Accepted Manuscript

Title: Pyrolysis of vegetable oil soapsPalm, olive, rapeseed

and castor oils
Authors: Hanna Lappi, Raimo Al en
PII: S0165-2370(11)00032-5
DOI: doi:10.1016/j.jaap.2011.02.003
Reference: JAAP 2535
To appear in: J. Anal. Appl. Pyrolysis
Received date: 14-9-2010
Revised date: 1-2-2011
Accepted date: 5-2-2011
Please cite this article as: H. Lappi, R. Al en, Pyrolysis of vegetable oil soapsPalm,
olive, rapeseed and castor oils, Journal of Analytical and Applied Pyrolysis (2010),
doi:10.1016/j.jaap.2011.02.003
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Pyrolysis of vegetable oil soaps Palm, olive, rapeseed and castor oils

Hanna Lappi, Raimo Aln

Laboratory of Applied Chemistry, Department of Chemistry, University of Jyvskyl, PO
BOX 35, FI-40014 University of Jyvskyl, Finland

Abstract

Saponified, palm, olive, rapeseed and castor oils were pyrolysed (at 750 C for 20 s) by
pyrolysis gas chromatography with mass selective and flame ionisation detection (Py-
GC/MSD and FID) to clarify their thermochemical behaviours. The liquefiable
compounds recovered from palm, olive and rapeseed oils mainly contained linear alkenes
(up to C
19
) and alkanes (up to C
17
), both similar to those found in gasoline (C
4
-C
10
) and
diesel fuel (C
11
-C
22
) boiling range fractions of petroleum, whereas in the case of castor oil
a significant amount of undesired oxygen-containing products (e.g., ketones and phenols)
were formed. The obtained data on reaction mechanisms can also be utilised in
applications where various biofuels are produced, for example, from the extractive-
derived by-product (tall oil) of kraft pulping.

Keywords: Pyrolysis, palm oil, olive oil, rapeseed oil, castor oil, vegetable oil soap,
biofuel


1. Introduction

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
availability [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 products 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 (C
16:0
) and stearic (C
18:0
) acids together with unsaturated oleic (C
18:1
) and linoleic
(C
18:2
) acids [8,11]. Many vegetable oils also contain, for example, lauric (C
12:0
), myristic
(C
14:0
) and erucic (C
22:1
) acids in significant amounts. For example, the content of
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unsaturated oleic acid (C
18:1
) 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 (C
16
) 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-hydroxy-9-octadecenoic
acid) (about 90%) with minor amounts of 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 promising 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 carboxylic acids, ketones, aldehydes and esters is a dominant step
in the thermochemical behaviour of triglycerides. After these initial decomposition
reactions, possible reaction routes include i) the decarboxylation and decarbonylation of
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saturated oxygenated hydrocarbons followed by the CC bond cleavage of the resulting
hydrocarbon radicals or ii) the CC bond cleavage of unsaturated oxygenated
hydrocarbons followed by decarboxylation and decarbonylation of the resulting short-
chain molecules. Radicals formed in these reactions then undergo various other reactions
such as disproportionation, -scission, isomerisation, hydrogen abstraction and
aromatisation. Heavy hydrocarbons are produced by polymerisation 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 matrices 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 chromatographic (GC) analysis of
the extractives were heneicosanoic acid (99%, Sigma), betulinol (98%, Sigma),
cholesteryl heptadecanoate (>97%, TCI) and 1,3-dipalmitoyl-2-oleyl-glycerol (~99%,
Sigma). The external standard used in the quantitative pyrolysis experiments was
adamantane (>99%, Fluka) in benzene (>99%, Fluka). The solvents used in the sample
preparation of extractives were analytical grade acetone (BDH), methyl tert-butyl ether
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(MTBE) (Lab-Scan), and analytical grade pyridine (BDH). The silylation reagents
bis(trimethylsilyl)trifluoroacetamide (BSTFA) and trimethylchlorosilane (TMCS) were
from Regis Technologies.

The chemicals used in the determination of saponification values were potassium
hydroxide (85%, Riedel de Han), sodium hydroxide (99%, Fluka), hydrochloric acid
(37%, Riedel de Han), denatured alcohol BA (99.5 w-%, Altia) and phenolphthalein
(Merck). Water was obtained from a Millipore Milli-Q water system.

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 one hour.
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
Programmable 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 rs and Holmbom [26]
were used. The injector temperature 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.

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Quantitative analysis of the individual compounds was carried 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, followed 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 analysis of the individual components was carried out with an Agilent 6890
Series GC System equipped with a 7683 injector and an Agilent 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
o
C/s using a CDS Pyroprobe 1000 heated-filament
pyrolyser coupled to an HP 5890 II gas chromatograph (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, qualitative analyses) or
alternatively with an HP 5890 GC/FID (quantitative analyses). The Py-GC interface
temperature was 250
o
C and the injector temperature 280
o
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
o
C and the temperature was
kept constant for 20 s. The GC oven temperature was 5 min at 35
o
C, an increase of 5
o
C/min to 125
o
C, 3
o
C/min to 285
o
C, 5
o
C/min to 360
o
C, and finally 5 min at 360
o
C.
Helium was used as the carrier gas and as an inert atmosphere in the pyrolysis interface.
The carrier gas flow rate was kept at 1 ml/min during the gas chromatographic analysis.
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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 pyrolysis
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 adamantane dissolved in benzene. The calibration was
performed using a similar method to Bocchini et al. [27] when adding the internal
standard 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 equilibration 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 (R
2
) 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.

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
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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
acid (~43 %). In contrast, castor oil had a distinctive chemical composition 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 linear monoalkenes (up to
C
19
) and alkanes (up to C
17
) (Figs. 1 and 2). Besides alk-1-enes, other alkenes with
double bonds at different positions appeared as well. The volatile products marked as
C
3
-C
6
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, C
16
) via the homolysis of the
weakest C-C bond adjacent to the carboxylic group [28]. Other compounds found in the
pyrolysate in significant amounts were monoalkenes with 11 carbon atoms and
alkadienes having 11, 12 and 17 carbon atoms. These compounds represented typical
degradation products of the sodium salt of oleic acid (C
18:1
). In general, the presence of
the double 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
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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 C
19
), alkanes (up to C
16
), and alkadienes (up to C
17
) (Fig. 2
and 3). Besides alk-1-enes, other alkenes and alkadienes with double bonds at different
positions also appeared. In general, the results supported the previously reported findings
[24,28].

The main volatile products detected in the pyrolysate were an 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 pyrolysis
product of palmitic acid (without a double bond) was 1-pentadecene, formed by the
homolysis of the weak CC bond adjacent to the carboxylic group.

As expected, the relative composition of the volatile pyrolysis products in the rapeseed
oil soap was rather similar to that obtained from the olive oil soap (Figs. 2 and 4). In
general, the relative amounts of alkadienes, monoalkenes and alkanes were somewhat
lower than those formed during the pyrolysis of olive oil soap, although, due to slightly
higher amounts of the initial unsaturated fatty acids, higher amounts of aromatics were
obtained. Some characteristic sterols which originated from the rapeseed oil were also
detected, whereas in the olive oil pyrolysate the peak of 10-demethylsqualene indicated
the presence of squalene at a high level (150-170 mg/100 ml) in the original oil.

The pyrolysate of the castor oil soap was rich in ketones and other oxygen-containing
compounds (i.e., aldehydes and alcohols), whereas the amount of monoalkenes and
alkanes in this case was notably low (Figs. 2 and 5). The thermochemical behaviour of
castor oil was mainly due to ricinoleic acid having one C=C bond and one -CO
2
H and
-OH group [33]. Hartgers et al. [28] pyrolysed the sodium salt of ricinoleic acid and, as in
the case of castor oil soap, the abundant pyrolysis products were octan-2-one and
heptanal. The reaction mechanism first comprises the formation of an unsaturated keto
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acid (NaO
2
C(CH
2
)
7
CH=CHCH
2
CO(CH
2
)
5
CH
3
) which then further degrades via different
reaction routes to various products. For example, octan-2-one is believed to result from a
six-membered ring rearrangement and the formation of heptanal can be rationalised by a
-cleavage adjacent to the keto group.

With respect to the pyrolytic behaviour of various vegetable oils, the key parameters are
differences in the lengths of the carbon chain and the number of C=C bonds in their fatty
acid components. When comparing our earlier results of model substances (the sodium
salt of C
18
, C
18:1
and C
18:2
[24]) and the selected vegetable oils obtained in this study, the
following general conclusion could be made. As expected, due to the ricinoleic acid, the
pyrolytic behaviour of the castor oil soap was clearly different from that of the other
feedstocks (Fig. 5). The degree of saturation of other oils did effect the characteristic
reactions, thus having an impact on the formation of various intermediates and final
products. For this reason, somewhat lower amounts of aromatics (and cycloalkenes) were
detected in the pyrolysate from the vegetable oil soaps with a lower amount of
unsaturation (i.e., containing a lower amount of C
18:1
), whereas an enhanced amount of
dienes was determined for the pyrolysates of olive and rapeseed oil soaps (i.e., containing
the highest amount of C
18:1
). On the other hand, a significant relative contents of alkanes
and alkenes were formed during the pyrolysis of palm oil and olive oil soap due to their
saturated nature (i.e., containing mainly monounsaturated C
18:1
and saturated C
16
).

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 4) derived from vegetable oil-type materials would not be very high.
According to Sjgren 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
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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 saturated palmitic acid, C
16
), 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 materials. Typical fragmentation patterns of the main product group
were detected in both pyrolysates and these results were in accordance 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 composed 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 gratefully acknowledged. Special thanks are due to Ms Merja Rintala, for her skilful
assistance with the analytical work.


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[33] D.S. Ogunniyi, Bioresour. Technol. 97 (2006) 1086-1091.
[34] M. Sjgren, H. Li, U. Rannug, R. Westerholm, Fuel. 74 (1995) 983989.




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Figure captions


Figure 1. The main products formed in the pyrolysis experiments (750
o
C and 20 s)
with saponified palm oil. Numbers indicate the amount of carbon atoms in
a molecule.

Figure 2. Relative amounts of the products formed in the pyrolysis of saponified
palm, castor, olive and rapeseed oils. The number of replicate pyrolysis
experiments was 12.

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

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

Figure 5. The main products formed in the pyrolysis experiments (750
o
C and 20 s)
with saponified castor oil. Numbers indicate the amount of carbon atoms
in a molecule.



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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 1
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Table 2. Relative compositions of the fatty acid fractions (free and esterified) in the vegetable oils studied, % of total
Fatty acid

Palm oil*

Olive oil

Rapeseed oil

Castor oil

Formula
Palmitelaidic acid - 0.7 0.2 - HO
2
C-(CH
2
)
7
-CH=CH-(CH
2
)
5
-CH
3

Palmitic acid 47.0 11.9 4.8 1.1 HO
2
C-(CH
2
)
14
-CH
3

Margaric acid 0.1 0.1 - - HO
2
C-(CH
2
)
15
-CH
3

Linoleic acid 0.2 0.3 0.6 3.5 HO
2
C-(CH
2
)
7
-CH=CH-CH
2
-CH=CH-(CH
2
)
4
CH
3

Oleic acid 42.9 81.3 87.6 3.5 HO
2
C-(CH
2
)
7
-CH=CH-(CH
2
)
7
-CH
3

Stearic acid 4.5 2.9 1.8 1.2 HO
2
C-(CH
2
)
16
-CH
3

Ricinoleic acid - - - 86.2 HO
2
C-(CH
2
)
7
-CH=CH-CH
2
-CH(OH)-(CH
2
)
5
-CH
3

Gondoic acid - 0.4 1.6 - HO
2
C-(CH
2
)
9
-CH=CH-(CH
2
)
7
-CH
3

Arachidic acid 0.4 0.4 0.6 - HO
2
C-(CH
2
)
18
-CH
3

Miscellaneous 3.0 2.0 2.8 4.5
* In addition, palm oil contained 0.3% of azelaic acid (HO
2
C-(CH
2
)
7
-CO
2
H), 0.4% lauric acid (HO
2
C-(CH
2
)
10
-CH
3
) and 1.2% myristic acid
(HO
2
C-(CH
2
)
12
-CH
3
).
Table 2
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Figure 1
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Figure 2
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Figure 3
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Figure 4
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Figure 5
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