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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, nº 100. Edifício Techplan, 1º andar – Saco Grande  Florianopolis/SC, Brazil. CEP: 88032700. (2) CENPES – PETROBRAS Research and Development Center, Cidade Universitaria Q.7  Ilha do Fundao  Rio de Janeiro/RJ, Brazil. CEP: 21949900.
© 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Unpublished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 tryanderror 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 leastsquare 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 widelyused process to produce hydrogen or syngas (mixture of hydrogen and carbon monoxide). A conventional steam methane reformer (SMR) consists of several fixedbed 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 smallscale or largescale applications (offshore methanol and GTL plants, fuel cells applications, carfuelling stations, CO2 capturing, etc). Steam methane reforming (SRM) using compact reactor has great potential to be a costeffective 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 minichannel 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 tryanderror approach and to minimize the total number of experiments, introducing a procedure through which numerical simulations are executed without any user intervention. MultiObjective 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 twodimensional 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, twodimensional 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; Multicomponent model with ideal mixture behavior; o o Ideal gas; 

Laminar flow (calculated Reynolds number inside channels less than 2100); 


Species in SMR side: CH _{4} , H _{2} O, CO, CO _{2} , H _{2} ; 

Species in CC side: CH _{4} , O _{2} , N _{2} , H _{2} O, CO _{2} (natural gas was simplified as 


pure methane for this study); 

The heat transfer between fluidsolid domains was considered 

Finite rate model was employed in order to include the chemical reactions. The 

reactions were treated as pseudohomogeneous, 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 steammethane reform reaction, Equation (2) represents Water Gas Shift reaction, and Equation (3) represents combustion reaction. Steammethane reform (1) and watergas 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 preexponential factor ( ) and the activation energy ( ).
(4)
Thus, in the present paper, 6 parameters were defined: preexponential 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, pseudohomogeneous 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 nonlinear 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 Gradientbased 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 multiobjective optimization was performed using the genetic algorithms NSGAII, available in the software modeFRONTIER®, version 4.4.1. NSGA–II (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 NSGAII was used combined with Response Surface Models, called Fast optimizers. Fast optimizers use Response Surface Models (MetaModels) 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 preexponential 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 Chatelier’s 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 multiobjective analysis in optimization process. The Figure
shows a graphic with the first objective function (
) on the xaxis and the second objective
function ( ) on the yaxis. 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: Multiobjective analysis: leastsquare.
Figure 5: Multiobjective analysis: leastsquare 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 

(%) 

(%) 
Combustion 

17,5 


53,5 

Steam methane reform 

1,4 


5,8 

Water gas shift 

9,3 


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 leastsquare 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: Leastsquares for temperature in SMR, temperature in CC, methane conversion in SMR and methane conversion in CC.
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 Chatelier’s 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 Chatelier’s 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 point’s 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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