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Accuracy and Flexibility of Simplified Kinetic


Models for CFD applications

Article · June 2009

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Accuracy and Flexibility of Simplified Kinetic Models for CFD
applications
A. Cuoci, A. Frassoldati, T. Faravelli, E. Ranzi
Dipartimento di Chimica, Materiali, Ingegneria Chimica – Politecnico di Milano - ITALY

1. Introduction
During the 80s there was a particular attention on the development of reliable global
mechanisms for the combustion of hydrocarbons [1-3]. The reason of such attention was
found in the fact that successful combustion modelling needs to take into account all the
fundamental aspects and not only detailed chemistry. Turbulence, heat and mass transfer
strongly affect simulation results. However, it was not possible at that time to couple detailed
fluid dynamics with more than a few reactions. Despite the increasing power and memory of
modern PC, there is still nowadays the need of simplified kinetic mechanisms to be coupled
with CFD codes. Several reasons explain this need. From one side, the increasing detail of
fluid dynamic description. RANS approaches are replaced by more accurate Large Eddy
Simulation, computationally very expensive. In the next future, the scientists are sighting the
Direct Numerical Simulations. On the other side, fuels different from simple methane are
considered. Liquid fuels, like diesel or jet fuels, are investigated because of their importance
in several applications like engines. In this last contest, a further push to revise actual
available global mechanisms is the presence of mixtures, where the synergistic effect of the
most reactive component has to be taken into account.
Literature about single or multi-step oxidation mechanisms refers the evaluation of kinetic
parameters and reaction orders to some ‘regression approaches’. Results carried out in Plug
Flow Reactors or flame speed measures are used to adjust the kinetic parameters. Starting
points are chemical analyses of the reaction pathways. More recently data from non adiabatic
PSR were also used to identify the rate constants [4].
This paper presents new estimations of the parameters of multistep oxidation mechanisms.
These evaluations are based on a regression of data with a very effective numerical algorithm
[5]. The main novelty is the definition of the set of comparison measures. In order to take into
account the quite broad temperature and stoichiometry ranges of a turbulent diffusive flame,
the regression analysis is performed over data obtained by a detailed kinetic scheme in
laminar diffusive counter-flow flames. These flames are assumed as a good representation of
the real flame [6], still maintaining a simple solution, compatible with the numerical effort
required by the regression algorithm.

2. Detailed and multistep kinetic models


The source of data to be regressed comes from a detailed kinetic mechanism (already
developed and validated for hydrocarbons up to 16 C atoms [7]), freely available on the web:
www.chem.polim.it/creckmodeling. The model showed to be accurate in predicting the
pyrolysis, oxidation and combustion of pure components and mixtures in wide ranges of
conditions (in terms of pressures, temperatures, stoichiometries and residence times). On
these bases, the results coming from this kinetic model are assumed as ‘correct measures’.
As mentioned, several global mechanisms are available in the literature. In principle, the

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Combustion Colloquia 2009 32nd Meeting on Combustion

Reaction Reaction rate


40700

1 CO + 0.5O2 ⎯⎯
→ CO 2 r1 = 2.24 ⋅ 1012 e RT
[CO ][ H 2O ]
40700

2 CO 2 ⎯⎯
→ CO + 0.5O2 r2 = 5 ⋅ 108 e RT
[CO2 ]
7400

3 H 2 + 0.5O2 ⎯⎯
→ H 2O r3 = 9.87 ⋅108 e RT
[ H 2 ][O2 ]
Units of reaction parameters are: cal, mol, l, s.

Table 1. Dryer-Westbrook mechanism (WD).

Reaction Reaction rate


20000
1 ⎯⎯
→ CO 2 + H 2
CO + H 2 O ←⎯
⎯ r1 = 2.75 ⋅ 109 e

RT
[CO ][ H 2O ]
40000

2 H 2 + 0.5O2 ⎯⎯
→ H 2O r2 = 6.80 ⋅1015 T e −1 RT
[ H 2 ]0.25 [O2 ]1.50
98000

3 H 2 O ⎯⎯
→ H 2 + 0.5O2 r3 = 1.25 ⋅1017 T −0.877 e RT
[ H 2O ][ H 2 ]−0.75 [O2 ]
Units of reaction parameters are: cal, mol, l, s.

Table 2. Jones-Lindstedt mechanism (JL).

present approach allows to consider any of them or to propose new schemes. In the present
paper, as an example of the whole strategy, the combustion of syngas (40% CO, 30% H2, 30%
N2 by volume) is analyzed. The starting point is represented by the global mechanisms of
Westbrook and Dryer [2] and Jones and Lindstedt [3, 8], reported in Table 1 and Table 2
respectively. The reverse rate constants of non elementary reactions have to be carefully
derived and in particular the reaction orders (see for example reaction WD1). Generally
speaking, assuming the following non elementary equilibrium reaction:
NS
→ cC+dD rf = k f ( T ) ∏ Ciυ f ,i
⎯⎯
aA + bB ←⎯
⎯ (1)
i =1

where υ f ,i is the order in the forward reaction of each of NS species and Ci its
concentration, the reverse reaction expression is:
kf NS

∏C
υb ,i
rb = NS
− ∑ ni
i (2)
K eq ⋅ ( RT ) i =1 i =1

where ni is the stoichiometric coefficient ( a, b, c, d ) of each species ( A, B, C , D ) and υb,i its


order in the reverse reaction. υb,i can be simply derived from the order of the forward reaction
and from the stoichiometric coefficient: υb,i = υ f ,i + ni .
Non elementary reactions with orders lower than 1 might cause numerical problems, because
of possible negative values of the concentration. A solution is a linearization of the rate
expression when the concentration of the reactants becomes lower than a certain value.
A simple example can show this approach. The species A is consumed with a reaction
rate r = kC αA , where α is less than one. The mass balance can be then written as
1 (1−α )
dC A dt = − kC αA , whose solution is C A = ⎡⎣C 1A−0α − (1 − α ) kt ⎤⎦ , being C A0 the initial A
concentration. When the time is higher than t = C 1A−0α ⎡⎣(1 − α ) k ⎤⎦ , C A becomes lower than

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Combustion Colloquia 2009 32nd Meeting on Combustion

zero with several problems arising if a numerical solution is adopted. To overcome these
difficulties it is possible identify a small threshold value ( C AT ) of C A , below which an order
one reaction is assumed: r = kC % α , where k% is estimated making equal the two reaction rates
A
α
for C A = C AT : kC AT = kC % % α −1
AT ⇒ k = kC AT . The transition between the two reaction rates is

obtained through an expression, able to avoid discontinuities in the function and in its
derivatives. The final rate constant expression covering the whole time range is then:
r = ξ kC αA + (1 − ξ ) kC αAT−1C A , where ξ is a proper function based on hyperbolic tangent, which
allow the continuous transition:
1⎡ ⎛ CA ⎞ ⎤
ξ = ⎢ tanh ⎜ σ − τ ⎟ + 1⎥ (3)
2⎣ ⎝ C AT ⎠ ⎦
where σ and τ are two constants. Figure 1 shows the impact of this approach on the solution.
The two results are very similar and only zooming at very low concentrations, it is possible to
observe the correction introduced.

Figure 1. Concentration of A with


(blue line) and without (red line) the
0.08 linearization (CA0=0.09 mol/l; =-0.3;
8e-9
0.06 k=10 mol0.3/l0.3/s). Small figure zooms
4e-9 the zone where the functions
cA

0.04 approach zero. The constants and


0.02 0.0 are chosen equal to 23 and 17
respectively.
0.00
0.000 0.002 0.004
t (s)

3. Tuning procedure
The proposed procedure to determine the kinetic parameters of a global mechanism and the
reaction orders is based on the ‘experimental measures’ generated by the detailed kinetic
model [7]. Turbulent diffusive flames can be thought as the results of laminar flamelets. In
this light, it is clear that selection of laminar counter-flow diffusion flames results particularly
convenient as regression device. Furthermore, a sensitivity analysis showed that the best
operative conditions where the temperature and composition profiles are affected by the rate
parameters are those close to the flame extinction. It is quite obvious that the chemistry plays
a fundamental role when the residence times are short, i.e. at high strain rates. The use of data
obtained also for lower strain rates did not significantly modify either the values of the
estimated parameters or the accuracy of the global model coming from the regression of just
the flame close to extension. On the contrary, different feed compositions allowed to improve
the performances. In particular, partially premixed flames were adopted. The introduction of
the oxidizer in the fuel feed allows to enlarge the reaction zone and to better characterize the
chemical phenomena in the rich side close to the flame front.
It has to be noted that typical kinetic regressions are challenging problems. As a matter of
facts, kinetic models are typically strongly nonlinear and, consequently, algorithms adopted
for parameter estimation must be both robust and flexible enough to deal with constraints that
are not always analytically definable. In this case the function evaluations are quite time
consuming and then the algorithm has also to be effective. This work applies a numerical
algorithm specifically conceived for kinetic regression: ‘BzzNonLinearRegression’ class [5],
which is a free software for non commercial use.

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4. Results
Several counter-flow diffusion flames, at different Flame I Flame II
strain rates (from 10 s-1 up to the extinction) and
with different fuel compositions, were adopted to strain rate (s-1) 100 500
carry out the regression. In particular, Table 3 vfuel (cm/s) 29.87 149.3
reports two of these flames (called Flame I and vair (cm/s) 25 125
Flame II), for which some numerical results will be
proposed. Table 3. Operative conditions of the
Figure 2 shows the calculated peak temperature of ‘experimental flames’.
counter flow diffusion flames at different strain
rates by using the detailed kinetic mechanism and the simplified mechanisms in their original
formulation (see Table 1 and Table 2). It is evident that the temperature is largely
overestimated by both the global mechanisms (more than 300K), especially when the strain
rate is low. Moreover, while the extinction strain rate predicted by the WD mechanisms is
much larger (~6500 s-1) than the corresponding value predicted by the detailed scheme (~4500
s-1), the JL mechanisms predicts a smaller value (~3500 s-1). Figure 3 shows the predicted
numerical profiles of temperature and carbon monoxide for Flame II. These curves mirror the
results reported in Figure 2, confirming that the simplified mechanisms are not able to
correctly describe the main reaction zone. It is reasonable to expect a similar trend also in a
turbulent flame.
The large differences in the predicted temperature profiles justify the need and the possibility
to revise the original simplified mechanisms to obtain a better agreement with the detailed
kinetic scheme. The first step in the ‘optimization’ procedure consists in finding the kinetic
parameters which are more suitable for the non linear regression. In other words, the
regression cannot be performed using all the available kinetic parameters, because their
number is usually too large. It is better to choose only the parameters to which the flame is
more sensitive. These parameters are chosen following the indications suggested by a
sensitivity analysis, with respect to every kinetic parameter in the global kinetic scheme.
Following this simple procedure, it is possible to select a relatively small number of
parameters (usually less than 10), in order to reduce the computational time and the
dimensions of the overall regression problem can be greatly reduced. The most significant
parameters for the problem under investigation were found using this approach and are
reported in Table 4 and Table 5.
The regression was performed on different sets of ‘experimental data’, obtained through
different combinations of counter flow diffusion flames. As previously mentioned, the
numerical results suggest that it is better to use flames with large strain rates, because in these
conditions the effects of the chemistry are more important and therefore the regression is

2300 Detailed 2200 Detailed Flame II


WD WD
flame temperature [K]

2100 JL 1800 JL
temperature [K]

1900 1400

1700 1000

1500 600

1300 200
0 1000 2000 3000 4000 5000 6000 7000 0.35 0.40 0.45 0.50 0.55 0.60 0.65
strain rate [s-1] distance from fuel nozzle [cm]

Figure 2. Flame temperature: comparison Figure 3. Temperature profiles in Flame II:


between kinetic schemes. comparison between kinetic schemes.

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Original Optimized Original Optimized


Reaction Parameter Reaction Parameter
Value Value Value Value
1 A 2.24·1012 2.30·1011 1 A 2.75·109 2.63·1010
1 Ea 40700 31700 1 Ea 20000 18500
2 A 5·108 4.45·109 2 A 6.70·1015 6.80·1014
2 Ea 40700 41300 2 Ea 40000 37700
3 A 9.87·108 1.35·108 3 A 1.25·1017 1.07·1018
3 Ea 7400 6900 3 Ea 98000 94000
3 υ f ,H 2
1 0.87 2 υ f ,H 2
0.25 0.33
3 υ f ,O 2
1 1.10 2 υ f ,O 2
1.50 1.40
Units of reaction parameters are: cal, mol, l, s. Units of reaction parameters are: cal, mol, l, s.

Table 4. Optimized WD mechanism. Table 5. Optimized JL mechanism.


performed on experimental data more sensitive to the kinetic parameters. For example, this
means that the parameters obtained from the regression on the single Flame II (large strain
rate) work pretty well also for Flame I (low strain rate), but the opposite is not true. Therefore,
if it is necessary to reduce the number of ‘experimental flames’ for reasons related to the
excessive computational time, it is more convenient to work on flames with a large strain rate.
The kinetic parameters obtained from the regression are summarized in Table 4 and Table 5.
These parameters describe pretty well the counter flow diffusion flames in a large range of
strain rates. As an example, Figure 4 compares the temperature profiles of Flames I and II
obtained using the optimized global kinetic schemes with the detailed kinetic scheme. The
agreement is largely improved if compared with the original result (Figure 3). In particular,
the peak temperature and the flame front are correctly predicted.
The optimized kinetic schemes were then applied to a turbulent flame, in order to check if a
real improvement with respect to the original mechanisms can be obtained under turbulent
conditions. A simple jet flame, fed with syngas (with the same composition used for the
counter flow diffusion flames), in a coflow of air, was chosen as a test case [9]. This is a
relatively simple system, which can be simulated using a 2D grid and applying the same
detailed kinetic model adopted for the regression. The simulations are performed on a
structured grid with ~16000 cells, by using a RANS approach and the modified - model
(C1 =1.60). The EDC model was chosen for describing the interactions between chemistry
and turbulence. Figure 5 shows the temperature profiles along the axis of this flame, as
obtained by using the detailed kinetic scheme and the original simplified mechanisms (Table
1 and Table 2) and the comparison with the experimental measurements. The detailed
mechanism predicts very well the temperature profile, while both the global mechanisms lead
to a large overestimation of the temperature, which confirms the results obtained in the

2200 2200
Detailed Flame I Detailed Flame II
WD WD
1800 1800
JL JL
temperature [K]

temperature [K]

1400 1400

1000 1000

600 600

200 200
0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.35 0.40 0.45 0.50 0.55 0.60 0.65
distance from fuel nozzle [cm] distance from fuel nozzle [cm]

Figure 4. Temperature profiles in Flame I and II: optimized kinetic schemes.

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2200
2200 Detailed WD
WD JL
1800
1800 JL Exp.
temperature [K]

temperature [K]
Exp.
1400
1400

1000
1000

600 600

200 200
0.00 100.00 200.00 300.00 400.00 500.00 0.00 100.00 200.00 300.00 400.00 500.00
axial coordinate [mm] axial coordinate [mm]

Figure 5. Axial profiles of temperature in the Figure 6. Axial profiles of temperature in the
turbulent flame: original kinetic schemes. turbulent flame: optimized kinetic schemes.
counter flow diffusion flames. This over-estimation (more than 250K) is not small and can
lead to negative consequences on the prediction of pollutant species, heat transfer
calculations, etc. On the contrary, the optimized kinetic schemes (Table 4 and Table 5)
strongly improve the numerical predictions, as reported in Figure 5. The revised WD and JL
mechanisms show a satisfactory agreement with the experimental measurements, by greatly
reducing the original temperature over-estimation, even if they tend to move the peak
temperature closer to the inlet.

5. Conclusions
In this work the need and the possibility to improve the existing simplified mechanisms
describing the combustion of syngas were demonstrated. A procedure based on non linear
regression was used to improve two simplified mechanisms, available in the literature and
largely adopted by the combustion community. The novelty of the proposed approach is
represented by the choice of ‘experimental data’, which correspond to an appropriate set of
counter flow diffusion flames. The ‘optimized mechanisms’ were applied to a turbulent jet
flame, showing a strong improvement with respect the original mechanisms.
Further investigations and improvements are needed to confirm the feasibility of this
procedure. In particular, the choice of the counter flow diffusion flames to adopt for the
optimization must be better defined. However, the results reported in this work appear
promising, especially for the formulation of new kinetic schemes for fuel mixtures.

6. Acknowledgments
The authors acknowledge the financial support of CNR/DET program “Gas naturale”.

7. References
1. Hautman D.J., Dryer F.L., Schug K.P., Glassman I., Combust. Sci. Technol., 25:219 (1981)
2. Westbrook C.K., Dryer F.C., Prog. Energy Combust. Sci., 10:1 (1984)
3. Jones W.P., Lindstedt R.P., Combust. Flame, 73:223 (1988)
4. Nicol D.G., Malte P.C., Hamer A.J., Roby R.J., Steele R.C., Proc. Intl. Gas Turbines and
Aeroengine Congress and Exhibition (1998)
5. Buzzi Ferraris G., Manenti F., Chem. Eng. Science, 64:1061 (2009)
6. Peters N., Prog. Energy Combust. Sci., 10:319 (1984)
7. Ranzi E., Frassoldati A., Granata S., Faravelli T., Ind. Eng. Chem. Res., 44:5170 (2005)
8. Andersen J., Rasmussen C.L., Giselsson T., Glarborg P., Energy Fuels, In press (2009)
9. Barlow R.S., Fiechtner G.J., Carter C.D., Chen J.Y., Combust. Flame, 120:549 (2000)

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