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Macroscopic and population balances for the simulation of surface reactions
Balances macroscópicos y poblacionales para la simulación de reacciones en la superficie
DOI:
https://doi.org/10.15446/dyna.v89n224.101583Palabras clave:
transport phenomena; population balances; kinetic cycle; surface catalyst (en)fenómenos de transporte; balances de población; ciclo cinético; superficie de catalizador (es)
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Modeling and computational simulation of the carbon monoxide oxidation process, taken as a key system to analyze the importance of the dynamic description of active sites into the process yield, are presented in this work. To this aim, the formalism of transport phenomena and population balances are used to implement a realistic model that involves heat exchange, transfer of mass and momentum, chemical reaction, and catalyst deactivation. The model is solved numerically, and the analysis is made by comparing isothermal pseudo-steady state approximation with non-isothermal non-steady state assumption for the catalytic cycle. The results show the advantage of considering the interface explicitly into the model since temporary changes of the reactive complex as well as the active sites of the catalyst have a great influence over the reaction yield. By considering this fact, the reaction description is made in a more proper way.
En este trabajo presentamos el modelamiento y simulación computacional de la oxidación del monóxido de carbono, proceso que tomamos como referente para analizar la importancia de describir la dinámica de los sitios activos en el rendimiento del proceso catalítico. Utilizamos el formalismo de los procesos de transporte y los balances poblaciones para desarrollar un modelo realístico que involucra el intercambio de calor, la transferencia de masa y de momentum, la reacción química y la desactivación del catalizador. El modelo propuesto se resuelve numéricamente y se hace un análisis comparativo de los resultados entre la aproximación de pseudo estado estacionario isotérmico y el estado no-estacionario no-isotérmico para el ciclo catalítico. Los resultados obtenidos muestran la importancia de considerar en el modelo la interfase de manera explícita, ya que la dinámica temporal de la reacción y de los sitios activos influyen de manera significativa en el rendimiento del proceso catalítico.
Referencias
Santillán, M., Chemical kinetics, stochastic processes, and irreversible thermodynamics. Springer International Publishing, New York, USA, 2014. DOI: https://doi.org/10.1007/978-3-319-06689-9.
Hossain, M.M., Atanda, L., Al-Yassir, N. and Al-Khattaf, S., Kinetics modeling of ethylbenzene dehydrogenation to styrene over a mesoporous alumina supported iron catalyst. Chem. Eng. J. (207-208), pp. 308-321, 2012. DOI: https://doi.org/10.1016/j.cej.2012.06.108.
Garayhi, A.R. and Keil, F.J., Modeling of microkinetics in heterogeneous catalysis by means of frequency response techniques. Chem. Eng. J., 82, pp. 329-346, 2001. DOI: https://doi.org/10.1016/S1385-8947(00)00364-8.
Kozuch, S. and Shaik, S., Kinetic-Quantum chemical model for catalytic cycles: the Haber−Bosch process and the effect of reagent concentration. J. Phys. Chem. A., 112, pp. 6032-6041, 2008. DOI: https://doi.org/10.1021/jp8004772.
Chumakov, G.A., Chumakova, N.A. and Lashina, E.A., Modeling the complex dynamics of heterogeneous catalytic reactions with fast, intermediate, and slow variables. Chem. Eng. J., 282, pp. 11-19, 2015. DOI: https://doi.org/10.1016/j.cej.2015.03.017.
Rubi, J.M., Bedeaux, D., Kjelstrup, S. and Pagonabarraga, I., Chemical cycle kinetics: removing the limitation of linearity of a non-equilibrium thermodynamic description. Int. J. Thermophys., 34, pp. 1214-1228, 2015. DOI: https://doi.org/10.1007/s10765-013-1484-1.
Schlexer, P., Computational Modeling in Heterogeneous Catalysis. Elsevier Inc., 2017. DOI: https://doi.org/10.1016/b978-0-12-409547-2.14273-8.
Randolph, A.D. and Larson, M.A., Theory of Particulate Processes. Elsevier, 1971. DOI: https://doi.org/10.1016/B978-0-12-579650-7.X5001-5.
Niemann, B. and Sundmacher, K., Reduced discrete population balance model for precipitation of barium sulfate nanoparticles in non-ionic microemulsions. Chem. Eng. J., 143, pp. 314-325, 2008. DOI: https://doi.org/10.1016/j.cej.2008.06.012.
Verkoeijen, D., Pouw, G. A., Meesters, G.M.H. and Scarlett, B., Population balances for particulate processes - A volume approach. Chem. Eng. Sci., 57, pp. 2287-2303, 2002. DOI: https://doi.org/10.1016/S0009-2509(02)00118-5.
Chorkendorff, I. and Niemantsverdriet, J.W., Concepts of Modern Catalysis and Kinetics. Wiley Ed., 2003. DOI: https://doi.org/10.1002/3527602658.
Parmon, V.N., Catalysis and non-equilibrium thermodynamics: modern in situ studies and new theoretical approaches. Catal. Today. 51, pp. 435-456, 1999. DOI: https://doi.org/10.1016/S0920-5861(99)00032-2.
Chattoraj, D.K. and Birdi, K.S., Adsorption and the Gibbs surface excess. Springer, Boston, MA, USA, 1984. DOI: https://doi.org/10.1007/978-1-4615-8333-2.
Bedeaux, D., Kjelstrup, S., Zhu, L. and Koper, G.J.M., Nonequilibrium thermodynamics - A tool to describe heterogeneous catalysis. Phys. Chem. Chem. Phys., 8, pp. 5421-5427, 2006. DOI: https://doi.org/10.1039/B610041D.
Zhu, L., Koper, G.J.M. and Bedeaux, D., Heats of transfer in the diffusion layer before the surface and the surface temperature for a catalytic hydrogen oxidation (H 2 + (1/2)O 2 → H 2 O) reaction. J. Phys. Chem. A., 110, pp. 4080-4088, 2006. DOI: https://doi.org/10.1021/jp056301i.
Sha, M., Liu, Y., Dong, H., Luo, F., Jiang, F., Tang, Z., Zhu, G. and Wu, G., Origin of heterogeneous dynamics in local molecular structures of ionic liquids. Soft Matter. 12, pp. 8942-8949, 2016. DOI: https://doi.org/10.1039/c6sm01797e.
Cruz, C., Barragán, D., Magnanelli, E., Lervik, A. and Kjelstrup, S., Non-equilibrium thermodynamics as a tool to compute temperature at the catalyst surface. Phys. Chem. Chem. Phys., 21, 2019. DOI: https://doi.org/10.1039/c9cp02389e.
Bedeaux, D. and Kjelstrup, S., Heat, mass and charge transport, and chemical reactions at surfaces. Int. J. Thermodyn., 8, pp. 25-41, 2005.
Bird, R.B., Stewart, W.E. and Lightfoot, E.N., Transport phenomena. Wiley, USA, 2007.
Deen, W.M., Analysis of Transport Phenomena. Oxford University Press, UK, 1998.
Barragán, D., Entropy production and Newton’s cooling law. Ing. e Investig., 29, pp. 88-93, 2009. http://www.bdigital.unal.edu.co/19213/1/15167-45952-1-PB.pdf.
Ramkrishna, D., Population balances. Elsevier, 2000. DOI: https://doi.org/10.1016/B978-0-12-576970-9.X5000-0.
Hendriksen, B.L.M., Ackermann, M.D., van Rijn, R., Stoltz, D., Popa, I., Balmes, O., Resta, A., Wermeille, D., Felici, R., Ferrer, S. and Frenken, J.W.M., The role of steps in surface catalysis and reaction oscillations. Nat. Chem. 2, pp. 730-734, 2010. DOI: https://doi.org/10.1038/nchem.728.
Vendelbo, S.B., Elkjær, C.F., Falsig, H., Puspitasari, I., Dona, P., Mele, L., Morana, B., Nelissen, B.J., Van Rijn, R., Creemer, J.F., Kooyman, P.J. and Helveg, S., Visualization of oscillatory behaviour of Pt nanoparticles catalysing CO oxidation. Nat. Mater., 13, pp. 884-890, 2014. DOI: https://doi.org/10.1038/nmat4033.
Khazanchi, R., Reddy, D. c Bhatia, D., Kinetic model for the reversible deactivation of a Pt/Al2O3 catalyst during NO oxidation. Chem. Eng. J., 314, pp. 139-151, 2017. DOI: https://doi.org/10.1016/j.cej.2016.12.042.
Ivanova, V., Baunach, T. and Kolb, D.M., Metal deposition onto a thiol-covered gold surface: a new approach. Electrochim. Acta. 50, pp. 4283-4288, 2005. DOI: https://doi.org/10.1016/j.electacta.2005.05.047.
Rawlins, W.T. and Gardiner, W.C., Rate constant of OH + OH = H2O + O from 1500 to 2000 K. J. Chem. Phys. 60, pp. 4676-4681, 1974. DOI: https://doi.org/10.1063/1.1680967.
Marchisio, D.L., Pikturna, J.T., Fox, R.O., Vigil, R.D. and Barresi, A.A., Quadrature method of moments for population-balance equations. AIChE J., 49, pp. 1266-1276, 2003. DOI: https://doi.org/10.1002/aic.690490517.
Dorao, C.A. and Jakobsen, H.A., Numerical calculation of the moments of the population balance equation. J. Comput. Appl. Math., 196, pp. 619-633, 2006. DOI: https://doi.org/10.1016/j.cam.2005.10.015.
Dorao, C.A. and Jakobsen, H.A., The quadrature method of moments and its relationship with the method of weighted residuals. Chem. Eng. Sci., 61, pp. 7795-7804, 2006. DOI: https://doi.org/10.1016/j.ces.2006.09.014.
Davis, M.E. and Davis, R.J., Fundamentals of Chemical Reaction Engineering, McGraw-Hill Higher Education , New York, USA, 2013.
Hegedus, L.L., Oh, S.H. and Baron, K., Multiple steady states in an isothermal, integral reactor: The catalytic oxidation of carbon monoxide over platinum-alumina. AIChE J. 23, pp. 632–642, 1977. DOI: https://doi.org/10.1002/aic.690230503.
Murray, J.D., Mathematical Biology. Springer New York, USA, 2002. DOI: https://doi.org/10.1007/b98868.
Fontes, E., COMSOL: modeling approaches in heterogeneous catalysis, [online]. 2015. Available at: https://www.comsol.com/blogs.
Pietrzyk, S., Dhainaut, F., Khodakov, A. and Granger, P., Catalytic Reactions under Unsteady-State Conditions. Modelling with COMSOL, COMSOL Users Conf. 2006, 2006.
Patan, A.K., Mekala, M. and Thamida, S.K., Dynamic Simulation Using COMSOL Multiphysics for Heterogeneous Catalysis at Particle Scale. 2016.
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