Evaluating A Novel Gasoline Surrogate Containing Isopentane Using A Rapid Compression Machine and An Engine

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ARTICLE IN PRESS [mNS;September 24, 2020;4:12]
Available online at www.sciencedirect.com
Proceedings of the Combustion Institute 000 (2020) 1–11

www.elsevier.com/locate/proci
Evaluating a novel gasoline surrogate containing

isopentane using a rapid compression machine and an
engine
Sandro Gail a,∗, Roger F. Cracknell b, Dáire Corrigan c, Andrea Festa b,
Varun Shankar b, Benoit Poulet a, Guy Lovett a, Rene D. Büttgen d,
Karl A. Heufer d, Roberto Mariconti c, Matteo Cucchi c, Fabio Mortellaro c
a Shell
Global Solutions GmbH, Hohe-Schaar Straße 36, D-21107 Hamburg, Germany
b Shell
Global Solutions (UK), Shell Centre, London SE17NA, United Kingdom
c Ferrari S.p.A., Via Abetone inf. 4; 41053 Maranello, MO, Italy
d Physico-Chemical Fundamentals of Combustion (PCFC), RWTH Aachen University, Schinkelstraße 8, D-52062 Aachen,
Germany
Received 7 November 2019; accepted 7 July 2020
Available online xxx
Abstract
Simple surrogate formulations for gasoline are useful for modelling purposes and for comparing experi-
mental results using a carefully designed fuel. Simple three-component surrogates based on primary reference
fuels (PRF) and Toluene (TPRF) are frequently used to match the antiknock properties of actual gasoline fu-
els through the RON and MON. However, using PRF or TPRFs to test or to calibrate gasoline engines is still
challenging, with the main difficulty being the capabilities of PRF fuels to match the physical properties of
the road fuel such density, volatility (DVPE) and the distillation curve. To overcome such issues, an alternative
to TPRF is presented in this work with a focus on premium fuel (RON98 EN228). This alternative consists
of replacing some or all of isooctane by isopentane. In the event of total replacement, a three-component
“THIP” (Toluene, Heptane, IsoPentane) surrogate fuel is produced. The physical and combustion properties
of isopentane makes it easier to create surrogates that can match the DVPE, RON, MON and distillation
characteristics of a real fuel. Furthermore, the use of isopentane allows the definition of a wider range of
surrogate fuel compositions that can replicate the RON and MON of a given fuel. Surrogate formulations
were developed at Shell Global Solutions that matched the RON, MON and selected physical properties of
a reference premium gasoline (RPG). A Rapid Compression Machine (RCM) in PCFC was used to demon-
strate that those surrogates can reproduce the essential autoignition characteristics of the selected RPG. Two
mechanisms were used to predict RCM data and showed reasonable agreement, opening some perspective
for further investigations. Finally, an engine test performed at Ferrari test facilities demonstrated that simple
surrogates containing isopentane can be used to closely match the knock-limited combustion phasing of an
∗ Corresponding author.
E-mail address: [email protected] (S. Gail).
https://doi.org/10.1016/j.proci.2020.07.103
1540-7489 © 2020 Published by Elsevier Inc. on behalf of The Combustion Institute.
Please cite this article as: S. Gail, R.F. Cracknell, D. Corrigan et al., Evaluating a novel gasoline surrogate containing
isopentane using a rapid compression machine and an engine, Proceedings of the Combustion Institute, https://doi.org/
10.1016/j.proci.2020.07.103
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2 S. Gail, R.F. Cracknell, D. Corrigan et al. / Proceedings of the Combustion Institute xxx (xxxx) xxx
RPG. In this paper, it is demonstrated such surrogates have advantages compared to TPRFs in being able to
match the properties of a real fuel and that the surrogate approach is consistent with RCM data and engine
results.
© 2020 Published by Elsevier Inc. on behalf of The Combustion Institute.
Keywords: Gasoline surrogate; Modelling; Ignition delay time; Engine; Isopentane
Nomenclature GDI Gasoline Direct Injection

TGDI Turbocharged Gasoline Direct Injec-
TPRF Toluene Primary Reference Fuel tion
PRF Primary Reference Fuel DVPE Dry Vapour Pressure Equivalent
PCFC Physico-Chemical Fundamentals of IDT Ignition Delay Time
Combustion - Research group ICE Internal Combustion Engine
RCM Rapid Compression Machine LHV Lower Heating Value
THIP Toluene, n-Heptane, IsoPentane LLNL Lawrence Livermore National Labo-
RON Research Octane Number ratory
MON Motor Octane Number KAUST King Abdullah University of Science
S octane sensitivity = RON-MON and Technology
MFB50 Crank Angle of 50% fuel Mass Frac- IBP Initial Boiling Point
tion Burned FBP Final Boiling Point
ATDCF After Top-Dead-Centre (Firing) E70 Volume of fuel evaporated at 70 °C
MAPO Maximum Amplitude of Pressure Os- RPG Reference premium gasoline
cillation
1. Introduction gate, the Dry Vapour Pressure Equivalent (DVPE)

ranges from 8 to 12 kPa, a value much lower than
Commercially available gasoline is composed of that of a commercially available gasoline. Proper-
hundreds of different hydrocarbon molecules, typ- ties like distillation, density and DVPE, strongly af-
ically ranging in chain length from 2 to 13 car- fect injector spray development, with spray pene-
bon atoms. To support the development of Inter- tration in gasoline direct injection systems (GDI)
nal Combustion Engines (ICEs), the impact of fuel being strongly influenced by the flash boiling be-
composition on performance has been widely stud- haviour of the lighter components [9]. In this work
ied [1]. Simplified surrogate fuels are frequently em- we discuss the advantages of including isopentane
ployed to emulate a certain set of properties of a within simple surrogate fuel formulations and show
real fuel. The best-known example of surrogate fu- that such surrogates can predict the performance
els are binary blends of isooctane and n-heptane of a premium gasoline (RON 98) in both Rapid
typically used to assess the RON and MON of Compression Machine (RCM) experiments and in
given gasoline fuel. These blends are also known a high-performance engine.
as Primary Reference Fuels (PRFs). Additionally,
toluene is frequently added to generate a Toluene
Primary Reference Fuel (TPRF), thereby reproduc- 2. Advantages of incorporating isopentane into
ing the effect of aromatic content and capturing the surrogate fuels
octane sensitivity of real fuels [2,3]. More complex
surrogates, with more components, can be designed When isooctane is completely replaced by
to match more features of the real fuel [4–6]. Al- isopentane in a TPRF a new three-component
ternative methods have been also proposed which surrogate called “THIP” (Toluene, n-Heptane,
focus on the elementary molecular parameters in IsoPentane) is obtained. The premium gasoline
the target fuel [7] or use empirical lumped kinetic surrogate developed for this study contains a small
parameters for modelling features of the oxidation amount of isooctane (1% v/v), hence we have re-
such as thermal and oxidative pyrolysis [8]. TPRF ferred to it as an isopentane-containing surrogate.
surrogates retain their popularity because they al- The presence of isooctane can be explained by the
low the autoignition properties of a gasoline to be original objectives of the study whereby the goal
represented using well-studied components. Due to was to progressively replace isooctane by isopen-
the nature of the components in a TPRF surro- tane until an appropriate surrogate was obtained.
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S. Gail, R.F. Cracknell, D. Corrigan et al. / Proceedings of the Combustion Institute xxx (xxxx) xxx 3
Fig. 1. Ternary plots showing DVPE (Chevron method, [12]) of TPRF and THIP surrogates.
Isooctane has traditionally been used in surrogate Table 1. In addition to the increase in DVPE and
formulations because of its role as a gasoline PRF, decrease in density, an isopentane-containing sur-
around which the octane tests are defined; thus rogate typically requires a lower volume of toluene
isooctane has a RON = MON =100. Isopentane than a TPRF to achieve a given sensitivity; this is
instead has a RON of 93.2, and a MON of 90.8 because isopentane’s own sensitivity is about 3.
[10]. It is therefore a non-zero sensitivity compo- Table 1 shows that an isopentane-containing
nent. This means that a lower amount of toluene surrogate (KM9096) can represent the sensitivity
needs to be included in a surrogate to give a typical of the RPG, whilst better approximating its DVPE
sensitivity of about 10. The reaction mechanism of and density. While THIP-like surrogates can repre-
three pentane isomers have been studied extensively sent the RON and MON of a selected fuel, they are
by Bugler et al. [11] suggesting emerging interest better than TPRFs in respect of all the parameters
around them. The main reason why the authors are listed in Table 1. H/C ratios for PR6918, KM9089
advocating the inclusion of isopentane into simple and KM9096 are 1.89, 1,67 and 1.77 respectively.
surrogates, is to be better able to predict the dis- It is also possible to prioritise accurate hydrogen to
tillation and physical properties of real gasolines. carbon (H/C) ratio or other ratios to generate sur-
Figure 1 illustrates the range of DVPE (according rogates. The extent to which achieving a higher H/C
to Chevron rule [12]) achieved with a THIP ternary ratio compromises other targeted parameters will
blend compared to TPRF. As discussed by van be less for THIP surrogates because isopentane has
Romunde et al. [9], front-end volatility significantly an intrinsically higher H/C ratio than isooctane due
affects evaporation and spray penetration, there- to having fewer carbon atoms.
fore matching the DVPE and front-end distillation The improved volatility predictions of the RPG
is critical to represent combustion in modern direct are shown in Fig. 3. Isopentane-containing surro-
injection gasoline engines. gates can better predict the 0–60% region on the
Another very important property where isopen- distillation curve. By contrast, the distillation of
tane extends the achievable range is the density. TPRF surrogates is dominated by isooctane re-
Figure 2 shows that lower densities are possible sulting in a horizontal-like distillation curve. As
with a THIP surrogates compared to TPRF surro- with TPRF surrogates, isopentane-containing sur-
gates. The surrogate developed for this study is re- rogates or THIP blends do not match the 60–100%
ferred to as “KM9096” and was designed to repli- region of the distillation curve of the RPG.
cate a premium winter grade gasoline with a RON To further investigate the isopentane-containing
of 98 referred to as “RPG or PR6918” in the rest surrogate’s ability to replicate the combustion prop-
of the paper. erties of the RPG it was decided to test both fuels
on the PCFC (Physico-Chemical Fundamentals of
Combustion - Research group) RCM and on an en-
3. Designing the surrogate gine test bench at Ferrari S.p.A.
By using empirical blending laws, it was possible

to design surrogate blends with measured RON and 4. RCM data and chemical kinetics modelling
MON values of 98 and 88 respectively. One surro-
gate with isopentane and one TPRF were generated A detailed description of the PCFC rapid com-
to match the octane numbers of the premium ref- pression machine (RCM) used in this study can be
erence fuel, as confirmed by the measured values in found in reference [13]. The PCFC RCM uses a
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Fig. 2. Ternary plots showing Density at 15 °C of TPRF and THIP surrogates.
Fig. 3. Measured distillation curves for the two surrogate fuels (KM9089, KM9096) and the RPG (PR6918) tested using
the DIN EN ISO 3405 standard method.
single creviced piston configuration, which is argon. To simulate the RCM experiments, the
pneumatically driven and hydraulically stopped non-idealities of the facility need to be measured
and can withstand peak ignition pressures of up and translated into an effective volume-profile.
to 100 MPa. The creviced piston design is used Sung and Curran have described this simulative
to suppress the formation of roll-up vortices and approach in detail [16]. Ignition delay times (IDTs)
ensures a homogenous temperature in the core of were measured using the PCFC RCM facility
the compressed gas [14]. A variable end wall en- described above. The RPG and KM9096 were
ables a continuously adjustable compression ratio measured. A typical experiment and its corre-
varying between ε =9–32. A piezoelectric sensor sponding non-reactive experiment are shown in
(Kistler 6125CU20) measures the pressure during Fig. 4.
the experiment. The compressed temperature (Tc ) To reflect engine relevant conditions, the oxy-
is deduced from the measured pressure assuming gen/diluent ratio was chosen to reproduce the at-
an isentropic compression of the core gas in the mospheric composition of 79% N2 to 21% O2 .
reaction chamber as stated by the adiabatic core The targeted end-of-compression pressure (pc ) was
hypothesis [15]. The variation in Tc can be reached 15 bar and all experiments were conducted for a
by either altering the compression ratio or by stoichiometric (φ = 1) composition. Both fuels re-
altering the diluent composition of nitrogen and vealed very similar reactivity, although KM9096
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60
reactive
non-reactive
45
Pressure [bar]
30
15
-30 -10 10 30 50
Time [ms]
Fig. 4. Typical pressure trace obtained for the RPG in PCFC Rapid Compression Machine at 15 bar and φ = 1.
Fig. 5. IDT (closed symbol) and 1st stage IDT (open symbol) plotted against 1000/T for the isopentane-containing surro-
gate fuel (KM9096) and the RPG tested. 20% error bars on the individual measurements are included for IDT.
exhibited lower reactivity at higher temperature ing the 1st stage ignition delay, it was decided to
compared to the RPG (Fig. 5). test some published chemical kinetic mechanisms
The results from the RCM confirm the ap- against the RCM experimental results. For this in-
propriateness of using isopentane as a key surro- vestigation, two mechanisms were selected based
gate component to improve the representation of on the presence of sub-mechanisms for isopen-
a real fuel’s chemical reactivity. Following good tane, isooctane, toluene and n-heptane. Simula-
agreement between experimental autoignition de- tions were performed using a mechanism pub-
lay time between KM9096 and the RPG, includ- lished in 2016 by Sarathy et al. [17] containing the
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Table 2
Details of test engine.
Isopentane
Engine Type F154FA
3990 cm3
7.47
54.6
Swept Volume
Number of Cylinders 8
0
n-Heptane Toluene Bore 88 mm
Stroke 82 mm
45.31
40.14
9.06 Number of valves 4
Injector Location Central
(%vol)
Fuel Pressure 350 bar

Specific Output 195 CV/l
12.26
4.16
1.6
sub-mechanisms for the components used in this

Isooctane
study. The second mechanism used was the Gaso-

line Surrogate mechanism ver. 1.0 2012-03-30
42.43
3.69
(LLNL-MI-536371) from LLNL [18]. The simu-

1.1
lations were performed with ANSYS CHEMKIN

PRO 12.9 package using the effective volume pro-
0.1
0.1
O
0
0
files. Figure 6 shows the comparison between exper-

imental and simulation results using both mecha-
12.1
12.2
10.5
12.1
H
nisms. Overall, simulation results show significant

discrepancies between the experiments and mod-
6.4
7.3
5.9
6.6
C
elling in both temperature ranges. Both mecha-

nisms are slower than the experimental data at low
and intermediate temperature regions and faster at
Value (MJ/kg)
Low Heating
high temperature.
42.16
42.43
42.77
42.07
5. Engine test results
The isopentane-containing surrogate fuel

(%vol)
(KM9096) and the reference premium gasoline

32.0
52.3
23.9
E70
(RPG - PR6918) were subsequently tested on a

–
Ferrari V8 turbocharged engine. The objective

Fuels composition and measured properties (RON, MON, DVPE, Density).
100.1
was to confirm if the good agreement in terms of

(°C)
22.4
28.0
31.4
IBP
RON, MON and ignition delay time seen between

reference and surrogate fuels translated into a close
MON
agreement in terms of knock limited combustion

87.9
88.4
88.0
86.7
phasing in a modern Turbocharged Gasoline

Direct Injection (TGDI) engine. Some details of
RON
the test engine are shown in Table 2.

98.0
97.7
97.9
98.7
Knock in an internal combustion engine occurs

if a region of unburnt charge, commonly known
DVPE
as the end-gas, auto-ignites before the flame front

(kPa)
87.9
10.9
85.1
57.3
initiated by the spark plug has time to consume it.

The end-gas heating is largely driven by the com-
bustion chamber pressure history as in a rapid com-
15 °C (kg/m³)
pression machine. Part of the end-gas compression

density at
is due to the movement of the engine piston but

738.0
774.3
729.5
754.5
a large part is driven by the flame-front consum-

ing fresh charge and hence releasing heat which re-
sults in a pressure increase across the entire com-
bustion chamber. Whilst the piston-driven pressure
KM9096 - Blend 14
KM9089 - Blend 7
Development fuel
rise is a highly repeatable phenomenon, the rate at

Fuel Description
PR6918 - RPG
which the flame front propagates shows significant

cyclic variability. Evidence for this can be seen com-
paring the variability of cylinder pressure measure-
(C103)
Table 1
ments with respect to engine crank angle during the

compression and combustion phases as is shown in
Fig. 7.
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Fig. 6. IDT curve comparison between experimental (closed symbol) and simulation (open symbol) results using both
KAUST [17] and LLNL [18] reaction mechanisms.
Fig. 7. 100 Consecutive cycles of cylinder pressure data with constant ignition timing. The pressure rise due to combustion
can be seen at around −5 °CA After Top Dead Centre Firing (ATDCF).
Figure 8 shows two consecutive cycles from the the knock propensity for a given ignition timing
same dataset. Cycle 239 exhibits a faster pressure and fuel. Two indices have been be considered in
rise followed by an autoignition event leading to this paper. The first is the 99.5th percentile MAPO
a high frequency oscillation on the pressure trace. value. A common method of calibration is to aim
The cylinder pressure trace was high pass filtered for a 99.5th percentile MAPO of the engine speed
and the amplitude of the pressure oscillation is divided by 1000.
taken as an indication of the severity of the knock A second index was also used in this paper where
of that cycle. This is known as the Maximum Am- the number of cycles with a MAPO value over a
plitude Pressure Oscilation (MAPO) value [19]. Cy- certain threshold is divided by the total number
cle 238 has a value of 1.2 bar whilst that of Cycle of cycles in the dataset. The threshold is based
239 is 14.6 bar. The cyclic variability of knocking on a factor of the median MAPO value. The me-
in an engine means that statistical values are nor- dian is a useful method of characterizing the base
mally constructed using a population of some hun- “noise” level of non-knocking cycles in the dataset.
dreds of cycles in order to adequately characterise As knock is statistically rare, the median value is
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Fig. 8. Example of consecutive cycles, the second of which is knocking.
Fig. 9. MAPO Values from 500 Consecutive Cycles and Median Based Threshold.
highly unlikely to be knocking. A comparison of combustion phasing differences for the different fu-
this threshold with the cyclic data is shown in Fig. 9. els using two different indices and at two different
Cycles above the threshold were considered to be levels of severity, hence increasing robustness in in-
knocking. The factor of the median which is used terpretation of the results.
to set the threshold is a tuning factor in the calcu- The engine was run at 3000 rpm and with an
lation to give adequate noise robustness and hence absolute inlet manifold pressure of 2 bar. Ignition
to avoid false positives. A desired percentage of timing sweeps were performed keeping all other
knocking cycles can be targeted through adjusting boundary conditions (air temperature, water tem-
the ignition timing. This is referred to as “Knock perature, oil temperature etc.) constant.
Frequency”. The target chosen in this test was de- The tests of the RPG and KM9096 were brack-
liberately more severe in terms of likely engine eted by a development fuel “C103” (Table 1) which
damage than that of the 99.5th percentile MAPO was available in larger quantities. This fuel had
target. This was in order to obtain knock-limited a higher RON value than that of the reference
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Fig. 10. Combustion Phasing Sweeps on C103, RPG and KM9096.
Fig. 11. Comparison of Knock Limited Combustion Phasing of C103, RPG and Surrogate Blend KM9096. Error bars
are based on the C103 Bracketing Fuel Test.
premium grade or the surrogates. The testing or- found to be advantageous in modern TGDI engines
der was: C103, RPG, C103, KM9096, C103. The [20]).
results over the entire combustion phasing sweeps A precise value of combustion phasing must be
are shown in Fig. 10 Considering firstly the C103 chosen during engine calibration defined by the tar-
results, it can be seen that the repeatability in terms get knock limit. Figure 11 shows average knock
of the knocking response for a given combustion limited combustion phasing values for the C103
phasing is of the order of 0.5 °CA. C103 clearly tests based on the two indices and thresholds dis-
permits a more advanced combustion phasing for cussed. Error bars were defined using the repeata-
a given level of knock in comparison to the other bility of the C103 knock limit over the three tests at
fuels as would be expected by its higher RON the threshold values. These error bars were then ap-
and higher sensitivity (high sensitivity is generally plied also to the RPG and KM9096 results. It can
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be seen that the error bars for the knock limit val- • Like TPRFs, they can be used to model both
ues between RPG and KM9096 are overlapping in- the RON and MON of real gasoline fuels.
dicating that the difference in their knock limit is
within the repeatability of the test procedure. The entire approach to replace isooctane with
isopentane in surrogate fuels was driven by the will-
ingness to crosscheck technical expertise or skills
from University and industries and to try to corre-
6. Discussion and conclusions late them.
The industry faces a challenge to develop
surrogates with limited components, which can Declaration of Competing Interest
mimic the chemical and physical properties of real
fuels. Building on the TPRF surrogate approach None.
but replacing some or all of the isooctane with
isopentane allows a wide range of blends to be
generated. Several kinetic mechanisms have been Supplementary materials
developed in the past decade to support PRF and
TPRF approach, and extension of the mechanisms Supplementary material associated with this ar-
to isopentane is relatively straightforward. Isopen- ticle can be found, in the online version, at doi:10.
tane also has a non-zero octane sensitivity, thereby 1016/j.proci.2020.07.103.
allowing a wider distribution of RON and MON
values to be generated for a given level of toluene.
A final major advantage of isopentane is that the References
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Evaluating A Novel Gasoline Surrogate Containing Isopentane Using A Rapid Compression Machine and An Engine

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JID: PROCI

ARTICLE IN PRESS [mNS;September 24, 2020;4:12]

Available online at www.sciencedirect.com

Proceedings of the Combustion Institute 000 (2020) 1–11

Evaluating a novel gasoline surrogate containing

Keywords: Gasoline surrogate; Modelling; Ignition delay time; Engine; Isopentane

Nomenclature GDI Gasoline Direct Injection

1. Introduction gate, the Dry Vapour Pressure Equivalent (DVPE)

By using empirical blending laws, it was possible

Fig. 2. Ternary plots showing Density at 15 °C of TPRF and THIP surrogates.

Fuel Pressure 350 bar

sub-mechanisms for the components used in this

study. The second mechanism used was the Gaso-

(LLNL-MI-536371) from LLNL [18]. The simu-

lations were performed with ANSYS CHEMKIN

files. Figure 6 shows the comparison between exper-

nisms. Overall, simulation results show significant

elling in both temperature ranges. Both mecha-

5. Engine test results

The isopentane-containing surrogate fuel

(KM9096) and the reference premium gasoline

(RPG - PR6918) were subsequently tested on a

Ferrari V8 turbocharged engine. The objective

was to confirm if the good agreement in terms of

RON, MON and ignition delay time seen between

agreement in terms of knock limited combustion

phasing in a modern Turbocharged Gasoline

the test engine are shown in Table 2.

Knock in an internal combustion engine occurs

as the end-gas, auto-ignites before the flame front

initiated by the spark plug has time to consume it.

pression machine. Part of the end-gas compression

is due to the movement of the engine piston but

a large part is driven by the flame-front consum-

rise is a highly repeatable phenomenon, the rate at

which the flame front propagates shows significant

ments with respect to engine crank angle during the

Fig. 8. Example of consecutive cycles, the second of which is knocking.

Fig. 10. Combustion Phasing Sweeps on C103, RPG and KM9096.

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