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Article history: Current trends in diesel transport anticipate that in the upcoming future a range of renewable fuels will
Received 23 May 2016 be necessary to comply with emission and sustainability legislations. Exhaust after-treatment devices
Received in revised form such as diesel particulate lters eDPFse will have to operate satisfactorily with this pool of biofuels. In
5 October 2016
particular, DPF regeneration is crucial to cut the fuel penalty and guarantee an acceptable lifetime for this
Accepted 30 November 2016
device. In the present work, an automotive diesel engine was run with fossil fuel and three renewable
Available online 30 November 2016
fuels: a conventional biodiesel, a fuel manufactured through Fischer-Tropsch eFTe process and a HVO
biofuel. The DPF was loaded and regenerated through an active process with fuel post-injections.
Keywords:
Renewable diesel fuels
Additionally, soot samples were investigated with thermo-gravimetry (TGA) and calorimetry (DSC) to
Soot properties conrm whether these techniques obtain relevant information for explaining DPF behavior. Both
Particle lter regeneration methods proved that biodiesel leads to a more economical regeneration being the biodiesel soot, more
Diesel engine reactive than the other samples, the main reason. DPF regenerations with parafnic fuels (FT-derived and
Biofuels HVO) did not reveal strong differences compared to diesel, though TGA and DSC results suggested that
soot from parafnic biofuels is more reactive than that from diesel. The exhaust gas temperature and
composition are behind this apparent discrepancy.
2016 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
1. Introduction trapped and removed in a diesel particle lter e DPF [13]. Euro 6
Standard, with a further 55% reduction of NOx with respect to Euro
The increase on the sale and use of diesel vehicles in Europe [1] 5 limits, obliges to depurate this scheme by including a NOx after-
and the effect of their emissions on human health [2,3] and the treatment system [14e17].
environment [4e6] have forced EU institutions to act. On one hand, Different DPF congurations are available [18,19], but wall-ow
transport emission legislation [7,8], recently set tighter limits on type lters are the most widely used. Wall-ow lters are honey-
particulate matter/NOx and will adopt a more demanding driving comb monoliths with parallel channels plugged alternately at each
cycle (WLTP - Worldwide Harmonized Light Vehicles Test Proced- end to force the exhaust gas through the porous lter wall where
ure) and tougher ambient conditions in the future. On the other soot is retained. Therefore, backpressure increases in the exhaust
hand, a broad diesel fuel mix combining fossil fuels, synthetic line penalizing the fuel consumption [20,21], but the high ltering
parafnic diesel and oxygenated biofuels [9,10], is being promoted efciency (about 90%) makes these lters essential for complying
in the transport sector to both tackle the GHG emissions (mainly with emission standards. When the backpressure reaches a
CO2) and increase the renewable energy share up to 10% by 2020 threshold, fuel post-injections are launched to increase the exhaust
[11]. temperature and oxidize the soot collected (lter regeneration)
Under this regulatory framework, manufacturers have intro- [22]. Apart from temperature, other factors such as the exhaust gas
duced advanced injection strategies and efcient aftertreatment (composition, ow rate) and the physicochemical properties of soot
techniques, and they will have to adapt their diesel vehicles to run affect the regeneration process [23e26]. Indeed the properties of
on multiple fuels. A typical approach consists in running with high soot modify its reactivity in a remarkable way [27,28]. The term
EGR ratios [12] to reduce NOx formation at the expense of reactivity is used hereinafter to refer to the soot ability to be
increasing emission of particulate matter, which is afterwards oxidized at higher rates and/or under a lower temperature envi-
ronment, which leads to a more efcient regeneration.
The production routes, properties and performance/emissions
of engines and vehicles fueled with alternative and renewable
* Corresponding author.
ndez).
E-mail address: Jose.RFernandez@uclm.es (J. Rodrguez-Ferna diesel fuels have been broadly studied [9,29e31]. Briey, biodiesel
http://dx.doi.org/10.1016/j.renene.2016.11.059
0960-1481/ 2016 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
ndez et al. / Renewable Energy 104 (2017) 30e39
J. Rodrguez-Ferna 31
(obtained from oils through transesterication reaction) and syn- conrm whether the trends obtained in laboratory match those in
thetic parafnic fuels (hydrogenation of bio oils and Fischer- the DPF. The information obtained is relevant to improve the per-
Tropsch process are typical routes) lead to similar engine ef- formance of modern after-treatment systems under new biofuels.
ciency, fuel economy that scales inversely with the heating value
and a benet in pollutant emissions, though the effect of biodiesel
on NOx is controversial and depends markedly on its composition. 2. Experimental setup
However, the effect of these future fuels on the performance of
advanced after-treatment technologies such as DPFs is a recent Engine tests were carried out in a 4-cylinder, 4-stroke, turbo-
issue that will raise the concern of manufacturers. charged, intercooled, common-rail, 2.0 L Nissan diesel engine
One research line involves the study of the soot oxidation pro- (model M1D), fullling Euro 5 Standard. Ambient temperature was
cess and its effect on lter regenerations. Some works characterized xed at 21e23 C. The engine is equipped with cooled exhaust gas
commercial soot surrogates [32,33], but this approach is invalid recirculation (EGR), and its temperature was externally controlled.
when the effect of fuel on soot reactivity is to be assessed. Others As after-treatment devices, a diesel oxidation catalyst eDOCe and a
used analytical techniques (TEM [26,34e37], XRD [26,36,38e40] or regenerative wall-ow type diesel particulate lter eDPFe (see
Raman spectroscopy [26,39,41e44]) to study real soot generated lter characteristics in Table 1) are tted in the engine exhaust
running engines with different fuels. Generally, the fuel used system. The main specications of the engine are given in Table 2.
modies the characteristics (structure, primary particle size, The engine was coupled to an asynchronous electric brake Schenck
graphitization) of soot generated [26,28,45]. This may affect the Dynas III LI250, equipped with speed and torque sensors that allow
soot reactivity and therefore oxidation rate in the DPF. As a rule, a measuring and controlling the engine speed and effective torque,
more disordered soot nanostructure presents more distance be- respectively. The INCA PC software and the ETAS ES 591.1 were used
tween graphene layers and a higher number of active sites where for the communication and management of the electronic control
oxidants, such as O2 or NO2, can be adsorbed initiating the soot unit (ECU). This allows dening the injection process (timing,
oxidation [27,39]. The presence of oxygenated moieties on the soot pressure, strategy) as well as measuring and recording temperature
surface [26] affect the soot reactivity as well, as the oxygen con- and pressure in different locations of the engine (temperature
tained in these groups may participate in the carbon oxidation upstream of the turbine, temperature and pressure upstream and
reactions. A higher concentration of oxygenated groups has been downstream of the DPF, oil temperature and ambient pressure,
reported for biodiesel soot, which may be behind its higher reac- among others).
tivity (compared to fossil diesel soot) [24,26,27]. NOx emissions were measured using a chemiluminescence
Temperature-programmed oxidation and thermal analysis Topaze 32 M analyzer able to distinguish between NO and NO2.
techniques [24,26,28,39,46], mainly TGA and DSC, under oxidant Furthermore, oxygen concentration was determined with a non-
atmospheres have been used to directly evaluate soot reactivity in dispersive infrared analyzer MIR2M. Particulate matter (PM) was
laboratory, but without a validation in a diesel DPF. Finally, few collected using a partial-ow dilution micro tunnel (Horiba DLS
researchers have carried out engine tests to evaluate soot reactivity 2300). This equipment sucks a portion of the exhaust gas through a
through the DPF pressure drop trace during regeneration, once the heated probe into the tunnel where it is diluted with ltered
DPF was previously loaded with soot [24,26,47]. Some authors ambient air, as required by emission directives, at a dilution ratio of
[24,48], showed that biodiesel or alternative fuels enhanced the 10:1. Particulate matter is then collected on Whatman GF/F glass
regeneration process, while others [25,26,47] concluded that bio- microber lters (47 mm diameter, 0.7 mm pore side). To obtain the
diesel did not improve the regeneration process because engine
calibration (ECU) was not adapted for fuels other than conventional Table 1
diesel. DPF characteristics.
In the present work, a Euro 5 diesel engine tted with a DPF has
Material Silicon Carbide (SiC)
been used to carry out load and regeneration processes in the lter Dimensions Width (190 mm)/Length (240 mm)
with four different fuels, including three renewable fuels. Tem- Conguration 16/200
perature and pressure drop in the lter were monitored to evaluate Catalyst Coated with Pt (0.0032 g/cm3)
soot reactivity. Furthermore, soot samples collected during the Volume 4.1 L
Channel width 1.39 mm
loading process were analyzed in laboratory with TGA and DSC to
Specic ltering surface 758.91 m2/m3
32 ndez et al. / Renewable Energy 104 (2017) 30e39
J. Rodrguez-Ferna
Table 3
Measuring equipment characteristics.
STAINLESS
STEEL STRUCTURE EXHAUST
GASES
DOC
INTAKE
AIR FILTER DIESEL
INTAKE PARTICULATE FILTER
HOT WIRE
AIR SENSOR
TOPAZE32M
Intake Air Temperature Co ntrol
MIR2M
Fuel
tank
INTAKE AIR
INTERCOOLER EGR
Temp erature Control MICRO TUNNEL SMPS
HORIBA DLS 2300 TSI 3936 L10
EG R CO O L ER
ASYNCHRONOUS BRAKE
(SCHENCK DYNAS LI 250)
COMUNICATION ELECTRONIC
CONTROL AND HARDWARE CONTROL UNIT (ECU)
ACQUISITIOMSYSTEM
(INCAPC) ETASES591.1
Table 5
Fuel properties.
Properties Diesel HVO GTL Biodiesel UNE EN 590 UNE EN 15940 UNE EN 14214
5. Results and discussion lower temperatures. The observed consistency between TGA and
DSC is expected since both share the same working principle and
5.1. Soot analysis results the samples were tested under equal temperature-atmosphere
programs. The minor differences in the temperature values from
An example of thermograms directly obtained in the TGA and TGA and DSC are understandable since the furnace conguration
DSC is shown in Fig. 3 a) and b), respectively. The shape of the (which affect the thermal inertia) and the thermocouple location
curves for all fuels is rather similar, though the fuel affects the curve are different in both instruments.
location on the temperature axis and therefore the soot oxidative Soot generated from diesel fuel is the least reactive sample
reactivity (the higher the temperature, the lower the oxidative (higher temperature indicates lower reactivity). The presence of
reactivity). As detailed in Ref. [46], several characteristic tempera- aromatic compounds in diesel fuel, well known as soot precursors
tures can be dened from the thermograms to determine the effect [50], may lead to a higher number of soot nuclei formed in the
of the fuel. One of these is the temperature for the maximum of the combustion chamber that, by coalescent coagulation [51], may
trace, denoted as MLRTmax (temperature for the maximum mass form larger primary particles. Previous publications show larger
loss rate) in the case of TGA or HRRTmax (temperature for the primary particle and agglomerate diameter in the case of soot from
maximum heat release rate) in the case of DSC, as presented in diesel fuels [26,27]. Larger particles and higher fractal dimensions
Ref. [28]. possess lower specic surface area, which may be responsible for a
Fig. 4 represents the MLRTmax and HRRTmax for the soot lower reactivity. In addition, the lower porosity of diesel soot [28]
generated with all fuels tested. As can be seen, the same trend is hinders the accessibility of oxygen to active sites, therefore
observed from mass loss rate and heat release: parafnic fuels and, reducing the oxidative reactivity. Biodiesel fuel generated the most
especially, oxygenated biodiesel, shift the soot oxidation towards reactive soot. Again, this may be explained by the lowest primary
Fig. 3. Typical soot oxidation thermograms in TGA (a) and DSC (b).
ndez et al. / Renewable Energy 104 (2017) 30e39
J. Rodrguez-Ferna 35
X
n
m fi $Vi $ri (1)
i1
X
n
A fi $Ai (2)
i1
Fig. 5. Particle size distributions (a) and specic surface area (b).
36 ndez et al. / Renewable Energy 104 (2017) 30e39
J. Rodrguez-Ferna
Fig. 6. a) DPF pressure drop during the loading process. b) nal DPF pressure drop and DPF temperature (a high emission variation of the operation mode was used for biodiesel and
parafnic fuels, as detailed in the text).
progress, since the exhaust gas composition and the particulate facilitated to reach the equilibrium between particle generation
emissions (which depend greatly on the fuel tested) also play a role. and oxidation in the DPF (i.e. to reach its BET temperature).
For example, both NO2 and O2 participate as oxidants during the Oppositely, the highest particulate emission with diesel fuel (much
oxidation process. NO generated can react with O2 generating NO2 higher than that of the rest of fuels) explains that diesel fuel was not
by a reversible reaction that takes place on catalytic sites in the DPF able to reach its BET during the whole loading process.
wall [54]. The reactivity of NO2 towards soot is much higher at low As commented above, BET is reached for parafnic and biodiesel
temperatures (150e350 C) [55] than that of O2, and some authors fuels and this is the reason why the pressure drop across the DPF
have studied the activation energy when soot reacts with different reaches a steady value, as shown in Fig. 6 a). To achieve a pressure
oxidants obtaining that this energy is lower with NO2 than with O2 drop across the DPF high enough to start an active regeneration
[56]. The oxidation pathway is different as well (the reaction be- process (about 80 hPa), U9 mode had to be modied to a higher
tween NO2 and soot generates NO, CO2, CO, N2 and N2O [57]). Also emission condition (increasing EGR ratio) during the loading test
NO could participate signicantly in soot oxidation reactions, but when running with biodiesel and parafnic fuels. Temperature and
only at temperature above 600 C [54]. Hence, the highest NOx backpressure across the DPF at the end of the modied loading
emissions for the biodiesel fuel, represented in Fig. 7, may be process are shown in Fig. 6 b). Starting the regeneration tests with a
responsible for enhancing the biodiesel soot oxidation. In addition, similar backpressure allows reducing the uncertainties when
the lowest particulate emissions for the biodiesel fuel (Fig. 8) determining the effect of the fuel on the subsequent regeneration
Fig. 7. NOx emissions during the loading test. Fig. 8. Particulate emissions during the loading test.
ndez et al. / Renewable Energy 104 (2017) 30e39
J. Rodrguez-Ferna 37
process.
The regeneration process in the REU8 mode is presented in
Fig. 9, with an enlarged window focused on the detail of diesel and
parafnic fuel traces. It can be observed that soot generated from
diesel fuel takes more time to regenerate than those of the other
fuels (longer regeneration processes is an indication of lower
reactivity). This result agrees with those obtained with TGA and
DSC. Nevertheless, there is no much difference between fossil
diesel and parafnic fuels, even though the temperature upstream
of the DPF when the engine is running with parafnic fuels is a bit
higher than that with diesel (a higher temperature favors a higher
oxidation rate). The regeneration of soot from parafnic fuels,
slower than expected according to TGA/DSC, can be partially
explained by the lower NOx emissions of these fuels, especially in
the case of HVO (see Fig. 10). As discussed above, as NOx emissions
increase, the regeneration process is enhanced [54]. Additionally,
the higher pressure drop after the loading process for HVO (Fig. 6)
may explain its relatively slow regeneration.
The temperature upstream of the DPF is a decisive variable in a
DPF regeneration. The lowest temperature was reached with the
biodiesel fuel, in accordance with its lowest volumetric heating
Fig. 10. NOx emissions during the regeneration test.
value (see Table 5), since the volume of fuel in the post-injections
was the same for all fuels. For the other three fuels, heating value
and temperature differences were smaller. However, the higher
volumetric heating value of diesel fuel does not explain its lower
upstream DPF temperature. This may be a consequence of the
combustion of the rst post-injection, around 60 CA aTDC
(Table 4), which is more fully burnt inside the combustion chamber
in the case of the parafnic fuels because of their markedly higher
cetane number. Therefore, cylinder exhaust temperature increases
with these fuels and contributes to a higher efciency in the
oxidation catalyst, leading to a higher upstream DPF temperature.
The fastest regeneration process was found for the biodiesel fuel
(Fig. 9), despite its lowest exhaust temperature. Biodiesel regen-
eration was completed in less than 400 s, around half of the time
required for the regeneration with the other fuels. In a previous
work [25,26] in the same installation, the even lower exhaust
temperature reached with biodiesel (around 60 C lower than that
of diesel) slowed down the regeneration process with respect to
that of diesel fuel. Differently, in the present work the temperature
difference between diesel and biodiesel fueling, only 30 C
approximately, was not sufcient for bringing diesel regeneration
closer to that of biodiesel. In addition to the enhanced biodiesel
soot reactivity, the increased biodiesel NOx emissions and, espe-
cially, exhaust O2 concentration (because of its stoichiometry) also
Fig. 11. Oxygen concentration during the regeneration test.
favors a faster regeneration process when biodiesel is used (Fig. 11).
Fig. 9. Effect of the fuel on the pressure drop across the DPF and upstream temperature during the regeneration test.
38 ndez et al. / Renewable Energy 104 (2017) 30e39
J. Rodrguez-Ferna
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