Combustion Modeling of Hydrocarbons & Scramjet Propulsion System Design .

Dr. Ivan A. Gargurevich

Combustion & ProcessTechnologies (2005)

Reference Document as: Gargurevich, Ivan A, , Combustion Modeling of Hydrocarbons &

Scramjet Propulsion System design, Combustion & Process Technologies, White paper/Private
Communication, 2005, Los Angeles, California, ivan_gargurevich@yahoo.com

The general research objective is to Develop a hydrocarbon chemical kinetics modeling approach and
capability suitable for design applications for scramjet propulsion for hypersonic flight. The objective will be
achieved through the development of detailed chemical kinetic models for the combustion of heavy
hydrocarbons such as JP fuel, and the application of kinetic model reduction methods to reduce the number
of reactions and species without the loss of accuracy. The reduced chemical kinetics model will be
designed to couple with a state-of-the-art 3-D Navier Stokes solver CFD model by other facility. The coupled
model will allow accurate and cost-effective profiling of the flow, heat release, and combustion chemistry in
scramjets, allowing the prediction of key design parameters such as ignition delay and extinction.

The proposed research is innovative in that:

(1) The development of Kinetic Model Reduction applicable to complex fluid flows. Only recently have CFD
simulations involving more than 10 chemical species become common; at present most reacting flow
simulations are done using rather drastic approximations (Schwer et al., An Adaptive Chemistry Approach
to Modeling Complex Kinetics in Reacting Flows, Comb. And Flame, vol. 133, pp. 451-465, 2003.).
(2) Most Scramjet combustor simulations are deficient in the description of the physical phenomena taken
place and for the most part have been 2-D ( Riggins et al., Modeling of Supersonic Combustor Flows Using
Parallel Computing, Computing Systems in Engineering, vol. 3, Nos 1-4, pp. 217-229, 1992). The work in
this proposal will result in more accurate, and robust CFD simulations in 3-D.
(3) The identification of a detailed chemical kinetic model to simulate JP fuel combustion, whether it consists
of a hydrocarbon mixture or a surrogate fuel molecule, which after reduction will accurately describe the
most important features of Scramjet combustors.

A. Detailed Chemical Kinetic Models Development

Due to the continuous development in computer power and speed as well as developments in techniques
for estimating rate coefficients and numerical methods for the solution of practical combustion problems,
chemical reaction engineering and detailed chemical kinetic modeling are becoming more predominant both
in academia and industry [1, 2]. Warnatz [3] and Simmie [4] outline the necessary steps in the development
of a working mechanism: (a) collection of the necessary elementary reactions, (b) gathering thermodynamic
data and kinetic rate coefficient data for the reactions from the literature or by computation, (c) validation of
the mechanism with the help of experimental data, and (c) application of sensitivity analysis to the model
results. As a result of the validation, modifications are made to the mechanism to better reproduce the
experimental results.

Sophisticated combustion mechanisms are available for the combustion of a simple molecule such as
methane [4].The mechanisms consist of hundreds of reactions and species despite the simplicity of the
molecular structure. However, most of the fuels involved in practical combustion devices are complex
mixtures of hydrocarbon molecules. Commercial gasoline includes hundreds of species that can affect the
operation and performance of gasoline engines. Detailed reaction mechanisms for gasoline can involve
1000 species and 4000 elementary reactions. Kinetic mechanisms for jet fuels and diesel fuels present the
same complexity, and comprehensive kinetic mechanisms for these fuels are still under development [2, 5].

For a comprehensive scramjet combustion design model, the chemical kinetics will need to be coupled into
a computational fluid dynamics (CFD) model (Navier-Stokes equations solver). The inclusion of chemical
reactions (with associated heat release) complicates the solution of the Navier- Stokes equations, and can

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lead to large computational requirements even for a small number of reactions. Kinetic mechanism
reduction methods have been developed by several authors [6, 7, and 8] and may have to be considered.

An integral part of the kinetic model is the thermodynamic properties for radical and intermediate species,
and temperature dependent rate coefficients. For uni-molecular reactions, and reactions involving chemical
activation, the situation is more complex since the rate coefficients may have also pressure dependence
depending on the temperature, and pressure of the system studied [9]. It is always preferable to use
experimentally determined data, and the same can be said of thermodynamic properties for the chemical
species composing the mechanism. An estimate of the thermodynamic properties of molecules and radicals
can be made by the methods described by Benson [18, 19] using group and bond additivity methods.
Software packages are available to perform this task [19]. Similarly, methods such as Quantitative
Structure-Reactivity relationships can be used for the estimation of reaction rate coefficients.

If experimental data is lacking, Computational chemistry allows the estimate of activation energy for a given
elementary reaction. Transition state theory can then be applied to generate the kinetic rate coefficient for
the elementary reaction in the high pressure limit .Quantum Rice-Rampsperger-Kassel (QRRK) methods
have been developed for handling uni-molecular and chemical activated reactions [11, 12] which are
pressure dependent.

B. 3-D Numerical Simulation of Scramjet Propulsion (By other facility; section included to
demonstrate the complexity of combustion system modeling)
A Scramjet engine or Supersonic Combustion Ramjet has no moving parts. The Scramjet achieves
compression of the intake air by the forward speed of the air, and combustion takes place at supersonic
speed through the engine. Thrust is developed by the expansion of the hot combustion gases through the
outlet nozzle. Hydrogen has been the conventional fuel used in this type of engine. However Hydrocarbon
fuels offer some advantages over Hydrogen fuel such as high density and low boiling points resulting in less
storage volume. One of the primary challenges facing scramjet propulsion is the ability to achieve and
maintain combustion at high speed. In essence, the combustion reaction must initiate and come to
completion within extremely short periods of time (on the order of 1 millisecond). At the present time,
scientists and engineers do not have the modeling tools for reliable design of scramjet propulsion.
Furthermore, engine conditions associated with scramjet propulsion are complicated by the fact that
chemical reaction time scales are comparable to transport time scales so that the assumption of chemical
equilibrium applicable to subsonic flow does not apply [15].

C. Approaches to Detailed Chemical Kinetic Model Reduction

Chemical Kinetic models are now available for processes such as combustion, and pyrolysis involving
hundreds of species and thousands of reactions for applications ranging from the design of steam crackers
to the design of combustion engines [8]. Wang and Frenklach [13] discuss some of several approaches that
have been pursued in the reduction of complex kinetic models: (a) Development of a small number of global
reactions that reproduce the dynamic evolution for a given set of conditions, (b) direct reduction of the size
of a detailed mechanism, (c) lumping of chemical systems with specific reaction topology, and (d) mapping
of the species concentration dependencies on model variables.

Wang and Frenklach use two different criteria to eliminate reactions in a mechanism of methane
combustion: a reference rate of reaction, and a reference heat of reaction. Their method seems to do a
reasonable job of predicting flame speeds and temperature profiles with the reduced methane mechanism.

Maas and Pope [6] use a dynamical approach based on decoupling from the detailed mechanism chemical
reactions with fast time scales since local equilibrium can be assumed, i.e., reactions are in partial
equilibrium and species are in steady state. Schwer et al. [8] use an adaptive chemistry approach. In this
approach, a set of reduced chemical kinetic models is used in simulation, each reduced model being used
only under reaction conditions where it is faithful to the full model. Bhattacharjee et al. [7] propose a
reaction-elimination approach. The reduced models thus retain the original species, but only a small subset
of the reactions in the original mechanism. The problem of selecting the reactions to be included in the
reduced mechanism has been well studied using optimization and other approaches. The number of

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reactions in the reduced mechanism is typically minimized subject to some constraint that aims to ensure
satisfactory agreement between the full and reduced mechanism

D. The Problem with Reduced Kinetic Models

Schwer et al. [8] states well the problems to be faced in the reduction of any detailed chemical kinetic
model: There have been important recent advances in kinetic model reduction, and in the related areas of
sensitivity analysis and uncertainty analysis. Work on low-dimensional manifolds1 and computational
singular perturbation theory suggests that excellent reductions exist for virtually all kinetic models, though it
remains a computationally expensive task to identify the optimal low-dimensional manifold (i.e., reduced
model) for any large kinetic model over a large range of conditions, and it is difficult to know if these
reduced mechanisms are accurate. There have also been many recent advances in so called Adaptive
Chemistry methods which make use of a set of reduced chemical kinetic models, each model being used
only under reaction conditions where it is faithful to a full kinetic model. However, the fact remains that any
reduced kinetic model will only be faithful to the original model over a limited range of conditions. This is a
very serious limitation in modeling any system where the reaction conditions (e.g., temperature and
composition) vary dramatically in space and time.

E. Development Challenges
Developing a detailed chemical kinetic model for JP fuels as called for in the research will represent a
significant challenge. As stated above, this is a result of the number of chemical species composing the fuel.
The number of radical species and intermediates involved in the destruction of the fuel can be in the
hundreds, the same can be said of the number of reactions.

Practical fuels are complex mixtures of several hundred hydrocarbons and the exact composition is very
difficult to determine. For liquid commercial fuels, the most precise information is generally the hydrocarbon
class distribution [5]. For this reason, and to avoid the almost impossible task of considering every
compound, simpler hydrocarbon blends or surrogate fuels are used to mimic the real fuel. One example of
this is the kinetic modeling of diesel fuel combustion. A surrogate fuel, n-heptane, has been used to model
the diesel since its cetane number is 56, which is close to that of commercial diesel [5]. Simmie [4] presents
a comprehensive review of chemical kinetic models for hydrocarbon fuels: alkanes up to decane, alkenes
and dienes such as ethane, propene, and butanes, alkynes up to five carbon atoms, and aromatics such as
benzene. However, comprehensive models for complex fuels such as gasoline, diesel or jet fuel are yet to
be developed.

F. Integration of a Combustion Model in the Navier- Stokes Simulation (included for completeness,
and to illustrate the complexity of modeling actual combustion devices)

The application of CFD for modeling scramjets is relatively recent, with most of the developments having
taken place over the last 5 years [20]. Although there are numerous experimental facilities dedicated to
studying scramjets, CFD must be used in order to evaluate performance of the vehicle at actual flight
conditions. Many of the CFD analysis to date are confined to 2-D representations due to the enormous
computer resources required to solve the entire 3-D flow field of the Scramjet combustor.

Oevermann [15] indicates some of the problems involved in the integration of kinetic models in scramjet
simulations. He indicates that analysis by other investigators of the combustion of hydrogen in scramjets
indicate that the combustion is in the flamelet regime These studies however have been applied to simple
geometries. The flow in scramjets is much more complicated including the formation of shock waves which
would tend to disrupt the flamelets. Furthermore, development is needed in the area of physical models and
sophisticated numerical techniques for an accurate computation. Another challenge in the development of
scramjet modeling consists of the development of numerical methods for the treatment of aerated liquid
injectors such as cavity flame holder configurations [17].

References
[1] Westbrook, C. K., and Dryer, F. L., Chemical Kinetic Modeling of Hydrocarbon Combustion, Prog. Energy
Combust. Sci., vol 10, pp. 1-57, 1984

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[2] Ranzi, E. et al., Lumping Procedures in Detailed Kinetic Modeling of Gasification, Pyrolysis, Partial Oxidation, and
Combustion of Hydrocarbon Mixtures, Prog. Energy Combust. Sci., vol. 27, pp. 99-139, 2001 [3] Warnatz, J.,
Hydrocarbon Oxidation High-Temperature Chemistry, Pure Appl. Chem., vol. 72, no. 1, pp. 2101-2110, 2000.
[4] Simmie, J. M., Detailed Chemical Kinetic Models for the Combustion of Hydrocarbon Fuels, Prog. Energy
Combust. Sci., vol. 29, pp. 599-634, 2003.
[5] Cathonnet, M., Advances and Challenges in Chemical Kinetics of Combustion, in the Proceedings of the
European Combustion Meeting, 2003.
[6] Maas, U. and Pope, S. B., Simplifying Chemical Kinetics: Intrinsic Low-Dimensional Manifolds in Composite
Space, Comb. And Flame, vol. 88, pp.293-264, 1992.
[7] Bhattacharjee, Binita et al., Optimally-Reduced Kinetic Models: Reaction Elimination in Large-Scale Kinetic
Models, Comb. And Flame, 135, pp. 91-208, 2003.
[8] Schwer, Douglas et al., An Adaptive Chemistry Approach to Modeling Complex Kinetics in Reactive Flows, Comb.
And Flame, vol 133, pp. 451-465, 2003.
[9] SEnkan, Selim M., Detailed Chemical Kinetic Modeling: Chemical Reaction Engineering of the Future, in Advances
in Chemical Engineering, vol. 18, pp. 95-195, Academic Press, 1992.
[10] Dorsett, H. and White, A., Overview of Molecular Modeling and Ab-Initio Molecular Orbital Methods Suitable for
use with Energetic Materials, DSTO Aeronautical and Maritime Research Laboratory, Weapons Systems Division,
Report DSTO-GD-0253, Salisbury South Australia, Australia, September 2000.
[11] Westmoreland, P. R. et al., AICHE Journal, vol 32, p 1971, 1986.
[12] Nguyen, Minh Tho et al., Kinetic Analysis Combining Quantum Chemical and Quantum Statistical Methods: Some
Case Studies. J. Phys. Chem., vol. 100, pp.10956-10966, 1996.
[13] Wang, H, and Frenklach, M., Detailed Reduction of Reaction Mechanisms for
Flame Modeling, Comb. And Flame, vol. 87, pp. 365-370, 1991.
[14] Bertin, John J et al., Fifty Years of Hypersonics: Where Weve been, Where Were Going, Progress in, Aerospace
Sciences, vol. 39, pp. 511-536, 2003.
[15]Oevermann, M., Numerical Investigation of Turbulent Hydrogen Combustion in a Scramjet Using Flamelet
Modeling, Aerosp. Sci. Technol., vol. 4, pp. 463-480, 2000.
[16] Mathur, T. et al., Supersonic Combustion Experiments with a Cavity-Based Fuel Injector, Journal of Propulsion
and Power, vol. 17, no. 6, p.1305, 2001.
[17] Fan, Thomas C. et al., Validation of a Hybrid Reynolds-Averaged/Large Eddy Simulation Method for Simulating
Cavity Flame holder Configurations, AIAA 2001-2929, 31st AIAA Fluid Dynamics Conference and Exhibit.
[18] Benson, S. W., Thermo chemical Kinetics, 2nd edition, Wiley, New York, 1976.
[19] Dahm, K. D. et al., Experimental Modeling Investigation of the Thermal decomposition of n-dodecane, J. Anal.
Appl. Pyrolysis, vol. 71, pp. 865-881, 2004.
[20] Riggins, D., Modeling of Supersonic Combustor Flows Using Parallel Computing, Computing Systems
Engineering, vol. 3, nos 1-4, pp. 217-229, 1992.

Experimental Validation of Chemical Kinetic Model

A good general reference in this area is the book by J. Warnatz, Maas and Dibblel, Combustion; Physical &
Chemical Fundamentals, Modeling & Simulation, Experiments, Pollutant Formation, 3rd edition, Springer,
2001.
A. Apparatus
The experimental validation of the chemical kinetic model constructed to deal with the reaction system at
hand can make use of different apparatus as described by the well known manuscript by Westbrook et al.
(Chemical Kinetics Modeling of Hydrocarbon Combustion, Prog. Energy Combust. Sci., 1984, vol. 10, pp.
1-57). These include: shock tubes, plug flow reactors, flame apparatus. Shock tubes can be used to
investigate the initiation reactions of fuels due to characteristic time limitations. Plug flow reactors operate at
relatively lower temperatures than flames, but allow a much better validation of a chemical kinetic
mechanism. Similarly flames can allow also the validation of complex kinetic mechanisms. The type of
flames that can be used for validation can be one-dimensional laminar flames (probably the simplest
technique for validation), non-turbulent diffusion flames (jet, counter-flow, co-flow configurations). The
selection of validation apparatus must be chosen with care considering system temperature and pressure,
transport phenomena, and system flow patterns and configuration.
B. Sampling
There are techniques that can be made use to sample the composition of the reacting system during
validation: optical probing with lasers, but are usually limited in the number of species that can be studied,
and the laser is relatively expensive. (See, Robert M. Fristrom, Flame Structures Studies: Past, Present
and Future, Pure & Appl. Chem., vol. 62, No. 5, pp. 839-849, 1990; and the review Katharina Kohse-

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Hoinghaus et al., Combustion at the Focus: Laser Diagnostics and Control, Proceedings of The
Combustion Institute, 30, (2005), pp. 89-123). One great application of laser sampling is the possibility of
measuring important radical species such as H, OH, and O.

Microprobes can be built to minimize flame disturbance for example. Microprobes make it possible a
complete analysis of the gas mixture when coupled with GC/MS analytical instruments, they are also
relatively inexpensive. (See Gargurevich, Ivan, Combustion Models and the Prediction of Polycyclic
Aromatic Hydrocarbons (PAH) in Laminar Flames of Simple Hydrocarbons: Methane, Methyl Chloride, and
1,1 Di-chloroethane, UCLA, PhD Dissertation, 1997; this work gives the specifications for such a sampling
system). Several areas of controversy are reaction freezing in the microprobe for proper sampling, and the
inability to measure radical species. Probe pressure seems to be a very important parameter for proper
sampling.
C. Temperature Measurements
1. The measurement of flame temperature with fine wire thermocouples is also a complicated issue
due to radiation losses, heat losses to ceramic support, heat losses to the gas phase as well as
possible solid accumulation in fuel rich flames. This is nevertheless a common method of
temperature measurement.
2. Another most recent development in flame temperature measurement is the use of Laser
Diagnostics (see Katharina Kohse-Hoinghaus review quoted above). However, this is a relatively
expensive alternative.

An excellent review of a flame study experimental apparatus describing microprobe issues , thermocouple
temperature measurements, as well as general system design can be found in Apparatus for Studying
Premix Laminar Flames Using Mass Spectrometry and Fiber-Optic Spectrometry by Jim O. Olsson et al,
Rev. Sci. Instrum., vol 6, no. 3, March 1990, pp. 1029-1036.

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