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Production of Hydroprocessed Esters and Fatty Acids (HEFA)—Optimisation

of Process Yield

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DOI: 10.2516/ogst/2014007

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Oil & Gas Science and Technology – Rev. IFP Energies nouvelles
Copyright Ó 2014, IFP Energies nouvelles
DOI: 10.2516/ogst/2014007
Dossier
Second and Third Generation Biofuels: Towards Sustainability and Competitiveness
Seconde et troisième génération de biocarburants : développement durable et compétitivité

Production of Hydroprocessed Esters and Fatty Acids

(HEFA) – Optimisation of Process Yield
Laurie Starck1*, Ludivine Pidol1, Nicolas Jeuland1, Thierry Chapus2,
Paul Bogers3 and Joanna Bauldreay3
1
IFP Energies nouvelles, 1-4 avenue de Bois-Préau, 92852 Rueil-Malmaison - France
2
IFP Energies Nouvelles, Rond-point de l'échangeur de Solaize, BP 3, 69360 Solaize - France
3
Shell Global Solutions Downstream, Shell Technology Centre Thornton, P.O. Box 1, Chester CH1 3SH - United Kingdom
e-mail: [email protected] - [email protected] - [email protected] - [email protected]
[email protected] - [email protected]

* Corresponding author

Abstract — Both Fischer-Tropsch (FT) and Hydroprocessed Esters and Fatty Acids (HEFA)
Synthetic Paraffinic Kerosine (SPK) fuels are considered as leading alternative replacements for
conventional jet fuel. To satisfy the requirements of Civil Aviation Authorities (CAA), their
drop-in incorporations have been subjected to a rigorous certification process. To reach the
ambitious incorporation targets, new routes for biofuels incorporation may need to emerge, involving
optimizing the production processes and the blending strategies. This paper focuses on a new strategy
for incorporating HEFA, allowing the process yield to be optimised.
One of the major steps limiting the process yield for HEFA remains the isomerisation that allows
production of a biofuel with very good cold flow properties. But this step introduces a substantial
decrease of the overall yield (fuel component per kg of starting material) due to the production of
light compounds, unsuitable for conventional jet fuel. In this work relaxing the freezing point require-
ment for the neat HEFA component (by decreasing the severity of the isomerisation step) is pro-
posed in order to minimize the production of less valuable light compounds. This strategy could
lead to a significant additional biofuel yield with respect to the oil compared to a process making
a better freezing point component. This allows the land surface area necessary for HEFA feedstock
cultivation to be reduced for a given amount of bio-jet fuel produced.

Résumé — Production d’huiles végétales hydrotraitées (Hydroprocessed Esters and Fatty Acids,
HEFA) – Optimisation du rendement — Le développement des carburants alternatifs est en
plein essor, notamment dans le domaine aéronautique. Cela se concrétise par la possibilité,
d’incorporer jusqu’à 50 % de carburants de synthèse de type Fischer-Tropsch (FT) ou
Hydroprocessed Esters and Fatty Acids (HEFA) dans du carburéacteur. Ces cibles
d’incorporation sont ambitieuses. C’est pourquoi, l’objectif de cet article est d’étudier une
stratégie innovante pour l’incorporation des carburants alternatifs, et plus précisément des
carburants de type HEFA, dans le domaine aéronautique en optimisant les stratégies de
mélanges c’est-à-dire en cherchant à optimiser les rendements des procédés.
En effet, l’un des moyens d’action permettant d’améliorer les rendements des procédés HEFA est
d’agir sur l’étape d’hydrotraitement. Cette étape permet d’améliorer les propriétés à froid.
Cependant la contre partie est l’impact que cela peut avoir sur le rendement : améliorer les
propriétés à froid est synonyme de perte en rendement (carburant produit par kg par rapport à
2 Oil & Gas Science and Technology – Rev. IFP Energies nouvelles

la masse de matière première) à cause de la production de produits légers qui ne sont pas
utilisables dans la coupe jet. Ce travail propose donc de relâcher la contrainte sur le point de
disparition des cristaux, exigée pour les carburants de type HEFA, en jouant sur la sévérité de
l’étape d’hydrotraitement et donc en minimisant la production de produits légers afin de
maximiser les rendements. Cette stratégie pourrait amener à avoir un meilleur rendement en
biojet par rapport à l’huile de départ comparée à une stratégie dans laquelle on recherche un
meilleur point de disparition des cristaux. Ainsi, il serait envisageable de réduire les surfaces
agricoles utilisées pour la culture des plantes pour un même volume de biojet produit.

DEFINITIONS / ABBREVIATIONS reducing CO2 emissions by 50% by 2050, compared to

the 2005 level, as illustrated in Figure 1. Consequently,
ASTM American Society for Testing and Materi- the search for new alternative fuels for aircraft seems
als International to be a promising and necessary solution from an energy
CAA Civil Aviation Authorities security and environmental perspective. If aviation
DCO Decarboxylation wants to reduce its greenhouse gas emissions, it has to
EU-ETS European Union Greenhouse Gas Emis- turn to biofuels, which are the only fuels having the
sion Trading Scheme potential to achieve significant greenhouse emissions
FT Fischer-Tropsch savings. Some of the steps towards a reduced CO2 goal
HDO Hydrodeoxygenation can be achieved with the efficiency increases anticipated
HEFA Hydroprocessed Esters and Fatty Acids through aircraft improvement, operational measures or
HIS Hydroisomerization infrastructure changes. But these measures are not
HRJ Hydroprocessed Renewable Jet enough and additional reductions are required. It is
why biofuel appears to be the main candidate to achieve
HVO Hydrotreated Vegetable Oil
these reductions. Significant emissions reduction can be
nP Normal (Linear) Paraffins
achieved with biofuel, provided that low emissions are
iP Iso Paraffins
achieved in the cultivation step of the biomass and if
SPK Synthetic Paraffinic Kerosene there is a rigorous control of land use change. Without
SWAFEA Sustainable Way for Alternative Fuel and these controls, some biofuels can have very poor CO2
Energy in Aviation footprints.
The effort to develop alternative aviation fuels has
already begun, focused on Fischer-Tropsch (FT) fuels.

INTRODUCTION

World wide air traffic has been steadily increasing for

“Frozen technology” emissions
many years and is predicted to grow at a rate of close
Known technology, operations and
to 4-5% per year, with even higher growth rates in the infrastructure measures
Middle East and Asia [1, 2]. Biofuels and additional technology No action
Moreover, the increased focus on climate change over Carbon-neutral growth 2020 Tech
the last decade has created pressure to reduce greenhouse Gross emissions trajectory Ops
CO2 emissions

Economic measures Infra

gases emissions. It has been estimated that the aeronau-
tics sector represents 2 to 3% of the global CO2 emis- Biofuels +
CNG 2020
sions [3]. Such a contribution may seem to be minor add. Tech

but the air traffic is expected to strongly increase in the

-50% by
next years while other industries move to lower carbon 2050
(schematic)
options. This is one reason it has been decided to include
the aeronautics sector in the EU-ETS (European Union 2005 2010 2020 2030 2040 2050
Greenhouse Gas Emission Trading Scheme) from 2012. Figure 1
International Air Transport Association (IATA) has CO2 emissions reduction targeted by IATA (Source
adopted a voluntary ambitious fuel efficiency goal: IATA).
 L. Starck et al. / Production of Hydroprocessed Esters and Fatty Acids (HEFA) – Optimisation of Process Yield 3

Generic FT Synthetic Paraffinic Kerosene (SPK) was This paper does not deal with the economics them-
approved for use in blends, at up to 50% volume, with selves but provides technical data that could assist in
Jet A-1 in ASTM D7566 in August 2009 [4, 5]. The sec- understanding the relationship between process costs
ond class of alternative fuels approved for certification is (usually related to process complexity), process yield,
Hydroprocessed Esters and Fatty Acids (HEFA), also HEFA quality, and blending rate. IFPEN and Shell Glo-
called Hydrogenated Vegetable Oil (HVO) or Hydropro- bal Solutions have joined their expertise to produce two
cessed Renewable Jet (HRJ); it covers hydrocarbon avia- different qualities of HEFA from the same original oil
tion fuel produced from animal oils or vegetable oils for the purposes of the SWAFEA project. The level of
(triglycerides) by hydroprocessing. This fuel has also hydroisomerisation applied to a hydroprocessed oil to
been called BioSPK, although one should remember that improve the low temperature properties was varied
the FT SPK include biomass to liquid fuels that can between the two HEFA:
equally be called BioSPK. The ASTM D7566 specifica- – if, as expected, important constraints are put on oil
tion is structured to support various classes of alterna- availability and HEFA production capacity, in the
tive fuels in its appendices and HEFA was approved short term the incorporation process will have to be
for use at up to 50% volume in blends with conventional optimised to incorporate this product into conven-
kerosene in ASTM D7566 in July 2011 [6]. It can now be tional Jet A-1. In this case, the global optimisation
used in ASTM D1655 fuels and, following an update to of the production yield will be of major importance.
DEF STAN 91-91, HEFA has also been approved under A major factor limiting the process yield remains the
“Check List”. The results of a study by the EU-funded isomerisation step, which allows production of a bio-
Sustainable Way for Alternative Fuels and Energy in fuel with very good cold flow properties. It also leads
Aviation (SWAFEA) [7] have shown that the incorpora- to a substantial decrease in the overall yield because of
tion of biofuels in aviation fuel is necessary to reach the the co-production of light compounds that cannot be
ambitious IATA targets in terms of CO2 reduction. incorporated in conventional jet fuel. To evaluate the
These conclusions also show that a massive incorpora- impact of this production step, an extreme view has
tion ratio will be needed, so that huge investments need been chosen: a specific HEFA has been produced to
to be made. Moreover, the question of biofuels deploy- have limited cold flow properties (target: freezing
ment has been raised, linked with a need for an optimised point around
20°C) and the resulting product has
production yield to meet those targets. been blended into conventional jet fuel at different
There is competition for biofuel components which blending ratios. The overall yield has been calculated,
affects the design and economics of facilities that convert to evaluate if a substantial gain can be obtained with
bio-oils into fuel. Specifically, there is competition between such a strategy, while keeping the final blend in the
gasoil (e.g. automotive Diesel, heating and industrial Diesel) limits of the Jet A-1 specification (freezing point
and kerosene users. Most bio-oils naturally yield product in 
47°C);
the gasoil range so further processing steps are needed to – the current specification limits the incorporation rate
make a product that is technically better suited to kerosene of HEFA to a maximum of 50% volume. To meet
(jet fuel) production, in particular having better low temper- the IATA targets, higher blending rates may eventually
ature features than required for Diesel applications. The be needed. Indeed, during the ramp-up period, this
objective of this work is to study product quality trade-offs product may not be available everywhere. The capacity
that could affect the economics of biojet production in the to blend higher ratios in some locations can therefore
initial periods when biofuel availability will be limited. Spe- help to meet the incorporation targets, taking into
cifically, it considers incorporating low levels (considerably account the local availability of the product. A specific
less than the 50% volume now approved) of SPK with freez- HEFA meeting the ASTM D7566 specifications has
ing points higher than those currently approved (
40°C been made to evaluate the potential of such a product
maximum) into Jet A-1, while keeping the blend freezing being blended at a high ratio (75%) in Jet A-1.
point specification unchanged. Increasing (worsening) the To summarize the different strategies:
freezing point decreases the level of processing of the – Case 1: aim for a reduced HEFA incorporation ratio
SPK, which should produce higher biofuel component for HEFA with poor cold flow properties (target:
yields [8] and a potentially better overall profitability than freezing point around
20°C). Blends of this HEFA
a route that produces a higher proportion of better freezing production (called HEFA1) with a conventional Jet
point products that can be incorporated at higher percent- A-1 have been prepared with 10%, 20% and 30% vol-
ages into the final Jet A-1. The recommendation for low ume of HEFA1;
or medium HVO (HEFA) concentrations is also studied – Case 2: aim for a larger HEFA incorporation ratio
for Diesel engines [9]. than permitted by ASTM D7566: one blend of HEFA
4 Oil & Gas Science and Technology – Rev. IFP Energies nouvelles

production (called HEFA2) with the same conven- TABLE 1

tional Jet A-1, has been prepared with an incorpora- Composition of a typical rapeseed oil
tion ratio of 75% volume of HEFA2. Origin Method Unit Rapeseed
oil

Density 15/4 NF EN ISO 12185 kg/m3 920.0

1 GENERAL INFORMATION ON THE HYDROTREATMENT
PROCESS OF VEGETABLE OILS Sulphur ASTM D5453 wt ppm 4.2

Nitrogen ASTM D4629 wt ppm 23.3

1.1 Vegetable Oil Composition
Carbon ASTM D5291 wt% 77.7
Renewable sources such as vegetable oils are mainly Hydrogen ASTM D5291 wt% 11.75
composed of triglycerides, which are tri-esters compris-
ing 3 fatty acid hydrocarbon chains and a glycerol back- Oxygen ASTM D5622 wt% 11.17
bone, as shown in Figure 2. The degree of unsaturation Acid value EN14104 mg KOH/g 0.03
of the fatty acid chains (i.e. the number of double
bonds), as well as the carbon distribution, varies accord- Water EN ISO 12937 wt ppm 485
ing to the nature of the oil.
Vegetable oils contain 6 oxygen atoms per mole, which
leads to oxygen contents of about 10 to 12 wt%. Accord-
ing to the nature of the starting vegetable oils, fatty acid – hydroisomerization.
hydrocarbon chains can exhibit various carbon atom dis- The hydrotreatment step consists of oxygen removal,
tributions, which are generally in the range C8 to C24. which leads to the production of a paraffinic middle dis-
The nature of the feedstock also impacts the degree of un- tillate (boiling at 150°C+). Oxygen removal can be
saturation of the hydrocarbon chain; there can be achieved via 2 pathways:
between 3 and 6 unsaturated bonds. Table 1 gives some – hydrogenation of the fatty acid chain, to produced
characteristics typically seen for rapeseed oils [10]. water and a paraffinic product, maintaining the
hydrocarbon chain length (HDO pathway for hydro-
deoxygenation, Eq. 1):
1.2 Main Process Steps
Fatty acid chain in
The present work has been achieved using a rapeseed oil
i
sent to hydrotreatment, followed by a hydroisomeriza- C18þ16 H2 ! 3 C18 þ 6 H2 O þ C3 H8
ð1Þ
tion step; rapeseed oil was chosen for reasons of feed- 100 kg of oil þ 3:6 kg of H2 ! 86:3 kg of n-paraffins
stock availability. It is important to note that it would
have been possible to use any other type of oil to demon- – hydrogenation of the fatty acid chain with production of
strate the two strategies for HEFA incorporation, carbon oxides (such as CO2 and CO), and a paraffinic
though the absolute results obtained could vary accord- product with a loss of one carbon atom in the chain
ing to the fatty acid distribution of the source oil. length (DCO pathway for decarboxylation, Eq. 2):
The hydrogenation process generally comprises two
steps [11, 12]: Fatty acid chain in
– hydrotreatment, which is a treatment involving i
C18 þ 7 H2 ! 3 C17 þ CO2 þ C3 H8
hydrogen, using an hydrotreatment catalyst in appro- ð2Þ
100 kg of oil þ 1:6 kg of H2 ! 81 kg of n-paraffins
priate operating conditions;
This is all a rather theoretical depiction; CO and CH are
also made. It is also important to note that, despite the
R-OCO-CH2 increased carbon yield in Equation (1), more H is required.
In practice the mechanisms of Equation (1) and Equation
R-OCO-CH (2) both occur but their relative contributions can vary

R-OCO-CH2

Figure 2 i
This number depends on the number of unsaturation of triglycerides.
Typical structure of triglycerides, major components of This equation has been established for triglycerides with 4 unsaturated
vegetable oils. bonds.
 L. Starck et al. / Production of Hydroprocessed Esters and Fatty Acids (HEFA) – Optimisation of Process Yield 5

TABLE 2 Diesel
Boiling and melting points of nC16, nC17 and nC18 Kero
Gasoline Melting point
120
nC16 nC17 nC18 (°C)
100

Cetane number
+28°C
Boiling point (°C) 286.9 302.2 316.7 80 +18°C

Melting point (°C) 18 22 28.6 60 -6°C

-23°C
40
-78°C
20
depending on conditions, catalyst, etc. However, the objec- -70°C
0 -106°C
tive is to favour the HDO pathway, to maximize the yield 4 6 8 10 12 14 16 18 20 22
of valuable fuel products. Carbon number
After this first hydrotreatment section, oxygen is com- N-paraffins Iso-paraffins
pletely removed, and a pure paraffinic product is
Figure 3
obtained, with typically the same carbon atom distribu-
Melting point and cetane number of some normal and iso-
tion as in the starting feedstock. For instance, starting paraffins present in the jet fuel and Diesel range [13].
from rapeseed oil, the paraffinic product after hydro-
treatment is mainly composed of linear (normal) paraf-
fins (nP) such as nC16, nC17 and nC18. This product
Here is a general description of the reactions which
exhibits a very high cetane, but very poor cold flow
take place in the HIS section:
properties. This product is located in the Diesel boiling
– after hydrotreatment, the hydrocarbon product is a
range, and the yield typically obtained is in the range
100% paraffinic Diesel product, with a boiling range
80-85 wt% relative to the feed.
280°C+. It is therefore necessary to convert nP into
Table 2 below gives the boiling and melting points of
iP, to improve cold flow properties, and convert the
some linear paraffins, which are the major hydrocarbon
Diesel boiling range product into a jet fuel boiling
components of the paraffinic product after hydrotreat-
range product (150-300°C);
ment. Note: for pure products, there is a discrete melting
– when the severity of the HIS section is increased, it
point; for fuels, the melting of wax crystals occurs over a
leads to a higher conversion of nP into iP, which leads
temperature range and the freezing point for jet fuels is
to lower boiling and melting points (improved cold
the temperature at which, on warming up a cold fuel,
flow) of the hydrocarbons. Consequently Diesel is
the last wax crystals disappear. Therefore for “melting
progressively converted into jet fuel (kerosene), and
point”, think freezing point.
then into gasoline and gases at higher HIS severities.
After hydrotreatment, the liquid hydrocarbon prod-
These lighter cuts (gasoline and gases) may be of lower
uct is a 100% paraffinic Diesel product, composed
value, for example in the EU where there is already a:
mainly of nC16 – nC18 linear paraffins. The boiling
surplus of gasoline. From biofuel producers’ perspec-
range of the product is consequently 280°C+, well
tives, the discussion would need to be: a) Diesel versus;
above the range seen for typical jet fuels.
b) Diesel+low amounts high freeze jet component
To improve the cold flow properties of this paraffinic
versus; c) not much Diesel+larger amounts of low
Diesel, it is necessary to subject the product to a hydro-
freeze jet component.
isomerization (HIS) treatment, which will convert linear
At the end of the HIS step, there is a final distillation
paraffins into iso-paraffins. This improves low tempera-
step to remove gasoline range material.
ture performance for kerosene applications but has a
detrimental effect on cetane quality in Diesel engine To summarize, the challenge of HIS operation for
applications as shown in Figure 3 [13]. HEFA production is to convert a paraffinic Diesel
The HIS step is generally achieved using an appropri- into a paraffinic jet fuel. As jet fuel is an intermedi-
ate catalyst in hydrogenation conditions. The catalyst is ate product between Diesel and gasoline, there is
a bifunctional one, comprising both a hydrogenation an optimum degree of conversion in terms of jet
function and an acid function. The objective, ideally, is fuel yield. This optimum can be attained by select-
to convert linear paraffins (nP) into iso-paraffins (iP), ing the more appropriate catalyst as well as care-
while avoiding cracking reactions which lead to yield loss fully tuning the operating conditions. This is the
by formation of gases and naphtha or gasoline cuts (that condition to reach the maximum jet fuel yield,
boil below 150°C). To be as close as possible to this ideal together with jet fuel quality meeting the specifica-
situation, an appropriate choice of the catalyst and oper- tions (distillation range and cold flow properties,
ating conditions has to be made. i.e. freezing point when referring to jet fuel).
6 Oil & Gas Science and Technology – Rev. IFP Energies nouvelles

Figure 4 below shows the typical evolution of yields avoid excessive production of less economically attrac-
during HIS operation. There is a maximum jet fuel yield, tive gases and gasoline (150°C) components.
which can be reached by carefully tuning the severity of
HIS operation. The severity has to be sufficient to con-
1.3 Final Product Properties
vert the hydrocarbons from the Diesel range (280°C+)
into the jet fuel range (150-300°C), but not too high, to The specifications requirements included in Table 3 have
to be met in the final jet fuel after blending. It should be
noted that it is necessary to blend the paraffinic jet fuel
with a conventional jet fuel from petroleum, since an
8% volume minimum aromatics content is specified, to
Naphtha and light comply with material compatibility requirements. The
Product distribution

ends
current certification for HEFA allows no more than
Diesel range
50% volume HEFA in the final jet fuel, in part to help
achieve this minimum aromatics level.

Jet range

2 PRODUCTION OF HEFA JET FUELS WITH VARIOUS

QUALITY REQUIREMENTS
Cold flow properties improvement

2.1 Neat Materials (HEFA and Jet Fuels)

Figure 4
Impact of cold flow properties on kerosene yield of HEFA The previous section showed that there is an optimum
(source: IFP Energies nouvelles). conversion in terms of jet fuel yield and quality.

TABLE 3
Characteristics of the Jet A-1 fuels used in this work

Analysis Unit Jet A-1 specifications Jet fuel A Jet fuel B

3
Density 15°C kg/m 775-840 803.3 821.0

Sulfur wt ppm 3 000 maximum 697 <5

Total aromatics vol% 25.0 max (FIA) 16.1 20.2

26.5 max (hplc) 18.9 20.4

Distillation Initial point °C 147.6 152.1

T10 D86 °C 205 max 167.0 170.2

T20 D86 °C 175.5 176.6

T50 D86 °C 199.0 201.5

T90 D86 °C 245.3 240.2

Final point D86 °C 300 max 270.6 258.9

T90-T10 D86 °C 22 min 78.3 70.0

Freezing point °C
47 max
49.6
64.9

Smoke point mm 25 min or 19 min (*) 21 19

Viscosity at
20°C 2
mm /s 8.0 max 4.04 4.19

Flash point °C 38 min 40.5 42.5

(*) and Naphthalenes < 3.0 wt% (D1840).

 L. Starck et al. / Production of Hydroprocessed Esters and Fatty Acids (HEFA) – Optimisation of Process Yield 7

TABLE 4 Tables 5 and 6 present the characteristics of blends of

Cold flow properties of HEFA1 and HEFA2 Jet fuel A with HEFA1 and HEFA2, respectively.
Analysis Unit HEFA1 HEFA2 The main conclusions from the analysis are as follows:
– all blends have densities that match predicted densi-
Freezing point °C
27°C
57.5°C ties, within method precision – the blending is reliably
Viscosity at
20°C mm2/s 11.72 7.52 linear by volume and the mixing steps have produced
homogeneous blends;
– all the blends met the current ASTM specifications
except for freezing point (for some blends with
The target which is set for HEFA jet fuel quality (freez- HEFA1) and aromatic content (blend with HEFA2);
ing point in particular) consequently has an impact on – blending HEFA in conventional fuels produces sub-
the overall jet fuel yield. stantial increases (improvements) in smoke point;
The objective of this work was to examine the possi- – all the HEFA blend fuels have Lower Heating Values
bility of relaxing the quality requirement for the freezing (LHV) higher than the minimum limit imposed by the
point of the HEFA jet fuel component, and to estimate specification and the blending of HEFA in conven-
the corresponding gain of yield. It was decided to set tional jet fuel resulted in an increase of mass LHV
two distinct freezing point targets for the jet fuel candi- as expected from the component data.
date HEFA: If we focus on cold flow properties, the main results
– one HEFA to have a freezing point close to
20°C; obtained for freezing points are presented in Figure 5.
– one HEFA to have a freezing point below
47°C. The main conclusions are:
Table 4 presents the cold flow properties, freezing – HEFA1 blending ratio is limited by the freezing point.
point and viscosity at
20°C, for the HEFA that were Nevertheless, significant blending ratios can be
produced from rapeseed oil for this study. obtained before reaching this limit. With Jet fuel A
Two different jet fuels were used to prepare further this maximum blending ratio has been estimated to
blends with HEFA1 and HEFA2. A first Jet A-1 (Jet be 16%volume. Nevertheless, this point has to be fur-
fuel A) with conventional characteristics and a second ther checked and does not represent a fixed value;
Jet A-1 (Jet fuel B), with some more extreme but still there can be measurement uncertainties with freezing
“on spec” properties (in particular, exceptionally good points of highly hydroprocessed fuels and the maxi-
freezing point). The main characteristics of the conven- mum ratio will also be very dependent on the freezing
tional Jet A-1 used for this work are gathered in point of the crude oil based component;
Table 3. – HEFA2 can be blended at any concentration without
any limitation on the freezing point, due to the very
2.2 Strategy of Blending and Characterization good freezing point of the pure product;
– with Jet fuel A, the blend freezing point behaviour for
Two blending strategies were adopted to optimise the both HEFA seems to be close to linearity, which could
amount of each HEFA which could be incorporated into mean that the maximum blending ratio could be easily
Jet fuel A and Jet fuel B based on freezing point and vis- calculated according to pure product properties. The
cosity at
20°C. blending ratio of these HEFA could consequently be
Jet fuel A: this fuel offered a typical freezing point adjusted, taking into account the initial freezing point
of
49.6°C and a low blending ratio strategy of 10%, of the conventional Jet A-1. Nevertheless, this point still
20% and 30% volume was adopted for HEFA1 due has to be confirmed using other Jet A-1, to check that
to the
27°C freezing point of this product. HEFA2 this linearity is not dependent on Jet A-1 composition.
however, offered an excellent
57.5°C freezing point As far as viscosity is concerned, the best fit to the
was therefore blended at one high concentration, results is not always linear, particularly for HEFA1, a
75% volume. fuel whose freezing point is only slightly lower than the
Jet fuel B: this fuel offered an excellent freezing point
20°C test condition. Nevertheless, starting from a vis-
of
64.9°C allowing greater scope for blending HEFA1 cosity of 4 mm2/s for the pure Jet A-1 (which is represen-
and a concentration range of 20%, 30%, 40%, 50%, tative of typical Jet A-1 available on the market), a blend
60%, 70% volume was selected. While no freezing point of 75% HEFA2 still stays below the specification viscos-
issues were expected for blending HEFA2, a broad range ity limit. Moreover, all the blends made with HEFA2 are
of concentrations was also chosen 25%, 40%, 50%, 60% expected to pass the ASTM D7566 viscosity limit
and 75% volume to investigate if any other specification (8 mm2/s at
20°C). These results are presented in
constraints might limit incorporation. Figure 6.
8 Oil & Gas Science and Technology – Rev. IFP Energies nouvelles

TABLE 5
Characteristics of blends of Jet fuel A with HEFA1

Analysis Unit Jet A-1 Jet fuel HEFA1 Jet + 10% Jet + 20% Jet + 30%
specifications HEFA1 HEFA1 HEFA1

Density 15°C kg/m3 775-840 803.3 773.5 800.0 797.0 794.0

Total aromatics (hplc) vol% 26.5 max 18.9 0.0 16.9 15.0 13.3

Distillation Initial °C 147.6 174.2 148.7 153.6 152.4

T10 °C 205 max 167.0 201.2 170.2 174.5 174.5

T20 °C 175.5 218.4 179.6 183.3 184.0

T50 °C 199.0 267.5 204.7 210.7 214.5

T90 °C 245.3 288.9 260.8 271.1 277.4

Final °C 300 max 270.6 293.2 282.8 288.5 289.5

T90-T10 °C 22 min 78.3 87.7 90.6 96.6 102.9

Freezing point °C
47 max
49.6
27
49.0
46.5
44.5

Smoke point mm 25 min or 21 > 50 25.0 26.0 28.0

19 min (*)

Viscosity at
20°C mm2/s 8.000 max 4.04 11.72 4.426 4.859 5.363

Flash point °C 38 min 40.5 67 43 43.5 45

Specific energy, net MJ/kg 42.8 min 43.25 44.07 43.31 43.41 43.49

(*) and Naphthalenes < 3.0 wt% (D1840).

HVO in jet A-1(%vol.) 14

HEFA1
0 20 40 60 80 100
Viscosity at -20°C (mm2/s)

12 HEFA2
-20 Polynominal HEFA1 y = 0.2351x - 50.842
HEFA1 Linear HEFA2 R2 = 0.9927
-25 HEFA2 10
y = 0.2351x - 50.842
Linear HEFA1 Jet A-1 8 mm2/s max
R2 = 0.9927 8
Freezing point (°C)

-30 Linear HEFA2

-35 6
y = -0.0805x - 49.673
-40 4 R2 = 0.9961

-45 2
Jet A-1 -47°C min
-50 0
-55 0 20 40 60 80 100
y = -0.0805x - 49.673
R2 = 0.9961 HVO in jet fuel (%vol.)
-60

Figure 6
Figure 5
Impact of HEFA in Jet fuel A blending rate on final blend
Impact of HEFA content on final blend freezing point for viscosity at
20°C.
blends in Jet fuel A.

Following the blend production and test results dis- as shown in Table 3, it has a significantly better freeze
cussed above, blends were made with another Jet A-1, point than average and represents a close to “best case”
Jet fuel B, that has excellent low temperature results; blend partner for a poorer freezing point HEFA
 L. Starck et al. / Production of Hydroprocessed Esters and Fatty Acids (HEFA) – Optimisation of Process Yield 9

TABLE 6
Characteristics of blends of Jet fuel A with HEFA2

Analysis Unit Jet A-1 Jet fuel HEFA2 Jet + 75% HEFA2
specifications

Density 15°C kg/m3 775-840 803.3 765.9 775.0

Total aromatics (hplc) vol% 26.5 max 18.9 0.0 4.8

Distillation Initial °C 147.6 188.0 171.8

T10 °C 205 max 167.0 201.6 192.2

T20 °C 175.5 206.7 199.2

T50 °C 199.0 224.7 218.9

T90 °C 245.3 279.9 276.0

Final °C 300 max 270.6 287.3 287.2

T90-T10 °C 22 min 78.3 78.3 83.8

Freezing point °C
47 max
49.6
57.5
56

Smoke point mm 25 max or 19 max (*) 21 > 50 41

Viscosity at
20°C mm2/s 8.0 max 4.04 7.517 6.335

Flash point °C 38 min 40.5 68.0 58.0

Specific energy, net MJ/kg 42.8 min 43.25 44.11 43.89

(*) and Naphthalenes < 3.0 wt% (D1840).

component. Its freezing point of
64.9°C is the highest around 60% volume with an exceptionally low freezing
reported for the fuel; analysts sometimes prefer not to point (similar to behaviour seen with some GTL SPK
determine freezing points accurately below an arbitrary [14]); many of the results are likely to be affected by
temperature in the range
60 to
75°C as this takes the analyst’s observation preference and the overriding
more time and/or more effort to control such low tem- message is that all the HEFA2 blends in Jet fuel B have
peratures. With this greater than 15°C improvement in very good freezing points, with no limits on HEFA2 con-
freezing point compared to Jet fuel A, it was possible tent being caused by freeze point.
to consider higher levels of HEFA in the two sets of Viscosity data repeat the patterns seen with Jet fuel A:
blends created. Table 7 summarises data for the seven Figure 8 shows that the HEFA2 blends follow an
blends created with HEFA1 and Table 8 provides data approximately linear by volume behaviour while the
for the 5 blends with HEFA2; data for the neat HEFA HEFA2 blends are better fitted by a polynomial fit.
and Jet fuel A and B are in Table 3, and Table 4. HEFA1 blends above 63% volume fail the 8 mm2/s limit,
As shown in Figure 7, Jet fuel B has extended the while all HEFA2 blends pass.
range over which HEFA1 can be blended and still The limiting factor for HEFA2 blends would be set by
achieve Jet A-1 requirements. The best fit for HEFA1 the 8.8% volume total aromatics by hplc method, if the
is now polynomial, with freezing points being higher 50% maximum were not applied.
(poorer) than a linear blend rule would expect. Based In summary, the maximum volume percentages of
on the fit the highest level of HEFA1 to pass the Jet the HEFA in the two Jet A-1 are as in Table 9,
A-1 freezing point would be about 35% volume (or Figure 9 and Figure 10. Given that in a country using
30% based on actual data points). This is higher than Jet A rather than Jet A-1 there may not be many very
seen with Jet fuel A. If only a Jet A freezing point needed good freezing point fuels like Jet fuel B, this does
to be met (
40°C maximum), the fit and actual data indicate that HEFA1 will probably have an upper
points would both suggest upper limits of 51% volume. limit of 30 to 35% volume; more typically HEFA1
For the HEFA2 blends the results are best described as be limited to values in the range 15 to 20% volume
“scattered”; there may or may not be a sweet spot for Jet A-1 production.
10 Oil & Gas Science and Technology – Rev. IFP Energies nouvelles

TABLE 7
Properties of blends of HEFA1 with Jet fuel B

%vol. HEFA1 in Jet fuel B 20 30 40 50 60 70

Analysis Unit

Density 15°C kg/m3 811.3 806.7 802.1 797.4 792.7 788.1

Total aromatics (hplc) vol% 17.5 15.1 12.9 10.8 8.8 6.7

Distillation Initial °C 153.9 155.4 157.1 159.6 161.9 165.7

T10 °C 172.5 174.4 176.3 179.1 182.2 185.7

T20 °C 179.9 182.6 185.6 188.5 192.9 197.0

T50 °C 208.9 213.9 219.4 227.0 234.3 243.1

T90 °C 264.3 273.2 277.4 282.1 283.7 285.4

Final °C 283.5 286.7 289.1 289.6 290.6 290.9

T90-T10 °C 91.8 98.8 101.1 103.0 101.5 99.7

Freezing point °C
58.8
47.8
42.8
40.2
37.1
34.6

Smoke point mm 21.5 22.0 24.5 25.5 30.0 34.0

Viscosity at
20°C mm2/s 5.063 5.504 6.059 6.100 7.412 8.229

Flash point °C 44.0 46.0 47.0 49.5 51.0 53.5

Specific energy, net MJ/kg 43.215 43.325 43.426 43.535 43.636 43.741

HVO in jet fuel (%vol.) 14

HEFA1
Viscosity at -20°C (mm2/s)

0 20 40 60 80 100 HEFA2
-20 12 y = 0.0006x2 + 0.0153x + 4.35
y = -0.0024x2 + 0.6317x - 66.171 Polynomial HEFA1
-25 HEFA1 R² = 0.9915
R² = 0.9754 10 Linear HEFA2
HEFA2
-30 Jet A-1 8 mm2/s max
Polynomial HEFA1
-35 8
Freezing point (°C)

Linear HEFA2
-40
6 y = 0.033x + 3.9928
-45
-50 Jet A1 -47°C min R² = 0.9802
4
-55
-60 2
-65 y = 0.0683x - 68.786 0
-70 R² = 0.158 0 20 40 60 80 100
-75
Lower than
HVO in jet fuel (%vol.)
-80

Figure 8
Figure 7
Viscosity for HEFA blends made with Jet fuel B.
Freezing points for blends of HEFA1 and HEFA2 with Jet
fuel B.

For a given quantity of jet fuel produced, this poten-

2.3 Production Yield
tially allows a reduction in the land surface area necessary
Figure 11 shows the yield improvement for HEFA1 and for cultivation of the HEFA feedstock by at least 10%.
HEFA2 production. It appears that lowering the severity
of HIS operation, for production of HEFA1, leads to a SUMMARY AND CONCLUSIONS
gain of jet and Diesel fuel yield and particularly a gain of
jet fuel yield to more than +10 points of mass yield rel- World wide air traffic has been steadily increasing for
ative to the oil. many years and is predicted to grow in the future.
 L. Starck et al. / Production of Hydroprocessed Esters and Fatty Acids (HEFA) – Optimisation of Process Yield 11

TABLE 8
Properties of blends of HEFA2 with Jet fuel B

%vol. HEFA2 in Jet fuel B 25 40 50 60 75

Analysis Unit

Density 15°C kg/m3 807.0 799.0 793.6 788.0 779.6

Total aromatics (hplc) vol% 16.2 13.1 11.0 9.1 5.5

Distillation Initial °C 157.0 159.9 165.1 168.2 175.7

T10 °C 174.9 178.5 181.7 185.4 191.0

T20 °C 182.3 186.4 189.5 192.4 197.2

T50 °C 205.6 209.1 211.3 213.9 217.4

T90 °C 251.7 260.3 263.5 268.2 272.8

Final °C 275.7 280.1 282.2 283.2 284.5

T90-T10 °C 76.8 81.8 81.8 82.8 81.8

Freezing point °C
65.9
67.3
67.0 <
75.0
60.0

Smoke point mm 20.5 22.0 26.0 33.0 34.0

Viscosity at
20°C mm2/s 4.811 5.190 5.495 5.876 6.412

Flash point °C 45.5 47.5 49.5 52.0 56.0

Specific energy, net MJ/kg 43.262 43.423 43.531 43.642 43.819

60 51 70 59
Max blend for HEFA (%)

50 46
60 52
Max blend for HEFA (%)

40 35
50
30 40
16.3
20 30
10 20

0 10
Jet fuel A Jet fuel B
0
Jet A-1 specification Jet A specification Jet fuel A Jet fuel B

Figure 9 Figure 10
Maximum blend % volumes for HEFA1 / Jet fuels combi- Maximum blend % volumes for HEFA2 / Jet fuels combi-
nations neglecting current 50% specification limit. nations neglecting current 50% specification limit.

Besides, the increased focus on climate change over the steps: hydrotreatment and hydroisomerization. The
last decade has created pressure to reduce greenhouse process yield for HEFA remains limited because of
gases emissions. One solution for the aeronautics sector the isomerisation step that allows production of a bio-
to satisfy the objective of CO2 reduction is the use of fuel with very good cold flow properties. This work
alternative fuel such as HEFA. proposes to relax the freezing point requirement for
HEFA are produced from hydrogenation of mainly the neat HEFA component (by decreasing the severity
vegetable oils. This process generally comprises two of the isomerisation step) in order to minimize the
12 Oil & Gas Science and Technology – Rev. IFP Energies nouvelles

TABLE 9
Maximum blend % volumes for HEFA/Jet A-1 combinations neglecting current 50% specification limit

HEFA Jet A-1 Limit %vol. Limiting property Blend rule

HEFA1 Jet fuel A 16.3 Freezing point Jet A-1

46 Freezing point Jet A

HEFA1 Jet fuel B 35 (fit) or 30 (data point) Freezing point Jet A-1

51 Freezing point Jet A

HEFA2 Jet fuel A 52 Total aromatics Linear by volume

HEFA2 Jet fuel B 59 Total aromatics (hplc) Linear by volume

production of less valuable light compounds. This

strategy could lead to a significant additional biofuel Naphtha and light

Product distribution
ends
yield with respect to the oil. Then this experimental
Diesel range
study determines if a combination of processing/blend-
ing is possible to optimise HEFA incorporation for
industry benefit.
A rapeseed oil was used for this study. The choice of

HEFA1

HEFA2
this oil has been done for reasons of feedstock availabil- Jet range
ity. It was decided to set two distinct freezing point tar-
gets for the jet fuel candidate HEFA: one HEFA to have Cold flow properties improvement
a freezing point close to
20°C and the other one HEFA
to have a freezing point below
47°C. Moreover two dif- Figure 11
ferent jet fuels were used for the blends. A first Jet A-1
Yield improvement for HEFA production (source: IFP
with conventional characteristics and a second Jet A-1, Energies nouvelles).
with some more extreme but still “on spec” properties
(in particular, exceptionally good freezing point).
It has been shown that these HEFA can be blended in incorporation of high freezing point HEFA in smaller
significant volumes in a conventional Jet A-1. The upper %vol. could allow HEFA incorporation to be started
limits in terms of incorporation are: in the shorter term, while optimizing the process yield.
– the freezing point for the HEFA1 (
27°C). HEFA1 This strategy is more in accordance with biomass avail-
can be incorporated at up to 30-35% volume before ability. Nevertheless, it has to be stressed that these are
failing Jet A-1 freezing point. The incorporation ratio only preliminary results and need important validation
is dependant of the jet fuel quality regarding cold flow work, such as fitness for purpose tests recommended in
behavior; ASTM D4054, before going into the certification process
– the aromatic content of the final blend for the intro- and being industrially used.
duction of HEFA2 (
57.5°C). However, HEFA2
can be incorporated at up to 59% before failing to
achieve the minimum total aromatics content. With ACKNOWLEDGMENTS
a higher aromatics jet fuel that has excellent freezing
point characteristics, higher levels of HEFA can be This work was done as an additional contribution to the
incorporated, though the limiting properties remain SWAFEA Project and the contributors are Shell Global
the same. Solutions and IFP Energies nouvelles.
These preliminary tests have shown that by combining
processing conditions in combination with blending
strategies there is a potential to enhance the incorpora- REFERENCES
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