Technical Management: Dr. Julian Tishkoff, AFOSR AFOSR MURI FA

Similar documents
Generation of Comprehensive Surrogate Kinetic Models and Validation Databases for Simulating Large Molecular Weight Hydrocarbon Fuels

Flow Reactors for Validation Data Base Development

RECENT PROGRESS IN THE DEVELOPMENT OF DIESEL SURROGATE FUELS

Fundamental Kinetics Database Utilizing Shock Tube Measurements

Jp-8 Surrogates For Diesel Engine Application: Development, Validation, And Cfd Simulation

A surrogate for emulating the physical and chemical properties of jet fuel Doohyun Kim, Jason Martz, Angela Violi

Confirmation of paper submission

Study on cetane number dependence of. with a controlled temperature profile

The ignition, oxidation, and combustion of kerosene: A review of experimental and kinetic modeling

An Empirical Correlation to Predict the Ignition Delay Time for Some Hydrocarbon Fuels

Jet fuels and Fischer-Tropsch fuels: Surrogate definition and chemical kinetic modeling

DARS FUEL MODEL DEVELOPMENT

Laminar Flame Speeds and Markstein Lengths of n-decane/air, n- Decane/O 2 /He and MCH/Air Flames

Group-Type Analysis (PiPNA) in Diesel and Jet Fuel by Flow Modulated GCxGC FID.

NOx EMISSIONS OF A MILD COMBUSTION BURNER OPERATED WITH JET FUEL SURROGATES

Simulation of single diesel droplet evaporation and combustion process with a unified diesel surrogate

FORMULATION OF A SURROGATE FOR THE SIMULATION OF JET FUEL POOL FIRES

Stanford University Research Program Shock Tube/Laser Absorption Studies of Chemical Kinetics. Ronald K. Hanson

Surrogate Fuels for Transportation Fuels

Ignition delay studies on hydrocarbon fuel with and without additives

Research Article Experimental Study of the Combustion of Kerosene and Binary Surrogate in the Model Combustion Chamber

Flame Studies of Small Hydrocarbons and Oxygenated Fuels

A RCM study on DME-methane-mixtures under stoichiometric to fuel-rich conditions

Introduction to combustion

Nomenclature. I. Introduction. Research Assistant, Department of Mechanical Engineering University of Connecticut, Student Member AIAA.

Module8:Engine Fuels and Their Effects on Emissions Lecture 36:Hydrocarbon Fuels and Quality Requirements FUELS AND EFFECTS ON ENGINE EMISSIONS

REPORT DOCUMENTATION PAGE

Optimization of Synthetic Oxygenated Fuels for Diesel Engines

Synthetic Fuel Formulation from Natural Gas via GTL: A Synopsis and the Path Forward

Fuels, Combustion and Environmental Considerations in Industrial Gas Turbines - Introduction and Overview

Combustion model advances of industrial applications of heating and diesel fuels

INVESTIGATION OF AUTO-IGNITION OF HEPTANE-CNG MIXTURE IN HCCI ENGINE. Firmansyah. Universiti Teknologi PETRONAS

EVALUATION OF JP-8 SURROGATE UNDER SPRAY DIESEL CONDITIONS USING DETAILED CHEMICAL KINETIC MODELS

The Ignition of C 7 -C 16 Normal and Branched Alkanes at Elevated Pressures

CFD Combustion Models for IC Engines. Rolf D. Reitz

Overview & Perspectives for Internal Combustion Engine using STAR-CD. Marc ZELLAT

Shock-tube study of the addition effect of CF 2 BrCl on the ignition of light hydrocarbons

Numerical Study of Multi-Component Spray Combustion with a Discrete Multi- Component Fuel Model

Experimental measurement of ignition delay times of thermally cracked n-decane in shock tube

INVESTIGATION OF THE FUEL PROPERTY INFLUENCE ON NUMBER OF EMITTED PARTICLES AND THEIR SIZE DISTRIBUTION IN A GASOLINE ENGINE WITH DIRECT INJECTION

Prediction of Physical Properties and Cetane Number of Diesel Fuels and the Effect of Aromatic Hydrocarbons on These Entities

ANALYSIS OF GASOLINE RANGE HYDROCARBONS ON BP1-PONA

STUDY OF CHANGES IN THE HYDROCARBON COMPOSITION OF GASOLINE AFTER EACH STAGE REFORMING REACTOR

is the crank angle between the initial spark and the time when about 10% of the charge is burned. θ θ

IGNITION DELAY STUDY OF NEXT GENERATION ALTERNATIVE JET FUELS IN A RAPID COMPRESSION MACHINE KYUNGWOOK MIN THESIS

GCEP. C. T. Bowman, R. K. Hanson, H. Pitsch, D. M. Golden Department of Mechanical Engineering. R. Malhotra SRI International

Geochemical de-risking in Arctic Regions: Identifying Hydrocarbon Phase Before Drilling. Finding Petroleum: Exploring the Arctic 11 th October 2011

Homogeneous Charge Compression Ignition combustion and fuel composition

Potentials of higher alcoholes and oxygenates for engine application

CONVERSION OF WASTE PLASTIC TO FUEL FOR THE DI-CI ENGINE

Autoignition Studies of Alternative Fuels

University Turbine Systems Research Industrial Fellowship. Southwest Research Institute

ABSTRACT INVESTIGATION OF JP-8 AUTOIGNITION UNDER VITIATED COMBUSTION CONDITIONS. Casey Charles Fuller, M.S., 2011

Experimental Investigation of Hot Surface Ignition of Hydrocarbon-Air Mixtures

A Rapid Compression Study of the Butanol Isomers at Elevated Pressure

CHEMKIN-PRO Exhaust Aftertreatment for Gas Turbine Combustors

COOPER BASIN CRUDE OIL. Santos Limited

Ignition Delay Measurements of Iso-octane/Ethanol Blend Fuel in a Rapid Compression Machine

THE USE OF Φ-T MAPS FOR SOOT PREDICTION IN ENGINE MODELING

Internal Combustion Engines

"Power-to-X": Fuel quality - Potential of P2X-Fischer-Tropsch products in aviation

Lecture 4 CFD for Bluff-Body Stabilized Flames

Shock-tube Investigation Of Ignition Delay Times Of Blends Of Methane And Ethane With Oxygen

EXPERIMENTAL VALIDATION AND COMBUSTION MODELING OF A JP-8 SURROGATE IN A SINGLE CYLINDER DIESEL ENGINE

Fundamental Combustion Characteristics of Gasoline Compression Ignition (GCI) Fuels. S. Mani Sarathy, Clean Combustion Research Center, KAUST

FLAME STUDIES ON CONVENTIONAL, ALTERNATIVE, AND SURROGATE JET FUELS, AND THEIR REFERENCE HYDROCARBONS

[Kurrey*, 4.(10): October, 2015] ISSN: (I2OR), Publication Impact Factor: 3.785

CONTROLLING COMBUSTION IN HCCI DIESEL ENGINES

FACE gasoline surrogates formulated by an. enhanced multivariate optimization framework

Estimation Procedure for Following Vapor Pressure Changes

REPORT DOCUMENTATION PAGE

LES of Spray Combustion using Flamelet Generated Manifolds

IGNITION DELAY TIMES OF NATURAL GAS/HYDROGEN BLENDS AT ELEVATED PRESSURES. A Thesis MARISSA LYNN BROWER

Control of PCCI Combustion using Physical and Chemical Characteristics of Mixed Fuel

University of Michigan

Foundations of Thermodynamics and Chemistry. 1 Introduction Preface Model-Building Simulation... 5 References...

MODELING AND ANALYSIS OF DIESEL ENGINE WITH ADDITION OF HYDROGEN-HYDROGEN-OXYGEN GAS

INFLUENCE OF DIESEL SURROGATES ON THE BEHAVIOR OF SIMPLIFIED SPRAY MODELS

Laminar flame speed measurement of multicomponent Jet A-1 and LUCHE kerosene surrogate fuels in elevated pressure and temperature conditions

Oil & Gas. From exploration to distribution. Week 3 V19 Refining Processes (Part 1) Jean-Luc Monsavoir. W3V19 - Refining Processes1 p.

Charles J. Mueller Sandia National Laboratories Livermore, California

METHYLCYCLOHEXANE IGNITION DELAY TIMES UNDER A WIDE RANGE OF CONDITIONS. Thesis. Submitted to. The School of Engineering of the UNIVERSITY OF DAYTON

Ulrich Niemann a, Reinhard Seiser a & Kalyanasundaram Seshadri a a Department of Mechanical and Aerospace Engineering,

Dual Fuel Engine Charge Motion & Combustion Study

AFRL-PR-WP-TP

Effect of Unsaturated Bond on NO x and PAH Formation in n Heptane and 1 Heptene Triple Flames

EXPERIMENTAL INVESTIGATION OF THE EFFECT OF HYDROGEN BLENDING ON THE CONCENTRATION OF POLLUTANTS EMITTED FROM A FOUR STROKE DIESEL ENGINE

Usage Issues and Fischer-Tropsch Commercialization

White Paper.

CRN Application to Predict the NOx Emissions for Industrial Combustion Chamber

Ignition Strategies for Fuel Mixtures in Catalytic Microburners.

INFLUENCE OF FUEL TYPE AND INTAKE AIR PROPERTIES ON COMBUSTION CHARACTERISTICS OF HCCI ENGINE

REDUCTION OF EMISSIONS BY ENHANCING AIR SWIRL IN A DIESEL ENGINE WITH GROOVED CYLINDER HEAD

Combustion Properties of Alternative Liquid Fuels

Chapter 2 : The Composition of Petroleum and its products

Chapter 2 Outline: Alkanes

FUEL FLEXIBLE, ULTRALOW-EMISSIONS COMBUSTION SYSTEM FOR INDUSTRIAL GAS TURBINES

4. With a neat sketch explain in detail about the different types of fuel injection system used in SI engines. (May 2016)

CRN Application to Predict the NOx Emissions for Industrial Combustion Chamber

Lecture 3: Petroleum Refining Overview

Transcription:

Brief Summary of Work in Progress (presented at the Surrogate Fuels Working Group meeting, Jan 6 th 2008, Reno, NV) posted on MURI Website Jan 16, 2008 Principal Investigator: Prof. Frederick L. Dryer Other Co-Investigators and Institutions: Prof. Yiguang Ju Princeton University (PU) Prof. Chih-Jen Sung Case Western Reserve University (CWRU) Prof. Kenneth Brezinsky University of Illinois at Chicago (UIC) Prof. Thomas A. Litzinger Penn State University (PSU) Prof. Robert J. Santoro Penn State University (PSU) Visiting Researchers: Prof. Henry J. Curran (NUI Galway) Princeton University (PU) Technical Management: Dr. Julian Tishkoff, AFOSR AFOSR MURI FA9550-07-1-0515

Objective Brief descriptive summary of some of the efforts underway over the period July 1 December 31, 2007 on this program. Specifics will appear in preprints and publications as well as at the annual progress review being scheduled for early fall, 2008 (Date, Location to be determined)

Current Large Molecule High Temperature Models (Dryer, PU) n-decane Zhao et al. (2005), Burning Velocities and a High Temperature Skeletal Kinetic Model for n-decane, Combust. Sci Tech. 177,89-106. (Updated model available by request; mchaos@princeton.edu) Primary Reference Components Chaos et al. (2007) A High- Temperature Chemical-Kinetic Model for Primary Reference Fuels, Int. J. Chem Kin. 39, 399-414. (Model available in IJCK supplemental materials) Primary Reference + 1 (Toluene) Full range and High T models completed and in use by HONDA, others (Model available on the PU (Dryer) website soon) n-nonane, n-dodecane, n- Hexadecane High T Model developments complete, some validation (Models available by request; mchaos@princeton.edu) τ ign [C total ] 0.86 ; ms (mol/cc) 0.86 τ ign [nc 7 H 16 ] -0.40 [O 2 ] 1.20 ; ms (mol/cc) 0.80 τ ign (ms) 10-4 10-5 10-6 10-4 10-5 0.6 0.65 0.7 0.75 0.8 0.65 0.7 0.75 0.8 0.85 1 0.1 0.4% nc 7 H 16 1.05 atm Vermeer et al. (1972) Model Colket and Spadaccini (2001) Model (a) (c) (e) φ = 0.5 φ = 1.0 φ = 2.0 Model 0.55 0.6 0.65 0.7 0.75 0.8 1000/T (1/K) τ ign [nc 7 H 16 ] -0.40 [O 2 ] 1.30 ; ms (mol/cc) 0.90 τ ign (ms) τ ign (ms) 10-4 10-5 10-6 10-7 1 0.1 10 1 0.1 Burcat et al. (1981) Model 0.6 0.7 0.8 0.9 0.4% nc 7 H 16 1 atm φ 0.6 0.65 0.7 0.75 0.5 0.9 1.0 2.0 Vermeer et al. (1972) Burcat et al. (1981) Colket and Spadaccini (2001) Horning et al. (2002) Smith et al. (2005) Model 4.4% O 2 φ = 1.0 0.6 0.65 0.7 0.75 0.8 1000/T (1/K) (b) (d) 0.65 0.7 0.75 P 1 atm 2 atm 4 atm 6 atm (f) Data Normalized to: 4.4% O 2 1 atm φ = 1.0

Recent Flame Modeling (Dryer, PU) 100 Flame Speed (cm/s) 80 60 40 n-c 10 H 22 T u = 360 K T u = 400 K T u = 470 K Flame Speed (cm/s) 70 60 50 40 30 n-c 12 H 26 T u = 400 K CWRU USC - Linear extrapolation USC - Nonlinear extrapolation 20 0.6 0.8 1 1.2 1.4 φ 0.6 0.8 1 1.2 1.4 1.6 φ Flame Speed (cm/s) 100 80 60 40 n-c 12 H 26 T u = 400 K T u = 470 K Modeling of laminar flame speed data from CWRU (K. Kumar and C.-J. Sung, Combust. Flame 151, 2007, 209-224) using the PU high temperature models for n-decane and n-dodecane are encouraging; similar agreement with recent USC Data for n-dodecane (see AIAA-2008-0972). 0.6 0.8 1 1.2 1.4 φ

n-decane Reactivity VPFR (Dryer, PU) (Low/Int T models in Development) Φ= 1.0; P = 12.5 atm; Res. Time = 1.8 s Mole Fraction (%) 0.8 0.6 0.4 0.2 NTC (Pre-ignition) Hot Ignition O2 CO2 CO H2O 0.0 500 600 700 800 900 Temperature (K)

n-decane Reactivity VPFR (Dryer, PU) (Low/Int T models in Development) Φ= 1.0; P = 12.5 atm; Res. Time = 1.8 s Mole Fraction (%) 0.06 0.04 0.02 n-c10h22 CH2O CH4 C2H4 C3H6 1-C4H8 0.00 500 600 700 800 900 Temperature (K)

Generation of Comprehensive Surrogate Kinetic Models and Validation Databases for Simulating Large Molecular Weight Hydrocarbon Fuels (Ju, PU) Technical Accomplishments Developing the evaporation systems for liquid fuels Validation of evaporation with FTIR Concentration fluctuation < 1% Counterflow experiment for nonpremixed flame extinction Toluene, methane Validation with previous experimental results Future Work Observing extinction & ignition limits For n-dodecane, 1,3,5 trimethylbenzene Effect of fuel blending on ignition & extinction Concentration and temperature measurement With Laser diagnostics (PLIF and Rayleigh scattering) To provide experimental results of flame structure for the validation of kinetic model. Extinction strain rate a E [1/s] Fuel 250 200 150 100 50 Nitrogen Heater & insulation T Heater 1 T 2 Direct photo of non-premixed flame In counterflow burner for toluene Y F = 0.25, a = 76 s -1, and T o = 473 K Present experiment Seshadri (2007) Fuel side temperature T o = 503 K 473 K To burner Schematics of evaporation system Toluene 0 0.1 0.15 0.2 0.25 0.3 0.35 0.4 Fuel mass fraction Y F Comparison of extinction strain rate for toluene

Generation of Comprehensive Surrogate Kinetic Models and Validation Databases for Simulating Large Molecular Weight Hydrocarbon Fuels (Sung, CWRU) Technical Accomplishments (Highlights) Autoignition experiments for two real jet fuels JP-8 and S8 Compressed pressures of 15 and 30 bar Two air fuel mass ratios of 19 (fuel lean) and 13 (fuel rich) Autoignition experiments for three neat surrogate components n-decane, n-dodecane, and Methyl Cyclohexane (MCH) Obtained extensive experimental data and assessed model performances for n- decane autoignition Compressed pressures of 7, 14.3, and 30 bar Equivalence ratios from 0.5 to 2.2 Future Work Complete autoignition experiments of real jet fuels and neat fuels of n- dodecane and MCH Measurement of atmospheric pressure laminar flame speeds of real jet fuels Pressure (bar) Pressure (bar) 25 20 JP-8/Air Mixtures ( Air-to-Fuel Mass Ratio=13.0 ) 15 Initial Conditions T i P i 105.0 C; 1270 Torr 10 112.5 C; 1275 Torr 120.0 C; 1272 Torr 127.5 C; 1290 Torr 5 135.0 C; 1305 Torr End of Compression 0-10 0 10 20 30 40 Time (ms) 25 20 15 10 5 S8/Air Mixtures ( Air-to-Fuel Mass Ratio=13.0 ) End of Compression Initial Conditions T i P i 105.0 C; 1300 Torr 112.5 C; 1290 Torr 120.0 C; 1310 Torr 127.5 C; 1305 Torr 135.0 C; 1305 Torr 0-10 0 10 20 Time (ms) 30 40

Shock Tube and Modeling (Brezinsky, UIC) Researched available vaporizers for high molecular weight fuels Concluded a nebulizer based vaporizer is best Purchased the main component of the vaporizer Aeroneb Lab Nebulizer from Aerogen Designed the casing for the nebulizer Developed protocol for shock tube investigation of aromatic components of jet fuel Purchased 1,2,4- and 1,3,5-trimethyl benzene and n-propylbenzene in preparation for experiments Acquired publicly available published literature models Ran the available low-pressure xylene and propyl-benzene models for the conditions in High Pressure Single Pulse Shock Tube using CHEMKIN in order to establish expected species Planned out experiments on oxidation of m-, o-, and p-xylene using the High Pressure Shock Tube to begin soon Developing models using xylene mechanisms as a basis for extrapolation to 1,2,4- and 1,3,5-trimethyl benzene Techniques: CHEMKIN, Gaussian, group additivity High Pressure experiments and model comparisons for n-heptane and n- heptene oxidation (ESSCI, Paper A-18, 2007)

Sooting and High Pressure Autoignition (Santoro/Litzinger, PSU) Two New Graduate Projects underway Amy Mensch - TSI technique, application to determining Smoke Heights of surrogate fuel mixtures and real fuels Measurements of the TSI values for n-decane, n-dodecane, n-propybenzene, 1,3,5 trimethylbenzene and 1- methylnaphthalene. Check formulation rules for surrogate components and conversion of TSI measurements to Soot Points. Venkatesh Lyer - high-pressure autoignition work and will start officially on January 2, 2008.

Surrogate Composition Effects: A Comparison of Surrogate Mixture Candidates with Combustion Targets (H/C, TSI, CN) (Work in Progress) Zhiwei Yang, Marcos Chaos, Frederick L. Dryer Mechanical and Aerospace Engineering Princeton University January 15, 2008 AFOSR MURI FA9550-07-1-0515

Objectives A comparison of surrogate mixtures of various components with combustion targets: overall H/C ratio, sooting characteristics, autoignition characteristics Utilize mixture TSI, CN as representatives for sooting and autoignition Experimental verification of these choices is required Further refinements for diffusive ignition/extinction to be considered in future

Reference Information TSI values are obtained from Olson et al. (1985) CN numbers are taken from Santana et al. (2006) Linear relationships for TSI (Yang et al., 2007) and CN (Murphy et al., 2004) were adopted for computing mixture values TSI mix = Σx i TSI i CN mix = Σv i CN i where x i and v i are the mole and volumetric fractions, respectively, of each species. Limits of H/C, TSI, CN, were estimated or taken from data listed in the Petroleum Quality Information System (PQIS) 2006 report: http://www.desc.dla.mil/dcm/files/2006pqisreport.pdf

Jet Fuel Survey (2006 PQIS Report) JP-8 JA-1 Hydrogen Content (mass %) Min Max Avg. Min Max Avg. 13.40 14.78 13.81 NR NR NR H/C Ratio 1.844 2.067 1.909 NR NR NR Cetane Index 31.8 56.8 43.9 NR NR NR Smoke Point (SP, mm) Aromatics (liq. vol %) 19.0 31.0 22.7 24.0 27.0 26.2 0.10 24.60 17.86 15.20 19.40 17.58 TSI (*) 15.72 25.66 21.47 19.71 22.17 20.31 Density (g/ml, 15 o C) 0.7800 0.8325 0.8038 0.7865 0.7986 0.7904 NR Not Reported (*) TSI values are estimated here assuming C 11 H 21 for JP-8 and C 12 H 23 for Jet-A using TSI=3.18(MW/SP) (Yang et al., 2007), where MW is the molecular weight.

4- to 6-Component Surrogates

Violi et al. (2002a) Sur_1 Objective: Match distillation curve and sooting propensity important for pool fire. H/C, TSI and CN of the jet fuel were not reported. All targets within listed ranges. Mole fraction % H/C TSI Cetane# m-xylene 20.9 1.25 49-13 iso-octane 10.4 2.25 6.4 15 n-dodecane 22.5 2.167 5.1 87 n-tetradecane 13.2 2.143 5.4 95 methylcyclohexane 26.8 2.0 4.9 22 tetralin 6.2 1.2 61 13 Goal Aromatic (liq. vol. %) 1.84-2.07 16-26 32-57 Actual 20.0% 1.91 17.88 49.45

Violi et al. (2002a) Sur_3 Objective: Match distillation curve and sooting propensity important for pool fire. H/C, TSI and CN of the jet fuel were not reported. TSI and CN values significantly outside target ranges. Mole fraction % H/C TSI Cetane# iso-octane 6.2 2.25 6.4 15 n-dodecane 59.8 2.167 5.1 87 methylcyclohexane 14.5 2.0 4.9 22 benzene 2.1 1.0 29 0 toluene 17.4 1.143 44 10.0 Goal Aromatic (liq. vol. %) 1.84-2.07 16-26 32-57 Actual 11.0% 2.02 12.43 67.85

Violi et al. (2002b) H/C, TSI and CN of the jet fuel were not reported. CN value higher that target. Mole fraction % H/C TSI Cetane# n-decane 22.4 2.2 4.2 76.73 iso-octane 5.3 2.25 6.4 15 n-dodecane 19.2 2.167 5.1 87 n-tetradecane 13.4 2.143 5.4 95 methylcyclohexane 6.8 2.0 4.9 22 toluene 32.9 1.143 44 10 Goal Aromatic (liq. vol. %) 1.84-2.07 16-26 32-57 Actual 20.0% 1.92 17.78 63.72

Objective: (unspecified) Montgomery et al. (2002) TSI and CN values significantly outside target ranges. Mole fraction % H/C TSI Cetane# n-dodecane 34.7 2.167 5.1 87 methylcyclohexane 10 2.0 4.9 22 n-decane 32.6 2.2 4.2 77 butylbenzene 16 1.4 62 15 Goal Aromatic (liq. vol. %) 1.84-2.07 16-26 32-57 Actual 13.8% 2.03 14.28 66.20

Agosta et al. (2003) S1 Objective: Match autoignition behavior of JP-8 in a flow reactor. The H/C, TSI and CN of the JP-8 in this work were not reported. Marginal TSI on high end. Mole fraction % H/C TSI Cetane# iso-cetane 18.4 2.125 14.6 15 n-dodecane 37.2 2.167 5.1 87 methylcyclohexane 23.2 2.0 4.9 22 1-methylnaphthalene 21.2 0.91 91 0.0 Goal Aromatic (liq. vol. %) 1.84-2.07 16-26 32-57 Actual 15.0% 1.87 25 44.57

Agosta et al. (2003) S5 Objective: Match autoignition behavior of JP-8 in a flow reactor. The H/C, TSI and CN of the JP-8 in this work were not reported. Linear Cetane number prediction of the mixture is 33. Paper reports CN as 43 from nonlinear empirical blending rules based upon NTC kinetic comparisons Mole fraction % H/C TSI Cetane# iso-cetane 24.1 2.125 14.6 15 n-dodecane 22.2 2.167 5.1 87 methylcyclohexane 21.3 2.0 4.9 22 decalin 7.4 1.8 15 33.0 1-methylnaphthalene 25 0.91 91 0.0 Goal Aromatic (liq. vol. %) 1.84-2.07 16-26 32-57 Actual 18.0% 1.81 29.57 32.91

Cooke et al. (2005) Objective: Match temperature profile in OPPDIF. TSI and CN values significantly outside target ranges. Mole fraction % H/C TSI Cetane# m-xylene 15 1.25 49-13 iso-octane 10 2.25 6.4 15 n-dodecane 30 2.167 5.1 87 n-tetradecane 20 2.143 5.4 95 methylcyclohexane 20 2.0 4.9 22 tetralin 5 1.2 61 13 Goal Aromatic (liq. vol. %) 1.84-2.07 16-26 32-57 Actual 13.5% 1.99 14.63 61.35

Eddings et al. (2005) Hex-11 Objective: Match distillation curve, burning rate, radiant heat flux, and sooting tendency in pool fire. TSI of the Jet-A fuel in this work is 26.7, CN not available. Marginal TSI on low end, high CN. Mole fraction % H/C TSI Cetane# m-xylene 8.5 1.25 49-13 n-dodecane 40 2.167 5.1 87 decalin 35 1.8 15 33 n-octane 3.5 2.25 3.2 64 n-hexadecane 5 2.125 6 100 tetralin 8 1.2 61 13 Goal Aromatic (liq. vol. %) 1.84-2.07 16-26 32-57 Actual 11.4% 1.92 16.75 61.64

Eddings et al. (2005) Hex-12 Objective: Match distillation curve, burning rate, radiant heat flux, and sooting tendency in pool fire. TSI of the Jet-A fuel in this work is 26.7, CN not available. Marginal H/C on low end, high CN. Mole fraction % H/C TSI Cetane# m-xylene 15 1.25 49-13 n-dodecane 30 2.167 5.1 87 decalin 27 1.8 15 33 n-octane 3 2.25 3.2 64 n-hexadecane 12 2.125 6 100 tetralin 13 1.2 61 13 Goal Aromatic (liq. vol. %) 1.84-2.07 16-26 32-57 Actual 19.4% 1.86 21.68 59.70

Vasu et al. (2008) Stanford A Objective: Match ignition delay behind reflected shock wave of JP-8. The JP-8 in this work has a CN of 43.3. TSI and CN values significantly outside target ranges. H/C close to the upper limits. Mole fraction % H/C TSI Cetane# iso-octane 25 2.25 6.4 15 n-dodecane 54 2.167 5.1 87 methylcyclohexane 10 2.0 4.9 22 benzene 1 1.0 29 0 toluene 10 1.143 44 10.0 Goal Aromatic (liq. vol. %) 1.84-2.07 16-26 32-57 Actual 6.1% 2.09 9.5 62

Vasu et al. (2008) Stanford B Objective: Match ignition delay behind reflected shock wave of JP-8. The JP-8 in this work has a CN of 43.3. Marginal TSI value CN outside target ranges Mole fraction % H/C TSI Cetane# iso-octane 5.5 2.25 6.4 15 n-dodecane 54 2.167 5.1 87 methylcyclohexane 10 2.0 4.9 22 benzene 1 1.0 29 0 toluene 29.5 1.143 44 10.0 Goal Aromatic (liq. vol. %) 1.84-2.07 16-26 32-57 Actual 18.2% 1.93 16.87 64.45

3-Component Surrogates

Guéret et al. (1990) Objective: study species concentration in a jet-stirred reactor. TSI of the mixture is 11, Cetane number is significantly higher than upper limit. Marginal H/C Mole fraction % H/C TSI Cetane # n-undecane 74.7 2.18 4.5 81 n-propylcyclohexane 11.7 2 4.9 52 1,2,4-trimethylbenzene 13.5 1.33 52 10 Goal Aromatic (liq. vol. %) 1.84-2.07 16-26 32-57 Actual 9.5% 2.07 11 71.46

Dagaut et al. (1990) Objective: match jet-stirred reactor species profile of Jet A1 fuel. TSI of the mixture is 10.8 Cetane number is significantly higher than upper limit. Mole fraction % H/C TSI Cetane# n-decane 74 2.2 4.2 76.73 n-propylcyclohexane 11 2 4.9 52 n-propylbenzene 15 1.33 47 17 Goal Aromatic (liq. vol. %) 1.84-2.07 16-26 32-57 Actual 18.4% 2.06 10.75 65.48

SERDP Surrogates (from the SERDP Website)

SERDP Soot Project SERDP1 Source: Med Colket 2007 SERDP Workshop presentation. Objective: development of surrogates matching engine soot emissions of jet fuels TSI computed using the relationship of Yang et al. (2007) with measured smoke point Mole fraction % H/C TSI Cetane# iso-cetane 23.9 2.125 14.6 15 n-decane 42.4 2.2 4.2 77 methylcyclohexane 15.4 2.0 4.9 22 n-propylbenzene 7 1.33 47 16 1,3,5-trimethylbenzene 7.1 1.33 52 2 1-methylnaphthalene 4.2 0.91 91 0 Goal Aromatic (liq. vol. %) 1.84-2.07 16-26 32-57 Actual 13% 1.997 19.6 40.45

SERDP Soot Project SERDP2 Source: Med Colket 2007 SERDP Workshop presentation. Objective: development of surrogates matching engine soot emissions of jet fuels TSI computed using the relationship of Yang et al. (2007) with measured smoke point Marginal CN Mole fraction % H/C TSI Cetane# iso-cetane 32.5 2.125 14.6 15 n-decane 32.5 2.2 4.2 77 methylcyclohexane 16 2.0 4.9 22 n-propylbenzene 7.3 1.33 47 16 1,3,5-trimethylbenzene 7.3 1.33 52 2 1-methylnaphthalene 4.4 0.91 91 0 Goal Aromatic (liq. vol. %) 1.84-2.07 16-26 32-57 Actual 13% 1.991 20.9 33.66

SERDP Soot Project SERDP3 Source: Med Colket 2007 SERDP Workshop presentation. Objective: development of surrogates matching engine soot emissions of jet fuels TSI computed using the relationship of Yang et al. (2007) with measured smoke point Mole fraction % H/C TSI Cetane# iso-cetane 32.6 2.125 14.6 15 n-decane 39.7 2.2 4.2 77 methylcyclohexane 6.6 2.0 4.9 22 n-propylbenzene 6 1.33 47 16 1,3,5-trimethylbenzene 12.1 1.33 52 2 1-methylnaphthalene 3 0.91 91 0 Goal Aromatic (liq. vol. %) 1.84-2.07 16-26 32-57 Actual 14% 2.000 21.5 36.77

Other Surrogates

Others (1 or 2 Components) The following models using 1 or 2 components (composition in mol %) all have some values outside target ranges. H/C TSI Cetane# Goal 1.84-2.07 22-30 32-57 n-decane (100%); Dagaut et al. (1994) 2.20 4.2 76.7 n-decane (89%), ethylbenzene (11%); Lindstedt and Maurice (2000) n-dodecane (46%), iso-cetane(54%); Agosta et al. (2004) n-dodecane (25%), methylcyclohexane (75%); Agosta et al. (2004) n-dodecane (39%), 1-methylnaphthalene (61%) Agosta et al. (2004) n-decane (80%), n-propylbenzene (20%); Eberius et al. (2001) 2.12 9.7 71.8 2.14 10.2 43.8 2.06 5.0 45.3 1.43 57.5 44.4 2.04 12.8 67.5

Large Surrogates ( > 10 components) Schulz (1991) 12-component surrogate matching chemical classes found in JP-8: n-decane (15%), n-dodecane (20%), n-tetradecane (15%), n- hexadecane (10%), iso-octane (5%), MCH (5%), cyclooctane (5%), o- xylene (5%), butylbenzene (5%), tetramethylbenzene (5%), 1- methylnaphthalene (5%), tetralin (5%) Note: mass fractions Aromatics (liq. vol.) 21.5%; H/C 1.87; TSI 21.6; CN 59.70 Wood et al. (1989) 14-component surrogate for JP-4, matching compound classes and distillation curve: n-hexane (5.5%), n-heptane (8%), n-octane (8%), n-nonane (10%), n- decane (10%), n-dodecane (10%), n-tetradecane (10%), cyclohexane (8%), methylcyclohexane (8%), cyclooctane (8%), toluene (8%), decalin (5%), tetralin (1%), 1-methylnaphthalene(0.5%) Note: liquid volume fractions Aromatics (liq. vol.) 9.5%; H/C 1.94; TSI 10.28; CN 52.20 Comments: Choosing so many components is not warranted with current understanding of jet fuel surrogate properties, kinetic models, and available validation data.

Matching Jet Fuel with Gasoline Surrogate Components

(Modified) Gasoline Surrogate Components (1) For the combination of n-c 7 H 16 /i-c 8 H 18 /toluene: To match TSI first, i-c 8 H 18 is preferable over n-c 7 H 16, the minimum amount of toluene needed is 25.5 mol% (18.1 vol%) in the i- C 8 H 18 /toluene mixture. To match H/C first, i-c 8 H 18 is also preferable over n-c 7 H 16, the highest amount of toluene allowed is 39.8 mol% (30 vol%). It is possible to match TSI, H/C, and CN, as shown in the table. The highest possible CN is 42.7, the highest possible TSI is 19.4. Low average molecular weight (~100 g/mol) Mole fraction H/C TSI Cetane# n-heptane 55% 2.29 2.6 54 iso-octane 10 % 2.25 6.4 15 toluene 35 % 1.143 44 10.0 Goal Aromatic (liq. vol. %) 1.84-2.07 16-26 32-57 Actual 27.7% 1.89 17.5 37

(Modified) Gasoline Surrogate Components (2) For the combination of n-c 10 H 22 /i-c 8 H 18 /toluene: To match TSI first, i-c 8 H 18 is preferable over n-c 10 H 22, the minimum amount of toluene needed is 25.5 mol% (18.1 vol%) in the i- C 8 H 18 /toluene mixture To match H/C first, n-c 10 H 22 is preferable over i-c 8 H 18, the highest amount of toluene allowed is 42.1 mol% (28.4 vol%). It is possible to match TSI, H/C, and CN, as shown in the table. The highest possible CN is 56.2, the highest possible TSI is 21.2. Low average molecular weight (~125 g/mol) Mole fraction H/C TSI Cetane# iso-octane 40.9 % 2.25 6.4 15 n-decane 31.6% 2.2 4.2 76.73 toluene 27.5 % 1.143 44 10.0 Goal Aromatic (liq. vol. %) 1.84-2.07 16-26 32-57 Actual 18.5% 1.98 16.0 38.1

Match Species Classes Matching the species classes exactly using surrogate candidates Marginal CN values. Mole fraction H/C TSI Cetane# n-decane 27.0% 2.2 4.2 76.73 i-cetane 28.3% 2.125 14.6 15 decalin 7.8% 1.8 15 46 methylcyclohexane 17.3% 2.0 4.9 22 n-propylbenzene 12.7% 1.33 47 17 1-methylnaphthalene 6.8% 0.91 91 0 Goal Aromatic (liq. vol. %) 1.84-2.07 16-26 32-57 Actual 13.9% 1.94 19.44 32.71

Summary Most of the surrogate formulations in literature have TSI and cetane number significantly outside the range of average JP 8 fuels. Aromatic liq. vol. fraction H/C (1.84-2.07) TSI (16-26) Cetane# (32-57) Violi (2002a), Sur_1 20.0% 1.91 17.9 49.5 Violi (2002a), Sur_3 11.0% 2.02 12.4 67.9 Violi (200b) 20.0% 1.92 17.8 63.7 Cooke (2005) 13.5% 1.99 15 61.4 Eddings (2005), Hex_11 11.4% 1.92 16.8 61.6 Eddings (2005), Hex_12 19.4% 1.86 21.7 59.7 Agosta (2003), S5 18.0% 1.81 29.6 32.9 Vasu (2008), Stanford A 6.1% 2.09 9.5 62.0 Vasu (2008), Stanford B 18.2% 1.93 16.9 64.5

Target Issues Experimental verification of TSI for components and mixture predictions. Comparison of mixture and jet fuel TSIs. Experimental verification of CN blending rules for surrogate mixture candidates (investigating IQT as comparison method). Comparison of mixture and jet fuel CNs. Verification of ignition qualities of surrogate mixtures and jet fuels using other merits (VPFR reactivity, RCM, Shock Tube Ignition delay measurements).

References A. Agosta, N.P. Cernansky, D.L. Miller, T. Favarelli, E. Ranzi, Exp. Therm. Fluid Sci. 28 (2004) 701 708. A. Agosta, D.B Lenhert, D.L. Miller, N.P. Cernansky, Proceedings of the 3rd Joint Meeting of the US Sections of the Combustion Institute (2003) paper E07. J.A. Cooke, M. Bellucci, M.D. Smooke, A. Gomez, A. Violi, T. Faravelli, E. Ranzi, Proc. Combust. Inst. 30 (2005) 439 446. P. Dagaut, A. El Bakali, A. Ristori, Fuel 85 (2006) 944-956. P. Dagaut, M. Reuillon, J.-C. Boettner, M. Cathonnet, Proc. Combust. Inst. 25 (1994) 919-926. E.G. Eddings, S. Yan, W. Ciro, A.F. Sarofim, Combust. Sci. Tech. 177 (2005) 715 739. H. Eberius, P. Frank, T. Kick, C. Naumann, U. Steil, C. Wahl, EU project computational fluid dynamics for combustion no. GRD1-1999 10325, Final report for subtask 1.2.3. (D 1.7); 2001. C. Guéret, M. Cathonnet, J.-C. Boettner, F. Gaillard, Proc. Combust. Inst. 23 (1990) 211 216. R.P. Lindstedt, L.Q. Maurice, J. Prop. Power 16 (2000) 187 195. C.J. Montgomery, S.M. Cannon, M.A. Mawid, B. Sekar, AIAA Paper No. 2002-0336. M.J. Murphy, J.D. Taylor, R.L. McCormick, http://www.nrel.gov/vehiclesandfuels/pdfs/sr368051.pdf D.B. Olson, J.C. Pickens, R.J. Gill, Combust. Flame 62 (1985) 43-60. R.C. Santana, P.T. Do, M. Santikunaporn, W.E. Alvarez, J.D. Taylor, E.L. Sughrue, D.E. Resasco, Fuel 85 (2006) 643-656. W.D. Schulz, ACS Petrol. Chem. Div. Preprints 37 (1991) 383-392. S.S. Vasu, D.F. Davidson, R.K. Hanson, Combust. Flame 152 (2008) 125-143. A. Violi, S. Yan, E.G. Eddings, A.F. Sarofim, S. Granata, T. Faravelli, E. Ranzi, Combust. Sci. Tech. 174 (2002a) 399-417. A. Violi, S. Yan, E.G. Eddings, A.F. Sarofim, S. Granata, T. Faravelli, E. Ranzi, Proceedings of the 2nd Mediterranean Combustion Symposium, Sharm El-Sheikh, Egypt, January 6-11 (2002b) p.961-971. C.P. Wood, V.G. McDonell, R.A. Smith, G.S. Samuelsen, J. Prop. Power 5 (1989) 399-405. Y. Yang, A.L. Boehman, R.J. Santoro, Combust. Flame 149 (2007) 191-205.

Cetane Determination Methods Cetane Engine Testing (ASTM D-613 ) This method requires the use of an industry standard test engine equipped with accepted instrumentation and operated under specific conditions. In this test, the engine compression ratio is varied for the test sample and reference fuels of known cetane number to obtain a fixed ignition delay. The compression ratio of the sample is bracketed by those of two reference fuels. The cetane number of the sample fuel is determined by estimating between the two reference fuel points (iso-cetane (15) and n-hexadecane (100). Cetane Index (ASTM D-976 or D-4737) Often substituted for cetane number because D-613 is expensive and time-consuming. The calculated cetane index is derived from the fuel's density and boiling range. While useful for estimating the cetane number of distillate fuels, this technique can not be applied to fuels containing additives that raise cetane number. These additives do not change the fuel density or distillation profile, so they do not alter the calculated cetane index. IQT Ignition Quality Testing (ASTM D6890, IP 498) A rapid, constant volume combustion method based upon Southwest Research Institute apparatus development that determines the pressure- and temperaturedependent autoignition characteristics of fuels. Emerging as an internationally accepted testing method for fuel qualification. Can be easily applied to single components, mixtures, and real (both petroleum derived and alternative) fuels to determine CN and test CN emulations.