Fuel 126 (2014) 250–255

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Thermal cracking of free fatty acids in inert and light hydrocarbon gas
atmospheres
Justice Asomaning, Paolo Mussone, David C. Bressler ⇑
Biorefining Conversions and Fermentations Laboratory, Department of Agricultural, Food and Nutritional Science, 4-10 Agriculture/Forestry Centre, University of Alberta,
Edmonton, AB T6G 2P5, Canada

h i g h l i g h t s

 Oleic acid was pyrolyzed under hydrocarbon gases to produce liquid hydrocarbons.
 Saturated hydrocarbon gases did not influence liquid product yield and composition.
 Unsaturated hydrocarbon gases significantly increased conversion and liquid yield.
 Branched compounds significantly increased under unsaturated hydrocarbon gases.
 Deoxygenation was promoted when unsaturated hydrocarbon gases were used.

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

Article history: The aim of this work was to study the pyrolytic conversion of free fatty acids to renewable hydrocarbons
Received 18 December 2013 in the presence of short-chain alkane and alkene hydrocarbon gases. Oleic acid (cis-9-octadecanoic acid)
Received in revised form 25 February 2014 was used as model for fatty acids produced from hydrolysis of lipids from animal and plant feedstock.
Accepted 26 February 2014
Batch pyrolysis reactions were conducted at 410 °C for 2 h at an initial pressure between 130 psi
Available online 12 March 2014
(896.3 kPa) and 500 psi (3447.4 kPa) under constant agitation. Identification and quantification of the
pyrolysates in the gas and liquid phase were carried out using gas chromatography and mass spectrom-
Keywords:
etry. Under inert N2 atmosphere liquid product yields were between 74 and 81 wt% of feed with lower
Oleic acid
Ethylene
pressure giving the highest product yields. Liquid product was composed mainly of alkanes and alkenes
Thermal cracking ranging in carbon number from 6 to 19 and fatty acids from carbon numbers 4 to 18. Pyrolysis reactions
Deoxygenation conducted in the presence of short-chain alkane gases did not appreciably influence the liquid product
Branching yield and the composition compared to the inert atmosphere. On the other hand, pyrolysis reaction in
presence of short-chain alkene gases resulted in a marked increase in the liquid product yield, the pro-
duction of branched alkanes and alkenes and increased fatty acid decarboxylation. This work demon-
strates a novel approach to concurrently increase the liquid product yield in pyrolysis of free fatty
acids and produce highly valuable branched hydrocarbons for fuel and solvent applications.
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction and widespread availability compared to other biomass sources

The development of renewable alternatives to petroleum de-
rived fuels and chemicals has become imperative due to socio-eco-
nomic, geopolitical and environmental concerns. This has led to the
development of several technologies to convert lipids and lignocel-
lulosic biomass into renewable chemicals and fuels. One of the
most promising technologies being developed for converting bio-
mass is pyrolysis [1–4]. Lipids in the form of triglycerides are a par-
ticularly important feedstock because of their high energy density
⇑ Corresponding author. Tel.: +1 780 492 4986; fax: +1 780 492 4265.
E-mail address: david.bressler@ualberta.ca (D.C. Bressler).
[5].
Pyrolysis of whole triglycerides has been the focus of intense re-
search and development as well as commercialization efforts. Typ-
ical feedstocks include canola oil, soybean oil, sunflower oil,
jatropha oil, lard and tallows as well as vegetable oil soaps and
waste cooking oils. Pyrolysis products at room temperature and
atmospheric pressure may be liquid, gas and/or solids depending
on the feedstock used and on process reaction conditions such as
temperature, time, pressure, atmosphere, catalyst, etc. [6–9]. An
analysis of the main products reported from the pyrolysis of these
fats and oils revealed the presence of compounds such linear,
branched and cyclic hydrocarbons, aromatics, carbonyls, alcohols,

http://dx.doi.org/10.1016/j.fuel.2014.02.069
0016-2361/Ó 2014 Elsevier Ltd. All rights reserved.
 J. Asomaning et al. / Fuel 126 (2014) 250–255
carboxylic acids, carbonic gases and hydrogen. The distribution of
the classes of compounds is also dependent on the feedstock and
reaction conditions employed [10–12]. The thermal and thermo-
catalytic deoxygenation and pyrolysis of free fatty acids have also
been reported in the literature with product composition and dis-
tribution being influenced by the aforementioned feedstock and
reaction conditions employed [13–17].
Pyrolysis of biomass has generally been conducted under inert
atmosphere with gases such as nitrogen, helium or argon although
some studies involving the use of reactive atmosphere have been
reported in the literature. Both thermal and thermo-catalytic bio-
mass pyrolysis under steam atmosphere at various temperatures
have been studied and compared to inert atmospheres [10,18–
20]. In these cases, an increase in organic liquid product yields
was measured compared to inert atmospheres. The thermo-cata-
lytic deoxygenation and pyrolysis of fatty acids under hydrogen
atmosphere has been reported to increase both reactions rate
and product yields over inert atmosphere [15,21–23]. However,
Kubatova et al. [12] and Luo et al. [24] found that at reaction tem-
peratures above 400 °C the thermal cracking of canola oil, soybean
oil and their methyl esters under hydrogen did not positively im-
pact the liquid product yields.
Recycling of the product gas stream has been suggested as an
economical way of operating large scale pyrolysis plants [9,25].
The gas product stream is typically composed of CO, CO2, light
hydrocarbons and H2 depending on the feedstock composition
and reactions conditions [26–28]. Literature on biomass pyrolysis
under CO, CO2 and hydrocarbon atmosphere to study the effect
of recycling the gas product is scarce. Mante and co-workers [29]
and Zhang et al. [26] studied the effect of lignocellulosic biomass
pyrolysis under the non-condensable gases CO, CO2, CH4 and com-
pared it with reactions done under inert atmospheres. Both studies
reported an increase in liquid product yield. In the case of Mante’s
work, a decrease in char/coke yield was also observed. To the best
of our knowledge, there are no studies reported in the literature on
the pyrolysis of lipids, particularly fatty acids from under reactive
non-condensable hydrocarbon gases. The purpose of this work is to
address these knowledge gaps by studying the effect of short-chain
non-condensable alkane and alkene gases on the pyrolysis of free
fatty acids by uncovering the dominant chemical pathways. In par-
ticular this work seeks to study the effect of such gases on the
product portfolio and the overall product yield.
2. Materials and methods
2.1. Materials
Oleic acid (P99%), internal standard for GC analysis of liquid
product, nonadecanoic acid methyl ester (P99 %), pentane
(P99%), diethyl ether (P99%), CO standard (P99%), gaseous al-
kanes and alkene standards (C1–C4) were purchased from Sig-
ma–Aldrich (St. Louis, MO). N2 (99.998%), CO2 standard (99.9%),
methane (99%), ethane (99%), ethylene (99%), propane (99%) and
propylene (99%) were obtained from Praxair (Mississauga, ON).
Diazomethane for derivatization of fatty acids was prepared using
a Diazald kit (Sigma–Aldrich, St. Louis, MO) following the manufac-
turer’s procedures. All chemicals were used as received.
2.2. Pyrolysis reactions
Pyrolysis reactions were conducted in 15 mL batch microreac-
tors constructed with stainless steel Swagelok fittings and tubing
(0.75-in.) and heated in a fluidized bed sand bath (Techne, Burling-
ton, NJ) as previously described [13]. Approximately 1 g of oleic
acid was weighed into a clean and dry microreactor which was
then closed, checked for leaks, purged with the desired gas (N2,
251
methane, ethane, ethylene, propane or propylene). The reactor
was then pressurized to between 130 and 500 psi (896.3 and
3447.4 kPa) with the desired gas and the microreactor was sealed.
The microreactor was heated at 410 °C under constant agitation for
2 h and then immediately quenched in a bucket of water at room
temperature. The reaction temperature and time used were se-
lected based on work conducted by our group on the thermal
cracking of oleic acids [28]. The reaction conditions selected for
this study maximizes fatty acid feed conversion and liquid product
yield while minimizing gas, aromatic compounds and solids forma-
tion. The outside surface of the microreactor was then cleaned and
dried using compressed air to ensure the microreactor was clean of
sand from the sand bath.
2.3. Analytical methods – Gas product analysis
The weight of the gas fraction produced was determined by
weighing the microreactors before and after venting the gas prod-
uct in the microreactor. A 0.25 in. stainless steel Swagelok tube fit-
ting with a septum was screwed onto the microreactor in order to
sample gas product for gas chromatograph (GC) analysis according
to the method described by Maher et al. [13]. Gas samples were
then analyzed on a GC–FID and GC–TCD using instruments, sup-
plies and methods described elsewhere [28].
2.4. Analytical methods – Liquid product analysis
After venting, the microreactors were opened and the weight of
liquid product was determined. The liquid product was then ana-
lyzed on GC–FID and GC–MS using instruments, supplies and
methods described elsewhere [28].
2.5. Elemental composition of liquid product
The elemental composition (C, H, N, S and by difference O) of
the liquid was performed using a Carlo Erba EA1108 Elemental
Analyzer at the Analytical and Instrumentation Laboratory at the
Chemistry Department, University of Alberta.
2.6. Products identification and quantification
Compounds in the gas product were identified by comparing
their retention times with the retention times of known standards
and quantified using external standards of the pure compounds.
Hydrocarbons in the gas phase were quantified using methane as
external standard. Liquid products were identified based on reten-
tion times and by comparison of the mass spectra to the National
Institute of Standards and Testing (NIST) 2011 mass spectral library
and recognition of the fragmentation pattern of the mass spectra.
Only quality matches 90 and greater were regarded as tentatively
identified products. Quantification of the compounds in the pentane
extract was done semi-quantitatively by comparing the peak areas
of the compounds with the peak area of the known concentration
of the nonadecanoic acid methyl ester internal standard.
3. Results and discussion
3.1. Liquid product yield
Pyrolysis of oleic acid under nitrogen and light hydrocarbons re-
sulted in the formation of liquid and gas products under all the con-
ditions tested. Solid products were not observed in any experiments.
A water/aqueous fraction was not observed in the liquid product ob-
tained under all conditions. It is important to note that this does not
imply water was not produced during the reaction. The reason why
252 J. Asomaning et al. / Fuel 126 (2014) 250–255
water was not observed could be because the amount produced was
too small to be visible as a result of the very small feed mass (about
1 g) used in this study. Previous study on a larger sample size
showed the production of a water/aqueous fraction during the pyro-
lysis of free fatty acids [30]. The liquid product yield (calculated as
mass of liquid product as a percentage of mass of oleic acid feed)
at 130 psi initial headspace pressure are shown in Table 1. While
oleic acid pyrolysis in presence of methane, ethane and propane
did not result in higher liquid product yields, significant increases
were measured under ethylene (17%) and propylene (26%) com-
pared to reaction conducted under nitrogen atmosphere. This phe-
nomenon may be explained in terms of increased reactivity of the
pi bond electrons in these compounds compared to the saturated
light hydrocarbon gases’ sigma bonds [31]. The increased reactivity
implies the unsaturated hydrocarbon gases could act as reactants
compared to the saturated hydrocarbon, resulting in the observed
increase in the liquid product yield. A possible explanation for this
increase may be found in the formation of branched alkanes and al-
kenes (described in detail in Section 3.4). Additionally, the increased
liquid product yield could be due to ethylene–ethylene or propyl-
ene–propylene radical addition reactions [32].
3.2. Liquid product composition
The classes of compounds in the liquid pyrolysis product under
inert and light hydrocarbon headspace at 130 psi are shown in Ta-
ble 2. The unidentified represents GC eluted peaks that could not
be unambiguously identified. Unaccounted fraction represents
the difference between the GC eluted peaks percentage and
100%. This fraction represents compounds which have molecular
weight lower than or equal to C5, which could not be integrated
due to solvent peak overlap and possibly high molecular weight
compounds which could not be eluted on the GC.
The liquid product was composed primarily of linear, cyclic and
branched hydrocarbon, fatty acids and aromatics with carbon
number between C6 and C19. Irrespective of the headspace gas
used, n-alkanes (C6–C19) were the most abundant class of com-
pounds and they constituted on average about 23% of the liquid
product with the exception of propylene headspace, which had
19%. A similar observation was made with the linear alkenes where
there was only limited difference between the inert headspace and
the hydrocarbon headspace. Linear alkanes and alkenes are well-
known products of the direct deoxygenation of the fatty acid feed
or cracking product of feed and the cracking of deoxygenated
hydrocarbon product through free radical mechanism
[10,12,13,28]. Evidence of deoxygenation was found in the gas
product analysis where CO and CO2 which are decarbonylation
and decarboxylation [33,34] products respectively of free fatty
acids were found (discussed in Section 3.5).
Cyclic alkanes and alkenes ranging in carbon number from 6 to
13, which were mostly substituted, are shown in Table 2. There
Table 1
Headspace gas and pyrolysis liquid product yields at 410 °C for 2 h.
Headspace gas/ Mole ratio (feed: Liquid product yield (wt% of oleic
pressure (psi) gas)a acid feed)
Nitrogen (130) 1: 1.8 81.4 ± 2.6b
Ethylene (130) 1: 1.9 98.2 ± 0.9
Ethane (130) 1: 1.9 83.0 ± 1.4b
Propylene (130) 1: 2.0 107.4 ± 2.6
Propane (130) 1: 2.0 83.8 ± 1.1b
Methane (130) 1: 1.8 76.7 ± 1.1
a
Moles of gas calculated using the Peng–Robinson equation of state.
b
Values with the same superscript letters are not significantly different at 95%
confidence level.
were no significant differences in the total cyclic hydrocarbons
with the different headspaces gases. The cyclic hydrocarbons were
predominantly C5 (cyclopentanes and cyclopentenes) and C6
(cyclohexanes and cyclohexenes) cyclic structures. The cyclic
hydrocarbons accounted for 9.2–11.2% of the liquid product. Under
N2 atmosphere, cyclopentanes and cyclopentenes accounted for
34% and cyclohexanes and cyclohexenes were 51% of the cyclic
hydrocarbon composition. Similar results were observed when
ethylene atmosphere was used resulting in 39% 5 carbon and
49% 6 carbon rings.
It is accepted widely that six carbon numbered rings are formed
predominantly by the Diel–Alder reaction involving a diene and a
dienophile [10,34,35]. However, Kubatova et al. [36] recently pro-
posed a new path to cyclic compound formation in pyrolysis tri-
glycerides which involves the intramolecular cyclization of
alkenyl radical with terminal double bond. The data from this
study does not support the predominance of the Diels–Alder reac-
tion in the formation of 6 carbon numbered rings since the pres-
ence of the excess dienophile (ethylene or propylene) did not
result in an increase in the C6 ring cyclic compounds compared
to inert (N2) atmosphere.
Total aromatic compounds are also presented in Table 2. Under
inert N2 atmosphere total aromatics accounted for 4.7% of the li-
quid product. The results showed that methane, ethane ethylene
and propane had total aromatic compounds, which were not sig-
nificantly different from N2 atmosphere. On the other hand pyroly-
sis in presence of propylene resulted in increased total aromatics
content to 6.1%. The majority of the aromatic compounds produced
under the conditions used in this study were predominantly mono-
aromatic (65–75% of the aromatic compounds) compounds with
BTEX (benzene, toluene, ethylbenzene and xylenes) accounting
for nearly 40% of the total aromatic compounds. Mono-aromatic
compounds are formed through dehydrogenation of six carbon
numbered cyclic alkanes and alkenes [10,35–37]. Polyaromatic
compounds are then formed through polymerization and dehydro-
genation of the mono-aromatic compounds [10,38] and alterna-
tively via an intramolecular radical cyclization mechanism [36].
The total branched hydrocarbon compounds in the liquid prod-
uct are reported in Table 2. Similar to the total aromatic com-
pounds the saturated light hydrocarbon gases atmosphere
resulted in total branched hydrocarbon compounds, which were
not significantly different from the inert atmosphere accounting
for about 3.5% of the liquid product. The unsaturated hydrocarbon
atmosphere resulted in a significantly higher total branched hydro-
carbon representing 7.8% of the liquid product under ethylene
atmosphere and 6.9% of the liquid product under propylene atmo-
sphere. The results indicated that the unsaturated hydrocarbon
atmosphere promoted branching reaction possibly through radical
addition reactions discussed in detail in Section 3.4.
Fatty acid deoxygenation was promoted during pyrolysis in
presence of unsaturated short-chain hydrocarbon gases compared
to inert atmosphere (Table 2). The total fatty acids weight percent-
age in the pyrolysates decreased significantly from 15.5 under inert
N2 atmosphere to 10.9 and 9.0 respectively when ethylene and
propylene were used. Short-chain alkenes also increased conver-
sion of the feed when compared to inert atmosphere (Table 2).
The increased rate of fatty acid deoxygenation is discussed in detail
in Section 3.5.
The weight percentage of alkanes and alkenes (linear, branched
and cyclics) in the pyrolysates is reported in Fig. 1A and B respec-
tively. Between carbon numbers 6 and 13 there was generally higher
total alkanes and alkenes when unsaturated hydrocarbon atmo-
sphere was used compared to inert atmosphere. The trend is gener-
ally reversed between carbon numbers 14 and 17 where the inert
atmosphere resulted in relatively higher total alkanes and alkenes.
Irrespective of the atmosphere there is marked selectivity towards
 J. Asomaning et al. / Fuel 126 (2014) 250–255 253

Table 2
Liquid product composition at an initial pressure of 130 psi under inert and light hydrocarbon gas atmosphere.

Class of compounds Weight % of liquid product

Headspace gas
Nitrogen Methane Ethane Propane Ethylene Propylene
C6–C12 1-Alkenes 3.5 ± 0.2 4.1 ± 0.4 3.4 ± 0.2 3.3 ± 0.4 3.8 ± 0.4 4.9 ± 1.5
C6–C18 Internal alkenes 11.3 ± 0.7 11.7 ± 0.9 12.5 ± 0.5 12.6 ± 1.3 11.2 ± 0.2 10.6 ± 1.4
C6–C19 n-Alkanes 23.6 ± 1.9a 23.3 ± 2.5a 22.4 ± 2.6a 23.5 ± 1.1a 23.9 ± 0.9a 19.5 ± 0.9a
Aromatics 4.7 ± 0.3a 4.4 ± 0.4a 4.6 ± 0.5a 4.7 ± 0.1a 5.5 ± 0.2a 6.1 ± 0.3b
Branched hydrocarbons 3.5 ± 0.4a 3.4 ± 0.4a 3.0 ± 0.7a 2.8 ± 0.6a 7.8 ± 1.5b 6.9 ± 0.9b
Cyclic hydrocarbons 9.8 ± 0.7a 9.2 ± 0.4a 10.2 ± 0.5a 10.9 ± 0.7a 10.8 ± 0.3a 11.2 ± 0.4a
C4–C18 Fatty acids 15.5 ± 0.8a 12.6 ± 2.4a 11.7 ± 1.7a 13.8 ± 1.3a 10.9 ± 1.9b 9.0 ± 0.2b
Unreacted feed + isomers 2.1 ± 0.6 2.5 ± 0.8 2.8 ± 1.9 2.5 ± 0.8 1.0 ± 0.3 1.0 ± 0.5
Unidentified 18.5 ± 2.8 17.2 ± 1.8 15.9 ± 0.2 16.0 ± 1.9 18.1 ± 2.9 19.9 ± 1.8
Unaccounted 8.8 ± 3.4 11.5 ± 4.3 13.6 ± 1.1 9.9 ± 1.9 6.9 ± 2.0 10.6 ± 3.1
a,b
Values in the same row are not significantly different at the 95% confidence level from N2 atmosphere if they have the same letters.

C6–C12 total alkanes and alkenes (Fig. 1). This observation may be presence of ethylene at 200 and 500 psi. The liquid product yields
attributed to the influence of the carbon double bond on the fatty are presented in Fig. 2. Increasing initial pressure did not positively
acid feed on the pyrolysis reaction. The details of the influence of influence the liquid product yield under N2 atmosphere, but rather
the fatty acid double bond on the pyrolysis reaction reported else- there was a slight decrease in the liquid product yield from 81% at
where [28] and will not be discussed further in the study. The ob- 130 psi to 74% at 500 psi. However, under ethylene atmosphere,
served higher C17 alkenes (Fig. 1B) maybe explained in terms of increasing initial pressure positively influenced the liquid product
the direct deoxygenation of the fatty acid feed resulting in the for- yield, increasing from 98% to 152% when compared to the starting
mation of heptadecene isomers. fatty acid mass at 130 psi and 500 psi respectively.

3.3. Effect of headspace initial pressure 3.4. Increased branching reactions and products

The effect of the initial headspace pressure on the pyrolysates Fig. 3 shows a section of GC–FID chromatogram of liquid oleic
distribution was studied by conducting pyrolysis reactions in the acid pyrolysis products. The increase in branched hydrocarbons
under unsaturated light hydrocarbon gas (ethylene) atmosphere
10
compared to inert atmosphere as previously mentioned in Sec-
Total alkanes in liquid product (wt %)

9 Nitrogen headspace tion 3.2 can be clearly observed. The effect is enhanced when the
A
8 Ethylene headspace initial headspace pressure is increased as shown in Fig. 4. The total
7 branched hydrocarbon in the liquid fraction remained mostly un-
Propylene headspace
6 changed with increasing initial pressure under inert atmosphere
whereas under ethylene it increased from 7.8% to more than dou-
5
ble the amount when the initial headspace pressure was increased
4
from 130 psi to 500 psi.
3 A possible explanation for the increase in total branched hydro-
2 carbons under unsaturated light hydrocarbon gases could be the
1 direct addition of the unsaturated light hydrocarbon gas to free
0 radicals resulting from the cracking of the oleic acid feed. Also,
6 7 8 9 10 11 12 13 14 15 16 17 18 19 the formation of ethyl and ethenyl radicals from the disproportion-
Carbon number

6 160
Liquid product yield (wt % of oleic acid feed)
Total alkanes in liquid product (wt %)

B
140 130 psi
5
200 psi
120
500 psi
4
100

3 80

60
2

40
1
20

0 0
6 7 8 9 10 11 12 13 14 15 16 17
Ethylene Nitrogen
Carbon number
Headspace gas
Fig. 1. Total alkanes (linear, branched, cyclic) (A) and total alkenes (linear,
branched, cyclic) (B) composition by carbon number in liquid pyrolysis product at Fig. 2. Liquid product yields at different initial headspace pressure under nitrogen
130 psi initial pressure. and ethylene atmosphere.
254 J. Asomaning et al. / Fuel 126 (2014) 250–255

Fig. 5. GC–FID chromatogram of liquid oleic acid pyrolysis product from reactions
conducted under initial pressure of 500 psi using nitrogen and ethylene.

Fig. 3. Sections of GC–FID chromatograms showing liquid pyrolysis product under

60
initial pressure of 130 psi using nitrogen (A) and ethylene (B). A 2
1 1
1 c a
1 1 a

Total amount of CO produced (mg)

50 a,c
20 a a,b
Branched alkanes and alkenes (wt %)

40
Ethylene
15 Nitrogen
30

10 20

5 10

0
0 130 200 500
130 200 500 Initial headspace pressure (psi)
Initial headspace pressure (psi)

Fig. 4. Total branched alkanes and alkenes in the liquid product under nitrogen and
ethylene atmosphere at different initial headspace pressures. 2
40 c
B
Total amount of CO2 produced (mg)

ation of two ethylene molecules has been suggested as one of the 2

2
most important radical initiation steps in ethylene pyrolysis a,b
30 a 1
[32,39–42]. Therefore another possible explanation of the increase
1 a
in total branched hydrocarbons under ethylene is the addition of
a
ethyl and ethenyl radicals formed from the disproportionation of 20 1
ethylene to cracking products of fatty acid feed. a

3.5. Deoxygenation 10

Fig. 5 shows typical GC–FID chromatograms of the liquid prod-

uct from oleic acid pyrolysis conducted at 410 °C for 2 h under in-
ert atmosphere and in presence of ethylene with an initial pressure
of 500 psi. In both reactions, the deoxygenation product of the feed
(C17 alkenes) as well as the deoxygenation product of C18:0 (n-
heptadecane) were clearly visible. It must be noted that the n-hep-
tadecane could also be the product of C17 alkenes (heptadecenes)
saturation reactions. A greater degree of deoxygenation was ob-
served for reactions conducted in presence of ethylene. The total
fatty acids remaining under inert atmosphere were 15.5% at
130 psi and 9.4% at 500 psi, whereas when processed under an eth-
ylene headspace the total fatty acid decreased to 10.9% and 5.3% at
the same pressures.
In order to understand the influence of ethylene on the deoxy-
genation, CO and CO2 were analyzed and quantified in the gas
product after pyrolysis reaction. Fig. 6 shows the presence of both
CO and CO2, indicating deoxygenation proceeded through both
0
200 500
130
Initial headspace pressure (psi)
Fig. 6. Carbon monoxide (A) and carbon dioxide (B) content in the gas product of
nitrogen and ethylene headspace at different initial pressure. (1Values with the
same numbers are not significantly different at the 95% confidence level between
the headspace gases at the same pressure. aValues with the same letters are not
significantly different at the 95% confidence level for the same headspace gas at
different initial headspace pressures.)
decarbonylation and decarboxylation. Whereas the decarbonyla-
tion reaction was minimally influenced by the use of ethylene, a
significant increase in CO2 was observed at all of the pressures
studied. The results indicated the positive influence on enhanced
deoxygenation observed under ethylene atmosphere was due to
increased decarboxylation.
 J. Asomaning et al. / Fuel 126 (2014) 250–255 255

Table 3 [7] Ito T, Sakurai Y, Kakuta Y, Sugano M, Hirano K. Biodiesel production from waste
Elemental composition of liquid product together with oleic acid feed. animal fats using pyrolysis method. Fuel Process Technol 2012;94:47–52.
[8] Smagala TG, Christensen E, Christison KM, Mohler RE, Gjersing E, McCormick
Headspace gas/pressure Elements (wt%) RL. Hydrocarbon renewable and synthetic diesel fuel blendstocks: composition
(psi) and properties. Energy Fuel 2013;27:237–46.
C H N S Oa
[9] Jindarom C, Meeyoo V, Rirksomboon T, Rangsunvigit P. Thermochemical
Feed 76.7 ± 0.1 12.1 ± 0.0 BDL BDL 11.3 ± 0.1 decomposition of sewage sludge CO2 and N-2 atmosphere. Chemosphere
Nitrogen (130) 83.8 ± 0.2 12.6 ± 0.0 BDL BDL 3.6 ± 0.1 2007;67:1477–84.
Ethylene (130) 83.8 ± 0.2 12.6 ± 0.0 BDL BDL 3.6 ± 0.3 [10] Idem RO, Katikaneni SPR, Bakhshi NN. Thermal cracking of canola oil: reaction
Nitrogen (200) 84.4 ± 0.2 12.2 ± 0.1 BDL BDL 3.0 ± 0.3 products in the presence and absence of steam. Energy Fuel 1996;10:1150–62.
Ethylene (200) 84.3 ± 0.2 12.6 ± 0.0 BDL BDL 3.1 ± 0.1 [11] Garcia-Perez M, Chaala A, Pakdel H, Kretschmer D, Roy C. Characterization of
bio-oils in chemical families. Biomass Bioenergy 2007;31:222–42.
Nitrogen (500) 84.5 ± 0.3 12.7 ± 0.1 BDL BDL 2.8 ± 0.3
[12] Kubatova A, Luo Y, Stavova J, Sadrameli SM, Aulich T, Kozliak E, et al. New path
Ethylene (500) 85.1 ± 0.2 12.8 ± 0.0 BDL BDL 2.1 ± 0.1
in the thermal cracking of triacylglycerols (canola and soybean oil). Fuel
BDL – below detection limit (10 ppm). 2011;90:2598–608.
a
Calculated by difference. [13] Maher KD, Kirkwood KM, Gray MR, Bressler DC. Pyrolytic decarboxylation and
cracking of stearic acid. Ind Eng Chem Res 2008;47:5328–36.
[14] Maki-Arvela P, Kubickova I, Snare M, Eranen K, Murzin DY. Catalytic
The elemental composition of liquid products under ethylene deoxygenation of fatty acids and their derivatives. Energy Fuel 2007;21:30–41.
[15] Maki-Arvela P, Snare M, Eranen K, Myllyoja J, Murzin DY. Continuous
and nitrogen headspace is shown in Table 3. The results show both decarboxylation of lauric acid over Pd/C catalyst. Fuel 2008;87:3543–9.
nitrogen and sulfur were below the detection limit of 10 ppm in [16] Jurg JW, Eisma E. Petroleum hydrocarbons – generation from fatty acid.
the feed and as a consequence the liquid product also had nitrogen Science 1964;144:1451–2.
[17] Lestari S, Maki-Arvela P, Simakova I, Beltramini J, Lu GQM, Murzin DY.
and sulfur content below detection limit. The results also show
Catalytic deoxygenation of stearic acid and palmitic acid in semibatch mode.
there is deoxygenation during the pyrolysis reaction irrespective Catal Lett 2009;130:48–51.
of the headspace has used. Additionally, the results show increase [18] Ates F, Putun AE, Putun E. Catalytic pyrolysis of perennial shrub, Euphorbia rigida
in deoxygenation as initial headspace pressure increases. This in the water vapour atmosphere. J Anal Appl Pyrolysis 2005;73:299–304.
[19] Putun E, Ates F, Putun AE. Catalytic pyrolysis of biomass in inert and steam
observation corroborates the results shown in Fig. 6 where an in- atmospheres. Fuel 2008;87:815–24.
crease in initial headspace pressure resulted in higher total CO2 [20] Putun E, Uzun BB, Putun AE. Production of bio-fuels from cottonseed cake by
content under both headspaces. catalytic pyrolysis under steam atmosphere. Biomass Bioenergy
2006;30:592–8.
[21] Immer JG, Kelly MJ, Lamb HH. Catalytic reaction pathways in liquid-phase
deoxygenation of C18 free fatty acids. Appl Catal A-Gen 2010;375:134–9.
4. Conclusion
[22] Maier WF, Roth W, Thies I, Schleyer PV. Hydrogenolysis. 4. Gas-phase
decarboxylation of carboxylic-acids. Chem Ber-Recl 1982;115:808–12.
The pyrolysis of a model free fatty acid in the presence of short- [23] Arend M, Nonnen T, Hoelderich WF, Fischer J, Groos J. Catalytic deoxygenation
chain alkanes and alkenes was studied at different initial pressures of oleic acid in continuous gas flow for the production of diesel-like
hydrocarbons. Appl Catal A-Gen 2011;399:198–204.
to determine the dominant reaction pathways and effect on liquid [24] Luo Y, Ahmed I, Kubatova A, St’avova J, Aulich T, Sadrameli SM, et al. The
product yield. While saturated short-chain alkane gases (methane, thermal cracking of soybean/canola oils and their methyl esters. Fuel Process
ethane and propane) did not influence the liquid product yields Technol 2010;91:613–7.
[25] Fonts I, Gea G, Azuara M, Abrego J, Arauzo J. Sewage sludge pyrolysis for liquid
and composition, unsaturated short-chain alkenes (ethylene and production: a review. Renew Sust Energy Rev 2012;16:781–2805.
propylene) resulted in increased liquid product yield and greater [26] Zhang HY, Xiao R, Wang DH, He GY, Shao SS, Zhang JB, et al. Biomass fast
feed conversion. For the latter reactions, chromatographic analysis pyrolysis in a fluidized bed reactor under N2, CO2, CO, CH4 and H2
atmospheres. Bioresour Technol 2011;102:4258–64.
of the products portfolio revealed the presence of desirable [27] Asadullah M, Rahman MA, Ali MM, Motin MA, Sultan MB, Alam MR, et al. Jute
branched compounds and increased conversion of the fatty acid stick pyrolysis for bio-oil production in fluidized bed reactor. Bioresour
feedstock. The observed influence of the unsaturated light hydro- Technol 2008;99:44–50.
[28] Asomaning J, Mussone P, Bressler DC. Thermal deoxygenation and pyrolysis of
carbon gases could be attributed to the presence of the relatively oleic acid. J Anal Appl Pyrolysis 2014;105:1–7.
electron rich reactive pi bonds. The results of this study show li- [29] Mante OD, Agblevor FA, Oyama ST, McClung R. The influence of recycling non-
quid product yield and feed conversion of fatty acid pyrolysis can condensable gases in the fractional catalytic pyrolysis of biomass. Bioresour
Technol 2012;111:482–90.
be improved through recycling of gaseous product.
[30] Asomaning J, Mussone P, Bressler DC. Two-stage thermal conversion of
inedible lipid feedstocks to renewable chemicals and fuels; 2014. doi: http://
Acknowledgements dx.doi.org/10.1016/j.biortech.2014.01.136.
[31] Vollhardt KPC, Schore EN. Organic chemistry: structure and function. 5th
ed. New York: W.H. Freeman and Company; 2007.
The authors would like to express their gratitude to the [32] Roscoe JM, Bossard, Back MH. A kinetic modeling study of ethylene pyrolysis.
National Science and Engineering Research Council of Canada, Can J Chem-Rev Can Chim 2000;78:16–25.
[33] Immer JG, Lamb HH. Fed-batch catalytic deoxygenation of free fatty acids.
the Alberta Livestock and Meat Agency, Alberta Innovates Biosolu- Energy Fuel 2010;24:5291–9.
tions Corporation and the Biorefining Conversions Network at the [34] Chang CC, Wan SW. Chinas motor fuels from tung oil. Ind Eng Chem
University of Alberta for providing financial support to this project. 1947;39:1543–8.
[35] Schwab AW, Dykstra GJ, Selke E, Sorenson SC, Pryde EH. Diesel fuel from
thermal-decomposition of soybean oil. J Am Oil Chem Soc 1988;65:1781–6.
References [36] Kubatova A, St’avova J, Seames WS, Luo Y, Sadrameli SM, Linnen MJ, et al.
Triacylglyceride thermal cracking: pathways to cyclic hydrocarbons. Energy
Fuel 2012;26:672–85.
[1] Lappi H, Alen R. Production of vegetable oil-based biofuels – thermochemical
[37] Melero JA, Clavero MM, Calleja G, Garcia A, Miravalles R, Galindo T. Production
behavior of fatty acid sodium salts during pyrolysis. J Anal Appl Pyrolysis
of biofuels via the catalytic cracking of mixtures of crude vegetable oils and
2009;86:274–80.
nonedible animal fats with vacuum gas oil. Energy Fuel 2010;24:707–17.
[2] Maher KD, Bressler DC. Pyrolysis of triglyceride materials for the production of
[38] Melero JA, Vicente G, Morales G, Paniagua M, Bustamante J. Oxygenated
renewable fuels and chemicals. Bioresour Technol 2007;98:2351–68.
compounds derived from glycerol for biodiesel formulation: influence on EN
[3] Tian H, Li CY, Yang CH, Shan HH. Alternative processing technology for
14214 quality parameters. Fuel 2010;89:2011–8.
converting vegetable oils and animal fats to clean fuels and light olefins. Chin J
[39] Roscoe JM, Jayaweera IS, Mackenzie AL, Pacey PD. The mechanism of ethylene
Chem Eng 2008;16:394–400.
pyrolysis at small conversions. Int J Chem Kinet 1996;28:181–93.
[4] Huber GW, Corma A. Synergies between bio- and oil refineries for the
[40] Roscoe JM, Bossard AR, Back MH. A kinetic modeling study of ethylene
production of fuels from biomass. Angew Chem Int Ed 2007;46:7184–201.
pyrolysis. Can J Chem 2000;78:16–25.
[5] Sonntag NOV. Structure and composition of fats and oils. 4th ed. New
[41] Kunugi T, Sakai T, Soma K, Sasaki Y. Kinetics and mechanism of thermal
York: John Wiley & Sons; 1979.
reaction of ethylene. Ind Eng Chem Fund 1969;8:365–604.
[6] Buzetzki E, Sidorova K, Cvengrosova Z, Cvengros J. Effects of oil type on
[42] Dahlgren G, Douglas JE. Kinetics of the thermal reactions of ethylene. J Am
products obtained by cracking of oils and fats. Fuel Process Technol
Chem Soc 1958;80:5108–10.
2011;92:2041–7.