RESEARCH PAPER New Biotechnology  Volume 32, Number 2  March 2015

Research Paper

Catalytic cracking of non-edible sunflower

oil over ZSM-5 for hydrocarbon bio-jet fuel
Xianhui Zhao1, Lin Wei1, James Julson1, Qiquan Qiao2, Ashish Dubey2 and
Gary Anderson1
1
Department of Agricultural and Biosystems Engineering, South Dakota State University, Brookings, SD 57007, USA
2
Department of Electrical Engineering and Computer Science, South Dakota State University, Brookings, SD 57007, USA

Non-edible sunflower oils that were extracted from sunflower residual wastes were catalytically cracked
over a ZSM-5 catalyst in a fixed-bed reactor at three different reaction temperatures: 4508C, 5008C and
5508C. The catalyst was characterized using XRD, FT-IR, BET and SEM. Characterizations of the upgraded
sunflower oils, hydrocarbon fuels, distillation residues and non-condensable gases were carried out. The
effect of the reaction temperature on the yield and quality of liquid products was discussed. The results
showed that the reaction temperature affected the hydrocarbon fuel yield but had a minor influence on
its properties. The highest conversion efficiency from sunflower oils to hydrocarbon fuels was 30.1%,
which was obtained at 5508C. The reaction temperature affected the component content of the non-
condensable gases. The non-condensable gases generated at 5508C contained the highest content of light
hydrocarbons (C1–C5), CO, CO2 and H2. Compared to raw sunflower oils, the properties of hydrocarbon
fuels including the dynamic viscosity, pH, moisture content, density, oxygen content and heating value
were improved.

Introduction There are various methods being explored to upgrade vegetable

Due to environmental impact concern, finite fossil fuel reserves
and national energy security, vegetable oils are investigated as
an affordable alternative to petroleum-derived jet fuels. The
advantages of using vegetable oils for biofuel production include
being liquid portable, renewable, readily available, low aromatic
content, low sulfur content and bio-degradable. However,
some properties of the vegetable oil including high viscosity,
high freezing point and low energy density are still barriers
for the vegetable oil to be used as jet fuel. To be used as fuel for
aircraft engines, jet fuel should have low freezing point (408C),
high flash point, high energy density, superior fluidity and be
compatible with the materials in aircraft engines. Generally,
raw vegetable oils have to be refined to remove the undesirable
substances to improve their properties to meet the jet fuel
standards [1–4].
Corresponding author: Wei, L. (lin.wei@sdstate.edu)
oils to biofuels. Thermal cracking is one method to produce
biofuels from vegetable oils without using a catalyst. The thermal
decomposition of vegetable oils involves either the free radical
mechanism or the carbonium ion mechanism. However, high
temperature (typically 450–7508C) and high pressure (about
6.89  106 Pa) are needed for the thermal cracking of vegetable
oils. In addition, yield of the biofuel is relatively low and the cost is
relatively high compared to those using a catalytic cracking [5].
Transesterification techniques could be used to convert triglycer-
ides in vegetable oils to glycerol and esters through chemical
reactions with solvents such as methanol and ethanol. However,
they are usually used to produce biodiesel [6]. Hydrocracking can
convert vegetable oils into biofuels. The introduction of hydrogen
is helpful to remove oxygen atoms in the form of H2O, CO and
CO2. The hydrocracking reactions become possible only under
severe conditions such as high hydrogen pressure and high cata-
lyst activity. Some noble metal catalysts have high activity, but

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New Biotechnology  Volume 32, Number 2  March 2015
they are limited due to the availability and high price. Addition-
ally, the noble metal catalysts are sensitive to the catalyst con-
taminates that could deactivate the catalysts [7,8].
Catalytic cracking of vegetable oils is technically achievable to
produce biofuels similar to petroleum based fuels under suitable
processing conditions [9]. The triglycerides could be cracked into
fatty acids through the catalytic decomposition. The fatty acids are
then converted into products such as gasoline, light gaseous
hydrocarbons and heavy hydrocarbons [1,2]. After vegetable oils
are upgraded to liquid hydrocarbons, the liquid hydrocarbons will
be delivered to a petroleum refinery to obtain ‘standard’ jet fuels.
Catalysts with an excellent selectivity and long life might improve
the product yield and reduce the cost. Vegetable oils with superior
fatty acid profiles might easily be upgraded to desired liquid
hydrocarbons [10,11]. Researchers have reported the conversion
of vegetable oils into hydrocarbons over a variety of catalysts
lately. Wang et al. proved that using both continuous thermal
hydrolysis and catalytic decarboxylation could make it feasible to
convert triglycerides in canola oil into hydrocarbon fuels (HF) or
other useful chemicals with suitable refining [12]. Biswas et al.
studied the catalytic cracking of soybean oils over the catalyst Zr–
Zr covalently bonded with alumina without using hydrogen. Only
non-condensable gases and liquid products were found with a
total absence of residues [9]. Distillation is usually used to separate
a mixture with wide boiling ranges into products with narrower
boiling ranges. The mixture can be heated to vaporize the lightest
components.
Zeolite catalyst was reported to be promising for the conversion
of biomass derived feedstocks into chemicals and biofuels [13]. The
addition of zeolite into the reactor with feedstocks could increase
the formation of aromatics. Zeolite can catalyze a wide variety of
reactions due to its shape selectivity. It is vital to improve the
cracking process conditions to obtain a high yield of hydrocarbons
and to reduce the coke formation on the zeolite. Zeolite catalysts
include ZSM-5, SBA-15, Beta, mordenite, Y, Mor, FCC, and so on.
Of these zeolite catalysts, ZSM-5 shows the highest olefin and
aromatic yield from lignocellulosic biomass [14,15]. In addition,
ZSM-5 is acidity and it is widely used in the petroleum refinery
process [12,16].
However, the use of the catalytic cracking method on an indus-
trial scale was limited by the high cost and the availability of the
vegetable oil feedstock [9]. Only a few researchers have studied the
catalytic cracking of non-edible vegetable oils in fixed-bed reactors
that are not expensive and easy to construct. A great number of
non-edible vegetable oils have become available in recent years.
Non-edible vegetable oils do not compete with food, thus provid-
ing more sources for bio-jet fuel production. These non-edible
vegetable oil sources are generally classified into three categories:
non-edible plant oils (e.g. sterculia foetida, babassu and camelina
sativa), waste cooking vegetable oils, and vegetable oils produced
from wastes derived from the processing of edible oilseeds. For
instance, sunflower seeds are a typical edible oil crop. There are
about 5–15% broken seed kernels (fine meat particles and shell
pieces) left over residual wastes after sunflower seeds are dehulled.
Sunflower residual wastes contain up to about 48% oil. However,
the oils extracted from these sunflower residual wastes are non-
edible due to their quality not meeting the food standards
[3,17,18].
RESEARCH PAPER
Nelson and Kephart found it was feasible to develop sunflowers
in the North Central region of the United States [19]. The produc-
tion of sunflower seeds in the United States and in the world
through 2012/2013 was 2.53  106 tons and 7.11  107 tons, re-
spectively [20]. The average price of sunflower seeds received by
farmers was 508$/ton through 2012/2013 [21]. It was estimated
that there were 3.56–10.67 million tons of sunflower residual
wastes in the world through 2012/2013 available for the biofuel
production. Due to the widespread production and high yield of
sunflower seeds, those sunflower residual wastes are considered as
important renewable energy sources. Seed dehulling is still very
Research Paper
popular for the production of snacks or high grade food oil in the
sunflower seed industry. Solvent extraction and cold pressing are
two conventional technologies for the oil extraction from oil-
seeds. Solvent extraction is an expensive technique which
involves organic solvents such as hexane and ethyl acetate. In
addition, it can cause the production of undesirable residues.
Although the oil recovery of oilseeds using the cold press method
is not as high as that using the solvent extraction method, the cold
press method has low capital cost. The extracted oilseed meals
with residual oils could be reused in poultry, paper coating and
bio-composite industries to improve the economic viability of the
biofuel production. Additionally, the cold press involves no
organic solvent so that the extracted oils are chemically contami-
nant free. Furthermore, it is suitable for extracting oil on farms
and other rural areas, which is helpful in improving the rural
economy [3].
In this study, the oils extracted from sunflower residual wastes
(simply called sunflower oils in this study, unless specified) were
catalytically cracked over the ZSM-5 catalyst in a fixed-bed reactor.
Distillation, a further step during the catalytic cracking process in
this study, was used to separate hydrocarbons from the upgraded
sunflower oils (USO). The effect of the reaction temperature on the
liquid product yield and properties such as moisture content,
density, pH, dynamic viscosity, oxygen content and chemical
compositions is discussed. The chemical compositions of non-
condensable gases generated during the catalytic cracking process
are analyzed.
Experimental materials and methods
Feedstocks and devices preparation
Sunflower seeds were grown in a local farm in South Dakota. After
being harvested, the sunflower seeds were delivered to an oilseed
company (Sunbird Inc., Huron, SD 57350, USA). The sunflower
residual wastes used for this study were purchased from this
company for oil extraction. The sunflower oils were produced at
the Advanced Biofuel Laboratory in the Department of Agricultur-
al and Biosystems Engineering, South Dakota State University
(SDSU) using the cold press method. The sunflower oil extraction
was carried out under different processing conditions such as
screw rotary frequency and nozzle size. After oil extraction, the
obtained sunflower oils were stored in sealed dark glass bottles in a
ventilated hall at ambient temperature. The sunflower oils were
characterized and their yield was determined. In about four
months, the optimum processing conditions were found: frequen-
cy of 15 Hz with a nozzle of 6.35 mm inside diameter, based on the
sunflower oil yield and properties. The sunflower oils obtained at
the optimum processing conditions were used for the catalytic
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TABLE 1
Main physicochemical properties of sunflower oils
Physicochemical properties Sunflower oils
Main chemical compositions (area %) C18H34O2: 26.1;
C29H50O: 15.4;
C29H50O2: 39.8
O (%) 10.2
pH 3.57
Density (g/mL) 0.88
Moisture content (%) 0.10
Research Paper
Dynamic viscosity (cP) 73.9
Heating value (MJ/kg) 39.6
cracking trials. Table 1 shows main physicochemical properties of
the sunflower oils obtained at the optimum processing conditions
[17]. It usually takes up to six months for the oil logistics including
oil extraction and collection, transportation, and storage in the
oilseed industry. It was reported that the shelf life of sunflower oils
stored properly at ambient temperature is about 12 months [22]. In
addition, there were no rancid smell or spoiling sunflower oils
found during the catalytic cracking trials.
Catalyst preparation
The zeolite powders were purchased from Zeolyst International,
Kansas City, USA. The silica-to-alumina atomic ratio was 15:1. A
wet impregnation method was used to prepare the ZSM-5 catalyst.
The catalyst in strip shape was obtained by pressing it through a
sieve in a hydraulic press (Owatonna Tool Company, Minnesota
State). The obtained catalyst was sealed and stored at room tem-
perature for 12 hours and then calcined in air at 5508C for four
hours. The catalyst was stored in a sealed vial in a desiccator, which
minimizes the adsorption of the atmospheric moisture [23,24].
The fresh calcined ZSM-5 catalyst, with a volume of 60 mL, was
placed in the middle of the reactor tube.
Catalyst characterization
Automated multipurpose X-ray Diffractometer (XRD, SmartLab,
Rigaku Corporation) was used to examine the ZSM-5 catalyst. The
scan range was 5–508 and the scan speed was 28/min. Fourier
transform infrared spectroscopy (FT-IR) of the ZSM-5 catalyst
was performed on a Nicolet 6700 FT-IR spectrometer using KBr
pellets. The surface area, pore size and pore volume of the catalyst
were measured using a Micromeritics TriStar 3000 automated gas
adsorption analyzer. Physisorption analysis with nitrogen was
carried out using an ASAP 2010 Micropore Analyzer at 77 K (liquid
nitrogen bath). The catalyst sample was first degassed using a
Micromeritics FlowPrep 060 unit at 2008C for a minimum of five
hours to ensure that moisture was removed before the nitrogen
isotherm analysis. The specific surface area was calculated using a
Brunauer–Emmett–Teller (BET) model for the nitrogen adsorption
isotherm [25]. The total pore volume was obtained at a relative
pressure of P/P0 = 0.979. The pore size was calculated by 4VT/SBET.
The pore size distribution was determined using a Barrett–Joyner–
Halenda (BJH) adsorption model. The surface morphology of the
ZSM-5 catalyst was characterized using a scanning electron micro-
scope (SEM, Hitachi S-3400N).
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New Biotechnology  Volume 32, Number 2  March 2015
FIGURE 1
Schematic diagram of a fixed-bed reactor system.
Experimental procedure
The sunflower oil cracking was done on a fixed-bed reactor with
the ZSM-5 catalyst at a liquid hourly space velocity (LHSV) of three
per hour and three different reaction temperatures. In this study,
three typical reaction temperatures (4508C, 5008C and 5508C) were
assessed according to the catalyst cracking activity, the liquid
product yield and quality. The reactor system, shown in Fig. 1,
was purged with nitrogen at a pressure of 1.38  105 Pa (20 pound-
force per square inch (psi)). The reactor contained a stainless steel
tube 508 mm long with a 25.4 mm internal diameter. The tube
filled with ZSM-5 catalyst was fixed coaxially in a furnace. Sun-
flower oils were pumped into the reactor system until N2 had been
blown out of the reactor for 15 min to remove the air throughout
the system. Catalytic cracking of sunflower oils would proceed in
the tube with the activation of the ZSM-5 catalyst. Some cracked
molecules were collected in the form of liquids through a con-
denser system. The top phase of the liquids was considered as
upgraded sunflower oil and the bottom phase was considered as an
aqueous solution. Some cracked molecules deposited on the ZSM-5
catalyst to form coke. Other cracked molecules could not be
condensed under this condenser system and they formed non-
condensable gases. Some non-condensable gases would be collect-
ed in a gas sampling bag for the chemical composition analysis.
The upgraded sunflower oils were then distilled to isolate
hydrocarbons. The distillation temperature was set as 2308C,
which aimed to obtain biofuel size hydrocarbons for future bio-
jet fuel production. During the distillation process, the small
molecules became vapors. These vapors flowed into an overhead
condenser, which cooled the vapors back to a liquid. The liquid
was collected and considered as a hydrocarbon fuel. The compo-
nents, which were too heavy to vaporize under this distillation
condition, were left in the distillation flask and considered to be
the distillation residues (DR).
Data collection
The obtained upgraded sunflower oils, hydrocarbon fuels and
distillation residues were characterized by testing their pH, dy-
namic viscosity, density, moisture content, chemical composi-
tion, oxygen content and higher heating value. The pH was
New Biotechnology  Volume 32, Number 2  March 2015 RESEARCH PAPER

 
measured using a pHTestr 20 (Fisher Scientific) and pH testing mass of upgraded oil
Yield of USO ¼  100% (1)
papers. Dynamic viscosity was determined using a Viscoanalyzer mass of sunflower oil feed
(Reologica Instruments AB Company) at 208C. Water content was
determined using a Karl Fischer Titrator V20 (Mettler Toledo  
Company) at room temperature, American Society for Testing mass of HF
Yield of HF ¼  100% (2)
mass of USO feed
and Materials (ASTM) E1064. Density was tested for three times
by the ratio of the mass to the volume of the sample at room
 
temperature. The average value of these three tests was used as the mass of DR
Yield of DR ¼  100% (3)
density value. mass of USO feed
The major chemical compositions were analyzed using a Gas
Chromatography–Mass Spectrometry (GC–MS) (Agilent GC-
Results and discussion

Research Paper
7890A and MSD-5975C). Hydrogen was used as the carrier gas
Catalyst characterization
with a flow rate of 1 mL/min. The capillary columns were
XRD analysis
30 m  0.25 mm  0.25 mm DB-5MS. Before being tested, the sam-
The XRD analysis gives information about the bulk structure of the
ples were pretreated by derivatization. The liquid product with
catalyst. Figure 2a shows the XRD spectrum of the catalyst. The
30 mg was placed in a container. Hexane (4 mL of 95% purity) was
main peak was observed at 2u = 23.1948 and other peaks were
dropped in the container and then the mixture was shaken for
observed at 2u = 8.0368, 8.8868, 23.3218, 23.7758 and so forth.
2 min. Then 2 mL 12%-BF3 in methanol and 2 mL of CH3OH
The XRD diffraction peaks of the crystal form in this catalyst
(99.9%, extra pure) were added. The mixture was heated at
showed the ZSM-5 structure and these peaks are characteristic
608C using a water bath for 5 min and then cooled down to room
of ZSM-5. The peak position and intensity of the ZSM-5 catalyst
temperature. After that, 1 mL distilled water and 2 mL hexane
sample are in good accord with the previously reported spectrum
were added to remove the excess reagents. The mixture was then
[15,23,27,28].
centrifuged at 2500  g for 10 min. The obtained organic phase
was carefully taken out and the anhydrous sodium sulfate was
FT-IR spectrum
added to dry it. Finally, 1.5 mL organic phase solution without
Figure 2b displays the FT-IR spectrum of the ZSM-5 catalyst,
water was filtered into a vial for GC–MS testing. The GC–MS test
ranging between 4000 cm1 and 400 cm1. The ZSM-5 catalyst
parameters were as follows. One microliter of the sample was
exhibited O–H groups in the band near 3605 cm1. The O–H
injected through a splitless mode at 2858C. The splitless time
groups might result from the framework of adsorbed water or
was 30 s. The original column temperature was 1758C and then
aluminum. It indicates the existence of the catalytic activity. Also,
reached 2608C after 5.67 min at a rate of 158C/min. The holding
it indicates that the ZSM-5 catalyst possessed acid sites that are
time at 2608C was about 16 min. The major chemical composi-
important for the catalytic activity to take place. These findings are
tions were identified through a NIST Mass Spectral library and
consistent with the results reported by Zakaria et al. [27]. The
literature [3,12,17].
water-bending vibration near 1630 cm1 was observed, which
The higher heating value was determined using a Calorimeter
indicates that the adsorbed H2O might be present in the ZSM-5
System (C 2000, IKA-Works, Inc.), according to ASTM D4809.
catalyst sample. The presence of H2O might occur during the
About 0.5 g sample was added in a crucible which was sealed in
incipient wet impregnation process. The Si–O–Si asymmetric
a bomb. The sample was ignited with a cotton twist. The higher
stretching vibration near 796 cm1 was observed that might be
heating value was determined based on the temperature change of
due to the internal linkages in AlO4 or SiO4 of the ZSM-5 lattices.
water inside a measuring cell. The oxygen content of samples was
The double ring vibration band near 554 cm1 was present for the
determined using a CE-440 Elemental Analyzer (Exeter Analytical,
ZSM-5 catalyst. It indicates that only the ZSM-5 phase was formed.
Inc.), based on ASTM D4057. The combustion temperature and
Similar observations were reported by Khatamian and Irani [29].
reduction temperature were 9608C and 7708C, respectively. Acet-
anilide was used for the calibration. Helium was used for purging
the instrument and carrying the combustion products from the BET and BJH analysis
analytical system to the atmosphere. The helium pressure was set The N2 adsorption and desorption isothermal curve is shown in
as 1.17  105 Pa (17 psi). Fig. 2c. According to the IUPAC classification of physisorption
The chemical compositions of non-condensable gases generat- isotherms, the ZSM-5 catalyst exhibited a combination of type I
ed during the upgrading of sunflower oil were measured using a and type IV isotherms with enhanced uptake of nitrogen at higher
Gas Chromatography (GC) system. An Agilent GC (7890A) with a relative pressure. The adsorption quantity at very low relative
flame ionization detector (FID) and a thermal conductivity detec- pressures (P/P0) was high, which indicates the presence of micro-
tor (TCD) was utilized for the chemical composition analysis. The porous adsorption. The curve was accompanied by a hysteresis
FID is used for the analysis of CH4 and C2–C5 hydrocarbons. loop between the relative pressures of 0.5–1.0. This might be due to
The TCD is used for the analysis of H2, O2, CO, CO2, N2 and the crystalline agglomerates that resulted in the formation of
H2S [26]. mesoporous structures. A remarkable increase in the adsorption
The yield of upgraded sunflower oils, hydrocarbon fuels and quantity of the low relative pressure region and the hysteresis loop
distillation residues obtained during the catalytic cracking in the high relative pressure region indicate the presence of both
and distillation process could be calculated by the following micropores and mesopores. This is consistent with the experiment
equations: results of Huber’s study and Xiang’s study [15,30]. The BJH pore

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Research Paper

FIGURE 2
Characterization of the ZSM-5 catalyst: (a) XRD spectrum; (b) FT-IR spectrum; (c) adsorption and desorption isotherm of nitrogen at 77 K; (d) BJH pore size
distribution; (e) SEM image (15.0k); and (f) SEM image (3.00k).

size distribution of the ZSM-5 catalyst is presented in Fig. 2d. The
BJH pore size model also confirmed the presence of mesoporosity
in the ZSM-5 catalyst. Thus, the isothermal type of the ZSM-5
catalyst was a combination of type I and type IV. Through the
specific surface area analysis using the BET model, the calculated
surface area of the ZSM-5 catalyst was 417.0 m2/g. The total pore
volume of the pores, less than 933.3 Å width, was 0.40 cm3/g. The
average pore size was 38.1 Å. The specific pore structures of the
ZSM-5 catalyst made it effective for cracking sunflower oils. The
small pore volume and pore size might make the ZSM-5 catalyst
difficult for larger aromatic coke precursors to form inside the
pores [14].

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New Biotechnology  Volume 32, Number 2  March 2015 RESEARCH PAPER

TABLE 2
Main chemical compositions of upgraded sunflower oils produced at 4508C, 5008C and 5508C
Temp. (8C) No. Component Formula RT (min) Area %
450 1 9-Octadecenoic acid, (E)- C18H34O2 (C18:1) 9.118 81.20
2 Heptadecanoic acid, 16-methyl- C18H36O2 (C18:0) 9.347 4.00
3 4-Methyldocosane C23H48 (C23:0) 10.708 1.26
4 Nonadecane, 9-methyl- C20H42 (C20:0) 11.366 1.50
5 Hexadecane C16H34 (C16:0) 11.990 1.77
6 1,13-Tetradecadiene C14H26 (C14:2) 12.322 4.46
7 13-Hexacosyne C26H50 (C26:2) 12.385 1.34
8 Heptadecane C17H36 (C17:0) 12.688 1.20
500 1 Octadecane C18H38 (C18:0) 9.982 4.33

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2 Tricosane C23H48 (C23:0) 10.731 9.70
3 Diisooctyl adipate C22H42O4 (C22:0) 11.309 2.35
4 Tetracosane C24H50 (C24:0) 11.389 14.74
5 Phenol, 2,20 -methylenebis[6-(1,1-dimethylethyl)-4-ethyl- C25H36O2 (C25:6) 12.002 43.63
6 Tetracosane C24H50 (C24:0) 12.568 11.49
7 Tetracosane C24H50 (C24:0) 13.198 5.89
8 Tricosane C23H48 (C23:0) 13.941 3.86
9 3-Eicosene, (E)- C20H40 (C20:1) 14.840 2.08
10 Triacontane C30H62 (C30:0) 15.956 1.93
550 1 9,12-Octadecadienoic acid, (E,E)- C18H32O2 (C18:2) 9.020 1.78
2 9-Octadecenoic acid, (E)- C18H34O2 (C18:1) 9.095 29.39
3 Octadecanoic acid C18H36O2 (C18:0) 9.341 6.52
4 Eicosane C20H42 (C20:0) 9.959 4.18
5 Tricosane C23H48 (C23:0) 10.703 9.61
6 Tetracosane C24H50 (C24:0) 11.361 11.84
7 Hexadecane C16H34 (C16:0) 11.984 14.73
8 Heptadecane C17H36 (C17:0) 12.688 12.91
9 Tetratetracontane C44H90 (C44:0) 13.529 4.84
10 Octadecane C18H38 (C18:0) 14.559 2.52
11 1-Nonadecene C19H38 (C19:0) 17.466 1.68

SEM analysis Chemical properties of products

Figure 2e,f shows the surface morphologies of the ZSM-5 catalyst
with different magnitude scales. The ZSM-5 catalyst was spherical
structure that contained small pores. It contained the agglomera-
tion of particles on the top surface. In addition, the small particles
were interconnected with each other. The ZSM-5 catalyst had rod-
like crystals, similar to the observation reported by Huber et al.
[15].
FIGURE 3
Liquid products produced: USO, HF and DR. USO, upgraded sunflower oils; HF,
hydrocarbon fuels; and DR, distillation residues.
Main chemical compositions
Figure 3 shows the obtained upgraded sunflower oils, hydrocarbon
fuels and distillation residues using the catalytic cracking method.
Apparently, hydrocarbon fuels look more transparent than
upgraded sunflower oils and distillation residues. Table 2 shows
the major chemical compositions of upgraded sunflower oils
produced at 4508C, 5008C and 5508C. For upgraded sunflower oils
produced at 4508C, an unsaturated fatty acid of 9-octadecenoic
acid, (E)- was the main component. The unsaturated fatty acid
would reduce the viability of the upgraded sunflower oils since it is
prone to be oxidized. A total hydrocarbon content from C14 to C26
in the upgraded sunflower oils produced at 4508C was 11.53%. The
upgraded sunflower oils produced at 4508C contained the highest
content of carboxylic acid among all upgraded sunflower oils. It
indicates that the ZSM-5 catalyst was unfavorable to the removal of
carbonyl at relatively low reaction temperature, which is in agree-
ment with Yang’s research regarding pyrolysis of vegetable oils
[31]. When the reaction temperature was 5008C, the content of
hydrocarbons increased to 54.02%. The carbon distribution of
these hydrocarbons was between C18 and C30. In the upgraded
sunflower oils produced at 5008C, there were also a large amount of
oxides. When the reaction temperature reached 5508C, the con-
tent of hydrocarbons increased further to 62.31%. The content of
hydrocarbons increased with the increase in the reaction temper-
ature from 4508C to 5508C. Also, the upgraded sunflower oils
produced at 5508C contained a higher content of small-molecule

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TABLE 3
Main chemical compositions of hydrocarbon fuels produced at 4508C, 5008C and 5508C
Temp. (8C) No. Component Formula RT (min) Area %
450 1 13-Tetradecenal C14H26O (C14:1) 9.095 9.74
2 Tetradecanoic acid, 12-methyl- C15H30O2 (C15:0) 9.347 3.53
3 Pentadecane C15H32 (C15:0) 9.959 6.47
4 Heptacosane C27H56 (C27:0) 10.703 10.52
5 Tetracosane C24H50 (C24:0) 11.367 17.08
6 4,5-Nonadiene C9H16 (C9:2) 11.744 1.95
7 10-methylnonadecane C20H42 (C20:0) 11.985 19.07
8 1,2-Benzenedicarboxylic acid, mono(2-ethylhexyl) ester C16H22O4 (C16:3) 12.185 6.66
9 Hentriacontane C31H64 (C31:0) 12.688 12.69
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10 Decane, 2,3,5-trimethyl- C13H28 (C13:0) 13.530 6.34

11 Cyclotetradecane C14H28 (C14:0) 14.560 3.25
12 Tetrapentacontane C50H110 (C50:0) 15.841 2.70
500 1 Tritetracontane C43H88 (C43:0) 9.976 4.84
2 Tricosane C23H48 (C23:0) 10.720 11.09
3 Tetracosane C24H50 (C24:0) 11.384 17.06
4 Docosane, 11-butyl- C26H54 (C26:0) 11.990 39.54
5 Octadecane C18H38 (C18:0) 12.557 13.00
6 Tritetracontane C43H88 (C43:0) 13.186 6.80
7 Octacosane C28H58 (C28:0) 13.930 3.49
8 Nonacosane C29H60 (C29:0) 14.828 2.20
9 Triacontane C30H62 (C30:0) 15.933 1.98
550 1 Cyclooctene, 3-ethenyl- C10H16 (C10:2) 8.900 6.91
2 E-1,9-Dodecadiene C12H22 (C12:2) 8.952 27.70
3 3-Octanol C8H18O (C8:0) 9.187 1.98
4 8,11-Octadecadiynoic acid C18H28O2 (C18:4) 9.255 4.47
5 2-Heptyn-1-ol C7H12O (C7:2) 10.754 2.17
6 cis-1-Methyl-2-(20 -propenyl)cyclopropane C7H12 (C7:1) 11.041 42.70
7 1,2-Benzenedicarboxylic acid, mono(2-ethylhexyl) ester C16H22O4 (C16:3) 12.088 6.04
8 2,4,4-Trimethyl-3-hydroxymethyl-5a-(3-methyl-but-2-enyl)-cyclohexene C15H26O (C15:2) 12.746 1.92
9 Ethanol, 2-(3,3-dimethylbicyclo[2.2.1]hept-2-ylidene)- C11H18O (C11:1) 17.575 1.97

hydrocarbons such as C16 and C17 compared to upgraded sunflow-
er oils produced at both 4508C and 5008C. It indicates that a higher
reaction temperature is more helpful in breaking large molecules
in raw sunflower oils to smaller molecules.
Table 3 lists the major chemical compositions of hydrocarbon
fuels produced at 4508C, 5008C and 5508C. After distillation, all the
hydrocarbon fuels contained a higher content of hydrocarbons than
that in the upgraded sunflower oils. It proves that the distillation
treatment was effective at isolating mixed hydrocarbons from the
upgraded sunflower oils. Hydrocarbon fuels produced at 4508C
contained 19.93% oxides. When the reaction temperature was
5008C, the hydrocarbon fuels only contained pure hydrocarbons,
ranging from C18 to C43. Hydrocarbon fuels produced at 5508C
contained 77.31% hydrocarbons (C7–C12). The results indicate that
the reaction temperature affected the distribution of hydrocarbon
fuels, which is consistent with the finding of Yang’s study [31]. Table
4 lists the major chemical compositions of distillation residues
produced at 4508C, 5008C and 5508C. For all distillation residues,
their main chemical component was the same, which was 9-octa-
decenoic acid, (E)-. The content of 9-octadecenoic acid, (E)- was
higher than 78%, indicating that the distillation residues might be
reused for further catalytic cracking. There was a low content of
hydrocarbons in all distillation residues, especially for distillation
residues produced at 5508C.
Figure 4 represents the GC–MS profiles of upgraded sunflower
oils, hydrocarbon fuels and distillation residues. For upgraded
sunflower oils produced at 4508C and 5508C, the same main
chemical composition of 9-octadecenoic acid, (E)- was assigned
the peak eluting at 9.118 min and 9.095 min, respectively. For
upgraded sunflower oils produced at 5008C, phenol, 2,20 -methy-
lenebis[6-(1,1-dimethylethyl)-4-ethyl- was assigned the peak
eluting at 12.002 min. Phenol, 2,20 -methylenebis[6-(1,1-dimethy-
lethyl)-4-ethyl- might be helpful to form aromatic hydrocarbons
for bio-jet fuel production in the future. After distillation, 10-
methylnonadecane was the main chemical composition in the
hydrocarbon fuels produced at 4508C, eluting at 11.985 min.
Docosane, 11-butyl- was the main chemical composition in the
hydrocarbon fuels produced at 5008C, eluting at 11.990 min. cis-1-
Methyl-2-(20 -propenyl)cyclopropane was the main chemical com-
position in the hydrocarbon fuels produced at 5508C, eluting at
11.041 min. The results prove that the reaction temperature af-
fected the main chemical component of hydrocarbon fuels. For all
distillation residues, the same main chemical composition of 9-
octadecenoic acid, (E)- was assigned the peak eluting at 9.124 min,
9.152 min and 8.981 min, respectively.
Oxygen content
The oxygen content of oils affects their specific energy and com-
bustion [32]. After the catalytic cracking, some oxygen atoms in
sunflower oils were removed in the form of H2O, CO and CO2.
Some of the produced H2O was dissolved in the upgraded sun-
flower oils. CO and CO2 were evaporated away as components of
the non-condensable gases. It can be seen from Table 5 that the
oxygen content of the upgraded sunflower oils was between 6.19%

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New Biotechnology  Volume 32, Number 2  March 2015 RESEARCH PAPER

TABLE 4
Main chemical compositions of distillation residues produced at 4508C, 5008C and 5508C
Temp. (8C) No. Component Formula RT (min) Area %
450 1 9,17-Octadecadienal, (Z)- C18H32O (C18:2) 9.032 4.01
2 9-Octadecenoic acid, (E)- C18H34O2 (C18:1) 9.124 78.50
3 Methyl 16-methyl-heptadecanoate C19H38O2 (C19:0) 9.347 3.73
4 Heneicosane C21H44 (C21:0) 10.703 1.50
5 Hexadecane C16H34 (C16:0) 11.367 3.80
6 1,13-Tetradecadiene C14H26 (C14:2) 12.322 2.80
7 E,Z-1,3,12-Nonadecatriene C19H34 (C19:3) 12.379 1.67
8 Tricosane C23H48 (C23:0) 12.694 1.82
9 Pentacosane C25H52 (C25:0) 13.535 0.60

Research Paper
500 1 9-Octadecenoic acid, (E)- C18H34O2 (C18:1) 9.152 90.20
2 Octadecanoic acid C18H36O2 (C18:0) 9.358 5.56
3 4-Methyldocosane C23H48 (C23:0) 10.708 0.71
4 Heneicosane C21H44 (C21:0) 11.366 0.64
5 Tricosane C23H48 (C23:0) 11.990 0.74
6 Methyl 20-methyl-heneicosanoate C23H46O2 (C23:0) 12.190 0.78
7 13-Hexacosyne C26H50 (C26:2) 12.322 0.55
8 Heptadecane C17H36 (C17:0) 12.694 0.78
550 1 9-Octadecenoic acid, (E)- C18H34O2 (C18:1) 8.981 89.50
2 9-Octadecenamide, (Z)- C18H35NO (C18:1) 11.035 10.30
3 Bicyclo[4.1.0]heptane,-3-cyclopropyl,-7-hydroxymethyl, trans C11H18O (C11:0) 16.288 0.10
4 1H-indene, 1-(diphenylmethylene)- C22H16 (C22:11) 18.113 0.10

and 7.78%. There were several hydrocarbons produced in the
upgraded sunflower oils. However, oxides of more than 37% were
remaining in the upgraded sunflower oils. After distillation, the
oxygen content of hydrocarbon fuels decreased to 3.81–4.24%.
Similar observations were found in Yang’s study, where the oxygen
content of hydrocarbon oils varied from 1.97% to 4.50% [31].
Since sunflower oils have an oxygen content of 10.2%, the ZSM-5
catalyst was effective of reducing the oxygen content of the
hydrocarbon fuels. Hydrocarbon fuels contained a higher content
of hydrocarbons and a lower content of oxides than upgraded
sunflower oils, indicating distillation was effective of vaporizing
the lighter components to obtain products with narrower boiling
ranges. However, further refining is necessary to remove oxygen
atoms in the hydrocarbon fuels in the future. For distillation
residues, their oxygen content was between 8.12% and 8.78%.
This might be explained by the fact that many large molecules
such as oxides remained in distillation residues. The oxygen
content of distillation residues increased with the increase in
the reaction temperature from 4508C to 5508C, which was in
accord with the increasing oxide content of distillation residues
produced from 4508C to 5508C.
Physical properties of products
Table 6 shows some physical properties of upgraded sunflower oils,
hydrocarbon fuels, and distillation residues. Some undesirable
properties of sunflower oils were improved through the catalytic
cracking and distillation treatment. Acidity could cause poor fuel
stability, deposit formation and corrosion of mild steel. All the
liquid products in this study showed acidity. After the catalytic
cracking, the upgraded sunflower oils had a higher pH than that of
sunflower oils, which is a good sign. The pH of the upgraded
sunflower oils produced at different reaction temperatures showed
no significant difference, varying from 4.75 to 5.38. After distilla-
tion, the pH of hydrocarbon fuels did not change much. The pH of
hydrocarbon fuels in this study was similar to that of the light oil
upgraded over HZSM-5 reported by Zhang et al. [33]. The pH of
distillation residues varied from 4.16 to 5.71.
It is obvious from Table 6 that the dynamic viscosity of upgraded
sunflower oils decreased greatly compared to sunflower oils. Dynam-
ic viscosity is mainly affected by the chemical structure of the oils or
fuels such as chain length and unsaturation degree [34]. The dynamic
viscosity of the upgraded sunflower oils obtained at 4508C was
highest among all upgraded sunflower oils, which might be due to
their high fatty acid content. The dynamic viscosity of upgraded
sunflower oils cracked at 5008C was the lowest since there were no
fatty acids in them. After distillation, the dynamic viscosities of all
hydrocarbon fuels decreased and the dynamic viscosities of all distil-
lation residues increased compared to the upgraded sunflower oils.
Perhaps the light chemical molecules were condensed and collected
as hydrocarbon fuels, and the heavier chemical molecules and more
complicated molecular structures were left in the distillation residues.
The dynamic viscosity of jet fuel was not higher than 2.00 cP [35]. The
catalytic cracking method is quite helpful in producing hydrocarbon
fuels that meet the dynamic viscosity requirement of bio-jet fuel.
Distillation residues produced at 4508C had a much higher dynamic
viscosity than both distillation residues produced at 5008C and
5508C. This is probably caused by the higher content of large mole-
cules in the distillation residues produced at 4508C.
The water content of liquid products is given in Table 6. The
chemical reactions during the sunflower oil cracking process could
be illustrated in Eqns 4–6 [36].
Sunflower oils ! long-chain Cx Hy þ long-chain oxygenated Cx Hy
ðthermalÞ (4)
Long-chain Cx Hy ! paraffins þ olefins ðthermal þ catalyticÞ
(5)
Long-chain oxygenated Cx Hy ! long-chain Cx Hy þ H2 þ CO
(6)
þ CO2 þ H2 O ðthermal þ catalyticÞ

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 RESEARCH PAPER New Biotechnology  Volume 32, Number 2  March 2015
Research Paper

FIGURE 4
GC–MS analysis of USO obtained at (a) 4508C, (b) 5008C, and (c) 5508C; HF obtained at (d) 4508C, (e) 5008C, and (f) 5508C; DR obtained at (g) 4508C, (h) 5008C,
and (i) 5508C.

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New Biotechnology  Volume 32, Number 2  March 2015
Fig. 0020. (Continued ).
Obviously, water was one by-product during the catalytic crack-
ing process. The water content of upgraded sunflower oils cracked
at 4508C was 0.24%. For the upgraded sunflower oils cracked at
5008C and 5508C, the water content was much lower than 0.24%.
It indicates that the reaction temperature affected the chemical
reactions during the catalytic cracking process. For hydrocarbon
fuels and distillation residues produced at 4508C, the water con-
tent was undetected using the Karl Fischer Titrator V20. This
indicates that the water content was very low, considered as zero.
After distillation, the water content of hydrocarbon fuels was equal
to or lower than that of the upgraded sunflower oils. Also, the
water content of all hydrocarbon fuels was not higher than 0.04%.
The moisture content of jet fuel was lower than 0.1% [35]. There-
fore, hydrocarbon fuels have met the moisture content require-
ment of bio-jet fuel.
The densities of liquid products are shown in Table 6. The
density of fuel plays a significant role in airless combustion sys-
tems because it would affect the efficiency of fuel atomization [37].
For the upgraded sunflower oils cracked at 4508C and 5508C, the
RESEARCH PAPER
Research Paper
densities were the same (0.84 g/mL). The density of the upgraded
sunflower oils cracked at 5008C was 0.80 g/mL, which was lower
than 0.84 g/mL. After distillation, the large molecules and com-
plicated structures were left in the distillation residues. The small
molecules and compositions with simple structures were collected
as hydrocarbon fuels. The densities of hydrocarbon fuels produced
at 4508C, 5008C and 5508C were 0.81 g/mL, 0.79 g/mL and 0.83 g/
mL, respectively. During the chemical composition analysis, fatty
acid and ester were found in the hydrocarbon fuels produced at
4508C and 5508C. Nevertheless, only hydrocarbons were found in
the hydrocarbon fuels produced at 5008C, thus leading to their
lower density. The density of jet fuel was between 0.78 and 0.84 g/
mL [38,39], the densities of all hydrocarbon fuels are in the range
of the jet fuel density. The densities of distillation residues were
equal to or higher than those of hydrocarbon fuels.
The heating values of liquid products are listed in Table 6.
Energy is released by breaking carbon–hydrogen and carbon–car-
bon bonds in oils and converting them to hydrogen–oxygen and
carbon–oxygen bonds [40]. The heating values of the upgraded
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 RESEARCH PAPER New Biotechnology  Volume 32, Number 2  March 2015

TABLE 5
The oxygen content of upgraded sunflower oils, hydrocarbon fuels and distillation residues
Temp. (8C) Product Oxygen content (wt%)
450 Upgraded sunflower oils 7.78  0.13
Hydrocarbon fuels 3.81  0.18
Distillation residues 8.12  0.99
500 Upgraded sunflower oils 7.74  0.18
Hydrocarbon fuels 3.94  0.78
Distillation residues 8.35  2.42
550 Upgraded sunflower oils 6.19  0.03
Hydrocarbon fuels 4.24  0.72
Research Paper

Distillation residues 8.78  0.34

TABLE 6
Physical properties of upgraded sunflower oils, hydrocarbon fuels and distillation residues
Temp. (8C) Product pH Dynamic viscosity (cP) Moisture content (%) Density (g/mL) Heating value (MJ/kg)
Sunflower oils 3.57 73.9 0.10 0.88 39.6
450 Upgraded sunflower oils 5.38  0.06 1.64  0.04 0.24  0.01 0.84  0.02 42.0  0.08
Hydrocarbon fuels 5.10  0.14 0.93  0.02 Undetected 0.81  0.02 42.7  0.09
Distillation residues 5.71  0.02 27.1  0.85 Undetected 0.84  0.03 41.5  0.07
500 Upgraded sunflower oils 4.75  0.01 1.02  0.01 0.04  0 0.80  0.02 41.6  0.01
Hydrocarbon fuels 5.15  0.21 0.30  0.01 0.04  0 0.79  0.01 41.8  0.04
Distillation residues 4.16  0.01 2.02  0.04 0.07  0 0.79  0.06 41.2  0.24
550 Upgraded sunflower oils 5.62  0.05 1.23  0.06 0.05  0.01 0.84  0 41.7  0.02
Hydrocarbon fuels 5.75  0.35 0.97  0 0.02  0 0.83  0.01 42.1  0.05
Distillation residues 5.32  0.51 2.88  0.02 0.02  0 0.84  0.05 41.4  0.10
Jet fuel (ASTM standard) – 2.00 [35] <0.10 [35] 0.78–0.84 [38,39] 42.8 [38,41]

sunflower oils cracked at 4508C, 5008C and 5508C varied between The yield of products
41.6 and 42.0 MJ/kg. It is obvious that the upgraded sunflower oils Table 7 shows the yield of upgraded sunflower oils, hydrocarbon
had higher heating values than those of sunflower oils. After distil- fuels and distillation residues obtained during the catalytic crack-
lation, the heating values of hydrocarbon fuels increased further ing and distillation process. During the distillation trials, about
because a higher hydrocarbon content was obtained. The heating 3.0% of the oil vapor was lost using a sophisticated distillation
values of hydrocarbon fuels varied from 41.8 to 42.7 MJ/kg, which system. The oil vapor loss might be due to a fact that liquid
are similar to those of hydrocarbon oils in Yang’s study (41.2– particles remained inside the distillation tube on the wall. In this
43.8 MJ/kg) [31]. The heating values of distillation residues were study, the oil vapor loss was considered as 3.0%. The yield of
lower than those of hydrocarbon fuels. One probable reason is that upgraded sunflower oils cracked at 4508C and 5508C was similar,
breaking the carbon–oxygen bonds in the molecules does not but the yield of upgraded sunflower oils cracked at 5008C was
release energy because the bonds are reformed in the combustion much lower. The results suggest that the reaction temperature had
process. The heating value of jet fuel was higher than 42.8 MJ/kg an effect on the yield of upgraded sunflower oils, consistent with
[38,41] which is slightly higher than that of hydrocarbon fuels, the finding of Savage’s study [23]. The purpose of this study is to
indicating that the optimization of the cracking parameters is produce hydrocarbons for future bio-jet fuel production, which
needed to improve the heating value of hydrocarbon fuels. means hydrocarbon fuels are the final product. The highest
In summary, after catalytic cracking, the upgraded sunflower
oils have a lower dynamic viscosity and density, higher pH and TABLE 7
heating value than sunflower oils. The large molecules in the The yield of upgraded sunflower oils, hydrocarbon fuels and
sunflower oils were broken into smaller ones during the catalytic distillation residues
cracking process. However, the upgraded sunflower oils were a Temp. (8C) Product Yield (wt%)
mixture containing mainly oxygenates and hydrocarbons. Distil-
450 Upgraded sunflower oils 41.1
lation is an effective method of reconstructing the molecules to Hydrocarbon fuels 59.4
further improve the properties of the upgraded oils. After distilla- Distillation residues 37.6
tion, a higher content of hydrocarbons was obtained. Hydrocar- 500 Upgraded sunflower oils 33.2
bon fuels have a lower dynamic viscosity, lower density, lower or Hydrocarbon fuels 63.0
equal moisture content and higher heating value than upgraded Distillation residues 34.0
sunflower oils. The distillation residues contained a high content 550 Upgraded sunflower oils 40.7
of fatty acids, which means that they might be recycled for further Hydrocarbon fuels 73.9
catalytic cracking improving the hydrocarbon fuel yield. Distillation residues 23.1

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New Biotechnology  Volume 32, Number 2  March 2015
FIGURE 5
The relative content of non-condensable gas components produced at three
reaction temperatures.
conversion efficiency from sunflower oils to hydrocarbon fuels was
30.1% that was obtained at 5508C. The yield of hydrocarbon fuels
produced at 5508C was the highest followed by hydrocarbon fuels
produced at 5008C and 4508C. The reaction temperature affects
the chemical composition of upgraded sunflower oils, which
influences the hydrocarbon fuel yield.
GC analysis of non-condensable gases
The relative content of non-condensable gas components pro-
duced at three different reaction temperatures is presented in
Fig. 5. The main chemical reactions occurring inside the ZSM-5
catalyst included dehydration, decarbonylation, isomerization
and decarboxylation. These reactions could remove oxygen as
water, carbon dioxide and carbon monoxide. Also, the carbon
and hydrogen atoms could be converted into olefins and other
hydrocarbons. During the catalytic cracking of sunflower oils at
three different reaction temperatures, all the non-condensable
gases contained CH4, C2H6, C2H4, C3H8, C3H6, C4H10, C4H8,
C5H12, H2, CO and CO2. Similar non-condensable gas components
were found in Mo and Savage’s research [23]. The production of
CH4 indicates that the ZSM-5 catalyst was able to crack and convert
fatty acids into the smallest fraction of hydrocarbons. The multiple
chemical reactions such as dehydrogenation, deoxidation and
dehydration produced light hydrocarbons from C1 to C5. Hydro-
gen might be generated from the dehydrogenation reaction. This
is consistent with the finding of Amin et al. [27]. Nevertheless,
some hydrogens might be attracted to unstable species producing
more stable products such as C3H8 and C4H10. CO and CO2 might
be formed from light olefins such as C2H4 and C3H6.
At the reaction temperature of 4508C, the total light hydro-
carbons occupied 5.51%. The content sum of H2, CO and CO2 was
0.61%. For the catalytic cracking of sunflower oils at 5008C, the
total light hydrocarbons occupied 5.45%. The content sum of H2,
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Acknowledgements
This study was funded by the U.S. Department of Transportation
through NC Sun Grant Initiative under Grant No. SA0700149. The
authors would like to thank Dr Douglas Raynie, Ms Changling Qiu
and Ms Shanmugapriya Dharmarajan for helping in the GC/MS
measurement, and thank Ms Xiaomin Wang for helping in the BET
measurement. The XRD equipment is supported by the NSF MRI
grant (Award No. 1229577). All the support in experiment from Mr
Yang Gao, Yinbin Huang and Zhongwei Liu is gratefully
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