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Renewable and Sustainable Energy Reviews 79 (2017) 709–729

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews


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

A review on the production processes of renewable jet fuel MARK


a,⁎ b a b
C. Gutiérrez-Antonio , F.I. Gómez-Castro , J.A. de Lira-Flores , S. Hernández
a
Universidad Autónoma de Querétaro, Facultad de Química, Cerro de las Campanas s/n Col. Las Campanas, Querétaro 76010, Mexico
b
Universidad de Guanajuato, Campus Guanajuato, División de Ciencias Naturales y Exactas, Departamento de Ingeniería Química, Noria Alta s/n,
Guanajuato 38010, Mexico

A R T I C L E I N F O A BS T RAC T

Keywords: The aviation sector contributes with 2% of the total anthropogenic CO2 emissions, and predictions estimate that
Biojet fuel air traffic will double in the next 20 years, doubling fuel requirements and CO2 emissions. The International Air
Synthetic paraffinic kerosene Transport Association (IATA) has identified the development of renewable aviation fuel, known as biojet fuel, as
Renewable aviation fuel the most promising strategy to reduce the environmental impact of the aviation sector. The renewable
Renewable jet fuel
hydrocarbons that constitute biojet fuel are also known as synthetic paraffinic kerosene (SPK), and their
Production process
properties are almost identical to those of jet fuel. SPK has also the advantage of containing very little sulfur,
Technological advances
producing lower CO2 emissions than jet fuel. The focus of this paper is to review the scientific and technological
advances related to the existing pathways to produce biojet fuel, and to identify those that could lead to the
future implementation of a sustainable production chain for renewable aviation fuel. The production process of
biojet fuel is the key to satisfying both technical and economic goals required to obtain a more competitive
biofuel, and allow the sustainable development of aviation sector.

1. Introduction (2010–2050), therefore CO2 emissions due to transportation will grow


from 16% to 79% [4]. It is worth to mention that the increase in CO2
In recent decades, there has been a considerable increasing in the emissions is smaller than the growth in fuel consumption due to
concentration of pollutants in the atmosphere, particularly greenhouse increasing engine efficiency of vehicles. The large growth predicted for
gases which are, to a great extent, responsible for climate change. The the transport sector is due to the doubling of international air traffic,
consequences of this phenomenon have been observed in recent years, along with the increasing by 50% of transportation of goods by road.
and they include the accelerated melting of the polar ice caps, changes Jet fuel and diesel will be the primary fuels required for the growth of
in weather patterns and even the extinction of animal species. Among the transport sector.
the greenhouse gases, CO2 is the main contributor to climate change Therefore, the goals of reducing CO2 emissions in the transport
[1]. sector have become an important driver for the development of biofuels
According to the Intergovernmental Panel on Climate Change, [5]. The International Energy Agency estimates that by 2050 biofuels
annual CO2 emissions increased by 80% between 1970 and 2004; this will account for 27% of all fuels in the transport sector, particularly as a
increment is explained in terms of the growth rate of CO2 equivalent, replacement of diesel and jet fuel [5,6]. Therefore, it is of great interest
which from 1995 to 2004 was more than double (0.92 GtCO2-eq per to develop efficient and sustainable processes to produce renewable
year) than that of the previous period from 1970 to 1994 (0.43 GtCO2- diesel and renewable aviation fuel; this work focuses on the production
eq per year) [2]. CO2 emissions arise mainly from power generation processes of renewable aviation fuel, also known as biojet fuel.
and transport, which together represented 64% of the total anthro- Biojet fuel has recently started to attract interest, and it has been
pogenic CO2 emissions in 2009 [3]. This fact has driven the search for identified by the IATA as the most promising strategy to reduce CO2
alternative energy generation and renewable fuels to reduce emissions emissions in the aviation sector [7]. Additionally, it is expected that the
into the atmosphere. use of biojet fuel in the aviation sector will allow, at least, partial fuel
In particular, in 2014 the transport sector required 2627.02 million independence. Next, we will define fossil jet fuel in order to present
tons of oil equivalent, representing 27.9% of the total energy produced biojet fuel.
in the world [4]. In addition, it is estimated that energy consumption in Fossil jet fuel is composed of approximately 20% paraffins, 40%
this sector will increase between 80% and 130% in the next decades isoparaffins, 20% naphthenes and 20% aromatics [8]. This combination


Corresponding author.
E-mail addresses: claudia.gutierrez@uaq.mx, claugtez@gmail.com (C. Gutiérrez-Antonio).

http://dx.doi.org/10.1016/j.rser.2017.05.108
Received 21 October 2016; Received in revised form 7 January 2017; Accepted 18 May 2017
Available online 24 May 2017
1364-0321/ © 2017 Elsevier Ltd. All rights reserved.
C. Gutiérrez-Antonio et al. Renewable and Sustainable Energy Reviews 79 (2017) 709–729

Table 1
Some properties of fossil and renewable jet fuel.

Jet-A Jet-A1 Biojet fuel from jatropha Biojet fuel from camelina

Fuel type Kerosene Kerosene Synthetic paraffinic kerosene Synthetic paraffinic kerosene
Boiling range (°C) 170–300 170–300 172–243 188–263
Freezing temperature (°C) −40 −47 −57 −63.5
Flash temperature (minimum 38 °C) 38 38 46.5 42.0
Density at 15 °C (kg/m3) 775–840 775–840 751–840 751–840
Viscosity at −20 °C (maximum 8 mm2/s) 8.0 8.0 3.66 3.33
Energetic content (MJ/kg) 43.28 43.28 44.3 44.0

implementation of a sustainable supply chain for renewable aviation


fuel. The production process of biojet fuel is the key to satisfying both
technical and economic goals required to obtain a more competitive
biofuel.
The paper is organized as follows. First, the identified pathways to
produce biojet fuel are presented, giving a brief description of the
process involved in each one of them. Then, the scientific and
technological advances reported in each pathway are described.
Later, some insights into future efforts that could lead to the imple-
mentation of a sustainable supply chain for renewable aviation fuel are
addressed. Finally, the up-to-date compilation of the demonstration
flights where biojet fuel was used, along with industrial scale projects
associated with biojet fuel are mentioned.

2. Pathways to produce biojet fuel

Synthetic paraffinic kerosene (SPK) can be produced from coal,


Fig. 1. Identified pathways for the production of biojet fuel.
natural gas or biomass [12]. However, biomass is the only renewable
alternative; therefore, production processes where coal and natural gas
gives fossil jet fuel its physical properties, showed in Table 1, as
are used as raw materials are not included in this review. In general,
freezing point (−47 °C) and energy content (43.28 MJ/kg) [9,10].
the biojet fuel production processes transform the biomass through
Biojet fuel consists of renewable hydrocarbons in the boiling range of
different processing routes; the biomasses that can be used to produce
fossil jet fuel; in other words, it has a similar composition to fossil jet
biojet fuel include triglycerides, lignocellulosic biomass, sugar and
fuel, and it can contain aromatic compounds depending on the
starchy feedstock, as it is shown in Fig. 1. Depending on the renewable
production process used. If aromatic compounds are not present, the
raw material, the following pathways are identified: hydroprocessing of
emitted particles from burning biojet fuel are lower than those
triglyceride feedstock, thermochemical processing of biomass, and
generated with fossil jet fuel [11]. However, the lack of aromatic
alcohol to jet [19]. From these pathways, the hydroprocessing of
compounds can cause wear in certain types of engines [12], and they
triglyceride and the thermochemical conversion of biomass by gasifica-
are required to swell o-rings and seals in engines. Therefore, using
tion and Fischer-Tropsch are the only ones certified by ASTM for the
biojet fuel in mixtures of 50% volume with fossil fuels has been
production of biojet fuel for commercial use.
established as a standard [13]. However, aromatic compounds can be
These pathways offer different advantages and disadvantages. In
added to biojet fuel, and in this case it is technically feasible to use it at
general, those pathways with expensive feedstock, as materials contain-
100% in aircraft engines [14]. Biojet fuel, also known as synthetic
ing triglycerides, requires low cost processing. On the other hand, low
paraffinic kerosene (SPK), is constituted by renewable hydrocarbons
cost raw materials, as lignocellulosic biomass, require many stages of
which properties are almost identical, or in some cases superior [15], to
processing, which increases the cost. Therefore, the selection of the
those of fossil jet fuel, as can also be seen in Table 1. The combustion of
best production process must obey to the availability of the raw
SPKs produces lower CO2 emissions than fossil jet fuel [11]; also, they
materials; since the raw materials costs and its transportation will
have the advantage of containing very little sulfur. Therefore, biojet fuel
affect the supply chain, which plays an important role in the viability of
has been identified by the IATA as the most viable alternative for the
the production process of biojet fuel [20]. Next, a brief description of
replacement of fossil fuels in aviation [16,17].
each pathway along with the scientific and technological advances
Recently, two review papers have addressed the status of aviation
reported in the literature are presented.
fuel. In 2013, Liu et al. [12] wrote a review concerning the production
of fossil jet fuel. In their work, a section was included where the
commercially available processes for biojet fuel production were briefly 3. Hydroprocessing pathway
described; however, in this section only two scientific references were
included. On the other hand, Wang et al. [18] gave a review of the The hydroprocessing pathway consists on the chemical conversion
different pathways to produce biojet fuel; in their work, information of triglyceride feedstock through hydrodeoxygenation, hydroisomeriz-
about flow diagrams of different pathways were presented. ing and hydrocracking to produce biojet fuel [21]. Fig. 2 shows the
Nevertheless, a compilation of all the scientific works related to the block diagram of hydroprocessing pathway, where the main sections of
production of biojet fuel as well as the technological advances (patents) the process can be observed. In the reactive section the triglyceride
is still missing. feedstock is first converted to lineal long chain hydrocarbons, with
Therefore, the focus of this paper is to perform a review of the hydrogen and a solid catalyst at high pressure and temperature; for
scientific and technological advances related to the biojet fuel produc- this, deoxygenation and decarbonylation reactions are performed,
tion processes, identifying the future pathways that could lead to the generating water, carbon monoxide and carbon dioxide as byproducts.
The lineal long chain hydrocarbons generated in the first reactor enter

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C. Gutiérrez-Antonio et al. Renewable and Sustainable Energy Reviews 79 (2017) 709–729

Fig. 2. Hydroprocessing pathway: conversion of triglyceride feedstock to biojet fuel.

to a second one, where cracking and isomerizing occurs. In this way, gas oil. A pre-sulfided catalyst was applied with di-methyl-di-sulfide
the hydrocarbon chains are in the range of C8 and C16, corresponding and tetra-butyl-amine. Several parameters were evaluated to obtain
to biojet fuel. Additionally, light gases, naphtha and green diesel are better conversion and selectivity of the diesel, kerosene/jet and
produced; therefore, the separation of the renewable hydrocarbons is naphtha. In the work of Bezergianni et al. [31] three reactor tempera-
realized, usually by means of distillation. Triglyceride feedstock include tures (350, 370 and 390 °C) were studied, with a pressure of 13.8 MPa,
vegetable oils, animal fats, pyrolysis oil and bio-oil. Non-edible oils, a liquid hourly space velocity (LHSV)=1.5 h-1 and a relation H2/
such as jatropha oil, algae oil, animal fats and used cooking oils, are oil=1068 NPT m3/m3. The results indicated that as temperature
some triglyceride-based feedstock that can be converted into biofuels increases, the conversion increases from 73% to 82%. The kerosene/
[22]. Vegetable oils obtained from edible crops can also be used; jet and naphtha selectivity are below 20% (the major conversion was
however, this is not suggested because it creates a conflict with the food for diesel, 70%). They concluded that if more selectivity for kerosene/
sector. Vegetable oils can be obtained through mechanical, solvent jet was required, then the temperature reactor must be higher and the
aided or enzymatic extraction processes; from these alternatives the LHSV must be greater than 1.5 h-1 to favor cracking. In their second
higher efficiencies in a short period of time are obtained with solvent study, they employed three different feedstock and three different
aided extraction. Recently, supercritical CO2 has gained importance as catalysts [36]. The operation conditions were H2/oil=0–1600 NPT m3/
solvent for the oil extraction. Animal fats are waste from the animal m3, P=0–150 atm, T=25–450 °C, and a catalyst volume=6.5–50 ml.
processing industry, while waste oils are generated in the food services The analysis of the results shows that kerosene/jet selectivity depends
industry and in the domestic sector. On the other hand, bio-oil is a on the catalyst selection and the reactor temperature, but renewable
resulting product from pyrolysis, which is the thermal decomposition diesel fuel is still the primary product.
of biomass in the absence of oxygen, and it is carried out at low ( < In BioSynfining™, the SPK is produced from fatty acids and
450 °C) and high ( > 800 °C) temperatures [23]. In spite of the fact that triglycerides. Fatty acid chains are converted into n-paraffins via the
bio-oil is a fuel it usually needs upgrading, being hydroprocessing one hydrotreating process. The long straight-chain paraffins are hydro-
of the used strategies to achieve such objective. Next, the revision of the cracked into shorter branched paraffins. The hydrocracked products
scientific works related with this pathway are presented, and after that fall mainly in the kerosene and naphtha boiling range. During the first
the technological advances are going to be described. half of 2008, Syntroleum successfully produced over 600 gal with Bio-
Synfining™ [12]. This process is very similar to the developed by UOP
Honeywell.
3.1. Scientific advances
From these point, several catalysts, raw materials and conditions
were analyzed in experimental hydrotreating studies, which are pre-
The first biojet fuel production process was proposed by UOP
sented next. Shi et al. [33] obtained biojet-biodiesel hydrocarbons from
Honeywell Company. UOP and ENI S.p.A. (UOP/ENI Ecofining™)
cornstalk oil. The proposed process uses a hydrodeoxygenation step,
[24–27] developed a process to produce green diesel. A selective
whose operating conditions are a 10 wt% Ni/ZrO2 catalyst and
cracking process has been added to the previous one to produce green
cyclohexane loaded into a stainless steel reactor and pressurized to
jet aviation fuel [17,28,29]; with this process the maximum conversion
5 MPa with H2 at a temperature of 300 °C. After 4 h of reaction time,
to biojet fuel is 36%, being the total conversion to hydrocarbons of 70%
they obtained 81.6% carbon yield, with 90% diesel and jet range (C8–
[17,28,29]. This green jet fuel was used in a 50% blend in several
C22) hydrocarbons, and yields of 7% and 3% for gasoline-range (C6–
commercial airline flights across the United States in 2007 [29]. The
C7) hydrocarbons and other-range hydrocarbons, respectively. The
exact blend of components still needs to be optimized [17].
operating conditions and hydrogen requirements of this process are
Additionally, the UOP/Eni Ecofining™ process is associated with a
nobler than the previous ones; however, the reaction time is elevated
high consumption of hydrogen [30], which may represent a disadvan-
and implies a batch process which may not be the most economical
tage in terms of cost and process safety. It is worth to add that
alternative for industrial production.
according to UOP’s lifecycle analysis a reduction of 65–85% of green-
At the Indian Institute of Petroleum, Verma et al. [34] studied the
house gas emissions is obtained with this process, in comparison with
hydroprocessing of jatropha oil over sulfided NiMo and NiW catalysts
petroleum-based fuels [28]. Raw materials includes vegetable oils,
supported by SAPO-11. The study was performed in a fixed-bed reactor
waste oils and animal fats. With base on this process several research
with the following operating conditions: 375–450 °C and 60–80 bar.
works have been reported.
They reported obtaining 40% aviation kerosene selectivity of the liquid
Bezergianni et al., from the Chemical Process Engineering Research
hydrocarbon product (84 wt% yield). The jet fuel obtained contained
Institute (CEPI), produced biofuels by hydrocracking using cooking oil
8% of aromatic components. This result carries an interesting advan-
[31] and vacuum gas oil (VGO) of vegetable oil mixtures [32]. For both
tage, as hydrogen consumption was reduced in the process; also, a
raw materials they used a CEPI-hydroprocessing unit, which is a small-
desirable density and viscosity as well as low sulfur content were
scale pilot plant unit where hydrotreating and hydrocracking of various
reached. An important achievement is the production of aromatic
feedstock can be performed, varying from light gas oil to heavy vacuum

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C. Gutiérrez-Antonio et al.

Table 2
Summary of hydrotreating reported scientific studies.

Raw Material Operating Conditions Catalyst Reactor Yield Reference Comments


Oil/biojet
P (MPa) T (°C) H2 LHSV (h-1) fuel wt%

soybean oil, 3 300–350 500 ml/min 5–10 wt% nickel BASF continuous-flow reactor 40–52 [30] Bio fuel produced with tung oil had 60% aromatic
jatropha oil Nysofact 120 catalyst system content. This yield is for biocrude produced with soybean
and tung oil oil, jatropha oil and tung oil. Biocrude yield (% wt) was
85% for soybean oil, 76.2% for jatropha oil and 77.2% for
tung oil
Cooking oil 13.8 390 1068 N m3/m3 oil 1.5 Commercial pre- Fixed bed reactor < 16.4 [31] Diesel yield was 57.4%.
sulphided For mayor biojet fuel selectivity, temperature must be
catalyst+DMDS+TBA increased
VGO 13.8 350 1068 N m3/m3 oil 1.5 Commercial pre- Fixed bed reactor 21 [32] Diesel yield was 41.6%
sulphided
catalyst+DMDS+TBA

712
corn stalks bio oil 5 300 For pressurized 10 wt% Ni/ZrO2 catalyst Stainless steel reactor 90 [33] This yield is for diesel and jet range (C8-C22).
reactor to 5 MPa
Jatropha oil 6–8 (CH) 375−450 1500 ml H2/ ml gas 1 sulfided NiMo and NiW Fixed-bed reactor 40 [34] The jet fuel obtained contained 8% of aromatic
7 (DCO+DC (CH) (CH) catalysts supported by components
and HDO) 400 (DCO 1500 ml H2/ml oil SAPO-11
+DC and (DCO+DC and HDO)
HDO)
Castor oil 3 (HDO) 300 (HDO) 160 ml/min (HDO) Ni/MCM−41–APTES– Continuous flow fixed-bed 80.3 [35] They proposed two routes, one step route and two steps
USY bifunctional catalyst microreactor route. This result is for one step route
Jatropha oil 8 380–440 2500 H2/feed volume Ni-Mo/γ-Al2O3 catalyst Two laboratory scale reactors 46 [36] This yield is for microchannel reactor. Monolithic reactor
ratios (microchannel and yield was 36.2 wt%
monolithic)
soybean oil 3.04 370–385 800 N lt/lt 1 1% and 0.5% of Pt/Al2O3/ fixed-bed reactor 42–48 [37] > 12 wt% aromatics was achieved.
SAPO−11,
and Ni2P/HY

Catalytic Hydrotreating (CH), decarboxylation (DCO), decarbonylation (DC) and hydrodeoxygenation (HDO); [bmim]Cle2AlCl3 is (1-butyl-3-methylimidazolium chloroaluminate) ionic liquid.
Renewable and Sustainable Energy Reviews 79 (2017) 709–729
C. Gutiérrez-Antonio et al. Renewable and Sustainable Energy Reviews 79 (2017) 709–729

components, which may allow the use of higher amounts of renewable proposed the intensification of the hydrotreating process for biojet fuel
jet fuel in mixtures with fossil jet fuel. production, through the use of thermally coupled distillation. In their
In another study, Liu et al. [35] synthesized biojet fuel by hydro- study, two conventional and four thermally coupled distillation
processing castor oil in a continuous flow fixed-bed microreactor. The sequences were analyzed. These schemes were designed using a
hydrodeoxygenation reaction conditions were 300 °C, 3 MPa, and multiobjective genetic algorithm with constraints handling coupled to
LHSV=2 h-1 with a H2 flow rate of 160 ml/min at atmospheric Aspen Plus process simulator. They found that the direct thermal
pressure; the hydroisomerization reaction conditions were 360 °C, distillation sequence allows savings of 21% in operating costs, com-
3 MPa, and weight hourly space velocity (WHSV)=2 h-1 with a H2 flow pared to the best conventional distillation sequence. This contribution
rate of 160 ml/min at atmospheric pressure. Additionally, the authors is interesting since it explores the reduction in energy consumption in
produced biojet fuel via two routes; one was a two-step process, and the the separation zone.
other was a one-step process. In the two-step process, the hydrodeox- Recently, Gutiérrez-Antonio et al. [40] proposed the energy inte-
ygenation of castor oil with Ni/SAPO-11, Ni2P/SAPO-11 and Ni/MCM- gration of the hydrotreating process considering Jatropha curcas oil as
41 catalysts can produce high yields of C17–C18 (90–96 wt%); renewable raw material. The conventional process was compared with
however, the mole ratio of C17–C18 is higher for Ni/SAPO-11. the resulting of applying energy integration. They found that the
Hydrocracking of C17-C18 hydrocarbons along with the isomerization heating-cooling services are decreased when energy integration is used;
process produced C8-C15 alkanes with high isomerization selectivity; a however, capital costs are increased due to the additional equipment
series of catalysts with different Ni/Ag mole ratios supported by SAPO- required. Therefore, the effect on total annual costs is really small.
11 (Ni+Ag=25%) were used. The authors found that the level of Nevertheless, a reduction of 86% in CO2 emissions was found in the
cracking depended on the acid strength and the amount of the process where energy integration is applied. Later, considering the
catalysts. Additionally, an increase of Ni/Ag molar ratio produced same raw material, the simultaneous energy integration and intensifi-
higher yields of C8–C15 and isomerization selectivity. However, when cation in the separation zone was addressed [19]. Again, the main
the Ni/Ag molar ratio was higher than 44%, the yields of C8–C15 began effect was observed in the reduction of CO2 emissions.
to decrease. On the other hand, in the one-step processing, a Ni/MCM- All the previously presented works consider vegetable oil or waste
41–APTES–USY bifunctional catalyst was synthesized to produce oil as renewable raw materials. However, as mentioned before,
biojet fuel; APTES is (3-aminopropyl)-triethoxysilane while USY is a pyrolysis oil can also be hydrotreated in order to produce renewable
ultra-stable zeolite Y. Ni/MCM-41–APTES (7.5 wt%)–USY allowed jet fuel. Elliot et al. [41] have been working on hydroprocessing
yields of 80.3% for C8–C15 with high isomerization selectivity (i/n systems for more than twenty years, and have found that direct
4.4) under the reaction conditions of 300 °C, 3 MPa, and 2 h-1. In processing of bio-oil in conventional hydroprocessing systems has led
addition, the mesoporous–microporous system improved catalytic to failure in several cases [42,43]. A review considering the period of
efficiency; and when the temperature increased, the degree of cracking 1983–1990 [44] suggests the use of different operating conditions with
and isomerization selectivity improved as well. multiple catalysts to achieve the desired product; because depending
Sinha et al. [36] used a Ni-Mo/γ-Al2O3 catalyst in two laboratory on these conditions gasoline, diesel or jet fuel can be obtained.
scale reactors (microchannel and monolithic) to hydroprocess Jatropha Additionally, the hydrotreating process is used along with fast pyrolysis
oil, at 380–440 °C with an operational pressure of 80 bar at several H2/ to reduce oxygen levels in the bio-oil production, in order to decrease
feed volume ratios. The results showed that both reactors output up to hydrogen consumption [45]. Another outstanding review [46] dis-
6–20 times higher kerosene selectivity than a conventional trickle bed cusses the chemistry, catalysts, and challenges involved in biofuel
reactor. In this case the use of intensified equipment allows higher production through the conversion of biomass, derived from a feed-
selectivity, which positively impact in the production costs of biojet stock in fluid catalytic cracking and hydrotreating refinery units. On the
fuel. other hand, fast pyrolysis maximizes the oil production ( > 80 wt% of
Drop-in jet fuel was prepared from soybean oil by hydrodeoxygena- dry feedstock). This process involves heating finely ground feedstock
tion, mild hydrocracking and additional isomerization stages [37]. The (400–600 °C) for a few seconds, and then quenching the vapors
hydrodeoxygenation process was carried out in a fixed-bed reactor produced to generate a bio-oil [47]. Two reviews of the fast pyrolysis
using a 1% Pt/Al2O3/SAPO-11 catalyst at LHSV=1.0 h-1, 370–385 °C, process can be found in Chiaramonti et al. [48] and Radlein and
and 30 atm with a H2/oil flowrate ratio of 800 NPTl/l. This mild Quigmard [49]. Next, works related with hydroprocessing of pyrolysis
hydrocracking used the Ni2P/HY catalyst and the additional isomer- oil are presented.
ization used 0.5% Pt/Al2O3/SAPO-11 catalyst. A high yield (42–48 wt The cooperative research and development agreement between
%) of jet fuel with > 12% aromatics was achieved. UOP LLC, the National Renewable Energy Laboratory and the Pacific
Table 2 shows a summary of the experimental studies related with Northwest National Laboratory (PNNL) [12] have allowed the con-
hydroprocessing. From Table 2 it can observed that several catalysts struction and operation of a pilot-scale biorefinery. The pilot-scale
have been studied, mainly based on Ni, Mo and Pt. The higher yield is biorefinery includes the UOP Ecofining™ technology to upgrade the
obtained with Ni/MCM-41–APTES–USY bifunctional catalyst [35]. pyrolysis oil. This facility processes one ton of dry biomass per day
Also we can observe that the minor yield was obtained with cooking using fast pyrolysis [50] and hydrotreating to produce transportation
oil as raw material, even when the operating conditions are elevated fuel; in fast pyrolysis the biomass is heated very fast at 450–600 °C also
[31]; a similar situation is observed when VGO is used as raw material in absence of oxygen. These companies have developed the Rapid
[32]. Therefore, it is necessary to study the performance of another Thermal Processing process (RTP™ process) [51,52], where cellulosic
kind of catalysts for these raw materials, especially the cooking oil since biomass is rapidly heated in the absence of oxygen. The vaporized
it could be a low cost feedstock alternative. Moreover, another biomass is cooled to produce pyrolysis oil. This process uses a fluidized
important study [37] report a good yield to biojet fuel, 42%, with also bed reactor system. The typical process yields are between 65 wt% and
includes aromatic compounds; the main disadvantage of this work is 75 wt% pyrolysis oil from dried woody biomass, which can be used as a
that the raw material is used in human diet. fuel for industrial heating and generation of electrical power. The
On the other hand, few simulation studies related with hydrotreat- produced oil can also be upgraded by UOP Ecofining™ technology to
ing process can be found. In 2013, the modeling and optimization of produce green gasoline, diesel and jet fuel. This approach is interesting
the hydrotreating of castor oil to produce jet fuel was presented [38]. In since low cost and abundant biomass can be used to generate renew-
this study, a conversion of 22% was reported for biojet fuel. The able jet fuel. Nevertheless, it is important to take into account that
conventional distillation sequences were optimized with a multiobjec- pyrolysis usually requires high quantities of energy, causing high
tive genetic algorithm. Later, in 2015, Gutiérrez-Antonio et al. [39] environmental impact.

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C. Gutiérrez-Antonio et al. Renewable and Sustainable Energy Reviews 79 (2017) 709–729

Zhang et al. [53] synthetized jet fuel (paraffins and aromatics) using the transesterification process are nobler, and, therefore, reduction in
a hydrotreating upgrading process; the raw material was bio-oil, operating costs can be expected.
produced by catalytic microwave-induced pyrolysis of Douglas fir From these reported studies it can be observed that the hydrogen
pellets. The transformation process consists of the following two steps: requirements are high, and in some cases there is the necessity of high
a catalytic microwave pyrolysis (with a ZSM-5 catalyst) and a hydro- temperatures in order to produce more biojet fuel. As an alternative to
treating process (stirred stainless batch reactor, with 5 wt% or 10 wt% reduce hydrogen consumption from conventional hydrotreating pro-
Raney nickel catalysts). C8–C15 aromatics were produced by catalytic cess Li et al. [30] presented another process. They proposed a Catalytic
depolymerization of intact biomass at 375 °C. Up to 12.63% selectivity Hydrothermolysis Treatment, whose operating conditions are 450–
of C8–C15 paraffins and 19.48% selectivity of aromatic hydrocarbons 475 °C, 210 bar in the presence of water, with and without a catalyst.
was obtained by hydrotreating the bio-oil under a low-severity condi- Hydrothermolysis is the combination of hydrolysis and thermolysis. A
tion (for 2 h). In another contribution, Zang et al. [54] used catalytic continuous-flow reactor system was used. The raw materials were
microwave pyrolysis (ZSM-5 and Raney nickel catalysts at 500 °C) to soybean oil, jatropha oil, and tung oil. The post-treatment process
produce jet fuel from a lignocellulosic biomass. Up to 24.68% carbon involved decarboxylation and hydrotreating in an autoclave reactor
yield of the desired C8–C16 aromatic was achieved. The recovery of with the following operating conditions: 5–10 wt% nickel BASF
organic compounds could reach 94 wt% after the extracting process. Nysofact 120 catalyst, 300–350 °C, H2=500 ml/min, and 30 bar. The
The produced jet fuel obtained a selectivity of 84.59%, which makes obtained product contained n-paraffins, isoparaffins, cycloparaffins,
this process very attractive. Moreover, Zhang et al. [55] obtained jet and aromatic hydrocarbons ranging from 6 to 28 carbons. The product
fuel range alkanes from co-feeding of lignocellulosic biomass with was fractionated in an ace glass distillation device 40–52% for JP-8,
plastics via tandem catalytic conversions. The process also uses naval distillate, and gasoline fractions. The tung-oil-based biofuels
microwave pyrolysis and ZSM-5 as the catalyst at 375 °C. derived from the catalytic hydrothermolysis process contained up to
Table 3 shows a summary of theses experimental studies, where fast 60% aromatics. This process is interesting due to the reduction in
pyrolysis combines with hydrotreatment process. The highest yield to hydrogen consumption; however, the use of water as part of the process
jet fuel showed in the table was due to positive synergy for aromatics in involves concerns about its water footprint.
catalytic microwave co-pyrolysis and the performance of the home- Also, lignocellulosic material can be used as renewable raw material
made Raney Ni catalyst (better than commercial Raney Ni catalyst used to produce biojet fuel involving hydrotreating process. The MOGHI
in previews works). Also, fast pyrolysis optimal conditions was project uses PROESA technology (BioChemtex) to produce biojet fuel
achieved under 375 °C using ZSM-5 catalyst. Moreover, this work from lignocellulosic biomass. In this process, lignin is catalytically
[55] was the first one where plastic and biomass were used into deoxygenated and depolymerized (with a common industrial catalyst
microwave pyrolysis reactor, the result was better selectivity to biojet and hydrogen). These products can be converted into high value
range hydrocarbons than without plastic feed to the process. Finally, chemicals and fuels (including jet fuel) using standard industrial
the ratio biomass/plastic can be optimized and scaled in order to use processes [58]. The hydrotreated depolymerized cellulosic jet (HDCJ)
waste plastic and reduce pollution. process encompasses conversion routes based on pyrolysis, hydro-
On the other hand, fatty acids or fatty acid methyl esters can also be thermal liquefaction, or hybrid processes [23]. Wang et al. [59]
upgraded with hydroprocessing in order to obtain fuels. The C–L™ obtained a yield of 83% for liquid alkanes (C8–C15) and more than
process, developed at Tianjin University, is used to produce wide-cut 90% selectivity for C14/C15 hydrocarbons through the hydrodeoxy-
aviation biofuel. Fatty acids or fatty acid methyl esters are hydrotreated genation of C15 intermediate using a 10 wt% Ni/ZrO2–SiO2 catalyst.
and subject to Kolbe reactions to be converted into long chain The C15 intermediate was produced from the hydroxyalkylation/
hydrocarbons. The hydrocracking process is then used to change the alkylation condensation of 2-methylfuran and furfural; these com-
long chain hydrocarbons into the desired jet fuels. This process could pounds were synthesized by the acid hydrolysis of raw corncob and the
operate effectively at lower hydrogen pressures [12], which definitely hydrogenation process. In 2015, diesel and jet fuel were synthetized
will impact the operating and investments costs of the process. through the hydroxyalkylation/alkylation of lignocellulose followed by
Moreover, hydrotreating and hydrocracking may take place in the hydrodeoxygenation. The hydroxyalkylation/alkylation achieved high
equipment which exists nowadays in the petrochemical industry. yield (77%) using a protonated titanate nanotube catalyst. Zeolite
Moreover, Axens developed solid catalyst-based technologies for loaded Ni catalysts (Ni/H-ZSM-5) were used for the hydrodeoxygena-
the production of biojet and biodiesel from renewable lipids. Esterfip- tion process [60]. Wang et al. [61,62] proposed three reaction steps to
H™ is a transesterification technology for fatty acid methyl ester obtain biojet fuel: 1) catalytic cracking of bio-oil in a tube-reactor
(FAME) production [56], while Vegan™ is a hydrotreating technology system; 2) alkylation reactions of low-carbon aromatics with light
for isoparaffinic hydroprocessed ester and fatty acid (HEFA) produc- olefins (0–80 °C and atmospheric pressure) in batch reactor equipment
tion (hydrogenolysis and decarboxylation). Scharff et al. [57] declared using an ionic liquid catalyst of [bmim]Cl-2AlCl3 (1-butyl-3-methyli-
that higher severity must be applied with hydrocracking to produce jet midazolium chloroaluminate); and 3) the production of C8–C15 cyclic
fuel using Vegan hydroisomerization technology with a dedicated alkanes by the hydrogenation of C8–C15 aromatics. High selectivity
catalyst. This proposal is interesting since the conditions required for (88.4%) for C8–C15 aromatics was achieved, which gave desirable

Table 3
Summary of studies that report the combination of fast pyrolysis (FP) process with hydrotreating (HT) process.

Raw Material T (°C) Catalyst Yield wt% Reference Comments

Douglas fir pellets 375 ZSM−5 catalyst (FP) and 12.63 [53,62] Process under mild conditions operation
5–10 wt% Raney nickel
catalysts (HT)
lignocelluloic biomass 500 (FT) ZSM−5 catalyst (FP) and 24.68 [54,62] Up to 84.59% selectivity of jet fuel range cycloalkanes from intact
200 (HT) 10–20 wt% Raney nickel biomass under very mild conditions
catalysts (HT)
biomass to plastics ratio of 375 (FP) ZSM−5 catalyst (FP) and 34.20 [55] Process under mild conditions operation
0.75 home-made Raney nickel
catalysts (HT)

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Table 4
Summary of works related with processing of lignocellulosic raw material through alkylation and at less one step of hydroprocessing.

Raw Material Operation Condition Catalyst Yield Reference Comments

P of H2 T (°C) LHSV h-1


(MPa)

raw corncob 0.3 (Hy) 250 (Hy), 0.75 (HO) Raney Ni catalyst (Hy), formic 49.8 [59] Yield:71% for HH, 89% for Hy, 95% for HHA
0.10 55 (HHA), acid and sulfuric acid (HH and and 83% for HO (90% selectivity for C14/
(HHA) 553 K (HO) HHA) and C15 hydrocarbons).
5 (HO) 10 wt% Ni/ZrO2–SiO2 catalyst
(HO)
Lignocellulose 6 (HO) 260 (HO) Protonated titanate nanotube [60] Yield: 77% for HHA and 90% for HO and
catalyst (HHA), Ni/H-ZSM−5 Diesel and jet fuel
(HO) range alkanes
bio-oil 5 (Hy) 0–80 (AL); HZSM−5 zeolite with the Si/Al [61] The bio-oil-derived low carbon
derived from fast pyrolysis 120 −210 ratio 25 (CC), [bmim]Cl−2AlCl3, hydrocarbons were further transformed into
of straw stalk (Hy) ionic liquid (AL) C8-C15 aromatics
with the highest selectivity of 88.4%
lignin powder 550 HZSM−5 zeolite with the Si/Al 17.3 [62]
manufactured from wheat 60 ratio 25 (CC), [bmim]Cl−2AlCl3,
straw ionic liquid (AL)

CC=Catalytic cracking; AL=alkylation; HHA=hydroxyalkylation/alkylation; HO=hydrodeoxygenation; HH=hydrolysis and dehydration processes; Hy=Hydrogenation

values for the combustion heat, viscosity, and freezing point. An


interesting point is the use of an ionic liquid as catalyst, which
differentiates this process from the rest; nevertheless, this could be a
drawback, due to the high cost of the ionic liquids. Bi et al. produced
C8–C15 cycloparaffins and aromatics by depolymerizing lignin (C6-
C8), low temperature alkylation reactions using ionic liquids, and
hydrogenation of aromatics [63]. The C8-C15 aromatic and cyclic
alkanes yields were 0.173 ± 0.012 and 0.175 ± 0.015 kg/(kg lignin),
respectively.
Table 4 shows a summary information related of these works. The
Ni/ZrO2–SiO2 and Ni/H-ZSM-5 catalysts are used for hydrodeoxy-
genation step, both have similar performance at similar temperature.
For catalytic cracking and alkylation processes were used the same Fig. 3. Number of granted patents related to biojet fuel production process by year.
catalysts but biojet fuel production was better for lignin powder as raw
material. The mayor biojet yield was obtained in [59] where the approximately 260–370 °C, using NiW, NiMo or CoMo as catalysts on
combination of hydrogenation, hydrolysis and dehydration, hydro- an alumina support. Isomerization takes place at 68–137 bar and 304–
xyalkylation/alkylation hydrodeoxygenation was used under mild con- 360 °C, using platinum or palladium as catalysts on silica-alumina or
ditions. The disadvantage is that is a complex process. zeolite supports.
Finally, the commercial production of jet fuel from camelina oil via In 2009, Aulich et al. [66,67] proposed a process for the production
hydrolysis, decarboxylation, and reforming was simulated using Aspen of jet fuel from sources containing triglycerides and fatty acids of
Plus® and Icarus® [64]. In the reported work, decarboxylation was medium chain length (C8-C14). In the initial stage, the fatty acids must
compared with the commercial hydrotreating process. Results indicate be separated from the glycerol backbone. This may take place using a
that the use of decarboxylation have the best benefits when the refinery thermochemical approach or by hydrotreatment. Then, the glycerol is
is located near to the farm where the raw material is generated. This separated from the fatty acids, and then the fatty acids are deoxyge-
paper is one of the few works where simulation is used to analyze nated and/or decarboxylated. Finally, isomerization takes place and the
different production processes. obtained fractions are separated by distillation. In this patent the
obtained product is closer to jet fuel composition, but it does include
3.2. Technological advances the complete range of hydrocarbons.
In 2010, Novak et al. [68] reported a process for the production of
As previously mentioned, biojet fuel has recently gained attention diesel-range hydrocarbons from renewable sources, such as vegetable
in the scientific and technological community. Indeed, the first patent oils and/or animal fats. The process involves hydrotreating the raw
for a production process of biojet fuel was granted in 2008. To the date, material with posterior dewaxing using a molecular sieve. For hydro-
the growing of patents granted has been explosive. Fig. 3 shows that the treating, temperatures of 315–425 °C are proposed at pressures of 20–
total number of patents increased from 2 in 2008 to 60 in just 7 years. 210 bar. Some examples of catalysts for hydrotreating are Ni/Mo, Co/
This indicates the great interest in the development of production Mo and Ni/W. The dewaxing step consists of the remotion/isomeriza-
processes for biojet fuel. Next, a review of the technological develop- tion of long chain hydrocarbon molecules, and it takes place using
ments for biojet fuel production processes for hydrotreating pathway is zeolites (as ZSM-48) or silico-aluminophosphates. Reaction conditions
presented. for dewaxing are 280–380 °C and 20–210 bar.
Abhari et al. [65] presented a process to co-produce jet fuel and Markkanen et al. [69,70] presented a process where jet fuels are
liquefied petroleum gas from a renewable feedstock, such as vegetable obtained from renewable sources by hydrodeoxygenation and subse-
oils and/or animal fats. The process involves hydrotreating the feed- quent isomerization; then, the heavy fraction is recycled to the
stock, then isomerizing the obtained heavy fraction. The heavy isomerization reactor. Proposed catalysts for the hydrodeoxygenation
products of the isomerization step are recycled. Hydrotreating occurs step include NiMo/Al2O3 and CoMo/Al2O3. For the isomerization step,
under pressures of approximately 68–137 bar and temperatures of

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the use of Pt/SAPO-11/Al2O3, Pt/ZSM-22/Al2O3, Pt/ZSM-23/Al2O3 achieve the required characteristics for jet fuel or other liquid fuels. It is
and Pt/SAPO-11/SiO2, under pressures from 30 to 100 bar and claimed that catalysts with moderate acidity and strong dehydrogena-
temperatures from 280 to 400 °C has been proposed. This is indeed tion/hydrogenation activity enhance the production of the jet fuel
the first patent where a renewable fuel similar in composition to fossil fraction. Conditions for isomerization are reported as 280–380 °C and
jet fuel is obtained. 40–60 bar.
Moreover, McCall et al. [71] presented a process to produce Bao et al. [79] patented a process to produce hydrocarbons from
hydrocarbons in the aviation fuel range using plant and/or animal oils biomass, which may be previously mixed with hydrocarbons. Biomass
as feedstock. To remove the impurities on the feedstock, the use of an is first treated with hydrogen in a catalyst of Ni or Mo to obtain long
ion-exchange resin (e.g., AmberlystTM-15) is proposed, among other chain hydrocarbons. The authors claim that using such catalysts allow
pretreatment alternatives. The main process consists of the hydro- lower processing temperatures than those required with CoMo cata-
genation and deoxygenation of the oil, and further selective cracking lysts.
and isomerization of the produced hydrocarbons. This process is very Ramirez Corredores and Sanchez Iglesias [80] proposed the
attractive because it is very similar to those found in traditional integration of a bio-oil production system with a conventional petro-
refineries. Therefore, the existing infrastructure can be used to produce leum refinery. In this way, the bio-oil is co-processed with streams
biojet fuel. Also, this technology is approved by ASTM for its use in derived from petroleum. The proposed technology will allow the
biojet fuel production for commercial use. treatment of mixed feed, which can be useful during the transition
Kothandaraman et al. [72] patented a process for the production of period until petroleum no longer exists.
hydrocarbons from renewable feedstock containing high compositions Parimi and Nguyen [81,82] presented a method to synthesize a
of free fatty acids. According to the authors, such hydrocarbons can be catalyst for the deoxygenation of biological feedstock to produce
used as diesel or jet fuels. The process consists of first reacting the hydrocarbons suitable as fuels. The use of nanocoated palladium as a
feedstock with ammonia/amine and obtaining a solid fatty amine, catalyst supported by activated carbon is tested for the production of jet
which is further separated. This reaction occurs under conditions of fuel. The reactions take place under a pressure of approximately 69 bar
20–300 °C and 1–14 bar. The solid fatty amide then enters a hydro- and a temperature of 250–360 °C. Then, the obtained hydrocarbons
processing stage. The products of this reaction are hydrocarbons and pass through a reactor where isomerization and cracking occurs. The
ammonia. Some examples of amines that can be used are monoetha- authors claim that using a simulated distillation analysis, an 80% by
nolamine, diethanolamine, methylamine and ethylamine. As hydro- volume of jet fuel can be produced. On the other hand, Thota et al. [83]
treating catalysts, the use of Co-Mo, Ni-W, Co-W or Ni-Mo over an developed catalysts to convert vegetable oils into hydrocarbons in the
alumina support is proposed. Hydrotreating occurs under tempera- boiling range of diesel. They present a proposal for a procedure of
tures of approximately 260–430 °C and pressures of 7–52 bar. As can synthesis of catalysts for that purpose.
be observed, the efforts were focused to decrease the operating Powell and Johnson [84] presented a process to produce hydro-
pressure but keeping the kind of catalysts; also, different pretreatments carbons from biomass containing cellulose and water. The process
of the raw materials are addressed. consists of mixing the raw material with an organic solvent with partial
Lupton and Traynor [73] proposed a method to produce hydro- miscibility with water. This mixture is then introduced to a reactor
carbons from algae biomass. In this process, biomass is first liquefied where it is hydrotreated to obtain hydrocarbons. Two phases are
using a neutral solvent (such as hexadecane or hexane, among others) formed, which are then separated.
and water, obtaining an oil phase, a liquid phase and a solid phase. This Stark et al. [85] proposed a fuel composition with petroleum diesel
reaction occurs at approximately 7–21 bar and 200–400 °C. The liquid and an algal derived hydrotreated renewable fuel, treated with cold
and solid phases are then removed, and the oil phase is hydroprocessed flow additives. The authors claim that this type of mixture can be used
to obtain hydrocarbons, which can be further refined to obtain jet fuel. in cold climates. When treating the fuel mixture with 400 ppm of the
Moreover, and interesting and complementary approach to this patent additive BIOQUEST 9928 (a terpolymer), a flow point of approximately
is the possibility of integrate two parallel process where the algae oil −48 °C was observed.
and biomass can be used to produce biojet fuel. Nousiainen et al. [86] presented a process to produce hydrocarbons
Also, Gosling [74] presented a process to produce diesel and jet fuel from a biological source, including a previous purification of the
from renewable feedstock. The process involves hydrogenation and biological feed material. The pre-treatment steps consist of heating
deoxygenation of the raw material. For hydrotreating, the use of nickel, and vaporizing the water contained in the raw material. Then, the
nickel/molybdenum, platinum or palladium as catalysts are proposed, purified fraction is hydrotreated in order to obtain hydrocarbons,
the last two are supported on gamma-alumina. Hydrogenation occurs which are then cracked and isomerized.
at 200–300 °C and 1379–4826 kPa. Then, in order to obtain better Fjare et al. [87] proposed a process to convert bio-oil into
cold flow properties, an isomerization/hydrocracking step takes place transportation fuels. Such bio-oil is obtained by the pyrolysis of
under conditions of 150–360 °C and 1724–4726 kPa. To increase the biomass. First, bio-oil is converted into partially hydrogenated alcohols
solubility of the mixture with hydrogen, a fraction of the obtained using ruthenium supported on carbon as a catalyst or platinum
hydrocarbons is recycled. supported on silica-alumina. Then, the alcohols enter a cracking and
Roberts et al. [75,76] patented a process to convert animal fats into recombination step to obtain hydrocarbons. For this step, the use of
transportation fuels. Biomass is first hydrolyzed to obtain free fatty zeolites as catalysts is recommended. The process is intended to obtain
acids and glycerol, which must be separated. The fatty acids are then gasoline range hydrocarbons; nevertheless, the authors claim that
deoxygenated, obtaining n-alkanes. Hydrocarbons are finally isomer- other ranges can be obtained, such as that corresponding to jet fuel.
ized/cracked/aromatized to obtain the desired chain length and Bradin [88] presented a process to produce hydrocarbons in the
conformation. range of jet fuel and gasoline using renewable feedstock. Raw material
Moreover, Strege et al. [77,78] presented a process to produce fuels is first converted into fatty acids by the action of a genetically modified
or fuel blendstocks from renewable sources containing triglycerides, microorganism. Then, fatty acids enter a thermal decarboxylation/
free fatty acids and/or fatty acid alkyl esters. The process consists of deoxygenation process at temperatures of approximately 400–600 °C.
hydrotreating the raw material to obtain hydrocarbons. Some hydro- After these steps, alkanes are obtained as a main product. These
treating catalysts are Pd, Pt, Ni, NiMo or CoMo, using alumina as a alkanes enter an isomerization/cracking stage to obtain the desired
support. Hydrotreating takes place at temperatures of 150–800 °C and chain length and proportions of ramified hydrocarbons.
pressures of approximately 7–70 bar. Then, the produced hydrocar- Also, Bradin [89] proposed a process to produce jet fuel from a
bons are subjected to cracking, isomerization and aromatization to syngas obtained from biomass by gasification, pyrolysis or other

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C. Gutiérrez-Antonio et al. Renewable and Sustainable Energy Reviews 79 (2017) 709–729

methods. The syngas is converted to methanol, and then a fraction of supplies alternative fuels with potential environmental benefit of
the methanol is converted to olefins, which are then oligomerized, reduced life cycle greenhouse gas emissions [12]. Additionally, biomass
isomerized and hydrotreated to obtain the jet fuel composition. The gasification can occur at lower temperatures. The pyrolysis process is
second fraction of methanol is converted to dimethyl ether, and then is carried out in one simple reactor, where the important conditions to
dehydrated to hydrocarbons and aromatics. The dehydration step may maximize the liquid bio-oil production are the temperature, residence
occur using a zeolite catalyst. time and heating rate. The gasification (syngas, mixture of H2 and CO)
Zhou et al. [90,91] patented a process to produce diesel fuels and jet uses the pyrolysis products as raw materials, and it requires an
fuels from biodiesel and lipids. The process consists of the reaction of oxidizing agent. This process takes place in an entrained flow reactor
biodiesel (or lipids) over a catalyst under temperatures of approxi- at 1200 K and 21 bar. Finally, the syngas can be further processed into
mately 343–413 °C. In this step, individual chains are obtained, oxygen hydrocarbon chains, which can be refined to jet fuel. In this process the
is removed from the stock, double bonds are saturated and isomeriza- main disadvantage is the high amount of energy required for the syngas
tion occurs. To catalyze this reaction, the use of platinum or palladium production, which is not compensated by the low cost of the raw
is proposed, supported in a silicoaluminophosphate or a zeolitic material.
molecular sieve, such as SM-3, SAPO, SAPO-41, ZSM-22, ZSM-23, or Hanaoka et al. developed an effective jet fuel production method
ZSM-35, among others. using Fischer–Tropsch synthesis [96]. For the hydrocracking process,
Frey et al. [92] presented a method to produce renewable aviation they prepared Pt-loaded zeolite catalysts to process n-C28H58 and n-
fuel by hydroprocessing renewable feedstock. To improve the cold C36H74. A maximum jet fuel yield of 29.1%C-mol was obtained with Pt
properties of the obtained hydrocarbons, an isomerization/cracking at a particle size of 7.6 nm. The conditions used in their study were
stage follows the hydrotreating step. Also, Silverman et al. [93] 250 °C, an initial H2 pressure of 1 MPa, and a reaction time of 1 h
presented a set of processes to produce biofuels from a biorefinery using Pt-loaded zeolite catalysts with a low Pt content (0.1 wt%).
point of view. Among the obtained biofuels, hydrocarbons in the range Traditional FT catalysts, such as iron-, cobalt-, nickel- and ruthenium-
of jet fuel are produced by hydrotreating, cracking and isomerization. based catalysts, have been extensively studied in the literature [17]. In
In 2015, Wei et al. [94] presented a process to generate biological this process, hydrogen is required at moderate pressures; however, the
biojet fuel from castor oil through hydrogenation, deoxidization and yield to biojet fuel is low in comparison with the ones that can be
isomerization catalysts. In this process, the hydrogenation deoxidiza- obtained in the hydrotreating processes.
tion catalyst takes modified MCM-41 as a carrier, while Nix-Mo, Nix- Three fuels produced via Fischer-Tropsch synthesis, three produced
Co or Nix-W can be the active component. The hydrogenation via hydroprocessing and the JP-8 fuel were compared in the work of
isomerization catalyst uses hierarchical porous NiAPO-11, hierarchical Corporan et al. [97]. The fuels were supplied by Sasol, Shell, Rentech,
porous NiSAPO-11, hierarchical porous SAPO-11, microporous UOP, and the Syntroleum Corporation. The study demonstrated that
NiAPO-11 or microporous NiSAPO-11 as a carrier, and uses Pd, Pt, paraffinic fuels derived from different feedstock can provide fuels with
or Ni as an active component. very similar properties to conventional fuels, consisting of excellent
physical, chemical, and combustion characteristics for use in turbine
4. Thermochemical pathway engines. This is an interesting study since allows to focus on perform-
ing the multiobjective optimization of the process, in order to find the
There are three possible routes to convert biomass into liquid fuel best one from technical, economic, environmental and social points of
by thermochemical processes: pyrolysis, gasification and hydrothermal view. Therefore, the development and application of optimization
upgrading (HTU), the last one being the most attractive process strategies for production process and the entire supply chain must be
according to Goudriaan and Peferoen [95]. Among these processes, studied.
gasification followed by the Fischer-Tropsch process is a certified As was mentioned before, gasification followed by the Fischer–
pathway by ASTM for the production of biojet fuel for commercial Tropsch synthesis process is one of the best options for the production
use. The biomass to liquid (BTL) route involves the production of of biojet fuel. Next, some works related are described.
middle distillates (diesel and jet fuel “drop-in” fuels) via gasification Tijmensen et al. [98] explored the possibility of producing synthetic
and Fischer-Tropsch (FT) synthesis, which is shown in Fig. 4. In the hydrocarbons from biomass via gasification and Fischer-Tropsch
next paragraphs, some advances in this route are presented. synthesis. They indicated that if biojet fuel is the desired product, the
hydrocracking conditions must be fixed to have a selectivity of 50 wt%.
According to Sasol, the wax selectivity from a fixed bed reactor using an
4.1. Scientific advances
iron catalyst is approximately 50–55%, while for a slurry phase reactor
(SPR) using a similar catalyst it is approximately 55–60%. The SPR has
Recently, Liu et al. presented a technical review of jet fuel
an olefin selectivity in the C5–C18 range, approximately 50% higher
production [12]. According to their research, pyrolysis and gasification
than a fixed bed reactor operating under similar conditions [99]. This
followed by the Fischer–Tropsch synthesis is one of the best options for
result was obtained in low temperature mode. The high-temperature
the production of biojet fuel. The maximum energy efficiency of
process is carried out in a SAS reactor (conventional fluidized bed)
Fischer–Tropsch fuel from biomass (77%) is higher than that from
designed to operate at pressures ranging from 20 to 40 bar, and is
coal (64%) or natural gas (68%); the Fischer–Tropsch synthesis

Fig. 4. Thermochemical pathway: conversion of lignocellulosic biomass through gasification and Fischer-Tropsch synthesis.

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C. Gutiérrez-Antonio et al. Renewable and Sustainable Energy Reviews 79 (2017) 709–729

typically operated at a temperature of approximately 340 °C, using an main catalysts used were molecular sieve catalysts, activated alumina
iron catalyst similar to that used in the Synthol CFB reactors [100]. As catalysts, transition metal catalysts and sodium carbonate. The product
in the previous process, the main disadvantage is the high amount of depended on the catalyst type and the reaction conditions. From the
energy required for the gasification stage. technical point of view the use of triglyceride feedstock is feasible;
Kumabe et al. [101] used Fischer–Tropsch synthesis of syngas with however, considering the costs of the triglyceride raw material and the
Fe-based catalysts to produce kerosene. The process was conducted in associated costs of processing them, via pyrolysis, it seems a better
a downdraft continuous-flow-type fixed-bed reactor, under tempera- option to use oils in hydrotreating processes; for example, Şensöz and
tures of 533–573 K and a pressure of 3.0 MPa. The selectivity of CO to Angın [107] made bio-oils with safflower seed press cake by pyrolysis
the C11-C14 hydrocarbons, equivalent to kerosene, was found to be the under the following conditions: 50 °C min-1 heating rate and 500 °C
second highest, while the highest selectivity was to C20+ hydrocarbons, final temperature under nitrogen atmosphere; these bio-oils had
which are equivalent to wax. The amount of primary kerosene similar kerosene characteristics, but better ignition starting qualities.
produced was maximized under the following conditions: the prepared Additionally, bio-oils can be thermochemically upgraded to produce
Fe catalyst did not contain other chemical species, the feed ratio of the drop-in fuels. The term pyrolysis to jet (PTJ) is also used to describe
reduction gases H2:CO:N2 was 2:1:3, the catalyst reduction time was processes that producing jet fuel via pyrolysis. Choi et al. [108] studied
8 h, and the FT synthesis reaction temperature was 553 K. An the possibility of direct production of hydrocarbons in the range of jet
important clarification in this point is that the hydrocarbon range for fuel from stearic acid, waste soybean oil and palm fatty acid distillate. A
jet fuel goes from C8 to C16; therefore, the produced hydrocarbons are single-step process was developed without added hydrogen. The jet fuel
not strictly biojet fuel. conversion range was 69.3% over a Pd/beta-zeolite catalyst at 270 °C.
On the other hand, Viguié et al. presented the BioTfueL project, The catalytic process was carried out in a 50 ml batch reactor, whose
which is focused on the original concept of co-processing (biomass and operating conditions were 270–330 °C, 15 bar with N2, 1–2.5 g of
fossil feedstock) [102]; the process produce diesel and jet fuel, through catalyst and 10 g of reactant. The obtained jet fuel was composed of
gasification followed by Fischer-Tropsch synthesis, from second gen- normal, branched chain, and aromatic hydrocarbons (oxygen-free
eration raw materials. compounds). The degree of oxygen removal was approximately 95%
The Green Sky project, developed by British Airways and Solena, is for the conversion of bio-oils. This process is interesting since hydrogen
the first plant in Europe that has advanced technology to convert is not required and the conversion is high.
waste-biomass to biojet fuel [103]. The production process is based on Zhao et al. [109] used sunflower oil to produce hydrocarbon fuels
Fischer-Tropsch gasification technology. Approximately 575,000 tons that could be used for future biojet fuel generation through a catalytic
of post-recycled waste will be converted into 120,000 tons of clean cracking pathway. The ZSM-5 catalyst in a fixed-bed reactor was used
burning liquid fuels using Solena’s technology [104]. A variety of at three different reaction temperatures: 450 °C, 500 °C and 550 °C.
gasification technologies can be employed, depending on the charac- The results showed that the reaction temperature affected the hydro-
teristics of the feedstock [105]. An important aspect in this process is carbon fuel yield, but had a minor influence on its properties. The
that the yield to biojet fuel is low (around 20%); taking this into highest conversion efficiency of sunflower oils to hydrocarbon fuels,
account, it is clear that generated byproducts must to be commercia- C7-C12, was 30.1%, which was obtained at 550 °C. The main issue
lized in order to have a viable process from the economic point of view. about this process is the use of edible oil, which raises concerns about
In Folkedahl et al. [105], coal- and biomass-to-liquid (CBTL) food safety.
hydrocarbon fuel technology and an iron-based Fischer–Tropsch Table 6 shows a summary of process based on pyrolysis and
catalyst produced synthetic isoparaffinic kerosene. Synthesis gas was catalytic pyrolysis. The proposed process in [108] present more than
made from a fluidized-bed gasification system that is capable of 200% of the yield in [109] in one single step process without added
processing up to 9 kg/h of coal and biomass. This process proposes hydrogen (safer) and cracking temperature is the lowest value in the
the use of biomass, but also uses carbon; therefore the environmental table.
impact is expected to be higher. Finally, jet fuel-blends were produced through a thermal upgrading
Table 5 shows the compilation of three of cited works above that of alcohols generated from biomass-derived syngas and the Fischer–
include operation conditions about Fischer Tropsch for SPK synthesis. Tropsch process [110]. The production rate was 0.172 kg jet fuel/kg
The catalysts more used are iron, cobalt, nickel and ruthenium based feedstock, with a thermal efficiency of 40.5% using modified methanol.
catalysts but for SPK iron and platinum based catalyst are used. The
temperature conditions are between 250 – 300 °C. Moreover, the
blends used in [105] have more potential due to highest level of yield. 4.2. Technological advances
A review of pyrolysis reaction (thermo-chemical conversion) for
renewable fuels production was given by Maher and Bressler [106], In the thermochemical pathway several patents have been reported,
where vegetable oils and animal fats are used as raw materials. Their which are described next.
work was divided into the following two processes: direct thermal Cheiky and Malyala [111–114] and Cheiky et al. [115] presented a
cracking, and a combination of thermal and catalytic cracking. The process to produce renewable fuels from biomass decomposition. The
authors claim that the conditions of their process can be easily

Table 5
Summary of works that report gasification followed by Fischer-Tropsch synthesis.

Raw Material Operation Condition Catalyst Yield CO/ Reference Comments


SPK
P (MPa) T (°C)

n-C28H58 and n-C36H74 1 (P of 250 Pt-loaded zeolite catalysts 29.1% C-mol [96]
H2) (Pt content 0.1 wt%)
H2:CO2:N2 3 260–300 Fe-based catalysts 29.23 wt% [101]
(feed ratio 2:1:3)
sub-bituminous coal and blends of coal and various biomass Fe-based catalysts 65–70% wt* [105] *this conversion is not
sources such as olive pits, switchgrass, and dried distillers' only for SPK.
grain

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Table 6
Summary of process based on pyrolysis and catalytic pyrolysis.

Raw Material Main Process T (°C) Catalyst Yield wt% Reference Comments

safflower seed press cake Pyrolysis 500 – 36 [107] Yield of bio-oil


stearic acid, waste soy bean oil and palm fatty Catalytic cracking 270 Pd/beta-zeolite 69.3 [108] Single-step process was developed without added
acid distillate catalyst hydrogen
Sunflower residual wastes oil Catalytic cracking 550 ZSM−5 30.1 [109] The total yield for hydrocarbons was 73.9

modified to produce a variety of fuels, such as gasoline, diesel, jet fuel renewable jet fuel using vegetable oils with chains of 6–14 carbons as
and others. As a first step, biomass is pulverized and pyrolyzed to raw materials. The raw material is first transesterified to obtain methyl
obtain gas compounds, which is placed into different reactors for esters and glycerol. The glycerol, excess alcohol and catalyst are
dehydration, aromatization or gas-upgrading, depending on the de- separated, and the phase containing the methyl esters enters a vacuum
sired fuel composition. distillation column; where the components with 6–14 carbons are
Dayton et al. [116] presented a process to produce a bio-oil from obtained at the top of the column. Bottom products are then neutra-
lignocellulosic materials. First, biomass is pyrolyzed to obtain a vapor, lized. It is claimed that the top product on the distillation column may
which is then condensed to form oil with low oxygen content. The be used as an additive for commercial jet fuel, up to 20 wt%.
pyrolysis catalyst is described as a mixture of iron oxide and a metallic
oxide promoter (such as chromium oxide, nickel oxide or manganese
5. Alcohol to jet pathway
oxide, among others). Pyrolysis occurs under conditions of 200–700 °C
and approximately 25 bar. The obtained oil may be further refined to
Sugar and starchy feedstock can be processed into alcohols through
obtain liquid hydrocarbon fuels.
fermentation; these alcohols can be later transformed via dehydration,
Cheiky et al. [117] proposed a process to produce liquid fuels from
oligomerization and hydrogenation into biojet fuel [19]. This pathway
biomass. The process consists of the thermo-chemical decomposition
is usually called alcohol to jet. Several biofuel companies are using
of biomass into hydrocarbons and solids, followed by a catalytic
pyrolysis, enzymatic hydrolysis, and biobutanol fermentation.
upgrading of the hydrocarbons. The solid fraction produced in the
Enzymatic hydrolysis has received more investments that have ad-
first step is then gasified, resulting in synthesis gas, which is further
vanced the biochemical, gasification and pyrolysis pathways [103].
upgraded into fuels.
Ramirez Corredores et al. [118] proposed a thermo-catalytic
treatment of biomass to produce a bio-oil, followed by a molecular 5.1. Scientific advances
distillation system, which allows a bio-naphtha fraction to be obtained.
The thermo-catalytic process takes place at 200–1000 °C using zeolites Bio-alcohols cannot be used as jet fuel directly [124]. The alcohol to
as catalysts, among other alternatives. jet fuel (ATJ, also called alcohol oligomerization) process includes
Trewella et al. [119] presented an alternative composition for a fuel alcohol dehydration, oligomerization, distillation and hydrogenation to
derived from biomass. The obtained fuel for some approaches is in the obtain jet fuel, Fig. 5; however, the production of alcohol by fermenta-
distillation range of approximately 160–370 °C, and matches the tion is usually not included. In the search for a sustainable supply chain
specifications for jet fuel. As an example, the authors presented the for biojet fuel production, it is clear that the production of the alcohols
thermo-catalytic conversion of southern yellow pine wood chips must also consider the use of renewable raw materials. Drop-in fuels
followed by hydrotreating. under development include synthetic paraffinic kerosene (ATJ-SPK)
Also, patents related with hydrogenolysis reaction can be found as and synthetic kerosene with aromatics (ATJ-SKA). These processes are
alternatives to transform lignocellulosic biomass in fuels. based on the commercial ones presented in the petrochemical industry,
In 2012, Fraga et al. [120] presented a process to produce and do not require external hydrogen and hydroprocessing [103]. In
compounds to be used as additives in the composition of aviation fuel. 2012 and 2014, respectively, biojet fuel produced by ATJ was used to
This process consists of the hydrogenolysis of hydroxycycloalkane conduct the first test flights with an A-10 aircraft (USAF) and an F/A-
derived substrates (e.g., menthol), preferably under conditions of 18 Hornet fighter jet (US Navy) [125]. The alcohol production cost is
100–200 °C and 4–17 bar. The obtained product contains a proportion considered to be the greatest barrier to commercialization of ATJ fuels
of aromatic compounds. Pt/Al2O3, AMBERLYST 15(R) and zeolite [47].
ZSM-5 are presented as some of the preferred catalysts for the process. Bio alcohol can be produced [23] in the following ways: a) sugar
Komplin et al. [121] patented a method to produce hydrocarbons fermentation with yeast or microbes; b) starch hydrolyzation-fermen-
from lignocellulosic biomass. In this process, raw material is first tation; and c) hydrolyzation-fermentation of lignocellulosic feedstock
treated with a solvent to obtain soluble carbohydrates. This pretreated or thermochemical conversion (e.g., syngas) and fermentation or
biomass then reacts with hydrogen at 150–300 °C to obtain hydro- catalytic hydrogenation. The LanzaTech/Swedish Biofuel Process ob-
carbons that can be used as fuels. It is claimed that the reaction system tains biojet fuel from wood, forest residues, agricultural wastes and
is tolerant to nitrogen and sulfur. For the hydrogenolysis reaction, grains. The method of synthesis involves the production of sugar from
catalysts containing sulfur, Mo or W, and Co or Ni are used. the biomass feedstock followed by fermentation. The products can be
Seck and Olson [122] presented a process to produce a fuel drop-in hydrocarbon fuels such as gasoline, diesel, and jet fuel.
component consisting mainly of 1,2-(ditetrahydrofuryl) ethane. This Additionally, their technology captures waste CO-rich gases, as sources
component can be used as an additive for diesel and jet fuels to reduce of energy under the new process [103]. According to Güell, in 2012
greenhouse gases and particle emissions. 1,2-(Ditetrahydrofuryl) BioChemtex/Gevo, Cobalt/Albemarle Corporation/NREL and
ethane is obtained from lignocellulosic biomass by thermal reactions ZeaChem/US Government were also interested in developing ATJ
of hemicellulose to obtain furfural, then conversion of furfural to technologies [49].
furoin, and finally the catalytic hydrogenation of furoin to 1,2- Experimental studies of catalytic dehydration of ethanol into
(ditetrahydrofuryl) ethane. It is proposed that this component can be ethylene have demonstrated that lanthanum–phosphorous modified
used in mixtures with jet fuel from 5% to 80%. HZSM-5 (0.5%La-2%PHZSM-5) offers outstanding catalytic perfor-
Finally, Vidal Vieira et al. [123] proposed a process to produce mance, and enhanced anti-coking ability [126]. In other work, the
catalyst exhibited a high ethanol conversion (100%), ethylene selectiv-

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Fig. 5. Alcohol to jet pathway: conversion of cellulose and starch biomass.

ity (99%), and stability [127]. The high conversion is really interesting, Olcay et al. [130] synthesized liquid alkanes in the diesel and jet
since all the generated bioethanol can be transformed into hydrocar- fuel range from hemicellulose derived C5 sugar. Their process has four
bons; however, the main limitation is the conversion of biomass to steps: dehydration in a biphasic reactor, condensation with a NaOH
bioalcohol. It is worth to mention that the subsequent transformation catalyst, hydrogenation with a Ru/Al2O3 catalyst and hydrodeoxygena-
of ethylene to jet fuels must be performed. tion using Pt/SiO2–Al2O3.
The isobutanol dehydration reaction was studied with alumina The oligomerization of propene, as well as the alkylation of benzene
catalysts to determine the impact of process conditions. The results and toluene with propene, were evaluated at 160–240 °C, 3.8 MPa, and
demonstrated high conversion and high selectivity to isobutylene (at with aromatic to olefin ratios from 1:6 to 6:1 using solid phosphoric
325 °C, 0–60 psig, WHSV=5 h-1 and up to 15 wt% water in the acid as a catalyst. The result was a synthetic jet fuel that meets Jet A-1
isobutanol feed) [128]. In spite of that, isobutylene is not biojet fuel; specifications [131]. Propene can be produced from methanol, which is
therefore, the subsequent transformation of isobutylene to jet fuels obtained from the resulting syngas of the conversion of lignocellulosic
must be performed. Nevertheless, this study was interesting since biomass. Wright et al. [132–134] proposed a methodology to produce
explores another use of biobutanol as raw material for biofuels jet fuel from 1-butene, which is obtained from biomass. One of the
production. proposed strategies involves mixing linear hydrocarbons with catalyst,
A mixture of C16H32 hydrocarbons was achieved in the work of and then adding 1-butene and mixing. The contact of reactants occurs
Harvey and Quintana [129]. The method used montmorillonite K-10, at ambient temperature; the catalyst is bis(cyclopentadienyl) zirconium
and sulfated zirconia catalysts for the selective dimerization of 2-ethyl- dichloride activated with methylaluminoxane. Butane oligomers are
1-hexene. After hydrogenation over PtO2 and fractional distillation, obtained and then hydrogenated and mixed with 3-methyl heptane.
saturated dimer mixtures could be isolated with up to 90% yield. Table 7 summarize oligomerization process for biojet fuel produc-

Table 7
Summary or reported oligomerization processes in order to achieved biojet fuel (Hc=Hydrocycloaddition and HO=Hydrodeoxygenation).

Raw Material Operation Condition Catalyst Yield wt% Reference Comments

P (MPa) T (°C)

2-ethyl-1-hexene montmorillonite K-10, and sulfated 90%* [129] * A mixture of C16H32 hydrocarbons
zirconia
hemicellulose-derived C5 5.5–8.27 80–140 Ru/Al2O3 (Hc), NaOH and Pt/SiO2– 55%** [130] **For gasoline, jet fuel,
sugars (Hc), (Hc), Al2O3 (HO) diesel fuel and fuel oil
8.27 (HO) 300 (HO)
Propene, benzene and 3.8 Solid phosphoric acid [131] During benzene alkylation with propene,
toluene the selectivity ratio was 1,2-diisopropylbenzene
(23%), 1,3-
diisopropylbenzene (37%), and 1,4-
diisopropylbenzene (40%).
During toluene alkylation with propene, the
selectivity ratio was
o-cymene (48%), m-cymene (23%), and p-cymene
(29%)
1-butene Group 4 transition-metal with [132–134] highly efficient batch catalysis methodology for
methylaluminoxane and PtO2 conversion of 1-butene to a new class
of potential jet fuel blends.

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tion. The catalyst and operation conditions used depends of the of approximately 500–3000 MHz. In this patent, the first application of
monomer. These researches do not conclude with pure biojet fuel, in process intensification is proposed, which helps to reduce the tem-
all cases the obtained product are blends that needs additional perature conditions required to realize the reactions.
processing, at least one additional distillation stage. However, it is In 2011, Server Barcelo [141] proposed a process to obtain
one of the most attractive pathway for future industrial biojet fuel hydrocarbons from biomass and recycled materials. The process
production. consists of three steps, as follows: first, dehydration of the raw material
is performed; second, the dehydrated material is mixed with liquid
5.2. Technological advances hydrocarbons and pulverized; and third, zeolites are added and
hydrocarbons are obtained.
Rusek and Ziulkowski [135] and Rusek et al. [136] presented a Lotero et al. [142] presented methods to convert biomass into
process for the production of renewable fuel from biomass, containing liquid fuels consisting of hydrocarbons. Different processes for the
celluloses, lignin, starches and lignocelluloses, by reducing the biomass treatment of biomass are mentioned, such as hydrolysis/dehydration,
to sugars, and then fermenting the sugars to produce acetone, butanol separation of solids and water, hydrogenation, condensation/oligomer-
and ethanol. Acetone is separated by distillation, and then a fraction of ization, polishing and distillation.
the acetone is dimerized into isopentane in a catalytic reactor. The Moreover, Soriano et al. [143] proposed a process to produce jet
other portion of the acetone is trimerized into mesitylene by reacting fuel and other high-value chemicals using camelina oil as a raw
acetone with sulfuric or phosphoric acid. The authors claim that this material. The process consists of alkene metathesis, dehydrogenation,
mixture of components (mesitylene and isopentane) is the major hydrogenation, and vacuum distillation. Wright et al. [144] proposed
component of a fuel that can effectively replace the 100 LL aviation dehydrating 1-alcohols to 1-alkenes with high regioselectivity.
and turbine fuels. Also, Rusek et al. [136] presented different formula- Additionally, the 1-alkenes are useful to prepare copolymers with
tions to be used as biomass-derived turbine fuels. According to their ethylene and high flash point diesel and jet fuels.
results, a mixture of mesitylene (50–99 wt%) and alkanes (1–50 wt%) Also, a patent related with the use of mixtures of products as jet fuel
can be used as turbine fuel. Other proposed compositions consist of was found. Rusek et al. [145] presented compositions of high-octane
synthetic paraffinic kerosenes and/or hydroprocessed renewable jet fuels, claiming that such fuels may be formulated to replace 100 LL
fuel, mixed with 8–25 wt% mesitylene. aviation fuel and turbine engine fuels, among others. Straight chain
In 2011, Peters and Taylor [137] proposed the production of alkanes are obtained from polysaccharides, while aromatic hydrocar-
renewable jet fuel via the fermentation of cellulose containing biomass bons may be obtained from acetone or propyne (methylacetylene).
to produce C2-C6 alcohols (mainly isobutanol); with posterior dehy- Finally, two patents related with the enhancement of raw material
dration and oligomerization of the alcohols to obtain C8-C16 olefins, production are described next. Heichberger [146] patented a method to
followed by hydrogenation of a portion of the high molecular weight capture carbon dioxide from coal fuel gas. Carbon dioxide is then
olefins. Dehydration takes place under temperatures of approximately injected into algae ponds, which are used to obtain oil. According to the
250–350 °C and pressures of 0–7 bar, with a wide variety of potential author, algae oil can be further refined into different fuels, such as jet
catalysts (γ-alumina, β-type zeolites, sulfonic acid resins, among fuel. Finally, Goel [147] presented a method based on nanotechnolo-
others). Oligomerization may occur over catalysts such as sulfonic acid gies to produce biofuels using algae as raw material. Nano-technolo-
resins, solid phosphoric acid or acidic zeolites, under conditions of gical processes and/or nanoscale processes are used to control algae
100–300 °C and 0–70 bar. The product exceeds the requirements of growth, and ensure the desired properties to produce hydrocarbon-
ASTM D7566-10a. based fuels.
Harvey et al. [138] patented methods to convert branched chain
olefins into turbine and diesel fuels. Such olefins are derived from 7. Discussion of the identified pathways
products of the fermentation of biomass. The process consists of
mixing heterogeneous acid catalysts with olefins, heating them to Each one of the presented pathways has different cost in terms of
produce dimers; then removing the catalyst and hydrogenating the raw materials and processing requirements. In general, triglycerides
olefins. For the heating step, a Ziegler-Natta catalyst is proposed under feedstock are expensive but they are easy to process; on the other hand,
temperatures of 100 °C. lignocellulosic feedstock are very cheap but their processing is quite
expensive because they have a complicated composition, and the useful
6. Another processes components of the feedstock are usually enclosed by lignin. For sugars
and starches, the main problem is that most feedstock are obtained
As result of the patent search, another processes that does not rely from edible crops, and therefore compete with human consumption;
in the previous defined pathways were found. These references are also, another problem is the low yield for alcohol production, which
presented next. leads to small productions of jet fuel. Of all the pathways, hydro-
In 2008, Seames and Aulich [139] proposed a process for the processing is the most studied, due to its similarity to hydroprocessing
production of a fuel suitable for use as aviation turbine fuel; such fuel is in traditional refineries. It is worth mentioning that microbial biotech-
obtained from vegetable oils and/or animal fats. Feedstock goes nology could be used to complement the renewable production of jet
through a cracking procedure, which can occur by catalytic or thermal fuel (fermentative and direct photobiological routes) because feasibility
means. In a second process, the authors proposed the transesterifica- of engineered microbial biosynthesis of medium chain length alkanes
tion of biological feedstock; nevertheless, the low temperature proper- has recently been demonstrated [148].
ties of the biofuel obtained by this approach are not comparable to In particular, the hydrotreating pathway has been studied both
those necessary for an aviation fuel. from catalysis and separation points of view; however, most of the
Portnoff et al. [140] patented a process for the production of works are experimental which is understandable since the study of the
hydrocarbons from renewable sources, such as vegetable and/or involved reactions is relatively recent, especially for renewable raw
animal oils. The authors claim that the process can be adjusted to materials. The conversion of different raw materials has been evaluated
produce different fuels, e.g., gasoline, jet fuel or diesel. The process with several catalysts and operating conditions, but there are still other
involves the catalytic treatment of the feedstock along with the raw materials to be studied. With respect to raw materials is really
application of microwave or radio frequency (RF) energy. important to give emphasis to those of second and third generation; in
Temperatures from 150 to 250 °C are proposed for this process. order to guarantee the food security of the population. Also, the use of
Microwave or RF energy is applied in a preferable range of frequency blends of different raw materials to produce biojet fuel remains as an

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opportunity area, because it would help to develop a robust supply are more options for processing. The most popular alternatives are
chain for biojet fuel production. For instance, mixtures of non-edible hydrolysis and pyrolysis, both followed by hydroprocessing. Other
oils with wasted oils can assure the supply of raw materials for a process considers fermentation followed by dehydration and oligomer-
biorefinery, no matter the climatological phenomenon that may occur. ization. An interesting approach considers the use of algal biomass to
This implies the robust design of biorefineries for a set of different obtain algal oil; in this process, the authors claim that biojet fuel can be
mixture compositions, instead of a single one with small variations as obtained through liquefaction followed by hydroprocessing. It is well
in classic design. Another important issue is the supply of hydrogen, known that algae are very promissory raw materials, considering that
since in almost all the process is a required reactive for the production their productivity, in oil liters per hectare, is several times higher than
of biojet fuel. In a parallel way, different alternatives to produce any other energetic crop. However, one of the most energy consuming
renewable hydrogen must be explored. One of the most attractive steps is to obtain oil from algae because flocculation, cell wall rupture
alternatives nowadays is the use of photocatalysis to produce hydro- and oil extraction must be performed. Therefore, the use of algae
carbons and hydrogen from CO2, using water as reducing agent, which biomass will help reduce operating costs because the raw material is
also allows having a neutral carbon cycle. The hydrogen production is completely used. Another interesting finding is a patent where nano-
key in the achievement of the sustainability of the entire supply chain technological processes are used to control algae growth to ensure the
for biojet fuel production in this pathway. The risk analysis to the desired properties for the production of hydrocarbon-based fuels.
hydrotreating processes is another opportunity area which has not Finally, another process that captured our attention proposes proces-
been reported in the literature. The use of hydrogen along with the high sing biological raw material into biojet fuel; the process involves
operation conditions of the processes increase the risk of explosions; vaporization followed by hydroprocessing, cracking and isomerization
so, this problem must be tackled in order to find the optimal layout of to perform the transformation. However, the use of biomass as raw
the plant that minimizes the associated risk. More efforts must also be materials will be more popular when effective and cost reduced
focused on the use of process intensification equipment, which will pretreatments are developed. This is by far, the main barrier in order
allow decreasing in capital and operating costs; this will be traduced in to take advantage of this abundant and cost reduced raw material.
a higher profitability of the process and minor environmental impact. No matter the raw material used, until now, the application of
On the other hand, the thermochemical pathway includes several intensified equipment remains as an opportunity area to improve the
available processes to convert lignocellulosic biomass to jet fuel. yield of biojet fuel, and also reducing operating and investments costs.
Considering that 3–4% of the total biomass in the planet is used for Also, the development of more selective catalyst is an interesting
human consumption, it is really important to continue the research research area, which can help to increase the yield to biojet fuel.
efforts to develop processes that transform lignocellulosic biomass into Moreover, it will be desirable that the developed catalyst which allows
fuels and fine chemicals. Also, these raw materials are of low cost, and performing the reaction at lower operating conditions, decreasing the
in some cases they represent an environmental problem. So, the operating costs and environmental impact.
utilization of agroindustrial and forestry residues can transform a Of these processes, some have been proven at the pilot plant scale.
problem into a valuable product. However, the major challenge is to This has allowed the production of biojet fuel for different flight
develop conversion technologies with reduced energy consumption. demonstrations around the world. A compilation of the performed
This challenge can be addressed with two strategies. One is the flights achieved by different aviation companies is presented in Table 8;
incorporation of alternate energies to supply, at least partially, the from this table, we can see that almost half of the demonstration flights
energy requirements for the syngas production or gasification stage. have been performed with biojet fuel generated by the Ecofining
For instance, the use of parabolic concentrators can help to reduce the process of UOP Honeywell, and in some cases, in partnership with
energy requirements during operation; therefore, the impact of these other entities. Moreover, 35% of the flights were performed with biojet
alternative technologies in total annual costs must be determined. In fuel generated with Hydrotreated Esters and Fatty Acids, HEFA,
some process, hydrogen is required; this brings the concerns about its technology from SkyNRG. There have been other suppliers for these
sustainable generation. In general, the yields to biojet fuel are lower test flights; however, UOP Honeywell and SkyNRG are the main actors
than the presented in the hydrotreating processes. That is another in this area. It is interesting that both UOP Honeywell and SkyNRG use
reason to avoid the use of triglyceride feedstock, which is more hydroprocessing technology, even though Fischer-Tropsch technology
expensive, in this processing pathway. is also certified by the ASTM for biojet fuel production [188]. Recently,
The third pathway, alcohol to jet, is of recent interest, and 31 March 2016, KLM Royal Dutch Airlines launched a series of around
important results have been obtained in the transformation of bioalco- 80 biofuel flights from Oslo to Amsterdam operated with an EMBRAER
hol to biojet fuel. More research must be done, especially with higher 190 [189].
alcohols in order to determine the best raw material to produce biojet Test flights have been conducted all over the world. Despite this,
fuel. Nevertheless, the main barrier in this pathway is given by the low industrial scale plants for biojet fuel production are still missing, or in
yields associated in the bioalcohol production. This step is really the best case, are in development. According to IATA, the commercial
important in the sustainability and profitability of the biojet fuel availability of these fuels has remained limited, largely due to the price
production. being uncompetitive with conventional fossil kerosene, especially with
From the revision of granted patents, we can observe that there are production facilities being at demonstration or relatively smaller scale
two main types of renewable raw materials considered, as follows: [190].
biomass (lignocellulosic, starch, algal, sugar) and lipids (vegetable oils In 2013, United Airlines announced a purchase agreement with
and animal fats). If the raw materials are lipids, in most of the patents, AltAir for HEFA fuel to be produced in the Bakersfield refinery that
hydrotreating processes and their variants are the most used technol- AltAir is retrofitting. The plant should start production in 2016, with a
ogy for biojet fuel production. In one patent, catalytic treatments with nominal production capacity of 90 kt/y of renewable diesel and jet fuel
microwave or radio frequency energy are used; this is an interesting [190]. In 2014, the United States Department of Agriculture granted a
finding related to process intensification, and it could be desirable to loan guarantee to Fulcrum Sierra Biofuels, LLC, to build a biorefinery
explore from a scientific point view because patents usually give ranges for biojet fuel production from municipal solid waste [191].
for the operating values instead of specific ones. However, this could be Additionally, Altair began the construction of a biorefinery this year
bypassed with modeling proposals, which can also open the opportu- located in Los Angeles, California, for biojet fuel production; this
nity for process optimization. In another patent, alkene metathesis facility will employ UOP Honeywell technology to process non-food oil
followed by hydroprocessing is proposed. crops and farm waste feedstock [192]. In early 2015, Petrixo Oil & Gas
On the other hand, when biomass is used as a raw material, there declared that they will invest $800 million USD into building a

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Table 8
Demonstration and commercial flights using biojet fuel.

Flight Type Time Location Airlines Aircrafts Raw material % biojet fuel Fuel supplier

Ground test [149,150] 2006 Buenos Aires Argentina’s Air Force Lockheed C−130Hercules Soy and rapeseed 20 Argentina´s Air Force
Test [151] 10/2007 Nevada Green Flight International Aerovodochody L29 Delfin Used canola oil Not available Not available
Test [152–154] 02/2008 London-Amsterdam Virgin Atlantic Boeing 747–400 Coconut and Babassu 20 Imperium Renewables, Inc
C. Gutiérrez-Antonio et al.

Test [152,155] 12/2008 Auckland, New Zealand Air New Zealand Boeing 747–400 Jatropha oil 50 UOP LLC
Test [156] 01/ 2009 Houston Continental Airlines Boeing 737–800 Algae and Jatropha oil 50 UOP LLC
Test [154,157,158] 01/2009 Tokio Japan Airlines Boeing 747–300 Camelina oil (42%), Jatropha 50 UOP LLC
oil (7.5%) and algae (0.5%)
Test [154,159,160] 11/2009 Amsterdam-Paris Royal Dutch Airlines KLM Boeing 747–400 Camelina oil 50 UOP LLC
Test [149,161] 03/2010 Bozeman, US Air Force A−10 Camelina oil 50 Michigan Tech University - UOP LLC
Montana
Test [162,163] 04/2010 Patuxent River, Maryland US Navy F/A−18 "Green Hornet" Camelina oil 50 Michigan Tech University - UOP LLC
Test [164,165] 06/2010 Rijen, Netherlands Dutch Military Ah−64 Apache Helicopter Waste cooking oil and algae 50 UOP LLC
Test [166] 06/2010 Wiener Neustadt, Austria EADS Diamond DA42 Algae 100 Chubut S.A.-
VTS Verfahrenstechnik
Schwedt
Test [167] 11/2010 Patuxent River, Maryland US Navy MH−60S Seahawk Camelina oil 50 UOP LLC
Test [168] 11/2010 Rio de Janeiro TAM Airlines Airbus 320 Jatropha oil 50 UOP LLC
Test [169] 04/2011 Mexico City-Tuxtla Gutierrez Interjet Airlines Airbus A320–214 Jatropha oil 27 ASA- UOP LLC
Test [170,171] 06/2011 Washington-Paris Boeing Boeing 747-8F Camelina oil 15 UOP LLC
Test [170,172] 06/2011 North America to Europe Gulfstream Aerospace- Gulfstream G450 Camelina oil 50 UOP LLC
Honeywell
Commercial [149,173] 06/2011 Amsterdam-Paris KLM Boeing 737–800 Used cooking oil 50 SkyNRG
Test [174] 11/2011 Patuxent River, Maryland US Navy MH−60S Seahawk Algae-based oil 50 UOP LLC
Commercial [173,175] 07/2011 Hamburg to Frankfurt Lufthansa Airbus A321 Jatropha oil, Camelina oil 25 Neste Oil
plants and animal fats

723
Commercial [159] 07/2011 Amsterdam-Helsinki Finnair Airbus A319 Used cooking oil 50 SkyNRG
Commercial [173,176] 07/2011 Amsterdam-Helsinki Finnair Airbus A321 Used cooking oil 50 SkyNRG
Commercial 07/2011 Mexico City-Tuxtla Gutierrez Interjet Airlines Airbus A320 Jatropha oil 27 ASA-UOP LLC
[169,173,176]
Test [174] 08/2011 Patuxent River, Maryland US Navy MV−22 Osprey Camelina oil 50 UOP LLC
Test [177] 08/2011 Patuxent River, Maryland US Navy T−45 "Goshawk" Camelina oil 50 UOP LLC
Commercial [169,176] 08/2011 Mexico City-Madrid AeroMexico Boeing 777–200 Jatropha oil 25 ASA-UOP LLC
Test [174] 09/2011 Patuxent River, Maryland US Navy EA−6B Proweler Camelina oil 50 UOP LLC
Test [174] 09/2011 China Lake, California US Navy AV−8B Harrier Camelina oil 50 UOP LLC
Test [174] 09/2011 St. Inigoes, Maryland US Navy MQ-(B Fire Scout Camelina oil 50 UOP LLC
Commercial [173,178] 09/2011– Mexico City-San Jose AeroMexico Boeing 737–700 Camelina oil 25 ASA-UOP LLC
04/2012
Test [176,179] 10/2011 Beijing Air China Boeing 747–400 Jatropha oil 50 UOP LLC-PetroChina Ltd
Commercial 10/2011 Madrid-Barcelona Iberia Airbus A320 Camelina oil 25 ASA-UOP LLC
[169,173,174]
Commercial [176,180] 10/2011 Birmingham-Arrecife Thomson Airways Boeing 757–200 Used cooking oil 50 SkyNRG
Commercial [173] 10/2011 Toulouse-Paris AirFrance Airbus A321 Used cooking oil 50 SkyNRG
Commercial [173] 11/2011 Seattle-Portland and Seattle- Alaska Airlines Boeing 737 and Bombardier Used cooking oil 20 SkyNRG
Washington Q400
Commercial [173] 11/2011 Houston-Chicago United Airlines Boeing 737–800 Algae-Jatropha oil 40 SolaZyme
Commercial [173,181] 12/2011 Bangkok-Chiang Mai Thai Airways 777–200 Used cooking oil 50 SkyNRG
Commercial [176] 01/2012 Frankfurt-Washington Dc Lufthansa 747 Used cooking oil Not available Neste oil
Test [176] 01/2012 Etihad Airways Boeing 300ER Used cooking oil Not available Not available
Commercial [173] 03/2012 New York, JFK-Amsterdam KLM Boeing 777–200 Used cooking oil Not available SkyNRG
Test [173] 03/2012 Santiago- Concepción Lan Airlines Airbus A320 Used cooking oil Not available SkyNRG
Test [173] 04/2012 Sydney-Adelaide Qantas Airways Airbus A330 Refined cooking oil 50 SkyNRG
Test [173] 04/2012 Toronto-Ottawa Porter Airlines Bombardier Q400 Camelina oil (49%) and 50 UOP LLC, SkyNRG
Brassica carinata oil(1%)
Test [176] 04/2012 Ana Airlines Boeing 787 Dreamliner Used cooking oil Not available Not available
(continued on next page)
Renewable and Sustainable Energy Reviews 79 (2017) 709–729
Table 8 (continued)

Flight Type Time Location Airlines Aircrafts Raw material % biojet fuel Fuel supplier

Commercial [173] 04/2012 Melbourne - Hobart JetStar Airways Airbus A320 Refined cooking oil 50 SkyNRG
Commercial [173] 06/2012 Montreal - Toronto Porter Airlines Bombardier Q400 Camelina (49%) and Brassica 50 UOP LLC, SkyNRG
carinata oil (1%)
Test [176] 06/2012 Azul Embraer E190 Bioetanol Not available Amyris
C. Gutiérrez-Antonio et al.

Commercial [173,174] 06/2012 Mexico City-Sao Paulo Aeroméxico Boeing 777–200 Used cooking oil(44%), 50 ASA
Jatropha oil(1%) and
Camelina oil(5%)
Commercial [173] 06/2012 Toronto-Mexico City Air Canada Airbus A319 Used cooking oil 50 SkyNRG
Commercial [173] 06/2012 Amsterdam - Rio de Janeiro KLM Boeing 777–200 Used Cooking Oil Not available SkyNRG
Test [182] 07/2012 Abu Dhabi to Seattle Etihad Airways Boeing 777–300ER Vegetable cooking oil 50 SkyNRG
Commercial [183] 7/2012 Montreal-London (Olympic Air Canada Airbus A330 Cooking oil 50 SkyNRG
Games)
Test [184] 10/2012 Ontario National Research Council Falcon 20 Brassica carinata oil 100 Applied Research Associates (ARA) and Chevron
of Canada (NRC) Lummus Global (CLG)- Catalytic Hydrothermolysis
(CH)
Commercial [185] 11/2012 Savannah, Georgia-Orlando, Gulfstream Aerospace- Gulfstream G150, G280, Camelina oil 50 UOP LLC
Florida Honeywell G450, G550 and G650
Test [186] 03/2013 Rhode Island to Kill Devil Hills Paramus Flying Club Cessna 182 Waste cooking oil 50 SkyNRG
North Carolina
Commercial [159] 03/2013 New York –Amsterdam KLM Boeing 777–206ER Used cooking oil 25 SkyNRG
Commercial [187] 08/2013 Bogota-Calí LAN Airbus A320 Camelina oil 30 UOP LLC
Commercial [173] 05/2014 Amsterdam - Aruba KLM Airbus A330–200 Used cooking oil 20 SkyNRG
Commercial [173] 7 & 8/ 360 flights during the FIFA Gol Transportes Aéreos Boeing 737–700] Inedible corn oil and used 4 UOP LLC
2014 World Cup 2014 Rio de Janeiro cooking oil
Commercial [172] 09/2014 Frankfurt - Berlin Lufthansa Airbus A320 Farnesan sugar-based fuel 10 Amyris Total
Commercial [172] 09/2014 Helsinki - New York Finnair Airbus A330 Used cooking oil 10 SkyNRG

724
Commercial [172] 11/2014 Stockholm-Östersund Scandinavian Airlines Boeing 737–800 Used cooking oil 10 SkyNRG Nordic
Commercial [172] 11/2014 Trondheim and Oslo, Norway Scandinavian Airlines Boeing 737–800 Used cooking oil 48 SkyNRG Nordic
Commercial [172] 11/2014 Bergen-Oslo Norwegian Air Shuttle ASA Boeing 737–800 Used cooking oil 50 SkyNRG Nordic
Commercial [172,187] 03/2015 Shanghai- Beijing Hainan Airlines Boeing 747–800 Used cooking oil 50 Sinopec
Commercial [172,187] 03/2015 Shanghai- Hong Kong Dragonair Airbus A330–300 Used cooking oil 50 Not available
Renewable and Sustainable Energy Reviews 79 (2017) 709–729
C. Gutiérrez-Antonio et al. Renewable and Sustainable Energy Reviews 79 (2017) 709–729

biorefinery, also using UOP Honeywell technology [193]. Also, in 2015 hydrocarbons. However, the use of CO2 for biojet fuel production has
FedEx Express and Southwest Airlines entered into a jet fuel supply not been explored. The development of better photocatalysts could
agreement with Red Rock Biofuels to purchase its jet fuel once the produce hydrocarbons with longer chains; perhaps, this could even-
biorefinery is constructed and producing [194]. Also in 2015, United tually lead to the direct production of biojet fuel, or other long chain
Airlines announced a $30 million equity investment in Fulcrum hydrocarbons, in a series of photobioreactors. This alternative would
BioEnergy, Inc., the largest investment by a domestic airline in the allow the generation of a carbon neutral cycle.
alternative fuels market [194]. Recently, in 2016 British Airways says Finally, the full utilization of raw materials can be addressed with
that it has been forced to shelve a groundbreaking £340 m scheme to existing technologies. For instance, hydroprocessing technology uses
create 16 m gallons of jet fuel from London’s rubbish every year, partly vegetable oils as raw materials. Vegetable oil can be extracted from
due to a lack of government support [195]. non-edible crops, and a significant amount of biomass would be
generated in this process. Of course, this residual biomass could be
8. Future efforts used as livestock feed or fertilizer. However, it could also be used to
produce biojet fuel through gasification followed by Fischer-Tropsch,
The hydroprocessing method is currently the most popular tech- or the residual biomass could even be processed via pyrolysis and
nology to produce biojet fuel. The main reason is its similarity to zeolite upgrading to generate aromatic compounds. These types of
traditional refineries, for which much knowledge has been accumu- proposals are still missing in the literature; however, the analysis of
lated. Additionally, in a future scenario where petroleum no longer these strategies could help to develop a sustainable production of biojet
exists, the conventional refineries could be transformed to biorefi- fuel.
neries; this will allow the use of existing infrastructure, thus reducing
investment costs and therefore biofuel prices. Indeed, the projects 9. Concluding remarks
under development for industrial scale biorefineries for biojet fuel
production will use the hydroprocessing technology of UOP Honeywell. A review of hydroprocessing, thermochemical processing, and
With respect to hydroprocessing technology, some opportunity areas alcohol to jet pathways to produce biojet fuel has been presented.
are visualized. First, the development of better catalysts to improve the These routes allows processing triglyceride-containing materials, lig-
conversion to biojet fuel; this option is a very challenging task where nocellulosic biomass, sugar and starchy feedstock. The hydrotreating
research efforts must be focused. Also, it could be expected that the technology, developed by UOP Honeywell, is the most popular. Almost
new catalysts allow performing the reaction in nobler conditions of half of the test flights have been performed using biojet fuel produced
temperature and pressure, which will help to reduce operating costs. with this technology; the projects under development for industrial
Moreover, enhanced catalysts may increase the selectivity to biojet fuel. scale plants also utilize the hydroprocessing pathway. The thermo-
Another alternative to improve the hydroprocessing technology is the chemical pathway that process biomass have a major challenge to
application of strategies of process intensification and energy integra- decrease energy consumption, because pyrolysis and gasification
tion. These tools could help reduce both operating and capital costs, operations are used. In the other hand, processes that use vegetable
impacting the biojet fuel price. As a consequence, the minimization of oils must be intensified to reduce operating and capital costs. Alcohol
environmental impact could be achieved. Additionally, the use of to jet pathway faces great challenges, in order to increase the alcohol
renewable raw materials with competitive prices must be explored. production which is the main barrier for the development of this
An important issue is to guarantee the raw material supply for the technology. In addition to these pathways, other process alternatives
process. For instance, in petrorefineries the supplying of raw materials such as the use of CO2 for the production of biojet fuel via photo-
can be ensured; however, if crops are used to generate raw material for catalysis, and the genetic modification of algae and microalgae to
a biorefinery there is a risk associated with climatological phenomenon directly produce biojet fuel could be interesting to explore. However,
than could limit its provision. Considering this an important aspect is research efforts must be realized in all processing routes, in order to
the use of mixtures of raw materials; for instance, if a triglyceride have different processing alternatives for the available biomass in each
biorefinery is going to be designed, this design must take into account country; in this way, the biojet production process will be sustainable.
the use of mixtures of wasted oil and non-edible oil. The design must
consider that variations in the proportions of these components are Acknowledgements
expected, possibly due to climatological changes, and it is desirable that
those uncertainties can be compensated by modifying operating This work was supported by the Mexican Council of Science and
conditions. This would allow having a robust process and guarantee Technology (CONACYT) through the Bioenergy Thematic Network
the supply of biojet fuel. ("Red Temática de Bioenergía"), grant 260457, and the research
Another important direction to explore is the genetic modification project 239765.
of algae and micro-algae species that could directly produce biojet fuel.
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