Energy Conversion and Management 199 (2019) 112015

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Energy Conversion and Management

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

Renewable aviation fuel by advanced hydroprocessing of biomass: T

Challenges and perspective
Elaine Siew Kuan Whya, Hwai Chyuan Onga, , Hwei Voon Leeb, Yong Yang Gana,
⁎

Wei-Hsin Chenc,d, Cheng Tung Chonge

a
Department of Mechanical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia
b
Nanotechnology & Catalysis Research Centre (NANOCAT), Institute for Advanced Studies, University of Malaya, 50603 Kuala Lumpur, Malaysia
c
Department of Aeronautics and Astronautics, National Cheng Kung University, Tainan 701, Taiwan
d
Research Center for Energy Technology and Strategy, National Cheng Kung University, Tainan 701, Taiwan
e
China-UK Low Carbon College, Shanghai Jiao Tong University, Lingang, Shanghai 201306, China

ARTICLE INFO ABSTRACT

Keywords: Present-day, commercial airlines are getting into the use of bio-jet fuel, by blending vegetable oil derived bio-jet
Biodiesel fuel with fossil jet fuel in maximum up to 50%, which is ASTM-certified. In order to reduce the dependency on
Bio-jet fuel fossil jet fuel, recent research trend shows that most of the renewable aviation fuel or bio-jet fuel were derived
Biomass from the complex liquid biomass via hydroprocessing technology. Hence there is a necessity to have an insight
Deoxygenation
into the production technology, typically the hydroprocessing technology. Generally, hydroprocessing tech-
Hydroprocessing
Alternative energy
nology for the liquid biomass conversion into bio-jet fuel involved multi intermediate steps, such as deox-
ygenation, cracking and isomerization. This conventional process is further upgraded and simplified into single
step reaction, which minimizes the post-treatment effort to be done in every reaction step, and thus reduces the
production cost. Moreover, other economic factors such as catalyst price, hydrogen production cost and plant
size will also consider as major impacts towards biofuel production scale and cost. Therefore, this paper aims to
review the bio-jet fuel conversion technologies in a different perspective, by comparing the hydroprocessing
technology of bio-jet fuel (i.e. three-step process, two-step process, single step process), and the effect of reaction
variables (i.e. feedstock, catalyst, and reacting gas). The details of outputs for different hydroprocessing tech-
nology are also discussed herein. In summary, most research works have achieved positive findings in single step
process, by adapting hydrodeoxygenation process in majority. However, there are some limitation and chal-
lenges that can be further improved in the single step process, such as exploration on potential feedstock, de-
velopment of catalyst and optimization of reacting parameters. The energy, environmental and economic ana-
lysis on the advanced hydroprocessing of bio-jet fuel are yet to be conducted, in order to compare their merits.

1. Introduction
In recent decades, the impact of fossil fuels depletion and aug-
mentation of carbon emission from aviation sector have raised en-
vironmental awareness [1,2]. The aviation industry plays an important
role to generate socio-economic growth around the world. Thus, de-
mand of the fossil fuels usage in aviation sector has increased yearly
and expected to raise around 5% annually until 2030 [3]. According to
European Parliamentary Research Service (EPRS) in 2018, direct CO2
emissions from aviation sector in the European Union (EU) had ac-
counted for about 3% of global CO2 emissions. It is also expected that
CO2 emission from aviation sector will continuously to rise with the
anticipated growth in air traffic, by an annual average of 4.5–4.8% in
coming future. This could lead to a global fossil fuel CO2 emission grow
of 4.6–20.2% by mid-century [4,5].
Hence, the environmental concerns have urged for the vast devel-
opment of bio-jet fuel from renewable resources, in order to reduce
both reliance on fossil fuels and CO2 emission by maximum reduction of
68.1% in 2050 [5]. In 2018, the Federal Aviation Administration (FAA)
decided to replace 3.8 billion liters of petroleum fuel with bio-jet fuels,
which is approximately 5% of total aviation fuel consumption in U.S.
[6]. In the same year, International Air Transport Association (IATA)
reported that 165,000 flights had flown with bio-jet fuel blends. The
bio-jet fuel derived from renewable or recycled feedstocks can deliver
up to 80% reduction in carbon emissions over the complete life cycle of
the fuel [7,8]. Thus, current demand on bio-jet fuel has promoted the

⁎
Corresponding author.
E-mail addresses: onghc@um.edu.my, ong1983@yahoo.com (H.C. Ong).

https://doi.org/10.1016/j.enconman.2019.112015
Received 17 May 2019; Received in revised form 28 August 2019; Accepted 29 August 2019
Available online 11 September 2019
0196-8904/ © 2019 Elsevier Ltd. All rights reserved.
E.S.K. Why, et al.
needs on biofuel usage for aviation transportation [9]. In addition,
carbon price can also be marginally reduced by the availability of bio-
jet fuel, as the consumption of bio-jet fuel has covered 10% of total
bioenergy demand [10]. Moreover, such development will also lead to
high potential of job creation, income generation and regional devel-
opment in social sphere [11].
In general, bio-jet fuel is a mixture of hydrocarbons, which is
composed by n-paraffins, branched iso-alkanes (iso-paraffins), cyclic
alkanes (naphthenes) and aromatics [12]. However, the molecular
weights and carbon numbers of the fuel is highly depending on the
refinery process with specific fuel properties and usage. A typical mo-
lecular size distribution of jet fuel ranges from C8 to C16 [13]. In order
to replace fossil fuel with biofuel for aviation usage, renewable feed-
stock such as biomass is considered [14]. Common biomass feedstock
for bio-jet fuel production can be classified into groups as shown in
Fig. 1, which include (i) sugars and starch, (ii) oil crops, (iii) cellulosic
materials and (iv) wastes [15].
The listed feedstock in Fig. 1 can be processed into bio-jet fuel
through several conversion pathways, such as alcohol-to-jet, gas-to-jet,
oil-to-jet and sugar-to-jet as shown in Fig. 2 [12,16]. These conversion
technologies have been widely practiced by current industry, especially
the oil-to-jet conversion pathway which involves the method of hy-
droprocessing. Hydroprocessing technology has more advantages as
compared to other conversion pathways, which includes the flexibility
and utilization of low-quality feedstock. Besides, the separation stage of
the byproducts is not as complex as transesterification technology,
which additional cost is needed for product purification process
[17,18].
In current years, advanced hydroprocessing technology has been
improved either by simplifying the numbers of steps involved in hy-
droprocessing, or introduce other methods (i.e. co-pyrolysis, alkylation,
hydrothermal liquefaction) into the hydroprocessing pathway.
Although there are many literature studies focused on different con-
version pathway on bio-jet fuel synthesis that had been done by re-
searchers [19–21], the critical review specifically on hydroprocessed
bio-jet fuel alone is still lacking. In order to enhance the understanding
of hydroprocessing technology for future development and process
improvement, research gaps can be identified through reviewing of
published literatures. Therefore, this paper aims to review the pro-
duction of bio-jet fuel in a different perspective, by critically discuss the
Fig. 1. Potential feedstock for bio-jet fuel production [15].
2
Energy Conversion and Management 199 (2019) 112015
Dehydration,
Alcohol-to-jet Oligomerization,
Hydrogenation
Gasification,
Gas-to-jet Fischer-Tropsch,
Hydroprocessing
Bio-jet fuel
Oil-to-jet Hydroprocessing
Hydrolysis,
Sugar-to-jet Fermentation,
Hydroprocessing
Fig. 2. Conversion pathways of bio-derived jet fuel from various sources
[12,16].
possible conversion pathways of liquid biomass through hydroproces-
sing method (i.e. three-step process, two-step process, single step pro-
cess). In some cases, the intermediate hydroprocessing steps (i.e.
deoxygenation, isomerization, cracking, separation) can be achieved
simultaneously through a single process. Hence, this reduces the costs
of bio-based hydrocarbon production that renders the viability for in-
dustrial use with economic gains. Apart from that, this paper also
provides fundamental understanding of each intermediate stage in-
volves in the hydroprocessing method for conversion of liquid biomass
to bio-jet fuel.
2. State of the art of biofuel (bio-jet fuel) in aviation industry
The current production of biofuel is developed and improved from
three generations of feedstock as shown in Fig. 3 [22,23]. The first-
generation biofuel is produced via fermentation or transesterification of
feedstock (i.e. food crop and animal fats), which generates bioethanol
and biodiesel as the final products [24]. However, the biochemical
methods used in the first generation do not favor the production of bio-
jet fuel. This is because the carbon numbers produced in the end pro-
duct from this method do not meet the standard requirement of jet fuel.
Furthermore, food crop is involved as feedstock for biofuel production,
which it will affect the food security in long run [25].
Next, the biofuel production is further improved as second-genera-
tion, which non-edible feedstock such as oil crops, lignocellulosic bio-
mass and organic waste are applied in either biochemical or thermo-
chemical processes [26,27]. Biochemical conversion (i.e. fermentation
and transesterification) involves the use of microorganism or enzyme to
breakdown complex cellulosic material in biomass into simpler mono-
mers [28,29]. On the other hand, thermochemical conversion involves
heat input to achieve chemical transformations of biomass into desired
hydrocarbons and aromatics [30,31].
The second-generation biofuel feedstock are mostly dealing with
biomass and waste residues [32,33]. Hence, it is suitable to be used for
bio-jet fuel production in long run without affecting the food security.
Besides, it is also able to produce bio-jet fuel with fuel properties that
meet the standard ASTM certification of conventional Jet A1 fuel as
shown in Table 1 [34,35]. Normally, raw bio-oil derived from lig-
nocellulosic biomass has high viscosities and acidity, which will form
gums during storage, clogging of nozzles, poor atomization and com-
bustion, and hence compromising of jet engine life [36,37]. Therefore,
the raw bio-oil needs to be further upgraded for its compatibility with
Jet A1 fuel. This is considered a technical challenge to produce bio-jet
fuel from biomass as compared to conventional Jet A1 fuel. The stan-
dard bio-jet fuel should have desirable characteristics of high flash
point, high specific energy, high energy density, low freezing point and
adequate lubricity. By achieving such fuel criteria will ensure safe op-
eration during fuel ignition, decrease take-off weight, facilitates long-
range flight and proper functioning of fuel pumps, respectively [35,38].
In the third-generation biofuel, algae is developed as an alternative
renewable source for biofuel production [39–41]. The major benefit of
E.S.K. Why, et al. Energy Conversion and Management 199 (2019) 112015

Fig. 3. Generations of biofuel.

Table 1 Table 2
Physical properties of Jet A1 [34,35]. List of demonstration flights using bio-jet fuel.
Property Value(s) Year Aircraft Model Raw Material Blend Country Ref.

Flash point 42 °C 2018 Boeing 787 Carinata oil 30% Australia [48]
Freezing point −47 °C 2018 Boeing 787 Carinata oil 30% U.S.A. [49]
Density at 15 °C 0.775–0.840 kg/L 2018 Bombardier Q400 Jatropha oil 25% India [50]
Specific energy 43.2 MJ/kg 2017 Boeing 787 Waste cooking oil 15% China [51]
Energy density 34.7 MJ/L 2016 Boeing 737–800 Forest residuals 20% U.S.A. [52]
Kinematic viscosity at −20 °C 8 mm2/s 2015 Boeing 737–800 Waste cooking oil 50% China [53]
2014 Airbus A321 Farnesan 10% Germany [54]
2012 Falcon 20 Carinata oil 100% Canada [55]
2012 Bombardier Q400 Camelina & carinata oil 49%; 1% Canada [56]
algal biomass is its ability to be cultivated in either saltwater (open
2011 Boeing 737–800 Algal oil 40% U.S.A. [57]
pond) or on land (closed culture system), without posing a challenge to 2011 Boeing 747–400 Jatropha oil 50% China [58]
global food and freshwater supply [20]. In addition, algae cultivation is
able to purify polluted water and produce biofuel simultaneously [42].
Cultivation of algae in open ponds requires low investment, but it will aircraft [59–63]. In previous years, demonstration flight had been
encounter high risk of culture contamination due to open air. On the conducted in order to test the viability of drop-in fuel in real life. A list
other hand, cultivation of algae in indoor closed culture system with the of selected demonstration flights in past few years is shown in Table 2.
aid of photo-bioreactor will render higher lipid content for algae oil As seen in Table 2, bio-jet fuel derived from Carinata oil showed high
extraction in biofuel production [43]. Biofuel can be derived from algal adaptability to most of the demonstration flight, which 100% of bio-jet
biomass in some possible ways, either by biochemical or thermo- fuel without blending could meet petroleum specification. On the other
chemical pathway as illustrated in Fig. 4 [44–46]. Normally, thermo- hand, Farnesan, a sugar-based biofuel provided the lowest blend of 10%
chemical pathway is applied to derive bio-jet fuel from algal biomass, to commercial fossil fuel [54]. Bio-jet fuel derived from algal oil was
which the pyrolysis process is performed in prior, followed by deox- also reported to provide successful demonstration flight for aircraft,
ygenation process. However, high quality bio-jet fuel can also be pro- with drop-in of 40% biofuel [57]. In summary, most of the demon-
duced from algal biomass by biochemical process, in which the trans- stration flight with bio-jet fuel were derived from liquid biomass (i.e.
esterification process is proceeded by hydrogenation process [47]. raw vegetable oils, waste cooking oil, algal oil), except for raw material
Although bio-jet fuel is able to show similar fuel properties as of solid biomass (i.e. forest residuals and agriculture wastes) [52].
conventional jet fuel, however it can only act as drop-in fuel by As referred to recent trend, most of the bio-jet fuels were derived
blending with fossil jet fuel. A maximum blend of bio-jet fuel up to 50% from liquid biomass, especially from non-edible energy crop to main-
with fossil jet fuel is currently ASTM-certified, and allows sufficient tain food security. Thus, there is a need to have an insight for the
quantities of aromatics to ensure the integrity of engine seals of the production technology. Liquid biomass (oil from seed extraction and

Fig. 4. Possible biofuel conversion pathways from algal biomass [44].

3
E.S.K. Why, et al.
bio-oil from pyrolysis process) is usually used as the feedstock for bio-
jet fuel conversion via hydroprocessing technology. It is known that
petrochemical industry had been practicing this hydroprocessing
technology over the years, by involving the intermediate stages of
heteroatom (i.e. sulfur, nitrogen, oxygen, metals) removal, saturation of
olefins and aromatics compounds, isomerization and cracking, and final
product separation [40]. Besides, hydroprocessing technology con-
sumes lesser energy usage, and it is also known to have the best per-
formance characteristics in terms of energy efficiency, with 90% in
overall [64,65].
However, there are certain hydroprocessing parameters that will
affect the yield of bio-jet fuel, such as the reaction condition, type of
catalyst used and type of feedstock. Vasquez et al. [66] reported that
reaction temperature and acidic strength of the catalyst had great in-
fluence on the composition of final product. Besides, the feedstocks
with higher degree of saturation of iodine number (IV) are more fa-
vorable for bio-jet fuel yield, because it requires lesser amount of hy-
drogen during hydrogenation. The challenges of bio-jet fuel production
technologies and catalyst development had been reviewed by many
past researchers, typically on the operational condition, catalytic ac-
tivity and selectivity, and the life cycle assessment of feedstock
[37,64,67].
3. Hydroprocessing pathway for liquid biomass
In general, hydroprocessing of liquid biomass converts the content of
vegetable oil, bio-oil or lipid into hydrocarbons at high temperature and
pressures with the aid of catalysts under excess reacting gas (i.e. hydrogen,
nitrogen) atmosphere. The hydroprocessing reaction pathways of liquid
biomass are illustrated in Fig. 5. Each intermediate stage involves in the
hydroprocessing pathway is discussed in the following sub-sections.
Fig. 5. Hydroprocessing pathway to bio-jet fuel.
Fig. 6. Setup of biofuel deoxygenation process in lab scale [73].
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Energy Conversion and Management 199 (2019) 112015
3.1. Deoxygenation
Deoxygenation process is mainly responsible for the removal of
oxygenated compounds from fatty acid carboxyl group, with the pre-
sence of inert gas during the process to produce saturated or un-
saturated hydrocarbons [68,69]. Fig. 6 shows the common setup for
biofuel deoxygenation process in lab scale. Generally, liquid biomass-
derived biofuel showed denser, higher viscosity and oxygen content
than fossil fuel [70]. Such contrary between fuel properties will cause
an issue on the feasibility of biofuel replacement to conventional fuel.
The presence of oxygen will increase acidity, corrosivity, viscosity of
biofuel, due to the presence of water in fatty acids. Besides, the oxygen
content also reduces oxidation stability and heating value of final bio-
fuel, which is caused by the presence of carboxylic and carbonylic
double bonds [19,71]. On the other hand, ASTM D1655 and D7566 also
stated that the composition of final fuel must be at least 99.5% in
carbon and hydrogen. Any oxygenated molecules present in the final
fuel should not be considered as potential bio-jet fuel [62]. Hence, the
removal of oxygen is important in this case, in order to increase the
biofuel stability, miscibility with conventional fuel, and H/C molar
ratio [72].
There are several possible mechanisms for deoxygenation which are
commonly applied in hydroprocessing of bio-jet fuel, such as dec-
arboxylation, decarbonylation and hydrodeoxygenation. In decarbox-
ylation, carboxyl group is removed by releasing carbon dioxide and
paraffinic hydrocarbon. Decarbonylation process removes carbonyl
group and yields olefins, carbon monoxide and water. In hydro-
deoxygenation, cleavage of C-O bond in fatty acids is achieved by
pressurizing them with excess hydrogen gases, and therefore yielding
hydrocarbons and water [74]. The reaction pathways of decarboxyla-
tion, decarbonylation and hydrodeoxygenation, typically under hy-
drogen gas are presented in Fig. 7.
Table 3 summarizes the literature studies of some liquid biomass
deoxygenation. In most cases, hydrodeoxygenation is the most desired
route as the number of carbons is preserved and the by-product formed
is only water [78,80]. The highest yield of 97% bio-jet fuel via hy-
drodeoxygenation route was achieved by Wang et al. [78], which the
waste cooking oil was reacted at 300 °C under 4 MPa hydrogen pressure
with Ni-Mo/ɣ-Al2O3 catalyst for 7.5 h. They reported that the high yield
of biofuel was achieved by optimal weight fraction of catalyst loadings
of 10% Mo and 5% Ni. On the other hand, Anand et al. [85] performed
E.S.K. Why, et al.
Fig. 7. Different reaction pathways of deoxygenation under hydrogen gas.
hydrodeoxygenation on jatropha oil at 420 °C under 6–9 MPa hydrogen
pressure with Ni–W/SiO2-Al2O3 catalyst. The hydrodeoxygenation of
the feedstock was reacted at the highest temperature and pressure
among the literatures, however, their work showed the lowest bio-jet
fuel of 30%. They claimed that the triglyceride conversion over Ni–W
bimetallic catalyst system was strongly dependent on the temperature,
space velocity and hydrogen partial pressure. In general, most re-
searchers performed hydrodeoxygenation of feedstock with Pt, Pd and
Ni supported catalyst, and produced the highest bio-jet fuel yield of
90%, 82% and 97% respectively [78,83,89]. Therefore, the product
distribution in the hydrodeoxygenation route also depends on the cat-
alyst active metals. According to Oh et al. [88], they stated that the high
catalyst activity was correlated to the higher surface area and pore size
of the catalyst. Besides, Pham et al. [79] also carried out a similar at-
mospheric-pressure hydrodeoxygenation on waste cooking oil. The
highest hydrocarbon yield obtained from their work was 77.4 wt%,
which the product was mainly composed of n-alkanes in the range of
diesel fraction (C15–C19).
Besides, Cheng et al. [75] and Li et al. [77] adapted decarbonylation
of soybean oil and waste cooking oil in their studies respectively. Cheng
et al. [75] converted the soybean oil into bio-jet fuel with yield of
48.2% at 390 °C under 1 MPa hydrogen pressure with the aid of Ni-Mo/
HY catalyst for 8 h. They concluded that Ni-Mo/HY catalyst was able to
improve the bio-jet fuel quality, by increasing jet range alkane se-
lectivity and decreasing jet range aromatic hydrocarbon selectivity. Li
et al. [77] studied the conversion of waste cooking oil at temperature of
400 °C under 3 MPa hydrogen pressure for similar 8 h by using Ni/
Meso-Y catalyst. The process was able to exhibit a high jet range alkane
(i.e. C8–C16) yield of 40.5%. In summary, recent literatures show that
the usage of Ni as catalyst support is a trend for decarbonylation of bio-
jet fuel.
Furthermore, Fu et al. [81] and Silva et al. [82] applied decarbox-
ylation method to convert their feedstock into bio-jet fuel. Fu et al. [81]
experimented microalgae lipids (methyl stearate) at 360 °C in water
with Pt/C catalyst for 45 min. The catalytic decarboxylation process
was able to yield 90% of bio-jet fuel. Next, Silva et al. [82] experi-
mented macauba oil at 300 °C under 1 MPa hydrogen pressure with Pd/
C catalyst for 5 h. Their experimental work was able to achieve a higher
yield 85% of bio-jet fuel.
Generally, deoxygenation of liquid biomass is mostly performed in
the presence of hydrogen. In some cases, past researchers had im-
plemented a different deoxygenation method, such as by replacing re-
acting gas of hydrogen to inert nitrogen gas, and at different condition
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Energy Conversion and Management 199 (2019) 112015
for reacting condition. For example, Choi et al. [86] and Romero et al.
[87] had performed catalytic deoxygenation on Jatropha fatty acids in
the absence of hydrogen gas. In their work, the deoxygenation pro-
cesses were carried out in a pressurized condition with nitrogen gas,
and successfully yielded > 75% of bio-jet fuel. On the contrary, Shim
et al. [90] conducted a catalytic deoxygenation of oleic acid under inert
(N2) conditions at atmospheric pressure (1 atm.). They were able to
achieve diesel selectivity (C12–C20) of 48.1%, and 69.6% of oxygen
removal rate. Lastly, Zulkepli et al. [91] carried out the deoxygenation
process on triolein at vacuum state, and was able to achieve 95.2% of
diesel selectivity (C11–C20).
In short, the literatures in Table 3 shows that the hydro-
deoxygenation pathway is the most promising method for the produc-
tion of bio-jet fuel. This method was able to produce the highest yield of
97% bio-jet fuel as reported by Wang et al. [78]. The production rate
and selectivity of biofuel also depends on other reaction parameters,
such as catalyst, liquid hourly space velocity (LHSV) and H2/oil ratio.
Sonthalia et al. [92] reviewed that catalyst with optimum nickel con-
tent provides enough active metal sites for high hydrodeoxygenation
activity. They also stated that the fuel selectivity in deoxygenation
process increases as the LHSV increases, while oxygen removal cap-
abilities decrease as the LHSV increases. On the other hand, fuel se-
lectivity and conversion efficiency in deoxygenation process decreases
as the H2/oil ratio increases. Therefore, it is crucial to apply the oper-
ating parameters within optimal range during deoxygenation process
for maximum yield of bio-jet fuel. As referred to Table 3, the optimal
range of operating temperature and reacting gas pressure for hydro-
deoxygenation are 300–385 °C and 3–5 MPa respectively. Exceeding of
the optimal range of operating temperature and reacting gas pressure
will result in low yield of bio-jet fuel as reported by Anand et al. [85].
Nickel support catalyst favors the yielding of fuel in hydrodeoxygena-
tion. The optimal range of LHSV and H2/oil for bio-jet fuel conversion
via hydrodeoxygenation are reported to be 1–2 h−1 and 800–1500 NL/
L respectively. It is also possible to carry out a hydrogen-free and non-
pressurized (i.e. atmospheric or vacuum state) deoxygenation process
on liquid biomass as claimed by some studies [79,86,87,90,91,93].
3.2. Cracking and isomerization
After completing the deoxygenation stage in hydroprocessing pro-
cess, the straight chain paraffinic molecules are then further processed
with either cracking or isomerization as shown in Fig. 8. The purpose of
isomerization reaction aims to improve cold flow properties and
E.S.K. Why, et al. Energy Conversion and Management 199 (2019) 112015

Table 3
Summary of main parameters for deoxygenation process of some liquid biomass in the hydroprocessing technology.
Raw material Deoxygenation route Reaction condition Catalyst Bio-jet fuel yield (%) Ref.

Soybean oil Decarbonylation T = 390 °C Ni-Mo/HY 48.2 [75]

P = 1 MPa (H2)
Residence time = 8 h
Hydrodeoxygenation T = 370–385 °C Pt/Al2O3/SAPO-11 42–48 [76]
P = 3 MPa (H2)
LHSV = 1 h−1
H2/oil = 800 NL/L
Waste cooking oil Decarbonylation T = 400 °C Ni/Meso-Y 40.5 [77]
P = 3 MPa (H2)
Residence time = 8 h
Hydrodeoxygenation T = 300 °C Ni-Mo/ɣ-Al2O3 97 [78]
P = 4 MPa (H2)
Residence time = 7.5 h
Hydrodeoxygenation T = 300 °C Ni2P/AC 77.4 (biodiesel) [79]
P = 1 atm. (H2)
GHSV = 2.33 min−1
Castor oil Hydrodeoxygenation T = 300–360 °C NiAg/SAPO-11; 91.6; [80]
P = 3 MPa (H2) Ni/USY-APTES-MCM-41 80.3
WHSV = 2 h−1
Algal oil Decarboxylation T = 360 °C Pt/C 90 [81]
Solvent = water
Residence time = 45 min
Macauba oil Decarboxylation T = 300 °C Pd/C 85 [82]
P = 1 MPa (H2)
Residence time = 5 h
Palm oil Hydrodeoxygenation T = 300 °C Pd/C 82 [83]
P = 1 MPa (H2)
Residence time = 5 h
Hydrodeoxygenation T = 330 °C Ni-MoS2/ɣ-Al2O3 58 [84]
P = 5 MPa (H2)
LHSV = 1 h−1
H2/oil = 1000 Ncm3/cm3
Jatropha oil Hydrodeoxygenation T = 420 °C Ni–W/SiO2-Al2O3 30 [85]
P = 6–9 MPa (H2)
LHSV = 0.5–2 h−1
H2/oil = 1500 NL/L
Deoxygenation without H2 T = 200 °C WOx/Pt/TiO2 75 [86]
P = 4 MPa (N2)
LHSV = 1.33 h−1
Deoxygenation without H2 T = 400 °C CaO 77.4 (biodiesel) [87]
P = 2 MPa (N2)
Residence time = 6 h
Liriodendron tulipifera plant oil Hydrodeoxygenation T = 300 °C Ni/SBA-15 76 [88]
P = 3 MPa (H2)
Residence time = 60 min
Amygdalus Pedunculata plant oil Hydrodeoxygenation T = 340 °C Pt/ZSM-22 60 [89]
P = 3 MPa (H2)
Residence time = 1 h
Oleic acid Deoxygenation without H2 T = 300 °C CoMo 48.1 (biodiesel) [90]
P = 1 atm. (N2)
Residence time = 3 h
Triolein Deoxygenation without H2 T = 380 °C Ni/HMS 95.2 (biodiesel) [91]
P = vacuum
Residence time = 2 h

GHSV: Gas hourly space velocity.

LHSV: Liquid hourly space velocity.
WHSV: Weight hourly space velocity.

freezing point of bio-jet fuel, while the cracking reaction is to further
convert the molecule into desired carbon chain (C8–C16) and boiling
point range of conventional jet fuel [94]. In some studies, the cracking
and isomerization reactions can be carried out either concurrent or
sequential, where cracking reaction comes after isomerization of
straight carbon chain [16].
In order to produce a bio-jet fuel with high adaptability to cold
climate, especially when the aircraft is travelling in high altitude, iso-
merization or hydroisomerization of hydrocarbon chain in bio-jet fuel is
a crucial step. Isomerization of hydrocarbon is performed, by creating a
carbocation within the hydrocarbon chain at double bond site in the
presence of solid acid catalyst. Then, the carbocation rearranges and
forms a methyl or ethyl branch on the hydrocarbon chain. On the other
hand, hydroisomerization has the similar reaction mechanism, except
that it requires extra hydrogenation or dehydrogenation step to saturate
the double bond of molecule beforehand [96].
Next, the cracking reaction path is decided based on the size of
carbon chain to be achieved as final product. In some hydroprocessing
cases, the cracking reaction takes place initially before deoxygenation,
in order to break down large triglyceride molecule into carboxylic acids
and propane. Cracking reaction might happen simultaneously during
catalytic hydrotreatment of pyrolysed oil from solid biomass, which
will produce polyaromatic and aromatic compounds. In this case,
cracking of long saturated chain of paraffinic molecule is occurred after

6
E.S.K. Why, et al.
Fig. 8. Setup of biofuel cracking process in lab scale [95].
deoxygenation and isomerization, so that a small chain paraffins can be
obtained [71]. Both the reaction pathways of cracking and isomeriza-
tion process is illustrated in Fig. 9.
A series of literatures on cracking and isomerization studies of ve-
getable oils to produce bio-jet fuel is summarized in Table 4. Eller et al.
[98] improved the cold flow properties of bio-jet fuel derived from
coconut oil, by isomerizing it at 360 °C under 4.5 MPa hydrogen pres-
sure with Pt/SAPO-11 catalyst. Their work was able to obtain the
highest yield of bio-jet fuel by 77.6 wt%, which was mainly because of
the highest saturated fatty acids of 91.4% in raw material as shown in
Table 4. However, the freezing point of their isomerized product is seen
to be the highest (−45 °C) among the other studies. On the contrary,
isomerization of jatropha oil that was conducted by Anand et al. [85]
produced the lowest yield of bio-fuel by 30%. In despite of the lowest
fuel yield, the isomerization work was able to produce a lower freezing
point of −49.3 °C of biofuel as compared to the study from Eller et al.
(−45 °C) [98]. In their work, they used zeolite supported nickel catalyst
instead of zeolite supported platinum, which was generally used by
other researchers. The catalyst with nickel content provided sufficient
active metal sites for high hydrodeoxygenation activity, and the pre-
sence of acid sites for isomerization of alkanes [92]. Next, Rabaev et al.
[76] isomerized soybean oil at 350 °C under 3 MPa hydrogen pressure
with Pt/Al2O3/SAPO-11 and successfully yielded 48 wt% of bio-jet fuel
with the highest aromatics content of 14.3% as presented in Table 4.
Although the maximum allowable aromatics content in bio-jet fuel is
25% according to ASTM D7566, it is better to maintain a low aromatics
content in jet fuel to reduce swelling volume of fuel tank, which consists
of polythioether and polysulfide sealants [99]. Lastly, Kasza et al. [97]
were able to yield 56–76 wt% of bio-jet fuel, by isomerizing sunflower
Fig. 9. Reaction pathways for isomerization and cracking process.
7
Energy Conversion and Management 199 (2019) 112015
oil at 360 °C under 4 MPa hydrogen pressure with Pt/SAPO-11 catalyst.
Even though sunflower oil has the lowest content of saturated fatty acid
(11%) as seen in Table 4, the isomerization of the feedstock was able to
develop the lowest freezing point of bio-jet fuel (−55 °C) and free of
aromatics content.
In essence, the improvement of freezing point and yield of bio-jet
fuel through isomerization is strongly depending on fatty acids profile
of raw material and the reaction condition. Table 4 shows that raw
material with the highest saturated fatty acids (91.4%) was able to
produce highest yield of bio-jet fuel (77.6 wt%). Next, the increase of
reacting temperature up to 360 °C was able to enhance the isoparaffin
content and degree of isomerization of fuel. However, increasing of
reacting temperature beyond 360 °C would favor cracking of hydro-
carbon chain, and exerted negative effect on isomers selectivity [97].
Finally, Table 4 also summarized that most researchers applied Pt
supported on zeolite as the catalyst in isomerization process for bio-jet
fuel production. According to Galadima et al. [67], hydrocracking and
isomerization of alkanes can be carried out simultaneously using acidic
zeolite or bifunctional (containing both the metal and acid sites) cata-
lysts. However, they also emphasized that the catalyst must be mod-
erately acidic, because the high acidity will tend to shift the reaction
towards hydrocracking and consequently reduces isomers yield. Thus,
this will affect the final quality (alkane structure) of the bio-jet fuel.
3.3. Separation
The final stage of bio-jet fuel separation aims to separate the fuel
mixture into light gases, naphthas, bio-jet fuel and green diesel as il-
lustrated in Fig. 5. In this stage, the final products are heated and
E.S.K. Why, et al. Energy Conversion and Management 199 (2019) 112015

Table 4
Summary of cracking and isomerization/hydroisomerization reactions effect on bio-jet fuel quality.
Raw material FA profile of raw material Reaction condition Profile of isomerized bio-jet fuel Ref.

Unsaturated FA Saturated Aromatics Boiling Flash point Density at Freezing Viscosity at Yield
(%) FA (%) (%) point (°C) (°C) 15 °C (kg/ point (°C) −20 °C (wt%)
m3) (mm2/s)

Soybean oil Poly = 57.5 16.5 T = 350 °C 14.3 (ASTM 283 (ASTM 48.5 (ASTM 0.776 −50 (ASTM 3.30 (ASTM 48 [76]
Mono = 26.0 P = 3 MPa (H2) D7566) D7566) D56) (ASTM D2386) D445)
Cat. = Pt/Al2O3/ D1298)
SAPO-11
LHSV = 4 h−1
H2/oil = 200 NL/L
Jatropha oil Poly = 27.3 27.4 T = 340–420 °C 11.3 (ASTM 260 (ASTM 45.9 (ASTM 0.781 −49.3 3.78 (ASTM 30 [85]
Mono = 45.4 P = 6–9 MPa (H2) D1319) D1655/ D3828F) (ASTM (ASTM D445)
Cat. = Ni–W/SiO2- D7566) D4052) D5972
Al2O3
H2/oil = 1500–2500
NL/L
Sunflower oil Poly = 59 11.0 T = 360 °C none 240 – – −55 – 56–76 [97]
Mono = 30 P = 4 MPa (H2) (EN 590: (EN 590:
Cat. = Pt/SAPO-11 2009) 2009)
LHSV = 1 h−1
H2/oil = 400 Nm3/
m3
Coconut oil Poly = 1.6 91.4 T = 360 °C < 0.1 – – 0.760 (EN −45 (ASTM – 77.6 [98]
Mono = 7.0 P = 4.5 MPa (H2) (EN 12916: 12185: D5972)
Cat. = Pt/SAPO-11 2000) 1998)
LHSV = 1.1 h−1
H2/oil = 350 Nm3/
m3

FA: Fatty acid.

Poly: Poly-unsaturated fatty acid.
Mono: Mono-unsaturated fatty acid.
Cat.: Catalyst.

pressurized according to their different boiling point, and then the
vaporized chemical compounds are fractionated through common
method of distillation. Through distillation, high purity of bio-jet fuel
can be obtained, where the unreacted oil components, metals, catalysts,
salts and pigmentation are left over at the column bottoms [111]. There
are many different options and processes of distillation being im-
plemented in the oil refinery industry, depend on the type of fuel to be
handled. Processes such as atmospheric distillation, vacuum distillation
and simulated distillation have been applied in laboratory-scale to
purify the bio-jet fuel.
In short, separation of bio-jet fuel through distillation can improve
the respective distillate fractions based on physical, chemical and
compositional quality [102]. However, distillation can also cause loss of
bio-jet fuel yield with approximately of 1–5% by weight and low oxi-
dative stability, depending on the feedstock and conversion process.
Therefore, adding additive in the final distilled product is required
[111]. Product yield of bio-jet fuel obtained from distillation process of
different studies are summarized as shown in Table 5. The reaction
conditions of different distillation processes are discussed in the fol-
lowing sections.
3.3.1. Atmospheric distillation
Atmospheric distillation process is suitable for biofuel with low
boiling temperature of less than 100 °C at atmospheric pressure, fol-
lowed with the distillation in the range of 250–280 °C [102]. Based on
Table 5, Mancio et al. [102] performed atmospheric distillation on palm
oil-derived biofuel by heating it at temperature ranges of 160–245 °C
and 245–340 °C, in order to produce final fuel with organic (light)
phase and aqueous (heavy) phase respectively. Their work was able to
yield 67.19 wt% of bio-jet fuel. They concluded that increase of catalyst
amount for thermal catalytic cracking process of palm oil-derived bio-
fuel is able to improve the yield and selectivity of bio-jet fuel distillates.
Silva et al. [107] conducted atmospheric distillation on biofuel derived
from grease traps at temperature ranges of 196–396 °C. Their work
managed to yield 14.90 wt% of bio-jet fuel, due to carboxylic acids
content was still remained in the biofuel. Therefore, this factor had
caused the physicochemical properties of the distillation fractions to
decrease, although the effort of increasing the temperature of boiling
point during distillation had been made.
In general, Table 5 shows that atmospheric distillation of bio-jet fuel
conducted in past studies which involved cracking of raw material as
prior reaction. Although this distillation method is known to be the
simple and economically feasible, the high thermal sensitivity of biofuel
limits the operating temperature at atmospheric temperature. Thus,
vacuum distillation was developed to reduce the boiling point of biofuel
[112].
3.3.2. Vacuum distillation
Vacuum distillation of biofuel is known to be performed under re-
duced pressure, in order to separate the chemical components with high
boiling points. This technique is used when the boiling points of organic
liquid are difficult to be achieved. Llamas et al. [100] applied vacuum
distillation on bio-jet fuel derived from coconut oil and palm oil, under
pressure of 0.27 kPa, with heating temperature range of 47–114 °C and
35–113 °C, respectively. The bio-jet fuel derived from both feedstocks
were able to blend with commercial Jet A1 fuel up to 10 vol%. Besides,
Ranucci et al. [103] implemented vacuum distillation to separate the
trans-esterified organic liquid from palm oil, babassu oil and jatropha
oil. However, they reduced the reacting pressure to 95.99 kPa and
98.66 kPa, respectively, which were slightly lower than atmospheric
pressure (101.32 kPa). Similarly, the results showed that the esters
obtained from these feedstock were able to blend in 10 vol% with Jet
A1 fuel.
In addition, Iakovlieva et al. [108] proposed vacuum distillation at
165–215 °C under 0.4–0.7 kPa pressure to remove by-products formed
during transesterification. They concluded that vacuum distillation

8
E.S.K. Why, et al. Energy Conversion and Management 199 (2019) 112015

Table 5
Summary of different types of distillation effect on bio-jet fuel yield.
Raw material Prior reaction(s) Reaction condition of distillation Ref.

Distillation process Temperature Pressure Bio-jet fuel

(°C) (kPa)
Yield (wt%) Blend (vol %)

Palm oil i. Transesterification Vacuum distillation 35–113 0.27 – 10 [100]

i. Hydrocracking Simulated distillation 30–300 101.32 46.30 – [101]
ii. Centrifugation separation
i. Thermal catalytic cracking Atmospheric distillation 160–340 101.32 67.19 – [102]
i. Transesterification Vacuum distillation 110–145 98.66 – 10 [103]
Algae oil i. Hydrocracking Simulated distillation 50–350 101.32 52.0 – [104]
i. Hydrogenation Simulated distillation 270–350 101.32 76.47 – [105]
Coconut oil i. Transesterification Vacuum distillation 47–114 0.27 – 10 [100]
i. Transesterification Vacuum distillation 185 9.33 65.0 – [106]
Babassu oil i. Transesterification Vacuum distillation 115–157 98.66 – 10 [103]
Jatropha oil i. Transesterification Vacuum distillation 170–190 95.99 – 10 [103]
Grease traps i. Hydrocracking Atmospheric distillation 196–396 101.32 14.90 – [107]
Rapeseed oil i. Transesterification Vacuum distillation 165–215 0.4–0.7 – 30 [108]
Aspen wood flour i. Hydrothermal liquefaction Vacuum distillation 73–350 0.13 27.6 – [109]
ii. Gravimetrical separation
iii. Dewatering distillation
Cardoon oil i. Pyrolysis Simulated distillation 90–310 101.32 34.72 – [110]
ii. Rotary evaporation

applied in their work was able to produce esters without the formation
of secondary products. The bio-additives produced based on rapeseed
oil fatty acids methyl esters (FAME) and fatty acids ethyl esters (FAEE)
was able to blend with conventional jet fuel up to 30 (vol%). Pedersen
et al. [109] had carried out vacuum distillation on organic liquid pro-
duced from aspen wood flour. The solid biomass initially underwent
hydrothermal liquefaction, followed by gravimetrical separation and
dewatering distillation to remove solid residue. In the following va-
cuum distillation, the organic liquid was then reacted at 73–350 °C
under the lowest pressure of 0.13 kPa among all literatures in Table 5.
However, the distillate was further processed by hydrotreatment, in
order to remove certain oxygen functionalities and saturate hydro-
carbon chains. The final yield of bio-jet fuel in this work was measured
to be 27.6 wt%.
Another common technique of vacuum distillation which has been
widely used is the rotary evaporation. The separation of biofuel is
achieved by using a rotary evaporator under high vacuum with heating.
Saifuddin et al. [106] applied rotary evaporation to obtain bio-jet fuel
from biodiesel at 185 °C under 9.33 kPa pressure, after the transester-
ification of coconut oil and methanol assisted by microwave heating.
Their work was able to yield 65.0 wt% of bio-jet fuel. They also stated
that the quality of bio-jet fuel obtained, especially the freezing point,
could be improved by addition of aromatics. However, Duong et al.
[113] studied that cycloparaffins have better blending with bio-jet fuel,
and have higher freezing point than aromatics.
In summary, Table 5 shows that vacuum distillation of bio-jet fuel
was performed mostly after the transesterification of liquid biomass.
The maximum boiling point of organic liquid applied in vacuum dis-
tillation after transesterification process was 215 °C, which was lower
than atmospheric distillation (396 °C). This was mainly because of the
lower pressure maintained within the vacuum distillation column
lowered the boiling point of organic liquid. Therefore, the heavy re-
sidues presented at atmospheric pressure were further cracked or being
distilled out. Although the biodiesel fractions were largely obtained due
to the use of transesterification process, biodiesel will never be an ac-
ceptable blend stock for alternative jet fuels.
3.3.3. Simulated distillation
Simulated distillation of biofuel is a gas chromatography (GC)
method, which samples are analyzed by using non-polar chromato-
graphic column that separates the hydrocarbons fractions based on
their boiling points. Later, comparison of boiling range calibration
curves between samples are made [114]. For an example, Biller et al.
[115] analyzed the bio-crude of microalgae by using simulated dis-
tillation. Five distillate fractions of gasoline (< 190 °C), diesel cuts 1
and 2 (190–290 °C and 290–340 °C), vacuum gas oil (340–538 °C) and
vacuum residue (> 538 °C) were defined in their work. This distillation
method was able to provide a faster analysis speed as compared to
conventional distillation methods. Therefore, simulated distillation can
be considered as a matured technology, especially when the demand of
samples to be analyzed is high.
There are several studies that had used simulated distillation to
separate and analyze the composition of organic liquid as shown in
Table 5. Li et al. [101] employed simulated distillation on palm oil-
derived bio-jet fuel at 30–300 °C, in prior to hydrocracking and cen-
trifugation for separation. Their work was able to yield 46.30 wt% of
bio-jet fuel. Next, Liu et al. [104] and Shi et al. [105] also conducted
simulated distillation on algae derived bio-jet fuel, by using Flame-Io-
nization Detection (FID) − Gas Chromatography (GC) with capillary
column. The highest yield of 76.47 wt% bio-jet fuel extracted from
wet algae lipid was achieved by Shi et al. [105], prior to hydrogenation
process. Lastly, Gutierrez et al. [110] carried out simulated distillation
on cardoon oil-derived biofuel at 90–310 °C, and process of pyrolysis
and rotary evaporation were performed beforehand. Rotary evapora-
tion of cardoon oil-derived biofuel at 40 °C and 5.33 kPa was carried out
beforehand, in order to extract the excess organic solvent. The final
yield of bio-jet fuel in this work was reported to be 34.72 wt%.
To sum up, vacuum distillation was being widely used, followed by
both simulated and atmospheric distillation. Table 5 shows that most of
the vacuum distillation applied after transesterification of liquid bio-
mass, while atmospheric distillation and simulated distillation were
performed in prior to cracking and additional separation of biofuel. The
highest boiling point of 396 °C of biofuel fractionation was applied in
atmospheric distillation. Both atmospheric and simulated distillation of
biofuel were reacted at atmospheric pressure (101.32 kPa), whereas
vacuum distillation of biofuel was able to be reacted at lowest reduced
pressure of 0.13 kPa. The highest yield of 76.47 wt% bio-jet fuel was
obtained from simulated distillation of algae oil, which was also treated
by hydrogenation in advance [105]. The highest blend of bio-jet fuel
30 vol% with commercial Jet A1 fuel was achieved by transesterifica-
tion of rapeseed oil and vacuum distillation of its final product [108].
According to Mancio et al. [102], the differences in the yields of bio-oil
can be due to the type of distillation employed and the composition of
the bio-oil itself.

9
E.S.K. Why, et al.
Fig. 10. Overview of advanced methods used in bio-jet fuel production.
4. Advanced methods for bio-jet fuel production
As discussed in Section 3, the conventional method of hydro-
processing of bio-jet fuel can be generally recognized as a 3-step pro-
cess, where step processes such as deoxygenation, cracking/ iso-
merization and final separation of bio-jet fuel are involved in one
conversion cycle. However, researchers of recent days have made ad-
vancement on this conventional method. Fig. 10 shows an overview of
the advanced methods used in bio-jet fuel production, which are being
discussed in this paper. Table 6 shows a series of bio-jet fuel with ad-
vanced production methods that were developed by past researchers in
bench-scale, including the major findings.
4.1. 3-step process
Zhang et al. [116], Wang et al. [117] and Wu et al. [118] developed
a 3-step process for bio-jet fuel production, which shared the similar
processes of feedstock pyrolysis, alkylation and hydrogenation. After
the catalytic cracking of the raw material, they further implemented
alkylation reaction at low temperature (25–80 °C), using ionic liquid of
[bmim] Cl-2AlCl3 to produce C8–C15 aromatics. The final step of hy-
drogenation enabled a nearly full conversion of aromatics to saturated
cycloparaffins. According to Wang et al. [117] and Wu et al. [118], the
carbon number distribution in the resulting biofuel was adjustable to
desired range, by varying the reaction temperature, time, and hydrogen
pressure. As seen in Table 6, Wu et al. [118] yielded the highest bio-jet
fuel of 84.3 wt% from commercial vegetable oil by using 3-step process,
which may due to the favorable elemental composition of the raw
material itself. In Table 7, the raw material of commercial vegetable oil
used by Wu et al. [118] consisted the highest carbon composition of
77.32 wt%, highest hydrogen composition of 10.91 wt%, and the lowest
oxygen composition of 11.61 wt% among the raw materials. As the
commercial vegetable oil has highest carbon and hydrogen content, the
number of saturated hydrocarbon chain existed in the oil would be
higher, and eventually would have a higher possibility to yield alkane
in bio-jet fuel range. Hence, this raw material was able to yield the
highest amount of bio-jet fuel by 84.3 wt%. In contrast, solid biomass
such as straw stalk that was used by Wang et al. [117] had the lowest
carbon composition of 42.10 wt%, lowest hydrogen composition of
7.50 wt%, and the highest oxygen composition of 50.20 wt%. Due to its
lowest carbon and hydrogen content, the number of saturated hydro-
carbon chain contained in the derived bio-oil would be lower, and
10
Energy Conversion and Management 199 (2019) 112015
would lead to a low yield of alkane in bio-jet fuel range. The high
oxygen content in the bio-oil would also be the major factor to cause the
increment of unsaturation. Therefore, this raw material yielded the
lowest amount of bio-jet fuel of 72.50 wt% as shown in Table 7
[116–118].
4.2. 2-step process
The 3-step process of bio-jet fuel production can also be subse-
quently simplified into 2-step process as listed in Table 6. Nakaji et al.
[119] were able to produce the highest yield of 64.0 wt% bio-jet fuel by
adapting 2-step process of hydrogenation and hydrogenolysis from
algal oil. They observed that a large loss of carbon balance happened
for all tested catalyst if the main products were in large molecules, and
hence would lead to complex isomerization later on. In their findings,
Ir/SiO2 catalyst involved in hydrogenolysis was able to yield the highest
64.0 wt% of jet range hydrocarbons (C8–C16). Sousa et al. [120] in-
cluded hydrolysis simultaneous deoxygenation, cracking-isomerization
process in their 2-step process of bio-jet fuel production from palm
olein. Their studies showed that HBeta zeolite catalyst was able to yield
61.0 wt% of bio-jet fuel by simultaneous deoxygenation-cracking-iso-
merization process under hydrogen pressure of 1 MPa. However, the
final bio-jet fuel had low freezing point (-30 °C), and thus requires ad-
ditional refining step to separate the fraction. Xu et al. [121] processed
the microalgae by using hydrothermal liquefaction and hydro-up-
grading processes. They reported that microalgae had higher yield of
bio-oil than the macroalgae, due to its high lipid content. All of the
hydro-upgraded bio-oils had higher energy densities and lower ni-
trogen, oxygen, sulfur contents and lower viscosities than their corre-
sponding crude bio-oils. On the other hand, Ju et al. [122] carried out a
hydro-conversion of neutral fraction of algal lipid, by reacting it with
Pt/Meso-ZSM-5 catalyst under high pressure of hydrogen. The process
was then continued with pressure gas–liquid separation. However, their
work produced the lowest yield of 38.0 wt% bio-jet fuel as shown in
Table 6. Shah et al. [123] used pyrolysis and hydrogenation to produce
bio-jet fuel from Eucalyptus sawdust and discarded soybean frying oil.
Based on their findings, they stated that an increase of 40–50% bio-jet
fuel production was obtained after the adding of discarded soybean
frying oil into pyrolysis of sawdust. Besides, the hydrogenation process
involved in their studies was able to convert > 60% of oxygen and
nitrogen containing compounds to hydrocarbons. Thus, this had im-
proved the stability and fuel quality, by decreasing the oxygenate
 E.S.K. Why, et al.

Table 6
Summary of different advanced methods for bio-jet fuel production.
Raw material Production step(s) Bio-jet fuel yield Major finding(s) Ref.
(wt%)

3-step process
Saw dust i. Pyrolysis 80.4 i. The production of desired C8–C15 aromatics from saw dust with the highest selectivity of 92.4% [116]
ii. Alkylation was achieved by the low temperature alkylation reaction, using the ionic liquid of [bmim] Cl-
iii. Hydrogenation 2AlCl3.
Straw stalk i. Pyrolysis 72.5 i. The carbon number range of the hydrocarbons was expediently tunable by varying reaction [117]
ii. Alkylation temperature and time.
iii. Hydrogenation
Commercial vegetable oil i. Pyrolysis 84.3 i. The conversion of aromatics hydrocarbon increased when hydrogen pressure, reaction [118]
ii. Alkylation temperature and time were increased.
iii. Hydrogenation

2-step process
Algal oil (Botryococcus braunii) i. Hydrogenation 64.0 i. A large loss of carbon balance was observed for tested catalysts (i.e. Ru/SiO2, Ru/CeO2, Ir/SiO2) if [119]
ii. Hydrogenolysis the main products were large molecules.
Palm olein i. Hydrolysis 61.0 i. The products had low freezing temperatures (-30 °C) and requires an additional refining step. [120]
ii. Simultaneous deoxygenation, cracking &
isomerization

11
Microalgae (Schizochytrium limacinum) i. Hydrothermal liquefaction 54.42 i. Microalgae produced a higher crude bio-oil yield than the macroalgae due to their high lipid [121]
ii. Hydro upgrading content.
Algae lipid (Scendesmus dimorphus) i. Hydroconversion 38.0 i. The algal oil extracted can be converted into jet fuel range paraffin by one-step hydrocracking [122]
ii. Gas-liquid separation over Pt/Meso-ZSM-5 catalyst directly.
Eucalyptus sawdust & soybean frying oil i. Pyrolysis 60.0 i. An increase of 40–50% was observed in the production of bio-oil from the pyrolysis of lignin of [123]
ii. Hydrogenation sawdust after adding discarded soybean frying oil.

Single step process

Mesua ferrea L. seed oil i. Hydrodeoxygenation 22.0 i. The cost of bio-crudes obtained is primarily dependent on the cost of the raw vegetable oil, and [124]
35% of the oil cost is accountable as hydroprocessing cost.
Soybean oil, palm oil i. Deoxygenation 31.0 i. The result showed that bio-jet fuel can be produced by using PB811 catalyst with nitrogen (no [125]
hydrogen added).
Waste cooking oil i. Simultaneous hydrodeoxygenation, cracking & 39.7 i. Isomerization activity was improved over the NiMo/USY@Al-SBA-15 catalyst. [126]
isomerization ii. The optimum reaction temperature of 380 °C was obtained for the jet fuel production.
iii. A high H2/oil ratio was not favorable to improve the selectivity for C8–C16 hydrocarbons.
Camelina sativa oil, Brassica carinata oil i. Hydrodeoxygenation 53.5 i. Feedstock with a higher degree of bond unsaturation consume more hydrogen compared to [127]
feedstock with less unsaturated bonds.
Cotton seed oil dregs i. Micropyrolysis 26.0 i. The presence of water in the biomass favored the cracking process. [128]
ii. The production of C8–C16 hydrocarbons increases with the increasing of reaction temperature.
iii. The best hydrocarbon production performance was achieved using the tungsten-TiO2 (WT)
catalyst.
Bamboo wastes, Spirulina platensis, i. Deoxygenation co-pyrolysis 35.0–37.0 i. Oil fraction yields from co-pyrolysis of bamboo wastes and microalgae decreased with biochar [93]
Nannochloropsis sp. addition.
ii. However, biochar catalytic co-pyrolysis could efficiently remove oxygen over 90 wt%.
Energy Conversion and Management 199 (2019) 112015
E.S.K. Why, et al.
Table 7
Properties of the bio-oil used and the bio-jet fuel yield in 3-step process
[116–118].
Elemental compositions Saw dust Straw stalk (wt%) Com. veg. oil (wt%)
(wt%)
C 46.20 42.10 77.32
H 6.02 7.50 10.91
O 47.30 50.20 11.62
N 0.48 0.20 0.74
S – less than 0.10 – feedstock molecule which is larger than catalyst size (surface area and
Bio-jet fuel yield (wt%) 80.40 72.50 84.30
compound such as organic acids, ketones, aldehydes and others reactive
compounds.
4.3. Single step process
Furthermore, the production of bio-jet fuel can be done by single
step process, either by a direct deoxygenation method or simultaneous
processes of deoxygenation-cracking-isomerization. As referred to
Table 6, Aslam et al. [124] applied direct hydrodeoxygenation to
convert Mesua ferrea L. seed oil at 400 °C under 7.5 MPa of hydrogen for
4 h with the presence of Na2CO3 catalyst. At the end, their work yielded
the lowest amount 22.0 wt% of bio-jet fuel as seen in Table 6 for single
step process. This may due to the high reaction temperature and pres-
sure which exceeded the optimum range, and subsequently affected the
yield of hydrocarbon chain for jet fuel range, which was also previously
reported by Anand et al. [85]. Contrarily, Choi et al. [125] performed a
direct deoxygenation on soybean oil, by using PB811 catalyst in the
presence of nitrogen gas instead of hydrogen gas. Their methodology of
work was able to achieve approximately 95% of deoxygenation rate and
yielded the amount of 31.0% bio-jet fuel. Next, Zhang et al. [126]
conducted simultaneous hydrodeoxygenation-cracking-isomerization
on waste cooking oil at 380 °C and 3 MPa of hydrogen for 4 h with
NiMo/USY@Al-SBA-15 catalyst, and cyclohexane was used as solvent.
A yield of 39.7 wt% bio-jet fuel was obtained in their work, which was
mainly due to good acid and pore distribution of the catalyst, and hence
significantly enhance the selectivity of bio-jet fuel hydrocarbons
(C8–C16) during isomerization. Chu et al. [127] implemented hydro-
deoxygenation on Camelina sativa oil and Brassica carinata oil at 400 °C
under 9.2 MPa of hydrogen for 2 h with NiMo-based catalyst. Their
work was able to yield the highest amount of 53.5 wt% of bio-jet fuel.
They also reported that feedstocks with higher degree of unsaturated
bond consumed more hydrogen during the hydrodeoxygenation pro-
cess. Souza et al. [128] carried out micropyrolysis on cottonseed oil
dregs with flow of nitrogen gas. They concluded that the presence of
water in the biomass encouraged the cracking process, resulting in a
yield of bio-oil that was about 10% higher than obtained with dry
biomass. The production of C8–C16 hydrocarbons are proportional to
reaction temperature. However, the best hydrocarbon production per-
formance was achieved at 500 °C by using the tungsten-TiO2 (WT)
catalyst, which could be attributed to its higher surface area. Lastly,
Chen et al. [93] performed a catalytic deoxygenation co-pyrolysis of
bamboo wastes and microalgae (i.e. spirulina platensis, nanno-
chloropsis sp.) with biochar catalyst. Their work concluded that oil
fraction yielded from co-pyrolysis of bamboo waste and microalgae was
20% higher than without biochar catalyst. Nonetheless, the addition of
biochar in the co-pyrolysis process was able to yield oil fraction with
higher high heating value (HHV) and remove oxygen of the bio-oil over
90 wt%.
4.4. Summary
As overall, Table 6 shows that bio-jet fuel production of 3-step
process that was reported by Wu et al. [118] showed highest amount of
12
Energy Conversion and Management 199 (2019) 112015
bio-jet fuel (84.3 wt%) production; while single step process done by
Aslam et al. [124] by using Mesua ferrea L. seed oil yielded the lowest
amount of bio-jet fuel (22.0 wt%). Nonetheless, the single step process
was also able to achieve the highest yield of 53.5 wt% bio-jet fuel by
Chu et al. [127] with the usage of Camelina sativa oil and Brassica
carinata oil. Although the single step process has lower yield of bio-jet
fuel as compared to 3-step process in general, past researchers had
pointed out some factors that can be further improved to achieve a
higher yield of bio-jet fuel. Firstly, Nakaji et al. [119] stated that
porosity) will experience a large loss of carbon balance. In this case, the
size of feedstock molecule can be minimized, either through pyrolysis in
prior to deoxygenation or increase the reaction temperature during
deoxygenation process. Chu et al. [127] also stated that the consump-
tion of hydrogen gas during the hydroprocessing of bio-jet fuel depends
on the saturation of fatty acids in feedstock. According to past re-
searchers, the saturation of hydrocarbon bonds can be managed by
increasing the hydrogen pressure during hydrogenation, hydrogenolysis
and hydrodeoxygenation. However, both of the reacting temperature
and pressure should be maintained within optimum range. This is be-
cause extreme reacting temperature (> 400 °C) and hydrogen pressure
(> 5 MPa) will result in undesirable cracking of hydrocarbon into
shorter carbon chain, subsequently end up with a very low yield of bio-
jet fuel, which is less than 30 wt% [85,107,124]. Besides, the type of
acid-base catalyst used in hydroprocessing of bio-jet fuel also plays a
major factor in improving the yield of bio-jet fuel. Zhang et al. [126]
reported that structure and acid distribution of the zeolite catalyst
would affect the isomerization activity and selectivity of jet fuel hy-
drocarbons. In addition, Shahinuzzaman et al. [129] suggested the use
of non-sulphide supported zeolite catalysts in bio-jet fuel production,
due to its uniform pore structure, higher surface area, higher pore vo-
lume, higher concentrations of active acid sites, and high reusability.
5. Challenges and future perspective
Based on the summary of bio-jet fuel production via hydroproces-
sing technology, some challenges and limitation are highlighted for
further improvement in the future. Firstly, the choices and selection of
feedstock for bio-jet fuel production can be varied, by exploring more
potential non-edible feedstock with supply guarantee in long run. Raw
biomass feedstock with complex composition of fatty acid and im-
purities, which will hinder the selectivity and activity of catalysts in the
conversion process [130]. In some studies, researchers claimed that the
distillation profile of feedstock affects the quality of final fuel quality
and fuel properties [131]. Hence, in order to obtain a higher yield of
bio-jet fuel, a potential feedstock should have a higher saturation of
fatty acids, smaller size of molecule, and higher elemental composition
of carbon and hydrogen [119,127]. In addition, there is a knowledge
gap on the studies dealing with the valorization of residue remained
after the hydroprocessing of bio-jet fuel. The utilization of residual
biomass can be further processed via pyrolysis and zeolite upgrading, so
that a sustainable bio-jet fuel production can be achieved [40].
Apart from that, feedstock such as algae can be further explored on
its various species, cultivation conditions, and oil extraction method to
improve the bio-jet fuel production. Although algae can be cultivated
either in open pond or closed loop system, the temperature main-
tenance and energy requirement for the algae culture is always a major
challenge [132,133]. Hence, new species of algae can be explored
through genetic modification, and the cultivation condition should
exhibit the growth and lipid content of the algae, in order to gain a
higher crude bio-oil yield [134–136]. Moreover, there are some po-
tential pathways highlighted in the literature for the conversion of
algae into bio-jet fuel. Researchers suggested that hydrotreated
pathway might be worthy for algae with high lipid content, while Fi-
scher-Tropsch pathway is suitable to algae with low lipid content and
high carbohydrate [137,138].
E.S.K. Why, et al.
Next, the development of better hydroprocessing catalyst can be
done, in order to increase the selectivity of bio-jet fuel. The improve-
ment of catalyst properties can be done regarding its metal active sites
or high hydrodeoxygenation activity [92]. Besides, improvement on
zeolite catalyst structure, concentration of active acid sites, surface
area, pore volume, and its reusability, can aid in simultaneous hydro-
cracking and isomerization process of alkanes [126,129,139]. On top of
that, some researchers had also developed catalyst for bio-oil pyrolysis
and deoxygenation from waste char (i.e. bamboo waste and scrap tyre)
[93,140]. The catalytic performances of char catalysts were found
comparable to synthetic catalyst under similar reacting condition. An
ideal catalyst is expected to have optimum performance in yielding
maximum bio-jet fuel from feedstock at lower reacting temperature and
pressure. Thus, this will help to reduce the operating costs involved in
hydroprocessing.
Furthermore, there are necessaries to improve the single step pro-
cess of bio-jet fuel production. Past researchers had implemented si-
multaneous hydroprocessing steps of hydrodeoxygenation-cracking-
isomerization in the bio-jet fuel production. Although bio-jet fuel could
be yielded successfully from single step process, they could only yield a
low amount of bio-jet fuel, which was less than 40.0 wt% [124,126]. In
addition, effect of parameters such as extreme reacting temperature and
pressure beyond optimum range would also end up low yield of bio-jet
fuel as claimed by past researchers [85,124]. Hence, it is necessary to
explore more potential feedstock and development of new catalyst,
which are suitable to yield a higher amount of bio-jet fuel in single step
process. Apart from that, past researchers had also developed deox-
ygenation of bio-oil by using nitrogen gas instead of hydrogen gas. This
method enabled them to yield the highest amount of bio-jet fuel
(53.5 wt%) among the reviewed work of single step process [127].
Therefore, more studies can be conducted by using nitrogen gas for bio-
oil deoxygenation process, especially for the bio-jet fuel production,
under different reacting conditions, such as at atmospheric pressure or
vacuum state [90,91]. The use of nitrogen gas will also help in reducing
the sole dependent on hydrogen gas for deoxygenation process.
Finally, there is no ample comparison work of energy consumption,
green metrics and economic analysis on different hydroprocessing
method found in the literature. The energy consumption analysis (i.e.
electricity consumption, thermal energy for heating and cooling, me-
chanical energy for stirring and pumping stream) can be evaluated from
different hydroprocessing technology. On the environmental aspect,
cultivation of feedstock and hydroprocessing of biomass to bio-jet fuel
will have impacts on the land use and water. Improper land use for
feedstock cultivation will affect the biodiversity and soil fertility to
sustain biomass production [141]. On the other hand, water scarcity
may occur due to the biomass production, which consumes 5.5% of the
total available drinking water for humans [142]. Thus, the efficiency
and environmental performance of the advanced hydroprocessing
processes for bio-jet fuel conversion can be quantified by using green
metrics [143].
Furthermore, the economic analysis can be estimated by considering
the cost of raw material, cost of electricity demand for hydroprocessing
process and cost of final bio-oil yield from different intermediate steps
per gallon. In some studies, the economic analyses were done on a
specified feedstock (e.g. Jatropha, forest-based biofuel), starting from
farming processes to refinery processes in different countries, and their
minimum jet fuel selling prices (MJSP) were compared [144,145]. This
gives the idea to further carry out the economic analysis on more dif-
ferent types of feedstock in different farming regions, in order to
compare their cultivation cost. Lastly, through the development of bio-
jet fuels, the incentives for the use of bio-jet fuels in commercial flight
can reduce bio-jet fuel price, as the conventional jet fuel price will be
increased due to the higher charging of CO2 emission tax [146].
13
Energy Conversion and Management 199 (2019) 112015
6. Conclusion
A review on bio-jet fuel production via hydroprocessing technology
has been discussed, including the advanced methods (3-step, 2-step and
single step process) that were performed by past researchers in recent
years. The options of feedstock processed by the advanced methods are
not only restricted to liquid biomass (vegetable oil and animal fats), but
also include solid biomass such as saw dust, straw stalk and oil dregs.
The adoption of these biomass were able to yield favorable amount of
bio-jet fuel. Besides, single step process being the latest trend of bio-jet
fuel hydroprocessing is further investigated, by adapting hydro-
deoxygenation process in majority. However, there are challenges and
limitations that can still be further improved in the single step process,
such as the selection of feedstock, development of catalyst and reacting
parameters. Although it is inevitable for producing fractions of diesel
and gasoline as end products, it is believed that such research efforts
and exploration can aid to maximize the yield of bio-jet fuel production
in single step process. Other than that, the energy, environmental and
economic analysis on the advanced hydroprocessing method are yet to
be conducted, in order to compare their merits. Hence, the feasibility
and sustainability of hydroprocessing of bio-jet fuel can be assured in
long run.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
The authors would like to acknowledge the financial support of the
University of Malaya and Ministry of Education, Malaysia under FRGS-
MRSA (MO014-2016) and Partnership Grant (RK002-2019).
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