Modeling the Influence of Molecular Interactions

on the Vaporization of Multi-component Fuel Sprays

Qi Jiao, Youngchul Ra, Rolf D. Reitz Funding Sponsors U.S. DOE& Sandia National Labs
Motivation Verification of the model Spray cases: ethanol+gasoline

Preferential vaporization of real fuels (diesel, Binary component fuel: benzene + ethanol Tamb=495.51K
Pamb=7.36bar
gasoline, bio-diesel, JP8) captured by multi-
component fuel vaporization models (DMC, CMC, T-x phase diagram

DC) benzene+ethanol

1. Initial boiling point (IBP), final boiling point (FBP)

80 noUNIFAC
UNIFAC
78

Temperature [ C]
0
2. Vaporization sequence 76

74

3. Combustion process, emissions formation 72

70

E00
Ideal-mixing using Raoults Law in current DMC 68

0.0 0.2 0.4 0.6 0.8 1.0

0.025 fuel injected 1.0x10
-2
E00

KIVA code misses the azeotropic behavior of mixtures experiment [1] simulation
xbenzene
0.020
E00
8.0x10
-3
C2
C3
C4

composed of polar components like ethanol and C5

Vapor mass [g]

vapor@noUNIFAC

fuel mass [g]

C6
0.015 vapor@UNIFAC -3

distillation curve 6.0x10

benzene 81 -3
noUNIFAC B00 0.010 4.0x10
B20 86 UNIFAC
benzene+ethanol B40 benzene+ethanol
B50 84
80

Temperature [ C]
B00 -3
B60 82 0.005 2.0x10

Temperature [ C]
B70 B20

0
Objective 80

0
B80 B40
B100 B50
79 78 B60
0.000 0.0
76 B70
0.0000 0.0005 0.0010 0.0015 0.0020 0.0025 0.0000 0.0005 0.0010 0.0015 0.0020 0.0025
B80
74 B100
Time [s] Time [s]
78 72
70
68
E10
Molecular interactions are taken into account to treat 77
0.0 0.2 0.4 0.6 0.8 1.0 66
0.0 0.2 0.4 0.6 0.8 1.0
0.025 fuel injected
-2
1.0x10
-3
9.0x10
E10
C1
Volume distilled
non-ideal mixing under vapor-liquid equilibrium ideal-mixing (noUNIFAC): without the non-ideal mixing (UNIFAC): with the
Volume distilled
0.020
E10
-3
8.0x10
-3
7.0x10
C2
C3
C4
conditions by implementing the UNIFAC model into

Vapor mass [g]

vapor@noUNIFAC

fuel mass [g]

C5
consideration of molecular interactions consideration of molecular interactions 0.015 vapor@UNIFAC -3
6.0x10
C6

a discrete multi-component fuel vaporization code.

-3
5.0x10

Multi-component fuel: ethanol+gasoline

-3
0.010 4.0x10

-3
3.0x10
-3
0.005 2.0x10

combinatorial residual -3

ln i ln i ln i
1.0x10

T-x phase diagram @ simulation distillation curve @ experiment [2] 0.000

0.0000 0.0005 0.0010 0.0015 0.0020 0.0025
0.0
0.0000 0.0005 0.0010 0.0015 0.0020 0.0025
Time [s] Time [s]

Interactions between functional groups

80

75
ethanol & 9-component surrogate for gasoline
Pamb=1bar
noUNIFAC
E85 0.025
-3
2.0x10
E85
UNIFAC fuel injected
Temperature [ C]

-3
1.8x10
C1
0

70
Differences in size and shape of molecules 65
0.020
-3
1.6x10
-3
C2
C3
E85 1.4x10
C4

Vapor mass [g]

60 vapor@noUNIFAC -3 C5

fuel mass [g]

1.2x10
0.015 vapor@UNIFAC C6
Pva p , i 55 -3
1.0x10

xi i x L ,i 50
0.010
-4
8.0x10

Pm 0.0 0.2 0.4 0.6 0.8 1.0

-4
6.0x10

xethanol -4
4.0x10
0.005
-4
2.0x10

distillation curve @ simulation 0.0

Where 0.000
0.0000 0.0005 0.0010 0.0015 0.0020 0.0025
0.0000 0.0005 0.0010 0.0015
Time [s]
0.0020 0.0025

Time [s]
140 noUNIFAC 140 UNIFAC Note: the black line indicating ethanol is not shown completely because it

i is the activity coefficient for component i .

9comp-surrogate for gasoline 9comp-surrogate for gasoline
has far more vapor mass than other components.
gasoline+ethanol gasoline+ethanol
120 120

Ongoing work
Tamb=500K Tamb=500K
Pamb=1bar Pamb=1bar
Temperature [ C]
Temperature [ C]

Pm is the total mixture pressure or the ambient atmospheric

0
0

100 E00 100

E00

Application to cold start in diesel engines and low

E10 E10
E20
pressure. 80 E40
E50
80
E20
E40
E50

Pva p , i is the vapor pressure of the pure component i . 60

E60
E85
E90
60
E60
E85
E90
temperature combustion especially with ethanol should be
E100

x L , i is the mole fraction of the component in the liquid phase. 40

0 20 40 60 80 100
40
0 20 40 60 80 100
E100
studied.
x i is the mole fraction of the gas phase for each component . Volume [%] Volume [%]
The application of the UNIFAC model to surrogates for other
ideal-mixing (noUNIFAC): without the non-ideal mixing(UNIFAC): with the real fuels like diesel, bio-diesel and JP8 are needed.
consideration of molecular interactions consideration of molecular interactions Reference:
[1]. Hadler, A.B., Ott, L. S., Bruno, T. J. , Study of Azeotrope Mixtures with the Advanced Distillation Curve Approach,
Note: Ref. [2] did not provide the chemical composition of the base gasoline used in the experiments, this makes matching the Fluid Phase Equilib. 2009, 281, 49-59.
distillation curve and the properties of gasoline difficult. However, it is of interest to see whether the UNIFAC model can capture the [2]. Andersen V.F., Andersen J.E., Wallington T.J., Mueller S.A., Nielsen O.J., Energy&Fuels 2010, 24, 2683-2691.
important characteristics seen by adding different amounts of ethanol to gasoline .

UNIVERSITY OF WISCONSIN - ENGINE RESEARCH CENTER