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OPTIMIZATIONOFAPDBASEDMEMBRANEREACTORFOR�
HYDROGENPRODUCTIONFROMMETHANESTEAMREFORMING

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The results predicted by the model were validated using experimental data. MURATA (4) (1. ASSIS (1) C. Assis: Tel. propõe-se um modelo fenomenológico no estado estacionário para descrever o desempenho de um reator com membrana na produção de hidrogênio a partir da reforma a vapor do metano e realiza-se a otimização das condições operacionais. MG. vazão molar de gás de arraste (FI). RESUMO Neste trabalho. sweep gas flow rate (FI). Usaram-se duas cinéticas intrínsecas disponíveis na literatura para descrever as reações da reforma a vapor do metano. foram avaliados os efeitos de cinco parâmetros importantes do processo. temperatura externa do reator (TW) e razão molar de alimentação entre vapor d’água e metano (M). vazão molar de alimentação de metano (FCH40). HORI (2) L. sensivity analysis.4) School of Chemical Engineering – Federal University of Uberlandia – Uberlandia. it is proposed a phenomenological model in steady state to describe the performance of a membrane reactor for hydrogen production through methane steam reform as well as it is performed an optimization of operating conditions. using the optimized conditions. que por sua vez faz uso do código computacional DIRCOL em FORTRAN. J. SILVA (3) V. simultaneamente na conversão do metano (XCH4) e na recuperação do hidrogênio (YH2). hidrogênio. OPTIMIZATION OF A PD-BASED MEMBRANE REACTOR FOR HYDROGEN PRODUCTION FROM METHANE STEAM REFORMING A. Brazil. O modelo é composto por equações diferenciais ordinárias advindas dos balanços de massa. both on methane conversion (XCH4 ) and hydrogen recovery (YH2 ). energy and momentum balances and constitutive relations. e-mail: adilsonjassis@gmail. KEYWORDS Modeling and simulation. reações de reforma. As melhores condições operacionais foram obtidas por otimização paramétrica simples e por um método baseado no gradiente. reforming reactions. Na otimização. inlet reactor pressure (PR0). DIRCOL. V. J. pressão de entrada do reator (PR0). The model is composed by a set of ordinary differential equations from mass. hydrogen. The best operating conditions were obtained through simple parametric optimization and by a method based on gradient.3.com 1 . 1 Correspondence should be sent to A. Os resultados previstos pelo modelo foram validados com dados experimentais. nas condições ótimas.2. energia e quantidade de movimento e equações constitutivas. DIRCOL. análise de sensibilidade. E. Altas conversões de metano (96%) e recuperações de hidrogênio (91%) foram atingidas. ABSTRACT In this work. They were used two different intrinsic kinetic expressions from literature. PALAVRAS-CHAVE Modelagem e simulação. which uses the computer code DIRCOL in FORTRAN. It is shown that high methane conversion (96%) as well as hydrogen recovery (91%) can be obtained. methane feed flow rate (FCH40). They were investigated the effect of five important process parameters.: +55(34) 3239-4292. external reactor temperature (TW) and steam to methane feed flow ratio (M). C.

Several studies [3-7] have studied the influence of the factors such as operating pressure. 1. The catalyst is packed in the annular region. carbon dioxide and hydrogen that present greater probability to occur during methane steam reforming are: CH 4 + H 2O Ç CO + 3 H 2 − ∆H 298 K = −206. Since the maximum conversion that could be achieved is the equilibrium conversion. H2O: 2 .2) CH 4 + 2 H 2O Ç CO2 + 4 H 2 − ∆H 298 K = −165. displacing the chemical equilibrium and enabling operation at moderate temperatures. in a membrane reactor.1 kJ / mol (0. In this work a combination of a parametric optimization and a gradient-based optimization is made to provide an insight about the choice of some parameters that maximize the hydrogen recovery and the methane conversion for a small-scale reactor. which implies on the conventional technology. methane feed flow rate.15 kJ / mol (0. water. monoxide of carbon. Membrane reactors are generally constituted by concentric tubes in which one of them is the membrane. 3.0 kJ / mol (0.1. Satisfactory conversions are dependent on many factors such as the operating parameters [2]. etc. operating temperature.. OBJECTIVES The objectives of this work are to carry out the mathematical modeling of a membrane reactor.1) CO + H 2O Ç CO2 + H 2 − ∆H 298 K = 41. INTRODUCTION Nowadays. to validate the model with experimental data. to verify the influence of important process variables and to find the best operating conditions that optimize the hydrogen recovery and the methane conversion. on the methane conversions. MATHEMATICAL MODELING In accordance with [8] the reactions among methane. methane steam reforming is the main route for hydrogen production. CO. hydrogen is continuously removed from the reaction zone. CO2. 2. The balance equations are: • Mass balance in the reaction chamber: For i= CH4. area of permeation.3) The reactor modeled is schematically represented in Figure. sweep gas flow rate. in laboratory scale. The inner tube is the Pd- based membrane and the outer one is the shell. the membrane technology is an alternative process that can overcome this limitation. The membrane is usually made of Palladium or an alloy of Palladium-Silver that is only permeable by hydrogen. The inert or sweep gas passes into the inner tube in co-current flow mode. in high operating temperatures to reach satisfactory conversions [1]. Methane steam reforming reactions are endothermic and reversible. for the methane steam reforming. Therefore. Figure 1: Membrane reactor scheme considered in this work.

12) dZ dp Where f is calculated by the Ergun's equation: 1− ε  b(1 − ε )  f = 3  a+  (0. • The catalytic bed pressure drop: dPR ρ u2 =−f r s (0. Additional hypotheses adopted in the model development were: nonisothermal/nonisobaric. All thermodynamic mixture properties were calculated using the Virial equation of state.8) r dZ ∂T V dZ Van j =1 • Energy balance in the permeate side: dTp ∂P d v p 1 ρ p Cv v p · = Tp + (Q2 + H H2 J H2 Am ) (0.7) dZ • Energy balance in the reaction chamber: ∂P d vr 3 ρ r Cv vr · dTR = TR + 1 (Q1 − Q2 + W ∑ ( −∆H j )rj − H H2 J H2 Am ) (0. with van der Waals mixing rules.10) Q2 = U 2 A2 (TR − TP ) (0.6) δ • Mass balance in the permeate side: dFH 2 p = J H 2 Am (0.13) ε  Re  The mathematical model considered real gases for thermodynamic properties calculations.4) dZ  j =1  For i= H2 dFi  3  = W  ∑ν ij rj  − J H 2 Am (0. steady-state operation. nonexistence of boundary layer on the membrane and hydrogen diffusion in the membrane is the rate determining step for hydrogen permeation. The reactor dimensions used in this work were taken from [5]. The values of constants a and b of Ergun’s equation are 150 and 1. plug-flow behavior was adopted for the permeate and reaction zone. Methane conversion and hydrogen recovery were defined as: 0 FCH − FCH 4 X CH 4 = 4 0 (0. Other catalyst properties used were taken from [8].5 (0.75 respectively [11]. and Q2 is the heat exchanged between the reaction chamber and the permeate: Q1 = U1 A1 (Tw − TR ) (0.11) The overall heat transfer coefficients were taken from [7].5 J H2 = H2 − pH 2 p )0.9) p dZ ∂T V dZ V pe Q1 is the heat exchanged between the reactor wall and the reaction chamber.14) FCH 4 3 . dFi  3  = W  ∑ν ij rj  (0. pseudo-homogeneous model.5) dZ  j =1  Where JH is given by: 2  E    (( p ))  RTm  A0 e ) ( 0. The gases and the gaseous mixture viscosities were calculated by Chung’s method [10].

Model Validation Two different intrinsic kinetics available for the reactions of methane steam reforming were used. FH 2 p YH 2 = (0. 4 . The basic difference between them is that the first one was developed for catalysts of Ni/MgAl2O4 and only one of the products. hydrogen and carbon monoxide. Methane conversions were evaluated for different steam to methane feed flow ratio. Methane conversions obtained by the model were compared with the experimental ones reported by [5]. The second one was developed for catalysts of Ni/Al2O3 in which two products. the hydrogen. RESULTS AND DISCUSSION 4. Figure 2: Methane conversion versus reactor temperature. The first one is reported by [8] and it is the oldest and widely used.1 . and in this paper only a sample of the results are presented (Fig. by [12] is more recent and there is no reference about its use in a reactor model.15) FH 2 p + FH 2 4. These two kinetics were evaluated during the validation of the model. adsorbs on the surface. in this work. The second one. Figure 3: Methane conversion profiles along the reactor. adsorb on the surface. different operating temperatures and different operating pressures. 2). The validation of each model was carried out using given experimental data of a Pd-based membrane reactor reported by [5] with the same design and operating conditions.

As it will be discussed further.92 to 99. Particularly. an increase in methane conversion and hydrogen recovery is caused by a decrease in methane inlet flow. the gain obtained in methane conversion.The agreement between the simulated results and the experimental ones was good as it can be seen in the Fig. Conversely. an increase in steam to methane feed flow ratio (M) has an opposite effect on the methane conversion and hydrogen recovery. Froment’s kinetics [8] predicts an abrupt change for the composition at the reactor beginning. As it can be seen in the Fig. it is imperative to perform the optimization taking into account these interactions. it can concluded that the use of the upper values of pressure. FI = 2. the optimization problem was posed as: 5 . In this case. These problems are caused by the presence equations. low -4 values were used (1. different values around the standard parameters reported by [5] were adopted. Therefore.3 . it can be noticed that the highest value for this parameter leads to the maximal methane conversion + hydrogen recovery. However. the two available kinetics leads to similar results. 2. TW = 773. during the optimization using a gradient based method. Therefore. This behavior is somewhat different when Hou’s kinetics [12] was used. Froment’s kinetics was chosen due to two mainly reasons. defined by Eqs. an increase in M causes an increase in the sum (XCH4 + YH2 ). temperature and sweep gas and the lower methane feed value leads to the maximal methane conversion and hydrogen recovery.99%) and high recoveries (from 96. analyzing methane conversion and hydrogen recovery sum (Fig. regardless of the interactions among the parameters. 4.Parametric and gradient based optimization At first. 3. depending on the values of the other parameters. M = 3.4. This kinetics is widely known and used. the lower admissible value for methane feed flow rate was 1.0·10 ) as initial conditions for these products.Parametric optimization In order to try to maximize methane conversion and hydrogen recovery. whereas the Hou’s kinetics foresees a less sudden change. the optimization using the gradient based -4 optimization could not be performed for values smaller than 1x10 mol/s of methane feed.28%) could be achieved varying the steam to methane feed ratio and keeping the pressure.82 to 99. is less than the setback obtained in the hydrogen recovery. molar methane feed flow rate less then 1x10-4 mol/s cause dramatic changes the compositions at the reactor beginning.2 . Both kinetics demand products feed. keeping the others parameters in the considered best conditions. 4 A and B. and also because it implies in less mathematical problems. On the other hand. 1. However. the interactions between the parameters are important in the optimization.15 K.0·10-4 mol/s and using the Hou’s kinetics only.75·10-5 mol/s. Moreover. In order to carry out this task a gradient based algorithm of optimization (DIRCOL) was used [13]. As it is shown in Fig. high conversions (from 99. 5 A). Indeed. The lower and upper bounds were chosen based on operating characteristics of the membrane reactors and on the Shu’s work [5].Optimization by a gradient based method (DIRCOL) Having in mind the importance of the interaction between the parameters. The optimization was performed directly from the differential equation by discretization. In other words. methane conversion has an abrupt rise at the reactor beginning. the Froment’s kinetics requires hydrogen feed and Hou’s kinetics requires hydrogen and carbon monoxide feed. an increase in pressure. a standard or reference operational condition for membrane reactors in methane steam reforming were taken according to [5]: PR0 = 136000 Pa. Therefore. 4. Therefore. Even so.75·10-5 mol/s and FCH40 = 2. 4. The difference between them resides on their behavior along the reactor. the use of the Froment’s kinetics cause failure of the algorithm. In other words.15. and this difference increases as the methane feed flow rate increases. To perform the optimization. The upper and lower bounds are shown in Table 1. the trend of this effect change from an increase to a decrease in the objective (methane conversion plus hydrogen recovery). temperature and sweep gas at the highest values and the methane feed at the lowest value.14 and 1. and as a result. temperature and sweep gas flow cause an increase in methane conversion and hydrogen recovery.

This figure also shows the profiles of methane conversion along the reactor.13). a) b) Figure 5: a) Effect of steam to methane feed flow ratio. Subject to: • Model equations (Equations 1.57% and 11. as can be seen in Fig. a) b) Figure 4: Parametric optimization: a) Effect of the pressure and temperature. b) Profiles along the reactor obtained by parametric optimization and optimization with DIRCOL.90% obtained in the adopted standard conditions changing methane feed -5 -4 -4 from 2. 5 B. The best parameters values are shown in Table 1. The initial estimates for the state variables were based on a non linear fit on the integrated model. It is also import to cite that this optimization could be carried out only with the Hou’s kinetics. Due to a numerical instability in the optimizer’s code the methane feed was kept in 1·10-4 mol/s.0 Pa. • Bounds of the state variables (for all state variables. The optimization was carried out using the following input information supplied by the user: optimal tolerance and nonlinear feasibility tolerance equal 1.375·10-4 mol/s. TW. and the others parameters (PR0.26%. • Parameters bounds from Table 1. 6 . other initial estimates for the parameters were used.75·10 to 1. the range is between 0 and 1 due to a normalization).0·10 mol/s. initial estimates for the parameters equal PR0 = 506625. initial grid points equal 15. probably because the dramatic change in composition in the reactor beginning achieved for low values of methane feed. that are higher than 41. FI = 1.4 to 1.27% and a hydrogen recovery of 91.0·10-3. M and FI) were taken as variable decision. It is important to emphasize that values lower than 1.5.Maximize: XCH4 + YH2 . These parameters lead to a methane conversion of 96.15K e M = 2. but all converged to the same values. with equidistant grid points. iscale equal 0.0·10 mol/s cause numerical instability. To avoid reaching local maxima. TW = 873. probably due to the fact that the Froment’s kinetics lead to a more dramatic change in composition than the Hou’s kinetics. b) Effect of the sweep gas flow rate and methane feed flow rate.

JH2 .Reaction pressure.375x10-4 1.75x10-5 1. CONCLUSIONS Comparing methane conversion obtained by the developed model using two available kinetics for methane steam reforming.Hydrogen dimensionless flow rate in the permeate side. [-]. [-].375x10-4 2. it can be concluded that both characterize a good representation of the real reactor. However.27% and hydrogen recovery of 91. [-].The inlet reactor pressure.5 A0 . [m]. 7 .Activation energy. [J/(mol K)]. A methane conversion of 96.Surface area of membrane permeance.15 573.5 6 2.Steam to methane feed flow ratio. PR .15 873. Table 1: Lower.15 873. E . pH2p .Friction factor. [-].Area of heat exchange between the reaction chamber and the external reactor temperature. fH2p .Molar flow rate of inert or sweep gas.The permeate mixture specific heat at constant volume. LIST OF SYMBOLS a . [-]. [mol/m2s].Dimensionless reaction pressure.Dimensionless flow rate of the i component in the reaction side.Hydrogen enthalpy.Hydrogen partial pressure in the permeate side.375x10-4 1. Cvp .15 873. FI . [Pa]. f . [-].Reactor length.5 6 (not conclusive) 2. 6.Ergun's equation constant. upper bounds and best values of the parameters. The use of the DIRCOL to perform the optimization could only be possible with the use of Hou’s kinetics in the model. By parametric optimization. [mol/s].Hydrogen permeation flux. [m2]. even so for a value of methane feed of 1·10-4mol/s. Cvr . b . pH2 . 2 Am .15 Sweep gas (mol/s) 2. [Pa]. Fi . This value is about three times the standard value. the conversion profile obtained using Hou’s kinetics describes smoother concentration profiles along the reactor.15 873.Permeate pressure. [m ].The reaction mixture specific heat at constant volume. L .5 to 6 methane ratio 2.Molar flow rate of component i in the reaction side. [mol/s].Ergun's equation constant. [J/mol]. the best value could not be evaluated with assurance. [Pa]. PR0 . [Pa].Hydrogen partial pressure in the reaction side. [J/mol]. [mol/s]. Parametric optimization Optimization with DIRCOL lower Upper Best lower Upper best Parameters bound bound value bound bound value Pressure (Pa) 101325 506625 506625 101325 506625 506625 Temperature (K) 573. Pp . 2 0.Hydrogen flow rate in the permeate. [Pa].Pre-exponential factor of the permeability. 7. [m ].779 Methane feed (mol/s) 5x10-6 1x10-4 5x10-6 Fixed=1x10-4 5. fi . [-]. FH2p . HH2 . 2 A2 . A1 . ACKNOWLEDGEMENT This work has been supported by Brazilian funding agency CNPq (Grant n.Methane feed flow rate. [mol/s]. it was possible to obtain high conversions and recoveries (more than 99 and 96 %) but. Pr . 475934/2006-7). [J/(mol K)].375x10-4 Steam to 2.Area of heat exchange between the reaction chamber and the permeate side. M .75x10-5 1. [mol/(m s Pa )].26% were obtained for the best parameters choice. FCH40 .

M. [4] Lin. J.The external temperature. [m3]. G.. [-].Gas constant. 2523- 2555. Chuanga. USA: Princeton University. Tr .Permeate density. R . µij . [K]. 2006. Marrelli and Nardella. 31.Heat of the reaction j. D.Dimensionless permeate temperature. Di Paola. Tp . Chemical Engineering Journal.Annular volume.(1989) Methane Steam Reforming.Void fraction.Heat exchanged between the reaction side and the permeate side. Tw . P. 3 Vpe .. J. L. 128. CO2. [3] Falco. [m ]. [m/s]. J.Mean velocity of the gaseous mixture in the permeate. [-]. ∆Hj . [5] Shu. Techno-economic prospects of small-scale membrane reactors in a future hydrogen-fuelled transportation sector. vr . Tm . rj . [-]. Liu. S. 2. Intrinsic Kinetics. 8 . Damen. and Chub. ρp . 1.-L. Van .Catalyst mass. C.Permeate volume. Princeton. 88-96. IEA/H2/TR-02/002. [K]. F. 82. 305-325.Dimensionless axial position. YH2 . K. [m/s]. [J/(mol K)]. 3 (reactions 1. [-]. [J/s]. J. [J/mol]. • Subscripts i = CH4. [W/(m K)].Axial position. M. Methane steam reforming in asymmetric Pd- and Pd-Ag/porous SS membrane reactors. and Faaij.Membrane temperature. Review of small stationary reformers for hydrogen production. W . Y. [-]. r = reaction side. and Kaliaguine. REFERENCES [1] Ogden. TR. Effect of incipient removal of hydrogen through palladium membrane on the conversion of methane steam reforming: experimental and modeling. U1 . Z .Gaseous velocity of the reaction chamber.Methane conversion.Mean velocity of the gaseous mixture in the reaction chamber. Simulation of large-scale membrane reformers by a two-dimensional model. A. [m/s]. H2O...Q1 . z . 2 U2 . 127-139. [-]. Q2 . [Kg/m3]. L. [-]. Grandjean. P. Applied Catalysis A: General. Y-T.Dimensionless temperature of the reaction. [-]. M. and Froment. C. S. 115-125.Rate of the reaction j. H2. k = CH4. 2001.2. T.Stoichiometric coefficient of the component i in the reaction j. [Kg/m ]. A. ε . p = permeate side.Heat exchanged between the reaction side and external environment. 2003.Reaction density.-M. 1994. CO.-H. [Kg]. CO. • Greek letters δ . H2O. us .Overall heat transfer coefficient (reaction side and external side).3). Catalysis Today. 35(1). j = 1. 3 ρr . Energy.. [-]. 1. H2. XCH4 .. 2006. 8. [m]. [W/(m2K)]. [Kmol/(Kg s)]. Re . Methanation andWater-Gas Shift: I.Temperature of the reaction side.Overall heat transfer coefficient (reaction and permeation zone). vp . AIChE Journal . [J/s]. [K]. 119.Hydrogen recovery. Report No. [2] Sjardin. [6] Xu.1.Membrane thickness.Reynolds' number.

[8] Tong. and Bischoff. [10] Poling. 928-933. Yamamoto. p. [9] Ohmori. W. J. Res. 9 View publication stats . H.. R. A. Paturzo. 2005.30(10). Version 2. [11] Froment. 2001. Chem. A. F.. 2005. Basile. New York. Chemical Reactor Analysis and Design.A Direct Collocation Method for the Numerical Solution of Optimal Control Problems. Industrial and Engineering Chemistry Research . J. W.. P. K. [13] Von Stryk O..1990. A. and Haraya. M. The Properties of Gases and Liquids. T. Simulation of a porous ceramic membrane reactor for hydrogen production. 1454- 1465. J. L. J. E. Experimental Study of the Methane Steam Reforming Reaction in a Dense Pd/Ag Membrane Reactor... Prausnitz. [7] Gallucci.. O’Connell. 2004. McGraw-Hill.. Matsumura. Hughes. N. B.. 43. Nakaiwa. Y. Chemical Engineering Journal. Hayakawa. and Itoh.. 44. YU. Experimental Study of Steam Reforming of Methane in a Thin (6 µM) Pd-Based Membrane Reactor. v. . Endo.. Y. Hydrogen Energy. K. K. Suda. T. User’s Guide for DIRCOL . [12] Hou.. John Wiley. 5th ed.: The kinetics of methane steam reforming over a Ni/α α−Al2O3 catalyst. Eng.311-328. 2004. 82. 1071-1079.1 of November 1999 (Updated: April 2002). B. Ind.. K. M. Int. A.. Fama.