UNCLASSIFIED: Distribution Statement A. Approved for public release.
Paper # 070IC-0269
Topic: Laminar Flames
8th U. S. National Combustion Meeting
Organized by the Western States Section of the Combustion Institute
and hosted by the University of Utah
May 19-22, 2013
A surrogate for emulating the physical and chemical properties of
jet fuel
Doohyun Kim, Jason Martz, Angela Violi
Mechanical Engineering, University of Michigan, Ann Arbor MI-48109
To address the need for more accurate jet fuel surrogates, two four-component surrogates, UM1 and UM2, were formulated to
emulate both the physical and chemical properties of a representative real jet fuel, Jet-A POSF-4658. The surrogate target properties
include cetane number, lower heating value, hydrogen to carbon ratio, molecular weight and temperature dependent density, viscosity,
surface tension and distillation characteristics. Candidate species were constrained to include only those available within existing
chemical mechanisms, while the surrogate composition was defined to minimize the difference between the surrogate and target fuel
properties. With the exception of surface tension, the average absolute difference between the surrogate and Jet-A properties was less
than 5% for the UM2 surrogate. Finally, the volume fractions of the major hydrocarbon classes were reasonably captured.
Properties of the newly developed surrogates and existing surrogate formulations obtained from the literature were compared to
real JP-8 properties to evaluate the merits and demerits of each. Simulations of non-reacting jet fuel sprays within a constant volume
bomb were performed with the newly developed and existing surrogate formulations. In turn, the simulation predictions were
compared to experimental liquid and vapor spray penetration data.
Introduction
The U.S. Army’s single fuel policy mandates the use of jet fuel for the simplification of supply chain logistics [1].
As a result, the Army’s diesel engines must be capable of operating with JP-8, which is derived from aviation kerosene,
Jet-A. The resulting difference between the fuels is the additive package within JP-8, which includes a corrosion
inhibitor/lubricity enhancer, an icing inhibitor and a static dissipater [2]. It has been reported that the gas-phase ignition
characteristics of JP-8 and Jet-A are very similar [3]. Gas turbines are the main consumer of Jet-A and JP-8, and
combustion within these devices is only marginally affected by the autoignition characteristics of fuel, which is
measured by the cetane number (CN). Due to the lack of CN regulation for JP-8, batch to batch variations in JP-8 can
range from 36 – 50 [4]. The mean CN variation becomes even more drastic with non-petroleum-derived jet fuels, where
the CN of coal-derived jet fuel (SASOL IPK) is on the order of ~ 31 [5], while the CN of a natural-gas-derived jet fuel
(S8) is ~ 60 [6].
It is well known that during the ignition delay period in a diesel engine, complex fuel dependent physical and
chemical phenomena prepare the stratified fuel-air charge for combustion [7]. The variations in JP-8 CN can present
significant challenges for compression ignition engines, often manifesting themselves in ignition behaviors ranging from
instantaneous ignition to no ignition at all. In computational fluid dynamics (CFD), a number of phenomenological and
physical sub-models are used to determine the atomization, evaporation and gaseous fuel-air mixture preparation.
Chemical kinetic models are also used to describe the autoignition of the mixture that has been physically prepared for
combustion. Real fuels are often composed of thousands of molecules, and the use of such a large number of species is
beyond the current reach of engine level CFD applications. Therefore, surrogate fuels can be formulated to represent the
physical and chemical properties of the real fuel.
The current work reports the development of a conventional jet fuel surrogate intended for the use in the CFD
simulation of diesel combustion. The surrogate emulates both the chemical and physical properties of JP-8; starting with
the properties known to affect mixture preparation and ignition within diesel engines, eight target properties were chosen
for the formulation of new JP-8 surrogates, which were developed with only those species readily available in existing
kinetic mechanisms. The resulting properties of the newly developed jet fuel surrogates are compared to the properties
of real jet fuel and existing surrogates. Additional surrogate performance assessment is performed with liquid length and
vapor spray penetration data from non-reacting constant-volume spray experiments.
UNCLASSIFIED
Surrogate Formulation Methodology
Table 1 shows the eight target properties chosen for the development of the JP-8 surrogate. Three of the property
targets are chemical in nature, including CN, Lower Heating Value (LHV) and Hydrogen-Carbon ratio (H/C). Molecular
Weight (MW) is chosen as a fourth property as it can be used to calculate the molecular diffusivity of the fuel species.
Also, three thermo physical property targets widely used in the spray breakup sub-models of CFD simulation are selected,
including liquid density, viscosity and surface tension. These sub-models include the KH-RT spray breakup model and
the dynamic drop drag model [8]. Finally, the distillation curve is used to represent the volatility of fuel, and emulating
the volatility, which is critical for predicting evaporation process.
The candidate species for the surrogate formulation are selected based upon the following considerations:
1. The relevance to the hydrocarbon (HC) molecules in real jet fuels in terms of HC class and molecular size.
2. The existence of chemical mechanism(s) that are capable of predicting the ignition process of the neat component.
3. Previous use in other jet fuel surrogate studies or use that has been suggested in the literature [9-13].
Based upon these criteria, seven pure hydrocarbons were considered as candidate species. These species include ndecane and n-dodecane for n-alkane representation, iso-octane and iso-cetane for iso-alkane representation,
methylcyclohexane (MCH) and decalin for cycloalkane representation, and toluene as an aromatic representative.
The properties of the target fuel used in this work, Jet-A POSF-4658, are summarized in Table 1. POSF-4658 is a
composite of a number of different Jet-A batches, so its properties can be considered as representatives of nominal Jet-A.
Moreover, a wide range of experimental data is readily available for POSF-4658. This is critical for the complete
specification of property targets and for the validation of various characteristics of the surrogate mixture. Available
experimental data include ignition delay measurements from shock tubes [3] [14] and rapid compression machines [15],
chemical composition [16], along with a number of chemical properties [11] and physical properties [13] [17].
Table 1: Eight surrogate target properties for POSF-4658.
Target properties
CN
LHV
H/C
MW
Density
Viscosity
Surface Tension
Distillation Curve
POSF-4658
47.1 (DCN) [11]
43.23 MJ/kg [18]
1.957 [11]
142 [11]
Temperature dependent [17]
Temperature dependent [17]
Temperature dependent [19]
Temperature dependent [13]
An optimizer was developed and utilized to formulate the surrogate composition for POSF-4658. The surrogate
optimizer iteratively determines the optimum surrogate mixture composition that minimizes the objective function,
which is defined as the overall deviation from the target properties. The surrogate properties were estimated using the
following models. The surrogate CN was estimated with the linear volume fraction of the pure component CN’s, as
suggested by Murphy et al. [20]. The density of the mixture was estimated with the volume fraction average. The
viscosity of the mixture was estimated using the Grunberg-Nissan equation [21] with the regression term Gij set to zero,
which is applicable to hydrocarbon mixtures [22]. The Parachor correlation [23] was used to estimate the mixture surface
tension while neglecting the vapor mixture molar density, which is very small compared to liquid mixture molar density.
The distillation curve of the mixture was estimated by the mixture bubble point calculation using Raoult’s law. The
procedure of the mixture distillation was discretized with a constant volume of liquid mixture leaving the liquid phase,
similar to the approach of Huber et al. [24]. The distillation curve model was validated against the experimental data of
75/25 and 50/50 mixtures of n-decane and n-tetradecane in [24]. The iterative optimization procedure employed a
genetic algorithm to find the global minimums, while the MATLAB function fmincon was used to search for local
minimums. The optimizer started with the genetic algorithm and then transitioned to fmincon with the best composition
from genetic algorithm as the starting point to ensure that the global minimum in the search space was found.
2
UNCLASSIFIED
Formulation Results and Discussion
Initially, attempts were made to formulate a surrogate with six molecules (n-dodecane/n-decane/iso-cetane/isooctane/MCH/toluene) focused on four temperature independent properties (CN, LHV, H/C, MW) as well as the liquid
density at room temperature. Although the optimization process was initialized with six components, the concentrations
of n-decane and iso-octane in the optimized mixture were zero or negligibly small, resulting in a four-component
surrogate (UM1). The composition of UM1 is shown in Table 2. This result indicates that all the properties of ndodecane and iso-cetane are favored over lighter components such as n-decane and iso-octane. As shown in Table 3,
UM1 successfully emulated all targeted temperature independent properties of POSF-4658 within 1.2% relative error.
However, as shown in Figure 1, the temperature dependent physical properties of UM1 shows notable discrepancy
compared to those of POSF-4658. Although the liquid density was matched with a relatively small error of ~ 3.3%,
liquid viscosity and surface tension errors were ~ 21% and ~ 9%, respectively. Also, the surrogate was estimated to be
significantly more volatile than the target jet fuel, as indicated by the lower distillation temperatures. Most notably,
boiling of the UM1 starts ~ 50K lower than the target fuel. This is primarily caused by the inclusion of highly volatile
species such as MCH and toluene, which constitute more than 45% of UM1 on a mole fraction basis.
In order to improve the physical property match of UM1, decalin was added as a cycloalkane representative. This
decision was based upon decalin’s higher density, viscosity and lower vapor pressure compared to MCH. Such physical
property variations were in turn expected to increase the mixture density and viscosity, as well as the distillation
temperatures. Additional optimization with all seven candidate components (n-dodecane/n-decane/iso-cetane/isooctane/MCH/decalin/toluene) generated another four component surrogate, UM2. As shown in Table 3, CN and LHV
are very well matched, within 1% error. The MW and H/C of mixture UM2 are still reasonably matched but when
compared to UM1, the error is increased from 1% to 4.6% for MW and from 0.5% to -3.9% for H/C. Since decalin has a
higher MW and a lower H/C than MCH, such a change in the MW and H/C match were as expected.
Comparing to UM1, all temperature dependent physical properties except for surface tension were significantly
improved for UM2. As shown in the plot titles in Figure 1, the average absolute error for density and viscosity decreased
from 3.4% to 0.6% and from 21.2% to 3.6%, respectively. Also, the distillation characteristics that were trend wise
poorly emulated by UM1 improved notably for UM2. The distillation curve of the UM2 at the early stages of the
distillation process better matches that of the real fuel when compared to UM1, due to the reduced volatility of the
mixture as noted above. Also, the large curvature in the distillation curve of UM1 has been significantly reduced. This
results from the better distribution of vapor pressures among the surrogate components. Although the surface tension
match is not as good as UM1, the property emulation of UM2 is thought to be better than UM1 mainly because of the
improved density and distillation curve matches. A previous CFD simulation study by Ra et al. [25] showed that the
spray breakup/evaporation process and resulting cylinder pressure development during diesel combustion has the highest
sensitivity to density and vapor pressure characteristics.
Figure 2 shows the HC class composition of the UM surrogates as well as average jet fuel composition suggested in
[16]. The overall distribution of the major HC classes (n-alkane, iso-alkane, cycloalkane and aromatics) of the UM
surrogates is similar to that of real jet fuel.
Table 2: Composition of the UM surrogates in mole fraction.
n-dodecane
iso-cetane
MCH
decalin
toluene
UM1
Mole fraction
0.3844
0.1484
0.2336
0.0000
0.2336
UM2
Mole fraction
0.2897
0.1424
0.0000
0.3188
0.2491
Table 3: The estimated temperature independent target properties of the UM surrogates vs. POSF-4658
Property
CN
LHV (MJ/kg)
H/C
MW
POSF-4658
Target
47.1
43.23
1.957
142
UM1
Estimated
46.8
43.62
1.967
143.5
UM2
Error (%)
-0.59
0.91
0.52
1.08
3
Estimated
46.7
43.36
1.881
148.6
Error (%)
-0.80
0.30
-3.86
4.66
UNCLASSIFIED
Figure 1: Estimated target physical properties of the UM surrogates vs. POSF-4658. Solid dots are measurements of POSF-4658
while lines are surrogate properties for (a) liquid density (b) liquid viscosity (c) surface tension and (d) distillation curve.
100%
Volume fraction
80%
aromatic
60%
cyclo-alkane
40%
iso-alkane
20%
n-alkane
0%
World Average
UM1
UM2
Figure 2: The HC class composition in volume fraction of the UM surrogates and of the average jet fuel suggested in [16].
4
UNCLASSIFIED
Comparison to Existing Jet Fuel Surrogates
The newly developed UM surrogates are compared with existing surrogates to assess the property emulation
capability as well as the ability to properly simulate JP-8 cold flow spray characteristics. The temperature independent
properties of the UM and select jet fuel surrogates [10-12, 26-29] are shown in Table 4. The UM1, UM2 and MURI2 are
shown to match all temperature independent targets within 5%, while the UCSD surrogate matches within 9%. The
Aachen surrogate, Violi #3 and UTAH HEX12 reasonably match MW, LHV and H/C, but the predicted CN of those
surrogates is significantly higher than the real fuel.
The surrogates physical properties, predicted with the same models used above in the surrogate optimization are
plotted in Figure 3. Among the tested surrogates, the UM2, UTAH HEX12 and DrexelS5 are shown to emulate all of the
target physical properties, except for surface tension, with reasonable error. However, as shown in Table 4, the
temperature independent property emulation of the UTAH HEX12 and DrexelS5 shows a significant discrepancy with
the real fuel. The MURI2 also matches all of the properties in Table 4 with less than 5% error, however there is a large
discrepancy shown for the temperature dependent physical properties in Figure 3. For all of the surrogate evaluated
above, the UM2 surrogate most successfully emulates both the chemical and the physical properties of Jet-A with
reasonable errors.
Fuel spray simulations were performed with multi-component surrogates using the CFD software CONVERGE [8].
The simulation results were compared to non-reacting Jet-A constant volume spray bomb experiments from Sandia
National Laboratories [30]. Prior to conducting these simulations, model tuning, grid sensitivity and validation studies
were performed with n-dodecane and were compared against experimental data in [31]. As summarized in Table 6,
identical injector, injection pressure and ambient conditions were employed for both the Jet-A blend and n-dodecane
experiments. The finalized modeling parameters used in the following simulations are summarized in Table 5.
The spray simulations results for both UM surrogates as well as four other surrogates are shown in Figure 4. The
MURI1 and MURI2 surrogates are selected since their fundamental gas phase combustion kinetic phenomena have been
experimentally validated against POSF-4658. The DrexelS5 and UTAH HEX12 surrogates are also selected for their
good physical property emulations.
As shown in Figure 4 (a), the calculated liquid penetration length is observed to have a strong correlation to the
surrogate physical properties. Among the six surrogates tested, the density, viscosity, distillation temperatures as well as
the predicted liquid penetration are shown to have exactly same order: S5>HEX12>UM2>UM1>MURI2>MURI1. Such
an observation is expected as higher density, higher viscosity and higher distillation temperatures all contribute to longer
liquid breakup time. Although the surface tension emulation of the MURI1 and MURI2 surrogates is significantly better
than that of the other tested surrogates, the liquid penetration length is under predicted by over 20%. This observation
infers that the effects of surface tension are less important to liquid length penetration than density, viscosity and
volatility. The vapor penetration length of the leading edge of the jet is shown in Figure 4 (b). The results are nearly
identical for all surrogates, indicating that the liquid fuel property variations within the tested surrogates have marginal
affect on the vapor penetration.
Table 4: Estimated/reported temperature independent properties of the UM surrogates and currently available jet fuel surrogates.
POSF-4658
UM1
UM2
Aachen [26]
USCD [27]
MURI1 [11]
MURI2 [12]
DrexelS5 [28]
Violi#3 [10]
UTAH HEX12 [29]
CN
47.1
value
46.8
46.7
63.1
51.1
47.4
48.5
32.1
64.3
60.5
error (%)
-0.6
-0.8
34.1
8.4
0.6
3.0
-31.8
36.5
28.4
LHV
43.23
value
43.61
43.36
43.76
43.33
43.88
43.55
43.02
43.73
43.12
MJ/kg
error (%)
0.9
0.3
1.2
0.2
1.5
0.7
-0.5
1.2
-0.3
5
H/C
1.957
value
1.96
1.88
1.99
1.92
2.01
1.96
1.81
2.01
1.86
error (%)
0.3
-3.9
1.7
-2.1
2.5
0.1
-7.7
3.0
-5.2
MW
142
value
143.6
148.6
136.5
132.9
120.7
138.7
159.2
140.9
152.1
kg/kmol
error (%)
1.1
4.7
-3.9
-6.4
-15.0
-2.3
12.1
-0.8
7.1
UNCLASSIFIED
Figure 3: Estimated physical properties of the UM surrogates and available jet fuel surrogates. Solid dots are measurements of POSF4658 while lines are surrogate properties for (a) liquid density (b) liquid viscosity (c) surface tension and (d) distillation curve.
Table 5: CONVERGE sub-models and parameters used for the spray simulations. More details are available in [8].
Turbulence modeling
RANS with the RNG k-ε
Spray submodels
Breakup
KH-RT breakup
Drop drag
Dynamic drop drag
Evaporation
Frossling correlation
Collision/coalescence
NTC, Post outcome
Numerical parameters
Minimum grid size
0.25mm
Number of injected parcels
512000
6
KH time constant (B1) = 30
Automatic Mesh Refinement
UNCLASSIFIED
Table 6: Conditions for the constant volume, non-reacting spray experiments in Sandia National Laboratories.
Fuel
Chamber
Ambient composition
Ambient temperature
Ambient density
Injection pressure
Nozzle diameter
Jet-A blend [30], n-dodecane [31]
Sandia Constant Volume Chamber, Cubic, 108mm
N2:CO2:H2O=0.8971:0.0652:0.0377 in mole fraction
900K
22.8 kg/m3
1500 bar
90 µm
Figure 4: Liquid penetration length (a) and vapor penetration length (b) of the surrogates predicted by CFD spray simulation vs.
experimental Jet-A data [30]. Time-averaged liquid length at quasi steady state is plotted for the experimental data in (a). Expected
uncertainty for the experimental vapor penetration measurement in (b) is up to 2mm as noted in [30].
Summary and Conclusion
Two jet fuel surrogates were formulated for the CFD simulation of diesel combustion. Eight target properties,
including both chemical and physical ones, were considered in the optimization. UM1, composed of n-dodecane/isocetane/MCH/toluene, successfully emulated the temperature independent target properties of a representative real jet fuel,
POSF-4658. In order to improve the physical property match, decalin was included as an additional cycloalkane
component in the surrogate UM2, which was a mixture of n-dodecane/iso-cetane/decalin/toluene. Properties as well as
the spray characteristics of the UM surrogates were compared to existing surrogates. The results imply that UM2 has
potential to successfully emulate the various chemical and physical properties important to the mixture formation and
ignition processes in diesel engines. Finally, the surface tension variation of the surrogate is shown to have a relatively
minor affect on the spray liquid length, while the liquid fuel property variations within the tested surrogates have
marginal affect on the vapor penetration.
Acknowledgements
Funding for this work was provided by the Automotive Research Center (ARC), A U.S. Army Center of Excellence
in the modeling and simulation of ground vehicles at the University of Michigan, with funding from government contract
DoD-DoA W56HZV-04-2-0001 through the U.S. Army Tank Automotive Research, Development, and Engineering
Center.
The authors wish to thank Dr. Daniel Lee of Convergent Science for his technical assistance and for the provision of
the CONVERGE CFD code used in this work. The authors also gratefully acknowledge the assistance of Dr. Peter Kelly
Senecal of Convergent Science and Dr. Sibendu Som of Argonne National Laboratory for their technical assistance with
the CFD simulations.
7
UNCLASSIFIED
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