Journal of Analytical and Applied Pyrolysis 163 (2022) 105498

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Journal of Analytical and Applied Pyrolysis

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A step change towards sustainable aviation fuel from sewage sludge

Muhammad Asif Bashir a, Sergio Lima b, Hessam Jahangiri a, Artur J. Majewski a,
Martin Hofmann a, Andreas Hornung a, c, d, Miloud Ouadi a, *
a
University of Birmingham, School of Chemical Engineering, Edgbaston, Birmingham B15 2TT, UK
b
Green Fuels Research Ltd, Gloucestershire Science & Technology Park, Berkeley GL13 9FB, UK
c
Fraunhofer UMSICHT, Fraunhofer Institute for Environmental, Safety and Energy Technology, An der Maxhütte 1, 92237 Sulzbach-Rosenberg, Germany
d
Friedrich-Alexander University Erlangen-Nuremberg, Schlossplatz 4, 91054 Erlangen, Germany

A R T I C L E I N F O A B S T R A C T

Keywords: Sewage sludge, an abundant and problematic organic waste, was successfully converted into sustainable jet fuel
Biofuels range hydrocarbons (C8-C16). Sewage sludge was pre-conditioned and processed through a Thermo-Catalytic
Waste Reforming (TCR) system (2 Kg/h) at 450 ºC pyrolysis and 700 ºC post-reforming temperature to produce a
TCR
biocrude oil. The bio-crude oil was subsequently conditioned and upgraded via consecutive two-step hydro­
Hydrodeoxygenation
Hydrocracking
processing, comprising hydrodeoxygenation and hydrocracking as two separate unit operations. The two-step
Jet Fuel hydroprocessing was carried out in a bench-scale batch high-pressure reactor (autoclave). The process param­
eters such as temperature, feed volume, catalyst loading, and batch time were held constant, whilst the H2
pressure was varied. The effect of H2 pressure across 30 – 60 bar on the quality of the hydroprocessed oil was
evaluated in terms of elemental composition, chemical compound distribution, and fuel properties. Hydro­
processing at 60 bar H2 resulted in better fuel properties compared to hydroprocessing at 30 bar H2. Hence,
approximately 25% by weight jet fuel fraction, including normal, cyclo and iso-paraffins and aromatics in the
C8–C16 range, was recovered via atmospheric distillation of the hydroprocessed oil at 60 bar H2. Sewage sludge
derived jet fuel range fraction met the majority of the jet fuel specifications for calorific value, viscosity, density,
and freeze point under the ASTM D7566 standard. Some parameters such as smoke, flash point and total acid
number slightly fell out of specifications. The process also produced green naphtha and diesel as by-products. In
addition, the process was further tested for catalyst reusability and regeneration potential that showed promising
results for future research.

1. Introduction transport of cargo and people [2,3].

The aviation industry is an integral part of the transport sector [2]
In recent times, climate change has immensely accelerated due to and consumes annually approximately 1.5–1.7 billion barrels of petro­
increased greenhouse gas emissions, and CO2 is a major greenhouse gas leum jet fuel. Out of every barrel of crude oil, 4 gallons of kerosene are
contributor. Two main contributors to CO2 emissions are power gener­ produced [4]. In 2007, the EU parliament legislated for the addition of
ation and transportation. The two sectors combined accounts for 64% of the aviation sector to their greenhouse gas (GHG) emission trading
total CO2 emissions worldwide [1]. CO2 emissions from the transport system. This legislation has taken effect from 2012 that obliges all air­
sector have been estimated to increase by 80% by 2030 [2]. This will lines operating within Europe to cut down their CO2 emissions by 10%
only become more prevalent as other sectors begin to decarbonise. The or buy CO2 allowances. Furthermore, fuel consumption is also a high
transport sector uses fossil-petroleum derived liquid fuels, which are the cost for the aviation industry that constitutes 10 − 15% of the total
primary source of energy to date. In addition, the demand for these fossil operating cost of an airline [5].
fuels is also increasing proportionally to the increasing demand for more Jet fuel for use in aircraft gas turbine engines is mostly petroleum-

Abbreviations: SAF, Sustainable aviation fuel; IATA, International Air Transport Association; SPK, Synthetic paraffinic kerosene; HRJ, Hydroprocessed renewable
jet; HEFA, Hydroprocessed esters and fatty acids; FT-BTL, Fischer-Tropsch – Biomass to Liquid; TCR, Thermo-Catalytic Reforming; HDO, Hydrodeoxygenation; HC,
Hydrocracking; MAH, Monocyclic aromatic hydrocarbons; BAH, Bicyclic aromatic hydrocarbons; DoD, Degree of deoxygenation.
* Corresponding author.
E-mail address: h.jahangiri@bham.ac.uk (M. Ouadi).

https://doi.org/10.1016/j.jaap.2022.105498
Received 6 September 2021; Received in revised form 7 March 2022; Accepted 9 March 2022
Available online 12 March 2022
0165-2370/© 2022 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
M.A. Bashir et al. Journal of Analytical and Applied Pyrolysis 163 (2022) 105498

derived [6]. The most common aviation fuels consumed by commercial esters (FAME), sugar derived hydrocarbons, dimethyl ether (DME), and
and military aircraft are Jet A, Jet A-1 and JP-8 that are produced from hydrogen were also considered to be used in jet gas turbine engines;
petroleum refining [7,8]. It has been estimated that between 2% and 6% however, stringent and high quality performance criteria for commer­
of all global carbon emissions come from the aviation industry. It is cial jet fuel limits their application without engine modifications or
perceived that sustainable aviation fuels (SAF) can potentially substitute disruption to the current fuel distribution infrastructure [5].
petroleum-derived jet fuels in the short term as blend components and Conventional jet fuel is a mixture of alkanes, cyclic alkanes and ar­
can significantly reduce GHG emissions [4]. SAF, derived from organic omatics. However, the SPKs derived from the catalytic hydro-treatment
waste biomass resources, can significantly contribute to carbon savings of triglycerides and FT process lack sufficient cyclic alkanes and aro­
when compared to its fossil fuel equivalents. This is because a proportion matics levels which are required for the adequate function of aircraft
of the CO2 emitted upon its combustion is considered to be carbon seals and valves and must be present within the fuel up to 25%; hence,
neutral, consequently producing less net CO2. SAF can also contain very they are blended with fossil kerosine jet fuel to bring this level up[8].
little sulphur, which leads to a reduction in SOx emissions. The pyrolytic conversion of lignocellulosic biomass to liquid hydrocar­
The utilisation of SAF in the aviation industry has been recognised by bon drop in transport fuels is usually performed by fast pyrolysis. This is
the International Air Transport Association (IATA) as the most prom­ extremely challenging due to the fact that fast pyrolysis bio-oil has un­
ising way to reduce air emissions and dependence on fossil jet fuels [1]. desirable fuel properties such as high acidity, high viscosity, poor sta­
Accordingly, IATA aims to add 30% SAF as a fuel blend in conventional bility, and low calorific value. These unwanted properties make fast
jet fuel by 2030 [2]. pyrolysis derived bio-oil unsuitable for engine applications. The cata­
Hence, increased CO2 emissions, rise in fuel demand, price, and strict lytic upgrading of fast pyrolysis bio-oil over zeolites or other catalysts
environmental legislations have led the aviation industry to adopt have been demonstrated; however, the bio-oil composition is still not
renewable and sustainable fuels, which may provide a long-term solu­ sufficient to be upgraded into SAF [14,15]. There are also concerns
tion [7,8]. SAF fuel, and more specifically in this context known as raised over catalyst deactivation and poisoning.
synthetic paraffinic kerosene (SPK), is composed of renewable hydro­ Hence, new and improved methods and systems are needed to rise to
carbons in the same carbon range as fossil kerosene. SPK has a similar the challenges associated with SAF production [6]. Sewage sludge, the
composition to fossil jet fuel that gives it almost the same or, in some solid by-product of municipal and industrial wastewater treatment
cases, superior characteristics as fossil jet fuel. However, some proper­ plants [16], is a negative cost lipid-rich feedstock [17]. Due to con­
ties, such as the aromatic content in SPK, may be more variable and is taining a significant proportion of lipids, sewage sludge has been pro­
highly influenced by the processing route as well as biomass feedstock posed as a potential feedstock for biodiesel production [18]. The lipids
being processed [1]. content in sewage sludge materials varies between 2.9% and 12.3%
There are very few technologies available that can convert biomass [19]. Thermo-chemical processing (combustion, gasification, and py­
feedstock into SAF, and only a minority of these processes are currently rolysis) are some of the most promising routes to convert sewage sludge
ASTM approved routes and commercially available to enter the jet pool, into biofuels and energy [20]. Intermediate pyrolysis with catalytic
whilst other technologies are still either in demonstration stages or in reforming has the advantage of producing liquid fuels with less tar
early research and development [4]. SAF fuels derived from second formation and is preferred over other processing routes. It is perceived
generation biomass feedstock (camelina, jatropha, and algae) have been as a promising pathway to valorise biomass wastes into transport fuels
successfully tested in commercial flights with an 80% reduction in car­ and chemicals [20–22].
bon footprint relative to fossil jet fuel [5]. Thermo-Catalytic Reforming (TCR) Technology, an advanced inter­
The existing SAF production pathways can largely be categorised mediate pyrolysis-based technology, can process a wide range of waste
into hydroprocessing, thermo-chemical processing, and biochemical biomass into energy vectors. Previous TCR studies [23–27] have suc­
processing. The aviation fuel derived from hydroprocessing is called cessfully converted various organic wastes into crude bio-oils with
hydroprocessed renewable jet (HRJ) or sometimes hydroprocessed es­ enhanced physiochemical properties suitable for upgrading into drop-in
ters and fatty acids (HEFA). HRJ technology is commercially available fuels.
HRJ fuels that fall within specification with ASTM D7566 can be used up Previously, a few studies have been conducted for the pyrolytic
to a maximum blend ratio of 50% with fossil jet fuel without requiring conversion of biomass into jet fuel at lab scale. Zhang et al. [6] studied
any engine modifications or further approvals [9]. The Ecofining™ the novel transformation of sawdust (lignocellulosic biomass) into sus­
process, developed by Honeywell UOP in collaboration with ENI, is the tainable jet fuel range hydrocarbons using catalytic fast pyrolysis tech­
first technology under the hydroprocessing route to produce SAF from nology. As a result, it was found that the production of the preferred
biomass resources [1]. C8–C15 aromatics with the maximum selectivity of 92.4% was reached
Thermochemical pathways, also called biomass to liquid (BTL) pro­ by low-temperature alkylation reactions using an ionic liquid. Wang
cesses convert biomass into liquid fuel via three possible routes – gasi­ et al. [8] investigated a new conversion of bio-oil from fast pyrolysis of
fication, pyrolysis and hydro-thermal upgrading [1,10,11]. Gasification straw stalk (lignocellulosic biomass) into bio-jet fuel. Accordingly, it was
followed by Fischer-Tropsch (FT) synthesis is considered to be one of the concluded that the production of C8–C15 aromatics (selectivity of 88.4%)
alternative production routes for SAF fuel [1,12,13]. Fischer-Tropsch – was achieved by the alkylation reactions using an ionic liquid.
Biomass to Liquid (FT-BTL) via gasification is also an ASTM D7566 Furthermore, a new pathway was studied to form bio-jet fuel range
certified technology to produce renewable jet fuel. It is approved for a paraffins and aromatics through catalytic microwave-induced pyrolysis
50% blend with fossil kerosene (Jet A-1) [6,8]. of intact biomass which was integrated with the hydrotreating upgrad­
Alcohol to Jet (ATJ) and catalytic upgrading of sugars to hydrocar­ ing process, achieving the highest yield (12.6%) of sustainable jet fuel
bons, also known as Aqueous Phase Reforming (APR), are the two main range cycloalkanes [28]. Lately, Tomasek et al. [1] investigated bio-jet
processes which exist under the biochemical conversion route [4,9]. fuel production from cracked fractions of waste polyethylene and
LenzaTech’s ethanol to Jet technology has recently been certified in polypropylene plastics on commercial NiMo/Al2O3/P catalyst. As a
ASTM D7566 under the Annex A5 ATJ route for production and result, it was concluded that olefins affect the hydro-de-aromatisation
blending with fossil jet from 30% to 50% [4,5]. and hydrodesulphurisation at 240 ◦ C and 220 ◦ C, respectively.
There are a number of stringent quality specifications that SAF must This work presents novelty is to produce SAF from sewage sludge via
meet to be accepted within the jet pool [8]. ASTM D7566 is the certi­ TCR technology followed by hydroprocessing of TCR crude oil which has
fying standard for the new SAF that defines its production route and not been previously reported in the literature. Production of SAF from
quality specifications [4]. Previously, other renewable alternatives such hazardous and regulated waste, such as sewage sludge, has not been
as synthetic alcohols (bio-ethanol and bio-methanol), fatty acid methyl previously investigated, whilst recent lab-scale studies utilised

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M.A. Bashir et al. Journal of Analytical and Applied Pyrolysis 163 (2022) 105498

lignocellulosic biomass and plastics and mainly targeted a specific type 2.2. Experimental set-up
of jet fuel hydrocarbons [1,6,8,28]. This work aims to achieve a SAF
with conventional jet fuel paraffins (e.g., normal, cyclo, and iso) and 2.2.1. Thermo-catalytic reforming (TCR) system
aromatics using established hydroprocessing techniques that are The experiment was carried out in a 2 kg/h pilot-scale TCR unit
commercially practised in crude oil refining. With the ambition of future located at the University of Birmingham (Fig. 1). The TCR run was
integration as a SAF blend component with conventional jet fuels. The carried out under fixed optimum process conditions (constant pyrolysis
TCR-SAF product was characterised for its major fuel properties and and reforming temperatures). The main components of the TCR rig and
compared with ASTM D7566. the process are described as follows:
With the global pandemic outbreak (COVID-19), the aviation in­
dustry has been severely hit with a drop in air travel and subsequent I. Hopper/Feed Tank
lower aviation fuel consumption. Still, the aviation sector is an essential The sealed hopper had a batch feed capacity of 7 Kg. Before
part of the global economy. In terms of future assessment, the aviation feeding the tank, the whole system was purged with nitrogen to
sector will recover as travel restrictions are eased; however, it may be create an oxygen-free atmosphere. The tank was charged with 5
slow. As a result, there will be a lower demand for massive aircraft and a Kg of dried sewage sludge feedstock pellets.
possible return to smaller and single-aisle aircraft, which in turn have II. Pyrolysis Reactor
lower fuel demands [29,30]. However, with regards to commercial-scale The first reactor was an intermediate pyrolysis screw (auger)
production of SAF, recently, there has been a surge of research and reactor, and the temperature was at 450 ◦ C, producing pyrolysis
development projects and initiatives. The main challenges in the large gas and char.
scale production of SAF are the cost of jet fuel and its composition. The III. Reforming Reactor
UK department for transport has recently launched a competition, The second reactor (post reformer) was a fixed bed reforming
‘Green Fuels Green Skies’ for large scale process development for SAF reactor. In this section, the pyrolysis gas and char from the py­
[31]. Some major players, including LanzaTech, develop technologies to rolysis reactor undergo reforming at 700 ºC. The reforming
produce SAF from waste biomass [31,32]. However, this work has been temperatures and increased gas/solid residence time serve to
carried out as part of the GreenFlexJET project, which aims to design produce H2 rich syngas and a reformed lower molecular weight
and build a precommercial demonstration plant to produce SAF. condensable organic fraction.
Through an innovative technology which is not yet commercially IV. Cooling System
available. The condensable and incondensable fractions from the
reforming reactor were cooled in a U-tube shell and tube
2. Materials and methods condenser. The condenser contained a water/glycol mixture as a
service fluid at a temperature of − 5 ºC to ensure complete
2.1. Raw material condensation of the organic vapours. The condensable fraction
was recovered as condensate, while the remaining permanent
Sewage Sludge was sourced from SABESP, Brazil – a water and waste syngas fraction passed through an ice-bath cooler. The second
management company. The sewage sludge contained an initial moisture stage ice-bath cooling ensured the maximum recovery of con­
content of 80 wt%, which was reduced to approximately 20 wt% densable vapours, which might have escaped the first stage
through natural open-air drying in Brazil. Post-drying, the sewage cooling.
sludge was pelletised at the University of Birmingham UK using DORN- V. Cleaning System
TEC PTE 50 pelletiser. The final pellets were approximately 1.5 cm long
and 0.7 cm in mean diameter. The permanent gas containing aerosols and impurities is passed
through a cleaning system. Wash bottles containing aqueous phases
were used to capture aerosols, while a bottle filled with a fibrous filter

Fig. 1. Process schematic diagram of the TCR (2 kg/h) technology. Reproduced with permission from ref. [21], Copyright © 2020, Elsevier.

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M.A. Bashir et al. Journal of Analytical and Applied Pyrolysis 163 (2022) 105498

removed particles from the gas. Post-cleaning, the gas was routed to the 2.2.4. Fractionation
Pollutek 3100 P gas analyser for detection and then on to the flare, Fractional distillation is one of the most important unit operations of
where it was combusted using a propane support fuel. a crude oil refinery which physically separates petroleum products into
valuable fractions. The separation takes place due to differences in the
2.2.2. Hydroprocessing experiments boiling points of the components. After hydroprocessing, the fuel was
The hydroprocessing of the TCR crude oil was carried out in two distilled using a lab-scale distillation kit. The distillation apparatus
steps; the TCR crude oil was first hydrodeoxygenated (HDO) in the comprised a heating mantle, round bottom flask, a fractionating column
presence of a catalyst which was followed by hydrocracking (HC) using a containing rasching rings, a thermometer, a condenser with cold water
different catalyst. Commercial catalysts from HALDOR TOPSOE were flow, and a distillate receiving flask. The fractionation was carried out
used for hydroprocessing. NiMo catalyst supported on alumina (NiMo/ up to 285 ºC under atmospheric pressure to separate three fractions –
γ-Al2O3) was used for HDO, whilst (HC) utilised NiW catalyst supported naphtha, kerosene and diesel. Naphtha was collected at 140 ºC; the
on silica-alumina (NiW/SiO2-Al2O3) under the same process parameters. second cut collected at 235 ºC which separated the kerosene range;
The TCR crude oil was hydrodeoxygenated and hydrocracked in a mini- while from 235 ºC to 285 ºC, a green diesel fraction was recovered.
bench top high-pressure batch reactor system from Parr autoclave series
4560. The autoclave used was a 300 ml pressure vessel manufactured in 2.3. Analytical methods and measurements
T316 stainless steel and fitted with high torque sealed magnetic stirrer
drive unit in T316SS. The vessel was a fixed head style with a PTFE flat Ultimate analysis was performed by an external company Medac Ltd.
gasket and C-clamp closure. The working pressure and temperature The ultimate analysis was performed on a dry basis using the Fla­
limits for the pressure vessel were 200 bar and 350 ºC. The internal shEA®112 analyser that works on the quantitative dynamic flash com­
diameter and depth of the vessel were 6.5 cm and 10 cm, respectively. In bustion method. During ultimate analysis, the calorific value was also
addition, the vessel head was fitted with a pressure gauge (0–200 bar), measured. Before hydroprocessing, the TCR crude oil was filtered to
gas inlet, vent needle valves, safety rupture disk, and a J-type thermo­ remove entrained fine char particles. This was done using a 20–25 µ
couple. Before each HDO and HC run, the autoclave was purged with Whatman™ filter paper from which the bio-oil was passed under grav­
nitrogen to remove oxygen from the system. The system was pressurised ity. In addition to solid filtration, the crude oil for any potential miscible
with hydrogen to desired initial pressures (30–60 bar) and heated to a water was also separated using a Thermo-Scientific CL31R Multispeed
set point temperature (350 ºC). For the hydroprocessing and hydro­ centrifuge. The centrifugation was carried out at 3000 RPM for 15 min.
cracking steps, the amount of catalyst was adjusted to keep the catalyst The same settings were used for the separation of water after the
to oil ratio constant (1 g catalyst/10 ml TCR oil). In this study, the HDO- hydrodeoxygenation of TCR crude oil.
30 and HDO-60 denote oils produced from hydrodeoxygenation at 30 GC-MS analyses were carried out in Green Fuels Research, Berkeley,
and 60 bar H2, respectively, whilst HC-30 and HC-60 represent oils from UK. Approximately 10 µL of the sample was dissolved in 1000 µL of
hydrocracking at 30 and 60 bar H2, respectively. hexane as solvent. The mixture was further stabilised in the GC-MS vials
using a vortex mixer. An Agilent 8890 GC system linked to Q-TOF MS
2.2.3. Catalyst activation and reusability operating in EI mode with a scan range between 50 and 600 m/z was
Both hydrodeoxygenation and hydrocracking catalysts were acti­ used for GC-MS analyses. A DB5 MS column (30 m, 250 µm, 0.25 µm)
vated in-situ before each hydroprocessing experiment. Dimethyl disul­ was used for GC with a gas flow of He (1 ml/min) under 50 ºC holdup for
phide (99% purity, Alfa Aesar) as sulphiding agent was used to activate 1 min and then 5 ºC/min ramp up to 300 ºC. The chemical compounds
the catalysts at 350 ºC under 20 bar H2 for 4 h. Both hydro­ were identified using the NIST library. The mass spectra evaluation was
deoxygenation and hydrocracking spent catalysts were also tested to calculated in terms of peak area relative abundance (the percentage is
determine their reusability potential. The spent catalysts were reused the individual peak area as a proportion to the total).
with and without regeneration. Prior to regeneration, the spent catalysts The biocrude oil and hydroprocessed fuels were measured for acid
from the previous experiments were washed using hexane to remove number by manual titration, which was carried out in line with ASTM
organic species (contaminants) adsorbed on the catalyst surface and method D974 [21]. The unit of measurement is mg KOH/g. The water
later dried at 110 ºC for 24 h. The catalyst calcination was done in an content of the bio-oil was determined using Karl Fisher (KF) volumetric
oxidising atmosphere in a convective oven at 450 ºC. The heating rate auto-titrator as per ASTM D1744 [27]. The Karl Fisher method is based
was approximately 3 ºC/min, while the regeneration time was kept 4 h on the oxidation of SO2 by Iodine in a methanol hydroxide solution. The
(the same as activation). For the reusability tests without catalyst unit of measurement is % (w/w). All samples were measured by
regeneration, no calcination was performed, whilst the spent catalysts Houillon viscometer at a fixed temperature of 40 ºC for kinematic vis­
were washed and dried only. In this study, the HPWR denote hydro­ cosity. This was performed in line with ASTM method D445 [27]. The
processed oil over spent catalysts (without regeneration), whilst HPR-1 viscosity for the kerosene fraction was also measured at − 20 ºC with
and HPR-2 represent hydroprocessed oils produced (with first and sec­ respect to ASTM D445 [27]. The unit of measurement is cSt. A sample of
ond regeneration, respectively). Also, the HPF denotes hydroprocessed each oil was analysed in line with ASTM method D4052 by using an
oil produced over the fresh catalyst. Table 1 shows the summary of the Anton-Paar DMA 35 Digital density metre. The unit of measurement is
hydroprocessing parameters: g/ml [21]. The freezing point was tested with a HUBER refrigeration
bath system with a controlled freezing temperature up to − 50 ºC
following the ASTM D2386 test method for the freezing point of aviation
fuels [33,34]. Flash point was tested using the IP523 method [35], for
Table 1
Process parameters for two-step hydroprocessing (HDO and HC). which the unit of measurement is degree Celsius. The smoke point was
made in line with ASTM 1332 [36]. The unit of measurement is mm.
Unit Value

Batch time h 4 3. Results and discussion

Temperature ºC 350
Pressure bar 30–60
Catalyst Loading g catalyst/ml TCR oil 1/10 3.1. Sewage sludge TCR crude oil
Catalyst Activation Time h 4
Catalyst Activation Temperature ºC 350 Pelletised sewage sludge was processed through the TCR system. The
Catalyst Regeneration Temperature ºC 450 mass balance revealed 6 wt% of the dried sewage sludge converted to
Catalyst Regeneration Time h 4
phase-separated TCR crude oil, 25.4 wt% converted to syngas composed

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M.A. Bashir et al. Journal of Analytical and Applied Pyrolysis 163 (2022) 105498

of CO, CO2, CH4, H2 and CxHy, and 48.5 wt% converted to char, and the from the TCR crude oil. The O and N content decreased whilst C and H
remaining 20.1 wt% converted into water effluent. Table 2 contains content increased as a function of H2 pressure.
elemental composition, calorific value, and fuel characteristic data of A noticeable degree of deoxygenation and denitrogenation was
sewage sludge derived TCR crude oil. The TCR crude oil was rich in observed in both HDO and HC steps. The highest deoxygenation (100%)
hydrocarbons with 78.9 wt% carbon and 10.3 wt% hydrogen content and denitrogenation (89%) were observed in HDO and HC at 60 bar H2,
with calorific value of 39.4 MJ/kg. indicating that HDO/HC catalysts had significant catalytic effects and
The nitrogen content was slightly high, which is not desirable due to were not deactivated. The molar H/C ratio and the gross calorific value
potential NOx emissions. The nitrogen content in the bio-oil is attributed for the HC-60 oil reached 1.56 and 43.4 MJ/Kg, respectively. With the
to the presence of protein in sewage sludge [37,38]. Due to low oxygen upgrade of the elemental content of the oil, other properties such as
content, the TCR crude oil also showed excellent fuel heating properties density, TAN (total acid number), water and viscosity are also enhanced
comparable to biodiesel. The oil was characterised as lower in density in parallel. Under the hydroprocessing at 60 bar H2, an upgraded oil
(0.97 g/cm3), and viscosity (7.2 cSt). Low viscosity is desirable for good with zero water content, lower viscosity (1.6 cSt) and lean in acidity
flow properties as high viscosity can cause serious pumping issues. The (0.6 mg KOH/g) was produced.
oil was also found to be lean in acidity (5.7 mg KOH/g), which is
essential to avoid corrosion in the pipelines and engines [37]. Further­ 3.3. Two-step hydroprocessing
more, the oil was not miscible in water and contained a total water
content (3.0 wt%). The first step, known as HDO, involved the catalytic conversion of
Fig. S1 shows the gas chromatograms of the TCR crude oil. The oxygenated organic (TCR crude oil) compounds to saturated hydrocar­
compounds identified in the TCR crude oil were largely mono-aromatic bons (alkanes) by removing oxygen. Besides hydrodeoxygenation, other
hydrocarbons (ethylbenzene, p-Xylene, o-Xylene, styrene, benzene, 1- reactions such as hydrodesulphurisation (HDS) and hydro­
propynyl-); polycyclic aromatic hydrocarbons (naphthalene, 1-methyl, denitrogenation (HDN) also take place, which results in sulphur and
naphthalene, 2-methyl, azulene, biphenyl); free fatty acids methyl es­ nitrogen removal, respectively. The second step, known as HC, dealt
ters (hexadecanoic acid, methyl ester, 9, 12-octadecadienoic acid, with the catalytic conversion of long-chain paraffins (alkanes) from the
methyl ester, 9-octadecenoic acid (Z)-, methyl ester); and N-heterocyclic HDO process into small chain paraffins corresponding to the jet fuel
compounds (benzonitrile, 1 H-indole, 4-methyl-). range (C8-C16). Besides cracking, isomerisation and hydrodealkylation
reactions also take place. However, the range and extent of reactions are
highly influenced by the initial composition of the feed and process
3.2. Physiochemical characteristics of hydroprocessed oils
parameters.
The hydrogen pressure is one of the key parameters in hydro­
The sewage sludge derived TCR crude oil was further processed and
processing that affects product distribution. In order to effectively un­
converted into synthetic paraffinic kerosene. The purpose of hydro­
derstand the effect of H2 pressure on the distribution of chemical
processing is to remove heteroatoms from the bio-oil; saturate unsatu­
compounds, the hydroprocessed oils have been compared for their
rated hydrocarbons; and decrease O/C and increase H/C ratios. This was
relative distribution of components in HDO and HC processes as a
achieved via two-step catalytic hydrotreating under fixed process pa­
function of pressure. For comparison, only chemical compounds
rameters, except H2 pressure which was varied between 30 and 60 bar.
appeared with consistency and identified with more than 80% match
The comparative chemical composition, calorific values, H/C ratios,
with the NIST library have been presented. Furthermore, the chemical
degree of deoxygenation (DoD) achieved during HDO step and the major
compound in the hydroprocessed oils found were distributed across
fuel properties of the hydroprocessed oils across 30–60 bar H2 pressure
several organic groups. Hence for the purpose of discussion, the GC-MS
are tabulated in Table 2. The elemental composition of the TCR crude oil
results (Fig. S1) has been arranged on the basis of their organic classi­
was greatly enhanced during each hydrodeoxygenation and hydro­
fication and their corresponding carbon number (Table S1).
cracking step as more and more hydrogenation removed heteroatoms
3.3.1. Distribution of monocyclic and bicyclic aromatic hydrocarbons
Table 2 (MAH and BAH)
Physiochemical characteristics of oils in two-step hydroprocessing. Figs. 2 and 3 show the distribution of monocyclic and bicyclic aro­
Analyses TCR Crude (HDO and HC) @ 30 (HDO and HC) @ 60 matic hydrocarbons (MAH and BAH, respectively) of hydroprocessed
Oil Bar H2 Bar H2 oils. In HDO of the sewage sludge oil, the C8-C9 monocyclic (Fig. 2a) and
Reference HDO-30 HC-30 HDO-60 HC-60 C10-C12 bicyclic (Fig. 2b) aromatics constituted the majority of the ar­
Oil Oil Oil Oil omatics detected in the hydroprocessed oils. The C8-C9 monocyclic ar­
Ultimate omatics detected were essentially the isomers of benzene and its
analysis substituted derivatives, whilst the C10-C12 bicyclic aromatics were
C (wt%) 78.9 84.3 86.4 86.3 88.0 naphthalene and its derivatives.
H (wt%) 10.3 10.4 11.0 11.0 11.5
N (wt%) 4.5 2.8 1.8 2.0 0.5
Increasing H2 pressure in the HDO process favoured the formation of
S (wt%) 2.1 < 0.10 < 0.10 < 0.10 < 0.10 C8-C13 monocyclic with greater selectivity towards C8 (Fig. 2a). The
O (wt%) 4.2 2.5 0.8 0.7 0 relative abundance of C8 increased from 22.5% to 26.1% by increasing
Molar H/C 1.56 1.48 1.52 1.53 1.56 pressure from 30 to 60 bar H2. The monocyclic aromatics across C9-C13
DoD (%) 40 81 83 100
–
also showed a minor increase. On the other hand, increasing H2 pressure
Fuel
properties to 60 bar in the HDO step curtailed the formation of C10-C12 bicyclic
HHV (MJ/kg) 39.4 40.5 42.1 42.1 43.4 aromatics, indicating that some simultaneous cracking of the heavy
Ash (wt%) < 0.001 < 0.001 < 0.001 < 0.001 < 0.001 aromatics occurred in the HDO step. The relative content of the bicyclic
Water (wt%) 3.0 1.7 0.3 1.6 0 aromatics in the HDO-60 oil reduced to 8.9% compared to 12.7% in
Density (g/ 0.97 0.90 0.87 0.86 0.84
cm3)
HDO-30 oil (Fig. 2b).
TAN (mg KOH/ 5.7 1.6 0.8 0.7 0.6 Increasing H2 pressure to 60 bar in the HC step influenced the oil
g) composition by cracking light and heavy aromatics (Fig. 3). Monocyclic
Viscosity at 40 7.2 3.9 2.5 2.3 1.6 aromatics’ relative abundances significantly decreased in the HC-60 oil
ºC (cSt)
across the entire carbon range compared to HC-30 oil (Fig. 3a). The
O = calculated by the difference; DoD = degree of deoxygenation. relative areas of C8-C9 combined reduced from 36.1% to 18.8%, with

5
M.A. Bashir et al. Journal of Analytical and Applied Pyrolysis 163 (2022) 105498

Fig. 2. The product distribution in HDO oil at different H2 pressures for (a) MAHs and (b) BAHs.

Fig. 3. The product distribution in HC oil at different H2 pressures for (a) MAHs and (b) BAHs.

Fig. 4. Distribution of paraffin at different H2 pressures for (a) HDO oil and (b) HC oil.

6
M.A. Bashir et al. Journal of Analytical and Applied Pyrolysis 163 (2022) 105498

also more than 50% reduction across C10-C13 monocyclic aromatics. The branched/cyclic paraffins in order to meet essential jet fuel character­
relative abundances of bicyclic aromatics changed considerably across istics. In hydrocracking, n-paraffins crack and self-isomerise between
the entire carbon range (Fig. 3b). The C10 bicyclic aromatics dropped temperature 310 ◦ C–350 ◦ C where longer chain n-paraffins such as n-
from 5.5% to 2.6% by increasing HC pressure from 30 to 60 bar. How­ C16–C18 have been reported to exhibit enhanced transformation in
ever, the C11 bicyclic aromatics escalated from 2.6 to 4.3 by increasing comparison to shorter chain n-paraffins (< n-C16) where the tempera­
pressure. The C15 bicyclic aromatic compound emerged in the HC-30 oil, ture is a key factor [41]. In HC, cracking and isomerisation reactions are
possibly due to oligomerisation reactions of lighter aromatics [8]. competitive reactions that can occur either simultaneously or sequen­
tially [41,43].
3.3.2. Distribution of paraffins
Paraffins were the second most abundant chemical compounds in 3.3.4.3. Conversion of phenols to cyclo-paraffin. In the HDO/HC, the
terms of relative abundance on the GC spectrum of the hydroprocessed phenols were converted into cyclohexane (C6H12). The phenols con­
oils. The paraffins were distributed across cyclo-alkanes, n-alkanes, and version into cyclohexane during hydroprocessing fall under three
iso-alkanes. However, only n-alkanes were detected and identified in the possible reaction pathways as follows: First, direct deoxygenation breaks
hydro-treated oils with consistency. The n-alkanes detected and identi­ the C-O bond in the aromatic chain to produce benzene, followed by
fied by the NIST library were n-C9– C11 and n-C15–C18 (Fig. 4). cyclohexene and cyclohexane. Second, the phenol aromatic ring on
In the HDO step at 30 bar H2 pressure, the relative area distribution hydrogenation forms cyclohexanol. The intermediate cyclohexanol un­
of the fuel range C9-C11 and C15-C18 was 7.3% and 30%, respectively. On dergoes deoxygenation to produce cyclohexene and cyclohexane. The
the other hand, applying 60 bar H2 pressure in HDO influenced all the third pathway is the combination of simultaneous hydrogenation and
carbon numbers by increasing the n-C9-C11 to 10% and the n-C15-C18 to HDO that results in cyclohexanol as an intermediate. Further hydroge­
30.5% (Fig. 4a). This suggests that some cracking and isomerisation of nation yields cyclohexene and cyclohexane [42]. It is worth mentioning
the n-alkanes also took place in the hydrodeoxygenation at 60 bar H2. that isomerisation can also convert cyclohexane to methylpentane [42].
However, the n-C18 emerged with a greater relative area under 60 bar Operating parameters such as temperature, pressure, type of catalyst,
than 30 bar H2 pressure that can be associated with the relatively and support influence the above pathways, leading to the formation of
greater conversion of FAME in the feed to n-C18 due to higher hydro­ different intermediates and products.
genation saturation pressure [39].
Applying 60 bar H2 pressure in hydrocracking influenced the entire 3.3.4.4. Hydrogenation of naphthalene. In the HDO reaction, naphtha­
spectrum of n-alkanes across n-C9-C18 with enhanced cracking and iso­ lene was converted into tetralin (detected as naphthalene, 1,2,3,4-tetra­
merisation of n-C17-C18 (Fig. 4b). In hydrocracking, cracking and iso­ hydro-) and its substituted derivative (naphthalene, 1,2,3,4-tetrahydro-
merisation reactions are competitive reactions that can occur either 6-methyl-) in the hydroprocessed oils. Naphthalene is hydrogenated to
simultaneously or sequentially [40,41]. Although a range of produce tetralin, and tetralin, on further hydrogenation, converts into
cyclic-paraffin was present and identified, only cyclohexane was decalin [44]. Hydrogenation of naphthalene to tetralin is easier than
detected in the hydroprocessed oils (Table S1). The relative content of decalin due to the high rate of reaction, which has been reported to be 30
cyclohexane increased with the hydrogen pressure and reached 4.8% at times higher than decalin [44].
60 bar H2.
3.3.4.5. Hydrocracking of tetralin to monoaromatic hydrocarbons. Tetra­
3.3.3. Oxygenates and N-heterocyclic lin, the hydrogenated derivative of naphthalene, under high pressure of
The only oxygenated compound detected in hydrotreated oils were H2 can undergo simultaneous hydrogenation, dehydrogenation, ring
phenols and nitrile (Table S1). At 30 bar HDO, phenols were detected contraction, ring-opening, and cracking to produce light monoaromatic
with the relative area which was reduced in the HC step, showing little (< C10). The high yield of monoaromatic hydrocarbons has been re­
conversion. At 60 bar H2, the phenols appeared to have completely ported at 350 ◦ C and 60 bar H2 [45].
hydrogenated and hydrocracked into cyclohexane. Indole, a nitrile
compound, was the only N-heterocyclic compound identified in the
3.3.4.6. Hydrodenitrogenation of indole. Indole on hydrogenation con­
hydroprocessed oils. The relative content of indole decreased in both verts into 2,3-dihydroindole. Further hydrogenation of 2,3-dihydroin­
HDO and HC reactions. At 30 bar H2, it was detected with the relative
dole can transform it into octahydroindole as an intermediate
area of 2.5% in the HDO-30 oil and was reduced to 1.4% in HC-30 oil. compound. The octahydroindole further converts into ethyl-
Increasing pressure to 60 bar H2 in the HDO step reduced indole further
cyclohexane and ethylcyclohexene as the final compounds. Besides,
to 1.1%, and further cracking at 60 bar enhanced the removal. Indole the octahydroindole can further convert to intermediate o-ethylaniline
was not detected post hydrocracking at 60 bar H2.
through ring-opening and subsequently to ethylbenzene. Denitrogenat­
ing is rather difficult compared to desulphurisation [46] because H2
3.3.4. Possible reaction mechanisms in hydroprocessing of sewage sludge
saturation of aromatic ring is an essential reaction step in denitrogena­
TCR crude oil tion, whilst it is not needed in sulphur removal [47].
To sum up Section 3.3, monocyclic and bicyclic aromatic hydrocar­
3.3.4.1. Hydrodeoxygenation of FAME. The FAME during HDO was bons (MAH and BAH, respectively) were the main compounds of
converted to paraffins (n-alkanes). Unsaturated FAME under hydroge­ hydroprocessed TCR oils. However, other products of the hydro­
nation gets converted into saturated FAME. Then, the saturated FAME is processing reactions were mainly water, carbon monoxide, carbon di­
decomposed into one less carbon through a hydrogenolysis reaction. The oxide, methane and ethane [40]. The carbon balance of these
formed carboxylic acid further undergoes decarboxylation, decarbon­ compounds will be studied as a future work.
ylation and HDO reactions to form paraffins. Finally, cracking and iso­
merisation reactions convert longer-chain alkanes into shorter-chain
alkanes [42].
Table 3
The product distribution from sewage sludge hydroprocessed oil at 60 bar H2.
3.3.4.2. Hydrocracking of n-paraffins. The HDO of FAME resulted in the
Fraction Mass Yield (%) Volumetric Yield (%)
formation of n-paraffins across the n-C9–C18 carbon range. During hy­
drocracking, the n-C17–C18 paraffins, in particular, underwent cracking Kerosene 25 25.5
Gasoline (Naphtha) 18 20.5
and isomerisation to yield more n-C9–C15 range to produce lighter and
Diesel 25.5 29

7
M.A. Bashir et al. Journal of Analytical and Applied Pyrolysis 163 (2022) 105498

3.4. Distillation Yields Cyclo-paraffin gives lower H/C [55] but produce less soot and are
considered to be thermally more stable than iso-paraffin and aromatics.
Table 3 shows the percentage mass and volumetric yields of the Due to higher density, the cyclo-paraffin also give shorter ignition time
products recovered from sewage sludge, the most hydroprocessed oil at and faster flame speed [49]. The paraffin distribution into straight, cy­
60 bar H2 after distillation. Naphtha and diesel were recovered as by- clic and branched alkanes varies and depends on the composition of
products. The kerosene fraction was 25 wt%, but naphtha and diesel crude oil used in the refining process [55].
were 18 wt% and 25.5 wt%, respectively. Hetero-atoms (others) such as ketones were also detected, which
possibly formed due to initial oxidation of jet fuel which can lead to
deposit precursors [53,54].
3.5. GC-relative distribution of kerosene
3.6. Fuel properties of sewage sludge derived jet fuel
The GC-MS data (Fig. S2) of the jet fuel (C8-C16) range fraction,
including chemical compounds, retention times and their relative peak
There are a number of strict specifications that jet fuels are required
areas, are shown in Table S2. The chemical compounds detected in the
to meet in order to be approved as jet fuel. The ASTM D7566 (an
jet fuel range can be classed as MAHs, BAHs, n-paraffins, cyclo-paraffins,
expansion of D1655) is a certifying standard that defines the SPK fuel
iso-paraffins and traces of esters, phenols and ketones. The overall dis­
performance criteria to control the production and quality of bio-jet fuel.
tribution of aromatics was across C8-C13, which is in line with the aro­
Table 4 summarises some essential fuel characteristic data of previously
matics carbon range (C8-C15) mainly found in jet fuel. The aromatics are
commercially produced SPKs through FT and HRJ technology and the
vital for elastomer swelling, lubricity and material compatibility [48].
sewage sludge jet fuel produced in this work against the ASTM D7566
Fig. 5 shows the relative area of kerosene compounds. The C8-C13
standard. In addition, Table 4 provides a comparison of sewage sludge
monocyclic aromatics were detected as relatively the most abundant
derived Jet fuel produced in this work with commercial/military jet
chemical compounds with approximately 60% relative combined rela­
fuels.
tive area on the GC spectrum. The C8-C10 aromatics detected in the jet
The sewage sludge derived jet fuel range met the majority of the
fuel range were mainly alkylbenzenes such as ethylbenzene, benzene, 1,
ASTM fuel specification such as acceptable minimum heating value
2, 3-trimethyl-, benzene, propyl-, benzene, 1-ethyl-4-methyl- etc. which
(42.8 MJ/Kg), maximum freeze point (− 47 ºC), maximum allowable
are considered as desirable aromatics in jet fuel as they tend to produce
viscosity (8 cSt at − 20 ºC) and sulphur content (0.3 wt%.). The sewage
less soot on combustion compared to other aromatics [49]. Further, they
sludge TCR jet fuel showed high net energy content (43.4 MJ/Kg). The
produce less NOx in combustion due to methyl radicals which act as
sewage sludge TCR jet fuel exhibited excellent low-temperature prop­
sinks for O radicals [49].
erties such as freezing point (− 50 ºC) and viscosity at − 20 ºC (3.2 cSt),
The bicyclic aromatics (C10–C12) detected were essentially naph­
which is essential for the aircraft to fly at high altitude [4]. Likewise, the
thalene and its isomers. They are undesirable in fuels as they are known
high viscosity of jet fuel can cause pumping problems, poor atomisation
to produce high smoke and soot. Moreover, they are considered toxic
and incomplete combustion [52]. These excellent low-temperature
and environmentally hazardous [50]. JP-8 jet fuel has been reported to
characteristics can be attributed to a large number of cyclo-paraffins
contain 0.26–1% naphthalene as an aromatic compound [51]. However,
[55] which were detected at several retention times in the sewage
naphthalene in jet fuels has also been reported to cause greater swelling
sludge TCR jet fuel during GC-MS. The amount of sulphur (<0.10)
in elastomers [52] which is essential to avoid leakage in aircraft com­
detected was well within the ASTM limit. The sulphur is present in jet
ponents. In addition, tetra-hydro-naphthalene (tetralin), a derivative of
fuels in the form of mercaptans, sulphides, thiosulphides or other
naphthalene hydrogenation, was also present in the fuel, which is
sulphur containing compounds [55].
known to negatively affect the oxidative stability of jet fuels by pro­
However, the flash and smoke points for the sewage sludge TCR jet
ducing peroxides [53,54].
fell below the minimum allowable limit due to higher aromatics [56].
Paraffins were the second most abundant compounds in the hydro­
Which suggests the fuel may be suitable as a blend component only. The
processed oil, with approximately 27% combined relative abundancy in
quantification of the aromatics was not done; however, higher flash and
gas chromatography. Paraffins were mainly distributed across n-paraffin
the smoke points are an indication that the aromatics present in the
with a considerable presence of cyclo-paraffin. A high concentration of
sewage sludge TCR jet fuel are above the ASTM limit (25 vol%).
n-paraffin results in a higher H/C ratio but relatively increases the
Reducing the number of bicyclic aromatics (C10–C12) will increase the
freezing point. A couple of iso-paraffins were also detected in the fuel.
flash point and smoke point of the fuel, which can be done by greater
hydrogenation/cracking of bicyclic aromatics. Furthermore, blending
with a low aromatic jet fuel such as HRJ-SPK and FT-SPK will help the
sewage sludge TCR jet fuel be in specification. Similarly, the TAN
(0.6 mg KOH/g), generally associated with naphthenic and cresylic
acids, can be reduced in many ways, such as casting washing, blending
with non-acidic crude [57]. As a future work, optimising the hydro­
processing conditions of TCR jet fuel will be investigated to bring all
properties within the ASTM range.

3.7. Catalyst reusability and regeneration

The catalyst reusability and regeneration tests were carried out

under the same process parameters used for the production of the jet fuel
range (Fig. S3). The gas chromatogram relative area distribution of
chemical compounds in catalyst reusability tests is shown in Table S3.
The catalytic performance has been evaluated by comparing the physi­
ochemical properties of the hydroprocessed oils from spent and regen­
erated catalysts with the hydroprocessed oils from the fresh catalytic
test.
Fig. 5. Gas chromatogram relative area percentage of compounds in kerosene. The elemental composition, degree of deoxygenation and the fuel

8
M.A. Bashir et al. Journal of Analytical and Applied Pyrolysis 163 (2022) 105498

Table 4
Fuel Properties of sewage sludge derived kerosene fraction.
Specification ASTM D7566 TCR Jet Fuel JP-8 Shell FT Sasol FT R8-HRJ Camelina HRJ

HHV (MJ/Kg) Min 42.8 43.4 44.1 44.2 44.1 44.1

43
S (wt%) Max 0.3 < 0.1 < 0.001 < 0.001 < 0.001 < 0.0003
0.064
Freezing Point (ºC) Max − 47 -50 -55 -77 -49 -77
-49
Density, 15 ºC (g/cm3) 0.75–0.84 0.84 0.73 0.76 0.76 0.75
0.79
TAN (mg KOH/g) Max 0.1 0.6 0.002 0.002 0.002 0.002
0.03
Viscosity, − 20 ºC (cSt) Max 8 3.2 2.6 3.8 5.5 5.3
4.1
Smoke Point (mm) Min 25 13 40 > 40 > 40 > 40
22
Flash Point (◦ C) Min 38 < 38 44 44 48 43
48

Min = minimum; Max = maximum.

properties of the hydroprocessed oil for without regeneration (HPWR) 45.5%, respectively. However, a significant decline in the aromatics and
and regenerated catalysts (HPR-1, HPR-2) have been compared to the paraffins in the HPWR oil is associated with poor hydrodeoxygenation
hydroprocessed oil produced over the fresh catalysts (HPF) in Table 5. It (DoD, 33%) over the spent catalyst without regeneration. The main
can be seen that the highlighting difference in the elemental composi­ difference was observed across C8–C9 MAHs and C9–C18 n-paraffins
tion is the higher oxygen content of the HPWR oil compared to the rest of (Table S3), for which the relative content declined by approximately
the oils. The spent HDO catalyst without regeneration exhibited poor 50% compared to HPF, HPR-1 and HPR-2 oils. In addition, phenols were
deoxygenation efficacy, dropping to 33% compared to 83% in the HPF also detected with higher relative content in the HPWR oil, indicating
oil. This is likely due to the deposition of coke on the catalyst active sites. lower conversion of phenols in the HDO step due to coking.
It is well known that the formation of coke and coke-like polymers is the In the HC reaction, the aromatics and paraffins’ relative content was
root reason for catalyst deactivation during the bio-oil HDO process moderately similar across all the hydroprocessed oils (HPF, HPR-1, HPR-
[58]. 2 and HPWR), indicating that the HC catalyst without regeneration did
Coking is associated with the thermal instability and re- have a significant catalytic effect and was not deactivated.
polymerisation of phenolic compounds in HDO [59]. However, the
following HC step compensated for the poor deoxygenation by removing 4. Conclusion
66% of the oxygen content. The fuel properties of all the hydroprocessed
oils were also comparable. The poor deoxygenation in HPWR oil is also Sewage sludge was converted to crude oil through the TCR system
reflected in its fuel properties with relative higher TAN, water, density and was successfully upgraded to sustainable aviation fuel within the
and viscosity. hydrocarbon range. The TCR crude oil had a low oxygen content (<5 wt
Fig. 6 shows the total relative aromatics and paraffin content in %) content due to which the oil was conveniently deoxygenated in the
hydrodeoxygenation and hydrocracking reactions over the fresh cata­ hydroprocessing step requiring less hydrogen partial pressure. Both
lysts (HPF), spent catalysts without regeneration (HPWR) and regener­ hydroprocessing steps showed high catalytic activity at 60 bar H2. It was
ated catalysts. (HPR-1 and HPR-2). found that both hydrodeoxygenation and hydrocracking steps resulted
In the HDO reaction, the relative aromatics distribution of the HPR-1 in oxygen and nitrogen removal, which will be an important consider­
(52.9%) and HPR-2 (52%) oils were comparable to the HPF oil (57.1%). ation from the process design point of view in the scale-up of the process.
The relative paraffin distribution of HDO oils was also similar across the The yield of the jet fuel fraction can be optimised by running the hy­
HPR-1, HPR-2 and HPF oils with relative content of 40.3%, 40.2%, and drocracker at a higher H2 pressure which will increase the jet fuel range

Table 5
Physicochemical characteristics of hydroprocessed oils in catalyst reusability and regeneration tests.
Physicochemical Properties HPF Oil HPWR Oil HPR-1 Oil HPR-2 Oil

(As Reference) (without Regeneration) (First Regeneration) (Second Regeneration)

HDO HC HDO HC HDO HC HDO HC

Ultimate analysis
C (wt%) 86.3 88.0 83.7 86.2 86.1 86.7 86.2 87
H (wt%) 11.0 11.5 11.3 11.5 11.2 12.2 11.0 11.0
N (wt%) 2.0 0.5 2.2 0.9 1.5 0.3 2.0 0.6
S (wt%) < 0.10 < 0.10 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1
O (wt%) 0.7 0 2.8 1.4 1.2 0.8 0.8 1.4
Molar H/C 1.53 1.56 1.62 1.60 1.56 1.68 1.53 1.52
DoD (%) 83 100 33 66 71 80 80 66
Fuel properties
HHV (MJ/Kg) 42.1 43.4 42.2 43.5 43.1 44.5 43.0 43.2
Ash (wt%) < 0.001 < 0.001 < 0.001 < 0.001 < 0.001 < 0.001 < 0.001 < 0.001
Water (wt%) 1.6 0 1.8 0.3 1.6 0 1.6 0
Density (g/cm3) 0.86 0.84 0.87 0.85 0.86 0.83 0.87 0.83
TAN (mg KOH/g) 0.7 0.6 1.6 0.9 0.6 0.6 0.8 0.5
Viscosity (cSt) 2.3 1.6 2.8 1.9 2.3 1.6 2.6 2.0

O = calculated by difference; DoD = degree of deoxygenation.

9
M.A. Bashir et al. Journal of Analytical and Applied Pyrolysis 163 (2022) 105498

Fig. 6. Total relative aromatics and paraffin content in a) hydrodeoxygenation, and b) hydrocracking.

paraffins at the expense of C17+ paraffins separated as a diesel fraction. Declaration of Competing Interest
The jet fuel fraction for the majority of its fuel characteristics fell within
the ASTM D7566 specification standard. The quality parameters such as The authors declare that they have no known competing financial
total acid number, smoke point and flash point can be certainly be interests or personal relationships that could have appeared to influence
improved through additional treatment and process optimisation. Upon the work reported in this paper.
testing the process for catalyst reusability and regeneration potential, it
was observed that the efficiency of the spent NiMo/γ–Al2O3 catalyst Acknowledgements
(without regeneration) in the HDO process had significantly declined,
possibly due to coking. However, both HDO and HC spent catalysts were The authors would like to acknowledge the European Union’s Ho­
successfully regenerated, showing similar catalytic activities as the fresh rizon 2020, GreenFlexJET project (Reference Number: 792216) and To-
catalysts during hydrotreatment. The potential of catalyst regeneration Syn-Fuel project (Reference Number: 745749) for financial support.
is also of considerable importance in the scale-up of the process. As a
result, the TCR conversion of sewage sludge can be a sustainable Appendix A. Supporting information
pathway for jet fuel production and promising valorisation route for
sewage sludge. Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.jaap.2022.105498.
CRediT authorship contribution statement
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