Fuel 260 (2020) 116345

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Fuel
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Full Length Article

The production of bio-jet fuel from palm oil derived alkanes T

Cheng-Han Lin, Yu-Kai Chen, Wei-Cheng Wang

Department of Aeronautics and Astronautics, National Cheng Kung University, Tainan 70101, Taiwan

ARTICLE INFO ABSTRACT

Keywords: Bio-jet fuel currently represents one of the solutions for reducing the emissions from aircraft without engine modi fications.
Bio-jet fuel This study mainly focused on producing the jet fuel blendstock from glyceride-based oil through hydro-processing and hydro-
Hydro-processing Hydro- cracking/isomerization. The palm oil was selected as the glyceride-based feedstock and was first converted into hydro-
isomerization/cracking Nickel- processed alkanes within the diesel range through hydro-processing, which has been reported in the authors ’ previous work.
based catalyst SAPO-11 zeolite
The hydro-processed alkanes, in this paper, were turned into jet fuel range products through hydro-cracking/isomerization
Aircraft engine emission
over the nickel-silver (NiAg) supported on silico-aluminio-phosphates (SAPO-11) catalyst. Catalyst characterizations were
first performed through XRD for the fresh and used catalysts for understanding the performance of the catalyst during the
reaction. The effects of the reaction parameters such as temperature, pressure, and liquid hourly space velocity (LHSV) on the
carbon distributions, isomer-to-normal (I-to-N) alkane ratios and aromatics contents were investigated to find the proper
conditions for producing bio-jet fuel over the NiAg/SAPO-11 catalyst.

1. Introduction
Bio-jet fuel represents the fuel produced from bio-resource and can be
used in present aviation engines. Compared to the aviation fossil-fuel, bio-jet
fuel has advantages such as: (1) reduced greenhouse gas emission (2)
renewable resources (3) compatible with conventional fuel
(4) sustainable and clean combustion [1]. To maintain the function of
aviation vehicles, the properties of aviation fuel must meet the speci-fications.
Currently, aviation biofuel can be produced through several routes as shown
in Table 1 [2].
Hydro-treating free fatty acids (HFFA) has been the most promising
technology among all processes owing to its sustainable feedstock and
production process. HFFA produces aviation biofuel from glycerides through
a series of hydrogenation including hydro-processing and hydro-
isomerization/cracking. Ester and fatty acid from vegetable oil and other
triglycerides are treated by hydro-processing to remove oxygen and produce
long chain of normal alkanes. The long chain of normal alkanes are converted
by hydro-isomerization/cracking into straight and branched chain alkanes. In
the hydro-processing, oxygen inside ester and fatty acid is removed through
hydro-deoxygenation, decarboxylation, and decarbonylation reaction.
Alkanes with even-number carbons are obtained from hydro-deoxygenation
and Alkanes with odd-number carbons are obtained from both
decarboxylation and decarbonylation [3]. The alkanes produced from hydro-
processing are the hydrocarbons within the diesel range, therefore, the
product can
also be used as alternative diesel fuel [4]. The deoxygenated alkanes is then
converted through hydro-isomerization/cracking at high tem-perature and
high hydrogen pressure environment, which hydro-cracking is to produce
short-chain straight alkanes for reducing the freezing point while ensuring a
certain flash point and energy density and hydro-isomerization is for
producing suitable isomers and ensuring the product to have good cold flow
property [5].
The quality of hydro-processed alkanes is important to the perfor-mances
of further hydro-isomerization/cracking. Co/H-ZSM-22 has been used as a bi-
functional catalyst in hydro-deoxygenation and hydro-isomerization of
palmitic acid at the temperature of 260 °C, the hydrogen pressure of 2 MPa
and the reaction time of 4 h, resulting in 99% of conversion and the ratio of
isomer and normal alkanes of 2 [6]. This indicated that the hydro-processed
product would be easier to be hydro-cracked. Most of the deoxygenated
alkanes are produced from sulfided catalyst such as NiMo-S/Al 2O3 [7],
however, sulfur component would contain in the deoxygenated product which
leads to the reduced selectivity of hydro-isomerization. Therefore, developing
a new non-sulfide catalyst of deoxygenation is necessary [8].
Producing high-quality aviation biofuel for petro-jet blending strongly
depends on the catalyst and reaction parameters, and the front one is more
significant than the latter one. Yang and co-works [9] discussed the influences
of transitional metal (nickel) and its promoter (copper) on hydro-cracking and
hydro-isomerization, and found that 3% of nickel and 1.5% of copper could
produce higher isomer

Corresponding author.
E-mail address: wilsonwang@mail.ncku.edu.tw (W.-C. Wang).

https://doi.org/10.1016/j.fuel.2019.116345
Received 7 July 2019; Received in revised form 30 September 2019; Accepted 2 October 2019
0016-2361/ © 2019 Elsevier Ltd. All rights reserved.
C.-H. Lin, et al.
Table 1
The technologies for producing aviation biofuel.
Technology Research unit
Fischer-Tropsch Synthetic Paraffin Kerosene (FT-SPK) Sasol, Shell
Alcohol-To-Jet Synthetic Paraffin Kerosene (ATJ) Honeywell, UOP
Hydro-processing Ester and Fatty Acid (HFFA) Honeywell, UOP Neste Oil
Synthesized Iso-Paraffin (SIP) Total
selectivity than a monometallic nickel, owing to the change in elec-tronic
behaviors of nickel by copper. Conventional hydro-cracking and hydro-
isomerization catalysts in petroleum plant were Pt-supported by active
alumina dioxide or zeolites, Pt/Al 2O3 or Pt/SAPO-11. Compared to platinum,
palladium is more reactive towards hydrogen. Pd/SAPO-11 was viewed to
have better activity in hydro-cracking and hydro-isomerization [10], however,
due to the economic consideration, it is necessary to find a cheaper metal for
the feasibility of commercializa-tion. Liu and co-works [11] carried out a new
hydro-isomerization/ cracking catalyst, a nickel-based catalyst promoted by
silver, to produce aviation fuel-like hydrocarbons.
A two-step production process, including hydro-processing and hydro-
isomerization/cracking, was proposed in this study. NiMo-S/ Al2O3 was
selected as the hydro-procssing catalyst and NiAg/SAPO-11 was chosen as
the hydro-isomerization/cracking catalyst, due to its high reactivity and
selectivity, and additionally the availabilities of nickel and silver [11]. As for
the support, SAPO-11 is considered as a superior hydro-cracking and hydro-
isomerization support in hydro-processed diesel-ranged hydrocarbon to
aviation fuel-ranged hydro-carbon [12]. The effects of the reaction conditions
and characteristics of the catalyst were also studied.
2. Experimental
2.1. Material
In this study, the feedstock was selected as crude palm oil provided by
local chemical raw material store. The main compositions of the crude palm
oil and hydro-processed products are shown in Table 2. Before the hydro-
processing experiment, the crude palm oil was heated to the temperature of 70
°C in order to increase its fluidity. Hydrogen (99.999%) and nitrogen
(99.99%) were provided by Yun Shan In-dustrial Corporation. The catalyst
for hydro-processing was selected as NiMo-S/Al 2O3 (2% Ni, 18% Mo,
sulfided) provided by A-plus Inc. The hydro-isomerization/cracking catalyst,
NiAg/SAPO-11 (25 wt% Ni, Ni/ Ag molar ratio = 44, was prepared in-house
[11] through the wet im-pregnation method. The commercial SAPO-11
support (SAPO-11, (SiO2)0.6(Al2O3)1(P2O5)1, 40.0 g, Si/Al molar ratio = 0.3,
provided by A-plus Inc.) (The EDX elemental analysis of SAPO-11 is
presented in Table 3) was wetted with a solution containing the mixture of Ni
(NO3)2 6H2O (nickel(II) nitrate hexahydrate, 66.35 g) , AgNO 3 (silver nitrate,
0.28 g) salts and deionized water (40 ml). The mixing suspen-sion and clay
were homogeneously stirred for 8 h at room temperature. After stirring, the
impregnated catalyst was dried at 180 °C for 8 h in the oven. Then the dried
solid was calcined at 500 °C for 5 h in the air to remove the ionic solvent. The
weight loss was about 35% after
Table 2
The compositions of feedstocks for hydro-processing and hydro-cracking/iso-merization
(wt %).
Palmitic, Stearic, 18:0 Oleic, Linoleic,
C16:0 C18:1 C18:2
Crude palm oil 49.8 3.6 36.2 7.9
n-C15 n-C16 n-C17 n-C18
Hydro-processed 14 56 5 25
alkanes
2
Fuel 260 (2020) 116345
Feedstock Aromatics
Coal, Nature gas, Biomass Low
Starch, Carbohydrate, Cellulose Low
Vegetable oil, Animal fat, Waste oil Low
Starch, Carbohydrate, Cellulose Low
Table 3
Elemental Analysis of SAPO-11.
SAPO-11 Al Si P
Weight (%) 40.22 13.16 46.62
Atomic (%) 43.03 13.53 43.45
calcination and the color was changed from light green to gray. The calcined
catalyst was reduced at 400 °C and 900 psi for three hours. After reduction,
the color of the catalyst became black. The surface area, pore size and average
2 −1
pore volume of the NiAg/SAPO-11 catalyst are 42.7 m g , 11.6 nm and
3 −1
0.152 cm g , respectively.
2.2. Catalyst characterization
In this study, the catalyst characterization was focused on the home-made
NiAg/SAPO-11. The powder X-ray diffraction (XRD) was applied to confirm
the impregnated catalyst. The powder X-ray diffraction was operated using
the CuKα radiation (λ = 1.5406 Å) at 40 kV, 40 mA and a scanning angle of
2θ = 10˚-80˚.
2.3. Experiment equipment
Fig. 1 shows the system for hydro-processing and hydro-cracking/
isomerization, which can be divided into three sections: (1) reactant system:
the gas (hydrogen) and liquid (feedstock) reactants were sent into the reactor
through a mass flow controller (model 5850i, brooks, 407 West Vine Street
Hatfield, PA, USA) controlled by a Lab-view software and a high-pressure
pump with a flow rate of 0.2 to 40 ml/min (SN-26158, Eldex, Napa, CA,
USA), respectively; (2) reaction system: a fixed bed reactor made of SUS
316L stainless steel with a diameter of 12.7 mm and the length of 400 mm
was applied and was filled up with the catalysts (5 g each). A pressure relief
valve (R3A, Swagelok, Solon, OH, USA) was installed at top of the reactor
for the safety pressure release and an electric heater (Cl-35E, Ching Ying,
Taiwan) covering the reactor was used to supply the heat; (3) sampling
system: tube-in-tube heat exchangers were used for the condensations before
the sample collection. Gas-liquid separators were applied to split the gas and
liquid products by gravity. In the gas–liquid separator, the gas and liquid
products were separated by gravity. In addition, a back pressure regulator
(BPR, Tescom, St. Louis, MO, USA) was installed within the sampling
system to control the system pressure.
(1: H2 Tank; 2: N2 Tank; 3: Mass Flow Controller; 4: Pressure Gauge;
5: Hot plate Stirrer; 6: High Pressurized Pump; 7: Pressure Relief Valve;
8: K Type Thermocouple; 9: Reactor; 10: Heater; 11: Temperature
Controller; 12: Condenser; 13: Circulator; 14: Liquid-Gas Separator; 15: Back
Pressure Regulator 16: Empty Gas Cylinder 17: Pressure Relief Regulator 18:
Product Container; 19: 5 ports Valve; 20: Lab view Interface System; 21: GC-
TCD)
2.4. Experimental procedures
Before each experiment, a leaking test was performed to ensure no system
leakage. Nitrogen was used to purge the system for removing the oxygen
content in the system. The crude palm oil was first hydro-pro-cessed into
diesel-range alkane products at the temperature of 400 °C,
C.-H. Lin, et al. Fuel 260 (2020) 116345

Fig. 1. Experimental setup.

the pressure of 6 MPa, the hydrogen-to-oil molar ratio of 13.6 and the weight temperature was 200 °C. The initial oven temperature was 70 °C and was held
−1 for 2 min, and then increased to 180 °C at 10 °C / min, and held for 5 min.
hour space velocity (WHSV) of 4 h . Detail experimental procedures can be
found in the authors’ previous study [13,14]. For further processing hydro- The gaseous products were quantified by the external standard method. The
processed alkanes into jet fuel range products, the reactor was heated to 400 experimental error of the GC measurements was ± 5%.
°C and hydrogen was flowed at a rate of 50 sccm for two hours to reduce and
activate the catalyst. After this, the temperature, pressure and hydrogen The conversion, selectivity, I-to-N ratio and aromatics
flowrate were adjusted to the re-action conditions. The feedstock was then
results were obtained through the following equations:
injected into the reactor through a high-pressure pump. The products, after
condensation and gas–liquid separation, the gas and liquid products were Conversion (%) = TG − TG × 100%
palmoil product
collected for further analysis.
TG (1)
palmoil

where TGpalmoil and TGproduct are the quantities of triglyceride in the palm oil
2.5. Product analysis and the product, respectively.
Si
Selectivity(%) = × 100%
Gas chromatography with flame ionization detector and mass
spectrometer (GC-FID, GC–MS-QP2010, SHIMADZU) equipped with the Tp (2)
same HT-5 Agilent J & W columns (length 30 m, diameter 0.250 mm, film where Si andTp are the quantities of C8-C16 hydrocarbons and the total
0.25 µm) was used to analyze the liquid samples. The samples were diluted product, respectively.
with solvent (HPLC grade hexane, Fisher Scientific) with ratio of 60, and then IA (3)
1μL diluted sample was injected into GC–MS/FID. The flow rate of column I − to − Nratio =
was 2 ml/min with a split ratio of 50. An injection temperature was set at 200 NA
°C, column oven temperature at 35 °C and detector temperature at 280℃. where IA and NA are the quantities of isomerized alkanes and normal
The temperate gradient in the program was from 35 to 200 °C. The n-alkanes
alkanes, respectively.
standard (C8-C20, 99.99%, 40 mg/ L, PC-code 101685440) was used to
Ta
calibrate the liquid sample quan-tification. Inorganic gaseous products, Aromatics(%) = × 100%
including CO, CO2, CH4, and H2 were analyzed through GC-TCD with a Tp (4)
packed column (TDX-01 column, 3 m × 3 mm) using He as the carrier gas.
The injector where Ta and Tp are the quantities of total aromatics and total product,
respectively.

3
C.-H. Lin, et al.
Fig. 2. XRD patterns of NiAg/SAPO-11 catalyst (a) fresh (activated), (b) spent.
3. Results and discussions
Turning the glyceride-based oil into jet fuel includes the process of hydro-
processing and hydro-cracking/isomerization. The results of hydro-
processing, including the catalyst characterization and reaction testing, can be
found in the authors’ previous study [13,14]. This paper focused on the
examination of NiAg/SAPO-11 catalyst as well as the reactions of converting
hydro-processed alkanes into jet fuel range products.
3.1. Characteristics of the catalyst
Fig. 2 presents the difference of catalyst structures between fresh and
spent catalyst. The fresh one (Fig. 2a) has lower diffraction peaks at 2θ = 37°,
43°, and 63°, which were suspected to be nickel oxide (NiO) [15]. Obviously,
the diffraction peaks of NiO decreased while the dif-fraction peaks of metal
nickel (2θ = 52°, 57°, and 76°) increased. This proved that NiO has been
reduced to Ni [15]. At 2θ = 43° the in-tensities of the peaks for the fresh and
used catalysts were around 2000 and they are quite similar, owing to the
incomplete reduction of NiO to Ni. On the other hand, the peaks at 37° and
63° have shown that the NiO was well-reduced. Although the reduced nickel
metal has high hydrogenation capability, the growth of the metal grain led to
the de-crease in dispersion. Poor dispersion represents fewer active site on the
catalyst surface, which indicated that spent catalyst was worse than the fresh
catalyst in terms of hydrogenation capability. It would be inter-esting to
determine the Ni crystallite size in the future work for de-veloping the
reusability of the catalyst.
3.2. Distribution of carbon number and isomer-to-normal alkane ratio (I-to-N)
at various parameters
The impacts of reaction parameters including temperature, pressure and
liquid hourly space velocity (LHSV) on the carbon number and I-to-N ratio of
the products were studied.
3.2.1. Effects of temperature on the distributions of carbon number and I-to-N
ratio
The distribution of carbon number with different temperatures is shown in
Fig. 3. The experiment was conducted with varying reaction
4
Fuel 260 (2020) 116345
−1
temperature while fixing the pressure at 3 MPa, the LHSV at 1 h and the
hydrogen/oil molar ratio of 13.6). The major carbon numbers in the feed of
hydro-isomerization/cracking (hydro-processed alkanes) was n-C 15, n-C16,
and n-C18. With the increase in temperature, the contents of C 15 to C18
decreased and the ones of C 8 to C14 increased, due to the occurrence of
cracking. Compared to isomerization, which is a weak exothermic reaction,
cracking is an endothermic reaction and is more sensitive to the temperature
[16]. Because the cracking of the long chain hydrocarbons mostly happens in
the middle of the chain, C8 and C9 have the highest contents in cracked
product. Additionally, as the temperature reached 360 °C, the carbon
distribution was similar to the one in jet fuel [17]. As shown in Fig. 4, the
isomerization reaction in-creased with increasing temperature until 360 °C.
The I-to-N ratio of 1.5 was achieved at the temperature of 360 °C. It is
interesting to see that the I-to-N ratio was increased sharply between the
temperatures of 340 °C and 360 °C, meaning that the isomerization reaction
was active within this temperature region. Above 360 °C, the increase in
shape-selective cracking reactions made the SAPO-11 catalyst be a shape-se-
lective catalyst by possessing 10-MR pores, which reduced the I-to-N ratio.
3.2.2. Effects of pressure on the distributions of carbon number and I-to-N
ratio
Various pressures were conducted at the fixed reaction conditions
−1
(temperature of 380 °C, LHSV of 1 h and hydrogen/oil molar ratio of 13.6).
Figs. 5 and 6 show the carbon distributions and I-to-N ratio at varying
pressures. Dramatically conversions of C 15, C16 and C18 were found when the
pressure reached 3 MPa. The I-to-N ratio reached 2.2 as the pressure went up
to 6 MPa. It can be seen that the lighter hydro-carbons and the yield of
isomers increased gradually with increasing pressure, which agreed with the
results reported by Chao and his co-workers [18]. The high pressure
environment increases the level of cracking, resulting in the yields of lighter
fraction. Also the isomer contents increase simultaneously. As the pressure is
further raised, the hydrogen is more likely combined with hydrocarbon free
radical and therefore the isomer yields would be suppressed. It can be seen
from experimental results that the yields of lighter faction and isomers were
increased with increases in pressure within the pressure range from 3 MPa to
6 MPa. Isomerization reaction follows alkyl-carbenium ion mechanism and
the consecutive steps shown in Fig. 7 are (1)
C.-H. Lin, et al. Fuel 260 (2020) 116345

−1
Fig. 3. Distribution of carbon numbers at various temperature (pressure of 3 MPa, LHSV of 1 h and the hydrogen/oil molar ratio of 13.6). (HDO is the hydro-processed alkanes, the
feedstock for hydro-isomerization/cracking).

−1
Fig. 4. I-to-N ratio at various temperatures (pressure of 3 MPa, LHSV of 1 h and the Fig. 6. I-to-N ratio with various pressures (temperature of 380 °C, LHSV of 1 h
−1
and
hydrogen/oil molar ratio of 13.6).
hydrogen/oil molar ratio of 13.6).

Dehydrogenation on metal sites; (2) Protonation of olefins at Bronsted acid
sites resulting in the formation of a secondary alkycarbenium ion;
(3) Rearrangement of the alkycarbenium ion via the formation of transition
state cyclic alkycarbenium ion transition state; (4) Deproto-nation; (5)
Hydrogenation [19]. In alkycarbenium ion mechanism, as alkene gets
protonated to be alkycarbenium ion, enhancing the reaction pressure increases
the collision probability of the dissociated hydrogen and the alkycarbenium
ion, leading to faster reaction completion and higher catalytic efficiency.
Higher pressure decreases the long chain
hydrocarbons and increases medium chain hydrocarbons, which makes the
fuel meet the range of jet fuel.
3.2.3. Effects of LHSV on the distributions of carbon number and I-to-N ratio
LHSV represents a processing capacity of the catalyst at a stable
parameter. Figs. 8 and 9 show the variations of carbon numbers and I-to-N
ratio with changing LHSV, with fixed temperature of 360 °C, pressure of 6
MPa and hydrogen/oil molar ratio of 13.6. The shorter

−1
Fig. 5. Distribution of carbon numbers with various pressures (temperature of 380 °C, LHSV of 1 h and hydrogen/oil molar ratio of 13.6).

5
C.-H. Lin, et al. Fuel 260 (2020) 116345

Fig. 7. Functional pathways of hydro-isomerization and hydro-cracking of n-paraffins (Reproduced from Ref [19]).

hydrocarbon chains (C8 to C10) and isomers decreased with increasing LHSV LHSV. Al-Kandari et al. [20] had similar results and explanations on the
and the longer ones (C15 to C18) increased simultaneously. Sig-nificant effects of various LHSVs. Although the I-to-N ratio decreased with in-
−1 creasing LHSV, no significant change in isomerization selectivity was
conversions of C15, C16 and C18 occurred at the LHSV of 1 h . Increase
−1 −1
LHSV from 2 h to 4 h resulted in a decrease in I-to-N ratio by 44%. The observed.
−1 −1
carbon number changes with varying LHSV from 1 h to 4 h were minor.
This is caused by the longer reaction time. For the lower LHSV, reactants 3.3. The content of aromatics at various parameters
have sufficient time to diffuse into the channel as well as a cage of zeolite and
to contact the active site of catalyst, which results in more cracking and
The content of aromatics in jet fuel is an important index because
isomerization products compared to higher
aromatics improves the sealing performance and enhances the flash

Fig. 8. Distribution of carbon numbers at various LHSVs (temperature of 380 °C, pressure of 6 MPa and hydrogen/oil molar ratio of 13.6).

6
C.-H. Lin, et al. Fuel 260 (2020) 116345

Fig. 10 demonstrated that the content of aromatics increased with in-creasing

Fig. 9. I-to-N ratio at various LHSVs (temperature of 380 °C, pressure of 6 MPa and
hydrogen/oil molar ratio of 13.6).
temperature and reached 20% at the temperature of 380 °C, which agreed
with the results reported by Li et al [23]. The composi-tions of the aromatic
component at the temperature of 380 °C were detected as 10% benzene, 7%
di-aromatics and 3% poly-aromatics. Linear hydrocarbons could be converted
into aromatics through cycli-zation and aromatization at high reaction
temperature. The formation mechanism of aromatics are as follows: (1)
Alkanes are catalytically dehydrogenated into olefins on metal sites; (2)
Cycloalkanes was formed through the cyclization reaction on the acid sites;
(3) Part of the cycloalkanes are converted into aromatics and H 2 through the
dehy-drogenation reaction on the metal sites; (4) Another part of cycloalk-
anes are turned into aromatics and alkanes through the hydrogen transfer
reaction with olefins on the acid site. All of the above processes are metal and
acid bi-catalyzed reactions [24]. The dehydrogenation step is a rate
determining step in aromatics production and is ad-ditionally an endothermic
reaction which is favored by high tempera-ture and low pressure. This was
proved by observing the results in Figs. 10 and 11. The content of aromatics
dropped by 40% when doubling the pressure from 3 MPa to 6 MPa. Higher
hydrogen pressure led to high catalytic efficiency on isomerization instead of
aromatiza-tion. The minimum requirement of aromatic content in jet fuel is
8%, based on the ASTM D7566 specification [25]. This can be obtained by
performing the reaction at the temperature of 360 °C and the pressure of 3
MPa over the NiAg/SAPO-11 catalyst. Additionally, the experiment with the
optimal conditions (the temperature of 360 °C, the pressure of 3 MPa, the
−1
LHSV of 1 h and the H2/oil molar ratio of 13.6) was re-peated for
confirming the reproducibility of the catalyst behavior and the product yields,
as shown in Table 4. It can be seen that the devia-tions for the three repeating
experiment were acceptable.

3.4. The GC composition examination

The GC chromatography of the product obtained at the temperature of

Fig. 10. The content of aromatics at various temperatures. −1
380 °C, pressure of 6 MPa, LHSV of 1 h and hydrogen/oil molar ratio of
13.6 is shown in Fig. 12, and compared with the one of JP-5, as shown in Fig.
13. It can be seen that the glyceride-derived jet has slightly higher
hydrocarbon components on C8, C10, C16, C17 and C18 and slightly lower
ones on C11-C12 compared to petro-jet (JP-5), since the glyceride-derived jet
came from the fatty acids with 18 carbons. With proper distillation process,
the product can serve as the jet fuel blendstock. In terms of catalyst
improvement, stronger hydrogenation capability and acidity of the catalyst are
required for increasing the cracking activity to reduce the contents of C17 and
C18. The addition of citric acid can improve the metal dispersion to provide
better hydro-genation capability [26]. In addition, the Si-Al ratio as well as
the surface area of the SAPO-11 support can be modified to improve the
performance of the catalyst [27]. Further investigation in the future should be
conducted for improving the yield of renewable jet fuel.

Fig. 11. The content of aromatics at various pressures. 4. Conclusion

Table 4 The glyceride-based oil was converted into jet fuel blendstock through
Repetitions of the experiment with the optimal conditions. hydro-processing and hydro-isomerization/cracking, which in this study
mainly focused on turning the hydro-processed alkanes into jet fuel range
Aromatics content (%) I-to-N ratio Liquid product yield (%)
products over the catalyst of NiAg/SAPO-11. The XRD characterization of
1 9.0 1.5 55.6 the catalyst showed the reduced dispersion of metal on the surface of used
2 9.2 1.5 55.0 catalyst, which decreased the performance of the catalyst. High temperature
3 8.7 1.6 56.4
decreased the contents of C15 to C18 and increased the ones of C 8 to C14, due
to the occurrence of cracking. The hydrocarbons of C 8 and C9 showed high
point by its special physical and chemical properties [21]. In this study, the concentrations because the cracking of long chain hydrocarbons mostly
content of aromatics in the products was investigated with various happens at the middle of the chain. The I-to-N ratio increased sharply
temperature and pressure. The aromatics content was confirmed with the tests between the temperatures of 340 °C and 360 °C, indicating an active
in a certified laboratory at a local petroleum company. Tem-perature is the isomerization reaction within this temperature range. Increasing the reaction
most important parameter for producing aromatics [22]. pressure gradually in-creased the lighter hydrocarbons and the yields of
isomers, owing to the

7
C.-H. Lin, et al. Fuel 260 (2020) 116345

−1
Fig. 12. GC-FID chromatography of the product (temperature of 380 °C, pressure of 6 MPa, LHSV of 1 h and hydrogen/oil molar ratio of 13.6). (1.n-octane, 2.n-nonane, 3.n-decane,
4.n-undecane, 5.n-dodecane, 6.n-tridecane, 7.n-tetradecane, 8.n-pentadecane, 9.n-hexadecane, 10.heptadecane, 11.n-octadecane).

Fig. 13. GC-FID chromatography of JP-5. (1.n-octane, 2.n-nonane, 3.n-decane, 4.n-undecane, 5.n-dodecane, 6.n-tridecane, 7.n-tetradecane, 8.n-pentadecane, 9.n-hexadecane,
10.heptadecane, 11.n-octadecane).

collision of dissociated hydrogen and alkycarbenium ion. Increasing LHSV contents of C17 and C18 hydrocarbons, which can obtain high quality and high
resulted in the decrease in shorter hydrocarbon chains and iso-mers as well as yield of jet fuel blendstock without further distillation process.
the increase in longer hydrocarbon chains, but these changes within the
−1 −1
LHSV of 1 h – 4 h were minor. The first step of forming aromatics, the Acknowledgment
dehydrogenation step, favors high temperature and low pressure, which are
not favored by the isomerization reaction. The reaction conditions (the This project was supported by the Ministry of Science and Technology,
−1 Taiwan, through grant 107-2221-E-006 -135-.
temperature of 360 °C, the pressure of 3 MPa, the LHSV of 1 h and the
hydrogen/oil molar ratio of 13.6) performed in this study obtained 9% of
aromatics, which was sufficient to meet the jet fuel specifications. The metal References
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