16th European Symposium on Computer Aided Process Engineering

and 9th International Symposium on Process Systems Engineering

W. Marquardt, C. Pantelides (Editors) 383
© 2006 Published by Elsevier B.V.

Automatic generation of reduced reaction

mechanisms for hydrocarbon oxidation with
application to autoignition boundary prediction for
explosion hazards mitigation
R. Portera, M. Fairweathera, J.F. Griffithsb, K.J. Hughesb, A.S. Tomlina
a
School of Process, Environment and Materials Engineering and bSchool of Chemistry,
University of Leeds, Leeds LS2 9JT, UK

Abstract
In this work we present an automatic method for removing species and reactions from
comprehensive reaction mechanisms without significant detriment to model
performance. Numerical methods are applied to a lean n-butane - air closed vessel
system. A method for the automatic construction of closed vessel ambient temperature -
composition (Ta – φ) ignition diagrams is presented, which is used to evaluate the
comprehensive and reduced models. Application of the quasi-steady state
approximation to the reduced mechanism has been proven to significantly reduce the
number of species with very little loss of output accuracy.

Keywords: Combustion, autoignition, lean n-butane-air, QSSA, sensitivity analysis.

1. Introduction

Despite our considerable knowledge of the potential hazards associated with the
chemical process industries, explosion hazards continue to occur during hydrocarbon
processing under partial oxidation conditions. Among the reasons for this is the change
of conditions that arise from process intensification, combined with an incomplete
knowledge of the oxidation characteristics of the processed materials. The ability to
couple chemical kinetics with fluid dynamics and simulate these processes in reactive
multi-dimensional flows would be a powerful process engineering tool that would
constitute a significant advance in methodologies available to predict such hazards.
Detailed combustion kinetic mechanisms contain hundreds of chemical species and
thousands of reactions, making them too computationally expensive to be solved in
computational fluid dynamics (CFD) codes. By adopting formal mathematical
procedures, more compact and computationally efficient kinetic models can be
generated by reducing the numbers of species and reactions from the detailed
mechanisms. Currently, this involves running full kinetic models with multiple initial
conditions in a non CFD-based environment, interpreting the results using local
sensitivity methods, identifying and removing redundant species and reactions, and then
testing the reduced mechanisms. Many hours can be saved by automating these tasks
using programming techniques.
In this paper we describe software which can be used to automatically minimise the
numbers of chemical species and reactions without loss of important kinetic detail. The
codes are based on the use of UNIX shell scripts to completely automate the utilisation
of numerical integration and local sensitivity analysis software. Reduced chemical
models which can be used in higher dimensional simulations are obtained as output.
384 R. Porter et al.

The bench-mark is set by the performance of the full scheme and the criteria for
performance of the reduced models are matched to this.
As well as being fundamental to the potential hazards, an important basis for
validation of the models is the ignition diagram as a function of ambient temperature
versus composition or pressure, in which is mapped a wide range of combustion
regimes. The construction of the numerically predicted ignition diagram is also a
laborious process which is amenable to automatic generation. This new software,
encompassing automation in both areas, is applied in the present work to illustrate the
accurate reproduction of ignition and cool flame boundaries over a range of operating
conditions using significantly reduced kinetic schemes when compared with the full
models adopted at the outset.

2. Methodology and Models

The comprehensive model to which the methods were applied was derived at CNRS-
DCPR, Nancy [1] for n-butane oxidation, comprising 125 species in 314 irreversible
reactions and 417 reversible reactions. The reversible reactions can be expressed as
irreversible pairs equivalent to a total of 1148 irreversible reactions for the full scheme.
The resulting system of ordinary differential equations was solved using the SPRINT
integration package [2] for a closed vessel system with spatial uniformity assumed. An
ambient temperature – composition (Ta – φ) ignition diagram was automatically
constructed using developed software which can categorise the various non-isothermal
behaviour such as 2-stage autoignition, cool flames, and slow reaction by monitioring
temperature and gradient changes in the predicted temperature profiles. The software
works by conducting a series of simulations over the selected temperature range of 550
– 750 K at specified intervals of 5 K and at a fixed pressure and composition where
exclusively 2-stage ignition occurs. Then a bisection method is employed in which the
partial fuel pressure is initially halved (while maintaining the total pressure), and then
progressively adjusted in order to locate the boundary between ignition and cool flame
or slow reaction behaviour, and similarly for the cases where cool flame behaviour is
observed, to locate the cool flame/slow reaction boundary. These calculations proceed
until the desired level of accuracy is obtained, in this case to 0.5 torr. Similar software
has been developed to compute the pressure – ambient temperature ignition diagram.
The resulting Ta – φ ignition diagram was used as the benchmark against which the
reduced models were tested.
Using the ignition diagram as reference, a number of different operating conditions
were selected covering a representative range of the temperature/composition space at
which sensitivity analysis and mechanism reduction are to be performed. A shell script
was set up to run the integration code at each chosen condition, and manipulate the
output data files. Time points from the calculated temperature profiles at the chosen
operating conditions were automatically selected on the basis of ΔT and the gradient of
each trajectory, as shown in fig. 1. Information related to these conditions and rate data
from the mechanism were used to identify necessary species via the investigation of the
Jacobian matrix [3] using algorithms incorporated into the SPRINT code originally
implemented in the KINALC package [4, 5]. The necessary species include selected
important species as defined by the user, and other species for which realistic
concentrations are required in order to reproduce the concentrations of important
species or important reaction features. The union of identified necessary species was
taken at the selected time points and the irreversible consuming and reversible reactions
Automatic Generation of Reduced Reaction Mechanisms for Hydrocarbon Oxidation 385

of all redundant species removed. The resulting mechanism was then converted to
irreversible form for further analysis.
Via a similar process, techniques were then used to identify reactions that can be
eliminated. Local sensitivity analysis was used to identify redundant reactions by
consideration of the rate sensitivity matrix F~ :
~ k j ∂f i
F= , (1)
f i ∂k j
where kj is the rate parameter of the jth reaction and fi is the rate of production of
species i. The effect of a change of each rate parameter on the rates of production of
necessary species is given by a least-squares objective function:
2
⎛ k j ∂f i ⎞
Bj = ∑⎜ ⎟ . ( 2)
⎜ ⎟
i ⎝ f i ∂k j ⎠

A reaction is considered important if it has a Bj value above a user specified threshold.

Finally, principal component analysis based on the eigenvalue-eigenvector
~ ~
decomposition of the cross-product matrix FT F , was used to identify redundant
reactions. Each eigenvector represents a set of coupled reactions whose relative
contributions are shown by the relative size of the eigenvector elements. Thresholds
were defined for the significant magnitudes of the eigenvalues and eigenvectors and this
provided an automatic way of deciding which reactions can be eliminated [6-8].
Considerable improvement in the performance of the reduced models can be
achieved by using subsets of necessary species relevant for each specific time point
within the objective function, rather than the combined set of necessary species acquired
from the species reduction. This is illustrated in Fig. 2 by comparing reduced
mechanisms obtained using Equation 2, with either the full set of species included in the
summation i, or time point specific sets as identified by the local Jacobian matrix. A
similar result would follow from principal component analysis.

1200 1200

1000 1000
T/K
T/K

800 800

600 600
0.35 0.40 0.45 0.50 0.35 0.40 0.45 0.50
t/s t/s

Fig. 1. Automatically selected time points
during simulated 2-stage ignition in the viscinity
of the transition from cool flame to ignition.
The first time point was automatically selected
at 0.003 seconds.
Fig. 2. Comparison of using all necessary
species or a subset at each time point in the
objective function. Unbroken line – species
reduced, 715 reaction mechanism. Dotted line –
subset reduced, 449 reaction mechanism.
Dashed line – all necessary species reduced, 449
reaction mechanism.
386 R. Porter et al.

3. Application of the Quasi-Steady State Approximation

The application of the above sensitivity methods leads to a skeleton mechanism with
all redundant species and reactions removed. However, in many cases the level of
reduction achieved by such methods is not sufficient for application of the chemical
model within complex flow computations. Subsequent reduction may be based on
exploiting the time-scales present in the mechanism, with a range of reduction
techniques falling into this category including intrinsic low dimensional manifold
(ILDM) based methods [9] and methods based on the application of the quasi-steady
state approximation (QSSA). QSSA based methods are commonly used in kinetic
model reduction by assuming that fast reacting species locally equilibrate with respect
to the slower species within the system. The concentration of the QSSA species can
then be approximated via the algebraic expression f i q = 0, rather than a differential
equation, where the superscript q denotes a QSSA species. In many cases QSSA species
can be removed via simple reaction lumping. Alternatively, the concentration of species
ci can be expressed in terms of the concentrations of other species in the system and the
rate parameters. Such expressions can be solved either analytically or via iterative
techniques for sets of highly coupled species. The choice species suitable for application
of the QSSA can be determined in a variety of ways including using perturbation
methods. The instantaneous QSSA error for a single species, was defined in [10] using a
local linear perturbation method as:
1 fi
Δ c is = , (3)
c i J ii
where Jii is the diagonal element of the chemical Jacobian for species i. Although the
QSSA errors vary throughout the simulations, peaking during ignition, for many species
the errors remain below a certain threshold throughout. Using a tolerance of 1% across
all selected time-points for the QSSA error, 31 QSSA species can be automatically
identified. Many have fairly simple reaction structures and therefore can be removed via
the methods illustrated in the following example.
1 2 3 4
RH R RO2 QOOH O2QOOH
-2 -3 -4

6 5

R' + alkene OH + product

Fig. 3. Reaction sequence to which the QSSA was applied.

In the reaction sequence shown in Fig. 3, solving the algebraic expressions resulting
from the application of the QSSA for the highlighted species can be demonstrated to be
equivalent to the lumping of several of the individual reaction steps resulting in the
removal of RO2, QOOH and O2QOOH. The central part of the reaction sequence can
then be replaced by:
R ⎯⎯→
2'
OH + product,
where
k 2' = k 2 (1 − k − 2 (k −2 + k 3 − k 3 k −3 (k −3 + k 4 − k 4 k − 4 (k −4 + k 5 )))).
Automatic Generation of Reduced Reaction Mechanisms for Hydrocarbon Oxidation 387

Then R can be removed to leave the final reaction sequence:

RH ⎯
⎯→
7
R ' + alkene
RH ⎯
⎯→
8
OH + product,
where

⎛ k ⎞ ⎛ k' ⎞
k 7 = k1 ⎜⎜ ' 6 ⎟⎟ and k 8 = k1 ⎜⎜ ' 2 ⎟⎟.
⎝ k 2 + k6 ⎠ ⎝ k2 + k6 ⎠

In the simplest approach, k2’ is assumed to be a constant fraction of k2, and set at the
fraction calculated in the region of maximum flux through R to OH + product. A rate of
production analysis of the full scheme shows this to be a good approximation in this
instance, and applying it gives simulated temperature profiles in excellent agreement
with those obtained from the original scheme. The ratio of k7 to k8 is not constant, and
changes significantly with temperature, favouring k8 at low temperatures and switching
over to k7 at high temperatures. Even so, assuming a constant ratio based on that
applicable at low temperatures still gives very good agreement in the simulated
temperature profiles, with only slight deviation at the later times and higher
temperatures where this approximation is no longer valid. A more rigorous approach is
to program directly the variation of k2’, k7 and k8 with temperature, although this results
in a loss of compatibility of the reduced mechanism with commercial simulation
packages such as CHEMKIN. Of the QSSA species identified, 14 were easily removed
by applying the method highlighted above resulting in a final mechanism of 58 species
and 270 reactions.

4. Model Validation and Application of Sensitivity Analysis

Fig. 4 shows the experimental and simulated Ta – φ ignition diagrams for n-butane +
air. The qualitative features of the experimental Ta – φ ignition boundary [11], shown in
Fig. 4, are captured by the numerical models showing both cool flame and two stage
ignition behaviour. The reverse “s” shape of the ignition boundary is displayed by the

Slow
750 Reaction 750

Cool flame
700 700

Experiment
Ta / K
Ta / K

650 650
2-stage
Cool flame ignition 2-stage
600 600 ignition

Slow
Reaction
550 550
0.0 0.5 1.0 1.5 2.0 2.5 1.6 1.8 2.0 2.2
% n-C4H10 by volume in air % n-C4H10 by volume in air

Fig. 4. Comparison of experimental and full Fig. 5. Comparison of full scheme (solid line),
scheme Ta – φ ignition diagrams. species reduced (dotted line) and QSSA reduced
(dashed line) Ta – φ ignition boundaries.
388 R. Porter et al.

models and this is an important validation. However, quantitative disagreements with

the experiment remain, especially at higher temperatures where the model over-predicts
the autoignition temperatures. This may imply a shortcoming in the way that the
intermediate molecular products that lead to high-temperature reactions are interpreted.
There may also be some discrepancy due to inhomegeneities of temperature in the
unstirred vessel [11].
Comparison of the model results shows that both reduced mechanisms illustrated in
Fig.5 reproduce the behaviour of the full scheme extremely well. The scheme produced
by removal of redundant species from the full scheme produced a mechanism
comprising of 72 necessary species and 713 irreversible reactions, generated a Ta – φ
ignition diagram that matched that of the full scheme very closely. Further reduction by
removal of redundant reactions and applying the QSSA to remove a further 14 species,
giving a scheme of 58 necessary species and 270 reactions, also behaved very well, with
only minor deviations to the full scheme prediction. It is possible to apply different cut
off values in these methods in order to reduce the mechanisms still further but at a cost
of a reduced level of agreement with the full scheme. By specifying higher thresholds
for the eigenvalues and eigenvectors of principal component analysis, prior to QSSA, it
is possible to reduce the numbers of reactions even further. However, the increasing
error induced by this reduction was considered to be unsatisfactory since it gave little
extra computational saving.

5. Conclusions

Software for the automatic construction of ignition diagrams has been developed.
Programming techniques have allowed the automatic and systematic reduction of a lean
n-butane - air kinetic model, simulated in a closed vessel. Comparisons of the
predictions of full and reduced schemes have shown that the numbers of species and
reactions have been successfully reduced. Further reductions have been achieved using
the quasi-steady state approximation to lump reactions and further reduce species.

Acknowledgement
The authors gratefully acknowledge financial support from the EU (EVG1-CT-2002-
00072-SAFEKINEX) and from EPSRC (GR/R42726/01).

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