 (3), 248–268.
(4) VenkatReddy, C. R.; Oshel, R.; Verkade, J. G. Room-temperature
conversion of soybean oil and poultry fat to biodiesel catalyzed by
nanocrystalline calcium oxides. Energy Fuels 2006, 20 (3), 1310–1314.
animal fat. This is probably due to the fact that animal fat use
at a larger scale is limited; also, a high degree of free fatty acids
gives rise to difficult production processes.5
Studies regarding the mixture of raw materials for biodiesel
production are currently limited; however, in a study by
Meneghetty et al.,6 the use of castor oil, which had a viscosity
of 225.8 mm2 s-1 at 40 °C enabled biodiesel production by
mixing it with either soybean or cottonseed oil. In a study by
Lebedevas et al.,7 the use of three component mixtures also
allowed for the reduction of emission and harmful components
of the fuel. Soybean oil has a high iodine value; therefore, the
product obtained using this raw material alone often does not
fulfill the European biodiesel standard EN 14214. On the other
hand, animal fat is known to have a low iodine value, and
therefore, its use in mixtures with soybean oil will probably
result in a fuel with improved iodine values (lower than the
limit).
The use of wastes as raw materials for biodiesel production
has three major advantages: (i) does not compete with the food
market, (ii) recycles waste, and (iii) reduces production costs.8
The great amount of waste animal fat, produced at several
(5) Ngo, H. L.; Zafiropoulos, N. A.; Foglia, T. A.; Samulski, E. T.; Lin,
W. Efficient two-step synthesis of biodiesel from greases. Energy Fuels
2008, 22 (1), 626–634.
(6) Meneghetti, S. M. P.; Meneghetti, M. R.; Serra, T. M.; Barbosa,
D. C.; Wolf, C. R. Biodiesel production from vegetable oil mixtures:
cottonseed, soybean, and castor oils. Energy Fuels 2007, 21 (6), 3746–
3747.
(7) Lebedevas, S.; Vaicekauskas, A.; Lebedeva, G.; Makareviciene, V.;
Janulis, P.; Kazancev, K. Use of waste fats of animal and vegetable origin
for the production of biodiesel fuel: Quality, motor properties, and emissions
of harmful components. Energy Fuels 2006, 20 (5), 2274–2280.
(8) Wang, Y.; Ou, S.; Liu, P.; Xue, F.; Tang, S. Comparison of two
different processes to synthesize biodiesel by waste cooking oil. J. Mol.
Catal. A: Chem. 2006, 252 (1-2), 107–112.

10.1021/ef8005383 CCC: $40.75  2008 American Chemical Society

Published on Web 10/15/2008
3890 Energy & Fuels, Vol. 22, No. 6, 2008
slaughterhouses and other meat-processing units, might be an
attractive and cheap raw material. One of the great concerns
regarding the use of animal fat as a raw material for biodiesel
production is its cold-weather properties and oxidation stability;
however, it is known that the obtained fuel might be used in
100% in boilers for heat generation. Other waste materials that
can be used for biodiesel production are the waste-frying
oils.8-11 Because of the scarce availability of these low-cost
materials, their use at an industrial scale is limited; however,
their mixture with other raw materials might be an attractive
alternative.
The current knowledge regarding the use of mixtures of raw
materials including wastes is yet very scarce. Aiming to improve
this knowledge, the objective of the present work was (i) to
study biodiesel production using vegetable oils (virgin and
waste) mixed with animal fat, (ii) to analyze the variations in
biodiesel composition, aiming its prediction when mixtures with
different fat contents are used as raw materials, and (iii) to
understand how mixture composition influences biodiesel
quality.
Experimental Section
General. The soybean oil used was from the brand “olisoja”
and was donated by Sovena, SA, Portugal. This oil met Portuguese
specifications for food oil. The pork lard was from the brand “Dilop
Carnes” and was purchased at the food market. The waste frying
oil was obtained from a voluntary collection system implemented
at the Faculty and consisted of waste frying oil from different
domestic sources. The same mixture of waste frying oils was used
in all experiments. The reagents used during biodiesel production
procedures were methanol (99.5%, analytical grade, Fischer
Scientific), sodium hydroxide powder (97%, reagent grade, Aldrich),
and anhydrous sodium sulfate (99%, analytical grade, Panreac).
Biodiesel production was performed in three steps: pretreatment
of raw material, synthesis, and purification.
Raw Materials Pretreatment. Waste frying oil was filtered
under vacuum, dehydrated using anhydrous sodium sulfate (left
overnight), and finally again filtered under vacuum. The pork lard
was first heated at 100 °C to eliminate residual water and cooled
to near the reaction temperature (60 °C).
Raw Materials Characterization. Different properties of the
starting raw materials were determined: (i) composition [using gas
chromatography (GC) according to EN 14103 (2003) and NP EN
ISO 5508 (1996)], (ii) acid value, by volumetric titration according
to the standard NP EN ISO 660 (2002), (iii) iodine value, by
volumetric titration using Wijs reagent, according to the standard
ISO 3961 (1996), and (iv) water content, using coulometric Karl
Fischer titration.
Biodiesel Synthesis. Synthesis of biodiesel was carried out by
transesterification. The mixtures of vegetable oil and fat were
prepared considering the increase in the fat fraction of the mixture,
varying from 0 to 1 (w/w), in 0.2 intervals. The fat was weighted
and added to the reactor, which already contained the necessary
amount of vegetable oil (soybean oil or waste frying oil). A defined
amount of methanol (6:1 molar ratio to oil) premixed with NaOH
(0.8 wt % of the starting mixture weight) was added to the reactor,
which already had 100 g of the raw material mixture, preheated at
the reaction temperature. The catalyst concentration was chosen
(9) Al-Widyan, M. I.; Al-Shyoukh, A. O. Experimental evaluation of
the transesterification of waste palm oil into biodiesel. Bioresour. Technol.
2002, 85 (3), 253–256.
(10) Felizardo, P.; Neiva Correia, M. J.; Raposo, I.; Mendes, J. F.;
Berkemeier, R.; Bordado, J. M. Production of biodiesel from waste frying
oils. Waste Manage. 2006, 26 (5), 487.
(11) Zheng, S.; Kates, M.; Dube, M. A.; McLean, D. D. Acid-catalyzed
production of biodiesel from waste frying oil. Biomass Bioenergy 2006, 30
(3), 267–272.
Dias et al.
according to a previous study by Dias et al.12 At this point, the
reaction started; the reactor consisted of a 1 L flat-bottom flask
immersed in a temperature-controlling bath, equipped with a water-
cooled condenser and a magnetic stirrer. Suggested by the literature
review, the reaction occurred for 60 min under vigorous stirring;
at the end of the reaction, products were left to settle for 1 h to
allow for the separation of the two phases: biodiesel and glycerol.
Biodiesel Purification. Both phases were separated, and excess
methanol was recovered from each phase, using a rotary evaporator
under reduced pressure. Biodiesel was then filtered (S&S, grade
589/1) and washed, first with 50% (v/v) of an acid solution (0.2%
HCl) and then repeatedly with 50% (v/v) of distilled water until
the pH of the washing water was the same as the distilled water.
The filtering stage was adopted because of the fact that it
significantly improved the washing stage, reducing emulsion
formation. Regarding biodiesel dehydration, different procedures
were adopted to evaluate which would be the best one. Such
procedures were based on the use of an anhydrous salt and
evaporation at reduced pressure under different conditions.
Biodiesel Characterization. The biodiesel quality was evaluated
according to the European biodiesel standard EN 14214 (2003).
The following parameters were determined: (i) acid value, by
volumetric titration according to the standard EN 14104 (2003),
(ii) kinematic viscosity, determined at 40 °C using glass capillary
viscometers according to the standard ISO 3104 (1994), (iii) density,
determined using a hydrometer method according to the standard
EN ISO 3675 (1998), (iv) flash point, using a rapid equilibrium
closed cup method according to the standard ISO 3679 (2004), (v)
copper corrosion, using a copper strip test according to the standard
ISO 2160 (1998), (vi) water content, by Karl Fischer coulometric
titration according to the standard NP EN ISO 12937 (2003), (vii)
ester and linolenic acid methyl ester contents by GC according to
the standard EN 14103 (2003), and (viii) iodine value, determined
from ester content according to annex B of EN 14214 (2003). With
regard to chromatographic analysis, a Dani GC 1000 DPC gas
chromatograph (DANI Instruments S.p.A.), with an AT-WAX
(Heliflex capillary, Alltech) column (30 m, 0.32 mm internal
diameter and 0.25 µm film thickness) was used. The injector
temperature was set at 250 °C, while the flame ionization detector
(FID) temperature was set at 255 °C. The carrier gas used was N2,
with a flow of 2 mL/min. Injection was made in a split mode, using
a split flow rate of 50 mL/min (split ratio of 1:25), and the volume
injected was 1 µL.
Results and Discussion
Raw Materials Properties. The fatty acid composition and
the mean molecular weight (calculated from the composition)
as well as some other measured properties of the starting raw
materials are presented in Table 1. Considering the typical fatty
acid composition of vegetable oils as determined using GC,13
the waste frying oil composition indicates that both soybean
and sunflower oil might be present; the low C18:3 content and
the content in C18:1 might indicate that sunflower is present in
a higher amount.13 As expected, the acid value of the soybean
oil was lower than the waste frying oil; however, much higher
acid values have been reported for waste frying oils.8,14 The
low acid value found might indicate a smaller degree of both
oxidation and hydrolysis reactions. This can be justified because
the waste frying oils were from a domestic source and they
(12) Dias, J. M.; Alvim-Ferraz, M. C. M.; Almeida, M. F. Comparison
of the performance of different homogeneous alkali catalysts during
transesterification of waste and virgin oils and evaluation of biodiesel quality.
Fuel 2008, 87 (17-18), 3572–3578.
(13) Rossel, J. B. Classical analysis of oils and fats. In Analysis of Oils
and Fats; Hamilton, R. J., Rossel, J. B., Eds.; Elsevier Applied Science:
London, U.K., 1986.
(14) Graboski, M. S.; McCormick, R. L. Combustion of fat and vegetable
oil derived fuels in diesel engines. Prog. Energy Combust. Sci. 1998, 24
(2), 125–164.
Mixtures of Oils and Fat for Biodiesel Production Energy & Fuels, Vol. 22, No. 6, 2008 3891

Figure 1. Transesterification of triglycerides (overall reaction).

Table 1. Starting Raw Materials Properties Including Acid Table 3. Dehydration Methods Used and Final Water Contents
Value, Iodine Value, Water Content, Fatty Acid Composition of the Biodiesel Samples
(wt %), and Mean Molecular Weighta soybean oil/lard mixture waste frying oil/lard mixture
waste frying lard fraction dehydration water content dehydration water content
raw material properties soybean oil pork lard oil (wt) method (wt %) method (wt %)
acid value (mg of KOH/g) 0.21 0.71 0.82 0 AS 0.127 AS 0.100
iodine value (g of I2/100 g) 127 67 117 0.2 Ev40/45 0.154 Ev90/210 0.040
water content (wt %) 0.04 0.03 0.05 0.4 Ev65/90 0.095 Ev80/90 0.100
fatty acid composition (wt %) 0.6 Ev45/90 0.153 Ev90/120 0.045
miristic (C14:0) nd 1.3 nd 0.8 Ev40/45 0.155 Ev90/120 0.056
palmitic (C16:0) 11.0 23.7 8.4 1 Ev40/45 0.114 Ev40/45 0.114
palmitoleic (C16:1) nd 2.2 0.2
heptadecenoic (C17:1) nd 0.4 nd Effect of Different Dehydration Treatments in Biodiesel
stearic (C18:0) 3.3 12.9 3.7
oleic (C18:1) 25.4 41.4 34.6 Water Content. High water contents will improve biodiesel
linoleic (C18:2) 53.6 15.0 50.5 degradation because of hydrolysis,17 therefore affecting the
linolenic (C18:3) 5.3 1.0 0.6 storage life of the fuel. The standard limit according to EN
arachidic (C20:0) 0.4 0.2 0.4 14214 is 0.05 wt %. With the objective of selecting an
eicosenoic (C20:1) 0.3 0.9 0.4
appropriate dehydration method, each sample produced was
eicosadienoic (C20:2) 0.0 0.7 nd
eicosatrienoic (C20:3) nd 0.2 nd subjected to a different treatment. The following treatments were
behenic (C22:0) 0.4 nd 0.8 performed: 30 wt % of anhydrous salt (AS) or evaporation (163
docosadienoic (C22:2) 0.2 nd nd mbar) including heating at 40 °C during 45 min (Ev40/45), heating
lignoceric (C24:0) 0.1 nd 0.3 at 45, 65, and 80 °C during 1 h and 30 min (Ev45/90, Ev65/90,
mean molecular weight (g/mol) 874.0 861.6 877.5
and Ev80/90), heating at 90 °C during 2 h (Ev90/120), and heating
a nd ) not detected. at 90 °C during 3 h and 30 min (Ev90/210). Table 3 shows which
samples were used in each treatment as well as the final water
Table 2. Biodiesel Production Yields (wt %) Using Different
Vegetable Oil/Lard Mixtures as Raw Materials contents. The same dehydration treatment led to different final
water contents depending upon the water content after the
lard fraction soybean oil/ waste frying oil/
(wt) lard mixture lard mixture
washing stage. When evaporating during 1 h and 30 min, the
effect of increasing the temperature was mainly noted when
0 88.8 82.2
0.2 87.4 87.1
going from 45 to 65 °C. The increase in evaporation time was
0.4 85.2 87.6 not very much reflected in terms of decreasing biodiesel water
0.6 87.6 85.2 content; however, independent of the sample used, a great
0.8 88.6 88.0 decrease in the biodiesel water content was observed when
1 81.7 81.7 increasing the temperature from 45 to 90 °C. Considering the
might have been exposed to high temperatures for short obtained results, evaporation at 90 °C, 163 mbar, and a holding
periods.15 Pork lard also presented a low acid value, probably time of 3 h and 30 min seemed to be enough to ensure that
resulting from pretreatment processes; however, the commonly biodiesel samples fulfill the European biodiesel standard EN
referred value for commercial lard is slightly higher (1.3 mg of 14214.
KOH/g of fat).16 Biodiesel Composition. Biodiesel composition resulting from
Yield. Biodiesel production yields are presented in Table 2. the transesterification of soybean and waste frying oil mixed
They varied from 81.7 to 88.8 wt %. Production using only with lard was evaluated, aiming its prediction when mixtures
soybean oil as raw material presented a yield almost 7% higher with different lard contents are used as raw materials.
than when using only waste frying oil or lard as raw materials; It was postulated that the fatty acid content of biodiesel
however, considering all oil/lard mixtures, the differences corresponded to the weighted average of its content in each
between yields were less than 3.4%. component of the mixture, therefore

(15) Çetinkaya, M.; Karaosmanoǧlu, F. Optimization of base-catalyzed

transesterification reaction of used cooking oil. Energy Fuels 2004, 18,
1888–1895.
(16) Codex Alimentarius Commission (CAC). Codex standard for fats
and oils from animal sources (CODEX-STAN 211-1999). In Fats, Oils and
Related Products, 2nd ed.; Joint FAO/WHO Food Standards Program. Food
and Agriculture Organization of the United Nations: Rome, Italy, 2001;
Vol. 8.
Cmix ) CoilXoil + ClardXlard S Cmix ) (Clard - Coil)Xlard + Coil (1)
where Cmix is the fatty acid content (wt %) of the mixture, Clard
is the fatty acid content (wt %) of the lard, Coil is the fatty acid
(17) Leung, D. Y. C.; Koo, B. C. P.; Guo, Y. Degradation of biodiesel
under different storage conditions. Bioresour. Technol. 2006, 97 (2), 250–
256.
3892 Energy & Fuels, Vol. 22, No. 6, 2008 Dias et al.

Table 4. Fitting of Fatty Acid Content (wt %) of Biodiesel

versus Lard Mass Fraction Incorporated in the Oil and Linear
Regression Parametersa
fatty acid mixture a b r2 p value Coil Clard Clard - Coil
sb/l 1.3 0.0 0.991 <0.0001 nd 1.3 1.3
C14:0
wfo/l 1.3 0.1 0.989 <0.0001 nd 1.3 1.3
C16:0 sb/l 12.2 11.1 0.994 <0.0001 11.0 23.7 12.7
wfo/l 15.3 8.5 1.000 <0.0001 8.4 23.7 15.4
C18:0 sb/l 9.3 3.3 0.993 <0.0001 3.3 12.9 9.6
wfo/l 9.1 3.8 1.000 <0.0001 3.7 12.9 9.2
C18:1 sb/l 15.8 26.0 0.952 <0.001 25.4 41.4 16.0
wfo/l 6.8 34.8 0.994 <0.0001 34.6 41.4 6.9
C18:2 sb/l -37.5 53.2 0.993 <0.0001 53.6 15.0 -38.6
wfo/l -35.3 50.2 1.000 <0.0001 50.5 15.0 -35.5
C18:3 sb/l -4.5 5.2 0.892 <0.05 5.3 1.0 -4.4
wfo/l 0.3 0.6 0.995 <0.0001 0.6 1.0 0.3
C20:0 sb/l -0.1 0.4 0.987 <0.0001 0.4 0.2 -0.1
wfo/l -0.2 0.4 0.997 <0.0001 0.4 0.2 -0.2
C20:1 sb/l 0.6 0.3 0.985 <0.0001 0.3 0.9 0.6
wfo/l 0.5 0.4 0.996 <0.0001 0.4 0.9 0.5
C22:0 sb/l -0.5 0.5 0.878 <0.01 0.5 nd -0.5 Figure 2. Methyl ester content (wt %) of biodiesel samples obtained
wfo/l -0.9 0.9 1.000 <0.0001 0.8 nd -0.8 using different mixtures of vegetable oil and lard.
a C , fatty acid content of oil; C
oil lard, fatty acid content of lard; a,
slope; b, intercept; r2, determination coefficient; p, probability value
(using a F test); sb, soybean; wfo, waste frying oil; nd, not detected. and iodine value were the ones that were not fulfilled by all
samples. It was verified that the minimum purity of biodiesel
Table 5. Quality Parameters of Biodiesel from Oil/Lard
(96.5 wt %) was only achieved when using waste frying oil or
Mixtures and the Respective Standard Limits According to
EN 14214 soybean oil alone as raw material (Figure 2); when using 100%
lard, lowest purity was obtained (94.4%). The lowest purity
property results EN 14214
obtained using lard alone led to a decrease in biodiesel purity
acid value (mg of KOH/g) 0.02-0.10 <0.5 with an increased incorporation of lard, despite the high yields
kinematic viscosity at 40 °C (mm2 s-1)
lard/soybean oil mixture 4.46-4.71 3.50-5.00
obtained. However, it should be referred that purity might be
lard/waste frying oil mixture 4.67-4.77 improved, namely, by increasing either catalyst concentration
density at 15 °C (kg m-3) 875.7-883.6 860-900 (for instance, 1 wt %) or temperature (for instance, 65 °C). 12,18
flash point (°C) 174-179 >120 As for the composition, it was postulated that the parameter
copper corrosion (3 h/50 °C) all samples class 1a class 1 of the biodiesel obtained from the mixture corresponded to the
methyl ester content (wt %) 93.9-96.6 >96.5
linolenic methyl ester content (wt %) weighted average of the parameter of biodiesel resulting from
lard/soybean oil mixture 1.0-5.3 <12.0 each component. Therefore
lard/waste frying oil mixture 0.6-1.0
iodine valuea (g of I2/100 g) Pmix ) PoilXoil + PlardXlard S Pmix ) (Plard - Poil)Xlard + Poil (2)
lard/soybean oil mixture 67-127 <120
lard/waste frying oil mixture 67-117 where Pmix is the parameter of biodiesel from the mixture, Plard
a Calculated from the methyl ester composition. is the parameter of biodiesel from the lard, Poil is the parameter
of biodiesel from the oil, Xoil is the weight fraction of oil, and
content (wt %) of the oil, Xoil is the weight fraction of oil, and Xlard is the weight fraction of lard.
Xlard is the weight fraction of lard. A linear correlation was also found between some of the
In fact, it was found that the fatty acid content of biodiesel quality parameters and the lard fraction incorporated in the oil;
was linearly correlated to the mass fraction of lard incorporated those parameters were iodine value, density, viscosity, methyl
in the raw material, with a determination coefficient r2 > 0.88 ester content, and linolenic methyl ester content. Such correla-
and p value < 0.05 (probability of falsely rejecting the null tions had r2 > 0.79 (p < 0.05), except in the case of viscosity
hypothesis, using a F test) for fatty acids corresponding to >96% and methyl ester content of biodiesel resulting from the mixture
of the biodiesel composition. Table 4 shows the linear regression of waste frying oil and lard. Table 6 shows the linear regression
parameters. From those, it was possible to verify that the slope parameters of the fitting. It was possible to verify that,
(a) was similar to the difference between the fatty acid content considering the fittings with determination coefficients > 0.8,
in fat and oil (Clard - Coil) and also that the intercept (b) was the slope (a) was similar to the difference between the property
similar to the fatty acid content in the oil (Coil) and differences in fat and oil (Plard - Poil) and also that the intercept (b) was
were lower than 5%. Such results show that eq 1 might be used similar to the property of the oil (Poil) (differences were less
to predict the fatty acid content of biodiesel resulting from than 3.5%). The very low determination coefficient found
mixtures of soybean oil/lard and waste frying oil/lard when regarding biodiesel viscosity resulting from waste frying oil/
mixtures with different lard contents are used. lard mixtures might be explained by the fact that biodiesel
Biodiesel Quality. As it can be observed in Table 5, all samples obtained from these two raw materials had very similar
produced samples fulfilled the European standard limit in terms viscosities and experimental errors were much more reflected.
of acid value, kinematic viscosity, density, flash point, copper The results showed that eq 2 might be used to predict the
corrosion, and linolenic methyl ester content. High flash points property of biodiesel resulting from mixtures of soybean oil/
indicate effective methanol recovery, which should be reflected lard and waste frying oil/lard when mixtures with different lard
in low methanol contents of biodiesel. Kinematic viscosity was contents are used for the following properties: iodine value,
slightly higher for mixtures using waste frying oil; however, it
(18) Leung, D. Y. C.; Guo, Y. Transesterification of neat and used frying
was always within the standard limits according to EN 14214. oil: Optimization for biodiesel production. Fuel Process. Technol. 2006,
Among the measured parameters, methyl ester content (purity) 87 (10), 883–890.
Mixtures of Oils and Fat for Biodiesel Production Energy & Fuels, Vol. 22, No. 6, 2008 3893

Table 6. Fitting of Some Quality Parameters of Biodiesel from Oil/Lard Mixtures versus Incorporated Lard Fraction and Linear
Regression Parametersa
property mixture a b r2 p value Poil Plard Plard - Poil
sb/l -59 127 0.991 <0.0001 127 67 -60
iodine value (g of I2/100 g)
wfo/l -50 118 1.000 <0.0001 117 67 -50
sb/l -7.9 883.4 0.993 <0.0001 883.6 875.7 -7.8
density (kg m-3)
wfo/l -7.4 883.4 0.989 <0.0001 883.4 875.7 -7.6
sb/l 0.25 4.46 0.815 <0.05 4.46 4.71 0.25
viscosity (mm2 s-1)
wfo/l 0.02 4.70 0.040 0.705 4.69 4.71 0.02
sb/l -2.5 96.3 0.788 <0.05 96.6 94.4 -2.2
methyl ester content (wt %)
wfo/l -2.5 96.1 0.615 0.0647 96.3 94.4 -1.9
sb/l -4.5 5.2 0.892 <0.05 5.3 1.0 -4.4
linolenic methyl ester content (wt %)
wfo/l 0.3 0.6 0.995 <0.05 0.6 1.0 0.3
a P , property of oil; P 2
oil lard, property of lard; a, slope; b, intercept; r , determination coefficient; p, probability value (using a F test); sb, soybean; wfo,
waste frying oil.
density, viscosity (considering soybean/lard mixtures only), copper corrosion, and linolenic acid methyl ester content using
methyl ester content (considering soybean/lard mixtures only), different incorporation percentages of lard in soybean oil and
and linolenic methyl ester content. waste frying oil. Methyl ester content (purity) and iodine value
The iodine value gives the degree of unsaturation of the were the ones that were not fulfilled in some cases. Minimum
biodiesel samples. The existence of double bonds might lead purity was achieved when using waste frying oil or soybean
to polymerization of glycerides by heating, which could lead oil alone as raw material; however, it was always close to the
to gum formation.19 As expected, the increase in the lard fraction limit (93.9-96.6 wt %).
led to a decrease in the iodine value. In the case of the mixture
with soybean oil, this had a positive effect because biodiesel It was postulated and confirmed by a linear model that (i)
obtained from soybean oil alone does not meet the standard the fatty acid content of biodiesel corresponds to the weighted
specification according to EN 14214. From the linear model, it average of its content in each component of the mixture and
was possible to estimate that the use of 12% lard in the soybean/ (ii) the parameter of the biodiesel obtained from the mixture
lard mixture would decrease the biodiesel iodine value to the corresponded to the weighted average of the parameter of
maximum limit according to the European biodiesel standard. biodiesel resulting from each component. For the first, it could
Therefore, the incorporation of lard in the soybean oil was found be applied for fatty acids corresponding to >96% of the
to be effective in reducing the iodine value of biodiesel to biodiesel composition (linear fittings with determination coef-
acceptable values. ficient r2 > 0.88 and p value < 0.05). For the second, it could
Overall, in terms of using virgin or waste oil, the mixture be applied for iodine value, density, viscosity (considering
behavior was not very different, which can indicate that soybean/lard mixtures), methyl ester content (considering
incorporating waste frying oil might be a good alternative to
soybean/lard mixtures), and linolenic methyl ester content (linear
obtain a biodiesel that fulfils European standard at a lower cost.
fittings with determination coefficient r2 > 0.79 and p value <
0.05). It was predicted that the use of at least 12% lard in a
Conclusions
soybean oil/lard mixture would be effective in reducing the
Synthesis of biodiesel by transesterification of several raw iodine value of biodiesel to acceptable values.
material mixtures of virgin/waste frying oil/pork lard results in
yields varying from 81.7 to 88.8 (wt %). Evaporation at 90 °C, Considering all studied production and quality parameters,
163 mbar during 3 h and 30 min was established as an efficient there was not much difference regarding the use of refined or
dehydration method for biodiesel production using such raw waste oil, which can indicate that the use of waste frying oil
material mixtures. might be a good alternative to obtain a biodiesel that fulfils
Biodiesel met the European biodiesel quality standard EN European standard EN 14214 at a lower cost.
14214 in terms of acid value, viscosity, density, flash point,
Acknowledgment. J. M. Dias thanks the FCT for the fellowship
(19) Encinar, J. M.; González, J. F.; Rodrı́guez-Reinares, A. Biodiesel SFRD/BD/22293/2005.
from used frying oil. Variables affecting the yields and characteristics of
the biodiesel. Ind. Eng. Chem. Res. 2005, 44, 5491–5499. EF8005383