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312824 Development of a Methodology to Obtain

the Kinetic Mechanism of Steam Methane
Reforming Compact Reactor Using...

Conference Paper November 2013

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Development of a methodology to obtain the kinetic mechanism of
steam methane reforming compact reactor using CFD coupled with
a hybrid genetic/surface response optimization model
Moreira, R. P. M.(1), Almeida, L. C.(1), Ropelato, K., Bacchi, R. D. A. (1), Passarelli, F.
M.(2), Bidart, A. M. F.(2), Quintella Coelho, E. F. A.

(1) ESSS Engineering Simulation and Scientific Software, Rua Orlando Phillipi, n 100. Edifcio
Techplan, 1 andar Saco Grande - Florianopolis/SC, Brazil. CEP: 88032-700.
(2) CENPES PETROBRAS Research and Development Center, Cidade Universitaria Q.7 - Ilha
do Fundao - Rio de Janeiro/RJ, Brazil. CEP: 21949-900.

ESSS - Engineering Simulation and Scientific Software and PETROBRAS S.A.

Prepared for Presentation at Topical Conference on Catalysys and Reaction Engineering

2013 AIChE Annual Meeting, November 3 8, 2013, Hilton San Francisco Union Square, San
Francisco, CA, at the session:
Computational Fluid Dynamics in Chemical Reaction Engineering
Unpublished
AIChE shall not be responsible for statements or opinions contained
in papers or printed in its publications

ABSTRACT

The present work describes an application of CFD simulation coupled with a genetic multi-
objective algorithm in order to obtain a reaction mechanism for steam methane reforming, water gas
shift and methane combustion inside a catalytic reactor. The optimization methodology makes it
possible for the engineering professional to prevent the tedious task of manually executing analyses
in a try-and-error approach and to minimize the total number of experiments, introducing a
procedure where numerical simulations are executed without much user intervention. Multi-
Objective Genetic Algorithm is used in the minimization of error between numerical results and
experimental data. Two objectives, based on least-square difference between numerical and
experimental results were applied and 6 kinetic parameters of reaction rate equations of single step
methane reforming, water gas shift and methane combustion were evaluated as optimizing
variables. Due to heat transfer effects between the plates, between the catalyst and the gas mixture,
due to the uncertainties regarding the catalyst load, the direct application of the reaction rate
obtained from the references could not be applied. Instead, a CFD simulation of a representative
domain was used to calculate the conjugate heat transfer with reactive flow and reaction rates which
are not represented on catalyst mass basis.

KEYWORDS: CFD, optimization, nonlinear regression, chemical reaction engineering.

INTRODUCTION

The process intensification characteristics of compact reactors (enhance heat and mass
transfer properties) represent a breakthrough technology for heat and mass controlled reactions
since it allows exploring the full potential of catalytic systems during highly endothermic or
exothermic reactions. Concerning this issue, special attention is drawn to the steam methane
reforming (SMR) reactor, a widely-used process to produce hydrogen or syngas (mixture of
hydrogen and carbon monoxide). A conventional steam methane reformer (SMR) consists of
several fixed-bed reactor tubes filled with steam methane reforming catalysts (pellets), which
converts a mixture of hydrocarbons and water into hydrogen and carbon monoxide via an
endothermic reaction. The SMR reaction is supported by the heat provided by fuel combustion in
the process furnace (exothermic reaction). Besides the large use of the conventional technology,
efforts are made to improve process efficiency, reduce production cost and footprint, decrease the
formation of pollutants for small-scale or large-scale applications (offshore methanol and GTL
plants, fuel cells applications, car-fuelling stations, CO2 capturing, etc). Steam methane reforming
(SRM) using compact reactor has great potential to be a cost-effective means to achieve such goal.
The reaction mechanism for the SMR and catalytic combustion (CC) reaction is a key step to
optimize the compact reformer reactor. Despite many kinetic mechanisms for the catalytic
combustion and steam methane reforming reaction available, there are some uncertainties
concerning different number of reactions, type of catalyst, inhibition effects by carbon dioxide and
water. There are many discussion in the literature, which renders information available
controversial preventing it from being used in all cases.
This article aims to show the application of CFD coupled to a genetic algorithm
optimization in order to obtain a reaction mechanism for steam methane reforming, water gas shift
and combustion inside a catalytic reactor. The reactions were simulated considering a catalytic
compact mini-channel reactor composed by stacked plates containing parallel arrays of mini-
channels. The process channels (steam methane reaction) are filled with metal catalyst and the
necessary heat for the reaction is provided by the intercalated plates containing parallel arrays of
catalytic combustion channels. The optimization methodology makes it possible for the engineering
professional to prevent the tedious task of manually executing analyses in a try-and-error approach
and to minimize the total number of experiments, introducing a procedure through which numerical
simulations are executed without any user intervention. Multi-Objective Genetic Algorithm is used
in the minimization of error between numerical results and experimental data. Two objectives,
based on the summation of the squared absolute error in each point, were used and six kinetic
parameters of reaction rate equations for single step methane reforming, water gas shift and
methane combustion were evaluated as optimizing variables. Due to heat transfer effects between
the plates, between the catalyst and the gas mixture and the uncertainties due to carbon dioxide and
water inhibition, the standard reaction rate parameters to obtain the reaction rate could not be used.
Instead, a CFD simulation of a representative domain was used to calculate the conjugate heat
transfer with reactive flow and reaction rates which are not represented on catalyst mass basis. The
optimization was applied to minimize the relative error between a simplified CFD simulation,
which was evaluated in a two-dimensional reactive flow and the experimental results obtained from
experiments. The methane conversion and temperature for the combustion and reforming ducts
were evaluated. The reaction mechanism obtained will feed a more complex CFD study,
considering the complete reactor geometry, allowing the prediction of hot spots and heat
distribution in some regions. Furthermore, the model permits the analysis of the thermodynamic
equilibrium for coke formation, and the methane conversion for several flow rates and gas
composition, which allows provides a safety operational window for the process.

MATHEMATICAL MODELING

The results of this work are based on a steady state, two-dimensional models with a surface
finite reaction rate model of a set of channels from a compact reactor using computational fluid
dynamics techniques (CFD).
 For this study, the reactor is represented by means of a simplified 2D geometrical model.
Figure 1 shows a schematic of the simplified 2D model, explaining the main considerations on
numerical approach of CFD simulation. Among the main features of the geometric model, there is
the consideration of one and a half reforming channel section and one and a half combustion
channel section, besides a solid region between these sections. The decision of simulating one and a
half channel for each section (reform and combustion) was made with the purpose of using a
symmetry boundary condition and representing a large number of channels. A sensibility test was
performed to guarantee the minimum number of channels required.
This simplified approach (2D) was performed in order to realize a great number of
simulations, as required for a parameter estimation approach in the present work.

Figure 1: Geometric scheme of 2D geometry developed for CFD simulations.

The computational mesh was generated in ANSYS Meshing software. The rectangular
elements have been chosen due to the simplicity of the geometry and higher quality of these
elements for flow field solution when the mesh is aligned with gas flow direction. Figure 2
illustrates a region of computational mesh, showing further refinement in regions close to the wall
(i.e. the region of the boundary layer and higher heat flux). The mesh used in simulations was
formed by 100 thousand elements.

Figure 2: Computational meshing of the reactor domain.

The software ANSYS Fluent 14.0 was employed in the numerical solution of the transport
equations (continuity, momentum and species equations) through finite volume method. The
hypothesis applied for the numerical model was:
 Steady state condition;
Laminar flow (calculated Reynolds number inside channels less than 2100);
Multicomponent model with ideal mixture behavior;
o Species in SMR side: CH4, H2O, CO, CO2, H2;
o Species in CC side: CH4, O2, N2, H2O, CO2 (natural gas was simplified as
pure methane for this study);
Ideal gas;
The heat transfer between fluid-solid domains was considered
Finite rate model was employed in order to include the chemical reactions. The
reactions were treated as pseudo-homogeneous, i.e volumetric reaction rates were
used;
Fluid domain was treated as a porous media, in order to represent catalysts bed.

From the above hypotheses, the boundary conditions were defined, which represent the
input, output and exchange phenomena between the computational domains. Figure 2 illustrates
schematically the application of boundary conditions. In summary, the boundary conditions used
were:
Steam methane reforming inlet feed: prescribed mass flow rate, temperature and
molar fractions;
Combustion inlet feed: prescribed mass flow rate, temperature and molar fractions;
Steam methane reform outlet section: prescribed pressure;
Combustion outlet section: prescribed pressure;
No slip walls coupled with heat transfer;
Symmetry in the upper and lower limits, representing a greater number of mini-
channels.

Equations (1), (2) and (3) represent the three reaction rates used in parameter estimation
step (Tonkovich et. Al, 2007; Hayes et. Al., 2000). Initially, these simplified reaction rates were
adopted in order to execute a preliminary step to define the accurate reaction rates. In these
templates, Equation (1) represents steam-methane reform reaction, Equation (2) represents Water-
Gas Shift reaction, and Equation (3) represents combustion reaction. Steam-methane reform (1) and
water-gas shift reactions (2) were treated as reversible and elementary reactions (Tonkovich et. al,
2007), although combustion reaction (3) was treated as irreversible and with vapor inhibition
(Hayes et. al., 2000).

(1)

(2)

(3)

Therefore, analyzing the reaction rates defined by (1), (2) and (3), the unacknowledged
parameters of this mathematical model ( , and ) were found. The reaction rate constants
were represented by Arrhenius Equation (Equation (4)), so for each reaction rate constant there are
2 others parameters, the pre-exponential factor ( ) and the activation energy ( ).

(4)

Thus, in the present paper, 6 parameters were defined: pre-exponential factor and activation
energy for , and (Equations (1), (2) and (3)). The water adsorption constant parameters
also need to be adjusted. However for this study, these parameters were considered constant (future
adjusts can be done to improve the mathematical model).
Considering these 6 parameters unacknowledged, the nonlinear regression technique was
employed to obtain these values.
The traditional nonlinear regression model fits Equation (5).

(5)

Where is a vector of parameters to be estimated, and is a vector of

independent variables for ith of n observations, and is the vector of dependent variables.
Also, the definition of an objective function for nonlinear regression is necessary, defined in
Equation (6) as least square function.

(6)

(7)

Where is the experimental value, is the point obtained by the model, and is the
number of evaluated points.
Based on above definitions, it is valid as a procedure for parameter estimation to realize the
Hypothesis of Perfect Model Fit, which means that the proposed mathematical model adequately
represents the phenomenon involved (SCHWAAB & PINTO, 2007). This hypothesis is obviously
an idealization about understanding the physical problem and can not be completely satisfied, as it
was discussed above about the hypothesis made to simplify the CFD simulation (2D, laminar, ideal
gas, pseudo-homogeneous reaction, reactions rates treated as elementary reactions, etc.). Thus the
model can not indeed be perfect.
Based on Hypothesis of Perfect Model Fit, The Equation (6) defines the least square
objective function. The minimization of the objective function (Equation (5)) gives the best
estimation of vector . To solve the problem and find the vector that satisfies the minimum value
of objective function, the problem of minimization of objective function in Equation (5) can be
rewritten as a gradient of in relation to , as defined by Equation (7).
However, the solution of the non-linear system defined by Equation (7) could be difficult
due to the need to derivate F analytically. Therefore, numerical techniques have been proposed to
solve the minimization problems. One class of numerical techniques for optimization problem is
Gradient-based algorithms, which are based on numerical derivatives of the objective function.
These methods are iterative and the new point is computed towards a higher function increase
(gradient) and it needs to approximate derivatives by finite differences. The advantages of Gradient-
based algorithms are a higher accuracy of the solution and a higher convergence speed. The
disadvantages are a lower robustness, an initial guess for the solution should be provided , the
possibility of finding local minimums and also the fact that an optimization based on derivative
function does not fit multi objective optimization. In this context, for a parameter estimation
technique, Genetic Algorithm is frequently used, due to the fact that it can be combined with multi
objective functions and are more robust for reach global optimums (ESTECO, 2012).
Also, genetic algorithms can handle a very large variety of optimization tasks knowing only
a few details of their structure. Once the input parameters of the problem are properly encoded, the
algorithm engine is able to explore profitably the design space even without true objective
functions, but in theory only with pairwise comparison criteria. The more data on the structure are
offered to the algorithm, the more effective it becomes. The backbone of this class of algorithms is
the following scheme: a parent population produces through appropriate genetic operators a child
population; a new parent population is selected among children and/or parents, depending on the
chosen elitism procedure and the loop is iterated.
In the present work it was applied the least square minimization technique using two
objective functions: least squares on temperature (Equation (9)) and least squares of methane
conversion (Equation (10)), comparing the CFD result with an existent reference result, called
reference result in this paper. The two objective functions were defined because each function has a
different order of magnitude and units, although it is known that if one objective is reached, the
other one must also be reached due to direct relation with methane conversion and heat of reaction.
However, in order to reach a robust solution, both objectives were considered in the optimization
step.

(9)

(10)

Thus, a multi-objective optimization was performed using the genetic algorithms NSGA-II,
available in the software modeFRONTIER, version 4.4.1. NSGAII (TURCO, 2010) is a
sophisticated algorithm which, nonetheless, maintains a large flexibility. It requires the definition of
one objective function for each optimization task. The values of these functions are employed for
sorting the generated individuals in order to choose the best possible parents for the next population.
A first partial sorting is performed according to Pareto dominance: the points are grouped in subsets
called fronts. Each front is composed by points which do not dominate each other. Inside each front,
points are sorted depending on the crowding distance operator which promotes individuals located
at less populated regions of the objective space.
Due to the fact that CFD simulations are computationally expensive, the genetic algorithm
NSGA-II was used combined with Response Surface Models, called Fast optimizers. Fast
optimizers use Response Surface Models (Meta-Models) to speed up the optimization process.
Different RSM are implemented within the algorithm: the best ones, in terms of performance on
some validation points, are chosen and used for a virtual optimization. The so obtained "virtual"
Pareto front is then validated (i.e., evaluated by means of the real solver), obtaining some designs
that iteration by iteration progress toward the real Pareto front. At each iteration, the newly
evaluated designs enrich the training database, permitting a more and more accurate RSM to be
built in an adaptive and iterative way (Rigoni, 2010).
 As it is demanded by a genetic algorithm, an initial set of experiments was generated using
the Incremental Space Filler design of experiments in order to initialize the optimization algorithm.
This algorithm implements the maximum criterion: new points are added sequentially where the
minimum distance from the existing points is maximized (ESTECO, 2012). The initial population
was defined as 100 simulations.
The CFD simulations were performed in parallel configuration with 12 processors of Intel
Xeon X5670@2.93 GHz and each simulation had a computational cost between 10 and 15
minutes.

RESULTS

For parameter estimation of kinetic constants, it was necessary to define the reference
result, which is used to calculate least square objective functions. The Figure 3 illustrates the
reference result that is applied in objective functions in Equation (9) and Equation (10). The goal of
this study is reproduce this behavior modifying pre-exponential factor ( ), activation energy
factor and activation energy ( ) for each reaction (steam methane reform, water gas shift and
combustion).
It is noteworthy that the SMR reaction is an equilibrium reaction and the methane
conversion will be influenced by operational conditions (Le Chateliers principle). On the other
hand, the combustion reaction is irreversible.
It is important to highlight the existence of several uncertainties in this reference result
(experimental), and the mathematical model hypothesis may hinder the correct representation of
these curves. However, the technique presented in this paper will guarantee the best fit for the
experimental result, for the defined mathematical model. To improve the simulated result it will be
necessary to review the boundary conditions and mathematical model assumptions.
The total number of analyzed points in the simulated result was 100, and they were set as
equally spaced in reactor length. Also, as the uncertain of reference result (experimental) is
unknown, it was neglected and all points have the same weight.

Figure 3: Reference result for nonlinear regression.

In this optimization study, 1622 simulations were performed. The multipurpose

optimization software modeFRONTIER allowed an automatically change of inputs parameters
(kinetic constants) in the CFD simulation in order to calculate temperature and methane conversion
profiles.
 The Figure 4 illustrated the multi-objective analysis in optimization process. The Figure
shows a graphic with the first objective function ( ) on the x-axis and the second objective
function ( ) on the y-axis. The points marked in the graph are design points obtained in
simulations. It was observed that, as expected, the two objective functions are directly correlated,
i.e., if one decreases the other one tends to decrease too. It was expected because the temperature
profile is directly related with the heat of the reaction, which is associated with the reaction rate.
Thus, this may characterize an absence of Pareto curve.
On the other hand the Figure 5 illustrated the same graphic in Figure 4 but on another scale.
In this scale, the Figure shows that there is a small region of points characterizing a Pareto frontier.
The design points that belong to Pareto curve are marked in green. An analysis of the existence of
the Pareto frontier is presented at the end of the article.

Figure 4: Multi-objective analysis: least-square.

 Figure 5: Multi-objective analysis: least-square with modified scale to visualize Pareto
frontier.

The identified factor analyses were presented in Table 1. The results show the influence of
input parameters (percentage) in the optimization objectives. It indicates that combustion reaction
parameters have greater influence in the reaction system than others. Also, the steam methane
reform reaction parameters have less influence in reaction system. This behavior can be explained
once the steam methane reform is an equilibrium reaction, so the reaction rate constant becomes
less significant.

Table 1: Factor analysis of input parameters.

Reaction Parameter (%) (%)

14,5 17,5
Combustion
49,3 53,5
0,4 1,4
Steam methane reform
7,3 5,8
4,5 9,3
Water gas shift
24,0 12,5

The model optimization was done by selecting the best five of 1622 design points
(referenced here by their simulation Id) from the Pareto curve (Figure 5). Figure 6 illustrates the
results obtained for least square functions comparing the CFD with reference result (experimental)
in a dimensionless scale, ie, dimensionless by the highest least-square value among the five selected
points. The analysis shows that, with the except of Id 985, the other simulations have relatively the
same agreement with reference results. Some of them with lower differences in temperature profile
(as simulation Id 1396 and 997), and others with lower differences in methane conversion profile
(as Id 989). Figure 7, Figure 8, Figure 9, Figure 10 and Figure 11 illustrate temperature and
methane conversion profile for SMR and CC sections, compared with reference results.
 Figure 6: Least-squares for temperature in SMR, temperature in CC, methane conversion in
SMR and methane conversion in CC.

(a) (b)

(c) (d)
Figure 7: Results for Id 985: Temperature profile in SMR channel (a), Temperature profile
in CC channel (c), Methane conversion profile in SMR channel (c), Methane conversion profile in
CC channel (d).
 (a) (b)

(c) (d)
Figure 8: Results for Id 989: Temperature profile in SMR channel (a), Temperature profile
in CC channel (c), Methane conversion profile in SMR channel (c), Methane conversion profile in
CC channel (d).

(a) (b)

(c) (d)
 Figure 9: Results for Id 997: Temperature profile in SMR channel (a), Temperature profile
in CC channel (c), Methane conversion profile in SMR channel (c), Methane conversion profile in
CC channel (d).

(a) (b)

(c) (d)
Figure 10: Results for Id 1009: Temperature profile in SMR channel (a), Temperature
profile in CC channel (c), Methane conversion profile in SMR channel (c), Methane conversion
profile in CC channel (d).

(a) (b)
 (c) (d)
Figure 11: Results for Id 1396: Temperature profile in SMR channel (a), Temperature
profile in CC channel (c), Methane conversion profile in SMR channel (c), Methane conversion
profile in CC channel (d).

All profiles for conversion in CC channel showed that the reaction rate for combustion
reaction in CFD simulations were higher in the region immediately close to the reactor inlet than the
reference results. It indicates that the combustion reaction rate template is not well set. One of the
reasons could be the effect of the water adsorption constant ( ) which in combustion reaction
rate (equation 3) was preliminarily set as a constant value (value predict from HAYES, 2001).
Another reason could be the assumption of considering just methane as fuel for the combustion. The
other components in the feed (i.e.: ethane, propane, etc.) could lead to a different reaction rates. So,
this parameter should be included in a nonlinear regression model to improve results. Also, this
reaction rate template can be replaced by another, taking into account other inhibitions, such as the
carbon dioxide.
Furthermore, for SMR conversion, it was observed that the CFD simulation achieved less
methane conversion than the reference result. Also, it can be observed that temperature profiles for
CFD simulation achieved greater values for temperature than reference result. Taking in account the
Le Chateliers principle, this result explains the small region of obtained Pareto curve. Once the
temperature increase, it reduces the curve fitting for the temperature profile, but consequently the
conversion increases (by Le Chateliers principle) and improves the curve fitting for conversion
profile; and if the temperature decrease it enhances the curve fitting for the temperature profile, but
it worsens the curve fitting for the methane conversion in SMR side. Then, it can be noted that this
objectives are competing and the optimization proposed was correctly set. This behavior is due to
uncertainties in some of the operating and boundary conditions with respect to the reference data.
However, it is observed that Pareto curve is not significant, due to small region of points in curve,
compared with the total design points area, confirming the validity of obtained parameters. The
model shows a good fitting between numerical and experimental reference, despite the number of
hypothesis made, the complexity of the CFD simulation and the large number of parametric
uncertainties (including operational conditions),

CONCLUSIONS

This paper has presented a methodology to obtain the kinetic mechanism of steam methane
reforming compact reactor using CFD coupled with hybrid genetic/surface response optimization
model.
To obtain kinetic parameters, two objective optimization based on least square were
executed comparing temperature and methane conversion profiles. The results showed a great curve
fitting obtained in CFD optimized simulations when compared with the reference results.
 Also, this paper presented a factor analysis, which was able to show which kinetic constants
have more influence in the reaction system. Through this analysis, it was found that combustion
reaction parameters have more influence in reaction system than steam methane reform and water
gas shift reactions do this behavior is explained because the SMR and WGS reaction are both
equilibrium reactions whereas combustion reaction is not.
The parametric uncertainties explain the deviations between the model and the experimental
results. However, based on proximity with the CFD simulations profiles compared to the reference
result, the parameters determined from this study have a good degree of reliability and can be used
for analyzing the behavior of the reaction in other operating conditions.
This study showed that the parameter estimation technique coupled with CFD simulation is
a powerful tool to determine unknown parameters of models. Specifically in this case, the
complexity of the reaction system including surface reactions, strongly dependent on heat transfer,
and large number of reactions involved, the performed method allowed to obtain simplified reaction
rates that can be applied in more complex models to predict methane conversion for several flow
rates and gas composition, which permits the determination of a safety operational window for the
process.

FUTURE STUDIES

Future studies are being carried out analyzing a more complex CFD model with 3D
geometry and considering the geometry of catalysts and surface reactions instead of volumetric
ones.
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