energies

Article
Selection of Blends of Diesel Fuel and Advanced
Biofuels Based on Their Physical and
Thermochemical Properties
José Rodríguez-Fernández * , Juan José Hernández , Alejandro Calle-Asensio, Ángel Ramos
and Javier Barba
Universidad de Castilla-La Mancha, Escuela Técnica Superior de Ingenieros Industriales, Avda. Camilo José
Cela s/n, 13071 Ciudad Real, Spain; juanjose.hernandez@uclm.es (J.J.H.); alejandro.calle@uclm.es (A.C.-A.);
angel.ramos@uclm.es (Á.R.); javier.barba@uclm.es (J.B.)
* Correspondence: Jose.RFernandez@uclm.es; Tel.: +34-926-295300 (Ext. 6472)




Received: 9 May 2019; Accepted: 23 May 2019; Published: 28 May 2019


Abstract: Current policies focus on encouraging the use of renewable energy sources in transport to
reduce the contribution of this sector to global warming and air pollution. In the short-term, attention
is focused on developing renewable fuels. Among them, the so-called advanced biofuels, including
non-crop and waste-based biofuels, possess important benefits such as higher greenhouse gas (GHG)
emission savings and the capacity not to compete with food markets. Recently, European institutions
have agreed on specific targets for the new Renewable Energy Directive (2018/2001), including 14%
of renewable energy in rail and road transport by 2030. To achieve this, advanced biofuels will
be double-counted, and their contribution must be at least 3.5% in 2030 (with a phase-in calendar
from 2020). In this work, the fuel properties of blends of regular diesel fuel with four advanced
biofuels derived from different sources and production processes are examined. These biofuels
are (1) biobutanol produced by microbial ABE fermentation from renewable material, (2) HVO
(hydrotreated vegetable oil) derived from hydrogenation of non-edible oils, (3) biodiesel from waste
free fatty acids originated in the oil refining industry, and (4) a novel biofuel that combines fatty
acid methyl esters (FAME) and glycerol formal esters (FAGE), which contributes to a decrease in the
excess of glycerol from current biodiesel plants. Blending ratios include 5, 10, 15, and 20% (% vol.)
of biofuel, covering the range expected for biofuels in future years. Pure fuels and some higher
ratios are considered as well to complete and discuss the tendencies. In the case of biodiesel and
FAME/FAGE blends in diesel, ratios up to 20% meet all requirements set in current fuel quality
standards. Larger blending ratios are possible for HVO blends if HVO is additivated to lubricity
improvers. For biobutanol blends, the recommended blending ratio is limited to 10% or lower to
avoid high water content and low cetane number.

Keywords: advanced biofuels; diesel blends; fuel properties; quality standards

1. Introduction
Increasing the renewable energy fraction in transport is an urgent necessity to tackle global
warming and air pollution. Recent pollution episodes in big cities have prompted the adoption of local
and regional policies that will progressively (from the present to 2040–2050) ban internal combustion
vehicles. Electricity from renewable sources will be decisive to achieve and maintain a fully sustainable
mobility system as it has been analyzed in detail elsewhere [1], but the short-and-mid-term attention
must be focused on developing renewable and sustainable fuels, especially those with a more beneficial
carbon balance [2].
Advanced biofuels, including some non-crop and waste-based biofuels, possess important benefits
such as higher GHG emission savings and the capacity not to strain food markets [3]. European

Energies 2019, 12, 2034; doi:10.3390/en12112034 www.mdpi.com/journal/energies

Energies 2019, 12, 2034 2 of 13

institutions agreed to specific targets that have been set in a new Renewable Energy Directive
(2018/2001) [4] published in December 2018, including 14% of renewable energy in rail and road
transport by 2030. To achieve this, advanced biofuels will be double-counted, and their contribution
must be at least 3.5% in 2030 (with a phase-in calendar from 2020). Moreover, crop-derived biofuels
will be capped at levels achieved in 2020 and not higher than 7% whereas raw materials with a high
risk of ILUC (indirect land-use change) must be fully abandoned by 2030.
In the case of diesel fuels, the pool of advanced biofuels is still wide. Alcohol-diesel blends, if the
alcohol comes from lignocellulosic wastes, biodiesel fuels derived from residual oleaginous materials
and/or paraffinic fuels such as BTL (Biomass-To-Liquid) or HVO (Hydrotreated Vegetable Oil) can be
considered advanced biofuels.
So far, biodiesel fuels are the most studied but also the most controversial biofuels. The final
product consists on a mix of a few fatty acid methyl esters (FAME); therefore, the fuel properties vary
within narrow ranges around values generally close to those exhibited by conventional fossil diesel
fuels. But the reduction of lifecycle GHG emissions of biodiesel fuels depends largely on the origin of
the raw vegetable oil/animal fat. Even some biodiesel origins have been reported to increase GHG
emissions [5]. Two approaches, both treated in the present work, are gaining attention as a means to
ensure a beneficial lifecycle GHG emission balance: (i) biodiesel fuels partially or totally derived from
other industrial wastes and (ii) biodiesel routes that reduce the production of low valued byproducts
(such as low-grade glycerol). The esterification of residual free fatty acids recovered from the palm
oil industry is a way of dealing with a very abundant waste coming from the palm oil industry [6].
Some works have been focused on the reactions involved in the production process and the selection
of catalysts [7,8], whereas properties and engine emissions have not received much attention although
they are expected to depend on the purity and quality of the final methyl ester product. In the second
approach, esters of glycerol formal (FAGE) yielded from waste oils and glycerol as reagents have been
proved as a reliable option. However, the high viscosity and poor cold flow properties of FAGE [9]
make desirable to blend FAGE and FAME to obtain a renewable biofuel with properties suitable for
diesel applications. The reactions needed for both, FAGE and FAME, may be implemented jointly in
current biodiesel plants thus making the whole process more economic. When used in diesel engines,
benefits in carbon monoxide, hydrocarbons and particulate matter were found and supported based
on their oxygen content [10].
Alcohol-diesel blends are reported to reduce particle and other emissions mainly because of their
oxygen content. Ethanol is the most conventional alcohol [11–13] used for blending, but n-butanol
has some advantages over ethanol, such as higher heating value, higher cetane number and better
miscibility with diesel [14,15]. Recently, chemical and biological processes to produce n-butanol from
renewable and waste sources have gained attention [16]. Among them, bacterial fermentation may
reduce greenhouse emissions on a life-cycle basis [17] and, thus, is a promising technique [18,19].
Highly paraffinic fuels such as gas-to-liquid (GTL), biomass-to-liquid (BTL) and hydrotreated
vegetable oil (HVO) have emerged as alternative diesel fuels with some outstanding diesel properties
(mainly cetane number and heating values) that offer potential to reduce fuel consumption, and thus
CO2 emissions, and harmful emissions of diesel vehicles [20]. Moreover, these fuels have been claimed
to be fully compatible with current engine technologies. HVO has the best economic perspectives since
the chemical process may be integrated in current oil refineries [21,22], using the existing reactors and
hydrogen streams. HVO production technology removes the O-atoms and the double bonds of the raw
material through a process called hydrotreating catalysis. The raw material is the same than in the case
of biodiesel, but the chemical route and the final product are different. Many works have examined
and compared both fuels, and even ternary blends (diesel-biodiesel-HVO) have been proposed to
exploit the advantages of both biofuels.
The selection of fuels and blends should not be made ignoring the properties of the final blends.
A correct blending proportion based on the property’s ranges set in current fuel quality standards
may guarantee the absence of vehicle failures, such as those episodes encountered at some places
Energies 2019, 12, 2034 3 of 13

when using certain biodiesel blends in cold ambient conditions. Besides, many of the fuel properties
directly affect the engine-out emissions [23]. The current European legislative framework imposes
that any final diesel fuel (neat or blended) to be used in road transport must meet all the EN 590
requirements; besides, biodiesel and paraffinic fuels must fulfill, before blending in regular diesel,
the additional requirements set in EN 14214 for biodiesel and EN 15940 for paraffinic fuels. In this
frame, the present work examines the main fuel properties of feasible blends of four advanced biofuels
in regular fossil diesel fuel and proposes ranges and target values for each biofuel. The selected blends
will be tested in a diesel engine and/or vehicle, in a different study, to check whether the suggested
blending proportions work as expected under real driving conditions.

2. Materials and Methods

Density was measured at 15 ◦ C according to EN 3675 introducing an appropriate densimeter
into the flask that contain the fuel tested. The flask is surrounded by water in a thermostatic bath
from Fisher Scientific (Tamson TV 2000, with a temperature control precision of ± 0.1 K). Kinematic
viscosity was measured using Cannon-Fenske viscometers introduced in the same bath. In this case,
the temperature of the water during the viscosity tests was maintained at 40 ◦ C, according to standard
EN ISO 3104.
Higher heating value (HHV) analysis was conducted according to standard ASTM D4809, using
a Parr 6100 calorimetric bomb. Lower heating value (LHV) was also calculated from the HHV value
and the elemental analysis, which was carried out using a Carlo Erba EA1108 analyzer.
Lubricity was carried out according to EN 12156-1 in a high frequency reciprocating rig (HFRR)
from PCS Instruments. The wear scar was measured with an Optika SZR1 microscope equipped with
a 100x magnification lens. All lubricity tests were made inside a climatic chamber (provided by PCS
Instruments) where the ambient temperature and humidity were controlled according to the limits set
in EN 12156-1:2016 with the use of a potassium carbonate solution.
The Cold Filter Plugging Point (CFPP) and the Cloud Point (CP), representative of cold flow
properties, were measured according to the standards EN 116/ASTM D6371 for CFPP and EN
23015/ASTM D2500 for CP. The device used to measure the CFPP was PACFPP 5Gs whereas the
instrument used for measuring CP was PAC-CPP 5Gs.
Derived Cetane Number (DCN) was measured in the equipment Cetane ID510 by Herzog.
This equipment consists of a constant-volume combustion chamber (0.473 L) and a common-rail diesel
injector (operating at 1000 bar injection pressure) similar to those used in commercial engines (Bosch
part no 0445110181) with 6 nozzles with orifice diameter of 0.17 mm. Synthetic air (21% O2 and 79%
N2 v/v) was used as oxidant and the initial absolute pressure was kept constant at 21 bar. In every
test, 15 fuel injections for each fuel were carried out. DCN is determined through the ignition and
combustion delays according to ASTM D7668, both calculated from the pressure signal.
Finally, water content measurement was carried out by using Karl-Fischer 831 KF according to
EN 12937.

3. Fuels and Blends

The reference diesel fuel of this work was supplied by Repsol S.A. This fuel meets all requirements
in the European Standard EN 590. Unlike commercial fuels available in filling stations, this fossil fuel
does not contain biodiesel or HVO; thus, it can be used for blending with the biofuels evaluated here.
Four advanced biofuels were selected:

• an HVO fuel, donated by NESTE, produced from camelina and other waste vegetable oils;
• biobutanol supplied by Green Biologics and produced from bacterial fermentation;
• a biodiesel fuel supplied by Masol Iberia Biofuel, which is composed of fatty acid methyl esters
(FAME). Instead of producing this fuel through a conventional transesterification reaction using
vegetable oil and methanol as reagents, it was derived from waste fatty acids recovered from the
palm oil industry and transformed into methyl esters by an esterification reaction;
Energies
Energies 2019,
2019, 12,
12, x2034
FOR PEER REVIEW 4 4of
of 13
13

• a target blend of 70% FAME (±1%), 27% fatty acid glycerol formal esters—FAGE (±1%) and 3%
• a target(±0.2%),
acetals blend ofproduced
70% FAME and(±1%),
supplied27%by fatty acid glycerol(this
Inkemia-IUCT formal
blendesters—FAGE
is commercially (±1%) and 3%
known as
acetals (±0.2%),
o.bio®). The FAME produced and
fraction wassupplied
produced by Inkemia-IUCT
from waste cooking(this blend
oil andis commercially known to
was used as reagent as
®
o.bio ). the
TheFAGEFAME fraction was produced from waste cooking oil and Acetals
was used as reagent to
produce through transesterification-transketalization reactions. were yielded as
produce the FAGE
by-products in thesethrough transesterification-transketalization reactions. Acetals were yielded as
reactions.
by-products in these reactions.
For all four biofuels, biofuel-diesel blends at blending ratios of 5, 10, 15 and 20% (in volume
basis)For
were prepared
all four biofuels, and tested. To gain
biofuel-diesel blendsaccuracy
at blendingin the targeted
ratios of 5, 10,blending
15 and 20% ratios, appropriate
(in volume basis)
laboratory
were prepared glassware material
and tested. was employed
To gain accuracy in (volumetric
the targeted flasks and pipettes).
blending The volumes
ratios, appropriate of both
laboratory
components were measured
glassware material was employedseparately prior toflasks
(volumetric blending. Considering
and pipettes). Thethe presentofand
volumes boththe proposals
components
for
werefuture standards,
measured low-content
separately prior toblends such Considering
blending. as those evaluated here are
the present andthethemost interesting.
proposals For
for future
completeness, the properties
standards, low-content blendsofsuch
diesel fuel and
as those the neathere
evaluated biofuels were
are the mostalso measured,
interesting. Forand in the case
completeness,
of
thebiodiesel
properties and of HVO,
diesel blends
fuel andatthe
30 neat
and 50% were
biofuels included
were as well (these
also measured, and in two
thebiofuels show no
case of biodiesel
incompatibility
and HVO, blends withat current
30 and 50%diesel engines
were and 30
included asand
well50% blends
(these two are typically
biofuels showused
no in captive fleets
incompatibility
and
withincurrent
other demonstration
diesel engines and programs).
30 and 50%Biobutanol-diesel blends used
blends are typically at higher biobutanol
in captive fleets content than
and in other
20% were not tested as they have no interest in the diesel fuel market and
demonstration programs). Biobutanol-diesel blends at higher biobutanol content than 20% were they could show blending
stability
not tested problems
as they have at low no temperature
interest in theordiesel
with fuelwater contamination.
market and they couldThe values of all measured
show blending stability
properties are tabulated in Appendix A.
problems at low temperature or with water contamination. The values of all measured properties are
tabulated in Appendix A.
4. Results and Discussion
4. Results and Discussion
4.1. Density
4.1. Density
Figure 1 presents the density of all the blends and neat fuels tested. Each blend/fuel was tested
Figure 1 presents the density of all the blends and neat fuels tested. Each blend/fuel was tested
three times and the average value is displayed in the figure. None of the replicated measurements
three times and the average3 value is displayed in the figure. None of the replicated measurements
deviated more than 2 kg/m from the average value. Fuel dispensers in filling stations operate in
deviated more than 2 kg/m3 from the average value. Fuel dispensers in filling stations operate in volume
volume units. In diesel vehicles, electronic injection adjusts the fuel mass introduced into the
units. In diesel vehicles, electronic injection adjusts the fuel mass introduced into the combustion
combustion chamber by modifying the injection time (i.e. the volume of fuel) and assuming a
chamber by modifying the injection time (i.e., the volume of fuel) and assuming a standard density
standard density set in the ECU cartography. In view of these, fuel quality standards impose a narrow
set in the ECU cartography. In view of these, fuel quality standards impose a narrow density range,
density range, as suggested elsewhere [24]. In the case of EN 590, density is specified at 820‒845
as suggested elsewhere [24]. In the case of EN 590, density is specified at 820–845 kg/m3 .
kg/m3.
920
Biodiesel
900
HVO
BioButanol
880 o.bio
Density (kg/m3)

860

840

820

800

780

760
0 10 20 30 40 50 60 70 80 90 100
Biofuel content (%v/v)

Figure 1.
Figure Density of
1. Density of fuels
fuels and
and blends.
blends.

Compared to
Compared to the
the density
density ofof diesel
diesel fuel
fuel (biofuel content ==0%),
(biofuel content 0%),blends
blends with
with biodiesel
biodiesel (FAMEs)
(FAMEs) oror
o.bio ® (FAMEs and FAGEs, mainly) increase density, while blends with HVO or butanol have the
o.bio® (FAMEs and FAGEs, mainly) increase density, while blends with HVO or butanol have the
opposite effect.
opposite effect. The
The density
density of of biobutanol
biobutanol is
is closer
closer to
to that
that of
of diesel
diesel than
than that
that of
of ethanol
ethanol (ethanol
(ethanol was
was
not tested
not testedhere,
here,but
butititisisthe
the most
most common
common alcohol
alcohol usedused
for for diesel
diesel blending
blending despite
despite its miscibility
its miscibility and
and hygroscopic problems), which is one of the advantages of biobutanol
hygroscopic problems), which is one of the advantages of biobutanol blending over blending over ethanol.
ethanol.
Considering the importance of limiting the variations of density, it would be possible to design a
Energies 2019, 12, 2034 5 of 13

Energies 2019, 12,

Considering x FOR
the PEER REVIEW
importance of limiting the variations of density, it would be possible to design a 5diesel of 13
blend with a selected composition of two of the biofuels here tested (biodiesel and HVO, for example,
diesel the
since blend with a selected
production processescomposition of two ofhave
of both biofuels the biofuels here tested
been suggested (biodiesel
to be combined andinHVO, for
a single
example, since the production processes of both biofuels have been
plant [22]) obtaining a ternary blend which keeps the density at the same value than diesel’s. suggested to be combined in a
single plant [22]) obtaining a ternary blend which keeps the density at the same
As expected, the trend of the density is quite linear with the blend composition, which indicates value than diesel’s.
As expected,
that there the trend
is no change of the density
of volume on mixingis quite
(or linear with the blend
it is negligible). composition,
Therefore, whichofindicates
the density a blend
that there is no change of volume on mixing (or it is negligible). Therefore,
at any other composition than tested here could be calculated with minor error by multiplying the density of a blendtheat
any other
density of composition than tested
the two components here
by the could fractions;
volume be calculated withbeminor
this can errortoby
extended multiplying
blends with morethe
density of the two components by the volume fractions; this can be extended
than two components. In order to fulfill the required regulated density range, the content of biofuel to blends with more
than two
cannot components.
exceed In order
20% (it could to fulfill
be higher thecase
in the required regulated
of butanol density
blends, thoughrange,
in thisthe content
case of biofuel
high biobutanol
cannot exceed
contents are not20% (it could
debated in the be higher
diesel fuel in the case of butanol blends, though in this case high
market).
biobutanol contents are not debated in the diesel fuel market).
4.2. Lower Heating Value
4.2. Lower Heating Value
The heating value of a fuel indicates its energy content per unit mass (MJ/kg) or volume (MJ/L).
EachThe heatingwas
blend/fuel value of a fuel
tested three indicates its energy
times, and contentdeviation
the average per unit mass
was 0.10(MJ/kg)
MJ/kg or volume (MJ/L).
(the maximum
Each blend/fuel
difference between was tested three
replications wastimes, and the Although
0.40 MJ/kg). average deviation was 0.10
the instruments MJ/kg
used (the maximum
to perform heating
value measurements usually provide mass units, volume units are preferred in the transportheating
difference between replications was 0.40 MJ/kg). Although the instruments used to perform sector
value measurements
because of the reasonsusually
outlined provide
previouslymass(density
units, volume
section).units are preferred in the transport sector
because of the reasons
Although outlined
this property is notpreviously
currently (density
limited insection).
diesel quality standards, its effect is meaningful.
Although this property is not currently
Low values lead to higher fuel consumption and a loss of engine limited in diesel
powerquality standards,
at full load. In modern its effect
vehicles,is
meaningful.
the lean NOxLow trap values lead to higher
(LNT) purging and thefuel consumption
Diesel and(DPF)
Particle Filter a lossregeneration
of engine power at full load. by
are accomplished In
modern vehicles,
post-injecting fuelthe lean NOxexhaust
to increase trap (LNT) purging and
temperature. Thethe Dieseland
volume Particle
timing Filter (DPF)
of these regeneration
post-injections
are set
are accomplished by post-injecting
in the electronic control unit (ECU)fuel to by
increase exhaust temperature.
the manufacturer The volume
engine calibration and timing
department. Butof if
these
the post-injections
heating value of the arefuel
setused
in the
by aelectronic
user during control unit (ECU)
real driving by the
is not high manufacturer
enough, it may deriveengine in
acalibration
lower exhaust department. But ifthan
temperature the needed
heating and,
value of the fuel
therefore, used by a user
in unsuccessful or during
incompletereal driving is not
regenerations
high enough, it may derive
and eventually vehicle failure [25,26]. in a lower exhaust temperature than needed and, therefore, in
unsuccessful or incomplete regenerations and eventually vehicle failure [25,26].
45.0 36.0
Lower Heating Value (MJ/kg)

42.5
Lower Heating Value (MJ/L)

33.5
40.0

37.5 31.0
Biodiesel Biodiesel
35.0 HVO HVO
BioButanol 28.5 BioButanol
o.bio o.bio
32.5

30.0 26.0
0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100
Biofuel content (%v/v) Biofuel content (%v/v)

Figure 2.
Figure Lower heating
2. Lower heating value
value of
of fuels
fuels and
and blends,
blends, in
in mass
mass units
units (left)
(left) and
and volume
volume units
units (right).
(right).

As
As in
in the
the case of density,
case of density, the
the heating
heating values
values ofof the
the blends
blends tested
tested changes
changes quite
quite linearly
linearly with
with the
the
blend
blend composition (Figure 2). This confirms, together with the nil change of volume on mixing, that
composition (Figure 2). This confirms, together with the nil change of volume on mixing, that
these fuel blends
these fuel blends can
can be
be treated
treated as
asideal
idealmixtures.
mixtures.The Thelower
lowerheating
heatingvalue
value ofof
HVOHVO inin mass
mass units
units is
is higher than that of the diesel fuel; on the contrary, in volume units, it is lower. This
higher than that of the diesel fuel; on the contrary, in volume units, it is lower. This trend can be trend can be
extrapolated
extrapolated toto all
all paraffinic
paraffinic fuels
fuels (HVO, XTL), since
(HVO, XTL), since paraffins
paraffins in
in the
the C-range
C-range typical
typical ofof diesel
diesel fuels
fuels
usually display high heating values in mass units but lower densities than other hydrocarbons
usually display high heating values in mass units but lower densities than other hydrocarbons (such (such as
aromatics). Nevertheless, the loss of volumetric heating value of HVO compared to
as aromatics). Nevertheless, the loss of volumetric heating value of HVO compared to diesel is only diesel is only 3%;
therefore, this property
3%; therefore, does not
this property doeshinder the usethe
not hinder of use
neatofHVO
neatinHVO
vehicles with nowith
in vehicles (or just
no minor)
(or justchanges
minor)
in
changes in the engine calibration. The opposite case is biobutanol, which heating valuelow.
the engine calibration. The opposite case is biobutanol, which heating value is unassumingly is
unassumingly low. The content of biobutanol in diesel blends should be limited around 10% if
admissible loss of heating value is to be set at 3%.
About o.bio® and biodiesel fuels, the heating values of both are close to each other, especially
when given in volume units, as their components are quite similar (ester-based). Compared to diesel,
Energies 2019, 12, 2034 6 of 13

The content of biobutanol in diesel blends should be limited around 10% if admissible loss of heating
value is to be set at 3%.
About o.bio® and biodiesel fuels, the heating values of both are close to each other, especially
Energies 2019, 12, x FOR PEER REVIEW 6 of 13
when given in volume units, as their components are quite similar (ester-based). Compared to diesel,
the heating
the heating value
value ofof neat o.bio® and
neat o.bio® and biodiesel
biodiesel is
is approximately
approximately 10%
10% lower,
lower, in
in volume
volume units,
units, thus
thus the
the
recommended content
recommended content in
in diesel
diesel blend
blend should
should not
not be
be higher
higher than
than 30%.
30%.

4.3. Lubricity
4.3. Lubricity
Fuel lubricity is essential in the injection system as it reduces wear and scuffing between parts
Fuel lubricity is essential in the injection system as it reduces wear and scuffing between parts
in relative motion [27], such as in the interior of diesel fuel pumps and fuel injectors. The concern
in relative motion [27], such as in the interior of diesel fuel pumps and fuel injectors. The concern
about fuel lubricity has increased over the years due to the sulphur removal in the fuel (the process
about fuel lubricity has increased over the years due to the sulphur removal in the fuel (the process
used in oil refineries for this task eliminates natural lubricant hydrocarbons) and the lower mechanical
used in oil refineries for this task eliminates natural lubricant hydrocarbons) and the lower
tolerances allowed in injection system components.
mechanical tolerances allowed in injection system components.
Each fuel/blend was replicated twice, being the average deviation between replications lower
Each fuel/blend was replicated twice, being the average deviation between replications lower
than 10 µm, which is below the maximum deviation admitted in the test standard EN 12156-1:2016
than 10 μm, which is below the maximum deviation admitted in the test standard EN 12156-1:2016
(50 µm maximum in one case out of twenty).
(50 μm maximum in one case out of twenty).
Figure 3 presents the lubricity of the fuels and blends of this work. Neat diesel and HVO are
Figure 3 presents the lubricity of the fuels and blends of this work. Neat diesel and HVO are
commercial fuels, additivated with lubricity enhancers by the fuel manufacturers to fulfill the limit
commercial fuels, additivated with lubricity enhancers by the fuel manufacturers to fulfill the limit
(lower than 460 µm) set in EN 590 (for automotive diesel fuels) and EN 15940 (for paraffinic fuels).
(lower than 460 μm) set in EN 590 (for automotive diesel fuels) and EN 15940 (for paraffinic fuels).
The highest wear scar diameter (i.e., poorest lubricity) was found for biobutanol, though this alcohol
The highest wear scar diameter (i.e. poorest lubricity) was found for biobutanol, though this alcohol
is better lubricant than ethanol [15]. The biobutanol tested has no lubricant additive as it was used
is better lubricant than ethanol [15]. The biobutanol tested has no lubricant additive as it was used as
as received from the chemical supplier. Both ester-based fuels, biodiesel, and o.bio® , exhibited the
received from the chemical supplier. Both ester-based fuels, biodiesel, and o.bio®, exhibited the best
best lubricity. The ester functionality present in FAME (biodiesel) molecules can be adsorbed on
lubricity. The ester functionality present in FAME (biodiesel) molecules can be adsorbed on metal
metal surfaces while the rest of the chain (long aliphatic chain) creates a film that prevents wear.
surfaces while the rest of the chain (long aliphatic chain) creates a film that prevents wear. The
The extremely good lubricant properties of biodiesel have been proved previously [28,29], but the
extremely good lubricant properties of biodiesel have been proved previously [28,29], but the results
results here presented confirm now the same result for FAGE/FAME blends.
here presented confirm now the same result for FAGE/FAME blends.
600
Biodiesel
550 HVO
Wear scar dialmieter (μm)

BioButanol
500
o.bio
450
400
350
300
250
200
150
0 10 20 30 40 50 60 70 80 90 100
Biofuel content (%v/v)

Figure 3.
Figure Wear scar
3. Wear scar diameter
diameter (lubricity)
(lubricity) of
of fuels
fuels and
and blends.
blends.

The lubricity
The lubricityofofthe
theblends
blendsdiddidnot
notchange
change linearly
linearly with
with thethe blend
blend composition.
composition. In the
In the casecase of
of the
the ester-based biofuels, the lubricity improved strongly with the addition of low
ester-based biofuels, the lubricity improved strongly with the addition of low biofuel content into biofuel content into
diesel until
diesel until reaching
reaching aa “saturation”
“saturation” level.
level. From
From this,
this, no
no further
further lubricity
lubricity gain
gain was
was manifested
manifested even
even at
at
higher biofuel concentrations. Comparing both biofuels, o.bio ® (FAGE/FAME blend) was the most
higher biofuel concentrations. Comparing both biofuels, o.bio® (FAGE/FAME blend) was the most
promising one
promising one since
since only
only 10%
10% was
was needed
needed to to achieve
achieve the
the maximum
maximum reduction
reduction of of the
the wear
wear scar.
scar.
In the
In the case
case of
of biobutanol
biobutanol andand HVO
HVO blends
blends in in diesel,
diesel, the
the lubricity
lubricity deteriorated
deteriorated with
with the
the biofuel
biofuel
content and the lubricity loss was more significant in the low content range
content and the lubricity loss was more significant in the low content range (0‒10%). Low biofuel(0–10%). Low biofuel
content is
content is the
the most
most likely
likely future
future scenario
scenario in in the
the fuel
fuel market;
market; therefore,
therefore, this
this finding
finding must
must be
be observed
observed
carefully by all involved agents. For example, in case the lubricity of the reference diesel fuel used for
blending was too close to the permitted value, even blends with biobutanol or HVO at 10% or lower
could lead to blends out of the lubricity specification.
All blends HVO/diesel tested fulfill the maximum limit set in quality standards, but the results
in Figure 3 evidence some synergistic interaction between both fuels that results in poorer lubricant
fuel-air mixing thus affecting combustion process and emissions. Outside the chamber, viscosity has
effects on the injection system. Unlike other properties, neither too high nor too low values are
desirable. Very high viscosity can reduce fuel flow rate and even damage the fuel pump. Very low
viscosity increases leakages in the injection system, which is aggravated at increased ambient
Energies 2019, 12, 2034 7 of 13
temperatures. Fuel quality standards are aware of these issues and fix a valid viscosity range: 2‒4.5
cSt in EN 590 and EN 15940, and 3.5‒5 cSt in EN 14214 (since methyl esters in biodiesel are more
viscous
carefullysubstances).
by all involved agents. For example, in case the lubricity of the reference diesel fuel used for
In the
blending present
was work,
too close each
to the samplevalue,
permitted was even
measured
blendsthree
with times, and or
biobutanol theHVO
deviation
at 10% between
or lower
replications never exceeded 0.02 cSt. The viscosity
could lead to blends out of the lubricity specification. values are illustrated in Figure 4. The neat biofuels
ranked as follows: biobutanol showed the lowest value; followed by HVO, which viscosity
All blends HVO/diesel tested fulfill the maximum limit set in quality standards, but the results was close
to that of diesel fuel; and biodiesel and o.bio® finally, the latter with the highest value.
in Figure 3 evidence some synergistic interaction between both fuels that results in poorer lubricant Glycerol esters
(FAGE)
capacityare for characterized
30 and 50% blends by higher
than viscosities thantwo
for any of the methyl esters As
neat fuels. (FAME); therefore,
both fuels if FAGE is
were additivated
blended in FAME as in the present o.bio® fuel and the final FAGE/FAME blend
in origin to enhance lubricity, this result could be a consequence of some incompatibility between is desired to meet
the
bothcurrent biodiesel standard, a low viscosity FAME is preferred to enlarge the feasible FAGE
additives.
content window.
The viscosity
4.4. Kinematic of the biofuel/diesel blends changed non-linearly with the composition; in general,
Viscosity
when any of the biofuels examined is blended in diesel, the viscosity of the least viscous fuel prevails
Inside the combustion chamber, fuel viscosity affects the fuel jet features, fuel atomization and
in the blend. This makes the viscosity of the blends to be lower than expected if this property were
fuel-air mixing thus affecting combustion process and emissions. Outside the chamber, viscosity has
linear with composition. All biofuel/diesel blends fall in the permitted viscosity range, but the
effects on the injection system. Unlike other properties, neither too high nor too low values are desirable.
viscosity of all the blends (especially at up to 20% HVO) is clearly lower than those of neat diesel or
Very high viscosity can reduce fuel flow rate and even damage the fuel pump. Very low viscosity
HVO. Once more, if the viscosity of any of these two neat fuels was closer to the minimum limit, a
increases leakages in the injection system, which is aggravated at increased ambient temperatures.
blend could exhibit lower viscosity than allowed in the standards. Biodiesel/diesel and o.bio® /diesel
Fuel quality standards are aware of these issues and fix a valid viscosity range: 2–4.5 cSt in EN 590 and
blends up to 20% do not change substantially the viscosity of the diesel fuel (a slight decrease is
EN 15940, and 3.5–5 cSt in EN 14214 (since methyl esters in biodiesel are more viscous substances).
observed for biodiesel, at has been reported elsewhere [30]); therefore, this blending range is
In the present work, each sample was measured three times, and the deviation between replications
recommended.
never exceeded 0.02 cSt. The viscosity values are illustrated in Figure 4. The neat biofuels ranked as
Finally, viscosity and lubricity in fuel are often associated in discussions (the higher the viscosity,
follows: biobutanol showed the lowest value; followed by HVO, which viscosity was close to that of
the better the lubricity). Comparing Figure 3 and Figure 4, it is obvious that better lubricity is not
diesel fuel; and biodiesel and o.bio® finally, the latter with the highest value. Glycerol esters (FAGE)
necessarily expected in a blend with higher viscosity. Indeed, the HFRR test used to evaluate lubricity
are characterized by higher viscosities than methyl esters (FAME); therefore, if FAGE is blended in
works in the boundary lubrication region [31], where the friction coefficient is not dependent on the
FAME as in the present o.bio® fuel and the final FAGE/FAME blend is desired to meet the current
fluid viscosity as demonstrated in basic rheology [32] (unlike the hydrodynamic lubrication region,
biodiesel standard, a low viscosity FAME is preferred to enlarge the feasible FAGE content window.
where a liquid film separates the parts in relative motion and fluid viscosity plays a role).
6.5
6.0 Biodiesel
5.5 HVO
BioButanol
5.0 o.bio
Viscosity (cSt)

4.5
4.0
3.5
3.0
2.5
2.0
0 10 20 30 40 50 60 70 80 90 100
Biofuel content (%v/v)

Figure 4. Kinematic viscosity of fuels and blends

Figure 4. Kinematic viscosity of fuels and blends
The viscosity of the biofuel/diesel blends changed non-linearly with the composition; in general,
when any of the biofuels examined is blended in diesel, the viscosity of the least viscous fuel prevails in
the blend. This makes the viscosity of the blends to be lower than expected if this property were linear
with composition. All biofuel/diesel blends fall in the permitted viscosity range, but the viscosity of all
the blends (especially at up to 20% HVO) is clearly lower than those of neat diesel or HVO. Once more,
if the viscosity of any of these two neat fuels was closer to the minimum limit, a blend could exhibit
lower viscosity than allowed in the standards. Biodiesel/diesel and o.bio® /diesel blends up to 20%
do not change substantially the viscosity of the diesel fuel (a slight decrease is observed for biodiesel,
at has been reported elsewhere [30]); therefore, this blending range is recommended.
Energies 2019, 12, 2034 8 of 13

Finally, viscosity and lubricity in fuel are often associated in discussions (the higher the viscosity,
the better the lubricity). Comparing Figures 3 and 4, it is obvious that better lubricity is not necessarily
expected in a blend with higher viscosity. Indeed, the HFRR test used to evaluate lubricity works in the
boundary lubrication region [31], where the friction coefficient is not dependent on the fluid viscosity
as demonstrated in basic rheology [32] (unlike the hydrodynamic lubrication region, where a liquid
film separates the parts in relative motion and fluid viscosity plays a role).
Energies 2019, 12, x FOR PEER REVIEW 8 of 13
4.5. Cold Flow Properties
4.5. Cold Flow Properties
Assuring enough fuel fluidity is necessary to move the fuel along the supply system (passing
Assuring
through enough
the filter/s) andfuel fluidity isirregular
preventing necessary to move
idling the fuel along
and startability the supply
problems. Cold system (passing
flow properties
through
are a hotthe filter/s)
issue and preventing
at present as there have irregular
been idling and startability
some recent episodes problems.
related to Cold flow properties
insufficient values evenare
a hot issue at present as there have been some recent episodes related to insufficient
though the fuels involved did meet the requirements in the in-force standards. The suspicions point values even though
the towards
out fuels involved did meet
some minor the requirements
components (saturatedin the in-force standards.
monoglycerides, The suspicions
sterol glucosides, point out
soaps) present in
towards
the somefraction
biodiesel minor components (saturatedfuels.
of current automotive monoglycerides, sterol glucosides, soaps) present in the
biodiesel fraction
In this work,of current
the automotive
measured properties fuels.
were cloud point—CP (temperature at which some of the
In this work,start
fuel components the measured properties
to crystallize) and cold were cloud
filter point—CP
plugging (temperature
point—CFPP at whichatsome
(temperature whichof the
fuel does
components start to crystallize) and cold filter plugging point—CFPP (temperature
not pass through a filter in a required time, under standardized instrument and operating at which the
fuel does not pass through a filter in a required time, under standardized instrument
conditions). Each sample was replicated three times, and the maximum deviation between replications and operating
conditions).
was 1 ◦ C forEach
CFPPsample
and 0.4was
◦ C replicated
for CP. The three times,
average and the
results aremaximum
presenteddeviation
in Figurebetween
5. replications
was 1 °C for CFPP and 0.4 °C for CP. The average results are presented in Figure 5.
20 20 Biodiesel
HVO
10 BioButanol
Cold Filter Plugging Point (ºC)

10 o.bio

0
Cloud Point (ºC)

0
Biodiesel -10
HVO
-10 BioButanol
o.bio -20
-20
-30
-30 -40

-40 -50
0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100
Biofuel content (%v/v) Biofuel content (%v/v)

Figure 5.
Figure Cloud point
5. Cloud point (left)
(left) and
and Cold
Cold filter
filter plugging
plugging point
point (right)
(right) of
of fuels
fuels and
and blends.
blends.

Both
Both properties
properties evolved
evolved quite
quite similarly,
similarly, andand the
the values
values were
were very
very close.
close. Biobutanol
Biobutanol was was not
not
measured as its CP and CFPP values, around −90 ◦ C (the freezing point of n-butanol), are outside
measured as its CP and CFPP values, around −90 °C (the freezing point of n-butanol), are outside the
the instrument range. ® were better than for biodiesel, this being
instrument range. The The CP/CFPP
CP/CFPP values
values for for o.biowere
o.bio® better than for biodiesel, this being a
aconsequence
consequenceofofthe theacetal
acetalcontent
contentinino.bio®, ®
o.bio ,which
whichacts
actsasas aa cold
cold flow
flow improver. Moreover, neat
improver. Moreover, neat
biodiesel is out of the POFF specification in EN 14214 (−10 ◦ C in winter and 0 ◦ C in summer, in Spain),
biodiesel is out of the POFF specification in EN 14214 (−10 °C in winter and 0 °C in summer, in Spain),
which
which should
should be be corrected
corrected by by increasing
increasing the the flow
flow improvers
improversdose.dose.
Despite the low freezing point of n-butanol,
Despite the low freezing point of n-butanol, blends blends up toup20%tobiobutanol content content
20% biobutanol did not decrease
did not
the diesel CP/CFPP values, which indicates that, for diesel/biobutanol blends,
decrease the diesel CP/CFPP values, which indicates that, for diesel/biobutanol blends, the cold flowthe cold flow properties
are exclusively
properties determined by
are exclusively the diesel by
determined fraction. Diesel/HVO
the diesel fraction.blends behaved
Diesel/HVO linearly,
blends being the
behaved HVO
linearly,
properties better than those of diesel fuel. In the case of neat HVO, the difference
being the HVO properties better than those of diesel fuel. In the case of neat HVO, the difference between CP and
CFPP
betweenis larger
CP and than for the
CFPP other than
is larger fuels.for
Larger differences
the other between
fuels. Larger CP and CFPP
differences are typical
between CP and in CFPP
fuels that
are
have been largely additivated with flow improvers, since these additives are not
typical in fuels that have been largely additivated with flow improvers, since these additives are not effective in depleting
CP as they
effective in are in CFPP.
depleting CP as they are in CFPP.
The ® blends in diesel did not change linearly, and the
The cold flowproperties
cold flow propertiesofofbiodiesel
biodieseland ando.bio
o.bio® blends in diesel did not change linearly, and
values exhibited
the values exhibitedby the
by blends resulted
the blends worse
resulted thanthan
worse expected
expectedif the
if tendency
the tendencyhadhad
beenbeenlinear. In the
linear. In
case of biodiesel/diesel blends, blends up to 20% biodiesel content meet the
the case of biodiesel/diesel blends, blends up to 20% biodiesel content meet the specification for specification for winter,
winter, POFF lower than −10 °C (comparatively, if the CFPP of these blends had evolved linearly with
the biodiesel content, up to 35% biodiesel would have been admissible).

4.6. Cetane Number

Cetane number evaluates the autoignition quality of diesel fuel. The higher the cetane number,
Energies 2019, 12, 2034 9 of 13

POFF lower than −10 ◦ C (comparatively, if the CFPP of these blends had evolved linearly with the
biodiesel content, up to 35% biodiesel would have been admissible).

4.6. Cetane Number

Cetane number evaluates the autoignition quality of diesel fuel. The higher the cetane number,
the shorter the ignition delay time of the fuel (defined as the elapsed time between the fuel injection and
theEnergies
start of the
2019, 12,fuel
x FORcombustion)
PEER REVIEWwhen injected into the combustion chamber. Historically, high cetane
9 of 13
numbers are preferred to improve cold startability and reduce combustion noise (also emissions have
pressures,
been reported downsized
to depend engines
on cetaneand number
multi-injection strategies
[24]), but the usehave made
of high cetane number
injection lessdownsized
pressures, critical.
Even in new combustion modes and dual fuel concepts, a lower cetane number
engines and multi-injection strategies have made cetane number less critical. Even in new combustion could be beneficial
[33]. Nevertheless,
modes and dual fuelfuel standards
concepts, in Europe
a lower cetanesetnumber
a minimumcouldvalue of 51 (diesel,
be beneficial [33]. biodiesel) and 70
Nevertheless, fuel
(paraffinic fuels).
standards in Europe set a minimum value of 51 (diesel, biodiesel) and 70 (paraffinic fuels).
Each sample was measured once, but the given value is the average of 15 fuel injection events in
Each sample was measured once, but the given value is the average of 15 fuel injection events
the measuring instrument. Diesel fuel was replicated twice, and the deviation was less than 0.5 units.
in the measuring instrument. Diesel fuel was replicated twice, and the deviation was less than
The results, presented in Figure 6, show that HVO fuel has a very high cetane number as usual in
0.5 units. The results, presented in Figure 6, show that HVO fuel has a very high cetane number
paraffinic fuels, while neat biobutanol has an extremely low value (pure alcohols are more
as usual in paraffinic fuels, while neat biobutanol has an extremely low value (pure alcohols are
appropriate for spark ignition than for compression ignition engines). For diesel automotive
more appropriate
applications, for spark ignition
biobutanol/diesel blends than for compression
should be limited atignition engines).content
10% biobutanol For diesel automotive
to maintain a
applications, biobutanol/diesel blends should be limited at 10% biobutanol content
cetane number higher than 51. Sometimes the addition of biodiesel to alcohol-diesel blends has been to maintain a cetane
number
exploredhigher than 51. Sometimes
to compensate for the lowthe addition
cetane of biodiesel
number to alcohol-diesel
of alcohols [34]. blends has been explored
to compensate for the low cetane number of alcohols [34].
The cetane number of the o.bio® fuel was close to that of diesel, therefore all blends tested
The cetane number ® fuel was close to that of diesel, therefore all blends tested
displayed similar values ofas the
well.o.bio
In the case of the biodiesel fuel, the cetane number was higher than
displayed similar
that of diesel fuelvalues as well.
on account Inhigh
of its the case of theester
saturated biodiesel fuel,
content. the cetane
Cetane numbernumber was
does not higherthe
impede than
that
useofofdiesel fuel on account
o.bio®/diesel of its high saturated
and biodiesel/diesel blends atester content. Cetane
any concentration, numberhigh
although doesconcentrations
not impede the
usemay not ®fulfill
of o.bio /dieselthe
andcetane number limit
biodiesel/diesel if other
blends at anymore unsaturated
concentration, sourceshigh
although are concentrations
used for biofuel may
notproduction.
fulfill the cetane number limit if other more unsaturated sources are used for biofuel production.
90

80
Derived Cetane Number

70

60

50

40 Biodiesel
HVO
30 BioButanol

20 o.bio

10
0 10 20 30 40 50 60 70 80 90 100
Biofuel content (%v/v)
Figure 6. Derived cetane number of fuels and blends.
Figure 6. Derived cetane number of fuels and blends.
4.7. Water Content
4.7.The
Water Content
water content of a fuel is an important property to be controlled since a high presence of
water could lead content
The water to corrosion issues,
of a fuel is anmicrobial
important growth andtodecrease
property fuel lubricity.
be controlled To prevent
since a high presencethese,
of
European Standards EN 590 and EN 15940 limit the water content under 200 mg/kg.
water could lead to corrosion issues, microbial growth and decrease fuel lubricity. To prevent these,
Figure 7Standards
European shows the ENwater
590 and content of the
EN 15940 samples
limit tested
the water in this
content work.
under All the fuels and blends
200 mg/kg.
were measured three times
Figure 7 shows and content
the water deviation never
of the exceed
samples 20 mg/kg
tested in thisbetween
work. Allreplications.
the fuels andNeat diesel
blends
and HVO showed water contents below 50 mg/kg. Both fuels meet their respective
were measured three times and deviation never exceed 20 mg/kg between replications. Neat diesel quality standards,
andandtherefore
HVO showedall HVO/diesel blends.
water contents belowBiodiesel
50 mg/kg.presented a higher
Both fuels meet theirwater content
respective than
quality HVO and
standards,
and therefore
diesel, all HVO/diesel
but still below the limit ofblends. Biodiesel
the standard EN presented
14214 (500a higher
mg/kg). water
O.Bio ® fuel than
content HVO similar
presented and
diesel,
values ofbut stillcontent
water below the
thanlimit of the standard
biodiesel, EN 14214
which proves the(500 mg/kg).
higher O.Bio® fuel presented
hygroscopicity similar
of esters compared
to values of water content than biodiesel, which proves the higher hygroscopicity of esters compared to
hydrocarbons.
hydrocarbons.
 Energies 2019, 12, 2034 10 of 13
Energies 2019, 12, x FOR PEER REVIEW 10 of 13

400

350 Biodiesel
HVO

Water Content (mg/kg)

300 BioButanol
o.bio
250

200

150

100

50

0
0 10 20 30 40 50 60 70 80 90 100
Biofuel Content (%v/v)

Watercontent
Figure7.7.Water
Figure content of
of fuels
fuels and
andblends.
blends.

5. Conclusions
5. Conclusions
The work presented measured the main fuel properties of four selected advanced biofuels and
The work presented measured the main fuel properties of four selected advanced biofuels and
their blends with a fossil diesel fuel. Analyzing the properties and comparing the values with the
their blends
limits with in
imposed a the
fossil diesel fuel.
involved Analyzing
fuel quality the properties
standards, and comparing
the feasibility of some blends the values with the
at low biofuel
limits imposed
content has beenin the involved
proved. Biofuelfuel quality standards,
properties, along with the
otherfeasibility of some blends
features (sustainability, at low biofuel
greenhouse gas
content has been proved. Biofuel properties, along with other features (sustainability,
balance, economic prospective), must be considered when selecting the most adequate biofuels and greenhouse gas
balance,
blendingeconomic
ratios toprospective),
be accepted by must be considered
all stakeholders when selecting the most adequate biofuels and
involved.
blending In the case of HVO, waste acid-derived biodiesel and o.bio® (a blend of fatty acid methyl esters
ratios to be accepted by all stakeholders involved.
andInfatty
the case
acid of HVO,formal
glycerol wastemethyl
acid-derived
esters),biodiesel
blends upand o.bio®
to 20% (a blend
content of fatty
in biofuel haveacid
beenmethyl esters
suggested
and fatty acid glycerol formal methyl esters), blends up to 20% content in biofuel
here. For HVO blends, higher blending ratios could provoke a lubricity loss if the HVO was not have been suggested
here. For HVO
additivated withblends, higher
lubricity blending
enhancers. For ratios could provoke
the ester-based biofuels,ahigher
lubricity loss ifratios
blending the HVO was not
could derive
additivated
in poor cold with
flowlubricity enhancers.
properties For the
and density andester-based biofuels,
heating values higher blending
too different from those ratios couldwhen
assumed derive
calibrating
in poor the cartography
cold flow properties of thedensity
and engine.andBiobutanol
heatingblends
valuesmust be furtherfrom
too different restricted
thosetoassumed
10% butanol
when
content to avoid excessive water content and very low cetane number and heating
calibrating the cartography of the engine. Biobutanol blends must be further restricted to 10% butanol value.
contentThough
to avoidnot evaluated
excessive here,content
water the results
andfound
very anticipate
low cetanethe potential
number andof heating
ternary blends
value. prepared
with diesel not
Though andevaluated
two of the here,
biofuels
thehere explored.
results The effect of
found anticipate theone biofuel in
potential of one particular
ternary blendsproperty
prepared
with diesel and two of the biofuels here explored. The effect of one biofuel in one particularwith
can be compensated with the reverse effect of other biofuels, resulting in a neutral blend the
property
cansame property value
be compensated withthanthethat of theeffect
reverse reference diesel
of other fuel. This
biofuels, wouldinbea the
resulting case blend
neutral of density
withofthe
diesel/biodiesel/HVO blends, which could be produced in a single plant and whose composition could
same property value than that of the reference diesel fuel. This would be the case of density of
be selected to have, in the final blend, the same density as the diesel fuel used for blending.
diesel/biodiesel/HVO blends, which could be produced in a single plant and whose composition
could be selected
Author to have,
Contributions: in the final blend,
Conceptualization, J.J.H. the
andsame
J.R.-F.;density as theJ.R.-F.;
methodology, dieselvalidation,
fuel usedA.C.-A.,
for blending.
Á.R. and
J.B.; formal analysis, Á.R.; investigation, A.C.-A.; data curation, J.B.; writing—original draft preparation, A.C.-A.,
Author Contributions:
Á.R. and Conceptualization,
J.B.; writing—review and editing,J.J.H. and
J.R.-F.; J.R.-F.; methodology,
supervision, J.R.-F.;
J.J.H.; funding validation,
acquisition, J.J.H. A.C.-A., Á.R. and
and J.R.-F.
J.B.; formal analysis, Á.R.; investigation, A.C.-A.; data curation, J.B.; writing—original draft preparation, A.C.-
Funding: The Spanish Ministry of Economy, Industry and Competitiveness is also acknowledged for financing
A.,the
Á.R. and J.B.;
research writing—review
project and editing,
ENE2016-79641-R and forJ.R.-F.; supervision,
and for funding A.J.J.H.;
Calle funding
through acquisition, J.J.H.grant
the pre-doctoral and J.R.-F.
with
reference BES-2017-079668.
Funding: The Spanish Ministry of Economy, Industry and Competitiveness is also acknowledged for financing
theAcknowledgments: Repsol, NESTE, Masol
research project ENE2016-79641-R and forIberia
and Biofuel, Green
for funding A.Biologics and Inkemia-IUCT
Calle through are gratefully
the pre-doctoral grant with
acknowledged for supplying the fuels tested in this work.
reference BES-2017-079668.
Conflicts of Interest: The authors declare no conflict of interest.
Acknowledgments: Repsol, NESTE, Masol Iberia Biofuel, Green Biologics and Inkemia-IUCT are gratefully
acknowledged forValues
Appendix A. supplying theProperties
of the fuels testedMeasured
in this work.
in This Work and by the Suppliers
Conflicts
Theof values
Interest:ofThe
all authors declare
properties hereno conflict of
analyzed interest.
are collected in Table A1, together with some other
properties of the diesel fuel that were not measured in this work (but the values were measured
Appendix A. Values of the Properties Measured in This Work and by the Suppliers
by the supplier).
The values of all properties here analyzed are collected in Table A1, together with some other
properties of the diesel fuel that were not measured in this work (but the values were measured by
the supplier).
Energies 2019, 12, 2034 11 of 13

Table A1. Values of the properties measured in this work and by the suppliers.

Biodiesel HVO BioButanol o.bio

Properties Diesel
5 10 15 20 30 50 100 5 10 15 20 30 50 100 5 10 15 20 100 5 10 15 20 100
Density at 15 ◦ C (kg/m3 ) 829 831 833 837 840 845 853 876 828 825 823 821 815 805 780 829 827 826 826 813 833 836 839 843 907
Kinematic viscosity at
2.92 2.68 2.82 2.87 3.00 3.14 3.42 5.08 2.65 2.71 2.64 2.72 2.83 2.86 3.21 2.56 2.43 2.34 2.34 2.48 2.90 2.92 2.95 3.01 6.07
40 ◦ C (cSt)
Lower Heating Value
43.0 42.6 42.4 42.1 41.8 41.1 39.9 36.9 43.1 43.2 43.2 43.2 43.4 43.6 44.3 42.3 42.0 41.4 40.7 32.7 42.5 42.2 41.8 41.2 35.0
(MJ/kg)
Lubricity (µm) 330 315 286 196 195 213 194 186 372 396 408 424 454 467 416 386 372 381 409 568 278 194 191 189 183
Cloud Point (◦ C) −22.1 −16.6 −12.4 −9.7 −6.8 −1.9 4.6 13.1 −23.0 −23.3 −24.2 −25.4 −26.1 −26.7 −32.5 −22.4 −22.8 −22.8 −22.5 −128.6 −19.4 −17.0 −14.4 −12.9 3.5
Cold filter plugging point
−24 −22 −17 −13 −9 −5 2 12 −24 −26 −27 −28 −31 −32 −44 −24 −24 −24 −25 - −20 −19 −17 −16 2
(◦ C)
Derived cetane number 58.29 60.47 61.75 62.56 62.47 63.77 64.81 66.94 62.53 63.36 64.33 63.95 68.27 71.60 80.06 54.81 51.36 49.62 47.14 15.92 58.27 58.50 57.33 56.98 54.83
Water content (mg/kg) 24 68 94 100 110 136 184 276 26 28 29 30 31 35 40 106 171 242 344 1582 37 53 71 93 307
T10 (◦ C) 229.5 - - - - - - - - - - - - - 262.4 - - - - - - - - -
T50 (◦ C) 261.5 - - - - - - - - - - - - - 278.9 - - - - - - - - -
T95 (◦ C) 304.0 - - - - - - - - - - - - - 296.1 - - - - - - - - -
Sulfur (mg/kg) 7 - - - - - - <5 - - - - - - <1 - - - - - - - - -
Energies 2019, 12, 2034 12 of 13

References
1. García-Olivares, A.; Solé, J.; Osychenko, O. Transportation in a 100% renewable energy system.
Energy Conversion and Management 2018, 158, 266–285. [CrossRef]
2. Chen, W.-H.; Lee, K.T.; Ong, H.C. Biofuel and Bioenergy Technology. Energies 2019, 12, 290. [CrossRef]
3. De Oliveira, J.J., Jr.; Mendes de Farias, A.C.; Martins Alves, S. Evaluation of the biodiesel fuels lubricity using
vibration signals and multiresolution analysis. Tribol. Int. 2017, 109, 104–113. [CrossRef]
4. European Parliament. Directive (EU) 2018/2001 of the European Parliament and of the Council of
11 December 2018 on the Promotion of the Use of Energy from Renewable Sources. 2018. Available online:
https://eur-lex.europa.eu/legal-content/EN/TXT/?uri=uriserv:OJ.L_.2018.328.01.0082.01.ENG (accessed on 27
May 2019).
5. Transport and Environment. Biodiesel Increasing EU Transport Emissions by 4% Instead of Cutting CO2 .
2016. Available online: https://www.transportenvironment.org/news/biodiesel-increasing-eu-transport-
emissions-4-instead-cutting-co2 (accessed on 27 May 2019).
6. Supardan, M.D.; Satriana, S. Esterification of Free Fatty Acid in Crude Palm Oil Off Grade. Rekayasa Kimia
Lingkung. 2009, 7, 70–74.
7. Deng, Y.; Hu, X.; Cheng, L.; Wang, H.; Duan, L.; Qiu, R. Zirconocene-catalysed biodiesel synthesis from
vegetable oil with high free fatty acid contents. J. Organometall. Chem. 2018, 870, 116–120. [CrossRef]
8. Somnuk, K.; Soysuwan, N.; Prateepchaikul, G. Continuous process for biodiesel production from palm fatty
acid distillate (PFAD) using helical static mixers as reactors. Renew. Energy 2019, 131, 100–110. [CrossRef]
9. Lapuerta, M.; Rodríguez-Fernández, J.; Estevez, C.; Bayarri, N. Properties of fatty acid glycerol formal ester
(FAGE) for use as a component in blends for diesel engines. Biomass Bioenergy 2015, 76, 130–140. [CrossRef]
10. Lapuerta, M.; Rodríguez-Fernández, J.; García-Contreras, R. Effect of a glycerol-derived advanced
biofuel—FAGE (fatty acid formal glycerol ester)—on the emissions of a diesel engine tested under the New
European Driving Cycle. Energy 2015, 93, 568–579. [CrossRef]
11. Alan, C.H.; Qin, Z.; Peter, W.L.L. Ethanol–diesel fuel blends—-A review. Bioresour. Technol. 2005, 96, 277–285.
12. Boretti, A. Advantages of converting diesel engines to run as dual fuel ethanol-Diesel. Appl. Therm. Eng.
2012, 47, 1–9. [CrossRef]
13. Lapuerta, M.; Armas, O.; Herreros, J.M. Emissions from a diesel-bioethanol blend in an automotive diesel
engine. Fuel 2008, 87, 25–31. [CrossRef]
14. Lapuerta, M.; Armas, O.; García-Contreras, R. Effect of ethanol on blending stability and diesel engine
emissions. Energy Fuels 2009, 23, 4343–4354. [CrossRef]
15. Lapuerta, M.; García-Contreras, R.; Campos-Fernández, J.; Dorado, M.P. Stability, Lubricity, Viscosity,
and Cold-Flow Properties of Alcohol-Diesel Blends. Energy Fuels 2010, 24, 4497–4502. [CrossRef]
16. Van Haveren, J.; Scott, E.L.; Sanders, J. Bulk chemicals from biomass. Biofuels Bioprod. Biorefin. 2008, 2, 41–57.
[CrossRef]
17. Pereira, L.G.; Chagas, M.F.; Dias, M.O.S.; Cavalett, O.; Bonomi, A. Life cycle assessment of butanol production
in sugarcane biorefineries in Brazil. J. Clean. Prod. 2015, 96, 557–568. [CrossRef]
18. Green, E.M. Fermentative production of butanol-the industrial perspective. Curr. Opin. Biotechnol. 2011, 22,
337–343. [CrossRef]
19. Grisales, V.; Olivar, G. Butanol production from lignocellulose by simultaneous fermentation, saccharification
and pervaporation or vacuum evaporation. Bioresour. Technol. 2016, 218, 174–182.
20. Hassaneen, A.; Munack, A.; Ruschel, Y.; Schroeder, O.; Krahl, J. Fuel economy and emission characteristics of
Gas-to-Liquid (GTL) and Rapeseed Methyl Ester (RME) as alternative fuels for diesel engines. Fuel 2012, 97,
125–130. [CrossRef]
21. Lapuerta, M.; Rodríguez-Fernández, J.; Agudelo, J.R.; Boehman, A. Blending scenarios for soybean oil
derived biofuels with conventional diesel. Biomass Bioenergy 2013, 49, 74–85. [CrossRef]
22. Torres-Ortega, C.E.; Gong, J.; You, F.; Rong, B. Optimal synthesis of integrated process for coproduction of
biodiesel and hydrotreated vegetable oil (HVO) diesel from hybrid oil feedstocks. In Proceedings of the
27th European Symposium on Computer Aided Process Engineering, Barcelona, Spain, 1–5 October 2017;
pp. 673–678.
23. Labeckas, G.; Slavinskas, S.; Kanapkiene, I. Study of the Effects of Biofuel-Oxygen of Various Origins on
a CRDI Diesel Engine Combustion and Emissions. Energies 2019, 12, 1241. [CrossRef]
Energies 2019, 12, 2034 13 of 13

24. ACEA; Auto Alliance; EMA® ; JAMA. Worldwide Fuel Charter, Fifth Edition ed. 2013. Available online:
http://www.oica.net/wp-content/uploads//WWFC5-2013-Final-single-page-correction2.pdf (accessed on 27
May 2019).
25. Peterson, A.; Lee, P.; Lai, M.; Wu, M.; DiMaggio, C. Impact of Biodiesel Emission Products from a Multi-Cylinder
Direct Injection Diesel Engine on Particulate Filter Performance; SAE Technical Paper 2009-01-1184; SAE
International: Warrendale, PA, USA, 2009.
26. Rodríguez-Fernández, J.; Lapuerta, M.; Sánchez-Valdepeñas, J. Regeneration of diesel particulate filters:
Effect of renewable fuels. Renew. Energy 2017, 104, 30–39. [CrossRef]
27. Cesur, E.; Ayhan, V.; Parlak, A.; Savaş, Ö.; Aydin, Z. The Effects of Different Fuels on Wear between Piston
Ring and Cylinder. Adv. Mech. Eng. 2014, 1–8. [CrossRef]
28. Chong, W.W.F.; Ng, J.H. An atomic-scale approach for biodiesel boundary lubricity characterization.
Int. Biodeterior. Biodegrad. 2016, 113, 34–43. [CrossRef]
29. Sundus, F.; Fazal, M.A.; Masjuki, H.H. Tribology with biodiesel: A study on enhancing biodiesel stability
and its fuel properties. Renew. Sustain. Energy Rev. 2017, 70, 309–412. [CrossRef]
30. Knothe, G.; Steidley, K.R. Kinematic viscosity of biodiesel fuel components and related compounds. Fuel
2005, 84, 1004–1009. [CrossRef]
31. Alves, S.M.; Barros, B.S.; Trajano, M.F.; Ribeiro, K.S.B.; Moura, E. Tribological behavior of vegetable oil-based
lubricants with nanoparticles of oxides in boundary lubrication conditions. Tribol. Int. 2013, 65, 28–36.
[CrossRef]
32. Avitzur, B. Boundary and hydrodynamic lubrication. Wear 1990, 139, 49–76. [CrossRef]
33. Reijnders, J.; Boot, M.; de Goey, P. Impact of aromaticity and cetane number on the soot-NOx trade-off in
conventional and low temperature combustion. Fuel 2016, 186, 24–34. [CrossRef]
34. Al-Esawi, N.; Al Qubeissi, M.; Kolodnytska, R. The Impact of Biodiesel Fuel on Ethanol/Diesel Blends.
Energies 2019, 12, 1804. [CrossRef]

© 2019 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).