Characterization of Biodiesel and Biodiesel Particulate Matter by

TG, TG-MS, and FTIR

Yi-Chi Chien,*
,
Mingming Lu,

Ming Chai,

and F. James Boreo

Department of EnVironmental Engineering and Science, Fooyin UniVersity,

Kaohsiung County 831, Taiwan, and Department of CiVil and EnVironmental Engineering and Department
of Materials Science and Engineering, UniVersity of Cincinnati, Cincinnati, Ohio 45221
ReceiVed May 23, 2008. ReVised Manuscript ReceiVed October 25, 2008
Biodiesel is a potential renewable and carbon-neutral alternative to fossil fuels, and it is environmentally
and economically attractive. This paper studies the decomposition kinetics of biodiesel using thermal gravimetric
analysis (TGA) in one-stage pyrolysis. Biodiesel can be decomposed at 119-237 C. The kinetic parameters
for biodiesel pyrolysis were obtained from the TGA experiments. The global rate equation for biodiesel pyrolysis
can be expressed as dX/dt )2.6 10
7
exp(-16.2/8.314 10
-3
T)(1 -X)
0.52
(X denotes the reaction conversion).
Characteristics of diesel and biodiesel and the associated diesel particulate matter (DPM) emitted from a nonroad
diesel generator were also analyzed by Fourier transform infrared (FTIR) spectroscopic methods. The FTIR
spectra of biodiesel showed a CdO stretching band of methyl ester at 1743 cm
-1
and C-O bands at 1252,
1200, and 1175 cm
-1
. Furthermore, the FTIR spectra of DPM were similar to those of the fuels, an indication
that the chemical structures of DPM are closely related to the fuel and engine oil properties, consistent with
our previous study. The temperature series of 11 fragments have been analyzed in nitrogen, which include m/z
29, 31, 44, 74, 87, 105, 143, 263, 294, 296, and 298. The fragments at m/z 294, 296, and 298 represent the
methyl ester components of biodiesel, and the fragment at m/z 44 is carbon dioxide, fragments at m/z 29 and
105 represent aldehyde compounds, and fragments at m/z 87 and 143 are shorter chain methyl esters, all of
which can be byproducts from biodiesel combustion. The fragments at m/z 57, 67, 95, and 109 represent
hydrocarbon components, which may be fragmented from the long carbon chains of methyl esters, and the
fragment at m/z 31 is a methoxy group, which may be fragmented from methyl esters. The information of
TG-MS as analyzed above can offer a better understanding of the byproduct formation mechanisms of biodiesel
combustion.
1. Introduction
With the gradual depletion of fossil fuels, the development
of renewable energy sources is of increasing importance.
Biodiesel is dened as the monoalkyl ester derivatives of long
chain fatty acids, produced from oil crops, waste cooking oil,
or animal fat via a relative simple transesterication process.
The transesterication process is the reaction of a lipid with a
short chain alcohol such as methanol to form esters and
byproducts.
1-3
Biodiesel is a renewable and biodegrable fuel
and is becoming environmentally and economically attractive.
1
The biodegradability of biodiesel is evidenced by the much
shorter half-life comparing with petroleum diesel. As an
example, the half-life of approximately 100 ppm B20 in
rainwater is 6.8 days.
4
Due to its high solubility and biodegrada-
tion, biodiesel has a potential to be used in bioremediation to
remove oils or polycyclic aromatic hydrocarbons (PAHs) in
contaminated soils.
5,6
Biodiesel has an energy density that is slightly less than that
of petroleum diesel. It has been proven that it is a technically
sufcient alternative diesel fuel in the fuel market. In European
countries and the United States, biodiesel has been accepted
for use in automobiles, ships, and heating systems.
7
Generally,
biodiesel can be used either as a direct substitute for fossil fuels
or blended with different amounts of petroleum diesel in
compression-ignition engines without any modication with
environmental and economic advantages.
8
In a biodiesel/diesel
blend, the greater the percentage of biodiesel present, the greater
the reduction of air pollution emission observed, except NO
x
and carbonyls.
9,10
Kulkarni and Dalai also have reported that
the biodiesel produced from waste cooking oil gives better
engine performance and emits less emission when tested on
* To whom correspondence should be addressed. Tel 011-8867-783-
0542. Fax 011-8867-782-1221. E-mail PL036@mail.fy.edu.tw.

Fooyin University.

Department of Civil and Environmental Engineering, University of

Cincinnati.

Department of Materials Science and Engineering, University of

Cincinnati.
(1) Conceicao, M. M.; Fernandes, V. J.; Araujo, A. S.; Farias, M. F.;
Santos, I. M. G.; Souza, A. G. Energy Fuels 2007, 21, 15221527.
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87, 865869.
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10.1021/ef800388m CCC: $40.75 2009 American Chemical Society
Published on Web 12/05/2008
commercial diesel engines.
11
Furthermore, neat biodiesel is free
from sulfur and yields a decrease of 48% CO, 55% hydrocarbon,
and 53% particulate matter.
12
Wang et al. has performed a study
that compared exhaust emissions from nine heavy trucks fueled
by petroleum diesel and biodiesel blend without engine modi-
cation. They have indicated that the heavy duty trucks fueled
with biodiesel blend emitted lower particulate matter, CO, and
hydrocarbon than the same trucks fueled with No. 2 diesel.
13
In addition, it has been reported that the engine performance is
almost unaffected by the use of biodiesel or biodiesel/diesel
blend.
9
Different vegetable oils, such as corn oil, castor oil, sunower
oil, and soybean oil, have been used to produce biodiesel in
Brazil. Some thermal behaviors of the corn biodiesel, babassu
biodiesel, castor oil biodiesel, and the soybean biodiesel have
been investigated. For example, the evaporation temperature of
babassu biodiesel starts around 52 and 60 C in air and nitrogen,
respectively.
14
Castor biodiesel presents stability up to 150 C.
Its thermal prole may be altered by the decomposition process
due to the formation of intermediate compounds.
1
Dantas et al.
indicates that the activation energy and pre-exponential constant
of the corn biodiesel decomposition in synthetic air atmosphere
are 73.94-87.65 kJ mol
-1
and from 8.8 10
4
to 3.2 10
6
s
-1
, respectively.
15
Because of the possibility of increasing use
of biodiesel, it is important to quantify the kinetics parameters
of biodiesel pyrolysis.
1,14-16
However, the kinetics of the
biodiesel made from soybean, a main feedstock in the United
States, is not well understood.
In recent years, thermal analysis tools including thermo-
gravimetry (TG) and differential scanning calorimetry (DSC)
are becoming important in providing useful information in terms
of kinetic parameters, thermal stability, etc.
17
Continuous real-
time information regarding the weight loss and gaseous emission
can be obtained by coupling mass spectrometry to the thermo-
gravimetry (TG-MS).
18
It also gives the advantage of avoiding
the multistage sample preparation such as the digestion of
sample and can provide more detailed information on the
decomposition of biodiesel compounds by identifying fragments
ions from the original compounds with temperature changing.
19
In addition, characteristics of fresh biodiesel and the diesel
particulate matter (DPM) emitted from the nonroad engine were
also analyzed using Fourier transform infrared (FTIR) spec-
troscopy. Thus, the objective of this work is to obtain the
pyrolysis kinetics of biodiesel using TG analysis and understand
the fragmentation patterns of biodiesel, which can be used to
help interpret byproduct formation in biodiesel combustion
studies.
2. Experimental Methods
The sample of soybean biodiesel (BD-100, Nexsol biodiesel) used
in this study was purchased from Peter Cremer Co. The sample
was used as received for TG and was blended with diesel fuel for
use in the nonroad diesel engine. Ultimate analysis of the biodiesel
sample was determined by OKI Analytical, a commercial laboratory
in Cincinnati, OH.
Preliminary pyrolysis kinetics of biodiesel was determined using
TG (TA Instrument 5100/Dynamic TGA 2950, with the capability
of determining weight loss and temperature difference simulta-
neously). Approximately 4-6 mg of the biodiesel sample was
heated from room temperature to 400 C at heating rates of 3, 5, 8,
and 10 C min
-1
, respectively, in 100 mL min
-1
high purity
nitrogen. When the experiment was nished, the furnace power
was turned off but the carrier gas was kept owing until the furnace
was cooled down to room temperature. Aluminum oxide was used
as a reference in all TG experiments.
The TG-MS experiments were performed simultaneously using
a thermogravimeter (STA 409 CD, Netzsch Instruments, Inc.) and
a quadrupole mass spectrometer (QMA 400, Balzers Instruments,
Inc.). A Skimmer coupling system (Netzsch Instruments, Inc.) is
equipped to combine these two instruments together. About 2-8
mg biodiesel was decomposed with TG and the gas products were
introduced to the mass spectrometry for obtaining evolution curves.
The sample was heated up to 400 C at a heating rate of 5 C
min
-1
in 100 mL min
-1
of high purity nitrogen.
In addition, the functional groups of biodiesel and DPM were
investigated by using FTIR spectroscopy (Nicolet Nexus 870 FT-
IR, Thermo Electron Corp.). The DPM was collected from a
nonroad Generac diesel generator (1992, Model SD080, model No.
92A-03040-S), which operated at 0, 50, and 75 kW for idle, low-
load, and high-load modes, respectively. Detailed procedures of
DPM collection have been published elsewhere and are briey
described here.
20
DPM samples were collected by a high volume
sampler at a ow rate of approximately 300 L min
-1
with a
sampling time of approximately 30 min. Approximately 15 mg of
DPM was dissolved in dichloromethane (DCM) solution with sonic
vibration for 30 min. Then the solution was concentrated to about
1 mL from which three drops were placed onto a potassium bromide
(KBr) pellet for the FTIR analysis. In addition, a droplet of the
diesel or biodiesel sample was placed onto a KBr pellet and
measured by FTIR spectroscopy. For all spectra reported, a 64 scan
data accumulation was conducted at a resolution of 4 cm
-1
.
3. Results and Discussion
3.1. Ultimate Analysis. Ultimate analysis of the commercial
biodiesel sample is shown in Table 1. Note that the biodiesel
contains approximately 8% oxygen, which is not present in
petroleum diesel. In addition, there was no sulfur detected. The
high heating value of the biodiesel is 39 594 kJ kg
-1
(17 038
Btu lb
-1
).
(11) Kulkarni, M. G.; Dalai, A. K. Ind. Eng. Chem. Res. 2006, 45, 2901
2913.
(12) Haas, M. J.; Scott, K. M.; Alleman, T. L.; McCormick, R. L. Energy
Fuels 2001, 15, 12071212.
(13) Wang, W. G.; Lyons, D. W.; Clark, N. N.; Gautam, M.; Norton,
P. M. EnViron. Sci. Technol. 2000, 34, 933939.
(14) Santos, N. A.; Tavares, M. L. A.; Rosenhaim, R.; Silva, F. C.;
Fernandes, V. J.; Santos, I. M. G.; Souza, A. G. J. Therm. Anal. Calorim.
2007, 87, 649652.
(15) Dantas, M. B.; Conceicao, M. M.; Fernandes, V. J.; Santos, N. A.;
Rosenhaim, R.; Marques, A. L. B.; Santos, I. M. G.; Souza, A. G. J. Therm.
Anal. Calorim. 2007, 87, 835839.
(16) Candeia, R. A.; Freitas, J. C. O.; Souza, M. A. F.; Conceicao, M. M.;
Santos, I. M. G.; Soledade, L. E. B.; Souza, A. G. J. Therm. Anal. Calorim.
2007, 87, 653656.
(17) Chien, Y. C.; Shih, P. H.; Hsien, I. H. EnViron. Eng. Sci. 2005,
22, 601607.
(18) Otero, M.; D ez, C.; Calvo, L. F.; Garc a, A. I.; Moran, A. Biomass
Bioenerg. 2002, 22, 319329.
(19) E

hen, Z.; Novak, C.; Sztatisz, J.; Bene, O. J. Therm. Anal. Calorim.
2004, 78, 427440.
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Monit. 2005, 7, 983988.
Table 1. Typical Biodiesel Composition and Energy Content
element analysis (wt %)
carbon 79.01
hydrogen 12.90
oxygen 8.04 (balanced)
nitrogen 0.02
sulfur not detected
chlorine 0.03
high heating value 39 594 kJ kg
-1
(17 038 Btu lb
-1
)
Characterization of Biodiesel and DPM Energy & Fuels, Vol. 23, 2009 203
3.2. Infrared Analysis of Fuels. The FTIR spectra of B50
biodiesel (50% biodiesel and 50% diesel blend), diesel, and
B100 biodiesel (100% biodiesel) are shown in spectra a, b, and
c of Figure 1, respectively. The main components of diesel are
aliphatic hydrocarcons, whose chemical structures are similar
to long carbon sides chain of the main components of biodiesel.
The aliphatic hydrogen at 2928 and 2856 cm
-1
are indicated in
Figure 1. The observation of an absorption peak at 727 cm
-1
suggested the CH
2
out-of-plane bending. In addition, since the
biodiesel is mainly monoalkyl ester, the intense CdO stretching
band of methyl ester appears at 1743 cm
-1
. The medium C-O
bands at 1252, 1200, and 1175 cm
-1
are also expected in Figure
1a,c. The absorbance at 3010 cm
-1
indicated the HCdCH bond
association, while absorbance at 1376 cm
-1
indicated the -CH
3
bond.
3.3. Thermogravimetric Analysis. In order to have a better
understanding of the biodiesel decomposition, the thermal
degradation behavior of the biodiesel molecules was investi-
gated. Typical TG curves of the biodiesel decomposition
obtained in this study are shown in the top of Figure 2.
Experimentally, the thermal decomposition of biodiesel at
heating rates of 3, 5, 8, and 10 C min
-1
, respectively, are in a
single step that describe the evaporation and decomposition of
biodiesel. It is consistent with that of corn-oil biodiesel
(produced by the ethanol routes) pyrolysis. However, the
decomposition begins at 119-125 C and is completed at
212-237 C with no residue left that is lower than that of corn-
oil biodiesel pyrolysis.
15
The heating rate is a crucial factor
affecting the decomposition results. The higher heating rate may
decrease the distribution of the heat in the biodiesel molecules
and make the decomposition start at higher temperature. Thus,
the shape of the TG curves, the initial decomposition temper-
ature, and the temperature for a given weight loss are increasing
with the increasing heating rates (shown in Figure 2, top). In
the bottom of Figure 2, DTG curves of biodiesel decomposition
presented one transition in the peak temperature of 183-219
C. The peak temperature was also increased with the higher
heating rate.
3.4. Kinetics Calculation. The kinetic parameters for the
pyrolysis of biodiesel molecules were calculated on the basis
of weight loss data at different heating rates (from room
temperature to 400 C at 3, 5, 8, and 10 C min
-1
). The
calculation was based on the classical law of kinetics and the
overall rate equation is expressed in the Arrhenius equation
dX
dt
)A exp
(
-
E
a
RT
)
(1 -X)
n
X)
w
0
-w
w
0
-w
f
k )A exp
(
-
E
a
RT
)
where t ) time (min), A ) pre-exponential factor (min
-1
), E
a
) activation energy (kcal mol
-1
), T ) reaction temperature (K),
R ) gas constant, w ) mass of the biodiesel sample at time t,
w
0
)initial mass of the samples, w
f
)nal mass of the samples,
X ) conversion, n ) reaction order for the unreacted sample,
and k ) rate constant (min
-1
).
The kinetic analysis indicates that the activation energy and
pre-exponential constant of the biodiesel sample are 68.75 kJ
mol
-1
(16.2 kcal mol
-1
) and 2.6 10
7
min
-1
, respectively.
The activation energy is slightly lower than that of the methanol-
based biodiesel (71.51-88.66 kJ mol
-1
) and ethanol-based
biodiesel (80.71-92.84 kJ mol
-1
), as reported by an oxidative
TG study in Brazil.
8
The lower activation energy may be
associated with better combustion properties and also as a result
of a different feed stock. In addition, the reaction order of the
decomposition of biodiesel sample is 0.52. The decomposition
of biodiesel molecules can be satisfactorily described by the
following rate equation:
dX
dt
)2.6 10
7
exp
(
-
16.2
8.314 10
-3
T
)
(1 -X)
0.52
The conversion and reaction time are the important informa-
tion related to optimize the engine operation conditions. On the
other hand, the decomposition temperature is the key factor that
affects the exhaust gas distribution.
Figure 1. Typical FTIR spectra of the (a) B50, (b) diesel, and (c)
biodiesel sample.
Figure 2. TG curves (top) and DTG curves (bottom) of biodiesel
decomposition at heating rates of (a) 3 C min
-1
, (b) 5 C min
-1
, (c)
8 C min
-1
, and (d) 10 C min
-1
in nitrogen.
204 Energy & Fuels, Vol. 23, 2009 Chien et al.
3.5. Infrared Analysis of DPM. The chemical structure of
DPM emitted from the petroleum diesel and biodiesel used in
a nonroad diesel engine operated in different loads was also
investigated by FTIR spectroscopy (shown in Figure 3, top). In
a previous study, we indicated that the chemical composition
of DPM emitted from the same diesel engine may be a
combination of fuel evaporation and engine oil generated by
combustion and is mostly alkanes, PAHs, and carboxylic acids.
20
Therefore, the FTIR spectra of DPM bear some resemblance to
that of diesel fuel (shown in Figure 3, top and Figure 1), with
the exception of the absorbance at 1747 cm
-1
, which indicated
a carboxylic functional group found only in the DPM FTIR
spectra. This is consistent with our previous studies that the
engine oil contains carboxylic and benzoic acids not present in
diesel.
20
Furthermore, there was a small peak at 1577 cm
-1
that
is due to a functional group containing a nitrogen atom. Overall,
operation at different loads has not signicantly altered the DPM
composition, as the FTIR spectra of DPM at different loads
appear similar. However, the distributions of individual com-
position at each load required further study, as FTIR is unable
to provide this information.
Interestingly, the spectra of DPM emitted from the B50 used
in the nonroad engine also bore close resemblance to that of
the B50 fuel (shown in Figure 3 bottom). The spectra also
showed the same trend in the different operation loads. It is
noted that the absorbances at 1648 and 1558 cm
-1
were not
found in the spectra of B50. It may be due to the monosubsti-
tuted amides in the solid state, which may be due to the minor
nitrogen composition in the biodiesel fuel.
3.6. Thermogravimetry-Mass Spectrometry (TG-MS)
Analysis. The following m/z ratio (mass-to-charge ratio)
analyses were obtained from TG-MS to better understand the
decomposition mechanisms of biodiesel: 29, 31, 44, 74, 87, 105,
143, 263, 294, 296, and 298. The temperature series of selected
MS fragments are shown in Figure 4. It suggests that the
decomposition of biodiesel occurs at approximately 120 C,
which is consistent with the previous TG result. The m/z 294,
296, and 298 fragments are considered molecular weight ions
of biodiesel components C18:0, C18:1, and C18:2, respectively.
The intensities of these three molecular peaks are lower than
those of other fragments peaks, which is consistent with MS
spectra reference.
21
Between 140 and 250 C, m/z 74 has the highest ion current,
followed by m/z 87. The other peaks follow the same trend:
increasing under low temperature, showing a peak between 150
and 240 C, and slightly decreasing under high temperature.
The m/z ratios not plotted in Figure 4 include m/z 57 (C
4
H
9
+
),
which may be fragment of alkanes; m/z 41 (C
3
H
5
+
) and 55
(C
4
H
7
+
), which may be fragments of alkenes; and m/z 67
(C
5
H
7
+
), 95 (C
7
H
11
+
), and 109 (C
8
H
13
+
), which may be
fragments of dienes. Those fragments are from C-C bond
cleavage of the long carbon chain of methyl esters, depending
on the numbers and locations of the CdC double bonds of the
original esters.
22
Peaks at m/z 87 (C
2
H
4
COOCH
3
+
) and 143 (C
6
H
12
COOCH
3
+
)
are shorter chain methyl esters, which are also from C-C bond
cleavage of the carbon chain of methyl esters. These compounds
may be expected from the byproducts of biodiesel decomposi-
tion, as the shorter chain esters have been reported.
23
A well-known McLafferty rearrangement could occur during
the MS analysis due to a six-member ring structure of an
intermediate, which will form the ion with m/z 74.
24
The
mechanism of this rearrangement is shown in Figure 5. The R
1
group in the gure could be C
12
H
25
, C
14
H
29
, C
14
H
27
, or C
14
H
25
,
representing the major fractions of biodiesel composition, such
as C16:0, C18:0, C18:1, and C18:2.
(21) Mass Spectrometry Data Centre. Eight Peak Index of Mass Spectra;
The Royal Society of Chemistry. Nottingham, UK, 1983.
(22) Silverstein, R. M.; Webster, F. X.; Kiemle, D. Spectrometric
Identication of Organic Compounds; John Wiley & Sons: Hoboken, NJ,
2005.
(23) Archambault, D.; Billaud, F. J. Chim. Phys. Phys.-Chim. Biol. 1999,
96, 778796.
(24) McLafferty, F. W. Interpretation of Mass Spectra; University
Science Books: Mill Valley, CA, 1980.
Figure 3. FTIR spectra of DPM emitted from the (top) diesel and
(bottom) biodiesel used in the nonroad diesel engine in the load of (a)
50 kW, (b) 0 kW, and (c) 75 kW.
Figure 4. TG-MS plots of selected ions of biodiesel and TG curve.
Characterization of Biodiesel and DPM Energy & Fuels, Vol. 23, 2009 205
Peaks at m/z 31 (methoxy, CH
3
O
+
) and 263 (C
17
H
31
CO
+
)
may be fragments of C-O bond cleavage of C18:2 methyl ester
(shown in Figure 6 with other selected MS ions). The pyrolysis
of an oxygen-containing compound can result in formaldehyde
and similar fragments.
25
The m/z 29 fragment represents
formaldehyde ion and m/z )105 represents benzalaldehyde
ion.
26
This is an indication that aldehydes can be formed in
biodiesel decomposition and is consistent with observations from
engine tests.
10,27
In addition to hydrocarbon fragments, the temperature series
of CO
2
(m/z 44) is also shown in Figure 6 (under nitrogen
environment, however, we were not able to track the m/z ratio
of CO). CO
2
has been reported from pyrolysis of vegetable oil
(triglycerides), which have similar structures as methyl esters
(biodiesel).
28,29
CO
2
can be a unique byproduct in the pyrolysis
of oxygenated fuels. Therefore, the TG-MS information may
be helpful in understanding the decomposition mechanisms of
biodiesel compounds and the potential byproducts formed.
4. Conclusions
The chemical functional groups of biodiesel and associated
particulate emissions from a nonroad diesel engine have been
determined by FTIR spectroscopy. The FTIR spectra of biodiesel
showed an CdO stretching band of methyl ester at 1743 cm
-1
and C-O bands at 1252, 1200, and 1175 cm
-1
, respectively.
The FTIR spectra of its particulate emissions were largely
similar to that of the fuel used. However, compared with diesel
fuel, the FTIR spectra of the particulate emissions show the
OdC-O functional group at 1747 cm
-1
that may be due to
the n-alkanoic acids. The absorbances at 1648 and 1558 cm
-1
were not found in the spectra of B50 that may be due to the
monosubstituted amides formed in solid state in the thermal
decomposition process. The thermal behavior of biodiesel
decomposition was also investigated in this paper with TG and
TG-MS. The activation energy, pre-exponential constant, and
reaction order of the pyrolysis of biodiesel sample are 67.75 kJ
mol
-1
(16.2 kcal mol
-1
), 2.6 10
7
min
-1
, and 0.52, respec-
tively. The global rate equation for pyrolysis of the biodiesel
can be expressed as dX/dt ) 2.6 10
7
exp(-16.2/8.314
10
-3
T)(1 - X)
0.52
(X denotes the reaction conversion). The
temperature series of 11 m/z fragments have been analyzed by
means of TG-MS. On the basis of the analysis above, it is
expected that smaller esters, CO
2
, and aldehydes may be found
as byproducts of biodiesel pyrolysis. The methoxy group may
be fragmented from the methyl ester of biodiesel components,
and many hydrocarbon fragments may be expected from the
carbon chain of biodiesel components. TG-MS can offer more
information on the expected byproducts from biodiesel decom-
position in a quicker and simpler way than the actual pyrolytic
experiments and may be helpful in understanding the reaction
mechanisms of byproduct formation.
Acknowledgment. The nancial support of the Taiwan National
Science Council is gratefully acknowledged. We are also grateful
for the help provided by Mr. Michael Starr, University of Cincinnati,
with the FTIR analysis and Prof. Soon Cheng and Mr. Chung-
Shen Kao, Taiwan University, with the TG-MS analysis.
EF800388M
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Figure 5. Mechanism of McLafferty rearrangement.
Figure 6. Selected TG-MS ions and TG curve.
206 Energy & Fuels, Vol. 23, 2009 Chien et al.