ABSTRACT: Fatty acid methyl esters are well established as

an alternative fuel called biodiesel. For economic reasons,

used frying oil is an interesting alternative feedstock for bio-
diesel production. The chemical changes that occur during
heating of rapeseed oil, especially the formation of polymers,
were investigated. Heated rapeseed oil samples were transes-
teried with methanol and analyzed by size-exclusion chroma-
tography. During heating, the amount of polymers in the start-
ing oil increased up to 15 wt%, but only up to 5 wt% in the
transesterified samples. So during transesterification, dimeric
and trimeric triglycerides in the starting oil were mainly con-
verted into monomeric and dimeric fatty acid methyl esters. The
amount of polymeric fatty acid methyl esters had a negative in-
uence on fuel characteristics. After 6 h of heating, the amount
of Conradson carbon residue and after 16 h the viscosity ex-
ceeded that of the existing specifications for biodiesel. There-
fore, the amount of polymers in waste oil is a good indicator for
the suitability for biodiesel production.
Paper no. J8981 in JAOCS 76, 545550 (May 1999).
KEY WORDS: Biodiesel, fatty acid methyl esters, polymers,
rapeseed oil, transesterication.
During the last 15 yr, the production and use of fatty acid
methyl esters (biodiesel) as alternative fuel have been estab-
lished worldwide (1,2). Adapting the fuel to the engine is pre-
ferred to adapting the engine to the fuel. Transesterifying veg-
etable oils to form fatty acid methyl esters, which can be used
directly in common diesel engines, has achieved more impor-
tance than using unmodified vegetable oils in specially de-
signed diesel engines. The main advantage of biodiesel over
neat vegetable oils is that biodiesel has similar fuel character-
istics to diesel, so either blends or 100% alternative fuel can
be used without major modications of the engine.
Today, world production capacity of biodiesel is estimated
at 1.3 million tons (3). The total production for 1997 was es-
timated at 660 thousand tons, mainly produced in Europe (3).
Owing to the limited availability of crop land leading to com-
petition with the food industry as well as the relatively high
price for vegetable oils at the present time, it is increasingly
important to look for alternative feedstocks for biodiesel pro-
duction, especially waste oils such as used frying oils.
As early as 1983 the first biodiesel production and engine
tests were done in Austria with used frying oil. In 1985, emis-
sion tests with 100% used frying oil methyl esters were done
in cooperation with AVL (Graz, Austria) (4). In 1994, the rst
plant for the production of methyl esters from used frying oil
was put into operation in Mureck, Austria (5). Up to the end
of 1998, 3,500 tons of used frying oil methyl esters have been
produced and used successfully as a 100% fuel substitute in a
series of different vehicles (6).
The fuel quality of biodiesel depends upon factors that
arise during and following transesterification, such as com-
pletion of reaction and presence of trace levels of catalyst or
alcohol. Therefore, in several countries specifications for
biodiesel have been developed that establish limits for the
most important parameters describing quality (7). Another
important factor in deriving feedstocks from used frying oils
is the presence of food and dust particles, which must be re-
moved prior to transesterification. Biodiesel quality also de-
pends on the quality of the used frying oil, especially on the
duration and temperature of its heating. During heating of
vegetable oils for frying purposes, thermal, oxidative, or hy-
drolytic reactions can cause chemical changes. Thermal reac-
tions, initiated by free radicals, can lead to intra- or intermol-
ecular cyclization and oligomerization (8,9); the Diels-Alder
reaction may be a possible cyclization mechanism (8). Also,
oxidation reactions are initiated by free radicals. The reaction
with oxygen leads to peroxy radicals and hydroperoxides
(10). Cleavage of hydroperoxides can lead to the formation
of volatile aldehydes and acids. In the presence of excess oxy-
gen, however, the alkoxy and peroxy radicals can be trans-
formed into dimeric and oligomeric compounds (8). Finally,
mono- and diglycerides, as well as free fatty acids, are formed
by hydrolytic reactions.
The formation of oligomers may be crucial for the use of
used frying oil as feedstock for biodiesel production. Higher
contents of these products may inuence viscosity, volatility,
and other fuel parameters. The objective of this paper was to
investigate how the oligomers, which are formed during heat-
ing of rapeseed oil, are transformed during transesterication
and how the remaining products inuence fuel characteristics.
Copyright 1999 by AOCS Press 545 JAOCS, Vol. 76, no. 5 (1999)
1
Presented in part at the 89th Annual Meeting, American Oil Chemists So-
ciety, Chicago, IL, May 1998.
*To whom correspondence should be addressed at Institute of Organic
Chemistry, Karl-Franzens-Universitt Graz, Heinrichstrasse 28, A-8010
Graz, Austria. E-mail: [email protected]
Transesterication of Heated Rapeseed Oil
for Extending Diesel Fuel
1
M. Mittelbach* and H. Enzelsberger
Institute of Organic Chemistry, Karl-Franzens-Universitt Graz, A-8010 Graz, Austria
MATERIALS AND METHODS
For the heating experiments, fully refined edible grade rape-
seed oil (canola) was used as starting material. The chemicals
used for the transesterification reaction were reagent grade;
high-performance liquid chromatography (HPLC)-grade
tetrahydrofuran for high-performance size exclusion chroma-
tography (HPSEC) was purchased from Promochem (Wesel,
Germany). A sample of dimeric fatty acid methyl ester was
prepared from a commercially available dimeric fatty acid
(Pripol 1014; Unichema, Emmerich, Germany) by methyla-
tion using a standard procedure (11).
Transesterification and sample preparation. Four liters of
oil were heated to 180C under constant stirring with a me-
chanical stirrer at 120 rpm in an open stainless-steel vessel.
At 2-h intervals, 200-mL samples were taken until the final
heating time of 20 h was reached. The samples were transes-
teried at room temperature using methanol and KOH as cat-
alyst (4). The degree of transesterification was measured by
gas chromatography (12); in all samples the sum of glycerides
was less than 1.0 %.
The separation of the oil samples into polar and nonpolar
fractions was done by column chromatography with silica gel
according to IUPAC (13). The sample (5 g) was dissolved in
a petroleum ether/diethylether mixture (87:13, vol/vol) and
transferred to a chromatographic column packed with silica
gel. The different fractions were eluted with solvent mixtures
having different polarities. The separation was controlled by
thin-layer chromatography; the fractions were evaporated and
weighed.
Determination of polymers. A modified IUPAC method
using HPSEC was used to determine the polymer content
(13). The modication was the use of a second column in se-
ries to get better resolution. The reproducibility of the method
was within the ranges evaluated in a collaborative study with
the original method (14). Analyses were carried out with a
Hewlett-Packard model 1100 HPLC (Palo Alto, CA),
equipped with a quaternary pump, a vacuum degasser, an au-
tosampler, a chem station and a Knauer (Berlin, Germany)
differential refractometer detector. Two gel-permeation chro-
matography columns were connected in series (Phenomenex,
Torrance, CA), the first column 300 7.8 mm, pore size 10
nm: the second column 300 7.8 mm, pore size 50 nm. The
columns and detector were thermally controlled at 40C.
Tetrahydrofuran eluent at a flow rate of 1mL/min was used.
The samples were diluted in tetrahydrofuran (10 mg/mL) and
filtered; 50 g of sample solutions were injected. For each
sample a mean value was calculated from two analysis runs.
High-temperature gas chromatography was carried out
using a Hewlett-Packard 5890 gas chromatograph, Series II
(Palo Alto, CA), equipped with an autosampler, an on-col-
umn inlet system, and a flame-ionization detector. A fused-
silica column, 10 m 0.25 mm, 0.25 m DB-5 (J&W Scien-
tic, Inc., Folsom, CA), was used. The column was connected
with a 2 m 0.53 mm uncoated precolumn. The temperature
program was 50C (1 min), 15C/min to 180C (0 min),
7C/min to 230C (0 min), and 30C/min to 370C (10 min).
The detector temperature was 380C; carrier gas hydrogen;
and injection volume 1 L.
RESULTS AND DISCUSSION
Oil analyses. The heated oil samples were separated into
polar and nonpolar fractions by column chromatography. The
polar fraction rose from 2.8% for the unheated oil up to
16.8% after 20 h of heating (Fig. 1). With HPSEC the com-
pounds were separated according to their molecular masses.
As Cuesta et al. (15) have shown, the response factors for free
fatty acids, mono-, di-, and triglycerides, as well as polar and
polymeric compounds, were similar. Quantication was done
by normalizing the peak areas. The chromatograms of the
heated oil samples (Fig. 2) had good separation between
triglycerides and dimeric triglycerides, but traces of trimeric
triglycerides were also detected. Because the main part of the
polymers consisted of dimeric compounds, the dimers and
trimers were summed. The amount of polymers rose from
1.2% in the untreated oil to 14.6% after 20 h of heating
(Fig. 3). By comparing the HPSEC chromatograms of the
polar and nonpolar fractions, one can assume that most of the
dimeric and trimeric triglycerides were in the polar fraction.
Methyl ester analyses. A typical HPSEC chromatogram of
a methyl ester sample is shown in Figure 4. In front of the
methyl ester peak only one peak with higher molecular mass
was detected. This peak was identified as dimeric fatty acid
methyl esters by comparison with a standard. Because of pos-
sible interference with sterol esters, which have similar mo-
lecular mass as dimeric esters, the values were corrected by
subtracting the average content of sterol esters in fatty acid
methyl esters (approximately 0.7%) (16). The content of
dimeric fatty acid esters in all methyl ester samples was far
lower than the polymer content in the corresponding oil (Fig.
5). So during transesterication, dimeric and trimeric triglyc-
erides were mainly converted into monomeric and dimeric
fatty acid methyl esters; this comparison was made on a mass
basis. The dimeric methyl esters were also found by high-
temperature gas chromatography (12). However, owing to the
broad signal, exact quantication was not possible (Fig. 6).
Content of polymers and fuel characteristics. Higher con-
tent of oligomeric compounds in fatty acid methyl esters may
inuence the fuel characteristics, such as viscosity and poorer
burning characteristics, because lower volatility may result.
The viscosities of the oils and their corresponding methyl es-
ters at 40C are shown vs. time of heating (Fig. 7). For the
methyl esters, the viscosity limit of 5.0 cSt (16) in specifica-
tions for biodiesel was reached after 16 h of heating.
One of the most important parameters for characterizing
biodiesel is Conradson Carbon Residue (CCR). Despite the
fact that the procedure for determining CCR is an old method
compared to modern analytical techniques, this parameter is
an excellent quality indicator for biodiesel (7). It corresponds
to the content of glycerides as well as free fatty acids, soaps,
remaining catalyst, and other impurities. In most specifica-
546 M. MITTELBACH AND H. ENZELSBERGER
JAOCS, Vol. 76, no. 5 (1999)
tions it is limited to 0.05%. As one can see in Figure 8, the
value increased with heating time and correlated with the
amount of dimeric fatty acid methyl esters.
During heating of rapeseed oil, the amounts of polymers
and polar compounds continously increased. During transes-
terification with methanol the polymers were cleaved, lead-
ing mainly to monomeric and dimeric fatty acid methyl es-
ters. Because of higher molecular mass and lower volatility,
these esters influence fuel characteristics, mainly the viscos-
ity and the Conradson carbon residue. No other effect could
be observed. Because of the absence of glycerol these dimeric
methyl esters have no negative influence on engine perfor-
mance in long-term performance tests. In the frame of an AL-
TENER project (6) two city buses, equipped with catalytical
converters, were tested over a period of 3 yr covering a dis-
tance of almost 200,000 km each, equivalent to a running
time of almost 10,000 h each. In using 100% used frying oil
methyl esters for fuel, no negative inuences on performance
and engine parts were observed. Therefore, it does not seem
to be necessary to limit the content of dimeric methyl esters,
TRANSESTERIFICATION OF HEATED OIL FOR BIODIESEL 547
JAOCS, Vol. 76, no. 5 (1999)
FIG. 1. Formation of polar compounds during heating of rapeseed oil.
FIG. 2. High-performance size exclusion chromatogram of rapeseed oil after 14 h of heating.
548 M. MITTELBACH AND H. ENZELSBERGER
JAOCS, Vol. 76, no. 5 (1999)
FIG. 3. Formation of polymers during heating of rapeseed oil.
FIG. 4. High-performance size exclusion chromatogram of methyl esters prepared from rapeseed oil after 14 h of heating.
FIG. 5. Contents of polymers in the oils and dimeric fatty acid methyl esters after transesterication.
as an additional parameter in fuel specications for biodiesel,
because viscosity and carbon residue are good indicators for
the existence of higher levels of dimers.
ACKNOWLEDGMENTS
This work was supported in part by research grants from the Euro-
pean Commission (ALTENER program) as well as from the govern-
ment of Styria and the Federal Ministeries of Environment and Sci-
ence of Austria.
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[Received August 18, 1998; accepted February 24, 1999]
550 M. MITTELBACH AND H. ENZELSBERGER
JAOCS, Vol. 76, no. 5 (1999)
FIG. 8. Conradson carbon residue and percentage of dimers in transesteried methyl esters.