Energy Fuels 2010, 24, 44814489

Published on Web 07/15/2010

: DOI:10.1021/ef100406b

Effects of Triacetin on Biodiesel Quality

ngel P
erez
Abraham Casas, Jos
e Ram

on Ruiz, Mar a Jes

us Ramos,* and A
Department of Chemical Engineering, Institute for Chemical and Environmental Technologies (ITQUIMA),
University of Castilla-La Mancha, Avenida Camilo Jos

e Cela s/n, 13071, Ciudad Real, Spain
Received April 2, 2010. Revised Manuscript Received June 24, 2010

Triacetin is a byproduct obtained from the reaction between triglycerides and methyl acetate (interesterification)
and has a higher added value than that of glycerol. According to the reaction stoichiometry, the final product
contains 20 wt % of triacetin and 80 wt % of biodiesel in a single phase. The aim of this work was to test the
performance of biodiesel quality standards when triacetin is present at different concentrations in the biodiesel.
We therefore measured properties, such as the density, kinematic viscosity, cloud point, pour point, cold filter
plugging point, dynamic viscosity, cetane number, heating value, distillation curve, and flash point, for mixtures
of triacetin and biodiesel composed of various amounts of triacetin of up to 20 wt % and different biodiesels
(palm, soybean, sunflower, high-oleic sunflower, and rapeseed). Current biodiesel fuel standards would limit the
triacetin to about 10 wt % (EN 14214) if they considered that the effect of adding triacetin is different to that of
conventional triglycerides. There would not be any restriction for amounts of up to 20 wt % according to the
American Society for Testing and Materials (ASTM) D6751 guidelines.

amount of biofuel obtained from triglycerides will increase.

A stoichiometric analysis indicates that, if all of the triglycerides were completely converted into biodiesel and triacetin,
the weight content of triacetin in the biodiesel would be
19.8%. For every 100 kg of oil, approximately 100 kg of
biodiesel are obtained by classic transesterification. Interesterification with methyl acetate would also approximately
yield 25 kg of triacetin, i.e., 125 kg of biofuel (biodiesel
triacetin). In this case, the selling price of triacetin would be
the same as that of biodiesel, significantly above the selling
price of crude glycerol.
Although glycerol is a starting compound in the production
of a large number of commodity chemicals, the synthesis of
compounds from glycerol that can be added to biodiesel has
recently been considered. Noureddini6 focused on the conversion of glycerol into ethers by a reaction with isobutylene.
When 12 wt % of glycerol ethers and 88 wt % of methyl esters
from soybean oil were mixed, the kinematic viscosity was
reduced by more than 0.5 cSt (70 F or 21.1 C) and the cloud
point (CP) was reduced by 9 F (5 C) compared to raw
soybean biodiesel. Delgado7 investigated the production of
compounds such as ketals, acetals, and acetates of glycerol by
the reaction of glycerol with aldehydes, ketones, and acetic
acid, respectively. Delgado7 reported that the addition of
formal glycerol or glycerol triacetate in amounts of up to
10 wt % slightly increase the density and decrease the freezing
point and kinematic viscosity at -10 C. The decrease in
viscosity appears unlikely because the viscosity of triacetin is
higher than that of biodiesel. The compounds mentioned in
the patents of Noureddini6 and Delgado7 have the disadvantage that glycerol must first be separated from the transesterification reaction and purified before it can be converted into
ethers, ketals, acetals, and acetates. However, Delgado7
has already shown that glycerol acetates (such as triacetin)
can also be produced during a transesterification reaction

1. Introduction
In recent years, there has been an increase in interest in
renewable fuels because of the problems associated with fossil
fuels (limitations in supply and environmental contamination). Biodiesel is one of these renewable fuels and is
obtained through a transesterification reaction of the triglycerides contained in oleaginous vegetables or animal fats with
methanol. The main problem associated with using transesterification for biodiesel production is low profitability
because of the high price of the vegetable oil that is used as
the raw material. Moreover, the glycerol obtained as a
byproduct is difficult to sell because of market saturation.1
However, the interesterification of oils and fats with methyl
acetate provides a promising alternative because products are
formed that have a higher added value (e.g., glycerol
triacetate) than glycerol.2-4 Triacetin is used mainly as a
plasticizer and a gelatinizing agent in polymers and explosives
and as an additive in tobacco, pharmaceutical compounds,
and cosmetics.5 The application of triacetin in these industries
requires a purity of 99.9%, although the selling price is high.
However, these markets are usually mature, and the triacetin
demand is easily supplied. An increase in the production of
triacetin by interesterification could lead to a saturation of the
triacetin market, similar to what has happened in the glycerol
market. Nevertheless, it is possible to mix triacetin with
biodiesel, taking advantage of their mutual solubility. When
triacetin is included in the formulation of biodiesel, the
*To whom correspondence should be addressed. Telephone: 34-926295-300. Fax: 34-926-295-242. E-mail: mariajesus.ramos@uclm.es.
(1) Stephenson, A. L.; von Blottnitz, H.; Brent, A. C.; Dennis, J. S.;
Scott, S. A. Energy Fuels 2010, 24, 24892499.
(2) Du, W.; Xu, Y.; Liu, D.; Zeng, J. J. Mol. Catal. B: Enzym. 2004,
30, 125129.
(3) Xu, Y.; Du, W.; Liu, D. J. Mol. Catal. B: Enzym. 2005, 32, 241
245.
(4) Saka, S.; Isayama, Y. Fuel 2009, 88, 13071313.
(5) Bonet, J.; Costa, J.; Sire, R.; Reneaume, J. M.; Ples-u, A. E.; Ples-u,
V.; Bozga, G. Food Bioprod. Process. 2009, 87, 171178.
r 2010 American Chemical Society

(6) Noureddini, H. U.S. Patent 6,015,440, 2000.

(7) Delgado, J. U.S. Patent 0,167,681, 2003.

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Energy Fuels 2010, 24, 44814489

: DOI:10.1021/ef100406b

Casas et al.

by adding methyl or ethyl acetate via an interesterification

reaction.
On the basis of the works of Noureddini6 and Delgado,7
Melero et al.,8,9 Jaecker-Voirol et al.,10 Garc a et al.,11 and
Saka et al.4 have studied the synthesis of ethers, acetals, and
triacetin and monitored the properties of their mixtures with
biodiesel. Investigations made by Melero et al.8,9 mainly focus
on the synthesis reaction of glycerol ethers and acetates from
pure glycerol using acid heterogeneous catalysis. JaeckerVoirol et al.10 have proven that the addition of glycerol tertbutyl ether significantly reduces the cetane number and
pollutant emissions. However, such addition does not affect
the engine performance. Garc a et al.11 have investigated the
effect of the addition (up to 15 wt %) of acetals and triacetin
on the oxidation stability, density at 15 C, kinematic viscosity
at 40 C, flash point, cold filter plugging point, and the acid
value of biodiesel. Saka et al.4 have reported the production of
triacetin by interesterification of vegetable oils with methyl
acetate under supercritical conditions in the absence of a
catalyst. To study the effects of triacetin, methyl oleate was
chosen as the reference methyl ester. The addition of triacetin
decreased the cetane number, increased the density and
viscosity, and slightly improved the cold flow properties and
oxidation stability. Fabbri et al.12 reported the production of
fatty acid glycerol carbonates from glycerol. This is also an
interesting alternative because the addition of such compounds to biodiesel hardly changes the properties of biodiesel.
The production of triacetin has received much interest
because it can be obtained by simply replacing methanol by
methyl acetate. Moreover, triacetin can be considered as a
low-molecular-weight triglyceride that contains acetic acid
molecules instead of fatty acids. It is well-known that vegetable oils (triglycerides) can be used in diesel engines. However, the high viscosity of triglycerides leads to an operational
problem (the kinematic viscosity at 40 C is 35-40 cSt).
However, triacetin has a viscosity (7.83 cSt) that is closer to
that of fatty acid methyl esters (3.5-5 cSt). Thus, to determine
whether triacetin can be used in biodiesel formulations, the
properties of mixtures containing biodiesel and triacetin have
to be studied.
The aim of our work was to study the effects of the addition of
triacetin in biodiesel on the quality of the biodiesel obtained. We
also wanted to determine whether the quality of the obtained
biodiesel was in agreement with the American Society for
Testing and Materials (ASTM) D6751 and European EN
14214 standards, because the other national or regional regulations are inspired or based on these two to a greater or lesser
extent. Accordingly, the maximum content of triacetin in
biodiesel was set to meet the ASTM D6751 and EN 14214
quality requirements. Triacetin was added to biodiesel in different
concentrations (up to a stoichiometric maximum of 20 wt %),
and the influence of the biodiesel source [palm, soybean,
sunflower, high-oleic sunflower (HOS), and rapeseed] on the
quality of the final product was also investigated.

2. Experimental Section
2.1. Materials. Refined palm, soybean, and rapeseed oils were
provided by Henry Lamotte, GmbH. Sunflower and HOS oils
were supplied by Sovena Espa~
na. The diesel sample was provided by a local service station. Anhydrous methanol (99.8%),
acetic acid (99.5%), ortho-phosphoric acid (85%), and molecular sieves were purchased from Panreac. Methyl acetate (99%)
was purchased from Sigma-Aldrich. The catalyst (potassium
methoxide; 97%) was purchased by BASF, and triacetin (99%)
was provided by Alfa Aesar.
To determine the concentrations of methyl esters and fatty
acids according to EN 14103 and the concentrations of glycerol
and mono-, di-, and triglycerides according to EN 14105 and
ASTM D6584, we used heptane (puriss pa g99.5% GC, Fluka)
and methyl heptadecanoate (puriss pa, standard for GC,
g99.7%, Fluka). N-Methyl-N-(trimethylsilyl) trifluoroacetamide (MSTFA), butanetriol, and tricaprin were also purchased
from Sigma-Aldrich.
2.2. Equipment. Transesterification and interesterification
reactions were carried out in a 200 mL four-necked batch
reactor. The reactor was equipped with a total reflux condenser,
a magnetic stirrer, and a thermocouple connected to a heater
plate to control the temperature.
Blends of biodiesel and triacetin were prepared using an
analytical balance (Sartorius, TE 214S) with an accuracy of
(7  10-5 g.
2.3. Experimental Procedure. Transesterification reactions
were carried out using a methanol/oil molar ratio of 6:1 and a
catalyst/oil molar ratio of 0.1:1. The reactor was initially
charged with the oil and preheated until the desired temperature
(60 C) was reached. The catalyst (potassium methoxide) was
dissolved in methanol, and the resulting solution was added to
the reactor with stirring. The transesterification reaction then
began, and the reactor was maintained at approximately 60 C
for 60 min. The reaction was subsequently quenched with a
stoichiometric amount of acetic acid to neutralize the catalyst.
The mixture was washed 3 times with deionized water and
centrifuged (Orto Alresa, Digitor-C) to remove the aqueous
layer, which contained methanol, residual amounts of catalyst,
and glycerol. The residual methanol was separated from the
biodiesel portion using rotary evaporation (R-210; B
uchi,
Switzerland) under vacuum at 80 C for 1 h. Finally, molecular
sieves (3 A) were added to each sample to adsorb the remaining
traces of water.
Interesterification reactions were carried out using a methyl
acetate/oil molar ratio of 48:1 and a catalyst/oil molar ratio of
0.1:1. The catalyst used was potassium methoxide. The experimental procedure was similar to that used for the transesterification reactions, except that the methanol was replaced by
methyl acetate and the acetic acid was replaced by orthophosphoric acid to neutralize the catalyst. For both interesterification and transesterification reactions, a sample was taken
after less than 5 min of reaction to have an incomplete reaction
profile.
Next, the effects of triacetin were studied out blending it
with the synthesized biodiesels at various concentrations up to
20 wt %. The maximum concentration of triacetin was chosen
according to the interesterification reaction stoichiometry, because the reaction products are about 80 wt % biodiesel and
20 wt % triacetin. It should be noted that triacetin and biodiesel
were completely miscible in all proportions.
Finally, samples of pure biodiesel (B100) and all of the
prepared blends were analyzed according to analytical methods
detailed below.
2.4. Analytical Methods. Analyses were performed according
to procedures described in the EN 14214:2008 and ASTM
D6751-09 standards. All experiments were carried out in triplicate, and no statistically significant differences were observed
for the different measurements. The arithmetic mean of the three

(8) Melero, J. A.; Vicente, G.; Morales, G.; Paniagua, M.; Moreno,
J. M.; Rold

an, R.; Ezquerro, A.; P
erez, C. Appl. Catal., A 2008, 346, 44
51.
(9) Melero, J. A.; van Grieken, R.; Morales, G.; Paniagua, M. Energy
Fuels 2007, 21, 17821791.
(10) Jaecker-Voirol, A.; Durand, I.; Hillion, G.; Delfort, B.;
Montagne, X. Oil Gas Sci. Technol. 2008, 63, 395404.
(11) Garc a, E.; Laca, M.; P
erez, E.; Garrido, A.; Peinado, J. Energy
Fuels 2008, 22, 42744280.
(12) Fabbri, D.; Bevoni, V.; Notari, M.; Rivetti, F. Fuel 2007, 86, 690
697.

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: DOI:10.1021/ef100406b

Casas et al.

Table 1. Limits of Biodiesel Quality Parameters According to ASTM D6751-09 and EN 14214:2008 Standards
property
density at 15 C
kinematic viscosity at 40 C
CFPP
CP
cetane number
methyl ester content
distillation temperature
atmospheric equivalent temperature
90% recovered
flash point
sulfur content
carbon residue
sulfated ash content
water content
total contamination
copper strip corrosion (3 h at 50 C)
oxidation stability at 110 C
acid value
iodine value
cold soak filterability test
linolenic acid methyl ester
polyunsaturated (gdouble bonds) methyl esters
methanol content
monoglyceride content
diglyceride content
triglyceride content
free glycerol
total glycerol
group I metals (Na K)
group II metals (Ca Mg)
phosphorus content

units

ASTM D6751-09

kg/m
mm2/s
C
C

1.9-6
according to climate zone
g47

% (m/m)
C

e360

C
mg/kg
% (m/m)
% (m/m)

g93
e15
e0.05 (on 100% sample)
e0.02
e0.05% volume (sediment)

mg/kg
classification
h
mg of KOH/g
g of I2/g
s
% (m/m)
% (m/m)
% (m/m)
% (m/m)
% (m/m)
% (m/m)
% (m/m)
% (m/m)
mg/kg
mg/kg
mg/kg

e3
g3
e0.5

EN 14214:2008
860-900
3.5-5
according to climate zone
g51
g96.5

g101
e10
e0.3 (on 10% distillation residue)
e0.02
e500 mg/kg
e24
1
g6
e0.5
e120

e360
e0.2 or flash point g130 C

e0.02
e0.240
e5.0
e5.0
e10

e12.0
e1
e0.2
e0.8
e0.2
e0.2
e0.02
e0.25
e5.0
e5.0
e4.0

40 ( 0.07 C. Several Cannon-Fenske capillary viscometers, previously calibrated by Applus, were also used. The bath temperature
was measured with a thermometer (Ludwig Schneider, ASTM 120C/
IP 92 C), having an uncertainty of (0.07 C. A stopwatch with an
accuracy of (0.01 s was used to measure the time.
The low-temperature dynamic viscosities were determined at
several temperatures above the CP using a rotational viscometer
(Brookfield model DV-II).
The cold properties of the samples were evaluated in a cold
filter plugging point (CFPP), CP, and pour point (PP) measurement device (ISL, FPP 5GS).
The CP and PP analyses were performed according to EN
23015 and ASTM D97 standards, respectively. Temperature
measurements were carried out using a calibrated thermometer
(Terinber, ASTM 5C) with an uncertainty of (0.1 C.
CFPP measurements were carried out according to the EN
116 standard. Here, the FPP 5GS device was equipped with a
platinum temperature probe (Pt 100). The interchangeability
tolerances for this probe were in agreement with the IEC 751Class A standard (to an accuracy of (0.13 C).
Cetane number analyses were performed according to the EN
ISO 5165 and EN 15195 standards, i.e., using either a cooperative fuel research (CFR) engine or an ignition quality tester
(IQT). The tests were sub-contracted to an accredited laboratory (Caleb Brett Ib
erica, Intertek) according to ISO 17025. The
uncertainty was (2.5 for CFR and (1.4 for IQT.
Higher heating values (HHVs) were measured using an oxygen bomb calorimeter (Parr 1356, Biometa) according to ASTM
D240 guidelines. The uncertainty was lower than (1 kJ/kg in all
experiments.
Distillation curves were obtained according to the procedure
described in the ASTM D1160 guidelines. The half-automated
D1160 instrument was purchased by Normalab Analis SA.
Flash points were measured using a closed-cup flash point
analyzer (Stanhope-Seta, Setaflash series 3). This analyzer was
operated according to EN ISO 3679 guidelines. The test interval
was 0.5 C, and the uncertainty of the method was estimated to
be lower than (1 C.

determinations was taken as the final result. In addition, the

uncertainties were calculated to confirm that each instrument
met the accuracy requirements set by the specifications of the
standard method. All instruments were tested, verified with
certified reference materials, and calibrated periodically in
accordance with the ISO 9001:2008 and ISO 17025:2005 quality
assurance systems.
Total uncertainty of the different properties was estimated
and is shown in the corresponding figures. Total uncertainty has
been calculated using repeatability and reproducibility tests and
checking the accuracy of the instruments using the corresponding certified reference materials in the range of work.
The analyses and equipment used in this research as well as
the standard methods associated with them are as follows: The
methyl ester contents and fatty acid profiles were measured
according to EN 14103; glycerol, mono-, di-, and triglyceride,
and triacetin contents were determined according to EN 14105
and ASTM D6584 using a Hewlett-Packard model 6890 gas
chromatograph. The chromatographic conditions for methyl
ester contents and fatty acid profiles were as follows: a DBWAX column with length of 30 m, internal diameter of 0.32 mm,
and thickness of 0.25 m; a split ratio of 60; a constant pressure
of 11.6 psi; and an oven temperature of 200 C. For the glycerol,
mono-, di-, and triglyceride, and triacetin content measurements, the conditions were as follows: a DB5-HT column with
length of 15 m, internal diameter of 0.32 mm, and thickness of
0.10 m; an on-column injection at a constant pressure of 11.6
psi; an oven temperature of 50 C for 1 min that was first
increased to 180 C at a rate of 15 C/min, then to 230 C at 7 C/min,
and finally, to 370 C at 10 C/min. The carrier gas used was
helium in all cases.
The density was determined at 15 C according to EN ISO
3675 with a hydrometer (Stanhope-Seta, BS 718 M50SP), having an uncertainty of (0.0005 g cm-3. The temperature
was measured with a calibrated thermometer (Stanhope-Seta,
IP 39 C), having an uncertainty of (0.015 C.
The kinematic viscosity was measured according to EN ISO 3104
using a heating bath (Tamson, TV2000) at a temperature of
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Energy Fuels 2010, 24, 44814489

: DOI:10.1021/ef100406b

Casas et al.

3. Results and Discussion

Among all of the biodiesel parameters listed in the ASTM
D6751 and EN 14214 guidelines (shown in Table 1), we
studied the density at 15 C, kinematic viscosity at 40 C,
low-temperature parameters (i.e., CFPP and CP), cetane
number, methyl ester content, distillation temperature, and
flash point because we assumed that these would be most
significantly affected by the addition of triacetin. While not
listed in the ASTM D6751 and EN 14214 guidelines, other
parameters, including PP, dynamic viscosity at temperatures
below 5 C, and HHV, were also studied to understand the
effects of triacetin more completely.
All of the above parameters were also affected by the fatty
acid profile. Therefore, we measured the fatty acid profiles of
palm, soybean, sunflower, HOS, and rapeseed oils. The results
are shown in Figure 1.
As already mentioned, triacetin is a low-molecular-weight
triglyceride. In the ASTM D6751 and EN 14214 guidelines,
the triglyceride content is limited. The maximum content of
triglycerides is 0.2 wt % according to EN 14214 guidelines; the
total glycerol content, which is calculated using the glycerol
and mono-, di-, and triglyceride contents, must be below 0.25
and 0.24 wt % according to the EN 14214 and ASTM D6751
guidelines, respectively. The triglyceride and total glycerol
contents were measured according to the EN 14105 and
ASTM D6584 guidelines, i.e., using the same gas chromatographic method. The chromatograms of the incomplete transesterification and interesterification reactions are shown
in Figure 2. It can be observed that compounds such as
diacetinmono- and monoacetindiglycerides, which are only produced in interesterification reactions, share the same retention
time as the mono- and diglycerides obtained in the transesterification reactions. However, triacetin did not elute at the same
time as triglycerides. Indeed, triacetin eluted between the
glycerol and monoglyceride fractions. Therefore, the analysis
of triacetin should be included in the EN 14105 and ASTM
D6584 guidelines, and its content limit must be fixed, taking
into account the effect of triacetin on the parameters of the
biodiesel listed previously, as a first approach. Further investigations should focus on field tests using diesel engines.
3.1. Density. During the operation of a diesel engine, fixed
volumes of fuel are injected. Therefore, the density of the fuel
affects the consumption of fuel and the efficiency of fuel
atomization.13 The density of fossil diesel is 800-850 kg/m3,
whereas the density of biodiesel is 860-900 kg/m3. Under the
ASTM D6751 guidelines, the density of biodiesel is not
limited because it is assumed that it lies in the abovementioned range for all raw vegetable oils and animal fats.
However, under the EN 14214 guidelines, the density of
biodiesel is limited to avoid the presence of strange substances or residual methanol from the transesterification
reaction.14
The density of methyl esters depends upon the chain length
and number of double bonds. The density decreases with the
chain length, albeit only slightly for chains of greater than
eight carbon atoms in length. An increase in the number of
double bonds leads to a considerable increase of the density
of methyl esters.15 Triacetin has a high density (1183 kg/m3 at

Figure 1. Saturated, monounsaturated, and polyunsaturated (2,3)

methyl ester contents in biodiesels.

15 C), similar to that of glycerol. The two compounds have

an almost identical molecular structure, yielding an important degree of packing.
In Figure 3a, the density of various mixtures of triacetin
using various types of biodiesel is shown. As seen in the
figure, the addition of triacetin always results in an increase
of the density of the mixture in an almost linear fashion. This
observation agrees with previous investigations.11 The densities of soybean and sunflower biodiesels (which have a
larger content of C18:2) are higher than those of rapeseed
and HOS biodiesels (which are mostly C18:1). Palm biodiesel
has the lowest density because it has a higher content of
palmitic methyl esters (C16:0)
Thus, the maximum content of triacetin (according to the
EN 14214 guidelines) was found to be 9.50, 9.81, 11.10,
11.30, and 13.52 wt % for soybean, sunflower, HOS, rapeseed, and palm biodiesels, respectively. As mentioned above,
the content of triacetin is not limited by the density in the
ASTM D6751 guidelines.
3.2. Kinematic Viscosity. Viscosity has an important impact on fuel injection and combustion. An increase in the
viscosity leads to problems with the injection pump that
result in an increase of the injection pressure and volume. As
a direct consequence, the timing or delay between the fuel
injection and fuel ignition is slightly advanced. The combustion temperature and NOx emissions are therefore increased,
and the injection system can be blocked because of poor
atomization of the fuel.16
Triglycerides from vegetable oils and animal fats can be used
in diesel engines. However, their elevated viscosity (around
35-40 cSt at 40 C) is problematic. Biodiesel, which has a
viscosity that is close to that of fossil diesel (3.5-5 cSt at 40 C
compared to 2-4 cSt), is therefore more suitable than vegetable
oils for use in diesel engines. Triacetin has a viscosity that is
lower than those of natural triglycerides. The kinematic viscosity of triacetin is 7.83 cSt at 40 C, i.e., higher than those of
fossil diesel and biodiesel. Triacetin can, however, be mixed
with biodiesel in amounts of up to 20 wt %.17

(13) Knothe, G.; Van Gerpen, J.; Krahl, J. The Biodiesel Handbook;
American Oil Chemists' Society (AOCS) Press: Urbana, IL, 2005.
(14) Knothe, G. J. Am. Oil Chem. Soc. 2006, 83, 823833.
(15) Ott, L. S.; Huber, M. L.; Bruno, T. J. J. Chem. Eng. Data 2008,
53, 24122416.

(16) Mittelbach, M.; Remschmidt, C. Biodiesel: The Comprehensive

Handbook; Borsedruck GmbH: Vienna, Austria, 2004.
(17) Knothe, G.; Steidley, K. R. Fuel 2007, 86, 25602567.

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Energy Fuels 2010, 24, 44814489

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Casas et al.

Figure 2. Chromatograms of uncompleted transesterification and interesterification reactions according to the EN 1405 and ASTM D6584
guidelines: (1) glycerol, (2) triacetin, (3) standard reference 1, butanetriol, (4) diacetinmonoglycerides, monoglycerides, (5) standard reference 2,
tricaprin, (6) monoacetindiglycerides, diglycerides, and (7) triglycerides. Butanetriol and tricaprin were not added to the interesterification
samples.

The kinematic viscosity of methyl esters increases as the

chain length increases and decreases as the number of double
bonds increases. Thus, fatty acid methyl esters with a high
density have a low viscosity.17
To test the effects of triacetin on the viscosity of mixtures
of triacetin and biodiesels, the kinematic viscosity of mixtures of triacetin with several types of biodiesel was measured. The results are shown in Figure 3b. As mentioned
above, the viscosity increases with an increasing content of
saturated methyl esters, and the most viscous mixture was
that including palm biodiesel. From the obtained results, it
can be stated that the addition of triacetin results in an
increase of the viscosity. However, as the viscosity of the
mixture increases exponentially with respect to the concentration of triacetin, the viscosity is only increased slightly for
triacetin contents below 20 wt %. Similar results were
obtained in previous studies.4,11
The kinematic viscosity of the mixture does not exceed the
maximum limit set by the EN 14214 guidelines, even with the
highest triacetin content tested (i.e., 20 wt %). The maximum
limit set by the ASTM guidelines is higher than that set in the
EN 14214 guidelines (6 versus 5 cSt), because the D6751
guidelines were developed for biodiesels mixed with diesel in
amounts of up to 20%.
3.3. Low-Temperature Properties. A disadvantage of using
biodiesel rather than fossil diesel is the behavior of biodiesel
at low temperatures. The presence of saturated methyl esters
(mainly C16:0 and C18:0) with high freezing points results in
the presence of solid precipitates at higher temperatures than
is the case with fossil diesel. These precipitates may lead to
problems with fuel injection systems in colder climates.
Both diesel and biodiesel are mixtures. As such, they have
a freezing point range rather than an exact freezing point.

Because the fuel system of a vehicle can remain functional in

this range, it is necessary to study the behavior of the fuel
over this freezing point range. The standard methods that
were used for this purpose were CP, PP, and CFPP.
CP is defined as the temperature at which a liquid material
becomes cloudy because of the formation of crystals and the
solidification of high-freezing-point compounds. Therefore,
it represents the onset of fuel solidification. PP is related to
the lowest temperature at which a liquid can still flow under
gravity. Finally, CFPP represents the highest temperature at
which a given volume of liquid fails to pass through a
standardized filtration device in a specified amount of time
when cooled under standardized conditions.
The freezing point of pure methyl esters (in this case, the
freezing point agrees with the CP) increases with the chain
length and decreases with the number of double bonds. The
CP of biodiesel (a mixture of methyl esters) only depends
upon the content and type of saturated esters. The number of
double bonds of the unsaturated methyl esters does not affect
the CP.18
Although triacetin is a pure compound, its cold temperature behavior is quite unusual. Its freezing point has seldom
been studied, and the values that have been measured range
between 3.2 and 4.1 C.19,20 It has also been discovered that
crystallization is extremely slow and that the presence of
impurities or seed crystals is required for complete crystallization at these temperatures. In the absence of impurities or
seed crystals, triacetin did not solidify at temperatures above
-78 C.19
(18) Imahara, H.; Minami, E.; Saka, S. Fuel 2006, 85, 16661670.
(19) Hancock, B.; Sylvester, D. M.; Forman, S. E. J. Am. Chem. Soc.
1948, 70, 424.
(20) Baur, F. J. J. Phys. Chem. 1954, 58, 380.

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Energy Fuels 2010, 24, 44814489

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Casas et al.

higher for the rapeseed biodiesel (9 C for 20 wt % of

triacetin) than for the palm biodiesel (3 C for 20 wt % of
triacetin) because the rate of crystallization was rapid for
higher contents of saturated compounds, which prevent the
delay of the onset of the PP even with a reduced CP. Saka
et al.4 reported a decrease of only 2 C for a mixture of methyl
oleate as the biodiesel reference and 20 wt % of triacetin.
Finally, the behavior of the CFPP is different from those
of the CP and PP. It can be seen that palm biodiesel is the only
beneficiary (only 2 C with a triacetin content of 20 wt %).
Soybean, sunflower, and HOS biodiesels are barely influenced by
the presence of triacetin. However, adding triacetin resulted in a
decrease of the CFPP of rapeseed biodiesel.
Saka et al.4 and Garc a et al.11 have shown that adding
triacetin leads to different results. Saka et al.4 observed a
decrease of only 1 C (from -16 to -17 C) after 20 wt % of
triacetin was added to methyl oleate. Triacetin contents
greater than 20 wt % led to a rapid increase of the CFPP.
Garc a et al.11 observed that the addition of 5 wt % of
triacetin reduced the CFPP from -5 to -10 C. A higher
triacetin content increased the CFPP slightly, up to -9 C.
However, in that study, the characteristics of the biodiesel
were not in agreement with the EN 14214 guidelines (the acid
value was greater than 0.5 mg of KOH/g) and the triacetin
was synthesized in the laboratory instead of being purchased
with a high purity (>99%).
The effect of the triacetin content on dynamic viscosity at low
temperatures is shown in Figure 4d. It must be noted that
measuring the CFPP entails a filtration process and that the
filtration rate is inversely proportional to the viscosity. For the
rapeseed biodiesel, the CFPP was measured at temperatures
between -5 and -10 C, i.e., temperatures at which the triacetin
has a dynamic viscosity that is much higher than that of the
biodiesel and where the difference is the greatest.21 This increase
in the dynamic viscosity prevents the required volume of test fluid
from passing through the standardized filter in 60 s.
The CP is either improved or unchanged by the addition of
triacetin. It would therefore be in agreement with American
standards. However, the negative effect of adding triacetin
on the CFPP may cause problems with European norms in
certain regions.
3.4. Cetane Number. The cetane number is a measurement
of the combustion quality of diesel fuel during compression
ignition expressed as the mixture of cetane (hexadecane) and
isocetane (2,2,4,4,6,8,8-heptamethylnonane) that possesses
the same ignition delay. It is carried out in a CFR engine
under standard test conditions. Because of the complexity of
this test, measuring the ignition time delay and correlating
that with the cetane number through the IQT has recently
been considered as a substitute.
The cetane numbers of pure triacetin, the methyl ester of
palmitic acid, and stearic, oleic, and linoleic acids are 15,
85.9, 101, 59.3, and 38.2, respectively.4,22 Therefore, an
increase in the triacetin content is expected to reduce the
cetane number of the biodiesel. Figure 5a shows the effect of
the concentration of triacetin on the cetane number for
mixtures of rapeseed biodiesel and triacetin.
Determining the cetane number according to the EN ISO 5165
or ASTM D613 (CFR) guidelines presents a significantly higher

Figure 3. (a) Density at 15 C of various mixtures of triacetin and

biodiesel. (b) Kinematic viscosity at 40 C of various mixtures of
triacetin and biodiesel. In both cases, the uncertainty bars are
smaller than the plotting symbol. The uncertainty of density and
viscosity is 0.913-0.931 kg/m3 and 0.08-0.085 mm2/s, respectively.

The CP, PP, and CFPP of biodiesel mixed with triacetin

are shown in panels a, b, and c of Figure 4, respectively.
As shown in the figure, CP decreases significantly (by
approximately 4 C for 20 wt % of triacetin) when the CP of
the pure biodiesel being measured is above or below the
freezing point of triacetin, i.e., for palm (16 C) and rapeseed
(-3 C) biodiesels. When the pure biodiesel under observation has a CP close to the freezing point of triacetin, the
variation in the CP is negligible (i.e., 1 C difference). This
may be due to the presence of crystals of biodiesel at a
temperature close to the freezing point of triacetin that
facilitate the crystallization of triacetin. In their absence,
the biodiesel freezes at 16 C and mixing with triacetin
reduces the CP compared to the raw biodiesel. Rapeseed
biodiesel, which has a CP below that temperature, does not
facilitate the solidification of triacetin (i.e., it does not
solidify above -78 C), and this also lowers the CP of the
mixture of rapeseed biodiesel and triacetin.
A similar behavior was observed for the PP. The variation
was small for some types of biodiesel because they crystallize
in a range close to that of triacetin. The PP variation was

(21) Rodr guez, M.; Gal
an, M.; Mu~

noz, M. J.; Mart n, R. J. Chem.
Eng. Data 1994, 39, 102105.
(22) Knothe, G.; Matheaus, A. C.; Ryan, T. W., III Fuel 2003, 82,
971975.

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Energy Fuels 2010, 24, 44814489

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Casas et al.

Figure 4. (a) CP of various mixtures of triacetin and biodiesel. (b) PP of various mixtures of triacetin and biodiesel. (c) CFPP of various mixtures
of triacetin and biodiesel. (d) Dynamic viscosity of various mixtures of rapeseed biodiesel and triacetin.

uncertainty than using the EN 15195 (IQT) guidelines. It is

known that rapeseed biodiesel has a cetane number of 55,
whereas biodiesels from soybeans, sunflowers, and palms have
cetane numbers of 49, 50, and 61, respectively.23 As shown in
Figure 5a, the cetane number of rapeseed biodiesel agrees with the
value found in the literature.
It was also found that the cetane number of biodiesel remains
unchanged for low contents of triacetin. However, 10 wt % of
triacetin reduces the cetane number below the minimum limit
fixed by the EN 14214 guidelines. The cetane numbers of sunflower and soybean biodiesels are used as references to set the
minimum limit in the EN 14214 (>51) and ASTM D6751 (>47)
guidelines, respectively. The use of more than 10 wt % triacetin
with either of these biodiesels will prevent the minimum cetane
number from being reached.
3.5. HHV. The HHV of a substance is the amount of heat
released during the combustion of a specific amount and is
measured in units of energy per unit of substance (usually its
mass). It is determined by returning all of the products of
combustion to the original precombustion temperature and, in
particular, condensing any vapor produced. The HHV is identical
to the thermodynamic heat of combustion because the enthalpy
change for the reaction assumes a common temperature of the
compounds before and after combustion, in which case the water
produced by combustion is in the liquid phase.

Obviously, this parameter is very important for a combustion engine because it is related to the consumption of fuel.
Biodiesels or fatty acid methyl esters present a heating value
below that of fossil diesels because of their higher oxygen
content (from the ester bond). However, there is no limitation for this parameter in the EN 14214 and ASTM D6751
guidelines. This is mainly due to the facts that the HHV of
biodiesel slightly depends upon the type of biodiesel and that
it is always below the HHV of diesel fuel.
The oxygen content in triacetin is higher (49.5 wt %) than
that of biodiesel (11 wt %); therefore, the HHV of triacetin is
lower than that of biodiesel. The HHVs (on the basis of the
mass) of mixtures of triacetin and biodiesel are shown in
Figure 5b. As can be seen from the figure, adding triacetin
linearly reduces the HHV of biodiesel. A 10% decrease (on
the basis of the mass) was observed when 20 wt % of triacetin
was added. The higher density of triacetin, which is problematic for compliance with EN 14214 guidelines, becomes
advantageous here: In a diesel engine, a fixed volume of fuel
is injected into the engine. A higher density, therefore, leads
to a higher amount of fuel injected, releasing more energy by
combustion. Thus, to compare properly the HHVs of the
mixtures of triacetin and biodiesel, the comparison must
consider volume. In our case, the loss in heating value was
only 4% for 20 wt % of triacetin in biodiesel. A similar
situation occurs in relation to the use of aromatic compounds in fossil diesels. These compounds have lower HHVs
(on the basis of the mass) than diesel, but their higher density

(23) Ramos, M. J.; Fern
andez, C. M.; Casas, A.; Rodr guez, L.; P
erez,
A. Bioresour. Technol. 2009, 100, 261268.

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Energy Fuels 2010, 24, 44814489

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Casas et al.

Figure 5. (a) Cetane number of various mixtures of triacetin and sunflower biodiesel. All samples were measured by CFR, except for the 2 wt %
content, which was measured by IQT. (b) HHV of various mixtures of soybean biodiesel and triacetin and of soybean biodiesel and diesel. In
this test, the uncertainty bars are smaller than the plotting symbol. The uncertainty is 0.251-0.259 MJ/kg. (c) Distillation curve of various
mixtures of rapeseed biodiesel and triacetin and of rapeseed biodiesel and diesel. (d) Flash point of various mixtures of soybean biodiesel and
triacetin.

be detected.25 This test is preferred by the ASTM D6751

guidelines because of the low precision of the methyl ester
norm (EN 14103). Choosing this parameter implies that the
American standards are more permissive with respect to the
feedstock used in the production of biodiesel.
To study the effect of adding triacetin, the distillation curves
of rapeseed biodiesel, rapeseed biodiesel mixed with 20 wt % of
triacetin, and diesel were determined. These are shown in
Figure 5c. Obviously, the presence of a more volatile compound, such as triacetin (boiling point = 257 C), in the
biodiesel does not increase the T90. Therefore, according to
the norm, the content of triacetin is not limited.
3.7. Flash Point. Each flammable liquid requires a different concentration of its vapor in air to sustain combustion.
This concentration depends upon the vapor pressure of the
liquid, which is related to its temperature. The flash point of a
flammable liquid is the lowest temperature at which there is
sufficient flammable vapor to ignite when an ignition source
is applied.
Biodiesel has a flash point that is higher than that of fossil
diesels. Note that there is no reason to measure and limit the
flash point in biodiesel fuels. Thus, the flash point of a
biodiesel is only assessed to determine the presence of volatile
flammable liquids, mainly methanol that remains from the
transesterification reaction.16 Because triacetin has a boiling

increases the HHV of their mixtures expressed on the basis of

the volume.
3.6. Biodiesel Purity (Methyl Ester Content and Distillation
Curve). The purity of biodiesel is tested by measuring the
methyl ester content in Europe (EN 14214) and the distillation temperature in America (D6751).
The methyl ester content (from C14:0 to C24:1) is set to the
minimum limit of 96.5 wt % to avoid the presence of
undesirable compounds, such as unsaponifiable compounds
and polymers. Lauric oils (C12:0), such as coconut or palm
kernel, cannot be chosen for biodiesel production because
only particular types of methyl esters are selected and
because of the content limitation. As for lauric oils, a content
of triacetin of more than 3.5 wt % could not be added.24
The atmospheric equivalent temperature (AET) corresponds to the conversion of vacuum distillation temperatures under atmospheric pressure conditions according to
ASTM D1160 standards, which limit the AET to a temperature at which 90 vol % is recovered (T90) at 360 C. A
fraudulent mixture with heavier petroleum fractions can thus
(24) Schober, S.; Seidl, I.; Mittelbach, M. Eur. J. Lipid Sci. Technol.
2006, 108, 309314.
(25) Tripartite Task Force. White Paper on Internationally Compatible Biofuel Standards; Brazil, European Union, and United States of
America, 2007.

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Casas et al.

Table 2. Maximum Triacetin Content in Biodiesel According to ASTM D6751 and EN 14214 Quality Standards
property
density at 15 C
kinematic viscosity at 40 C
CFPP
CP
cetane number
methyl ester content
distillation temperature
AET T90
flash point
restriction
a

ASTM D6751

EN 14214
e10 wt % (the exact limit will depend upon the type of biodiesel)
maximum (e20 wt %)
triacetin addition will negatively affect
CFPP (the exact limit will depend upon the
type of biodiesel and the climate zone)

maximum (e20 wt %)

will not negatively affect CP

maximum (e20 wt %)

e10 wt % (the exact limit will depend upon the type of biodiesel)
e3.5 wt %

maximum (e20 wt %)
maximum (e20 wt %)
maximum (e20 wt %)

maximum (e20 wt %)
e3.5 wt %a

If the limit of the methyl ester content is not taken into account, then the triacetin content limit would be e10 wt %.

point approximately 100 C lower than that of biodiesel, we

studied the effect of adding triacetin on the flash point. The
results are shown in Figure 5d.
The presence of triacetin, a more volatile substance,
reduces the flash point of biodiesel, and the results are in
agreement with those found in the literature.4,11 However,
the flash point values reached are over the minimum limits
set by EN 14214 (101 C) and ASTM D6751 [93-130 C (if
methanol is not measured)].
3.8. Summary: Limitation of the Triacetin Content According to the ASTM D6751-09 and EN 14214:2008 Guidelines.
Table 2 summarizes the amounts of triacetin that can be
added to biodiesel (up to 20 wt %) to comply with the ASTM
D6751 and EN 14214 standards. The triacetin content is not
limited by the American standards. As discussed before, this
standard is more permissive regarding the feedstock used in
the production of biodiesel because it favors the addition
of substances, such as triacetin. On the other hand, the
European norms limit the content of triacetin to 3.5 wt %
(taking into account the methyl ester content) or to a value
close to 10 wt % (taking into account the limits of density and
cetane number). The CFPP parameter can be monitored when
adjusting the levels of triacetin. On the basis of the triglyceride
and total glycerol contents, triacetin can be considered as a
triglyceride. However, it does not have the disadvantages of
triglycerides, i.e., their high viscosity and high boiling points
that limit their use in biodiesels. Furthermore, because triacetin
does not contain free -OH groups, it does not have the
problems associated with glycerol and mono- and diglycerides.
Thus, unlike triglycerides and glycerol, the content of triacetin

does not have to be limited. The chromatograms presented on

the basis of the EN 14105 and ASTM D6584 guidelines
(Figure 2) show that triacetin does not have the same elution
time as any of these compounds (glycerol and mono-, di-, and
triglycerides). These results indicate that biodiesel standards
were not fixed on the basis of the presence of substances such
as triacetin. The study of the effects of the presence of triacetin
on biodiesel properties must be completed with tests in diesel
engines and vehicles. Moreover, the problems associated with
the hydrolysis of triacetin (producing acetic acid) have to be
taken into account during the storage of the biodiesel-triacetin
mixtures. Further studies are necessary to set the limit of the
water content and avoid the possible increase of the acid value
during storage.
4. Conclusions
The triacetin content does not have to be limited according to
the ASTM D6751 guidelines. On the other hand, the EN 14214
guidelines impose a maximum value of approximately 10 wt %.
The freezing point of triacetin is responsible for the decrease
in CP and PP. However, the higher viscosity of triacetin
prevents a decrease of the CFPP.
As expected, the density and viscosity of mixtures increased as
the content of triacetin increased, while the flash point, heating
value, and cetane number decreased. The distillation temperature (AET, 90% recovered) was not affected by triacetin.
Acknowledgment. Ecoproductos Ib
ericos SA (Ecopriber) is
gratefully acknowledged for its financial support.

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