“Development of Assessment Methods for Alternative Fuels

for Naval Diesel Engines”

Rolf Reitz
Jaal Ghandhi, Youngchul Ra, Dave Rothamer, Chris Rutland,
Scott Sanders, Mario Trujillo
Engine Research Center, University of Wisconsin-Madison
September 26, 2013

FOA ONR BAA12-001:

Sea Warfare and Weapons Department, Naval Alternative Energy and Fuels Program:
Code 33 specific thrust (4)
Focus:
Understanding physical effects of incorporating alternative fuels into Naval systems.
Identifying fuel characteristics needed for acceptable operation of current diesel
engines deployed by the Navy and Marine Corps.
Research goals:
a.) Development and validation of modeling/simulation tools that predict engine
performance/degradation using wide variety of alternative fuels.
b.) Increasing the knowledge of physical properties and chemical reactions of
alternative fuels in a maritime environment.

1 MACCCR Meeting 9/26/2013

“Development of Assessment Methods for Alternative Fuels
for Naval Diesel Engines”
Approach
Project develops a methodology using validated state-of-the-art
Computational Fluid Dynamics (CFD) models for identifying the fuel
characteristics needed for acceptable operation of diesel engines deployed
by the Navy and the Marine Corps.
Research is divided into 3 main tasks –

Task 2.2 – Cnst. Vol.

spray/combust expts
Task 2.1 - HCCI Task 3.2 - DNS spray
engine experiments atomization models

Task 1 – Implementation/application
of fuels in CFD engine models
Task 3.1 - spray
Task 2.3 – Direct injection models for fuel effects
CI engine experiments

Linkages between project tasks

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“Development of Assessment Methods for Alternative Fuels
for Naval Diesel Engines”

Project schedule and milestones (2013)

Reitz
*

Rothamer

Trujillo

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 “Development of Assessment Methods for Alternative Fuels
for Naval Diesel Engines”

Task 1: Youngchul Ra, Xingyuan Su and Rolf Reitz

 Overview
 Approach:
Physical Surrogate, Group Combustion Representation (PSGCR)
 Current Progress
- Surrogate models for F-76 and HRD
- Improvement of the PSGCR model
- Model validation and application using Task 2 data.
 Summary and Conclusions
 Future work

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Multi-component fuel modeling approach

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 Physical Surrogate: 56 component database
F-76 surrogate
Chemical class Physical surrogate component
base
Propane, n-Butane, n-Pentane, n-Hexane, n-Heptane (C7H16), n-Octane,
n-Nonane, n-Decane, n-Undecane, n-Dodecane, n-Tridecane, n-
n-Alkanes: 10
Tetradecane, n-Pentadecane, n-Hexadecane, n-Heptadecane, n-
Octadecane, n-Nonadecane, n-Eicosane, n-Heneicosane
i-pentane, i-hexane, i-heptane, i-octane, 2,2,3,3-Tetramethylhexane,
iso-Alkanes: 6
2,2,4,4,6,8,8-Heptamethylnonane
Cyclopentane, Cyclohexane, Methycyclohexane, cis-1,3-
Naphthenes: 3
dimethylcyclohexane, Decalin
Alkenes: 1-Pentene, 1-Hexene, 1-Heptene, 1-Octene 2
Benzene, Toluene, m-Xylene, ethylbenzene, ethyltoluene, iso-
Propylbenzene, Trimethylbenzene, Butylbenzene, m-Cymene, m-
Mono-aromatics: 8
Diethylbenzene, n-Pentylbenzene, Biphenyl, Diisopropylbenzene, n-
Hexylbenzene, n-Heptylbenzene
Indene, Tetralin, Naphthalene, Acenaphthalene, Acenaphthene,
Poly-aromatics: 3
Phenanthrene, Pyrene
Ethanol, Di-Methyl-Ether, Methyl tert-Butyl Ether, Methyl-butanoate,
Oxygenates: methyl-palmitate, methyl-linolenate, methyl-linoleate, Methyl-oleate, 0
methyl-stearate

 Oxygenates in F-76 are mostly alcohols (C16H34O) and ketones

(C10H16O) and they are in relatively small amounts
 32 components were selected to represent physical properties of F-76
6 MACCCR Meeting 9/26/2013
 Physical property modeling of F-76
Methodology
• Fuels modeled as mixtures of surrogate Surrogate models for F76 fuel
components - properties calculated using discrete Species Tb [K] MassFrac MassFrac
multi-component (DMC) model (from the 56 n-heptane 371.5 0.003392
component database). iso-octane 372.39 0.005970 0.058126
• Surrogate components and their composition methycyclohexane 374 0.047096
1-octene 394.44 0.017554 0.010467
chosen to match measured distillation profiles and
tetramethylhexane 429.15 0.066570
physical properties of the target fuel. n-decane 447.3 0.031780
• Distillation profiles obtained by calculating m-cymene 448.2 0.012754
evaporation history of a single drop in the boiling cis-decalin 468.97 0.004612 0.046435
n-pentylbenzene 478.61 0.021796 0.028999
condition (True Boiling Point).
tetralin 480.77 0.014899
• Properties of mixture calculated from the properties diisopropylbenzene 483.15
0.015830
0.012754
of individual pure components using appropriate n-dodecane 489.47 0.056447 0.140660
blending equations. naphthalene 491.14 0.005588 0.041497
• Processes are automated  Surrogate Builder n-tridecane 508.62 0.029471 0.006720
heptamethylnonane 519.5 0.181270 0.191390
No. Physical property No. Physical property n-tetradecane 526.73 0.083634
p1 Liquid density p7 Vapor heat capacity n-hexadecane 560.01 0.183337 0.173920
p2 Vapor pressure p8 Vapor diffusivity n-octadecane 589.86 0.081714 0.147410
phenanthrene 613.45 0.008777 0.000972
p3 Surface tension p9 Vapor viscosity
n-eicosane 616.93 0.064088 0.139270
p4 Liquid viscosity p10 Vapor thermal conductivity n-heneicosane 629.7 0.065566
p5 Liquid thermal conductivity p11 Liquid Heat capacity total 21 13
p6 Heat of vaporization p12 Critical properties
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 Physical property modeling of F-76

21-component model 13-component model

Property Measurement Model Error[%]

Non-reacting spray
n-Alkane [%] 59.88 60.797323 1.5
iso-Alkane [%] 25.38 24.951961 1.7
Naphthene [%] 4.73 4.643497 1.8
- Physical properties
Aromatics [%] 7.23 7.146858 1.2
Tetralin [%] 1.52 1.489869 2.0 influence spray
Olefins [%] 1.26 1.046732 16.9 behavior (Task 3)
Density [g/ml] 0.845 0.786762 6.9
Viscosity [cSt] 3.0 2.9694 1.0
LHV [MJ/kg] 42.6 43.6 2.3
H/C ratio 1.8249 1.985596 8.8
CN 51 67.58 32.5

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 Surrogate model for HRD

Property Measurement Model Error[%]

4-component model Aromatic [%] 0.6 0
Olefins [%] 0.9 0
Species Mass fraction Saturate [%] 98.5 100 1.5
Surface Tension
iC16H34 0.200 24.9 26.19887 5.2
[dynes/cm]
C14H30 0.281 Density [g/ml] 0.7613 0.756816 -0.6
C16H34 0.349 Viscosity [cSt] 2.748 2.12 -22.8
LHV [MJ/kg] 43.963 41.66 -5.2
C18H38 0.110 C/H 5.62 5.64 0.4
CN 74.7 77.01 3.1

 With 4-component model, physical

properties are in good agreement
(except for viscosity.).
 Since saturate contents are dominant,
CN is adjusted by iC16H34 (HMN)

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 Physical Surrogate Group Chemistry Representation
Physical surrogate components Chemical surrogate components (PSGCR)
in spray model in chemistry model

m 1  spc1
m  chem1 + O2 = ….
spc2
m   ….
2

m 3  spc3 chem2 + oh = ….

Td
ro   ….
m 4  spc4
m 5  chem3 + ho2 = ….
spc5
  ….
   …
Generic reaction pathways
 Physical surrogate components represent physical properties of multi-component
fuels (PS)
 Reaction pathways of base surrogate components (chem1, chem2, …) - detailed
mechanisms used to represent reaction characteristics of a chemical class (GCR)
 Reactivity of physical surrogate components captured by generic reactions
connecting the PSC and the base chemical surrogate components (CSC).
 Ideally, # of PSC = # of CSC, but likely, # of PSC > # of CSC
10 MACCCR Meeting 9/26/2013
 Physical Surrogate Group Chemistry Representation

 Reaction kinetics mechanisms for individual CSC

 Comprehensive vs. Reduced LLNL collaboration
 Detailed vs. Generic

 Reliability of reaction mechanisms tested with:

 Ignition delay times, pressure and temperature histories
 Species profiles; tracking of functional groups along
oxidation pathways
 Multi-component effects: Co-oxidation, radical
reproduction/scavenging

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 Chemical Surrogate: 35 component database
Physical surrogates: 32 components for F-76
Chemical surrogates: 35 components  mechanism 225 species, 1087 reactions

 Base component: w/ detailed reactions for oxidation processes

 Extended component: w/ generic reactions + detailed reactions
12 MACCCR Meeting 9/26/2013
 Chemical Surrogates: Base components
 Detailed reaction pathways are described
 Comprehensive mechanism or Reduced (skeletal) mechanism
nc7h16=c4h9+c3h7
RH nc7h16+h=c7h15-2+h2
nc7h16+o=c7h15-2+oh
1 nc7h16+oh=c7h15-2+h2o
R. R’. + olefin 1 nc7h16+ho2=c7h15-2+h2o2
nc7h16+ch3=c7h15-2+ch4
3 2 nc7h16+o2=c7h15-2+ho2
nc7h16+c2h5=c7h15-2+c2h6
RO2 nc7h16+ch3o2=c7h15-2+ch3o2h
c7h15-2=c4h9+c3h6
4 HO2 + olefin 2 c7h15-2=c4h8+c3h7
5
QOOH OH + cyclic ether 3 c7h15-2+o2=c7h15o2
nc7h16+c7h15o2=c7h15-2+c7h15o2h
6 -scission products c7h15o2+ho2=c7h15o2h+o2
h2o2+c7h15o2=ho2+c7h15o2h
O2QOOH
4 c7h15o2=c7h14ooh
7 c7h14ooh=>oh+c4h9cho+c2h4
5 c7h14ooh=>oh+c3h7cho+c3h6
Ketohydroperoxide 6 c7h14ooh+o2=o2c7h14ooh
o2c7h14ooh=nc7ket23+oh
8 7 nc7ket23=>c4h9cho+ch2cho+oh
nc7ket23=>c4h9cho+ch3co+oh
Low T Branching 8 nc7ket23=>ch3cho+c4h9co+oh
13 nc7ket23=>ch2o+c4h9coch2+oh
MACCCR Meeting 9/26/2013
 Chemical Surrogate: Extended components
 When i) detailed reaction kinetics are not available
or ii) detailed mechanism is prohibitively large.
 Two levels of oxidation pathways;
Upper level (Generic reactions) + Lower level (detailed reactions)
 Generic reactions: PSC  smaller base CSC’s and their radicals.
 Reaction characteristics employed:
H-abstraction, radical decomposition, olefin formation, carbonyl
(aldehyde) formation, active radical reproduction (OH, O, HO2),
unimolecular decomposition
 Reaction rate constants to give correct reactivity of the fuel;
ignition delay times matching available experimental data or
known CN behavior.
Olefins
C20H42 + Radicals C16H34/C16H33
Aldehydes
H2, H2O, H2O2
Radicals
Pentyl benzene Toluene/benzyl
Olefins
Aldehydes
+ Radicals H2, H2O, H2O2, Radicals
 Generic reaction modeling
Type-1: pentylbenzene, hexylbenzene, heptylbenzene, m-cymene,
isopropylbenzene, n-C13H28, n-C18H38, n-C20H42, n-C21H44, i-C10H22

Variation:
Type-2: mXylene, Type-3: iC16H34 (HMN), Type-4: Tetralin,
Type-5: Naphthalene (C10H8), Type-6: PAH cascade
 Improvement of reaction kinetics mechanism

 Improvement of low-C reactions

 Updated H2/O2 reactions and CO oxidation reactions
(Acknowledgement : Princeton CEFRC mechanisms)
 Reaction rate constant adjustment based on equivalence
ratio sensitivity analysis of reactions before low-T branching
 When building generic reactions, equivalence ratio effects
are considered.
 Benzene/Phenyl are added as base CSC in generic
reactions of alkyl-benzenes.
(Acknowledgement: Marco Mehl and Bill Pitz at LLNL)
 Multi-component effects are being improved.

16 MACCCR Meeting 9/26/2013

 Improvement of reaction kinetics mechanism

iso-Alkanes

PRF fuel

Olefins

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 Improvement of reaction kinetics mechanism

n-Alkanes
C-number
C-number increase
increase

50% blends

50% blends
Alkyl benzenes w/ C7

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 Model Validation –
F-76 spray combustion at constant volume
Interior chamber diameter 146 [mm]
Height 75[mm]
Injector hole diameter 0.182 [mm]
Number of holes 7
Spray included angle 143 [degree]
71.5o Injection amount (variable) 0.1374 [g]
Injection duration 2000 [us] (2523 us)

 Initial condition: Spark-ignited

burned gas of premixed C2H2/O2/N2
(1/7th sector grid, Cell size ~ 3.9 mm)  Tini = 800 ~ 1200 K, Pini : variable

Mole fraction at SOI

Species Mole fraction
O2 0.179990
N2 0.673117
Injection rate CO2 0.097929
H 20 0.048964
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F-76 spray combustion at constant volume
21 comp. (CN=51) C14-C14 (CNC14=96)

C14-C7 (CNC7=52) C14/Tol=90/10 (CNC14/Tol=86.5)

20 MACCCR Meeting 9/26/2013

 F-76 spray combustion at constant volume

f=2.0 f=2.0
f=3.0 f=3.0

C14 spray + C14 kinetics C14 spray + C7 kinetics

Time=1.35 ms Time=2.4 ms

21 MACCCR Meeting 9/26/2013

 Application to engine combustion

Small-bore high-speed diesel engine (GM-1.9)

Base Engine GM 1.9L Diesel

Displacement (L) 0.477

Stroke (mm) 90.4

Bore (mm) 82.0

Swirl Ratio 1.5

Common Rail
Bosch CRI2.2
Injector
Number of Holes 7

Hole Diameter 0.14 mm

Spray Angle 148°

Rail Pressure 500 bar

GM 1.9L
Acknowledgement: F. Perini (CR=16.2)
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 Application to engine combustion
GM-1.9 with 13-component model for F76

Operating conditions Case1 Case2 Case3 Case4 Case5

Start of injection command [deg atdc] -13 -10 -4 -1 2
Pressure at IVC [bar] 2.25 2.25 2.26 2.26 2.26
Temperature at IVC [K] 361 363 354 348 340
gIMEP [bar] 9.72 9.76 9.64 9.45 9.14

Pressure HRR

23 MACCCR Meeting 9/26/2013

 Application to engine combustion
Temperature distribution Equivalence ratio distribution

SOIC=
24 -13 deg atdc MACCCR Meeting 9/26/2013
 Application to engine combustion

Engine size-scaling:
Large-bore diesel engine

CAT3500
BxS 170 x 215 mm
Con_rod 392.5 mm
CR 15.2
Engine speed 1800 rev/min
Swirl ratio 0.67
No. nozzle holes 8

45-deg sector
(23968 cells) Acknowledgement: R. Hessel
25 MACCCR Meeting 9/26/2013
 Application to engine combustion

Large-bore diesel engine CA = -5 CA = +5

(CAT3500)

CA = -4 CA = +10

21-component model
CA = -2
CA = +20

CA = TDC

Contour: 2200 K CA = +30

20 bar imep, Pivc= 3.69 bar

EGR= 0 %, Dur_inj=44.4 deg
CA = +50

26 MACCCR Meeting 9/26/2013

 Summary and Conclusions

• Surrogate models for the physical properties of F-76

and HRD fuels have been developed and validated
against measured data.
• A new chemistry modeling approach, Physical
Surrogate, Group Chemistry Representation (PSGCR)
has been developed.
• PSGCR kinetics are based on both detailed (reduced)
and generic reaction pathways to correctly model multi-
component effects.
• Performance of the PSGCR model has been tested for
prediction of spray combustion ignition delay times.
• 21 and 13 component versions of the PSCGR model
for F-76 fuel have been applied to engine simulations
and capture combustion behavior well.

27 MACCCR Meeting 9/26/2013

 Future work

• Further development of reaction mechanisms for heavy

olefins and naphthenes and oxygenated species.
• Further improvement of the PSGCR combustion model
to improve multi-component and co-oxidation effects,
and to include oxygenated species.
• Incorporation of results and findings from Tasks 2 & 3.
• CFD simulations of engine combustion/spray behavior
(F-76, HRD and blended fuels, together with exploration
of cetane improver effects).
• Investigation of engine size scaling effects.
Research Impact: Improved understanding of fuel effects
can provide guidelines for design of synthetic fuels to
extend the operational range of naval assets.

28 MACCCR Meeting 9/26/2013

Backup slides

29 MACCCR Meeting 9/26/2013

 Your logo here
Development of Assessment Methods for Alternative
Fuels for Naval Diesel Engines - N000141210650

Objective: Research goals include – Figure: Left – predicted and measured in-cylinder
pressures with various injection timings in a GM 1.9L
a.) Development and validation of modeling/simulation tools
diesel engine. Right - example DNS-predicted F-76
that predict engine performance/degradation using a wide
diesel spray breakup injected at 200 m/s from 200 m
variety of alternative fuels.
diameter nozzle. Grid resolution 6.25 m.
b.) Increasing the knowledge of physical properties and
chemical reactions of alternative fuels in a maritime
environment.

The project develops a methodology using state-of-the-art

Computational Fluid Dynamics (CFD) models for identifying
the fuel characteristics needed for acceptable operation of
diesel engines deployed by the Navy and Marine Corps.

Approach: Research is divided into 3 main tasks –

Task 1 – Implementation and Application of Multi-
component Fuel Spray Combustion CFD Models;
Task 2 - Experimental Validation of Flow and Chemistry
Models
2.1 – HCCI Engine Experiments;
2.2 - Constant Volume Chamber Ignition Experiments;
2.3 – Direct Injection Compression Ignition Engine Scientific or Naval Impact/ Results: 21 component
Experiments; F-76 diesel fuel surrogate model developed and
Task 3 – Advanced Spray Combustion Models tested using program experimental data. The resulting
3.1 – Development of Spray Submodels for Fuel Effects; improved understanding of fuel effects can provide
3.2 – DNS Spray Atomization and Breakup Models. guidelines for the design of synthetic fuels to extend
the operational range of naval assets.

Non Proprietary Information Only

 Group Chemistry Representation (GCR) model 31
Cyclo alkanes
cyclohexane
cyclohexane
decalin

100 species, 348 reactions

MultiChem Mechanism
n-alkane

n-dodecane n-heptane

n-alkane
n-octadecane n-tetradecane

iso-alkanes
heptamethyl nonane iso-octane 857 species 25 species
tetramethyl hexane 3586 reactions 51 reactions

Aromatics
naphthalene
mcymene
tetralin toluene
n-pentylbenzene
n-heptylbenzene

Physical surrogates Chemistry surrogates Detailed ERC reduced

 (PSC)  (CSC) mechanism mechanism*
* Ra and Reitz, Combustion & Flame 2011
Comparison of 13 and 21 component mechanisms
Ignition at const. volume

Spray combustion
at const. volume
HCCI combustion

32 MACCCR Meeting 9/26/2013

 33
Improvement of reaction kinetics mechanism
UW Princeton
H2/O2 reactions
# of species 8 8
# of reactions 12 19
A n Ea
3.0e12 0.0 0 UW
1.9322e11 0.0 -1409 Princeton
8.7241e13 0.0 11040 Duplicate
HO2 + HO2 = H2O2 + O2 4.2e14 0.0 1.1982e4 Burke
1.3e11 0.0 -1.6293e3 Duplicate
4.2e14 0.0 1.1982e4 Li
1.3e11 0.0 -1.6293e3 Duplicate

Equivalence ratio effect (nC7H16)

Old Updated
 Multi-component effects
Mixture-A: high reactivity fuel-A (e.g., n-hexadecane) with f=1.0
Mixture-B: low reactivity fuel-B (e.g., toluene) with f=1.0
Mixture-C: mixture of blended fuel-AB (e.g., C16/Tol=50%/50%) with f=1.0
Mixture-D: just high reactivity fuel-A with f=0.5

Reported: Ignition delay tA < tC < tB and tA < tD

How about relation b/w Mixture-C and Mixture-D ?

i) tC < tD : enhancing effect of low-reactivity fuel
ii) tC > tD : suppressing (scavenging) effect of low-reactivity fuel
iii) tC ~ tD : neutral (inert) effect of low-reactivity fuel

Predicting correct trend is very important in generic reaction model:

high sensitivity to HC + OH = S1R + S2 (+ S3) + H2O (T1-3)
Dependency on
i) Class of A & B
ii) Reactivity difference between A & B
iii) Operating conditions (Low, NTC and high temperature ranges)
iv) Selection of S1R, S2 34and S3 MACCCR Meeting 9/26/2013
 Improvement of reaction kinetics mechanism

 Benzene/Toluene reactions improved - relative reactivity of aromatic

blends with aliphatic components is correctly modeled.
35 MACCCR Meeting 9/26/2013