IASH 2013, the 13TH INTERNATIONAL CONFERENCE ON

STABILITY, HANDLING AND USE OF LIQUID FUELS

Rhodes, Greece
6-10 October 2013

BIOMASS PYROLYSIS OIL AS A RENEWABLE FEEDSTOCK FOR BIO-JET FUEL

Mariam Ajam1, Chris Woolard1, and Carl L Viljoen2

1
Sasol Advanced Fuels Laboratory, Department of Chemical Engineering, University of Cape
Town, Private Bag X3, Rondebosch, Cape Town, 7700, Republic of South Africa
mariam.ajam@sasol.com and chris.woolard@sasol.com
2
Sasol Technology Fuels Research, P.O. Box 1, Sasolburg, 1947, Republic of South Africa
carl.viljoen@sasol.com

Environmental and energy security concerns have stimulated interest in the development of
conversion technologies for renewable transportation fuels. Fast pyrolysis of biomass is an
emerging renewable energy process that has gained considerable interest as a method to produce
renewable liquid fuels. Biomass pyrolysis oil is potentially an attractive renewable source of bio-
jet fuel components.

The biomass pyrolysis oil produced from fast pyrolysis cannot be used directly, as a “drop-in”
fuel, because of its chemical and physical properties. The undesirable properties of the biomass
pyrolysis oil, such as high corrosivity, low energy density and poor thermal instability, are due to
the presence of a variety of oxygenates in the oil. Biomass pyrolysis oil requires upgrading in
order for the resultant kerosene fraction and/or blends to be compliant with existing jet fuel
specifications and compatible with existing logistical systems and engine technology. Catalytic
hydrotreatment is an upgrading technology commonly used to improve the product properties of
biomass pyrolysis oils by reducing the oxygen content of the oil, amongst others. This
technology involves the treatment of biomass pyrolysis oil with hydrogen in the presence of a
heterogeneous catalyst. The bio-jet fuel produced from biomass pyrolysis oil upgrading is a high
density fuel component with a high aromatic and cycloparaffinic content. It is hence ideal for
blending with lower density Fischer-Tropsch Synthetic Paraffinic Kerosene (FT-SPK) and
Hydroprocessed Esters and Fatty Acids (HEFA) kerosenes.

This paper summarises the typical fuel properties and thermal oxidative stability properties of
bio-jet fuel derived from biomass pyrolysis oils in comparison with crude-derived jet fuel. The
stability of model compound systems, representative of a range of refractory oxygenates in
biomass pyrolysis oil, are also evaluated in this paper. Applied thermal oxidative stability
techniques reported on in this paper include the Jet Fuel Thermal Oxidation Test (JFTOT TM),
Quartz Crystal Microbalance (QCM), static flask oxidation and the PetroOXYTM instrument.
Insights into the catalytic hydrotreatment of biomass pyrolysis oil to produce a bio-jet fuel
component are also discussed.
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 1. INTRODUCTION

Currently, the aviation industry relies on jet fuels derived from fossil fuel sources, primarily
petroleum. Aviation contributes 2-2.5% of global carbon dioxide emissions.1 This contribution is
anticipated to double in the next 20 years because of rapid growth in global air traffic. 2 The
aviation industry has consequently proposed ambitious targets to reduce commercial aviation’s
environmental impact, e.g. carbon neutral growth by 2020.3 Sustainable, renewable jet fuels will
play a major role in meeting these challenging targets.

In addition to conventional petroleum-derived fuels, two alternative classes of fuel are approved
for commercial aviation use.4 These are Fischer-Tropsch Synthesized Paraffinic Kerosene (FT-
SPK), derived from coal, natural gas or biomass, and Hydroprocessed Esters and Fatty Acids
(HEFA), derived from oils and fats. These alternative fuels have been approved for commercial
use at levels of up to 50 vol% with conventional petroleum-derived Jet A-1. FT-SPK and HEFA
kerosene are mainly paraffinic in nature and require aromatics and cycloparaffins to meet current
specifications. Aromatic hydrocarbons in jet fuel are required for sustaining the sealing
effectiveness of O-rings in the fuel system. Paraffinic fuels have the potential to cause shrinkage
of elastomeric seals that can, consequently, result in age-hardened seals leaking when exposed to
aromatics-free fuels.5

Kerosene derived from biomass pyrolysis oil, while broadening the range of bio-feedstocks for
jet fuel, would provide a route to renewable aromatic hydrocarbons which would be
complementary to the highly paraffinic, lower density FT-SPK and HEFA fuels. A jet fuel from
biomass pyrolysis oil is not approved for commercial aviation use under the current jet fuel
specifications and would require extensive evaluation of its physical and chemical properties
before it could be approved. One area of concern would be the thermal stability of such fuels, an
aspect which forms the basis of this study.

Jet fuel is used to cool critical aircraft and engine components and consequently may reach
temperatures between 140 and 300 °C. The fuel is required to be thermally stable at these
temperatures.6 If not, jet fuel could potentially undergo degradation reactions involving
hydrocarbons, dissolved oxygen and trace impurities leading to deposit formation.7 Phenols in jet
fuel, for instance, have been shown to promote the formation of thermal oxidative deposits via
condensation and oxidative coupling reactions during thermal stressing of the fuel.8

Pyrolysis oil, produced from biomass, has been shown to be rich in oxygenates, in particular
phenolic compounds.9 Jet fuel components, derived from biomass pyrolysis oil, would require a
reduction in the level of these oxygenated species, to produce a fit-for-purpose fuel. The
presence of significant quantities of oxygenates in jet fuel is currently constrained because of
their detrimental impact on the ability of a jet fuel to meet stringent specifications such as
minimum energy density, volatility, water solubility, corrosion and stability effects.10

As indicated, jet fuel derived from biomass pyrolysis oil, would require treatment to reduce the
level of oxygenates, especially phenols, which reduce jet fuel thermal stability. This could entail
significant hydrodeoxygenation to convert these species to more stable aromatic hydrocarbons,
which will not impact detrimentally on jet fuel stability. Currently, little is understood of the fuel
properties and thermal oxidative stability of bio-jet fuel derived from biomass pyrolysis oil. This
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paper summarises the typical fuel properties and thermal oxidative stability properties of bio-jet
fuel derived from biomass pyrolysis oils.

2. EXPERIMENTAL PROCEDURE

a) Origin of biomass pyrolysis oil, stabilised pyrolysis oil and fuels

The biomass pyrolysis oil, stabilised pyrolysis oil and the wide boiling-range fuels used in this
study were purchased from Biomass Technology Group (BTG) in the Netherlands. BTG
developed a process (refer to Figure 1) to produce stabilised pyrolysis oil (SPO) from the
original pyrolysis oil (OPO) using proprietary catalysts (referred to as Picula™ catalysts).11 The
stabilised pyrolysis oil was then further hydroprocessed using a classical hydrotreating catalyst
(sulphided CoMo catalyst supported on alumina) and reaction conditions (350 – 400 °C, 200 bar
H2) to produce a wide boiling-range fuel (boiling range from 75 to 535 °C according to
simulated distillation analysis). Depending on the severity of this step, the wide boiling-range
fuels can contain different oxygen concentrations. In this study, three different grades of wide
boiling-range fuels produced by different reaction severities (350, 375 and 400 °C) were
analysed by two-dimensional GC to determine the levels and types of oxygenates remaining in
the wide boiling-range fuel after catalytic hydrodeoxygenation. Also, two completely different
grades of wide boiling-range fuels were used in this study to fractionate into bio-jet fuel fractions
(in the kerosene boiling range from 150 – 280 °C), which were further analysed for jet fuel
properties.

TM Classical hydrotreating
Picula catalyst catalysts Fractionation
OPO SPO Wide boiling-range fuel Bio-jet fuel
Original pyrolysis oil Stabilised pyrolysis oil < 1 wt% O
50 wt% O 15 - 30 wt% O Oxygen varies depending on
Water removed severity of hydrotreatment

Figure 1. BTG’s proposed biomass pyrolysis oil upgrading process by catalytic

hydrodeoxygenation.

b) Biomass pyrolysis oil characterisation

The chemical and physical properties of the biomass pyrolysis oil and stabilised pyrolysis oil
were evaluated using standard analytical techniques available in Sasol laboratories. Analyses
include elemental composition, pH, water content, solids content and heating value. The
compositions of the pyrolysis oils were evaluated using GC-MS and 13C-NMR. NMR was
especially useful in providing detailed information on the functional groups present in the
pyrolysis oils. An NMR technique developed by Mullen and co-workers to characterise fast
pyrolysis oils were used in this study.12 This technique provides a means to calculate the
percentage of carbons in different chemical functional groups based on the integration of peaks
at different chemical shifts in the 13C-NMR spectra (refer to Table 1 below).

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Table 1. Chemical shifts in 13C-NMR spectra and their corresponding carbon assignments.
Chemical shift (ppm) Carbon assignments
4 – 30 ppm Short aliphatics
30 – 55 ppm Long and branched aliphatics
55 – 95 ppm Alcohols, ethers, methoxyphenols,
carbohydrate sugars
95 – 165 ppm Aromatics and olefins
165 – 180 ppm Esters and carboxylic acids
180 – 215 ppm Ketones and aldehydes

c) Selected fuel analyses

Fuel analyses on the wide boiling-range fuels and the bio-jet fuels were carried out according to
the American Society for Testing and Materials (ASTM) test methods as contained in the British
DEFSTAN 91-91 for Jet A-1. Two-dimensional gas chromatography (2D GC or GCxGC) was
also performed on the neat fuels to provide insight into the hydrocarbon composition of the fuels.

d) Model compounds

Four oxygenated model compounds, typically found in biomass pyrolysis oil, were used in this
study to determine their effects (at a 3 volume% level) on the thermal and oxidative stability of a
jet fuel surrogate fuel (dodecane and n-butylbenzene, at 90 :10 volume ratio respectively). Figure
2 below shows the chemical structure of the oxygenated model compounds used in this study.

OH OH
O O
O

Anisole Benzylmethylether 2-Methoxyphenol 2-Ethylphenol

Figure 2. Model compounds used in this study.

e) Thermal and oxidative stability tests

In this study, different thermal oxidative stability techniques covering a range of temperatures
from 140 to 325 °C were used. These had been selected to mimic the range of conditions under
which jet fuel may be stressed during use.

i) PetroOXY™ test

The PetroOXY™ is normally used to evaluate oxidation stability measured as induction period
for diesel (ASTM D7545) and gasoline (ASTM D7525). The induction period, or break point, is
used as an indication of the oxidative stability of the fuel. In this study, the PetroOXY™ was
used to evaluate the oxidative stability of neat model fuel systems to provide insight into the
degradation of model compounds in the presence of oxygen.

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In this method, a 5 mL sample is introduced into a pressure vessel, which is charged with 700
kPa of pure oxygen at ambient temperature. The test is started upon heating of the pressure
vessel to a temperature of 160 °C. The oxygen pressure is recorded continuously until the
pressure reaches a 50% drop (this is considered the break point or induction period). The results
of each jet fuel surrogate fuel in the presence of model oxygenate compound were compared to
each other. The stressed sample after the test is subsequently analysed using GC-MS.

In the case of the neat oxygenated model compounds, these were stressed in the PetroOXY™ at
160 °C for 9 hours under 700 kPa of oxygen, and evaluated after oxidation using GC-MS. Before
the PetroOXY™, the neat model compounds were treated with alumina to remove any impurities
and ensure that the molecule is in its purest form.

ii) Flask oxidation test

Thermal stressing of the jet fuel surrogate fuel in the presence of an oxygenated model
compound (50 mL) was performed in a 3-necked round-bottomed flask (100 mL) equipped with
a reflux condenser using a heated oil bath at elevated temperatures (160 °C) under a constant
atmosphere of air (100 mL/min). Liquid samples were taken at 1, 3, 5, 7, 9 hour intervals and
analysed using GC-MS in order to give insight into the degradation of the model fuel system in
the presence of an oxygenate.

iii) Jet Fuel Thermal Oxidation Test (JFTOT™)

The JFTOT™ method based on the ASTM D3241 standard method is used world-wide to
determine if jet fuel meets the current thermal stability specification i.e. to measure the deposit
formation tendencies of jet fuel when heated at a specified temperature in the presence of oxygen
and a metal surface. JFTOT™ is used as a qualitative pass/fail rating instrument for thermal
oxidation stability at 260 °C (for crude-derived jet fuels) and 325 °C (for synthetic and
renewable jet fuels). The degree of fuel degradation due to thermal oxidation is then measured
by the deposits formed. The amount of deposit on the tube can be rated using a tube deposit rater
(TDR) on a scale from 0 (no deposit) to 4 (heavy deposit). Oxygenated model compounds were
doped at 1 volume% into a thermally stable FT-SPK. The thermal oxidative stability of the
doped FT-SPK was evaluated using JFTOT™, to determine the effect of the different oxygenates
on a stable jet fuel (FT-SPK).

iv) Quartz Crystal Microbalance (QCM)

The QCM device was used to monitor oxygen consumption and carbon deposition in-situ (solids
deposit on the quartz crystal) during thermal stressing of bio-jet fuel and its blends with FT-
SPK.13 The fuel (60 mL) was stressed in the reactor at a temperature of 140 °C for 15 hours,
while the pressure transducer monitors the pressure decay in the reactor as oxidation reactions
take place. The instrument measures the frequencies of the quartz crystal which changes as
deposits are laid on the crystal. The quartz crystal frequency, the temperature and headspace
pressure is monitored using a computer. The change in the quartz crystal frequency with time is
used to monitor the deposit formation. The QCM studies provided more detail into the oxygen
consumption and carbon deposition profiles of the bio-jet fuels and its blends with FT-SPK
during thermal stressing.
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 3. RESULTS AND DISCUSSION

3.1. BIOMASS PYROLYSIS OIL PROPERTIES

Biomass pyrolysis oil is produced by a high temperature decomposition process where biomass
is heated rapidly in the absence of air or oxygen, typically under a nitrogen atmosphere (called
fast pyrolysis).14 Pyrolysis oil consists of a complex mixture of many different components
derived from the breakdown of three key biomass building blocks; cellulose, hemi-cellulose and
lignin.15 Pyrolysis oils, produced from fast pyrolysis, are not suitable as “drop-in” renewable
transportation fuel components. This is because the chemical composition and physical
properties of pyrolysis oils are significantly different from those of petroleum-derived fuels. The
physical properties of an original biomass pyrolysis oil and a stabilised or semi-upgraded
pyrolysis oil (both derived from wood chips) are compared to those of a petroleum-derived
heavy fuel oil in Table 2 below.

Table 2. Physical properties of an original biomass pyrolysis oil and stabilised or semi-
upgraded pyrolysis oil compared to petroleum-derived heating oil.
Physical Property Units Original Stabilised Petroleum-
pyrolysis oil pyrolysis oil derived heavy
(wood chips) (wood chips) fuel oil16
pH - 2.53 2.80 4.00
Water content wt% 26.3 7.5 0.1
Solids content wt% 0.015 0.010 1.0
Ash content wt% 0.042 0.040 0.1
Carbon wt% 40.8 58.9 85.0
Hydrogen wt% 6.1 9.0 11.0
Nitrogen wt% <0.1 <0.1 0.3
Sulphur wt% <0.1 <0.1 -
Oxygen, by difference wt% 53.1 32.0 1.0
Density at 40 °C kg/m3 - 1.11 0.94
Viscosity at 40 °C cP 18.9 195.5 180.0
Higher heating value MJ/kg 15.9 26.8 40.0
Total Acid Number mg KOH/g 49 45 -

Pyrolysis oils generally have a high oxygen content, low pH, high viscosity and exhibit poor
storage and thermal stability.17 Consequently, the biomass pyrolysis oil requires upgrading to
meet the stringent jet fuel specifications. Upgrading of biomass pyrolysis oil can be performed
by catalytic hydrodeoxygenation (HDO) to remove oxygen to very low levels, suitable for jet
fuel. In general, hydroprocessing biomass pyrolysis oil requires a two stage process at a high
hydrogen partial pressure (100-200 bar, at a high hydrogen/pyrolysis oil ratio of greater than 100
L(NTP)/L/hr)18: i) a mild stabilisation step operating at about 200-275 °C, ii) a more severe
hydrotreating step operating at 350-400 °C. The initial stabilisation step is undertaken to remove
reactive oxygenates such as aldehydes and sugars and is also essential to avoid polymerisation of
the pyrolysis oil at higher hydrotreating temperatures which could then lead to coking of the
catalyst. The instability of the biomass pyrolysis oil is believed to be due to the presence of these
reactive oxygenates causing the viscosity of the oil to increase with storage as well as the
6|Page
separation of a water phase to take place. The stabilised pyrolysis oil, which was produced from
such a stabilisation stage, shows a lower oxygen and water content and a higher heating value
(due to the removal of reactive oxygenates) compared to the original pyrolysis oil (as seen in
Table 2).

Gas chromatographic (GC) analysis of the biomass pyrolysis oil showed that only 40% of the
volatile species eluted on the GC column, with the heavier species remaining in the GC inlet.
Species such as acids, aldehydes, ketones, furans, phenols and methoxyphenols were observed in
the GC-MS analysis. A GC method is therefore not an ideal method for characterising the
pyrolysis oils. Carbon-13 NMR analysis of the biomass pyrolysis oil proved to be a better
technique of characterising the biomass pyrolysis oil as the entire oil is analysed as opposed to
only a volatile fraction of it. The breakdown of compound classes in the original biomass
pyrolysis oil, stabilised pyrolysis oil and upgraded wide boiling-range fuel is shown in Figure 3
below, as obtained from carbon-13 NMR analysis.

2.9 0
100.0 7.4
6.7 15.8
6.3
0.3
Ketone and Aldehydes
% of carbon based on 13C NMR analysis

80.0 17.8 27.7

Esters, carboxylic acids
38.2
60.0 11.0 Aromatics and olefins

39.9
Alcohols, ethers, phenolic-methoxys,
24.3 carbohydrate sugars
40.0
Long and branched aliphatics

7.0
45.7 Short aliphatics
20.0
27.4
21.5

0.0
Original oil Stabilised oil Upgraded Fuel

Figure 3. Percentage of carbon based on 13C-NMR analysis of the original biomass

pyrolysis oil, stabilised pyrolysis oil and the upgraded fuel, grouped according to chemical
shift ranges.

Figure 3 shows the difference between the original biomass pyrolysis oil and stabilised pyrolysis
oil, where there is a decrease in the percentage fractions of ketones/aldehydes and alcohols,
ethers, methoxyphenols, sugars and an increase in the aliphatics and aromatics in the stabilised
oil. This corresponds to a decrease in the oxygen content and an increase in the heating value of
the stabilised pyrolysis oil as shown in Table 2. The amount of carboxylic acids/esters remains
the same in both the stabilised and original pyrolysis oil, as the low temperature stabilisation
reaction conditions is not adequate for removing the relatively unreactive acids. In the upgraded
fuel compared to the pyrolysis oils, there is a further increase in the aliphatics and a decrease in
the aromatics fractions. The decrease in aromatics in the upgraded fuel is due to the reaction
severity causing aromatics to be saturated to cycloparaffins.

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 3.2. WIDE BOILING-RANGE FUELS FROM BIOMASS PYROLYSIS OIL

Three wide boiling-range fuels that were upgraded under different severity conditions (namely
reaction temperatures of 350, 375 and 400 °C) during the second stage hydrotreating process
with a sulphided CoMo/Al2O3 catalyst were analysed to provide insight into the resultant
changes in hydrocarbon composition as well as identifying the refractory oxygenates. The
hydrocarbon compositions of the three wide boiling-range fuels, as measured by two
dimensional GC, are shown in Table 3 below.

Table 3. Hydrocarbon composition of the wide boiling-range fuels produced by different

reaction severities over a CoMo/Al2O3 catalyst as measured by two dimensional GC.
Hydrocarbon Upgraded wide Upgraded wide Upgraded wide
Composition boiling-range fuel / boiling-range fuel / boiling-range fuel /
mass% (350 °C) mass% (375 °C) mass% (400 °C)
Total aliphatics 71.96 76.90 76.91
Total aromatics 21.95 22.00 23.17
Polycyclic aromatics 6.85 7.00 6.46
Total oxygenates 6.0900 1.0960 0.0099
Aromatic oxygenates 5.6900 1.0928 0.0088
Other oxygenates 0.4000 0.0032 0.0011
Total 100.00 100.00 100.00

From Table 3, it is shown that there is an increase in the total aliphatics and a decrease in the
total oxygenates in the wide boiling-range fuels, corresponding to reaction severity. There is also
a slight increase in the concentration of aromatics with increasing reaction severity. It seems,
from these results, that more severe temperatures (400 °C) are required to remove most of the
oxygenate species in the wide boiling-range fuels. The levels and types of oxygenates present in
the different upgraded wide boiling-range fuels are shown in Figure 4 below.

0.010 6
Data for 375 and 400 C Data for 350 C
Mass% of oxygenates in 375 and 400 °C fuel

5
0.008
Mass% of oxygenate in 350 °C fuel

4
0.006

3 375 °C
400 °C
0.004
350 °C
2

0.002
1

0.000 0
Acid Alcohol Ester Ether Furan Ketone Phenol
Oxygenate Class

Figure 4. Oxygenate composition of the different wide boiling-range fuels produced by

different reaction severity, as measured by two dimensional GC analysis.
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From Figure 4, it is evident that, at a reaction severity temperature of 350 °C for the second stage
hydroprocessing step, there are still significant quantities of oxygenates present, with phenol as
the predominant refractory oxygenate. Phenols and their derivatives are known to have low
hydrodeoxygenation reactivity due to the greater bond strength of oxygen attached to an
aromatic carbon compared to oxygen attached to an aliphatic carbon.19 Hydrodeoxygenation of
phenols and aromatic ethers is therefore more difficult than alcohols and aliphatic ethers. At a
reaction temperature of 400 °C, the quantity of oxygenates has been significantly reduced with
negligible quantities of phenol and acids still present.

A larger quantity of two different wide boiling-range fuels, produced by a two-stage

hydroprocessing step of wood-derived biomass pyrolysis oil, was also obtained from BTG.
These wide boiling-range fuels were used for fractionation to produce bio-jet fuel for further
analysis. The hydrocarbon composition of the two wide boiling-range fuels before fractionation,
as determined by means of two dimensional GC analyses, is shown in Table 4 and Figure 5
below.

Table 4. Hydrocarbon composition of the wide boiling-range fuels measured by two

dimensional GC analyses.
Hydrocarbon Composition Wide boiling-range fuel 1 / Wide boiling-range fuel 2 /
mass% mass%
Total aliphatics 79.06 82.01
Total aromatics 20.93 17.97
Polycyclic aromatics 5.61 4.97
Total oxygenates 0.0127 0.0119
Aromatic oxygenates 0.0114 0.0082
Other oxygenates 0.0013 0.0037
Total 100.00 100.00

The aromatic oxygenates present in the wide boiling-range fuels are predominantly phenolic-
type species. The other oxygenated species include, amongst others, ketones, esters and furanes.
Also notable is the polycyclic aromatics content, which is greater than 3 mass% in the wide
boiling-range fuels. The wide boiling-range fuel 2 was upgraded more severely at a higher
reaction temperature, as can be noted by the reduced percentage of total oxygenates (0.0119
mass% versus 0.0127 mass%) and aromatic content (17.97 mass% versus 20.93 mass%). The
carbon number distribution of the two wide boiling-range fuels evaluated was similar, hence only
the wide boiling-range fuel 1 compositional data is given in Figure 5 below for illustration
purposes.

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 Wide boiling-range fuel 1
Hydrocarbon Composition / mass% 10.0
9.0
8.0
7.0
6.0
n-paraffins
5.0
iso-paraffins
4.0
cyclo-paraffins
3.0
aromatics
2.0
1.0
0.0
C5
C6
C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
C22
C23
C24
C25
Hydrocarbon Number Distribution

Figure 5. Hydrocarbon composition of the wide boiling-range fuel 1 by two dimensional

GC analysis.

The wide boiling-range fuels consist predominantly of cycloparaffins, up to carbon number 22,
and aromatics to a lesser extent, up to carbon number 17. The iso- and n-paraffins are present to
a much lesser extent. The simulated distillation of the two wide boiling-range fuels is shown in
Figure 6 below. It would appear that 44 – 46% of the wide boiling-range fuels are in the
kerosene boiling range (150 – 300 °C). Based on the boiling range from simulated distillation
data, it seems there is no discernible difference between the two wide boiling-range fuels.

600

500

400
Boiling point / C

Wide boiling-range fuel 1

300
Wide boiling-range fuel 2
Kero range 150 C
200
Kero range 300 C

100

0
0% 20% 40% 60% 80% 100%
Simdist recovered mass%

Figure 6. A simulated distillation of the two wide boiling-range fuels produced from
hydrodeoxygenation of wood-derived biomass pyrolysis oil.

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 3.3. BIO-JET FUEL FROM BIOMASS PYROLYSIS OIL

Two bio-jet fuels were fractionated in the boiling range of 150 – 280 °C, from the two different
wide boiling-range fuels derived from wood-derived biomass pyrolysis oil, discussed above.
Figure 7 below shows the hydrocarbon composition of bio-jet fuel derived from wide boiling-
range fuel 1, as measured by two dimensional GC analysis.

Bio-jet fuel 1 (150 - 280 C)

14.0
Hydrocarbon Composition / mass%

12.0

10.0

8.0 n-paraffins

6.0 iso-paraffins
cyclo-paraffins
4.0 aromatics

2.0

0.0
C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19
Hydrocarbon Number Distribution

Figure 7. Hydrocarbon composition of a bio-jet fuel (150 – 280 °C boiling range)

fractionated from wide boiling-range fuel 1, measured by two dimensional GC analysis.

The bio-jet fuel fractionated from the wide boiling-range fuel also consists predominantly of
cycloparaffins and aromatics to a lesser extent. The selected fuel properties of the two bio-jet
fuels derived from wood-derived pyrolysis oil are shown in Table 5 below.

Table 5. Selected fuel properties of two bio-jet fuels derived from biomass pyrolysis oil
upgrading.
Fuel property Method Jet A-1 Bio-jet fuel 1 Bio-jet fuel 2
specification
Aromatics, mass% 2D-GC 25 max 17.23 18.78
Polynuclear 2D-GC 3 max 0.02 0.05
aromatics, mass%
Cycloparaffins, 2D-GC - 73.59 72.75
mass%
Density at 20 °C, ASTM D7042 0.771 – 0.836 0.837 0.844
3
kg/m
Viscosity at -20 °C, ASTM D7042 8 max 5.70 7.18
2
mm /s
Freezing point, °C ASTM D5972 -47 max <-65.0 <-65.0
Flash point, °C Grabner 38 min 54.9 56.9
Miniflash
Phenol levels, ppm 2D-GC - 952 123
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Aromatics and cycloparaffins are important high density fuel molecules, which are required to
meet certain fuel specification requirements as well as provide seal swelling capability. The bio-
jet fuel has a very high density due to its high cycloparaffinic and aromatic content (above the
maximum jet fuel density specification of 0.836 kg/m3). HEFA and FT-SPK are normally
paraffinic in nature and do not meet the minimum jet fuel density requirement. Blending bio-jet
fuel into these predominantly paraffinic fuels can hence be expected to bring the resultant jet fuel
blend within the required jet fuel density specification. This is one of the synergistic properties
that are immediately observed. The freezing point of the bio-jet fuels is also good and this is
most probably due to the cycloparaffins present in the bio-jet fuel. The flash point of the bio-jet
fuel samples is also above the minimum flash point specification due to fractionating above 150
°C.

Selected properties of a blend of bio-jet fuel and FT-SPK in a 40:60 volume% blend ratio, to
meet the minimum jet fuel density specification of 0.771 kg/m3, are shown in Table 6 below.

Table 6. Selected fuel properties of two bio-jet fuels blended with FT-SPK to meet the
minimum density specification.
Fuel property Method Jet A-1 Bio-jet fuel 1 Bio-jet fuel 2
specification /FT-SPK blend /FT-SPK blend
(40:60 vol%) (40:60 vol%)
Aromatics, mass% 2D-GC 25 max 10.34 11.27
Polynuclear 2D-GC 3 max 0.005 0.002
aromatics, mass%
Cycloparaffins, 2D-GC - 44.15 43.65
mass%
Density at 20 °C, ASTM D7042 0.771 – 0.836 0.7739 0.7746
3
kg/m
Viscosity at -20 °C, ASTM D7042 8 max 3.28 3.35
2
mm /s
Freezing point, °C ASTM D5972 -47 max -62.6 -62.4
Flash point, °C Grabner 38 min 43.0 42.0
Miniflash
Phenol levels, ppm 2D-GC - NM 31

Blending bio-jet fuel into FT-SPK produces a jet fuel that meets the minimum jet fuel density
specification. The minimum aromatic specification of 8 vol% for jet fuel containing synthetic jet
fuel components is also met with these blends. All other selected properties such as freezing
point, viscosity and flash point are also within the Jet A-1 specification. FT-SPK is a paraffinic
fuel containing negligible quantities of hetero-atomic species and is therefore considered to have
superior stability characteristics.20 Blending FT-SPK into bio-jet fuel provides a means of
diluting the problematic hetero-atomic species (phenol, in this case) and possibly improving the
thermal oxidative stability characteristics of the resulting blend.

The chemical structures of the phenolic and aromatic ether species, seen at ppm levels in the neat
bio-jet fuels, are shown in Figure 8 below. Phenols are the predominant species present in bio-jet
fuel as they are the refractory oxygenates that are the least resistant to hydrodeoxygenation. The

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aromatic ether species were only present in minor quantities. Phenols in jet fuel, have been
shown to promote the formation of thermal oxidative deposits via condensation and oxidative
coupling reactions during thermal stressing of the fuel.

OH OH OH OH OH OH

OH OH OH OH OH OH

OH OH OH OH OH

O O

Figure 8. Phenolic and aromatic ether type species present in bio-jet fuel derived from
biomass pyrolysis oil, as measured by two dimensional GC analysis.

The bio-jet fuels and its blends with GTL kerosene were evaluated for their thermal oxidative
stability using the quartz crystal microbalance (QCM) apparatus. These results were compared to
a South African crude-derived Jet A-1 fuel. The results are shown in Figure 9 (comparison of
neat fuels) and Figure 10 (GTL kerosene and bio-jet fuel and its blend).

From the results in Figure 9, the South African crude-derived Jet A-1 fuel is a high depositor and
a slow oxidising fuel. This is due to the trace natural hetero-atomic species present acting as
antioxidants thereby slowing the autoxidation cycle. These trace hetero-atomic species are also
responsible for the deposit formation of this fuel. GTL kerosene is a low depositor and a fast
oxidising fuel due to the absence of these natural antioxidants. The two bio-jet fuel samples have
moderate depositing characteristics and a slower oxidising behaviour, most probably due to the
presence of phenolic species. Phenols slow the autoxidation cycle by acting as antioxidants
thereby reducing the formation of radicals. Interestingly, the bio-jet fuels have a lower depositing
behaviour when compared to crude-derived Jet A-1. The deposition in the bio-jet fuels levels off
once all the oxygen has been consumed (between 5 and 7 hours).

From Figure 10, it is shown that the blended fuel containing 60 vol% GTL kerosene and 40 vol%
bio-jet fuel 2 have an improved stability behaviour based on mass accumulation. This is most
probably due to the dilution of problematic trace hetero-atomic species. This improvement in
thermal oxidative stability of crude-derived jet fuel by diluting with a paraffinic solvent has been
observed previously by Zabarnick.21
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 GTL Kerosene/Bio Jet 1/Bio Jet 2/SA Jet A1
Red/Blue/Black/Green

12 40

35
10

Mass Accumulation (g/cm )

2
30

8
25

O Percent
2
6 20

15
4

10

2
5

0 0
0 2 4 6 8 10 12 14 16

Time (hours)

Figure 9. QCM plots of mass accumulation and oxygen consumption versus time for South
African Jet A-1, bio-jet fuel 1, bio-jet fuel 2 and GTL kerosene.

GTL/Bio fuel 2/Blend

Red/Black/Purple

8 40

7 35
Mass Accumulation (g/cm )
2

6 30

5 25
O Percent
2

4 20

3 15

2 10

1 5

0 0
0 2 4 6 8 10 12 14 16

Time (hours)

Figure 10. QCM plots of mass accumulation and oxygen consumption versus time for bio-
jet fuel 2 and its blend with GTL kerosene and neat GTL kerosene.

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 3.4. THERMAL OXIDATIVE STABILITY RESULTS OF MODEL COMPOUNDS

Based on the two dimensional GC analysis of the bio-jet fuels above, phenols and aromatic
ethers are the refractory oxygenates most likely to remain in the kerosene fraction after catalytic
hydrodeoxygenation. It is for this reason that we looked into the effect of these oxygenates on
the stability of a jet fuel surrogate fuel.

Oxygenated model compounds, typically found in biomass pyrolysis oil and in bio-jet fuel
derived from biomass pyrolysis oil, were blended into a jet fuel surrogate fuel (dodecane and
butylbenzene, at 90:10 volume ratio respectively) at a 3 vol% level. This level was chosen as an
absolute maximum to exacerbate the effect of the chosen oxygenate on the thermal oxidative
stability of the jet fuel surrogate fuel. It is acknowledged that this high oxygenate level may not
be allowed in commercial jet fuel without affecting other jet fuel properties such as freezing
point, energy density, stability and water separation characteristics.

a) PetroOXY™ test

Firstly, pure oxygenated model compounds were introduced into the PetroOXY™ at 160 °C for
9 hours to provide insight into the oxidation reactivity of the neat molecules. Figure 11 below
shows the percentage oxygen pressure drop with time for each of the neat oxygenated
compounds. The oxygen pressure drop indicates the oxidation of the neat molecule with time.

100

90

80
% of MaximumOxygen Pressure

70

60
Anisole
50
2-Methoxyphenol
40 2-Ethylphenol

30 Benzyl methyl ether

20

10

0
0 1 2 3 4 5 6 7 8 9 10
Time / hr

Figure 11. Oxygen pressure drop in the PetroOXY™ of neat oxygenated model
compounds.

The results from Figure 11 show that benzyl methyl ether is very reactive towards oxidation
(exhibiting a 78.3% pressure drop) followed by 2-ethylphenol (68.0% pressure drop), 2-
methoxyphenol (34.9% pressure drop) and lastly anisole (only 7.0% pressure drop). Anisole was
thus found to be the least reactive to oxidation. GC-MS analysis of the stressed neat model
compounds showed that benzyl methyl ether, 2-ethylphenol and 2-methoxyphenol formed
oxidation products whereas anisole was unreactive with no oxidation products detected. Figure
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12 below shows oxidation products for each of the neat oxygenated model compounds after
stressing in the PetroOXY™ for 9 hours at 160 °C.

O O O O

O O2 OH
H OH O H O
160 C

OH O O OH
O2
H
160 C
OH OH O

OH
O2
O
OXIDATIVE COUPLING PRODUCTS
160 C

O O2
UNREACTIVE
160 C

Figure 12. Oxidation products identified by GC-MS analysis of stressed oxygenated model
compounds.

Benzyl methyl ether is the most reactive towards oxidation and this is believed to be due to the
presence of weak benzylic hydrogens that are prone to oxidation. Stressed 2-methoxyphenol
showed no oxidation products by GC-MS, but the sample turned into a viscous black coloured
liquid, which indicates that oxidation did take place. The oxidation products may be heavier
polymerised products that cannot be identified by GC-MS. Interestingly, anisole was unreactive
towards oxidation and showed no oxidation products on GC-MS. Aryl ethers are known for their
stability due to the strong bond strength of the ether linkage. It should be noted that these are
severe oxidation conditions in the PetroOXY™, that a jet fuel may not realistically see in a jet
engine, but it does provide insight into the oxidation stability of a fuel or model compound.

Secondly, anisole at different concentration levels in dodecane (1, 3 and 5 vol%), was stressed in
the PetroOXY™ at 160 C until a 50% oxygen pressure drop is achieved. The results for the
different model systems are shown in Figure 13 below.

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 100

90

% of MaximumOxygen Pressure
80

70
Dodecane
Dod/Anisole 1%
60
Dod/Anisole 3%
Dod/Anisole 5%
50

40

30
0 10 20 30 40 50 60 70 80 90 100
Time / min

Figure 13. Oxygen pressure drop in the PetroOXY™ of dodecane in the presence of anisole
at different concentration levels.

With increasing levels of anisole in dodecane, the oxidative stability of the model fuel was
increased. This is an unusual result, as anisole has no labile hydrogen to donate to free radicals to
inhibit oxidation of dodecane. The presence of phenol was however noted on analysing the
stressed samples, with GC-MS, after the PetroOXY™ experiment. Phenol is produced in-situ
and may therefore inhibit the oxidation of dodecane, thereby realising slower induction times.

b) Flask oxidation test

Stressing of a jet fuel surrogate fuel (dodecane and butylbenzene) containing a 3 vol% oxygenate
level was undertaken in a flask oxidation test to determine the effect of the oxygenate on the
surrogate fuel’s stability under a constant oxygen-rich environment. Only two of the model
systems will be shown here, representing the stability results of a jet fuel surrogate fuel in the
presence of an aromatic ether versus a phenolic type compound. The oxidation results for anisole
(aromatic ether) and 2-methoxyphenol (phenol) in a jet fuel surrogate fuel are shown in Figure
14 and 15 below respectively.

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Figure 14. The oxidation of a jet fuel surrogate fuel in the presence of 3 vol% anisole at
160 °C.

In the presence of anisole, the jet fuel surrogate fuel oxidises into dodecane oxidation products
(ketones, alcohols, acids, furanones and aldehydes) and n-butylbenzene oxidation products
(benzaldehyde and benzoic acid). This would be expected as anisole has no labile hydrogens to
interfere with the autoxidation cycle. Phenol was detected in the GC-MS results as an oxidation
product of anisole at a level of 0.09%. This conclusion was made based on the fact that in the
oxidation of only the jet fuel surrogate fuel, without any oxygenated model compounds present,
no phenol was detected.

Figure 15. The oxidation of a jet fuel surrogate fuel in the presence of 3 vol% 2-
methoxyphenol at 160 °C.

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In the presence of 2-methoxyphenol, the jet fuel surrogate fuel is inhibited from oxidising into its
oxidation products as is evidenced in Figure 15 above. As with other phenolic type species, 2-
methoxyphenol with its labile hydrogen, acts as an antioxidant and inhibits oxidation of the jet
fuel surrogate fuel from taking place. There were no oxidation products of 2-methoxyphenol
detected in the GC-MS results. However, it is known that phenolic type species react by
oxidative coupling reactions to produce heavier molecules that cannot be detected by GC-MS.

c) JFTOT™ analysis

An investigation was undertaken to determine the effect of typical model oxygenate compounds
present in biomass pyrolysis oil on jet fuel stability to identify problematic species that may
remain in partially hydrotreated pyrolysis oil. Pure oxygenates were doped in FT-SPK at 1 vol%
and their effect on jet fuel stability tested using the standard JFTOT™ method (ASTM D3241) at
a temperature of 325 °C (test temperature at which a pass is required of synthetic jet fuels). The
results are shown in Table 7 below.

Table 7. The effect of pure oxygenated model compounds (1 vol%) typically found in
biomass pyrolysis oil on FT-SPK stability.
# Model Oxygenate (1 vol%) in FT-SPK Chemical Structure JFTOT result
1 None None Pass

2 Anisole Pass

3 Benzyl methyl ether Pass

4 2-Methoxyphenol Fail

5 2-Ethylphenol Fail

Model oxygenates such as aromatic ethers (entry 2 and 3 in Table 7) displayed good stability
under the conditions of the JFTOT™ tests. Phenolic species such as 2-methoxyphenol and 2-
ethylphenol (entry 4 and 5 in Table 7) failed the JFTOT™ test, highlighting the negative effect
of these compounds on jet fuel stability.

4. CONCLUSIONS

A jet fuel derived from biomass pyrolysis oil is not approved for commercial aviation use under
the current jet fuel specifications and would require extensive properties analysis and engine
testing before it could be approved. This initial study provides some insight into the properties of
bio-jet fuel derived from biomass pyrolysis oil. Bio-jet fuel derived from biomass is highly
cyclo-paraffinic in nature, producing a fuel with excellent cold flow properties and a high fuel
density. It has been demonstrated in this study that it is possible to produce an acceptable bio-jet
fuel from biomass pyrolysis oil with the required amount of hydrotreatment. Jet fuels derived
from biomass pyrolysis oil, while broadening the range of bio-feedstocks for jet fuel, provide a
route to renewable aromatic hydrocarbons which are complementary to the highly paraffinic,
lower density FT-SPK and HEFA fuels. A blend of bio-jet fuel and FT-SPK met the critical
19 | P a g e
properties of Jet A-1 such as density, freezing point and viscosity. Further work on the properties
of bio-jet fuel and its blend with FT-SPK is on-going in our laboratories.

Pyrolysis oil, produced from biomass, has been shown to be rich in oxygenates, in particular
phenolic compounds. Bio-jet fuel derived from biomass pyrolysis oil has been shown to still
contain trace levels of refractory phenolic and aromatic ether species, after significant catalytic
hydrodeoxygenation. While phenols have been implicated in the formation of thermal oxidative
deposits in both jet fuel and diesel, aromatic ethers have not. Little is understood of the thermal
stability of aromatic ethers under the conditions to which jet fuels would be exposed. The
thermal oxidative stability of the bio-jet fuels derived from biomass pyrolysis oil, measured by
the QCM device, are better than a South African crude-derived Jet A-1. The thermal oxidative
stability characteristics of the bio-jet fuel are improved upon blending the bio-jet fuel with highly
paraffinic FT-SPK. This is due to the dilution of the problematic hetero-atomic species such as
phenols present in the bio-jet fuel.

Thermal oxidative stability of model oxygenated compounds, typically present in biomass

pyrolysis oil and bio-jet fuel, show that aryl ethers have good stability whereas benzyl ethers and
phenolic type species have poor stability and will have negative effects on the overall bio-jet fuel
stability. This suggests that the conversion of phenols to aromatic ethers could possibly be a
feasible route to improve the thermal stability of bio-jet fuel derived from biomass pyrolysis oil.
Further studies in this particular area are currently being conducted in our laboratory.

5. ACKNOWLEDGEMENTS

The authors would like to acknowledge BTG for their biomass pyrolysis oil and wide boiling-
range fuel samples, Dr. Rina van der Westhuizen for the two dimensional GC analysis on the
fuels and Dr. Sibusiso Mtongana for the NMR analysis on the biomass pyrolysis oils and fuels.

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