6

Production of Biojet Fuel from

Waste Raw Materials: A Review
Ana Laura Moreno-Gómez1 , Claudia Gutiérrez-Antonio1 , Fernando
Israel Gómez-Castro2 , and Salvador Hernández2
1 Facultad de Química, Universidad Autónoma de Querétaro, Querétaro, 76010 Querétaro, México
2 Departamento de Ingeniería Química, Universidad de Guanajuato, Guanajuato, 36050 Guanajuato,
México

6.1 Introduction
In the transport sector, aviation has the highest growth. The forecasts of the International
Air Transport Association, IATA, indicate that in the next two decades aviation will have
a compound annual growth rate of 3.5%, which implies that the number of passengers
could double to 8200 million in 2037 (IATA 2018a,b). As consequence, there will be an
increase of both fuel usage and carbon dioxide emissions. Therefore, in order to guarantee
the sustainable development of aviation sector, the Four-Pillar strategy was proposed (IATA
2009); this strategy considers technological improvements in engines and aircraft struc-
tures, operational improvements through online optimization of flight paths, market-based
measures, and development of alternative fuels (Gutiérrez-Antonio et al. 2016a). From these
alternatives, the IATA and the International Civil Aviation Organization, ICAO, agree that
renewable aviation fuel is the one that contributes most to the sustainable development of
the aviation sector.
Fossil aviation fuel consists of hydrocarbons in the boiling point range from C8 to C16,
including paraffinic, naphthenic and aromatic compounds. On the other hand, renewable

Process Systems Engineering for Biofuels Development, First Edition.

Edited by Adrián Bonilla-Petriciolet and Gade Pandu Rangaiah.
© 2020 John Wiley & Sons Ltd. Published 2020 by John Wiley & Sons Ltd.
150 Process Systems Engineering for Biofuels Development

aviation fuel contains paraffinic and naphthenic compounds, but it may or may not contain
aromatic compounds, depending on the processing pathway. The absence of aromatic com-
pounds could cause leaks in the tank fuels, since aromatic compounds interact with the
elastomers in the tank seals. Due to this, renewable aviation fuel must be used blended with
fossil jet fuel, with a maximum composition of renewable fuel of 50%, according to the
standard ASTM D7566 (ASTM 2018).
Renewable aviation fuel is also known as biokerosene, biojet fuel or synthetic paraffinic
kerosene; and it can be generated from triglyceride, lignocellulosic, sugar and starchy
feedstock. The feedstock is transformed in biojet fuel through different pathways, which
include hydroprocessing of triglyceride feedstock, thermochemical processing of biomass,
and alcohol-to-jet (Gutiérrez-Antonio et al. 2016a). At present, five pathways have
been certified under ASTM D7566 standard: gasification followed by Fischer–Tropsch
synthesis, hydroprocessing of esters and fatty acids, hydroprocessing of fermented sugars,
Fischer–Tropsch synthesis with aromatics, and alcohol-to-jet (IATA 2018a,b). However,
another seven pathways are in the evaluation stage to reach certification (CAAFI 2019).
The certified conversion routes allow the production of renewable aviation fuel that meets
or even exceeds the quality standards. Despite these pathways being different, three possible
scenarios are observed: raw material of high cost with low processing costs, raw material of
low cost with high processing costs, and both raw material and processing with intermediate
costs. The reduction in the processing costs can be reached through several strategies, such
as process intensification or energy integration; several works have reported the application
of these tools to the production processes of biojet fuel (Gutiérrez-Antonio et al. 2016a,b,
2018a,b). On the other hand, the raw material costs depend on several factors, such as the
variety of the crops, the automation of the cultivation task, along with the transportation
distances; due to this an optimal supply chain must be established, and some works are
reported on this topic (Reimer and Zheng 2017; Domínguez-García et al. 2017a,b; Leila
et al. 2018). Another alternative is the use of waste raw materials, which are abundant and
have low cost; some of them even constitute a pollution problem, due to the high volumes
in which they are generated. In this way, a problem can be transformed into an energetic
solution. Therefore, the focus of this work is the review of the use of waste raw materi-
als to produce biojet fuel. As shown in Figure 6.1, there are three main waste feedstocks:
(i) triglyceride-containing materials, (ii) lignocellulosic, and (iii) sugar and starchy. Any of
this feedstock can be transformed into biojet fuel through different processing pathways.
Moreover, the main challenges found in these production processes are analyzed, and future
research trends are discussed.
The chapter is organized as follows: the conversion of waste triglycerides through
hydroprocessing is discussed in Section 6.2. The transformation of lignocellulosic
residues, through different technologies, to produce renewable aviation fuel is presented
in Section 6.3. The production of biojet fuel from sugar and starchy residues is shown in
Section 6.4. Finally, the main challenges and future trends in the use of residues to produce
aviation biofuel are discussed in Section 6.5.

6.2 Waste Triglyceride Feedstock

Waste triglyceride feedstock includes waste cooking oil, animal fats, oil extracted from
agroindustrial residues, and bio-oil obtained from pyrolysis. Waste cooking oil and animal
 Production of Biojet Fuel from Waste Raw Materials: A Review 151

Catalytic
Lipids
Hydrothermolysis

Bio -
Processing
Waste sugar Alcohol
and starchy
feedstock H
Saccharification Sugar Thermo - y
Processsing d
Waste r
lignocellulosic o
feedstock Bio-oil p
Pyrolysis Biojet
r
fuel
Fischer- o
Tropsch c
Gasification Syngas e
s
Thermo- s
Processing i
Waste n
triglyceride g
feedstock

Figure 6.1 Pathways to process waste feedstock to produce renewable aviation fuel.

fats are usually a by-product of food industries and/or residues from residential and
commercial sectors; they represent a contamination problem due to the high volume in
which they are generated, and usually there is a non-appropriated disposal of such residues.
For instance, in the United States the availability of 10 million tons of waste cooking oil
has been reported (Gui et al. 2008). In Mexico, the information is scattered; there are
some reports that indicate nearly 8300 and 60 000 l/yr of waste cooking oil in the Puerto
Interior Industrial Park, in Guanajuato (IEEG 2016), and Emiliano Zapata, in Tabasco
(Gasca González 2017), respectively. In Europe, the potential of waste cooking oil was
estimated as 3.55 million tons in 2015, with 1.748 million tons generated in the domestic
sector (EUBIA 2015).
Other interesting waste material is the spent coffee ground, which represents a good
source of triglycerides to produce biojet fuel. According to McNutt and He (2019), in 2016
the worldwide production of coffee was around 9.3 billion kilograms, and it is possible to
recover between 10% and 20% of oils from spent coffee grounds by conventional extraction
methods.
Therefore, there is a great amount of these polluting residues to produce biojet fuel
through hydroprocessing technology. The first production process to obtain biojet fuel
through hydroprocessing was proposed by UOP Honeywell (Vera-Morales and Schäfer
2009), and it consist of two consecutive reactors and a distillation train (Figure 6.2).
In the first reactor, the triglyceride feedstock is converted, at high pressure and tempera-
ture, to long lineal chain hydrocarbons; these hydrocarbons are cracked and isomerized in
the second reactor, which also operates at high pressure and temperature. In both reac-
tors, hydrogen is used as reactant along with solid catalysts. The reactor outlet stream
contains renewable hydrocarbons that include light gases, naphtha, biojet fuel and green
diesel; these products are purified through a distillation sequence. The UOP Honeywell’s
technology was proposed as an extension of a green diesel production process, in which
a selective cracking stage was added (Regalbuto 2010; Verma et al. 2015); therefore, the
152 Process Systems Engineering for Biofuels Development

CO2
H2O light gases
cracking/
pretreatment deoxygenation isomerization
naphtha
Waste Physical
Chemical
triglyceride Thermal
feedstock biojet fuel
Biological

green diesel

Water H2 H2 Distillation
Reactants

Figure 6.2 Hydrotreating process to produce renewable aviation fuel from waste triglyceride feedstock.

maximum selectivity to biojet fuel is 36%, with total conversion to hydrocarbons of 70%
(Regalbuto 2010; Verma et al. 2015). Another hydrotreating process is BioSynfining™, in
which renewable aviation fuel is produced from fatty acids and triglycerides. The fatty acid
chains are converted to n-paraffins through deoxygenation, and the long-chain paraffins are
hydrocracked to short-chain paraffins. The hydrocracked products have boiling points in
the ranges of kerosene and naphtha. The BioSynfining process was successfully used to
produce about 600 gal of biojet fuel (Liu et al. 2013), and it is very similar to that proposed
by UOP Honeywell.
The hydrotreating process can employ diverse catalysts, raw materials and different pro-
cessing conditions (Vásquez et al. 2017). In the hydrotreating process different catalysts
have been utilized, either nickel-based or bifunctionals, as well as different types of reac-
tors such as the fixed bed reactor. In most of the studies, a large amount of hydrogen is
required to perform the conversion to biojet fuel. Moreover, almost all the studies report
the use of vegetable oils, both edible and inedible, such as soybean, Jatropha curcas, castor
and microalgae oil (Gutiérrez-Antonio et al. 2017). However, the use of waste oils repre-
sents a good alternative to reduce the price of biojet fuel, and, at the same time, to solve
a contamination problem due to the accumulation of these materials. Next, we present a
review of the works where waste triglyceride feedstock is treated to generate biojet fuel.
The paper published by Tian et al. (2008) reported the production of different biofuels
through the cracking of animal fats. They obtained a high yield for liquefied petroleum gas
(45%) and olefins (47%), but a low yield for naphtha (approximately 4.17%). In the reactor,
CoRh was used as catalyst, and the hydrogen requirement was not reported. Additionally,
aromatic compounds in the range C7–C10 were obtained.
Other works (Bezergianni et al. 2009; Bezergianni and Kalogianni 2009) point out that
cracking is a prominent technology for biojet fuel production. These works compare the
yield of products and the quality of hydrocracking at three different temperatures, consid-
ering non-used oil and waste cooking oil as raw materials. The evaluation indicates that, for
both raw materials, a high diesel production is observed, while the yield for kerosene and
gasoline is low. They also noted that as temperature increases, the selectivity toward diesel
also increased for both raw materials; however, at 390 ∘ C the selectivity toward kerosene
was favored (22.24%).
 Production of Biojet Fuel from Waste Raw Materials: A Review 153

Later, Bezergianni et al. (2012) reported the conversion of waste cooking oil toward
biojet fuel using three catalysts: a hydrotreating catalyst, a mild-hydrocracking catalyst and
a severe hydrocracking catalyst. They used conditions of high temperature (330–390 ∘ C)
and pressure (8.27–13.79 MPa). As products, hydrocarbons in the range of gasoline and
diesel were obtained. The highest yield was 80% for diesel at 370 ∘ C and 8.27 MPa, with a
hydrotreating catalyst.
Shi et al. (2014) showed a new path for converting bio-oils, prepared from cornstalks liq-
uefaction, to diesel and hydrocarbons in the boiling point range of biojet fuel. The reaction
was carried out using Ni/ZrO2 as catalyst in the presence of supercritical cyclohexane at
573 K and 5 MPa of hydrogen. They obtained a hydrocarbon yield of 81.6%, with 90% of
hydrocarbons in the range of diesel and biojet fuel, and 7% in the range of gasoline.
Mosisa et al. (2018) studied the cracking of waste cooking oil for the production of liquid
fuels in a semi-batch reactor with a nitrogen atmosphere; they used zirconia oxide (ZrO2 )
as catalyst. It is important to mention that the raw material was cracked without the need
of a pretreatment using the mentioned catalyst. A yield of 83% for organic liquid products
was obtained. An important aspect of this process is that it does not require high energy
consumption, and the catalyst is easily regenerated and recycled, being environmentally
friendly.
Next, we present the review of the works where waste triglyceride feedstock is deoxy-
genated and cracked to generate biojet fuel.
Charusiri et al. (2006) studied the conversion of waste vegetable oils into liquid fuels
over sulfated zirconia, HZSM-5 and HZSM-5 hybrid catalysts; their experiments were per-
formed in a batch micro-reactor at temperature range of 380–430 ∘ C, the hydrogen initial
pressure was in the range of 10–20 bar, and the reaction time was 45–90 minutes. Most of
the obtained products were liquids (gasoline, kerosene), gases and a small amount of solids.
Waste cooking oil, which contains a high acidity value (28.7 mg KOH/g oil), is converted
through the hydrocracking process over a ruthenium catalyst to obtain diesel as product (Liu
et al. 2012); the advantage of obtaining diesel is that it can be cracked and then converted
to biojet fuel. The temperature, hydrogen pressure, retention time and H2 /oil ratio were
350 ∘ C, 2 MPa, 15.2 h, and 400 ml/ml, respectively. Free fatty acids and triglycerides present
in oil were deoxygenated at the same time to form hydrocarbons; the liquid hydrocarbons
had a yield of 98.9%, with octadecane, heptadecane, hexadecane, and pentadecane as the
predominant ones.
I.H. Choi et al. (2015) performed a study to obtain biojet fuel through deoxygenation,
isomerization, and cracking in a single stage. In order to carry out such reaction 300–420 m3
of H2 per m3 of waste oil were required. With this proposal, they achieved simplification of
the process, and simultaneously they decreased the consumption of hydrogen and energy.
In such study, they prepared a Pd catalyst supported in beta-zeolite. As raw materials, waste
soybean oil and palm fatty acid distillate were used.
Moreover, the work proposed by Hanafi et al. (2016) reported the production of hydro-
carbons in the boiling point range of jet fuel, as well as naphtha and light gases; this work
is important because fatty acids are deoxygenated and cracked in a single reactor, which
allows a reduction in the investment costs. Furthermore, waste chicken fats, obtained from
a company, are employed as raw material. In their work, the physical characteristics of the
raw material and activation energy are provided; the yield toward kerosene/diesel fraction
is 53%. The operating conditions for temperature, pressure, retention time and H2 feed are
400 ∘ C, 6 MPa, 4 h, and 450 v/v H2 /oil, respectively.
154 Process Systems Engineering for Biofuels Development

The study reported by Zhang et al. (2017) showed the production of fuel for airplanes
in a one-stage process; they used animal fat as raw material and Pt/SAPO-11 as catalyst in
a micro-reactor that operated at high pressure. According to their experimental results, the
optimum operation conditions to produce a bigger amount of hydrocarbons in the C8–C16
range are 4 MPa, 400 ∘ C, and 1000 ml H2 /ml oil; under such conditions there is a 96.6%
conversion and the selectivity toward C8–C16 hydrocarbons is 50.25% with selectivity to
their corresponding isomers around 35.68%. It should be noticed that the retention time
of the micro-reactor is 1.2 hours. In that study, they mentioned that isomerization gradually
increases with the rise of temperature, but when the temperature reaches 380 ∘ C the isomer-
ization of the hydrocarbons decreases gradually. The increase in the H2 /oil ratio is beneficial
for the hydrocarbon conversion and for the isomerization of alkanes; however, when the
H2 /oil ratio is too large, the hydrocarbon selectivity decreases, and thus the isomerization
percentage reduces.
In the following paragraphs, we present a review of the works where waste triglyceride
feedstock is deoxygenated to generate biojet fuel.
Zhang et al. (2014) carried out a kinetic study of the hydrodeoxygenation of waste
cooking oil with a CoMoS catalyst. Their results show that the hydrodecarbonyla-
tion/decarboxylation (HDC) are the predominant reaction paths for oxygen elimination;
the catalyst activity decreases as the amount of sulfur in the catalyst also reduces.
Moreover, the hydrodecarbonylation of fatty acids controls the HDC path; while through
the hydrodeoxygenation path fatty acids are transformed to aldehydes/alcohols, and
subsequently to C18 hydrocarbons as final product. The difference between the C18/C17
ratio with supported and unsupported catalyst shows that the acid Lewis sites are related to
the selectivity for the hydrodeoxygenation path, thus giving as a result a product of high
quality. The experiment was performed in a batch reactor using 0.6 g of catalyst and 120 g
of waste oil, with catalyst to oil ratio of 1:200 w:w.
Three types of zeolites (Meso-Y-SAPO-34, y HY) mixed with nickel were used to con-
vert waste cooking oil to aviation fuel (Li et al. 2015). The mesoporous-Y zeolite exhibited
53% selectivity and 13.4% of selectivity to aromatic compounds in the liquid products; this
zeolite showed a 40.5% yield at 400 ∘ C, but the yield for aromatic compounds decreased
2.1%. The experimental results show that the deoxygenated raw materials tend toward hep-
tadecane and pentadecane, through a decarbonylation path during the three first hours. In
this experiment, the raw material was previously dried in order to eliminate the water con-
tent (Li et al. 2015).
The direct conversion of waste oil to biojet fuel was researched by Zhang et al. (2018);
in this process a zeolite support with a core-shell structure USY-AL-SBA-15 and NiMo
as catalyst were used. The use of this support and catalyst contributed significantly to
improve the selectivity toward biojet fuel from 9.3% over NiMo/USY to 35.7% over
NiMo/USY-AL-SBA-15, with a high isomerization ratio (iso-n/n-paraffin = 2.7) and
18.7% of aromatic compounds. The authors mention that through a single path, using
either NiMo or NiW catalysts supported on ZSM-5, it is possible to obtain high yields to
biojet fuel, 40–45%, with an excellent isomer/alkane ratio in the range 2–6.
An interesting work proposes the one-step hydroprocessing of bio-oil generated in
the hydrothermal liquefaction of microalgae cultivated in wastewater (Ranganathan and
Savithri 2019). In this process, renewable hydrogen is also obtained from the biogas
generated from the anaerobic digestion of the sludge from the wastewater treatment.
 Production of Biojet Fuel from Waste Raw Materials: A Review 155

However, renewable hydrogen can also be obtained from the electrolysis of water (IEA
2017). Fu et al. (2015) proposed the direct conversion of microalgae lipids in water to
renewable aviation fuel. The catalyst used was Pt/C, and the optimal conditions were
360 ∘ C with a reaction time of 45 minutes; in these conditions, a total conversion was
observed with a selectivity of 90% to heptadecane. There are several works in the literature
where the hydroisomerization of model compounds is reported, mainly n-hexadecane and
n-dodecane. These works are important since in most cases the hydroprocessing consists
of two stages; in the first one the hydrodeoxygenation is performed, while the hydroiso-
merization and hydrocracking are carried out after that. These works are described next.
The first work in this category was presented by Zhang et al. (2000). They reported
the activity, selectivity and long-term stability of platinum-promoted tungstate-modified
zirconia (Pt/WO3 /ZrO2 ), under mild conditions; in the hydroisomerization reaction,
n-hexadecane was used as a model compound. A trickle bed reactor was used for the
experiments. The best results were a conversion of n-hexadecane of 79.1 wt%, while for
iso-hexadecane a selectivity of 89.9 wt% and a yield of 71.1 wt% i-C16 were reported.
Later, Zhang et al. (2001) studied the effect of activity and selectivity of tungstated zirconia
(8% w) on the isomerization of n-hexadecane. The study was carried out in a trickle bed
continuous reactor. The results showed that temperatures between 300 ∘ C and 400 ∘ C, for
three hours, were slightly beneficial for achieving high yields of iso-hexadecane. Gomes
et al. (2017) studied the performance of bifunctional Pt/alumina-beta zeolite catalysts for
the hydroisomerization of n-C16. A biphasic micro-reactor of plug flow was used to study
the effect of nC16 isomerization on the pour point of the products. They found that as
the pour point decreases at constant rate, the formation of cracked products was small;
products are essentially composed of mono- and disubstituted C16 isomers, while 50%
of n-C16 was converted. Moreover, the hydroisomerization of n-hexadecane was studied
in order to evaluate the activity of Pt/AlSBA-15 catalysts (Jaroszewska et al. 2017);
they determined that the catalyst AlSBA-15 using aluminum isopropoxide showed better
isomerization selectivity than AlSBA-15 using aluminum sulfate.
De Lucas et al. (2005) studied the performance of palladium and platinum beta
zeolite-based catalysts with or without binder in the hydroisomerization of n-octane, along
with the influence of Si/Al ratio. As result, they found that the catalytic activity of beta
zeolite catalysts decreased when the Si/Al ratio increased, in samples with or without
binder. In addition, the isomer selectivity rose from 54.3 to 67.8% in samples without
binder when the Si/Al ratio increased.
Wang et al. (2008) investigated the hydroisomerization of n-dodecane over Pt supported
in ZSM-22 unmodified and ZSM-22 modified with two treatments. The ZSM-22 unmodi-
fied showed low activity in the hydroisomerization of n-dodecane. The catalyst treated with
NH4 + ion and (NH4 )2 SiF6 showed a high selectivity for iso-dodecane (88.0%) and good
conversion (87.5%) at 300 ∘ C. The experiments were carried out in a fixed bed flow reactor
with an internal diameter of 12 mm.
Other studies were reported for the hydroisomerization of n-butane (Adeeva et al. 1998),
n-hexane and n-octane (Amanza et al. 1999), n-hexane, n-octane, and n-hexatriacontane
(Calemma et al. 2000), and n-hexane, n-heptane, and n-octane (Dhar et al. 2017).
To summarize, Table 6.1 presents the reported articles where waste triglyceride feedstock
is used to produce biojet fuel.
Table 6.1 Summary of the use of waste triglyceride feedstock to obtain biojet fuel.
Hydrogen
Raw material Catalyst Temperature(∘ C) Pressure requirements Reactor type Yield (%) References
Animal CORH 500 (first 1 atm Not TSRFCC∗ LPG: 47; liquid total: Tian et al. (2008)
Fats stage); mentioned 77.6
LTB-2 520 (second
stage)
Non used oil DMDS∗∗ 350 13 789.5 1068 nm3 /m3 Fixed bed Waste oil: 20.04; Bezergianni et al.
TBA∗∗∗ 370 kPa H2 /oil fresh (2009),
Waste 390 oil: 22.24 Bezergianni
cooking oil and Kalogianni
(2009)
Waste HDT 330–390 8.27–13.79 MPa 3000 l at NTP Fixed bed Gas oil: Bezergianni et al.
cooking oil MID-HDC 15; (2012)
HDC diesel:
79
Bio-oils Ni/ZrO2 573 5 MPa Not Nantong Hydrocarbon: 81.6; Shi et al. (2014)
mentioned Huaxing diesel-biojet fuel: 90;
Petroleum gasoline: 7
Waste Zirconia oxide 400–500 Not mentioned Not mentioned Semi-batch Liquid organic product: Mosisa et al.
cooking oil (ZrO2 ) 83 (2018)
Waste Sulfated Zirconia 380–430 10–20 bar Not mentioned Batch Gas oil: 6.5; Charusiri et al.
vegetable oil (HZSM-5); micro-reactor gasoline: 26.57; (2006)
Hybrid catalyst kerosene: 10.65;
(HZSM-5) light gases: 23.62;
residues: 12.88
Waste Ru supported on 350 2 MPa 400 ml H2 /ml oil Fixed-bed Liquid hydrocarbons: Liu et al. (2012)
cooking oil (Al13-Mont)† 98.9
Non-edible Pd/ beta-zeolite 270 15 bar 300–420 m3 H2 /m3 Not mentioned Biojet fuel: 40 I.H. Choi et al.
oil oil (2015)
Waste NiW/SiO2 -Al2 O3 400 60 atm 450 v/v, H2 /oil Fixed-bed Total conversion: 94; Hanafi et al.
Chicken selectivity to (2016)
kerosene: 40
Animal Pt/SAPO-11 400 4 MPa 1000 ml H2 /ml oil Micro-reactor Conversion: 96.6; Zhang et al.
Fat selectivity C8-C16: (2017)
50.25; isomers: 35.68
Waste CoMoS 375 88.4 atm Not mentioned Batch Naphtha: 10; diesel: 81 Zhang et al.
cooking oil (2014)
Waste Meso-Y 400 3 MPa 350 ml/min Batch reactor Aromatics: 13.4; jet Li et al. (2015)
cooking SAPO-34 fuel: 40.5
oil HY
Waste USY-AL-SBA-15 380 30 atm 250 ml H2 /ml oil Fixed bed flow Jet fuel: 39.7; aromatic Zhang et al.
oil NiMo fraction: 18.7 (2018)
n-Hexadecane Pt/WO3 /ZrO2 218 160 psig H2 /n-C16 mole Trickle bed Selectivity i-C16: 89.9; Zhang et al.
ratio = 2 total conversion: 79.1 (2000)
n-hexadecane Tungstated 300–400 500 psig; Not mentioned Trickle bed Iso-hexadecane: 87 Zhang et al.
zirconia (8% w) pressure drop continuous (2001)
73 psig
n-Hexadecane Bifunctional 260–320 50–100 bar 500 NTP l/l Micro-reactor of Conversion of n-C16: 50 Gomes et al.
Pt/alumina-beta H2 /reactant plug flow (2017)
zeolite
n-Hexadecane AlSBA-15 320–360 5 MPa H2 :CH = 350 Pressure fixed Conversion to iso-C16: Jaroszewska
NTP m3 /m3 bed 61 et al. (2017)
microreactor
Table 6.1 (continued)
Hydrogen
Raw material Catalyst Temperature(∘ C) Pressure requirements Reactor type Yield (%) References
n-dodecane Pt/ZSM-22 480 6.0 MPa H2 /n-C12 = 600:1 Not mentioned Unmodified ZSM-22 Wang et al.
unmodified showed low activity. (2008)
Pt/ZSM-22 Modified ZSM-22: 88.0
modified
n-octane Platinum 548 2.0 MPa 24 H2 /n-C6 Not mentioned n-Hexane: 52; n-octane: Amanza et al.
n-hexane 27 (1999)
n-hexadecane 0.3% platinum/ 345–380 2–13.1 MPa Not mentioned Stirred Iso-hexadecane: 58–62; Calemma et al.
n-octacosane amorphous microautoclave iso-octacosane: (2000)
n-hexatriacontane silica–alumina 49–46;
(MSA/E) iso-hexatriacontane:
39–32
n-hexane Pt doped on 140 20 bar Not mentioned Batch At 180 ∘ C Dhar et al.
n-heptane gamma alumina 160 n-hexane: 85; (2017)
n-octane 180 n-heptane: 68;
n-octane: 40
∗ Two-stage riser fluid catalytic cracking.
∗∗ DMDS, dimethyl disulfide.
∗∗∗ TBA,tert-butylamine.
† Aluminum-polyoxocation-pillared montmorillonite.
 Production of Biojet Fuel from Waste Raw Materials: A Review 159

6.3 Waste Lignocellulosic Feedstock

Waste lignocellulosic feedstock includes wood waste, agricultural residues, textile residues,
solid urban waste, among others. Lignocellulosic materials such as agricultural wastes
are attractive feedstock for biojet fuel production, since they are abundant and renew-
able. In Mexico during 2011, 52% of the solid urban waste included waste food and waste
organic materials (SEDESOL 2012); also, 75.73 millions of tons of agroindustrial residues
were generated in Mexico in 2006 (Saval 2012). On the other hand, Brazil generates large
amounts of agricultural residues from sugarcane cultivation; this residue could be used as
raw material to produce biojet fuel (Nicodème et al. 2018). This type of feedstock is trans-
formed through different types of processing technologies, such as gasification followed by
Fischer–-Tropsch synthesis, pyrolysis followed by hydroprocessing, or alcohol production
plus oligomerization. A review of the works where alcohol is generated as intermediate for
the subsequent production of biojet fuel is presented next.
Waste lignocellulosic feedstock can be converted to ethanol; however, a pretreatment
(hydrolysis) is needed in order to extract the sugar contained. Sun and Cheng (2002) did
a review of the hydrolysis of lignocellulosic materials for ethanol production. The studied
materials include agricultural residues and wastes such as nutshells, grasses, paper, and
newspaper. In this context, waste papers from chemical pulps are an interesting and new
raw material, which have been little explored to obtain bioethanol, and later biojet fuel.
Once bioethanol is produced, it can be processed to obtain biojet fuel (Figure 6.3).
In this context, a review for the production of biojet fuel from agricultural residues
through the production of alcohol as intermediate is not available in the literature. However,
Sarkar et al. (2012) did a comprehensive review of bioethanol production from agricultural
waste. The review includes different processes and methods to increase the concentra-
tion of fermentable sugars. In addition, information about the conversion of glucose and
xylose to ethanol through fermentation technologies is discussed. Other works reported
the production of bioethanol from kitchen waste (Tang et al. 2008), grape and sugar beet
pomaces (Rodríguez et al. 2010), lignocellulosic agro-waste (Mutreja et al. 2011), date
wastes (Acourene and Ammouche 2012), non-marketable dates (Louhichi et al. 2013),
sugarcane bagasse (Lin et al. 2013), oil palm fronds (Ofori-boateng and Lee 2014), and
a mixture of waste fruits juice (Mansouri et al. 2016). An important aspect to the selection

light gases
pretreatment hydrolysis fermentation oligomerization hydrogenation
naphtha
Physical
Waste Chemical
lignocellulosic Thermal biojet fuel
Biological
feedstock

green diesel

Water H2 Distillation
Reactants

Figure 6.3 Alcohol production plus oligomerization process to produce renewable aviation fuel from
waste lignocellulosic feedstock.
160 Process Systems Engineering for Biofuels Development

of the waste to produce bioethanol is the lignin content. The best lignocellulosic feedstocks
to produce bioethanol are those with reduced amount of lignin, since it is hydrophobic in
nature and is tightly bound to cellulose and hemicellulose (Sarkar et al. 2012).
After the generation of the alcohol, it is possible to obtain biojet fuel through thermopro-
cessing, as shown in Figure 6.1. The thermoprocessing includes several stages: dehydra-
tion, oligomerization, hydrogenation, and fractionation. In the dehydration stage, the water
molecule is removed from ethanol using a catalyst and heat. According to Sakthivel (2018),
the thermal decomposition of ethanol takes place in a temperature range of 400–450 ∘ C and
11 bar, and the catalyst is alumina or transition metal oxides. The oligomerization process
is the conversion of short chain into linear 𝛼-oleofins (long chain); this step needs a catalyst
such as chromium diphosphine and zeolites, in the case where acidic zeolites are used the
temperature range is 100–300 ∘ C at high pressure.
Brooks et al. (2016) showed a summary of biojet fuel production processes from alco-
hol, considering different intermediates. The best processes were those where butane and
carbonyl are intermediates, both with conversions of 70–90%; in comparison with a direct
alcohol to jet process with 30–70% of ethanol converted. Recently, in a review article about
biojet fuel production processes, a summary of oligomerization processes for biojet fuel
production was reported (Gutiérrez-Antonio et al. 2017). In that work the authors reported
that the catalyst and conditions depend on the monomer; however, these researches do not
conclude with the production of biojet fuel. In this context, the first research was realized by
Harvey and Quintana (2010); the raw material employed was 2-ethyl-1-hexene, the catalyst
was montmorillonite K-10 and sulfated zirconia, and the yield was 90% with a mixture of
diesel and jet fuel.
The oligomerization of propene, on solid phosphoric acid as catalyst, was studied by
Sakuneka et al. (2008). The operating conditions were 3.8 MPa and 160–240 ∘ C; also, the
alkylation of benzene and toluene with propene was analyzed. The results show that it is
possible to realize both reactions in the same catalyst, producing a synthetic jet fuel that
meets Jet-A1 specifications.
Olcay et al. (2013) studied the conversion of C5 sugars derived from lignocellulosic
feedstock to produce hydrocarbons. The yield was 55%, and the hydrocarbons included
gasoline, jet fuel, diesel fuel, and fuel oil. The operation conditions were 80–140 ∘ C,
5.5–8.27 MPa and Ru/Al2 O3 catalyst for the hydrocycloaddition stage, and for the
hydrodeoxygenation stage NaOH and Pt/SiO2 –Al2 O3 were employed.
In all the proposed studies the obtained products need additional processing, at least
one additional distillation stage. Next, a review on the production of biojet fuel through
pyrolysis and hydroprocessing of waste lignocellulosic feedstock is presented.
In the pyrolysis, the waste lignocellulosic feedstock is heated in a special process to
produce an oily product, bio-oil, which subsequently is refined to obtain biojet fuel (Air
Transport Action Group 2011), as shown in Figure 6.4. The pyrolysis is the thermal cracking
of biomass in the absence of oxygen (Jenkins et al. 2016); the product yield and distribution
depends on the operating conditions, such as temperature, pressure, and residence time.
Jenkins et al. (2016) presented an extensive review of different pyrolysis technologies,
operating conditions and obtained yields of the pyrolysis products; the conversion technol-
ogy was classified as slow (300–700 ∘ C; 5–500 mm), fast (400–800 ∘ C; <3 mm) and flash
(800–1000 ∘ C; <0.2 mm) pyrolysis according to the operating conditions. In fast pyrolysis,
the amount of bio-oil increased while biochar decreased. In addition, there were different
 Production of Biojet Fuel from Waste Raw Materials: A Review 161

CO2
H2O light gases
cracking/
pretreatment pyrolysis deoxygenation isomerization
naphtha
Waste Physical
lignocellulosic Chemical
feedstock Thermal biojet fuel
Biological

green diesel

Water H2 H2 H2 Distillation
Reactants

Figure 6.4 Pyrolysis followed by hydroprocessing process to produce renewable aviation fuel from waste
lignocellulosic feedstock.

type of reactors, whose selection depended on the feed size and desired purity of the bio-oil
(Thangalazhy-gopakumar and Adhikari 2016).
There are different waste raw materials that can be processed through pyrolysis. After the
pyrolysis stage, hydroprocessing must be performed in order to obtain biojet fuel. In addi-
tion, pyrolysis has been studied for power generation (Chiaramonti et al. 2007). Table 6.2
contains some of the reported waste raw materials studied for bio-oil production, which can
be further converted to biojet fuel; however, the conversion to biojet fuel is not included in
those works.
Another technology for the conversion of lignocellulosic materials into biofuels is the
Fischer–Tropsch synthesis, which was developed to convert synthesis gas, containing
hydrogen and carbon monoxide, to hydrocarbon products (Steynberg 2004). German
researchers Franz Fischer and Hans Tropsch developed this technology, which is an
indirect liquefaction process where raw material is the synthesis gas produced from
biomass. The composition of the oil product from Fischer–Tropsch synthesis depends on
the raw material and the operations conditions. In order to produce aviation fuels, three
stages are needed: conversion of biomass to synthesis gas, conversion of synthesis gas
to oil, and oil refining to aviation fuels (Figure 6.5; De Klerk 2016). According to the
applied temperature, the Fischer–Tropsch process can be divided into low-temperature
Fischer–Tropsch (LTFT) and high temperature Fischer–Tropsch (HTFT), where the
temperature ranges are 200–240 ∘ C and 300–350 ∘ C, respectively (Liu et al. 2013).
There are different works related to the conversion of waste lignocellulosic biomass to
renewable aviation fuel through Fischer–Tropsch synthesis. Schablitzky et al. (2011) used
biowaxes for the production of hydrocarbon fuels using Fischer–Tropsch synthesis. They
obtained as products naphtha, kerosene and diesel, with a selectivity of 12.7% to kerosene.
According to Liu et al. (2013), the Atomic and Alternative Energy Commission (CEA)
announced the construction of a pilot plant to produce diesel, kerosene and naphtha using
wood/straw/green waste. In 2014, the United States Department of Agriculture (USDA)
granted a loan guarantee to Fulcrum Sierra Biofuels, LLC, to build a biorefinery for bio-
jet fuel production from municipal solid waste using Fischer–Tropsch synthesis (USDA
2014).
Table 6.2 Summary of the use of waste lignocellulosic feedstock in the pyrolysis process, as an initial step to obtain biojet fuel.
Raw material Temperature (∘ C) Catalyst Products Yield Description References
Wood 350 Not mentioned Liquid products Not mentioned More than 99.925% of Helsen et al.
waste Gas heavy metals and (1998)
Heavy metals minerals are
Wood waste Coal captured.
impregnated The raw material was
with CCA dried in a conventional
oven with air
circulation, at a
temperature of 120 ∘ C
for 90 min
Peanut shell 500 Not mentioned Char 65% pine wood; None Wang et al.
Bio-oil 54% peanut shell; (2007)
Maize stalk Gas 45% maize stalk

Pine wood
Waste 350–700 Not mentioned Char Waste wood Slow pyrolysis Phan et al.
wood Liquid (% w/w): (2008)
Gas char (33.2%), Composition of each
Card-board liquid (44.7%), product:
gas (33.1%) Liquids: water,
Textile Cardboard: char (33.9%), oxygenated
residues liquid (32.0%), compounds, heavy oil
gas (42.3%) Gases: CO, CO2 , CH4 ,
Textile: H2
char (31.6%), Liquid had a high
liquid (47.0%), calorific value of
gas (45.8%) 10–12 MJ/kg
Waste rice husk 500 Meso-MFI Acids With Meso-MFI good The sample particles Jeon et al. (2012)
Hydrocarbons selectivity to aromatics were 8–10 mm long,
Pt-Meso-MFI Oxygenates 2.0–2.5 mm wide,
Phenolics 0.1–0.15 mm thick
Non-catalytic Anhydro sugars
Aromatics
Gas
Jatropha waste 500 HZSM-5 Acid The highest yield was 95% to The raw material was Vichaphund
Alcohol aromatic and aliphatic dried at 60 ∘ C for et al. (2014)
Aldehyde hydrocarbons 24 h, with particle
Aromatic HC size equal or less than
Ether 125 μm
HC
Ketone
Nitrogen compounds
Phenol
Sugar
Waste pepper stems 550 HZSM-5 (23) and Gas 15% by aromatics with Fast pyrolysis Park et al. (2015)
SiO2 /Al2 O3 Acids HZSM-5(23) The raw material has
Oxygenates hard texture
HZSM-5 (280) with Phenolics Large lignin content
SiO2 /Al2 O3 Aliphatics
Aromatics
Without catalyst PAHs
Nitrogen compounds
Camelina straw 500 HZSM-5 zeolite Char 55 wt% toward bio-oil in The catalyst was Hernando et al.
Coke sample partially de-ashed pelletized with a (2017)
Gas particle size of
H2 O 180–250 μm; the raw
Bio-oil material was reduced
to 0.5–1 mm and
dried at 105 ∘ C for
48 h
Waste pepper 500 Waste FCC Char 58% Oil; The reported yield is for Yoo et al. (2018)
Oil 10% char; the relation
HY zeolite Gas 35% gas FCC:acetone 1:10
164 Process Systems Engineering for Biofuels Development

CO
CO2
H 2O light gases
Fischer-Tropsch cracking/
gasification synthesis hydrotreating isomerization
naphtha
Waste
lignocellulosic
feedstock biojet fuel

H2O
green diesel

H2 H2 Distillation

Figure 6.5 Gasification followed by Fischer–Tropsch synthesis to produce renewable aviation fuel from
waste lignocellulosic feedstock.

Yamamoto et al. (2016) produced biojet fuel from woody biomass. The first step was the
pulverization of the biomass, followed by its gasification; thus, syngas consisting mainly
of H2 and CO was generated. The syngas was cooled and cleaned, before being supplied
to the synthesis process; the gas was pressurized to normal conditions in order to acceler-
ate the Fischer–Tropsch reaction. The CO2 was recovered through decarbonation after the
pressurization. Hydrogen was fed to the hydrocarbon generated by the synthesis, and then
the isomerization process generated isoparaffins; the products such as light oil, jet fuel, and
wax were recovered through distillation. The process converted 37% of the biomass into
biofuels, including biojet fuel, light oil, and wax.
Kim et al. (2016) studied the production and evaluation of diesel using the
Fischer–Tropsch process at pilot scale. Wood pellets were used as raw material. The
produced fuel reached the automotive fuel standard. Diesel could be hydrocracked and
hydroisomerized later to generate biojet fuel; however, this additional processing was not
included in the study.
In the study reported by Snehesh et al. (2017), 1000 kg/h of casuarina wood chips were
gasified in order to enter into a Fischer–Tropsch unit. The maximum conversion was 73%.
In addition, through an economic analysis, they found that a 50% increase in the biomass
cost led to an 18% increase in the cost of the fuel.

6.4 Waste Sugar and Starchy Feedstock

Waste sugar and starchy feedstock include mainly the residues from the food industry,
which produces large amounts of these materials each year. Big amounts of fruit waste are
produced daily, from agricultural processes worldwide; many of these residues are often
dumped into landfills or the ocean (I.S. Choi et al. 2015). Fruit wastes have high levels of
sugar, including sucrose, glucose, and fructose. Therefore, these residues can be used as
raw material to produce biojet fuel, generating an alcohol as an intermediate component.
Russ and Meyer-Pittroff (2004) studied the use of waste from the food production and
processing industries. In particular, waste sugar feedstock can be obtained from sugar
 Production of Biojet Fuel from Waste Raw Materials: A Review 165

light gases
pretreatment fermentation oligomerization hydrogenation
naphtha
Physical
Waste Chemical
sugar and Thermal biojet fuel
Biological
starchy
feedstock

green diesel

Water H2 Distillation
Reactants

Figure 6.6 Alcohol generation plus oligomerization process to produce renewable aviation fuel from
waste sugar and starchy feedstock.

production, preparation and processing of fruit, vegetables, grain, edible oil, cocoa, coffee
and tobacco, waste from the production of baked goods, along with sweets, waste bakeries,
confectioners and candy producers. These residues can be converted to bioethanol through
a fermentation process; this bioethanol can be used as raw material to produce biojet fuel
(Figure 6.6).
Mahro and Timm (2007) explored the possibilities of using residues from food pro-
cessing to generate bioenergy, biomaterial production, chemical feedstock or animal feed.
They reported that from some residues, such as whey, molasses and pomace, sugars can be
extracted; these sugars can be converted into alcohol through a fermentation process, and
later converted to biojet fuel. An important aspect is that these types of residues contains
large amounts of water; thus, they have to be used as local resources, since they degrade
easily.
Another interesting proposal considered the use of coffee pulp as raw material for a
biorefinery, where valuable bioproducts and biofuels are obtained (Hughes et al. 2014).
With regard to biofuels, bioethanol was produced using Kluyveromyces marxianus yeast.
Moreover, I.S. Choi et al. (2015) proposed a pathway to produce bioethanol through the
combination of fruits and waste fruits. A high conversion, 90%, was obtained after 48 hours.

6.5 Main Challenges and Future Trends

Waste feedstock is an interesting renewable raw material for the production of biojet fuel. It
has as its main advantage its high-volume, periodical generation, which guarantees the sup-
ply for the production process. Moreover, in most of the cases these residues are not used
to generate value-added products. Additionally, they have potential to be harmful for the
environment and are produced in a big volume, thus representing a contamination problem;
therefore, its use as raw material for the production of renewable aviation fuel helps to solve
the issue of their disposal while a new energetic source emerges. The cost of waste feed-
stock is another advantage. Now, these raw materials can be obtained free or with reduced
costs, mainly due to its transportation; however, its price could increase with time if the
commercialization of the value-added products is successful.
166 Process Systems Engineering for Biofuels Development

The main disadvantage of waste feedstock is that usually it is scattered in different cul-
tivation sites or processing industries. Thus, the transportation costs play an important role
in the profitability of the production processes. This shows the importance of the devel-
opment of regional or local supply chains to produce renewable aviation fuel, in order to
decrease the transportation costs, especially of lignocellulosic materials with low densities.
Thus, the optimization of the supply chain for the production of biojet fuel is mandatory.
Another disadvantage is the heterogeneity of the composition of the waste feedstock, as a
function of the period where it is generated as the main product from where the residue
is obtained. This issue could be addressed through pretreatments, where the raw material
composition can be standardized; nevertheless, this means additional processing and the
need of a specially designed control structure, which leads to an increase in the production
costs.
An interesting challenge is the flexible design of the production processes in order to
manage mixtures of waste feedstock, which helps to guarantee the supply of raw materials
to the process. In order to reach this flexible design, more studies are needed of the con-
version of mixtures of waste feedstock at different proportions and operating conditions.
On this topic, only one study is reported (I.S. Choi et al. 2015). Another challenge is the
development of more robust and flexible pretreatment operations, which helps to reduce
the processing costs. Moreover, energy integration and process intensification are powerful
tools to decrease operation and capital costs in the processing of waste feedstock to produce
renewable aviation fuel. In addition, the production of biojet fuel in a biorefinery scheme
from waste feedstock has not been reported, and it represents an important challenge from
the design point of view.
According to the review of the literature, in the case of waste triglyceride feedstock most
reported works are focused on the use of waste cooking oil, and some of them on the use
of animal fats as raw materials. However, to the best knowledge of the authors, there are no
reported works about the use of waste oil from the industrial sectors, where different kind
of machines are employed. Moreover, research in the use of different animal fats must be
intensified. In addition, the production of biojet fuel with oil extracted from spent coffee
grounds remains an area of opportunity, following reports on the production of biodiesel
with such raw materials (McNutt and He 2019).
Regarding the waste lignocellulosic feedstock, most of the works are focused on the use
of agriculture and forest residues through different pathways to produce biojet fuel. As
suggested by Sun and Cheng (2002), the use of paper and newspaper residues represent an
interesting feedstock to produce renewable aviation fuel, especially because of their homo-
geneous composition. Other residues such as used tires or plastics have not been analyzed
for their potential use to produce renewable aviation fuel.
On the other hand, few works have reported the use of waste sugar and starchy feed-
stock. The existing works are focused on the use of fruit residues to produce bioethanol.
No reported works for the production of biojet fuel from this waste feedstock were found.
For all type of waste feedstock, the use of mixtures has not been addressed in the
literature. From the design point of view the processing of mixtures is a great challenge,
especially for the heterogeneity of the composition of the feedstock; however, it will help
to guarantee the constant supply of raw material for the processing centers. Moreover, the
application of energy integration and process intensification remains an area of opportunity
in the processing of all types of waste feedstock (Gutiérrez-Antonio and Hernández 2019).
 Production of Biojet Fuel from Waste Raw Materials: A Review 167

The use of waste feedstock for the production of renewable aviation fuel will help to reach
the objectives established for the aviation sector related to its sustainable development. In
addition, it will incorporate the circular economy in other productive chains, which will
help to produce biojet fuel with the required quality and at competitive prices.

6.6 Conclusions
A review on the use of waste feedstock for the production of renewable aviation fuel
has been presented. The waste feedstock can be classified according to its nature in
triglyceride-containing materials, lignocellulosic, sugar and starchy. Waste cooking
oil, animal fats, along with agriculture and forest residues have been explored for the
production of biojet fuel; in the case of food processing residues only the production of
bioethanol has been tackled, but this biofuel can be further processed to produce biojet
fuel. The use of mixtures of waste feedstock for the production of renewable aviation
fuel remains an area of opportunity, as well as the application of energy integration and
process intensification strategies for the decrease of operating and capital costs. Therefore,
research efforts must be focused on the processing of waste feedstock to produce biojet
fuel to contribute to the sustainable development of the aviation sector.

Acknowledgments
Financial support provided by CONACyT, grants 239765 and 279753, for the develop-
ment of this project is gratefully acknowledged. Moreover, Ana Laura Gómez-Moreno is
supported by a scholarship from CONACYT-SENER.

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