Journal of Analytical and Applied Pyrolysis 91 (2011) 154–158

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Journal of Analytical and Applied Pyrolysis

journal homepage: www.elsevier.com/locate/jaap

Pyrolysis of vegetable oil soaps—Palm, olive, rapeseed and castor oils

Hanna Lappi ∗ , Raimo Alén
Laboratory of Applied Chemistry, Department of Chemistry, University of Jyväskylä, PO Box 35, FI-40014 University of Jyväskylä, Finland

a r t i c l e i n f o a b s t r a c t

Article history: Saponified, palm, olive, rapeseed and castor oils were pyrolysed (at 750 ◦ C for 20 s) by pyrolysis gas
Received 14 September 2010 chromatography with mass selective and flame ionisation detection (Py-GC/MSD and FID) to clarify their
Accepted 5 February 2011 thermochemical behaviours. The liquefiable compounds recovered from palm, olive and rapeseed oils
Available online 12 February 2011
mainly contained linear alkenes (up to C19 ) and alkanes (up to C17 ), both similar to those found in gasoline
(C4 –C10 ) and diesel fuel (C11 –C22 ) boiling range fractions of petroleum, whereas in the case of castor oil
Keywords:
a significant amount of undesired oxygen-containing products (e.g., ketones and phenols) were formed.
Pyrolysis
The obtained data on reaction mechanisms can also be utilised in applications where various biofuels are
Palm oil
Olive oil
produced, for example, from the extractive-derived by-product (tall oil) of kraft pulping.
Rapeseed oil © 2011 Elsevier B.V. All rights reserved.
Castor oil
Vegetable oil soap
Biofuel

1. Introduction hydroxy-9-octadecenoic acid) (about 90%) with minor amounts of

Biofuels which can be used as fuel or fuel additives have
recently become more attractive because of their environmental
benefits and the uncertainties concerning petroleum availabil-
ity [1–5]. Among the different possible renewable raw materials,
extractive-based glycerides (i.e., esters of fatty acids with glycerol)
in plants present one source for producing hydrocarbon-rich prod-
ucts resembling petroleum [6,7].
Vegetable oils are primarily composed of triglycerides (about
90%) with lesser amounts of mono- and diglycerides, as well as
free fatty acids [8–10]. In addition, some other compounds such
as phospholipids, sterols and their esters, tocols, hydrocarbons
and fat-soluble vitamins are present. The most common fatty acid
compounds comprise saturated palmitic (C16:0 ) and stearic (C18:0 )
acids together with unsaturated oleic (C18:1 ) and linoleic (C18:2 )
acids [8,11]. Many vegetable oils also contain, for example, lau-
ric (C12:0 ), myristic (C14:0 ) and erucic (C22:1 ) acids in significant
amounts. For example, the content of unsaturated oleic acid (C18:1 )
is typically 55–85% in olive oil, about 60% in rapeseed oil and
about 40% in palm oil [4–6]. On the other hand, saturated palmitic
acid (C16 ) is also a prominent acid component in palm oil (about
45%), whereas clearly lower amounts (<5%) of this acid can be
found in rapeseed and olive oils (8–20%). In contrast, castor oil
is practically comprised of monounsaturated ricinoleic acid (12-
∗ Corresponding author at: Department of Chemistry, University of Jyväskylä, Sur-
vontie 9, FI-40014 Jyväskylä, Finland. Tel.: +358 14 2602577; fax: +358 14 2602581.
E-mail address: hanna.e.lappi@iyu.fi (H. Lappi).
oleic and palmitic acids [12–14]. Due to the hydroxyl group of this
acid, its pyrolytic behaviour may differ characteristically from other
vegetable oils, making castor oil one of the most interesting raw
materials.
Pyrolysis reactions offer a potential way of producing fuels and
chemicals from vegetable oils [15]. This option is especially promis-
ing in areas where the hydroprocessing industry is well established
because the technology is rather similar to that of conventional
petroleum refining. Pyrolysis, which is the thermal decomposition
of materials in the absence of oxygen, is the simplest and oldest
method of processing one fuel to produce a better one [11].
The pyrolysis of triglycerides has been investigated for over
more than 100 years, especially in areas of the world that lack
deposits of petroleum [16]. Earlier studies were also conducted on
the thermal cracking of soaps of various oils. In 1974 Chang and
Wan [17] reported a large-scale thermal cracking of tung oil calcium
soap which yielded diesel-like fuel and small amounts of gasoline
and kerosene. Fortes and Baugh [18] made a product with a similar
composition to diesel fuel, besides the presence of some ketones,
when pyrolysing the calcium soap of Macauba fruit vegetable oil.
In general, free radical pathways dominate the mechanisms
for various pyrolysis reactions of organic materials [19,20]. Due
to the complexity of possible radical reactions taking place, a
wide range of products is also to be expected. According to
Chang and Wan [17], Alencar et al. [21] and Idem et al. [22],
the elimination of heavily-oxygenated hydrocarbons such as car-
boxylic acids, ketones, aldehydes and esters is a dominant step
in the thermochemical behaviour of triglycerides. After these ini-
tial decomposition reactions, possible reaction routes include (i)

0165-2370/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jaap.2011.02.003
 H. Lappi, R. Alén / Journal of Analytical and Applied Pyrolysis 91 (2011) 154–158
the decarboxylation and decarbonylation of saturated oxygenated
hydrocarbons followed by the C–C bond cleavage of the resulting
hydrocarbon radicals or (ii) the C–C bond cleavage of unsaturated
oxygenated hydrocarbons followed by decarboxylation and decar-
bonylation of the resulting short-chain molecules. Radicals formed
in these reactions then undergo various other reactions such as dis-
proportionation, ␤-scission, isomerisation, hydrogen abstraction
and aromatisation. Heavy hydrocarbons are produced by polymeri-
sation and polycondensation reactions [23].
This investigation, dealing with the pyrolysis of vegetable oil
soaps, continues our earlier studies [24] on the thermochemical
behaviour of fatty acid sodium salts during pyrolysis. The selected
raw materials were palm oil from the fruits of the palm tree (Elaeis
guineensis), castor oil from the castor beans of the castor plant
(Ricinus communis), olive oil from the olive tree (Olea europaea)
and rapeseed oil from the rapeseed plant (Brassica napus). Based
on this approach, the main aims of the present study were to
clarify the pyrolysis chemistry of fatty acid soaps in natural matri-
ces and to verify earlier findings obtained from model substances.
Furthermore, fatty acid sodium salts form a significant fraction
(20–40% of the total extractives) of the tall oil soap recovered
from kraft pulping [25]. For this reason, it can be assumed that
a better understanding of pyrolytic fatty acid reactions will also
be of benefit to the development of the tall oil-based production
of biofuels. This topic will be discussed in detail in forthcoming
papers.
2. Materials and methods
2.1. Chemicals and vegetable oils
The compounds used as internal standards in the gas chro-
matographic (GC) analysis of the extractives were heneicosanoic
acid (99%, Sigma), betulinol (≥98%, Sigma), cholesteryl heptade-
canoate (>97%, TCI) and 1,3-dipalmitoyl-2-oleyl-glycerol (∼99%,
Sigma). The external standard used in the quantitative pyroly-
sis experiments was adamantane (>99%, Fluka) in benzene (>99%,
Fluka). The solvents used in the sample preparation of extrac-
tives were analytical grade acetone (BDH), methyl tert-butyl ether
(MTBE) (Lab-Scan), and analytical grade pyridine (BDH). The
silylation reagents bis(trimethylsilyl)trifluoroacetamide (BSTFA)
and trimethylchlorosilane (TMCS) were from Regis Technolo-
gies.
The chemicals used in the determination of saponification val-
ues were potassium hydroxide (≥85%, Riedel de Haën), sodium
hydroxide (≥99%, Fluka), hydrochloric acid (≥37%, Riedel de Haën),
denatured alcohol BA (99.5 (wt.%), Altia) and phenolphthalein
(Merck). Water was obtained from a Millipore Milli-Q water sys-
tem.
The vegetable oils selected for this research were refined,
bleached and deodourised palm oil (RDB), water-degummed crude
rapeseed oil (Raisio Chemicals), olive oil (Sigma–Aldrich) and castor
oil (Sigma–Aldrich).
2.2. Analysis of vegetable oils
For the analysis of the vegetable oils (lipophilic fractions and
individual compounds as such and after the alkaline hydrolysis), the
samples were diluted in acetone (0.5 mg/ml) and derivatised for the
GC analysis with a mixture of BSTFA and TMCS (99:1, respectively).
Derivatisation of samples was done by keeping them at 70 ◦ C for
1 h. Two replicate analysis were done for all the oils.
Quantitative analysis of the lipophilic extractives fraction
was carried out on a Hewlett Packard HP 5890 Series II
plus System equipped with an HP 7673 injector and a Pro-
155
grammable Cool On-Column Inlet. A short HP-1SIMDIS capillary
column (7.5 m × 0.53 mm, film thickness 0.15 ␮m) and the method
reported by Örså and Holmbom [26] were used. The injector tem-
perature was 90 ◦ C; after injection the temperature was raised to
320 ◦ C at a rate of 200 ◦ C/min. The detector temperature was 290 ◦ C.
The GC oven temperature programme was 1 min at 90 ◦ C, followed
by an increase of 12 ◦ C/min to 320 ◦ C and 10 min at 320 ◦ C.
Quantitative analysis of the individual compounds was car-
ried out on an Agilent 6850 Series GC System with an Equity-5
(30 m × 0.32 mm, film thickness 0.25 ␮m) column. The injector
temperature was 290 ◦ C and the detector temperature was 300 ◦ C.
The GC oven temperature programme was 1.5 min at 100 ◦ C, fol-
lowed by an increase of 6 ◦ C/min to 180 ◦ C, 10 min at 180 ◦ C, an
increase of 4 ◦ C/min to 290 ◦ C and 20 min at 290 ◦ C. Qualitative anal-
ysis of the individual components was carried out with an Agilent
6890 Series GC System equipped with a 7683 injector and an Agi-
lent 5973 mass selective detector (MSD). The capillary column used
was an HP-5MS (30 m × 0.32 mm, film thickness 0.25 ␮m) and the
GC oven temperature programme was the same as that used in the
quantitative analyses.
Saponification values for the vegetable oils were determined
according to the procedure described in TAPPI standard T621 cm-
01. Two replicate analysis were performed for all the oils.
2.3. Pyrolysis experiments
Vegetable oils were saponified with sodium hydroxide (the
amount was 1.5 times the equivalent amount) prior to their
pyrolysis. Soap samples (700–900 ␮g) were pyrolysed in quartz
tubes at a heating rate of 1000 ◦ C/s using a CDS Pyroprobe 1000
heated-filament pyrolyser coupled to an HP 5890 II gas chromato-
graph (Py-GC). The column was a ZB-5HT capillary GC column
(30 m × 0.25 mm, film thickness 0.25 ␮m). Detection was carried
out either with an HP 5972 mass selective detector (MSD, qualita-
tive analyses) or alternatively with an HP 5890 GC/FID (quantitative
analyses). The Py-GC interface temperature was 250 ◦ C and the
injector temperature 280 ◦ C. Pyrolysis parameters were chosen
according to the results of the previous research with the model
fatty acid salts [24]. In each experiment, the pyrolysis temperature
was 750 ◦ C and the temperature was kept constant for 20 s. The GC
oven temperature was 5 min at 35 ◦ C, an increase of 5 ◦ C/min to
125 ◦ C, 3 ◦ C/min to 285 ◦ C, 5 ◦ C/min to 360 ◦ C, and finally 5 min at
360 ◦ C. Helium was used as the carrier gas and as an inert atmo-
sphere in the pyrolysis interface. The carrier gas flow rate was kept
at 1 ml/min during the gas chromatographic analysis.
Due to the multiplicity of pyrolysis products, the identification
of all constituents in pyrolysates only by the retention time with
respect to some internal standards appeared to be impossible. For
this reason, a proper interpretation of the mass spectra of the pyrol-
ysis products (based on a commercial database, Wiley 7n, together
with recognition of fragmentation patterns) was used. Only quality
matches of above 85% were included.
The calibration curve for quantitative determination of the
pyrolysis products was determinated by the pyrolysis of adaman-
tane dissolved in benzene. The calibration was performed using a
similar method to Bocchini et al. [27] when adding the internal stan-
dard for pyrolysis. Solutions of adamantane in the 40–110 ␮g/ml
range were carefully added to the quartz capillary tube which
was immediately inserted into the Py-GC interface. After an equi-
libration period of 30 s, the pyrolysis was performed. Six different
concentrations were pyrolysed using the same parameters as for
the samples. Two replicates were made for each concentration. The
correlation coefficient (R2 ) of the calibration curve obtained was
0.990. Due to the multitude of peaks in the vegetable oil pyrolysates,
adamantane was only used as an external standard.
156 H. Lappi, R. Alén / Journal of Analytical and Applied Pyrolysis 91 (2011) 154–158

Table 1
Relative compositions of the lipophilic extractive fractions in the vegetable oils studied, % of total, and saponification values.

Palm oil Olive oil Rapeseed oil Castor oil

Fatty acids 1.1 1.3 1.8 0.5

Sitosterol – 0.2 0.3 0.2
Steryl esters 8.8 3.0 3.2 2.3
Diglycerides 7.1 6.3 2.0 2.2
Triglycerides 83.0 89.2 92.7 94.8
Saponification values 196 184 186 173

Table 2
Relative compositions of the fatty acid fractions (free and esterified) in the vegetable oils studied, % of total.

Fatty acid Palm oila Olive oil Rapeseed oil Castor oil Formula

Palmitelaidic acid – 0.7 0.2 – HO2 C–(CH2 )7 –CH CH–(CH2 )5 –CH3

Palmitic acid 47.0 11.9 4.8 1.1 HO2 C–(CH2 )14 –CH3
Margaric acid 0.1 0.1 – – HO2 C–(CH2 )15 –CH3
Linoleic acid 0.2 0.3 0.6 3.5 HO2 C–(CH2 )7 –CH CH–CH2 –CH CH–(CH2 )4 CH3
Oleic acid 42.9 81.3 87.6 3.5 HO2 C–(CH2 )7 –CH CH–(CH2 )7 –CH3
Stearic acid 4.5 2.9 1.8 1.2 HO2 C–(CH2 )16 –CH3
Ricinoleic acid – – – 86.2 HO2 C–(CH2 )7 –CH CH–CH2 –CH(OH)–(CH2 )5 –CH3
Gondoic acid – 0.4 1.6 – HO2 C–(CH2 )9 –CH CH–(CH2 )7 –CH3
Arachidic acid 0.4 0.4 0.6 – HO2 C–(CH2 )18 –CH3
Miscellaneous 3.0 2.0 2.8 4.5
a
In addition, palm oil contained 0.3% of azelaic acid (HO2 C–(CH2 )7 –CO2 H), 0.4% lauric acid (HO2 C–(CH2 )10 –CH3 ) and 1.2% myristic acid (HO2 C–(CH2 )12 –CH3 ).

3. Results and discussion

3.1. Raw materials

As expected, the vegetable oil analysis revealed that, with

respect to the main fractions, olive and rapeseed oils had a rather
similar chemical composition (Table 1). Palm oil had slightly higher
amount of diglycerides and slightly lower amount of triglycerides
than other oils, and remarkably higher amount of steryl esters.
Castor oil had the highest amount of triglycerides of the selected
oils.
Selected vegetable oils had some typical differences between
the chemical composition of the total fatty acid fractions (free acids
and esters with glycerol) (Table 2). In olive and rapeseed oils, oleic
acid was clearly the most abundant component (over 80%). The
chemical composition of palm oil was characterised by having over
50% of its total fatty acids fraction accounted for by saturated fatty
acids (i.e., palmitinic, stearic and behenic acids). Another notable
property of its chemical composition was a high amount of oleic Fig. 1. The main products formed in the pyrolysis experiments (750 ◦ C and 20 s) with
acid (∼43%). In contrast, castor oil had a distinctive chemical com- saponified palm oil. Numbers indicate the amount of carbon atoms in a molecule.

position with a remarkable amount (∼86% of total fatty acids) of

ricinoleic acid, which has a hydroxyl group attached to its carbon
skeleton.
The saponification values for the oils are presented in Table 1.

3.2. Pyrolysis of the vegetable oil soaps

The pyrolysate of palm oil soap was mainly characterised by lin-

ear monoalkenes (up to C19 ) and alkanes (up to C17 ) (Figs. 1 and 2).
Besides alk-1-enes, other alkenes with double bonds at different
positions appeared as well. The volatile products marked as “C3 –C6
compounds” primarily corresponded to both alkenes and alkanes,
but other highly volatile compounds were also present in minor
amounts. However, due to the low resolution of these numerous
low-molecular-mass compounds, their proper identification was
not possible in all cases.
The main pyrolysis product, 1-pentadecene, could be considered
as being formed from the main sodium salt fatty acid component
(palmitic acid, C16 ) via the homolysis of the weakest C–C bond Fig. 2. Relative amounts of the products formed in the pyrolysis of saponified palm,
adjacent to the carboxylic group [28]. Other compounds found in castor, olive and rapeseed oils. The number of replicate pyrolysis experiments was
the pyrolysate in significant amounts were monoalkenes with 11 12.
 H. Lappi, R. Alén / Journal of Analytical and Applied Pyrolysis 91 (2011) 154–158 157

Fig. 4. The main products formed in the pyrolysis experiments (750 ◦ C and 20 s)
Fig. 3. The main products formed in the pyrolysis experiments (750 ◦ C and 20 s) with
with saponified rapeseed oil. Numbers indicate the amount of carbon atoms in a
saponified olive oil. Numbers indicate the amount of carbon atoms in a molecule.
molecule.

carbon atoms and alkadienes having 11, 12 and 17 carbon atoms.

These compounds represented typical degradation products of the
sodium salt of oleic acid (C18:1 ). In general, the presence of the dou-
ble bond in a fatty acid alkyl chain favours homolytic C–C cleavages
at these positions, rather than the homolytic C–C cleavages adjacent
to the carboxylic group [28], due to the lower dissociation energies
of allyl bonds. In addition, the synthesis of aliphatic ketones from
fatty acid metal salts is a well-known reaction [29–31]. In our case,
the formation of a symmetrical ketone (16-hentriacontanone) and
its further degradation to 2-heptadecanone (a methyl ketone) was
also detected. Although no sterols were observed as such (present
as sterol glucosides [32]) in the initial raw material, a GC peak from
stigmast-4-en-3-one was detected in the pyrolysate (Fig. 1).
In addition to some aromatics, the pyrolysate of olive oil soap
was mainly characterised by linear monoalkenes (up to C19 ), alka-
nes (up to C16 ), and alkadienes (up to C17 ) (Figs. 2 and 3). Besides
alk-1-enes, other alkenes and alkadienes with double bonds at dif-
ferent positions also appeared. In general, the results supported the
previously reported findings [24,28].
Fig. 5. The main products formed in the pyrolysis experiments (750 ◦ C and 20 s) with
The main volatile products detected in the pyrolysate were an saponified castor oil. Numbers indicate the amount of carbon atoms in a molecule.
monoalkene with 11 carbon atoms and alkadienes with 11, 12
or 17 carbon atoms, typical degradation products derived from
the main fatty acid component, oleic acid. In contrast, the main oil soap, the abundant pyrolysis products were octan-2-one and
pyrolysis product of palmitic acid (without a double bond) was heptanal. The reaction mechanism first comprises the formation of
1-pentadecene, formed by the homolysis of the weak C–C bond an unsaturated keto acid (NaO2 C(CH2 )7 CH CHCH2 CO(CH2 )5 CH3 )
adjacent to the carboxylic group. which then further degrades via different reaction routes to vari-
As expected, the relative composition of the volatile pyroly- ous products. For example, octan-2-one is believed to result from a
sis products in the rapeseed oil soap was rather similar to that six-membered ring rearrangement and the formation of heptanal
obtained from the olive oil soap (Figs. 2 and 4). In general, the can be rationalised by a ␣-cleavage adjacent to the keto group.
relative amounts of alkadienes, monoalkenes and alkanes were With respect to the pyrolytic behaviour of various vegetable oils,
somewhat lower than those formed during the pyrolysis of olive oil the key parameters are differences in the lengths of the carbon
soap, although, due to slightly higher amounts of the initial unsatu- chain and the number of C C bonds in their fatty acid compo-
rated fatty acids, higher amounts of aromatics were obtained. Some nents. When comparing our earlier results of model substances
characteristic sterols which originated from the rapeseed oil were (the sodium salt of C18 , C18:1 and C18:2 [24]) and the selected veg-
also detected, whereas in the olive oil pyrolysate the peak of 10- etable oils obtained in this study, the following general conclusion
demethylsqualene indicated the presence of squalene at a high could be made. As expected, due to the ricinoleic acid, the pyrolytic
level (150–170 mg/100 ml) in the original oil. behaviour of the castor oil soap was clearly different from that of
The pyrolysate of the castor oil soap was rich in ketones and the other feedstocks (Fig. 5). The degree of saturation of other oils
other oxygen-containing compounds (i.e., aldehydes and alcohols), did effect the characteristic reactions, thus having an impact on
whereas the amount of monoalkenes and alkanes in this case was the formation of various intermediates and final products. For this
notably low (Figs. 2 and 5). The thermochemical behaviour of cas- reason, somewhat lower amounts of aromatics (and cycloalkenes)
tor oil was mainly due to ricinoleic acid having one C C bond were detected in the pyrolysate from the vegetable oil soaps with
and one –CO2 H and –OH group [33]. Hartgers et al. [28] pyrol- a lower amount of unsaturation (i.e., containing a lower amount of
ysed the sodium salt of ricinoleic acid and, as in the case of castor C18:1 ), whereas an enhanced amount of dienes was determined for
158 H. Lappi, R. Alén / Journal of Analytical and Applied Pyrolysis 91 (2011) 154–158
the pyrolysates of olive and rapeseed oil soaps (i.e., containing the
highest amount of C18:1 ). On the other hand, a significant relative
contents of alkanes and alkenes were formed during the pyroly-
sis of palm oil and olive oil soap due to their saturated nature (i.e.,
containing mainly monounsaturated C18:1 and saturated C16 ).
The total amount of pyrolysis products recovered from
laboratory-scale pyrolysers is normally low. In our experiments,
quantitative analyses indicated that the detectable amounts of
volatile products were (expressed as % of the initial dry solids) 1.4%
from palm oil, 1.52% from olive oil, 1.60% from rapeseed oil and
1.50% from castor oil. However, it was concluded that the portion
of aromatic compounds (aromatics and phenols in Table 1) derived
from vegetable oil-type materials would not be very high. Accord-
ing to Sjögren et al. [34], diesel fuels typically contain between
2.7 (vol%) and 22.5 (vol%) (f.i.a.) aromatics, whereas the allowed
amount reported by the ASTM D 975 requirements is 35 (vol%)
[15]. Furthermore, it was evident that a more technical pyrolysis
apparatus is needed for the proper evaluation of product quality
and yield, as well as the suitability of these products for diesel oil.
4. Conclusions
Pyrolysis of the vegetable oil soaps obtained from the alkaline
(aqueous NaOH) hydrolysis of palm, olive and rapeseed oils mainly
resulted in volatile products (mainly alkanes and monoalkenes)
similar to those found in the gasoline and diesel fuel boiling
range fractions of petroleum, although some undesired oxygen-
containing products (e.g., ketones) were formed as well. However,
due to its saturation (i.e., it contains a significant amount of satu-
rated palmitic acid, C16 ), the pyrolysate of palm oil soap had a lower
relative content of aromatics and alkadienes. The differences in
the chemical compositions of the pyrolysates obtained from these
raw materials could be explained by variations in the raw mate-
rials. Typical fragmentation patterns of the main product group
were detected in both pyrolysates and these results were in accor-
dance with previous data on the pyrolysis of sodium salt model
compounds thus indicating only a slight matrix effect.
An exception to these vegetable oil soaps is castor oil soap, which
contains a high amount of ricinoleic acid. Due to this hydroxy fatty
acid component, the pyrolysate of castor oil soap was mainly com-
posed of various oxygen-containing long-chained products, like
ketones and aldehydes, rather than different hydrocarbons.
Acknowledgements
Financial support from the Finnish Ministry of Education, within
the framework of the International Doctoral Programme in Pulp
and Paper Science and Technology (PaPSaT), is greatfully acknowl-
edged. Special thanks are due to Ms. Merja Rintala, for her skilful
assistance with the analytical work.
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