Bioresource Technology 102 (2011) 1090710914

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Study of biodiesel production from animal fats with high free fatty acid content
J.M. Encinar , N. Snchez, G. Martnez, L. Garca
Departamento de Ingeniera Qumica y Qumica Fsica, Universidad de Extremadura Avda, Elvas s/n, 06071 Badajoz, Spain

a r t i c l e

i n f o

Article history:
Received 25 July 2011
Received in revised form 14 September
2011
Accepted 15 September 2011
Available online 20 September 2011
Keywords:
Biodiesel
Animal fats
Free fatty acids
Esterication

a b s t r a c t
The aim of this work was to obtain biodiesel from animal fats, an inedible feedstock. Three different types
of fats were used to produce biodiesel; their main characteristic was high free fatty acid content. Animal
fats were transesteried with acid catalyst and basic catalyst with and without pre-esterication. Biodiesel of 89.0 wt.% ester content was obtained by acid-transesterication (9 wt.% H2SO4, 6:1 methanol:fats
molar ratio, 60 C, 48 h). Pre-esterication conditions were studied for different fats and acid catalysts:
0.5 wt.% H2SO4 or 1.0 wt.% p-TsOH, 6:1 methanol:fats molar ratio, 65 C and 4 h made it possible to obtain
fats with acid value less than 0.5% FFA. Pre-treatment was effective for fats with different FFA content.
Alkali transesterication of esteried fats resulted in a product with 97.3 wt.% ester content. Biodiesel
quality was evaluated and most of properties were well within EN 14214.
2011 Elsevier Ltd. All rights reserved.

1. Introduction
By Directive 2003/30/EC, biodiesel is dened as a methyl-ester
produced from vegetable oil or animal fats, of diesel quality, to be
used as biofuel (Directive 2003/30/EC, 2003). The use of biodiesel
in internal combustion engines, especially in compression ignition
engine, represents an excellent option on the ecological point of
view. Most of CO2 emissions are from renewable carbon stocks. Biodiesel is usually produced from high quality vegetable oils. These
feedstocks have high cost, which currently accounts for over 85%
of biodiesel production expenses (Moser, 2008). In recent years, a
wide range of studies have been carried out on biodiesel production
from feedstocks of low cost. Frying oils (Encinar et al., 2005, 2007;
Tomasevic and Siler-Marinkovic, 2003; Zhang et al., 2003), new
vegetable species (Encinar et al., 2002; Kulkarni et al., 2007; Meher
et al., 2006) and animal fats (Canakci and Van Gerpen, 2001, 2003;
Dias et al., 2008, 2009; Ngo et al., 2007) have been researched. The
last kind of low cost feedstock has not been developed in depth
(Berrios et al., 2009).
Animal fats are waste raw materials more abundant than frying
oils. Such fats were usually used as animal feeds, but this practice
strongly decreased due to the possibility of severe animal disease
(Dias et al., 2009). The utilization of animal fats for biodiesel production is a good alternative to recycle these wastes. Different animal fats, as pork lard, beef tallow, chicken fat, yellow grease and
brown grease, were used for biodiesel production (Moser, 2009).
Biodiesel was obtained from lard using basic transesterication

Corresponding author. Tel.: +34 924 289672; fax: +34 924 289385.
E-mail address: jencinar@unex.es (J.M. Encinar).
0960-8524/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2011.09.068

(Berrios et al., 2009; Jeong et al., 2009). However, the most of waste
feedstock have high free fatty acid content. The free fatty acids
(FFA) present major problem when using a base-catalyzed transesterication process since the FFA react with the base catalyst to
form soaps, which leads to loss of catalyst and ester product, and
increases production processing costs (Lotero et al., 2005). This
reason makes necessary acid catalyst for transesterication of triglycerides and esterication of FFA. Strong acid catalysts are less
sensitive to FFA and can conduct esterication and transesterication simultaneously (Di Serio et al., 2005). The FFA can react with
alcohol to form ester (biodiesel); this reaction is very useful for
handling oils of fats with high FFA, as is shown in the equation.
H

R1 - COOH ROH ! ROCOR1 H2 O

FFA

alcohol

fatty acid ester

water

It is usual to employ 6:1 methanol to oil molar ratio during acid

esterication, although higher ratios were used too (Demirbas,
2009).
Most of high FFA feedstock was processed by two-step, rst carrying out the acid-catalyzed pre-esterication of the FFA prior the
base-catalyzed triglyceride transesterication. Canakci and Van
Gerpen used a two-step method, a pre-treatment to reduce the
FFA of yellow grease from 12% and brown grease from 33% to less
than 1%, and the transesterication reaction was completed with,
an alkaline catalyst to produce biodiesel (Canakci and Van Gerpen,
2001, 2003). Pork wastes were transformed to biodiesel by sulfuric
acid pre-treatment (esterication) and sodium hydroxide transesterication; a purity of 99.6 wt.% was obtained (Dias et al.,
2009). A yellow and brown greases mixture was also pre-treated
by esterication in presence of diarylammonium catalysts, the

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J.M. Encinar et al. / Bioresource Technology 102 (2011) 1090710914

FFA contents were reduced less 1%. The transesteried greases

were then readily converted to total esters by base-catalyzed
transesterication, the obtained biodiesel reached 99 wt.% fatty
acid methyl esters (FAME) (Ngo et al., 2007).
Biodiesel from animal fats compared with biodiesel from vegetable origin has the advantage a higher cetane number, the most
signicant indicator of diesel combustion behavior (Tong et al.,
2011); nevertheless, the fuel produced from fats has higher cold lter plugging point because of this raw material has signicant content of saturated fatty acids (Lebedevas et al., 2006). Furthermore
biodiesel from animal fats is less stable for oxidation, this fact being
attributed to the absence of natural antioxidants as compared to
biodiesel of vegetable origin (Sendzikiene et al., 2005). For these
properties, the biodiesel produced from animal fats might not be
adequate to use it 100% pure in vehicles during cold weather; however might be used 100% pure in boilers for heat generation. Alternatively, fats might be mixed with other raw materials to get a
biodiesel obeying such quality specications, being even possible
to enhance some biodiesel properties by incorporation of fats in
the raw material (Canoira et al., 2008; Dias et al., 2008).
In this report, an overview of acid and basic-transesterication
to obtain biodiesel from animal fats is showed, studying the effect
of the esterication as pre-treatment to decrease fats FFA content.
The rst studied process was acid transesterication using high
amount of sulfuric acid as catalyst, methanol as alcohol and a long
time. And the second process was a two-step treatment consisted
of pre-esterication followed by basic-transesterication. In preesterication, catalysts were sulfuric, phosphoric and p-toluenesulfonic acids and alcohol was methanol; in transesterication,
catalyst was potassium hydroxide and alcohol was methanol, too.
The most important variables from both processes were studied.
2. Methods
2.1. Materials
Three different types of animal fats (10.7%, 4.9% and 13.5% FFA)
provided by Extremea de Grasas S.A., Mrida, Spain, were used to
produce biodiesel. Such raw materials were waste inedible fats
from slaughterhouses of Extremadura (Spain). Methanol (96 v/
v%), sulfuric acid (98 wt.%), phosphoric acid (85 wt.%), p-toluenesulfonic acid monohydrate (98 wt.%), potassium hydroxide
(85 wt.%) were purchased from Panreac. Methyl myristate, methyl
palmitate, methyl palmitoleate, methyl estearate, methyl oleate,
methyl linoleate, methyl linolenate and methyl nonadecanoate
(employed as standards in the chromatographic determination)
were purchased from SigmaAldrich. The reagents used in biodiesel characterization were of analytical grade.
2.2. Experimental procedure
Two methods to obtain biodiesel were tried: acid-transesterication with H2SO4 as catalyst and pre-esterication with acid as
catalyst followed by basic-transesterication with KOH as catalyst.
Acid-transesterication was carried out in a 1 L glass reactor,
immersed in a temperature controlling bath, equipped with a thermostat, mechanical stirring, sampling outlet, and condensation
system. Pre-esterication and basic-transesterication reactions
were carried out in a 500 mL spherical glass reactor, provided with
a thermostat, magnetic stirring, sampling outlet and condensation
system. This installation was similar to that previously employed
in other studies (Ma et al., 1998a). Before reactions all material
was completely dry.
In acid-transesterication reaction, 500 g of animal fats were
heated in the reactor, when fats reached 60 C, methanol and

catalyst (H2SO4) were added, in established amounts for each

experiment, and the stirring system was connected, taking this
moment as zero time. The mixture was stirred vigorously at reux
of methanol for 48 h, samples of 20 cm3 were taken out at 10 h
spaced intervals. Samples and reaction nal mixture were placed
in decantation funnels and allowed to stand overnight to ensure
the complete phase separation (methyl esters and glycerol). The
glycerol phase (bottom phase) was removed and the biodiesel
phase (upper phase) was heated at 85 C to remove methanol.
The biodiesel was neutralized with KOH (20% needed KOH to neutralize the added H2SO4 as catalyst) and it was washed with deionised water to reach neutral pH.
In pre-esterication, 250 g of animal fats were heated in the
reactor at the reaction temperature; in this moment methanol
and acid catalyst were added and stirring of the mixture started
(zero time). At evenly spaced intervals, samples of 1 cm3 were
taken out from the reaction mixture and its acid value was measured. After the established reaction time under vigorous stirring,
the mixture was placed in a decantation funnel and allowed to
stand overnight. Two phases could be identied, the upper phase
consisted of methanol, catalyst, H2O and impurities and the bottom
phase mainly consisted of fats and the esteried fatty acids
(Canoira et al., 2008). The phases were separated and the esteried
product was then transesteried by basic catalysis, using same system as pre-esterication and similar procedure. The esteried
product was weighed and the suitable amount of methanol and
catalyst (KOH) were added. After reaction time, the mixture was
placed in a decantation funnel; glycerol phase was separated,
methanol was eliminated and biodiesel phase was washed with
deionized water to remove catalyst.
Viscosity at 40 C and FAME content were measured for every
obtained biodiesel.
2.3. Analytical procedure
Similar methods for the biodiesel evaluation, described below,
were used to characterize the raw material. Acid value determination was made according to UNE-EN 14111:2003 norm, to monitor
esterication reaction.
Biodiesel quality was evaluated according to biodiesel European
Standard EN 14214. The content and composition of the methyl esters were analyzed by gas chromatography (GC) (VARIAN 3900.
FID), using a capillary column Agilent Technologies 1909-BD-113,
of 30 m length, 0.32 mm inner diameter and 0.25 lm lm thickness. Helium was used as carrier gas. The chromatography was taken out in constant ow mode with a ow rate of 0.6 mL min1
(6 psi). A split injector was used with a split ratio of 100:1 and a
temperature of 270 C. The FID (ame ionization detector) was
operated at 300 C. The oven was maintained initially at 200 C
and remained for 21 min, and then it was elevated to 240 C at
20 C min1, and remained for 11.5 min. Total run time for this
method was 33.5 min. The method proposed by EN 14103 (methyl
heptadecanoate as internal standard) was not appropriate for
methyl ester content determination when fats are used as raw
materials (Dias et al., 2009). For this reason, methyl nonadecanoate
was used as internal standard. The fatty acid prole in raw material
was determined by gas chromatography, esteried fats having a
FFA content of not greater than 2% were transesteried according
to ISO 5509:2000, the FAME were analyzed by gas chromatography, identifying each FAME by comparison with standards and
the quantities of individual FAME were calculated from the peak
areas on the chromatogram. Other determined parameters were
the following: density at 15 C (pycnometry), viscosity at 40 C
(capillary viscometer ISO 3104:1994), water content (Karl Fischer
coulometric titration UNE-EN ISO 12937:2000), cetane number
(estimation by a correlation of cetane number with its FAME

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J.M. Encinar et al. / Bioresource Technology 102 (2011) 1090710914

3. Results and discussion

3.1. Raw material
Raw material properties and its fatty acid prole are showed in
Table 1. The main problem with processing these fats is that they
contain large amounts of free fatty acids that could not be converted to biodiesel using an alkaline catalyst due to formation of
fatty acids salts (soap). Soaps can prevent separation of the biodiesel from the glycerine fraction. In a study of transesterication of
beef tallow with alkaline catalyst, fatty acids content needs to be
kept below 0.5% (1 mgKOH g1) was stated; this means that fats
and vegetable oils, as fats used in this study, must be rened to
remove free fatty acids (Ma et al., 1998b).
The water content of the fats is relatively low; however conversion could be affected, according to Kusdiana and Saka (2004). For
alkaline-catalyzed method, the conversion was slightly reduced
when more water was added; nevertheless in the acid-catalyzed
method, only as little as 0.1% of water added led to some reduction
of the yield of methyl esters. For esterication reaction, using
H2SO4 as catalyst, the conversion of oleic acid to methyl oleate
was somewhat reduced when the water content was increased.
They suggested that the methyl oleate formed may be hydrolyzed
over a prolonged treatment and high temperature; but these results correspond to high water content. In our study, water content
is very low (Table 1) so its effect could only be expected in acidtransesterication reactions.
The major fatty acids of the feedstocks were palmitic (2728%)
and oleic (4344%), acids with low degree of unsaturation. Most of
properties of biodiesel depend on the used feedstock. It has been
reported that biodiesel viscosity and density can be predicted
based on feedstock fatty acid prole. High viscosity is expected
because the main fatty acids have long chain of carbon and low
degree of unsaturation, as well as no high density is expected for
the same reasons. Density increases with decreasing chain length
and increasing number of double bonds (Refaat, 2009).
3.2. Acid-transesterication process
When raw material with high FFA content is used, biodiesel
obtaining by direct basic-transesterication is not possible; an

100
80
60
40
5 % H2SO4
7 % H2SO4
9 % H2SO4

20
0

(a)

10

20
30
Time (h)

40

50

1.4
27.3
4.0
11.7
44.4
10.4
0.6
21.2
10.7
908
48.8
0.08
66.8
189
727

1.5
28.1
4.0
12.0
44.6
9.4
0.5
9.7
4.9
895
61.2
0.13
62.9
189
808

1.5
27.9
4.5
12.1
42.8
10.5
0.7
26.9
13.5
912
42.6
0.12
66.2
186
703

Estimation using acid value and saponication value. The same molecular weight
was considered for esteried fats.

Methyl ester content (wt %)

100

Table 1
Fatty acid prole and properties in raw material.

C14:0 myristic
C16:0 palmitic
C16:1 palmitoleic
C18:0 stearic
C18:1 oleic
C18:2 linoleic
C18:3 linolenic
Acid value, mgKOH g1
FFA content,%
Density 15 C, kg m3
Viscosity 40 C, cSt
Water content, %
Iodine value, gI2(100 gmuestra)-1
Saponication value, mgKOH g1
Estimated molecular weight, g mol1,*

alternative method is the use of acid catalysis, which is able to

transesterify triglycerides as well as to esterify FFA. Although this
method resulted in a lower conversion when free fatty acids content increased in the reaction system (Kusdiana and Saka, 2004).
In general, acid-catalyzed reactions are slow, and high amount
of alcohol and catalyst are needed. Catalyst (H2SO4) and alcohol
(CH3OH) amounts were studied in this research, at 60 C and using
long reaction time (48 h), to transesterify fats A.
Fig. 1a shows the inuence of catalyst amount on ester content
of the obtained biodiesel. High amounts of catalyst were needed to
obtain high ester content. Ester content increased as sulfuric
amount and reaction time were increased. For FFA content of
10%, as the used feedstock, using 3 wt.% sulfuric acid as catalyst
for 48 h of reaction, methyl ester content of 70 wt.% was reached
in previous research (Kusdiana and Saka, 2004). As can be seen
from examination of Fig. 1a, it is necessary to use high catalyst
amount to obtain good ester content in acid-transesterication of
animal fats (>10% FFA).
Alcohol:triglycerides molar ratio is usually one of the main
factors that inuence the transesterication. Acid-transesterication is characterized by slow reaction rate and high ratio of alcohol
and triglyceride requirement (30:1 and more). Acid-transesterication usually achieves greater and faster conversions at high
alcohol concentrations; nevertheless, the ideal alcohol:triglycerides ratio has to be established empirically in every process. An
excess of alcohol favors the formation of the products but makes
glycerol recovery difcult (Lotero et al., 2005). As can be seen in
Fig. 1b, in the process put into practice, methanol:fats molar ratio
did not affect development of the reaction in high degree.

Methyl ester content (wt %)

composition (Tong et al., 2011)), ash and combustion points (UNE

51-023-90), cold lter plugging point (CFPP) (UNE-EN 116:1997),
acid value (UNE-EN 14104:2003), and saponication and iodine
values (UNE-EN 55012 and UNE-EN 14111:2003).

80
60
40

(b)

18:1 MeOH:fats
12:1 MeOH:fats
6:1 MeOH:fats

20

10

20
30
Time (h)

40

50

Fig. 1. Methyl ester content, as function of catalyst amount (a) and methanol:fats
molar ratio (b). Reaction conditions: fats A; reaction temperature, 60 C;
methanol:fats molar ratio, 6:1 (a); catalyst amount, 9 wt.% (b).

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J.M. Encinar et al. / Bioresource Technology 102 (2011) 1090710914

To reach an ester content of 90 wt.%, it is necessary a catalyst

amount of 9 wt.%, a methanol:fats ratio of 6:1 and to keep the
reaction for 48 h.

Acid value (mgKOHg-1)

30

3.3. Two-step process

3.3.1. Pre-esterication conditions
To obtain high ester content by pre-esterication, with H2SO4 as
catalyst, followed by basic-transesterication, with KOH as
catalyst, the main variables of both steps were studied. Firstly
pre-esterication conditions were studied changing catalyst
amount, methanol:fats molar ratio, and reaction temperature,
whereas the transesterication conditions were kept constant
(1.5 wt.% KOH, 6:1 methanol:esteried fats molar ratio, 65 C and
2 h of reaction time). This is a high catalyst amount to get the
reaction of all tri-, di- and monoglycerides from esteried fats to
methyl esters if the raw material does not have an excessive acid
value.
Esterication conditions, acid value of esteried fats, ester content and viscosity of obtained biodiesel are summarized in Table 2.
Acid value was measured after the fats were separated from the
methanol and sulfuric phase. Water content of these fats was measured too, this parameter is important for the development of basic-transesterication. All fats were close to 0.3% water content,
this value is low enough to get a insignicant effect (Kusdiana
and Saka, 2004).
The effect of H2SO4 amount as catalyst in esterication reaction
was studied. In Fig. 2 the acid value is shown as a function of esterication time for 0.1, 0.5 and 1.0 wt.% catalyst. Acid value of animal
fats was 21.2 mgKOH g1; but, in the reactions, initial acid values
were different due to the presence of H2SO4 and methanol in the
medium. When 0.5 or 1.0 wt.% of catalyst were used, the reaction
progressed quickly immediately after addition of the alcohol/acid
mixture. The decrease of the acid value was high initially and then
tended to stabilize. This behavior is according to previous research
and the lack of acid decrease at later times may be due to accumulation of water, because the sulfuric acid tends to migrate into the
water, out of the methanol, rendering it unavailable for the
reaction (Diaz-Felix et al., 2009; Van Gerpen et al., 2004).
The acid value obtained by esterication after methanol, sulfuric and water phase removal are shown in Table 2. As shown this
table and Fig. 2, 0.1 wt.% sulfuric was not enough to reduce the
FFA of the fats. The least value was obtained by esterication with

0.1 % H2SO4
0.5 % H2SO4
1.0 % H2SO4

25
20
15
10
5
0

50

100
150
Time (min)

200

250

Fig. 2. Acid value, as function of catalyst amount. Esterication conditions: fats A;

catalyst type, H2SO4; methanol:fats molar ratio, 6:1; reaction temperature, 65 C.

0.5 wt.% of H2SO4. This catalyst amount was the optimal for the
esterication because decreases FFA and is a little catalyst amount.
The effect of methanol:fats molar ratio in esterication reaction
is shown in Fig. 3; acid value is plotted as a function of esterication time for 3:1, 6:1, 12:1 and 18:1 methanol:fats molar ratios. As
can be seen from Fig. 3, the acid value decreased in the reaction
time with increasing methanol:fats molar ratio. The initial acid
value was lower with increasing methanol:fats molar ratio because
fats and sulfuric acidity was dissolved in higher volume. For this
reason, it is necessary to examine Fig. 3 together with nal acid
value shown in Table 2 (Exp.: 2, 46). As can be seen, the higher
methanol amount was, the faster acidity decreased; the least nal
acid value was obtained for esterication with 18:1 methanol:fats
molar ratio. Excess of methanol promotes reaction completion
keeping the sulfuric acid in methanol phase (Van Gerpen et al.,
2004). The disadvantage of this approach is that the more methanol is used, the more process costs will increase.
Final acid value by esterication with 6:1 methanol:fats molar
ratio is low enough to continue the process with basic-transesterication. The esterication time to reach the least FFA content using
6:1 ratio was similar to the esterication time when 12:1 and 18:1
were used. Moreover, the utilization of less methanol amount reduces costs. For these reasons, we think it is more convenient to
use a methanol:fats molar ratio of 6:1 for the rest of the research.

Table 2
Pre-esterication conditions, acid value of esteried fats, ester content and viscosity of obtained biodiesel (transesterication conditions: 0.5% KOH, 6:1 methanol:fats, 65 C, 2 h).
Exp.

Fat

Pre-esterication conditions

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20

A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
B
B
C
C

1.0%
0.5%
0.1%
0.5%
0.5%
0.5%
0.5%
0.5%
0.5%
0.5%
1.5%
5.0%
0.5%
1.0%
1.5%
2.0%
0.5%
1.0%
0.5%
1.0%

H2SO4
H2SO4
H2SO4
H2SO4
H2SO4
H2SO4
H2SO4
H2SO4
H2SO4
H3PO4
H3PO4
H3PO4
p-TsOH
p-TsOH
p-TsOH
p-TsOH
H2SO4
p-TsOH
H2SO4
p-TsOH

6:1
6:1
6:1
3:1
12:1
18:1
6:1
6:1
6:1
6:1
6:1
6:1
6:1
6:1
6:1
6:1
6:1
6:1
6:1
6:1

65 C
65 C
65 C
65 C
65 C
65 C
55 C
45 C
35 C
65 C
65 C
65 C
65 C
65 C
65 C
65 C
65 C
65 C
65 C
65 C

4h
4h
4h
4h
4h
4h
4h
4h
4h
4h
4h
4h
4h
4h
4h
4h
4h
4h
4h
4h

Acid value (mgKOH g1)

Ester content (m/m%)

Viscosity 40 C (cSt)

2.03
0.92
18.84
5.76
0.54
0.35
1.61
3.58
5.86
23.67
34.62
60.43
5.47
2.04
1.91
2.97
0.84
1.56
1.50
2.18

97.1
98.6
Soap
88.0
97.6
93.8
99.9
99.8
99.7
Soap
Soap
Soap
94.4
96.0
94.6
98.9
94.1
93.7
96.8
92.8

4.74
4.67
Soap
4.73
4.67
4.74
4.66
4.73
4.70
Soap
Soap
Soap
5.28
4.85
4.74
4.43
4.68
4.70
4.72
4.74

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J.M. Encinar et al. / Bioresource Technology 102 (2011) 1090710914

3:1 MeOH:fats
6:1 MeOH:fats
12:1 MeOH:fats
18:1 MeOH:fats

25
20
15
10
5
0
0

50

100
150
Time (min)

200

250

Fig. 3. Acid value, as function of methanol:fats molar ratio. Esterication conditions: fats A; catalyst type, H2SO4; catalyst amount, 0.5 wt.%; reaction temperature,
65 C.

The effect of temperature in esterication reaction was studied.

Acid value as a function of esterication time for 35, 45, 55 and
65 C is shown in Fig. 4. As can be seen, acid value decreased in
reaction time with increasing reaction temperature. This decrease
was faster with the highest temperature. Variations in temperature
showed that the reaction displayed typical endothermic behavior.
Only when 55 and 65 C were used, it seems that the reactions
reached equilibrium. These results are according to those obtained
in previous reports (Dias et al., 2009; Marchetti and Errazu, 2008).
Considering catalyst amount, methanol:fats molar ratio and
reaction temperature studies, the most suitable conditions for
esterication reaction were 0.5 wt.% H2SO4, 6:1 of methanol:fats
molar ratio and 65 C of reaction temperature.
Esterication time was studied together with basic-transesterication time. The results are shown in Section 3.3.5.
3.3.2. Pre-esterication catalyst
Pre-esterication conditions were studied using H2SO4 as catalyst, but there are more acids that could be used, organic or mineral
acids. As mineral acids, sulfuric, phosphoric and hydrochloric acids
are the most familiar. Hydrochloric acid usually has 35 wt.% of
assay, so large water amount is introduced in the reaction media,
which works against the reaction (Van Gerpen et al., 2004). Sulfuric
and phosphoric acids usually have higher assay and lower impurity
amount. On other hand, according to previous research p-Toluenesulfonic acid could be a good catalyst for esterication reaction
(Canoira et al., 2008).

The effect of H3PO4 and p-TsOH amount in esterication reaction is shown in Fig. 5a and b, respectively. As can be seen in
Fig. 5a, H3PO4 cannot be used as catalyst for this reaction because
does not manage to reduce FFA content. As function of catalyst
amount acid value of reaction mixture changed, but it remained
constant over time. However, as H2SO4, p-TsOH worked as catalyst
in esterication reaction; 1 wt.% is the least catalyst amount which
was able to lead fats to low acid value, and, as can be seen in Table
2, among the reactions carried out with p-TsOH (Exp. 1316), only
when 1 and 1.5 wt.% were used fats with an acid value less than
2 mgKOH g1 was led. H2SO4 as well as p-TsOH are strong acids,
with pKa < 0 (Guthrie, 1978), for that it is natural their capacity
for fats esterication. However H3PO4 is a rather weak acid (pKaH3PO4 = 2.15 (Meites, 1963)) and its acid strength appears not to be
enough to reduce FFA content of the fats.
If the obtained results are examined, the following conclusion is
drawn; for fats with 10.7% of FFA content, the most adequate
conditions for their esterication are 0.5 wt.% H2SO4 or
1.0 wt.% p-TsOH, a methanol:fats ratio of 6:1 and 65 C.
3.3.3. Pre-esterication of different fats
This study tried to know the effect of raw material in esterication process, as well as, to compare the efcacy of H2SO4 and
p-TsOH for each feedstock. In this way three types of fats (see
Table 1) were subjected to reaction with these acids and the obtained results are shown in Fig. 6. The main difference between
these fats was FFA content, fats A 10.7%, fats B 4.9% and fats C
13.5%; since, the rest of the properties were more similar and the
fatty acid proles were practically the same.

70
Acid value (mgKOHg-1)

Acid value (mgKOHg-1)

30

60
0.5 % H 3PO4
1.5 % H 3PO4

50

5.0 % H 3PO4

40
30
20

50

(a)

100
150
Time (min)

200

250

30
Acid value (mgKOHg-1)

Acid value (mgKOHg-1)

25
65 C
55 C
45 C
35 C

20
15
10
5

20
15
10
5
0

50

100
150
Time (min)

200

250

Fig. 4. Acid value, as function of temperature. Esterication conditions: fats A;

catalyst type, H2SO4; catalyst amount, 0.5 wt.%; methanol:fats molar ratio, 6:1.

(b)

0.5 % p-TsOH
1.0 % p-TsOH
1.5 % p-TsOH
2.0 % p-TsOH

25

50

100

150

200

250

Time (min)

Fig. 5. Acid value, as function of catalyst amount, H3PO4 (a), p-TsOH (b).
Esterication conditions: fats A; methanol:fats molar ratio, 6:1; reaction temperature, 65 C.

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J.M. Encinar et al. / Bioresource Technology 102 (2011) 1090710914

methanol concentration was studied, too, for this goal several reactions were carried out with a methanol:esteried fats molar ratio
ranged between 3:1 and 12:1 (Exp. 22, 2426 in Table 3). A molar
ratio of 3:1 is too low, the reached ester content is less than the
reached with others ratios. A ratio of 6:1 is enough to achieve high
ester content, the 9:1 ratio appears to give the best results, but the
improvement is small and not too signicant. For ratios higher
than 9:1, the excess of alcohol could favor slightly the recombination of esters and glycerol to monoglycerides because their concentration kept increasing during the course of the reaction, contrary
to reactions conducted with molar ratios of 9:1 and lower, in accordance with the conclusion of other researchers (Fillires et al.,
1995). Krisnangkura and Simamaharnnop (1992) also observed
that when glycerol remained in solution it helped drive the equilibrium back to the left, lowering the yield of esters.

Acid value (mgKOHg-1)

30
A Fat: 0.5 % H2SO4
A Fat: 1.0 % p-TsOH
B Fat: 0.5 % H2SO4
B Fat: 1.0 % p -TsOH
C Fat: 0.5 % H2SO4
C Fat: 1.0 % p-TsOH

25
20
15
10
5
0

50

100
150
Time (min)

200

250

Fig. 6. Acid value, as function of fat and catalyst type. Esterication conditions:
methanol:fats molar ratio, 6:1; reaction temperature, 65 C.

Fig. 6 shows acid value variation for the esterication of different raw material with various acid catalysts. Regardless of FFA content of the fats, esterication reactions were developed with high
initial rate and this rate was decreasing over time. But, the higher
the FFA content was, the faster the rate of reaction was. The same
was observed in other researches and this is natural because
esterication reaction is a chemical equilibrium where the FFA
are reagents (Marchetti and Errazu, 2008). There is another important matter, reaction conditions were able to reduce fats acid value
until values less than or close to 2 mgKOH g1, as can be seen in
Table 2. Therefore these conditions are adequate for the pre-esterication of fats with different FFA content.
3.3.4. Basic-transesterication conditions
After studying the esterication reaction, the basic-transesterication conditions were studied, too. For this study the following
reaction conditions in the pre-esterication were kept: fats A,
0.5 wt.% H2SO4, 6:1 of methanol:fats, 65 C and 4 h. In Table 3 the
experiments carried out to study this process and the obtained
results are showed.
The experiments 2, 2123 (Table 3) show basic-catalyst amount
effect. Catalyst amount of 0.5 wt.% KOH was enough to obtain biodiesel with high ester content by basic-transesterication. Adding
0.1 wt.% the reaction hardly progressed; however, more amount
than 0.5 wt.% hardly increased the ester content. The effect of

3.3.5. Study of pre-esterication and basic-transesterication time

Esterication time of previous reactions, 4 h, could be reduced;
as seen in Figs. 24, constant acid value was reached at the last
minutes of reaction. Esterication and basic-transesterication
times were studied using 0.5 wt.% H2SO4, 6:1 of methanol:fats
and 65 C and 0.5 wt.% KOH, 6:1 methanol:esteried fats molar ratio and 65 C, respectively. Esterication time was reduced from 4
to 2 and 2 h, 1 h and 30 min were checked in transesterication
reaction, Table 4 summarizes performed reactions.
As seen in the table, esterication time decrease from 4 to 2 h
produced an increase in nal acid value from a value close to
1 mgKOH g1 (0.5%) to a value close to 2 mgKOH g1 (1%). Therefore
fats of 0.5% and 1% of acid value were subjected to basic-transesterication. In their study of transesterication of beef tallow,
Ma et al. (1998a), stated that the fatty acids content needs to be
kept below 0.5%. However, in our study (Table 2), fats of acid value
close to 1% were transesteried correctly with high ester content.
Although esterication time decrease would cause higher basic
catalyst consumption in soap formation.
On the other hand, transesterication time was decreased from
2 h to 30 min. As can be seen in Table 4, ester contents and viscosities were similar for different times; therefore, transesterication
time could be decreased to 30 min.
3.4. Biodiesel specications
The main parameters of a generic biodiesel obtained by
pre-esterication followed by basic-transesterication were

Table 3
Transesterication conditions, ester content and viscosity of obtained biodiesel (Pre-esterication conditions: 0.5% H2SO4, 6:1 methanol:fats, 65 C, 4 h).
Exp.

Transesterication conditions

2
21
22
23
24
25
26

1.5%
1.0%
0.5%
0.1%
0.5%
0.5%
0.5%

KOH
KOH
KOH
KOH
KOH
KOH
KOH

6:1
6:1
6:1
6:1
3:1
9:1
12:1

65 C
65 C
65 C
65 C
65 C
65 C
65 C

2h
2h
2h
2h
2h
2h
2h

Ester content (m/m%)

Viscosity 40 C(cSt)

98.6
99.1
97.3
24.4
91.9
99.9
94.6

4.67
4.67
4.74
23.86
4.85
4.74
4.82

Table 4
Pre-esterication and basic-transesterication time, acid value of esteried fats, ester content and viscosity of obtained biodiesel (pre-esterication conditions: 0.5% H2SO4, 6:1
methanol:fats, 65 C; transesterication conditions: 0.5% KOH, 6:1 methanol:fats, 65 C).
Exp.

Pre-esterication time (h)

Acid value (mgKOH g1)

Transesterication time (h)

Ester content (m/m%)

Viscosity 40 C (cSt)

22
27
28
29

4
2
2
2

1.08
2.11
2.04
1.93

2
2
1
0.5

97.3
92.5
97.2
95.7

4.74
4.84
4.77
4.81

J.M. Encinar et al. / Bioresource Technology 102 (2011) 1090710914

10913

received and G. Martnez thanks the Junta de Extremadura for

FPI grant received.

Table 5
Biodiesel characterization (Exp. 22).
Parameter

Biodiesel

EN 14214

Methyl ester content (wt.%)

Density 15 C (kg m3)
Viscosity 40 C (cSt)
Water content (wt.%)
Estimated cetane number
Acid value (mgKOH g1)
Iodine value (g I2 100 g1)
Saponication value (mgKOH g1)
Flash point (C)
Combustion point (C)
CFPP (C)

97.3
870
4.74
0.05
56.9
0.23
66.7
189.2
175
193
8

>96.5
860900
3.505.00
<0.05
>51.0
<0.50
<120
>120
-20 to 5

determined. The obtained results and the specications of European Standard EN 14214 are summarized in Table 5.
Methyl ester content, density and viscosity met European
Standard. Although pure animal fats as feedstock usually give high
viscosity, slightly out of the specication. This is due to viscosity
increase with the number of CH2 groups in the FAME chain characteristic of the most saturated animal fats (Canoira et al., 2008).
However, the obtained biodiesel in this research is in the range
of the standard, close to upper limit.
Water content, acid value and ash point are in the ranges of
the specications. Cetane number was estimated by a correlation
of cetane number with FAME composition of biodiesel, this correlation was used to predict this parameter in biodiesel from soybean, sunower, rapeseed, cottonseed, palm and tallow and the
results were satisfactory (Tong et al., 2011). The high value obtained for cetane number is natural for biodiesel from animal fats
because of its high content in saturated compounds.
All biodiesels from animal fats normally give iodine values
much lower than the upper value xed by the EN 14214 standard.
Animal fats can be incorporated into vegetable oils aiming to
achieve a product with an iodine value according to the specication (Canoira et al., 2008; Dias et al., 2008).
When animal fats were used as feedstock, the biggest problems
were encountered with regard to CFPP of biodiesel. In this work the
obtained CFPP was 8 C, this is because the saturated FAME that
characterize the biodiesel of this origin increase the CFPP in a substantial way. Similar value was obtained using lard as raw material
in previous research. The inherent problems to CFPP can be resolved by blending with other biodiesel or petro-diesel and the
use of additives (De Torres et al., 2011; Jeong et al., 2009).

4. Conclusions
Animal fats characterized by high free fatty acids were suitable
feedstock to obtain biodiesel. By acid-transesterication a biodiesel with 89.0 wt.% ester content was produced. By esterication
with 0.5 wt.% H2SO4 or 1.0 wt.% p-TsOH and 6:1 methanol:fats molar ratio an acid value less than 0.5% FFA was achieved for fats with
different FFA content, which were transesteried with only
0.5 wt.% KOH and 6:1 of methanol:fats molar ratio, reaching
97.3 wt.% ester content in the biodiesel. The main biodiesel parameters were compared with European Standard and most of properties achieved these specications.
Acknowledgements
The authors express their gratitude to the Junta de Extremadura and Extremea de Grasas, S.A. for the nancial support received
to perform this study by means of Projects PDT 09 A 037.
N. Snchez thanks the Spanish Ministry of Education for FPU grant

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